Indian Patents. 271312:HAFNIUM COMPLEXES OF HETEROCYCLIC ORGANIC LIGANDS

Title of Invention	HAFNIUM COMPLEXES OF HETEROCYCLIC ORGANIC LIGANDS
Abstract	Abstract HAFNIUM COMPLEXES OF HETEROCYCLIC ORGANIC LIGANDS Hafnium complexes of heterocyclic organic ligands having improved soiubilitj' in aliphatic hydrocarbon solvents and their use as components of olefin polymerization catalysts as well as novel syntheses of component parts thereof are disclosed.

Full Text	HAFNIUM COMPLEXES OF HETEROCYCLIC ORGANIC LIGANDS CROSS REFERENCF. STATEMENT This applicarion claims the benefit of U.S. Provisional Applications 60/798,108, filed May 5, 2006. BACKGROUND OF THE INVENTION This invention is directed to certain hafnium complexes, to catalyst compositions comprising the same, and io iiddilion polymsrizaiiun processes, especially olcHp polymeriiation processes, using such hafnium complexes as one component of a coordination p jiymerizaiton catalyst composition. Advances in polymerization and catalysis have resulted in the capability to produce many new polymers having improved physical and chemical properties, useful in a ivide variety of superior products and applications. With the development of new catalysts the choice of Additionally, according to the present invention there is provided a calaiys! composition comprising one or fTiore of (he foregoing hafnium compiexes of formula 11) and a.n aciivaung cocatalysi capable of convening sdid metal complex into an active catalyst for addition polymerization. Additional components of such catalyst composition may include a carrier or support, a liquid solvent or diluent, a tertiary component such as a scavenger or secondary activator, and/or one or more additives or adjuvants such as processing aids, iiequestranis, chain transfer agents, and/or chain shuttling agents. In addition, the present invention provides an addition polymerization process, especially an oiefm polymerization process, wherein one or more addition polymerizable monomers are polymerized in the presence of the foregoing catalyst composition, including the preferred and more preferred embodiments thereof, to form a high molecular weight polymer. Preferred polymerization processes are soltition polymerizations, most preferably solution processes wherein ethylene, propylene, mixtures of ethylene and propylene, or mixtures of ethylene and/or propylene with one or more C4.20 olefins or diolefins are polymenzed or copolymerized. Desirably, the processes are capable of operation at high polymerization temperatures to prepare polymers having desirable physical propertie;.. Highly desirably, the present invention pro "-'ides a process wherein oflc or more addition poKmeriz^ble monomfcr> arr potvmerized at a rclativeiv h.sX) r-civrnerizaticr, ierrrr-sriiiuri in ;lis presence of the forego ins; c.-itjlys.! composinoii '0 form a his!^ n'o'ecolar weiglu r^c!ic poi vmf. especially a polynner that is isotaciic or highly isotactic. with improved operating efriciency and the u.se of non-aromatic solvents. Additionally the present inventors have discovered improved techniques for synthesizing high purity formylimidazoles, a new class cf stable borate esters of alkyIbenzofurans. and high purity bromoalkylbenzofurans. The metal complexes arid catalysts of the invention mav be used alone or combined with other metal complexes or catalyst compositions and the polymerization process may be used in scries or in parallel with one or more other polymerization processes. Suitable additional polymerization catalyst compositions for use in combination with the metal complexes of the present invention include conventional Ziegler-Natta-type transition metal polymerization catalysis as well a^ Ji-bonded transition metal cofnpounds such as meiallocene-iype caspl.vsis, constrained geometry or other transition metal complexes, including other donor ligand complexes. The metal complexes of the invention are preferred for use as components of olefin polymerization catalysts because they are capable of producing polymers at higher reactor temperatures while utilizing aliphatic or cycloaliphatic hydrocarbon solvents to convey them inio the reactor. An additional advantage of the present invention is the ability to prepare the metal complexes in extremely high purity and consequeni high activity due to nearly complete removal of meial salts, especially magnesium salt by-products from the syiitSiesis. through iriiuraiion or washing with aliphatic hydrocartxins. Another advantage is the ability in prepare propylene homopolymers or propylene/ethylene inierpolymers containing 6.5 percent or more polymerized propylene moieiies while retaining relatively high isotacticity, Tne polymers and copolymers of the invention possess improved toughness, making them well suited for use in injection molding applications as well as for use in preparing fibers, especially by means of mett-blown or extrusion spinning processes. Moreover, the polymers are usefully employed in adhesive formulations or in multi-layer films and laminates demonstrating improved compatibility and adhesion to polyethylene substrates, layers or films. DETAILED DESCRIPTION OF THE INVENTION All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Pres.s. Inc., 2003. Unless stated to the contrary, clear from the context, orconventiona! in the art. all parts and percentsare ha.sed on wajgfii. .Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC syssstn for numbering groups. The ierm "comprising" and dcrivati\es thereof ii The term "heiero" or "hetero-atom" refers to a non-carbon atom, especially Si, B, N. P, S, or O. "Heieroaryl", "heieroalkyl", "heterocycloalky!" and "heteroaralkyl" refer to aryl, alky!, cycloalkyl, or aralkyi groups respectively, in which at least one carbon atom is replaced by a heteroatom. "Inertly substituted" refers to substituents on a ligand that neither destroy uperability of the invention nor the iigand's identity. For example, an alkoxy group is not a substituted alkyi group Preferred inert substituents are halo, di(C\|.e hydrocarbyOatnino. Ci^ hydrocarbyleneamino, C\|.6 halohydrocarbyl, and tri(C,^ hydrocarhyl)si)yl. The term "'alkyl' is usc^i to signify a monovalent hydrocarbyl ligand of the formula, CnH2„+i. The term "alkylation" refers to a chemical process by which an alkyi or substituted alkyl group is incorporated into an organic or organometallic compound. The term "polymer", as used herein, includes both homopolymers, that than 0.95. Measurement of isotactic triads by the foregoing technique is known in ihe art and previously disclosed m USP 5,504, [72, WO 00/01745 and elsewhere. The previously descrilaed nieial complexes according to the inveiiuoii are typically activated in various ways to yield catalyst compounds having a vacant coordination site that wiii coordinate, insert, and polymerize addition polymerizabie monomers, especially olefin(s). For the purposes of this patent specification and appended claims, the term "activator" or "cocaialysi" is defined to he any compound or component or method which can activare any of the catalyst compounds of the invention as described above. Non-limiting examples of suitable activators include Lewis acids, non-coordinating ionic activators, ionizing activators, organome'.al compounds, and combinations of the foregoing substances thai can convert a neutral catalyst compound to a catalyticaliy active species. It is believed, without desiring lo be bound by such belief, thai in utie ^i.ibodiment of the invention, catalyst aclivaiion may involve formation of a cationic, partially cationic. or zwittenonic species, by means of proton transfer, oxidation, or other suitable activation process. It is to be understood that the present iiiverilioti is operable and fully enabled regardless of whether or not such an identifiable cationic, partially cationic, or zwitterionic species actually results during the ac'.ivation process. GISO interchat^geably referred to herein as an "'ionization" Drocess ov "'ionic One suitable, class of organometal activators or cocat2i>.^ts arc alum:..-,ane.';. also rcfcrrea to as alkylaluminoxanes. Alumosanes are well known activators for use with metallocene type catalyst compounds to prepare addition polymerization catalysts. There are a variety of methods for preparing aiumoxanes and modified alumoxanes. non-iimiting examples of which are described in U.S. Patents 4,665,208.4,952,540, 5,091,352. 5,206,199. 5,2a4.J 19, 4,S74,7.«. 4.924. 01S. 4,908,463, 4.968,827, 5,308,815, 5,329,032, .T,248,S0I. 5,235,081, 5. 157.137. 5.103 .'.13 I, 5,391.793.5,391,529, 5,693.838. 5,731,253, 5,731,45! 5.744,656; European publications EP-.^-561476, EP-A-279586 and EP-A-594218; and PCT publication WO 94/'10180. Preferred alumoxanes arc tri(Cj.6)a'l^yl^'Li'Tfitnum modified methyialumoxane, especially tri(isobulyl)aluminum modified methalumoxane, available commercially as MMA0-3A or tri(n-octyl)aluminum modified methalumoxane. available commercially as MMAO-12, from Akza Nobel, Inc. !t is within the scope of this invention lo use alumoKane(s) or modified alumo)tane(s) as an activator or as a tertiary component in the invented proce.s.s. That i.s, the compound may be used aione or in combination with other activators, neutral or ionic, such as tri(alkyl)ammonium tetrak.i£(pentanuorophenyl)borate compounds, trisperfluoroaryl compounds, po!yhalogenated hctcroborane anions (WO 98/43983). and combinations thereof When used as a tertiary component, the amounl of alumoxane employed is generally less than tha: noccs^ary to sffectively activate the metal complex when employed alone. In this embodtmsnt, It is believed, without wishing to be bound by such belief, ihai ihe alumoxane does not conmbufe significanily to actual catalyst aciivaiion. Not withstanding the foregoing, it is to be understood that some paaicipafion of the alumoxane in the activation process is not necessarily excluded. Ionizing cocatalysts may contain an active proton, or some other cation associaled with, but not coordinated to or only loosely coordinated to, an anion of the ionizing compound. Such compounds are described in European publications EP-A-570982, EP-A-520732. EP-A~495375, EP-A-500944, EP-A-277 003 and EP-A-277004, and U.S. Patents: 5.153,157. 5,198 401.5,066,74!, 5,206,]97, 5,241,025, 5.384.299 and 5,502,124. Preferred aniong ihe foregoing activators are ammoniLim cation containing salts, especially ihose containing irihydrocarbyl- ssibsiiiuied ammonium caiions containing one or two C,{>jo aikyl grotips, especially methylbis(ocladecyl>ammoniam- and methylbis(tetradecyl)-ammonium- cations and a non-coordinatmg anion, especially a ietrakis(perfluoro>arylborate anion, especiallv ietrakis(pent;afluorophenyl>borate. It is further understood that the cation may comprise a mixture letrakisCpentarlEiorophenyiiborate. Activation methods using ionizing ionic corr.poiinds not containing an a.live proicri. but capable of forming active carajvst compositions, such as ferrocenium saits of the ioregoing non-coordinating anions are also contemplated for use herein, and are described in EP-A--i26637. EP-A-573403 and U.S. Patent 5.387.568. A class of cocatalysts comprising non-coordinating anions genericall> referred to as expanded anions, further disclosed in U. S. Patent 6.395,67 i, may be suitably employecj to activate the metai complexes of Ihe present invention for olefin polymerization. Generally, these cocatalysts (illustrated by those having imidazolide, substituted imidazolide. imidazoiinide, substituted imidazolinide. benzimidazoiide. or substituted benzimidazoHde anions) may be depicted as follows: as organic ether, polyeiher. amine, and poiyamme compounds, rvlony of the Toregoing compounds and their use in polymerizations is disclosed in U. S. Patents 5, 7 12,352 and 5,763,543. and in WO 96/08520. Preferred eitamples of the foregoing leniary components include Irialkylaluminum compounds, dialkylaluminum aryloxideb, alkylaiuminum diaryloxides. dialkylalummum amides, alkylaluminum diamides, dialkyialuminum triChydrocarbylsilyDamides, alkylaiuminum bis(iri(hydrocarbylsiiyl)amides>, alumoxanes, and modified aiumoxanes. Highly preferred tertiary components are alumoxanes, modified alumoxanes, or compounds corresponding to the formula R'-Al(OR^) or R%Al(NR^j> wherein R"^ is d.