EP0719294A1

EP0719294A1 - A new catalyst for ring-opening metathesis polymerization

Info

Publication number: EP0719294A1
Application number: EP94921445A
Authority: EP
Inventors: Bruce Allan Harrington
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 1993-06-30
Filing date: 1994-06-30
Publication date: 1996-07-03
Also published as: CA2166193A1; JPH09501191A; WO1995001388A1

Abstract

This invention relates to ring-opening metathesis polymerizations of cyclic olefins utilizing a transition metal catalyst system comprising a cyclopentadienyl transition metal compound and a non-coordinating anion.

Description

Title: A New Catalyst for Ring-Opening Metathesis Polymerization

Field of the Invention

This invention relates to ring-opening metathesis polymerizations of cyclic olefins utilizing a transition metal catalyst system comprising a cyclopentadienyl transition metal complex and a noncoordinating anion.

Background of the Invention

In the early lθδt^s, new classes of olefin catalysts based on group 4 transition metals having one or two cyclopentadienyl groups or derivatives thereof attached to a metal center combined with an alumoxane activator were disclosed by elborn. These catalysts were found useful for the polymerization of many olefins and created new polymers with controllable molecular weight and composition distributions. A next class of catalysts based on the cyclopentadienyl group 4 metal complexes was developed by Turner and Hlatky in the mid 1980's. These catalyst systems used a non¬ coordinating anion as the activator in place of the alumoxanes used in the above catalysts. These systems were also found useful for polymerizing a wide variety of olefins. In particular these catalysts polymerized not only typical alpha-olefins but they also polymerized and copolymerized cyclic olefins without ring-opening the cyclic monomers. For example, European patent application 0 504 418 published September 23, 1992, discloses an efficient process for producing cycloolefin polymer and cyclo-olefin copolymer without causing any ring-opening of the cycloolefin utilizing cyclopentadienyl transition metal complexes activated by non-coordinating anions. The above catalysts and catalyst systems have heretofore not been used as ring-opening metathesis polymerization catalysts (hereinafter referred to as ROMP catalysts or ROM polymerizations) .

Other catalysts containing a metal carbene have been used to ring open cyclic olefins and although these metathesize alpha olefins quite well, they suffer from the inability to polymerize alpha olefins. Thus, it has been difficult to make copolymers of alpha olefins and ring-opened cyclic monomers.

One answer to this problem has been to use an active alpha olefin catalyst in conjunction with or sequentially with a ring opening metathesis polymerization catalyst. For example Japanese kokia JO 4020-510-A published January 24, 1990 discloses a catalyst system using Ziegler-Natta catalyst and a metathesis catalyst which claims to form an alpha olefin polymer and a metathesis polymer in the same particle. The catalyst system comprises contacting a solid which contains Ti, Mg and halogen and a transition metal (groups 5-7) compound having a metal metathesis catalyst function. In essence, two separate catalysts are used at the same time to produce an intimate blend of the two polymer products. However, some catalyst components in this system contain metal halides which can initiate the cationic polymerization of many cyclic olefins in the presence of trace amounts of a proton source. Alumoxane activated catalyst suffer from the same problems since alumoxanes are strong Lewis acids that typically have trace amounts of water that can act as the proton source. U.S. Patent 5,015,710 discloses a similar process for preparing a blend of metathesis polymer and a radical polymer utilizing a redox catalyst. Thus, there exist in the art a need for developing a method to produce an intimate blend of alpha olefin polymer and ROMP polymer or even a copolymer of alpha olefin and ring-opened cyclic monomer with a catalyst systems that is essentially free of metal halides.

Summary of the Invention

This invention relates in part to the discovery that cyclopentadienyl transition metal complexes activated by ion exchange non-coordinating anions are capable of performing ring opening metathesis polymerizations. This invention relates to methods utilizing these catalyst systems for ring opening metathesis polymerizations alone, sequentially or in conjunction with using these catalyst systems in olefin and alpha olefin coordination (•'Ziegler-Natta") type polymerizations.

Description of Preferred Embodiments

In a preferred embodiment, this invention utilizes a catalyst system to ring-open metathesis polymerize (ROMP) cyclic olefins and utilizes the same catalyst system to polymerize any olefin without ring-opening. A unique aspect of this invention is that under certain conditions when the catalyst system is present with non-cyclic olefins and cyclic olefins, the cyclic olefins generally incorporate into the growing polymer chain without ring-opening. However, when only cyclic monomers are present or when the monomer feed contains predominantly cyclic olefins, the cyclic monomers do ring-open and form ROMP polymers. Because the catalysts systems are essentially free of metal halides and or strong Lewis acids and essentially free of a proton containing Lewis base, the potential for cationically polymerizing the cyclic olefins is significantly limited. This simplifies the overall polymerization mechanism and limits the cyclic olefins to either Ziegler-Natta or metathesis polymerization. Thus, from a single catalyst/cocatalyst system there exists the ability to form Zeigler/Natta polyolefins and/or ROM polymers in a single reaction by adjusting reaction conditions.

CATALYST

This invention is practiced with the class of catalysts referred to, disclosed, and described in the following publications EPA 277,003, published 1988; EPA 277,004, published 1988; EPA 520732, published 1992; WO 9403506, published 1994 and WO 9200333, published 1992, and U.S. Patents 5,153,157 and 5,198,401, all of which are incorporated by reference herein. Preferred ionic catalysts used in this invention can be represented by one of the following general formulae (all references to groups being the new group notation of the Period Table of the Elements as described by Chemical and Engineering News, 63(5), 27, 1985):

1. [{[(A-Cp)MX₁]+)_d]{[B']d-}

2. [{[(A-Cp)MX₁L]⁺}_d]{[B»]d-> wherein: (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted- hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl- substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C2₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;

A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;

M is a transition metal, preferably a group 4, 5, 6, 7 or 8 transition metal, even more preferably group 4 or 6 transition metal, even more preferably titanium, zirconium or hafnium;

X_± is a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl- substituted organometalloid radical or halocarbyl- substituted organometalloid radical which radical may optionally be covalently bonded to both or either M and L or all or any M, S or S';

L is an olefin, diolefin or aryne ligand; B is a chemically stable, non-nucleophilic anionic complex having a molecular diameter of 4 angstroms or greater or an anionic Lewis-acid activator resulting from the reaction of a Lewis-acid activator with the precursor to the cationic portion of the catalyst system described in formulae 1 or 2. When B' is a Lewis-acid activator, X-^ can also be an alkyl group donated by the Lewis-acid activator; and d is an integer representing the charge of B.

Another class of preferred catalysts includes systems represented by the formulae (all references to groups being the new group notation of the Periodic Table of the Elements as described by Chemical and

Engineering News. 63(5), 27, 1985): - 6 -

wherein :

A' is a bridging group;

(C5H5_y__xS_x) is a cyclopentadienyl ring substituted with from zero to five S radicals each S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C2₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; x is from 0 to 5 denoting the degree of substitution;

M is titanium, zirconium or hafnium; Xl ^{and X}2 are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M, S or S' ;

^JS'₍z-_l-y) i-^{3 a} heteroato ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl- substituted organometalloid; and z is the coordination number of the element J; y is 0 or 1;

L is an olefin, diolefin or aryne ligand, or a neutral Lewis base; L can also be a second transition metal compound of the same type such that the two metal center M and M* are bridged by X and *i wherein M* has the same meaning as M, X'l has the same meaning as X- and X'2 has the same meaning as X2 where such dimeric compounds which are precursors to the cationic portion of the catalyst are represented by the formula:

wherein

B¹ is a chemically stable, non-nucleophilic anionic complex having a molecular diameter of 4 angstroms or greater or an anionic Lewis-acid activator resulting from the reaction of a Lewis-acid activator with the precursor to the cationic portion of the catalyst system described in the formulae. When B* is a Lewis-acid activator, X^ can also be an alkyl group donated by the Lewis-acid activator; and d is an integer representing the charge of B' .

