Process for olefin polymerization

A PROCESS FOR OLEFIN POLYMERIZATION bw *pbnn 1

The present invention relates to a process for olefin polymerization and to the use of a Group IV B transition metal compound in said process.

The present specification is divided from Israel Specification No. 95549, filed August 31, 1990. In order that the invention may be better understood and appreciated, description from Israel Specification No. 95549 is included herein, it being understood that this is for background purposes only, the subject matter of Israel Specification No. 95549 being specifically disclaimed and not forming a part of the present invention.

Background of the Invention

As is well known, various processes and catalysts exist for the homopolymerization or copolymerization of olefins. For many applications, it is of primary importance for a polyolefin to have a high average molecular ' weight, while having a relatively narrow molecular weight distribution. A high average molecular weight, when accompanied by a narrow molecular weight distribution, provides a polyolefin or an ethylene-a-olefin copolymer with high strength properties.

Traditional Ziegler-Natta catalyst systems (a transition metal compound cocatalyzed by an aluminum alkyl) are capable of producing polyolefins having a high molecular weight but a broad molecular weight distribution.

More recently, a catalyst system has been developed wherein the transition metal compound has two or more cyclopentadienyl ring ligands, such transition metal compound being referred to as a "metallocene," which catalyzes the production of olefin monomers to polyolefins. Accordingly, metallocene compounds of the Group IV B metals, particularly titanocene and zirconocene, have been utilized as the transition metal component in such metallocene-containing catalyst system for the production of polyolefins and ethylene-a-olefm copolymers. When such metallocenes are cocatalyzed with an aluminum alkyl, as is the case with a traditional type Ziegler-Natta catalyst system, the catalytic activity of such metallocene catalyst system is generally too low to be of any commercial interest.

It has since become known that such metallocenes may be cocatalyzed with an alumoxane rather than an aluminum alkyl, to provide a metallocene catalyst system of liigh activity which catalyzes the production of polyolefins. A wide variety of Group IV B transition metal compounds of the metallocene type have been named as possible candidates for an alumoxane cocatalyzed catalyst system. Hence, although bis(cyclopentadienyl)' Group IV B transition metal compounds have been the most preferred and heavily investigated type of metallocenes for use in metallocene/alumoxane catalysts for polyolefin production, suggestions have appeared that mono- and tris(cyclopentadienyl) transition metal compounds may also be useful. See, for example, U.S. Patents Nos. 4,522,982; 4,530,914 and 4,701,431. Such mono(cyclopentadienyl) transition metal compounds as have heretofore been suggested as candidates for a metallocene/alumoxane catalyst are mono(cyclopentadienyl) transition metal trihalides and trialkyls.

More recently, International Publication WO 87/03887 has appeared, which describes the use of a composition comprising a transition metal coordinated to at least one cyclopentadienyl and at least one heteroatom ligand as a metallocene type component for use in a metallocene/alumoxane catalyst system for α-olefm polymerization. The composition is broadly defined as a transition metal, preferably of Group IV B of the Periodic Table, which is «coordinated with at least one cyclopentadienyl ligand and one to three heteroatom ligands, the balance of the coordination requirement being satisfied with cyclopentadienyl or hydrocarbyl ligands. The metallocene/alumoxane catalyst system described in illustrated solely with reference to transition metal compounds, which are bis(cyclopentadienyl) Group IV B transition metal compounds.

Even more recently, at the Third Chemical Congress of North America, held in Toronto, Ontario, Canada in June 1988, John Bercaw reported upon efforts to use a compound of a Group III B transition metal coordinated to a single cyclopentadienyl heteroatom bridged ligand as a catalyst system for the polymerization of olefins. Although some catalytic activity was observed under the conditions employed, the degree of activity and the properties observed in the resulting polymer product were discouraging of a belief that such a transition metal compound could be usefully employed for commercial polymerization processes. A need still exists for discovering catalyst systems that permit the production of higher molecular weight polyolefins and desirably with a narrow molecular weight distribution.

In Israel Specification No. 95549, there is described and claimed a compound of the general formula: 4 (CsH^xRx)

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Β wherein: M is Zr, Hf or Ti; (C5H4-xRx) is a cyclopentadienyl ring which is substituted with up to five c » groups R; x is 1, 2, 3, or 4, denoting the degree of substitution, and each substituent group R is, independently, a radical selected from the group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen atom, C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group IV A of the Periodic Table of Elements, and halogen radicals; or (CsEh-xRx) is a cyclopentadienyl ring in which two adjacent R-groups are joined from C4-C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; each R' is, independently, a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and z is the coordination number of the element J; each Q or Q' is, independently, any univalent anionic ligand, or Q and Q' are a divalent anionic chelating agent; M' has the same meaning as M; B is a covalent bridging group containing a Group IV A or V A element; and L is a Lewis base, where w denotes a number from 0 to 3, but excluding compounds of the general formula:

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wherein: M has the same meaning as above; R" is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl and combinations thereof having up to ten carbon atoms; X is independently selected from halo, alkyl, aryl, aryloxy or alkoxy of up to ten carbons, n being 1 or 2, depending on the valence of M; and ‘. I -, Y is nitrogen.

Said specification also claims a catalyst system for olefin polymerization, comprising said compound and a process for preparing an olefin polymer using said catalyst system.

According to the present invention, there is now provided a process for olefin polymerization, comprising polymerizing ethylene and a monomer selected from C3-C20 α-olefm or a C5-C20 diolefin excluding 1-hexene, 4-methyl-1-pentene and vinyl aromatic monomer in the presence of a catalyst system comprising: (A) a compound of the general formula:

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(«' x-l-y’ or «=5η5.,Λ&gt; q /\ /

. M \/l \ ^z.l./ σ ff v.· I's'Vy./x’ wherein: M is Zr, Hf or Ti; (CsHs-y-xRx) is a cyclopentadidnyl ring which is substituted with from zero to five groups R; x is 1, 2, 3, 4 or 5, denoting the degree of substitution, and each R is, independently, a radical selected from the group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group IV A of the Periodic Table of Elements, and halogen radicals; (JR'z-i-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements; 119,415/2

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each R' is, independently, a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and z is the coordination number of the element J; each Q or Q' is, independently, halogen, hydride or a substituted or unsubstituted C1-C20 hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphide, provided that where Q or Q’ is a hydrocarbyl, such Q or Q’ is different from (CsHs-y-xRx) , or both Q and Q' together are an alkylidene or cyclometallated hydrocarbyl, and M' has the same meaning as M; y is 0 or 1 when w is greater than 0; y is 1 when w is 0; when y is 1, B is a covalent bridging group containing a Group IV A or V A element; and L is a neutral Lewis base, where w denotes a number from 0 to 3, and (B) an alumoxane. with the exclusions of: i) polymerizing ethylene and vinyl aromatic monomer; and ii) where the compound (A) is (N-t-butylamino)(dimethyl)(n5-2,3,4,5-tetramethylcyclopentadienyl)silane zirconium dichloride, polymerizing ethylene and 1-hexene or 4-methyl-l-pentene.

In preferred embodiments of the present invention, said α-olefm is 1-butene or 1-octene.

The present invention is also directed to the use of a compound of the general formula:

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B or

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B s

Q σ

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y

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wherein: M is Zr, Hf or Ti; (CsHs-y-xRx) is a cyclopentadienyl ring which is substituted with from zero to five groups R; x is 1, 2, 3, 4 or 5, denoting the degree of substitution, and each R is, independently, a radical selected from the group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group IV A of the Periodic Table of Elements, and halogen radicals; (JR'z-i-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements; each R' is, independently, a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and z is the coordination number of the element J; each Q or Q' is, independently, halogen, hydride or a substituted or unsubstituted C1-C20 hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphide, provided that where Q or Q' is a hydrocarbyl, such Q or Q' is different from (CsHs-y-xRx) , or both Q and Q' together are an alkylidene or cyclometallated hydrocarbyl, and M' has the same meaning as M; y is 0 or 1 when w is greater than 0; y is 1 when w is 0; when y is 1, B is a covalent bridging group containing a Group IV A or V A element; and L is a neutral Lewis base, where w denotes a number from 0 to 3, 9 119,415/2 (B) an alumoxane. with the exclusions of: i) polymerizing ethylene and vinyl aromatic monomer; and ii) where the compound (A) is (N-t-butylamino)(dimethyl)(n5-2,3,4,5-tetramethylcyclopentadienyl)silane zirconium dichloride, polymerizing ethylene and 1-hexene or 4-methyl-l-pentene.

The alumoxane component of the catalyst system may be represented 5 an Integer ranging from 1 to about 50 and preferably is from about 13 to about 25.

