Monocyclopentadienyl Titanium Metal Compounds for Ethylene-.Alpha.-Olefin-Copolymer Production Catalysts

This invention relates to certain monocyclopentadienyl titanium compounds, to a catalyst system comprising a monocyclopentadienyl titanium compound and an alumoxane, and to a process using such catalyst system for the production of polyolefins, particularly ethylene-.alpha.-olefin copolymers having a high molecular weight and high level of .alpha.-olefin incorporation. The catalyst system is highly active at low ratios of aluminum to the titanium metal, hence catalyzes the production of a polyolefin product containing low levels of catalyst metal residue.

This invention relates to the discovery of various catalyst ligand structure affects which are reflected in the activity of the catalyst system and in the physical and chemical properties possessed by a polymer produced with a monocyclopentadienyl titanium metal catalyst system. Accordingly, various species within the general class of monocyclopentadienyl titanium catalyst as disclosed by commonly-owned U.S. patent application Ser. No. 581,841, have been discovered to be vastly superior in terms of the ability of such species to produce ethylene-.alpha.-olefin copolymers of high molecular weight with high levels of .alpha.-olefin comonomer incorporation and at high levels of catalyst productivity.

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 weight average molecular weight while having a relatively narrow molecular weight distribution. A high weight average molecular weight, when accompanied by a narrow molecular weight distribution, provides a polyolefin or an ethylene-.alpha.-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 a Group IV B metal, particularly, titanocenes and zirconocenes, have been utilized as the transition metal component in such "metallocene" containing catalyst system for the production of polyolefins and ethylene-.alpha.-olefin 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 high activity for the production of polyolefins.

The zirconium metallocene species, as cocatalyzed or activated with an alumoxane, are commonly more active than their hafnium or titanium analogous for the polymerization of ethylene alone or together with an .alpha.-olefin comonomer. When employed in a non-supported form--i.e., as a homogeneous or soluble catalyst system--to obtain a satisfactory rate of productivity even with the most active zirconium species of metallocene typically requires the use of a quantity of alumoxane activator sufficient to provide an aluminum atom to transition metal atom ratio (Al:TM) of at least greater than 1000:1; often greater than 5000:1, and frequently on the order of 10,000:1. Such quantities of alumoxane impart to a polymer produced with such catalyst system an undesirable content of catalyst metal residue, i.e., an undesirable "ash" content (the nonvolatile metal content). In high pressure polymerization procedures using soluble catalyst systems wherein the reactor pressure exceeds about 500 bar only the zirconium or hafnium species of metallocenes may be used. Titanium species of metallocenes are generally unstable at such high pressures unless deposited upon a catalyst support.

A wide variety of Group IV B transition metal compounds have been named as possible candidates for an alumoxane cocatalyzed catalyst system. Although bis(cyclopentadienyl) Group IV B transition metal compounds have been the most preferred and heavily investigated for use in alumoxane activated catalyst systems for polyolefin production, suggestions have appeared that mono and tris(cyclopentadienyl) transition metal compounds may also be useful. See, for example U.S. Pat. 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 an alumoxane activated catalyst system are mono(cyclopentadienyl) transition metal trihalides and trialkyls.

More recently, International Publication No. WO 87/03887 describes the use of a composition comprising a transition metal coordinated to at least one cyclopentadienyl and at least one heteroatom ligand as a transition metal component for use in an alumoxane activated catalyst system for .alpha.-olefin 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 transition metal coordination requirement being satisfied with cyclopentadienyl or hydrocarbyl ligands. Catalyst systems described by this reference are illustrated solely with reference to transition metal compounds which are metallocenes, i.e., bis(cyclopentadienyl) Group IV B transition metal compounds.

Even more recently, at the Third Chemical Congress of North American held in Toronto, 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 monocyclopentadienyl transition metal compound could be usefully employed for commercial polymerization processes.