The catalysts are preferably prepared by combining at least two components. In one preferred method, the first component is a cyclopentadienyl derivative of a transition metal compound containing at least one ligand which will combine with the second component or at least a portion thereof such as a cation portion thereof. The second component is an ion-exchange compound comprising a cation which will irreversibly react with at least one ligand contained in said transition metal compound (first component) and a non- coordinating anion which is either a single coordination complex comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central formally charge-bearing metal or metalloid atom or an anion comprising a plurality of boron atoms such as polyhedral boranes, carboranes and metallacarboranes.

The cation portion of the second component may comprise Bronsted acids such as protons or protonated Lewis bases or may comprise reducible Lewis acids such as ferricinum, tropyliu , triphenylcarbenium or silver cations.

In another preferred method, the second component is a Lewis-acid complex which will react with at least one ligand of the first component, thereby forming an ionic species described in the formulae above with the ligand abstracted from the first component now bound to the second component.

In general, suitable anions for the second component may be any stable and bulky anionic complex having the following molecular attributes: 1) the anion should have a molecular diameter greater than 4 A; 2) the anion should form stable ammonium salts; 3) the negative charge on the anion should be delocalized over the framework of the anion or be localized within the core of the anion; 4) the anion should be a relatively poor nucleophile; and 5) the anion should not be a powerful reducing to oxidizing agent. Anions meeting these criteria - such as polynuclear boranes. carboranes, metallacarboranes, polyoxoanions (including alumoxane anions) , and anionic coordination complexes are well described in the chemical literature. Upon combination of the first and second components, the second component reacts with one of the ligands of the first component, thereby generating an anion pair consisting of a Group 4 metal cation and the aforementioned anion, which anion is compatible with and noncoordinating towards the Group 4 metal cation formed from the first component. The anion of the second compound must be capable of stabilizing the Group 4 metal cation's ability to function as a catalyst and must be sufficiently labile to permit displacement by an olefin, diolefin or an acetylenically unsaturated monomer during polymerization. The catalysts of this invention may be supported. U.S. Patents 4,808,561, issued 2-28-89; 4,897,455 issued 1-3-90; and 5,057,475 issued 10-15-91 disclose such supported catalysts and the methods to produce such and are herein incorporated by reference.

A. The Transition Metal Component

The transition metal compounds useful as first compounds in the preparation of the improved catalyst of this invention are cyclopentadienyl derivatives of group 4, 5, 6, 7 or 8 transition metals, preferably titanium, zirconium and hafnium. In general, useful cyclopentadienyl compounds may be represented by the following general formulae:

(A-Cp)MX₁X₂ (Cp*) (CpR)MX_! (CsHs- - Sx)

/ \

1

(A')y M

\ / ^ * 2

JS'(n-y) wherein: (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted- hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl- substituted organometalloid, disubstituted boron, disubstituted pnicftogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C₄ to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;

R is a substituent on one of the cyclopentadienyl radicals which is also bonded to the metal atom;

L is an olefin, diolefin or aryne ligand; and Xl and X₂ are, independently, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, and hydrocarbyl- and halocarbyl-substituted organometalloid radicals, substituted pnictogen radicals, or substituted chalcogen radicals; or X-^ and X2 are joined and bound to the metal atom to form a metallacycle ring containing from 3 to 20 carbon atoms; or X_j and X2 together can be an olefin, diolefin or aryne ligand; (C5H5_y__xS_x) is a cyclopentadienyl ring substituted with from zero to five S radicals, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl- substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or any two adjacent S groups which are joined forming a C4 to C2₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; x is from 0 to 5 denoting the degree of substitution;

M is titanium, zirconium or hafnium; X_! and X₂ are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M and L or all or any M, S or S' ;

(JS_z_ι_y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; and z is the coordination number of the element J; y is 0 or 1; L is an olefin, diolefin or aryne ligand, or a neutral Lewis base.

A number of final components may be formed by permuting all possible combinations of the constituent moieties with each other. Illustrative compounds include: bis(cyclopentadienyl)hafnium dimethyl, ethylenebis(tetrahydroindenyl)zirconium dihidryde, bis(pentamethyl)zirconium ethylidene, dimethylsilyl(l- fluorenyl) (cyclopentadienyl)zirconium dimethyl and the like; bis(cyclopentadienyl) (1,3-butadiene(zirconium) , bis(cyclopentadienyl) (2,3-dimethyl-1,3-butadiene) zirconium, bis(pentamethylcyclopentadienyl) (benzene) zirconium, bis(pentamethylcyclopentadienyl) titanium ethylene and the like; (pentamethylcyclopentadienyl) (tetramethylcyclopentadienylmethylene) zirconium hydride, (pentamethylcyclopentadienyl) (tetramethylcyclopentadienyl)-

(tetramethylcyclopentadienylmethylene) zirconium phenyl and the like.

B. The Activator Component

Preferred ionic catalysts can be prepared by reacting the transition metal compound with some neutral Lewis acids, such as B(C5Fs)₃, which upon reaction with the hydrolyzable ligand (x) of the transition metal compound forms an anion, such as ([B(C₆F5)3(X) ]~) , which stabilizes the cationic transition metal species generated by the reaction. Ionic catalysts can be, and preferably are, prepared with activator components which are ionic compounds or compositions. The above ionic compounds may comprise non-coordinating counter cations such as Bronsted acids(, for example R3NH+) , carbonium ions (for example ph3C⁺) , reducible cations (for example Cp Fe⁺) and the like.

Two classes of compatible non-coordinating anions have been disclosed in copending U.S. Patent Application Nos. 133,052 and 133,480: 1) anionic coordination complexes comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central charge-bearing metal or metalloid core, and 2) anions comprising a plurality of boron atoms such as carboranes, metallacarboranes and boranes. In general, the activator compounds containing single anionic coordination complexes which are useful in this invention may be represented by the following general formula: [(L^»-H)⁺]_d[(M')^m+Qι...Q_n]^d~ wherein:

H is a hydrogen atom; [L"-H] is a Bronsted acid; M* is a metal or metalloid; Qi to Q_n are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted- hydrocarbyl radicals, halocarbyl and substituted- halocarbyl radicals and hydrocarbyl and halocarbyl- substituted organometalloid radicals and any one, but not more than one, of Q-^ to Q_n may be a halide radical; m is an integer representing the formal valence charge of M; and n is the total number of ligands g.

As indicated above, any metal or metalloid capable of forming an anionic complex which is stable in water may be used or contained in the anion of the second compound. Suitable metals, then, include, but are not limited to , aluminum, gold, platinum and the like. Suitable metalloids include, but are not limited to, boron, phosphorus, silicon and the like. Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. In light of this, salts containing anions comprising a coordination complex containing a single boron atom are preferred. The preferred activator compounds comprising boron may be represented by the following general formula:

[L^»-H]⁺[BAr₁Ar₂X₃X₄]- wherein: B is a boron in a valence state of 3;

Ar_x and Ar₂ are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from 6 to 20 carbon atoms and may be linked to each other through a stable bridging group; and X₃ and 4 are, independently, hydride radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals, hydrocarbyl- and halocarbyl-substituted organometalloid radicals, disubstituted pnictogen radicals, substituted chalcogen radicals and halide radicals, with the provision that X₃ and X4 will not be halide at the same time.