^o alkyt, R' independently each occurrence is O^jo aryl, preferably phenyl or2,6-di-t-butyM-methyIphenyl. and R^ is Cu alky! or tri(Cualkyl}si!yl, preferably trimethylsilyl. Most highly preferred tertiary components include methylalumoxane, trifisobutylaluminum)- rriodified methylalumoxane, di(n-oclyl)atuminum 2,6- Another example of a suitable tertiary component is a hydroxycarbc^yiate metal salt, by which is mean! any hydroxy-substituted. mono-, di- or tri-carbosyiic acid salt wherein the metal poaion is a caiionic derivative of a metal from Groups 1-13 of the Periodic Table of Eiemenis. This compound may be used to improve polymer morphology especially in a gas phase poiymentanon Non- limiting examples include saturated, unsaturated, aliphatic, aromatic or saruraied c>'clic, syb;titured carboxylic acid ?."i!ts where the carboxviate l^sand h:i£ from o:>e ec trirce r, .-QYOX-. substiluents and frorr; ! io 24 carbon atoms. Exaniples include hydroxvacetaie, hydrc-.vpropionate, hydroxybutyraie, hydroxyvalcrate, hydroxypivalate, hydroxycaproale, hydroxycapryiaie, hydrOAvheptanaie, hydroxypelargonafe. hydroxyundecanoaie, hydroAyoJeate. hydroAyocioaie, hydroxyalmitate, hydroxymyristate, hydroxymargarate, hydroxyscearate, hydroxyarachaie and hydroxytercosanoaie. Nor- limiting examples of the metal ponion includes a metal seiecied from the group consisting of Al, Mg, Ca. Sr, Sn,Ti. V, Ba, Zn.Cd, Hg, Mn, Fe. Co, Ni. Pd, 1.; .ind Na. Preferred metal salts are zinc salts. In one embodiment, the hydroxycarboxylate metal salt is represented by the following general formula: M(Q).(OOCR)j,. where M is a metai from Groups 1 lo 16 and the Lanthanide and Actinide series, preferably from Groups I to 7 and 12 to 16. more preferably from Groups 3 lo 7 and 12 to 14, even more preferably Group 12, and most preferably Zn; Q is halogen, hydrogen, hydroxide, or an alkyl, alkoxy. aryloxy. siioxy. siiane, sulfonate or siloxane group of up lo 20 atoms not counting hydrogen; R is a hydrocarbyl radical having from 1 to 50 carbon atoms, preferably I to 20 carbon atoms, and optionally substituted with one or more hydroxy, alkoxy, N,N-dihydrocarbylamino, or nitrides, and halides. Other cajtiers include resinous support maieriais such as fiaiysijrene. a funciionafized or crosslinked organic supports, such as polystyrene divinyl btinzcnL: polyoieftns or polymeric compounds, or any other organic or inorganic support material, or mixtures thereof. The preferred carriers are inorganic oxides that include those Group 2. ?, 4, 5, 13 or I-metai oxides. The preferred suppjorts include silica, alumina, silica-alumina, silicon carbide, boron nitride, and mixtures thereof. Other useful supports include trwgnesia, ticania, zirconia, and clays. Also, combinations ofthese .';upporl materials may bs used, for example, silica-chromium and silica-titania. It is preferred that the carrier has a surface area in the range of from 10 to 700 mVg. pore volume in the range of from 0.1 lo 4.0 cc/g and average particle .size in the rangt of from 10 to 500 p.m. More preferably, the surface area of the carrier is in the range of from 50 to 5O0 m'/g, pore volume of from 0.5 to 3.5 cc/g, and average particle si7.e of from 20 to 200 jjjn, Mosi preferably the surface area of the carrier is in the range of from !00 lo 400 m'^/5, pore volume from O.S 10 3 0 cc/'g and average particle size is from 20 to 100 (im. The average pore size of a carrier of the invention is typically in the range of from 1 lo 100 nm. preferably 5 to 50 nm, and most preferably 7.5 to 35 nm. Exampies of suppored catalyst compcsiiions s\iiiably eiTioloyed ;n t.ie prejcn! ;r:^-:t','.ion tire Jftvjrib^d in U S, Paiinis. ~~0].i:-,:., ;.SJ£, 561, 4.911.':!::. ^SZ5.--,1 - J"'., "■ 5 '^"'- 22= 5,238,812, 5,240,894. 5.332 70fi, 5,346,925, 5,422,325. 5.466.6^9. 5,46'j.7(;6 ' 468.7^2. 5.529,965, 5,554,704, 5.629,25: Examples of techniques for supporting conventiorial-type cataly.st coiripo^itions liiai may also be employed in the present invention arc described in u. S. Patents 4.894,424, 4,376,062, 4,395.359, 4,379.759, 4,405,495 4,540758 and 5,096,869. It is contemplated that the catalyst compounds of the invention may be deposited on the same support together with an activator, or that the activator may be used in an unsupported form, or deposited on a suppon different from the supported calaly.st compounds af the invention, or any combination thereof. There are various other methods in Ihe art for supponing a polymerization catalyst compound or catalyst compositions suitable for use in the present invention. For example, the catalyst compound of the invention may contain a polymer bound ligand as described in USP 5,473,202 and USP 5,770,755. The support used with the catalyst compositrt-n ^f (he invention may be functionalized as described in European publication EP-A-802 203. At least one substituenl or leaving group of the catalyst may be selected as described in USP 5,688.880. The supported catalyst composition may include a surface modifier as describt;d in WO 96/11960. A preferred method for producing a supported catalyst composition iiccording ic^ the invention is descinbed in PCT publications WO 96/00245 and WO 96/00243, In this prefeired method, the catalyst compound and activators are combined in separate liquids. The liquids may be any compaiible solvent or other liquid capable of forming a solaiion or slurry with the catalyst compounds and/or activator. In the most preferred embodiment the liquids art l.ie same linear or cyclic aliphatic or aromatic hydrocarixin, most preferably hesane or loluene. The catalyst compound and activator mixtures or solutions are mixed together and optionallv added to s porous support or, alternatively, the porous support is added to the respective mixtures. The resulting supported composition may be dried lo remove diluent, if desired, or utilized separately or in combination in a polyme-rizaiion. Highly desirably the total volume of the catalyst compound solution and the activator solution or the mixtures thereof is (ess than five times the pore volume of the porous support, more preferably less than four times, even more preferably less than three lin^s; with most prefer ranges being from 1,1 times to 3,5 limes the pore volume of the support. The cataly!;t composition of the present invention may also be spray dried using techniques as described in USP 5,648.310, to produce a porous, particulate solid, optionallv containing structural reinforcing agents, such as certain silica or alumina compounds, especially fjmed silica, in these compositions the silica acts as :i thixoiropic agent fcr dr.ciet rcT:Ti2",'On ,'!nd -.ii.n\| j;.^ well 11$ a r^mfo^cir^ ii"-'^'^', 'r the resui!^i^ si^^^^'-dried '^iirtfcle^. P.'occdures fi'-r measuring the totiii pore "^ oJ'jins :■:" 2 por"Lis Tiater'ii are ■■■.e/ ■:_■".:■■ r. ■■' '.hi an. The preferred procedure is BET nitrogen absorption .A.notber suitable method well Known in the an is described in Innes. Total Porosity and Panicle Density of Fluid Catalysts By Liquid Titration, Analytical Chemistry, f 1956) 2S, 332-334. It IS fiirther contemplated by the in\'ention that other catalysts can be combined with the catalyst compounds of the invention. Examples of siich other cats!yits are disclosed m U.S. Patents 4,937,299, 4,935,474, 5,281,679, 5,359.015. 5.470,81 1, 5,719,241, 4.159.965. 4.325,837, 4,701.432, 5.124,418, 5,077.255. 5,183,867. 5.391,660, 5,355.810. 5,691,264, 5,723. 399 and 5,767,031; and PCT Publication WO 96/23010. In particular, the compounds that may be combined with the rr^tai complexes of the invention to produce mixtures of polymers in one embodiment of the invention include conventional Ziegler-Nalta transition metai compounds a^ well as coordination complexes, including transition metal complexes. Conventional Ziegler-Natta transition metal compounds include the well known magnesium dichloride supported compound^;, vanadium compounds, and chromium catalysts (also known as "Phillips type catalysts"). Examples of these catalysts are discu.ssed in U.S. Patents 4.115,639, 4,077,904 4,482,687,4,564,605, 4.721.763. 4.879.359 and 4.960,741. Suitable transition metal complexes that may be used in the present invention include transition metal compounds from Groups 3 to 8. preferably Group 4 of the Periodic Table of Elements containrng men hgund groups and capable of activation by contact with a cocataiyst. SuLtable Ziegler-Natta catalyst compounds include alkoxy, phenos>. bromidt;, chloride aiuf fluoride derivatives of the foregoing metals, especially titanium. Preferred 11 tan itim compounds include TiCti , TiBr,, Ti{OC2H5)3CI, Ti(OC2H5)Cb, Ti(OC4H9>3CI, Ti Non-limiting examples of vanadium catalyst compounds include vanadyl tnhaJide, alkoxy halides and atkoxides such as VOCb. VOCh(OBu) where Bu is butyl and VOfOCjHs);; vanadium letra-halide and vanadium alkoxy halides such as VCU and VCl-,(OBu); vanadium and vanadyl acetyl acetonaies and chloroacetyl acetonates such as V(AcAc)3 and VOCIjCAcAc) where (AcAc) is an aceiyl acetonale. Conventional-type chromium catalyst compounds suitable for use in the present inventior include CrOj , chromocerie, silyl chromate, chromyl chloride ICrO^CU), chromium-2-ethyi-hexanoate, and chromium acetylacetonate fCr(AcAc)T)- Non-itmitmg example? a.^'e disclosed in U.S. Pal. Nos, 2,285.721. 5,242,099 and ?,231.550. Sti!! '^thsr ccn'er:t:c na'i-tvpe transiTrcn metz] ■catalv-! ^r.rrD-'iund^ 'LI:I.5I;.I? 'C 'i^e in !hr-present invention are dtsclo,'-;ed in U.S. Pat. Nos. 4,124,532. J.302,565. 4,302.566 i^r-.d 5.76?,723 and EP-.A^I68I5 and EP-.A.-420436, Cocatalysi compounds for use with the above conventional-type catalyst compounds are typically organometallic derivatives of metals of Groups i,2, 12or 13, Non-iimiting examples include meihylliihium, bulyliiihium, dihexylmercury. butylmagnesium. dierhytcadmium, betizylpoiassium, dielhvlzinc. iri-n-btilylaluminum, diisobuivl e'h> Iboron. dieihylcadrnjum. di-n-bulylzinc and tri-n-a my Iboron, and, in particular, aluminum trialkyl compounds, such as tn-hexylaluminum, triethylaluminitm, trimeihylaluminum, and triisobutylaluminum. Other suitable cocatalyst compounds include mono-organohalides and hydrides of Group 13 metals, and mono- or di'Organohal ides and hydrides of Group 13 metals. Non-limiting examples of such conveniional-type cocatalyst compounds include di-isobutylalumintim bromide, isobutylboron Oichloride, methyl magnesium chloride, ethylberyliium chloride, ethylcalcium bromide, di-isobuiylaluminum hydride, methylcadmlum hydride, diethyiboron hydride, hexyiberyllium hydride, dipropylbornn hydride, octylmagnesium hydride, butylzinc hydride, dichioroboron hydride, dibromoaluminum hydride and bromocadmium hydride. Conventional-type organometal lie cocatalyst compounds are known to those in the an and a more complete discussion of these compounds may be found in U. S. Patents 3.221,002 and 5.093,415. in the foregoing formulas, the supportive suhsdtuent formed by Q', V and Z' i-; a uncharged polydentate ligand exeriing electronic effects due to its high polarizabiliiy, similar to the cydopeniacJienyf ligand. In (he mosi referred embodtmefif^ of this ini'enKoft, ihv dssiionaiutad carbamates and the hydroxycarboxylates are employed. Non-limiting examples of these catalyst compounds include indenyl zirconium in'ifdiethy I carbamate), indenyl zirconium lris(trimethyiacetalej. indenyl zirconium tris(p-roiuale), mdenyl zirconium tris(h!;n7.oate), (1-methyiindenyl)zirconium iris(trimethylacetate), Q-methyiindenyl) zirconium tris(diethylcarbamate), !n anotherembodiment of the invention the additional catalysi compounds are those nitrogen containing heterocyclic ligand complexes, based on bidentate Hgands containing pyridine or quinoiine moieties, such as those described in WO 96/33202. WO 99/014S-;, WO 98/42664 and U. S. Patent 5,637,660. It "i within the ^cooi of ^hls in^^.n:ion. m or.e ?rnhodiine:;'. that c.-a.,!^'- .', ~::-~:\-:\. rA .>.■_. r-, , T, ._>K:. Catalysis forPoUrnerizatioi! of Eth>lene and a-Olefins'. J..^.C.