Although the metallocene/alumoxane catalyst system constituted an improvement relative to a traditional Ziegler-Natta catalyst system, a need existed for discovering catalyst systems that permit the production of higher molecular weight polyolefins and desirably with a narrow molecular weight distribution. Further desired was a catalyst which, within reasonable ranges of ethylene to .alpha.-olefin monomer ratios, will catalyze the incorporation of higher contents of .alpha.-olefin comonomers in the production of ethylene-.alpha.-olefins copolymers.

Commonly owned copending U.S. application Ser. No. 581,841 disclosed the discovery of a class of monocyclopentadienyl Group IV B transition metal compounds which, when activated with an alumoxane, may be employed as a catalyst system in solution, slurry or bulk phase polymerization procedure to produce a polyolefin of high weight average molecular weight and relatively narrow molecular weight distribution.

The "Group IV B transition metal component" of the catalyst system disclosed in application Ser. No. 581,841 is represented by the formula: ##STR1## wherein: M is Zr, Hf or Ti in its highest formal oxidation state (+4, d.sup.0 complex);

(C.sub.2 H.sub.5-y-x R.sub.x) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C.sub.1 -C.sub.20 hydrocarbyl radicals, substituted C.sub.1 -C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, and alkoxy radical or any other radical containing a Lewis acidic or basic functionality, C.sub.1 -C.sub.20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or any other radical containing Lewis acidic or basic functionality; or (C.sub.5 H.sub.5-y-x R.sub.x) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C.sub.4 -C.sub.20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;

(JR'.sub.z-1-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, preferably nitrogen, phosphorus, oxygen or sulfur, and each R' is, independently a radical selected from a group consisting of C.sub.1 -C.sub.20 hydrocarbyl radicals, substituted C.sub.1 -C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical or any other radical containing a Lewis acidic or basic functionality, and "z" is the coordination number of the element J;

each Q may be independently any univalent anionic ligand such as a halide, hydride, or substituted or unsubstituted C.sub.1 -C.sub.20 hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphide, provided that where any Q is a hydrocarbyl such Q is different from (C.sub.5 H.sub.5-y-x R.sub.x), or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand;

"y" is 0 or 1 when w is greater than 0; y is 1 when w is 0; when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element such as but not limited to, a dialkyl, 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 a neutral Lewis base such as diethylether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like; and "w" is a number from 0 to 3. L can also be a second transition metal compound of the same type such that the two metal centers M and M' are bridged by Q and Q', wherein M' has the same meaning as M and Q' has the same meaning as Q. Such dimeric compounds are represented by the formula: ##STR2##

The alumoxane component of the catalyst may be represented by the formulas: (R.sup.3 --Al--O).sub.m ; R.sup.4 (R.sup.5 --Al--O).sub.m --AlR.sub.2.sup.6 or mixtures thereof, wherein R.sup.3 -R.sup.6 are, independently, a C.sub.1 -C.sub.5 alkyl group or halide and "m" is an integer ranging from 1 to about 50 and preferably is from about 13 to about 25.

Catalyst systems may be prepared by placing the "Group IV B transition metal component" and the alumoxane component in common solution in a normally liquid alkane or aromatic solvent, which solvent is preferably suitable for use as a polymerization diluent for the liquid phase polymerization of an olefin monomer.

As further disclosed in U.S. application Ser. No. 581,841, that class of the Group IV B transition metal component wherein the metal is titanium have been found to impart beneficial properties to a catalyst system which are unexpected in view of what is known about the properties of bis(cyclopentadienyl) titanium compounds which are cocatalyzed by alumoxanes. Whereas titanocenes in their soluble form are generally unstable in the presence of aluminum alkyls, the monocyclopentadienyl titanium metal components, particularly those wherein the heteroatom is nitrogen, generally exhibit greater stability in the presence of aluminum alkyls, higher catalyst activity rates and higher .alpha.-olefin comonomer incorporation.

Further, the titanium class of the Group IV B transition metal component catalyst of the invention described by application Ser. No. 581,841 generally exhibit higher catalyst activities and the production of polymers of greater molecular weight and .alpha.-olefin comonomer contents than catalyst systems prepared with the zirconium or hafnium species of the Group IV B transition metal component.

