WO2001004167A1

WO2001004167A1 - Coordination polymerization catalysts comprising an ion exchange resin

Info

Publication number: WO2001004167A1
Application number: PCT/US2000/014707
Authority: WO
Inventors: Tao Sun; Juan M. Garces
Original assignee: The Dow Chemical Company
Priority date: 1999-07-13
Filing date: 2000-05-30
Publication date: 2001-01-18
Also published as: AU5047400A

Abstract

A catalyst composition for use in the coordination polymerization of an olefin comprising: A) a Group 3-10 transition metal complex, B) a polymer comprising perfluorinated sulfonic acid functional groups, and C) an organoaluminum compound containing up to 50 atoms not counting hydrogen.

Description

COORDINATION POLYMERIZATION CATALYSTS COMPRISING AN

ION EXCHANGE RESIN This invention relates to novel materials especially suited for use as activators in combination with a Group 3-10 metal complex for the addition polymerization of monomers such as olefins to make high molecular weight homopolymers and copolymers. The materials may be used in both homogeneous and heterogeneous catalyst compositions to provide highly active polymerization systems.

It is widely known that addition polymerization processes utilizing metallocene catalysts have been used to produce a wide range of new polymers for use in a variety of applications and products. Supported oiefin polymerization catalysts are widely known and used in the gas phase and slurry polymerization of such olefins. Suitable support materials have included silica, alumina, aluminosilicates, clays, and other metal oxides.

Catalysts for olefin polymerization comprising a transition metal compound, an ion exchanging compound, especially a clay, and an organic aluminum compound, such as a trialkyl aluminum compound, are disclosed in US-A-5,308,811. More recently, EP-A-658,576 disclosed the formation of modified clay containing supported catalysts containing a metallocene, wherein an ionic compound, especially a Bronsted acid salt, such as dimethylaniiinium chloride, was included in the clay. The use of both Bronsted acid and Lewis acid activators in olefin polymerization catalyst compositions is previously known from references such as US-A-5, 198,401 , US-A-5,721 ,185, and elsewhere. US-A-5,427,991 discloses use of a resin material, such as a sulfonated polystyrene resin, which has been reacted with a Bronsted acid activator to form a supported cocatalyst containing non-coordinating anions for use in coordination polymerizations.

Despite the advance in the arts resulting from the use of the foregoing inventions and discoveries, it remains desirable to provide catalyst supports and catalyst components having improved physical and chemical properties. In particular, a catalyst support or catalyst component for olefin polymerizations lacking in added cocatalytic substances, especially alumoxane or alumoxane type materials or

Bronsted acid salts containing non-coordinating anions, are desired in order to reduce catalyst material costs.

According to one embodiment of the present invention there is provided a catalyst composition for use in the coordination polymerization of an olefin comprising:

A) a Group 3-10 transition metal complex, B) a polymer comprising perfluorinated sulfonic acid functional groups, and

C) an organoaluminum compound containing up to 50 atoms not counting hydrogen. In another embodiment of the invention there is provided a support material for use in preparing supported catalysts for addition polymerizations comprising a polymer comprising perfluorinated sulfonic acid functional groups. When combined with a transition metal compound and an organoaluminum compound containing up to 50 atoms not counting hydrogen, the composition results in a highly active supported catalyst for preparation of high molecular weight olefin polymers.

Finally according to the present invention there is provided a process for polymerizing an addition polymerizable monomer comprising contacting under polymerization conditions an addition polymerizable monomer or a mixture comprising said monomer, with a composition comprising: A) a Group 3-10 transition metal complex,

B) a polymer compπsing perfluorinated sulfonic acid functional groups, and

C) an organoaluminum compound containing up to 50 atoms not counting hydrogen.

Advantageously, the catalyst compositions of the invention do not require the use of a conventional cocatalyst in order to be active olefin polymerization catalysts. Accordingly, the invention provides a simplified and economical polymerization process. The use of the present catalyst compositions results in the highly efficient production of high molecular weight polymers over a wide range of polymerization conditions, especially at elevated temperatures. The present compositions are especially useful for catalyzing the solution phase, gas phase or slurry homopolymerization of ethylene or propylene or the solution phase, gas phase or slurry copolymerization of ethylene/propylene (EP polymers), ethylene/octene (EO polymers), ethylene/styrene (ES polymers) and ethylene/propylene/diene (EPDM polymers) wherein the diene is ethylidenenorbornene, 1 ,4-hexadiene, or similar nonconjugated diene. The foregoing polymeric materials are useful in the preparation of films for packaging or other uses, foamed structures for cushioning or insulating applications, and the preparation of fibers and solid molded objects.

Preferred support/ activator materials (component B)) for use herein are copolymers of tetrafluoroethylene and a perfluorinated sulfonic acid functionalized monomer. Such polymers are readily available commercially. A preferred source of such resins is E. I. DuPont Nemours and Company which sells such resins under the trade designation Nation™. A more preferred support/ activator material for use herein is a copolymer of tetrafluoroethylene and a perfluoronated sulfonic acid functionaiized monomer. A most preferred support/ activator material for use herein is a copolymer of tetrafluroethylene and perfluoro-2-(fluorosulfonylethoxy)propyl vinyl ether, available under the trade designation Nation™ SAC-13.