Catalyst systems of the Invention may be prepared by placing the "Group IV B transition metal component" and the alumoxane component 1n common solution in a normally liquid alkane 10 or aromatic solvent, which solvent is preferably suitable for use as a polymerization diluent for the liquid phase polymerization of an olefin monomer. A typical polymerization process of the invention such as for the polymerization or copolymerization of olefins comprises the 15 steps of contacting ethylene or β-oleflns alone or with other unsaturated monomers Including e-olefins, C5-C20 diolefins, and/or acetylenically unsaturated monomers either alone or in combination with other olefins and/or other unsaturated monomers, 20 with a catalyst comprising, in a suitable polymerization diluent, the Group IV B transition metal component illustrated above; and a methylalumoxane in an amount to provide a molar aluminum to transition metal ratio of from about 1:1 to about 20,000:1 or more; and reacting such monomer in the presence of such catalyst system at 25 a temperature of from about -100"C to about 300"C for a time of from about 1 second to about 10 hours to produce a 10 polyolefin having a weight average molecular weight of from about 1,000 or less to about 5,000,000 or more and a molecular weight distribution of from about 1.5 to about 15.0.

Lower molecular weight species may be produced 5 by using catalyst species of reduced activity; higher temperatures and/or the use of transfer ; agents such as hydrogen.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Catalyst Component 0 The Group IV B transition metal component of the catalyst system Is represented by the general formula:

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wherein: M 1s Zr, Hf or T1 and 1s 1n Its highest formal oxidation state (+4, d° complex); ^5Η5-γ-χ^χ) 4 cyclopentadlenyl ring which is 15 substituted with from zero to five substituent groups R, "x" 1s 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R 1s, Independently, a radical selected from a group consisting of hydrocarbyl radicals, substituted C^-C^q hydrocarbyl radicals wherein one or more hydrogen atoms 20 1s replaced by a halogen atom, C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid 1s selected from the Group IV A of the Periodic Table of Elements, and halogen radicals or iC5H5-y-xV 1s a cycloPentadlenyl ring 1n which two adjacent R-groups are joined forming C4-C20 ring to give a saturated or 25 unsaturated polycyclic cyclopentadlenyl ligand such as Indenyl, tetrahydrolndenyl, fluorenyl or octahydrofluorenyl; 11 (0R'z_l y) 1$ a heteroatoa ligand 1n which J 1s an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen 5 or sulfur with nitrogen being preferred, and each R* Is, Independently a radical selected from a group consisting of Ci-C20 hydrocarbyl radicals, substituted C^-Cjq hydrocarbyl radicals wherein one or more hydrogen atoms Is replaced by a halogen atom, and "z" 1s the coordination number of the element J; 10 each Q 1s, Independently any univalent anionic ligand such as halogen, hydride, or substituted or unsubstituted Cj-C2q hydrocarbyl, alkoxide, aryloxlde, amide, arylamlde, phosphide or aryl phosphide, provided that where any Q Is a hydrocarbyl such Q 1s different from (C5Hg_y_xRx), or both Q together may be be an 15 alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating Hgand; "y" Is 0 or 1 when w Is greater than 0, and y Is 1 when w-0; when ”y" 1s 1, B 1s a covalent bridging group containing a ' Group IV A or V A element such as, but not limited to, a d1alkyl, 20' alkylaryl or diaryl silicon or germanium radical, alkyl.or aryl ,--- phosphine or amine radical, or a hydrocarbyl radical such as methylene, ethylene and the like. L Is defined as heretofore. Examples of the B group which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system 25 are Identified 1n Column 1 of Table 1 under the heading "B".

Exemplary hydrocarbyl radicals for the Q are methyl, ethyl, propyl, butyl, amyl. Isoamyl, hexyl, Isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl and the like, with methyl being preferred. Exemplary halogen atoms for Q Include 30 chlorine, bromine, fluorine and Iodine, with chlorine being preferred. Exemplary alkoxides and aryloxldes for Q are methoxide, phenoxlde and substituted phenoxldes such as 4-methy1phenox1de. Exemplary amides for Q are dimethyl amide, diethylamide, methyl ethyl amide, d1-i-buty1 amide, d1 Isopropyl amide and the like. Exemplary aryl amides are diphenylamide and any other spbstltuted 12 phenyl amides. Exemplary phosphides for Q are diphenyl phosphide, d1cyclohexyl phosphide, di ethyl phosphide, dimethyl phosphide and the like. Exemplary alkyl diene radicals for both Q together are methylIdene, ethyl1dene and propylIdene. Examples of the Q group 5 which are suitable as a constituent group or element of the Group IV B transition metal component of the catalyst system are Identified In Column 4 of Table 1 under the heading "Q".

Suitable hydrocarbyl and substituted hydrocarbyl radicals, which may be substituted as an R group for at least one hydrogen 10 atom 1n the cyclopentadienyl ring, 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, alkyl-substituted aromatic radicals and cyclopentadienyl rings containing 1 or more fused saturated or 15 unsaturated rings. Suitable organometallic radicals, which may be substituted as an R group for at least one hydrogen atom 1n the cyclopentadienyl ring, Include trimethyl silyl, tr1ethyl silyl, ethyldimethyls1lyl, methyl diethyl silyl, tr1phenylgermyl, tr1methylgermyl and the like. Examples of cyclopentadienyl ring 20'groups (C5H52y_xRx) which are suitable as a constituent group of the Group/IV B transition metal component of the catalyst system are Identified 1n Column 2 of Table 1 under the heading ^5^5-y—M^x^ *

Suitable hydrocarbyl and substituted hydrocarbyl radicals, 25 which may be substituted as an R1 group for at least one hydrogen atom 1n the heteroatom J ligand group, 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 30 radicals. Examples of heteroatom ligand groups which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are Identified 1n Column 3 of Table 1 under the heading

Table 1 depicts representative constituent mole,ties for 3 5 the "Group IV B transition metal component", the 11st Is for Illustrative purposes only and should not be construed to be 13 limiting 1n any way. A number of final components may be formed by permuting all possible combinations of the constituent moieties with each other. Illustrative compounds are: dimethylsllyltetra- methylcyclopentadlenv1-tert-butylamido zirconium dlchlorlde, . 5 dimethyls 11 vi tetramethylcvclooentadlenvl-tert-hutvl ami do hafnium dlchlorlde, d1methyls1lyl-tert-butvlcyclopentadleny1-tert-buty1-amido zirconium dlchlorlde, dimethyl silyl-tert-butvlcyclopenta-dlenyl-ifiit-butylamido hafnium dlchlorlde, dimethylsllyltrlmethyl-s11vieye1ooentadlenvi-tert-butylamido zirconium dlchlorlde, 10 d1methy1s11y1tetramethylcyclopentad1enylpheny1am1do zirconium d1chior1de, d1methyls11yltetramethylcycl opentadlenylphenyl ami do hafnium di chi or1de, methyl phenyls1lyltetramethylcyclopentadlenyl-tert-butyl ami do zirconium dlchlorlde, methyl phenyls1lyltetramethyl cyclopentadlenyl-tert-butvlamido hafnium dlchlorlde, 15 methylpheny1s11y1 tetramethyl eye1opentadlenyl-tert-butvlami do hafnium dimethyl, d1methyls11y1tetramethy1cyclopentad1eny1-p-n-butylphenyl amido zirconium dlchlorlde, d1raethyls1lyltetramethy1-cydopentadienyl-p-n-butyl phenyl ami do hafnium dlchlorlde. For Illustrative purposes, the; above compounds and those permuted from 20 Table 1 does not Include the Lewis base ligand (L). The conditions under which complexes containing Lewis base ligands such as ether or those which form dimers Is determined by the steric bulk of the ligands about the metal center. For example, the t-butyl group 1n Me2S1(He4C5)(N-t-Bu)ZrCl2 has greater steric requirements 25 than the phenyl group In He2S1(Me4C5)(NPh)ZrCl2*Et20 thereby not permitting ether coordination in the former compound. Similarly, due to the decreased steric bulk of the trimethyl silylcyclopentadlenyl group 1n [Me2S1(Me3S1C5H3)(N-i-Bu)ZrCl2]2 versus that of the 30 tetramethylcyclopentadlenyl group In He2S1(Me^Cg)(N-i-Bu)-ZrC12, the former compound Is dimeric and the latter is not.

