Title of Invention	PROCESS FOR THE PREPARATION OF POLYPROPYLENE
Abstract	The present invention relates to a process for the preparation of polypropylene using a catalyst system of low porosity, the catalyst system comprising an asymmetric catalyst, wherein the catalyst system has a porosity of less than 1.40 ml/g.

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FORM 2 THE PATENTS ACT, 1970 (39 of 1970) & THE PATENTS RULES, 2003 COMPLETE SPECIFICATION (See Section 10; rule 13) PROCESS FOR THE PREPARATION OF POLYPROPYLENE" BOREALIS TECHNOLOGY OY of the address: P.O. Box 330, FIN-06101 Porvoo, Finland. The following specification particularly describes and ascertains the nature of this invention and the manner in which it has to be performed: Process for the Preparation of polypropylene The present invention relates to a process for the preparation of polypropylene. Well-known polypropylenes of commerce are particularly isotactic, semi-crystalline, thermoplastic polymer mixtures. Although the poly-propylenes of commerce have many desirable and beneficial proper-ties, they also possess some important drawbacks such as low melt strength making them unsuitable for many applications, such as for blown films, extrusion coating, foam extrusion and blow-molding. These shortcomings have partially been overcome by introduction of branchings in the linear polymer backbone. This can be achieved through post-reactor treatment, copoiymerization with dienes, and through polymerization with specific catalysts at high temperatures. However, the processes presently available still do not result in poly¬propylene having a high melt stability which is of particular relevance in extrusion processes under extensional flow". To overcome this drawback and to develop a polypropylene which is suitable for advanced polypropylene applications, there is still the desire to provide a process resulting in polypropylene with improved rheological properties such as high melt strength. The finding of the present invention is to provide a process for the preparation of a polypropylene using a catalyst system of low poros¬ity comprising an asymmetric catalyst. According to the present invention, a process for the preparation of a polypropylene is provided which uses a catalyst system of low poros¬ity, the catalyst system comprising an asymmetric catalyst, wherein the catalyst system has a porosity of less than 1-40 mi/g. An asymmetric catalyst according to this invention is preferably a catalyst comprising at least two organic ligands which differ in their chemical structure. More preferably the asymmetric catalyst accord¬ing to this invention is a metallocene compound comprising at least two organic ligands which differ in their chemical structure. Still more preferably the asymmetric catalyst according to this invention is a asymmetric catalyst, yet more preferably a metallocene compound, comprising at least two organic ligands which differ in their chemical structure and the metallocene compound is free of C2-symmetry and/or any higher symmetry. Preferably the asymetric catalyst, more preferably the asymmetric metallocene compound, comprises only two different organic ligands, still more preferably comprises only two organic ligands which are different and linked via a bridge. Due to the use of the catalyst system with a very low porosity in combination with an asymmetric catalyst, the process defined above results in polypropylene with improved rheological properties such as high melt strength. Preferably, the catalyst system has a porosity of less than 1.30 ml/g, more preferably less than 1.00 ml/g. The porosity has been meas¬ured according to DIN 66135 (N2). In another preferred embodiment, the porosity is below the detection limit when determined with the method applied according to DIN 66135 (N2). Furthermore it is preferred, that the catalyst system has a surface area of of lower than 25 m2/g, yet more preferred lower than 20 m2/g, still more preferred lower than 15 m2/g, yet still lower than 10 m2/g and most preferred lower than 5 m2/g. The surface area according to this invention is measured according to ISO 9277 (N2). It is in particular preferred that the catalytic system according to this invention comprises an asymmetric catalyst, i.e. a catalyst as de¬fined above and/or below, and has porosity not detectable when ap¬plying the method according to DIN 66135 and has a surface area measured according to ISO 9277 lower than 5 m2/g. Preferably, the asymmetric catalyst employed comprises an organo-metallic compound of a transition metal of group 3 to 10 or the peri¬odic table (IUPAC) or of an actinide or lanthanide. The asymmetric catalyst is preferably of a transition metal compound of formula (I) (L)mRnMXq (1) wherein M is a transition metal of group 3 to 10 or the periodic table (IUPAC), or of an actinide or lantanide, each X is independently a monovalent anionic ligand, such as G-ligand, each L is independently an organic ligand which coordinates to M, R is a bridging group linking two ligands L, m is 2 or 3, n is 0 or 1, q is 1,2 or 3, m+q is equal to the valency of the metal, and with the proviso that at least two ligands "L" are of different chemical structure. Said asymmetric catalyst is preferably a single site catalyst (SSC). In a more preferred definition, each "L" is independently (a) a substituted or unsubstituted cycloalkyldiene, i.e. a cyclopentadI-ene, or a mono-, bi- or muitifused derivative of a cycloalkyldiene, i.e. a cyclopentadiene, which optionally bear further substituents and/or one or more hetero ring atoms from a Group 13 to 16 of the Periodic Table (IUPAC); or (b) an acyclic, ligand composed of atoms from Groups 13 to 16 of the Periodic Table, and in which the open chain ligand may be fused with one or two, preferably two, aromatic or non-aromatic rings and/or bear further substituents; or (c) a cyclic mono-, bi- or multidentate ligand com-posed of unsubstituted or substituted mono-, bi- or rnulticyclic ring systems selected from aromatic or non-aromatic or partially satu-rated ring systems and containing carbon ring atoms and optionally one or more heteroatoms selected from Groups 15 and 16 of the Periodic Table. The term ligand" is understood in the whole description in a known manner, i.e. a group bonded to the metal at one or more places via a sigma bond. A preferred monovalent anionic ligand is halogen, in particu-lar chlorine (CI). In a preferred embodiment, the asymmetric catalyst is preferably of a transition metal compound of formula (I) wherein M is a transition metal of group 3 to 10 or the periodic table (IUPAC), or of an actinide or lantanide, each X is independently a monovalent anionic ligand, such as c- ligand, each L is independently an organic ligand which coordinates to M, wherein the organic ligand is an unsaturated organic cyclic ligand, preferably a substituted or unsubstituted, cycloalkyldiene, i.e. a cyclopentadiene, or a mono-, bi- or multifused derivative of a cycloalkyldi-ene, i.e. a cyclopentadiene, which optionally bear further substituents and/or one or more hetero ring atoms from a Group 13 to 16 of the Peri-odic Table (IUPAC), R is a bridging group linking two ligands L, m is 2 or 3, n is 0 or 1, q is 1,2 or 3, m+q is equal to the valency of the metal, and with the proviso that at least two ligands "L" are of different chemical structure. According to a preferred embodiment said asymmetric catalyst compound (I) is a group of compounds known as metallocenes. Said metallocenes bear at least one organic ligand, generally 1, 2 or 3, e.g. 1 or 2, which is bonded to the metal, e.g. ligand, such as a ligand. Preferably, a metallocene is a Group 4 to 6 transition metal, more preferably zirco¬nium, which contains at least one ligand. Preferably the asymmetric catalyst compound has a formula (II): wherein M is Zr, Hf or Ti, preferably Zr each X is independently a monovalent anionic ligand, such as ligand, each Cp is independently an unsaturated organic cyclic ligand which coordinates to M, R is a bridging group linking two ligands L, n is 0 or 1, more preferably 1, q is 1,2 or 3, more preferably 2, m+q is equal to the valency of the metal, and at least one Cp-ligand, preferably both Cp-figands, is(are) selected from the group consisting of unsubstituted cyclopenadienyl, unsubsti- tuted indenyl, unsubstituted tetrahydroindenyl, unsubstituted fluo- renyl, substituted cyclopenadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted fluorenyl, with the proviso in case both Cp-figands are selected from the above stated group that both Cp-ligands must chemically differ from each other. Preferably, the asymmetric catalyst is of formula (II) indicated above, wherein M is Zr each X is C1, n is 1, and q is 2. Preferably both Cp-ligands have different residues to obtain an asymmetric structure. Preferably, both Cp-ligands are selected from the group consisting of substituted cyclopenadienyi-ring, substituted indenyl-ring, substituted tetrahydroindenyl-ring, and substituted fluorenyl-ring wherein the Cp-ligands differ in the substituents bonded to the rings. The optional one or more substituent(s) bonded to cyclopenadienyl, indenyl, tetrahydroindenyl, or fluorenyl may be independently se-lected from a group including halogen, hydrocarbyl (e.g. alkyl, alkenyl, alkynyl, :ycloalkyl, aryl or C7-C20-aryialkyl), cycloalkyl which contains 1, 2, 3 or 4 heteroa-tom(s) in the ring moiety, C6-C2o-heteroaryl, haloalkyl, -$iR"3, and wherein each R" is independently a hydrogen or hydrocarbyl, e.g. alkyl,alkenyl, alkynyl, cycloalkyl or aryl. More preferably both Cp-ligands are indenyl moieties wherein each indenyl moiety bear one or two substituents as defined above. More preferably each Cp-ligand is an indenyl moiety bearing two substitu-ents as defined above, with the proviso that the substituents are chosen in such are manner that both Cp-ligands are of different chemical structure, i.e both Cp-ligands differ at least in one substitu-ent bonded to the indenyl moiety, in particular differ in the substitu-ent bonded to the five member ring of the indenyl moiety. Still more preferably both Cp are indenyl moieties wherein the inde-nyl moieties comprise at least at the five membered ring of the inde-nyl moiety, more preferably at 2-position, a substituent selected from the group consisting of alkyl, such as alkyl, e.g. methyl, ethyl, isopropyl, and trialkyloxysiloxy, wherein each alkyl is independently selected from alkyl, such as methyl or ethyl, with proviso that the indenyl moieties of both Cp must chemically differ from each other, i.e. the indenyl moieties of both Cp comprise different