Prior to use, residual water and organic contaminants are desirably removed from the resin. This can be readily accomplished by exposing the resin to reduced pressure, optionally while heating for a period of time from 10 minutes to 48 hours. Desirably the resin is employed in a finely divided, particulated form, having a particle size (number average) from 0.1 μm to 1000 μm, preferably from 1 to 100 μm, the reduced pressure used is less than 100 Pa, preferably less than 10 Pa, and the temperature is from 50 to 150⁵C, preferably from 75 to 120 °C. Desirably the water content of the resin is less than 0.5 percent by weight, more preferably less than 0.1 percent by weight. Suitable organoaluminum compounds (component C)) correspond to the formula: AIAr^f,Q¹ _gQ² _h, or a dimer, adduct, or mixture thereof; where: Ar* is a fluorinated aromatic ligand group;

Q¹ is a C1-20 hydrocarbyl group, optionally substituted with one or more cyclohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, hydrocarbylsilyl, si lyl hydrocarbyl, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, or hydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen, or, further optionally, such substituents may be covalently linked with each other to form one or more fused rings or ring systems; Q² is hydride, halide or an aryloxy, arylsulfide or di(hydrocarbyl)amido group, optionally substituted with one or more hydrocarbyl, cyclohydrocarbyl, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, hydrocarbylsilyl, silylhydrocarbyl, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, or hydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen, or, further optionally such substituents may be covalently linked with each other to form one or more fused rings or ring systems, said Q² having from 3 to 20 atoms other than hydrogen; f is an integer from 0 to 3, g is an integer from 0 to 3, and h is an integer from 0 to 2, and the sum of f, g and h is three.

The organoaluminum compound is desirably a trialkylaluminum compound containing from 1 to 6 carbons in each alkyl group. A most preferred organoaluminum compound is tri(n-propyl)aluminum. Suitable transition metal compounds (component A)) especially include complexes or compounds of a metal of Groups 3-10 of the Periodic Table of the Elements capable of being activated to polymerize ethylenically unsaturated compounds in combination with the present supports/ activator.

Examples of suitable metal complexes or compounds for use herein include Group 10 diimine derivatives corresponding to the formula:

. . CT-CT

^"M^** X'₂ wherein N N is Ar^*-N N-Ar^*

( N

M" is Ni(ll) or Pd(ll);

X' is halo, hydrocarbyl, or hydrocarbyloxy; Ar^* is an aryl group, especially 2,6-diisopropylphenyl or aniline group; and

CT-CT is 1 ,2-ethanediyl, 2,3-butanediyl, or form a fused ring system wherein the two T groups together are a 1 ,8-naphthanediyl group.

Similar compounds to the foregoing are also disclosed by M. Brookhart, et al., in J. Am. Chem. Soc. 118, 267-268 (1996) and J. Am. Chem. Soc. 1 17, 6414 -6415 (1995), as being active polymerization catalysts especially for polymerization of α- olefins, either alone or in combination with polar comomoners such as vinyl chloride, alkyl acrylates and alkyl methacrylates.

Additional complexes or compounds include derivatives of Group 3, 4, or Lanthanide metals which are in the +2, +3, or +4 formal oxidation state. Preferred are those containing from 1 to 3 π-bonded anionic or neutral ligand groups, which may be cyclic or non-cyclic delocalized π-bonded anionic ligand groups. Exemplary of such π- bonded groups are conjugated or nonconjugated, cyclic or non-cyclic diene and dienyl groups, allyl groups, boratabenzene groups, phosphole, and arene groups. By the term "π-bonded" is meant that the ligand group is bonded to the transition metal by a sharing of electrons from a partially delocalized π-bond.

Each atom in the delocalized π-bonded group may independently be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substituted heteroatoms wherein the heteroatom is selected from Group 14-16 of the Periodic Table of the Elements, and such hydrocarbyl- substituted heteroatom radicals further substituted with a Group 15 or 16 hetero atom containing moiety. In addition two or more such radicals may together form a fused ring system, including partially or fully hydrogenated fused ring systems, or they may form a metallocycle with the metal. Included within the term "hydrocarbyl" are C1 -20 straight, branched and cyclic alkyl radicals, Cg-20 aromatic radicals, C7.20 alkyl-substituted aromatic radicals, and C7.20 aryl-substituted alkyl radicals. Suitable hydrocarbyl-substituted heteroatom radicals include mono-, di- and tri-substituted radicals of boron, silicon, germanium, nitrogen, phosphorus or oxygen wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples include N,N-dimethylamino, pyrrolidinyl, trimethylsilyl, triethylsilyl, t- butyidimethylsilyl, methyldi(t-butyl)silyl, triphenylgermyl, and trimethylgermyl groups. Examples of Group 15 or 16 hetero atom containing moieties include amino, phosphino, alkoxy, or alkylthio moieties or divalent derivatives thereof, e. g. amide, phosphide, alkyleneoxy or alkylenethio groups bonded to the transition metal or Lanthanide metal, and bonded to the hydrocarbyl group, π-bonded group, or hydrocarbyl- substituted heteroatom.