In general, Ar^ and Ar may, independently, be any aromatic of substituted-aromatic hydrocarbon radical.

Suitable aromatic radicals include, but are not limited to, phenyl, naphthyl and anthracenyl radicals. Suitable substituents on the substituted-aromatic hydrocarbon radicals, include, but are not necessarily limited to, hydrocarbyl radicals, organometalloid radicals, alkoxy and aryloxy radicals, alkylamido radicals, fluorocarbyl and fluorohydrocarbyl radicals and the like such as those useful as X₃ and X4. The substituent may be ortho, meta or para, relative to the carbon atoms bonded to the boron atom. When either or both X₃ and X₄ are a hydrocarbyl radical, each may be the same or a different aromatic or substituted- aromatic radical as are Ar^ and Ar2, or the same may be a straight or branched alkyl, alkenyl or alkenyl radical, a cyclic hydrocarbon radical or an alkyl- substituted cyclic hydrocarbon radical. X₃ and X₄ may also, independently be alkoxy or dialkylamido radicals wherein the alkyl portion of said alkoxy and dialkylamido radicals, hydrocarbyl radicals and organometalloid radicals and the like. As indicated above, Ar_x and Ar2 could be linked to either X₃ or X4. Finally, X₃ and X₄ may also be linked to each other through a suitable bridging group.

Illustrative, but not limiting, examples of boron compounds which may be used as an activator component in the preparation of the improved catalysts of this invention are trialkyl-substituted ammonium salts such as triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n- butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o- tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium te- tra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p- tri-fluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron and the like; N,N-dialkyl anilinium salts such as N,N-dimethylanilinium tetra(pentafluorophenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N-2,4,5-pentamethylanilinium tetra(phenyl)boron and the like; dialkyl ammonium salts such as di(i-propyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron and the like; and triaryl phosphonium salts such as triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron and the like.

Similar lists of suitable compounds containing other metals and metalloids which are useful as activator components may be made, but such lists are not deemed necessary to a complete disclosure. In this regard, it should be noted that the foregoing list is not intended to be exhaustive and that other useful boron compounds as well as useful compounds containing other metals or metalloids would be readily apparent to those skilled in the art from the foregoing general equations.

The most preferred activator compounds comprising boron may be represented by the following general formula:

[L^»-H]⁺[B(C₆F₅)₃Q]- wherein: F is fluorine, C is carbon and B, L' , and Q are defined hereinabove. Illustrative but not limiting, examples of most preferred activator compounds comprising boron which may be used in the preparation of the improved catalysts of this invention include N,N-dialkylanilinium salts (L- = N,N-dialkylaniline) where Q is a simple hydrocarbyl such as methyl, butyl, cyclohexyl, or phenyl or where Q is a polymeric hydrocarbyl of indefinite chain length such as polystyrene, polyisoprene, or poly-paramethylstyrene. Polymeric Q substituents on the most preferred anion offer the advantage of providing a highly soluble ion- exchange activator component and final ionic catalyst. Soluble catalysts and/or precursors are often preferred over insoluble waxes, oils, phases, or solids because they can be diluted to a desired concentration and can be transferred easily using simple equipment in commercial processes.

Activator components based on anions which contain a plurality of boron atoms may be represented by the following general formulae: [L»-H]_c[(CX)a(BX)_mX_b]c- or

[L»-H]_d, [ [ [ (CX₆) _a, (BX₇)m« (Xβ)b' ]C-]₂Mn' + ]d'- wherein

[L"-H] is either H+ or a Bronsted acid derived from the protonation of a neutral Lewis base;

X, X', X", X6, X7 and Xs are, independently, hydride radicals, halide radicals, hydrocarbyl radicals, substituted-hydrocarbyl radicals, halocarbyl radicals, substituted-halocarbyl radicals, or hydrocarbyl- or halocarbyl-substituted organometalloid radicals;

M is a transition metal; a and b are integers .> 0; c is an integer > 1; a + b + c = an even-numbered integer from 2 to 8; and m is an integer ranging from 5 to 22; a and b are the same or a different integer or 0; c is an integer > 2; a + b + c = an even-numbered integer from 4 to 8; m is an integer from 6 to 12; n is an integer such that 2c - n = d; and d is an integer > l.

Preferred anions of this invention comprising a plurality of boron atoms comprise:

(1) A trisubstituted ammonium salt of a borane or carborane anion satisfying the general formula:

[(CHJaxfBHJ_bxjex- wherein: ax is either 0 or 1; ex is either 1 or 2 ; ax + ex = 2; and bx is an integer ranging from 10 to 12;

(2) A trisubstituted ammonium salt of a borane or carborane or a neutral borane or carborane compound satisfying the general formula:

[(CH)_ay(BH)_my(H)_by]cy- wherein: ay is an integer from 0 to 2; by is an integer from 0 to 3; cy is an integer from 0 to 3; ay + by + cy = 4; and my is an integer from 9 to 18; or

(3) A trisubstituted ammonium salt of a metallaborane or metallacarborane anion satisfying the following general formula:

[[[₍CH_)az(BH_)mz(H_)bz]«-]₂Mnz+]d2- wherein: az is an integer from 0 to 2; bz is an integer from 0 to 2; cz is either 2 or 3; mz is an integer from 9 to 11; az + bz + cz = 4; and nz and dz are, respectively, 2 and 2 or 3 and 1.

Illustrative, but not limiting, examples of second components which can be used in preparing catalyst systems utilized in the process of this invention wherein the anion of the second component contains a plurality of boron atoms are mono-, di-, trialkylammonium and phosphonium and dialkylarylammonium and -phosphonium salts such as bis[tri(n-butyl)ammonium] dodecaborate, bis[tri(n- butyl)ammonium]decachlorodecaborate, tri(n- butyl)ammonium dodecachlorododecaborate, tri(n- butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaudecaborate, tri(n-butyl)ammonium 1- carbadodecaborate, tri(n-butyl)ammonium 1- trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium dibromo-1-carbadodecaborate; borane and carborane complexes and salts of borane and carborane anions such as decaborane(14) , 7,8-dicarbaudecaborane(13) , 2,7- dicarbaundecaborane(13) , undecahydrido-7,8-dimethy1- 7,8-dicarbaundecaborane, tri(n-butyl)ammonium 6- carbadecaborate(12) , tri(n-butyl)ammonium 1- carbaundecaborate, tri(n-butyl)ammonium 7,8- dicarbaundecaborate and metallaborane anions such as tri(n-butyl)ammonium bis(nonahydrido-1,3-dicarbanonabo- rato)cobaltate(III) , tri(n-butyl)ammonium bis(undecahydrido-7,8-dicarbaundecaborato) ferrate(III) , tri(n-butyl)ammonium bis(undecahydrido- 7,8-dicarbaundecaborato) cobaltate(III) , tri(n- butyl)ammonium bis(undecahydrido-7,8-dicarbaunaborato) nikelate(III) , tri(n-butyl)ammonium bis(nonahydrido- 7,8-dimethyl-7,8-dicarbaundecaborato)ferrate(III) , tri(n-butyl)ammonium bis(tribromooctahydrido-7,8- dicarbaundecaborato)cobaltate(III) , tri(n-butyl) ammonium bis(undecahydridodicarbadodecaborato) cobaltate(III) and bis[tri(n-butyl)ammonium] bis(undecahydrido-7-carbaundecaborato) cobaltate(III) . A similar list of representative phosphonium compounds can be recited as illustrative second compounds, but for the sake of brevity, it is simply noted that the phosphonium and substituted-phosphonium salts corresponding to the listed ammonium and substituted- ammonium salts could be used as second compounds in the present invention.