sub-stituents. Still more preferred both Cp are indenyl moieties wherein the indenyl moieties comprise at least at the six membered ring of the indenyl moiety, more preferably at 4-position, a substituent selected from the group consisting of a aromatic ring moiety, such as phenyl or naphthyl, preferably phenyl, which is optionally substituted with one or more substitutents, such as alkyl, and a heteroaromatic ring moiety, with proviso that the indenyl moieties of both Cp must chemically differ from each other, i.e. the indenyl moieties of both Cp comprise different substituents. Yet more preferably both Cp are indenyl moieties wherein the inde-nyl moieties comprise at the five membered ring of the indenyl moi-ety, more preferably at 2-position, a substituent and at the six mem-bered ring of the indenyl moiety, more preferably at 4-position, a fur-ther substituent, wherein the substituent of the five membered ring is selected from the group consisting of alkyl, such as alkyl, e.g. methyl, ethyl, isopropy!, and trialkyloxysiloxy, wherein each alkyl is independently selected from afkyl, such as methyl or ethyl, and the further substituent of the six membered ring is selected from the group consisting of a aromatic ring moiety, such as phenyl or naphthyl, preferably phenyl, which is optionally substituted with one or more substituents, such as alkyl, and a heteroaromatic ring moiety, with proviso that the indenyl moieties of both Cp must chemi-cally differ from each other, i.e. the indenyl moieties of both Cp comprise different substituents. It is in particular preferred that both Cp are idenyl rings comprising two substituentes each and differ in the substituents bonded to the five membered ring of the idenyl rings. Concerning the moiety "R" it is preferred that "R" has the formula (III) wherein Y is C, Si or Ge, and R' is to C20 alkyl, aryl, arylalkyl or trimethyisilyl. In case both Cp-ligands of the asymmetric catalyst as defined above, in particular case of two indenyl moieties, are linked with a bridge member R, the bridge member R is typically placed at 1-position. The bridge member R may contain one or more bridge atoms se-lected from e.g. C, Si and/or Ge, preferably from C and/or Si. One preferable bridge wherein R' is selected independ- ently from one or more of e.g. alkyl, alkyl, such as C6- C12 aryl, or such asarylalkyl, wherein alky! as such or as part of arylalkyl is preferably alkyl, such as ethyl or methyl, preferably methyl, and aryl is preferably phenyl. The bridge -Si(R')2-is preferably e.g. alkyl)2-, -Si(phenyl)2- or C6 alkyl)(phenyl)-, such as In a preferred embodiment the asymmetric catalyst is defined by the formula (IV) wherein each X is independently a monovalent anionic ligand, such as ligand, in particular halogen, like chlorine both Cp coordinate to M and are selected from the group consisting of unsubstituted cyclopenadienyl, unsubstituted indenyl, unsubsti- tuted tetrahydroindenyl, unsubstituted fluorenyl, substituted cyclopenadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted fluorenyl, with the proviso that both Cp-ligands must chemically differ from each other, and R is a bridging group finking two ligands L, wherein R is defined by the formula (III) wherein Y is C, Si or Ge, and arylalkyl or trimethylsilyl. More preferably the asymmetric catalyst is defined by the formula (IV), wherein both Cp are selected from the group consisting of sub¬stituted cyclopenadienyl, substituted indenyl, substituted tetrahydro¬indenyl, and substituted fluorenyl. Yet more preferably the asymmetric catalyst is defined by the for-mula (IV), wherein both Cp are selected from the group consisting of substituted cyclopenadienyl, substituted indenyl, substituted tetrahy-droindenyl, and substituted fluorenyl with the proviso that both Cp-ligands differ in the substituents, i.e. the subtituents as defined above, bonded to cyclopenadienyl, inde¬nyl, tetrahydroindenyl, or fluorenyl. Still more preferably the asymmetric catalyst is defined by the for-mula (IV), wherein both Cp are indenyl and both indenyl differ in one substituent, i.e. in a substiuent as defined above bonded to the five member ring of indenyl. It is in particular preferred that the asymmetric catalyst is a non-silica supported catalyst as defined above, in particular a metallocene catalyst as defined above. In a preferred embodiment the asymmetric catalyst is dimethylsi-landiyl [(2-methyl-(4'-tert.butyl)-4-phenyl-indenyl)(2-isopropyl-(4'-tert.butyl)-4-phenyl-indenyl)]zirkonium dichloride. More preferred said asymmetric catalyst is not silica supported. It is in particular preferred that the asymmetric catalyst is obtainable by the emulsion solidification technology as described in WO 03/051934. This document is herewith included entirely by refer-ence. Hence the asymmetric catalyst is preferably in the form of solid catalyst particles, obtainable by a process comprising the steps of a) preparing a solution of one or more asymmetric cata¬lyst components; b) dispersing said solution in a solvent immiscible therewith to form an emulsion in which said one or more catalyst components are present in the droplets of the dispersed phase, c) solidifying said dispersed phase to convert said drop-lets to solid particles and optionally recovering said particles to obtain said catalyst. Preferably a solvent, more preferably an organic solvent, is used to form said solution. Still more preferably the organic solvent is se¬lected from the group consisting of a linear alkane, cyclic alkane, lin¬ear alkene, cyclic alkene, aromatic hydrocarbon and halogen-containing hydrocarbon. Moreover the immiscible solvent forming the continuous phase is an inert solvent, more preferably the inmiscible solvent comprises a fiuorinated organic solvent and/or a functionalized derivative thereof, still more preferably the inmiscible solvent comprises a semi-, highly-or perfluorinated hydrocarbon and/or a functionalized derivative thereof. It is in particular preferred, that said immiscible solvent com-prises a perfluorohydrocarbon or a functionaiised derivative thereof, pref-erably perfluoroalkanes, -alkenes or -cycloalkanes, more preferred perfiuoro-alkanes, -alkenes or-cycloalkanes, particularly preferred perfluorohexane, perfluoroheptane, perfluorooctane or perfluoro (methyl-cyciohexane) or a mixture thereof. Furthermore it is preferred that the emulsion comprising said continuous phase and said dispersed phase is a bi-or multiphasic system as known in the art. An emulsifier may be used for forming the emulsion. After the formation of the emulsion system, said catalyst is formed in situ from catalyst components in said solution. In principle, the emulsifying agent may be any suitable agent which contributes to the formation and/or stabilization of the emulsion and which does not have any adverse effect on the catalytic activity of the catalyst. The emulsifying agent may e.g. be a surfactant based on hydrocarbons optionally interrupted with (a) heteroatom(s), pref¬erably halogenated hydrocarbons optionally having a functional group, preferably semi-, highly- or perfluorinated hydrocarbons as known in the art. Alternatively, the emulsifying agent may be pre¬pared during the emulsion preparation, e.g. by reacting a surfactant precursor with a compound of the catalyst solution. Said surfactant precursor may be a halogenated hydrocarbon with at least one func¬tional group, e.g. a highly fluorinated to alcohol, which reacts e.g. with a cocatalyst component, such as aluminoxane. In principle any solidification method can be used for forming the solid particles from the dispersed droplets. According to one preferable em¬bodiment the solidification is effected by a temperature change treatment. Hence the emulsion subjected to gradual temperature change of up to 10 °C/min, preferably 0.5 to 6 °C/min and more preferably 1 to 5 °C/min. Even more preferred the emulsion is subjected to a temperature change of more than 40 °C, preferably more than 50 °C within less than 10 sec¬onds, preferably less than 6 seconds. The recovered particles have preferably an average size range of 5 to 200 urn, more preferably 10 to 100 urn. Moreover, the form of solidified particles have preferably a spherical shape, a predetermined particles size distribution and a surface area as mentioned above of preferably less than 25 m2/g, still more preferably less than 20 m2/g, yet more preferably less than 15 m2/g, yet still more preferably less than 10m2/g and most preferably less than 5 m2/g, wherein said particles are obtained by the process as described above. For further details, embodiments and examples of the continuous and dispersed phase system, emulsion formation method, emulsifying agent and solidification methods reference is made e.g. to the above cited inter¬national patent application WO 03/051934. The catalyst system may further comprise an activator as a cocata-lyst, as described in WO 03/051934, which is enclosed hereby with reference. Preferred as cocatalysts for metallocenes and non-metallocenes, if desired, are the aluminoxanes, in particular the alkylaluminoxanes, most particularly methylaluminoxane (MAO). Such aluminoxanes can be used as the sole cocataiyst or together with other cocatalyst(s). Thus besides or in addition to aluminoxanes, other cation complex forming catalysts activators can be used. Said activators are commercially available or can be prepared according to the prior art literature. Further aluminoxane cocatalysts are described i.a. in WO 94/28034 which is incorporated herein by reference. These are linear or cyclic oligomers of having up to 40, preferably 3 to 20, repeat units (wherein R"' is hydrogen, alkyl (preferably methyl) or C6- C18-aryl or mixtures thereof). The use and amounts of such activators are within the skills of an expert in the field. As an example, with the boron activators, 5:1 to 1:5, preferably 2:1 to 1:2, such as 1:1, ratio of the transition metal to boron activator may be used. In case of preferred aluminoxanes, such as methylaluminumoxane (MAO), the amount of Al, provided by aluminoxane, can be chosen to provide a molar ratio of transition metal e.g. in the range of 1 to 10 000, suitably 5 to 8000, preferably 10 to 7000, e.g. 100 to 4000, such as 1000 to 3000. Typically in case of solid (heterogeneous) catalyst the ratio is preferably below 500. The quantity of cocataiyst to be employed in the catalyst of the in-vention is thus variable, and depends on the conditions and the par-ticular transition metal compound chosen in a manner well known to a person skilled in the art. Any additional components to be contained in the solution compris-ing the