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Β («Βη y · 1)

“A ·&gt; SSvSiiyl-

Abqrlailyl a yiayylailyl laaysayylallyl -arba&amp;amp;ylallyl &lt;-b«tylaUyl baBjIailyl Jylybaoylsllyl vl—tbylallyl 4«a—lailyl (y-t-bakylyb—ak^rlallyl) uyiZiiyi tiatma—o?iZZii?i «lakrfa rt ty 1 M»llyl rl batylybaayblia bylybaaybi4a cyrl ay—ka41aayl —tbylcyclayeata4iaayl 1.2- 41—kbylcyclay—k«41«ay 1 1.3- 41—Uqrltyeli&gt;«aiti&lt;laayl la4—yl 1.2-41akbgrlcyelay«Mka41aayl katraaMkbgrlcyclay—k«4i—yl atbylcyclayaat«41aayl a-batylcyclay—ta41aayl -cyclabaayl—tbylcyclay—ta41aayl a-actylcyclay—*«41—yl ? ¢1 laylyrayylcyclky—tiflaayl yrayylcyclayaafcadlawyl t-feotylcyclayaatWiaaqrl Sa—ylcyelay—ta41—yl 41ybaayl—kbylcyclay—ka4iaayl kri—kbylya—ylcyvlayeak«4iaayl kri—tbylat—yleyelayeataai—yl krlakbgrlyl—bylcyclay—t«4i—yl krlflac—atbylcyclayaat«4i—yl . tri—tbylallylcyclay—ta4iaayl yaaka—Uplcyclcayaa*a41aayl («4m fluorenyl octahydrofluorenyl y-o) tylaa* aatiyiatbyla— atbylatkyla— 1-41—Uarl-3,3-4i—tbyiyrayyi 4ca—tfcyldlalla··— iXb-MU—aUyUiailylaUiyl ίΛ^ι-,&gt; . Q M t-batylaadda bydr 14a airs—1— ybaayl aaU4a cblara ba fat— y-a-butylybaayl—14a aatbyl kitaal— ryrlabaayl—i 4a atbyl yarfltnaybaaylaMida ybaayl a-batyl—i 4a fl— —tbyl—14a km •tbyl—14a ia4a a1 yrayy laal 4a a yrayyl iaayreyyl—ida ba—yl—14* t-bukylybaaybida •tbylybaaybida yb—ylybaaybida cycl«barylyb»^bl4a a— (ab— y - 1) —Ifida («4— y « 1) —kb—14« («4k— y · O) akb—14· (abaa y 0) —kbylkbia («4— y · 0) ekbylkbia (abaa y 0)

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but—y di—tbyl—14a 4ia tbyl—44a —tbylaklylaMl4a 41-t bar yl—14a 4iySaaqrl—44a 4iybaMylybaaybl4a 4icyclib«Tlfbk»abl4a 41—kbylybaeybi4a —kbylt4a— (bakb «) •tbyl 14a— (batb Q) yaayyll4a— (batb Q) «thylanaglycol dianlon 15

Generally the bridged species of the Group IV B transition metal compound ("y"-l) are preferred. These compounds can be prepared by reacting a cyclopentadienyl lithium compound with a dihalo compound whereupon a lithium halide salt Is liberated and a 5 monohalo substituent becomes covalently bound to the cyclopentadienyl compound. The so substituted cyclopentadienyl reaction product Is next reacted with a lithium salt of a phosphide, oxide, sulfide or amide (for the sake of Illustrative purposes, a lithium amide) whereupon the halo element of the 10 monohalo substituent group of the reaction product reacts to liberate a lithium halide salt and the amine moiety of the lithium amide salt becomes covalently bound to the substituent of the cyclopentadienyl reaction product. The resulting amine derivative of the cyclopentadienyl product 1s then reacted with an alkyl 15 lithium reagent whereupon the labile hydrogen atoms, at the carbon atom of the cyclopentadienyl compound and at the nitrogen atom of the amine'moiety covalently bound to the substituent group, react with the alkyl of the lithium alkyl reagent to liberate the alkane and produce a d111th1um salt of the cyclopentadienyl compound. 20 Thereafter the bridged species of the Group IV B transition metal * '· s compound Is produced by reacting the di lithium salt cyclopentadienyl compound with a Group IV B transition metal preferably a Group IV B transition metal halide.

Unbridged species of the Group IV B transition metal 25 compound can be prepared from the reaction of a cyclopentadienyl lithium compound and a lithium salt of an amine with a Group IV B transition metal halide.

Suitable, but not limiting, Group IV B transition metal compounds which may be utilized 1n the catalyst system of this 30 Invention Include those bridged species Cy"«l) wherein the B group bridge Is a dialkyl, diaryl or alkylaryl silane, or methylene or ethylene. Exemplary of the more preferred species of bridged Group IV B transition metal compounds are dlmethylsllyl, methyl phenyl silyl, d1ethyls1lyl, ethyl phenyl silyl, diphenyls1lyl, 16 ethylene or methylene bridged compounds. Host preferred of the bridged species are dimethylsilyl, dlethylsllyl and methyl phenyl silyl bridged compounds.

Suitable Group IV B transition metal compounds which are - 5 Illustrative of the unbridged ("y"-0) species which may be utilized

In the catalyst systems of this Invention are exemplified by pentamethylcyclopentadlenyld1-i-butylphosphlnodimethyl hafnlurn; pentamethylcyclopentadlenyld1-1-butylphosphlnomethyl ethyl hafnlurn; cyclopentadlenyl-2-methy1butox1de dimethyl titanium. 1° To Illustrate members of the Group IV B transition metal component, select any combination of the species 1n Table 1. An example of a bridged species would be dimethylsilyl-cyclopentadlenyl-.£-butylam1dod1 chloro zirconium; an example of an unbridged species would be cyclopentadienyld1-i-butylamidod1chl0ro 15 zirconium.

The alumoxane component of the catalyst system Is an oligomeric compound which may be represented by the general formula (R -A1-0) which 1s a cyclic compound, or may be 3 4™ 5 R (R —Al—0—Jjjj-AIR^ which Is a linear compound. An 20 alumoxane 1s generally a mixture of both the linear and cyclic 2 3 4 compounds. In the general alumoxane formula R , R, R , and R5 are, Independently a univalent anionic ligand such as a alkyl radical, for example, methyl, ethyl, propyl, butyl, pentyl or halide and "m“ 1s an Integer from 1 to about 50. Host 2 3 4 5 25 preferably, R , R , R and R are each methyl and "ra" Is at least 4. When an alkyl aluminum halide is employed 1n the 2-5 preparation of alumoxane, one or more of R could be halide.

As 1s now well known, alumoxanes can be prepared by various procedures. For example, a trialkyl aluminum may be 30 reacted with water, 1n the form of a moist Inert organic solvent; or the trialkyl aluminum may be contacted with a hydrated salt, such as hydrated copper sulfate suspended 1n an Inert organic solvent, to yield an alumoxane. Generally, however prepared, the reaction of a tri alkyl aluminum with a United amount of water 1.7 yields a mixture of both the linear and cyclic species of alumoxane.

Suitable alumoxanes which may be utilized In the catalyst systems of this Invention are those prepared by the hydrolysis of a 5 alkyl aluminum reagent; such as tr1methyl aluminum, tr1ethya1um1num, tr1 propylalum1num; tr11sobuty 1 alum1num, di methylalumlnumchlor1de, d11sobutylaluminumchloride, d1ethylalumlnumchlorlde, and the like. The most preferred alumoxane for use Is methylalumoxane (MAO), particularly methylalumoxanes having a reported average degree of 10 oligomerization of from about 4 to about 25 (Ίη**-4 to 25) with a range of 13 to 25 being most preferred.

Catalyst Systems

The catalyst system may include an alkyl aluminum and water which may react at least partly with each other 15 and/or with the metallocene compound outside of a polymerization vessel for what may be a reaction in situ in the polymerization vessel, j

The catalyst systems employed 1n the method of the invention comprise a complex formed upon admixture of the Group IV 20 B transition metal component with an alumoxane component. The catalyst system may be prepared by addition of the requisite Group IV B transition metal and alumoxane components to an Inert solve··.: 1n which olefin polymerization can be carried out by a solution, slurry or bulk phase polymerization procedure. 25 The catalyst system may be conveniently prepared by placing the selected Group IV B transition metal component and the selected alumoxane component, 1n any order of addition, 1n an alkane or aromatic hydrocarbon solvent — preferably one which 1s also suitable for service as a polymerization diluent. Hhere the 30 hydrocarbon solvent utilized 1s also suitable for use as a polymerization diluent, the catalyst system may be prepared 1n situ in the polymerization reactor. Alternatively, the catalyst system may be separately prepared. In concentrated form, and added to the polymerization diluent 1n a reactor. Or, If desired, the 3 5. components of the catalyst system may be prepared as separate solutions and added to the polymerization diluent 1n a reactor, In appropriate ratios, as 1s suitable for a continuous liquid polymerization reaction procedure. Alkane and aromatic 18 hydrocarbons suitable as solvents for formation of the catalyst system and also as a polymerization diluent are exemplified by, but are not necessarily limited to, straight and branched chain hydrocarbons such as Isobutane, butane, pentane, hexane, heptane, 5 octane and the like, cyclic and allcycl1c hydrocarbons such as cyclohexane, cycloheptane, methyl cyclohexane, methylcycloheptane and the like, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene and the like. Suitable solvents also Include liquid olefins which may act as monomers or comonomers 10 Including ethylene, propylene, 1-butene, 1-hexene and the like.

