MXPA00007833A - Improved olefin polymerization process - Google Patents

Abstract

A process for preparing homopolymers and copolymers of addition polymerizable monomers, or mixtures of such monomers, and the resulting polymer, wherein the process comprising contacting said monomer or mixture under high monomer conversion polymerization conditions with a catalyst composition comprising:a) a catalyst system comprising a Group 3-10 metal complex;and c) a silane, or hydrocarbylsilane corresponding to the formula:JjSiH4-j or AnJjSiH4-(n+j) wherein:J is C1-40 hydrocarbyl, A is a C2-20 alkenyl group, n is 1 or 2, and j is 0 or 1;wherein the polymer comprises from 0.1 to 100 long chain branches per 10,000 carbons, and at least some of which comprise a silane branching center.

Description

PROCESS OF POLY MERIZATION OF OLEFINA M EJORADA The present invention relates to a process for polymerizing addition polymerizable monomers, such as ethylene or propylene, or combinations of one or more olefin monomers such as combinations of ethylene with one or more C3.8 a-olefins, and optionally one or more copolymerizable dienes for producing polymers having a high degree of long chain ramification (LCB) using a catalyst composition comprising a metal complex of Group 3-1 0 and a silane or hydrocarbylsilane branching agent. The resulting polymers can be usefully employed in the preparation of solid objects such as molds, films, sheets and foamed objects when molding, casting or similar processes. In WO 97/42234 a process for the preparation of polymers of vinylidene aromatic monomers having a stereoregular structure of high syndiotacticity is described, by the use of Group 4 metal coordination catalysts and a hydrocarbylsilane or dihydrocarbylsilane coadjuvant. In Journal of the American Chemical Societv, 1995, 17, 10747-19748, the use of silanes as chain transfer agents in metallocene-mediated olefin polymerizations was described. The products formed included polyolefins terminated in silyl. In US-A-5,272,236, 5,278,272, 5, 525,695, some ethylene homopolymers are disclosed and ethylene / α-olefin copolymers having an LCB of at least 3 chains per 1,000 carbon and a process for their preparation are described. wherein the reincorporation of oligomers or finished polymers of vinyl generated in situ in the developing polymer chain, especially by means of n continuous polymerization process. Although such a process is relatively effective in preparing ethylene homopolymers and copolymers, it is not particularly effective or possible to use to form long chain branches in homopolymers of C3-8 α-olefins, or co -omers of mixtures of C3.8 α-olefins. In US-A-5,665,800 the above-described process was used to prepare EPDM copolymers having a melt flow ratio, 1 1 0/12 greater than 5.63, a molecular weight distribution, Mw / Mn, defined by the equation : Mw / Mn < (11 0/12) - 4.63, and a critical cut stress at the beginning of the coarse melt fracture of more than about 4 x 1 06 dynes / cm2. Generally an increased long chain branching content in olefin polymers is desired due to the improved melting rheology of the resulting polymer. In US-A-5,444,145, copolymers of ethylene and a branched olefin monomer are described. Disadvantageously, the preparation of such copolymers by the use of the prior art requires the use of a relatively expensive olefin, which contains the desired preformed branched structure. Such a process is relatively inflexible and not suitable for commercial use. A process for forming long chain branched α-olefin copolymer products which can utilize normal monomers, for example, unbranched olefin, is still desired in the industry. For the teachings contained therein, prior US patents, publications and patent applications are incorporated herein by reference. In accordance with the present invention there is now provided a process for preparing homopolymers and copolymers of polymerizable addition monomers, or mixtures of such monomers, the process comprising contacting said monomer or mixture under conditions of high monomer conversion polymerization with a catalyst composition. comprising: a) a catalyst system comprising a metallic complex of the Group 3-1 0; and c) a silane compound corresponding to the formula; JjSih .j or AnJJSiH4. (N + J) where: J is C1 - 0 hydrocarbyl, A is a C2.20 alkenyl group, n is 1 or 2, and j is 0 or 1; wherein the polymer comprises from 0. 1 to 1 00 long chain branches per 10,000 carbons, at least some of which comprise a silane branching center. Compared to a polymerization process using a similar catalyst composition lacking the aforementioned silane branching agents, the present process achieves significantly improved efficiency in the generation of long chain branches. In addition, the present process can be used in the polymerization of monomers which are not amenable to the reincorporation of the β-hydride elimination products, thus allowing the first time preparation of polymers containing long chain branching from such monomers. Because the multiple reactive sites contained in the alkenyl substituted silane, the amount of silane necessary to achieve the desired branching is small and dependent on the polymerization conditions rarely exceeds 5 weight percent of the reaction mixture. The use of substituted silane with alkenyl may result in the formation of a degraded polymer. Any reference to the Periodic Table of the Elements herein must refer to the Periodic Table of the Elements, published and which has reserved the right of reproduction for CRC Press, I nc. , 1985. Also, any reference to a Series Group must be to the Series Group as reflected in this Periodic Table of the Elements, using the I UPAC system for numbering groups. Preferred silane or hydrocarbylsilane branching agents used herein include SiH 4, methylsilane, ethylsilane, n-butylsilane, octadecylsilane, phenylsilane and benzylsilane. Mixtures of the above silanes can also be used. Although SiH4 is a gas and is easily added to modern polymerization processes and subsequently extracted from the reaction mixture by devolatilization, the aryl silanes, especially phenyl silane or benzylsilane, are more reactive under the present polymerization and polymerization conditions. According to the above, they are more effective in forming long chain branches. Preferred alkenyl substituted silane branching agents used herein include ethenylsilane, 3-butenylsilane, 5-hexenylsilane, vinylcyclohexenylsilane, 7-octenylsilane, 3-butenyl methylsilane, 7-octadecenyl, 7-octenyl ethylsilane, ethanyl n-butylsilane, 7-octenyl octadecylsilane, butenyl phenylsilane and 7-octenyl benzylsilane. Mixtures of the above silanes can also be used. Although alkenyl silanes are preferably terminally unsaturated, alkenyl silanes containing internal unsaturated bonds, such as 6-octenylsilane, may also be employed as long chain branching agents in the present invention. The alkenylsilanes used to form the novel polymers of the present invention are obtained by the addition reaction of a diene, such as octadiene, to silane or to a silane substituted with hydrocarbyl under conditions well known to those skilled in the art. As used herein, the term "long chain branching" refers to pendent oligomeric hid rocarbyl groups attached to a polymer chain, groups which have a length of six or greater but which are not the result of comonomer polymerization. deliberately added, for example, propene, 1-butene, 1 -hexene, 1-ketene, or ramified olefin polymerization. The long chain branching in the present context includes polymer branches resulting from the reincorporation of remnants resulting from the ß-hydride removal process, with or without the participation of the silane. Such long chain branches further reflect the diversity of monomer present in the polymerization reactor, because in effect, are portions of preformed polymer which are reincorporated into a developing polymer chain. Various techniques already exist for measuring the extent of long chain branching in a copolymer. The main analytical techniques include those based on 13 C NMR analysis, optionally coupled with low angle laser light scattering or similar particle size measurement techniques. In addition, it is possible to arrive at an estimate of short chain branches, i.e., branches due to the remnant of comonomer C3.8, by preparing a control copolymer using a labeled monomer, such as 1-ketene or ethylene enriched of 1 3C. , under the assumption that a similar level of branch distribution will exist in copolymers made under comparative conditions using unmodified monomers. Therefore, the long chain branching level is determined by subtraction. In the present art, the long chain branching level can be further quantified from an understanding of the synbol branching centers present in the resulting copolymer, determined, for example, by NMR, in addition to which some chain branching may occur long conventional due to the previous continuous high conversion process technique. Preferred polymers according to the present invention contain from 0.3 to 10 long-chain branches per 10,000 carbons. The incidence of long chain branching can be increased by careful control of treatment conditions. For example, the use of a continuous solution polymerization process (in which reactor and catalyst agents are continuously added to a polymerization reactor and the product is continuously extracted from it) operating at high conversion conditions favors the incorporation of long chain branch due to a relative increased molar concentration of a long chain vinyl terminated monomer generated in situ. In addition, process conditions that result in high local concentrations of ß-hydride removal products, for example gas phase polymerization processes, also favor the formation of long chain branches. In the processes and products present, some of the long chain branches are the result of successive reactions of Si-H link metathesis involving the active catalyst center, the developing polymer chain and the silane. This is an iterative process that requires at least three interactions with the silane branching agent which can be represented as follows: M - polymer + SiH3J? M - H + SiH2J - polymer M - polymer + SiH2J - polymer? M - H + SiHJ - (polimer) 2 M - polimer + SiHJ - (polymer) 2? M - H + SiJ - (polymer) 3 wherein M indicates the active catalyst site bound to a developing polymer or hydrogen chain, and J is as previously defined. The resulting polymers contain only long chain, silane branch centers. It can be easily seen that the long chain ramification agent SiH4 is capable of an additional metathesis reaction in the above scheme, which could generate a novel tertiary substituted silane long chain center. In addition to the effect on the long chain branching achieved in accordance with the present invention, the hydrocarbyl silane silane branching agent can affect the polymerization process thereby resulting in the reduction of the molecular weight of the polymer. In addition, the chain branching process is further enhanced by the presence of the ethylenically unsaturated functional group of the substituted silane with alkenyl, if present, which is capable of becoming either a part of the main polymer chain or a long chain branch. The reaction of the remaining Si-H functionality of such silane compounds substituted with alkenyl is as previously depicted. Metal complexes suitable for use herein include any complex of a metal of Groups 3-1 0 of the Periodic Table of the Elements capable of polymerizing or activating to polymerize the above polymerizable addition compounds., especially olefins. Examples include diimine derivatives of Group 1 0 corresponding to the formula: N * M * X'2A "(N Where, M * is Ni (ll) or Pd (ll); X 'is halo, hydrocarbyl or hydrocarbyloxy; Ar * is an aryl group, especially 2,6-diisopropylphenyl or group Aniline: The two nitrogen atoms are linked by a bivalent bridging group of up to 60 different hydrogen atoms, in particular, a 1,2-ethanediyl, 2,3-butanediyl, dimethylenosilane, or a fused ring system, such as 1,8-naphthanediyl, and A "is the anionic component of the above separate charge activators.The above complexes are described by M. Brookhart, et al, in J. Am. Chem. Soc, 118, 267-268 (1996 ), J. Am. Chem. Soc. 117, 6414-6415 (1995), and J. Feldman et al., Orqanometallics, 1997, 16, 1514-1516, being polymerization catalysts active especially for the polymerization of α-olefins. , either alone or in combination with polar comonomers such as vinyl chloride, alkyl acrylates and alkyl methacrylates. Group 3, 4 or Lanthanide metals containing from 1 to 3 p-linked neutral or anionic linking groups, which may be cyclic or non-cyclic delocalized p-linked anionic linking groups.