This invention comprises the discovery of a subgenus of monocyclopentadienyl titanium compounds which, by reason of the presence therein of ligands of a particular nature, provide a catalyst of greatly improved performance characteristics compared to other members of the genus of monocyclopentadienyl titanium compounds as described in copending U.S. application Ser. No. 581,841. The subgenus of monocyclopentadienyl titanium catalyst most preferred is that wherein the heteroatom ligand is an amido group, the nitrogen atom of which is bridged through a bridging group (T) to the cyclopentadienyl ring and wherein the nitrogen atom is covalently bonded through a 1.degree. or 2.degree. carbon atom to an alicyclic or aliphatic hydrocarbyl group. Herein a 1.degree. carbon atom is one which is methyl or a carbon atom which is bonded to only one other carbon atom; a 2.degree. carbon atom is one which is bonded to only two other carbon atoms, and a 3.degree. carbon atom is bonded to three other carbon atoms. Preferably the alicyclic or aliphatic hydrocarbyl group has three or more carbon atoms and is bonded to the nitrogen atom through a 2.degree. carbon atom, most preferably the hydrocarbyl group is alicyclic. Monocyclopentadienyl titanium compounds within this subgenus have been discovered to produce a highly productive catalyst system which produces an ethylene-.alpha.-olefin copolymer of significantly greater molecular weight and .alpha.-olefin comonomer content as compared with other species of monocyclopentadienyl titanium compounds when utilized in an otherwise identical catalyst system under identical polymerization conditions. Further, within this subgenus of titanium compounds it has been found that the nature and degree of substitution groups (R) of the cyclopentadienyl ring can be varied to produce a catalyst system having a "catalyst reactivity ratio (r.sub.1)" which may be varied from a high to a low value as may be most desired to best suit the catalyst system to a particular type of polymerization process. Particularly it has been found that as the number of substituents (R), which are preferably hydrocarbyl substituents, increases the reactivity ratio (r.sub.1) decreases, the lowest reactivity ratios being obtained by a titanium compound having a tetrahydrocarbyl substituted cyclopentadienyl group, preferably a tetramethylcyclopentadienyl group.

A typical polymerization process of the invention comprises the steps of contacting ethylene and a C.sub.3 -C.sub.20 .alpha.-olefin alone, or with other unsaturated monomers including C.sub.3 -C.sub.20 .alpha.-olefins, C.sub.4 -C.sub.20 diolefins, and/or acetylenically unsaturated monomers with a catalyst comprising, in a suitable polymerization diluent, a monocyclopentadienyl titanium compound as described above; and a methylalumoxane in an amount to provide a molar aluminum to titanium metal ratio of from about 1:1 to about 20,000:1 or more; and reacting such monomers in the presence of such catalyst system at a temperature of from about -100.degree. C. to about 300.degree. C. for a time of from about 1 second to about 10 hours to produce a copolymer 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.

The disclosure of U.S. application Ser. No. 581,841 is hereby incorporated by reference.

As disclosed in U.S. application Ser. No. 581,841, wherein it is desired to produce an .alpha.-olefin copolymer which incorporates a high content of .alpha.-olefin, the class of Group IV B transition metal compound preferred is one of titanium. The most preferred class of titanium metal compounds are represented by the formula: ##STR3## wherein Q, L, R', R, "x" and "w" are as previously defined and R.sup.1 and R.sup.2 are each independently a C.sub.1 to C.sub.20 hydrocarbyl radicals, substituted C.sub.1 to C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom; R.sup.1 and R.sup.2 may also be joined forming a C.sub.3 to C.sub.20 ring which incorporates the silicon bridge.