organotransition compound may be added to said solution before or, alternatively, after the dispersing step. Preferably, the process of the present invention is a multi-stage process to obtain multimodal polypropylene. Multistage processes also include bulk/gas phase reactors known as multizone gas phase reactors for producing multimodal polypropyl-ene. A preferred multistage process is a "loop-gas phase"-process, such as developed by Borealis A/S (known as BORSTAR® technology) described e.g. in EP 0 887 379 or WO 92/12182. Multimodal polymers can be produced according to several proc-esses which are described, e.g. in WO 92/12182, EP 0 887 379 and WO 97/22633. A multimodal polypropylene according to this invention is produced preferably in a multi-stage process in a multi-stage reaction se-quence as described in WO 92/12182. The contents of this document are included herein by reference. It has previously been known to produce multimodal, in particular bimodal, polypropylene in two or more reactors connected in series, i.e. in different steps (a) and (b). Preferably the process as defined above and further defined below is a slurry polymerization, even more preferred a bulk polymerization. According to the present invention, the main polymerization stages are preferably carried out as a combination of a slurry polymeriza-tion/gas phase polymerization, more preferred the main polymeriza-tion stages are preferably carried out as a combination of bulk po-lymerization/gas phase polymerization. The bulk polymerization is preferably performed in a so-called loop reactor. As used herein, the term "slurry polymerization" means a polymerization process that involves at least two phases, e.g. in which particulate, solid polymer (e.g. granular) is formed in a liquid or polymerization medium, or in a liquid/vapour polymerization medium. Certain embodiments of the processes described herein are slurry polymerizations, e.g. processes in which the products of polymerization are solid. The polymerization prod-ucts (e.g. polypropylenes) in those processes preferably have melting points sufficiently high to avoid melting during polymerization, so that they can in many cases be recovered as granular polymer. A slurry polymeri-zation may include solvent (i.e. which is also referred to as diluent), or it may be a bulk process, discussed below. As used herein, the term "bulk process" means a polymerization process in which the polymerization medium consists entirely of or consists essen-tially of monomers and any products of polymerization that has taken place, e.g. macromers and polymers, but does not include solvent (i.e. which also means that no diluent is present), or includes minor amounts of solvent, defined as less than 50 volume percent, and preferably much less. \n order to produce the multimodal polypropylene according to this invention, a flexible mode is preferred. For this reason, it is preferred that the composition be produced in two main polymerization stages in combination of loop reactor/gas phase reactor. Optionally, and preferably, the process may also comprise a pre-polymerization step in a manner known in the field and which may precede the polymerization step (a). If desired, a further elastomeric comonomer component, so called ethylene-propylene rubber (EPR) component as in this invention, may be incorporated into the obtained propylene polymer to form a propylene copolymer as defined above. The ethylene-propylene rub¬ber (EPR) component may preferably be produced after the gas phase polymerization step (b) in a subsequent second or further gas phase polymerizations using one or more gas phase reactors. The process is preferably a continuous process. Preferably, in the process for producing the propylene polymer as defined above the conditions for the bulk reactor of step (a) may be as follows: the temperature is within the range of 40 °C to 110 °C, pref-erably between 60 °C and 100 °C, 70 to 90 °C, the pressure is within the range of 20 bar to 80 bar, preferably between 30 bar to 60 bar, hydrogen can be added for controlling the molar mass in a manner known per se. Subsequently, the reaction mixture from the bulk reactor (step a) is transferred to the gas phase reactor, i.e. to step (b), whereby the conditions in step (b) are preferably as follows: the temperature is within the range of 50 °C to 130 °C, pref-erably between 60 °C and 100 °C, the pressure Is within the range of 5 bar to 50 bar, preferably between 15 bar to 35 bar, hydrogen can be added for controlling the molar mass in a manner known per se. The residence time can vary in both reactor zones. In one embodi-ment of the process for producing the propylene polymer the resi-dence time in bulk reactor, e.g. loop is En the range 0.5 to 5 hours, e.g. 0.5 to 2 hours and the residence time in gas phase reactor will generally be 1 to 8 hours. If desired, the polymerization may be effected in a known manner under supercritical conditions in the bulk, preferably loop reactor, and/or as a condensed mode in the gas phase reactor. The process of the invention or any embodiments thereof above en-able highly feasible means for producing and further tailoring the propylene polymer composition within the invention, e.g. the proper-ties of the polymer composition can be adjusted or controlled in a known manner e.g. with one or more of the following process pa-rameters: temperature, hydrogen feed, comonomer feed, propylene feed e.g. in the gas phase reactor, catalyst, the type and amount of an external donor (if used), split between components. The above process enables very feasible means for obtaining the reactor-made propylene polymer as defined below. With the process defined above, it is possible to obtain polypropyl ene having improved rheological properties such as high melt strength. In particular, it is possible to provide a multi-branched poly-propylene, i.e. not only the polypropylene backbone is furnished with a large number of side chains (branched polypropylene) but also some of the side chains are provided with further side chains. Ac-cordingly the process of the instant invention is in particular suitable to produce a polypropylene as defined in detail below. Hence, the present invention is also related, in a first embodiment, to a polypropylene having a. a branching index g' of less than 1.00 and/or b. a strain hardening index (SHI@1s"1) of at least 0.30 measured by a deformation rate ds/dt of 1.00 at a temperature of 180 °C, wherein the strain hardening in- dex (SHI) is defined as the slope of the logarithm to the basis 10 of the tensile stress growth function as function of the logarithm to the basis 10 of the Hencky strain (Ig in the range of Hencky strains between 1 and 3. Surprisingly, it has been found that polypropylenes with such charac-teristics have superior properties compared to the polypropylenes known in the art. Especially, the melt of the polypropylenes in the extrusion process has a high stability. The new polypropylenes are characterized in particular by exten-sional melt flow properties. The extensional flow, or deformation that involves the stretching of a viscous material, is the dominant type of deformation in converging and squeezing flows that occur in typical polymer processing operations. Extensional melt flow measurements are particularly useful in polymer characterization because they are very sensitive to the molecular structure of the polymeric system be-ing tested. When the true strain rate of extension, also referred to as the Hencky strain rate, is constant, simple extension is said to be a "strong flow" in the sense that it can generate a much higher degree of molecular orientation and stretching than flows in simple shear. As a consequence, extensional flows are very sensitive to crystalfinity and macro-structural effects, such as long-chain branching, and as such can be far more descriptive with regard to polymer characteri-zation than other types of bulk Theological measurement which apply shear flow. The first characteristic of the polypropylene is that the branching in-dex g' shall be less than 1.00, more preferably less than 0.90, still more preferably less than 0.80. In the preferred embodiment, the branching index g' shall be less than 0.75. The branching index g" defines the degree of branching and correlates with the amount of branches of a polymer. The branching index g' is defined as in which g' is the branching index, is the intrinsic viscosity of the branched polypropylene and is the intrinsic vis- cosity of the linear polypropylene having the same weight average molecular weight (within a range of ±10%) as the branched polypro¬pylene. Thereby, a low g'-value is an Indicator for a high branched polymer. In other words, if the g'-value decreases, the branching of the polypropylene increases. Reference is made in this context to B.H. Zimm and W.H. Stockmeyer, J. Chem. Phys. 17,1301 (1949). This document is herewith included by reference. The intrinsic viscosity needed for determining the branching index g' is measured according to DIN ISO 1628/1, October 1999 (in Decalin at135°C). A further requirement and/or an alternative characteristic is that the strain hardening index shall be at least 0.30, more pre- ferred of at least 0.40, still more preferred of at least 0.50. In a pre-ferred embodiment the strain hardening index (SHI@1s"1) is at least 0.55. The strain hardening index is a measure for the strain hardening be-havior of the polypropylene melt. In the present invention, the strain hardening index (SHI@1s"1) has been measured by a deformation rate ds/dt of 1.00 at a temperature of 180 °C for determining the strain hardening behavior, wherein the strain hardening index (SHI) is defined as the slope of the tensile stress growth function as a function of the Hencky strain s on a logarithmic scale between 1.00 and 3.00 (see figure 1). Thereby the Hencky strain s is defined by the formula wherein the Hencky strain rate is defined by the formula with is the fixed, unsupported length of the specimen sample being stretched which is equal to the centerline distance between the master and slave drums "R" is the radius of the equi-dimensional windup drums, and is a constant drive shaft rotation rate. in turn the tensile stress growth function is defined by the formula with and wherein the Hencky strain rate is defined as for the Hencky strain "F" is the tangential stretching force "R" is the radius of the equi-dimensional windup drums "T" is the measured torque signal, related to the tangential stretching force"F" "A" is the instantaneous cross-sectional area of a stretched molten specimen is the cross-sectional area of the specimen in the solid state (i.e. prior to melting), "ds" is the solid state density and "dM" the melt density of the polymer. In addition, it is preferred that the polypropylene shows strain rate thickening which means that the strain hardening increases with ex-tension rates. Similarly to the measurement of SHI@1s-1, a strain hardening index (SHI) can be determined at different strain rates. A strain hardening index (SHI) is defined as the slope of the logarithm to the basis 10 of the tensile stress growth function as function of the logarithm to the basis 10 of the Hencky strain between Hencky strains 1.00 and 3.00 at a temperature of 180 °C, where a [email protected] s-1 is determined with a deformation rate of 0.10 s"1, a [email protected] s-1 is determined with a deformation rate of 0.30 s-1, a SH)@3 s-1 is determined with a deformation rate of 3.00 s-1, a SH!