$. (1995) H", 641^-64 if and Johnson, et al., "Copolymerization of Ethylene and Propylene with Functionalized Vmyl Monomers by Pa]Iadium(II)Ca!a()Sfs".J,AC£, (1996) ) (8, 267-268. and WO 96^23010, msy be combined with the present metal complexes for use in the process of the invention. These complaxe.'; can be either djalkyl ether adducLs. or alkylated reaction products of the described dih.i:'.]ds complexes that can be activated to a cationic state by the conventional-type cocataly.ci; or ;he activ^icrs of this invention described below. Additional suitable catalyst compounds for use in the foregoing mixed catalyst compositions are diimine based ligands containing Group 8 to 10 meial compounds disclosed in PCT publications WO 96/23010 and WO 97/48735 and Gibson, et al., Chem. Comm.. {19981 849-850- Other catalysts are those Group 5 and 6 metal imido complexes described in EP-A-0 816 3S4 and U, S. Patent 5,851,945. In addition, catalysts include bridged bisCar>'lamido) Group 4 compounds described by D, H. IMcConville, et a!.. Orsanometallics (1995) 14. 5478-5480. Other catalysts are described as bis(hydroxy aromatic nitrogen ligands) in U. S. Patent 5,852,146, Other metailocene-type catalysis containing one or more Group 15 atoms include those described in WO 98/4665 1. Still another metallocene-type catalysts include those mullinuclear caiaiyst? as described in WO 99/20665. It is contemplated in some emfaodimenis, that ih& catalyst compounds employees in addition to those of [he invention described above may be asymmetrically substituted in temij of additional subslituenls or type^ of substiiuents, and/or unbalanced in terms of the number of additional substituents on the 7t-bonded ligand groups, it i,s also contempiaied that such addiiional catalysts may include their siruciural or optical or enantiomeric isomers (msso and racemic isoniersi and mixtures thereof, or they may be chiral and/or a bridged catalyst compounds. in one embodiment of the invention, one or more olefins, preferably one or more C;,>u olefins, preferably ethylene and/or propylene are prepolymerized in the presence of the catalyst composition prior to the main polymerization. The prepolymeri^aiion can be cairicd out balchwise or continuously in gas, solution or slurry phase including at elevated pressures. The prepolymerization can take place with any olefin monomer or combination and/or in the presence of any molecular weight controlling agent such as hydrogen. For examples of prepoiymer;za:ion procedures, see U. S. Patents 4,748,221, 4.7g9,359, 4,923,S.^3, 4,92 [.§25, 5,283.278 and 5,705,578. European publication EP-A-279863. and PCT Publication WO 9'7i4^3~ 1. A prepolymerized catalvsi composition for purr'Oses of this patent ^peciftc.ition and 5D:x;ndcd claims prsfc-ibl'. i > a supported ciLalvsi svitem. Thfc nteihod for making tht caialysi com;:'OK;'i.ion generally iri'T.lw.s the i:o:i"ib!n,:!;. contacting, blending, and/or mixing of the respective catalys; con-jponents, opiionaily in ihc presence of the monomer or monomers to be polymerized, fdeal'y. ihe contacting is conducted under men conditions or under poiymerizaiion conditions at a lemperalure in the range of frcirri 0 to 200 ""C, more preferably from 15 to !90 'C. and preferably a; pressures from arnbi^ni (6l.t0 [;Fa) to 1000 psig (7 MPa). The contacting is desirably performed under an inert ga.sgors atrr,ospriere, such as nitrogen, however, it is also contemplated that the combination may be performed in the presence of olenn(s), solvents, and hydrogen. .Mixing techniques and equipment contemplated for use in the method of the invention are well known. Mixing techniques tnay involve any mechanical mixing means, for example shaking, stirring, tumbling, and rolling. Another technique contemplated involves the use of fluidization, for example in a fluid bed reactor vessel where circulated gases provide the mixing. For SLipponed catalyst compositions, the catalyst composition is substantially dried and/or free flowing. In a preferred embodiment, the various components are contacted in a rotary mixer, tumble mixer, or in a fiuidized bed mixing process, imder a nitrogen atmosphere, and any iiquid diluent is subsequently removed. Suitable addition polymerization processes wherein the present catalyst somposnion; may be employed include solution, gas phase, slurry phase, high pressure, or combinations thereof. Particularly preferred is a solution or slurry polymerization of one or more olefins ar least one of which is ethylene, 4-iTiethyl-S-penleiie, or propylene. The invention is particularly well suited to processes wherein propylene, 1-butene, or 4-methyl-I-pentene is homopoiymsrized. ethylene and propylene are copolymerized. or ethylene, propylene, or a mixture thereof is copolymeri7£d with one or more monomers selected from the group consisting of 1-octsne, 4-methyl-l-pentene, buiadiene, norbomene, ethylidenenorbomene, 1.4-hexadiene, I.S-hesadiene, tiorbomadiene, and 1-buiene. The homopolymers of butene-1 and 4'methyl-i-pentene and copolymers therei^f, especially with ethylene or propylene arc desirably highly isotactic. Other monomers useful in the process of the inveniion include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, pofyenes, vinyl monomers and cyclic olefins. Non-limiting monomers useful in the invention include norbomene, isobutylene, vmylbenzo^yclobutane, styrenss, aikyl substicjied styretie, ethyiidene norbomene, isoprene. 1-pentene, dicyclopentadiene and cyciopentene. Typical ly, in a gas phase polymerization process a continuous cycle is employfcci where m one part of the cycle of a reactor system, a cycling gas stream, oiher^ise tcnc.'.'n us a reeve le stream or tluid]Z,jn£ rriedium. is hiat^d in the reactor bv the heal of ooi- ^Tierii'atiO!' 1 rrj heiit ;^^ r&:~'7i-ed from the recycle composition in another part of the eye's by a cooling s;-siem tucrrial i.o the reactor. Generally, in a gas fiuidizcd bed process for producing polymers, a gaseous stream containing one or more monomers is continuously cycled ihroueh a fluidiT-^d bed m the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back mto the reactor Simultaneously, polymer product is ".nhdrawT from the reac'or and fresh monor:ier is added to replace the poKmerized monomer, f^xa—ipies Df ?uch proce^'Si's are disclosed in U. S. Patents 4,543,399. 4,588,790. 5,028,670, 5,3 I 7,0.36, 5,352.749. 5405,922, 5,436.304, 5. 453.471. 5.462.999. 5.616.661 and 5,668,228. The reactor pressure in a gas phase process may vary from 100 psig (7O0 kPa) to 500 psig (3500 kPa), preferably in the range of from 200 psig (1400 kPa) to 400 psig (2800 kPa). more preferably in the range of from 250 psig (1700 kPa) to 350 psig (2400 kPa). The reactor temperature in the gas phase process may vary from 30 to 120 °C. preferably from 60 to 115 °C, more preferably from 70 to 110 °C, and most preferably from 70 to 95 "C. A slurry polymerization process generally uses prss.sure.s in the range at from HMi kP?. in 5 MPa, and temperatures in the range of 0 to 120 °C. In a slurry pxilymerization. a suspension of solid, particulate polymer is formed in a liquid polymerization diluent to which monomers and often hydrogen along with catalyst are added. The diluent is intermittently or continuously removed from the reactor where (he volatile components are separated from the poiynier and recycied to the reactor. The liquid diluent employed should remain a liquid under the conditions of poiymerization atid be relatively inert. Preferred diluents are aliphatic or cycloaliphaiic hydrocarbons, preferably propane, n-butane, isobutane, pentane, isopeniane, hexane. cyclohexane. or a mixture thereof i.s employed. Examples of suitable slurry polymerization processes for use herein are disclosed in U, S. Paienis3,24S.179 and 4,613.484. Examples of solution processes that are suitably employed wilh the catalyst conipo5iltons of the present mveniion are described in U. S. Patents 4.271.060. 5,001,205, 5.256.998 antl 5,589.555. Highly preferably, the solution process is an ethylene polymerizaiicn or an ethylene/propylene copolymerizaiion operated in a continuous or semi-continuous manner with high ethylene conversion, preferably greater than 98 percent, more preferably greater than 99.5 percent ethylene conversion. Typical temperatures for solution polymerizations are from 70 lo 200 "C. more preferably from lOOto \50°C- Regardless of the process conditions employed (gas phase, slurry or solution phase) m order to achieve the benefits of [he present invention, the present polymerization is desirably conducted at a temperature greater than or equal lo 100 °C, more preferabiv srealer than or eoual to I 10 %., and most preferably greater than or eqiial to 115 ""C. Polymer properties The polymers produced by the proccj.; of the :rverjiic^- ;sti bt ii'.ed .- > ■^-■-.■dc ^r-rier- of product? and end-use applications. The polymers produced by the process of die irvenjion include high density polyethyienss, low density poiyeihiJene, linear, (o'^ density pc'Veihylens leihyiene/a-olefln copolymers), polypropylene, copolymers of propylene and ethylene, and eihylene/propylene/diene terpolymers. Especially preferred pfolyrners are propylene/eihvlcne- or propylene/ethylene/diene inlerpolymers containing 65 percent or more, preferably o5 F-stcent or more polymerized propylene and substantialiy isolactic propylene segments. The ethylene homopolymers and high ethylene content copolymers formed by the present process preferably have a density in the range of from 0.85 g/cc to 0.97 g/cc, more preferably in the range of from 0.86 g/cc lo 0.92 g/cc. Desirably they additionally have melt index (h) determined according to ASTMD-l 238, Condition E, from ! to lOOdg/min, preferably from 2 to lodg/min. Propylene/ethylene copolymers prepared according to the present process desirably have a AH( (j'g) from 25 (o 55, preferably from 29-52. Highly desirably polymers prepared according to the present invention are propylene/ethylene copolymers containing 85 to 95 percent, preferably 87 to 95 percent polymerized propylene, a density from 0.860 to 0.885, and a melt flow rate (MpR) determined according to ASTM D-1238. Condition L. from 0.1 to 500, preferably 1.0 to lO. Typically, the polymers produced by the process of the inventior. iicve a molecular weight distribuLion or polydispcrsity index (Mw/Mn or PDIl from 2,0 to 15.0, preferabiv from 2.0 to 10.0. "Broad polydispcrsity". "broad molecular weight distribution", "broad MWD" and similar terms mean a PDI greater than or equal to 3,0, preferably from 3.0 to 8.0. Poiymers for use in fiber and extrusion coaling applications typically have a relatively broad polydispersity. Catalysts comprising a complex according to formula (T) are especially adapted for preparing such propylene/ethylene inlerpolymers having a broad molecular weight distribution for this end use. "Narrow polydispersity", "narrow molecular weight distnhulion"', "n.^rrow MWD" and similar terms mean a PDI of less than 3.0, preferably from 2,0 to 2.7. Polymers for use in adhesive applications preferentially have a narrower polydispersity. Catalysis comprising a complex according to formula (D are especially adapted for preparing such narrow molecular weight dislribution propylene/ethylene inlerpolymers for this end use. A suitable technique for determining molecular weight distribution of the polymers is gel permeatLOn chromatography (GPC) usiQg a Polymer Laboratories PL-GPC-220 high icinperature chromatographic unit equipped with four linear mixed bed columns (Polymer Laboraiones ('20-,um particle si;:e)). The oven temperature i> set at 160 "C wiui ihc auiosampier hoi ^on= di i 60 "C and the warm zone at 145 "C 'J'he solveni ts I .I.^-tri.chlornbenjene roniainini? 20L"' Dpm 2 (^wJi-t-binvt- 'i-msth'-'iDhen^i Th= flo^i r.-.te. t^; 1.0 rTiiUi'^ter,"niTi J;L- an J -he .- ■.■_^l..'..j" . z .' ■ . . .■. 'L.": Abou: 0.2 percent solution; of the samples are prepared for injerLion by d;£^:i ■-■.-,- .ir. ;jr-.pie in nitrogen purged ! ,2.4-trichiDrobenzene containing 200 ppm 2,6-di-i-biityl-4-:r(eir,ylphenol for 2.5 hours ai 160 "C with gentle mixing. The iTiolecular weight is determined by using ten narrow molecular weight distribution polystyrene standards tfrom Polymer Laboratories. EasiCal PSl ranging from 5S0 lo ^.fOCOOO g/mcle,i in conjunction v-ith theirelunon volumes. TTie equivalent pclypropviene T"jOleci;'ar weights are deiemiined by using appropriate Mark-Houwink coefficieniii for polypropylene (J_, Appl. Poivm, Sci.. 29. 3763 - 3782 (I9S4)) and polystyrene (Macromolecules, 4, S07(1Q71)) in the Mark-Houwink equation: jN\| = KMa, where Kpp-1.90X lO"^. Opp = 0.725 and Kp. = 1.26 x 10', ap.. = 0.702 One suitable technique for measuring polymer thermal properties is by means of differential scanning calorimeiry (DSC). General principles of DSC measurements and application.