Examples of suitable anionic, delocalized π-bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, and boratabenzene groups, as well as C_MO hydrocarbyl-substituted or C,.^ hydrocarbyl-substituted silyl substituted derivatives thereof. Preferred anionic delocalized π-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2- methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, 1 - indacenyl, 3-pyrrolidinoinden-1 -yl, 3,4-(cyclopenta(/)phenanthren-1 -yl, and tetrahydroindenyl.

The boratabenzenes are anionic ligands which are boron containing analogues to benzene. They are previously known in the art having been described by G. Herberich, et al., in Orαanometallics, 14,1 , 471 -480 (1995). Preferred boratabenzenes correspond to the formula:

wherein R" is selected from the group consisting of hydrogen, hydrocarbyl, silyl, or germyl, said R" having up to 20 non-hydrogen atoms. In complexes involving divalent derivatives of such delocalized π-bonded groups one atom thereof is bonded by means of a covalent bond or a covalently bonded divalent group to another atom of the complex thereby forming a bridged system.

Phospholes are anionic ligands that are phosphorus containing analogues to a cyclopentadienyl group. They are previously known in the art having been described by WO 98/50392, and elsewhere. Preferred phosphole ligands correspond to the formula:

wherein R" is as previously defined.

Phosphinimine/ cyclopentadienyl complexes are disclosed in EP-A-890581 and correspond to the formula [(R^**)3-P=N]bM^**(Cp)(L¹ )3._D, wherein:

R^** is a monovalent ligand, illustrated by hydrogen, halogen, or hydrocarbyl, or two R^** groups together form a divalent ligand, M^** is a Group 4 metal, Cp is cyclopentadienyl, or similar delocalized π-bonded group, L¹ is a monovalent ligand group, illustrated by hydrogen, halogen or hydrocarbyl, and b is 1 or 2.

A further suitable class of transition metal complexes for use herein correspond to the formula: K'kMZ'_mL|Xp, or a dimer thereof, wherein:

K' is an anionic group containing delocalized π-electrons through which K' is bound to M, said K' group containing up to 50 atoms not counting hydrogen atoms, optionally two K' groups may be joined together forming a bridged structure, and further optionally one K' may be bound to Z';

M is a metal of Group 4 of the Periodic Table of the Elements in the +2, +3 or +4 formal oxidation state;

Z' is an optional, divalent substituent of up to 50 non-hydrogen atoms that together with K forms a metallocycle with M; L is an optional neutral ligand having up to 20 non-hydrogen atoms; X each occurrence is a monovalent, anionic moiety having up to 40 non- hydrogen atoms, optionally, two X groups may be covalently bound together forming a divalent dianionic moiety having both valences bound to M, or, optionally 2 X groups may be covalently bound together to form a neutral, conjugated or nonconjugated diene that is bound to M by means of delocalized π-electrons (whereupon M is in the +2 oxidation state), or further optionally one or more X and one or more L groups may be bonded together thereby forming a moiety that is both covalently bound to M and coordinated thereto by means of Lewis base functionality; k is 0, 1 or 2; m is O oM ;

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 when 2 X groups together form a neutral conjugated or non-conjugated diene that is bound to M via delocalized π-electrons, in which case the sum k+m is equal to the formal oxidation state of M.

Preferred complexes include those containing either one or two K' groups. The latter complexes include those containing a bridging group linking the two K' groups. Preferred bridging groups are those corresponding to the formula (ER'2)_X wherein E is silicon, germanium, tin, or carbon, R' independently each occurrence 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 is 1 to 8. Preferably, R' independently each occurrence is methyl, ethyl, propyl, benzyl, tert- butyl, phenyl, methoxy, ethoxy or phenoxy. Examples of the complexes containing two K' groups are compounds corresponding to the formula:

wherein: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the +2 or +4 formal oxidation state;

R³ in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R³ having up to 20 non-hydrogen atoms, or adjacent R³ groups together form a divalent derivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system, and

X" independently each occurrence is an anionic ligand group of up to 40 non- hydrogen atoms, or two X" groups together form a divalent anionic ligand group of up to 40 non-hydrogen atoms or together are a conjugated diene having from 4 to 30 non- hydrogen atoms bound by means of delocalized π-electrons to M, whereupon M is in the +2 formal oxidation state, and

R', E and x are as previously defined.

The foregoing metal complexes are especially suited for the preparation of polymers having stereoregular molecular structure. In such capacity it is preferred that the complex possesses C_s symmetry or possesses a chiral, stereorigid structure. Examples of the first type are compounds possessing different delocalized π-bonded ligand groups, such as one cyclopentadienyl group and one fluorenyl group. Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefin polymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980). Examples of chiral structures include rac bis-indenyl complexes. Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparation of isotactic olefin polymers in Wild et al., J. Orαanomet. Chem.. 232, 233-47, (1982).