@10s-1 is determined with a deformation rate of 10.0 s-1. In comparing the strain hardening index (SHI) at those five strain rates of 0.10, 0.30, 1.00, 3.00 and 10.0s-1 the slope of the strain hardening index (SHI) as function of the logarithm to the basis 10 of is a characteristic measure for multi-branching. Therefore, a multi-branching index (MBI) is defined as the slope of SHI as a function oflg.e. the slope of a linear fitting curve of the strain hardening index (SHI) versus applying the least square method, preferably the strain hardening index (SHI) is de¬fined at deformation rates between 0.05 s"1 and 20.0 s"1, more preferably between 0.10 s"1 and 10.0 s"1, still more preferably at the deformations rates 0.10, 0.30, 1.00, 3.00 and 10.0 s"1. Yet more preferably the SHI-values determined by the deformations rates 0.10, 0.30, 1.00, 3.00 and 10.0 s"1 are used for the linear fit accord-ing to the least square method when establishing the multi-branching index (MBI). Hence, a further preferred requirement of the invention is a multi-branching index (MBI) of at least 0.15, more preferably of at least 0.20, and still more preferred of at least 0.25. In a still more pre-ferred embodiment the multi-branching index (MBI) is at least 0.28. It is in particular preferred that the polypropylene according to this invention has branching index g' of less than 1.00, a strain hardening index (SHI@1s"1) of at least 0.30 and multi-branching index (MBI) of at least 0.15. Still more preferred the polypropylene according to this invention has branching index g' of less than 0.80, a strain hardening index (SHI@1s-1) of at least 0.40 and multi-branching index (MBI) of at least 0.15. In another preferred embodiment the polypropylene according to this invention has branching index g' of less than 1.00, a strain hardening index (SHI@1s"1) of at least 0.30 and multi-branching index (MBI) of at least 0.20. In still another preferred em-bodiment the polypropylene according to this invention has branch-ing index g' of less than 1.00, a strain hardening index (SHI@1s-1) of at least 0.40 and multi-branching index (MBI) of at least 0.20. In yet another preferred embodiment the polypropylene according to this invention has branching index g' of less than 0.80, a strain hardening index (SHi@1s"1) of at least 0.50 and multi-branching index (MBI) of at least 0.30. Accordingly, the polypropyienes of the present invention, i.e. multi-branched polypropylenes, are characterized by the fact that their strain hardening index (SHI) increases with the deformation rate i.e. a phenomenon which is not observed in other polypropylenes. Single branched polymer types (so called Y polymers having a back-bone with a single long side-chain and an architecture which resem-bles a or H-branched polymer types (two polymer chains cou-pled with a bridging group and a architecture which resemble an "H") as well as linear or short chain branched polymers do not show such a relationship, i.e. the strain hardening index (SHI) is not Influenced by the deformation rate (see Figures 2 and 3). Accordingly, the strain hardening index (SHI) of known polymers, in particular known poly-propylenes and polyethylenes, does not increase or increases only negligible with increase of the deformation rate Industrial conversion processes which imply elongational flow operate at very fast extension rates. Hence the advantage of a material which shows more pronounced strain hardening (measured by the strain harden-ing index SHI) at high strain rates becomes obvious. The faster the material is stretched, the higher the strain hardening index (SHI) and hence the more stable the material will be in conversion. Especially in the fast extrusion process, the melt of the multi-branched polypro-pylenes has a high stabifity. For further information concerning the measuring methods applied to obtain the relevant data for the branching index the tensile stress growth function the Hencky strain rate the Hencky strain s and the multi-branching index (MBI) it is referred to the example sec-tion. In a second embodiment, the present invention is related to a poly-propylene showing a strain rate thickening which means that the strain hardening increases with extension rates. A strain hardening index (SHI) can be determined at different strain rates. A strain hardening index (SHI) is defined as the slope of the tensile stress growth function as function of the Hencky strain s on a logarith-mic scale between 1.00 and 3.00 at a at a temperature of 180 °C, where a [email protected]"1 is determined with a deformation rate of 0.10 s-1, a [email protected]"1 is determined with a deformation rate of 0.30 s-1, a SHI@3s'1 is determined with a deformation rate of 3.00 s-1, a SHI@10s"1 is determined with a deformation rate of 10.0 s-1. In comparing the strain hardening index at those five strain rates of 0.10, 0.30, 1.0, 3.0 and 10s-1, the slope of the strain hardening index (SHI) as function of the logarithm to the basis 10 of is a characteristic measure for multi -branching. There-fore, a multi-branching index (MBI) is defined as the slope of SHI as a function of i.e. the slope of a linear fitting curve of the strain hardening index (SHI) versus applying the least square method, preferably the strain hardening index (SHI) is defined at de¬formation rates between 0.05 s"1 and 20.0 s-1, more preferably between 0.10 s-1 and 10.0 s-1, still more preferably at the deforma-tions rates 0.10, 0.30, 1.00, 3.00 and 10.0 s-1.Yet more preferably the SHI-values determined by the deformations rates 0.10, 0.30, 1.00, 3.00 and 10.0 s-1 are used for the linear fit according to the least square method when establishing the multi-branching in-dex (MBI). Hence, in the second embodiment the polypropylene has a multi-branching index (MBI) of at least 0.15. Surprisingly, it has been found that polypropylenes with such charac-teristics have superior properties compared to the polypropylenes known in the art. Especially, the melt of the polypropylenes in the extrusion process has a high stability. The new polypropylenes are characterized in particular by exten-sional melt flow properties. The extensional flow, or deformation that involves the stretching of a viscous material, is the dominant type of deformation in converging and squeezing flows that occur in typical polymer processing operations. Extensional melt flow measurements are particularly useful in polymer characterization because they are very sensitive to the molecular structure of the polymeric system be-ing tested. When the true strain rate of extension, also referred to as the Hencky strain rate, is constant, simple extension is said to be a "strong flow" in the sense that it can generate a much higher degree of molecular orientation and stretching than flows in simple shear. As a consequence, extensional flows are very sensitive to crystallinity and macro-structural effects, such as long-chain branching, and as such can be far more descriptive with regard to polymer characteri-zation than other types of bulk rheological measurement which apply shear flow. The first requirement according to the present invention is that the polypropylene has a multi-branching index (MBI) of at least 0.15, more preferably of at least 0.20, and still more preferred of at least 0.30. As stated above, the multi-branching index (MBI) is defined as the slope of the strain hardening index(SHI) as a function of Ig [d Accordingly, the polypropylenes of the present invention, i.e. multi-branched polypropylenes, are characterized by the fact that their strain hardening index (SHI) increases with the deformation rate i.e. a phenomenon which is not observed in other polypropylenes. Single branched polymer types (so called Y polymers having a back-bone with a single long side-chain and an architecture which resem-bles a "Y") or H-branched polymer types (two polymer chains cou-pled with a bridging group and a architecture which resemble an "H") as well as linear or short chain branched polymers do not show such a relationship, i.e. the strain hardening index (SHI) is not influenced by the deformation rate (see Figures 2 and 3). Accordingly, the strain hardening index (SHI) of known polymers, in particular known poly-propylenes, does not increase or increases only negligible with in-crease of the deformation rate Industrial conversion proc-esses which imply elongational flow operate at very fast extension rates. Hence the advantage of a material which shows more pro-nounced strain hardening (measured by the strain hardening index (SHI)) at high strain rates becomes obvious. The faster the material is stretched, the higher the strain hardening index and hence the more stable the material will be in conversion. Especially in the fast extrusion process, the melt of the multi-branched polypropylenes has a high stability. A further requirement is that the strain hardening index (SHI@1s-1) shall be at least 0.30, more preferred of at least 0.40, still more pre¬ferred of at least 0.50. The strain hardening index (SHI) is a measure for the strain harden¬ing behavior of the polypropylene melt. In the present invention, the strain hardening index (SHI@1s-1) has been measured by a deforma-tion rate of 1.00 s-1at a temperature of 180 °C for determining the strain hardening behavior, wherein the strain hardening in-dex (SHI) is defined as the slope of the tensile stress growth func-tion a function of the Hencky strain s on a logarithmic scale between 1.00 and 3.00 (see figure 1). Thereby the Hencky strain is defined by the formula wherein the Hencky strain rate is defined by the formula is the fixed, unsupported length of the specimen sample being stretched which is equal to the centerline distance between the master