Among this class of titanium compounds various substituent and ligand affects have been discovered which significantly affect the properties of a catalyst system. The nature and degree of substitutions (R) in the cyclopentadienyl ring was found to significantly influence the catalyst ability to incorporate .alpha.-olefin comonomers when producing an ethylene-.alpha.-olefin copolymer. For the greatest amount of comonomer incorporation, the cyclopentadienyl ring should be fully substituted (x=4) with hydrocarbyl groups (R), most preferably methyl groups. This affect is demonstrated by a comparison between Examples 83 to 85. Next, the nature of the R' ligand of the amido group significantly influences the capability of a catalyst to incorporate .alpha.-olefin comonomer. Amido group R' ligands which are aliphatic or alicyclic hydrocarbyl ligands bonded to the nitrogen atom through a 1.degree. or 2.degree. carbon atom provide for a greater degree of .alpha.-olefin comonomer incorporation than do R' groups bonded through a 3.degree. carbon atom or bearing aromatic carbon atoms. Further, wherein the R' ligand is bonded to the nitrogen atom through a 2.degree. carbon atom, the activity of the catalyst is greater when the R' substituent is alicyclic than when R' is bonded to the nitrogen through a 1.degree. carbon atom of an aliphatic group of identical carbon number. With regard to an alicyclic hydrocarbyl R' ligand it has been found that as the number of carbon atoms thereof increases the molecular weight of the ethylene-.alpha.-olefin copolymer increases while the amount of .alpha.-olefin comonomer incorporated remains about the same or increases. Further, as the carbon number of the allcyclic hydrocarbyl ligand increases the productivity of the catalyst system increases. This is demonstrated by Examples 71-76. Accordingly, the R' ligand most preferred is cyclododecyl (C.sub.12 H.sub.23).

The affects of the bridging group ligands R.sup.1 and R.sup.2 has been found to be of less significance. The nature of the R.sup.1 and R.sup.2 ligands exerts a small effect upon the activity of a catalyst. For greatest catalyst activity the R.sup.1 and R.sup.2 ligands are preferably alkyl, most preferably methyl. The Q anionic ligands of the transition metal have not been observed to exert any particular influence on the catalyst or polymer properties, as demonstrated by comparison of Examples 71 and 86. Accordingly, as a convenience in the production of the transitional metal component the Q ligands are preferably chlorine or methyl.

The compounds most preferred for reasons of their high catalyst activity in combination with an ability to produce high molecular weight ethylene-.alpha.-olefin copolymers of high comonomer contents is represented by the formula: ##STR4## wherein R.sup.1 and R.sup.2 are each independently a C.sub.1 to C.sub.3 hydrocarbyl radical, each Q is independently a halide or alkyl radical, R' is an aliphatic or an alicyclic hydrocarby radical of the formula (C.sub.n H.sub.2n+b) wherein "n" is a number from 3 to 20 and "b" is +1 in which case the ligand is aliphatic or -1 in which case the ligand is alicyclic. Of these compounds, the most preferred is that compound wherein R.sup.1 and R.sup.2 are methyl, each Q is chlorine or methyl, n is 12, and the hydrocarbyl radical is allcyclic (i.e., b is -1). Most preferred is that compound wherein the (C.sub.n H.sub.2n-1 l) hydorcarbyl radical is a cyclododecyl group. Hereafter this compound is referred to for convenience as Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.23)TiQ.sub.2.

The alumoxane component of the catalyst system is an oligomeric compound which may be represented by the general formula (R.sup.3 --Al--O).sub.m which is a cyclic compound, or may be R.sup.4 (R.sub.5 --Al--O--).sub.m --AlR.sup.6.sub.2 which is a linear compound. An alumoxane is generally a mixture of both the linear and cyclic compounds. In the general alumoxane formula R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are, independently a C.sub.1 -C.sub.5 alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl and "m" is an integer from 1 to about 50. Most preferably, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are each methyl and "m" is at least 4. When an alkyl aluminum halide is employed in the preparation of the alumoxane, one or more R.sup.3-6 groups may be halide.

As is now well known, alumoxanes can be prepared by various procedures. For example, a trialkyl aluminum may be reacted with water, in 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 in an inert organic solvent, to yield an alumoxane. Generally, however prepared, the reaction of a trialkyl aluminum with a limited amount of water yields a mixture of both 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 trialkylaluminum; such as trimethylaluminum, triethyaluminum, tripropylaluminum; triisobutylaluminum, dimethylaluminumchloride, diisobutylaluminumchloride, diethylaluminumchloride, and the like. The most preferred alumoxane for use is methylalumoxane (MAO). Methylalumoxanes having an average degree of oligomerization of from about 4 to about 25 ("m"=4 to 25), with a range of 13 to 25, are the most preferred.