Examples of such p-linked anionic linking groups are cyclic or non-cyclic, conjugated or non-conjugated dienyl groups, allyl groups, boratabenzene groups, and arene groups. By the term "p-linked" it is meant that the linking group is linked to the transition metal by electron sharing from a partially delocalized p-bond. Each atom in the delocalized p-linked group can be independently substituted with a radical selected from the group consisting of substituted hydrocarbon, halogen, hydrocarbyl, haiohydrocarbyl substituted hydrocarbyl radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements, and such hydrocarbyl or substituted hydrocarbyl metalloid radicals additionally substituted with an element containing heteroatoms of Group 1 5 or 16. Included within the term "hydrocarbyl" are straight, branched and branched alkyl radicals. cyclic, the C6.2 aromatic radicals, the aromatic substituted C7.20 radicals with alkyl, and the C7.20 alkyl radicals substituted with aryl. In addition, two or more such radicals can jointly form a fused ring system, which includes partially or fully hydrogenated ring fused systems, or can form a metallocycle with the metal. Suitable hydrocarbyl substituted organometalloid radicals include mono-, bi- and tri-substituted organometalloid radicals with Group 14 elements wherein each of the hydrocarbon groups contains from 1 to 20 carbon atoms. Examples of suitable hydrocarbyl substituted radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups. Examples of elements containing heteroatoms of Group 1 5 or 1 6 include elements of amine, phosphine, ether or thioether or bivalent derivatives thereof, for example, amide, phosphide, ether or thioether groups bound to the transition metal or metal Lantánido, and linked to the hydrocarbyl group or to the group that contains the substituted hydrocarbyl metalloid. Examples of suitable delocalized, anionic, p-linked groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl, and boratabenzene groups, as well as C1-O silyl substituted derivatives. substituted with hydrocarbyl or C1.10 substituted with hydrocarbyl thereof. The preferred anionic delocalized p-linked groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl and tetrahydroindenyl. Boratabenzenes are anionic binders which are boron which contains benzene analogues. They are previously known in the art, having been described by G. Herberich, et al., In Orqanometallics, 14, 1, 471-480 (1,995). The preferred boratabenzenes correspond to the formula: Where R "is selected from the group consisting of hydrocarbyl, silyl, N, N-dialkylamino, N, N-diarylamino or germyl, said R" having up to 20 non-hydrogen atoms. In complexes involving bivalent derivatives of such delocalized p-linked groups an atom thereof is linked by means of a covalent bond or a bivalent group linked covalently to another atom of the complex thus forming a bridged system. A suitable class of catalysts are the metal complexes in transition corresponding to the formula: K'kMZ'mL | Xp, or a dimer of the same where: K 'is an anionic group that contains delocalized p-electrons or medium of which K 'is linked to M, said g rupe K' containing up to 50 atoms without counting the hydrogen atoms, optionally two K 'groups can be grouped together forming a bridged structure, and optionally a K' can be linked to Z '; M is a metal of Group 4 of the Periodic Table of the Elements in the oxidation state +2, +3, or +4; Z 'is an optional, bivalent substituent of up to 50 non-hydrogen atoms which together with K' forms a metallocycle with M; L is an optional neutral binder having up to 20 non-hydrogen atoms; Each occurrence of X is a monovalent, anionic element having up to 40 non-hydrogen atoms, optionally, two X groups can be linked together covalently to form a bivalent dianionic element having both valences linked to M, u, optionally 2 X groups that can be linked covalently together to form a neutral, conjugated or unconjugated diene that binds to M by means of delocalized p-electrons (after which M is in the oxidation state +2), or optionally in addition one or more X and one or more L groups can be linked together thus forming an element that binds covalently to M as well as coordinates to it by means of the Lewis base functionality; k is 0, 1 or 2; m is 0 or 1; I is a number from 0 to 3; p is an integer from 0 to 3; and the sum, k + m + p, is equal to the formal oxidation state of m, except that when the 2X groups together form a conjugated or neutral non-conjugated diene that binds to M by means of delocalised p-electrons, in whose case the sum k + m is equal to the state of formal oxidation of M. Preferred complexes include those which contain either one or two K 'groups. This last complex includes those that contain a bridging group that links the two groups. Preferred bridging groups are those corresponding to the formula (ER'2) X wherein E is silicon, germanium, tin or carbon, each occurrence of R 'independently is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R 'having up to 30 carbon or silicon atoms, and x being 1 to 8. Preferably, each occurrence of R' independently is methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy Examples of complexes containing two K 'groups are compounds corresponding to the formula: Wherein: M is titanium, zirconium, or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2, +3 or +4; R3 in each occurrence independently is selected from the group consisting of hydrocarbon, silyl, germyl, halo, haiohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy, N, N-di (hydrocarbylsilyl) amino, N-hydrocarbyl-N-silylamine, N, Nd i (h id rock rbil) amino, hydrocarbylene amino, di (hydrocarbyl) phosphino, hydrocarbyl sulphide; or hydrocarbyl substituted with hydrocarbyloxy, said R3 having up to 20 non-hydrogen atoms or the adjacent R3 groups together form a bivalent derivative thereby forming a fused ring system, and Each occurrence of X "independently is an anionic linking group of up to 40 atoms of non-hydrogen, or two "X" groups together that form a bivalent anionic binder group of up to 40 non-hydrogen atoms, Each occurrence of X '"independently is a stabilizing anionic binder group selected from 2- (N, N-dimethylaminobenzyl), m - (N, N-dimethylaminomethyl) phenyl, allyl, and allyl substituted with C? .1 hydrocarbyl, after which M is in the formal oxidation state +3, or each occurrence of X "independently is a conjugated diene, neutral, or a silyl, germyl, or a substituted derivative thereof, having up to 40 different atoms to hydrogen, after which M is in the formal oxidation state +2, E is silicon, germanium, tin or carbon, each occurrence of R 'independently is hydrogen or group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R' having up to 30 carbon or silicon atoms, and x is 1 to 8. The above metal complexes are especially ad ecuados for the preparation of polymers that have stereoregular molecular structure. In such a capacity it is preferred that the complex possesses Cs symmetry or possesses a stereorigid, chiral structure. Examples of the first type are compounds possessing different delocalized p-linked linking groups, such as a cyclopentadienyl group and a fluorenyl group. Similar systems based on Ti (IV) or Zr (IV) were described for the preparation of syndiotactic olefin polymers in Ewen, et al., J. Am. Chem. Soc. 1 1 0 ^ 6255-6256 (1980). Examples of chiral structures include bis-indenyl complexes rae. Similar systems based on Ti (IV) or Zr (IV) were described for the preparation of isotactic olefin polymers in Wíld, et al., SJ. Oraanomet. Chem. 232, 233-47, (1 982). Exemplary bridged binders containing two p-linked groups are: dimethylbis (cyclopentadienyl) silane, dimethylbis (tetramethylcyclopentadienyl) silane, dimethylbis (2-ethylcyclopentadien-1-yl) silane, dimethylbis (2-t-butylcyclopentadien-1-yl) silane , 2, 2-bis (tetramethylcyclopentadienyl) propane, dimethylbis (inden-1-l) silane, dimethylbis (tetrahydroinden-1-yl) silane, dimethylbliss (fIuoren-1 -yl) silane, dimethylbis (tetrahydroforen-1-ethyl) ) silane, di methyl bis (2-m eti I-4-phenylinden-1-yl) -silane, dimethylbis (2-methylinden-1-yl) silane, dimethyl (cyclopentadienyl) (fluoren-1-yl) silane, dimethyl (cyclopentadienyl) (octahydrofluoren-1-yl) silane, dimethyl (cyclopentadienyl) (tet ra h id rof I u oren- 1 -l) yes tin, (1, 1, 2, 2-tetramethyl) -1, 2- bis (cyclopentadienyl) disilane, (1,2-bis (cyclopentadienyl) ethane, and dimethyl (cyclopentadienyl) -1 - (fluoren-1-yl) methane The preferred groups X "are selected from hydride, hydrocarbyl, silyl groups , germyl, haiohydrocarbyl, halosilil or, silylhydrocarbyl and aminohydrocarbyl, or two X groups "together form a bivalent derivative. The most preferred "X" groups are hydrocarbyl groups C.sub.1-20 The preferred groups X '"are 1,3-pentadiene and 1,4-diphenylbutadiene. An additional class of metal complexes used in the present invention corresponds to the preceding formula K'kMZ'mLnXp, or a dimer thereof, wherein Z 'is a bivalent substituent of up to 50 non-hydrogen atoms which together with K' form a metallocycle with M. Preferred bivalent Z 'substituents include groups containing up to 30 non-hydrogen atoms comprising at least one atom which is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly attached to K ', and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur which is covalently bonded to M. A preferred class of such Group 4 metal coordination complexes used in accordance with the present invention corresponds to the formula: wherein: M is titanium or zirconium; R3 in each occurrence independently is selected from the group consisting of hydrocarbyl, silyl, germyl, halo, haiohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy, N, N-di (hydrocarbylsilyl) amino, N-hydrocarbyl-N-silylamino, N, N- di (hydrocarbyl) amino, hydrocarbylene amino, di (hydrocarbyl) phosphino, hydrocarbyl sulfite; or hydrocarbyl substituted with hydroxycarbyloxy, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups which together form a bivalent derivative thereby forming a fused ring system. each X is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, each group having up to 20 non-hydrogen atoms, or two X groups which together form a bivalent derivative thereof; X '"is a conjugated diene, neutral or a derivative substituted with a siliio, germilo or haiohidrocarbilo of the same, having up to 40 different atoms of hydrogen, after which M is in the formal oxidation state +2, and is -OR-, -S-, -NR'-, or -PR'-, and Z is SiR'2, CR'2, SiR'2SiR'2, CR'2CR'2, CR '= CR', CR ' 2SiR'2 lo, GeR'2, wherein each occurrence of R 'independently is hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R' having up to 30 carbon or silicon atoms. The additional suitable complexes correspond to the formula: Rc R wherein: M is titanium zirconium, preferably titanium in the formal oxidation state +3; R3 in each occurrence independently is selected from the group consisting of hydrocarbyl, silyl, germyl, halo, haiohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy, N, N-di (hydrocarbylsil) amino, N-hydrocarbyl-N-silylamino, N, N-di (hydrocarbyl) amino, hydrocarbylene amino, di (hydrocarbyl) phosphino, hydrocarbyl sulphide; or hydrocarbyl substituted with hydrocarbyloxy, said R 3 having up to 20 non-hydrogen atoms, or adjacent R 3 groups which together form a bivalent derivative thereby forming a fused ring system, each X being a halo, hydrocarbyl, hydrocarbyloxy or silyl group, having each group up to 20 non-hydrogen atoms, or two X groups which together form a bivalent derivative thereof; E is silicon, germanium, tin or carbon, Each occurrence of R 'independently is hydrogen or a group selected from silyl, hydrocarbon, hydrocarbyloxy and combinations thereof, said R' having up to 30 carbon or silicon atoms, x is 1 to 8, Y is -OR, or -NR2; and Z is SiR'2, CR'2, SiR'2S¡R'2, CR'2CR'2) CR '= CR', CR'2SiR'2 or GeR'2, where R 'is as previously defined . The additional suitable complexes correspond to the formula: wherein: M is titanium or zirconium, preferably titanium in the formal oxidation state +3; Each occurrence of R3 independently is selected from the group consisting of hydrocarbyl, silyl, germyl, halo, haiohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy, N, N-di (hydrocarbylsilyl) amine, N-hydrocarbyl-N-silamino, N, N-di (hydrocarbyl) amino, hydrocarbylene amino, di (hydrocarbyl) phosphino, hydrocarbylsulfide; or hydrocarbyl substituted with hydrocarbyloxy, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups which together form a bivalent derivative thereby forming a fused ring system, X "" is 2- (N, N-dimethylaminobenzyl), m - (N, N-dimethylamethyl) phenyl, allyl and allyl substituted with C ^ or hydrocarbyl; Y is -O-, -S-, -NR'-, -PR'-, and Z is SiR'2, CR'2, SiR'2SiR'2, CR'2CR'2, CR '= CR', CR '2SR'2 or GeR'2, where R' is as previously defined. Illustrative Group 4 metal complexes that may be employed in the practice of the present invention include: biscyclopentadienyl complexes such as bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dimethyl, (fluorenyl) (cyclopentadienyl) zirconium dichloride, dimethyl (fluorenyl) (cyclopentadienyl) zirconium, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dimethyl, rac-dimethylsilane-bis (cyclopentadienyl) zirconium dichloride, rac-dimethyl silane-bs dimethyl (cyclopentadienyl) zirconium, rac-dimethylsilane-bis (tetramethylcyclopentadienyl) zirconium dichloride, di-methyl-racmethyl ester and non-bis (tetramethyl cyclopentadienyl) zirconium, rac-dimethylsilane-bis dichloride. { 1- (2-methyl-4-phenylindenyl)} zirconium, rac-dimethylsilane-bis dichloride. { 1- (2-ethyl-4-a-naphthyl) ndenyl)} zirconium, rac-dimethylsilane-bis dichloride. { 1- (2-methyl-4- (ß-naphthyl) indenyl} zirconium, rac-1 dichloride, 2-ethylene-bis. {1 - (2-methyl-4-phen-linden il).} zirconium, rac-1 dichloride, 2-ethylene-bis. {1- (2-methyl-4- (a-naphthyl) indenyl) zirconium, 1,4-Diphenyl-1,3-butadiene from rac-dimethylsilane-bis (cyclopentadienyl) zirconium (II), 2,4-hexadiene from rac-dimethylsilane-bis (cyclopentadienyl) zirconium (II), 1,3-pentadiene of rac-dimethylsilane-bis. { 1- (2-methyl-4-phenylindenyl)} zirconium (ll), 1,3-pentadiene of rac-dimethylsilane-bis. { 1- (2-methyl-4- (a-naphthyl) indenyl)} zirconium (ll), 1,3-pentadiene of rac-1, 2-etiieno-bis. { 1- (2-methyl-4-phenylindenyl)} zirconium (ll), 1,3-pentadiene of rac-1, 2-ethylene-bis. { 1- (2-methyl-4 (a-naphthyl) indenyl)} zirconium (ll), rac-1,2-ethylene-bis 1,3-pentadiene. { 1- (2-methyl-4-β-naphthyl) indenyl} zirconium (ll), rac-1,2-ethylene-bis 1,3-pentadiene. { 1- (2-methyl-4- (1-anthracenyl) indenyl)} zirconium (ll), 1,3-pentadiene of rac-1, 2-ethylene-bis. { 1- (2-methyl-4- (2-anthracenyl) indenyl)} zirconium (ll), 1,3-pentadiene of rac-1, 2-ethylene-bis. { 1 - (2-methyl-4- (9-anthracenyl) indenyl)} zirconium (ll), 1,3-pentadiene of rac-1, 2-ethylene-bis. { 1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium (ll), 1, 4-dif in i 1-1, 3-butadiene of rac-1, 2-ethylene-bis. { 1- (2-methyl-4-phenylindenyl)} zirconium (ll), 1, 4-dif in i 1-1, 3-butadiene of rac-1, 2-ethylene-bis. { 1- (2-methyl-4- (a-naphthyl) indenyl)} zirconium (ll), and 1, 4-d-faith or 1-1, 3-butadiene of rac-1,2-ethylene-bis. { 1- (2-methyl-4- (ß-naphthyl) indenyl} zirconium (ll) Examples of metal complexes containing a single cyclic binder containing delocalized p-electrons and a bridging structure towards metal (known as complexes of restricted geometry) used in the present invention wherein the metal is in the formal oxidation state +4 include the following complexes: (tert-butylamido) (tetramethylcyclopentadiphenyl) dimethylsilanetitanium dichloride, dichloride (cyclohexylamido) (tetramethylcyclopentadienyl) dimethylsilanethane, dichloride (cyclododecylamido) (tetramethylcyclopentadienyl) d, methyl silanotitanium, (tert-butylamido) dichloride (2-methyl-4-phenylinden-1-yl) dimethylsilanetitanium, (tert-butylamido) dichloride (3-) pyrrolylinden-1-yl) d-methylanotitan, dichloride of (cyclohexylamido) (3-pyrrolylniden-1-yl) dimethylsilanetitanium, dichloride of (tert-butylamido) (? 5-3-phenyl) -s-indacen-1-yl) dimethylsilanetitanium, (tert-butylamido) dichloride (? 5-2-methyl-3-biphenyl-s-indacen-1-yl) dimethylsilanetitanium, (tert-butylamido) dichloride (? -3-phenyl-gem-dimethylnacenaftalen-1-yl) dimethylsilanetitanium dimethyl (tert-butylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium, dimethyl (cyclohexylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium, dimethyl (cyclododecylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium, dimethyl (tert-butylamido) (2-methyl-4-phenylinden-1-yl) dimethylsilanetitanium, di methyl (tert-butylamido) (3-pyrrolylinden-1-yl) dimethylsilanetitanium , di-methyl or of (cyclohexylamido) (3-pyrrolidin-1-yl) dimethylsilanetitanium, dimethyl (tert-butylamido) (? 5-3-phenyl-s-indacen-1-yl) dimethylsilyanoititanium, dimethyl (tert-butylamido) (? 5-2-methyl-3-bifeniI-s-indancen-1-yl) dimethylsilanetitanium, di methyl or (tert-butylamido) (? 5-3-phenyl-gem-dimethylacenaphthalene-1yl) dimethylsilanetitanium, 1,4-diphenyl-1,3-butadiene from (tert-butylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium, 1,4-diphenyl-1,3-butadiene from (cyclohexylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium, 1,4-diphenyl-1,3-butadiene from (cyclododecylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium, 1,4-diphenyl-1,3-butadiene (tert-butylamido) (2-methyl-4-phenylinden-1-yl) dimethylsilanetitanium, 1,4-dif in i 1-1 , 3-butadiene of (tert-butylamido) (3-pyrrolylinden-1-yl) dimethylsilanetitanium, 1,4-dif in 1-1-3-butadiene of (cyclohexylamido) (3-pyrrolylinden-1-yl) dimethylsilanetitanium, 1, 4-d-phenyl 1-1, 3-butadiene of (tert-butylamido) (? 5-3-phenyl-s-indancen-1-yl) dimethylsilanetitan, 1,4-diphenyl-1,3- butadiene (tert-butylamido) (? 5-2-methyl-3-biphenyls-indancen-1-yl) d -methylsilanetitanium, 1,4-diphenyl-1,3-butadiene (tert-butylamido) ) (? 5-3-phenyl-gem-di-methylnaphthalene-1-yl) dimethylsilanetitanium, 1,3-pentadiene (tert-butylamido) (tetramethylcyclopentadityl) -methasone-titanium , 1,3-pentadiene of (cyclohexylamido) (tetramethylcyclopentadiphenyl) dimethylsilanetitan 1,3-pentadiene (cyclododecylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium 1,3-pentadiene (tert-butylamido) (2-methyl-4-phenylinden-1-yl) dimethylsilanetitanium, 1,3-pentadiene (tert-butylamido) (3-pyrrolylinden-1) - il) dimethylsilanetitan, 1,3-pentadiene of (cyclohexylamido) (3-pyrrolidinden-1-yl) dimethylsilanetitanium, 1,2-pentadiene of (tert-butylamido) (? 5-3-phenyl-s-indacen) -1-yl) dimethylsilanetitanium, and 1,3-pentadiene of (tert-butylamido) (? 5-2-methyl-3-biphenyl-s-indacen-1-yl) dimethylsilanetitanium. Other complexes, especially those containing other Group 4 metals, will, of course, be apparent to those skilled in the art. Preferred Group 4 metal complexes are produced catalytically by combination with an activating cocatalyst or by the use of an activation technique. Activating cocatalysts suitable for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, modified triisobutyl aluminum methylalumoxane, diisobutylalumoxane or perfluoroaryl-modified alumoxane; strong Lewis acids, such as compounds of Group 1 3 substituted with C ^ 30 hydrocarbyl, especially tri (hydrocarbyl) aluminum or tri (hydrocarbyl) boron compounds and halogenated derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl group or halogenated hydrocarbyl, especially tris (pentafluorophenyl) borane; and non-coordinated, compatible, inert, non-polymeric ion formation compounds (which include the use of such compounds under oxidizing conditions). A suitable activation technique is volumetric electrolysis (explained in more detail hereinafter). The combinations of the above activating cocatalysts and activation techniques have been previously taught with respect to different metal complexes in the following references: EP-A-277, 003, US-A-5, 1 53, 57, US-A- 5, 064, 802, EP-A-468, 651, EP-A-520, 732 and WO93 / 2341 2. Conveniently, the oligomeric or polymeric alumoxanes, when used, are present in a molar amount compared to the metallic layer from 10: 1 to 1000: 1, preferably from 50: 1 to 200: 1. it is generally considered that aluminoxanes, or alkylaluminoxanes are oligomeric or polymeric alkylaluminoxy compounds, including cyclic oligomers. Generally such compounds contain, on average about 1.5 alkyl group per aluminum atom, and are prepared by reaction of trialkylaluminum compounds or mixtures of compounds with water. Alkanoxanes substituted with perfluoroaryl are easily prepared by combining an alkylalumoxane, which may also contain residual amounts of trialkylaluminum compound, with a fluoroaryl binder source, preferably a strong Lewis acid containing fluoroaryl binders, followed by extraction of by-products formed for the binder exchange. Preferred fluoroaryl binder sources are trifluoroaryl boron compounds, more preferably tris (pentafluorophenyl) boron, which can result in trialkyl boron binder exchange products, which are relatively volatile and easily extractable from the reaction mixture.