and slave drums, "R" is the radius of the equi-dimensional windup drums, and is a constant drive shaft rotation rate. Inturn the tensile stress growth function is defined by the formula the Hencky strain rate is defined as for the Hencky strain s "F" is the tangential stretching force, calculated from the measured torque signal "T" "R" is the radius of the equi-dimensional windup drums "T" is the measured torque signal, related to the tangential stretching forceT" "A" is the instantaneous cross-sectional area of a stretched molten specimen "A0" is the cross-sectional area of the specimen in the solid state (i,e. prior to melting), "ds" is the solid state density (determined according to ISO 1183) and "dM" the melt density (determined according to ISO 1133; procedure B) of the polymer. In addition, it is preferred that the branching index g' shall be less than 1.00, more preferably less than 0.90, still more preferably less than 0.80. In the preferred embodiment, the branching index g' shall be less than 0.70. The branching index g' defines the degree of branching and correlates with the amount of branches of a polymer. The branching index g' is defined as in which g' is the branching index, is the intrinsic viscosity of the branched poly- propylene and is the intrinsic viscosity of the linear polypropyl- ene having the same weight average molecular weight (within a range of ±10%) as the branched polypropylene. Thereby, a low g'-value is an indicator for a high branched polymer. In other words, if the g'-value decreases, the branching of the polypropylene in-creases. Reference is made in this context to B.H. Zimm and W.H. Stockmeyer, J. Chem. Phys. 17,1301 (1949). This document Is herewith included by reference. The intrinsic viscosity needed for determining the branching index g' is measured according to DIN ISO 1628/1, October 1999 (in Decalin at135°C). For further information concerning the measuring methods applied to obtain the relevant data for the a multi-branching index (MBI), , the tensile stress growth function the Hencky strain rate the Hencky strain s and the branching index g'it is referred to the exam-pie section. It is in particular preferred that the polypropylene according to this invention has branching index g' of less than 1.00, a strain hardening index (SHI@1s"1) of at least 0.30 and multi-branching index (MBI) of at least 0.15. Still more preferred the polypropylene according to this invention has branching index g' of less than 0.80, a strain hardening index (SHI@1s"1) of at least 0.40 and multi-branching index (MBI) of at least 0.15. In another preferred embodiment the polypropylene according to this invention has branching index g' of less than 1.00, a strain hardening index (SHl@1s-1) of at least 0.30 and multi-branching index (MBI) of at least 020. In still another preferred em-bodiment the polypropylene according to this invention has branch-ing index g' of less than 1.00, a strain hardening index (SHI@1s-1) of at least 0.40 and multi-branching index (MBI) of at least 020. In yet another preferred embodiment the polypropylene according to this invention has branching index g' of less than 0.80, a strain hardening index (SHI@1s-1) of at least 0.50 and multi-branching index (MBI) of at least 030. The further features mentioned below apply to both embodiment, i.e. the first and the second embodiment as defined above. Furthermore, it is preferred that the polypropylene has a melt flow rate (MFR) given in a specific range. The melt flow rate mainly de-pends on the average molecular weight. This is due to the fact that long molecules render the material a lower flow tendency than short molecules. An increase in molecular weight means a decrease in the MFR-value. The melt flow rate (MFR) is measured in g/10 min of the polymer discharged through a defined dye under specified tempera-ture and pressure conditions and the measure of viscosity of the polymer which, in turn, for each type of polymer is mainly influenced by its molecular weight but also by its degree of branching. The melt flow rate measured under a load of 2.16 kg at 230 °C (ISO 1133) is denoted as Accordingly, it is preferred that in the present in- vention the polypropylene has an in a range of 0.01 to 1000.00 g/10 min, more preferably of 0.01 to 100.00 g/10 min, still more preferred of 0.05 to 50 g/10 min. In a preferred embodiment, the MFR is in a range of 1.00 to 11.00 g/10 min. In another preferred embodiment, the MFR is in a range of 3.00 to 11.00 g/10 min. The number average molecular weight (Mn) is an average molecular weight of a polymer expressed as the first moment of a plot of the number of molecules in each molecular weight range against the mo-lecular weight. In effect, this is the total molecular weight of all mole-cules divided by the number of molecules. In turn, the weight aver-age molecular weight (Mw) is the first moment of a plot of the weight of polymer in each molecular weight range against molecular weight. The number average molecular weight (Mn) and the weight average molecular weight (Mw) as well as the molecular weight distribution are determined by size exclusion chromatography (SEC) using Wa-ters Alliance GPCV 2000 instrument with online viscometer. The oven temperature is 140 °C. Trichlorobenzene is used as a solvent. It is preferred that the polypropylene has a weight average molecular weight (Mw) from 10,000 to 2,000,000 g/mol, more preferably from 20,000 to 1,500,000 g/mol. More preferably, the polypropylene according to this invention shall have a rather high pentade concentration, i.e. higher than 90 %, more preferably higher than 92 % and most preferably higher than 93 %. In another preferred embodiment the pentade concentration is higher than 95 %. The pentade concentration is an indicator for the narrowness in the regularity distribution of the polypropylene. tn addition, it is preferred that the polypropylene has a melting tem-perature Tm of higher than 125 °C. It is in particular preferred that the melting temperature is higher than 125 °C if the polypropylene is a polypropylene copolymer as defined below, in turn, in case the polypropylene is a polypropylene homopolymer as defined below, it is preferred, that polypropylene has a melting temperature of higher than 150 °C, more preferred higher than 155 °C. More preferably, the polypropylene according to this invention is mul-timodal, even more preferred bimodal. "Multimodal" or "multimodal distribution" describes a frequency distribution that has several rela-tive maxima. In particular, the expression "modality of a polymer" re-fers to the form of its molecular weight distribution (MWD) curve, i.e. the appearance of the graph of the polymer weight fraction as a func-tion of its molecular weight. If the polymer is produced in the sequen-tial step process, i.e. by utilizing reactors coupled in series, and us-ing different conditions in each reactor, the different polymer frac- tions produced in the different reactors each have their own molecu¬lar weight distribution which may considerably differ from one an¬other. The molecular weight distribution curve of the resulting final polymer can be seen at a super-imposing of the molecular weight distribution curves of the polymer fraction which will, accordingly, show a more distinct maxima, or at least be distinctively broadened compared with the curves for individual fractions. A polymer showing such molecular weight distribution curve is called bimodal or multimodal, respectively. The polypropylene is preferably bimodal. The polypropylene according to this invention can be homopoiymer or a copolymer. Accordingly, the homopoiymer as well as the co-polymer can be a multimodal polymer composition. The expression homopoiymer used herein relates to a polypropylene that consists substantially, i.e. of at least 97 wt%, preferably of at least 99 wt%, and most preferably of at least 99.8 wt% of propylene units. tn case the polypropylene according to this invention is a propylene copolymer, it is preferred that the comonomer is ethylene. However, also other comonomers known in the art are suitable. Preferably, the total amount of comonomer, more preferably ethylene, in the propyl-ene copolymer is up to 30 wt%, more preferably up to 25 wt%. In a preferred embodiment, the polypropylene is a propylene co-polymer comprising a polypropylene matrix and an ethylene-propylene rubber (EPR). The polypropylene matrix can be a homopolymer or a copolymer, more preferably multimodal, i.e. birnodal, homopolymer or a multi-modal, i.e. birnodal, copolymer, in case the polypropylene matrix is a propylene copolymer, then it is preferred that the comonomer is eth-ylene or butene. However, also other comonomers known in the art are suitable. The preferred amount of comonomer, more preferably ethylene, in the polypropylene matrix is up to 8.00 Mol%. In case the propylene copolymer matrix has ethylene as the comonomer compo¬nent, it is in particular preferred that the amount of ethylene in the matrix is up to 8.00 Mol%, more preferably less than 6.00 Mol%. In case the propylene copolymer matrix has butene as the comonomer component, it is in particular preferred that the amount of butene in the matrix is up to 6.00 Mol%, more preferably less than 4.00 Mol%. Preferably, the ethylene-propylene rubber (EPR) in the total propyl-ene copolymer is up to 80 wt%. More preferably the amount of ethyl-ene-propylene rubber (EPR) in the total propylene copolymer is in the range of 20 to 80 wt%, still more preferably in the range of 30 to 60 wt%. In addition, it is preferred that the polypropylene being a copolymer comprising a polypropylene matrix and an ethylene-propylene rubber (EPR) has an ethylene-propylene rubber (EPR) with an ethylene-content of up to 50 wt%. In the following, the present invention is described by way of exam-ples. Examples 1. Definitions/Measuring Methods The following definitions of terms and determination methods apply for the above general description of the invention as well as to the below examples unless otherwise defined. A. Pentad Concentration For the meso pentad concentration analysis, also referred herein as pentad concentration analysis, the assignment analysis is under-taken according to T Hayashi, Pentad concentration, R. Chujo and T. Asakura, Polymer 29 138-43 (1988) and Chujo R, et al., Polymer 35 339(1994) B. Multi-branching Index 1. Acquiring the experimental data Polymer is melted at T=180 °C and stretched with the SER Universal Testing Platform as described below at deformation rates of 0.3 1.0 3.0 and 10 s"1 in subsequent experiments. The method to acquire the raw data is described in Sentmanat et al., J. Rheol. 