^ of DSC to Studying crystalline poiymers are described in standard texts such as, E. A. Tun. ed.. "Thermal Characierization of Polymeric Materials", Academic Press, (19811. A suitable lecbnique for conducting DSC analyses is by using a model QiOOO DSC device from TA instruments. Inc. To calibrate the instrument, first a baseline is obtained by running the DSC from -90 "C to 290 "C without any sample in the aluminum DSC pan. Then 7 grams of a fresh indium sample is analyzed by heating the sample to 180 "C, cooling the sample to 140 "C ai a cooling rate of iO "C/min followed by keeping the sample isothermally ai 140'^C for 1 minute, followed bv heacing the sample from 140 °C to 180 "C at a healing raie of 10 "C/min, The heat of fusion and the onset of melting of the indium sample are determined and checked to be within 0,5 °C frorr^ 156.6 °C for ihs onset of melting and within 0,5 J/g from 28.71 J/g for the iieat of fusion. Then deinniT-^.d water is analyzed by cooling a small drop of fresh sample m the DSC pan from 25 "C to -30 '^C at a cooling rate of IO°C/min. Ttie sample is retained at -30 °C for 2 mmutes and heated to 30 °C at a heating rate of 10 °C/min. The onset of melting is determined and checked to be within 0.5 °C from 0 '^C, The samples are prepared by pressing the polymer imo a ihin film at a temperature of 100 "C, About 5 to 8 mg of film sample is weighed and placed m the DSC pan. The iid is crimped on the pan to ensure a closed atmosphere, The sample pan is placed in the DSC ceil and then heated at a rate of about 100'C/min to a temperature of about 30 °C above the melt temperature. The sample is kepr at this temperature for about 3 minutes then cooled at a rate of 10 "C/min to ^0 'C, and held at that temperature for 3 minutes. Next the sample is again heated at a rare of !0 '-"Cmm until melting is complete. The resulting enthalpy curves are analyzed for peak melt temperature, onset and peak crystallization lemperarures. heat of fusion, and hea; of crystallization The present inierpolvmers of propvlene -.^iih ethylene and or-Iionai A' Ci. , 2 oif.'fini ruvc a rcU".r-,L]j broad raeUing poir.; a.'; i". Jdenctd by ihe DSC .'isaiirig ;-J:"-"J. :: .i b,^ii-'^ -"- ::..i'. '.^'i ~".a'.' be due io the unique disiribunon of eihNlene polyrrcr sequcrr^es ■.. nh-.n zm oo\yir:S.' zr.zw.-,. =.■; a consequence of ihe foregoing fact, melting point data, Tm. are not geierai'> rcpcrtsd hereiti or uiilized in describing polymer properties, Crystailinity is determined based on SH; measure.Tienis, with percent crystailinity determined by the formula: AH\|/if)5(j/g) .^ 100, Generally, a relabvely narrow- msliing peak is observed for propylene/ethylene ir.terpoivmers prep:ired asmg 'J meiallocene catalyst whereas the polymer.'; according to the present invention possess a iciaii-.e!;' broad melimg point cur\'e. Polymers having a broadened melting point have t>een found to be highly useful in applications requiring a combination of elaslit;ity and high temperature performance, such as elasEomeric fibers or adhesives, for example. One characteristic in the DSC curve of propylene/ethylene polymers possessing a relatively broad melting point is that the T„, the temperature at which the melting ends, reiuaiiis essentially the same and Tnm. the peak melting temperature, decreases as the amount of ethylene in the copolymer is increased. An additional feature of such polymers is that the skewness of the TREF curve IS generally greater than -i.6U, more pi^ferably greater than -1,00. The determination of crystallizable sequence length distribution in a copolymer can be measured by the technique oF temperature-rising elution fractionation (TT?£F), as disclosed by L, Wild, et al.. Journal of Polvmer Science: Polymer. Physics Ed.. 20,441 (1982), Hazlitt. Jour^o/ The vaiue, T™,, is defined as the temperature of the largsst weight fraction eluting between 50 and 90 "C in the TREF curve. T, and w, are the elution ^empe^atu^s and weight fraction respectively of an arbitrary, i* fraction in the TREF disiribuiion. The distributions are normaiized (the sutn of the w, equals 100 percent) w\{h respect to the lota! area of thccur'vc L^luimg above 30 °C. Thus, the index reflects only the propenies of the crystallized polymer and any influence due to uncrystallized polymer (polymer still in solution at or belou/ 30 "O is omitted from tne calculation. Certain of the jjolymers according to the invention having a relatively broad mehing point on the DSC curve desirably are characterized by a skewness indfc!( greater than -1.6, more preferably greater than -1.2. Polymer tacticity, propylene content, regio-eirors and other properties aredelerminsd by standard NMR techniques, Tacticilies (uini) or (rr) are calculated based oi\ meso- or regio-triads, and may be expressed as ratios less than one or as percents. Propylene isotacticity at the triad level ("mm; 1^ deterrrtinsd from the integrals of the mm triad ("22 ^0-2' 29. ppm\. -.hs r-ir :.r;2J !'2! 2^-20.67 ppm; £-^d tiis r- :riad (2'j 61-] 9.^^]. The mm iftotac'.ir;!; ■; z-ji^-.rr'.r.^c ':>. : ■. 'J.ns :r; I'l'e'?'; vf the mm triad by the sum of the mm, mr, and rr triads. For ethyleric coniaining ■rte-pr-l; mer? th;-, mr region is corrected by subtracting the 37.5-39 ppm peak integral. For copolymers with other monomers that produce peak.-i in the regions of the mm, mw, and rr ti-iads, the integral^ for ^bese regions are simiiarly corrected by subtracting the Eniensiry of the interfering peak using s[ar)dard NMR techniques, once the peaks have been identified. This can be accomplished, for example, by analysis of a .series of copolymers of various levels of monomer incorporation, by literature assignments, by isotopic labeling, or other means which are known in the art. Specific Embodiments The following specific embodiments of the invention and combinations thereof are especially desirable and hereby delineated in order to provide detailed disclosure for the appended claims. I. A metal complex corresponding to the formula: quenched with 200 mL of water. The contents of the reactor are then transferred to a 1L separatory funnel and extracted with 4x50 tnL of ethyl acetate. The organic layers are combined and the solvent removed in vacuo. The product is redissolvcd in methylene chloride and extracted with a NaOH aqueous solution to remove phenolic byproducts. The organic layer is then dried over MgSOa to give a yellow sotutioti. The solvent is removed in vacuo to give 50.06 g of 3-pinacolate boronato-2-ethylbenzofuran as a pale yellow liquid (yield: 82.2 percent, purity by GC/MS: 96 percent). c) To a dry. N; purged, 500 mL three neck flask equipped with a stir bar is added 200 mL of dry diethyl ether and 4-bromo-N-mechy!imidazole {50.0 g. 311 mmo!). The flask is then cooled to -10 °C with an acetone/ ice bath. A 2.0 M heptane/ THF/ eihylbenzene solution of lithium diisopropylamide (171 mL, 342 mmol) is then added via syringe while maintaining the reaction temperature at 0 "C or lower. After 1 hour, dimethylformamlde (DMF) (36.1 mL, 466 mmol) is added dropwise over 5 minutes. The reaction mixture is allowed to stir for 45 minutes at or below 5 "C and then quenched with a saturated aqueous solution of citric acid. The resulting mixture is stirred vigorously until the two phases separate. The organic layer is recovered and washed (3x200 mL) with water. The solvent is removed in vacuo to give the desired product, 2-formyI-4-bromo- (! iN-methy'imidazole, as a ^rown cn'sialhrpe solid (yield: 55.7 g, 95 percent. s6 perccnl piiritv bv GC'l. AddiLiondi purincaiiorj may ht achieved by eiulion ihrough aium.ina uiir.i mt'-ii'lsnc chloride solvent. d) 3-pinacolaie boronato-2-etliyibenzofuran (6 1,6 g, 226 minul), Na;CO-. I40,0 g, 37S mmol) and 2-formyl-4-bromo-{l)N-meihylimida2ole i2S.4 g. 151 mmoVi are added to a 5L flask equipped with mechanical stirring containing a solution of degassed water (600 mL) and dimethyl ether (60O tnL). Inside of a dry box, 1,41 gof tetrakistriphenylphosphine-palladiumCOJ is di.'^solved in 40 mL of anhydrous degassed toluene. The toluene Pd solution is removed from the dry box: and charged into the reactor via syringe under a blanket of N;. The biphasic solution is vigorously stirred and healed to 73 °C for 14 hours. On cooling to ambient temperature, the organic phase is separated. The aqueous layer is washed twice with 150 mL of ethy! acetate. All organic phases are combined and the solvent removed in vacuo to give an oil. Recrysiallization from hexane gives the product. 4-(2-ethylbenzofuran-3-yl)-2-formyl-(l>N-methylimidazole, as a brown solid (yield: 25.6 g. 66.8 percent). e) A dry, 250 mL ! -neck round bottom flask is charged with a wluttfin yf (5"?.9 g. 236 mmol) 4-(2-ethylbenzofuran)-2-formyl-(l)-N-methylimidazole and 2,6-diisopropylaniiine (4!.S g, 236 mmot) in 50 nriL of anhydrous toluene. A catalytic amount (10 mg) of p-(oluenesu!fonic acid is added to the reaction flask. The reactor is equipped with a Dean Stark trap with a condenser and a thermocouple well. The mixture is heated to I 10 "C under N^ for 12 hours. The solvent is then toluene. To this solution is added 0.35 mmol of solid HfCU. The flask is Filted with art air-cooiea reflux condenser and the mixture heated at reflux for 4 hours. After cooling, 1.23 mmol of BuMgCI (3-5 equivalents, 2.0 M solution in diethyl ether) is added by syringe and tlie resulting mixture Stirred overnight at ambient temperature. Solvent (lolcenc and diethyl ether) is removed from the reaction mixture by vacuum. Hexane (30 mL) is added to the residue, then removed by filtration, and the solids washed again with additional hexane (30 mL). The white glassy solid product is recovered from the combined hexane extracts and converted to the dibutyl derivative by heaimg in benzene solution at 50 "C overnight. The solubility of the complex in methylcyclohexane measured at 20 °C is greater than 5 percent. 'H NMR(C6D6): 5 7.6! (d. J = 8 Hi. IH>, 7,43{d, J ^8 Hz, IH), 7 25-7.05 (muliiplets, 7H). 6.94 (dd. J = 2. 7 Hz:. IH), 6.22 (s, IH), 5.84 (s. IH). 3.96 (septet. J =7 Hz, JH). 3-75 (septet. J = 7 Hz. IH), 3.59(.septet, J = 7Hz, IH), 2.S6 (multiplets. 3H). 2.26 (s. 3H). 2.0-1.15 (multipleis, alkyl chain methylene protons), 1.55 (d, J = 7 Hz, 3H). 1.51 (d, J = 7 Hz, 3H), 1 41 (t.J - 7 Hz. 3H). l.02(d.J = 7Hz, 3H),0.91 (l, J = 7 Hz. 9H), 0.75 (d, J =7 Hz. 3H), 0.72 (d, J = 7 Hz, 3HI, 0.71 (d. J = 7 Hz, 3H). 0.52 (d, J = 7 Hz. 3H), 0.27 (d. J = 7 Hz, 3H). Tbe meti! ccrnplex may be cor."erted '.o rh-; or:ho-m;-r?,i\|.'!!ed dibu"-': ■.'■:-r".-'^i'^: T; hc-zj'-iig in toluene soluiion £[ 30 "C overnight. Batch Reactor Propylene Homopolymerizations Polymerizations are conducted in a computer controlled, stirred, jacketed I S L siainlei;? steel autoclave solution batch reactor. The bottom of the reactor is fitted with a large orifice botfom discharge valve, which empties the reactor contents into a 6 L siainles; ste^l conii:iner Th^ container is vented to a 30 gal. blowdown tank, with both the container and the tank are purged with nitrogen. .-Mi chemicals used for polymerization or catalyst makeup are run through purification columns, to remove any impurities. Propylene and solvents are passed through 2 columns, the first containing alumina, the second containing a purifying reactant (Q5''^ available from Englehardt Corporation). Nitrogen and hydrogen gases are passed through a single column conlaining Q5^" reactant. The autoclave is cooled to 50 "C before loading. It is charged with 667 g mixed alkanes, hydrogen (using a calibrated 50 mL shot tank and a differential pressure in the shot lank of 0.4!MPa). followed by 286g of propylene using a micro-motior flowmeter. The reactor is then brought to 90 "C before addition of catalyst composition. " The metal complex (catalyst) is employed as a 0.20 mM solution in toluene (run I), as 75.0 mg dissolved in 675 mg methylcyclohexane (run 2), or as 75.0 mg dissolved in a mixture of 659 mg CLAIMS: I with the proviso that the metat complex has a methylcyclohexane solubility at 20 °C (plus or minus I °C) of at least 5 percent. compound corresponding to the formula: 20, A process for preparing a stable 2-substituied ben2ofuran-3->i borate esier corresponding to ihe formula:

Full Text

HAFNIUM COMPLEXES OF HETEROCYCLIC ORGANIC LIGANDS
CROSS REFERENCF. STATEMENT
This applicarion claims the benefit of U.S. Provisional Applications 60/798,108, filed May 5, 2006.
BACKGROUND OF THE INVENTION
This invention is directed to certain hafnium complexes, to catalyst compositions comprising the same, and io iiddilion polymsrizaiiun processes, especially olcHp polymeriiation processes, using such hafnium complexes as one component of a coordination p jiymerizaiton catalyst composition.
Advances in polymerization and catalysis have resulted in the capability to produce many new polymers having improved physical and chemical properties, useful in a ivide variety of superior products and applications. With the development of new catalysts the choice of

Additionally, according to the present invention there is provided a calaiys! composition comprising one or fTiore of (he foregoing hafnium compiexes of formula 11) and a.n aciivaung cocatalysi capable of convening sdid metal complex into an active catalyst for addition polymerization. Additional components of such catalyst composition may include a carrier or support, a liquid solvent or diluent, a tertiary component such as a scavenger or secondary activator, and/or one or more additives or adjuvants such as processing aids, iiequestranis, chain transfer agents, and/or chain shuttling agents.
In addition, the present invention provides an addition polymerization process, especially an oiefm polymerization process, wherein one or more addition polymerizable monomers are polymerized in the presence of the foregoing catalyst composition, including the preferred and more preferred embodiments thereof, to form a high molecular weight polymer. Preferred polymerization processes are soltition polymerizations, most preferably solution processes wherein ethylene, propylene, mixtures of ethylene and propylene, or mixtures of ethylene and/or propylene with one or more C4.20 olefins or diolefins are polymenzed or copolymerized. Desirably, the processes are capable of operation at high polymerization temperatures to prepare polymers having desirable physical propertie;..
Highly desirably, the present invention pro "-'ides a process wherein oflc or more addition poKmeriz^ble monomfcr> arr potvmerized at a rclativeiv h.sX) r-civrnerizaticr, ierrrr-sriiiuri in ;lis presence of the forego ins; c.-itjlys.! composinoii '0 form a his!^ n'o'ecolar weiglu r^c!ic poi vmf. especially a polynner that is isotaciic or highly isotactic. with improved operating efriciency and the u.se of non-aromatic solvents. Additionally the present inventors have discovered improved techniques for synthesizing high purity formylimidazoles, a new class cf stable borate esters of alkyIbenzofurans. and high purity bromoalkylbenzofurans.
The metal complexes arid catalysts of the invention mav be used alone or combined with other metal complexes or catalyst compositions and the polymerization process may be used in scries or in parallel with one or more other polymerization processes. Suitable additional polymerization catalyst compositions for use in combination with the metal complexes of the present invention include conventional Ziegler-Natta-type transition metal polymerization catalysis as well a^ Ji-bonded transition metal cofnpounds such as meiallocene-iype caspl.vsis, constrained geometry or other transition metal complexes, including other donor ligand complexes.
The metal complexes of the invention are preferred for use as components of olefin polymerization catalysts because they are capable of producing polymers at higher reactor temperatures while utilizing aliphatic or cycloaliphatic hydrocarbon solvents to convey them inio the reactor. An additional advantage of the present invention is the ability to prepare the metal complexes in extremely high purity and consequeni high activity due to nearly complete removal of

meial salts, especially magnesium salt by-products from the syiitSiesis. through iriiuraiion or washing with aliphatic hydrocartxins. Another advantage is the ability in prepare propylene homopolymers or propylene/ethylene inierpolymers containing 6.5 percent or more polymerized propylene moieiies while retaining relatively high isotacticity, Tne polymers and copolymers of the invention possess improved toughness, making them well suited for use in injection molding applications as well as for use in preparing fibers, especially by means of mett-blown or extrusion spinning processes. Moreover, the polymers are usefully employed in adhesive formulations or in multi-layer films and laminates demonstrating improved compatibility and adhesion to polyethylene substrates, layers or films.
DETAILED DESCRIPTION OF THE INVENTION
All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Pres.s. Inc., 2003. Unless stated to the contrary, clear from the context, orconventiona! in the art. all parts and percentsare ha.sed on wajgfii. .Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC syssstn for numbering groups.
The ierm "comprising" and dcrivati\es thereof ii The term "heiero" or "hetero-atom" refers to a non-carbon atom, especially Si, B, N. P, S, or O. "Heieroaryl", "heieroalkyl", "heterocycloalky!" and "heteroaralkyl" refer to aryl, alky!, cycloalkyl, or aralkyi groups respectively, in which at least one carbon atom is replaced by a heteroatom. "Inertly substituted" refers to substituents on a ligand that neither destroy uperability of the invention nor the iigand's identity. For example, an alkoxy group is not a substituted alkyi group Preferred inert substituents are halo, di(C|.e hydrocarbyOatnino. Ci^ hydrocarbyleneamino, C|.6 halohydrocarbyl, and tri(C,^ hydrocarhyl)si)yl. The term "'alkyl' is usc^i to signify a monovalent hydrocarbyl ligand of the formula, CnH2„+i. The term "alkylation" refers to a chemical process by which an alkyi or substituted alkyl group is incorporated into an organic or organometallic compound. The term "polymer", as used herein, includes both homopolymers, that

than 0.95. Measurement of isotactic triads by the foregoing technique is known in ihe art and previously disclosed m USP 5,504, [72, WO 00/01745 and elsewhere.
The previously descrilaed nieial complexes according to the inveiiuoii are typically activated in various ways to yield catalyst compounds having a vacant coordination site that wiii coordinate, insert, and polymerize addition polymerizabie monomers, especially olefin(s). For the purposes of this patent specification and appended claims, the term "activator" or "cocaialysi" is defined to he any compound or component or method which can activare any of the catalyst compounds of the invention as described above. Non-limiting examples of suitable activators include Lewis acids, non-coordinating ionic activators, ionizing activators, organome'.al compounds, and combinations of the foregoing substances thai can convert a neutral catalyst compound to a catalyticaliy active species.
It is believed, without desiring lo be bound by such belief, thai in utie ^i.ibodiment of the invention, catalyst aclivaiion may involve formation of a cationic, partially cationic. or zwittenonic species, by means of proton transfer, oxidation, or other suitable activation process. It is to be understood that the present iiiverilioti is operable and fully enabled regardless of whether or not such an identifiable cationic, partially cationic, or zwitterionic species actually results during the ac'.ivation process. GISO interchat^geably referred to herein as an "'ionization" Drocess ov "'ionic
One suitable, class of organometal activators or cocat2i>.^ts arc alum:..-,ane.';. also rcfcrrea to as alkylaluminoxanes. Alumosanes are well known activators for use with metallocene type catalyst compounds to prepare addition polymerization catalysts. There are a variety of methods for preparing aiumoxanes and modified alumoxanes. non-iimiting examples of which are described in U.S. Patents 4,665,208.4,952,540, 5,091,352. 5,206,199. 5,2a4.J 19, 4,S74,7.«. 4.924. 01S. 4,908,463, 4.968,827, 5,308,815, 5,329,032, .T,248,S0I. 5,235,081, 5. 157.137. 5.103 .'.13 I, 5,391.793.5,391,529, 5,693.838. 5,731,253, 5,731,45! 5.744,656; European publications EP-.^-561476, EP-A-279586 and EP-A-594218; and PCT publication WO 94/'10180. Preferred alumoxanes arc tri(Cj.6)a'l^yl^'Li'Tfitnum modified methyialumoxane, especially tri(isobulyl)aluminum modified methalumoxane, available commercially as MMA0-3A or tri(n-octyl)aluminum modified methalumoxane. available commercially as MMAO-12, from Akza Nobel, Inc.
!t is within the scope of this invention lo use alumoKane(s) or modified alumo)tane(s) as an activator or as a tertiary component in the invented proce.s.s. That i.s, the compound may be used aione or in combination with other activators, neutral or ionic, such as tri(alkyl)ammonium tetrak.i£(pentanuorophenyl)borate compounds, trisperfluoroaryl compounds, po!yhalogenated hctcroborane anions (WO 98/43983). and combinations thereof When used as a tertiary

component, the amounl of alumoxane employed is generally less than tha: noccs^ary to sffectively activate the metal complex when employed alone. In this embodtmsnt, It is believed, without wishing to be bound by such belief, ihai ihe alumoxane does not conmbufe significanily to actual catalyst aciivaiion. Not withstanding the foregoing, it is to be understood that some paaicipafion of the alumoxane in the activation process is not necessarily excluded.
Ionizing cocatalysts may contain an active proton, or some other cation associaled with, but not coordinated to or only loosely coordinated to, an anion of the ionizing compound. Such compounds are described in European publications EP-A-570982, EP-A-520732. EP-A~495375, EP-A-500944, EP-A-277 003 and EP-A-277004, and U.S. Patents: 5.153,157. 5,198 401.5,066,74!, 5,206,]97, 5,241,025, 5.384.299 and 5,502,124. Preferred aniong ihe foregoing activators are ammoniLim cation containing salts, especially ihose containing irihydrocarbyl- ssibsiiiuied ammonium caiions containing one or two C,{>jo aikyl grotips, especially methylbis(ocladecyl>ammoniam- and methylbis(tetradecyl)-ammonium- cations and a non-coordinatmg anion, especially a ietrakis(perfluoro>arylborate anion, especiallv ietrakis(pent;afluorophenyl>borate. It is further understood that the cation may comprise a mixture

letrakisCpentarlEiorophenyiiborate.
Activation methods using ionizing ionic corr.poiinds not containing an a.live proicri. but capable of forming active carajvst compositions, such as ferrocenium saits of the ioregoing non-coordinating anions are also contemplated for use herein, and are described in EP-A--i26637. EP-A-573403 and U.S. Patent 5.387.568.
A class of cocatalysts comprising non-coordinating anions genericall> referred to as expanded anions, further disclosed in U. S. Patent 6.395,67 i, may be suitably employecj to activate the metai complexes of Ihe present invention for olefin polymerization. Generally, these cocatalysts (illustrated by those having imidazolide, substituted imidazolide. imidazoiinide, substituted imidazolinide. benzimidazoiide. or substituted benzimidazoHde anions) may be depicted as follows:

as organic ether, polyeiher. amine, and poiyamme compounds, rvlony of the Toregoing compounds and their use in polymerizations is disclosed in U. S. Patents 5, 7 12,352 and 5,763,543. and in WO 96/08520. Preferred eitamples of the foregoing leniary components include Irialkylaluminum compounds, dialkylaluminum aryloxideb, alkylaiuminum diaryloxides. dialkylalummum amides, alkylaluminum diamides, dialkyialuminum triChydrocarbylsilyDamides, alkylaiuminum bis(iri(hydrocarbylsiiyl)amides>, alumoxanes, and modified aiumoxanes. Highly preferred tertiary components are alumoxanes, modified alumoxanes, or compounds corresponding to the formula R'-Al(OR^) or R%Al(NR^j> wherein R"^ is d.^o alkyt, R' independently each occurrence is O^jo aryl, preferably phenyl or2,6-di-t-butyM-methyIphenyl. and R^ is Cu alky! or tri(Cualkyl}si!yl, preferably trimethylsilyl. Most highly preferred tertiary components include methylalumoxane, trifisobutylaluminum)- rriodified methylalumoxane, di(n-oclyl)atuminum 2,6- Another example of a suitable tertiary component is a hydroxycarbc^yiate metal salt, by which is mean! any hydroxy-substituted. mono-, di- or tri-carbosyiic acid salt wherein the metal poaion is a caiionic derivative of a metal from Groups 1-13 of the Periodic Table of Eiemenis. This compound may be used to improve polymer morphology especially in a gas phase poiymentanon Non- limiting examples include saturated, unsaturated, aliphatic, aromatic or saruraied c>'clic, syb;titured carboxylic acid ?."i!ts where the carboxviate l^sand h:i£ from o:>e ec trirce r, .-QYOX-. substiluents and frorr; ! io 24 carbon atoms. Exaniples include hydroxvacetaie, hydrc-.vpropionate, hydroxybutyraie, hydroxyvalcrate, hydroxypivalate, hydroxycaproale, hydroxycapryiaie, hydrOAvheptanaie, hydroxypelargonafe. hydroxyundecanoaie, hydroAyoJeate. hydroAyocioaie, hydroxyalmitate, hydroxymyristate, hydroxymargarate, hydroxyscearate, hydroxyarachaie and hydroxytercosanoaie. Nor- limiting examples of the metal ponion includes a metal seiecied from the group consisting of Al, Mg, Ca. Sr, Sn,Ti. V, Ba, Zn.Cd, Hg, Mn, Fe. Co, Ni. Pd, 1.; .ind Na. Preferred metal salts are zinc salts.
In one embodiment, the hydroxycarboxylate metal salt is represented by the following general formula:
M(Q).(OOCR)j,. where
M is a metai from Groups 1 lo 16 and the Lanthanide and Actinide series, preferably from Groups I to 7 and 12 to 16. more preferably from Groups 3 lo 7 and 12 to 14, even more preferably Group 12, and most preferably Zn;
Q is halogen, hydrogen, hydroxide, or an alkyl, alkoxy. aryloxy. siioxy. siiane, sulfonate or siloxane group of up lo 20 atoms not counting hydrogen;
R is a hydrocarbyl radical having from 1 to 50 carbon atoms, preferably I to 20 carbon atoms, and optionally substituted with one or more hydroxy, alkoxy, N,N-dihydrocarbylamino, or