The monomers that may be ring-opening metathesis polymerized (ROMPed) with the above catalyst system include any cyclic or multicyclic olefin, cyclic diolefin or cyclic polyene. Preferred cyclics include strained olefins and diolefins, preferably norbornene, dicyclopentadiene, ethylidene norbornene, vinyl norbnene, cyclopentene, cyclobutene, tetracyclododecene and their substituted isomers. Especially preferred cyclics include norbornene and cyclopentene.

Olefin and alpha olefin monomers that may be polymerized by the above catalyst system include monoenes, dienes, and polyenes in linear branched or cyclic structures. Preferred monomers include alpha olefins, particularly alpha olefins having 2 to 40 - 20 -

carbon atoms. Especially preferred monomers include the alpha-olefins, ethylene and propylene.

The Cvcloolefins

In general, any cycloolefin can be copolymerized with an olefin in the present process. The cycloolefin includes cyclized ethylenic or acetylenic unsaturation which polymerizes in the presence of the metallocene catalyst substantially by insertion polymerization, generally without ring opening, so that the ring structure in which the unsaturation is present is incorporated into the polymer backbone. However when alpha olefin is not present or is present in very limited concentrations the cyclo-olefin including cyclized ethylenic or acetylenic unsaturation ROMP's in the presence of the activated transition metal catalyst substantially without insertion so that the ring structure containing the double bond is opened and becomes a part of the linear polymer backbone.

Suitable cycloolefins generally correspond to one of the formulae:

- 21 -

A.

C .

wherein each Ra through Rs is independently hydrogen, halogen, hydrocarbyl, or halohydrocarbyl; ac and dc are integers of 2 or more, and be and cc are integers of 0 or more.

Specific representative cycloolefins according to formula A are cyclobutene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene,

3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohexane, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, cyclododecene and the like. Preferred monocycloolefins according to formula A have from 4 to 12 carbon atoms, more preferably 4 to 5 or 7 to 8 carbon atoms.

Cycloolefins according to formulae B and C can be prepared by condensing cyclopentadienes with the corresponding olefins and/or cycloolefins in a Diels-

Alder reaction. Specific representative cycloolefins according to formula B are as follows: bicyclo(2.2.1)hept-2-ene; 6-methylbicyclo(2.2.1)hept-2-ene;

5,6-dimethylbicyclo(2.2.1)hept-2-ene;

1-methylbicyclo (2.2.1)hept-2-ene;

6-ethylbicyclo(2.2.1)hept-2-ene;

6-n-butylbicyclo(2.2.1)hept-2-ene; 6-isobutylbicyclo(2.2.1)hept-2-ene;

7-methylbicyclo(2.2.1)hept-2-ene;

5-phenylbicyclo(2.2.1)hept-2-ene;

5-methyl-5-phenylbicyclo(2.2.1)hept-2-ene;

5-benzylbicyclo(2.2.1)hept-2-ene; 5-tolylbicyclo(2.2.1)hept-2-ene;

5-ethylphenylbicyclo(2.2.1)hept-2-ene;

5-isopropylphenylbicyclo(2.2.1)hept-2-ene;

5-alpha-naphthylbicyclo(2.2.1)hept-2-ene;

5-acetoracenylbicyclo(2.2.1)hept-2-ene; tetracyclo(4.4.0.12,5.ι7,10)-3-dodecene;

2-methyltetracyclo(4.4.0.12,5.ι7,10)-3-dodecene;

2-ethyltetracyclo(4.4.0.12,5.ι7,10)-3-dodecene;

2-propyltetracyclo(4.4.0.12,5.ι7,10)-3-dodecene;

2-hexyltetracyclo(4.4.0.12,5.ι7,10)-3-dodecene; 2-stearyltetracyclo(4.4.0.12,5.ι7,10)-3-dodecene;

2,10-dimethyltetracyclo(4.4.0.1 ,5.ι7,10)-3-dodecene;

2-methyl-10-ethyltetracyclo(4.4.0.12,5.χ7,10)-3- dodecene;

2-chlorotetracyclo (4.4.0.12 , 5. ι7 , 10) -3-dodecene ; 2-bromotetracyclo (4.4.0.1 , 5. ι7 , 10) -3-dodecene ;

2 , 10-dichlorotetracyclo ( 4.4.0.12 , 5. ι7 , 10 ) -3-dodecene ; 2-cyclohexyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

2-n-butyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

2-isobutyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

5,10-dimethyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene; 2,10-dimethyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

11,12-dimethyltetracyclo(4.4.0.12,5.x-7,10)-3-dodecene;

2,7,9-trimethyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

9-ethyl-2,7-dimethyltetracyclo(4.4.0.12 ,5.χ7 ,10)-3- dodecene; 9-isobutyl-2,7-dimethyltetracyclo(4.4.0.12 ,5.χ7,10)-3- dodecene;

9,11,12-trimethyltetracyclo(4.4.0.12,5.χ7,10)-3- dodecene;

9-ethyl-ll,12-dimethyltetracyclo(4.4.0.12,5.χ7,10)-3- dodecene;

9-isobutyl-ll ,12-dimethyltetracyclo (4.4.0.12,5.χ7 ,10)-

3-dodecene;

5,8,9,10-tetramethyltetracyclo(4.4.0.12,5.χ7,10)-3- dodecene; 8-methyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

8-ethyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

8-propyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

8-hexyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

8-stearyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene; 8,9-dimethyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

8-methyl-9-ethyltetracyclo(4.4.0.12,5.χ7,10)-3- dodecene;

8-chlorotetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

8-bromotetracyclo(4.4.0.12,5.χ7,X0)-3-dodecene; 8-fluorotetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

8,9-dichlorotetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

8-cyclohexyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

8-isobutyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene;

8-butyltetracyclo(4.4.0.12,5.χ7,10)-3-dodecene; 8-ethylidenetetracyclo(4.4.0.12,5.χ7,10)-3-dodecene; - 24 -

8-ethylidene-9-methyltetracyclo(4.4.0.12,5.χ7,10)-3- dodecene;

8-ethylidene-9-ethyltetracyclo(4.4.0.12,5.χ7,10)-3- dodecene; ₈-ethylidene-9-isopropyltetracyclo(4.4.0.1 ,5. χ7,10)-

3-dodecene;

8-ethylidene-9-butyltetracyclo(4.4.0.12,5.χ7,10)-3- dodecene;

8-n-propylidenetetracyclo(4.4.0.1 ,5.χ7,10)-3-dodecene; 8-n-propylidene-9-methyltetracyclo (4.4.0.12,5.χ7,10)-

3-dodecene;

8-n-propylidene-9-ethyltetracyclo(4.4.0.12,5.χ7,10)-3- dodecene;

8-n-propylidene-9-isopropyltetracyclo (4.4.0.12,5.χ7,10)-3-dodecene;