2005, Measuring the Transient Elongational Rheology of Polyethylene Melts Using the SER Universal Testing Platform. Experimental Setup A Paar Physica MCR300, equipped with a TC30 temperature control unit and an oven CTT600 (convection and radiation heating) and a SERVP01- 025 extensional device with temperature sensor and a software RHEO-PLUS/32 V2.66 is used. Sample Preparation Stabilized Pellets are compression moulded at 220°C (gel time 3min, pressure time 3 min, total moulding time 3+3=6min) in a mould at a pres-sure sufficient to avoid bubbles in the specimen, cooled to room tempera-ture. From such prepared plate of 0.7 mm thickness, stripes of a width of 10 mm and a length of 18 mm are cut. Check of the SER Device Because of the low forces acting on samples stretched to thin thick-nesses, any essential friction of the device would deteriorate the precision of the results and has to be avoided. In order to make sure that the friction of the device is less than a thresh¬old of 5x10-3 mNm (Milli-Newtonmeter) which is required for precise and correct measurements, following check procedure is performed prior to each measurement: • The device is set to test temperature (180 °C) for minimum 20 minutes without sample in presence of the clamps • A standard test with 0.3 s-1 is performed with the device on test temperature (180 °C) • The torque (measured in mNm) is recorded and plotted against time • The torque must not exceed a value of 5x mNm to make sure that the friction of the device is in an acceptably low range Conducting the experiment The device is heated for 20 min to the test temperature (180 °C measured with the thermocouple attached to the SER device) with clamps but with¬out sample. Subsequently, the sample (0.7x10x18 mm), prepared as de¬scribed above, is clamped into the hot device. The sample is allowed to melt for 2 minutes +/- 20 seconds before the experiment is started. During the stretching experiment under inert atmosphere (nitrogen) at constant Hencky strain rate, the torque is recorded as function of time at isothermal conditions (measured and controlled with the thermocouple attached to the SER device). After stretching, the device is opened and the stretched film (which is winded on the drums) is inspected. Homogenous extension is required. It can be judged visually from the shape of the stretched film on the drums if the sample stretching has been homogenous or not. The tape must me wound up symmetrically on both drums, but also symmetrically in the up-per and lower half of the specimen. If symmetrical stretching is confirmed hereby, the transient elongational viscosity calculates from the recorded torque as outlined below. 2. Evaluation For each of the different strain rates applied, the resulting ten- sile stress growth function is plotted against the total Hencky strain z to determine the strain hardening behaviour of the melt, see Figure 1. In the range of Hencky strains between 1.0 and 3.0, the tensile stress growth function can be well fitted with a function -37- where c1 and c2 are fitting variables. Such derived c2 is a measure for the strain hardening behavior of the melt and called Strain Hardening Index SHI. Dependent on the polymer architecture, SHI can - be independent of the strain rate (linear materials, structures) - increase with strain rate (short chain-, hyper- or multi-branched structures). This is illustrated in Figure 2. For polyethylene, linear (HDPE), short-chain branched (LLDPE) and hyperbranched structures (LDPE) are well known and hence they are used to illustrate the structural analytics based on the results on ex-tensional viscosity. They are compared with a polypropylene with Y and H-structures with regard to their change of the strain-hardening behavior as function of strain rate, see Figure 2 and Table 1. To illustrate the determination, of SHI at different strain rates as well as the multi-branching index (MB!) four polymers of known chain chitecture are examined with the analytical procedure described above. . The first polymer is a H- and Y-shaped polypropylene homopoiymer made according to EP 879 830 ("A") example 1 through adjusting the MFR with the amount of butadiene. It has a MFR230/2.16 of 2.0g/10min, a tensile modulus of 1950 MPa and a branching index g'of 0.7.. I he second polymer is a commercial hyperbranched LDPE, Borealis "B", made in a high pressure process known in the art. It has a MFR190/2.16 of 4.5 and a density of 923 kg/m3. The third polymer is a short chain branched LLDPE, Borealis "C, made in a low pressure process known in the art. It has a MFR190/2.16 of 1.2 and a density of 919 kg/m3. The fourth polymer is a linear HDPE, Borealis "D", made in a low pressure process known in the art. It has a MFR190/2.16 of 4.0 and a density of 954 kg/m3. The four materials of known chain architecture are investigated by means of measurement of the transient elongationa! viscosity at 180 °C at strain rates of 0.10, 0.30, 1.0, 3.0 and 10 s"1. Obtained data (transient elongational viscosity versus Hencky strain) is fitted with a function and c2 is the strain hardening index (SHI) at the particular strain rate. for each of the mentioned strain rates. The parameters c1 and c2 are found through plotting the logarithm of the transient elongational vis-cosity against the logarithm of the Hencky strain and performing a linear fit of this data applying the least square method. The parame-20 ter c-1 calculates from the intercept of the linear fit of the data versus fg(s) from This procedure is done for a!) five strain rates and hence, are determined, see Figure 1 and Table 1. Table 1: SHl-values From the strain hardening behaviour measured by the values of the SHi@1s'1 one can already clearly distinguish between two groups of polymers: Linear and short-chain branched have a signifi- cantly smaller than 0.30. In contrast, the Y and H-branched as well as hyper-branched materials have a significantly larger than 0.30. In comparing the strain hardening index at those five strain rates of 0.10, 0.30, 1.0, 3.0 and 10s"1, the slope of SHI as function of the logarithm of is a characteristic measure for multi- branching. Therefore, a multi-branching index (MBI) is calculated from the slope of a linear fitting curve of SHI versus The parameters c3 and MBI are found through plotting the SHI against the logarithm of the Hencky strain rate and performing a linear fit of this data applying the least square method. Please con¬fer to Figure 2. Tabie 2: Multi-branched-index (MBI) The multi-branching index MBI allows now to distinguish between Y or H-branched polymers which show a MBI smaller than 0.05 and hyper-branched polymers which show a MBI larger than 0.15. Fur-ther, it allows to distinguish between short-chain branched polymers with MBI larger than 0.10 and linear materials which have a MBI smaller than 0.10. Similar results can be observed when comparing different polypro-pylenes, i.e. polypropylenes with rather high branched structures have higher SHI and MBI-values, respectively, compared to their lin-ear counterparts. Similar to the hyper-branched polyethylenes the new developed polypropylenes show a high degree of branching. However the polypropylenes according to the instant invention are clearly distinguished in the SHI and MB[-vaiues when compared to known hyper-branched polyethylenes. Without being bound on this theory, it is believed, that the different SHI and MBI-values are the result of a different branching architecture. For this reason the new found branched polypropylenes according to this invention are des-ignated as multi-branched. Combining both, strain hardening index (SHI) and multi-branching index (MB!), the chain architecture can be assessed as indicated in Table 3: Table 3: Strain Hardening Index (SHI) and Multi-branching Index (MBI) for various chain architectures C. Further Measuring Methods Particle size distribution: Particle size distribution is measured via Coulter Counter LS 200 at room temperature with n-heptane as me-dium. NMR NMR-spectroscopy measurements: The 13C-NMR spectra of polypropyienes were recorded on Bruker 4O0.MHz specframetar si 130 °C .from samples. dissoJved in 1,2,4-trichlorobenzene/benzene-d6 (90/10 w/w). For the pentad analysis the assignment is done according to the methods described in literature: (T. Hayashi, Y. Inoue, R. Chujo, and T. Asakura, Polymer 29 138-43 (1988).and Chujo R, et al,Po\ymer 35 339 (1994). The NMR-measurement was used for determining the mmmm pentad concentration in a manner well known in the art. Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (MWD) are determined by size exclusion chromatography (SEC) using Waters Alliance GPCV 2000 instrument with online viscometer. The oven temperature is 140 °C. Trichlorobenzene is used as a solvent (fSO 16014). Melting temperature Tm, crystallization temperature Tc, and the de¬gree of crystallinity: measured with Mettler TA820 differential scanning calorimetry (DSC) on 5-10 mg samples. Both crystallization and melting curves were obtained during 10°C/min cooling and heating scans be-tween 30 °C and 225 °C. Melting and crystallization temperatures were taken as the peaks of endotherms and exotherms. Aiso the melt- and crystallization enthalpy (Hm and He) were measured by the DSC method according to ISO 11357-3. MFR2: measured according to ISO 1133 (230°C, 2.16 kg load). Intrinsic viscosity: is measured according to DIN ISO 1628/1, Oc-tober 1999 (in Decalin at 135 °C). Comonomer content is measured with Fourier transform infrared spec-troscopy (FTIR) calibrated with 13C-NMR. When measuring the ethylene content in polypropylene, a thin film of the sample (thickness about 250 mm) was prepared by hot-pressing. The area of -CH2- absorption peak (800-650 cm"1) was measured with Perkin Elmer FTIR 1600 spectrome¬ter. The method was calibrated by ethylene content data measured by 13C-NMR. Porosity: is measured according to DIN 66135 Surface area: is measured according to !SO 9277 2. Examples Example 1 (comparison) A silica supported metallocene catalyst (I) was prepared according to WO 01/48034 (example 27). The porosity of the support is 1.6 ml/g. An asymmetric metallocene dimethylsilyl phenyI-indeny()(2-isopropyl zirkonium dichloride has been used. A 5 liter stainless steel reactor was used for propylene polymeriza-tions. 110 g of liquid propylene (Borealis polymerization grade) was fed to reactor. 