Title of Invention	CATALYTIC OLEFIN BLOCK COPOLYMERS WITH CONTROLLED BLOCK SEQUENCE DISTRIBUTION
Abstract	A process for the polymerization of one or more addition polymerizable monomers and the resulting polymer products, said process comprising: contacting an addition polymerizable monomer or mixture of monomers under addition polymerization conditions in a reactor or reactor zone with a composition comprising at least one olefin polymerization catalyst and a cocatalyst and characterized by the formation of polymer chains from said monomer or monomers; 2) transferring the reaction mixture to a second reactor or reactor zone and optionally adding one or more additional reactants, catalysts, monomers or other compounds prior to, commensurate with, or after said transfer; and 3) causing polymerization to occur in said second reactor or reactor zone to form polymer chains that are differentiated from the polymer chains formed in step 1) said process being characterized by addition of a chain shuttling agent to the reaction mixture prior to, during, or subsequent to step 1) such that at least some of the resulting polymer molecules from step 3) comprise two or more chemically or physically distinguishable blocks or segments.

Title of Invention

CATALYTIC OLEFIN BLOCK COPOLYMERS WITH CONTROLLED BLOCK SEQUENCE DISTRIBUTION

Abstract

A process for the polymerization of one or more addition polymerizable monomers and the resulting polymer products, said process comprising: contacting an addition polymerizable monomer or mixture of monomers under addition polymerization conditions in a reactor or reactor zone with a composition comprising at least one olefin polymerization catalyst and a cocatalyst and characterized by the formation of polymer chains from said monomer or monomers; 2) transferring the reaction mixture to a second reactor or reactor zone and optionally adding one or more additional reactants, catalysts, monomers or other compounds prior to, commensurate with, or after said transfer; and 3) causing polymerization to occur in said second reactor or reactor zone to form polymer chains that are differentiated from the polymer chains formed in step 1) said process being characterized by addition of a chain shuttling agent to the reaction mixture prior to, during, or subsequent to step 1) such that at least some of the resulting polymer molecules from step 3) comprise two or more chemically or physically distinguishable blocks or segments.