The reaction can be carried out in an aliphatic, alicyclic or aromatic liquid diluent or mixture thereof. Preferred are aliphatic and alicyclic C6-8 hydrocarbons and mixtures thereof, which include hexane, heptane, cyclohexane and mixed fractions such as Isopar ™ E, available from Exxon Chemicals Inc. After contacting the alkylalumoxane and the source of the binder. The fluoroaryl should be purified from the reaction mixture to extract the binder exchange products, especially some trialkylboron compounds by some suitable technique. Alternatively, the metal complex catalyst of Group 3-10 can be combined first with the reaction mixture before extracting the residual binder exchange products. Suitable techniques for the extraction of alkyl exchange by-products from the reaction mixture include optional degassing at reduced pressures., distillation solvent exchange solvent extraction, extraction with a volatile agent, contact with a zeolite or molecular sieve, and combinations of the above techniques, all of which are carried out according to conventional procedures. The purity of the resulting product can be determined by 13B NMR of the resulting product. Preferably, the amount of residual alkyl exchange product is less than 10 percent, based on the solids content, preferably less than 1.0 percent by weight, more preferably less than 0.1 percent by weight. Ion-coordinated, non-coordinated, inert, nonpolymeric ion-forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a "compatible" anion not The preferred anions are those that contain a single coordination complex comprising a metal or metalloid core that supports charges whose anion is capable of balancing the charge of the active catalyst species (the metal cation) which is formed when The two components are also combined, said anion can be displaced by unsaturated olefinic, biolefinic, and acetylenic compounds or other neutral Lewis bases such as ethers or nitriles Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon Compounds containing anions which comprise complex Coordination proteins containing a single metal or metalloid atom are well known and many, particularly such compounds containing a single boron atom in the anion portion, are commercially available. Preferably such cocatalysts can be represented by the following general formula: (L * H) + dAd "where: L * is a neutral Lewis base; (L * -H) + is a Bronsted acid; Ad "is an uncoordinated compatible anion, which has a charge of d-, and d is an integer from 1 to 3. Most preferably d is one, which is, Ad" is A. "Highly preferable, A" corresponds to the formula ula: [BQ4] "where: B is boron in the formal oxidation state +3; and Each occurrence of Q independently is selected from hydride, bialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl, and hydrocarbyl radicals halosubstituted, having said Q up to 20 carbons with the proviso that in no more than one occurrence is Q halide. In a more preferred embodiment, q is a C ^ group or fluorinated hydrocarbyl, more preferably, a fluorinated aryl group, especially pentafluorophenyl. Illustrative, but not limiting, examples of ion-forming compounds comprising donable proton cations which can be used as activating cocatalysts in the preparation of the catalysts of this invention are tri-substituted ammonium salts such as: trimethylammonium tetraphenyl borate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripopilammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, methyltetradecylcycloacetamide tetraphenylborate, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, Nd-methyl (2, 4, 6-trimethylene glycol) tetraphenylborate, titanium ester (pentaf-fluorophenyl)) trimethylammonium borate, titanium ester (pentaf luorofeniill)) methylditetradecylammonium borate, titanium ester (pentaf luorofeniill)) methyldioctadecylammonium borate, titanium ester ( pentaf ¡uorofeniill)) triethylammonium borate, titanium ester (pentaf luorofeniil) l)) tripropylammonium borate, titanium ester (pentaf luorofeniill)) tri (n-butyI) ammonium borate, titanium ester (pentaf luorofeniilI)) tri (sec-butyl) ammonium borate, titanium ester (pentaf luorofeniill) ) N, N-dimethylanilinium borate, titanium ester (pentaf luorofeniill)) N, N-diethylanilinium borate, N, N-dimethyl (2,4,6-trimethylanilinium) titanium ester (pentafluorophenyl) borate, titanium (2,3,4,6-tetrafluorophenylborate) of trimethylammonium, titanium ester (2, 3,4,6-tetrafluoro-phenyl-borate) of triethylammonium, titanium ester (2, 3,4,6-tetrafluorophenylborate) of tripropylammonium ester of titanium (2, 3,4,6-tetrafluorophenylborate) of tri (n-butyl) ammonium, titanium ester (2, 3,4,6-tetrafluorophenylborate) of dimethyl (t-butyl) ammonium, titanium ester (2, 3,4,6-tetrafluorophenylborate) , 3,4,6-tetrafluorophenylborate) of N, N-dimethylanilinium, titanium ester (2,3,4,6-tetrafluorophenylborate) of N, N-diethylanilinium, titanium ester (2, 3, 6-tetrafluorophenolborate) of N, N-dimethyl- (2,4,6-trimethylanilin) io). Dialkyl ammonium salts such as: dioctadecylammonium titanium (pentafluorophenyl) borate ester, ditetradecylammonium titanium (pentafluorophenyl) borate ester, and dicyclohexylammonium titanium (pentafluorophenyl) borate ester. Tri-substituted phosphonium salts such as: triphenylphosphonium titanium (pentafluorophenyl) borate ester, methyldioctadecylphosphonium titanium (pentafluorophenyl) borate ester, and tri (2,6-dimethylphenyl) phosphonium titanium (pentafluorophenium) ester borate. The preferred salts of titanium (pentafluorophenyl) borate ester of mono- and bisubstituted long-chain alkyl ammonium complexes, especially titanium (pentafluorophenyl) borate methyldi (octadecyl) ammonium ester and titanium (pentafluorophenyl) borate methyldi ester ( tetradecyl) -ammonium, or mixtures including the same. Such mixtures include protonated ammonium cations derived from amines comprising two C14, C16 or Cie groups and a methyl group. Such amines are available from Witco Corp. under the tradename Kemamine ™ T97Ó 1 and Akzo-Nobel under the trade name Armeen ™ M2HT. Another suitable ion-forming activating cocatalyst comprises a salt of a cationic oxidizing agent and a compatible, uncoordinated anion represented by the formula: (Oxe +) d (Ad ") e, wherein: Oxe + is a cationic oxidizing agent which has charge e +; e is an integer from 1 to 3, and Ad ", and d are as previously defined. Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl substituted ferrocenium, Ag +, or Pb + 2. preferred embodiments of Ad "are those previously defined anions with respect to Bronsted acid containing activating cocatalysts, especially titanium ester (pentafluorophenyl) borate Another suitable ion-forming activating cocatalyst comprises a compound which is a salt of a carbenium ion or a silyl ion and a compatible, uncoordinated anion, represented by the formula: © + A "where: © + is a C1-2o carbenyl or silylium ion; and A "is as previously defined: The preferred carbenium ion of A is the triphenyl cation, which is triphenylcarbenium, A preferred silylium ion is triphenylsilyl, The technique of volumetric electrolysis involves the electrochemical oxidation of the metal complex under the conditions of electrolysis in the presence of a support electrolyte comprising an inert, uncoordinated anion In the art, solvents, electrolytes support and electrolytic potentials for electrolysis are used so that the electrolysis by-products that would produce the inactive metal complex They are catalytically not formed substantially during the reaction, more particularly, suitable solvents are materials which are: liquids under the conditions of electrolysis (generally temperatures from 0 to 1 00 ° C), capable of dissolving the supporting electrolyte and inerts. "Inert solvents" are those that are not reduced or oxidized under the conditions Reactions used for electrolysis. It is generally possible in view of the desired electrolysis reaction to choose a solvent and a supporting electrolyte that are not affected by the electrical potential used for the desired electrolysis. Preferred solvents include difluorobenzene (all isomers), DME, and mixtures thereof. The electrolysis can be carried out in a standard electrolytic cell containing an anode and cathode (also referred to as the operating electrode and the counter electrode respectively). The suitable building materials for the cell are glass, plastic, ceramic and glass-coated metal. The electrodes are prepared from inert conductive materials, by which is meant conducting materials that are not affected by the reaction mixture or reaction conditions. Inert platinum or palladium conducting materials are preferred. Normally, an ion permeable membrane such as a fine glass mixture separates the cell into separate compartments, the electrode compartment and the counter electrode compartment. The functional electrode is immersed in a reaction medium comprising the metal complex to be activated, solvent, support electrolyte and some other desired materials to moderate the electrolysis or stabilize the resulting complex. The counter electrode is immersed in a mixture of the solvent and supporting electrolyte. The desired voltage can be determined by theoretical calculations or experimentally scanning the cell using a reference electrode such as a foot electrode immersed in the cell electrolyte. The cell support current is also determined, the current call in the absence of the desired electrolysis.