0.2 m/ triethylaluminum (100%, purchased from Crompton) was fed as a scavenger and 3.7 mmol hydrogen (quality 6.0, supplied by Aga) as chain transfer agent. Reactor temperature was set to 30 °C. 21 mg catalyst was flushed into to the reactor with nitrogen overpressure. The reactor was heated up to 60 in a pe- riod of about 14 minutes. Polymerization was continued for 30 minutes at then propylene was flushed out, the polymer was dried and weighed. Polymer yield was weighed to 182 g. The SHI@1s-1 is 0.29. The MB( is 0.04. The g' is 1.00. This indi- cates linear structure. The 10min. The melting temperature is 155 °C. Example 2 (comparison) The catalyst (II) was prepared as described in example 5 of WO 03/051934. A 5 liter stainless steel reactor was used for propylene polymeriza¬tions. 1100 g of liquid propylene (Borealis polymerization grade) was fed to reactor. 0.1 ml triethylalumin'um (100 %, purchased from Crompton) was fed as a scavenger and 15 mmol hydrogen (quality 6.0, supplied by Aga) as chain transfer agent. Reactor temperature was set to 30 °C. 21 mg catalyst was flushed into to the reactor with nitrogen overpressure. The reactor was heated up to 70 °C in a pe-riod of about 14 minutes. Polymerization was continued for 50 minutes at 70 °C, then propylene was flushed out, 5 mmol hydro-gen were fed and the reactor pressure was increased to 20 bars by feeding (gaseous-) propylene. Polymerization continued in gas-phase for 210 minutes, then the reactor was flashed, the polymer was dried and weighed. Polymer yield was weighed to 790 g, that equals a productivity of 36,9 The SHI@1s"1 is 0.15. The MB! is 0.12. The g' is 0.95. This indicates short-chain branched structure (SCB). Example 3 (inventive) A support-free catalyst (III) has been prepared as described in ex-ample 5 of WO 03/051934 whilst using an asymmetric metadocene dimethylsilyl [(2-methyl-(4'-tert.butyl)-4-phenyl-indenyl)(2-isopropyl-(4'-tert.butyl)-4-phenyl-indenyl)]zirkonium dichloride. A "5 liter stainless steel reactor was used for propylene polymeriza-tions. 1100 g of liquid propylene (Borealis polymerization grade) was fed to reactor. 0.1 ml triethylaluminum (100 %, purchased from Crompton) was fed as a scavenger and 3.7 mmol hydrogen (quality 6.0, supplied by Aga) as chain transfer agent. Reactor temperature was set to 30 °C. 20 mg catalyst were flushed into to the reactor with nitrogen overpressure. The reactor was heated up to 70 °C in a pe-riod of about 14 minutes. Polymerization was continued for 30 minutes at 70 °C, then propylene was flushed out, the polymer was dried and weighed. Polymer yield was weighed to =390 g. The SHI@1s"1 is 0.55. The MBI is 0.32. The g' is 0.70. The MFR is 10.7. This indicates multi-branched structure. More data is given in Table 4 and Figure 4. Example 4 (inventive) The same catalyst (III) as that of example 3 was used. A 5 liter stainless steel reactor was used for propylene polymeriza-tions. 1100 g of liquid propylene + 50 g of ethylene (Borealis polym-erization grade) was fed to reactor. 0.1 ml triethylaluminum (100 %, pcrrcrrased from Crompfan) was fed as a scavenger and 7.5 mmol hydrogen (quality 6.0, supplied by Aga) as chain transfer agent. Re-actor temperature was set to 30 °C. 21 mg catalyst were flushed into to the reactor with nitrogen overpressure. The reactor was heated up to 70 °C in a period of about 14 minutes. Polymerization was contin-ued for 30 minutes at 70 °C, then propylene was flushed out, the polymer was dried and weighed. The total ethylene content is 4.2 wt%. The melting point is 125.6 °C. Polymer yield was weighed to 258 g. The SHI@1s-1 is 0.66. The MBI is 0.28. The g' is 0.70. The MFR is 8.6. This indicates multi-branched structure. More data is given in Table 4 and Figure 4. Table 4: Results New Claims A process for the preparation of a polypropylene using a catalyst system of low porosity, the catalyst system comprising an asymmetric catalyst, wherein the catalyst system has a porosity of less than 1.40 ml/g determined according to DIN 66135, and wherein the asymmetric catalyst is in the form of solid catalyst particles. The process according to claim 1, the catalyst system being a non-silica supported system. The process according to claim 1 or 2, wherein the catalyst system has a surface area of less than 25 m2/g, measured according to ISO 9277. The process according to any of the preceding claims, wherein the asymmetric catalyst has at least two chemically different organic ligands. Process according to claim 4, wherein the two different organic ligands of the asymmetric catalyst are linked via a bridge, preferably via a bridge as defined in any one of the claims 14 to 16. The process according to any one of the preceding claims, wherein the asymmetric catalyst is a transition metal compound of formula (I) wherein M is a transition metal of group 3 to 10 or the periodic table (IUPAC), or of an actinide or lantanide, each X is independently a monovalent anionic ligand, such as a- ligand, each L is independently: an organic ligand which coordinates to M, R is abridging group linking two ligands L m is 2 or 3, n is 0 or 1, q is 1,2 or 3, m+q is equal to the valency of the metal, and with the proviso that at least two ligands "L" are of different chemical structure. The process according to claim 6, wherein the ligand L is (a) a substituted or unsubstituted cycloalkyldiene, or (b) an acyclic, igand composed of atoms from Groups 13 to 16 of the Periodic Table, or (c) a cyclic mono-, bi- or multidentate ligand composed of unsubstituted or substituted mono-, bi- or multicyclic ring systems selected from aromatic or non-aromatic or partially saturated ring systems and containing carbon ring atoms. The process according to any one of the preceding claims, wherein the asymmetric catalysthas a formula (II) wherein M is Zr, Hf or Ti, preferably Zr each X is independently a monovalent anionic ligand, such as a- ligand, each Cp is independently an unsaturated organic cyclic ligand which coordinates to M, R is a bridging group linking two ligands L, m is 2, n is 0 or 1, more preferably 1, q is 1,2 or 3, m+q is equal to the valency of the metal, and at least one Cp-ligand is selected from the group consisting of unsubstituted cyclopentadienyl, unsubstituted indenyl, unsubstituted tetrahydroindenyl, unsubstituted fluorenyl, substituted cyclopentadienyl, substituted indenyl, substituted tetrahydroindenyl, and substituted fluorenyl, - with the proviso in case both Cp-ligands are selected from the above stated group that both Cp-ligands must chemically differ from each other. The process according to claim 8, wherein M is Zr, X is CI, n is 1, and q is 2. The process according to claim 9, wherein both Cp-ligands are selected from the group consisting of substituted cyclopenadienyl-ring, substituted indenyl-ring, substituted tetrahydroindenyl-ring, and substituted fluorenyl-ring, and wherein the Cp-ligands differ in the substituents bonded to the rings. The process according to any one of the preceding claims, wherein the organic ligands are substituted indenyl-rings. The process according to any one of the preceding claims 7 to 11, wherein the substituents bonded to the ring are independently selected from the group consisting of Ci-C6 alkyl moiety, aromatic ring moiety and heteroaromatic ring moiety. The process according to any one of the preceding claims 8 to 12, wherein both Cp-rings have two substituents, wherein one substituent is a substituted phenyl moiety and the other substituent is a C1-C6 alkyl moiety, wherein both Cp-rings preferably differ in theC1-C6 alkyl moiety. The process according to any one of the preceding claims, wherein the moiety "R" has the formula (III) wherein Y is C, Si or Ge, and R' isC1to C2o alkyl, C1-C6 aryl, C7-C12 arylalkyl or trimethylsilyl. The process according to claim 14, wherein Y is Si. The process according to claim 14 or 15, wherein "R" is selected from the group consisting of -Si(C1-C6 alkyl)2- _Si(phenyl)2-, and -Si(C1-C6 alkyl)(phenyl)- The process according to any one of the preceding claims, wherein the asymmetric catalyst is dimethylsilandiyi [(2-methyl-(4'-tert. butyl)-4-phenyl-indenyl)(2-isopropyl-(4'-tert. buty|)_4-phenyl-indenyl)]zirconium dichloride. The process according to any one of the preceding claims, wherein the process temperature is higher than 60 °c. The process according to any one of the preceding claims, being a multi-stage process. The process according to claim 19, wherein polymerization is carried out in at least two reactors in serial configuration. The process according to claim 19 or 20, wherein polymerization is carried out in at least one bulk reactor whjch is a loop reactor and at least one gas phase reactor. The process according to claim 21, wherein the bulk reactor is operated at a temperature of 40 °C to 110 °C and a pressure of 20 bar to 80 bar. The process according to claim 21 or 22, wherein the gas phase reactor is operated at a temperature of 50 °C to 130 °C and a pressure of 5 bar to 50 bar. The process according to one of the preceding claims, wherein the polypropylene has a. a branching index g' of less than 1.00 and b. a strain hardening index (SHI@1s"1) of at least 0.30 measured by a deformation rate de/dt of 1.00 s"1 at a temperature of 180 °C, wherein the strain hardening index (SHI) is defined as the slope of the logarithm to the basis 10 of the tensile stress growth function as function of the logarithm to the basis 10 of the Hencky strain in the range of Hencky strains between 1 and 3. The process according to one of the preceding claims, wherein the polypropylene has a multi-branching index (MBI) of at least 0.15, wherein the multi-branching index (MBI) is defined as the slope of strain hardening index (SHI) as function of the logarithm to the basis 10 of the Hencky strain rate wherein s the deformation rate, is the Hencky strain, and the strain hardening index (SHI) is measured at 180 °C, wherein the strain hardening index (SHI) is defined as the slope of the logarithm to the basis 10 of the tensile stress growth function as function of the logarithm to the basis 10 of the Hencky strain in the range of Hencky strains between 1 and 3. The process according to one of the preceding claims, wherein the polypropylene is a propylene copolymer comprising a propylene matrix and an ethylene-propylene rubber (EPR). A process for the preparation of a polypropylene using a catalyst system of low porosity, the catalyst system comprising an asymmetric catalyst, wherein the catalyst system has a porosity of less than 1.40 ml/g determined according to DIN 66135 substantially as herein described with reference to the foregoing description, examples and the accompanying drawings. Dated this 15th day of October 2008 SHARAD VADEHRA of KAN AND KRISHILM ATTORNEY FOR THE APPLICANTS To The Controller of Patents The Patent Office Mumbai