8-n-propylidene-9-butyltetracyclo(4.4.0.12,5.χ7,10)-3- dodecene;

8-isopropylidenetetracyclo(4.4.0.12,5.χ7,10)-3- dodecene; 8-isopropylidene-9-methyltetracyclo(4.4.0.12,5. χ7,10)-

3-dodecene;

8-isopropylidene-9-ethyltetracyclo(4.4.0.12,5. χ7,10)-

3-dodecene;

8-isopropylidene-9-isopropyltetracyclo(4.4.0.12,5. 17,10)-3-dodecene;

8-isopropylidene-9-butyltetracyclo(4.4.0.12,5. χ7,10)-

3-dodecene; hexacyclo(6.6.1.l3,6. X0,13.o2,7.o9,14)-4-heptadecene;

12-methylhexacyclo(6.6.1._l3,6. X0,13.o2,7.o9,14)-4- heptadecene;

12-ethylhexacyclo(6.6.1.13,6. io,13.02,7.o9,14)-4- heptadecene;

12-isobutylhexacyclo(6.6.1.1 ,6.χχo,13.02,7.o9,14)-4- heptadecene; 1,6,10-trimethyl-12-isobutylhexacyclo

(6.6.1.13,6.χX0,13.02,7.o9,14)-4-heptadecene; octacyclo(8.8.0.χ2,9.χ4,7.χll,18.χl3,16.o3,8. o!2,17)-

5-dococene;

15-methyloctacyclo(8.8.0.12,9.χ4,7.χll,18.χl3,16.

0 ,8.012,17)-5-dococene; and

15-ethyloctacyclo(8.8.0.12,9.χ4,7.χll,18.χl3,16.

03,8.ol2,17)-5-dococene. pentacyclo(4.7.0.12,5.08,13.χ9,12)-3-pentadecene; methyl-substituted pentacyclo(4.7.0.l2,5.o8,13. χ9,12)-

3-pentadecene;

Specific representative cycloolefins according to formula C are as follows: tricyclo(4.3.0.12,5)-3-decene; tricyclo(4.3.0.12,5)-3.7-decediene; 2-methyltricyclo(4.3.0.l2,5)-3-decene;

5-methyltricyclo(4.3.0.1 ,5)-3-decene; tricyclo(4.4.0.12,5)-3-undecene;

10-methyltricyclo(4.4.0.12,5)-3-undecene; pentacyclo(6.5.1.l3,6.o2,7.o9,13)-4-pentadecene; 1,3-dimethylpentacyclo(6.5.1.13,6.o2,7.o9,13)-4- pentadecene;

1,6-dimethylpentacyclo(6.5.1.13,6.o2,7.o9,13)-4- pentadecene;

14,15-dimethylpentacyclo(6.5.1.13,6.o2,7.o9,13)-4- pentadecene; pentacyclo(6.6.1.l ,6.o2,7.o9,14)-4-hexadecene;

1,3-dimethylpentacyclo(6.6.1.l3,6.o2,7.o9,14)-4- hexadecene;

1,6-dimethylpentacyclo(6.6.1.13,6.o2,7.o9,14)-4- hexadecene;

15,16-dimethylpentacyclo(6.6.1.13,6.o2,7.o9,14)-4- hexadecene; heptacyclo(8.7.0.l2,9.χ4,7.χll,17.o3,8.ol2,16)-5- eicosene; heptacyclo(7.8.0.13,6.₀2,7.χl0,17.oil,16. l2,13)-4- eicosene; heptacyclo(8.8.0.12, .χ4,7. ll,18.o3,8.ol2,17)-5- heneicosene; nonacyclo(9.10.1.14,7.o3,8.o2,18.ol2,21.χl3,20. 014,19.χl5,18)-5-pentacosene; 1,4-methano-l,la,4,4a-tetrahydrofluorene;

1,4-methano-l,la,4,4a,5,lOa-hexahydroanthracene; and cyclopentadiene-acenaphthylene adduct.

With the catalysts described above it is often the case that one olefin of a polyene is substantially more reactive for polyermization than another. This enables one to use dienes and polyenes as a major component of the polymer without obtaining substantial crosslinking. For example, dicyclopentadiene or ethylidene norbornene can be polymerized exclusively through the norbornene- li e olefin in an addition polymerization. However, polyenes having two or more double bonds can optionally be used in a relatively minor proportion to impart higher molecular weight to the copolymer and/or provide residual pendant side chain unsaturation for functionalization or crosslinking. Where the polyenes can participate in polymerization at two (or more) sites, these monomers tend to promote chain extension which can double or quadruple the molecular weight at low incorporation. Ideally the polyene is not present in such high amounts which might result in excessive crosslinking and produce insoluble gel formation. Preferably, the molecular weight is suitably increased by including the optional polyene in the copolymer at from 0.5 to 3 mole percent

Suitable chain-extending, molecular-weight- increasing polyenes include, for example, alpha-omega dienes having from 5 to 18 carbon atoms, such as 1,4- pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7- octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10- - 27 -

undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13- tetradecadiene, 1,14-pentadecadiene, 1,15- hexadecadiene, 1 ,16-heptadecadiene, 1,17-octadecadiene, or the like.

When two (or more) of the double bonds are sufficiently reactive under the particular reaction conditions to participate in the polymerization reaction, or when the second olefin on a given monomer or polyene is not polymerizable in an addition reaction (such as a tri-substituted olefin) , but can be used to crosslink in post-polymerization, free-radical, crosslinking reactions, then suitable polyenes generally also include other linear or branched aliphatic dienes and trienes, monocyclic dienes and trienes, bicyclic dienes and trienes, polycyclic dienes and trienes, aromatic dienes, and the like.

Specific representative examples of non-conjugated branched aliphatic dienes and polyenes include 1,4- hexadiene, 6-methyl-l,4-heptadiene, 4-isopropyl-l,4- hexadiene, 4-methyl-l,4-hexadiene, 5-methyl- 1,4hexadiene, 4-ethyl-l,4-hexadiene, l-phenyl-4propyl- 1,4-hexadiene, 4,5-dimethyl-l,4-hexadiene, 6-phenyl- 1,4-hexadiene, 5-methyl-l,5-octadiene, 6-methyl-l,5- octadiene, 6-methyl-l,5-heptadiene, 5,7-dimethyl-l,5- octadiene, 4,5-dipropyl-l,4-octadiene, 5-propyl-6- methyl-1,5-heptadiene, 5-ethyl-7-methyl-l,6-octadiene, 4,7-dimethyl-l,4,7-nonatriene, and 5,8-dimethyl-l,4,7- nonatriene.

Specific representative examples of non-conjugated monocyclic dienes and polyenes include 4- vinylcyclohexene, 4-propenylcyclohexene, 1,4- cyclohexadiene, l-vinyl-4-l(l-propenyl)-cyclohexane, 4- methyl-l,4-cyclooctadiene, 4-methyl l-5-propyl-l,4- cyclooctadiene, 5-methylcyclopentadiene, 1,5,9- cyclododecatriene, trans-l,2-divinylcyclobutane, and 1,4-divinylcyclohexane.

