SUPPORTED IONIC METALLOCENE CATALYSTS FOR OLEFIN POLYMERIZATION

Background of the Invention

1. Field of the Invention The invention relates to supported catalysts for polymerization of olefins including gas or slurry phase polymerization of olefins, dlolefins, cyclic olefins and acetylenically unsaturated monomers. These catalysts, which may be supported on known catalyst supports, Include a Group IV-B metal metallocene compound and an ionic activator compound. Hhlle the homogeneous variant of this catalyst system has been previously disclosed In copending U.S. Serial No. 133,480, a supported form of the catalyst system has not heretofore been produced. The supported catalyst, suitable for use in gas or slurry phase olefln polymerization, provides a polymer product having a narrower particle size distribution and higher bulk density than achievable with the homogeneous catalyst system. Furthermore, the use of the supported

catalyst in the gas phase results 1n greatly reduced reactor fouling as compared to the unsupported or homogeneous variant. By employing suitably sized supports, the catalyst system can be employed in solution and high pressure polymerization processes.

2. Background Ziegler-Natta type catalysts for the polymerization of olefins are well known. The traditional Ziegler-Natta type systems comprise a metal halide activated to a catalyst species by reaction with a metal alkyl cocatalyst, particularly an aluminum alkyl cocatalyst. The activation of these traditional Ziegler-Natta catalysts generates a variety of different active sites. As a consequence of this non-uniformity of the active sites, the catalysts produce polymer products of broad molecular weight distribution (MWD). Furthermore, the copolymer products exhibit broad composition distribution (CD), poor comonomer incorporation and blocky sequence distribution. Recently it has been found that active catalysts are formed when a bis(cyclopentadienyl) compound of the Group IV-B metals, 1n particular zirconium and hafnium, is activated by an alu oxane. The metal locene-alumoxane catalysts whether homogeneous or supported generally possess high activity and are more versatile than conventional Ziegler-Natta catalysts in that they may be effectively used to produce a variety of polymer products Including, for example, high density linear polyethylene (HDPE), linear low density polyethylene (LLDPE), ethyl ene-propylene copolymer (EP), non-crystalline polypropylene and crystalline polypropylene. The metal locene-alumoxane catalysts also offer the significant advantage over the traditional Ziegler-Natta catalysts of being able to produce polymers with narrow- MWD. Hhlle the metal locene-alumoxane catalysts do offer significant advantages over the traditional Ziegler-Natta catalysts, they nevertheless have limitations 1n practical commercial applications. These limitations include the relatively high cost of the alumoxane cocatalysts. Alumoxane is also air sensitive and

difficult to manipulate. Furthermore, the metallocene-alumoxane catalysts, while producing a narrow MWD polymer product, have a limited capability to produce high molecular weight polymers or polymers having a high comonomer content. Copending U.S. Patent Application Serial No. 133,480, also published as European Patent Application 277,004 which is hereby incorporated by reference, describes a further advance 1n metallocene catalysts: a new metallocene catalyst which does not require either an alkyl aluminum or an alumoxane as an activator. The Group IV-B metallocene catalyst 1s prepared as a reaction product of a Group IV-B metal metallocene compound and an 1on1c activator compound. The 1on1c activator comprises a cation having a donatable proton and a labile, bulky anion which Is a single coordination complex having a plurality of lipophilic radicals covalently coordinated to and shielding a central charge-bearing metal or metalloid atom, the bulk of said anion being such that upon reaction of the activator cation donatable proton with a proton reactable substltuent of a bls(cydopentadlenyl) Group IV-B metal compound to form a Group IV-B metal cation, the anion of the activator is sterically hindered from covalently coordinating to the Group IV-B metal cation. Hence, as described in the copending application, an active catalytic species of a metallocene 1s formed, namely an Ionic pair comprising a metallocene transition metal cation paired with a noncoordlnatlng anion of the activator component. The new metallocene catalyst system (hereafter referred to as an "ionic metallocene catalyst") eliminates the need for an expensive alumoxane activator. The ionic metallocene catalyst also offers other advantages over the metallocene-alumoxane catalysts such as permitting the production of polyolefln products of narrow MWD and of significantly higher weight average molecular weight at high rates of catalytic activity while also permitting better Incorporation of comonomers and the control of the chain end chemistry of the polymer The new ionic metallocene catalyst of the copending application 1s, however, a homogeneous catalyst and generally can not be practically used for gas phase polymerization. The use of a

supported catalyst offers the possibility of gas phase compatibility. Control of the particle size distribution of the polymeric product in the various polymerization processes eliminates or reduces the extent of reactor fouling. Supported catalysts for olefin polymerization are well known in the art. These catalysts offer, among others, the advantages of being usable in gas or slurry phase reactors allowing the control of polymer particle size and thereby the control of product bulk density. Gas phase reactors also eliminate the need for a solvent and the equipment for solvent handling and separation. However, the known Ziegler-Natta olefin polymerization supported catalysts also present disadvantages which Include broad MWD and composition distribution (CD), Inefficient incorporation of comonomers, poor sequence distribution and, In the case of lower activity catalysts, the need for a product deashing step. Supported metallocene-alumoxane catalysts for olefin polymerization are described In U.S. Patent 4,701,432 of Welborn. These supported metallocene-alumoxane catalysts are obtained by reacting a metallocene and an alumoxane In the presence of the solid support material. The supported catalyst may then be employed either as the sole catalyst component or may be employed in combination with an organometallic cocatalyst. The supported metallocene-alumoxane catalyst, however, still produces polymers of generally lower molecular weight and comonomer incorporation than desired for certain applications. It would be desirable to provide a supported catalyst for gas or slurry phase olefin polymerization that eliminates the need for either an alumoxane or an alkyl aluminum cocatalyst. It would be further desirable that such supported catalyst be capable of providing a polymer product having a high molecular weight, narrow MWD and CD, good comonomer incorporation, good sequence distribution, high bulk density and controlled particle size for ease of removal from the reactor.

Summary The Invention provides a supported 1on1c metallocene catalyst which 1s suitable for use In the polymerization of olefins including gas or slurry phase polymerization of olefins. The heterogeneous catalyst, like its homogeneous counterpart disclosed .n our European Patent Application EP 277004, permits the production of polyoleflns of high molecular weight and narrow molecular weight distribution (MWD) at high rates. Moreover, the polyolefln products of the supported catalyst have a narrow composition distribution (CO) and Improved sequence distribution of comonomers as compared to the products of prior art conventional supported Ziegler-Natta catalysts. The possibility of producing a supported catalyst was surprising since 1t would have been predicted that the reaction of ionic catalyst as described in the copending application with a Lewis base such as is present on a metal oxide surface would result in catalyst deactlvation. This invention is even more surprising since aluminum alkyls are not present during catalyst preparation and furthermore the polymer products are similar to that obtained with the unsupported catalyst. The supported 1on1c metallocene catalyst of this invention comprises the Ionic, metallocene catalyst and a suitable support material. The metallocene component of the 1on1c metallocene catalyst may be selected from a bls(cyclopentadlenyl) derivative of a Group IV-B (Periodic Table of Elements, published and copyrighted by CRC Press, Inc., 1984) metal compound containing at least one Hgand which will combine with an activator component or at least a portion thereof such as a cation portion thereof. The activator component 1s an ionic compound coaprising a cation which will irreversibly react with at least one Hgand contained In said Group IV-B metal compound (metallocene component) and an anion which is a single coordination complex comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central formally charge-bearing metal or metalloid atom, which anion 1s bulky, labile and stable to any reaction involving the cation of the activator component. The charge-bearing metal or metalloid may be any metal or metalloid