Documents:

2199-MUMNP-2008-ABSTRACT(3-11-2011).pdf

2199-MUMNP-2008-ABSTRACT(GRANTED)-(26-3-2012).pdf

2199-mumnp-2008-abstract.doc

2199-mumnp-2008-abstract.pdf

2199-MUMNP-2008-ASSIGNMENT(26-12-2008).pdf

2199-MUMNP-2008-CANCELLED PAGES(9-3-2011).pdf

2199-MUMNP-2008-CLAIMS(AMENDED)-(3-11-2011).pdf

2199-MUMNP-2008-CLAIMS(AMENDED)-(9-3-2012).pdf

2199-MUMNP-2008-CLAIMS(GRANTED)-(26-3-2012).pdf

2199-mumnp-2008-claims.doc

2199-mumnp-2008-claims.pdf

2199-MUMNP-2008-CORRESPONDENCE(15-11-2011).pdf

2199-MUMNP-2008-CORRESPONDENCE(15-2-2012).pdf

2199-MUMNP-2008-CORRESPONDENCE(16-2-2012).pdf

2199-MUMNP-2008-CORRESPONDENCE(2-12-2008).pdf

2199-MUMNP-2008-CORRESPONDENCE(26-12-2008).pdf

2199-MUMNP-2008-CORRESPONDENCE(9-3-2009).pdf

2199-MUMNP-2008-CORRESPONDENCE(IPO)-(26-3-2012).pdf

2199-mumnp-2008-correspondence.pdf

2199-mumnp-2008-description(complete).doc

2199-mumnp-2008-description(complete).pdf

2199-MUMNP-2008-DESCRIPTION(GRANTED)-(26-3-2012).pdf

2199-MUMNP-2008-DRAWING(GRANTED)-(26-3-2012).pdf

2199-mumnp-2008-drawing.pdf

2199-MUMNP-2008-FORM 1(15-2-2012).pdf

2199-mumnp-2008-form 1.pdf

2199-MUMNP-2008-FORM 13(15-2-2012).pdf

2199-MUMNP-2008-FORM 18(2-12-2008).pdf

2199-MUMNP-2008-FORM 2(GRANTED)-(26-3-2012).pdf

2199-MUMNP-2008-FORM 2(TITLE PAGE)-(GRANTED)-(26-3-2012).pdf

2199-mumnp-2008-form 2(title page).pdf

2199-mumnp-2008-form 2.doc

2199-mumnp-2008-form 2.pdf

2199-MUMNP-2008-FORM 3(3-11-2011).pdf

2199-MUMNP-2008-FORM 3(9-3-2009).pdf

2199-mumnp-2008-form 3.pdf

2199-mumnp-2008-form 5.pdf

2199-MUMNP-2008-FORMAL DRAWING(2-12-2008).pdf

2199-MUMNP-2008-MARKED COPY-(9-3-2012).pdf

2199-mumnp-2008-pct-ib-301.pdf

2199-mumnp-2008-pct-ib-304.pdf

2199-mumnp-2008-pct-ib-311.pdf

2199-mumnp-2008-pct-ib-345.pdf

2199-mumnp-2008-pct-ib-346.pdf

2199-mumnp-2008-pct-ipea-401.pdf

2199-mumnp-2008-pct-ipea-402.pdf

2199-mumnp-2008-pct-ipea-405.pdf

2199-mumnp-2008-pct-ipea-409.pdf

2199-mumnp-2008-pct-ipea-416.pdf

2199-mumnp-2008-pct-isa-202.pdf

2199-mumnp-2008-pct-isa-210.pdf

2199-mumnp-2008-pct-isa-220.pdf

2199-mumnp-2008-pct-isa-237.pdf

2199-mumnp-2008-pct-ro-101.pdf

2199-mumnp-2008-pct-ro-105.pdf

2199-mumnp-2008-pct-ro-106.pdf

2199-mumnp-2008-pct-ro-132.pdf

2199-MUMNP-2008-POWER OF ATTORNEY(3-11-2011).pdf

2199-MUMNP-2008-REPLY TO EXAMINATION REPORT(3-11-2011).pdf

2199-MUMNP-2008-REPLY TO HEARING(9-3-2012).pdf

2199-MUMNP-2008-SPECIFICATION(AMENDED)-(9-3-2012).pdf

2199-mumnp-2008-wo international publication report a1.pdf