The electrolysis is completed when the current falls from the desired level to the support level. In this way, the complete conversion of the initial metal complex can be easily detected. Suitable supporting electrolytes are salts comprising a cation and an inert, compatible, non-coordinated anion A. Preferred support electrolytes are salts corresponding to the formula: G + A "; wherein: G + is a cation which is non-reactive with respect to the initial complex and the resulting one; and A 'is an uncoordinated, compatible anion. Examples of cations, G +, include ammonium or phosphonium cations substituted with tetrahydrocarbyl having up to 40 non-hydrogen atoms. A preferred cation is the tetra-n-butylammonium cation. During the activation of the complexes of the present invention by massive electrolysis, the cation of the supporting electrolyte passes to the counter electrode and A "migrates towards the functional electrode to become the anion of the resulting oxidizing product." Either the solvent or the cation of the Support electrolyte is reduced in the counter electrode in equal molar quantity with the amount of oxidized metal complex formed in the functional electrode Preferred support electrolytes are tetrahydrocarbylammonium salts of titanium ester (perfluoroaryl) borates having from 1 to 10 carbons in each hydrocarbyl group, especially titanium (pentafluorophenyl) borate tetra-n-butylammonium ester In general, the active catalyst can be prepared by combining the metal complex and the activator in a suitable solvent at a temperature within the range of -100 ° C. up to 300 ° C. The silane or hydrocarbyl silane adjuvant can be added separately or simultaneously with the remaining components. The catalyst composition can be prepared separately before the addition of the monomers to be polymerized or prepared in situ by combining the various components in the presence of the monomers to be polymerized. The catalyst components are sensitive to both moisture and oxygen and must be handled and transferred in an inert atmosphere. Preferred monomers for use herein include olefins having from 2 to 20,000, preferably from 2 to 20, more preferably from 2 to 8 carbon atoms and combinations of two or more of such olefins. Particularly suitable olefins include: ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-ketene, 1-naene, 1 -decene, 1-undecene, 1- dodecene, 1 -tridicene, 1-tetradecene, 1 -pentadecene or combinations thereof, as well as oligomeric or polymeric reaction products terminated in long chain vinyl formed during the polymerization and C? -30 a-olefins specifically added to the reaction mixture in order to produce relatively long chain branches in the resulting polymers. Preferably, the olefins are ethylene, propene, 1-butene, 4-methyl-1-pentene, 1 -hexene, 1-ketene, styrene, halo- or styrenes substituted with alkyl and tetrafluoroethylene. Other suitable monomers include vinylcyclobutene and dienes, such as 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and 1,7-octadiene. The mixtures of the aforementioned monomers can also be used. Solvents or diluents for catalyst preparation include any of the solvents known in the prior art which include, but are not necessarily limited to straight or branched chain hydrocarbons such as C6-? 2 alkanes (pentane, hexane, heptane) , octane and mixtures thereof); C6.12 cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof and aromatic and aromatic compounds substituted with C6-? 2 alkyl such as benzene, toluene, xylene, decalin and mixtures thereof, as well as also mixtures of the above compounds. The polymerization can be carried out under pulp conditions, solution, mass, gaseous phase or suspension or other suitable reaction conditions. The polymerization can be carried out at temperatures from 0 ° C to 1 60 ° C, preferably from 25 ° C to 100 ° C for a sufficient time to produce the desired polymer. Typical reaction times are from one minute to 1 00 hours, preferably from 1 to 10 hours. The optimum reaction time or residence time of the reactor will vary depending on the temperature, solvent and other reaction conditions employed. Polymerization can be carried out at subatmospheric pressures as well as super-atmospheric pressure, suitably at a pressure within the range of 1 to 500 psig (6.9 kPa-3.400 kPa). The use of ambient or low pressures is preferred, for example, 1 -5 psig (6.9-34.5 kPa) in order to decrease capital and equipment costs. The polymerization can be carried out in the presence of an inert diluent or solvent or in the absence thereof, that is, in the presence of the excess monomer. Examples of suitable diluents or solvents include aromatic or aliphatic hydrocarbons, • C6.20 halogenated cycloaliphatics, aromatics and aliphatics. the diluents comprise the C6-? or alkanes, toluene and mixtures thereof. A particularly desirable diluent for the polymerization is io-octane, σ-nonane or mixtures thereof such as Isopar-E ™, available from Exxon Chemical Company. Suitable amounts of solvent are used to provide a monomer concentration from 5 percent to 100 percent by weight. The molar ratio of additive monomer to catalyst (in terms of the metal content of Group 3-1 0) can range from 1: 00: 1 to 1: 1: 0: 1, preferably from 1,000: 1 to 1: 1: 06 : 1 . Typically, in the preparation of ethylene / olefin copolymers the molar ratio of comonomer to monomer (s) used depends on the density desired for the composition that is being produced and is about 0.5 or less. Desirably, when materials with a density range of from about 0.91 to about 0.93 are produced, the comonomer to monomer ratio is less than 0.2, preferably less than 0.05, still more preferably less than 0.02, and may even be less than 0.01. Typically, the molar ratio of hydrogen to monomer in the process is less than about 0.5, preferably less than 0.2, more preferably less than 0.05, even more preferably less than 0.02, due to the presence of the silane ramifying agent, the which performs many of the functions of hydrogen with respect to molecular weight control. The molar ratio of the silane or hydrocarbylsilane branching agent to monomer charged to the reactor is desirably less than about 0.5, preferably less than 0.2, and more preferably less than 0. 1. As in other similar polymerizations, it is highly desirable that the monomers and solvents used be of a sufficiently high purity that deactivation of the catalyst does not occur. Any suitable technique for the purification of the monomer such as devolatilization at reduced pressures, contact with molecular sieves or high surface area alumina, deaeration, or a combination thereof can be employed. Purification of the resulting polymer to extract the catalyst and cocatalyst carried by the professional may also be desired. Such contaminants can generally be identified by the ash residues in the polymer pyrolysis that are attributable to the values of the catalyst metal or cocatalyst. A suitable technique for extracting such compounds is by extraction of the solvent, for example, extraction using solvents, acids or bases, hot, chlorinated, high-boiling such as caustic followed by filtration. A gaseous phase or paste polymerization can optionally be present in the catalyst formulation. Suitable supports include any inert, particulate material, but more suitably is a metal oxide, preferably alumina, silica or an aluminosilicate material. Suitable particle sizes are from up to 1 0,000 μM, preferably from 1 0 to 1 00 μM. the most desired supports are calcined silica, which can be treated to reduce surface hydroxyl groups by reaction with a silane, or similar reagent compound. Any suitable means can be used to include such support in the catalyst formulation, such as by dispersing the components in a liquid and contacting them with the support and thereafter drying, by spraying or coating the support with such liquid and extracting. then the liquid, or by coprecipitating the cocatalyst and a support material from a liquid medium. The polymerization is desirably carried out as a continuous polymerization, in which the catalyst components, the monomer (s), the chain branching agent, and optionally the solvent and diene are continuously supplied to the reaction zone and the product polymer is extracted therefrom. Within the scope of the terms "continuous" and "continuously" as used in this context are those processes in which there are intermittent additions of reactors and product extraction at small regular intervals, so that, over time, the The general process is continuous. In one embodiment, the polymerization is carried out in a continuous solution polymerization system comprising two reactors connected in series or in parallel. In a reactor, a relatively high molecular weight product is formed (Mw from 300,000 to 600,000, more preferably 400,000 to 500,000) although in the second reactor a relatively low molecular weight product is formed ( Mw 50,000 to 300,000). The final product is a mixture of two effluent reactors which are combined before devolatilization to result in a uniform mixture of the product polymers. Such a double reactor process allows the preparation of products that have improved properties. In a preferred embodiment, the reactors are connected in series, ie, effluents from the first reactor are charged to the second reactor and fresh monomer, solvent and hydrogen are added to the second reactor. The reactor conditions are adjusted such that the weight ratio of polymer produced in the first reactor to that produced in the second reactor is from 20.80 to 80:20. In addition, the temperature of the second reactor is controlled to produce the low molecular weight product. This system allows the production of EPDM products that have a low range of Mooney viscosities, as well as excellent resistance and processability. Preferably, the Mooney viscosity (ASTM D 1 646-94, ML1 +4 @ 125 ° C) of the resulting product is adjusted to fall in the range from 1 to 200, preferably from 5 to 1 50 and more preferably from 10 to 1 1 0. The polymerization process of the present invention can also be used to take advantage of the gas phase copolymerization of olefins. Such processes are used commercially on a large scale for the production of high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LLDPE). The gaseous phase process employed can be, for example, of the type which employs a bed or mechanically agitated gas fluidized bed as the polymerization reaction zone. Processes are preferred in which the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended above a perforated plate, the fluidization grid, by a gas flow of fluidization. The gas used to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a means of exchanging heat to extract the heat of reaction from the bed. The hot gases emerge from the upper part of the reactor, usually through a zone of reassurance, also known as a velocity reduction zone, which has a wider diameter than the fluidized bed and where the fine particles carried in the gas stream have an opportunity to gravitate back to the bed. It may also be advantageous to use a cyclone to extract ultra-fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to extract the gas from the polymerization heat. A preferred method of cooling the bed, in addition to the cooling provided by the cooled recycle gas, is fed to a volatile liquid to the bed in order to provide an evaporative cooling effect., often referred to as operation in condensation mode. The volatile liquid used in this case can be, for example, an inert volatile liquid, for example, a saturated hydrocarbon having from 3 to 8, preferably 4 to 6, carbon atoms. In the event that the monomer or comonomer itself is a volatile liquid, or that it can be condensed to supply such a liquid, this can conveniently be fed to the bed to provide an evaporative cooling effect. Examples of olefin monomers which can be used in this manner are olefins containing about three to about eight, preferably three to six, carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form gas which is mixed with the fluidizing gas. If the volatile liquid is a monomer or comonomer, you will experience some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the heat exchange / compression part of the recycling loop. The recycle gas is cooled in the heat exchanger, and if the temperature at which the gas cools is below the dew point, the liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is pose to recycle the precipitated liquid to the bed as droplets of the liquid carried in the recycle gas stream. This type of process is described, for example in EP-89691; E. OR . 4, 543, 399; WO 94/25495 and E.U. 5,352,749. A particularly preferred method of recycling liquid to the bed is to separate the liquid from the recycle gas stream and to reinject this liquid directly into the bed, preferably using a method which generates fine droplets of the liquid within the bed. This type of process is described in WO-94/28032. For the teaching contained therein, prior patents or publications, and their corresponding equivalent United States applications are hereinafter incorporated for reference. The polymerization reaction that occurs in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst. Such a catalyst can be supported in an organic or inorganic carrier material as described above. The catalyst may be subjected to a prepolymerization step, for example, by polymerizing a small amount of olefin monomer in a liquid inert diluent, to supply a catalyst compound comprising catalyst particles incorporated into olefin polymer particles. The polymer is produced directly in the fluidized bed by catalyzed copolymerization of the monomer and one or more comonomers in the fluidized particles of catalyst, supported catalyst or prepolymer within the bed. The start of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to the target polyolefin, and conditioning the bed by drying it with inert gas or nitrogen before introducing the catalyst, monomers and some other gases which one wishes to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensation mode. The polymer produced is discharged continuously or discontinuously from the fluidized bed as desired. The gaseous phase processes most suitable for the practice of this invention are continuous processes which are provided for the continuous supply of the reactors to the reaction zone of the reactor and the extraction of products from the reaction zone of the reactor, thus providing a permanent state environment at the macro scale in the reaction zone of the reactor. The products are easily recovered by exposure under reduced pressure and optionally at elevated temperatures (devolatilization) according to known techniques. The process readily extracts any residual silane or hydrocarbylsilane branching agent, as well as inert diluents and unreacted monomers which can be recycled to the reactor if desired. Typically, the fluidized bed of the gas phase process is operated at temperatures greater than 50 ° C, preferably from about 60 ° C to about 110 ° C, more preferably from about 70 ° C to about 110 ° C. A number of patents and patent applications describe gas phase processes which are adaptable for use in the process of this invention, particularly, U.S. Patent Nos. 4,588,790; 4,543,399; 5,352,749; 5,436,304; 5,405,922; 5,462,999; 5,461, 123; 5,453,471; 5,032,562; 5,028,670; 5,473,028; 5, 106,804; 5,556,238; 5,541, 270; 5,608,019; 5,616,661; and applications EP 659,773; 692,500; 780,404; 697,420; 628,343; 593,083; 676,421; 683, 176; 699,212; 699,213; 721, 798; 728, 150; 728, 151; 728,771; 728,772; 735,058; and PCT applications WO-94/29032, WO-94/25497, WO-94/25495, WO-94/28032, WO-95/1 3305, WO-94/26793, WO-95/07942, WO-97 / 25355, WO-93/1 1 1 71, WO-95/1 3305, and WO-95/1 3306, all of which, or their corresponding equivalent United States applications are hereinafter incorporated by reference. For the preferred polyolefin polymer compositions of this invention, which can be produced by the polymerization processes of this invention using the catalyst systems of this invention, the long chain branch is longer than the short chain branch that is the result of the incorporation of one or more comonomers of a -olefin to the main structure of the polymer. The empirical effect of the presence of the presence of long chain branching in the polymers of this invention manifests itself as improved rheological properties which are indicated by more leyend flow activation energies, and l2JI2 greater than that expected from other structural properties of the compositions Having described the invention, the following examples are provided as further illustrative and are not construed as limiting. The skilled artisan will appreciate that the invention described herein may be practiced in the absence of any component which has not been specifically described. Unless otherwise specified, all parts and percentages are based on weight.