In accordance with this Invention optimum results are generally obtained wherein the Group IV B transition metal compound is present 1n the polymerization diluent 1n a.concentration of from about 0.0001 to about 1.0 ml 111moles/11 ter of diluent and the alumoxane component Is present In an amount to provide a molar aluminum to transition metal ratio of from about 1:1 to about 20,000:1. Sufficient solvent should be employed so as to provide adequate heat transfer away from the catalyst components during reaction and to permit good mixing.

20 The catalyst system Ingredients — that 1s, the Group IV B transition metal, the alumoxane, and polymerization diluent can be added to the reaction vessel rapidly or slowly. The temperature maintained during the contact of the catalyst components can vary widely, such as, for example, from -10* to 300*C. Greater or 25 lesser temperatures can also be employed. Preferably, during formation of the catalyst system, the reaction Is maintained within a temperature of from about 25* to 100*C, most preferably about 25*C.

At all times, the Individual catalyst system components, 30 as well as the catalyst system once formed, are protected from oxygen and moisture. Therefore, the reactions are performed In an oxygen and moisture free atmosphere and, where the catalyst system k 1s recovered separately 1t 1s recovered 1n an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are 19 , performed 1n the presence of an Inert dry gas such as, for example, helium or nitrogen.

Polymerization Process

In a preferred embodiment of the process of this Invention 5 the catalyst system 1s utilized In liquid phase (slurry, solution, suspension or bulk phase and combination thereof), high pressure fluid phase or gas phase polymerization of an olefin monomer.

These processes may be employed singularly or In series. The liquid phase process comprises the steps of contacting an olefin 10 monomer with the catalyst system in a suitable polymerization diluent and reacting said monomer 1n the presence of said catalyst system for a time and at a temperature sufficient to produce a polyolefin of high molecular weight.

The monomer for such process may comprise ethylene alone, 15 for the production of a homopolyethylene, or ethylene In combination with an α-olefln having 3 to 20 carbon atoms for the production of an ethylene-a-olefIn copolymer. Homopolymers of higher α-olefln ^uch as propylene, butene, styrene and copolymers thereof with ethylene and/or or higher β-olefins and 20 d1olefins can also be prepared. Conditions most preferred for the homo- or co-polymer1zat1on of ethylene are those wherein ethylene 1s submitted to the reaction zone at pressures of from about 0.019 ps1a to about 50,000 ps1a and the reaction temperature 1s maintained at from about -100* to about 300*C. The aluminum to 25 transition metal molar ratio 1s preferably from about 1:1 to 18,000 to 1. A preferable range would be 1:1 to 1000:1. The reaction time 1s preferably from about 1 min to about 1 hr. Without limiting In any way the scope of the Invention, one means for carrying out the process of the present Invention Is as follows: 1n 30 a stirred-tank reactor liquid 1-butene monomer Is Introduced. The catalyst system 1s Introduced via nozzles 1n either the vapor or liquid phase. Feed ethylene gas Is Introduced either Into the vapor phase of the reactor, or sparged Into the liquid phase as 1s 35 well known In the 20 art. The reactor contains a liquid phase composed substantially of liquid 1-butene together with dissolved ethylene gas, and a vapor phase containing vapors of all monomers. The reactor temperature and pressure may be controlled’''via reflux of vaporizing α-olefin monomer (autorefrigeration), as well as by cooling coils, jackets, etc. The polymerization rate is controlled by the concentration of catalyst. The ethylene content of the polymer product is determined by the ratio of ethylene to 1-butene in the reactor, which is controlled by manipulating the relative feed rates of these components to the reactor.

Examples

In the examples which illustrate the practice of the invention, the analytical techniques described below were employed for the analysis of the resulting polyolefin product. Molecular weight determinations for polyolefin products were made by gel permeation chromatography (GPC), according to the following technique. Molecular weights and molecular weight distributions were measured using a Waters 150 gel permeation chromatograph equipped with a differential refractive index (DRI) detector and a Chromatix KMX-6 online light scattering photometer. The system was used at 135°C with 1,2,4-trichlorobenzene as the mobile phase. Shodex (Showa Denko America, Inc.) polystyrene gel columns 802, 803, 804 and 805 were used. This technique is discussed in "Liquid Chromatography of Polymers and Related Materials III," J. Cazes, Ed., Marcel Dekker, p. 2007 (1981), which is incorporated herein by reference. No corrections for column spreading were employed; however, data on generally accepted standards, e.g., National Bureau of Standards Polyethylene 1484, and anionically produced hydrogenated poly isoprenes (an alternating ethylene-propylene copolymer) demonstrated that such corrections 21 on Mw/Mn (=MWD) were less than 0.05 units. Mw/Mn was calculated from elution times. The numerical analyses were performed using the commercially available Beckman/CIS customized LALLS software in conjunction with the standard Gel Permeation package, run on a HP 1000 computer.

As indicated above, while described, exemplified and illustrated herein, the subject matter of Israel Specification No. 95549 no longer constitutes a part of the present invention, and is specifically disclaimed.

With specific reference now to the examples in detail, it is stressed that the particulars described are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only, and are presented in the cause of providing what is believed to be the most useful and readily .understood description of the principles and conceptual aspects of the invention. In this context, it is to be noted,.that only subject matter embraced in ‘the"scope of the claims appended hereto, whether in*the manner defined in J, ζ the claims or in a manner similar thereto and involving the main features as defined in the claims, is intended to be included in the scope of the present invention, while subject matter of Israel Specification 95549, although described and exemplified to provide background and better understanding of the invention, is not intended for inclusion as part of the present invention.

21A

All procedures were performed under an inert atmosphere of 5 helium or nitrogen. Solvent choices are often optional, for example, in most cases either pentane or 30-60 petroleum ether can be interchanged. The 11thiated amides were prepared from the corresponding amines and either n-BuL1 or MeLI. Published methods for preparing LiHCgMe^ include C.M. Fendrlck et al. 10 Orqanometallics. I, 819 (1984) and F.H. Kohler and K. H. Doll, I. Naturforsch. 376, 144 (1982). Other lithiated substituted cyclopentadienyl compounds are typically prepared from the corresponding cyclopentadienyl ligand and β-BuLI or HeLi, or by reaction of MeL1 with the proper fulvene. ZrCl4 and HfCl^ were L5 purchased from either Aldrich Chemical Company or Cerac. Amines, silanes and lithium reagents were purchased from Aldrich Chemical Company or Petrarch Systems. Methylalumoxane was supplied by either Sherri ng or Ethyl Corp.

Examples · A-L of Group IV B Transition Metal Components

20 Example A

Compound A: Part 1. Me^HCgll (10.0 g, 0.078 mol) was slowly added to a MegSlCl? (11.5 ml, 0.095 mol, 1n 225 ml of tetrahydrofuran (thf) solution). The solution was stirred for 1 hour to assure complete reaction. The thf solvent was then removed 25 via a vacuum to a cold trap held at -196*C. Pentane was added to precipitate out the L1C1. The mixture was filtered through Celite. The solvent was removed from the filtrate.

Me^HCgSIMe^CI (15.34 g, 0.071 mol) was recovered as a pale yellow liquid. 30 Part 2. Me4HC5S1Me2Cl (10.0 g, 0.047 mol) was slowly added to a suspension of L1HN-i-8u (3.68 g, 0.047 mol, -100 ml thf). The mixture was stirred overnight. The thf was then removed via a vacuum to a cold trap held at -196*C. Petroleum 22 ether &lt;-100 ml) was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me2Sl(Me4HC5)(HN-i-Bu) (11.14 g, 0.044 mol) was Isolated as a pale yellow liquid. 5 Part 3. Me2S1(Me4HC5)(HN-i-Bu) (11.14 g. 0.044 mol) was diluted with **100 ml Et20. MeL1 (1.4 M, 64 ml, 0.090 mol) was slowly added. The mixture was allowed to stir for 1/2 hour after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, 10 [Me2Sl(Me4C5)(H-i-Bu)]L12. was washed with several small portions of ether, then vacuum dried.

Part 4. [Me2S1(Me4C5XN-i-Bu)JL12 (3.0 g, 0.011 .mol) was suspended.in —150 ml Et2O. ZrC14 (2.65 g, 0.011 mol) was slowly added and the resulting mixture was allowed to stir 15 overnight. The ether was removed via a vacuum to a cold trap held at -196’C. Pentane was added to precipitate out the L1C1. The mixture was filtered through Celite twice. The pentane was significantly reduced 1n volume and the pale yellow solid was filtered off and washed with solvent. 20 Me2S1(Me4C5)(N-i-8u)ZrCl2 (1.07 g, 0.0026 mole) was recovered. Additional Me2S1(Me4C5)(N-i-Bu)ZrC12 was recovered from the filtrate by repeating the recrystallization procedure. Total yield, 1.94 g, 0.0047 mol).