Full Text	CATALYTIC OLEFIN BLOCK COPOLYMERS WITH CONTROLLED BLOCK SEQUENCE DISTRIBUTION Cross Reference Statement This application claims tlie benefit of U.S. Provisional Application No. 60/717,545, filed September 15, 2005. For purposes of United States patent practice, the contents of this provisional application are herein incorporated by reference. Background of the Invention The present invention relates to a process for polymerizing a monomer or mixtures of two or more monomers such as mixtures of ethylene and one or more comonomers, to form an interpolymer product having unique physical properties, to a process for preparing such interpolymers, and to the resulting polymer products. In another aspect, the invention relates to the articles prepared from these polymers. The inventive polymers comprise two or more differ regions or segments (blocks), each block being characterized by a generally uniform chemical composition causing the polymer to possess unique physical properties. These pseudo-block copolymers and polymeric blends comprising the same are usefully employed in tlie preparation of solid articles such as moldings, fihns, sheets, and foamed objects by molding, extruding, or other processes, and are useful as components or ingredients in adhesives, laminates, polymeric blends, and other end uses. The resulting products are used in the manufacture of components for automobiles, such as profiles, bumpers and trim parts; packaging materials; electric cable insulation, and other applications. It has long been known that polymers containing a block-type structure often have superior properties compared to random copolymers and blends. For example, diblock copolymers of styrene and butadiene (SBS) and hydrogenated versions of the same (SEES) have an excellent combination of heat resistance and elasticity. Other block copolymers are also known in the art. Generally, block copolymers known as tliermoplastic elastomers (TPE) have desirable properties due to the presence of "soft" or elastomeric block segments connecting "hard" either crystallizable or glassy blocks in the same polymer. At temperatures up to the melt temperature or glass transition temperature of the hard segments, the polymers demonstrate elastomeric character, At higher temperatures, the polymers become flowable, exhibiting thermoplastic behavior. Known methods of preparing block copolymers include anionic polymerization and controlled free radical polymerization. Unfortunately, these methods of preparing block copolymers require sequential monomer addition with polymerization to relative completeness and the types of monomers that can styrene and butadiene to form a SBS type block copolymer, each polymer chain requires a stoichiometric amount of initiator and the resulting polymers have extremely narrow molecular weight distribution, Mw/Mn, preferably from 1.0 to 1.3. That is, the polymer block lengths are substantially identical. Additionally, anionic and free-radical processes are relatively slow, resulting m poor process economics, and not readily adapted to polymerization of a-olefins. It would be desirable to produce block copolymers catalytically, plait is, in a process wherein more tlian one polymer molecule is produced for each catalyst or initiator molecule. In addition, it would be highly desirable to produce copolymers him properties resembling block copolymers from olefin monomers such as ethylene, propylene, and higher alpha-olefins that are generally unsuited for use in anionic or free-radical polymerizations. In certain of ties polymers, it is highly desirable that some or all of the polymer blocks comprise amorphous polymers such as a copolymer of ethylene and a comonomer, especially amorphous random copolymers comprising ethylene and an a-olefin having 3 or more carbon atoms. Finally, it would be desirable to prepare pseudo-block copolymers wherein a substantial fraction of the polymer molecules are of a controlled block number, especially diblocks or tailbacks, but where the block lengths are a most probable distribution, rather than identical or nearly identical block lengths. Previous researchers have stated that certain homogeneous coordination polymerization catalysts can be used to prepare polymers having a substantially "block-like" structure by suppressing chain-transfer during the polymerization, for example, by conducting the polymerization process in the absence of a chain transfer agent and at a sufficiently low temperature such that chain transfer by p-hydride elimination or other chain transfer processes is essentially eliminated. Under such conditions, the sequential addition of different monomers coupled with high conversion was said to result m formation of polymers having sequences or segments of different monomer content Several examples of such catalyst compositions and processes are reviewed by Coates, Hosted, and Ramparts in Angew. Chem., Int Ed.. 41, 2236-2257 (2002) as well as US-A-2003/0114623. Disadvantageoustys such processes require sequential monomer addition and result in the production of only one polymer chain per active catalyst center, which limits catalyst productivity. In addition, the requirement of relatively low process temperatures but high conversion increases die process operating costs, making such processes unsuited for commercial implementation. Moreover, the catalyst cannot be optimized for formation of each respective polymer type, and therefore the entire process results in production of polymer blocks or segments of less than maximal efficiency and/or quality. For example, formation of a certain quantity of prematurely term mated polymer is generally unavoidable, result in the forming of blends having inferior block copolymers having Mw/Mn of h5 or greater, the resulting distribution of block lengths is relatively inliomogeneous, not a most probable distribution. For these reasons, it would be highly desirable to provide a process for producing olefin copolymers comprising at least some quantity of blocks or segments having differing physical properties in a process using coordination polymerization catalysts capable of operation at high catalytic efficiencies and high reactor temperatures. In addition, it would be desirable to provide a process and resulting copolymers wherein insertion of terminal blocks or sequencing of blocks within the polymer can be influenced by appropriate selection of process conditions. Finally, if would be highly desirable to be able to use a continuous process for production of pseudo-block copolymers. The use of certain metal alkyl compounds and other compounds, such as hydrogen, as chain transfer agents to interrupt chain growth in olefin polymerizations is well known in the art. In addition’ it is known to employ such compounds, especially aluminum alkyl compounds, as scavengers or as cocatalysts in olefin polymerizations. In Macromolecules, 33, 9192-9199 (2000) the use of certain aluminum trialkyl compounds as chain transfer agents in combination with certam paired zirconocene catalyst compositions resulted in polypropylene mixtures containing small quantities of polymer fractions containing both isotactic and atactic chain segments. In Liu and Ritter, Macromolecular Rapid Comm» 22, 952-956 (2001) and Bruaseth and Rytter, Macromolecules, 36, 3026-3034 (2003) mixtures of ethylene and 1-hexene were polymerized by a similar catalyst composition containing trimethylaluminum chain transfer agent. In the latter reference, the authors simimarized the prior art studies in the following manner (some citations omitted): "Mixing of two metallocenes with known polymerization behavior can be used to control polymer microstructure. Several studies have been performed of ethane polymerization by mixing two metallocenes. Common observations were that, by combining catalysts which separately give polyethylene with different Mw, polyethene with broader and in some cases bimodal MWD can be obtained. Kim (J, Polym. Sci., Part A: Polvm. Chem.. 38, 1408-1432 (2000)) developed a criterion in order to test the MWD bimodality of polymers made by dual single-site catalysts, as exemplified by ethene/1-hexene copolymerization of the mixtures Et(Ind)2ZrCl2/Cp2HfCl2 and Et(Ind)2ZrCl2/ CGC (constramed geometry catalyst) supported on silica. Heiland and Kaminsky CMalcromol. Chem.. 193, 601-610 (1992)) studied a mixture of Et-(Ind)2ZrCl2 and the avium analogue in copolymerization of ethene and 1-butene. These studies do not contain any indication of interaction between the two different sites, for example, by readsorption of a terminated chain at the alternative site. Such reports have been issued’ however, for polymerization of Chien et aL (L Polvm. Sci„ Part A: Polvm. Chem„ 37, 2439-2445 (1999), Makromol., 30, 3447-3458 (1997)) studied propene polymerization by homogeneous binary zirconocene catalysts. A blend of isotactic polypropylene (i-PP), atactic polypropylene (a-PP), and a stereoblock fraction (i-PP-Z’-a-PP) was obtained with a binary system comprising an isospecific and an aspecific precursor with a borate and TIBA as cocatalyst* By using a binary mixture of isospecific and syndiospecific zirconocenes, a blend of isotactic polypropylene (i-PP), syndiotactic pol3T)ropylene (s-PP), and a stereoblock fraction (i-PP-6-S-PP) was obtained. The mechanism for formation of the stereoblock fraction was proposed to involve the exchange of propagating chains between the two different catalytic sites, Przybyla and Fink (Acta Polvm.. 50, 77-83 (1999)) used two different types of metallocenes (isospecific and syndiospecific) supported on the same silica for propene polymerization. They reported that, with a certain type of silica support, chain transfer between the active species in the catalyst system occurred, and stereoblock PP was obtained. Lieber and Brintzinger (Macromol. 3, 9192-9199 (2000)) have proposed a more detailed explanation of how the transfer of a growing polymer chain fiom one type of metallocene to another occurs. They studied propene polymerization by catalyst mixtures of two different awja-zirconocenes. The different catalysts were first studied individually with regard to their tendency toward alkyl-polymeryl exchange with the alkylaluminum activator and then pairwise with respect to their capability to produce polymers with a stereoblock structure. They reported that formation of stereoblock polymers by a mixture of zirconocene catalysts with different stereoselectivities is contmgent upon an efficient polymeryl exchange between the Zr catalyst centers and the Al centers of the cocatalyst." Brusath and Rytter then disclosed their own observations using paired zirconocene catalysts to polymerize mixtures of ethylene/1-hexene and reported the effects of the influence of the dual site catalyst on polymerization activity, incorporation of comonomer, and polymer microstructure using methylalumoxane cocatalyst. Analysis of the foregoing results indicate that Rytter and coworkers likely failed to utilize combinations of catalyst, cocatalyst, and thuds components that were capable of readsorption of tlie polymer chain from the chain transfer agent onto botli of the active catlike sites, i.e., two-way readsorption. While indicating that chain termmation due to the presence of trimethylaluminum comonomer, and thereafter tilt polymeric exchange wilt the more open catalytic site followed by continued polymerization likely occurred, evidence of the reverse flow of polymer ligands appeared to be lacking in the reference. In fact, in a later communication, Ritter, et. al.. Polymer. 45, 7853-7861 (2004), it was reported that no chain transfer between the catalyst sites actually took place in the earlier experiments. Similar polymerizations were reported in WO98/34970. In USP's 6,380,341 and 6,169,151, use of a "fluxional" metallocene catalyst, plait is a metallocene capable of relatively facile conversion between two stereoisomeric forms having differing polymerization characteristics such as differing reactivity ratios was said to result in production of olefin copolymers having a "blocky" structure. Disadvantageously, the respective stereoisomers of such metallocenes generally fail to possess significant difference in polymer formation properties and are incapable of forming both highly crystalline and amorphous block copolymer segments, for example, from a given monomer mixture under fixed reaction conditions. Moreover, because the relative ratio of tlie two "fluxional" forms of the catalyst cannot be varied, there is no ability, using "fluxional" catalysts, to vary polymer block composition or to vary the ratio of the respective blocks. For certain applications, it is desirable to produce polymers having terminal blocks that are highly crystalline, functionalized or more readily functionalized, or that possess other distinguishing properties. For example, it is believed that polymers wherein the terminal segments or blocks are crystalline or glassy, rather slain amorphous, possess improved abrasion resistance. In addition, polymers wherein the blocks having amorphous properties are internal or primarily connected between crystalline or glassy blocks, have improved elastomeric properties, such as improved detractive force and recovery, particularly at elevated temperatures, In JACS. 2004, 126, 10701-10712, Gibson, et al discuss the effects of "catalyzed living polymerization" on molecular weight distribution. The authors define catalyzed living poljonerization in this manner; "...if chain transfer to aluminum constitutes the sole transfer mechanism and the exchange of the growing polymer chain between the transition metal and the aluminum centers is very fast and reversible, the polymer chains will appear to be growing on the aluminum centers. This can then reasonably be described as a catalyzed chain grove reaction on aluminum.... An attractive manifestation of tiles type of chain growth reaction is a Poisson distribution of product molecular waitlist, as opposed to the Schulz-Florid distribution that arises when P-H transfer accompanies propagation." The authors reported the results for the catalyzed living homopolymerization of ethylene using an iron containing catalyst in combination with ZnEt2, ZnMe2, or Zn(i-Pr)2. Homiletic alkyls of aluminum, boron, tin, lithium, magnesium and lead did not induce catalyzed chain growth. distribution. However, after analysis of time-dependent product distribution the authors concluded this reaction was, "not a simple catalyzed chain growth reaction." Accordingly, the product would not have constituted a pseudo-block copolymer. Similar processes employing single catalysts have been described in USP's 5,210,338, 5, 276,220, and 6,444,867. Earlier workers had made similar clans to forming block copolymers using a single Ziegler-Natta type catalyst in multiple reactors arranged in series. Examples of such teachings include USP's 3,970,719 and 4,039,632. It is now known that no substantial block copolymer formation takes place under these reaction conditions. In USP's 6,319,989 and 6,683,149, the use of two loop reactors connected in series and operating under differing polymerization conditions to prepare either broad or anyhow molecular weight polymer products was disclosed. Tlie references fail to disclose the use of chain shuttling agents and the formation of pseudo-block copolymer products. Accordingly, there remains a need in the art for a polymerization process that is capable of preparing copolymers having properties approximating those of linear multi-block copolymers, in a high yield process adapted for commercial utilization. Moreover, it would be desirable if there were provided an improved process for preparing polymers, especially copolymers of two or more comonomers such as ethylene and one or more comonomers, by the use of a chain shuttling agent (CSA) to introduce block-like properties m the result polymer (pseudo-block copolymers). In addition it would be desirable to provide such an improved process operating at elevated temperatures that is capable of economically preparing diblock, relock or higher multi-block copolymers having a most probable distribution of chain lengths. Finally, it would be desirable to provide an improved process for preparing the foregoing pseudo-block copolymer products in a continuous process. Summary of the Invention According to the present mention there are now provided a process for the polymerization of one or more addition polymerizable monomers, preferably of two or more addition polymerizable monomers, especially ethylene and at least one copolymerizable comonomer, propylene and at least one copolymerizable comonomer, or 4-methyl-l-pentene and at least one copolymerizable comonomer, to form a copolymer comprising multiple blocks or segments of differentiated polymer composition or properties, especially blocks or segments comprising differing comonomer incorporation levels, said process comprising contacting an addition polymerizable monomer or mixture of monomers under addition polymerization conditions with a composition comprising at least one addition polymerization catalyst, a cocatalyst and a chain shuttling agent, said process differentiated process conditions in two or more reactors operating under steady state polymerization conditions or in two or more zones of a reactor operating under plug flow polymerization conditions. Because the polymer is comprised of two or more blocks or segments, preferably two or tliereof block or segments, which are joked to form a single polymer, and each block or segment is chemically or physically distinguishable (outlier than by molecular weight or molecular weight distribution) from adjoining blocks or segments, the resulting pseudo-block copolymer possesses unique physical and chemical properties compared to random copolymers of tlie same gross chemical composition. In another embodiment of the infraction there is provided a copolymer, especially such a copolymer comprising in polymerized form ethylene and a copolymerizable comonomer, propylene and at least one copolymerizable comonomer, or 4-methyH-pentene and at least one copolymerizable comonomer, said copolymer comprising two or more, preferably two or three intramolecular regions comprising differing chemical or physical properties, especially regions of differentiated comonomer incorporation. Highly preferably the copolymer possesses a molecular weight distribution, Mw/Mn, of less than 30, preferably less than 2.8. In yet another embodiment of the invention there is provided a process and the resulting pseudo-block copolymer, said process comprising: polymerizing one or more olefin monomers in the presence of an olefin polymerization catalyst and a chichi shuttling agent (CSA) in a polymerization reactor or zone operating under substantially steady state polymerization conditions resulting in the formation of at least some quantity of an initial polymer segment terminated with chain shuttling agent within the reactor or zone; discharging the reaction product from the first reactor or zone to a second polymerization reactor or zone operating under polymerization conditions that are distinguishable from those of the first polymerization reactor or zone; transferring at least some of the initial polymer segment terminated with chain shuttlmg agent to an active catalyst site in the second polymerization reactor or zone; and conducting polymerization in the second polymerization reactor or zone so as to form a second polymer segment bonded to said initial polymer segment and having distinguishable polymer properties from tlie initial polymer segment. Highly desirably, the polymer products herein comprise at least some quantity of a polymer containing two distinguishable blocks or segments characterized by a most probable distribution of block sizes. The polymer recovered from the second reactor or zone of a two reactor or two zone coupling agent to form a triblock- or a multiblock copolymer, including dendrimers, or functionalized by conversion of terminal chain shuttling agent into vinyl-j hydroxy!-, amine-, silane, carboxylic acid-, carboxylic acid ester, ionomeric, or otlier functional group, according to known techniques. In yet anotlier embodiment of the invention, tlie shuttling agent employed in the foregoing processes possesses multiple sites for undergoing polymer exchange, that is, it is multi-centered, especially two centered, which uniquely causes the formation of a polymer product comprising copolymers according to the invention containing three or more distinct polymer segments after undergoing sequential polymerization in two reactors or zones connected in series. Highly desirably, the pseudoblock copolymers formed according to the present invention are characterized by terminal blocks or segments of polymer having higher tacticity or crystallinity from the central block or segment. Even more preferably, the central polymer block or segment is relatively amorphous or even elastomeric. In a still further embodiment of the present invention, there is provided a polymer mixture comprising: (1) an organic or inorganic polymer, preferably a homopolymer of ethylene or of propylene and/or a copolymer of ethylene or propylene with one or more copolymerizable comonomers, and (2) a pseudo-block copolymer according to the present invention or prepared according to the process of the present invention. In a desirable embodiment component (1) is a matrix polymer comprising high density polyethylene or isotactic polypropylene and component (2) is an elastomeric pseudo-block copolymer containing two or three distinct regions of differentiated comonomer incorporation. In a preferred embodiment, component (2) comprises occlusions of the matrix polymer formed during compounding of components (1) and (2). While the foregoing process has been described as preferably forming a diblock product, it is an additional object of the invention to prepare multi-block copolymers, including hyper-branched or dendrhneric copolymers, through coupling of polymer terminated with a chain shuttling agent exiting the second reactor or zone (or any subsequent reactor or zone) using a difunctional or polyfunctional coupling agent In addition, if more than two reactors are employed, the product resembles that made by living polymerization in more than one reactor, with the difference tliat each block of the present polymers possesses a most probable distribution of molecular weights and composition. In particular, the polydispersity of tlie present polymers is generally less than 2.0 and approaches 1.5 for product made in two reactors. The theoretical limit of Mw/Mn generally equals the value of (1 + 1/n), where n is the number of reactors employed in the polymer's production, in accordance with the calculations of J. Appl. Poly. Sci., 92, 539-542 (2004). In general, the average number of blocks in tlie absence of coupling of the present polymers will be equal to the number of polymerization will normally include quantities of conventional polymer depending on tlie efficiency of the particular shuttling agent employed under the conditions of tlie polymerization. Brief Description of the Drawings Figure 1 is a schematic representation of tlie process of copolymer formation according to the present invention in two pr more different reactors. Figures 3-5 are test results for the polymer of Example 1, run A. Figures 6-9 are test results for the polymer of Example 1, run 1. Detailed Description of the InveirtiQn All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 2003. Also, any references to a Group or Groups shall be to the Group or Groups reflected in this Periodic Table of the Elements using the lUPAC system for numbering groups. Unless stated to the contrary, implicit from the context, or customary m the art, all parts and percents are based on weight. For purposes of United States patent practice, the contents of any patent, patent application, or publication referenced herem are hereby incorporated by reference in their entirety (or the equivalent US version tliereof is so incorporated by reference) especially with respect to tlie disclosure of synthetic techniques, definitions (to the extent not inconsistent witli any definitions provided herein) and general knowledge in the art. The term "comprising" and derivatives thereof is not intended to exclude tlie presence of any additional portion, component, step or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term "comprising" may include any additional additive, adjuvant, or compound whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, ‘'consisting essentially of excludes from the scope of any succeeding recitation any other portion, component, step or procedure, excepting those that are not essential to operability. The term "consisting of excludes any portion, component, step or procedure not specifically delineated or listed. The term "or", unless stated otherwise, refers to the listed members individually as well as m any combination. The term "polymer", includes both homopolymers, that is, homogeneous polymers prepared from a single monomer, and copolymers (interchangeably referred to herein as interpolymers), meaning polymers prepared by reaction of at least two monomers or otherwise containing chemically differentiated segments or blocks therein even if formed from a single monomer. More specifically, the term "polyethylene" includes homopolymers of ethylene and copolymers of that possesses a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or equivalent technique. The term may be used interchangeably with tlie term "semicrystalline". The term "amorphous" refers to a polymer lacking a crystalline melting point The term "elastomer" refers to a polymer or polymer segment having Tg less than O’C, more preferably less than -15°C, most preferably less than -25°C* The term "pseudo-block copolymer" refers to a copolymer comprising two or more blocks or segments of differing chemical or physical property, such as variable comonomer content, crystallinity, density, tacticity, regio-error, or other property. Non-adjacent blocks are not necessarily of identical chemical composition, but may vary in one or more of the foregoing respects, from the composition of all other blocks or regions. Compared to random copolymers, pseudo-block copolymers possess sufficient differences in chemical properties, especially crystallinity, between blocks or segments, and sufficient block length to the respective blocks to achieve one or more of the desired properties of true block copolymers, such as thermoplastic/ elastomeric properties, while at the same time being amenable to preparation in conventional olefin polymerization processes, especially continuous solution polymerization processes employing catalytic quantities of polymerization catalysts. Compared to block copolymers of the prior art, including copolymers produced by sequential monomer addition, fluxional catalysts, or anionic polymerization techniques, the copolymers of the invention are characterized by unique distributions of polymer polydispersity (PDI or Mw/Mn) and block length distribution, witli two or three, preferably two different block compositions. This is due, in a preferred embodiment, to the effect of the use of one or more shuttling agents in combination with a high activity metal complex based polymerization catalyst in two or more polymerization reactors or zones operating under differing polymerization conditions. More specifically, the copolymers of the mvention desirably possess PDI from 1.5 to 20, preferably from 1,7 to 15, and most preferably 1.8 to 10. The respective blocks of a pseudo-block copolymer desirably possess a PDI fitting a Schulz-Flory distribution rather than a Poisson distribution. The use of the present polymerization process results in a product having a number of distinguishable blocks per polymer equal to tlie number of reactors or distmct reaction zones employed in the process, with a polydisperse distribution of block sizes. This ultimates in the formation of polymer products having improved and distinguishable physical properties. Moreover’ the foregoing novel products may be formed in the presence of random copolymer or homopolymer formed in one or more of the associated polymerization processes due to early or intentional chain termination without chain transfer to the CSA, In tliis manner, a polymer blend containing z« situ prepared rubbery impact modifier or It may be readily appreciated by the skilled artisan that in one embodiment of the present hivented process the CSA may be added once, more than once (intermittently) or added continuously to each polymerization reactor or zone, preferably tlie initial one. Although the CSA may be added at a point inmiediately prior to discharge from tlae first reactor or zone, or even in an intervening conduit or conductor connecting the respective reactors or zones, it is preferably that the CSA be added to the reaction mixture prior to initiation of polymerization, at the same time as polymerization is initiated, or at least during a significant portion of the time in which polymerization is conducted in the first reactor. Thorough mixing of CSA and reaction mixture may be occasioned by active or static mixing devices or by use of any stirring or pumping device employed in mixing or transferring the reaction mixture. As used herein with respect to a chemical compound, unless specifically indicated otherwise, the singular includes all isomeric forms and vice versa (for example, "hexane", includes all isomers of hexane individually or collectively). The terms "compoimd" and "complex" are used interchangeably herein to refer to organic-, inorganic- and organometal compounds. The term, "atom" refers to the smallest constituent of an element regardless of ionic state, that is, whether or not the same bears a charge or partial charge or is bonded to another atom. The term "heteroatom" refers to an atom other than carbon or hydrogen. Preferred heteroatoms include: F, CI, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge. The term, "hydrocarbyl' refers to univalent substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic or noncyclic species. Examples include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, and alkynyl- groups. "Substituted hydrocarbyl" refers to a hydrocarbyl group that is substituted with one or more nonhydrocarbyl substituent groups. The terms, "heteroatom containing hydrocarbyl" or "heterohydrocarbyl" refer to univalent groups in which at least one atom other than hydrogen or carbon is present along with one or more carbon atom and one or more hydrogen atoms. The term "heterocarbyl" refers to groups containing one or more carbon atoms and one or more heteroatoms and no hydrogen atoms. The bond between the carbon atom and any heteroatom as well as tlie bonds between any two heteroatoms, may be saturated or unsaturated. Thus, an alkyl group substituted with a heterocycloalkyl-, substituted heterocycloalkyl-, heteroaiyl-, substituted heteroaryl-, alkoxy-, aryloxy-, dihydrocarbylboryl-, dihydrocarbylphosphino-, dihydrocarbylamino-, trihydrocarbylsilyl-, hydrocarbylthio-, or hydrocarbylseleno- group is within the scope of the term heteroalkyl. Examples of suitable heteroalkyl groups include cyano-, benzoyl-, (2-pyridyl)methyl-, and trifluoromethyl- groups. As used herein the term "aromatic" refers to a polyatomic, cyclic, conjugated ring system as used herein with respect to a ring system containing two or more polyatomic, cyclic rings means tliat with respect to at least two rings tliereof, at least one pair of adjacent atoms is included m both rings. The term aryl" refers to a monovalent aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linlced covalently, or linked to a common group such as a methylene or ethylene moiety. The aromatic ring(s) may include phenyl, naphtliyl, anthracenyl, and biphenyl, among otliers. "Substituted aryl" refers to an aryl group in which one or more hydrogen atoms bound to any carbon is replaced by one or more fimctional groups such as alkyl, substituted allcyl, cycloallcyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalos (e.g., CF3), hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, and botli saturated and unsaturated cyclic hydrocarbons which are fused to the aromatic ring(s), linked covalently or linked to a common group such as a methylene or etliylene moiety. The conunon linking group may also be a carbonyl as in benzophenone or oxygen as in diphenylether or nitrogen in diphenylamine. The term, "comonomer incorporation index", refers to the percent comonomer incorporated into a copolymer prepared by the catalyst under consideration. The selection of metal complexes or catalyst compositions having the greatest difference in comonomer incorporation indices under different polymerization conditions, in one embodiment of the present invention, results in copolymers fi-om two or more monomers having the largest difference in block or segment properties, such as density, for the same comonomer composition distribution. Comonomer incorporation index is generally determined by the use of NMR spectroscopic techniques. It may also be estimated based on monomer reactivities and reactor kmetics according to known theoretical techniques. In a very highly preferred embodiment, tlie polymers of the invention possess a most probable distribution of block lengths. Preferred polymers accordmg to the invention are pseudo-block copolymers containing 2 or 3 blocks or segments. In a polymer containing three or more segments (that is blocks separated by a distinguishable block) each block may be the same or chemically different and generally characterized by a distribution of properties. The invention involves the concept of using chain shuttling as a way to prolong the lifetime of a polymer chain such that a substantial fraction of the polymer chains exit at least the first reactor of a multiple reactor series or the first reactor zone in a multiple zoned reactor operating substantially under plug flow conditions in tlie form of polymer terminated with a chain shuttling agent, and the polymer chain experiences different polymerization conditions in the next reactor or polymerization zone. Different polymerization conditions in the respective reactors or zones include the use of different monomers, comonomers, or monomer/comonomer(s) ratio, different polymerization temperatures, gradients, or any other difference leading to formation of a distmguishable polymer segment. Thus’ at least a portion of tlie polymer resultmg from the present process comprises two, three, or more, preferably two or three, differentiated polymer segments arranged intramolecularly. Because tlie various reactors or zones form a distribution of polymers rather than a single specific polymer composition, the resulting product approximates the physical properties of a block copolymer and is referred to as a pseudo-block copolymer. In contrast with the previously discussed sequential polymerization tecliniques wherein no chain shuttling agent is utilized, polymer products can now be obtained according to the present invention by selecting highly active catalyst compositions capable of rapid transfer of polymer segments both to and from a suitable chain shuttling agent such that polymer blocks or regions of the resulting catalyst possess distinguishable polymer properties. Due to the use of chain shuttling agents and catalysts capable of rapid and efficient exchange of growing polymer chains, tlie growing polymer experiences discontinuous polymer growth, such that intramolecular regions of the polymer are formed under two or more different polymerization conditions. The following mathematical treatment of the resulting polyniers is based on theoretically derived parameters that are believed to apply to the present invented polymers and demonstrate that, especially in two or more steady-state, continuous reactors or zones connected in series, having differing polymerization conditions to which the growing polymer is exposed, tlie block lengths of the polymer being formed in each reactor or zone will conform to a most probable distribution, derived in the following manner, wherein pi is the probability of polymer propagation in a reactor with respect to block sequences from catalyst i. The theoretical treatment is based on standard assumptions and methods known in the art and used in predicting the effects of polymerization kinetics on molecular architecture, mcluding the use of mass action reaction rate expressions that are not affected by chain or block lengths, and the assumption that polymer chain growth is completed in a very short time compared to the mean reactor residence time. Such methods have been previously disclosed in W. H. Ray, J. Macromol. Sci,, Rev. Macromol. Chem.. C8, 1 (1972) and A. E. Hamielec and J. F. MacGregor, "Polymer Reaction Engineering", K.H. Reichert and W. Geisler, Eds., Hanser, Munich, 1983. In addition, it is assumed that each incidence of the chain shuttling reaction in a given reactor results in the formation of a single polymer block, whereas transfer of the chain shuttling agent terminated polymer to a different reactor or zone and exposure to different polymerization conditions results in formation of a different block. For catalyst i, the fraction of sequences of length n being produced in a reactor is given by Xi[n], where n is an integer from 1 to infinity representing the total number of monomer units m tlie block. Xi[n] = (l-Pi)p/""’ most probable distribution of block lengths If more than one catalyst is present in a reactor or zone, each catalyst has a probabilit>' of propagation (pi) and therefore has a unique average block length and distribution for polymer being made in that reactor or zone. In a most preferred embodiment the probability of propagation is defined as: Pi = Rp[i] + Rt[i] + Rs[i] + [Ci] ‘""‘ ‘‘‘‘ ‘‘‘‘‘y’* ' = {‘'2-}' ‘'‘‘'‘= Rp[i] = Local rate of monomer consumption by catalyst i, (moles/L/time)j Rt[i] = Total rate of chain transfer and termination for catalyst i, (moles/L/time), and Rs[i] = Local rate of chain shuttling with dormant polymer, (moles/L/time). For a given reactor the polymer propagation rate, Rp[i], is defined using an apparent rate constant, kpi, multiplied by a total monomer concentration, [M], and multiplied by the local concentration of catalyst i, [Ci],as follows: Rp[i] = i’[M][Ci] The chain transfer, termination, and shuttling rate is determined as a function of chain transfer to hydrogen (H2), beta hydride elimination, and chain transfer to chain shuttling agent (CSA), The quantities [H2] and [CSA] are molar concentrations and each subscripted k value is a rate constant for the reactor or zone: Rt[i] = kH2i[H2][Q] + kpi[Ci] + k’[CSA][Q] Dormant polymer chains are created when a polymer moiety transfers to a CSA and all CSA moieties that react are assumed to each be paired with a dormant polymer chain. The rate of chain shuttling of dormant polymer with catalyst i is given as follows, where [CSAd is the feed concentration of CSA, and the quantity ([CSAf]-[CSA]) represents the concentration of dormant polymer chains: Rs[i] = kai[Q]([CSAf]-[CSA]) As a result of the foregoing theoretical treatment, it may be seen that the overall block lengtli distribution for each block of the resultmg pseudo-block copolymer is a sum of the block length distribution given previously by Xi[n], weighted by the local polymer production rate for catalyst i. This means that a polymer made under at least two dififerent polymer forming conditions will have at least two distinguishable blocks or segments each possessing a most probable block length distribution. Monomers Suitable monomers for use in preparing the copolymers of the present invention include any a-oleum, and most preferably ethylene and at least one copolymerizable comonomer, propylene and at least one copolymerizable comonomer having from 4 to 20 carbons, or 4-methyH-pentene and at least one different copolymerizable comonomer having from 4 to 20 carbons. Examples of suitable monomers include straight-chain or branched a-olefins of 2 to 30, preferably 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyH-butene, 1-hexene, 4-metliyH-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cycloolefins of 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbomene, 5"methyl-2-norbomene, tetracyclododecene, and 2-methyH,4,5,8-dhnethano-l,2j3,4,4a,5,8,8a-octahydronaphthalene; di- and poly-olefins, such as butadiene, isoprene, 4-methyl-l,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, lj6-octadiene, 1,7-ootadiene, ethylidene norbomene, vinyl norbornene, dicyclopentadiene, 7-methyl-l,6-octadiene, 4-ethyHdene-8"methyl" 1,7-nonadienej and 5,9-dimethyHj4,8-decatriene; aromatic vinyl compounds such as mono- or poly-alkylstyrenes (including styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o’ethylstyrene, m-ethylstyrene and p-ethylstyrene), and functional group-containing derivativeSj such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropene, 4-phenylpropene and a-methylstyrene, vinylchloride, 1,2-difluoroethylene, 1,2-dichloroethylene, tetrafluoroethylene, and 3,3,3-trifluoro-l-propene, provided the monomer is polymerizable under the conditions employed. Preferred monomers or mixtures of monomers for use in combination with at least one CSA herein include ethylene; propylene; mixtures of ethylene with one or more monomers selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-l"pentene, l-octene, and styrene; and mixtures of ethylene, propylene and a conjugated or non-conjugated diene. Chain Shuttling Agents The term, ‘'shuttling agent" or "chain shuttling agent", refers to a compound or mixture of compounds that is capable of causing polymeryl transfer between tlie various active catalyst sites under the conditions of the polymerization. That is, transfer of a polymer fragment occurs both to and from an active catalyst site in a facile manner. In contrast to a shuttling agent, a "chain transfer agent" causes termination of polymer chain growth and amounts to a one-time transfer of growing polymer from the catalyst to the transfer agent. Desirably, the intermediate formed between the chain shuttling agent and the polymeryl chain is sufficiently stable tliat chain termination is relatively rare. Desirably, less than 10 percent, preferably less tlian 50 percent, more preferably less tlian 75 percent and most desirably less than 90 percent of shuttling agent-polymeryl products are terminated prior to attaining 2 distinguishable, intramolecular polymer segments or bloclcs. While attached to the growing polymer chain, the shuttling agent desirably does not alter the polymer structure or incorporate additional monomer. That is, tlie shuttling agent does not also possess significant catalytic properties for tlie polymerization of interest. Ratlier, the shuttling agent forms a metal-alkyl or other type interaction with the polymer moiety, for a time period such that transfer of the polymer moiety to an active polymerization catalyst site in a subsequent reactor may occur. As a consequence, the subsequently formed polymer region possesses a distinguishable physical or chemical property, such as a different monomer or comonomer identity, a difference in comonomer composition distribution, crystallinity, density, tacticity, regio-error, or other property. Subsequent repetitions of the foregomg process can result in formation of segments or blocks having differing properties, or a repetition of a previously formed polymer composition, depending on the rates of polymeryl exchange, number of reactors or zones within a reactor, and transport between the reactors or zones. The polymers of the invention desirably are characterized by at least two individual blocks or segments having a difference m composition and a most probable block length distribution. That is, adjacent blocks have altered composition within the polymer and a size distribution (Mw/Mn) greater than 1.0, preferably greater than 1.2. The process of the invention employing a catalyst one or more cocatalysts and chain shuttling agent may be further elucidated by reference to Figure 1, where there is illustrated an activated catalyst, 10, which in a first reactor operating under steady state polymerization conditions or in a first polymerization zone operatmg under plug flow polymerization conditions forms a polymer chain, 12. A chain shuttling agent, 14, added along with the initial charge of reactants or later in the polymerization process, mcluding just prior to or during transfer to a second reactor or zone, attaches to the polymer chain produced by an active catalyst site tliereby preventing termination of the polymer chain prior to entering the second reactor or zone. In the presence of modified polymerization conditions, the polymer block attached to the chain shuttling agent is transferred back to a catalyst site, and a new polymer segment, 16, which preferably is distinguishable from polymer segment 12, is produced. The resulting diblock copolymer may also attach to an available chain shuttling agent forming the combination of a chain shuttling agent with the diblock copolymer, 18 prior to exiting the second reactor or zone. Transfer of tlie growing polymer multiple times to an active catalyst site may occur with continued growth of the polymer segment. Under uniform polymerization conditions, the growing polymer chain is substantially homogeneous, although individual molecules may differ in size. The first and second polymer segments formed in the process are distinguishable because tlie polymerization conditions in shuttling agent is able to prolong the polymer life time (that is the time during which fiirther polymer growth may occur) until two or more different polymerization environments are experienced. The diblock copolymer chains, 2O5 may be recovered by termination, such as by reaction with water or other proton source, or functionalized, if desired, forming vinyl, hydroxyl, silane, carboxylic acid, carboxylic acid ester, ionomeric, or other functional terminal groups to replace the chain shuttling agent Alternatively, the diblock polymer segment may be coupled with a polyfunctional coupling agent, especially a difiinctional couplmg agent such as dichlorodimethylsilane or ethylenedichloride, and recovered as a triblock copolymer, 22* It is also possible to continue polymerization in a third reactor or zone under conditions differing from those in tlie second reactor or zone, and recovering the resultmg triblock copolymer, 21. If the third reactor's conditions are substantially identical to those of the mitial reactor or zone, tlie product will be substantially similar to a conventional triblock copolymer, but with block lengths that are a most probable distribution. Ideally, the rate of chain shuttling is equivalent to or faster than the rate of polymer termination, even up to 10 or even 100 times faster than the rate of polymer termination and significant with respect to tlie rate of polymerization. This permits formation of distinct polymer blocks in the first reactor or zone and discharge from said reactor or zone into a subsequent reactor or zone of a reaction mixture containing significant quantities of polymer chains terminated with chain shuttling agents and capable of continued monomer insertion under distinguishable polymerization conditions. By selecting diJBferent shuttling agents or mixtures of agents with a catalyst, by altering the comonomer composition, temperature, pressure, optional chain terminating agent such as Hjj or other reaction conditions in separate reactors or zones of a reactor operating under plug flow conditions, polymer products having segments of varying density or comonomer concentration, monomer content, and/or other distinguishing property can be prepared. For example, in a typical process employing two continuous solution polymerization reactors connected in series and operating under differing polymerization conditions, the resulting polymer segments will each have a relatively broad molecular weight distribution characteristic of typical olefin coordination polymerization catalysts, preferably a Mw/Mn from 1.7 to 15, more preferably from 1.8 to 10, but will reflect the polymer formed under the differing polymerization conditions. In addition, certain quantities of a conventional random copolymer may also be formed coincident witli formation of the pseudo-diblock copolymer of the present invention, resulting in a resin blend. The average block lengths in the resulting polymers may be controlled by the chain shuttling rate of the CSA, the amount of CSA added, and other process variables, such as polymer production rate, and tlie amount of optional chain termination agent, such as hydrogen, employed. Average block lengths of each block type can be individually controlled by altering process variables in each reactor. Highly desired copolymers comprise at least one block or segment tliat is highly crystalline polyethylene or polypropylene, especially highly isotactic polypropylene, joined intramolecularly with one or more separate blocks comprising an amorphous polymer, especially a copolymer of etliylene and a C3-8 comonomer, or a copolymer of propylene with ethylene and/or a C4.8 comonomer. Desirably the foregoing polymer is a pseudo- diblock copolymer. Additional desirable copolymers are pseudo- triblock copolymers comprising a central, relatively amorphous polymer block bonded between two relatively crystalline polyolefin polymer blocks. A suitable composition comprising catalyst, cocatalyst, and a chain shuttling agent especially adapted for use herein can be selected by means of the following multi-step procedure: I. One or more addition polymerizable, preferably olefin monomers are polymerized using a mixture comprising a potential catalyst and a potential chain shuttling agent. This polymerization test is desirably performed using a batch or semi-batch reactor (that is, without resupply of catalyst or shuttling agent), preferably with relatively constant monomer concentration, operating under solution polymerization conditions, typically using a molar ratio of catalyst to chain shuttling agent from 1:5 to 1:500. After forming a suitable quantity of polymer, the reaction is terminated by addition of a catalyst poison and the polymer's properties (Mw, Mn, and Mw/Mn or PDI) measured. n. The foregoing polymerization and polymer testing are repeated for several different reaction times, providing a series of polymers having a range of yields and PDI values. EH. Catalyst/ chain shuttling agent pairs demonstrating significant polymer transfer both to and from the chain shuttling agent are characterized by a polymer series wherein the minimum PDI is less than 2.0, more preferably less than 1.5, and most preferably less than 1.3. Furthermore, if chain shuttling is occurring, the Mn of the polymer will increase, preferably nearly linearly, as conversion is increased. Most preferred catalyst/ shuttling agent pairs are those giving polymer Mn as a function of conversion (or polymer yield) fitting a line with a statistical precision (R ) of greater than 0.95, preferably greater than 0.99. Steps I-HE are then carried out for one or more additional pairings of potential catalysts and/or putative shuttling agents. In addition, it is preferable that the chain shuttling agent does not reduce the catalyst activity (measured m weight of polymer produced per weight of catalyst per unit time) by more than 60 percent, more preferably such catalyst activity is not reduced by more tlian 20 percent, and most preferably catalyst activity of the catalyst is increased compared to tlie catalyst activity in tlie absence of a chain shuttling agent. A further consideration from a process viewpoint is that the producing a homogeneous reaction mixture or conveying the reaction mixture. In tliis regard, a monofunctional shuttling agent is preferred to a difiinctional agent which in turn is preferred to a trifunctional agent. The foregoing test is readily adapted to rapid tliroughput screenmg techniques using automated reactors and analytic probes and to formation of polymer blocks having different distinguishmg properties. For example, a number of potential chain shuttling agent candidates can be pre-identified or synthesized in situ by combination of various organometal compounds witli various proton sources and the compound or reaction product added to a polymerization reaction employing an olefin polymerization catalyst composition. Several polymerizations are conducted at varying molar ratios of shuttling agent to catalyst. As a minimum requirement, suitable shuttling agents are those that produce a PDI of less than 2.0 in variable yield experiments as described above, while not significantly adversely affecting catalyst activity, and preferably improving catalyst activity, as above described. Alternatively, it is also possible to detect desirable catalyst/shuttling agent pairs by performing a series of polymerizations under standard batch reaction conditions and measuring the resulting number average molecular weights, PDI and polymer yield or production rate. Suitable shuttling agents are characterized by lowering of tlie resultant Mn without significant broadening of PDI or loss of activity (reduction in yield or rate). Regardless of the method for identifying, apriorU a shuttling agent, the term is meant to refer to a compound that is capable of preparing the presently identified pseudo-block copolymers under the polymerization conditions herein disclosed. Suitable shuttlmg agents for use herein include Group 1,2,12 or 13 metal compounds or complexes containing at least one C1.20 hydrocarbyl group, preferably hydrocarbyl substituted aluminum, gallium or zmc compounds containing from 1 to 12 carbons in each hydrocarbyl group, and reaction products thereof with a proton source. Preferred hydrocarbyl groups are alkyl groups, preferably linear or branched, C2-B alkyl groups. Most preferred shuttling agents for use in the present invention are trialkyl aluminum and dialkyl zinc compounds, especially triethylaluminum, tri(i-propyl) aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, triethylgallium, or diethylzinc. Additional suitable shuttling agents include the reaction product or mixture formed by combinmg the foregoing organometal compound, preferably a triCCi-g) alkyl aluminum or di(Ci-g) alkyl zinc compound, especially triethylaluminum, tri(i-propyl) aluminum, tri(i-butyl)aluminum, tri(n"hexyl)aluminum, tri(n-octyl)aluminum, or diethylzmc, with less than a stoichiometric quantity (relative to the number of hydrocarbyl groups) of a secondary amine or a bydroxyl compound, especially bis(trimethylsilyl)amine, t-butyl(dimethyl)siloxane, 2- bis(2,336,7-diben20"l-azacycloheptaneamine), or 2,6-diphenylphenoL Desirably, sufficient amine or hydroxyl reagent is used such that one hydrocarbyl group remains per metal atom. The primary reaction products of the foregoing combinations most desired for use in the present invention as shuttling agents are n-octylaluminum di(bis(trimethylsilyl)amide), i-propylaluminum bis(dimethyl(t-butyI)siloxide), and n-octylaluminum di(pyridinyl-2-methoxide), i-butylaluminum bis(dimethyl(t-butyl)siloxane), i-butylaluminum bis(di(trimetliylsilyl)amide), n-octylaluminum di(pyridine"2-metlioxide)5 i-butylaluminum bis(di(n-pentyl)amide)5 n-octylaluminum bis(256-di-t-butylphenoxide), n-octylaluminum di(ethyl(l'-naphtliyl)amide)5 eihylaluminum bis(t-butyldimethylsiloxide), eihylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-dibenzo-1 -azacycloheptaneamide), n-octylaluminum bis(2,3,6,7-dibenzo-1 -azacycloheptaneamide), n-octylaluminum bis(dimethyl(t-butyI)siloxide5 ethylzinc (2,6-diphenylphenoxide), and ethylzinc (t-butoxide). Preferred shuttling agents possess the highest transfer rates of polymer transfer as well as the highest transfer efficiencies (reduced incidences of chain termination). Such shuttling agents may be used in reduced concentrations and still achieve tlie desired degree of shuttling. Highly desirably, chain shuttling agents with a single exchange site are employed due to, the fact that the effective molecular weight of the polymer in the reactor is lowered, thereby reducing viscosity of the reaction mixture and consequently reducing operating costs. Catalysts Suitable catalysts for use herein include any compound or combmation of compounds that is adapted for preparing polymers of the desired composition or type. Both heterogeneous and homogeneous catalysts may be employed. Examples of heterogeneous catalysts include die well known Ziegler-Natta compositions, especially Group 4 metal halides supported on Group 2 metal halides or mixed halides and alkoxides and the well known chromium or vanadium based catalysts. Preferably however, for ease of use and for production of narrow molecular weight polymer segments in solution, the catalysts for use herein are homogeneous catalysts comprising a relatively pure organometallic compound or metal complex, especially compounds or complexes based on metals selected from Groups 3-15 or the Lanthanide series of the Periodic Table of the Elements. Preferred metal complexes for use herein include complexes of metals selected from Groups 3 to 15 of the Periodic Table of the Elements containing one or more delocalized, 7c-bonded ligands or polyvalent Lewis base ligands. Examples mclude metallocene, half-metallocene, constrained geometry, and pol3’alent pyridylamine, or other polychelating base complexes. The complexes are generically depicted by the formula: MKkXxZz, or a dimer thereof, wherein M is a metal selected from Groups 3-15, preferably 3-10, more preferably 4-10, and most preferably Group 4 of the Periodic Table of the Elements; K independently each occurrence is a group containing deiocalized Tr-electrons or one or more electron pairs through which K is bound to M, said K group containing up to 50 atoms not counting hydrogen atoms, optionally two or more K groups may be joined together forming a bridged structure, and further optionally one or more K groups may be bound to Z, to X or to batik Z and X; X independently each occurrence is a monovalent, anionic moiety having up to 40 non-hydrogen atoms, optionally one or more X groups may be bonded together thereby forming a divalent or polyvalent anionic group, and, further optionally, one or more X groups and one or more Z groups may be bonded together thereby forming a moiety that is both covalently bound to M and coordinated tliereto; Z independently each occurrence is a neutral, Lewis base donor ligand of up to 50 non-hydrogen atoms containing at least one unshared electron pair through which Z is coordinated to M; k is an integer from 0 to 3; X is an integer from 1 to 4; z is a number from 0 to 3; and tlie sum, k+x, is equal to the formal oxidation state of M. Suitable metal complexes include those containing from 1 to 3 TT-bonded anionic or neuti-al ligand groups, which may be cyclic or non-cyclic delocalized 7C-bonded anionic ligand groups. Exemplary of such 7t-bonded groups are conjugated or nonconjugated, cyclic or non-cyclic diene and dienyl groups, allyl groups, boratabenzene groups, phospbole, and arene groups. By the term " 7i-bonded" is meant that the ligand group is bonded to the transition metal by a sharing of electrons from a partially delocalized Ti’bond. Each atom in the delocalized Tr-bonded group may independently be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substituted heteroatoms wherein the heteroatom is selected from Group 14-16 of the Periodic Table of the Elements, and such hydrocarbyl- substituted heteroatom radicals further substituted with a Group 15 or 16 hetero atom containing moiety. In addition two or more such radicals may togetlier form a fused ring system, mcluding partially or fully hydrogenated fused ring systems, or they may foim a metallocycle with the metal. Included within the term "hydrocarbyl" -are Ci-20 straight, branched and cyclic alkyl radicals, C6.20 aromatic radicals, C7.20 alkyl-substituted aromatic radicals, and C7_2o aryl-substituted alkyl radicals. Suitable hydrocarbyl-substituted heteroatom radicals uiclude mono-, di- and tri-substituted radicals of boron, silicon, germanium, nitrogen, phosphorus or oxygen wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples include HN-dimethylamino, pyrrolidinylj trimethylsilyl, trietliylsilyl, t-butyldimethylsilyl, methyldi(t"bu1yl)silyl, tiipheuylgermyl, and trimethylgermyl groups. Examples of Group 15 or 16 hetero atom containing moieties include amino, phosphino, alkoxy, or alkyltliio moieties or divalent derivatives thereof, for example, amide, phosphide, alkyleneoxy or alkylenethio groups bonded to the transition metal or Lanthanide metal, and bonded to the hydrocarbyl group, TU-bonded group, or hydrocarbyl- substituted heteroatom. Examples of suitable anionic, delocalized 7t-bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl’ cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, phosphole, and boratabenzyl groups, as well as inertly substituted derivatives thereof, especially CMO hydrocarbyl- substituted or tris(Ci.io hydrocarbyl)silyI- substituted derivatives thereof. Preferred anionic delocalized n-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl, 3'pyrrolidinoinden-l-yl, 3,4"(cyclopenta(/)phenanthren-l-yl, and teti-ahydroindenyl. The boratabenzenyl ligands are anionic ligands which are boron containing analogues to benzene. They are previously known in the art having been described by G. Herberich, et al., in Organometallics. 