Examples 1-9 All reactions and manipulations were carried out under an inert atmosphere in a dry box. The monomer and solvent were purified by passing through an activated alumina and supported copper catalyst (reactor agent Q5, available from Engelhardt Corporation, and otherwise handled using standard inert atmosphere techniques). The catalyst used in polymerizations 6 and 7 (catalyst B) was prepared as follows: Preparation of 1 H-cyclopentaphenanthrene-2-yl lithium To a 250 ml round bottom flask containing 1.42 g (0.00657 mole) of 1 H-cyclopenta [l] phenanthrene and 120 ml of benzene were added dropwise, 4.2 ml of 1.60 M n-BuLi solution in mixed hexanes. The solution was allowed to stir overnight. The lithium salt was isolated by filtration, rinsed twice with 25 ml of benzene and dried in vacuo. The isolated product was 1.426 g (97.7 percent). 1 H NMR analysis indicated that the predominant isomer was substituted at position 2. Preparation of (1 H-cyclopentanylphenanthrene-2-yl) dimethylchlorosilane To a 500 ml round bottom flask containing 4.1 6 g (0.0322 mole) of dimethyldichlorosilane (Me2SiCl2) and 250 ml of tetrahydrofuran (THF) a solution of 1.45 g (0.0064 mole) of 1 H-cyclopenta [l] phenanthrene-2-yl of lithium in THF was added dropwise. The solution was stirred for about 16 hours, after which the solvent was removed under reduced pressure, leaving an oily solid which was extracted with toluene, filtered through the diatomaceous earth filter aid (Celite ™), rinsed twice with toluene and dried under reduced pressure. The isolated product was 1.98 g (99.5 percent). Butylamino ^ ilane To a 500 ml round bottom flask containing 1.98 g (0.0064 mole) of (1 H-cyclopenta [l] phenanthrene-2-yl) dimethylchlorosilane and 250 ml of hexane was added 2.00 ml (0.01 60 mole) of butilam ino. The reaction mixture was allowed to stir for several days, then filtered using the diatomaceous earth filter aid (Celite ™), rinsed twice with hexane. The product was isolated by removing residual solvent under reduced pressure. The isolated product was 1.98 g (88.9 percent).