capable of forming a coordination complex which 1s not hydrolyzed by aqueous solutions. Upon combination of the metallocene component and activator component, the cation of the activator component reacts with one of the Hgands of the metallocene component, thereby generating an ion pair consisting of a Group IV-B metal cation with a formal coordination number of 3 and a valence of +4 and the aforementioned anion, which anion is compatible with and noncoordinatlng toward the metal cation formed from the metallocene component. The anion of the activator compound must be capable of stabilizing the Group IV-B metal cation complex without Interfering with the ability of the Group IV-B metal cation or its decomposition product to function as a catalyst and must be sufficiently labile to permit displacement by an olefin, dlolefln or an acetylenlcally unsaturated monomer during polymerization. Either the Ionic metallocene catalyst or both its components will be contacted with an Inorganic or organic solid support material, either thermally or chemically dehydrated before such contact, to form the supported ionic metallocene catalyst of this invention. The method for preparing these supported Ionic catalyst comprises the steps of, (a) combining, In a solvent or diluent (1) at least one metallocene component comprising a bis(cyclopentadlenyl) metal compound containing at least one Hgand capable of reacting with a proton, said metal being selected from Group IV B metals, (11) at least one activator component comprising a cation capable of donating a proton and an anion, said anion being a single coordination complex comprising a plurality of lipophilic radicals covalenty coordinated to and shielding a central charge-bearing metal or metalloid atom, said anion being bulky, labile and capable of stabilizing the metal cation formed as a result of reaction between the two, and (111) a catalyst support material suspended in a suitable solvent, and

(b) recovering a supported catalyst product as a free-flowing solid or slurry. The supported catalyst of this invention will polymerize olefins, dlolefins and/or acetylenically unsaturated monomers either alone or in combination with other olefins and/or other unsaturated monomers 1n liquid, slurry or gas phase reactions. In general, catalysts can be selected so as to produce the polymer products which will be free of certain trace elements generally found 1n polymers produced with Ziegler-Natta type catalysts such as aluminum, magnesium, chloride and the like. The polymer products produced with the catalysts of this Invention should, then, have a broader range of applications than polymers produced with either the more conventional Ziegler-Natta type catalysts containing a metal alkyl, such as an aluminum alkyl, or the metallocene-alumoxane catalysts.

Detailed Description of the Preferred Embodiments The present invention relates to supported catalysts eminently suited for use in various polymerization processes Including gas or slurry phase polymerization of olefins. The heterogeneous catalyst includes a metallocene of the Group IV-B transition metals, an ionic activator compound and a catalyst support. European Patent Application EP 277,004 Incorporated by reference, describes the homogeneous variant of the Group IV-B Ionic metallocene catalyst which 1s prepared as the reaction product of a Group IV-B metal metallocene compound and an Ionic activator compound.

The Metallocene Component The Group IV-B metal compounds, particularly the titanium, zirconium and hafnium compounds, useful as first compounds 1n the 1on1c metallocene catalyst system employed 1n the process of this invention are the bls(cyclopentadlenyl) derivatives of titanium, zirconium or hafnium. In general, such useful titanium, zirconium and hafnium compounds may be represented by the following general formulae:

- 8 -

1 . (A-Cp)MX _ι X ₂

2. (A-Cp)MX ⁷ ^X' ₂

3. (A-Cp)ML

4. CP*) CPRTMX _X

wherein: M 1s a metal selected from the Group consisting of titanium (Tl), zirconium (Zr) and hafnium (Hf); (A-Cp) 1s either (CpMCp*) or Cp-A'-Cp* and Cp and Cp* are the same or different substituted or unsubstituted cydopentadienyl radicals, and wherein A ¹ Is a covalent bridging group containing a Group IV-A element; L is an olefin, 0 dlolefln or aryne Hgand; X and X are, Independently, 1 selected from the group consisting of hydride radicals, hydrocarbyl ₂ radicals having from 1 to about 20 carbon atoms, 3 substituted-hydrocarbyl radicals, wherein 1 or more of the hydrogen 4 atoms are replaced with a halogen atom, having from 1 to about 20 5 carbon atoms, organo-metalloid radicals comprising a Group IV-A 6 element wherein each of the hydrocarbyl substituents contained in the 7 organo-portion of said organo-metalloid, independently, contain from 8 1 to about 20 carbon atoms and the Hke; X' and X' are 9 joined and bound to the metal atom to form a metallacy e, in which 0 the metal, X' and X' form a hydrocarbocycHc ring 1 containing from about 3 to about 20 carbon atoms; and R 1s a

22 substituent, preferably a hydrocarbyl substltuent, having from 1 to ³ 20 carbon atoms, on one of the cydopentadienyl radicals which is

24 also bound to the metal atom. Each carbon atom In the

25 cydopentadienyl radical may be, independently, unsubstituted or

26 substituted with the same or a different radical selected from the

27 Group consisting of hydrocarbyl radicals, substituted-hydrocarbyl

28 radicals wherein one or more hydrogen atoms Is replaced by a halogen

29 atom, hydrocarbyl-substituted metalloid radicals wherein the

30 metalloid is selected from Group IV-A of the Periodic Table of the

31 Elements, halogen radicals and the Hke. Suitable hydrocarbyl and

substituted-hydrocarbyl radicals which may be substituted for at least one hydrogen atom in the cydopentadienyl radical will contain from 1 to about 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals. Similarly, and when X _χ and/or X is a hydrocarbyl or substituted-hydrocarbyl radical, each may, independently, contain from 1 to about 20 carbon atoms and be a straight or branched alkyl radical, a cyclic hydrocarbyl radical, an alkyl-substituted cyclic hydrocarbyl radical, an aromatic radical or an alkyl-substituted aromatic radical. Suitable organometalloid radicals include mono-, di- and trlsubstituted organometalloid radicals of Group IV-A elements wherein each of the hydrocarbyl Groups contain from 1 to about 20 carbon atoms. Suitable organometalloid radicals Include trimethylsllyl, triethylsilyl, ethyldlmethylsilyl, ethyldlethylsilyl, trlphenylgermyl , trimethylgermyl and the like. Illustrative, but not limiting examples of b1s(cyclopentad1enyl)zircon1um compounds which may be used in the preparation of the Improved (ethylcyclopentadienyD(cyclopentadlenyl) and bis(ethylcyclopentadienyl)zircon1um dlhydrlde, (propylcyclopentadlenyD(cyclopentadienyl) and b1s(propylcyclopentadieny1)z1rcon1um dlhydrlde, (n-butylcydopentadienyl)(cydopentadienyl) and b1s(n-butylcyclopentad1enyl)z1rcon1um dlhydrlde, (t-butylcyclopentad1enyl)(cydopentad1enyl) and bis(t-butylcyclopentad1enyl)zircon1um dlhydrlde, (cyclohexylmethylcyclopentadlenyD(cydopentadienyl) and b1s(cyclohexylmethylcyclopentad1eny1)zircon1um dlhydride, (benzylcyclopentad1enyl)(cyclopentad1enyl) and bis(benzylcyclopentad1enyl)z1rconium dlhydride, (diphenylmethylcyclopeπtadienylMcyclopentadlenyl) and b1s(d1phenylmethylcyclopentad1enyl)zirconium dlhydrlde and the Hke; (polyhydrocarbyl-substituted-cyclopentadlenyl) zirconium compounds