nitrides, and halides. Other cajtiers include resinous support maieriais such as fiaiysijrene. a funciionafized or crosslinked organic supports, such as polystyrene divinyl btinzcnL: polyoieftns or polymeric compounds, or any other organic or inorganic support material, or mixtures thereof.
The preferred carriers are inorganic oxides that include those Group 2. ?, 4, 5, 13 or I-metai oxides. The preferred suppjorts include silica, alumina, silica-alumina, silicon carbide, boron nitride, and mixtures thereof. Other useful supports include trwgnesia, ticania, zirconia, and clays. Also, combinations ofthese .';upporl materials may bs used, for example, silica-chromium and silica-titania.
It is preferred that the carrier has a surface area in the range of from 10 to 700 mVg. pore volume in the range of from 0.1 lo 4.0 cc/g and average particle .size in the rangt of from 10 to 500 p.m. More preferably, the surface area of the carrier is in the range of from 50 to 5O0 m'/g, pore volume of from 0.5 to 3.5 cc/g, and average particle si7.e of from 20 to 200 jjjn, Mosi preferably the surface area of the carrier is in the range of from !00 lo 400 m'^/5, pore volume from O.S 10 3 0 cc/'g and average particle size is from 20 to 100 (im. The average pore size of a carrier of the invention is typically in the range of from 1 lo 100 nm. preferably 5 to 50 nm, and most preferably 7.5 to 35 nm.
Exampies of suppored catalyst compcsiiions s\iiiably eiTioloyed ;n t.ie prejcn! ;r:^-:t','.ion tire Jftvjrib^d in U S, Paiinis. ~~0].i:-,:., ;.SJ£, 561, 4.911.':!::. ^SZ5.--,1 - J"'., "■ 5 '^"'- 22= 5,238,812, 5,240,894. 5.332 70fi, 5,346,925, 5,422,325. 5.466.6^9. 5,46'j.7(;6 ' 468.7^2. 5.529,965, 5,554,704, 5.629,25: Examples of techniques for supporting conventiorial-type cataly.st coiripo^itions liiai may also be employed in the present invention arc described in u. S. Patents 4.894,424, 4,376,062, 4,395.359, 4,379.759, 4,405,495 4,540758 and 5,096,869. It is contemplated that the catalyst compounds of the invention may be deposited on the same support together with an activator, or that the activator may be used in an unsupported form, or deposited on a suppon different from the supported calaly.st compounds af the invention, or any combination thereof.
There are various other methods in Ihe art for supponing a polymerization catalyst compound or catalyst compositions suitable for use in the present invention. For example, the catalyst compound of the invention may contain a polymer bound ligand as described in USP 5,473,202 and USP 5,770,755. The support used with the catalyst compositrt-n ^f (he invention may be functionalized as described in European publication EP-A-802 203. At least one substituenl or leaving group of the catalyst may be selected as described in USP 5,688.880. The supported catalyst composition may include a surface modifier as describt;d in WO 96/11960.

A preferred method for producing a supported catalyst composition iiccording ic^ the invention is descinbed in PCT publications WO 96/00245 and WO 96/00243, In this prefeired method, the catalyst compound and activators are combined in separate liquids. The liquids may be any compaiible solvent or other liquid capable of forming a solaiion or slurry with the catalyst compounds and/or activator. In the most preferred embodiment the liquids art l.ie same linear or cyclic aliphatic or aromatic hydrocarixin, most preferably hesane or loluene. The catalyst compound and activator mixtures or solutions are mixed together and optionallv added to s porous support or, alternatively, the porous support is added to the respective mixtures. The resulting supported composition may be dried lo remove diluent, if desired, or utilized separately or in combination in a polyme-rizaiion. Highly desirably the total volume of the catalyst compound solution and the activator solution or the mixtures thereof is (ess than five times the pore volume of the porous support, more preferably less than four times, even more preferably less than three lin^s; with most prefer ranges being from 1,1 times to 3,5 limes the pore volume of the support.
The cataly!;t composition of the present invention may also be spray dried using techniques as described in USP 5,648.310, to produce a porous, particulate solid, optionallv containing structural reinforcing agents, such as certain silica or alumina compounds, especially fjmed silica, in these compositions the silica acts as :i thixoiropic agent fcr dr.ciet rcT:Ti2",'On ,'!nd -.ii.n| j;.^ well 11$ a r^mfo^cir^ ii"-'^'^', 'r the resui!^i^ si^^^^'-dried '^iirtfcle^.
P.'occdures fi'-r measuring the totiii pore "^ oJ'jins :■:" 2 por"Lis Tiater'ii are ■■■.e/ ■:_■".:■■ r. ■■' '.hi an. The preferred procedure is BET nitrogen absorption .A.notber suitable method well Known in the an is described in Innes. Total Porosity and Panicle Density of Fluid Catalysts By Liquid Titration, Analytical Chemistry, f 1956) 2S, 332-334.
It IS fiirther contemplated by the in\'ention that other catalysts can be combined with the catalyst compounds of the invention. Examples of siich other cats!yits are disclosed m U.S. Patents 4,937,299, 4,935,474, 5,281,679, 5,359.015. 5.470,81 1, 5,719,241, 4.159.965. 4.325,837, 4,701.432, 5.124,418, 5,077.255. 5,183,867. 5.391,660, 5,355.810. 5,691,264, 5,723. 399 and 5,767,031; and PCT Publication WO 96/23010. In particular, the compounds that may be combined with the rr^tai complexes of the invention to produce mixtures of polymers in one embodiment of the invention include conventional Ziegler-Nalta transition metai compounds a^ well as coordination complexes, including transition metal complexes.
Conventional Ziegler-Natta transition metal compounds include the well known magnesium dichloride supported compound^;, vanadium compounds, and chromium catalysts (also known as "Phillips type catalysts"). Examples of these catalysts are discu.ssed in U.S. Patents 4.115,639, 4,077,904 4,482,687,4,564,605, 4.721.763. 4.879.359 and 4.960,741. Suitable transition metal complexes that may be used in the present invention include transition metal compounds from

Groups 3 to 8. preferably Group 4 of the Periodic Table of Elements containrng men hgund groups and capable of activation by contact with a cocataiyst.
SuLtable Ziegler-Natta catalyst compounds include alkoxy, phenos>. bromidt;, chloride aiuf fluoride derivatives of the foregoing metals, especially titanium. Preferred 11 tan itim compounds include TiCti , TiBr,, Ti{OC2H5)3CI, Ti(OC2H5)Cb, Ti(OC4H9>3CI, Ti Non-limiting examples of vanadium catalyst compounds include vanadyl tnhaJide, alkoxy halides and atkoxides such as VOCb. VOCh(OBu) where Bu is butyl and VOfOCjHs);; vanadium letra-halide and vanadium alkoxy halides such as VCU and VCl-,(OBu); vanadium and vanadyl acetyl acetonaies and chloroacetyl acetonates such as V(AcAc)3 and VOCIjCAcAc) where (AcAc) is an aceiyl acetonale.
Conventional-type chromium catalyst compounds suitable for use in the present inventior include CrOj , chromocerie, silyl chromate, chromyl chloride ICrO^CU), chromium-2-ethyi-hexanoate, and chromium acetylacetonate fCr(AcAc)T)- Non-itmitmg example? a.^'e disclosed in U.S. Pal. Nos, 2,285.721. 5,242,099 and ?,231.550.
Sti!! '^thsr ccn'er:t:c na'i-tvpe transiTrcn metz] ■catalv-! ^r.rrD-'iund^ 'LI:I.5I;.I? 'C 'i^e in !hr-present invention are dtsclo,'-;ed in U.S. Pat. Nos. 4,124,532. J.302,565. 4,302.566 i^r-.d 5.76?,723 and EP-.A^I68I5 and EP-.A.-420436,
Cocatalysi compounds for use with the above conventional-type catalyst compounds are typically organometallic derivatives of metals of Groups i,2, 12or 13, Non-iimiting examples include meihylliihium, bulyliiihium, dihexylmercury. butylmagnesium. dierhytcadmium, betizylpoiassium, dielhvlzinc. iri-n-btilylaluminum, diisobuivl e'h> Iboron. dieihylcadrnjum. di-n-bulylzinc and tri-n-a my Iboron, and, in particular, aluminum trialkyl compounds, such as tn-hexylaluminum, triethylaluminitm, trimeihylaluminum, and triisobutylaluminum. Other suitable cocatalyst compounds include mono-organohalides and hydrides of Group 13 metals, and mono- or di'Organohal ides and hydrides of Group 13 metals. Non-limiting examples of such conveniional-type cocatalyst compounds include di-isobutylalumintim bromide, isobutylboron Oichloride, methyl magnesium chloride, ethylberyliium chloride, ethylcalcium bromide, di-isobuiylaluminum hydride, methylcadmlum hydride, diethyiboron hydride, hexyiberyllium hydride, dipropylbornn hydride, octylmagnesium hydride, butylzinc hydride, dichioroboron hydride, dibromoaluminum hydride and bromocadmium hydride. Conventional-type organometal lie cocatalyst compounds are known to those in the an and a more complete discussion of these compounds may be found in U. S. Patents 3.221,002 and 5.093,415.

in the foregoing formulas, the supportive suhsdtuent formed by Q', V and Z' i-; a uncharged polydentate ligand exeriing electronic effects due to its high polarizabiliiy, similar to the cydopeniacJienyf ligand. In (he mosi referred embodtmefif^ of this ini'enKoft, ihv dssiionaiutad carbamates and the hydroxycarboxylates are employed. Non-limiting examples of these catalyst compounds include indenyl zirconium in'ifdiethy I carbamate), indenyl zirconium lris(trimethyiacetalej. indenyl zirconium tris(p-roiuale), mdenyl zirconium tris(h!;n7.oate), (1-methyiindenyl)zirconium iris(trimethylacetate), Q-methyiindenyl) zirconium
tris(diethylcarbamate), !n anotherembodiment of the invention the additional catalysi compounds are those nitrogen containing heterocyclic ligand complexes, based on bidentate Hgands containing pyridine or quinoiine moieties, such as those described in WO 96/33202. WO 99/014S-;, WO 98/42664 and U. S. Patent 5,637,660.
It "i within the ^cooi of ^hls in^^.n:ion. m or.e ?rnhodiine:;'. that c.-a.,!^'- .', ~::-~:\-:\. rA
.>.■_. r-, , T, ._>K:.
Catalysis forPoUrnerizatioi! of Eth>lene and a-Olefins'. J..^.C.$. (1995) H", 641^-64 if and Johnson, et al., "Copolymerization of Ethylene and Propylene with Functionalized Vmyl Monomers by Pa]Iadium(II)Ca!a()Sfs".J,AC£, (1996) ) (8, 267-268. and WO 96^23010, msy be combined with the present metal complexes for use in the process of the invention. These complaxe.'; can be either djalkyl ether adducLs. or alkylated reaction products of the described dih.i:'.]ds complexes that can be activated to a cationic state by the conventional-type cocataly.ci; or ;he activ^icrs of this invention described below.
Additional suitable catalyst compounds for use in the foregoing mixed catalyst compositions are diimine based ligands containing Group 8 to 10 meial compounds disclosed in PCT publications WO 96/23010 and WO 97/48735 and Gibson, et al., Chem. Comm.. {19981 849-850-
Other catalysts are those Group 5 and 6 metal imido complexes described in EP-A-0 816 3S4 and U, S. Patent 5,851,945. In addition, catalysts include bridged bisCar>'lamido) Group 4 compounds described by D, H. IMcConville, et a!.. Orsanometallics (1995) 14. 5478-5480. Other catalysts are described as bis(hydroxy aromatic nitrogen ligands) in U. S. Patent 5,852,146, Other metailocene-type catalysis containing one or more Group 15 atoms include those described in WO