Example B 25 Compound B: The same procedure of Example A for preparing compound A was followed with the exception of the use of HfCl4 1n place of ZrCl4 1n Part 4. Thus, when [Me2Si(Me4Cg)- (N-i-8u)]L12 (2.13 g, 0.0081 mol) and HfCl4 (2.59 g, 0.0081 mol) were used, Me2S1(Me4C5)(N-i-Bu)HfCl2 (0.98 g, 0.0020 30 mol) was produced.

I

Example C

Compound C: Part 1. Me2SiC12 (7.5 ml, 0.062 mol) was 23 diluted with -30 ml thf. A t-BuH4C5L1 solution (7.29 g, 0.056 mol, -100 ml thf) was slowly added, and the resulting mixture was allowed to stir overnight. The thf was removed via a vacuum to a trap held at -196*C. Pentane was added to precipitate 5 out the L1C1, and the mixture was filtered through Cellte. The pentane was removed from the filtrate leaving behind a pale yellow liquid, i-BuH4Cs$1Me2C1 (10.4 g, 0.048 mol).

Part 2. To a thf solution of L1HN-i-Bu (3.83 g, 0.048 mol, -125 ml), i-8uH4C5S1Me2Cl (10.4 g, 0.048 mol) was 10 added drop wise. The resulting solution was allowed to stir overnight. The thf was removed via a vacuum to a trap held at -196*C. Pentane was added to precipitate out the L1C1, and the mixture was filtered through Cellte. The pentane was removed from the filtrate leaving behind a pale yellow liquid, 15 Me2S1(i-BuH4C5)(NH-i-8u) (11.4 g, 0.045 mol).

Part 3. He2S1(i-8uH4C5)(NH-i-Bu) (11.4 g, 0.045 mol) was diluted with -100 ml Et20. MeLI (1.4H, 70 ml, 0.098 mol) was slowly added. The mixture was allowed to stir overnigh'·. The ether was removed via a vacuum to a trap held at -196’C, 20 leaving behind a pale yellow solid, ‘ [Me2S1(i-BuH3C5)(N-i-Bu)]L12 (11.9 g, 0.045 mol).

Part 4. [Me2S1(i-BuH3C5)(N-i-Bu)]L12 (3.39 g, 0.013 mol) was suspended 1n -100 ml Et20. ZrC14 (3.0 g, 0.013 mol) was slowly added. The mixture was allowed to stir 25 overnight. The ether was removed and pentane was added to precipitate out the L1C1. The mixture was filtered through Cellte. The pentane solution was reduced 1n volume, and the pale tan solid was filtered off and washed several times with .small quantities of pentane. The product of empirical formula 30 Me2S1(t-8uH3C5)(N-i-Bu)ZrCl2 (2.43 g. 0.0059 mol) was Isolated.

Patrole. P

Compound 0: The same procedure of Example C for preparing 24 compound C was followed with the exception of the use of HfCI* In

Part 4. Thus, when [Me2S1&lt;i-8uH3C5&gt;&lt;N-i-Bu)]U2 &lt;3.29 g. 0.012 mol) and HfC14 &lt;4.0 g, 0.012 mol) were used, the product of the empirical formula Me2S1(t-BuH3C5)(N-i-Bu)HfCl2 &lt;1.86 g, 5 0.0037 mol) was produced.

Enaropig E

Compound-E: Part 1. Me2S1Cl2'(7.0 g, 0.054 mol) was diluted with -100 ml of ether. Me3S1C5H4L1 (5.9 g, 0.041 mol) was slowly added. Approximately 75 ml of thf was added and 10 the mixture was allowed to stir overnight. The solvent was removed via a vacuum to a cold trap held at -196*C. Pentane was added to precipitate out the L1C1. The mixture was filtered through Celite. The solvent was removed from the filtrate giving Me2S1(Ke3S1C5H4)C1 (8.1 g, 0.035 mol) as a pale yellow 15 liquid.

Part 2. Me2SKMe3S1C5H4)C1 &lt;3.96 g, 0.017 mol) was diluted with -50 ml of ether. L1HN-t-8u (1.36 g, 0.017 mol) .,. was slowly added, and the mixture was allowed to stir overnight.

The ether was removed via. a vacuum and pentane was added to " 20 precipitate the L1C1. The mixture was filtered through Celite, and the pentane was removed from the filtrate. He2S1-(He3S1C5H4)(NH-t-8u) (3.7 g. 0.014 mol) was Isolated as a pale yellow liquid.

Part 3. Me2SKMe3S1C5H4XNH-i-8u) &lt;3.7 g, 0.014 2s mol) as diluted with ether. MeL1 (25 ml, 1.4H In ether, 0.035 mol) was slowly added. The mixture was allowed to stir for 1.5 hours after the final addition of MeL1. The ether was removed via vacuum producing 4.6 g of a white solid formulated as L12CMe2S1-(Me3S1C5H3)(N-l-8u)]*3/4Et20 and unreacted HeLI which was 30 not removed from the solid.

Part 4. L12[Me2S1(Me3S1C5H3)(N-i-Bu)]*3/4Et20 (1.44 g, 0.0043 mol) was suspended In -50 ml of ether. ZrClj (1.0 g, 0.0043 mol) was slowly added and the reaction was allowed to 25 stir for a few hours. The solvent was removed via vacuum and pentane was added to precipitate the L1C1. The mixture was filtered through

Celite, and the filtrate was reduced 1n volume. The flask was placed 1n the freezer (-40*0 to maximize precipitation of the product. 5 ri The solid was filtered off giving 0.273 g of an off white solid. The filtrate was again reduced 1n volume, the precipitate filtered off to give an additional 0.345 g for a total of 0.62 g of the compound with empirical formula Me2S1(Me3S1C5H3)(N-t-Bu)ZrCl2. The x-ray crystal structure of this product reveals that the compound Is 10 dimeric 1n nature.

Example F

Compound F: Part 1. Me4HC5S1Me2C1 was prepared as described In Example A for the preparation of compound A, Part 1.

Part 2. LIHNPh (4.6 g, 0.0462 nol) was dissolved 1n **100 15 ml of thf. Me4HC5S1Me2Cl &lt;10.0 g, 0.0466 mol) was slowly added. The mixture was allowed to stir overnight. The thf was removed via a vacuum. Petroleum ether and toluene were added to precipitate the L1C1, and the mixture was filtered through Celite.

The solvent was removed, leaving behind a dark yellow liquid, 20 Me2S1(Me4HC5)(NHPh) (10.5 g, 0.0387 mol).

Part 3. He2S1(He4HC5)(NHPh) (10.5.g, 0.0387 mol) was diluted with **60 ml of ether. MeL1 (1.4 M 1n ether, 56 ml, 0.0784 mol) was slowly added and the reaction was allowed to stir overnight. The resulting white solid, L12CHe2S1(Me4C5)(NPh)«3/4Et20 25 (11.0 g), was filtered off and was washed with ether.

Part 4. L12CMe2S1(Me4C5)(NPh)*3/4Et20 &lt;2.81 g. 0.083 mol) was suspended 1n **40 ml of ether. ZrCl4 (1.92 g, Q.0082 mol) was slowly added, and the mixture was allowed to stir overnight. The ether was removed via a vacuum, and a mixture of petroleum ether 30 and toluene was added to precipitate the L1C1. The mixture was filtered through Celite, the solvent mixture was removed via vacuum, and pentane was added. The mixture was placed In the freezer at -40*C to maximize the precipitation of the product. The 26

It* solid was then filtered off and washed with pentane. Me2Sl(Me^CjXNPtOZrClj’EtgO was recovered as a pale yellow solid (1.89 g).

Example G 5 Compound 6: The same procedure of Example F for preparing compound F was followed with the exception of the use of HfC14 1n place of ZrCl4 In Part 4. Thus, when LigEMe^SI(Me^Cg)-(NPh)]*3/4Et2O (2.0 g, 0.0059 mol) and HfCl4 (1.89 g, 0.0059 mol) were used, Me2S1(Me4C5)(NPh)HfC12«1/2Et20 (1.70 g) 10 was produced. 15 20 25

Example H .

Compound H: Part 1. MePhSlC12 (14.9 g, 0.078 mol) was He4C5HL1 (10.0 g, 0.078 mol)

The reaction-solution was allowed to stir overnight. The solvent .was removed via,a vacuum to a cold trap held at -196*0. Petroleum ether was, added to precipitate out the L1C1. The mixture was filtered throughL Celite, and the pentane was removed from the filtrate. HePhSl(Me4C5H)Cl (20.8 g, 0.075 mol) was isolated as a yellow viscous liquid.