such as (dimethylcydopentadienyl) (cydopentadienyl) and' b1s(d1methylcyc1opentadieny1) zirconium dimethyl, (trimethylcydopentadienyl) (cydopentadienyl) and b1s(trimethylcydopentadienyl) zirconium dimethyl, (tetramethylcydopentadlenyl) (cydopentadienyl) and bis(tetramethylcydopentadlenyl) zirconium dimethyl, (per ethylcydopentadienyl) (cydopentadienyl) and bis(permethylcydopentadienyl) zirconium dimethyl, (ethyltetramethylcydopentadlenyl) (cydopentadienyl) and bis(ethyltetramethylcydopentadlenyl) zirconium dimethyl, (indenyl)(cydopentadienyl) and bisdndenyDzirconium dimethyl, (dimethylcydopentadienyl) (cydopentadienyl) and bis(dimethylcyclopentadienyl) zirconium dlhydride, (trlmethylcydopentadienyl) (cydopentadienyl) and bis(trimethylcyclopentadienyl) zirconium dlhydride, (tetramethylcydopentadlenyl) (cydopentadienyl) and bis(tetramethylcyclopentadienyDzirconium dlhydride, (permethylcydopentadienyl) (cydopentadienyl) and b1s(permethylcyclopentadienyl)z1rcon1um dlhydrlde, (ethyltetramethylcyclopentadienyl) (cydopentadienyl) and b1s(ethyltetramethylcyclopentadienyDzircon1um dlhydrlde, (Indenyl)(cydopentadienyl) and bisdndenyDzirconium dlhydrlde (propylcyclopentadlenyl) (cydopentadienyl) and bis(propylcyclopentad1enyl)z1rcon1um dlhydride, (n-butylcydopentadienyl) (cydopentadienyl) and bis(n-butylcydopentadienyl)z1rcon1uιs dlhydride, (t-butylcydopentadienyl) (cydopentadienyl) and bis(t-butylcyclopentadienyDzirconium dlhydrlde, (cyclohexylmethylcydopentadienyl) (cydopentadienyl) and bis(cyclohexylmethylcyclopentad1enyDzircon1um dlhydride, (benzylcydopentadienyl) (cydopentadienyl) and bis(benzylcyclopentad1enyl)zircon1um dlhydride, (diphenylmethylcydopentadienyl) (cydopentadienyl) and b1s(d1phenylmethylcyclopentad1enyl)zirconium dlhydride and the like; (metal hydrocarbyl-substituted cyclopentadienyDzirconium compounds

such as (tr1methyls1lylcydopentadienyl)(cyclopentad1enyD and b1s(tr1methyls1lylcyclopentad1enyl)zircon1um dimethyl, (tr1methylgermylcydopentadienyD(cydopentad1enyl) and b1s(trimethylgermylcyclopentad1enyDzirconium dimethyl, (trimethylstannylcydopentad1enyl) ⁽ cyc1opentad1enyD and b1s(trimethylstannyl cyclopentadienyDzirconium dimethyl, (tr1methylplumbylcyclopentad1enyl)(cyclopentad1enyl) and b1 s( trimethyl pi umbyl cyclopentadienyDzirconium dimethyl, (trimethyl si lylcyclopentad1enyl)(cyclopentad1enyD and b1s(tr1methyls1lylcydopentad1enyDzircon1um dlhydride, (trlmethylgermylcydopentadlenyD(cydopentadienyl) and b1s(tr1methylgermylcydopentad1enyl)zirconium dlhydrlde, (tr1methylstannylcydopentad1enyl)(cyc1opentad1enyl) and b1s(trimethylstannylcyclopentad1enyl)z1rcon1um dlhydrlde, (tr1methylplumbylcyclopentad1enyl)(cyclopentad1enyl) and b1s(tr1methylplumblycydopentad1enyl)z1rcon1um dlhydride and the like; (halogen-substituted-cyclopentadlenyl) zirconium compounds such as (tr1fluoromethy1cyclopentadienyD ⁽ cyclopentad1enyl) and b1s(trifluoromethylcyclopentadienyl)zirconium dimethyl (trifluoromethylcyclopentadlenyl)(cyclopentad1enyD and bis(tr1fluoromethylcyclopentad1enyl)z1rcon1um dlhydrlde and the Hke; s1lyl-subst1tuted bls(cy opentadienyl) zirconium compounds such as b1s(cyclopentad1enyl) (trlmethylsilyD(methyl)zirconiura, bis (cydopentadienyl) (triphenyls1lyD(methyl)z1rcon1um, bi s(cydopentad1 enyl ) ttri s(d1methyl s1 lyl )$1 lyl ] (methyl )z1 rconi urn, b1s(cydopentad1enyl)[b1s(mes1tyDs1lyl](methyDz1rconium, b1s(cyclopentad1 enyl) ( trimethyl si lyl) trimethyl si lylmethyl) zirconium, bis (cydopentadienyl) (trimethyl sllylbenzyl) and the like; (bridged-cydopentadi enyl )zi rconi urn compounds such as methylene b1s(cydopentadienyDzircon1υπ dimethyl , ethylene b1s(cyc1opentadienyl)z1rcon1uffl dimethyl , dimethyl si lyl b1s(cydopentadienyDzircon1uB dimethyl , methylene b1s(cyclopentadienyl)z1rcon1um dlhydrlde, ethylene bis(cydopentadienyl)z1rcon1u_n dlhydrlde and d1methyls1lyl bis(cydopentadienyl)z1rcon1u» dlhydrlde and the like; zlrconacycles

such as b1 s(pentamethyl cydopentadi enyl ) zl rconacyclobutane , bi s(pentamethylcydopentadl enyl ) zl rconacyclopentane, bi s(cyc1opentadi eny1 )z1 rcona1 ndane. l-bis(cyclopentad1 enyl )z1 rcona-3-d1methyl s1 la-cyclobutane and the Hke; ol efin, dlol efin and aryne Hgand substi tuted b1 s(cyclopentad1enyl )z1 rconi um compounds such as b1 s(cydopentad1 enyl ) (l ,3-butad1ene)z1 rcon1 um, bi s(cyclopentadi enyl ) (2 ,3-dimethyl-l ,3-butad1 ene)zi rcon1um, b1s(pentamethy1cyclopentadienyl)(benzyne)zirconium and the like; (hydrocarbylKhydrlde) bis(cyclopentad1enyl)z1rconium compounds such as bis(pentamethylcyclopentadienyDzirconium (phenyD(hydrlde), b1s(pεntamethy1cyclopentadienyl)zircon1um (methyl)(hydride) and the Hke; and bis(cydopentadlenyl) zirconium compounds in which a substituent on the cydopentadienyl radical 1s bound to the metal such as (pentamethylcydopentadienyl) (tetramethylcyclopentadienylmethylene) zirconium hydride, (pentamethylcydopentadienyl) (tetramethylcyclopentadlenylmethylene)zlrconium phenyl and the Hke. A similar list of illustrative bis(cyclopentadlenyl) hafnium and bis(cyclopentad1enyl)t1tan1um compounds could be made, but since the lists would be nearly identical to that already presented with respect to b1s(cyclopentadienyl)zirconium compounds, such lists are not deemed essential to a complete disclosure. Other bis(cydopentadienyl)hafnium compounds and other b1s(cydopentad1enyl)t1taniurn compounds as well as other bis(cyclopentadienyDzirconium compounds which are useful in the catalyst compositions of this invention will, of course, be apparent to those skilled in the art.