14,1,471-480 (1995). Preferred boratabenzenyl ligands correspond to the formula: wherein R' is an inert substituent, preferably selected from the group consisting of hydrogen, hydrocarbyl, silyl, halo or germyl, said R’ having up to 20 atoms not comiting hydrogen, and optionally two adjacent R' groups may be joined together. In complexes involving divalent derivatives of such delocalized 7c-bonded groups one atom thereof is bonded by means of a covalent bond or a covalently bonded divalent group to another atom of the complex thereby forming a bridged system. Phospholes are anionic ligands that are phosphorus containing analogues to a cyclopentadienyl group. They are previously known in the art having been described by WO 98/50392, and elsewhere. Preferred phosphole ligands correspond to the formula: wherein R' is as previously defined. Preferred transition metal complexes for use herein correspond to the formula: MKkXxZ’, or a dimer thereof, wherein: M is a Group 4 metal; K is a group containing delocalized 7c-electn)ns through which K is bound to M, said K group contaming up to 50 atoms not counting hydrogen atoms, optionally two K groups may be joined together fonning a bridged structur’j and further optionally one K may be bound to X or Z; X each occurrence is a monovalent, anionic moiety having up to 40 non-hydrogen atoms, optionally one or more X and one or more K groups are bonded together to form a metallocycle, and further optionally one or more X and one or more Z groups are bonded together thereby forming a moiety that is both covalently bound to M and coordinated thereto; Z independently each occurrence is a neutral, Lewis base donor ligand of up to 50 non-hydrogen atoms containing at least one unshared electron pair through which Z is coordinated to M; k is an integer from 0 to 3; X is an integer from 1 to 4; z is a number from 0 to 3; and the sum, k+x, is equal to the formal oxidation state of M, Preferred complexes include those containing either one or two IC groups. The latter complexes mclude those containing a bridging group linking the two K groups. Preferred bridging groups are those corresponding to the formula (EKW wherem E is silicon, germanium, tin, or carbon, R' independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combmations thereof, said R' having up to 30 carbon or silicon atoms, and e is 1 to 8. Preferably, R' independently each occurrence is methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy. Examples of the complexes containing two K groups are compounds corresponding to the formula: Examples of metal complexes of the foregoing formula suitable for use in the present invention include: bis(cyclopentadienyl)zirconiumdimethyl, bis(cyclopentadienyl)2h'coniumdibenzyl, bis(cyclopentadienyl)zirconiura methyl benzyl, bis(cycIopentadienyl)zirconium methyl phenyl, bis(cyclopentadienyl)zirconiumdiphenyl, bis(cyclopentadieiiyl)titanium-allyl, bis(cyclopentadienyl)zirconiummethybnethoxide, bis(cyclopentadienyl)zircomummethylchloride, bis(pentamethylcyclopentadienyl)zirconiumdimetliyl, bis(pentameihylcycIopentadieayl)titaniumdimethyl, bis(indenyl)zirconiumdimethyl, indenylfluorenylzirconixundimethyl, bis(indenyl)zirconiummBthyl(2-(dimethylamino)benzyl), bis(indenyl)zirconiummethyltrituethylsilyl, bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl, bisCpentametliylcyclopentadienyOzu-coniummethylbenzyl, bisCpentametliylcyclopentadienyOzh-coniumdibenzyl, bis(pentamethyIcyclopentadienyl)zirconiummethylmethoxide, bis(pentamethylcyclopentadienyl)zirconiummethylchloride, bis(methylethylcyclopentadienyl)zirconiumdimethyl, bis(butylcyclopentadienyl)zirconiumdibenzyl, bis(t"butylcyclopentadienyl)zirooniumdimethyl, bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl, bis(methylpropylcyclopentadienyl)zirconiumdiben2yl, bis(trimethylsilylcyclopentadienyI)zirconiumdibenzyl5 dimethylsilylbis(cyclopentadienyl)zirconiumdimethyl, dimethylsilylbis(tetramethylcyclopentadienyl)titanium (HI) allyl dimethylsilylbis(t-butylcyclopentadienyl)zirconiumdichloride, dimethylsilylbis(n-butylcyclopentadienyl)zirconiumdichloride, (methylenebis(tetramethylcyclopentadienyI)titanium(III)2-(dimetliylamino)benzyl, (methylenebis(n-butylcyclopentadienyl)titanium(]H)2-(dimethylamiiio)ben2yl, dimethylsilylbis(indenyl)zirconiumbenzylchloride, diraethylsilylbis(2-mediyl-4-phenylindenyl)zirconiumdiniethyI, dimethylsilylbis(2’nietIiylmdenyl)zirconium-l,4-diphenyl-l,3-butadiene, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium (n) 1,4-diphenyl-l’ dimethylsilylbis(tetraIiydroindenyl)zircoiiimn(n) l,4-diphenyl-l,3’butadiene, dimethylsilylbis(tetramethylcyclopeutadienyl)zirconium dimethyl dimethylsilylbis(fluorenyl)zirconiumdimetIiyl, dimethylsiiyl-bis(tetrahydrofluorenyl)zirconiumbis(trimethylsilyl), (isopropyUdene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyI, and dimethylsilyl(tetraniethylcyclopentadienyl)(fluorenyl)zirconium dimethyl. A further class of metal complexes utilized in the present invention corresponds to the preceding formula: MRZ’Xx, or a dimer thereof, wherein M, K, X, x and z are as previously defined, and Z is a substituent of up to 50 non-hydrogen atoms that together with K forms a metallocycle with M. Preferred Z substituents include groups containing up to 30 non-hydrogen atoms comprising at least one atom that is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly attached to K, and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur that is covalently bonded to M, More specifically this class of Group 4 metal complexes used according to tlie present invention includes "constrained geometry catalysts" corresponding to the formula: X is hydrogen, a monovalent anionic ligand group having up to 60 atoms not counting hydrogen, or two X groups are joined togetlier thereby forming a divalent ligand group; X is 1 or 2; and 2 is 0, 1 or 2. Preferred examples of the foregomg metal complexes are substituted at both tlie 3- and 4-positions of a cyclopentadienyl or indenyl group with an Ar group. Examples of the foregomg metal complexes include: (3-phenylcycIopentadien"l-yl)dimethyI(t-butylamido)silanetitanium dichloride, (3-phenylcyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium dimethyl, (3-phenylcyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanlum (H) 1,3-diphenyl-1,3 -butadiene; (3-(pyrroH-yl)cyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium dichloride, (3-(pyrroI-l-'yl)cyclopentadien-l"yI)dunethyl(t-butylamido)silanetitanium dimethyl, (3-(pyrrol-1 'yl)cyclopentadien-1 -yl))dunethyl(t-butylamido)silanetitanium (11) 1,4- diphenyl-1,3-butadiene; (3 -(1 -methylpyrrol-3-yl)cyclopentadien-1 -yl)dimethyI(t-butylamido)silanetitanium dichloride, (3 -(1 -methylpyrrol-3 -yl)cyclopentadien-1 -yl)dimethy l(t-buty lamido)silanetitanium dimethyl, (3-(l-methylpyrrol"3-yl)cyclopentadien-l-yl)dimethyl(t-butylamido)siIanetitanium(II) 1,4- diphenyl" 1,3 -butadiene; (3,4-diphenylcyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium dichloride, (3,4-diphenylcyclopentadien-1 -yl)dimethyl(t-butylamido)siIanetitanium dimethyl, (3,4-diphenylcyclopentadien-l-yI)dimethyl(t-butylamido)silanetitanium(n) 1,3- pentadiene; (3-(3-N,N-dmiethylamino)phenyl)cyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium dichloride, (3 dimethyl, (3-(3-N,N-dimethylamino)phenylcyclopentadien-l-yl)dimethyl(t-butylamido)silanetitaiiium (U) l,4-diphenyl-l,3"butadiene; (3-(4-methoxyphenyl)'4-methylcyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium dichloride, (3 -(4-methoxyphenyl)-4-phenylcyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium dimethyl, (3-4-methoxyphenyl)-4-phenylcyclopentadien-l"yl)dimethyl(t-butyIamido)silanetitanium(ir) 1,4-diphenyl-1,3-butadiene; (3-phenyl-4-methoxycyclopentadien"l-yl)dimetliyl(t-butylamido)silanetitanm’ (3-phenyl-4-methoxycycIopentadien"l-yl)dimethyl(t-butylamido)silanetitani’ diphenyl-1,3-butadiene; (3"phenyl-4-(N,N-dime%lammo)cyclopentadien-l-yl)dimethyl(t-butylamido dichloride, (3"phettyl-4-(N,N-dimethylammo)cyclopentadien-l-yl)dimethyl(t-bu1ylamido)si dimethyl, (3-phenyl-4- 2-methyK3,4-di(4-meAylphenyl)cyclopeatadien-l-yl)dimethyl(t-butylamido)silaneti’ dichloride, 2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1 -yl)dimethyl(t"butylamido)silanetitanium dimethyl, 2-methyl-(3,4-di(4"me1hylphenyl)cydopentadien" 1 "yl)dimethyl(t-butylamido)silanetitanium (n) l,4-diphenyH,3-butadiene; ((2,3 -diphenyl)-4-(N»N-dimethylaniino)cyclopentadien-1 "yl)dimethyl(t-butylamido)silane titanium dichloride, ((2,3-diphenyI)-4-(N,N-dimethylamino)cyclopeiitadien-l-yl)dimethyl(t-butylamido)silane titanium dimethyl, ((2,3 -diphenyl)-4-(N,N"dimethylamino)cyclopentadien-1 -yl)dimethyl(t- butylamido)silanetitanium (II) l,4-diphenyl-l,3-butadiene; (2,3,4-triphenyl-5-methylcyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium dichloride, (2,3,4-triphenyl-5-methylcyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium dimethyl, (2,3,4-triphenyl-5-methylcyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium (II) 1,4- diphenyl-1,3 -butadiene; (3 -phenyl-4-methoxycycIopentadien-1 -yI)dimethyl(t-butylamido)siIanetitanium dichloride, (3 -phenyl-4-methoxycyclopentadien-1 -yl)dimethyl(t-butyIamido)silanetitanium dimethyl, (3 -phenyl-4-methoxycyclopentadien-1 -yl)dimethyl(t-butylamido)siIanetitanium (11) 1,4- diphenyM ,3-butadiene; (2,3 -diphenyl-4-(n-butyl)cyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium dichloride’ (2,3 -diphenyl-4-(n-butyl)cyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium dimethyl, (2,3-diphenyl-4-(n-butyl)cyclopentadien"l "yl)dimethyl(t-butylamido)silanetitanium (II) 1,4- diphenyl-1,3 -butadiene; (2,3,4,5-tetraphenylcyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium dichloride, (2,3,4,5-tetraphenylcycIopentadien4-yl)dimethyl(t-butylamido)silanetitam 1,4- diphenyl-l,3-butadiene. Additional examples of suitable metal complexes for use herein are polycyclic complexes corresponding to tlie formula: where M is titanium in the +2, +3 or +4 formal oxidation state; R independently each occurrence is hydride, hydrocarbyl, silyl, germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneaminOj di(hydrocarbyl)phosphino, hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbylj hydrocarbylsilylamino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylene-phosphino-substituted hydrocarbyl, or hydrocarbylsulfido-substituted hydrocarbyl, said R’ group having up to 40 atoms not counting hydrogen, and optionally two or more of tlie foregoing groups may together form a divalent derivative; is a divalent hydrocarbylene- or substituted hydrocarbylene group forming a fused system with the remainder of the metal complex, said R’ containing from 1 to 30 atoms not counting hydrogen; X* is a divalent moiety, or a moiety comprising one a-bond and a neutral two electron pair able to form a coordinate-covalent bond to M, said X* comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen; X is a monovalent anionic ligand group having up to 60 atoms exclusive of tlie class of ligands that are cyclic, delocalized, 7r-bound ligand groups and optionally two X groups together form a divalent ligand group; Z independently each occurrence is a neutral ligating compound having up to 20 atoms; X is 0, 1 or 2; and z is zero or 1. (8-difluorometliylene-l,8-dihydrodibenzo[e,/j]azulen-l-yl)-N-(l,l- dimetliylethyl)dimethylsilanamide titanium (II) l,4-diphenyl-l,3"butadiene, (8-difluoromethylene-1,8-dihydrodibenzo[e, AJazulen-1 -yl)-N-( 1,1- dim©ihylethyl)dimetliylsilanamide titanium (II) lj3-pentadiene, (8-difluoromethylene-1,8-dihydrodibenzo [e, /zjazulen-1 -yl)-N-( 1,1- dimethyletliyl)dimetliylsilanamide titanium (HI) 2-(N,N-dimethylamino)benzyl, (8-difluoromethylene-l,8-diliydrodibenzo[e,A]azulen-l-yl)-N-(l,l- dimethyletliyi)dimethylsilanamide titanium (IV) dichloride, (8-difluoromethylene-l,8-dihydrodibenzo[e,A]azulen-l-yl)-N-(l,l- dimethylethyl)dimetiiylsilanamide titanium (TV) dimethyl, (8-difluoromethylene-l,8-dihydrodibenzo[5,/z]azulen-l-yl)-N-(l,l- dimethylethyl)dimethylsilanamide titanium (IV) dibenzyl, (8-methylene"l,8-dihydrodibenzo[e,A]azulen-2-yI)-N-(l,l-dimethylethyl)dimethylsilanamide titanium (D) l,4-diphenyl-13-butadiene, (8-methylene-1,8'-dihydrodiben2o[e, /i]azulen-2-yl)-N-( 1,1 -dimethylethyl)dimethylsilauamide titanium (n) 1,3-pentadiene, (S-methylene-1,8-dihydrodiben2o[e, /7]azulen-2"yl)-N-( 1,1 -dimethylethyl)dimethylsilanamide titanium (EI) 2-(N,N-dimethylamino)benzyl, (8-methylene-l,8-dihydrodibenzo[e,/7]azulen-2-yl)-N-(l>l-dimethylethyl)dimethylsilanamide titanium (IV) dichloride, (8-methylene-l,8-dihydrodiben2o[e,/i]azulen-2-yl)-N-(l,l-dimethylethyl)dimethylsilanamide titanium (TV) dimethyl, (8-methylene-l,8-dihydrodiben2o[e,/z]azulen-2-yl)-N-(l,l-dimethylethyl)dimethylsilanamide titanium (IV) dibenzyl, (8"difluorometliylene"l,8-dihydrodibenzo[e,A]azulen"2"yl)-N-(l,l- dimethyleihyl)dimethylsilanamide titanium (II) 1,4-diphenyH,3-butadiene, (8-difluoromethylene-l,8-dihydrodibenzo[e,/?]azulen-2-yl)-N-(l,l- dimethylethyl)dimethylsilanamide titanium (II) 1,3-pentadiene, (8-difluoromethylene-l,8-dihydrodibenzo[e,A]azulen-2"yl)-N-(l,l- dimethylethyl)dimethylsilanamide titanium (HI) 2-(N,N-dimethylamino)benzyl, (8-difluoromethylene-1,8-dihydrodiben2o[e, /z3azulen"2-yl)-N-( 1 j 1 - dimethylethyl)dimethylsilanamide titanium (TV) dichloride, (8-difluoromethylene- l,8"dihydrodiben2x>[c, /i]azulen-2-yl)-N-( 1,1- dimetliylethyl)dimetliylsilanamide titanium (IV) dimetliyl, (8-difluoromethylene-l,8-dihydrodibenzo[e,A]azulen-2-yl)-N-(l,l- dimetliylethyl)dimethylsilanamide titanium (IV) diben2yl, and mixtures tliereof, especially mixtures of positional isomers. Further illustrative examples of metal complexes for use according to tlie present invention correspond to the formula: where M is titanium in the +2, +3 or +4 formal oxidation state; T is "NR’- or -0-; R’ is hydrocarbyl, silyl, germyl, dihydrocarbylboryl, or halohydrocarbyl or up to 10 atoms not counting hydrogen; R’’ independently each occurrence is hydrogen, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, gerrayl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino, hydrocarbylene-phosphino, hydrocarbylsulfido, halo- substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl- substituted hydrocarbyl, hydrocarbylsiloxy- substituted hydrocarbyl, hydrocarbylsilylamino- substituted hydrocarbyl, di(hydrocarbyl)amino- substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino- substituted hydrocarbyl, hydrocarbylenephosphino- substituted hydrocarbyl, or hydrocarbylsulfido- substituted hydrocarbyl, said R'° group having up to 40 atoms not counting hydrogen atoms, and optionally two or more of the foregoing adjacent R'° groups may together form a divalent derivative thereby forming a saturated or unsaturated fused ring; X’ is a divalent moiety lacking in delocalized 7c-electrons, or such a moiety comprising one a-bond and a neutral two electron pair able to form a coordinate-covalent bond to M, said X' comprising boron, or a member of Group 14 of tlie Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen; X is a monovalent anionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic ligand groups bound to M through delocalized jc-electrons or two X groups together are a divalent anionic ligand group; Z independently each occurrence is a neutral ligating compound havmg up to 20 atoms; xis 0,1,23 or 3; and z is 0 or 1. Highly preferably T is =N(CH3), X is halo or hydrocarbyl, x is 2, X' is dimetliylsilane, z is 0, and R’’ each occurrence is hydrogen, a hydrocarbylj hydrocarbyloxy, dihydrocarbylamino, hydrocarbyleneamino, dihydrocarbylamino- substituted hydrocarbyl group, or hydrocarbyleneamino- substituted hydrocarbyl group of up to 20 atoms not counting hydrogen, and optionally two R° groups may be joined together. Illustrative metal complexes of the foregoing formula tliat may be employed in the practice of tlie present invention further mclude the following compounds: (t-butylamido)dimethyl-[6,7]benzO"[4,5:2' ,3'](1 -methylisoindol)-(3H)-indene-2-yl)siIanetitanium (H) l,4Kiiphenyl-l,3-butadiene, (t-butylanaido)dimethyl-[6,7]benzo-[4,5:2\3'](l-methylisoindol)-(3H)-mdene-2-yl)silanetitanium (H) 1,3-pentadiene, (t-butylamido)dimethyl-[6j7]benzo-[4,5:2' ,3'](1 -methyUsoindol)-(3H)-indene-2-yl)silanetitanium (HI) 2"(N,N-dimethylammo)benzyl, (t-butylamido)dimethyl-[6,7]benzo"[4,5:2',3'](l-methylisomdol)-(3H)-indene-2-yl)silanetitanium (IV) dichloride, (t-butylamido)dimethyl-[6,7]benzx)"[4j5:2%3'](l-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV) dimethyl, (t-butylamido)dunethyl-[657]ben2o-[4,5:2\3'](l-methylisomdol)-(3H)-indene-2-yl)silanetitanium (IV) dibenzyl, (t-butylamido)dimethyl46,7]benzo44,5:2\3'](l-methylisoindol)"(3H)-indene"2-yl)silanetitanium (IV) bis(trmiethylsilyl), (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2',3'](l-metliyIisomdol)-(3H)"indene-2- yl)silanetitanium (II) l,4-diphenyl-l,3-butadiene, (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2%3'](l-methylisoindol)-(3H)-indene-2- yl)silanetitanium (II) l S-pentadiene, (cycIohexylamido)dimethyl-[6,7]benzo-[4,5:2' ,3'](1 -methylisoiudoI)-(3H)-indene-2- yl)silanetitanium (IQ) 2-(N,N-dimethylamino)benzyl, (cyclohexylamido)dimethyl-[6,7]benzo44,5:2\3'](l-me%lisoindoI)-(3H)-indene-2- yl)silanetitanium (TV) dichloride, (cycloliexylamido)dimetliyl-[6,7]benzo-[4,5:2\3'](1 -methylisoindoI)"(3H)-mdene-2" yl)silaiietitanium (IV) dimethyl, (cyclohexylamido)dimethyl"[6 j7]benzo-[4,5 \2\3'](1 "methylisomdol)-(3H)-indene-2- yl)silanetitanium (TV) dibenzyl, (cyclohexylamido)dimethyI-[6J]benzo-[4,5:2\3'](l-metliyUsomdol>(3H)"indene-2- yl)silanetitanium (IV) bis(trimethylsilyl)5 (t"butylamido)di(p-methylphenyl)-[6,7]beiizo44,5:2\3'](l-methylisoindol’’ yl)silanetitanium (H) l,4-diphenyl-l,3-butadiene, (t-butylamido)di(p-me%lphenyl)-[6,7]benzo-[4,5:2’3'](l-methylisoindol)"(3H)"m yl)silanetitanium (n) Ij3-pentadiene5 (t-butylamido)di(p-methylphenyl)"[6,7]benzo-[4,5:2\3'](l-methyUsomdol)-(3’ yl)silanetitanium (in) 2-(N,N-dimethylammo)benzylj (t-butylamido)di(p-methylphenyl)-[6J]benzo-[4,5:2\3'](l-methylisoindol) yl)silanetitamum (IV) dichloride, (t-butylamido)di(p-methylphenyl)-[6J]benzo-[4,5:2\3'](l-methylisoindol)-(3H)-indene yl)silanetitanium (IV) dimethyl, (t-butylamido)di(p-mesylphenyl)-[6J]benzo-[4,5:2',3'](l-methylisoindol)-(3H)-indene"2’ yl)silanctitanium (IV) dibenzyl, (t-butylamido)di(p-methylphenyl)46,7]ben2»-[4,5;2\3'](l-methylisoindol)"(3H)-indene-2- yl)silanetitanium (IV) bis(trimethylsilyl)5 (cyclohexylamido)di(p-methylphenyl)-[6J]benzo-[4,5;2\3'](l"methylisoindol) yl)silaiietitamum (II) l,4-diphenyl-l,3-butadiene, (cyclohexylamido)di(p"methylphenyI)"[6,7]benzo-[4,5:2\3](l"methylisoindoI)r(3H)-indene-2’ yl)silanetitaiiium (H) l,3-pentadiene5 (cyclohexylamido)di(p-methylphenyl)-[6J]benzo-[4,5:2\3'](l-metliylisoindoI)-(3H)-indeiie-2’ yl)silanetitamum (HI) 2-(N,N-dimethylamino)benzyl, (cyclohexylamido)di(p-methylphenyl)-[6,7]benzO"[4,5:2\3 ](1-methylisomdol)-(3H)-indene-2- yl)silanetitanium (IV) dichloride, (cyclohexyiamido)di(p"metllylphenyl)46,7]benzo-[4,5:2’3'](l"methylisoindoI)-(3H)-indene-2-yl)silanetitanium (IV) dimethyl, (cyclohexylamido)di(p.methylphenyl)-[6,7]benzo-[4,5:2\3'](l-methylisoindol)-(3H)-indene-2-yl)silanetitanium (TV) dibenzyl; and (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2\3'](lmethylisoindol)-(3H)4ndene-2’ yl)silanetitanium (IV) bis(trimethylsilyl). Illustrative Group 4 metal complexes that may be employed in the practice of tlie present invention further include; (tert-butylamido)(l,l-dimethyl-2,3,4,9,10-Ti-l,4,5,6,7,8- hexaliydronaphthalenyl)dimethylsilanetitaniumdimethyl, (tert-butylamido)( 1,1,2,3-tetramethyl-2,3,4,9,10-ri-l ,4,5,6,7,8- hexahydronaphthalenyl)dimethylsilanetitaniumdimetiiyl, (tert-butylamido)(tetramethyl-r\|’-cyclopentadienyl) dimethylsilanetitanium dibenzyl, (tert-butylamido)(tetramethyl-Ti’-cyclopentadienyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-Ti’-cyclopentadienyl)-l,2-ethanediyltitaniumdmiethyl, (tert-butylamido)(tetramethyl'Ti’indenyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-Ti’-cyclopentadienyl)dimethylsilane titanium (UT) 2"(dimethylaniino)benzyl; (tert"butylamido)(tetramethyl-Ti’-cyclopentadienyl)dimethylsilanetitanium (IE) allyl, (tert-butylamido)(tetramethyl-'n ‘-cyclopentadienyl)dimethylsilanetitanium (HI) 2,4-duTiethylpentadienyl, (tert-butylamido)(tetramethyl-Ti’-cyclopentadienyl)dimethylsilanetitanium(n) 1,4-diphenyl-l ,3-butadiene, (tert-butylamido)(tetramethyl-r\| ‘-cyclopentadienyl)dimethylsilanetitanium (II) 1,3-pentadiene, (tert-butylamido)(2-methylindenyl)dunethylsilanetitanium(n) l,4-diplienyl-l,3- butadiene, (tert-butylamido)(2-methyUndenyl)dimetIiylsilanetitanium (H) 2,4-'hexadiene, (tert-butylamido)(2-methylindenyl)dimeihylsilanetitanium (IV) 2,3-dimethyM ,3- butadiene, (tert-butylamido)(2-methylindenyl)dimethylsilauetitanium (IV) isoprene, (tert-butylamido)(2-methylmdenyl)dimethylsilanetitauium (IV) 1,3-butadiene, (tert-butylamido)(2,3-dimetliylindenyl)dimethylsilanetitanium(IV) 2,3-dimethyH ,3-butadiene5 (tert"butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(rV) (tert-butylamido)(2,3-dimetiiylindenyl)dimethylsilanetitanium (IV) dibenzyl (tert-butylamido)(23-dimethylindenyl)dimethylsilanetitanium (IV) 1,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II) 1,3-pentadienej (tert-bu1ylaimdo)(2,3"dimetliylindenyl)dimethylsilanetitanium (11) 1,4-diphenyl- l,3"butadienep (tert"butylamido)(2-methylindenyI)dimethylsilanetitaniuin (E) 1,3 -pentadiene, (tert-butylamido)(2-methylmdenyI)dimethylsilanetitanium (IV) dimethyl, (tert-butylamido)(2-methylindenyI)dimethylsilanetitanium (TV) dibenzyl, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(n) 1,4-diphenyl-1,3 -butadiene, (tert-butylamido)(2-niethyM-phenylindenyl)dimethylsilanetitanium (H) 1,3-pentadiene, (tert-butyIamido)(2"methyl-4-phenylindenyl)dimethylsilanetitanium(n)2,4-hexadiene, (tert-butylainido)(tetramethyl-ri ‘-cyclopentadienyl)dimethyl- silanetitanium (IV) 1,3-butadiene, (tert-butylamido)(tetrainethyl-r\| ‘-cyclopentadienyl)dimethylsilanetitanium (IV) 2,3-dimethyl-1,3-butadiene, (tert-butylamido)(tetramethyl-r\|’-cyclopentadienyl)dimethylsilanetitanium(rV) isoprene, (tert-butylaniido)(tetramethyl-T\| ‘-cyclopentadienyl)dimethyl- silanetitanium (II) 134-dibenzyl-1,3-butadienej (tert-butyl]amido)(tetramethyl-Ti ‘-cyclopentadienyI)dimethylsilanetitanium (II) 2,4-hexadiene, (tert-butylamido)(tetramethyl-T\|’-cyclopentadienyl)dimethyl- silanetitanium (II) 3-methyH ,3-pentadiene, (tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(6,6"dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(lJ-dimethyl-2,3,4,9,10-r\|4,4,5,6,7,8-hexahydronaphthalen-4- yl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(l,l,2,3-tetramethyI-2,3,4,9,10"Ti-l,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl (tert-butylamido)(tetramethyl-Ti ‘-cyclopentadienyl methylphenylsilanetitanium (IV) dimethyl, (tert-butylamine)(tetramethyl-Ti’-cyclopentadienyl methylphenylsilanetitanium (II) 1.4-diDhenvl-1.3-butadiene. phenyl, 2,6-dimethylphenyl, 2j6-di(isopropyl)phenyl, 2,4,6-trimetliylphenyl, pentafluorophenyl, 3,5-trifluoromethylphenyl, and benzyl; g is 0 or 1; M’ is a metallic element selected from Groups 3 to 15, or the Lanthanide series of the Periodic Table of the Elements. Preferably, M’ is a Group 3-13 metals more preferably M’ is a Group 4-10 metal; L’ is a monovalent, divalent, or trivalent anionic ligand containing from 1 to 50 atoms, not counting hydrogen. Examples of suitable L' groups include halide; hydride; hydrocarbyl, hydrocarbyloxy; di(hydrocarbyl)amido, hydrocarbyleneamido, di(hydrocarbyl)phosphido; hydrocarbylsulfido; hydrocarbyloxy, tri(hydrocarbylsilyl)alkyl; and carboxylates. More preferred L’ groups are C1.20 alkyl, C7.20 aralkyl, and chloride; h is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3, and j is 1 or 2, with tiie value h x j selected to provide charge balance; Z’ is a neutral ligand group coordinated to M, and containing up to 50 atoms not counting hydrogen Preferred Z’ groups include aliphatic and aromatic amines, phosphines, and tellers, alkenes, alkaline, and inertly substituted derivatives thereof. Suitable inert substituents include halogen, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl, and nitrile groups. Preferred Z groups include triphenylphosphine, tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene; f is an integer from 1 to 3; two or three of T’, R and R’' may be joined together to form a single or multiple ring structure; h is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3; '~«'w' indicates any form of electronic interaction comprising a net columbic attraction, especially coordinate or covalent bonds, including multiple bonds; arrows signify coordinate bonds; and dotted lines indicate optional double bonds. In one embodiment, it is preferred that R have relatively low stearic hindrance with respect to X’. hi this embodiment, most preferred R** groups are straight chain alkyl groups, straight chain alkenyl groups, branched chain allcyl groups wherein the closest branching point is at least 3 atoms removed from X’, and halo, dihydrocarbylamino, alkoxy or trihydrocarbylsilyl substituted derivatives thereof. Highly preferred R’ groups m this embodiment are C 1.8 straight chain alkyl groups. At the same time, in this embodhnent R" preferably has relatively high steric hindrance with respect to Y’. Non-limiting examples of suitable R’' groups for this embodiment include alkyl bxampies of metal complexes useful employed according to tlie present invention include: \|>f-(2,6-di(l-metliyIethyl)phenyl)amido)(o-tolyl)(a"naphthalen-2-diyl(6-p>‘‘‘ diyl)metliane)]hafhium dimethyl; [N-(2,6-di(l-methylethyl)phenyl)amido)(o-tolyl)(a"naphflialen-2-diyl(6-pyridin"2-diyl)metliane)]hafnium di(N,N-dimetiiylamido); I>[ [N-(2,6-di(l-methylethyl)phenyI)amido)(24sopropylphenyl)(a-naphtlialen-2-diyl’ 2-diyl)methane)]hafiiium dimethyl; [N-(2,6-di(l-methylethyI)phenyl)amido)(2-isopropylphenyl)(a"naphthalen-2-diyl(6-pyridm’ 2-diyl)methane)]hafniumT(N,N-dimethylamido); IK-(2,6-di(l-methylethyl)phenyl)amido)(2-isopropylphenyl)(a-naphthalen-2-diyl(6-pyridiii-2-diyl)methane)]hafiiium dichloride; l>r-(2,6-di(l-methylethyl)phenyl)amido)(phenanthren-5-yl)(a'naphthalen-2-diyl(6-pyridin-2-diyI)methane)]hafnium dimethyl; [N-(2,6-di(l-methylethyl)phenyl)amido)(phenanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)m6thane)]hafniumT di(N,N-dimetliylamido); and [N-(2,6-di(l-methylethyl)phenyl)ainido)(phenanthren-5-yl)(a-naphthaIen-2-diyl(6-pyridin--2-diyI)m6thane)]hafnium dichloride. Under the reaction conditions used to prepare the metal complexes used in tlie present invention, the hydrogen of the 2-position of the a-naphthalene group substituted at the 6-position of tlie pyridin-2-yl group is subject to elimination, thereby uniquely forming metal complexes wherein the metal is covalently bonded to both the resulting amide group and to the 2-position of the a-naphthalenyl group, as well as stabilized by coordination to the pyridinyl nitrogen atom tlu-ough the electron pair of the nitrogen atom, Additional suitable metal complexes of polyvalent Lewis bases for use herein include compounds corresponding to the funnels: R’° is an aromatic or inertly substituted aromatic group contemn from 5 to 20 atoms not T is a hydrocarbylene or silkier group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof; M is a Group 4 metal, preferably zirconium or hafnium; G is an anionic, neutral or dianionic ligand group; preferably a halide, hydrocarbyl or dihydrocarbylamide group having up to 20 atoms not counting hydrogen; g is a number from 1 to 5 indicating the number of such G groups; and bonds and electron donatives interactions are represented by lines and arrows respectively. Preferably, such complexes correspond to the formula: T’ is a divalent bridging group of from 2 to 20 atoms not counting hydrogen, preferably a substituted or unsubstituted, C3-6 alkylene group; and Ar’ independently each occurrence is an arylene or an alkyl- or aryl-substituted arylene group of from 6 to 20 atoms not counting hydrogen; M’ is a Group 4 metal, preferably hafnium or zirconium; G independently each occurrence is an anionic, neutral or dianionic ligand group; g is a number from 1 to 5 indicating tlie number of such X groups; and electron donative interactions are represented by arrows* Preferred examples of metal complexes of foregoing formula include the foamy compounds : where M’ is Hf or Zr; AT* is C6.20 aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-lH-pyrrole-1-yl, or antliracen-5-yl, and T* independently each occurrence comprises a C3-6 allylene group, a C3-6 cycloallcylene group, or an inertly substituted derivative thereof; R independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atoms not counting hydrogen; and G, independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 G groups together are a divalent derivative of the foregoing hydrocarbyl or trihydrocarbylsilyl groups. Especially preferred are compounds of the formula: wherein Ar'* is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-lH-pyrrole-1-yl, or anthracen-5-yl, R’’ is hydrogen, halo, or CM alkyl, especially methyl T* is propan-l,3-diyl or butan-l,4-diyl, and G is chloro, methyl or benzyl. A most highly preferred metal complex of the foregoing formula is: wherein; X is as previously defined, preferably CMO hydrocarbyl, most preferably metliyl or benzyl; and R" is methyl, isopropyl, t-butyl’ oyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,4-dimethylcyclohexyl, 2-pyrrolyl, N-methyl-2-pyrrolyI, 2-piperidenyl, N-metliyl-2-piperidenyl, benzyl, o-tolyl, 2,6-dunethylphenyI, perfluorophenyl, 2,6-di(isopropyl)phenyl, or 2,4,6-trimethylphenyl. The foregoing complexes also include certain phosphmunine complexes are disclosed in EP-A-8905 81. These complexes correspond to the formula: [(R’)3-P=N]iM(K’)(R%.f, wherein: R is a monovalent ligand or two R’ groups together are a divalent ligand, preferably R’ is hydrogen or CM alkyl; M is a Group 4 metal, K’ is a group containing delocalized 7t-electrons through which K’ is bound to M, said K’ group containing up to 50 atoms not counting hydrogen atoms, and f is 1 or 2, Catalysts having high comonomer incorporation properties are also known to reincorporate in situ prepared long chain olefins resulting incidentally during the polymerization through \|3-hydride elimination and chain termination of growing polymer, or other process. The concentration of such long chain olefins is particularly enhanced by use of continuous solution polymerization conditions at high conversions, especially ethylene conversions of 95 percent or greater, more preferably at ethylene conversions of 97 percent or greater. Under such conditions a small but detectable quantity of vinyl group terminated polymer may be reincorporated into a groom polymer chain, resulting in the formation of long chain branches, that is, branches of a carbon length greater than would result from other deliberately added comonomer. Moreover, such chains reflect the presence of other comonomers present in the reaction mixture. That is, the chains may include short chain or long chain branching as well, depending on the comonomer composition of the reaction mixture. However, the presence of a CSA during polymerization can seriously Ichnite the incidence of long chain branchmg since the vast majority of the polymer chains become attached to a CSA species and are prevented from undergouig P-hydride elimination. In the present mention, the incidence of the foregoing long chain branched polymer containing segments or blocks may by enhanced by delaying the addition of the CSA to a point in the initial reactor or polymerization zone that is just prior to or even after the exit thereof. In this manner, frill polymerization under conventional conditions is attained and CSA is contacted with preformed polymer segments formed under steady state polymerization conditions. Uocatalvsts Each of the metal complexes (also interchangeably referred to harem as recitalists) may be activated to form the active catalyst composition by combination with a cocatalyst, preferably a cation forming cocatalyst, a strong Lewis acid, or a combination thereof. In a preferred embodhnent, the shuttling agent is employed both for purposes of chain transfer and as the optional cocatalyst component of the catalyst composition. The metal complexes desirably are rendered catalytically active by combination with a cation forming cocatalyst, such as toils previously known in the art for use wilt Group 4 metal olefin polymerization complexes. Suitable cation forming cocatalysts for use herein include neutral Lewis acids, such as C1.30 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds’ and most especially tris(pentafluorO"phenyl)borane; nonpolymeric, compatible, noncoordmating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium- salts of compatible, noncoordmating anions, or ferrocenium-, lead- or silver salts of compatible, noncoordinating anions; and combinations of the foregoing cation forming cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes for olefin polymerizations in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, US-A-5,321,106, US-A-5,721,185, US-A-5,3 50,723, US-A-5,425,872, US-A-5,625,087, US-A-5,883,204, US-A-5,919,983, US-A-5 J83,512, WO 99/15534, and W099/42467. Combinations of neutral Lewis acids, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tri(hydrocarbyl)boron compound having from 1 to 20 carbons in each hydrocarbyl group, especially tris(pentafluorophenyl)boranej further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane may be used as activating cocatalysts. Preferred molar ratios of metal complex:tris(pentafluorophenyl-borane:alumoxane are from 1:1:1 to 1:5:20, more preferably from 1:1:L5 to 1:5:10. Suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion, A". As used herein, the term "noncoordinating" means an anion and the catalytic derivative derived there from, or which is only weakly coordmated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base, A noncoordinating anion specifically refers to an anion which when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation tliereby forming neutral complexes. "Compatible anions" are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex. Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of tlie active catalyst species (the metal cation) which may be formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not lunited to, boron, phosphorus, and silicon* Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compoimds containing a single boron atom in tlie anion portion, are available commercially. Preferably such cocatalysts may be represented by the following general formula: (L-H)g’A)’-wherein: L is a neutral Lewis base; (L-!!)"" is a conjugate Bronsted acid of L; A’' is a noncoordinating, compatible anion having a charge of g-, and g is an integer from 1 to 3, More preferably A’' corresponds to the formula: [M'Q4]'; wherein: M' is boron or aluminum in the +3 formal oxidation state; and Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and halo- substituted silylliydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in US-A-5,296,433. in a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A'. Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this mvention may be represented by tlie following general formula: wherein: L is as previously defined; B is boron in a formal oxidation state of 3; and Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylliydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl. Preferred Lewis base salts are ammonium salts, more preferably trialkylammonium salts containing one or more Cn’o alkyl groups. Most preferablyj Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl group. Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as: trimethylammoniimi tetrakis(pentafluorophenyl) borate, triethylarmnonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate, N,N-dimethylanilimum benzyltris(pentafluorophenyl) borate, N,N-dimethylanilinium tetralds(4-(t-butyldimethylsilyl)-2, 3,5, 6-tetrafluorophenyl) borate, N,N"dimethylanilinium tetrakis(4'-(triisopropylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate, N,N-dunethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl) borate, dimethyloctadecylanmaonium tetrakis(pentafluorophenyl) borate, methyldioctadecylammonium tetrakis(pentafluorophenyl) borate, dialkyl ammonium salts such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, methyloctadecylammonium tetrakis(pentafluorophenyl) borate. metliyloctadodecylammonium tetrakis(pentafluorophenyl) borate, and dioctadecylammonium tetrakis(pentafluorophenyl) borate; tri-substituted phosphonium salts such as: triphenylphosphonium tetralcis(pentafluorophenyl) borate, metliyldioctadecylphosphoniura tetrakis(pentafluorophenyl) borate, and tri(2,6-dunethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate; di-substituted oxonium salts such as: diphenyloxonium tetrakis(pentafluorophenyl) borate, di(o"tolyl)oxonium tetrakis(pentafluorophenyl) borate, and di(octadecyl)oxonium tetrakis(pentafluorophenyl) borate; di-substituted sulfonium salts such as: di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate. Preferred (L-!!)"‘ cations are methyldioctadecylammonium cations, dimethyloctadecylammonium cations, and ammonium cations derived from mixtures of trialkyl amines containing one or 2 Ci4„i8 alkyl groups. Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula: (Ox’’)/A’"V wherein: Ox'"" is a cationic oxidizing ageift having a charge of h+; h is an integer from 1 to 3; and A’" and g are as previously defined. Examples of cationic oxidizmg agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag’ or Pb""‘. Preferred embodiments of A' are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate. Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula: [CfA-wherein: [C]"" is a Ci.20 carbenium ion; and A" is a noncoordinating, compatible anion having a charge of-1. A preferred carbenium ion is the trityl cation, that is triphenylmethylium. A tiirther suitable ion forming, activating cocatalyst comprises a compound whiich is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula: (Q’Si’A’ wherein: Q' is Ci-io hydrocarbyl, and A" is as previously defined. Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetralcispentafluorophenylborate and ether substituted adducts tliereof. Silylium salts have been previously generically disclosed in J. Chem Soc. Cham. Comm., 1993,383-384, as well as Lambert, J. B., et aL, Oreanometalhcs. 1994, 13, 2430-2443. The use of tlie above silylium salts as activating cocatalysts for addition polymerization catalysts is disclosed in US-A-5,625,087. Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used according to the present invention. Such cocatalysts are disclosed m US-A-5,296,433. Suitable activating cocatalysts for use herein also include polymeric or oligomeric alumoxanes, especially methylalumoxane (MAO), triisobutyl alummum modified methylalumoxane (MMAO), or isobutylalumoxane; Lewis acid modified alumoxanes, especially perhalogenated tri(hydrocarbyl)aluminum- or perhalogenated tri(hydrocarbyl)boron modified alumoxanes, having from 1 to 10 carbons in each hydrocatbyl or halogenated hydrocarbyl group, and most especially tris(pentafIuoropheny])borane modified alumoxanes. Such cocatalysts are previously disclosed in US Patents 6,214,760,6,160,146, 6,140,521, and 6,696,379. A class of cocatalysts comprising non-coordmating anions generically referred to as expanded anions, further disclosed in US Patent 6,395,671, may be suitably employed to activate the metal complexes of the present mvention for olefin polymerization. Generally, these cocatalysts (illustrated by those having imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) may be depicted as follows: A'"" is a cation, especially a proton containing cation, and preferably is a trihydrocarbyl ammonium cation containing one or two Cio’o alkyl groups, especially a methyldi (Ci4.2oallcyl)ammonium cation, Q’, independently each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, preferably Ci-20 alkyl, and Q’ is tris(pentafluorophenyl)boraue or tris(pentafluorophenyI)alumane). Examples of these catalyst activators include trihydrocarbylammonium- salts, especially, methyldi(Ci4_2oalkyl)ammonium- salts of: bis(tris(pentafluorophenyl)borane)imtdazolide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)borane)-2-heptadecylraiidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)iinidazolide, bis(tris(pentafluorophenyl)boraiie)-4,5-bis(heptadecyl)imida2oIide, bis(tris(pentafluorophenyl)borane)imidazolinide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imida2oIinide, bis(tris(pentafluorophenyl)borane)"5,6-dimethylbenzimidazolide, bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide, bis(tris(pentafluorophenyl)alumane)imidazolide, bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide, bis(tris(pentafluorophenyl)alumaue)imidazolinide, bis(tris(pentafluorophenyl)alunxane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)aIumane)-2-heptadecylimidazoIinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyI)imidazolinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimida2olide, and bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide. Other activators include those described in PCT publication WO 98/07515 such as tris (2, the invention, for example, aliunoxanes and ionizing activators in combinations, see for example, EP-A-0 573120, PCX publications WO 94/07928 and WO 95/14044 and US Patents 5,153,157 and 5,453,410. WO 98/09996 describes activating catalyst compounds with perchlorates, periodates and iodates, including tlieir hydrates. WO 99/18135 describes the use of organoboroaluminum activators. WO 03/10171 discloses catalyst activators that are adducts of Bronsted acids with Lewis acids. Other activators or methods for activating a catalyst compound are described in for example, US Patents 5,849,852, 5,859, 653, 5,869,723, EP-A-615981, and PCX publication WO 98/32775. All of the foregomg catalyst activators as well as any other know activator for transition metal complex catalysts may be employed alone or in combination according to the present invention, however, for best results alumoxane containing cocatalysts are avoided. Xhe molar ratio of catalyst/cocatalyst employed preferably ranges from 1:10,000 to 100:1, more preferably from 1:5 000 to 10:1, most preferably from 1:1000 to 1:1, Alumoxane, when used by itself as an activating cocatalyst, is employed m large quantity, generally at least 100 times the quantity of metal complex on a molar basis. Xris(pentafluorophenyl)borane, where used as an activating cocatalyst is employed in a molar ratio to the metal complex of from 0.5:1 to 10:1, more preferably from 1:1 to 6:1 most preferably from 1:1 to 5; 1. Xhe remaining activatmg cocatalysts are generally employed in approxunately equimolar quantity with the metal complex. During the polymerization, the reaction mbcture is contacted witli tlie activated catalyst composition according to any suitable polymerization conditions. Xhe process is desirably characterized by use of elevated temperatures and pressures. Hydrogen may be employed as a chain transfer agent for molecular weight control according to known techniques, if desired. As in other similar polymerizations, it is highly desirable that the monomers and solvents employed be of sufficiently high purity that catalyst deactivation or premature chain termination does not occur, unless a block copolymer modified polymer product is desired. Any suitable technique for monomer purification such as devolatilization at reduced pressure, contacting with molecular sieves or high surface area alumina, or a combination of the foregoing processes may be employed. Supports may be employed in the present invention, especially in slurry or gas-phase polymerizations. Suitable supports include solid, particulated, high surface area, metal oxides, metalloid oxides, or mixtures thereof (interchangeably referred to herein as an inorganic oxide). Examples include: talc, silica, alumina, magnesia, titania, zirconia, Sn203, aluminosilicates, borosilicates, clays, and mixtures thereof. Suitable supports preferably have a surface area as determined by nitrogen porosimetry using tlie B.E.X. method from 10 to 1000 m’/g, and preferably from 100 to 600 m /g. Xhe average particle size typically is from 0.1 to 500 nm, preferably from 1 to 200 urn, more preferably 10 to 100 \|im, In one embodhnent of tlie invention the present catalyst composition and optional support may be spray dried or otherwise recovered m solid, particulated form to provide a composition that is readily transported and handled. Suitable methods for spray drying a liquid containing slurry are well known in the art and usefully employed herein. Preferred tecliniques for spray drying catalyst compositions for use herein are described in US-A's-5,648,310 and 5,672,669. The polymerization is desirably carried out as a continuous polymerization, preferably a continuous, solution polymerization, in wliich catalyst components, monomers, and optionally solvent, adjuvants, scavengers, and polymerization aids are continuously supphed to one or more reactors or zones and polymer product contmuously removed therefrom. Withm the scope of the terms "continuous" and "continuously" as used in this context are those processes in which there are intermittent additions of reactants and removal of products at small regular or irregular intervals, so that, over time, tlie overall process is substantially continuous. Moreover, as previously explained, the cham shuttling agent(s) may be added at any point during the polymerization including in the first reactor or zone, at the exit or slightly before the exit of the first reactor, between the first reactor or zone and the second or any subsequent reactor or zone, or even solely to tlie second or any subsequent reactor or zone. Due to the difference in monomers, temperatures, pressures or other difference in polymerization conditions between at least two of the reactors or zones connected in series, polymer segments of differing composition such as comonomer content, crystallinity, density, tacticity, regio-regularity, or other chemical or physical difference, within the same molecule are formed in the different reactors or zones. The size of each segment or block is determined by continuous polymer reaction conditions, and preferably is a most probable distribution of polymer sizes. Each reactor in the series can be operated under high pressure, solution, slurry, or gas phase polymerization conditions. In a multiple zone polymerization, all zones operate under the same type of polymerization, such as solution, slurry, or gas phase, but at different process conditions. For a solution polymerization process, it is desirable to employ homogeneous dispersions of the catalyst components m a liquid diluent in which the polymer is soluble under the polymerization conditions employed. One such process utilizing an extremely fme silica or similar dispersing agent to produce such a homogeneous catalyst dispersion wherein normally either the metal complex or the cocatalyst is only poorly soluble is disclosed in US-A-5,783,512. A high pressure process is usually carried out at temperatures from 100°C to 400'C and at pressures above 500 bar (50 MPa). A slurry process typically uses an inert hydrocarbon diluent and temperatures of from 0°C up to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. Preferred temperatures in a slurry polymerization are from 30°C, preferably from 60°C up to 115°C, preferably up to lOO’’C, Pressures typically range from atmospheric (100 kPa) to 500 psi (3.4 MPa). In all of the foregoing processes, continuous or substantially contmuous polymerization conditions are preferably employed. The use of such polymerization conditions, especially continuous, solution polymerization processes, allows the use of elevated reactor temperatures which results in the economical production of tlie present block copolymers in high yields and efficiencies. The catalyst may be prepaied as a homogeneous composition by addition of the requisite metal complex or multiple complexes to a solvent in which the polymerization will be conducted or in a diluent compatible with the ultimate reaction mixture. The desired cocatalyst or activator and’ optionally, the shuttling agent may be combined with the catalyst composition either prior to, simultaneously with, or after combination of the catalyst with tlie monomers to be polymerized and any additional reaction diluent. At all times, the individual ingredients as well as any active catalyst composition must be protected from oxygen, moisture and other catalyst poisons. Therefore, the catalyst components, shuttling agent and activated catalysts must be prepared and stored in an oxygen and moisture free atmosphere, preferably under a dry, inert gas such as nitrogen, Without limiting in any way the scope of tlie invention, one means for carrying out such a polymerization process is as follows. In one or more well stirred tank or loop reactors operating under solution polymerization conditions, the monomers to be polymerized are introduced continuously together with any solvent or diluent at one part of the reactor. The reactor contains a relatively homogeneous liquid phase composed substantially of monomers together with any solvent or diluent and dissolved polymer. Preferred solvents include C4-10 hydrocarbons or mixtures thereof, especially alkanes such as hexane or mixtures of alkanes, as well as one or more of the monomers employed in the polymerization. Examples of suitable loop reactors and a variety of suitable operating conditions for use therewith, including the use of multiple loop reactors, operant in series, are found m USP's 5,977,251, 6,319,989 and 6,683,149, Catalyst along with cocatalyst and optionally chain shuttling agent are continuously or intermittently introduced in the reactor liquid phase or any recycled portion thereof at a minimum of one location. The reactor temperature and pressure may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by use of cooling or heating coils, jackets or both. The polymerization rate is controlled by the rate of catalyst addition. The content of a given monomer in the polymer product is influenced by the ratio of monomers in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. variables such as the temperature, monomer concentration, or by the previously mentioned chain shuttling agent, or a chain terminating agent such as hydrogen, as is well known in tlie art. Connected to the discharge of the reactor, optionally by means of a conduit or other transfer means, is a second reactor, such that the reaction mixture prepared in the first reactor is discharged to the second reactor without substantially termination of polymer growth. Between the first and second reactors, a differential in at least one process condition is established. Preferably for use in formation of a copolymer of two or more monomers, the difference is tlie presence or absence of one or more comonomers or a difference in comonomer concentration. Additional reactors, each arranged in a manner similar to the second reactor in the series may be provided as well Upon exiting the last reactor of the series, the effluent is contacted with a catalyst kill agent such as water, steam or an alcohol or with a coupling agent. The resulting polymer product is recovered by flashing off volatile components of the reaction mixture such as residual monomers or diluent at reduced pressure, and, if necessary, conducting further devolatilization in equipment such as a devolatilizing extruder. In a continuous process the mean residence time of the catalyst and polymer in the reactor generally is from 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours. Alternatively, the foregoing polymerization may be carried out m a plug flow reactor with a monomer, catalyst, shuttling agent, temperature or other gradient established between differing zones or regions thereof, optionally accompanied by separated addition of catalysts and/or chain shuttling agent, and operating under adiabatic or non-adiabatic polymerization conditions. The catalyst composition may also be prepared and employed as a heterogeneous catalyst by adsorbing the requisite components on an inert morganic or organic particulated solid, as previously disclosed. In a preferred embodhnent, a heterogeneous catalyst is prepared by co-precipitating the metal complex and the reaction product of an inert inorganic compound and an active hydrogen containing activator, especially the reaction product of a tri (CM alkyl) aluminum compound and an ammonium salt of a hydroxyaryltris(pentafluorophenyl)borate, such as an ammonium salt of (4-hydroxy-3,5-ditertiarybutylphenyl)tris(pentafluorophenyl)borate, When prepared in heterogeneous or supported form, the catalyst composition may be employed in a slurry or a gas phase polymerization. As a practical limitation, slurry polymerization takes place in liquid diluents in which tlie polymer product is substantially insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent. As with a solution polymerization, the a-olefin comonomer or a mixture of different a-olefin monomers may be used in whole or part as the diluent. Most preferably at least a major part of the Preferably for use in gas phase polymerization processes, tlie support material and resulting catalyst has a median particle diameter from 20 to 200 ‘im, more preferably from 30 ‘m to 150 \|xin, and most preferably from 50 [xm to 100 ‘m. Preferably for use in slurry polymerization processes, the support has a median particle diameter from 1 ‘m to 200 ‘m, more preferably from 5 fxm to 100 ‘m, and most preferably from 10 pxn. to 80 \|im. Suitable gas phase polymerization process for use herein are substantially similar to laiown processes used commercially on a large scale for the manufacture of polypropylene, ethylene/ a-olefm copolymers, and other olefin polymers. The gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone. Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended above a perforated plate or fluidization grid’ by a flow of fluidization gas. The gas employed to fluidize the bed comprises tlie monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. The hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, havmg a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization. A preferred method of cooling of the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect, often referred to as operation in the condensing mode The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon havmg 3 to 8, preferably 4 to 6, carbon atoms. In the case that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, this can suitably be fed to the bed to provide an evaporative cooling effect* The volatile liquid evaporates in tlie hot fluidized bed to form gas which mixes witli the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed. The evaporated liquid then emerges froin the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop. The recycle gas is cooled in die heat exchanger and, if the temperature to which the gas is cooled is below the dew pomt, liquid will precipitate from tlie gas. This liquid is desirably recycled continuously to tlie fluidized bed. It is possible to recycle the precipitated liquid to tlie bed as liquid droplets carried m WO-94/25495 and U.S. 5,352,749. A particularly preferred method of recyclmg the liquid to the bed is to separate the liquid from the recycle gas stream and to reinject tliis liquid directly into tlie bed, preferably using a metliod which generates fme droplets of the liquid within the bed. This type of process is described in WO-94/28032. The polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst composition according to the invention. The catalyst composition may be subjected to a prepolymerization step, for example, by polymerizing a small quantity of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising supported catalyst particles embedded m olefin polymer particles as well. The polymer is produced directly in the fluidized bed by polymerization of the monomer or mixture of monomers on the fluidized particles of catalyst composition, supported catalyst composition or prepolymerized catalyst composition within the bed. Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to the desired polymer, and conditioning the bed by drying with inert gas or nitrogen prior to introducing the catalyst composition, the monomers and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode. The produced polymer is discharged continuously or semi-continuously from the fluidized bed as desired. The gas phase processes most suitable for the practice of this invention are continuous processes wliich provide for the continuous supply of reactants to the reaction zone of the reactor and the removal of products fi-om the reaction zone of the reactor, thereby providing a steady-state environment on the macro scale in tlie reaction zone of the reactor. Products are readily recovered by exposure to reduced pressure and optionally elevated temperatures (devolatilization) according to known techniques. Typically, the fluidized bed of tlie gas phase process is operated at temperatures greater than 50°C, preferably from 60°C to 110°C, more preferably from 70°C to 110°C. Suitable gas phase processes which are adaptable for use in the process of this invention are disclosed in US Patents: 4,588 J90; 4,543,399; 5,352,749; 5,436,304; 5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562; 5,028,670; 5,473,028; 5,106,804; 5,556,238; 5,541,270; 5,608,019; and 5,616,661. As previously mentioned, functionalized derivatives of pseudo-block copolymers are also included within the present invention. Examples include metallated polymers wherein the metal is the remnant of the catalyst or chain shuttling agent employed, as well as further derivatives thereof. Because a substantial fraction of the polymeric product exiting tlie reactor is terminated with the can be utilized in well known chemical reactions such as those suitable for otlier alkyl-aluminum, alkyl-gallium, alkyl-zinc, or alkyl-Group 1 compounds to form amine-, hydroxy-, epoxy-, silane, vinylic, and other functionalized terminated polymer products. Examples of suitable reaction teclmiques that are adaptable for use here in are described m Negishi, "Organometallics in Organic Synthesis", Vol. 1 and 2, (1980), and otlier standard texts in organometallic and organic synthesis. Polymer Products Utilizing the present process, novel polymers, mcluding pseudo-block copolymers of one or more olefin monomers, are readily prepared. Preferred polymers comprise in polymerized form at least one monomer selected from the group consisting of ethylene, propylene and 4-methyH-pentene. Highly desirably, the polymers are interpolymers comprising in polymerized form ethylene, propylene or 4-methyl-l-pentene and at least one different C2-20 a-olefm comonomer, and optionally one or more additional copolymerizable comonomers. Suitable comonomers are selected from diolefins, cycUc olefins, and cyclic diolefins, halogenated vinyl compounds, and vinylidene aromatic compounds* CLAIMS: 1. A process for the polymerization of one or more addition polymerizable monomers to form a copolymer comprising two regions or segments of differentiated polymer composition or properties, said process comprising: 1) Contacting an addition polymerizable monomer or mixture of monomers under addition polymerization conditions in a reactor or reactor zone with a composition comprising at least one olefin polymerization catalyst and a cocatalyst and characterized by tlie formation of polymer chains from said monomer or monomers; 2) transferring the reaction mixture to a second reactor or reactor zone and optionally adding one or more additional reactants, catalysts, monomers or other compounds prior to, commensurate with, or after said transfer; and 3) causing polymerization to occur in said second reactor or reactor zone to form polymer chains that are differentiated from the polymer chains formed in step 1); said process being characterized by addition of a chasm shuttling agent to the reaction mixture prior to, during, or subsequent to step 1) such that at least some of the resulting polymer molecules from step 3) comprise two or more chemically or physically distinguishable blocks or segments. 2. A high molecular weight copolymer comprising two or more substantially homogeneous intramolecular segments or blocks comprising differing chemical or physical properties, said intramolecular segments characterized by possessing a most probable molecular weight distribution. 3. A polymer mixture comprising: (1) an organic or inorganic polymer and (2) a copolymer according to claim 2 or preparable according to claim 1. 4. A process according to claim 1 wherein the catalyst comprises a metal complex corresponding to the formula: wherein: R^^ is selected from alkyl, cycloalkyl, Heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives tliereof containing from 1 to 30 atoms not counting hydrogen or a divalent derivative thereof; T^ is a divalent bridging group of from 1 to 41 atoms other than hydrogen, preferably 1 to 20 atoms other than hydrogen, and most preferably a mono- or di- C1.20 hydrocarbyl substituted methylene or silane group; and R is a C5.-20 heteroaryl group containing Lewis base functionality; M is a Group 4 metal; X is an anionic, neutral or dianionic ligand group; x' is a number from 0 to 5 indicating the number of such Groups; and bonds, optional bonds and electron donatives interactions are represented by lines dotted lines and arrows respectively. 5. A process according to claim 1 wherein the catalyst comprises a metal complex corresponding to the formula: wherein is a metal of Groups 4-10 of the Periodic Table of the elements; T^ is a nitrogen, oxygen or phosphorus containing group; X^ is halo, hydrocarbyl, or hydrocarbyloxy; t is one or two; x" is a number selected to provide charge balance; and T^ and N are linked by a bridging ligand. 6. A process according to any one of claims 1,4 or 5 characterized by producing a plumier according to claim 2 or a polymer mixture according to claim 3. 7. A process according to any one of claims 1,4 or 5 wherein the chemically or physically distinguishable blocks or segments have different comonomer incorporation indices.