Part 2. L1HN-1-8U (4.28 g, 0.054 mol) was dissolved In HePhS1(He4C5H)C1 (15.0 g. 0.054 mol) was The yellow solution was allowed to stir overnight. The solvent was removed via vacuum. Petroleum ether was added to precipitate out the L1C1. The mixture was filtered through Celite, and the filtrate was evaporated down. MePhS1(He4C5H)(NH-i-8u) (16.6 g, 0.053 mol) was recovered as an diluted with -250 ml of thf. was slowly added as a solid. -100 ml of thf. added drop wise extremely viscous liquid.

Part 3. HePhS1(Me4CsH)(HH-i-8u) (16.6 g, 0.053 mol) was diluted with -100 ml of ether. HeL1 (76 ml, 0.106 mol, 1.4 M) was slowly added and the reaction mixture was allowed to st|r for -3 hours. The ether was reduced 1n volume, and the lithium salt was filtered off and washed with pentane producing 20.0 g of a pale 30 27 yellow solid formulated as L12CMePhSl(Me4Cs)(N-l-Bu)]*3/4Et2O. f Part 4. L12CMePhS1(Me4C5)(H-i-Bu)]*3/4Et20 &lt;5.0 g, 0.0131 mol) was suspended In **100 ml of Et20. ZrCl4 (3.06 g, 0.0131 mol) was slowly added. The reaction mixture was allowed to 5 stir at room temperature for **1.5, hours over which time the reaction mixture slightly darkened In color. The solvent was removed via vacuum and a mixture of petroleum ether and toluene was added.

The mixture was filtered through Celite to*'remove the L1C1. The filtrate was evaporated down to near dryness and filtered off. The io off white solid was washed with petroleum ether. The yield of product, MePhS1(He4C5)(N-t-Bu)ZrCl2, was 3.82 g (0.0081 mol).

Example I

Compound I: L12CMePhS1(Me4C5)(N-i-Bu)]*3/4Et20 was prepared as described In Example H for the preparation of 15 compound H, Part 3.

Part 4. L12CMePhS1(He4C5)(M-i-8u)]*3/4Et20 (5.00 g, 0.0131 mol) was suspended 1n -100 ml of Et20. HfCl4 (4.20 -g, 0.0131 moll was slowly added and the reaction·mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum 20 ether was added to precipitate out the L1C1. The mixture was filtered through Celite. The filtrate was evaporated down to near dryness and filtered off. The off white solid was washed with petroleum ether. MePhSI (Me^XN-i-BujHfClg was recovered (3.54 g, 0.0058 mole). 25 Example 3

Compound 3: MePhSI(Me4Cg)(N-i-8u)HfHe2 was prepared by adding a stoichiometric amount of MeL1 (1.4 H 1n ether) to MePhSI(Me4C,j)(N-i-Bu)HfC12 suspended 1n ether. The white solid could be Isolated 1n near quantitative yield.

I

30 Example K

Compound K: Part 1. Me4C5S1Me2Cl was prepared as 28 described 1n Example A for the preparation of compound A, Part 1.

Part 2. Me4C5S1Me2C1 (10.0 g, 0.047 mol) was diluted with -25 ml EtjO. l1HNC5H4-p-n-Bu»l/l0Et20 (7.57 g, ?i 0.047 mol) was added slowly. The mixture was allowed to stir for *.-'5 ~3 hours. The solvent was removed via vacuum. Petroleum ether was j added to precipitate out the L1C1, and the mixture was filtered through Cellte. The solvent was removed leaving behind an orange viscous liquid, Me2S1(Me4C5H)(HNCgH4-p-ii-8u) (12.7 g, 0.039 mol). 10 Part 3. Me2S1(Me4C5H)(HNC6H4-p-n-8u) (12.7 g. 0.039 mol) was diluted with -50 ml of Et20. HeLI (1.4 H, 55 ml. 0.077 mol) was slowly added. The mixture was allowed to stir for -3 hours. The product was filtered off and washed with Et20 producing L12[Me2S1(He4C5)(NC6H4-p-a-Bu)]*3/4Et20 as a 15 white solid (13.1 g, 0.033 mol).

Part 4. L12CMe2S1(Me4C5)(NC6H4-p-fl-Bu)]«3/4Et20 (3.45 g, 0.0087 mol) was suspended 1n -50 ml of Et20. ZrCl4 (2.0 g, 0;0086 mol) was slowly added and the mixture was allowed ίο r stir overnight. The ether was removed via vacuum, and petroleum 20. ether was added to precipitate out the L1C1. The mixture was filtered through Cellte. The filtrate was evaporated to dryness to give a yellow solid which was recrystal 11 zed from pentane and Identified as Me2S1(Me4C5)(NC6H4-p-n-Bu)ZrCl2«2/3Et20 (4.2 g).

25 Example L

Compound L: L12CMe£S1(Me4C5)(NC^-p-ii-Bu)]«3/4Εt20 was prepared as described In Example K for the preparation of compound K, Part 3.

Part 4. L12CMe2S1(He4C5)(NC6H4-p-n-8u)*3/4Et20 30 (3.77 g, 0.0095 mol) was suspended 1n -50 ml of Et20. HfC14 (3.0 g, 0.0094 mol) was slowly added as a solid and the&lt;a1xture was allowed to stir overnight. The ether was removed via vacuum and petroleum ether was added to precipitate out the L1C1. The mixture 29 was filtered through Celite. Petroleum ether was removed via a vacuum giving an off white solid which was recrystal 11 zed from pentane. The product was Identified as Me2S1(Me4C5)-&lt;NC6H4-p-fl-8u)HfC12 (1.54 g, 0.0027 mol). 5 Examples 1-34 of Polymerization

Example 1

Polymerization - Compound A The polymerization run was performed 1n a 1-11 ter autoclave reactor equipped with a paddle stirrer, an external water 10 jacket for temperature control, a regulated supply of dry nitrogen, ' ethylene, propylene, 1-butene and hexane, and a septum Inlet for

Introduction of other solvents, transition metal compound and alumoxane solutions. The reactor was dried and degassed thoroughly prior to use. A typical run consisted of Injecting 400 ml of .15 toluene, 6 ml of 1.5 H MAO, and 0.23 mg of compound A (0.2 ml of a 11.5 mg 1n 10 ml of toluene solution) Into the reactor. The reactor was then heated to 80’C and the ethylene (60 psi) was Introduced Into the system. The polymerization reaction was limited to 30 minutes. The reaction was ceased by rapidly cooling 20 and venting the system. The solvent was evaporated off of the polymer by a stream of nitrogen. Polyethylene was recovered (9.2 g, MW - 257,200, MHO . 2.275).

Example 2

Polymerization - Compound A 25 The polymerization was carried out as 1n Example 1 with the following changes: 300 ml of toluene, 3 ml of 1.5 M MAO, and 0.115 mg of compound A (0.1 ml of a 11.5 mg 1n 10 ml of toluene solution). Polyethylene was recovered (3.8 g, W4 - 359,800, MHO -2.425). 30

Example J

Polymerization - Compound A

The polymerization was carried out as In Example 2 using the Identical concentrations. The difference Involved running the 5 reaction at 40*C rather than 80*C as In the previous example. Polyethylene was recovered (2.4 g, MH - 635,000, MFD - 3.445).

Example 4

Polymerization - Compound A

The polymerization was carried out as In Example 1 except 10 for the use of 300 ml of hexane 1n place of 400 ml of toluene. Polyethylene was recovered (5.4 g, MH » 212,600, MW - 2.849).

Example 5

Polymerization - Compound A

Using the same reactor design and general procedure as In IS Example 1, 300 ml of toluene, 200 ml of propylene, 6.0 ml of 1.5 M MAO, and 0.46 mg of compound A (0.4 ml of a 11.5 mg 1n 10 ml of toluene solution) was Introduced Into the reactor. The reactor was heated.,to 80*C, the ethylene was added (60 psD, and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and 2o venting the system. After evaporation of the solvent, 13.3 g of an ethylene-propylene copolymer was recovered (MH - 24,900, MHO -2.027, 73.5 SC8/1000C by IR).

Example

Polymerization - Compound A 25 The polymerization was carried out as 1n Example. 5 except with the following changes: 200 ml of toluene and 0.92 mg of compound A (0.8 ml of a 11.5 mg 1n 10 ml of toluene solution). The reaction temperature was also reduced to 50*C. An ethylene-propylene copolymer was recovered ¢6.0 g, MH · 83,100, Mfl) - 2.370, 75.7 SC8/1000C by IR). 30 31

Example 7

Polymerization - Compound A

Using the same reactor design and general procedure as In Example 1, 150 ml of toluene, 100 ml of 1-butene, 6.0 ml of 1.5 H 5 MAO, and 2.3 mg of compound A (2.0 ml of a 11.5 mg 1n 10 ml of toluene solution) were added to the reactor. The reactor was

/X heated at 50"C, the ethylene was Introduced (65 ps1), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 10 25.4 g of an ethylene-butene copolymer was recovered (MH - 184,500, MWD . 3.424, 23.5 SC8/1000C by 13C NMR and 21.5 SCB/1000C by IR).