Exemplary bridged ligands containing two π-bonded groups are: dimethylbis(cyclopentadienyl)silane, dimethylbis(tetramethylcyclopentadienyl)silane, dimethylbis(2-ethylcyclopentadien-1 -yl)silane, dimethylbis(2-t-butylcyclopentadien-1 - yl)silane, 2,2-bis(tetramethyicyclopentadienyl)propane, dimethylbis(inden-1 -yl)silane, dimethylbis(tetrahydroinden-1 -yl)silane, dimethylbis(fluoren-1 -yl)silane, dimethylbis(tetrahydrofluoren-1 -yl)silane, dimethylbis(2-methyl-4-phenylinden-1 -yl)- silane, dimethylbis(2-methylinden-1-yl)siiane, dimethyl(cyclopentadienyl)(fluoren-1- yl)silane, dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane, dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane, (1 , 1 , 2, 2-tetramethy)-1 , 2- bis(cyclopentadienyl)disilane, (1 , 2-bis(cyclopentadienyl)ethane, and dimethyl(cyclopentadienyl)-1 -(fluoren-1 -yl)methane. Preferred X" groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl and aminohydrocarbyl groups, or two X" groups together form a divalent derivative of a conjugated diene or else together they form a neutral, π-bonded, conjugated diene. Most preferred X" groups are C-|_20 hydrocarbyl groups.

A further class of metal complexes utilized in the present invention corresponds to the preceding formula K'kMZ'_mL_nXp, or a dimer thereof, wherein Z' is a divalent substituent of up to 50 non-hydrogen atoms that together with K' forms a metallocycle with M.

Preferred divalent Z' substituents include groups containing up to 30 non- hydrogen atoms comprising at least one atom that is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly attached to K', and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur that is covalently bonded to M.

Another preferred class of Group 4 metal complexes used according to the present invention corresponds to the formula:

wherein:

M is titanium or zirconium, preferably titanium in the +2, +3, or +4 formal oxidation state;

R³ in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R³ having up to 20 non-hydrogen atoms, or adjacent R³ groups together form a divalent derivative (that is, a hydrocarbadiyl, siiadiyl or germadiyl group) thereby forming a fused ring system, each X is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, said group having up to 20 non-hydrogen atoms, or two X groups together form a neutral C5-30 conjugated diene or a divalent derivative thereof;

Y is -O-, -S-, -NR'-, -PR'-; and

Z is SiR'₂, CR'₂, SiR'₂SiR'₂, CR'₂CR'₂, CR'=CR', CR'₂SiR'₂, or GeR'₂, wherein R' is as previously defined. Illustrative Group 4 metal complexes that may be employed in the practice of the present invention include: cyclopentadienyltitaniumtrimethyl, cyclopentadienyltitaniumtriethyl, cyclopentadienyltitaniumtriisopropyl, cyclopentadienyltitaniumtriphenyl, cyclopentadienyltitaniumtribenzyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl«triethylphosphine, cyciopentadienyltitanium-2,4-dimethylpentadienyl»trimethylphosphine, cyclopentadienyltitaniumdimethylmethoxide, cyclopentadienyltitaniumdimethylchloride, pentamethylcyclopentadienyltitaniumtrimethyl, indenyltitaniumtrimethyl, indenyltitaniumtriethyl, indenyltitaniumtripropyl, indenyltitaniumthphenyl, tetrahydroindenyltitaniumtribenzyl, pentamethylcyclopentadienyltitaniumtriisopropyl, pentamethylcyclopentadienyltitaniumtribenzyl, pentamethylcyclopentadienyltitaniumdimethylmethoxide, pentamethylcyciopentadienyltitaniumdimethylchloride, bis(η⁵-2,4-dimethylpentadienyl)titanium, bis(η⁵-2,4-dimethylpentadienyl)titanium»trimethylphosphine, bis(η⁵-2,4-dimethylpentadienyl)titanium»triethylphosphine, octahydrofluorenyltitaniumtrimethyl, tetrahydroindenyltitaniumtrimethyl, tetrahydrofluorenyltitaniumthmethyl,

(tert-butylamido)(1 ,1 -dimethyl-2,3,4,9,10-η-1 ,4,5,6,7,8- hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(1 ,1 ,2,3-tetramethyl-2,3,4,9,10-η-1 ,4,5,6,7,8- hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl) dimethylsilanetitanium dibenzyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1 ,2-ethanediyltitanium dimethyl, (tert-butylamido)(tetramethyl-η⁵-indenyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilane titanium (III)

2-(dimethylamino)benzyl; (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III) allyl, (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III) 2,4-dimethylpentadienyl, (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (II)

1 ,4-diphenyl-1 ,3-butadiene, (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (II) 1 ,3- pentadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II) 1 ,4-diphenyl-1 ,3- butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II) 2,4-hexadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) 2,3-dimethyl-1 ,3- butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) isoprene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) 1 ,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) 2,3-dimethyl-1 ,3- butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) isoprene (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) dimethyl (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) dibenzyl (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV) 1 ,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II) 1 ,3-pentadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II) 1 ,4-diphenyl-1 ,3- butadiene,