The Activator Component Compounds useful as an activator component In the preparation of the catalyst of this Invention will comprise a cation, which 1s a Bronsted add capable of donating a proton, and a compatible noncoordinatlng anion containing a single coordination complex comprising a charge-bearing metal or metalloid core, which

anion 1s relatively large (bulky), capable of stabilizing the active catalyst species (the Group IV-B cation) which 1s formed when the two compounds are combined and said anion will be sufficiently labile to be displaced by olefln , d1olef1n1c and acetylenically unsaturated substrates or other neutral Lewis bases such as ethers, nitriles and the Hke. As indicated above, any metal or metalloid capable of forming a coordination 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 Hke. Suitable metalloids include, but are not limited to, boron, phosphorus, silicon and the Hke. 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 Hght of this, salts containing anions comprising a coordination complex containing a single boron atom are preferred. In general , the acti vator compounds useful In the preparation of the catalysts of thi s i nvention may be represented by the fol lowing general formula:

5. _ (L ^, -H) ⁺ ] ^d+ [(M' ) ^m+ Q ₁ Q ₂ . . .Q _n 3 ^d ~

Wherein: L ¹ is a neutral Lewis base; H Is a hydrogen atom; [L'-H] is a Bronsted add; M' 1s a metal or metalloid selected from the Groups subtended by Groups V-B to V-A of the Periodic Table of the Elements; I.e., Groups V-B, VI-B, VII-B, VIII-B, I-B, II-B, III-A, IV-A, and V-A; 0 to Q are selected, Independently, from the Group consisting of hydride radicals, dlalkylamldo radicals, alkoxlde and aryloxide radicals, hydrocarbyl and substituted-hydro-carbyl radicals and organometalloid radicals and any one, but not more than one, of 0 to Q may be a haHde radical - the remaining Q _χ to Q _n being, independently, selected from the foregoing radicals;

m 1s an Integer from 1 to 7; n 1s an Integer from 2 to 8; and n - m « d.

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

6. [L ^« H] ⁺ [BAr _χ Ar ₂ X _J X ₄ 3 ^"

Wherein: L* 1s a neutral Lewis base; H 1s a hydrogen atom; CL'-H3 ⁺ Is a Bronsted a d; B 1s boron in a valence state of 3; Ar and Ar are the same or different aromatic or substituted-aroatic hydrocarbon radicals containing from about 6 to about 20 carbon atoms and may be linked to each other through a stable bridging group; and X and X ₄ are radicals selected, independently, from the group consisting of hydride radicals, hallde radicals, with the proviso that only ^ or X ₄ will be hallde at the same time, hydrocarbyl radicals containing from 1 to about 20 carbon atoms, substituted-hydrocarbyl radicals, wherein one or more of the hydrogen atoms 1s replaced by a halogen atom, containing from 1 to about 20 carbon atoms, hydrocarbyl-substituted metal (organometalloid) radicals wherein each hydrocarbyl substitution contains from 1 to about 20 carbon atoms and said metal is selected from Group IV-A of the Periodic Table of the Elements and the like.

In general, Ar and Ar^ may, independently, be any aromatic or substituted-aromatic hydrocarbon radical containing from about 6 to about 20 carbon atoms. Suitable aromatic radicals Include, but are not limited to, phenyl, naphthyl and anthracenyl radicals. Suitable substituents Include, but are not necessarily limited to, hydrocarbyl radicals, organometalloid radicals, alkoxy radicals, alkyl ami do radicals, fluoro and fluorohydrocarbyl radicals and the like such as those useful as X ₃ and X ₄ . The substituent may be ortho, meta or para, relative to the carbon atoms bonded to the boron atom. When either or both X and X ₄ are

a hydrocarbyl radical, each may be the same or a different aromatic or substituted-aromatic radical as are Ar _χ and Ar , or the same may be a straight or branched alkyl, alkenyl or alkynyl radical having from 1 to about 20 carbon atoms, a cyclic hydrocarbon radical having from about 5 to about 8 carbon atoms or an alkyl-substituted cyclic hydrocarbon radical having from about 6 to about 20 carbon atoms. X _j and X ₄ may also, Independently, be alkoxy or dlalkylamldo radicals wherein the alkyl portion of said alkoxy and dlalkylamldo radicals contain from 1 to about 20 carbon atoms, 0 hydrocarbyl radicals and organometalloid radicals having from 1 to 1 about 20 carbon atoms and the Hke. As indicated above, Ar and 2 Ar may be linked to each otherN Similarly, either or both of 3 Ar. and Ar. could be linked to either X or X . 4 Finally, X or X ₄ may also be linked to each other through a 5 suitable bridging group. 6 Illustrative, but not limiting, examples of boron compounds 7 which may be used as an activator component 1n the preparation of the 8 improved catalysts of this Invention are trialkyl-substltute.d 9 ammonium salts such as tr1ethylammonium tetra(phenyDboron, 0 trlpropyl mmonium tetra(phenyl)boron, tr1(n-butyl)ammon1urn 1 tetra(phenyl)boron, trimethyl mmonium tetra(p-tolyl)boron, 2 tri ethyl mmonium tetra(o-to1yl)boron, tributylammonium 3 tetra(pentaf1uorophenyl)boron, trlpropylammonium 4 tetra(o,p-dimethylphenyl)boron, tributylammonium 5 tetra(m,ffl-di ethylphenyl)boron, tributyl monlurn 6 tetra(p-tr1-f1uoromethylphenyl)boron, tributylammonlurn 7 tetra(pentaf1uoropheny1)boron, trKn-butyDammonlum 8 tetra(o-tolyl)boron and the Hke; N,N-d1alky1 anlllnlum salts such as 9 N,N-d1methylanilin1um tetra(phenyl)boron, N,N-d1ethy1anilin1um ° tetra(phenyl )boron, N ,N-2 ,4,6-ρentamethylan1 H n1 um tetra(phenyl )boron and the Hke; dlalkyl ammoni um sal ts such as dK1-propyDammon1 um ² tetra(pentafl uorophenyl)boron, dicyc1ohexylammon1 um ³ tetra(phenyl)boron and the l ike; and trlaryl phosphonlum sal ts such as triphenylphosphonium tetra(phenyl )boron, 5 tri (methyl phenyDphosphoni urn tetra(phenyl )boron ,

trKdimethylphenyDphosphonlum tetra(phenyl)boron and the Hke. Suitable compounds containing other metals and metalloids which are useful as activator components can be usefully employed. In this regard, 1t should be noted that the foregoing Hst 1s 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 Catal ^y st Support Typically, the support can be any of the known sol id catalyst supports, particularly porous supports , such as talc, Inorganic oxides, and resinous support material s such as polyolefins . Preferably, the support material i s an Inorganic oxide 1n parti cul ate form. Suitable Inorganic oxide materials which are desi rably employed in accordance wi th thi s Invention incl ude Group II-A, III-A, IV-A or IV-B metal oxides. The most preferred catalyst support material s Include silica, alumina, and sl Hca-alumina and mixtures thereof. Other inorganic oxides that may be employed either alone or 1n combination wi th the silica, alumina or si l ica-alumina are magnesia, titania, zi rconia, and the like. Other suitable support material s , however, can be employed, for example, finely divided polyolefins such as finely divided polyethylene. The metal oxides generally contain surface hydroxyl groups which nay react with and deactivate the ionic metal locene catalyst when the catalyst is added to the s lurried metal oxide support. Therefore, it 1s preferred that the inorganic oxide support be dehydrated prior to use, I .e. subjected to a thermal treatment 1n order to remove water and reduce the concentration of the surface hydroxyl groups. The treatment may be carri ed out in vacuum or while purging with a dry inert gas such as nitrogen at a temperature of about lOO'C to about lOOO'C, and preferably, from about 300*C to about 800'C. Pressure considerations are not critical . The duration of the thermal treatment can be from about 1 to about 24 hours .