Example 8

PolymerizatlQn-τ Compound A

The polymerization was carried out as 1n Example 7 except 15 with the following changes: 100 ml of toluene and 150 ml of 1-butene. An ethylene-butene copolymer was recovered (30.2 g, MH -143,500, MWD - 3.097, 30.8 SCB/1000C by 13C NMR and 26.5 SCB/1000C by IR).

Example. 9

20 Polymerization - Compound A

The polymerization was carried out as 1n Example 7 except with the following changes: 200 ml of toluene, 8.0 ml of 1.0 H MAO, and 50 ml of 1-butene. An ethylene-butene copolymer was recovered (24.9 g. MH - 163,200, MWD . 3.290, 23.3 SCB/1000C by 13C NMR and 25 18.9 SCB/1000C by IR).

Example 10

Polymerization - Compound A

The polymerization was carried out as 1n Example 9 except for the replacement of 200 ml of toluene with 200 ml of hexane. An 30 ethylene-butene copolymer was recovered (19.5 g, MH - 150,600, MA) - 3.510, 12.1 SCB/1000 C by 13C NMR and 12.7 SCB/1000C by IR). 32

Example 11

Polymerization - Compound A

The polymerization was carried out as In Example 10 except with the following changes: 150 ml of hexane, and 100 ml of 5 1-butene.' An ethylene-butene copolymer was recovered (16.0 g, HH -116,200, HHD - 3.158, 19.2 SCB/1000C by 13C MMR and 19.4 SCB/1000C by IR).

Example 12

Polymerization - Compound A io Using the same reactor design and general procedure already described, 400 ml of toluene, 5.0 ml of 1.0 Η HAO, and 0.2 ml of a preactivated compound A solution (11.5 mg of compound A dissolved 1n 9.0 ml of toluene and 1.0 ml of 1.0 M HAO) were added to the reactor. The reactor was heated to 80*C, the ethylene was 15 Introduced (60 ps1), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 3.4 g of polyethylene was recovered (HH - 285,000, HHD - 2.808).

Example 13

20 Polymerization - Compound A A polymerization was carried out as 1n Example 12 with exception of aging the preactivated compound A solution by one day. Polyethylene was recovered (2.0 g, HH - 260,700, MO - 2.738)

Example..],*

25 Polymerization - Compound A

Using the same reactor design and general procedure already described, 400 ml of toluene, 0.25 ml of 1.0 H HAO, and 0.2 ml of a preactivated compound A solution (11.5 mg of compound A dissolved 1n 9.5 ml of toluene and 0.5 ml of 1.0 H HAO), were added 30 into the reactor. The reactor was heated to 80*C, the ethylene was Introduced (60 psi), and the reaction was allowed to run for 30 33 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 1.1 g of polyethylene was recovered (MH - 479.600, MHO - 3.130).

Example .15

5 Polymerization - Compound A

Using the same reactor design and general procedure already described, 400 ml of toluene and 2.0 ml of a preactivated compound A solution (11.5 mg of compound A dissolved In 9.5 ml of toluene and 0.5 ml of 1.0 M MAO) were added Into the reactor. The 10 reactor was heated to 80*C, the ethylene was Introduced (60 psD, and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 1.6 g of polyethylene was recovered (MH - 458,800, MHO » 2.037). 15 Example 16

Polymerization - Compound A ., Using the general procedure already described, 400 ml of toluene, 5.0 ml of 1.0 M MAO, 0.23 mg of compound A (0.2 ml of a 11.5 mg 1n 10 ml of toluene solution) was added to the reactor. 20 The reactor was heated to 80*C, the ethylene Introduced (400 psD., and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 19.4 g of polyethylene was recovered (MH 343,700, MHO -3.674). 25 Example,

EalyiMdzatlQn,, -..Compound a

The polymerization was performed 1n a stirred 100 ml stainless steel autoclave which was equipped to perform polymerizations at pressures up to 40,000 ps1 and temperatures up 30 to 300*C. The reactor was purged with nitrogen and heated to 160*C. Compound A and alumoxane solutions were prepared In 34

separate vials. A stock solution was prepared by dissolving 26 eg of compound A In 100 ml of toluene. The compound A solution was prepared by diluting 0.5 nl of the stock solution with 5.0 ml of toluene. The alumoxane solution consisted of 2.0 nl of a 41 MAO 5 solution added to 5.0 ml of toluene; The compound A solution was added to the alumoxane solution, then 0.43 ml of the mixed solutions were transferred by nitrogen pressure Into a constant-volume Injection tube. The autoclave was pressurized with ethylene to 1784 bar and was stirred at 1500 rpm. The mixed 10 solutions were Injected into the stirred reactor with excess pressure, at which time a temperature rise of 4’C was observed.

The temperature and pressure were recorded continuously for 120 seconds, at which time the contents of the autoclave were rapidly vented Into a receiving vessel. The reactor was washed with xylene 15 to recover any additional polymer remaining within. These washings were combined with the polymer released when the autoclave was vented to yield 0.7 g of polyethylene (MW - 245,500, MHO - 2.257)2

Example 18

Polymerization - Compound B 20 Using the general procedure described In Example 1, 400 ml of toluene, 5.0 ml of 1.0 M MAO and 0.278 mg compound B (0.2 ml of a 13.9 ng In 10 ml of toluene solution) was added to the reactor. The reactor was heated to 80*C and the ethylene (60 psD was introduced Into the system. The polymerization reaction was 25 limited to 10 minutes. The reaction was ceased by rapidly cooling and venting the system. The solvent was evaporated off the polymer by a stream of nitrogen. Polyethylene was recovered (9.6 g, MW -241,200, MHD . 2.628).

Example 19 30 Polymerization - Compound C &gt;

Using the general procedures described In Example 1, 300 ml of toluene, 4.0 ml of 1.0 M MAO and 0.46 mg compound C (0.4 ml 35 of a 11.5 mg 1n 10 ml of toluene solution) was added to the reactor. The reactor was heated to 80*C and the ethylene (60 ps1) was Introduced Into the system. The polymerization reaction was limited to 30 minutes. The reaction was ceased by-rapidly cooling 5 and venting the system. The solvent was evaporated off the polymer ,f by a stream of nitrogen. Polyethylene was recovered (1.7 g,HH« 278,400, MWD - 2.142).

EzWl&amp;amp;JQ

Polymerization - Compound D 10 Using the general procedure described 1n Example 1, 400 ml of toluene, 5.0 ml of 1.0 H MAO and 0.278 mg compound 0 (0.2 ml of 1 13.9 mg 1n 10 ml of toluene solution) was added to the reactor.

The reactor was heated to 80*C and the ethylene (60 psD was Introduced into the system. The polymerization reaction was 15 limited to 30 minutes. The reaction was ceased by rapidly cooling and venting the system. The solvent was evaporated off the polymer by a stream of nitrogen. Polyethylene was,.recovered (1.9 g, MH 229,700, MWD - 2.618).

Example 21

20 Polymerization - Compound E

Using the general procedure described 1n Example 1, 300 ml of hexane, 9.0 ml of 1.0 M MAO and 0.24 mg compound E (0.2 ml of a 12.0 mg In 10 ml of toluene solution) was added to the reactor.

The reactor was heated to 80"C and the ethylene (60 ps1) was 25 Introduced into the system. The polymerization reaction was limited to 30 minutes. The reaction was ceased by rapidly cooling and venting the system. The solvent was evaporated off the polymer by a stream of nitrogen. Polyethylene was recovered (2.2 g, MH -258,200, MHO . 2.348). 36

EttPPlg 22

Polymerization - Compound E

The polymerization was carried out as In Example 1 with the following reactor contents: 200 ml of toluene, 100 ml 5 1-butene, 9.0 ml of.’1.0 M MAO and 2.4 mg of compound E (2.0 ml of a 12.0 mg 1n 10 ml of toluene solution) at 50*C. The reactor was pressurized with ethylene (65 ps1), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 1.8 g of an 10 ethylene-butene copolymer was recovered (MH - 323,600, MHO 2.463, 33.5 SCB/1000C by IR technique).

Example 23

Polymerization - Compound F

The polymerization was carried out as 1n Example 1 with 15 the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 14 MAO, 0.242 mg of compound F (0.2 ml of a 12.1 ,,mg 1n 10 ml of toluene solution), 80*C, 60 ps1 ethylene, 30 minutes. The run provided 5.3 g of polyethylene (MW - 319,900, MWD - 2.477).

Example 24

20 Polymerization - Compound F

The polymerization was carried out as 1n Example 1 with the following reactor conditions: 150 ml of toluene, 100 ml of 1-butene, 9.0 ml of 1.0 M MAO, 2.42 mg of compound F (2.0 al of a 12.1 mg 1n 10 ml of toluene solution), 50*C, 65 ps1 ethylene, 30 25 minutes. The run provided 3.5 g of an ethylene-butene copolymer (MW - 251,300, MWD - 3.341, 33.28 SC8/1000C by IR technique).