Full Text

CATALYTIC OLEFIN BLOCK COPOLYMERS WITH CONTROLLED BLOCK SEQUENCE DISTRIBUTION
Cross Reference Statement
This application claims tlie benefit of U.S. Provisional Application No. 60/717,545, filed September 15, 2005. For purposes of United States patent practice, the contents of this provisional application are herein incorporated by reference.
Background of the Invention
The present invention relates to a process for polymerizing a monomer or mixtures of two or more monomers such as mixtures of ethylene and one or more comonomers, to form an interpolymer product having unique physical properties, to a process for preparing such interpolymers, and to the resulting polymer products. In another aspect, the invention relates to the articles prepared from these polymers. The inventive polymers comprise two or more differ regions or segments (blocks), each block being characterized by a generally uniform chemical composition causing the polymer to possess unique physical properties. These pseudo-block copolymers and polymeric blends comprising the same are usefully employed in tlie preparation of solid articles such as moldings, fihns, sheets, and foamed objects by molding, extruding, or other processes, and are useful as components or ingredients in adhesives, laminates, polymeric blends, and other end uses. The resulting products are used in the manufacture of components for automobiles, such as profiles, bumpers and trim parts; packaging materials; electric cable insulation, and other applications.
It has long been known that polymers containing a block-type structure often have superior properties compared to random copolymers and blends. For example, diblock copolymers of styrene and butadiene (SBS) and hydrogenated versions of the same (SEES) have an excellent combination of heat resistance and elasticity. Other block copolymers are also known in the art. Generally, block copolymers known as tliermoplastic elastomers (TPE) have desirable properties due to the presence of "soft" or elastomeric block segments connecting "hard" either crystallizable or glassy blocks in the same polymer. At temperatures up to the melt temperature or glass transition temperature of the hard segments, the polymers demonstrate elastomeric character, At higher temperatures, the polymers become flowable, exhibiting thermoplastic behavior. Known methods of preparing block copolymers include anionic polymerization and controlled free radical polymerization. Unfortunately, these methods of preparing block copolymers require sequential monomer addition with polymerization to relative completeness and the types of monomers that can