(tert-butylamido)(2-methyiindenyl)dimethylsilanetitanium (II) 1 ,3-pentadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) dimethyl, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) dibenzyl, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II) 1 ,4-diphenyl-1 ,3-butadiene, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II) 1 ,3-pentadiene, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II) 2,4-hexadiene, (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyi-silanetitanium (IV) 1 ,3- butadiene, (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (IV) 2,3-dimethyl-1 ,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (IV) isoprene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-siianetitanium (II) 1 ,4-dibenzyl- 1 ,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (II) 2,4- hexadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II) 3-methyl-1 ,3-pentadiene, (tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(6,6-dimethylcyciohexadienyl)dimethyisilanetitaniumdimethyl,

(tert-butylamido)(1 ,1 -dimethyl-2, 3,4,9,10-η-1 ,4,5,6,7,8-hexahydronaphthaien-4- yl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(1 ,1 ,2,3-tetramethyl-2,3,4,9,10-η-1 ,4,5,6,7,8-hexahydronaphthalen-4- yl)dimethylsilanetitaniumdimethyl

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl methylphenylsilanetitanium (IV) dimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl methylphenylsilanetitanium (II) 1 ,4-diphenyl-1 ,3-butadiene, 1 -(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitanium (IV) dimethyl, and

1 -(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyl- titanium (II) 1 ,4- diphenyl-1 ,3-butadiene.

Complexes containing two K' groups including bridged complexes suitable for use in the present invention include: bis(cyclopentadienyl)zirconiumdimethyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)zirconium methyl benzyl, bis(cyclopentadienyl)zirconium methyl phenyl, bis(cyclopentadienyl)zirconiumdiphenyl, bis(cyciopentadienyl)titanium-allyl, bis(cyclopentadienyl)zirconiummethylmethoxide, bis(cyclopentadienyl)zirconiummethylchloride, bis(pentamethylcyclopentadienyl)zirconiumdimethyl, bis(pentamethyicyclopentadienyl)titaniumdimethyl, bis(indenyl)zirconiumdimethyl, indenylfluorenylzirconiumdimethyl, bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl), bis(indenyl)zirconiummethyltrimethylsilyl, bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl, bis(pentamethylcyclopentadienyi)zirconiummethylbenzyl, bis(pentamethylcyclopentadienyl)zirconiumdibenzyl, bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide, bis(pentamethylcyclopentadienyl)zirconiummethylchloride, bis(methylethylcyclopentadienyl)zirconiumdimethyl, bis(butylcyclopentadienyl)zirconiumdibenzyl, bis(t-butylcyclopentadienyl)zirconiumdimethyl, bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl, bis(methylpropylcyclopentadienyl)zirconiumdibenzyl, bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl, dimethylsilyl-bis(cyclopentadienyl)zirconiumdimethyl, dimethylsilyl-bis(tetramethylcyclopentadienyl)titanium (III) allyl dimethylsilyl-bis(t-butylcyclopentadienyl)zirconiumdichloride, dimethylsilyl-bis(n-butylcyclopentadienyl)zirconiumdichloride, (methylene-bis(tetramethylcyclopentadienyl)titanium(lll) 2-(dimethylamino)benzyl,

(methylene-bis(n-butylcyclopentadienyl)titanium(lll) 2-(dimethylamino)benzyl, dimethylsilyl-bis(indenyl)zirconiumbenzylchloride, dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl, dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdimethyl, dimethylsilyl-bis(2-methylindenyl)zirconium-1 ,4-diphenyl-1 ,3-butadiene, dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium (II) 1 ,4-diphenyl-1 ,3-butadiene, dimethylsilyl-bis(tetrahydroindenyl)zirconium(ll) 1 ,4-diphenyl-1 ,3-butadiene, dimethylsilyl-bis(fluorenyl)zirconiummethylchioride, dimethylsilyl-bis(tetrahydrofluorenyi)zirconium bis(trimethylsilyl), (isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl, and dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconium dimethyl.

Other complexes, especially those containing other Group 4 metals, will, of course, be apparent to those skilled in the art.

The complexes are combined with the support/ activator by any suitable technique. Ideally mixtures or solutions of the respective components are combined or the metal complexes are deposited from solution in an aliphatic, cycloaliphatic or aromatic liquid, by contacting the same with a solution of the metal complex and removing the solvent. This may be accomplished by immersing the support/ activator in metal complex solution, or the solution may be coated, or sprayed onto the surface of the support/ activator composition. In a further embodiment the organoaluminum compound may be added separately to the polymer material, combined with the transition metal compound or solution thereof, or incorporated in the monomer solution to be polymerized.

The weight ratio of component A/ component B employed in the present invention preferably ranges from 1 :10,000 to 10:1 , more preferably from 1 :5000 to 10:1 , most preferably from 1 :1000 to 1 :1. The weight ratio of component B/ component C employed in the invention preferably ranges from 1 :100 to 1000:1 , more preferably from 1 :5 to 100:1 , most preferably from 1 :1000 to 1 :1.