Preparation of dilitium (1 H-cyclopentaphenanthrene-2-yl) d-methyl (t-butylamido) silane To a 250 ml round bottom flask containing 1.03 g (0.0030 mole) of (1 H-) cyclopenta [l] phenanthrene-2-yl) dimethyl (t-butylamino) silane) and 120 ml of benzene were added 3.90 ml of a 1.6 M solution of n-BuLi in mixed hexanes. The reaction mixture was stirred for about 16 hours. The product was isolated by filtration, rinsed twice with benzene and dried under reduced pressure. The isolated product was 1.08 g (100 percent). Preparation of (1 H-cyclopentaphenanthrene-2-yl) dimethyl (t-butylamido) silanetitan dichloride To a 250 ml round bottom flask containing 1.17 g (0.0030 mole) of TiCl 3"3THF and approximately 120 ml THF was added with 50 ml of a THF solution of 1.08 g of dilithium (1H-cyclopenta [l] phenanthrene-2-yl) dimethyl (t-butylamido) siRNA. The mixture was stirred at about 20 ° C for 1.5 h at which time 0.55 gm (0.002 mole) of solid PbCI2 was added. After stirring for an additional 1.5 h, the THF was removed in vacuo and the residue was extracted with toluene, filtered and dried under reduced pressure to deliver an orange solid. The product was 1.31 g (93.5 percent). Preparation of 1,4-diphenylbutadiene from (1 H-cyclopentam-phenanthrene-2-yl) dimethyl (t-butylamido) silanetitanium To a dichloride paste of (1 H-cyclopenta [l] phenanthrene-2-yl) dimethyl (t-butylamide ) silanotitanium (3.48 g, 0.0075 mole) (produced by adjusting Example 1) and 1,551 gm (0.0075 mole) of 1,4-diphenylbutadiene in approximately 80 ml of toluene at 70 ° C were added 9.9 ml of 1.6 M solution of n-BuLi (0.0150 mole). The solution darkened immediately. The temperature is it was increased to bring the mixture to reflux and the mixture was kept at that temperature for 2 hours. The mixture was cooled to about -20 ° C and the volatiles were removed under reduced pressure. The residue was converted to paste in 60 ml of hexanes mixed at about 20 ° C for about 16 hours. The mixture was cooled to about -25 ° C for about 1 h. The solids were concentrated in a glass mixture by vacuum filtration and dried under reduced pressure. The dried solid was placed on a solid fiber paper filter element and the solid was continuously extracted with hexanes using a soxhlet extractor. After 6 h a crystalline solid was observed at the boiling point. The mixture was cooled to approximately -20 ° C, it was isolated by filtration from the cold mixture and dried under reduced pressure to deliver 1.662 g of a solid crystalline solid. The filtrate was discarded. The solids in the extractor were stirred and the extraction continued with an additional amount of mixed hexanes to deliver an additional 0.46 gm of the desired product as a dark crystalline solid. The metal complex B can be represented by the following schematic structure: The polymerizations are carried out in a two liter Parr reactor which is charged with Isopar-E ™ mixed alkane solvent (available from Exxon Chemicals, I nc.) And the desired amount of comonomer (s). Silane (SiH4) is added by differential pressure expansion from a 75 mL addition tank. The reactor is heated to the desired initial reaction temperature and allowed to stabilize. The desired amount of catalyst and cocatalyst (trispentafluorophenylborane) as solutions in toluene are premixed in the dry box to deliver a 1: 1 molar ratio of catalyst and cocatalyst and charged to the polymerization reactor through a stainless steel transfer line that uses nitrogen and a "crusher" of toluene. The polymerization conditions are maintained during the indicated reaction periods with ethylene on demand using periodic catalyst additions to maintain the polymerization activity. The heat is continuously extracted from the reaction through an internal cooling coil. After polymerization for the indicated times, the resulting solution is extracted from the reactor, cooled with isopropyl alcohol and stabilized by the addition of an inhibited phenol antioxidant (Irganox ™ 1010 by Ciba Geigy Corporation). The solvent is extracted in a vacuum oven set at 140 ° C by heating the polymer solution for about 16 hours. The results are shown in Table 1. TABLE I Ex-Catalyst Temp silane time C2H4 C3H7 Styrene Isopar product Mw Mn Mz (μmole) (° C) (min) (? MPa) (MPa) (g) (g) (g) ) (g) x106 x106 x106 1 A (1.3) 140 22.5 0.3 3.4 0 0 860 15.5 575 249 988 2 A (1.5) "15.1 0.7" "" "7.3 466 182 761 3 AÍ6.3) "30.5 1.4" "11.2 434 186 732 A (8.0) 90 30.5 0.7 1.4 456 360 61.7 124 48 214 A (8.0) "30.6 1.4" "" "47.3 92 47 145 6 B (7.0) "30.6 0.7 • • • * 59.5 _ 107 50 260 7 B (20.0) "51.7 1.4 69.2 76 34 234 8 C (6.0) 70 15.8 0.7 150 650 76.9 12 6 19 9 C (6.0) '' 14.2 1.4 82.4 10 6 15 A = (1,3-pentadiene) of (t-butylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium B = 1,4-dienylbutadiene of (1 H-cyclopenta [l] phenanthrene-2-yl) dimethyl (t-butylamido) silanotitan or C = (trans, trans-1,4-diphenyl-1,3-butadiene) of (1,2-ethylene bis (1-indenyl)) zirconium.