styrene and butadiene to form a SBS type block copolymer, each polymer chain requires a stoichiometric amount of initiator and the resulting polymers have extremely narrow molecular weight distribution, Mw/Mn, preferably from 1.0 to 1.3. That is, the polymer block lengths are substantially identical. Additionally, anionic and free-radical processes are relatively slow, resulting m poor process economics, and not readily adapted to polymerization of a-olefins.
It would be desirable to produce block copolymers catalytically, plait is, in a process wherein more tlian one polymer molecule is produced for each catalyst or initiator molecule. In addition, it would be highly desirable to produce copolymers him properties resembling block copolymers from olefin monomers such as ethylene, propylene, and higher alpha-olefins that are generally unsuited for use in anionic or free-radical polymerizations. In certain of ties polymers, it is highly desirable that some or all of the polymer blocks comprise amorphous polymers such as a copolymer of ethylene and a comonomer, especially amorphous random copolymers comprising ethylene and an a-olefin having 3 or more carbon atoms. Finally, it would be desirable to prepare pseudo-block copolymers wherein a substantial fraction of the polymer molecules are of a controlled block number, especially diblocks or tailbacks, but where the block lengths are a most probable distribution, rather than identical or nearly identical block lengths.
Previous researchers have stated that certain homogeneous coordination polymerization catalysts can be used to prepare polymers having a substantially "block-like" structure by suppressing chain-transfer during the polymerization, for example, by conducting the polymerization process in the absence of a chain transfer agent and at a sufficiently low temperature such that chain transfer by p-hydride elimination or other chain transfer processes is essentially eliminated. Under such conditions, the sequential addition of different monomers coupled with high conversion was said to result m formation of polymers having sequences or segments of different monomer content Several examples of such catalyst compositions and processes are reviewed by Coates, Hosted, and Ramparts in Angew. Chem., Int Ed.. 41, 2236-2257 (2002) as well as US-A-2003/0114623.
Disadvantageoustys such processes require sequential monomer addition and result in the production of only one polymer chain per active catalyst center, which limits catalyst productivity. In addition, the requirement of relatively low process temperatures but high conversion increases die process operating costs, making such processes unsuited for commercial implementation. Moreover, the catalyst cannot be optimized for formation of each respective polymer type, and therefore the entire process results in production of polymer blocks or segments of less than maximal efficiency and/or quality. For example, formation of a certain quantity of prematurely term mated polymer is generally unavoidable, result in the forming of blends having inferior

block copolymers having Mw/Mn of h5 or greater, the resulting distribution of block lengths is relatively inliomogeneous, not a most probable distribution.
For these reasons, it would be highly desirable to provide a process for producing olefin copolymers comprising at least some quantity of blocks or segments having differing physical properties in a process using coordination polymerization catalysts capable of operation at high catalytic efficiencies and high reactor temperatures. In addition, it would be desirable to provide a process and resulting copolymers wherein insertion of terminal blocks or sequencing of blocks within the polymer can be influenced by appropriate selection of process conditions. Finally, if would be highly desirable to be able to use a continuous process for production of pseudo-block copolymers.
The use of certain metal alkyl compounds and other compounds, such as hydrogen, as chain transfer agents to interrupt chain growth in olefin polymerizations is well known in the art. In addition’ it is known to employ such compounds, especially aluminum alkyl compounds, as scavengers or as cocatalysts in olefin polymerizations. In Macromolecules, 33, 9192-9199 (2000) the use of certain aluminum trialkyl compounds as chain transfer agents in combination with certam paired zirconocene catalyst compositions resulted in polypropylene mixtures containing small quantities of polymer fractions containing both isotactic and atactic chain segments. In Liu and Ritter, Macromolecular Rapid Comm» 22, 952-956 (2001) and Bruaseth and Rytter, Macromolecules, 36, 3026-3034 (2003) mixtures of ethylene and 1-hexene were polymerized by a similar catalyst composition containing trimethylaluminum chain transfer agent. In the latter reference, the authors simimarized the prior art studies in the following manner (some citations omitted):
"Mixing of two metallocenes with known polymerization behavior can be used to control polymer microstructure. Several studies have been performed of ethane polymerization by mixing two metallocenes. Common observations were that, by combining catalysts which separately give polyethylene with different Mw, polyethene with broader and in some cases bimodal MWD can be obtained. Kim (J, Polym. Sci., Part A: Polvm. Chem.. 38, 1408-1432 (2000)) developed a criterion in order to test the MWD bimodality of polymers made by dual single-site catalysts, as exemplified by ethene/1-hexene copolymerization of the mixtures Et(Ind)2ZrCl2/Cp2HfCl2 and Et(Ind)2ZrCl2/ CGC (constramed geometry catalyst) supported on silica. Heiland and Kaminsky CMalcromol. Chem.. 193, 601-610 (1992)) studied a mixture of Et-(Ind)2ZrCl2 and the avium analogue in copolymerization of ethene and 1-butene.

These studies do not contain any indication of interaction between the two different sites, for example, by readsorption of a terminated chain at the alternative site. Such reports have been issued’ however, for polymerization of Chien et aL (L Polvm. Sci„ Part A: Polvm. Chem„ 37, 2439-2445 (1999), Makromol., 30, 3447-3458 (1997)) studied propene polymerization by homogeneous binary zirconocene catalysts. A blend of isotactic polypropylene (i-PP), atactic polypropylene (a-PP), and a stereoblock fraction (i-PP-Z’-a-PP) was obtained with a binary system comprising an isospecific and an aspecific precursor with a borate and TIBA as cocatalyst* By using a binary mixture of isospecific and syndiospecific zirconocenes, a blend of isotactic polypropylene (i-PP), syndiotactic pol3T)ropylene (s-PP), and a stereoblock fraction (i-PP-6-S-PP) was obtained. The mechanism for formation of the stereoblock fraction was proposed to involve the exchange of propagating chains between the two different catalytic sites, Przybyla and Fink (Acta Polvm.. 50, 77-83 (1999)) used two different types of metallocenes (isospecific and syndiospecific) supported on the same silica for propene polymerization. They reported that, with a certain type of silica support, chain transfer between the active species in the catalyst system occurred, and stereoblock PP was obtained. Lieber and Brintzinger (Macromol. 3, 9192-9199 (2000)) have proposed a more detailed explanation of how the transfer of a growing polymer chain fi*om one type of metallocene to another occurs. They studied propene polymerization by catalyst mixtures of two different awja-zirconocenes. The different catalysts were first studied individually with regard to their tendency toward alkyl-polymeryl exchange with the alkylaluminum activator and then pairwise with respect to their capability to produce polymers with a stereoblock structure. They reported that formation of stereoblock polymers by a mixture of zirconocene catalysts with different stereoselectivities is contmgent upon an efficient polymeryl exchange between the Zr catalyst centers and the Al centers of the cocatalyst."
Brusath and Rytter then disclosed their own observations using paired zirconocene catalysts to polymerize mixtures of ethylene/1-hexene and reported the effects of the influence of the dual site catalyst on polymerization activity, incorporation of comonomer, and polymer microstructure using methylalumoxane cocatalyst.
Analysis of the foregoing results indicate that Rytter and coworkers likely failed to utilize combinations of catalyst, cocatalyst, and thuds components that were capable of readsorption of tlie polymer chain from the chain transfer agent onto botli of the active catlike sites, i.e., two-way readsorption. While indicating that chain termmation due to the presence of trimethylaluminum

comonomer, and thereafter tilt polymeric exchange wilt the more open catalytic site followed by continued polymerization likely occurred, evidence of the reverse flow of polymer ligands appeared to be lacking in the reference. In fact, in a later communication, Ritter, et. al.. Polymer. 45, 7853-7861 (2004), it was reported that no chain transfer between the catalyst sites actually took place in the earlier experiments. Similar polymerizations were reported in WO98/34970.
In USP's 6,380,341 and 6,169,151, use of a "fluxional" metallocene catalyst, plait is a metallocene capable of relatively facile conversion between two stereoisomeric forms having differing polymerization characteristics such as differing reactivity ratios was said to result in production of olefin copolymers having a "blocky" structure. Disadvantageously, the respective stereoisomers of such metallocenes generally fail to possess significant difference in polymer formation properties and are incapable of forming both highly crystalline and amorphous block copolymer segments, for example, from a given monomer mixture under fixed reaction conditions. Moreover, because the relative ratio of tlie two "fluxional" forms of the catalyst cannot be varied, there is no ability, using "fluxional" catalysts, to vary polymer block composition or to vary the ratio of the respective blocks. For certain applications, it is desirable to produce polymers having terminal blocks that are highly crystalline, functionalized or more readily functionalized, or that possess other distinguishing properties. For example, it is believed that polymers wherein the terminal segments or blocks are crystalline or glassy, rather slain amorphous, possess improved abrasion resistance. In addition, polymers wherein the blocks having amorphous properties are internal or primarily connected between crystalline or glassy blocks, have improved elastomeric properties, such as improved detractive force and recovery, particularly at elevated temperatures, In JACS. 2004, 126, 10701-10712, Gibson, et al discuss the effects of "catalyzed living polymerization" on molecular weight distribution. The authors define catalyzed living poljonerization in this manner;
"...if chain transfer to aluminum constitutes the sole transfer mechanism and the exchange of the growing polymer chain between the transition metal and the aluminum centers is very fast and reversible, the polymer chains will appear to be growing on the aluminum centers. This can then reasonably be described as a catalyzed chain grove reaction on aluminum.... An attractive manifestation of tiles type of chain growth reaction is a Poisson distribution of product molecular waitlist, as opposed to the Schulz-Florid distribution that arises when P-H transfer accompanies propagation."
The authors reported the results for the catalyzed living homopolymerization of ethylene using an iron containing catalyst in combination with ZnEt2, ZnMe2, or Zn(i-Pr)2. Homiletic alkyls of aluminum, boron, tin, lithium, magnesium and lead did not induce catalyzed chain growth.

distribution. However, after analysis of time-dependent product distribution the authors concluded this reaction was, "not a simple catalyzed chain growth reaction." Accordingly, the product would not have constituted a pseudo-block copolymer. Similar processes employing single catalysts have been described in USP's 5,210,338, 5, 276,220, and 6,444,867.
Earlier workers had made similar clans to forming block copolymers using a single Ziegler-Natta type catalyst in multiple reactors arranged in series. Examples of such teachings include USP's 3,970,719 and 4,039,632. It is now known that no substantial block copolymer formation takes place under these reaction conditions.
In USP's 6,319,989 and 6,683,149, the use of two loop reactors connected in series and operating under differing polymerization conditions to prepare either broad or anyhow molecular weight polymer products was disclosed. Tlie references fail to disclose the use of chain shuttling agents and the formation of pseudo-block copolymer products.
Accordingly, there remains a need in the art for a polymerization process that is capable of preparing copolymers having properties approximating those of linear multi-block copolymers, in a high yield process adapted for commercial utilization. Moreover, it would be desirable if there were provided an improved process for preparing polymers, especially copolymers of two or more comonomers such as ethylene and one or more comonomers, by the use of a chain shuttling agent (CSA) to introduce block-like properties m the result polymer (pseudo-block copolymers). In addition it would be desirable to provide such an improved process operating at elevated temperatures that is capable of economically preparing diblock, relock or higher multi-block copolymers having a most probable distribution of chain lengths. Finally, it would be desirable to provide an improved process for preparing the foregoing pseudo-block copolymer products in a continuous process.
Summary of the Invention
According to the present mention there are now provided a process for the polymerization of one or more addition polymerizable monomers, preferably of two or more addition polymerizable monomers, especially ethylene and at least one copolymerizable comonomer, propylene and at least one copolymerizable comonomer, or 4-methyl-l-pentene and at least one copolymerizable comonomer, to form a copolymer comprising multiple blocks or segments of differentiated polymer composition or properties, especially blocks or segments comprising differing comonomer incorporation levels, said process comprising contacting an addition polymerizable monomer or mixture of monomers under addition polymerization conditions with a composition comprising at least one addition polymerization catalyst, a cocatalyst and a chain shuttling agent, said process

differentiated process conditions in two or more reactors operating under steady state polymerization conditions or in two or more zones of a reactor operating under plug flow polymerization conditions.
Because the polymer is comprised of two or more blocks or segments, preferably two or tliereof block or segments, which are joked to form a single polymer, and each block or segment is chemically or physically distinguishable (outlier than by molecular weight or molecular weight distribution) from adjoining blocks or segments, the resulting pseudo-block copolymer possesses unique physical and chemical properties compared to random copolymers of tlie same gross chemical composition.
In another embodiment of the infraction there is provided a copolymer, especially such a copolymer comprising in polymerized form ethylene and a copolymerizable comonomer, propylene and at least one copolymerizable comonomer, or 4-methyH-pentene and at least one copolymerizable comonomer, said copolymer comprising two or more, preferably two or three intramolecular regions comprising differing chemical or physical properties, especially regions of differentiated comonomer incorporation. Highly preferably the copolymer possesses a molecular weight distribution, Mw/Mn, of less than 3*0, preferably less than 2.8.
In yet another embodiment of the invention there is provided a process and the resulting pseudo-block copolymer, said process comprising:
polymerizing one or more olefin monomers in the presence of an olefin polymerization catalyst and a chichi shuttling agent (CSA) in a polymerization reactor or zone operating under substantially steady state polymerization conditions resulting in the formation of at least some quantity of an initial polymer segment terminated with chain shuttling agent within the reactor or zone;
discharging the reaction product from the first reactor or zone to a second polymerization reactor or zone operating under polymerization conditions that are distinguishable from those of the first polymerization reactor or zone;
transferring at least some of the initial polymer segment terminated with chain shuttlmg agent to an active catalyst site in the second polymerization reactor or zone; and
conducting polymerization in the second polymerization reactor or zone so as to form a second polymer segment bonded to said initial polymer segment and having distinguishable polymer properties from tlie initial polymer segment.
Highly desirably, the polymer products herein comprise at least some quantity of a polymer containing two distinguishable blocks or segments characterized by a most probable distribution of block sizes. The polymer recovered from the second reactor or zone of a two reactor or two zone

coupling agent to form a triblock- or a multiblock copolymer, including dendrimers, or functionalized by conversion of terminal chain shuttling agent into vinyl-j hydroxy!-, amine-, silane, carboxylic acid-, carboxylic acid ester, ionomeric, or otlier functional group, according to known techniques.
In yet anotlier embodiment of the invention, tlie shuttling agent employed in the foregoing processes possesses multiple sites for undergoing polymer exchange, that is, it is multi-centered, especially two centered, which uniquely causes the formation of a polymer product comprising copolymers according to the invention containing three or more distinct polymer segments after undergoing sequential polymerization in two reactors or zones connected in series.
Highly desirably, the pseudoblock copolymers formed according to the present invention are characterized by terminal blocks or segments of polymer having higher tacticity or crystallinity from the central block or segment. Even more preferably, the central polymer block or segment is relatively amorphous or even elastomeric.
In a still further embodiment of the present invention, there is provided a polymer mixture comprising: (1) an organic or inorganic polymer, preferably a homopolymer of ethylene or of propylene and/or a copolymer of ethylene or propylene with one or more copolymerizable comonomers, and (2) a pseudo-block copolymer according to the present invention or prepared according to the process of the present invention. In a desirable embodiment component (1) is a matrix polymer comprising high density polyethylene or isotactic polypropylene and component (2) is an elastomeric pseudo-block copolymer containing two or three distinct regions of differentiated comonomer incorporation. In a preferred embodiment, component (2) comprises occlusions of the matrix polymer formed during compounding of components (1) and (2).
While the foregoing process has been described as preferably forming a diblock product, it is an additional object of the invention to prepare multi-block copolymers, including hyper-branched or dendrhneric copolymers, through coupling of polymer terminated with a chain shuttling agent exiting the second reactor or zone (or any subsequent reactor or zone) using a difunctional or polyfunctional coupling agent In addition, if more than two reactors are employed, the product resembles that made by living polymerization in more than one reactor, with the difference tliat each block of the present polymers possesses a most probable distribution of molecular weights and composition. In particular, the polydispersity of tlie present polymers is generally less than 2.0 and approaches 1.5 for product made in two reactors. The theoretical limit of Mw/Mn generally equals the value of (1 + 1/n), where n is the number of reactors employed in the polymer's production, in accordance with the calculations of J. Appl. Poly. Sci., 92, 539-542 (2004). In general, the average number of blocks in tlie absence of coupling of the present polymers will be equal to the number of

polymerization will normally include quantities of conventional polymer depending on tlie efficiency of the particular shuttling agent employed under the conditions of tlie polymerization.
Brief Description of the Drawings
Figure 1 is a schematic representation of tlie process of copolymer formation according to the present invention in two pr more different reactors.
Figures 3-5 are test results for the polymer of Example 1, run A.
Figures 6-9 are test results for the polymer of Example 1, run 1.
Detailed Description of the InveirtiQn
All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 2003. Also, any references to a Group or Groups shall be to the Group or Groups reflected in this Periodic Table of the Elements using the lUPAC system for numbering groups. Unless stated to the contrary, implicit from the context, or customary m the art, all parts and percents are based on weight. For purposes of United States patent practice, the contents of any patent, patent application, or publication referenced herem are hereby incorporated by reference in their entirety (or the equivalent US version tliereof is so incorporated by reference) especially with respect to tlie disclosure of synthetic techniques, definitions (to the extent not inconsistent witli any definitions provided herein) and general knowledge in the art.
The term "comprising" and derivatives thereof is not intended to exclude tlie presence of any additional portion, component, step or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term "comprising" may include any additional additive, adjuvant, or compound whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, ‘'consisting essentially of excludes from the scope of any succeeding recitation any other portion, component, step or procedure, excepting those that are not essential to operability. The term "consisting of excludes any portion, component, step or procedure not specifically delineated or listed. The term "or", unless stated otherwise, refers to the listed members individually as well as m any combination.
The term "polymer", includes both homopolymers, that is, homogeneous polymers prepared from a single monomer, and copolymers (interchangeably referred to herein as interpolymers), meaning polymers prepared by reaction of at least two monomers or otherwise containing chemically differentiated segments or blocks therein even if formed from a single monomer. More specifically, the term "polyethylene" includes homopolymers of ethylene and copolymers of

that possesses a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or equivalent technique. The term may be used interchangeably with tlie term "semicrystalline". The term "amorphous" refers to a polymer lacking a crystalline melting point The term "elastomer" refers to a polymer or polymer segment having Tg less than O’C, more preferably less than -15°C, most preferably less than -25°C*
The term "pseudo-block copolymer" refers to a copolymer comprising two or more blocks or segments of differing chemical or physical property, such as variable comonomer content, crystallinity, density, tacticity, regio-error, or other property. Non-adjacent blocks are not necessarily of identical chemical composition, but may vary in one or more of the foregoing respects, from the composition of all other blocks or regions. Compared to random copolymers, pseudo-block copolymers possess sufficient differences in chemical properties, especially crystallinity, between blocks or segments, and sufficient block length to the respective blocks to achieve one or more of the desired properties of true block copolymers, such as thermoplastic/ elastomeric properties, while at the same time being amenable to preparation in conventional olefin polymerization processes, especially continuous solution polymerization processes employing catalytic quantities of polymerization catalysts.
Compared to block copolymers of the prior art, including copolymers produced by sequential monomer addition, fluxional catalysts, or anionic polymerization techniques, the copolymers of the invention are characterized by unique distributions of polymer polydispersity (PDI or Mw/Mn) and block length distribution, witli two or three, preferably two different block compositions. This is due, in a preferred embodiment, to the effect of the use of one or more shuttling agents in combination with a high activity metal complex based polymerization catalyst in two or more polymerization reactors or zones operating under differing polymerization conditions. More specifically, the copolymers of the mvention desirably possess PDI from 1.5 to 20, preferably from 1,7 to 15, and most preferably 1.8 to 10.
The respective blocks of a pseudo-block copolymer desirably possess a PDI fitting a Schulz-Flory distribution rather than a Poisson distribution. The use of the present polymerization process results in a product having a number of distinguishable blocks per polymer equal to tlie number of reactors or distmct reaction zones employed in the process, with a polydisperse distribution of block sizes. This ultimates in the formation of polymer products having improved and distinguishable physical properties. Moreover’ the foregoing novel products may be formed in the presence of random copolymer or homopolymer formed in one or more of the associated polymerization processes due to early or intentional chain termination without chain transfer to the CSA, In tliis manner, a polymer blend containing z« situ prepared rubbery impact modifier or

It may be readily appreciated by the skilled artisan that in one embodiment of the present hivented process the CSA may be added once, more than once (intermittently) or added continuously to each polymerization reactor or zone, preferably tlie initial one. Although the CSA may be added at a point inmiediately prior to discharge from tlae first reactor or zone, or even in an intervening conduit or conductor connecting the respective reactors or zones, it is preferably that the CSA be added to the reaction mixture prior to initiation of polymerization, at the same time as polymerization is initiated, or at least during a significant portion of the time in which polymerization is conducted in the first reactor. Thorough mixing of CSA and reaction mixture may be occasioned by active or static mixing devices or by use of any stirring or pumping device employed in mixing or transferring the reaction mixture.
As used herein with respect to a chemical compound, unless specifically indicated otherwise, the singular includes all isomeric forms and vice versa (for example, "hexane", includes all isomers of hexane individually or collectively). The terms "compoimd" and "complex" are used interchangeably herein to refer to organic-, inorganic- and organometal compounds. The term, "atom" refers to the smallest constituent of an element regardless of ionic state, that is, whether or not the same bears a charge or partial charge or is bonded to another atom. The term "heteroatom" refers to an atom other than carbon or hydrogen. Preferred heteroatoms include: F, CI, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge.
The term, "hydrocarbyl*' refers to univalent substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic or noncyclic species. Examples include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, and alkynyl- groups. "Substituted hydrocarbyl" refers to a hydrocarbyl group that is substituted with one or more nonhydrocarbyl substituent groups. The terms, "heteroatom containing hydrocarbyl" or "heterohydrocarbyl" refer to univalent groups in which at least one atom other than hydrogen or carbon is present along with one or more carbon atom and one or more hydrogen atoms. The term "heterocarbyl" refers to groups containing one or more carbon atoms and one or more heteroatoms and no hydrogen atoms. The bond between the carbon atom and any heteroatom as well as tlie bonds between any two heteroatoms, may be saturated or unsaturated. Thus, an alkyl group substituted with a heterocycloalkyl-, substituted heterocycloalkyl-, heteroaiyl-, substituted heteroaryl-, alkoxy-, aryloxy-, dihydrocarbylboryl-, dihydrocarbylphosphino-, dihydrocarbylamino-, trihydrocarbylsilyl-, hydrocarbylthio-, or hydrocarbylseleno- group is within the scope of the term heteroalkyl. Examples of suitable heteroalkyl groups include cyano-, benzoyl-, (2-pyridyl)methyl-, and trifluoromethyl- groups.
As used herein the term "aromatic" refers to a polyatomic, cyclic, conjugated ring system

as used herein with respect to a ring system containing two or more polyatomic, cyclic rings means tliat with respect to at least two rings tliereof, at least one pair of adjacent atoms is included m both rings. The term **aryl" refers to a monovalent aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linlced covalently, or linked to a common group such as a methylene or ethylene moiety. The aromatic ring(s) may include phenyl, naphtliyl, anthracenyl, and biphenyl, among otliers.
"Substituted aryl" refers to an aryl group in which one or more hydrogen atoms bound to any carbon is replaced by one or more fimctional groups such as alkyl, substituted allcyl, cycloallcyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkylhalos (e.g., CF3), hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, and botli saturated and unsaturated cyclic hydrocarbons which are fused to the aromatic ring(s), linked covalently or linked to a common group such as a methylene or etliylene moiety. The conunon linking group may also be a carbonyl as in benzophenone or oxygen as in diphenylether or nitrogen in diphenylamine.
The term, "comonomer incorporation index", refers to the percent comonomer incorporated into a copolymer prepared by the catalyst under consideration. The selection of metal complexes or catalyst compositions having the greatest difference in comonomer incorporation indices under different polymerization conditions, in one embodiment of the present invention, results in copolymers fi-om two or more monomers having the largest difference in block or segment properties, such as density, for the same comonomer composition distribution. Comonomer incorporation index is generally determined by the use of NMR spectroscopic techniques. It may also be estimated based on monomer reactivities and reactor kmetics according to known theoretical techniques.
In a very highly preferred embodiment, tlie polymers of the invention possess a most probable distribution of block lengths. Preferred polymers accordmg to the invention are pseudo-block copolymers containing 2 or 3 blocks or segments. In a polymer containing three or more segments (that is blocks separated by a distinguishable block) each block may be the same or chemically different and generally characterized by a distribution of properties. The invention involves the concept of using chain shuttling as a way to prolong the lifetime of a polymer chain such that a substantial fraction of the polymer chains exit at least the first reactor of a multiple reactor series or the first reactor zone in a multiple zoned reactor operating substantially under plug flow conditions in tlie form of polymer terminated with a chain shuttling agent, and the polymer chain experiences different polymerization conditions in the next reactor or polymerization zone. Different polymerization conditions in the respective reactors or zones include the use of different monomers, comonomers, or monomer/comonomer(s) ratio, different polymerization temperatures,

gradients, or any other difference leading to formation of a distmguishable polymer segment. Thus’ at least a portion of tlie polymer resultmg from the present process comprises two, three, or more, preferably two or three, differentiated polymer segments arranged intramolecularly. Because tlie various reactors or zones form a distribution of polymers rather than a single specific polymer composition, the resulting product approximates the physical properties of a block copolymer and is referred to as a pseudo-block copolymer.
In contrast with the previously discussed sequential polymerization tecliniques wherein no chain shuttling agent is utilized, polymer products can now be obtained according to the present invention by selecting highly active catalyst compositions capable of rapid transfer of polymer segments both to and from a suitable chain shuttling agent such that polymer blocks or regions of the resulting catalyst possess distinguishable polymer properties. Due to the use of chain shuttling agents and catalysts capable of rapid and efficient exchange of growing polymer chains, tlie growing polymer experiences discontinuous polymer growth, such that intramolecular regions of the polymer are formed under two or more different polymerization conditions.
The following mathematical treatment of the resulting polyniers is based on theoretically derived parameters that are believed to apply to the present invented polymers and demonstrate that, especially in two or more steady-state, continuous reactors or zones connected in series, having differing polymerization conditions to which the growing polymer is exposed, tlie block lengths of the polymer being formed in each reactor or zone will conform to a most probable distribution, derived in the following manner, wherein pi is the probability of polymer propagation in a reactor with respect to block sequences from catalyst i. The theoretical treatment is based on standard assumptions and methods known in the art and used in predicting the effects of polymerization kinetics on molecular architecture, mcluding the use of mass action reaction rate expressions that are not affected by chain or block lengths, and the assumption that polymer chain growth is completed in a very short time compared to the mean reactor residence time. Such methods have been previously disclosed in W. H. Ray, J. Macromol. Sci,, Rev. Macromol. Chem.. C8, 1 (1972) and A. E. Hamielec and J. F. MacGregor, "Polymer Reaction Engineering", K.H. Reichert and W. Geisler, Eds., Hanser, Munich, 1983. In addition, it is assumed that each incidence of the chain shuttling reaction in a given reactor results in the formation of a single polymer block, whereas transfer of the chain shuttling agent terminated polymer to a different reactor or zone and exposure to different polymerization conditions results in formation of a different block. For catalyst i, the fraction of sequences of length n being produced in a reactor is given by Xi[n], where n is an integer from 1 to infinity representing the total number of monomer units m tlie block.
Xi[n] = (l-Pi)p/""*’ most probable distribution of block lengths