Although not preferred, it is also within the scope of the present invention to include a known cocatalyst in the catalyst formulation. Suitable cocatalysts for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane, which may be generated in situ by reaction of for example, a trialkylaluminum compound with if desired. Additional suitable activating cocatalysts include Lewis acids, such as Cι. o hydrocarbyl substituted Group 13 compounds, especially tπ(hydrocarbyl)a!uminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 20 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluorophenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium-, sulfonium-, or ferrocenium- salts of compatible, noncoordinating anions; and combinations of the foregoing activating cocatalysts and techniques. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: US-A- US-A-5,132,380, US-A-5,153,157, US-A-5,064,802, US-A-5,321 ,106, US-A-5,721 ,185, US-A-5,350,723, and WO-97/04234.

The catalyst compositions may be used to polymerize ethylenically and/or acetylenically unsaturated monomers having from 2 to 100,000 carbon atoms either alone or in combination. Preferred monomers include the C2-20 α-olefins especially ethylene, propylene, isobutylene, 1 -butene, 1 -pentene, 1-hexene, 3-methyl-1 - pentene, 4-methyl-1 -pentene, 1 -octene, 1-decene, long chain macromolecular α-oiefins, and mixtures thereof. Other preferred monomers include styrene, C1.4 alkyl substituted styrene, tetrafluoroethylene, vinylbenzocyclobutane, ethylidenenorbornene, 1 ,4-hexadiene, 1 ,7-octadiene, vinylcyclohexane, 4- vinylcyclohexene, divinylbenzene, and mixtures thereof with ethylene. Long chain macromolecular α-olefins are vinyl terminated polymeric remnants formed in situ during continuous solution polymerization reactions. Under suitable processing conditions such long chain macromolecular units are readily polymerized into the polymer product along with ethylene and other short chain olefin monomers to give small quantities of long chain branching in the resulting polymer. Most preferably the present supported catalysts are used in the polymerization of propylene to prepare polypropylene having a high degree of isotacticity. Preferred isotactic polypropylene polymers produced using the present catalyst composition have, an isotacticity as measured by I^C NMR spectroscopy of at least 80 percent, preferably at least 90 percent, and most preferably at least 95 percent. In general, the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, such as temperatures from 0-250°C and pressures from atmospheric to 1000 atmospheres (0.1 to 100 MPa). Slurry or gas phase process conditions are most desired. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal) :support from 1 :100,000 to 1 :10, more preferably from 1 :50,000 to 1 :20, and most preferably from 1 :10,000 to 1 :30. Suitable gas phase reactions may utilize condensation of the monomer or monomers employed in the reaction, or of an inert diluent to remove heat from the reactor.

In most polymerization reactions the molar ratio of catalystpolymerizable compounds employed is from 10^"12:1 to 10^'1 :1 , more preferably from 10^"12:1 to 10^"5:1. Suitable diluents for polymerization via a slurry process are noncoordinating, inert liquids. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycioheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C _ιo alkanes, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, and xylene. Suitable diluents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1 -butene, butadiene, cyclopentene, 1 -hexene, 3-methyl-1 -pentene, 4-methyl-1 -pentene, 1 ,4- hexadiene, 1 ,7-octadiene, 1 -octene, 1 -decene, styrene, divinylbenzene, ethylidenenorbomene, aliylbenzene, vinyltoluene (including ail isomers alone or in admixture), 4-vinylcyclohexene, and vinylcyclohexane. Mixtures of the foregoing are also suitable.

The catalysts may also be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in the same or in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties.

The present catalyst compositions are advantageously employed in a process for preparing homopolymers of propylene, random or block copolymers of propylene and an olefin selected from the group consisting of ethylene, C4-10 olefins, and C4.

10 dienes, and random terpolymers of propylene and olefins selected from the group consisting of ethylene and C4.1 n olefins. The C4--10 olefins include the linear and branched olefins such as, for example, 1 -butene, isobutylene, 1 -pentene, 3-methyl-1 - butene, 1 -hexene, 3,4-dimethyl-1 -butene, 1 -heptene, and 3-methyl-1 -hexene. Examples of C4.1 n dienes include 1 ,3-butadiene, 1 ,4-pentadiene, isoprene, 1 ,5- hexadiene, and 2,3-dimethy!-1 ,3-hexadiene.

Preferred polypropylene products have a molecular weight (Mw) of at least 10,000, more preferably at least 50,000, and most preferably at least 100,000, and a molecular weight distribution, Mw/Mn of less than 6.0, more preferably less than 4.0, and most preferably less than 2.5.