Exampig 25

Polymerization - Compound G

The polymerization was carried out as 1n Example 1 with 30 the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 H MAO, 0.29 mg of compound G (0.2 ml of a 14.5 mg In 10 ml of 37 , toluene solution), 80*C, 60 ps1 ethylene, 30 minutes. The run provided 3.5 g of polyethylene (MH - 237,300, MHO · 2.549).

Example 26

Polymerization - Compound G 5 The polymerization was carried out In Example 1 with the following reactor conditions: 150 ml of toluene, 100 ml of 1-butene, 7.0 ml of 1.0 M MAO, 2.9 mg of compound G (2.0 ml of a 14.5 mg 1n 10 ml of toluene solution), 50*C, 65 ps1 ethylene, 30 minutes. The run provided 7.0 g of an ethylene-butene copolymer 10 (MW - 425,000, MWD - 2.816, 27.11 SC8/1000C by IR technique).

Example 27

Efli.Ymar.lj:atlfln.· Compound H

The polymerization was carried out as 1n Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 15 M MAO, 0.266 mg of compound H (0.2 ml of a 13.3 mg 1n 10 ml of , toluene solution), 80*C, 60 psi ethylene, 30 minutes. The run provided 11.1 g of polyethylene (MW - 299,800, MWD - 2.569).

Example. 28

Polymerization - Compound H -20 The polymerization was carried out as In Example 1 with the following reactor conditions: 150 ml of toluene, 100 ml of 1-butene, 7.0 ml of 1.0 M MAO, 2.66 mg of compound H (2.0 ml of a 13.3 mg 1n 10 ml of toluene solution), 50*C, 65 psi ethylene, 30 minutes. The run provided 15.4 g of an ethylene-butene copolymer 2 5 (MW - 286,600, MWD - 2.980, 45.44 SC8/1000C by IR technique).

Example 29

Polymerization - Compound I

The polymerization was carried out as In Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 30 MAO, and 0.34 mg of compound I (0.2 ml of a 17.0 mg 1n 10 ml of 38 toluene solution) was added to the reactor. The reactor was heated to 80*C, the ethylene was Introduced (60 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and

Renting the system. After evaporation of the solvent, 0.9 g of 5 ' polyethylene was recovered (MW - 377,000, MWD - 1.996).

j V

ExamDdJLJQ

Polymerization - Compound 3

The polymerization was carried out as 1n Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 10 M MAO, 0.318 mg of compound J (0.2 ml of a 15.9 mg In 10 ml of toluene solution), 80*C, 60 psi ethylene, 30 minutes. The run provided 8.6 g of polyethylene (MW - 321,000, MHO - 2.803).

Example 31

Polymerization - Compound 3 15 The polymerization was carried out as 1n Example 1 with the following reactor conditions: 150 ml of toluene, 100 ml of 1-butene, 7.0 ml of 1.0 M MAO, 3.18 mg of Compound 3 (2.0 ml of a • 15.9 mg 1n 10 ml of toluene solution), 50*C, 65 ps1 ethylene, 30 minutes. The run provided 11.2 g of an ethylene-butene copolymer 20 (MH - 224,800, MWD - 2.512, 49.57 SC8/1000C by IR technique, 55.4 SCB/1000C by NMR technique).

Example 32

Polymerization - Compound K

The polymerization was carried out as In Example 1 with 25 the following reactor conditions: 300 ml of toluene, 5.0 ml of 1.0 M MAO, 0.272 mg of compound K (0.2 ml of a 13.6 mg 1n 10 ml of toluene solution), 80*C, 60 psi ethylene, 30 minutes. The run provided 26.6 g of polyethylene (MH » 187,300, Mrffl - 2.401). 39

Example 33

Polymerization - Compound K

The polymerization was carried out as 1n Example 1 with the following reactor conditions: 150 ml of toluene, 100 ml of 5 1-butene, 7.0 ml of 1.0 H MAO, 2.72 mg of compound K (2.0 ml of a 13.6 mg in 10 ml of toluene solution), 50*C, 65 ps1 ethylene, 30 minutes. The run provided 3.9 g of an ethylene-butene copolymer (MW . 207,600, MHO - 2.394, 33.89 SC8/1000C by IR technique).

Example 34

10 Polymerization - Compound L

The polymerization was carried out as In Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 M MAO, 0.322 mg of compound L (0.2 ml of a 16.1 mg 1n 10 ml of toluene solution), 80*C, 60 psi ethylene, 30 minutes. The run 15 provided 15.5 g of polyethylene (MH . 174,300, MHO - 2.193).

Example 35

Polymerization - Compound A

The polymerization was carried out as in Example 1 with the following reactor contents: 250 ml of toluene, 150 ml of 20 1-hexene, 7.0 ml of 1.0 M MAO and 2.3 mg of compound A (2.0 ml of a 11.5 mg in 10 ml of toluene solution) at 50* C. The reactor was pressurized with ethylene (65 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 26.5 g of an 25 ethylene-hexene copolymer was recovered (MW 222,800, MWD - 3.373, 39.1 SCB/1000C by IR technique).

Example 36

Polymerization - Compound A

The polymerization was carried out as In Example 1 with 30 the following reactor contents: 300 ml of toluene, TOO ml of 1-octene, 7.0 ml of 1.0 H MAO and 2.3 mg of compound A (2.0 ml of a 40 11.5 mg 1n 10 ml of toluene solution) at 50* C. The reactor was pressurized with ethylene (65 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of, the solvent, 19.7 g of an 5 ethylene-octene copolymer was recovered (MH - 548,600, HWD · 3.007, 16.5 SCB/1000C by 13C NMR technique).

Example 37

Polymerization - Compound A

The polymerization was carried out as 1n Example 1 with 10 the following reactor contents: 300 ml of toluene, 100 ml of 4-methyl-l-pentene, 7.0 ml of 1.0 H HAO and 2.3 mg of compound A (2.0 ml of a 11:.5 mg In 10 ml of toluene solution) at 50* C. The reactor was pressurized with ethylene (65 psD, and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and 15 venting the system. After evaporation of the solvent, 15.1 g of an ethylene-4-methyl-l-pentene copolymer was recovered (HH - 611,800, &lt; MWD - 1.683, 1.8 moleX determined by 13C MMR).

Ex W.1 ¢-.38

Polymerization - Compound A 20 The polymerization was carried out as In Example 1 with the following reactor contents: 300 ml of toluene, 100 ml of a 2.2 M norbornene 1n toluene solution, 7.0 ml of 1.0 H HAO and 2.3 mg of compound A (2.0 ml of a 11.5 mg In 10 ml of toluene solution) at 50* C. The reactor was pressurized with ethylene (65 psi7, and the 25 reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 12.3 g of an ethylene-norbornene copolymer was recovered (MH -812,600. MWO - 1.711, 0.3 moleX determined by 13C NMR).

30 Polymerization - Compound A

The polymerization was carried out as 1n Example 1 with 41 the following reactor contents: 300 ml of toluene, 100 ml of iii-1,4-hexad1ene, 7.0 ml of 1.0 M MAO and 2.3 mg of compound A (2.0 ml of a 11.5 mg 1n 10 ml of toluene solution) at 50* C. The reactor was pressurized with ethylene (65ps1), and the reaction 5 was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 13.6 g of an ethylene-£li-1,4-hexad1 ene copolymer was recovered (MH - 163,400, MHO - 2.388, 2.2 mol el determined by 13C NMR).

Table 2 summarizes the polymerization conditions employed 10 and the properties obtained 1n the product polymers as set forth 1n Examples 1—34 above. si ii 42 *s 's "s Η H i if 3 S 5 J 5 &lt;·»·&lt;&lt; • · · · · * a * « ft *2 •b "2 *2 4 j &amp;amp;

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M M W V O o. pp 45

It may be seen that the requirement for the alumoxane component can be greatly diminished by premixing the catalyst with the alumoxane prior to Initiation of the polymerization (see Examples 12 through 15). 5 By appropriate selection of (1) the Group IV B transition metal component for use In the catalyst system; (2) the type and amount of alumoxane used; (3) the polymerization diluent type and ., volume; and (4) reaction temperature; (5) reaction pressure, one may tailor the product polymer to the weight average molecular io weight value desired while still maintaining the molecular weight distribution to a value below about 4.0.

The preferred polymerization diluents for practice of the process of the Invention are aromatic diluents, such as toluene, or alkanes, such as hexane. 15 The resins that are prepared 1n accordance with this

Invention can be used to make a variety of products Including films and fibers.

The Invention has been described with reference to Its preferred embodiments. Those of ordinary skill 1n the art may, 20 . upon reading this disclosure, appreciate changes or modifications which do not depart from the scope and spirit of the Invention as described above or claimed hereafter.