98/4665 1. Still another metallocene-type catalysts include those mullinuclear caiaiyst? as described in WO 99/20665.
It is contemplated in some emfaodimenis, that ih& catalyst compounds employees in addition to those of [he invention described above may be asymmetrically substituted in temij of additional subslituenls or type^ of substiiuents, and/or unbalanced in terms of the number of additional substituents on the 7t-bonded ligand groups, it i,s also contempiaied that such addiiional catalysts may include their siruciural or optical or enantiomeric isomers (msso and racemic isoniersi and mixtures thereof, or they may be chiral and/or a bridged catalyst compounds.
in one embodiment of the invention, one or more olefins, preferably one or more C;,>u olefins, preferably ethylene and/or propylene are prepolymerized in the presence of the catalyst composition prior to the main polymerization. The prepolymeri^aiion can be cairicd out balchwise or continuously in gas, solution or slurry phase including at elevated pressures. The prepolymerization can take place with any olefin monomer or combination and/or in the presence of any molecular weight controlling agent such as hydrogen. For examples of prepoiymer;za:ion procedures, see U. S. Patents 4,748,221, 4.7g9,359, 4,923,S.^3, 4,92 [.§25, 5,283.278 and 5,705,578. European publication EP-A-279863. and PCT Publication WO 9'7i4^3~ 1. A prepolymerized catalvsi composition for purr'Oses of this patent ^peciftc.ition and 5D:x;ndcd claims prsfc-ibl'. i > a supported ciLalvsi svitem.
Thfc nteihod for making tht caialysi com;:'OK;'i.ion generally iri'T.lw.s the i:o:i"ib!n,:!;. contacting, blending, and/or mixing of the respective catalys; con-jponents, opiionaily in ihc presence of the monomer or monomers to be polymerized, fdeal'y. ihe contacting is conducted under men conditions or under poiymerizaiion conditions at a lemperalure in the range of frcirri 0 to 200 ""C, more preferably from 15 to !90 'C. and preferably a; pressures from arnbi^ni (6l.t0 [;Fa) to 1000 psig (7 MPa). The contacting is desirably performed under an inert ga.sgors atrr,ospriere, such as nitrogen, however, it is also contemplated that the combination may be performed in the presence of olenn(s), solvents, and hydrogen.
.Mixing techniques and equipment contemplated for use in the method of the invention are well known. Mixing techniques tnay involve any mechanical mixing means, for example shaking, stirring, tumbling, and rolling. Another technique contemplated involves the use of fluidization, for example in a fluid bed reactor vessel where circulated gases provide the mixing.
For SLipponed catalyst compositions, the catalyst composition is substantially dried and/or free flowing. In a preferred embodiment, the various components are contacted in a rotary mixer, tumble mixer, or in a fiuidized bed mixing process, imder a nitrogen atmosphere, and any iiquid diluent is subsequently removed.

Suitable addition polymerization processes wherein the present catalyst somposnion; may be employed include solution, gas phase, slurry phase, high pressure, or combinations thereof. Particularly preferred is a solution or slurry polymerization of one or more olefins ar least one of which is ethylene, 4-iTiethyl-S-penleiie, or propylene. The invention is particularly well suited to processes wherein propylene, 1-butene, or 4-methyl-I-pentene is homopoiymsrized. ethylene and propylene are copolymerized. or ethylene, propylene, or a mixture thereof is copolymeri7£d with one or more monomers selected from the group consisting of 1-octsne, 4-methyl-l-pentene, buiadiene, norbomene, ethylidenenorbomene, 1.4-hexadiene, I.S-hesadiene, tiorbomadiene, and 1-buiene. The homopolymers of butene-1 and 4'methyl-i-pentene and copolymers therei^f, especially with ethylene or propylene arc desirably highly isotactic.
Other monomers useful in the process of the inveniion include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, pofyenes, vinyl monomers and cyclic olefins. Non-limiting monomers useful in the invention include norbomene, isobutylene, vmylbenzo^yclobutane, styrenss, aikyl substicjied styretie, ethyiidene norbomene, isoprene. 1-pentene, dicyclopentadiene and cyciopentene.
Typical ly, in a gas phase polymerization process a continuous cycle is employfcci where m one part of the cycle of a reactor system, a cycling gas stream, oiher^ise tcnc.'.'n us a reeve le stream or tluid]Z,jn£ rriedium. is hiat^d in the reactor bv the heal of ooi- ^Tierii'atiO!' 1 rrj heiit ;^^ r&:~'7i-ed from the recycle composition in another part of the eye's by a cooling s;-siem tucrrial i.o the reactor. Generally, in a gas fiuidizcd bed process for producing polymers, a gaseous stream containing one or more monomers is continuously cycled ihroueh a fluidiT-^d bed m the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back mto the reactor Simultaneously, polymer product is ".nhdrawT from the reac'or and fresh monor:ier is added to replace the poKmerized monomer, f^xa—ipies Df ?uch proce^'Si's are disclosed in U. S. Patents 4,543,399. 4,588,790. 5,028,670, 5,3 I 7,0.36, 5,352.749. 5405,922, 5,436.304, 5. 453.471. 5.462.999. 5.616.661 and 5,668,228.
The reactor pressure in a gas phase process may vary from 100 psig (7O0 kPa) to 500 psig (3500 kPa), preferably in the range of from 200 psig (1400 kPa) to 400 psig (2800 kPa). more preferably in the range of from 250 psig (1700 kPa) to 350 psig (2400 kPa). The reactor temperature in the gas phase process may vary from 30 to 120 °C. preferably from 60 to 115 °C, more preferably from 70 to 110 °C, and most preferably from 70 to 95 "C.
A slurry polymerization process generally uses prss.sure.s in the range at from HMi kP?. in 5 MPa, and temperatures in the range of 0 to 120 °C. In a slurry pxilymerization. a suspension of solid, particulate polymer is formed in a liquid polymerization diluent to which monomers and often hydrogen along with catalyst are added. The diluent is intermittently or continuously removed from

the reactor where (he volatile components are separated from the poiynier and recycied to the reactor. The liquid diluent employed should remain a liquid under the conditions of poiymerization atid be relatively inert. Preferred diluents are aliphatic or cycloaliphaiic hydrocarbons, preferably propane, n-butane, isobutane, pentane, isopeniane, hexane. cyclohexane. or a mixture thereof i.s employed. Examples of suitable slurry polymerization processes for use herein are disclosed in U, S. Paienis3,24S.179 and 4,613.484.
Examples of solution processes that are suitably employed wilh the catalyst conipo5iltons of the present mveniion are described in U. S. Patents 4.271.060. 5,001,205, 5.256.998 antl 5,589.555. Highly preferably, the solution process is an ethylene polymerizaiicn or an ethylene/propylene copolymerizaiion operated in a continuous or semi-continuous manner with high ethylene conversion, preferably greater than 98 percent, more preferably greater than 99.5 percent ethylene conversion. Typical temperatures for solution polymerizations are from 70 lo 200 "C. more preferably from lOOto \50°C-
Regardless of the process conditions employed (gas phase, slurry or solution phase) m order to achieve the benefits of [he present invention, the present polymerization is desirably conducted at a temperature greater than or equal lo 100 °C, more preferabiv srealer than or eoual to I 10 %., and most preferably greater than or eqiial to 115 ""C. Polymer properties
The polymers produced by the proccj.; of the :rverjiic^- ;sti bt ii'.ed .- > ■^-■-.■dc ^r-rier- of product? and end-use applications. The polymers produced by the process of die irvenjion include high density polyethyienss, low density poiyeihiJene, linear, (o'^ density pc'Veihylens leihyiene/a-olefln copolymers), polypropylene, copolymers of propylene and ethylene, and eihylene/propylene/diene terpolymers. Especially preferred pfolyrners are propylene/eihvlcne- or propylene/ethylene/diene inlerpolymers containing 65 percent or more, preferably o5 F-stcent or more polymerized propylene and substantialiy isolactic propylene segments.
The ethylene homopolymers and high ethylene content copolymers formed by the present process preferably have a density in the range of from 0.85 g/cc to 0.97 g/cc, more preferably in the range of from 0.86 g/cc lo 0.92 g/cc. Desirably they additionally have melt index (h) determined according to ASTMD-l 238, Condition E, from ! to lOOdg/min, preferably from 2 to lodg/min. Propylene/ethylene copolymers prepared according to the present process desirably have a AH( (j'g) from 25 (o 55, preferably from 29-52. Highly desirably polymers prepared according to the present invention are propylene/ethylene copolymers containing 85 to 95 percent, preferably 87 to 95 percent polymerized propylene, a density from 0.860 to 0.885, and a melt flow rate (MpR) determined according to ASTM D-1238. Condition L. from 0.1 to 500, preferably 1.0 to lO.

Typically, the polymers produced by the process of the inventior. iicve a molecular weight distribuLion or polydispcrsity index (Mw/Mn or PDIl from 2,0 to 15.0, preferabiv from 2.0 to 10.0.
"Broad polydispcrsity". "broad molecular weight distribution", "broad MWD" and similar terms mean a PDI greater than or equal to 3,0, preferably from 3.0 to 8.0. Poiymers for use in fiber and extrusion coaling applications typically have a relatively broad polydispersity. Catalysts comprising a complex according to formula (T) are especially adapted for preparing such propylene/ethylene inlerpolymers having a broad molecular weight distribution for this end use.
"Narrow polydispersity", "narrow molecular weight distnhulion"', "n.^rrow MWD" and similar terms mean a PDI of less than 3.0, preferably from 2,0 to 2.7. Polymers for use in adhesive applications preferentially have a narrower polydispersity. Catalysis comprising a complex according to formula (D are especially adapted for preparing such narrow molecular weight dislribution propylene/ethylene inlerpolymers for this end use.
A suitable technique for determining molecular weight distribution of the polymers is gel
permeatLOn chromatography (GPC) usiQg a Polymer Laboratories PL-GPC-220 high icinperature
chromatographic unit equipped with four linear mixed bed columns (Polymer Laboraiones ('20-,um
particle si;:e)). The oven temperature i> set at 160 "C wiui ihc auiosampier hoi ^on= di i 60 "C and
the warm zone at 145 "C 'J'he solveni ts I .I.^-tri.chlornbenjene roniainini? 20L"' Dpm 2 (^wJi-t-binvt-
'i-msth'-'iDhen^i Th= flo^i r.-.te. t^; 1.0 rTiiUi'^ter,"niTi J;L- an J -he .- ■.■_^l..'..j" . z .' ■ . . .■. 'L.":
Abou: 0.2 percent solution; of the samples are prepared for injerLion by d;£^:i ■-■.-,- .ir. ;jr-.pie in nitrogen purged ! ,2.4-trichiDrobenzene containing 200 ppm 2,6-di-i-biityl-4-:r(eir,ylphenol for 2.5 hours ai 160 "C with gentle mixing.
The iTiolecular weight is determined by using ten narrow molecular weight distribution polystyrene standards tfrom Polymer Laboratories. EasiCal PSl ranging from 5S0 lo ^.fOCOOO g/mcle,i in conjunction v-ith theirelunon volumes. TTie equivalent pclypropviene T"jOleci;'ar weights are deiemiined by using appropriate Mark-Houwink coefficieniii for polypropylene (J_, Appl. Poivm, Sci.. 29. 3763 - 3782 (I9S4)) and polystyrene (Macromolecules, 4, S07(1Q71)) in the Mark-Houwink equation: jN| = KMa,
where Kpp-1.90X lO"^. Opp = 0.725 and Kp. = 1.26 x 10', ap.. = 0.702
One suitable technique for measuring polymer thermal properties is by means of differential scanning calorimeiry (DSC). General principles of DSC measurements and application.^ of DSC to Studying crystalline poiymers are described in standard texts such as, E. A. Tun. ed.. "Thermal Characierization of Polymeric Materials", Academic Press, (19811. A suitable lecbnique for conducting DSC analyses is by using a model QiOOO DSC device from TA instruments. Inc. To calibrate the instrument, first a baseline is obtained by running the DSC from -90 "C to 290 "C without any sample in the aluminum DSC pan. Then 7 grams of a fresh indium sample is analyzed