However, shorter or longer times can be employed. As an alternative method of dehydration of the metal oxide support material, chemical dehydration can be advantageously employed. Chemical dehydration converts all water and hydroxyl groups on the oxide surface to inert species. Useful chemical agents are for example, chlorosllanes, such as trimethylchlorosllane, and the Hke and alkyl aluminum reagents such as tr1ethyl aluminum and the Hke. The chemical dehydration is accomplished by slurrylng the Inorganic particulate material, such as, for example, silica In an Inert low boiling hydrocarbon, such as, for example, hexane. During the chemical dehydration reaction, the silica should be maintained 1n a moisture and oxygen-free atmosphere. To the silica slurry Is then added a low boiling inert hydrocarbon solution of the chemical dehydrating agent. The inorganic oxide support used 1n the preparation of the catalyst may be any particulate oxide or mixed oxide as previously described which has been thermally or chemically dehydrated such that 1t Is substantially free of adsorbed moisture. The specific particle size, surface area and pore volume of the inorganic oxide determine the amount of Inorganic oxide that 1s desirable to employ 1n preparing the catalyst compositions, as well as affecting the properties of polymers formed with the aid of the catalyst compositions. These properties must frequently be taken Into consideration 1n choosing an Inorganic oxide for use 1n a particular aspect of the Invention. In general, optimum results are usually obtained by the use of Inorganic oxides having an average particle size 1n the range of about 0.1 to 600 microns, preferably about 0.3 to 80 microns; a surface area of about 50 to 1,000 square meters per gram, preferably about 100 to 400 square meters per gram; and a pore volume of about 0.5 to 3.5 cc per gram; preferably about 0.5 to 2 cc per gram.

Catal yst Preparation and Use The supported ioni c metal locene catalyst of thi s Invention may be prepared by combini ng the metal locene component, the activator

component and the support 1n suitable solvents In one or more steps.

A. Choice of Metallocene-Activator Pairs In general, while most metallocene components Identified above may be combined with most activator components identified above to produce an active olefin polymerization catalyst, It 1s desirable for continuity of the polymerization operations that either the metal cation initially formed from the metallocene component or a decomposition product thereof be a relatively stable catalyst. It is also desirable that the anion of the activator compound be stable to hydrolysis when an ammonium salt 1s used. Further, 1t is desirable that the acidity of the activator component be sufficient, relative to the metallocene component to facilitate the needed proton transfer. In general, bis(cydopentadienyl) metal compounds which can be hydrolyzed by aqueous solutions can be considered suitable as metallocene components to form the catalysts described herein. The chemical reactions which occur In forming the catalyst of this Invention may, when a preferred, boron-containing compound Is used as the second component, be represented by a reference to the general formulae set forth herein as follows:

7. (A-Cp)MX _χ X ₂ + CL ^, -H] ⁺ [BAr _ι Ar ₂ X _j X ₄ 3 ^" - [(A-Cp)MX,] ⁺ [BAr,Ar 2.X. tX ^" 4_r" + HX. ♦ L' c t(A-Cp)MX ₂ ] ⁺ rBAr _ι Ar ₂ X _| X ₄ ] ^" _χ ♦ L'

8. (A-Cp)ra ⁷ jx' ₂ + [L ^, -H] ⁺ [BAr _ι Ar ₂ X _J X ₄ ] ^" - C(A-Cp)M(X' _ι X ^, ₂ H)] ⁺ [BAr _ι Ar ₂ X _j X ₄ ] ^" + L' or E(A-Cp)M(X' ₂ X ^, _ι H)] ⁺ tBAr _ι Ar ₂ X _j X ₄ ] ^" + V

9. (A-Cp)ML + [L'-H] ⁺ CBAr _ι Ar ₂ X _j X ₄ ] ^" - C(A-Cp)M(LH)] ⁺ [BAr _ι Ar ₂ X _j X ₄ ] ^" + L'

10. -

In the foregoing reaction equations the symbols have been previously defined. In general, the stability and rate of formation of the products in the foregoing reaction equations, particularly the metal cation, will vary depending upon the choice of the solvent, the acidity of the [L'-H3 ⁺ selected, the particular L*. the anion, the temperature at which the reaction 1s completed and the particular b1s(cyclopentad1enyl) derivative of the metal selected. Generally, the Initially formed 1on-pa1r will be an active polymerization catalyst and will polymerize o-olef1ns, dlolefins, strained cyclic olefins and acetylenically unsaturated monomers either alone or in combination with other monomers. In some cases, however, the Initial metal cation will decompose to yield an active polymerization catalyst. With respect to the combination of the metallocene component with the activator component to form a catalyst of this Invention, 1t should be noted that the two compounds combined for preparation of the active catalyst must be selected to avoid transfer of a fragment of the anion, particularly an aryl group, to the metal cation, thereby forming a catalytically inactive species. This can be done by sterlc hindrance, resulting from substitutions on the cydopentadienyl carbon atoms as well as substitutions on the aromatic carbon atoms of the anion. It follows, then, that the metallocene components comprising perhydrocarbyl-substltuted cydopentadienyl radicals could be effectively used with a broader range of activator compounds than could metallocene components comprising unsubstituted cydopentadienyl radicals. As the amount and size of the substitutions on the cydopentadienyl radicals are reduced however, more effective catalysts are obtained with activator compounds containing anions which are more resistant to degradation, such as those with substituents on the ortho positions of the phenyl rings. Another means of rendering the anion more resistant to degradation 1s afforded by fluorine substitution, especially perfluoro-substUutlon, in the anion. Fluoro-substituted stabilizing anions may, then, be used with a broader range of metal compound (first components). Activators in which the anions comprise pentafluorophenyl groups are preferred for preparing ion-pa1r metallocene catalysts of this invention.