Specific representative examples of non-conjugated bicyclic dienes including: norbornadiene,

5-ethylidenenorbornene-2,

5-propylidenenorbornene-2, 5-butylidenenorbornene-2,

5-isopropylidene-norbornene-2, l-methyl-2,5-norbornadiene, l-ethyl-2,5-norbornadiene, χ-propyl-2 , 5-norbornadiene, l-butyl-2 , 5-norbornadiene , l-chloro-2,5-norbornadiene, l-bromo-2,5-norbornadiene,

2-methyl-2,5-norbornadiene,

2-ethyl-2,5-norbornadiene, 2-propyl-2,5-norbornadiene,

2-butyl-2,5-norbornadiene,

2-pentyl-2.5-norbornadiene,

2-hexyl-2,5-norbornadiene,

2-chloro-2,5-norbornadiene, 2-bromo-2,5-norbornadiene,

2-fluoro-2,5-norbornadiene,

7-methyl-2,5-norbornadiene,

7-ethyl-2,5-norbornadiene,

7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene,

7-chloro-2,5-norbornadiene,

7,7-dimethyl-2,5-norbornadiene,

7,7-diethyl-2,5-norbornadiene,

7,7-methylethyl-2,5-norbornadiene, 7,7-dichloro-2,5-norbornadiene,

5-methylene-2-norborene, 5-(2-butenyl)-2-norbornene,

3-heptyl-2,5-norbornadiene,

2,3-dimethyl-2,5-norbornadiene,

1,4-dimethyl-2,5-norbornadiene, 1,2,3,4-tetramethyl-2,5-norbornadiene,

1,2,3,4,7-pentamethyl-2,5-norbornadiene,

2-ethyl-3-propyl-l,2,5-norbornadiene, bicyclo(2.2.2)octadiene-2,5

5-isopropylidene-bicyclo(2.2.2)octene-2, 5,ethylidenebicyclo(2.2.2)octene-2,

5-butylidenebicyclo(2.2.2)octene-2,

2-ethylbicyclo(2.2.2)octadiene-2,5,

2-methyl-3-ethyl-bicyclo(2.2.2)octadiene-2,5,

2-hexylbicyclo(2.2.2)octadiene-2,5 2-(1^• ,5•-dimethylhexenyl-4)bicyclo(2.2.2)octadiene-2,5,

1-isopropylidenebicyclo(4.4.0)decadiene-2.6,

2-ethylidene-bicyclo(4.4.0)decene-6,

3-ethylidenebicyclo(3.2.0)heptadiene-2,6,

3-methylbicyclo(3.3.0)octadiene-2,6, tetrahydroindene,

3-methyltetrahydroindene,

9-methyltetrahydroindene,

7-propyltetrahydroindene,

7-isopropyltetrahydroindene and the like.

Specific representative examples of non-conjugated polycyclic dienes include: dicyclopentadiene, methyl substituted dicyclopentadienes, dimethyl substituted dicyclopentadienes,

4-methyl-5-ethyldicyclopentadiene,

5-isopropyldicyclopentadiene,

8-isopropyldicyclopentadiene, tetracyclododecadiene, methyl substituted tetracyclododecadienes, dimethyl substituted tetracyclododecadienes, trimethyl substituted tetracyclododecadienes, hexacycloheptadecadiene, methyl substituted hexacycloheptadecadienes, dimethyl substituted hexacycloheptadecadienes, trimethyl substituted hexacycloheptadecadienes, pentacyclo(6.5.1³ _* ⁶.0²'⁷.o9 ,13 -,_4 _fχo-pentadocadiene

(tricylopentadiene) , methyl substituted pentacyclo(6.5.l.l-³r⁶.o²/⁷.0⁹,!³)-

4,10-pentadocadienes, dimethyl substituted pentacyclo(6.5.1.1=3,60.² '⁷.o⁹, )-4.χo- pentadocadienes, pentacyclo(7.4.0.1³,6 __ ₀2,7 13)__{4 f}χχ-pentadocadiene,

11-methyl-pentacyclo(7.4.0.1³'⁶.0²/⁷.χl0,13j__4fχχ_ pentadocadiene,

12-methyl-pentacyclo(7.4.0.1³ > ⁶.0²,7.χl0,13)__{4 f}χχ_ pentadocadiene,

11-12-dimethyl pentacyclo(7.4.0.1³'⁶10²,7.χl-,13-,_ _fxx- pentadocadiene, and other alkyl substituted pentacyclo(7.4.01³'⁶.0²'⁷.χl0,13₍__4fχχ pentadocadienes.

Specific representative examples of non-conjugated aromatic dienes include alkyl styrenes and the like.

When dicyclopentadiene (or a similar cyclopolyene) is employed, it may be used in either the endo or exo form or both. In a preferred embodiment the exo form is used.

Polymerization Conditions

The polymerization may be conducted at any suitable temperature known to those of ordinary skill in the art. In a preferred embodiment the temperature may range from -100 degrees C to 250 degrees C, preferably from -50 to 200 degrees C. Further, the catalyst is preferably used in an amount to provide a starting monomer to catalyst ratio of from 1 to 10⁹, preferably 100 to 10⁷. The polymerization time may usually range from less than one minute to 10 hours or more. The reaction pressure may range from sub- atmospheric to atmospheric to 1000 MPa, preferably from atmospheric to 500 MPa. Polymerization methods are not particularly limited and include bulk polymerization, gas phase polymerization, solution polymerization and suspension polymerization. When utilizing solvents for polymerization, suitable solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; alicyclic hydrocarbons such as cyclopentane; cyclohexane and methylcyclohexane; aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; and halogenated hydrocarbons such as chloroform and di-chloromethane. These solvents can be used alone or in combination. Monomers such as alpha olefins and cyclic olefins can also be used as solvents. The polymerization may be conducted in any vessel suitable for the chosen reaction conditions. Furthermore, two or more vessels may be run in series or parallel to produce intimate blends of different polymers or blends of varieties of the "same" polymer, i.e. a 1000 Mw homopolyethylene blended with a 100,000 Mw homopolyethylene.

Products

The polymers produced by this invention can range from plastics, thermoplastics, thermoplastic olefins (TPO's) , thermoplastic elastomers(TPE's) , thermosets and elastomers. By varying the monomer feed(s) and reaction conditions many different polymers and polymer blends, specifically intimate polymer blends, and interpenetrating networks can be produced. For - 32 -

purposes of this invention and any claims thereto intimate blend is defined to be a mixed combination of at least two polymers neither of which are necessarily in network form provided that at least one of which is synthesized in the immediate presence of the other(s) such that the mixture does not significantly phase separate. Likewise for the purposes of this invention and any claims thereto interpenetrating network is defined to be an intimate combination of at least two polymers, at least one of which is in network form and at least one of which is synthesized in the immediate presence of the other(s) . Network is herein defined to include polymers having intra-chain associations, aggregations, or other interactions between segments of the same polymer chain or chain type as well as covalently crosslinked polymers For example, if a reactor was charged with cyclic monomer first, ROMP polymerization of the monomer would occur and produce ring-opened polymer chains. Then an alpha olefin could be introduced into the reactor and allowed to polymerize. This sequence would produce an intimate blend of ring-opened polymer and alpha-olefin polymer. Likewise, it is also possible to produce multiple polymer blends and intimate blends of many olefins and cyclic olefins. Furthermore the ring-opened cyclic polymer could be a polymer of one or more cyclic monomers and the olefin polymer could be a polymer of one or more olefins. Furthermore, the ROMP of cyclic dienes and alpha olefins could produce a network of ROM thermoset interdispersed with Ziegler-Natta thermoplastic olefin in an interpenetrating network or intimate blend. Likewise, an intimate blend or interpenetrating network of two or more ROMP polymers can also be produced, preferably by sequential addition of different cyclic monomers. As ROMP results in unsaturated chains, it is occasionally desirable to hydrogenate the resulting copolymers and/or polymer mixtures to make a predominantly saturated polymer mixture. Hydrogenation can improve oxidative and thermal stability.