by heating the sample to 180 "C, cooling the sample to 140 "C ai a cooling rate of iO "C/min followed by keeping the sample isothermally ai 140'^C for 1 minute, followed bv heacing the sample from 140 °C to 180 "C at a healing raie of 10 "C/min, The heat of fusion and the onset of melting of the indium sample are determined and checked to be within 0,5 °C frorr^ 156.6 °C for ihs onset of melting and within 0,5 J/g from 28.71 J/g for the iieat of fusion. Then deinniT-^.d water is analyzed by cooling a small drop of fresh sample m the DSC pan from 25 "C to -30 '^C at a cooling rate of IO°C/min. Ttie sample is retained at -30 °C for 2 mmutes and heated to 30 °C at a heating rate of 10 °C/min. The onset of melting is determined and checked to be within 0.5 °C from 0 '^C,
The samples are prepared by pressing the polymer imo a ihin film at a temperature of 100 "C, About 5 to 8 mg of film sample is weighed and placed m the DSC pan. The iid is crimped on the pan to ensure a closed atmosphere, The sample pan is placed in the DSC ceil and then heated at a rate of about 100'C/min to a temperature of about 30 °C above the melt temperature. The sample is kepr at this temperature for about 3 minutes then cooled at a rate of 10 "C/min to ^0 'C, and held at that temperature for 3 minutes. Next the sample is again heated at a rare of !0 '-"Cmm until melting is complete. The resulting enthalpy curves are analyzed for peak melt temperature, onset and peak crystallization lemperarures. heat of fusion, and hea; of crystallization
The present inierpolvmers of propvlene -.^iih ethylene and or-Iionai A' Ci. , 2 oif.'fini ruvc a rcU".r-,L]j broad raeUing poir.; a.'; i". Jdenctd by ihe DSC .'isaiirig ;-J:"-"J. :: .i b,^ii-'^ -"- ::..i'. '.^'i ~".a'.' be due io the unique disiribunon of eihNlene polyrrcr sequcrr^es ■.. nh-.n zm oo\yir:S.' zr.zw.-,. =.■; a consequence of ihe foregoing fact, melting point data, Tm. are not geierai'> rcpcrtsd hereiti or uiilized in describing polymer properties, Crystailinity is determined based on SH; measure.Tienis, with percent crystailinity determined by the formula: AH|/if)5(j/g) .^ 100, Generally, a relabvely narrow- msliing peak is observed for propylene/ethylene ir.terpoivmers prep:ired asmg 'J meiallocene catalyst whereas the polymer.'; according to the present invention possess a iciaii-.e!;' broad melimg point cur\'e. Polymers having a broadened melting point have t>een found to be highly useful in applications requiring a combination of elaslit;ity and high temperature performance, such as elasEomeric fibers or adhesives, for example.
One characteristic in the DSC curve of propylene/ethylene polymers possessing a relatively broad melting point is that the T„, the temperature at which the melting ends, reiuaiiis essentially the same and Tnm. the peak melting temperature, decreases as the amount of ethylene in the copolymer is increased. An additional feature of such polymers is that the skewness of the TREF curve IS generally greater than -i.6U, more pi^ferably greater than -1,00.
The determination of crystallizable sequence length distribution in a copolymer can be measured by the technique oF temperature-rising elution fractionation (TT?£F), as disclosed by L, Wild, et al.. Journal of Polvmer Science: Polymer. Physics Ed.. 20,441 (1982), Hazlitt. Jour^o/

The vaiue, T™,, is defined as the temperature of the largsst weight fraction eluting between 50 and 90 "C in the TREF curve. T, and w, are the elution ^empe^atu^s and weight fraction respectively of an arbitrary, i* fraction in the TREF disiribuiion. The distributions are normaiized (the sutn of the w, equals 100 percent) w\{h respect to the lota! area of thccur'vc L^luimg above 30 °C. Thus, the index reflects only the propenies of the crystallized polymer and any influence due to uncrystallized polymer (polymer still in solution at or belou/ 30 "O is omitted from tne calculation.
Certain of the jjolymers according to the invention having a relatively broad mehing point on the DSC curve desirably are characterized by a skewness indfc!( greater than -1.6, more preferably greater than -1.2.
Polymer tacticity, propylene content, regio-eirors and other properties aredelerminsd by standard NMR techniques, Tacticilies (uini) or (rr) are calculated based oi\ meso- or regio-triads, and may be expressed as ratios less than one or as percents. Propylene isotacticity at the triad level ("mm; 1^ deterrrtinsd from the integrals of the mm triad ("22 ^0-2' 29. ppm\. -.hs r-ir :.r;2J !'2! 2^-20.67 ppm; £-^d tiis r- :riad (2'j 61-] 9.^^]. The mm iftotac'.ir;!; ■; z-ji^-.rr'.r.^c ':>. : ■. 'J.ns :r; I'l'e'?'; vf the mm triad by the sum of the mm, mr, and rr triads. For ethyleric coniaining ■rte-pr-l; mer? th;-, mr region is corrected by subtracting the 37.5-39 ppm peak integral. For copolymers with other monomers that produce peak.-i in the regions of the mm, mw, and rr ti-iads, the integral^ for ^bese regions are simiiarly corrected by subtracting the Eniensiry of the interfering peak using s[ar)dard NMR techniques, once the peaks have been identified. This can be accomplished, for example, by analysis of a .series of copolymers of various levels of monomer incorporation, by literature assignments, by isotopic labeling, or other means which are known in the art. Specific Embodiments
The following specific embodiments of the invention and combinations thereof are especially desirable and hereby delineated in order to provide detailed disclosure for the appended claims.
I. A metal complex corresponding to the formula:

quenched with 200 mL of water. The contents of the reactor are then transferred to a 1L separatory funnel and extracted with 4x50 tnL of ethyl acetate. The organic layers are combined and the solvent removed in vacuo. The product is redissolvcd in methylene chloride and extracted with a NaOH aqueous solution to remove phenolic byproducts. The organic layer is then dried over MgSOa to give a yellow sotutioti. The solvent is removed in vacuo to give 50.06 g of 3-pinacolate boronato-2-ethylbenzofuran as a pale yellow liquid (yield: 82.2 percent, purity by GC/MS: 96 percent).
c) To a dry. N; purged, 500 mL three neck flask equipped with a stir bar is added 200 mL
of dry diethyl ether and 4-bromo-N-mechy!imidazole {50.0 g. 311 mmo!). The flask is then cooled
to -10 °C with an acetone/ ice bath. A 2.0 M heptane/ THF/ eihylbenzene solution of lithium
diisopropylamide (171 mL, 342 mmol) is then added via syringe while maintaining the reaction
temperature at 0 "C or lower. After 1 hour, dimethylformamlde (DMF) (36.1 mL, 466 mmol) is
added dropwise over 5 minutes. The reaction mixture is allowed to stir for 45 minutes at or below 5
"C and then quenched with a saturated aqueous solution of citric acid. The resulting mixture is
stirred vigorously until the two phases separate. The organic layer is recovered and washed (3x200
mL) with water. The solvent is removed in vacuo to give the desired product, 2-formyI-4-bromo-
(! iN-methy'imidazole, as a ^rown cn'sialhrpe solid (yield: 55.7 g, 95 percent. s6 perccnl piiritv bv GC'l. AddiLiondi purincaiiorj may ht achieved by eiulion ihrough aium.ina uiir.i mt'-ii'lsnc chloride solvent.
d) 3-pinacolaie boronato-2-etliyibenzofuran (6 1,6 g, 226 minul), Na;CO-. I40,0 g, 37S mmol) and 2-formyl-4-bromo-{l)N-meihylimida2ole i2S.4 g. 151 mmoVi are added to a 5L flask equipped with mechanical stirring containing a solution of degassed water (600 mL) and dimethyl ether (60O tnL). Inside of a dry box, 1,41 gof tetrakistriphenylphosphine-palladiumCOJ is di.'^solved in 40 mL of anhydrous degassed toluene. The toluene Pd solution is removed from the dry box: and charged into the reactor via syringe under a blanket of N;. The biphasic solution is vigorously stirred and healed to 73 °C for 14 hours. On cooling to ambient temperature, the organic phase is separated. The aqueous layer is washed twice with 150 mL of ethy! acetate. All organic phases are combined and the solvent removed in vacuo to give an oil. Recrysiallization from hexane gives the product. 4-(2-ethylbenzofuran-3-yl)-2-formyl-(l>N-methylimidazole, as a brown solid (yield: 25.6 g. 66.8 percent).
e) A dry, 250 mL ! -neck round bottom flask is charged with a wluttfin yf (5"?.9 g. 236 mmol) 4-(2-ethylbenzofuran)-2-formyl-(l)-N-methylimidazole and 2,6-diisopropylaniiine (4!.S g, 236 mmot) in 50 nriL of anhydrous toluene. A catalytic amount (10 mg) of p-(oluenesu!fonic acid is added to the reaction flask. The reactor is equipped with a Dean Stark trap with a condenser and a thermocouple well. The mixture is heated to I 10 "C under N^ for 12 hours. The solvent is then

toluene. To this solution is added 0.35 mmol of solid HfCU. The flask is Filted with art air-cooiea reflux condenser and the mixture heated at reflux for 4 hours. After cooling, 1.23 mmol of BuMgCI (3-5 equivalents, 2.0 M solution in diethyl ether) is added by syringe and tlie resulting mixture Stirred overnight at ambient temperature. Solvent (lolcenc and diethyl ether) is removed from the reaction mixture by vacuum. Hexane (30 mL) is added to the residue, then removed by filtration, and the solids washed again with additional hexane (30 mL). The white glassy solid product is recovered from the combined hexane extracts and converted to the dibutyl derivative by heaimg in benzene solution at 50 "C overnight.
The solubility of the complex in methylcyclohexane measured at 20 °C is greater than 5 percent.
'H NMR(C6D6): 5 7.6! (d. J = 8 Hi. IH>, 7,43{d, J ^8 Hz, IH), 7 25-7.05 (muliiplets, 7H). 6.94 (dd. J = 2. 7 Hz:. IH), 6.22 (s, IH), 5.84 (s. IH). 3.96 (septet. J =7 Hz, JH). 3-75 (septet. J = 7 Hz. IH), 3.59(.septet, J = 7Hz, IH), 2.S6 (multiplets. 3H). 2.26 (s. 3H). 2.0-1.15 (multipleis, alkyl chain methylene protons), 1.55 (d, J = 7 Hz, 3H). 1.51 (d, J = 7 Hz, 3H), 1 41 (t.J - 7 Hz. 3H). l.02(d.J = 7Hz, 3H),0.91 (l, J = 7 Hz. 9H), 0.75 (d, J =7 Hz. 3H), 0.72 (d, J = 7 Hz, 3HI, 0.71 (d. J = 7 Hz, 3H). 0.52 (d, J = 7 Hz. 3H), 0.27 (d. J = 7 Hz, 3H).
Tbe meti! ccrnplex may be cor."erted '.o rh-; or:ho-m;-r?,i|.'!!ed dibu"-': ■.'■:-r".-'^i'^: T; hc-zj'-iig in toluene soluiion £[ 30 "C overnight.
Batch Reactor Propylene Homopolymerizations
Polymerizations are conducted in a computer controlled, stirred, jacketed I S L siainlei;? steel autoclave solution batch reactor. The bottom of the reactor is fitted with a large orifice botfom discharge valve, which empties the reactor contents into a 6 L siainles; ste^l conii:iner Th^ container is vented to a 30 gal. blowdown tank, with both the container and the tank are purged with nitrogen. .-Mi chemicals used for polymerization or catalyst makeup are run through purification columns, to remove any impurities. Propylene and solvents are passed through 2 columns, the first containing alumina, the second containing a purifying reactant (Q5''^ available from Englehardt Corporation). Nitrogen and hydrogen gases are passed through a single column conlaining Q5^" reactant.
The autoclave is cooled to 50 "C before loading. It is charged with 667 g mixed alkanes,
hydrogen (using a calibrated 50 mL shot tank and a differential pressure in the shot lank of
0.4!MPa). followed by 286g of propylene using a micro-motior flowmeter. The reactor is then
brought to 90 "C before addition of catalyst composition. "
The metal complex (catalyst) is employed as a 0.20 mM solution in toluene (run I), as 75.0 mg dissolved in 675 mg methylcyclohexane (run 2), or as 75.0 mg dissolved in a mixture of 659 mg

CLAIMS:
I
with the proviso that the metat complex has a methylcyclohexane solubility at 20 °C (plus or minus I °C) of at least 5 percent.

compound corresponding to the formula:

20, A process for preparing a stable 2-substituied ben2ofuran-3->i borate esier
corresponding to ihe formula:

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Patent Number

271312

Indian Patent Application Number

5990/CHENP/2008

PG Journal Number

08/2016

Publication Date

19-Feb-2016

Grant Date

16-Feb-2016

Date of Filing

05-Nov-2008

Name of Patentee

DOW GLOBAL TECHNOLOGIES LLC

Applicant Address

2040 DOW CENTER, MIDLAND, MICHIGAN 48674

Inventors:

#	Inventor's Name	Inventor's Address
1	BOONE, HAROLD, W	7802 SILVER POND DRIVE, SUGAR LAND, TEXAS 77479
2	FRAZIER, KEVIN, A	1105 TANWOOD COURT, MIDLAND, MI 48642
3	IVERSON, CARL, N	4119 ALBANS ROAD, HOUSTON, TEXAS 77005
4	VOSEJPKA, PAUL, C	706 EAST CHIPPEWA RIVER ROAD, MIDLAND, MI 48640

PCT International Classification Number

C08F4/645

PCT International Application Number

PCT/US07/07882

PCT International Filing date

2007-03-29

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/798,108	2006-05-05	U.S.A.