Examples 10-13 Continuous Gas Phase Polymeratizations The continuous gas phase polymerizations are carried out in a 6 liter gas phase reactor having a fluidization zone of 30.48 centimeters long with a diameter of 5.08. centimeters and a zone of reduction of speed of 20.32 centimeters in length with diameter of 20.32 centimeters which are connected by a transition section that has tapered walls. Typical operating conditions range from 40 to 1 00 ° C, 1 00 to 350 psia of total pressure and up to 8 hours of reaction time. The monomer, comonomer and other gases enter the bottom of the reactor from where they pass through a gas distributor plate-the gas flow was 2 to 8 times the minimum particle fluidization rate. ÍFluidization Engineering, 2nd Ed., D Kunii and O. Levenspiel, 1 991, Butterworth-Heinemann]. Most of the suspended solids were released in the velocity reduction zone. The gases left the top of the velocity reduction zone and pass through a dust filter to extract any fine. The gases were then passed through a gas pressure booster pump. The polymer was allowed to accumulate in the reactor over the course of the reaction. The total pressure of the system was kept constant during the reaction by regulating the monomer flow to the reactor. The polymer was removed from the reactor to a recovery vessel by opening a series of valves located at the bottom of the fluidization zone thereby discharging the polymer in a recovery vessel maintained at a lower pressure than the reactor. Monomer pressures, comonomer and other gases reported refer to partial pressures. The catalyst is prepared and loaded into a catalyst injector in a box handled by gloves of inert atmosphere. The injector is removed from the box handled by g uantes and inserted into the upper part of the reactor. The appropriate amounts of monomer, comonomer and other gases are introduced into the reactor to bring the pressure to the desired reaction pressure. The catalyst is then injected and the polymer allowed to accumulate for 30 to 90 minutes. The total pressure of the system is kept constant during the reaction by regulating the monomer flow to the reactor. After 30 to 90 minutes, the reactor is emptied and the polymer powder is collected. Example 10 15.9 grams of silica ES70Y type Crosfield are heated (surface area = 31 5 m2 / g and a particle size Malvern [D50] = 106.8 μm) at 500 ° C for 4 hours in an inert stream of nitrogen. The silica is allowed to cool to room temperature in an inert stream of nitrogen. The silica calcination tube is sealed at both ends and is delivered to a box manipulated by gloves of inert atmosphere. The silica is removed from the calcination tube, then converted to paste with 80 μl of hexane at a ratio of 5 μl hexane / gram of silica. The silica converted into pulp was 2.93 g grams of a 93 weight percent solution of triethylaluminium (TEA) which corresponded to a treatment of 1.5 mmoles of TEA / gram of silica. The paste was allowed to settle for 2 hours with manual gentle agitation every 1 5 to 20 minutes. After 2 hours the silica was filtered and rinsed twice with a total of 1 00 ml of hexane to extract some soluble aluminum compound that was produced during the TEA treatment step. The silica is then dried at room temperature under vacuum to deliver a free-flowing powder. Example 11 An aliquot (200 μl) of 0.005 M of a solution of (s-trans-trans, trans-1,4-biphenyl-1,3-butadiene) of [1,2-ethylanediyl bis (1-indenyl) is combined. )] zirconium in toluene with 0.03 grams of the pre-treated Crosfield ES70Y silica described in example 10 which has been pre-wetted with 200 μl of toluene. Then an aliquot (220 μl) of 0.005 M tris (pentafluorophenyl) borane solution is added to this paste. After 10 minutes of stirring this mixture, the solvent is removed under vacuum to deliver a free-flowing powder. The above described formulated catalyst is added to the gas phase fluid bed reactor an ethylene pressure of 240 psi (1.7 MPa), a pressure of 1-butene of 5 psi (34 kPa), a silane pressure of 2 psi (14 kPa) and a nitrogen pressure of 50 psi (340 kPa). The temperature throughout the polymerization is maintained at 7 ° C. The polyethylene polymer is recovered after 30 minutes containing long chain branching. EXAMPLE 12 An aliquot (400 ml) of 0.00500 M of a solution of (s-trans-trans, trans-1,4-biphenyl-1,3-butadiene) of [1,2-ethiianodiyl bis (1-indenyl) is combined. )] zirconium in toluene with 0.03 grams of the pre-treated Crosfield ES70Y silica described in example 10 which has been pre-wetted with 200 μl of toluene. Then an aliquot (420 μl) of 0.005M tris (pentafluorophenyl) borane solution is added to this paste. After 10 minutes of stirring, the solvent is removed under vacuum to deliver a free-flowing powder. The formulated catalyst described above is added to the gas phase fluid bed reactor which was under a propylene pressure of 100 psi (700 kPa), a silane pressure of 2 psi (14 kPa), and a nitrogen pressure of 20 psi (140 kPa). The temperature throughout the polymerization was 70 ° C. The crystalline polypropylene polymer is recovered after 60 minutes containing long chain branching. Example 13 Crosfield TYPE silica ES70 (particle size = 40 μm) is heated at 250 ° C for 4 hours in an inert stream of nitrogen. The silica is allowed to cool to room temperature in an inert stream of nitrogen. The silica calcination tube is then sealed at both ends and delivered to a box manipulated by gloves of inert atmosphere. The silica is removed from the calcination tube, then 5 grams are converted to a solution of 5 ml of triethylaluminium (TEA) in 50 ml. of hexanes. The paste is allowed to settle for 15 minutes with occasional gentle manual agitation. After filtering the silica and rinsing three times with a total of 150 ml, of hexane to extract some soluble aluminum compound which has been produced during the TEA treatment step. The silica is then dried at room temperature under vacuum to deliver a free flowing powder. To 0.400 ml of 0.150 M of TEA solution, 0.400 ml of toluene are added. To this solution is added 0.400 ml of 0. 1 50 M solution of tris (pentafluorophenyl) - (4. Hydroxyphenyl) borate methyIdi (octadecyl) ammonium in toluene. This solution is allowed to settle for 10 minutes and then 1000 grams of the pretreated silica described above is added. The mixture is mixed thoroughly and allowed to settle for 5 m inutes, at which time 10 ml of hexanes are added. To this mixture is added a solution consisting of 33.2 mg of (s-trans-trans, trans-1,4-biphenyl-1,3-butadiene) of [bis (2-methyl-4-phenyl-1-indenyl) ) dimethylsilane] zirconium in 10 ml of hexanes. The resulting mixture is then stirred. After twenty hours, the supernatant of the settled solids is carefully decanted. Then 1 2 ml is added to the solids. The pasta is divided in half and only half is used during the rest of the example. 12.5 ml of saturated propylene hexanes are added to the half of the pulp and stirred for 5 minutes. The supernatant of the settled solids is decanted. The volatile materials are allowed to evaporate from the solid in the box handled by gloves. The formulated catalyst described above is added to the gas-phase fluid bed reactor under a propylene pressure of 1 00 psi (700 kPa), a silane pressure of 2 psi (14 kPa), and a nitrogen pressure of 20 psi (300 kPa). The temperature throughout the polymerization is 70 ° C. The crystalline polypropylene polymer containing long chain branching is recovered.