If more than one catalyst is present in a reactor or zone, each catalyst has a probabilit>' of propagation (pi) and therefore has a unique average block length and distribution for polymer being made in that reactor or zone. In a most preferred embodiment the probability of propagation is defined as:
Pi = Rp[i] + Rt[i] + Rs[i] + [Ci] ‘""‘ ‘‘‘‘ ‘‘‘‘‘y’* ' = {‘'2-}' ‘'‘‘'‘=
Rp[i] = Local rate of monomer consumption by catalyst i, (moles/L/time)j
Rt[i] = Total rate of chain transfer and termination for catalyst i, (moles/L/time), and
Rs[i] = Local rate of chain shuttling with dormant polymer, (moles/L/time).
For a given reactor the polymer propagation rate, Rp[i], is defined using an apparent rate
constant, kpi, multiplied by a total monomer concentration, [M], and multiplied by the local concentration of catalyst i, [Ci],as follows:
Rp[i] = i’[M][Ci]
The chain transfer, termination, and shuttling rate is determined as a function of chain transfer to hydrogen (H2), beta hydride elimination, and chain transfer to chain shuttling agent (CSA), The quantities [H2] and [CSA] are molar concentrations and each subscripted k value is a rate constant for the reactor or zone:
Rt[i] = kH2i[H2][Q] + kpi[Ci] + k’[CSA][Q]
Dormant polymer chains are created when a polymer moiety transfers to a CSA and all CSA moieties that react are assumed to each be paired with a dormant polymer chain. The rate of chain shuttling of dormant polymer with catalyst i is given as follows, where [CSAd is the feed concentration of CSA, and the quantity ([CSAf]-[CSA]) represents the concentration of dormant polymer chains:
Rs[i] = kai[Q]([CSAf]-[CSA])
As a result of the foregoing theoretical treatment, it may be seen that the overall block lengtli distribution for each block of the resultmg pseudo-block copolymer is a sum of the block length distribution given previously by Xi[n], weighted by the local polymer production rate for catalyst i. This means that a polymer made under at least two dififerent polymer forming conditions will have at least two distinguishable blocks or segments each possessing a most probable block length distribution.
Monomers
Suitable monomers for use in preparing the copolymers of the present invention include any

a-oleum, and most preferably ethylene and at least one copolymerizable comonomer, propylene and at least one copolymerizable comonomer having from 4 to 20 carbons, or 4-methyH-pentene and at least one different copolymerizable comonomer having from 4 to 20 carbons. Examples of suitable monomers include straight-chain or branched a-olefins of 2 to 30, preferably 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyH-butene, 1-hexene, 4-metliyH-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cycloolefins of 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbomene, 5"methyl-2-norbomene, tetracyclododecene, and 2-methyH,4,5,8-dhnethano-l,2j3,4,4a,5,8,8a-octahydronaphthalene; di- and poly-olefins, such as butadiene, isoprene, 4-methyl-l,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, lj6-octadiene, 1,7-ootadiene, ethylidene norbomene, vinyl norbornene, dicyclopentadiene, 7-methyl-l,6-octadiene, 4-ethyHdene-8"methyl" 1,7-nonadienej and 5,9-dimethyHj4,8-decatriene; aromatic vinyl compounds such as mono- or poly-alkylstyrenes (including styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o’ethylstyrene, m-ethylstyrene and p-ethylstyrene), and functional group-containing derivativeSj such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropene, 4-phenylpropene and a-methylstyrene, vinylchloride, 1,2-difluoroethylene, 1,2-dichloroethylene, tetrafluoroethylene, and 3,3,3-trifluoro-l-propene, provided the monomer is polymerizable under the conditions employed.
Preferred monomers or mixtures of monomers for use in combination with at least one CSA herein include ethylene; propylene; mixtures of ethylene with one or more monomers selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-l"pentene, l-octene, and styrene; and mixtures of ethylene, propylene and a conjugated or non-conjugated diene.
Chain Shuttling Agents
The term, ‘'shuttling agent" or "chain shuttling agent", refers to a compound or mixture of compounds that is capable of causing polymeryl transfer between tlie various active catalyst sites under the conditions of the polymerization. That is, transfer of a polymer fragment occurs both to and from an active catalyst site in a facile manner. In contrast to a shuttling agent, a "chain transfer agent" causes termination of polymer chain growth and amounts to a one-time transfer of growing polymer from the catalyst to the transfer agent. Desirably, the intermediate formed between the chain shuttling agent and the polymeryl chain is sufficiently stable tliat chain termination is relatively rare. Desirably, less than 10 percent, preferably less tlian 50 percent, more preferably less

tlian 75 percent and most desirably less than 90 percent of shuttling agent-polymeryl products are terminated prior to attaining 2 distinguishable, intramolecular polymer segments or bloclcs.
While attached to the growing polymer chain, the shuttling agent desirably does not alter the polymer structure or incorporate additional monomer. That is, tlie shuttling agent does not also possess significant catalytic properties for tlie polymerization of interest. Ratlier, the shuttling agent forms a metal-alkyl or other type interaction with the polymer moiety, for a time period such that transfer of the polymer moiety to an active polymerization catalyst site in a subsequent reactor may occur. As a consequence, the subsequently formed polymer region possesses a distinguishable physical or chemical property, such as a different monomer or comonomer identity, a difference in comonomer composition distribution, crystallinity, density, tacticity, regio-error, or other property. Subsequent repetitions of the foregomg process can result in formation of segments or blocks having differing properties, or a repetition of a previously formed polymer composition, depending on the rates of polymeryl exchange, number of reactors or zones within a reactor, and transport between the reactors or zones. The polymers of the invention desirably are characterized by at least two individual blocks or segments having a difference m composition and a most probable block length distribution. That is, adjacent blocks have altered composition within the polymer and a size distribution (Mw/Mn) greater than 1.0, preferably greater than 1.2.
The process of the invention employing a catalyst one or more cocatalysts and chain shuttling agent may be further elucidated by reference to Figure 1, where there is illustrated an activated catalyst, 10, which in a first reactor operating under steady state polymerization conditions or in a first polymerization zone operatmg under plug flow polymerization conditions forms a polymer chain, 12. A chain shuttling agent, 14, added along with the initial charge of reactants or later in the polymerization process, mcluding just prior to or during transfer to a second reactor or zone, attaches to the polymer chain produced by an active catalyst site tliereby preventing termination of the polymer chain prior to entering the second reactor or zone. In the presence of modified polymerization conditions, the polymer block attached to the chain shuttling agent is transferred back to a catalyst site, and a new polymer segment, 16, which preferably is distinguishable from polymer segment 12, is produced. The resulting diblock copolymer may also attach to an available chain shuttling agent forming the combination of a chain shuttling agent with the diblock copolymer, 18 prior to exiting the second reactor or zone. Transfer of tlie growing polymer multiple times to an active catalyst site may occur with continued growth of the polymer segment. Under uniform polymerization conditions, the growing polymer chain is substantially homogeneous, although individual molecules may differ in size. The first and second polymer segments formed in the process are distinguishable because tlie polymerization conditions in

shuttling agent is able to prolong the polymer life time (that is the time during which fiirther polymer growth may occur) until two or more different polymerization environments are experienced. The diblock copolymer chains, 2O5 may be recovered by termination, such as by reaction with water or other proton source, or functionalized, if desired, forming vinyl, hydroxyl, silane, carboxylic acid, carboxylic acid ester, ionomeric, or other functional terminal groups to replace the chain shuttling agent Alternatively, the diblock polymer segment may be coupled with a polyfunctional coupling agent, especially a difiinctional couplmg agent such as dichlorodimethylsilane or ethylenedichloride, and recovered as a triblock copolymer, 22* It is also possible to continue polymerization in a third reactor or zone under conditions differing from those in tlie second reactor or zone, and recovering the resultmg triblock copolymer, 21. If the third reactor's conditions are substantially identical to those of the mitial reactor or zone, tlie product will be substantially similar to a conventional triblock copolymer, but with block lengths that are a most probable distribution.
Ideally, the rate of chain shuttling is equivalent to or faster than the rate of polymer termination, even up to 10 or even 100 times faster than the rate of polymer termination and significant with respect to tlie rate of polymerization. This permits formation of distinct polymer blocks in the first reactor or zone and discharge from said reactor or zone into a subsequent reactor or zone of a reaction mixture containing significant quantities of polymer chains terminated with chain shuttling agents and capable of continued monomer insertion under distinguishable polymerization conditions.
By selecting diJBferent shuttling agents or mixtures of agents with a catalyst, by altering the comonomer composition, temperature, pressure, optional chain terminating agent such as Hjj or other reaction conditions in separate reactors or zones of a reactor operating under plug flow conditions, polymer products having segments of varying density or comonomer concentration, monomer content, and/or other distinguishing property can be prepared. For example, in a typical process employing two continuous solution polymerization reactors connected in series and operating under differing polymerization conditions, the resulting polymer segments will each have a relatively broad molecular weight distribution characteristic of typical olefin coordination polymerization catalysts, preferably a Mw/Mn from 1.7 to 15, more preferably from 1.8 to 10, but will reflect the polymer formed under the differing polymerization conditions. In addition, certain quantities of a conventional random copolymer may also be formed coincident witli formation of the pseudo-diblock copolymer of the present invention, resulting in a resin blend. The average block lengths in the resulting polymers may be controlled by the chain shuttling rate of the CSA, the amount of CSA added, and other process variables, such as polymer production rate, and tlie

amount of optional chain termination agent, such as hydrogen, employed. Average block lengths of each block type can be individually controlled by altering process variables in each reactor.
Highly desired copolymers comprise at least one block or segment tliat is highly crystalline polyethylene or polypropylene, especially highly isotactic polypropylene, joined intramolecularly with one or more separate blocks comprising an amorphous polymer, especially a copolymer of etliylene and a C3-8 comonomer, or a copolymer of propylene with ethylene and/or a C4.8 comonomer. Desirably the foregoing polymer is a pseudo- diblock copolymer. Additional desirable copolymers are pseudo- triblock copolymers comprising a central, relatively amorphous polymer block bonded between two relatively crystalline polyolefin polymer blocks.
A suitable composition comprising catalyst, cocatalyst, and a chain shuttling agent especially adapted for use herein can be selected by means of the following multi-step procedure:
I. One or more addition polymerizable, preferably olefin monomers are polymerized using a mixture comprising a potential catalyst and a potential chain shuttling agent. This polymerization test is desirably performed using a batch or semi-batch reactor (that is, without resupply of catalyst or shuttling agent), preferably with relatively constant monomer concentration, operating under solution polymerization conditions, typically using a molar ratio of catalyst to chain shuttling agent from 1:5 to 1:500. After forming a suitable quantity of polymer, the reaction is terminated by addition of a catalyst poison and the polymer's properties (Mw, Mn, and Mw/Mn or PDI) measured.
n. The foregoing polymerization and polymer testing are repeated for several different reaction times, providing a series of polymers having a range of yields and PDI values.
EH. Catalyst/ chain shuttling agent pairs demonstrating significant polymer transfer both to and from the chain shuttling agent are characterized by a polymer series wherein the minimum PDI is less than 2.0, more preferably less than 1.5, and most preferably less than 1.3. Furthermore, if chain shuttling is occurring, the Mn of the polymer will increase, preferably nearly linearly, as conversion is increased. Most preferred catalyst/ shuttling agent pairs are those giving polymer Mn as a function of conversion (or polymer yield) fitting a line with a statistical precision (R ) of greater than 0.95, preferably greater than 0.99.
Steps I-HE are then carried out for one or more additional pairings of potential catalysts and/or putative shuttling agents.
In addition, it is preferable that the chain shuttling agent does not reduce the catalyst activity (measured m weight of polymer produced per weight of catalyst per unit time) by more than 60 percent, more preferably such catalyst activity is not reduced by more tlian 20 percent, and most preferably catalyst activity of the catalyst is increased compared to tlie catalyst activity in tlie absence of a chain shuttling agent. A further consideration from a process viewpoint is that the

producing a homogeneous reaction mixture or conveying the reaction mixture. In tliis regard, a monofunctional shuttling agent is preferred to a difiinctional agent which in turn is preferred to a trifunctional agent.
The foregoing test is readily adapted to rapid tliroughput screenmg techniques using automated reactors and analytic probes and to formation of polymer blocks having different distinguishmg properties. For example, a number of potential chain shuttling agent candidates can be pre-identified or synthesized in situ by combination of various organometal compounds witli various proton sources and the compound or reaction product added to a polymerization reaction employing an olefin polymerization catalyst composition. Several polymerizations are conducted at varying molar ratios of shuttling agent to catalyst. As a minimum requirement, suitable shuttling agents are those that produce a PDI of less than 2.0 in variable yield experiments as described above, while not significantly adversely affecting catalyst activity, and preferably improving catalyst activity, as above described.
Alternatively, it is also possible to detect desirable catalyst/shuttling agent pairs by performing a series of polymerizations under standard batch reaction conditions and measuring the resulting number average molecular weights, PDI and polymer yield or production rate. Suitable shuttling agents are characterized by lowering of tlie resultant Mn without significant broadening of PDI or loss of activity (reduction in yield or rate).
Regardless of the method for identifying, apriorU a shuttling agent, the term is meant to refer to a compound that is capable of preparing the presently identified pseudo-block copolymers under the polymerization conditions herein disclosed.
Suitable shuttlmg agents for use herein include Group 1,2,12 or 13 metal compounds or complexes containing at least one C1.20 hydrocarbyl group, preferably hydrocarbyl substituted aluminum, gallium or zmc compounds containing from 1 to 12 carbons in each hydrocarbyl group, and reaction products thereof with a proton source. Preferred hydrocarbyl groups are alkyl groups, preferably linear or branched, C2-B alkyl groups. Most preferred shuttling agents for use in the present invention are trialkyl aluminum and dialkyl zinc compounds, especially triethylaluminum, tri(i-propyl) aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, triethylgallium, or diethylzinc. Additional suitable shuttling agents include the reaction product or mixture formed by combinmg the foregoing organometal compound, preferably a triCCi-g) alkyl aluminum or di(Ci-g) alkyl zinc compound, especially triethylaluminum, tri(i-propyl) aluminum, tri(i-butyl)aluminum, tri(n"hexyl)aluminum, tri(n-octyl)aluminum, or diethylzmc, with less than a stoichiometric quantity (relative to the number of hydrocarbyl groups) of a secondary amine or a bydroxyl compound, especially bis(trimethylsilyl)amine, t-butyl(dimethyl)siloxane, 2-

bis(2,336,7-diben20"l-azacycloheptaneamine), or 2,6-diphenylphenoL Desirably, sufficient amine or hydroxyl reagent is used such that one hydrocarbyl group remains per metal atom. The primary reaction products of the foregoing combinations most desired for use in the present invention as shuttling agents are n-octylaluminum di(bis(trimethylsilyl)amide), i-propylaluminum bis(dimethyl(t-butyI)siloxide), and n-octylaluminum di(pyridinyl-2-methoxide), i-butylaluminum bis(dimethyl(t-butyl)siloxane), i-butylaluminum bis(di(trimetliylsilyl)amide), n-octylaluminum di(pyridine"2-metlioxide)5 i-butylaluminum bis(di(n-pentyl)amide)5 n-octylaluminum bis(256-di-t-butylphenoxide), n-octylaluminum di(ethyl(l'-naphtliyl)amide)5 eihylaluminum bis(t-butyldimethylsiloxide), eihylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-dibenzo-1 -azacycloheptaneamide), n-octylaluminum bis(2,3,6,7-dibenzo-1 -azacycloheptaneamide), n-octylaluminum bis(dimethyl(t-butyI)siloxide5 ethylzinc (2,6-diphenylphenoxide), and ethylzinc (t-butoxide).
Preferred shuttling agents possess the highest transfer rates of polymer transfer as well as the highest transfer efficiencies (reduced incidences of chain termination). Such shuttling agents may be used in reduced concentrations and still achieve tlie desired degree of shuttling. Highly desirably, chain shuttling agents with a single exchange site are employed due to, the fact that the effective molecular weight of the polymer in the reactor is lowered, thereby reducing viscosity of the reaction mixture and consequently reducing operating costs.
Catalysts
Suitable catalysts for use herein include any compound or combmation of compounds that is adapted for preparing polymers of the desired composition or type. Both heterogeneous and homogeneous catalysts may be employed. Examples of heterogeneous catalysts include die well known Ziegler-Natta compositions, especially Group 4 metal halides supported on Group 2 metal halides or mixed halides and alkoxides and the well known chromium or vanadium based catalysts. Preferably however, for ease of use and for production of narrow molecular weight polymer segments in solution, the catalysts for use herein are homogeneous catalysts comprising a relatively pure organometallic compound or metal complex, especially compounds or complexes based on metals selected from Groups 3-15 or the Lanthanide series of the Periodic Table of the Elements.
Preferred metal complexes for use herein include complexes of metals selected from Groups 3 to 15 of the Periodic Table of the Elements containing one or more delocalized, 7c-bonded ligands or polyvalent Lewis base ligands. Examples mclude metallocene, half-metallocene, constrained geometry, and pol3’alent pyridylamine, or other polychelating base complexes. The complexes are generically depicted by the formula: MKkXxZz, or a dimer thereof, wherein

M is a metal selected from Groups 3-15, preferably 3-10, more preferably 4-10, and most preferably Group 4 of the Periodic Table of the Elements;
K independently each occurrence is a group containing deiocalized Tr-electrons or one or more electron pairs through which K is bound to M, said K group containing up to 50 atoms not counting hydrogen atoms, optionally two or more K groups may be joined together forming a bridged structure, and further optionally one or more K groups may be bound to Z, to X or to batik Z and X;
X independently each occurrence is a monovalent, anionic moiety having up to 40 non-hydrogen atoms, optionally one or more X groups may be bonded together thereby forming a divalent or polyvalent anionic group, and, further optionally, one or more X groups and one or more Z groups may be bonded together thereby forming a moiety that is both covalently bound to M and coordinated tliereto;
Z independently each occurrence is a neutral, Lewis base donor ligand of up to 50 non-hydrogen atoms containing at least one unshared electron pair through which Z is coordinated to M;
k is an integer from 0 to 3;
X is an integer from 1 to 4;
z is a number from 0 to 3; and
tlie sum, k+x, is equal to the formal oxidation state of M.
Suitable metal complexes include those containing from 1 to 3 TT-bonded anionic or neuti-al ligand groups, which may be cyclic or non-cyclic delocalized 7C-bonded anionic ligand groups. Exemplary of such 7t-bonded groups are conjugated or nonconjugated, cyclic or non-cyclic diene and dienyl groups, allyl groups, boratabenzene groups, phospbole, and arene groups. By the term " 7i-bonded" is meant that the ligand group is bonded to the transition metal by a sharing of electrons from a partially delocalized Ti’bond.
Each atom in the delocalized Tr-bonded group may independently be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substituted heteroatoms wherein the heteroatom is selected from Group 14-16 of the Periodic Table of the Elements, and such hydrocarbyl- substituted heteroatom radicals further substituted with a Group 15 or 16 hetero atom containing moiety. In addition two or more such radicals may togetlier form a fused ring system, mcluding partially or fully hydrogenated fused ring systems, or they may foim a metallocycle with the metal. Included within the term "hydrocarbyl" -are Ci-20 straight, branched and cyclic alkyl radicals, C6.20 aromatic radicals, C7.20 alkyl-substituted aromatic radicals, and C7_2o aryl-substituted alkyl radicals. Suitable hydrocarbyl-substituted heteroatom radicals uiclude mono-, di- and tri-substituted radicals of boron, silicon, germanium, nitrogen, phosphorus or oxygen wherein each of the hydrocarbyl groups contains from 1 to 20

carbon atoms. Examples include HN-dimethylamino, pyrrolidinylj trimethylsilyl, trietliylsilyl, t-butyldimethylsilyl, methyldi(t"bu1yl)silyl, tiipheuylgermyl, and trimethylgermyl groups. Examples of Group 15 or 16 hetero atom containing moieties include amino, phosphino, alkoxy, or alkyltliio moieties or divalent derivatives thereof, for example, amide, phosphide, alkyleneoxy or alkylenethio groups bonded to the transition metal or Lanthanide metal, and bonded to the hydrocarbyl group, TU-bonded group, or hydrocarbyl- substituted heteroatom.
Examples of suitable anionic, delocalized 7t-bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl’ cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, phosphole, and boratabenzyl groups, as well as inertly substituted derivatives thereof, especially CMO hydrocarbyl- substituted or tris(Ci.io hydrocarbyl)silyI- substituted derivatives thereof. Preferred anionic delocalized n-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl, 3'pyrrolidinoinden-l-yl, 3,4"(cyclopenta(/)phenanthren-l-yl, and teti-ahydroindenyl.
The boratabenzenyl ligands are anionic ligands which are boron containing analogues to benzene. They are previously known in the art having been described by G. Herberich, et al., in Organometallics. 14,1,471-480 (1995). Preferred boratabenzenyl ligands correspond to the formula:

wherein R' is an inert substituent, preferably selected from the group consisting of hydrogen, hydrocarbyl, silyl, halo or germyl, said R’ having up to 20 atoms not comiting hydrogen, and optionally two adjacent R' groups may be joined together. In complexes involving divalent derivatives of such delocalized 7c-bonded groups one atom thereof is bonded by means of a covalent bond or a covalently bonded divalent group to another atom of the complex thereby forming a
bridged system.
Phospholes are anionic ligands that are phosphorus containing analogues to a cyclopentadienyl group. They are previously known in the art having been described by WO 98/50392, and elsewhere. Preferred phosphole ligands correspond to the formula:

wherein R' is as previously defined.
Preferred transition metal complexes for use herein correspond to the formula: MKkXxZ’, or a dimer thereof, wherein:
M is a Group 4 metal;
K is a group containing delocalized 7c-electn)ns through which K is bound to M, said K group contaming up to 50 atoms not counting hydrogen atoms, optionally two K groups may be joined together fonning a bridged structur’j and further optionally one K may be bound to X or Z;
X each occurrence is a monovalent, anionic moiety having up to 40 non-hydrogen atoms, optionally one or more X and one or more K groups are bonded together to form a metallocycle, and further optionally one or more X and one or more Z groups are bonded together thereby forming a moiety that is both covalently bound to M and coordinated thereto;
Z independently each occurrence is a neutral, Lewis base donor ligand of up to 50 non-hydrogen atoms containing at least one unshared electron pair through which Z is coordinated to M;
k is an integer from 0 to 3;
X is an integer from 1 to 4;
z is a number from 0 to 3; and
the sum, k+x, is equal to the formal oxidation state of M,
Preferred complexes include those containing either one or two IC groups. The latter complexes mclude those containing a bridging group linking the two K groups. Preferred bridging groups are those corresponding to the formula (EKW wherem E is silicon, germanium, tin, or carbon, R' independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combmations thereof, said R' having up to 30 carbon or silicon atoms, and e is 1 to 8. Preferably, R' independently each occurrence is methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy.
Examples of the complexes containing two K groups are compounds corresponding to the formula:

Examples of metal complexes of the foregoing formula suitable for use in the present invention include:
bis(cyclopentadienyl)zirconiumdimethyl, bis(cyclopentadienyl)2h'coniumdibenzyl, bis(cyclopentadienyl)zirconiura methyl benzyl, bis(cycIopentadienyl)zirconium methyl phenyl, bis(cyclopentadienyl)zirconiumdiphenyl, bis(cyclopentadieiiyl)titanium-allyl, bis(cyclopentadienyl)zirconiummethybnethoxide, bis(cyclopentadienyl)zircomummethylchloride, bis(pentamethylcyclopentadienyl)zirconiumdimetliyl, bis(pentameihylcycIopentadieayl)titaniumdimethyl, bis(indenyl)zirconiumdimethyl, indenylfluorenylzirconixundimethyl, bis(indenyl)zirconiummBthyl(2-(dimethylamino)benzyl), bis(indenyl)zirconiummethyltrituethylsilyl, bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl, bisCpentametliylcyclopentadienyOzu-coniummethylbenzyl, bisCpentametliylcyclopentadienyOzh-coniumdibenzyl, bis(pentamethyIcyclopentadienyl)zirconiummethylmethoxide, bis(pentamethylcyclopentadienyl)zirconiummethylchloride, bis(methylethylcyclopentadienyl)zirconiumdimethyl, bis(butylcyclopentadienyl)zirconiumdibenzyl, bis(t"butylcyclopentadienyl)zirooniumdimethyl, bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl, bis(methylpropylcyclopentadienyl)zirconiumdiben2yl, bis(trimethylsilylcyclopentadienyI)zirconiumdibenzyl5 dimethylsilylbis(cyclopentadienyl)zirconiumdimethyl, dimethylsilylbis(tetramethylcyclopentadienyl)titanium (HI) allyl dimethylsilylbis(t-butylcyclopentadienyl)zirconiumdichloride, dimethylsilylbis(n-butylcyclopentadienyl)zirconiumdichloride, (methylenebis(tetramethylcyclopentadienyI)titanium(III)2-(dimetliylamino)benzyl,
(methylenebis(n-butylcyclopentadienyl)titanium(]H)2-(dimethylamiiio)ben2yl, dimethylsilylbis(indenyl)zirconiumbenzylchloride,

diraethylsilylbis(2-mediyl-4-phenylindenyl)zirconiumdiniethyI, dimethylsilylbis(2’nietIiylmdenyl)zirconium-l,4-diphenyl-l,3-butadiene, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium (n) 1,4-diphenyl-l’ dimethylsilylbis(tetraIiydroindenyl)zircoiiimn(n) l,4-diphenyl-l,3’butadiene, dimethylsilylbis(tetramethylcyclopeutadienyl)zirconium dimethyl dimethylsilylbis(fluorenyl)zirconiumdimetIiyl, dimethylsiiyl-bis(tetrahydrofluorenyl)zirconiumbis(trimethylsilyl), (isopropyUdene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyI, and dimethylsilyl(tetraniethylcyclopentadienyl)(fluorenyl)zirconium dimethyl.
A further class of metal complexes utilized in the present invention corresponds to the preceding formula: MRZ’Xx, or a dimer thereof, wherein M, K, X, x and z are as previously defined, and Z is a substituent of up to 50 non-hydrogen atoms that together with K forms a metallocycle with M.
Preferred Z substituents include groups containing up to 30 non-hydrogen atoms comprising at least one atom that is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly attached to K, and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur that is covalently bonded to M,
More specifically this class of Group 4 metal complexes used according to tlie present invention includes "constrained geometry catalysts" corresponding to the formula:

X is hydrogen, a monovalent anionic ligand group having up to 60 atoms not counting hydrogen, or two X groups are joined togetlier thereby forming a divalent ligand group;
X is 1 or 2; and
2 is 0, 1 or 2.
Preferred examples of the foregomg metal complexes are substituted at both tlie 3- and 4-positions of a cyclopentadienyl or indenyl group with an Ar group.
Examples of the foregomg metal complexes include: (3-phenylcycIopentadien"l-yl)dimethyI(t-butylamido)silanetitanium dichloride, (3-phenylcyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium dimethyl, (3-phenylcyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanlum (H) 1,3-diphenyl-1,3 -butadiene;
(3-(pyrroH-yl)cyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium dichloride, (3-(pyrroI-l-'yl)cyclopentadien-l"yI)dunethyl(t-butylamido)silanetitanium dimethyl, (3-(pyrrol-1 'yl)cyclopentadien-1 -yl))dunethyl(t-butylamido)silanetitanium (11) 1,4-
diphenyl-1,3-butadiene; (3 -(1 -methylpyrrol-3-yl)cyclopentadien-1 -yl)dimethyI(t-butylamido)silanetitanium dichloride, (3 -(1 -methylpyrrol-3 -yl)cyclopentadien-1 -yl)dimethy l(t-buty lamido)silanetitanium dimethyl, (3-(l-methylpyrrol"3-yl)cyclopentadien-l-yl)dimethyl(t-butylamido)siIanetitanium(II) 1,4-
diphenyl" 1,3 -butadiene; (3,4-diphenylcyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium dichloride, (3,4-diphenylcyclopentadien-1 -yl)dimethyl(t-butylamido)siIanetitanium dimethyl, (3,4-diphenylcyclopentadien-l-yI)dimethyl(t-butylamido)silanetitanium(n) 1,3-
pentadiene; (3-(3-N,N-dmiethylamino)phenyl)cyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium
dichloride, (3 dimethyl, (3-(3-N,N-dimethylamino)phenylcyclopentadien-l-yl)dimethyl(t-butylamido)silanetitaiiium (U) l,4-diphenyl-l,3"butadiene;
(3-(4-methoxyphenyl)'4-methylcyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium
dichloride,
(3 -(4-methoxyphenyl)-4-phenylcyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium dimethyl, (3-4-methoxyphenyl)-4-phenylcyclopentadien-l"yl)dimethyl(t-butyIamido)silanetitanium(ir) 1,4-diphenyl-1,3-butadiene;

(3-phenyl-4-methoxycyclopentadien"l-yl)dimetliyl(t-butylamido)silanetitanm’ (3-phenyl-4-methoxycycIopentadien"l-yl)dimethyl(t-butylamido)silanetitani’ diphenyl-1,3-butadiene;
(3"phenyl-4-(N,N-dime%lammo)cyclopentadien-l-yl)dimethyl(t-butylamido dichloride,
(3"phettyl-4-(N,N-dimethylammo)cyclopentadien-l-yl)dimethyl(t-bu1ylamido)si dimethyl,
(3-phenyl-4- 2-methyK3,4-di(4-meAylphenyl)cyclopeatadien-l-yl)dimethyl(t-butylamido)silaneti’ dichloride,
2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1 -yl)dimethyl(t"butylamido)silanetitanium
dimethyl, 2-methyl-(3,4-di(4"me1hylphenyl)cydopentadien" 1 "yl)dimethyl(t-butylamido)silanetitanium
(n) l,4-diphenyH,3-butadiene; ((2,3 -diphenyl)-4-(N»N-dimethylaniino)cyclopentadien-1 "yl)dimethyl(t-butylamido)silane
titanium dichloride, ((2,3-diphenyI)-4-(N,N-dimethylamino)cyclopeiitadien-l-yl)dimethyl(t-butylamido)silane
titanium dimethyl, ((2,3 -diphenyl)-4-(N,N"dimethylamino)cyclopentadien-1 -yl)dimethyl(t-
butylamido)silanetitanium (II) l,4-diphenyl-l,3-butadiene; (2,3,4-triphenyl-5-methylcyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium dichloride, (2,3,4-triphenyl-5-methylcyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium dimethyl, (2,3,4-triphenyl-5-methylcyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium (II) 1,4-
diphenyl-1,3 -butadiene; (3 -phenyl-4-methoxycycIopentadien-1 -yI)dimethyl(t-butylamido)siIanetitanium dichloride, (3 -phenyl-4-methoxycyclopentadien-1 -yl)dimethyl(t-butyIamido)silanetitanium dimethyl, (3 -phenyl-4-methoxycyclopentadien-1 -yl)dimethyl(t-butylamido)siIanetitanium (11) 1,4-
diphenyM ,3-butadiene; (2,3 -diphenyl-4-(n-butyl)cyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium dichloride’ (2,3 -diphenyl-4-(n-butyl)cyclopentadien-1 -yl)dimethyl(t-butylamido)silanetitanium dimethyl, (2,3-diphenyl-4-(n-butyl)cyclopentadien"l "yl)dimethyl(t-butylamido)silanetitanium (II) 1,4-
diphenyl-1,3 -butadiene; (2,3,4,5-tetraphenylcyclopentadien-l-yl)dimethyl(t-butylamido)silanetitanium dichloride,

(2,3,4,5-tetraphenylcycIopentadien4-yl)dimethyl(t-butylamido)silanetitam 1,4-
diphenyl-l,3-butadiene.
Additional examples of suitable metal complexes for use herein are polycyclic complexes corresponding to tlie formula:

where M is titanium in the +2, +3 or +4 formal oxidation state;
R independently each occurrence is hydride, hydrocarbyl, silyl, germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneaminOj di(hydrocarbyl)phosphino, hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbylj hydrocarbylsilylamino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylene-phosphino-substituted hydrocarbyl, or hydrocarbylsulfido-substituted hydrocarbyl, said R’ group having up to 40 atoms not counting hydrogen, and optionally two or more of tlie foregoing groups may together form a divalent derivative;
is a divalent hydrocarbylene- or substituted hydrocarbylene group forming a fused system with the remainder of the metal complex, said R’ containing from 1 to 30 atoms not counting hydrogen;
X* is a divalent moiety, or a moiety comprising one a-bond and a neutral two electron pair able to form a coordinate-covalent bond to M, said X* comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen;
X is a monovalent anionic ligand group having up to 60 atoms exclusive of tlie class of ligands that are cyclic, delocalized, 7r-bound ligand groups and optionally two X groups together form a divalent ligand group;
Z independently each occurrence is a neutral ligating compound having up to 20 atoms;
X is 0, 1 or 2; and
z is zero or 1.

(8-difluorometliylene-l,8-dihydrodibenzo[e,/j]azulen-l-yl)-N-(l,l-
dimetliylethyl)dimethylsilanamide titanium (II) l,4-diphenyl-l,3"butadiene, (8-difluoromethylene-1,8-dihydrodibenzo[e, AJazulen-1 -yl)-N-( 1,1-
dim©ihylethyl)dimetliylsilanamide titanium (II) lj3-pentadiene, (8-difluoromethylene-1,8-dihydrodibenzo [e, /zjazulen-1 -yl)-N-( 1,1-
dimethyletliyl)dimetliylsilanamide titanium (HI) 2-(N,N-dimethylamino)benzyl, (8-difluoromethylene-l,8-diliydrodibenzo[e,A]azulen-l-yl)-N-(l,l-
dimethyletliyi)dimethylsilanamide titanium (IV) dichloride, (8-difluoromethylene-l,8-dihydrodibenzo[e,A]azulen-l-yl)-N-(l,l-
dimethylethyl)dimetiiylsilanamide titanium (TV) dimethyl, (8-difluoromethylene-l,8-dihydrodibenzo[5,/z]azulen-l-yl)-N-(l,l-
dimethylethyl)dimethylsilanamide titanium (IV) dibenzyl,
(8-methylene"l,8-dihydrodibenzo[e,A]azulen-2-yI)-N-(l,l-dimethylethyl)dimethylsilanamide
titanium (D) l,4-diphenyl-13-butadiene, (8-methylene-1,8'-dihydrodiben2o[e, /i]azulen-2-yl)-N-( 1,1 -dimethylethyl)dimethylsilauamide
titanium (n) 1,3-pentadiene, (S-methylene-1,8-dihydrodiben2o[e, /7]azulen-2"yl)-N-( 1,1 -dimethylethyl)dimethylsilanamide
titanium (EI) 2-(N,N-dimethylamino)benzyl, (8-methylene-l,8-dihydrodibenzo[e,/7]azulen-2-yl)-N-(l>l-dimethylethyl)dimethylsilanamide
titanium (IV) dichloride, (8-methylene-l,8-dihydrodiben2o[e,/i]azulen-2-yl)-N-(l,l-dimethylethyl)dimethylsilanamide
titanium (TV) dimethyl, (8-methylene-l,8-dihydrodiben2o[e,/z]azulen-2-yl)-N-(l,l-dimethylethyl)dimethylsilanamide
titanium (IV) dibenzyl,
(8"difluorometliylene"l,8-dihydrodibenzo[e,A]azulen"2"yl)-N-(l,l-
dimethyleihyl)dimethylsilanamide titanium (II) 1,4-diphenyH,3-butadiene, (8-difluoromethylene-l,8-dihydrodibenzo[e,/?]azulen-2-yl)-N-(l,l-
dimethylethyl)dimethylsilanamide titanium (II) 1,3-pentadiene, (8-difluoromethylene-l,8-dihydrodibenzo[e,A]azulen-2"yl)-N-(l,l-
dimethylethyl)dimethylsilanamide titanium (HI) 2-(N,N-dimethylamino)benzyl, (8-difluoromethylene-1,8-dihydrodiben2o[e, /z3azulen"2-yl)-N-( 1 j 1 -
dimethylethyl)dimethylsilanamide titanium (TV) dichloride,

(8-difluoromethylene- l,8"dihydrodiben2x>[c, /i]azulen-2-yl)-N-( 1,1-
dimetliylethyl)dimetliylsilanamide titanium (IV) dimetliyl, (8-difluoromethylene-l,8-dihydrodibenzo[e,A]azulen-2-yl)-N-(l,l-
dimetliylethyl)dimethylsilanamide titanium (IV) diben2yl, and mixtures tliereof, especially mixtures of positional isomers.
Further illustrative examples of metal complexes for use according to tlie present invention correspond to the formula:

where M is titanium in the +2, +3 or +4 formal oxidation state;
T is "NR’- or -0-;
R’ is hydrocarbyl, silyl, germyl, dihydrocarbylboryl, or halohydrocarbyl or up to 10 atoms not counting hydrogen;
R’’ independently each occurrence is hydrogen, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, gerrayl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino, hydrocarbylene-phosphino, hydrocarbylsulfido, halo- substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl- substituted hydrocarbyl, hydrocarbylsiloxy- substituted hydrocarbyl, hydrocarbylsilylamino- substituted hydrocarbyl, di(hydrocarbyl)amino- substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino- substituted hydrocarbyl, hydrocarbylenephosphino- substituted hydrocarbyl, or hydrocarbylsulfido- substituted hydrocarbyl, said R'° group having up to 40 atoms not counting hydrogen atoms, and optionally two or more of the foregoing adjacent R'° groups may together form a divalent derivative thereby forming a saturated or unsaturated fused ring;
X’ is a divalent moiety lacking in delocalized 7c-electrons, or such a moiety comprising one a-bond and a neutral two electron pair able to form a coordinate-covalent bond to M, said X' comprising boron, or a member of Group 14 of tlie Periodic Table of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic ligand groups bound to M through delocalized jc-electrons or two X groups together are a divalent anionic ligand group;
Z independently each occurrence is a neutral ligating compound havmg up to 20 atoms; xis 0,1,23 or 3; and z is 0 or 1.
Highly preferably T is =N(CH3), X is halo or hydrocarbyl, x is 2, X' is dimetliylsilane, z is 0, and R’*’ each occurrence is hydrogen, a hydrocarbylj hydrocarbyloxy, dihydrocarbylamino, hydrocarbyleneamino, dihydrocarbylamino- substituted hydrocarbyl group, or hydrocarbyleneamino- substituted hydrocarbyl group of up to 20 atoms not counting hydrogen, and optionally two R*° groups may be joined together.
Illustrative metal complexes of the foregoing formula tliat may be employed in the practice of tlie present invention further mclude the following compounds: (t-butylamido)dimethyl-[6,7]benzO"[4,5:2' ,3'](1 -methylisoindol)-(3H)-indene-2-yl)siIanetitanium
(H) l,4Kiiphenyl-l,3-butadiene, (t-butylanaido)dimethyl-[6,7]benzo-[4,5:2\3'](l-methylisoindol)-(3H)-mdene-2-yl)silanetitanium
(H) 1,3-pentadiene, (t-butylamido)dimethyl-[6j7]benzo-[4,5:2' ,3'](1 -methyUsoindol)-(3H)-indene-2-yl)silanetitanium
(HI) 2"(N,N-dimethylammo)benzyl, (t-butylamido)dimethyl-[6,7]benzo"[4,5:2',3'](l-methylisomdol)-(3H)-indene-2-yl)silanetitanium
(IV) dichloride, (t-butylamido)dimethyl-[6,7]benzx)"[4j5:2%3'](l-methylisoindol)-(3H)-indene-2-yl)silanetitanium
(IV) dimethyl, (t-butylamido)dunethyl-[657]ben2o-[4,5:2\3'](l-methylisomdol)-(3H)-indene-2-yl)silanetitanium
(IV) dibenzyl, (t-butylamido)dimethyl46,7]benzo44,5:2\3'](l-methylisoindol)"(3H)-indene"2-yl)silanetitanium
(IV) bis(trmiethylsilyl),
(cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2',3'](l-metliyIisomdol)-(3H)"indene-2-
yl)silanetitanium (II) l,4-diphenyl-l,3-butadiene, (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2%3'](l-methylisoindol)-(3H)-indene-2-
yl)silanetitanium (II) l S-pentadiene, (cycIohexylamido)dimethyl-[6,7]benzo-[4,5:2' ,3'](1 -methylisoiudoI)-(3H)-indene-2-
yl)silanetitanium (IQ) 2-(N,N-dimethylamino)benzyl,

(cyclohexylamido)dimethyl-[6,7]benzo44,5:2\3'](l-me%lisoindoI)-(3H)-indene-2-
yl)silanetitanium (TV) dichloride, (cycloliexylamido)dimetliyl-[6,7]benzo-[4,5:2\3'](1 -methylisoindoI)"(3H)-mdene-2"
yl)silaiietitanium (IV) dimethyl, (cyclohexylamido)dimethyl"[6 j7]benzo-[4,5 \2\3'](1 "methylisomdol)-(3H)-indene-2-
yl)silanetitanium (TV) dibenzyl, (cyclohexylamido)dimethyI-[6J]benzo-[4,5:2\3'](l-metliyUsomdol>(3H)"indene-2-
yl)silanetitanium (IV) bis(trimethylsilyl)5
(t"butylamido)di(p-methylphenyl)-[6,7]beiizo44,5:2\3'](l-methylisoindol’’
yl)silanetitanium (H) l,4-diphenyl-l,3-butadiene, (t-butylamido)di(p-me%lphenyl)-[6,7]benzo-[4,5:2’3'](l-methylisoindol)"(3H)"m
yl)silanetitanium (n) Ij3-pentadiene5 (t-butylamido)di(p-methylphenyl)"[6,7]benzo-[4,5:2\3'](l-methyUsomdol)-(3’
yl)silanetitanium (in) 2-(N,N-dimethylammo)benzylj (t-butylamido)di(p-methylphenyl)-[6J]benzo-[4,5:2\3'](l-methylisoindol) yl)silanetitamum (IV) dichloride, (t-butylamido)di(p-methylphenyl)-[6J]benzo-[4,5:2\3'](l-methylisoindol)-(3H)-indene
yl)silanetitanium (IV) dimethyl, (t-butylamido)di(p-mesylphenyl)-[6J]benzo-[4,5:2',3'](l-methylisoindol)-(3H)-indene"2’
yl)silanctitanium (IV) dibenzyl, (t-butylamido)di(p-methylphenyl)46,7]ben2»-[4,5;2\3'](l-methylisoindol)"(3H)-indene-2-
yl)silanetitanium (IV) bis(trimethylsilyl)5
(cyclohexylamido)di(p-methylphenyl)-[6J]benzo-[4,5;2\3'](l"methylisoindol) yl)silaiietitamum (II) l,4-diphenyl-l,3-butadiene, (cyclohexylamido)di(p"methylphenyI)"[6,7]benzo-[4,5:2\3*](l"methylisoindoI)r(3H)-indene-2’
yl)silanetitaiiium (H) l,3-pentadiene5 (cyclohexylamido)di(p-methylphenyl)-[6J]benzo-[4,5:2\3'](l-metliylisoindoI)-(3H)-indeiie-2’
yl)silanetitamum (HI) 2-(N,N-dimethylamino)benzyl, (cyclohexylamido)di(p-methylphenyl)-[6,7]benzO"[4,5:2\3 *](1-methylisomdol)-(3H)-indene-2-
yl)silanetitanium (IV) dichloride,
(cyclohexyiamido)di(p"metllylphenyl)46,7]benzo-[4,5:2’3'](l"methylisoindoI)-(3H)-indene-2-yl)silanetitanium (IV) dimethyl,

(cyclohexylamido)di(p.methylphenyl)-[6,7]benzo-[4,5:2\3'](l-methylisoindol)-(3H)-indene-2-yl)silanetitanium (TV) dibenzyl; and
(cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2\3'](l*methylisoindol)-(3H)4ndene-2’ yl)silanetitanium (IV) bis(trimethylsilyl).
Illustrative Group 4 metal complexes that may be employed in the practice of tlie present invention further include; (tert-butylamido)(l,l-dimethyl-2,3,4,9,10-Ti-l,4,5,6,7,8-
hexaliydronaphthalenyl)dimethylsilanetitaniumdimethyl, (tert-butylamido)( 1,1,2,3-tetramethyl-2,3,4,9,10-ri-l ,4,5,6,7,8-
hexahydronaphthalenyl)dimethylsilanetitaniumdimetiiyl, (tert-butylamido)(tetramethyl-r|’-cyclopentadienyl) dimethylsilanetitanium dibenzyl, (tert-butylamido)(tetramethyl-Ti’-cyclopentadienyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-Ti’-cyclopentadienyl)-l,2-ethanediyltitaniumdmiethyl, (tert-butylamido)(tetramethyl'Ti’*indenyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-Ti’-cyclopentadienyl)dimethylsilane titanium (UT)
2"(dimethylaniino)benzyl; (tert"butylamido)(tetramethyl-Ti’-cyclopentadienyl)dimethylsilanetitanium (IE) allyl, (tert-butylamido)(tetramethyl-'n ‘-cyclopentadienyl)dimethylsilanetitanium (HI)
2,4-duTiethylpentadienyl, (tert-butylamido)(tetramethyl-Ti’-cyclopentadienyl)dimethylsilanetitanium(n)
1,4-diphenyl-l ,3-butadiene, (tert-butylamido)(tetramethyl-r| ‘-cyclopentadienyl)dimethylsilanetitanium (II)
1,3-pentadiene, (tert-butylamido)(2-methylindenyl)dunethylsilanetitanium(n) l,4-diplienyl-l,3-
butadiene, (tert-butylamido)(2-methyUndenyl)dimetIiylsilanetitanium (H) 2,4-'hexadiene, (tert-butylamido)(2-methylindenyl)dimeihylsilanetitanium (IV) 2,3-dimethyM ,3-
butadiene, (tert-butylamido)(2-methylindenyl)dimethylsilauetitanium (IV) isoprene, (tert-butylamido)(2-methylmdenyl)dimethylsilanetitauium (IV) 1,3-butadiene, (tert-butylamido)(2,3-dimetliylindenyl)dimethylsilanetitanium(IV)
2,3-dimethyH ,3-butadiene5 (tert"butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(rV)

(tert-butylamido)(2,3-dimetiiylindenyl)dimethylsilanetitanium (IV) dibenzyl (tert-butylamido)(23-dimethylindenyl)dimethylsilanetitanium (IV) 1,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II) 1,3-pentadienej (tert-bu1ylaimdo)(2,3"dimetliylindenyl)dimethylsilanetitanium (11) 1,4-diphenyl-
l,3"butadienep (tert"butylamido)(2-methylindenyI)dimethylsilanetitaniuin (E) 1,3 -pentadiene, (tert-butylamido)(2-methylmdenyI)dimethylsilanetitanium (IV) dimethyl, (tert-butylamido)(2-methylindenyI)dimethylsilanetitanium (TV) dibenzyl, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(n)
1,4-diphenyl-1,3 -butadiene, (tert-butylamido)(2-niethyM-phenylindenyl)dimethylsilanetitanium (H) 1,3-pentadiene, (tert-butyIamido)(2"methyl-4-phenylindenyl)dimethylsilanetitanium(n)2,4-hexadiene, (tert-butylainido)(tetramethyl-ri ‘-cyclopentadienyl)dimethyl- silanetitanium (IV)
1,3-butadiene, (tert-butylamido)(tetrainethyl-r| ‘-cyclopentadienyl)dimethylsilanetitanium (IV)
2,3-dimethyl-1,3-butadiene, (tert-butylamido)(tetramethyl-r|’-cyclopentadienyl)dimethylsilanetitanium(rV)
isoprene, (tert-butylaniido)(tetramethyl-T| ‘-cyclopentadienyl)dimethyl- silanetitanium (II)
134-dibenzyl-1,3-butadienej (tert-butyl]amido)(tetramethyl-Ti ‘-cyclopentadienyI)dimethylsilanetitanium (II)
2,4-hexadiene, (tert-butylamido)(tetramethyl-T|’-cyclopentadienyl)dimethyl- silanetitanium (II)
3-methyH ,3-pentadiene, (tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(6,6"dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(lJ-dimethyl-2,3,4,9,10-r|4,4,5,6,7,8-hexahydronaphthalen-4-
yl)dimethylsilanetitaniumdimethyl, (tert-butylamido)(l,l,2,3-tetramethyI-2,3,4,9,10"Ti-l,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl (tert-butylamido)(tetramethyl-Ti ‘-cyclopentadienyl methylphenylsilanetitanium (IV)
dimethyl, (tert-butylamine)(tetramethyl-Ti’-cyclopentadienyl methylphenylsilanetitanium (II)
1.4-diDhenvl-1.3-butadiene.

phenyl, 2,6-dimethylphenyl, 2j6-di(isopropyl)phenyl, 2,4,6-trimetliylphenyl, pentafluorophenyl, 3,5-trifluoromethylphenyl, and benzyl;
g is 0 or 1;
M’ is a metallic element selected from Groups 3 to 15, or the Lanthanide series of the Periodic Table of the Elements. Preferably, M’ is a Group 3-13 metals more preferably M*’ is a Group 4-10 metal;
L’ is a monovalent, divalent, or trivalent anionic ligand containing from 1 to 50 atoms, not counting hydrogen. Examples of suitable L*' groups include halide; hydride; hydrocarbyl, hydrocarbyloxy; di(hydrocarbyl)amido, hydrocarbyleneamido, di(hydrocarbyl)phosphido; hydrocarbylsulfido; hydrocarbyloxy, tri(hydrocarbylsilyl)alkyl; and carboxylates. More preferred L’ groups are C1.20 alkyl, C7.20 aralkyl, and chloride;
h is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3, and j is 1 or 2, with tiie value h x j selected to provide charge balance;
Z’ is a neutral ligand group coordinated to M**, and containing up to 50 atoms not counting hydrogen Preferred Z’ groups include aliphatic and aromatic amines, phosphines, and tellers, alkenes, alkaline, and inertly substituted derivatives thereof. Suitable inert substituents include halogen, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl, and nitrile groups. Preferred Z** groups include triphenylphosphine, tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene;
f is an integer from 1 to 3;
two or three of T’, R** and R’' may be joined together to form a single or multiple ring structure;
h is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3; '~«'w' indicates any form of electronic interaction comprising a net columbic attraction, especially coordinate or covalent bonds, including multiple bonds;
arrows signify coordinate bonds; and
dotted lines indicate optional double bonds.
In one embodiment, it is preferred that R** have relatively low stearic hindrance with respect to X’. hi this embodiment, most preferred R** groups are straight chain alkyl groups, straight chain alkenyl groups, branched chain allcyl groups wherein the closest branching point is at least 3 atoms removed from X’, and halo, dihydrocarbylamino, alkoxy or trihydrocarbylsilyl substituted derivatives thereof. Highly preferred R’ groups m this embodiment are C 1.8 straight chain alkyl groups.
At the same time, in this embodhnent R*" preferably has relatively high steric hindrance with respect to Y’. Non-limiting examples of suitable R*’' groups for this embodiment include alkyl

bxampies of metal complexes useful employed according to tlie present invention include:
|>f-(2,6-di(l-metliyIethyl)phenyl)amido)(o-tolyl)(a"naphthalen-2-diyl(6-p>‘‘‘ diyl)metliane)]hafhium dimethyl;
[N-(2,6-di(l-methylethyl)phenyl)amido)(o-tolyl)(a"naphflialen-2-diyl(6-pyridin"2-diyl)metliane)]hafnium di(N,N-dimetiiylamido);
I>[ [N-(2,6-di(l-methylethyl)phenyI)amido)(24sopropylphenyl)(a-naphtlialen-2-diyl’ 2-diyl)methane)]hafiiium dimethyl;
[N-(2,6-di(l-methylethyI)phenyl)amido)(2-isopropylphenyl)(a"naphthalen-2-diyl(6-pyridm’ 2-diyl)methane)]hafniumT(N,N-dimethylamido);
IK-(2,6-di(l-methylethyl)phenyl)amido)(2-isopropylphenyl)(a-naphthalen-2-diyl(6-pyridiii-2-diyl)methane)]hafiiium dichloride;
l>r-(2,6-di(l-methylethyl)phenyl)amido)(phenanthren-5-yl)(a'naphthalen-2-diyl(6-pyridin-2-diyI)methane)]hafnium dimethyl;
[N-(2,6-di(l-methylethyl)phenyl)amido)(phenanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)m6thane)]hafniumT di(N,N-dimetliylamido); and
[N-(2,6-di(l-methylethyl)phenyl)ainido)(phenanthren-5-yl)(a-naphthaIen-2-diyl(6-pyridin--2-diyI)m6thane)]hafnium dichloride.
Under the reaction conditions used to prepare the metal complexes used in tlie present invention, the hydrogen of the 2-position of the a-naphthalene group substituted at the 6-position of tlie pyridin-2-yl group is subject to elimination, thereby uniquely forming metal complexes wherein the metal is covalently bonded to both the resulting amide group and to the 2-position of the a-naphthalenyl group, as well as stabilized by coordination to the pyridinyl nitrogen atom tlu-ough the electron pair of the nitrogen atom,
Additional suitable metal complexes of polyvalent Lewis bases for use herein include compounds corresponding to the funnels:

R’° is an aromatic or inertly substituted aromatic group contemn from 5 to 20 atoms not

T is a hydrocarbylene or silkier group having from 1 to 20 atoms not counting hydrogen, or an inertly substituted derivative thereof;
M is a Group 4 metal, preferably zirconium or hafnium;
G is an anionic, neutral or dianionic ligand group; preferably a halide, hydrocarbyl or dihydrocarbylamide group having up to 20 atoms not counting hydrogen;
g is a number from 1 to 5 indicating the number of such G groups; and
bonds and electron donatives interactions are represented by lines and arrows respectively.
Preferably, such complexes correspond to the formula:

T’ is a divalent bridging group of from 2 to 20 atoms not counting hydrogen, preferably a substituted or unsubstituted, C3-6 alkylene group; and
Ar’ independently each occurrence is an arylene or an alkyl- or aryl-substituted arylene group of from 6 to 20 atoms not counting hydrogen;
M’ is a Group 4 metal, preferably hafnium or zirconium;
G independently each occurrence is an anionic, neutral or dianionic ligand group;
g is a number from 1 to 5 indicating tlie number of such X groups; and
electron donative interactions are represented by arrows* Preferred examples of metal complexes of foregoing formula include the foamy compounds :

where M’ is Hf or Zr;
AT* is C6.20 aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-lH-pyrrole-1-yl, or antliracen-5-yl, and

T* independently each occurrence comprises a C3-6 allylene group, a C3-6 cycloallcylene group, or an inertly substituted derivative thereof;
R independently each occurrence is hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atoms not counting hydrogen; and
G, independently each occurrence is halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 G groups together are a divalent derivative of the foregoing hydrocarbyl or trihydrocarbylsilyl groups.
Especially preferred are compounds of the formula:

wherein Ar'* is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-lH-pyrrole-1-yl, or anthracen-5-yl,
R’’ is hydrogen, halo, or CM alkyl, especially methyl
T* is propan-l,3-diyl or butan-l,4-diyl, and
G is chloro, methyl or benzyl.
A most highly preferred metal complex of the foregoing formula is:

wherein;
X is as previously defined, preferably CMO hydrocarbyl, most preferably metliyl or benzyl; and
R" is methyl, isopropyl, t-butyl’ oyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,4-dimethylcyclohexyl, 2-pyrrolyl, N-methyl-2-pyrrolyI, 2-piperidenyl, N-metliyl-2-piperidenyl, benzyl, o-tolyl, 2,6-dunethylphenyI, perfluorophenyl, 2,6-di(isopropyl)phenyl, or 2,4,6-trimethylphenyl.
The foregoing complexes also include certain phosphmunine complexes are disclosed in EP-A-8905 81. These complexes correspond to the formula: [(R’)3-P=N]iM(K’)(R%.f, wherein:
R is a monovalent ligand or two R’ groups together are a divalent ligand, preferably R’ is hydrogen or CM alkyl;
M is a Group 4 metal,
K’ is a group containing delocalized 7t-electrons through which K’ is bound to M, said K’ group containing up to 50 atoms not counting hydrogen atoms, and
f is 1 or 2,
Catalysts having high comonomer incorporation properties are also known to reincorporate in situ prepared long chain olefins resulting incidentally during the polymerization through |3-hydride elimination and chain termination of growing polymer, or other process. The concentration of such long chain olefins is particularly enhanced by use of continuous solution polymerization conditions at high conversions, especially ethylene conversions of 95 percent or greater, more preferably at ethylene conversions of 97 percent or greater. Under such conditions a small but detectable quantity of vinyl group terminated polymer may be reincorporated into a groom polymer chain, resulting in the formation of long chain branches, that is, branches of a carbon length greater than would result from other deliberately added comonomer. Moreover, such chains reflect the presence of other comonomers present in the reaction mixture. That is, the chains may include short chain or long chain branching as well, depending on the comonomer composition of the reaction mixture. However, the presence of a CSA during polymerization can seriously Ichnite the incidence of long chain branchmg since the vast majority of the polymer chains become attached to a CSA species and are prevented from undergouig P-hydride elimination.
In the present mention, the incidence of the foregoing long chain branched polymer containing segments or blocks may by enhanced by delaying the addition of the CSA to a point in the initial reactor or polymerization zone that is just prior to or even after the exit thereof. In this manner, frill polymerization under conventional conditions is attained and CSA is contacted with preformed polymer segments formed under steady state polymerization conditions.