The polymerization is generally conducted under continuous or semicontinuous slurry polymerization conditions in hydrocarbon diluents such as propylene, propane, butene, butene-2, isobutane, hexane, heptane, and mixtures of the foregoing, generally at temperatures from 50 to 100 °C, and pressures from atmospheric to 1 MPa. The polymerization may be conducted in one or more continuous stirred tank tubular reactors or fluidized bed, gas phase reactors, or both, connected in series or parallel. Condensed monomer or solvent may be added to the gas phase reactor as is well known in the art. The supported catalyst may also be prepolymerized prior to use as previously disclosed. In a continuous reaction system, the reaction mixture is typically maintained at conditions at which the polymer is produced as a slurry of powder in the reaction mixture. Use of highly active and highly stereospecific catalyst systems in propylene polymerization substantially eliminates the need to remove catalyst components or atactic polymer from the polymer product. The mixture of reaction components is fed continuously or at frequent intervals into the reactor system and is continuously monitored so as to ensure an efficient reaction and the desired product. For example, it is well known that supported coordination catalysts and catalyst systems of the type described above are highly sensitive, in varying degrees, to catalyst poisons such as water, oxygen, carbon oxides, acetylenic compounds and sulfur compounds. Introduction of such compounds may result in reactor upset and production of off- grade product. Typically, computer control systems are used to maintain process variables within acceptble limits, often by measuring polymer variables such as viscosity, density and tacticity, or catalyst productivity.

In the process, reactants and diluents, which may be a mixture of propylene, hydrogen, nitrogen, unreacted comonomers and inert hydrocarbons, are continuously recycled through the reactor, optionally with scavenging to remove impurities and condensation to remove the heat of polymerization. Catalyst and cocatalysts, fresh monomer or comonomer(s) and selectivity control agents, branching agents or chain transfer agents, if desired, are likewise continuously fed to the reactor. The polymer product is continuously or semi-continuously removed and volatile components removed and recycled. Suitable processes for preparing polypropylene polymers are known in the art and illustrated by those taught in US-A-4,767,735, US-A-4,975,403, and US-A-5,084,513, among others.

Utilizing the catalyst compositions of the present invention, copolymers having high comonomer incorporation and correspondingly low density, yet having a low melt index, may be readily prepared. Additionally, high molecular weight polymers are readily attained by use of the present catalysts, even at elevated reactor temperatures. This result is highly desirable because the molecular weight of α-olefin copolymers can be readily reduced by the use of hydrogen or similar chain transfer agent, however increasing the molecular weight of α-olefin copolymers is usually only attainable by reducing the polymerization temperature of the reactor. Disadvantageously, operation of a polymerization reactor at reduced temperatures significantly increases the cost of operation since heat must be removed from the reactor to maintain the reduced reaction temperature, while at the same time heat must be added to the reactor effluent to vaporize the solvent. In addition, productivity is increased due to improved polymer solubility, decreased solution viscosity, and a higher polymer concentration. Utilizing the present catalyst compositions, α-olefin homopolymers and copolymers having densities from 0.85 g/cm³ to 0.96 g/cm³, and melt flow rates from 0.001 to 10.0 dg/min are readily attained in a high temperature process. The catalyst compositions of the present invention are particularly advantageous for the production of ethylene homopolymers and ethylene/α-olefin copolymers having high levels of long chain branching. The use of the catalyst compositions of the present invention in continuous polymerization processes, especially continuous, solution polymerization processes, allows for elevated reactor temperatures which favor the formation of vinyl terminated polymer chains that may be incorporated into a growing polymer, thereby giving a long chain branch. The use of the present catalyst compositions advantageously allows for the economical production of ethylene/α-olefin copolymers having processability similar to high pressure, free radical produced low density polyethylene.

The present catalyst compositions may be advantageously employed to prepare olefin polymers having improved processing properties by polymerizing ethylene alone or ethylene/α-olefin mixtures with low levels of a "H" branch inducing diene, such as norbornadiene, 1 ,7-octadiene, or 1 ,9-decadiene. The unique combination of elevated reactor temperatures, high molecular weight (or low melt indices) at high reactor temperatures and high comonomer reactivity advantageously allows for the economical production of polymers having excellent physical properties and processability. Preferably such polymers comprise ethylene, a C₃-₂o α-olefin and a "H"-branching comonomer. The present catalyst compositions are also well suited for the preparation of

EP and EPDM copolymers in high yield and productivity. The process employed is preferably a slurry process such as that disclosed in US-A-5,229,478.

The present catalyst compositions may also be employed to advantage in the gas phase copolymerization of olefins. Gas phase processes for the polymerization of olefins, especially the homopolymerization and copolymerization of ethylene and propylene, and the copolymerization of ethylene with higher α-olefins such as, for example, 1 -butene, 1-hexene, 4-methyl-1 -pentene are well known in the cooling provided by the cooled the recycle gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect. The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having 3 to 8, preferably 4 to 6, carbon atoms. In the case that the monomer or comonomer itself is a volatile liquid (or can be condensed to provide such a liquid) this can be suitably be fed to the bed to provide an evaporative cooling effect. Examples of olefin monomers which can be employed in this manner are olefins containing three to eight, preferably three to six carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop. The recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as liquid droplets carried in the recycle gas stream. This type of process is described, for example in EP 89691 ; US-A-4,543,399; WO 94/25495 and US-A-5,352,749. A particularly preferred method of recycling the 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.

The polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst. Such catalyst can be prepolymerized as described above, if desired.