It is also envisioned that block copolymers and tapered block copolymers could be made by varying monomer addition, concentrations and other reaction conditions such as temperature and pressure. For example, the catalyst described above can be used to create vinyl terminated polymers or macromonomers. Such a vinyl terminated polymer could then be combined with cyclic monomers to produce block copolymers and/or long chain branches, depending on the reaction conditions and monomers chosen. There are many combinations of the ROMP'ed monomers and the olefin polymerized monomers that will occur to those of ordinary skill in the art. These combinations are within the scope of this invention and intended to be covered hereby. In particular, intimate blends of 3 to 50 weight percent ROMP polymer with 97 to 50 weight percent Ziegler-Natta polymer are preferred.

It is believed that a hydrogen abstraction, loss, shift or transfer from the alpha carbon of the metal alkyl, or some other occurrence causes the formation of a metal carbene in the above catalyst systems. Carbenes produced in this way and present in the system could possibly react with the alpha olefin monomers in non-polymerizing olefin metathesis reactions, but these reactions will not adversely affect the ongoing Zeigler/Natta polymerization. An olefin could cause a chain transfer of a growing ROMP chain leaving an olefin terminated ROMP polymer that could thereafter potentially insert into a growing Ziegler-Natta chain. On the other hand, a growing Ziegler-Natta chain could chain terminate in a terminal olefin that could metathesize with a metal carbene to act as an active ROMP catalyst to yield block copolymers with one block from a ROMP and one block from a Ziegler-Natta polymerization. Thus, this invention also provides for new species of carbenes based on Ti, Zr and Hf, particularly Zr and Hf. These carbenes may be represented by the formulae: (A-Cp)M=CR(R') , wherein (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted- hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl- substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C2₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;

A¹ is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings ; M is any group 4, 5, 6, 7 or 8 metal, preferably Ti, Zr of Hf;

R and R¹ are independently a hydrogen or a Cx to C4₀ linear, cyclic or branched alkyl, preferably a Oχ to C20 linear, cyclic or branched alkyl, even more preferably hydrogen, R and R¹ may be the same or different alkyl groups, although in a preferred embodiment R and R' are the same alkyl group

or - 35 -

(^c5^H5-y-χS_x)

/ \

(A')y M = CR(R')

\ /

JS'(r-^ay)

wherein

A' is a bridging group; (C5H₅_y__xS_x) is a cyclopentadienyl ring substituted with from zero to five S radicals each S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C₄ to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; x is from 0 to 5 denoting the degree of substitution;

M is any group 4, 5, 6, 7 or 8 metal, preferably titanium, zirconium or hafnium; JS'(z-l-y) *^{s a} heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S• is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl- substituted organometalloid; and z is the coordination number of the element J; y is 0 or 1; R and R' are independently a hydrogen or a Oχ to C₄o linear, cyclic or branched alkyl, preferably a Oχ to C2₀ linear, cyclic or branched alkyl, even more - 36 -

preferably hydrogen. R and R' may be the same or different alkyl groups, although in a preferred embodiment R and R¹ are the same alkyl group. Carbenes which are useful in the practice of this invention, however, include those which can be represented by the formula above where M is any group 4, 5, 6, 7 or 8 metal. Metal carbenes complex with olefins to form metalocycles that are possibly intermediates in metathesis reactions. Metalocycle structures are discussed in detail in "Olefin Metathesis" K.J. Ivin, Academic Press, New York (1989) .

For purposes of this invention a Ziegler-Natta polymer is a polymer that has incorporated a substantial amount of the cyclic monomers into the growing polymer chain resulting in a saturated chain, while maintaining the cyclic aspect of the monomer's structure. A ROMP polymer is a polymer that has incorporated the cyclic monomers into the growing polymer chain resulting in an unsaturated chain without maintaining the cyclic aspect on the monomer's structure.

Examples

Molecular weight (Mw and Mn) were measured by Gel Permeation Chromotography using a Waters 150 gel permeation chromatograph equipped with a differential refractive index (DRI) detector. The numerical analyses were performed using the commercially available standard Gel Permeation software package.

Proton NMR was used to detect ROM polymer and Ziegler-Natta polymer in the same sample.

Procedure; - 37 -

In general, to demonstrate the ROMP polymerization using catalyst discussed above, a vial containing 30 to 50 mg dicyclopentadienyl zirconium dimethyl(Cp ZrMβ2) or dicyclopentadienyl hafnium dimethyl (Cp₂HfMβ2) , 30 to 60 mg of N,N- dimethylanallimium (DMAH)B(pfp)4 was stirred in 3 ml of toluene until gas evolution has stopped. The catalyst system was then added to 10 to 20 g of freshly sublimed norbornene dissolved in 300 to 400 ml of toluene (freshly distilled from sodium/benzophenone) in a one liter flask in the dry box at room temperature to 80°C. The polymerization was allowed to proceed for 10 to 120 minutes or until the viscosity was such that the mixture flowed slowly or not at all. The polymerization was killed by adding isopropyl alcohol. White precipitate was filtered and dried. The proton NMR of the product matched that of commercially available ROMP polynorbornene and the integration of the olefinic region indicated that there was one olefin per monomer unit.

To demonstrate both Ziegler-Natta and ROMP products from the same catalyst system and reaction pot, the procedure above was repeated except that the reaction was allowed to proceed for 0.5 to 15 minutes and then transferred to a preheated (40-60 degrees C) two liter autoclave reactor via cannula. The reaction was sealed and propylene was added (10 to 50 psi) and the reactor was stirred. The polymerization was continued for 1 to 240 minutes and the polymer was precipitated into isopropyl alcohol. NMR showed the expected resonances for propylene/norbornene(Zeigler- Natta) copolymer and there were olefinic resonances, not from residual monomer, as well. The examples are reported in table 1. - 38 -

TABLE 1

Sample Catalyst Activator M ratio Yield Product

(mmole) (mmole) cat/ (mg) Descrip. act

1* Cp₂ZrMe₂ DMAH B(pfp) NB 1 230 ROMP

(0.090) (0.090) polymer

2* Cp₂ZrMβ2 DMAH B(pfp) NB .7 682 ROMP

(0.090) (0.129) polymer

3* Cp2ZrMβ2 DMAH B(pfp)₄ NB 2 974 ROMP

(0.096) (0.047) polymer

4* Cp2HfMβ2 DMAH B(pfp)₄ NB 1.5 570 ROMP

(-0.15) (-0.10) polymer

5*** Cp₂HfMe₂** DMAH B(pfp)₄ P/NB 1.5 300/ mix/ROMP

(-0.08) (-0.05) 570 polymer¹

M = Monomer; NB = norbornene; P = propylene

*Runs were at room temperature using g of norbornene in 10 ml toluene.

**Run was at room temperature using lOg of norbornene in 300 ml of toluene.

***Half was transferred to an autoclave by cannula and run at 40°C with 30 psi of propylene and lOg norbornene.

1 mix/ROMP polymer = 300g of a mixture of addition polymer and ROMP polymer and 570 g of ROMP polymer.