It i s preferred that the mol e ratio of metal locene component to activator component be 1 : 1 or greater. In a reaction correspondi ng to general formula 1 , when the anion compri ses pentafluorophenyl groups , two structural ly di sti nct forms of thermal ly stabl e ioni c catalysts have been identi fi ed by NMR spectroscopy and are shown 1n general formulae 5 and 6, using tetrak1s(pentaf1uorophenyl )boron as a representative anion:

11. [(A-Cp)MX _j (L ^, )3 tB(C _$ F _& ) ₄ 3 12. [{(A-Cp)MX _ι ) ₂ (μ-X ₁ )3 CB(C _$ F _| ) ₄ 3

In the foregoing formulae, the symbols A-Cp, M, L', and X, correspond to the definitions set forth in general formulae 1-4. The symbol "Y" indicates the Hgand X ¹ bridges the two metal centers. In both general formulae 5 and 6, NMR experiments indicate that the fluorinated boron anion is completely non-coordinating. When the molar ratio of metallocene component to activator component Is 1:1, L' weakly coordinates to an stabilizes the metallocene cation when L* is an aniline derivative, for example N,N-dimethylan1line, to give an ionic catalyst of general formula 5. When the molar ratio of metallocene component to activator component 1s greater than 1:1 an X group, for examples, a methyl group of an excess (A-Cp)M(CH ₃ ) ₂ molecule when (A-Cp)M(CH ₂ ) ₂ 1s the metallocene used, weakly coordinates to and stabilizes the metallocene cation to give an Ionic catalyst of general formula 6.

B. Catalyst Preparation The supported catalyst of this invention can be prepared by combining the metallocene, activator components and support in one or more suitable solvents or diluent. Suitable solvents and/or diluents Include, but are not necessarily limited to, straight and branched-chaln hydrocarbons such as Isobutane, butane, pentane, hexane, heptane, octane and the like; cyclic and alleyeHe hydrocarbons such as cyclohexaπe, cycloheptane, methyleyelohexane, methylcycloheptane and the like; and aromatic and

1 alkyl-substituted aromatic compounds such as benzene, toluene, xylene and the Hke. It 1s preferred that the catalyst components be handled in an inert, moisture-free, oxygen-free environment such as argon, nitrogen or helium because of the sensitivity of the catalyst components to moisture and oxygen. In a preferred method, the metallocene and activator components are combined In a first step 1n an aromatic solvent to produce a solution the reaction product. This reaction may be carried

10 out in the temperature range -100 ^* to about 300*C, preferably about 0*

11 to about 100*C. Holding times to allow for the completion of the

12 reaction may range from about 10 seconds to about 60 minutes depending

13 upon variables such as reaction temperature and choice of reactants.

14 The solution produced by combining the metallocene and

15 activator components is then contacted with the support. The method

16 of contact may vary, but it 1s preferred that the solution be added to

17 a rapidly stirred slurry of the catalyst support in a hydrocarbon

18 solvent, preferably an aliphatic solvent and especially pentane.

19 In another preferred method, 1n a first step, the activator

20 component 1s dissolved 1n an aromatic solvent with the support to

21 produce a supported activator component. This reaction 1s carried out

22 at a temperature sufficient to produce a homogeneous solution of the

23 activator component, preferably between about 25*C to about 200*C.

24 The aromatic solvent is then removed to leave a free-flowing supported

25 material. The supported material is then contacted with the

26 metallocene component, preferably In an aliphatic solvent to produce

27 the supported catalyst.

28 Regardless of the method, the active supported catalyst can

29 be recovered by evaporation of the solvent to obtain a free-flowing

30 solid or alternatively, the active supported catalyst can be

31 maintained 1n its slurry state for direct use.

32 Contact temperatures may range from about 0 ^* to about lOO'C

33 depending upon the solvents used. Contact times may vary from about

34 10 seconds to about 60 minutes, longer contact times than 60 minutes

35 not providing any significant additional benefits.

In the preparation of the supported catalyst, the reagents should be combined to provide a catalyst concentration (metallocene and activator) on the support of from about 0.01 wt X to about 20 wt X, preferably about 1 wt X to about 5 wt X based upon the weight of the support. In a most preferred embodiment of the present invention, b1s(cyclopentadienyl)zircon1um dimethyl or b1s(cyclopentad1enyl)hafnium dimethyl will be reacted with N, N-di methyl ani 11 ni urn tetra(pentafluorophenyl)boron and then contacted with an alumina, silica or silica-alumina support to produce the most preferred catalyst of the present Invention. The metallocene and activator components will be combined at a temperature within the range -100 ^* to about 300 ^* C, preferably from about O'C to about ICO'C, and preferably 1n an aromatic hydrocarbon solvent, most preferably toluene. A nominal holding time within the range from about 10 seconds to about 60 minutes will be sufficient before the mixture 1s contacted with a slurry of the dried support material In an aliphatic solvent for a contacting period of from about 10 seconds to about 60 minutes. In another preferred method, 1n a first step, N,N-dimethylan1l1nium tetra(pentafluorophenyl)boron Is dissolved in an aromatic solvent maintained at a temperature sufficient to dissolve the activator component. The support is slurried therein and the activator and support are reacted for about 1 minute to about 1 hour to produce a supported activator component. The aromatic solvent 1s removed to leave a free-flowing support material containing the activator component. This supported activator component Is then contacted with b1s(cyclopentadieny1)z1rcon1um dimethyl or bis(cydopentad1enyl)hafn1um dimethyl, preferably in an aliphatic solvent to produce the supported catalyst. With either method, the active supported catalyst can be recovered by evaporation of the solvent to obtain a free-flowing solid or, alternately, the active supported catalyst can be maintained 1n a slurry state for direct use.

C. Catalyst Use The supported Ionic metallocene catalyst may be used to

polymerize α-olef1ns and acetylenically unsaturated monomers having from 2 to about 18 carbon atoms and/or dlolefins having from 4 to about 18 carbon atoms either alone or 1n combination. The catalyst may also be used to polymerize o-olef1ns, dlolefins, strained cyclic olefins and/or acetylenically unsaturated monomers 1n combination with other unsaturated monomers. While the catalyst 1s active for this broad range of oleflnlc monomer feedstock, o-olef1n polymerization 1s preferred especially the homopolymerlzation of ethylene or the copolymerlzatlon of ethylene with olefins having from 3 to 10 carbon atoms. In a preferred embodiment of the present Invention, the metallocene component will be a b1s(cyclopentadienyl)-Group IV-8 metal compound containing two, Independently, substituted or unsubstituted cydopentadienyl radicals and one or two lower alkyl substituents and/or one or two hydride substituents and the activator component will be a trl-substituted ammonium salt of a fluorlnated tetraphenyl boron anion. Each of the tr1-subst1tut1ons in the ammonium cation will be the same or a different lower alkyl or aryl radical. By lower alkyl 1s meant an alkyl radical containing from 1 to 4 carbon atoms. N,N-dimethylan1Hn1um tetra(pentafluorophenyl)boron 1s particularly preferred. Alumina, silica or slHca-alumina will be the preferred support for producing the supported ionic metallocene catalyst. Certain of the catalysts of this Invention, particularly those based on hafnocenes - using the catalyst produced from the reaction of b1s(cyclopentadienyl)hafnium dimethyl and the trl-substituted ammonium salt of tetra(pentafluorophenyl)boron as an example - when used as described herein for the polymerization and copolymerlzatlon of α-olef1ns, dlolefins, and/or acetylenically unsaturated monomers, 1n the absence of a chain transfer agent, can lead to the production of extremely high molecular weight polymers and copolymers having relatively narrow molecular weight distributions. In this regard, 1t should be noted that homopolymers and copolymers having molecular weights up to about 2 x 10* or higher and molecular weight distributions within the range of about 1.5 to about 3 or greater can be produced with the catalysts of this Invention.