Uocatalvsts
Each of the metal complexes (also interchangeably referred to harem as recitalists) may be activated to form the active catalyst composition by combination with a cocatalyst, preferably a cation forming cocatalyst, a strong Lewis acid, or a combination thereof. In a preferred embodhnent, the shuttling agent is employed both for purposes of chain transfer and as the optional cocatalyst component of the catalyst composition.
The metal complexes desirably are rendered catalytically active by combination with a cation forming cocatalyst, such as toils previously known in the art for use wilt Group 4 metal olefin polymerization complexes. Suitable cation forming cocatalysts for use herein include neutral Lewis acids, such as C1.30 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds’ and most especially tris(pentafluorO"phenyl)borane; nonpolymeric, compatible, noncoordmating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium- salts of compatible, noncoordmating anions, or ferrocenium-, lead- or silver salts of compatible, noncoordinating anions; and combinations of the foregoing cation forming cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes for olefin polymerizations in the following references: EP-A-277,003, US-A-5,153,157, US-A-5,064,802, US-A-5,321,106, US-A-5,721,185, US-A-5,3 50,723, US-A-5,425,872, US-A-5,625,087, US-A-5,883,204, US-A-5,919,983, US-A-5 J83,512, WO 99/15534, and W099/42467.
Combinations of neutral Lewis acids, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tri(hydrocarbyl)boron compound having from 1 to 20 carbons in each hydrocarbyl group, especially tris(pentafluorophenyl)boranej further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane may be used as activating cocatalysts. Preferred molar ratios of metal complex:tris(pentafluorophenyl-borane:alumoxane are from 1:1:1 to 1:5:20, more preferably from 1:1:L5 to 1:5:10.
Suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion, A". As used herein, the term "noncoordinating" means an anion

and the catalytic derivative derived there from, or which is only weakly coordmated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base, A noncoordinating anion specifically refers to an anion which when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation tliereby forming neutral complexes. "Compatible anions" are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.
Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of tlie active catalyst species (the metal cation) which may be formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not lunited to, boron, phosphorus, and silicon* Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compoimds containing a single boron atom in tlie anion portion, are available commercially.
Preferably such cocatalysts may be represented by the following general formula:
(L*-H)g’A)’-wherein:
L* is a neutral Lewis base;
(L*-!!)"*" is a conjugate Bronsted acid of L*;
A’' is a noncoordinating, compatible anion having a charge of g-, and
g is an integer from 1 to 3,
More preferably A’' corresponds to the formula: [M'Q4]'; wherein:
M' is boron or aluminum in the +3 formal oxidation state; and
Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and halo- substituted silylliydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in US-A-5,296,433.

in a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A'. Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this mvention may be represented by tlie following general formula:
wherein:
L* is as previously defined;
B is boron in a formal oxidation state of 3; and
Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylliydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
Preferred Lewis base salts are ammonium salts, more preferably trialkylammonium salts containing one or more Cn’o alkyl groups. Most preferablyj Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl group.
Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as:
trimethylammoniimi tetrakis(pentafluorophenyl) borate, triethylarmnonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate, N,N-dimethylanilimum benzyltris(pentafluorophenyl) borate,
N,N-dimethylanilinium tetralds(4-(t-butyldimethylsilyl)-2, 3,5, 6-tetrafluorophenyl) borate, N,N"dimethylanilinium tetrakis(4'-(triisopropylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate, N,N-dunethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl) borate, dimethyloctadecylanmaonium tetrakis(pentafluorophenyl) borate, methyldioctadecylammonium tetrakis(pentafluorophenyl) borate, dialkyl ammonium salts such as:
di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, methyloctadecylammonium tetrakis(pentafluorophenyl) borate.

metliyloctadodecylammonium tetrakis(pentafluorophenyl) borate, and dioctadecylammonium tetrakis(pentafluorophenyl) borate; tri-substituted phosphonium salts such as:
triphenylphosphonium tetralcis(pentafluorophenyl) borate, metliyldioctadecylphosphoniura tetrakis(pentafluorophenyl) borate, and tri(2,6-dunethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate; di-substituted oxonium salts such as:
diphenyloxonium tetrakis(pentafluorophenyl) borate, di(o"tolyl)oxonium tetrakis(pentafluorophenyl) borate, and di(octadecyl)oxonium tetrakis(pentafluorophenyl) borate; di-substituted sulfonium salts such as:
di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.
Preferred (L*-!!)"‘ cations are methyldioctadecylammonium cations, dimethyloctadecylammonium cations, and ammonium cations derived from mixtures of trialkyl amines containing one or 2 Ci4„i8 alkyl groups.
Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
(Ox’’)/A’"V wherein:
Ox*'"*" is a cationic oxidizing ageift having a charge of h+;
h is an integer from 1 to 3; and
A’" and g are as previously defined.
Examples of cationic oxidizmg agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag’* or Pb"*"‘. Preferred embodiments of A*' are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.
Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula:
[CfA-wherein:
[C]"*" is a Ci.20 carbenium ion; and
A" is a noncoordinating, compatible anion having a charge of-1. A preferred carbenium ion is the trityl cation, that is triphenylmethylium.

A tiirther suitable ion forming, activating cocatalyst comprises a compound whiich is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula:
(Q’Si’A’ wherein:
Q' is Ci-io hydrocarbyl, and A" is as previously defined.
Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetralcispentafluorophenylborate and ether substituted adducts tliereof. Silylium salts have been previously generically disclosed in J. Chem Soc. Cham. Comm., 1993,383-384, as well as Lambert, J. B., et aL, Oreanometalhcs. 1994, 13, 2430-2443. The use of tlie above silylium salts as activating cocatalysts for addition polymerization catalysts is disclosed in US-A-5,625,087.
Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used according to the present invention. Such cocatalysts are disclosed m US-A-5,296,433.
Suitable activating cocatalysts for use herein also include polymeric or oligomeric alumoxanes, especially methylalumoxane (MAO), triisobutyl alummum modified methylalumoxane (MMAO), or isobutylalumoxane; Lewis acid modified alumoxanes, especially perhalogenated tri(hydrocarbyl)aluminum- or perhalogenated tri(hydrocarbyl)boron modified alumoxanes, having from 1 to 10 carbons in each hydrocatbyl or halogenated hydrocarbyl group, and most especially tris(pentafIuoropheny])borane modified alumoxanes. Such cocatalysts are previously disclosed in US Patents 6,214,760,6,160,146, 6,140,521, and 6,696,379.
A class of cocatalysts comprising non-coordmating anions generically referred to as expanded anions, further disclosed in US Patent 6,395,671, may be suitably employed to activate the metal complexes of the present mvention for olefin polymerization. Generally, these cocatalysts (illustrated by those having imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) may be depicted as follows:

A'"*" is a cation, especially a proton containing cation, and preferably is a trihydrocarbyl ammonium cation containing one or two Cio’o alkyl groups, especially a methyldi (Ci4.2oallcyl)ammonium cation,
Q’, independently each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, preferably Ci-20 alkyl, and
Q’ is tris(pentafluorophenyl)boraue or tris(pentafluorophenyI)alumane).
Examples of these catalyst activators include trihydrocarbylammonium- salts, especially, methyldi(Ci4_2oalkyl)ammonium- salts of:
bis(tris(pentafluorophenyl)borane)imtdazolide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)borane)-2-heptadecylraiidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)iinidazolide, bis(tris(pentafluorophenyl)boraiie)-4,5-bis(heptadecyl)imida2oIide, bis(tris(pentafluorophenyl)borane)imidazolinide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imida2oIinide, bis(tris(pentafluorophenyl)borane)"5,6-dimethylbenzimidazolide, bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,
bis(tris(pentafluorophenyl)alumane)imidazolide, bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide, bis(tris(pentafluorophenyl)alumaue)imidazolinide, bis(tris(pentafluorophenyl)alunxane)-2-undecylimidazolinide, bis(tris(pentafluorophenyl)aIumane)-2-heptadecylimidazoIinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyI)imidazolinide, bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide, bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimida2olide, and bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.
Other activators include those described in PCT publication WO 98/07515 such as tris (2,

the invention, for example, aliunoxanes and ionizing activators in combinations, see for example, EP-A-0 573120, PCX publications WO 94/07928 and WO 95/14044 and US Patents 5,153,157 and 5,453,410. WO 98/09996 describes activating catalyst compounds with perchlorates, periodates and iodates, including tlieir hydrates. WO 99/18135 describes the use of organoboroaluminum activators. WO 03/10171 discloses catalyst activators that are adducts of Bronsted acids with Lewis acids. Other activators or methods for activating a catalyst compound are described in for example, US Patents 5,849,852, 5,859, 653, 5,869,723, EP-A-615981, and PCX publication WO 98/32775. All of the foregomg catalyst activators as well as any other know activator for transition metal complex catalysts may be employed alone or in combination according to the present invention, however, for best results alumoxane containing cocatalysts are avoided.
Xhe molar ratio of catalyst/cocatalyst employed preferably ranges from 1:10,000 to 100:1, more preferably from 1:5 000 to 10:1, most preferably from 1:1000 to 1:1, Alumoxane, when used by itself as an activating cocatalyst, is employed m large quantity, generally at least 100 times the quantity of metal complex on a molar basis. Xris(pentafluorophenyl)borane, where used as an activating cocatalyst is employed in a molar ratio to the metal complex of from 0.5:1 to 10:1, more preferably from 1:1 to 6:1 most preferably from 1:1 to 5; 1. Xhe remaining activatmg cocatalysts are generally employed in approxunately equimolar quantity with the metal complex.
During the polymerization, the reaction mbcture is contacted witli tlie activated catalyst composition according to any suitable polymerization conditions. Xhe process is desirably characterized by use of elevated temperatures and pressures. Hydrogen may be employed as a chain transfer agent for molecular weight control according to known techniques, if desired. As in other similar polymerizations, it is highly desirable that the monomers and solvents employed be of sufficiently high purity that catalyst deactivation or premature chain termination does not occur, unless a block copolymer modified polymer product is desired. Any suitable technique for monomer purification such as devolatilization at reduced pressure, contacting with molecular sieves or high surface area alumina, or a combination of the foregoing processes may be employed.
Supports may be employed in the present invention, especially in slurry or gas-phase polymerizations. Suitable supports include solid, particulated, high surface area, metal oxides, metalloid oxides, or mixtures thereof (interchangeably referred to herein as an inorganic oxide). Examples include: talc, silica, alumina, magnesia, titania, zirconia, Sn203, aluminosilicates, borosilicates, clays, and mixtures thereof. Suitable supports preferably have a surface area as determined by nitrogen porosimetry using tlie B.E.X. method from 10 to 1000 m’/g, and preferably from 100 to 600 m /g. Xhe average particle size typically is from 0.1 to 500 nm, preferably from 1 to 200 urn, more preferably 10 to 100 |im,

In one embodhnent of tlie invention the present catalyst composition and optional support may be spray dried or otherwise recovered m solid, particulated form to provide a composition that is readily transported and handled. Suitable methods for spray drying a liquid containing slurry are well known in the art and usefully employed herein. Preferred tecliniques for spray drying catalyst compositions for use herein are described in US-A's-5,648,310 and 5,672,669.
The polymerization is desirably carried out as a continuous polymerization, preferably a continuous, solution polymerization, in wliich catalyst components, monomers, and optionally solvent, adjuvants, scavengers, and polymerization aids are continuously supphed to one or more reactors or zones and polymer product contmuously removed therefrom. Withm the scope of the terms "continuous" and "continuously" as used in this context are those processes in which there are intermittent additions of reactants and removal of products at small regular or irregular intervals, so that, over time, tlie overall process is substantially continuous. Moreover, as previously explained, the cham shuttling agent(s) may be added at any point during the polymerization including in the first reactor or zone, at the exit or slightly before the exit of the first reactor, between the first reactor or zone and the second or any subsequent reactor or zone, or even solely to tlie second or any subsequent reactor or zone. Due to the difference in monomers, temperatures, pressures or other difference in polymerization conditions between at least two of the reactors or zones connected in series, polymer segments of differing composition such as comonomer content, crystallinity, density, tacticity, regio-regularity, or other chemical or physical difference, within the same molecule are formed in the different reactors or zones. The size of each segment or block is determined by continuous polymer reaction conditions, and preferably is a most probable distribution of polymer sizes.
Each reactor in the series can be operated under high pressure, solution, slurry, or gas phase polymerization conditions. In a multiple zone polymerization, all zones operate under the same type of polymerization, such as solution, slurry, or gas phase, but at different process conditions. For a solution polymerization process, it is desirable to employ homogeneous dispersions of the catalyst components m a liquid diluent in which the polymer is soluble under the polymerization conditions employed. One such process utilizing an extremely fme silica or similar dispersing agent to produce such a homogeneous catalyst dispersion wherein normally either the metal complex or the cocatalyst is only poorly soluble is disclosed in US-A-5,783,512. A high pressure process is usually carried out at temperatures from 100°C to 400'C and at pressures above 500 bar (50 MPa). A slurry process typically uses an inert hydrocarbon diluent and temperatures of from 0°C up to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. Preferred temperatures in a slurry polymerization are

from 30°C, preferably from 60°C up to 115°C, preferably up to lOO’’C, Pressures typically range from atmospheric (100 kPa) to 500 psi (3.4 MPa).
In all of the foregoing processes, continuous or substantially contmuous polymerization conditions are preferably employed. The use of such polymerization conditions, especially continuous, solution polymerization processes, allows the use of elevated reactor temperatures which results in the economical production of tlie present block copolymers in high yields and efficiencies.
The catalyst may be prepai*ed as a homogeneous composition by addition of the requisite metal complex or multiple complexes to a solvent in which the polymerization will be conducted or in a diluent compatible with the ultimate reaction mixture. The desired cocatalyst or activator and’ optionally, the shuttling agent may be combined with the catalyst composition either prior to, simultaneously with, or after combination of the catalyst with tlie monomers to be polymerized and any additional reaction diluent.
At all times, the individual ingredients as well as any active catalyst composition must be protected from oxygen, moisture and other catalyst poisons. Therefore, the catalyst components, shuttling agent and activated catalysts must be prepared and stored in an oxygen and moisture free atmosphere, preferably under a dry, inert gas such as nitrogen,
Without limiting in any way the scope of tlie invention, one means for carrying out such a polymerization process is as follows. In one or more well stirred tank or loop reactors operating under solution polymerization conditions, the monomers to be polymerized are introduced continuously together with any solvent or diluent at one part of the reactor. The reactor contains a relatively homogeneous liquid phase composed substantially of monomers together with any solvent or diluent and dissolved polymer. Preferred solvents include C4-10 hydrocarbons or mixtures thereof, especially alkanes such as hexane or mixtures of alkanes, as well as one or more of the monomers employed in the polymerization. Examples of suitable loop reactors and a variety of suitable operating conditions for use therewith, including the use of multiple loop reactors, operant in series, are found m USP's 5,977,251, 6,319,989 and 6,683,149,
Catalyst along with cocatalyst and optionally chain shuttling agent are continuously or intermittently introduced in the reactor liquid phase or any recycled portion thereof at a minimum of one location. The reactor temperature and pressure may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by use of cooling or heating coils, jackets or both. The polymerization rate is controlled by the rate of catalyst addition. The content of a given monomer in the polymer product is influenced by the ratio of monomers in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor.

variables such as the temperature, monomer concentration, or by the previously mentioned chain shuttling agent, or a chain terminating agent such as hydrogen, as is well known in tlie art. Connected to the discharge of the reactor, optionally by means of a conduit or other transfer means, is a second reactor, such that the reaction mixture prepared in the first reactor is discharged to the second reactor without substantially termination of polymer growth. Between the first and second reactors, a differential in at least one process condition is established. Preferably for use in formation of a copolymer of two or more monomers, the difference is tlie presence or absence of one or more comonomers or a difference in comonomer concentration. Additional reactors, each arranged in a manner similar to the second reactor in the series may be provided as well Upon exiting the last reactor of the series, the effluent is contacted with a catalyst kill agent such as water, steam or an alcohol or with a coupling agent.
The resulting polymer product is recovered by flashing off volatile components of the reaction mixture such as residual monomers or diluent at reduced pressure, and, if necessary, conducting further devolatilization in equipment such as a devolatilizing extruder. In a continuous process the mean residence time of the catalyst and polymer in the reactor generally is from 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours.
Alternatively, the foregoing polymerization may be carried out m a plug flow reactor with a monomer, catalyst, shuttling agent, temperature or other gradient established between differing zones or regions thereof, optionally accompanied by separated addition of catalysts and/or chain shuttling agent, and operating under adiabatic or non-adiabatic polymerization conditions.
The catalyst composition may also be prepared and employed as a heterogeneous catalyst by adsorbing the requisite components on an inert morganic or organic particulated solid, as previously disclosed. In a preferred embodhnent, a heterogeneous catalyst is prepared by co-precipitating the metal complex and the reaction product of an inert inorganic compound and an active hydrogen containing activator, especially the reaction product of a tri (CM alkyl) aluminum compound and an ammonium salt of a hydroxyaryltris(pentafluorophenyl)borate, such as an ammonium salt of (4-hydroxy-3,5-ditertiarybutylphenyl)tris(pentafluorophenyl)borate, When prepared in heterogeneous or supported form, the catalyst composition may be employed in a slurry or a gas phase polymerization. As a practical limitation, slurry polymerization takes place in liquid diluents in which tlie polymer product is substantially insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent. As with a solution polymerization, the a-olefin comonomer or a mixture of different a-olefin monomers may be used in whole or part as the diluent. Most preferably at least a major part of the

Preferably for use in gas phase polymerization processes, tlie support material and resulting catalyst has a median particle diameter from 20 to 200 ‘im, more preferably from 30 ‘m to 150 |xin, and most preferably from 50 [xm to 100 ‘m. Preferably for use in slurry polymerization processes, the support has a median particle diameter from 1 ‘m to 200 ‘m, more preferably from 5 fxm to 100 ‘m, and most preferably from 10 pxn. to 80 |im.
Suitable gas phase polymerization process for use herein are substantially similar to laiown processes used commercially on a large scale for the manufacture of polypropylene, ethylene/ a-olefm copolymers, and other olefin polymers. The gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone. Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended above a perforated plate or fluidization grid’ by a flow of fluidization gas.
The gas employed to fluidize the bed comprises tlie monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. The hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, havmg a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.
A preferred method of cooling of the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect, often referred to as operation in the condensing mode* The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon havmg 3 to 8, preferably 4 to 6, carbon atoms. In the case that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, this can suitably be fed to the bed to provide an evaporative cooling effect* The volatile liquid evaporates in tlie hot fluidized bed to form gas which mixes witli the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed. The evaporated liquid then emerges froin the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop. The recycle gas is cooled in die heat exchanger and, if the temperature to which the gas is cooled is below the dew pomt, liquid will precipitate from tlie gas. This liquid is desirably recycled continuously to tlie fluidized bed. It is possible to recycle the precipitated liquid to tlie bed as liquid droplets carried m

WO-94/25495 and U.S. 5,352,749. A particularly preferred method of recyclmg the liquid to the bed is to separate the liquid from the recycle gas stream and to reinject tliis liquid directly into tlie bed, preferably using a metliod which generates fme droplets of the liquid within the bed. This type of process is described in WO-94/28032.
The polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst composition according to the invention. The catalyst composition may be subjected to a prepolymerization step, for example, by polymerizing a small quantity of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising supported catalyst particles embedded m olefin polymer particles as well.
The polymer is produced directly in the fluidized bed by polymerization of the monomer or mixture of monomers on the fluidized particles of catalyst composition, supported catalyst composition or prepolymerized catalyst composition within the bed. Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to the desired polymer, and conditioning the bed by drying with inert gas or nitrogen prior to introducing the catalyst composition, the monomers and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode. The produced polymer is discharged continuously or semi-continuously from the fluidized bed as desired.
The gas phase processes most suitable for the practice of this invention are continuous processes wliich provide for the continuous supply of reactants to the reaction zone of the reactor and the removal of products fi-om the reaction zone of the reactor, thereby providing a steady-state environment on the macro scale in tlie reaction zone of the reactor. Products are readily recovered by exposure to reduced pressure and optionally elevated temperatures (devolatilization) according to known techniques. Typically, the fluidized bed of tlie gas phase process is operated at temperatures greater than 50°C, preferably from 60°C to 110°C, more preferably from 70°C to 110°C.
Suitable gas phase processes which are adaptable for use in the process of this invention are disclosed in US Patents: 4,588 J90; 4,543,399; 5,352,749; 5,436,304; 5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562; 5,028,670; 5,473,028; 5,106,804; 5,556,238; 5,541,270; 5,608,019; and 5,616,661.
As previously mentioned, functionalized derivatives of pseudo-block copolymers are also included within the present invention. Examples include metallated polymers wherein the metal is the remnant of the catalyst or chain shuttling agent employed, as well as further derivatives thereof. Because a substantial fraction of the polymeric product exiting tlie reactor is terminated with the

can be utilized in well known chemical reactions such as those suitable for otlier alkyl-aluminum, alkyl-gallium, alkyl-zinc, or alkyl-Group 1 compounds to form amine-, hydroxy-, epoxy-, silane, vinylic, and other functionalized terminated polymer products. Examples of suitable reaction teclmiques that are adaptable for use here in are described m Negishi, "Organometallics in Organic Synthesis", Vol. 1 and 2, (1980), and otlier standard texts in organometallic and organic synthesis.
Polymer Products
Utilizing the present process, novel polymers, mcluding pseudo-block copolymers of one or more olefin monomers, are readily prepared. Preferred polymers comprise in polymerized form at least one monomer selected from the group consisting of ethylene, propylene and 4-methyH-pentene. Highly desirably, the polymers are interpolymers comprising in polymerized form ethylene, propylene or 4-methyl-l-pentene and at least one different C2-20 a-olefm comonomer, and optionally one or more additional copolymerizable comonomers. Suitable comonomers are selected from diolefins, cycUc olefins, and cyclic diolefins, halogenated vinyl compounds, and vinylidene aromatic compounds*

CLAIMS:
1. A process for the polymerization of one or more addition polymerizable monomers
to form a copolymer comprising two regions or segments of differentiated polymer composition or
properties, said process comprising:
1) Contacting an addition polymerizable monomer or mixture of monomers under addition polymerization conditions in a reactor or reactor zone with a composition comprising at least one olefin polymerization catalyst and a cocatalyst and characterized by tlie formation of polymer chains from said monomer or monomers;
2) transferring the reaction mixture to a second reactor or reactor zone and optionally adding one or more additional reactants, catalysts, monomers or other compounds prior to, commensurate with, or after said transfer; and
3) causing polymerization to occur in said second reactor or reactor zone to form polymer chains that are differentiated from the polymer chains formed in step 1);
said process being characterized by addition of a chasm shuttling agent to the reaction mixture prior to, during, or subsequent to step 1) such that at least some of the resulting polymer molecules from step 3) comprise two or more chemically or physically distinguishable blocks or segments.
2. A high molecular weight copolymer comprising two or more substantially homogeneous intramolecular segments or blocks comprising differing chemical or physical properties, said intramolecular segments characterized by possessing a most probable molecular weight distribution.
3. A polymer mixture comprising: (1) an organic or inorganic polymer and (2) a copolymer according to claim 2 or preparable according to claim 1.
4. A process according to claim 1 wherein the catalyst comprises a metal complex corresponding to the formula:

wherein:
R^^ is selected from alkyl, cycloalkyl, Heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives tliereof containing from 1 to 30 atoms not counting hydrogen or a divalent derivative thereof;
T^ is a divalent bridging group of from 1 to 41 atoms other than hydrogen, preferably 1 to 20 atoms other than hydrogen, and most preferably a mono- or di- C1.20 hydrocarbyl substituted methylene or silane group; and

R is a C5.-20 heteroaryl group containing Lewis base functionality; M is a Group 4 metal;
X is an anionic, neutral or dianionic ligand group; x' is a number from 0 to 5 indicating the number of such Groups; and bonds, optional bonds and electron donatives interactions are represented by lines dotted lines and arrows respectively.
5. A process according to claim 1 wherein the catalyst comprises a metal complex
corresponding to the formula:

wherein
is a metal of Groups 4-10 of the Periodic Table of the elements; T^ is a nitrogen, oxygen or phosphorus containing group; X^ is halo, hydrocarbyl, or hydrocarbyloxy; t is one or two;
x" is a number selected to provide charge balance; and T^ and N are linked by a bridging ligand.
6. A process according to any one of claims 1,4 or 5 characterized by producing a
plumier according to claim 2 or a polymer mixture according to claim 3.
7. A process according to any one of claims 1,4 or 5 wherein the chemically or
physically distinguishable blocks or segments have different comonomer incorporation indices.

Documents:

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Patent Number

268972

Indian Patent Application Number

1319/CHENP/2008

PG Journal Number

40/2015

Publication Date

02-Oct-2015

Grant Date

25-Sep-2015

Date of Filing

17-Mar-2008

Name of Patentee

DOW GLOBAL TECHNOLOGIES INC.

Applicant Address

WASHINGTON STREET1790 BUILDING, MIDLAND,MICHIGAN 48674

Inventors:

#	Inventor's Name	Inventor's Address
1	WENZEL, TIMOTHY, T	6909 NORTH JEFFERSON ROAD MIDLAND, MI 48642
2	CARNAHAN, EDMUND, M	4619 TWIN ELM DRIVE FRESNO, TX 77545
3	KUHLMAN, ROGER, L	117 DEWBERRY, LAKE JACKSON TX 77566
4	HUSTAD, PHILLIP, D	3618 ROSE WATER COURT MANVEL, TX 77578

PCT International Classification Number

C08F297/08

PCT International Application Number

PCT/US06/036038

PCT International Filing date

2006-09-14

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/717,545	2005-09-15	U.S.A.