The polymer is produced directly in the fluidized bed by catalyzed copolymerization of the monomer and one or more comonomers on the fluidized particles of supported catalyst within the bed. Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to the target polyolefin. Such processes are used commercially on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene.

The gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone. Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported above a perforated plate, the fluidization grid, by a flow of fluidization gas. The gas employed to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. The hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.

A preferred method of cooling of the bed, involves the use of a condensed liquid which vaporizes in the reactor thereby removing heat therefrom. Such a condensing agent generally is recondensed and recycled along with unreacted monomers. The monomer(s) and any other liquids or gases which it is desired to charge to the reactor, such as, for example a diluent gas or hydrogen chain transfer agent, are desirably thoroughly dried and purified prior to use. Suitably, such materials may be contacted with alumina or zeolite beds or otherwise purified prior to use.

The gas phase processes suitable for the practice of this invention are preferably continuous processes which provide for the continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thereby providing a steady-state environment on the macro scale in the reaction zone of the reactor. The produced polymer is discharged continuously or discontinuously from the fluidized bed as desired.

Typically, the fluidized bed of the gas phase process is operated at temperatures greater than 50°C, preferably from 60°C to 110°C, more preferably from 70°C to 110°C. Typically the molar ratio of comonomer to monomer used in the polymerization depends upon the desired density for the composition being produced and is 0.5 or less. Desirably, when producing materials with a density range of from 0.91 to 0.93 the comonomer to monomer ratio is less than 0.2, preferably less than 0.05, even more preferably less than 0.02, and may even be less than 0.01. Further typically, the ratio of hydrogen to monomer is less than 0.5, preferably less than 0.2, more preferably less than 0.05, even more preferably less than 0.02 and may even be less than 0.01.

The above-described ranges of process variables are appropriate for the gas phase process of this invention and may be suitable for other processes adaptable to the practice of this invention. 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. Patents US-A-4,588,790; US-A-4,543,399; US-A-5,352,749; US-A-5,436,304; US-A-5,405,922; US-A-5,462,999; US-A-5,461 ,123; US-A-5,453,471 ; US-A-5,032,562; US-A-5,028,670; US-A-5,473,028; US-A-5,106,804; US-A-5,541 ,270 and EP applications 659,773; 692,500; and PCT Applications WO 94/29032, WO 94/25497, WO 94/25495, WO 94/28032;

WO 95/13305; WO 94/26793; and WO 95/07942. Examples

The skilled artisan will appreciate that the invention disclosed herein may be practiced in the absence of any component which has not been specifically disclosed. The following examples are provided as further illustration of the invention and are not to be construed as limiting. Unless stated to the contrary all parts and percentages are expressed on a weight basis.

All syntheses of air or water sensitive compounds were performed under dry nitrogen or argon atmosphere using a combination of glove box and high vacuum techniques. Solvents were purified by passing through double columns charged with activated alumina and a supported metal catalyst (Q-5® available from Englehardt Chemical Company). The term "overnight", if used, refers to a time of approximately 16-18 hours. The term "room temperature", if used, refers to a temperature of 20-25 °C. Example 1 0.125 g of a solid copolymer of tetrafluoroethylene and perfluoro-2-

(fluorosulfonylethoxy)propyl vinyl ether (Nation™ SAC-13, available from Aldrich Chemical Inc.) was ground to a fine powder, and degassed under reduced pressure (25 ^SC, 10Pa, 2 h) and transferred to a glove box. In a 250 ml glass reactor, the powdered resin, and 150 ml of dry toluene were combined under magnetic stirring. To the resulting slurry held at 25 ^SC, 0.3 ml of a 1 M tri(n-propyl)aluminum solution in toluene and 0.5 ml of a 2.5 μM toluene solution of dimethysilane bis (2-methyl-4- phenylinden-1-yl)zirconium 1 ,4-diphenyl-1 ,3-butadiene were added.

The reactor was heated to 70^SC and propylene was added at 10 psig (69 kPa) accompanied by stirring. After 50 m reaction time with propylene supplied on demand the reactor was vented and the polymer removed. 14 g of isotactic polypropylene was produced. Comparison 1

When the above procedure was repeated without addition of tri(n- propyl)aluminum, no measurable amount of polypropylene was produced.

Claims

CLAIMS:

1. A catalyst composition for use in the coordination polymerization of an olefin comprising:

C) an organoaluminum compound containing up to 50 atoms not counting hydrogen.

2. A process for polymerizing an addition polymerizable monomer comprising contacting under polymerization conditions an addition polymerizable monomer or a mixture comprising said monomer, with a composition comprising:

A) a Group 3-10 transition metal complex,

B) a polymer comprising perfluorinated sulfonic acid functional groups, and

C) an organoaluminum compound containing up to 50 atoms not counting hydrogen.

3. A catalyst composition or process according to claims 1 or 2 wherein component B) is a copolymer of tetrafluoroethylene and perfluoro-2- (fluorosulfonylethoxy)propyl vinyl ether.

4. A catalyst composition or process according to claim 3 wherein the organoaluminum compound is a trialkylaluminum having from 1 to 10 carbons in each alkyl group.