Combinations of two or more ionic metallocene catalyst with the support can be employed in order to obtain broader MWD such as up to about 15 or greater. Alternatively, two or more separately supported catalysts can be used to obtain broad MWD polymers and copolymers. Supported catalysts of this invention containing a metallocene component which 1s either a pure enantlomer or the race ic mixture of two enantiomers of a rigid, chlral metallocene can polymerize prochiral olefins (propylene and higher α-olefins) to crystalline polymers Including syndiotactic and 1sotact1c polymers. Bis(cyc1opentadienyl)metal compounds 1n which each of the cydopentadienyl radicals Is substituted and containing a covalent bridging group between the two cydopentadienyl radicals are particularly useful for 1sotact1c polymerizations of this type. Prochiral metallocenes, for example those based on complexes of propy1-2-cyclopentad1enyl-2-(l-fluorenyl) hafnium, can be used to polymerize propylene or higher α-olef1ns to syndiotactic polymers. The supported catalysts may be most usefully employed In gas or slurry phase processes, both of which are known to those of skill in the art. Thus, polymerizations using the Invention supported catalysts may be conducted by either of these processes, generally at a temperature In the range of about 0*-160*C or even higher, and under atmospheric, subatmospheric, or superatmospheric pressure conditions. A slurry polymerization process can utilize sub- or super-atmospheric pressures and temperatures In the range of -80-25O C. In a slurry polymerization, a suspension of solid, particulate polymer is formed In a liquid polymerization medium to which ethylene, α-olefin, d1olefin, cyclic olefin or acetylenically unsaturated comonomer, hydrogen and catalyst are added. Alkanes and cycloalkanes, such as butane, pentane, hexane, or cyclohexane, are preferred with C ₄ to C alkanes especially preferred. Preferred solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3-methyl-l-pentene, 4-methyl-l-pentene, l,4-hexad1ene, 1-octene, 1-decene and the like. A gas-phase polymerization process utilizes superatmospheric

pressure and temperatures 1n the range of about 50* - 120*C. Gas-phase polymerization can be performed 1n a stirred or fluldized bed of catalyst and product particles in a pressure vessel adapted to permit the separation of product particles from unreacted gases. Thermostated ethylene, comonomer, hydrogen and an Inert diluent gas such as nitrogen can be introduced or recirculated so as to maintain the particles at a temperature of 50 ^* - 120'C. Polymer product can be withdrawn continuously or semi-contlnuously at a rate such as to maintain a constant product Inventory in the reactor. After polymerization and deactlvation of the catalyst, the product polymer can be recovered by any suitable means. In commercial practice, the polymer product can be recovered directly from the gas phase reactor, freed of residual monomer with a nitrogen purge, and used without further deactlvation or catalyst removal. The polymer obtained can be extruded into water and cut into pellets or other suitable comminuted shapes. Pigments, antloxldants and other additives, as 1s known 1n the art, may be added to the polymer. While 1t Is a characteristic of the Invention supported catalyst that the produced polymers have a narrow molecular weight distribution, broad molecular weight distribution polymers may be produced by using two or more metallocenes or two or more activators. The advantages of the Instant invention will be more readily appreciated by reference to the following Illustrative, non-Hmlting examples.

E am le 1 A supported catalyst was prepared by reacting bis(cyclopentad1enyl)hafnium dimethyl (30 g) with N,N-d1methylan1lin1um tetrak1s(pentaf1uorophenyl)boron (60 mg) in toluene (8 ml). This solution was added slowly to a suspension of basic alumina (Brock an Activity I, dried overnight at 100 ^# C under vacuum; 2.0 g) in pentane (25 ml). The mixture was allowed to stir for about 3 minutes at room temperature. The supernatant solution was then decanted from the solid material and the solids reslurrled with fresh pentane. The supernatant solution was again decanted from the

solids and the solids suspended in fresh pentane (ca. 30 ml). This suspension was transferred, under nitrogen, by means of a double-ended needle Into a 1 Hter stainless-steel autoclave containing 400 ml of dry, deoxygenated hexane and which had been previously flushed with nitrogen. The autoclave was then pressured to 90 pslg with ethylene and stirred at 40*C. After 30 minutes, the autoclave was cooled, vented and the contents separated by filtration. The yield of linear granular, free-flowing polyethylene was 11.2 g. The polymer had a weight-average molecular weight of 594,000 and a molecular weight distribution of 2.15.

Example 2 The supported catalyst of Example 1 was used to polymerize ethylene in a process similar to that of Example 1 except that the autoclave was pressured to 300 psig of ethylene. The yield of linear granular, free-flowing polyethylene was 48.5 g with a bulk density of 0.17 g/cc versus 0.07 g/cc when an unsupported, homogeneous catalyst 1s used.

Example 3 A supported catalyst was prepared by reacting b1s(cyclopentadienyl)zircon1um dimethyl (20 mg) with N,N-d1methylan1l1n1um tetrak1s(pentafluorophenyl)boron (60 mg) 1n toluene (20 ml). This solution was added slowly to a suspension of basic alumina (2.0 g) in pentane (25 ml). The mixture was allowed to stir for about 3 minutes at room temperature. The supernatant solution was decanted from the solid material and the solids reslurried with fresh pentane. The supernatant solution was again decanted from the solids and the solids were suspended in fresh pentane (ca.30 ml). This suspension was transferred, under nitrogen, by means of a double-ended needle Into a 1 Hter stainless-steel autoclave, previously flushed with nitrogen, containing 400 ml of dry, deoxygenated hexane. The autoclave was then pressured to 400 psig with ethylene and stirred at 40 ^* C. After 30 minutes, the autoclave was cooled and vented and the contents isolated by filtration. The

1 yi eld of l i near granul ar , free-flowi ng polyethyl ene was 4.7 g wi th a wei ght-average mol ecular wei ght of 515 ,000 and a MWD of 1 .74.

xample 4

4 A supported catalyst was prepared as in Example 1 except that

5 2.0 g of Davlson 948 s1Hca (dried at 800*C with a nitrogen purge) was

6 used In place of alumina. The catalyst was used to polymerize

7 ethylene in a process similar to that of Example 2. The yield of

8 linear granular, free-flowing polyethylene was 11.1 g with a

9 weight-average molecular weight of 1,384,000 and a MWD of 1.67.

Example 5

10 A supported catalyst was prepared as i n Exampl e 4 except that

11 20 mg of b1 s(cydopentadi enyl )z1 rconi urn dimethyl was used 1n place of

12 b1 s(cyclopentadi enyl )hafn1 um dimethyl . Thi s catalyst was used to

13 polymeri ze ethyl ene 1 n a process simi lar to that of Exampl e 2. The

14 yi eld of l i near granul ar , free-flowi ng polyethyl ene formed was 2.7 g

15 wi th a weight-average mol ecular weight of 759,000 and a MWD of 1 .67.

Exampl e 6

16 A supported catalyst was prepared by reacting

17 b1s(cyclopentad1enyl)hafnium dimethyl (45 mg) with

18 N, -d1methylanl11niurn tetrak1s(pentafluorophenyDboron (90 mg) in

19 toluene (20 ml). This solution was added slowly to a suspension of

20 basic alumina (3.0 g) In pentane (25 ml). The mixture was allowed to

21 stir for about 3 minutes at room temperature. The solution was

22 decanted from the solid material and the solids reslurrled with fresh

23 pentane. The supernatant solution was again decanted from the solids

24 and the solids were dried In an atmosphere of nitrogen. This

25 suspension was Injected Into a 1 Hter stainless-steel autoclave,

26 previously flushed with nitrogen, containing 300 ml of propylene, by

27 washing 50 ml of propylene through a stainless-steel catalyst addition

28 tube containing the solid catalyst. The autoclave was then pressured

29 to 100 psig with ethylene and stirred at 50*C. After 15 minutes, the

30 autoclave was cooled and vented and the polymer product was isolated.