The NMR indicated the presence of propylene/norbornene copolymer with some small resonances in the olefinic region attributed to the presence of ROMP polynorbornene.

Claims

Claims I claim:

1. A method of producing polymer by ring opening metathesis polymerization comprising: contacting under polymerization conditions one or more cyclic olefins with a catalyst system comprising a cyclopentadienyl transition metal complex and a non- coordinating anion.

2. A method of producing a polymer blend of Ziegler-Natta polymer and ROMP polymer comprising: contacting under one or more cyclic olefin monomers with a catalyst system comprising a cyclopentadienyl transition metal complex and a non- coordinating anion; and contacting under polymerization conditions one or more linear or branched olefins and the same catalyst system or a catalyst system comprising a cyclopentadienyl transition metal complex and a non- coordinating anion.

3. The method of claim 1 or 2 wherein the catalyst system is represented by the formulae:

1. [{[(A-Cp)MXχ]⁺}_d]{[B']d-_} 2. [{ [ (A-Cp)MXχL]+}_d] { [B^»]<*-) wherein: (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted- hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl- substituted organometalloid, disubstituted boron. disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C2₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;

A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings ;

M is a group 4, 5, 6, 7 or 8 transition metal; Xx is a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl- substituted organometalloid radical or halocarbyl- substituted organometalloid radical which radical may optionally be covalently bonded to both or either M and L or all or any M, S or S'; L is an olefin, diolefin or aryne ligand;

B' is a chemically stable, non-nucleophilic anionic complex having a molecular diameter of 4 angstroms or greater or an anionic Lewis-acid activator resulting from the reaction of a Lewis-acid activator with the precursor to the cationic portion of the catalyst system described in formulae 1 or 2; provided that when B' is a Lewis-acid activator, X can also be an alkyl group donated by the Lewis-acid activator; and d is an integer representing the charge of B.

4. The method of claim 1 or 2 wherein the catalyst system is represented by the formula:

- 41 -

wherein:

A' is a bridging group; (C₅H5_y-._xS_x) is a cyclopentadienyl ring substituted with from zero to five S radicals each S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C o ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; x is from 0 to 5 denoting the degree of substitution;

M is any group 4, 5, 6, 7 or 8 metal, preferably titanium, zirconium or hafnium; Xx ^an(* ^X2 are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M, S or S';

^JS'(z-_l-y) ¹-^{s a} heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S• is a - 42 -

radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl- substituted organometalloid; and z is the coordination number of the element J; y is 0 or 1;

B' is a chemically stable, non-nucleophilic anionic complex having a molecular diameter of 4 angstroms or greater or an anionic Lewis-acid activator; and d is an integer representing the charge of B• .

5. The method of claim 2 or 3, wherein the cyclic monomer is represented by the formulae:

A.

B.

- 43 -

C.

wherein each R^a through R^s is independently hydrogen, halogen, hydrocarbyl, or halocarbyl: ac and dc are integers of 2 or more and be and cc are integers of 0 or more.

6. The method of claim 1, 2, 3 or 4 wherein the cyclic olefin is a diene or a polyene.

7. The method of claim 1, 2, 3, or 4 wherein the cyclic olefin consists essentially of norbornene.

8. The method of claim 1 or 2 wherein the catalyst system is a biscyclopentadienyl group 4 metal compound or a derivative thereof or a monocyclopentadienyl group 4 metal compound or derivative thereof activated by a non-coordinating anion.

9. The method of claim 3 or 4, wherein B' is N,N- dimethylanallimiu tetraperflourophenyl boron.

10. The method of claim 1 further comprising adding a second cyclic olefin after a first cyclic olefin and the catalyst system have been allowed to react. - 44 -

11. The method of any of the above claims wherein the polymerizations are carried out in series reactors.

12. The method of any of the above claims wherein the polymerizations are carried out in the same reactor.

13. A carbene represented by the formulae:

(A-Cp)M=CR(R')

wherein M is titanium, zirconium or hafnium; (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted- hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl- substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C₂o ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;

A¹ is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;

R and R¹ are independently a hydrogen or a 0χ to C4₀ linear, cyclic or branched alkyl;

or

/ \

(A')y M = CR(R')

\ /

JS'(rι-y) wherein

A* is a bridging group; (C5H₅_y__xS_x) is a cyclopentadienyl ring substituted with from zero to five S radicals each S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C₄ to C₂o ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; x is from 0 to 5 denoting the degree of substitution;

M is titanium, zirconium or hafnium; ^JS'(z-l-y) i-^{s a} heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S* is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl- substituted organometalloid; and z is the coordination number of the element J; y is 0 or 1; R and R' are independently a hydrogen or a Oχ to C40 linear, cyclic or branched alkyl.

14. The carbene of claim 13 wherein M is Hf.

15. The carbene of claim 13 wherein M is Zr.

16. The carbene of claim 13 wherein R and R' are the same or different hydrogen or alkyl groups having 1 to 20 carbon atoms, preferably hydrogen or methyl groups.

17. An intimate blend of ROMP polymer and Ziegler-Natta polymer comprising 3 to 50 weight percent ROMP polymer produced by any of the above claims.

18. A method of producing block copolymer comprising: contacting a vinyl terminated macromonomer or vinyl terminated polymer chain with a compound represented by the formulae: (A-Cp)M=CR(R') wherein M is any group 4, 5, 6, 7, or 8 transition metal; (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted- hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl- substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C2₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;

A¹ is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings; R and R¹ are independently a hydrogen or a Cx to C4₀ linear, cyclic, branched or aromatic alkyl;

or

(C₅H₅ χSχ)

/ \

(A')y M = CR(R')

\ / wherein

A' is a bridging group;

(C5H-5_y__xS_x) is a cyclopentadienyl ring substituted with from zero to five S radicals each S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C₂o ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; x is from 0 to 5 denoting the degree of substitution;

M is any group 4, 5, 6, 7, or 8 transition metal; ^JS'₍z-_l-y) -^{s a} heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl- substituted organometalloid; and z is the coordination number of the element J; y is 0 or 1; R and R¹ are independently a hydrogen or a Cx to C40 linear, cyclic, branched or aromatic alkyl, to produce a long chain metathesis active metal carbene, thereafter contacting said active metal carbene under ROM polymerization conditions with one or more cyclic olefin monomers.

19. A method of producing block copolymer comprising: contacting cyclic olefins with a compound represented by the formulae: (A-Cp)M=CR(R') wherein

M is any group 4, 5, 6, 7, or 8 transition metal; (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted- hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl- substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C₄ to C₂o ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;

A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings; R and R' are independently a hydrogen or a Cx to C40 linear, cyclic, branched or aromatic alkyl;

or (C_δHs-ySx)

/ \ (A')y M = CR(R')

\ / wherein

A' is a bridging group; (CsH5»y«_xS_x) is a cyclopentadienyl ring substituted with from zero to five S radicals each S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C2₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; x is from 0 to 5 denoting the degree of substitution;

M is any group 4, 5, 6, 7, or 8 transition metal; ^JS' (z-_l-y) i-^{3 a} heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S¹ is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl- substituted organometalloid; and z is the coordination number of the element J; y is 0 or 1; R and R¹ are independently a hydrogen or a O to C40 linear, cyclic, branched or aromatic alkyl, to produce ROMP polymers terminated with a metal carbene or a Zeigler active olefin, thereafter contacting said active olefin or carbene under addition polymerization conditions with one or more olefin monomers.