Example 14 A. Preparation of Catalyst Components 1. Preparation of Kemamine ™ Hydrochloride T9701 Kemamine ™ T9701, (N me (C18_22H3 -45) 2 (1 3.4 grams, 25 mmol), available from Witco Corp. (Kemamine is a registered trademark of Witco, Corp.) in diethyl ether, was dissolved. (300 ml.) Hydrogen chloride gas was boiled directly into the solution for 5 minutes, until the pH was acidic as demonstrated by the pH paper.The mixture was stirred for 15 minutes and the white precipitate was collected by filtration, rinsed with three 50 ml portions of diethyl ether and dried in vacuo The product of N HCIMe (C1 8-22 H37.45) 2 was 1 2.6 grams. 2. Preparation of r (P-HOC »H -.) B (CBFs) airN HMe (C1 .7? H * 7 A«) ,} N HCIMe (C? 8.22H37.45) 2 (4.58 grams, 8 mmol) was dissolved in dichloromethane (50 ml). Triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate [(p-HOC6H4) B (C6F5) 3] [NH Et3] (5.66 grams, 8 mmol, prepared as substantially described in Example 1B of the application) was added. US Patent No. 08/61 0,647, filed March 4, 1996 (corresponding to WO 96/28480) followed by 40 ml of distilled water. The mixture was stirred rapidly for 4 hours and then the water layer was removed by syringe. The dichloromethane layer was then dried in sodium sulfate, filtered and dried under vacuum to produce an oil. The oil was extracted into toluene (200 ml), the resulting solution was filtered and the filtrate was dried in vacuo to yield 8.84 g bouquets of colorless oil. 3. Preparation of Catalyst Support 40 grams of silica SP 1 2 (Grace Davison XPO 2402) were converted into paste, which had been heated at 250 ° C for 3 hours under vacuum in toluene (400 ml) and then treated with 40 ml of triethyl aluminum (TEA) in 250 ml of toluene. The mixture was stirred for 1 hour, filtered and the treated silica was rinsed with toluene (100 ml, at about 1000 ° C) and dried under high vacuum. B. Preparation of Support Catalyst 0.4 ml of 0.1 M solution of [(p-HOC6H4) B (C6F5) 3] [NHMe (C1 8.22H37_45) 2] was mixed for approximately ten minutes with 0.4 ml of 0. 1 M of aluminum solution of triethyl in toluene and 0.4 ml of toluene. The resulting solution was divided into three portions and sequentially added to 1 g of the TEA treated silica. The resulting mixture was stirred and 20 mL of hexane was added with further stirring. After drying under vacuum for 30 minutes, 33.2 mg dissolved in Rac-dimethylsilanebis (2-methyl-4-phen i l-inden-1-yl) zirconium were added in toluene of 1,4-biphenyl-1,3-butadiene. (prepared according to USP 5, 278, 264) to the silica with stirring. The resulting catalyst was then rinsed with hexane and dried. It was found that the catalyst contained 35 μmol of Zr / g of support.

C. Polymerization. A 2 L Parr reactor was heated to 70 ° C and charged with 270 g of propylene and pressurized with 0.14 L of hydrogen. 7-Octenylsilane (containing about 14.6 percent of 6- octenylsilane) was charged 0.13 percent by weight based on the total monomer content, dissolved in 0.5 ml of toluene and pressurized to 100 psig on the reactor pressure with N2 to the beaker. Then 12 μmol of the Zr-containing catalyst, converted to paste in hexane under N2 pressure of 100 psig above the reactor pressure, was added to the vessel in order to initiate the polymerization. Polymerization was continued for 30 minutes and resulted in the formation of 45.3 g octenylsilane-modified polypropylene. The polymer had a molecular weight of 459,000 and a molecular weight distribution of 3.2. The contained copolymer added LCB as demonstrated by increasing the viscosity in the solution as a function of the increased absolute molecular weight and an increase in extensional flow stress strengthening as a function of the extension ratio as compared to a propylene made under comparative conditions . Based on such analyzes, the octenylsilane-containing polymer has the form of 0.2 to 0.5 sites / tetrafunctional branch chain.

EXAMPLE 15 Using the catalyst and polymerization process of Example 14, 0.25 weight percent of octenylsilane was copolymerized with propylene to deliver 28.7 g of a polypropylene modified with 7-octenylsilane. The polymer had a molecular weight of 440,000 and a molecular weight distribution (MWD) of 3.4. The contained copolymer added LCB as demonstrated by increasing the viscosity in the solution as a function of the increased absolute molecular weight and an increase in extensional flow stress strengthening as a function of the extension ratio as compared to a propylene made under comparative conditions . Based on such analyzes, the octenylsilane-containing polymer has the form of 0.2 to 0.5 sites / tetrafunctional branch chain.

Example 1 Using the catalyst and polymerization process of Example 14, 0.5 weight percent of octenylsilane was copolymerized with propylene to deliver 4.8 g of a polypropylene modified with 7-octenylsilane. The polymer had a molecular weight of 335,000 and a MWD of 4.2. The contained copolymer added LCB as demonstrated by the increase in viscosity in the solution as a function of the increased absolute molecular weight and an increase in extensional flow stress strengthening as a function of the extension ratio as compared to a propylene prepared under comparative Based on such analyzes, the octenylsilane-containing polymer has the form of 0.2 to 0.5 sites / tetrafunctional branch chain.

Example 1 7 (comparative) Using the catalyst and polymerization process of Example 14, propylene was copolymerized in the absence of a syllable to deliver 45.3 g of polypropylene. The polymer had a molecular weight of 351,000 and a MWD of 2.8.

Claims (7)

REVIVALATION IS

1 . A process for preparing homopolymers and copolymers of addition polymerizable olefin monomers, or mixtures of such monomers, the process comprising contacting said monomer or mixture under conditions of high monomer conversion polymerization with a catalyst composition comprising: a) a catalyst system comprising a metal complex of Group 3-1 0; and c) a silane, or hydrocarbylsilane corresponding to the formula; JjSihU-j or AnJJSiH4. (N + J) where: J is C1.40 hydrocarbyl, A is a C2-20 alkenyl group, n is 1 or 2, and j is 0 or 1; wherein the polymer comprises from 0. 1 to 1 00 long chain branches per 10,000 carbons, at least some of which comprise a silane ramification center.

2. A process according to claim 1, characterized in that the silane is, SiH4, phenylsilane or 7-octenylsilane.

3. A process according to claim 1, characterized in that the number of long chain branches is from 0.3 to 1.0 for 10. 000 carbons.

4. A process according to claim 1, characterized in that the monomer is propylene.

5. An olefin polymer comprising from 0.1 to 1 00 long chain branches per 1,000 carbon, at least some of which comprise a branch center derived from a syllable.

6. An olefin polymer according to claim 4, characterized in that the silane is SiH4, phenylsilane or 7-octenylsilane.

7. An olefin polymer according to claim 5, characterized in that the olefin is propylene. SUMMARY A process for preparing homopolymers and copolymers of polymerizable addition monomers, or mixtures of such monomers, and the resulting polymer, wherein the process comprising contacting said monomer or mixture under high polymerization conversion conditions of monomer with a catalyst composition comprises: a) a catalyst system comprising a metal complex of Group 3-10; and c) a silane, or hydrocarbylsilane corresponding to the formula: JjSiH .jo AnJjSiH4. (n + j) where: J is C1 - 0 hydrocarbyl, A is a C2.20 alkenyl group, n is 1 or 2, and j is 0 or 1; wherein the polymer comprises from 0.1 to 1 00 long chain branches per 1,000 carbon, and at least some of which comprise a silane branching center.