The yield of granular ethyl ene-propylene copolymer was 38 g. This polymer, which contained 21 wt. X ethylene, had a weight-average molecular weight of 423,000 and a molecular weight distribution of 2.88.

Example 7 Ethylene and propylene was copolymerlzed 1n a manner similar to Example 6, with the exceptions that the ethylene pressure was Increased to 200 psig and the autoclave was heated to 45*C. The yield of granular ethyl ene-propylene copolymer was 57.1 g. This polymer, which contained 52 wt. X ethylene, had a weight-average molecular weight of 1,006,000 and a molecular weight distribution of 2.01.

Example 8 A supported catalyst of this Invention was prepared by reacting rac-dimethyls1lylbis(1ndenyl)hafn1um dimethyl (29 mg) with N.N-dimethylaniHnium tetrak1s(pentafluorophenyl)boron (45 mg) In toluene (10 ml). This solution was added slowly to a suspension of basic alumina (1.5 g) 1n pentane (25 ml). The mixture was allowed to stir for about 3 minutes at room temperature. The supernatant solution was decanted from the solid material and the sol Ids reslurried with fresh pentane. The supernatant solution was again decanted from the solids and the solids were suspended 1n fresh pentane (ca. 30 ml). This suspension was transferred under nitrogen, by means of double-ended needle Into a I liter stainless-steel autoclave, previously flushed with nitrogen, containing 400 ml of dry, deoxygenated hexane. Propylene (200 ml) was added to the autoclave, which was stirred at 50*C. After 1.75 hours, the autoclave was cooled and vented and the contents separated by filtration. The yield of Isotactlc polypropylene was 9.5 g. This polymer had a melting point of 127*C, as determined by differential scanning calorimetry, a weight average molecular weight of 181,000 and a molecular weight distribution of 1.95. Analysis by C-13 NMR spectroscopy indicated that the polypropylene was 92X isotactlc.

Example 9

1 A 1 liter stainless-steel autoclave was charged with virgin

2 polypropylene (14 mesh, 190 g) and heated to 85'C under a dynamic

3 nitrogen purge. After cooling to 50'C, the catalyst of Example 1 <2.0

4 g) was added to the reactor from a stainless-steel catalyst addition

5 tube using high-pressure nitrogen. After venting off the excess

6 nitrogen pressure, ethylene was admitted to the stirred polymer bed to

7 maintain a constant flow. The pressure Inside the autoclave ranged

8 from 10 to 35 psig. The maximum temperature 1n the autoclave reached

9 70*C. After 1 hour, the autoclave was cooled and vented and the

10 polymer mixture isolated. The net Increase 1n the polymer weight was

11 38 g. A portion of the polyethylene was sieved from the polypropylene

12 stirring aid and was found to have a weight-average molecular weight

13 of 175,000 and a MWD of 2.53.

Example 10

14 Al umi na ( 1 .0 g) , sl urried 1n 10 ml of pentane, was treated

15 for 15 minutes wi th 1 ml of a 1 M solution of tr1 ethyl alumi num 1n

16 hexane. The support was separated from the l iquid by decantatlon,

17 washed twice wi th 10 ml of pentane and dri ed in vacuo.

18 N,N-d1methylan1 l in1um tetrakl s (pentafl uorophenyl ) boron (30

19 mg) was heated i n toluene (25 ml ) to produce a homogeneous sol ution.

20 The warm solution was added dropwl se to the support prepared as

21 descri bed above. The solvent was removed 1n vacuo to leave a

22 free-flowing supported material .

23 Thi s support material (1.0 g) was slurried In 10 ml of

24 pentane. To this was added dropwlse 5 ml of a pentane solution

25 containing bls(cyclopentadienyl ) hafnium dimethyl (15 mg) . After

26 sti rri ng at room temperature for 15 minutes , the solvent was removed

27 1n vacuo to leave a free-flowing supported catalyst.

Example 11 8 500 mg. of the supported catalyst of Example 10 was used to 9 polymerize ethylene in a process similar to Example 1 except that the 0 autoclave was pressured to 400 psig with ethylene and was heated to

80 ^# C. The yi eld of l i near granular, free-flowi ng polyethyl ene was 132 g *

Al though the invention has been described wi th reference to I ts preferred embodiments , those of ordi nary ski l l i n the art may, upon reading thi s di sclosure , appreciate changes and modi fications whi ch do not depart from the scope and spi ri t of the I nvention as described above or claimed hereafter.

Example 12

Davison 952 silica (1 g) was slurried in pentane and treated with 1 ml of a 1 solution of triethylaluminum ^ in hexane. The support was separated from the liquid by 1 decantation, washed twice with pentane and dried in vacuo.

² N,N-dimethylanilinium tetra is ³ (pentafluorophenyl)boron (30 mg) was heated in toluene to produce a homogeneous solution. The warm solution was added ⁵ dropwise to the support prepared as described above. The solvent was removed in vacuo to leave a free-flowing supported material.

^ This support material was slurried in 10 ml of ⁹ pentane. To this was added dropwise 10 ml of a pentane 0 solution containing 15 mg of rac- 1 dimethylsilylbis(tetrahydroindenyl) - zirconium dimethyl. 2 After stirring at room temperature for 15 minutes, the 3 solvent was removed in vacuo to leave a free-flowing 4 supported catalyst.

Example 13

1 The catalyst of Example 12 (887 mg) was injected

2 by means of high-pressure nitrogen into a 1 liter stainless-

3 steel autoclave, which was previously flushed with nitrogen,

4 containing 300 ml dry, deoxygenated propylene at 40 degrees

5 c. After 20 minutes, the contents isolated the yield of

⁶ isotactic polypropylene was 101.7 g.

Example 14

7 Davison 948 silica (3 g) , dehydrated at 800

° degrees with an nitrogen purge was slurried in pentane and

⁹ treated with 8 ml of a 1.5 M solution of triethylaluminum in 0 hexane. The support was separated from the liquid by 1 decantation, washed six times with pentane, and dried in 2 vacuo.

3 N,N-dimethylanilinium

14 tetrakis(pentafluorophenyl)baron (96 mg) was heated in 30 ml

15 warm toluene, to produce a homogeneous solution. The warm ° solution was added dropwise to a toluene slurry of the 7 support prepared as described above. The solvent was 8 removed in vacuo with gentle heating to leave a free-flowing 9 supported material. ₀

^•w This supported material was reslumed in pentane. 1 To this was added dropwise 20 ml of a pentane solution

22 containing 48 mg of bis(cydopentadienyl)hafnium dimethyl.

23 After stirring at room temperature for 15 minutes, the

24 solvent was removed in vacuo to leave a free-flowing 5 supported catalyst.

Example 15

The catalyst of Example 14 (100 mg) was injected with 100 ml hexane into a 1 liter stainless-steel autoclave, which was previously flushed with nitrogen, containing 300 ml of dry, deoxygenated hexane and pressurized with 200 psi ethylene at 60 degrees C. After 20 minutes the autoclave was cooled and vented and the contents isolated by filtration. The yield of linear polyethylene was 78.7 g.