Catalyst Systems

The catalyst systems employed in the method of the invention comprise a complex formed upon admixture of the titanium metal component with an alumoxane component. The catalyst system may be prepared by addition of the requisite titanium metal and alumoxane components to an inert solvent in which olefin polymerization can be carried out by a solution, slurry or bulk phase polymerization procedure.

The catalyst system may be conveniently prepared by placing the selected titanium metal component and the selected alumoxane component, in any order of addition, in an alkane or aromatic hydrocarbon solvent--preferably one which is also suitable for service as a polymerization diluent. Where the hydrocarbon solvent utilized is also suitable for use as a polymerization diluent, the catalyst system may be prepared in situ in the polymerization reactor. Alternatively, the catalyst system may be separately prepared, in concentrated form, and added to the polymerization diluent in a reactor. Or, if desired, the components of the catalyst system may be prepared as separate solutions and added to the polymerization diluent in a reactor, in appropriate ratios, as is suitable for a continuous liquid phase polymerization reaction procedure. Alkane and aromatic 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, pentans, hexane, heptane, octane and the like, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, 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 including ethylene, propylene, 1-butene, 1-hexene and the like.

In accordance with this invention optimum results are generally obtained wherein the titanium metal compound is present in the polymerization diluent in a concentration of from about 0.0001 to about 1.0 millimoles/liter 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.

The catalyst system ingredients--that is, the titanium metal component, 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 -100.degree. to 300.degree. C. Greater or lesser temperatures can also be employed. Preferably, during formation of the catalyst system, the reaction is maintained within a temperature of from about 25.degree. to 100.degree. C., most preferably about 25.degree. C.

Polymerization Process

In a preferred embodiment of the process of this invention the catalyst system is utilized in the liquid phase (slurry, solution, suspension or bulk phase or 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 ethylene and a .alpha.-olefin monomer with the catalyst system in a suitable polymerization diluent and reacting the monomers in the presence of the catalyst system for a time and at a temperature sufficient to produce an ethylene-.alpha.-olefin copolymer of high molecular weight.

The monomers for such process comprise ethylene in combination with an .alpha.-olefin having 3 to 20 carbon atoms for the production of an ethylene-.alpha.-olefin copolymer. It should be appreciated that the advantages as observed in a ethylene-.alpha.-olefin copolymer produced with a catalyst system of this invention would also be expected to be obtained in a copolymer of different .alpha.-olefins wherein ethylene is not used as a monomer as viewed in comparison to a copolymer of the same or different .alpha.-olefins produced under similar polymerization conditions with a catalyst system which does not use a monocyclopentadienyl titanium compound as defined herein. Accordingly, although this invention is described with reference to an ethylene-.alpha.-olefin copolymer and the advantages of the defined catalyst system for the production thereof, this invention is not to be understood to be limited to the production of an ethylene-.alpha.-olefin copolymer, but instead the catalyst system hereof is to be understood to be advantageous in the same respects tot he production of a copolymer composed of two or more C.sub.3 or higher .alpha.-olefin monomers. Copolymers of higher .alpha.-olefin such as propylene, butene, styrene or higher .alpha.-olefins and diolefins can also be prepared. Conditions most preferred for the homo- or copolymerization of ethylene are those wherein ethylene is submitted to the reaction zone at pressures of from about 0.019 psia to about 50,000 psia and the reaction temperature is maintained at from about -100.degree. to about 300.degree. C. The aluminum to titanium metal molar ratio is preferably from about 1:1 to 18,000 to 1. A more preferable range would be 1:1 to 2000:1. The reaction time is preferably from about 10 seconds to about 1 hour.

The .alpha.-olefin to ethylene molar ratio often bears importantly upon the production capacity of a reactor of any design--i.e., whether for solution or gas phase production, etc.--for production of an ethylene based copolymer (i.e.--a copolymer the molar ratio of which is 50% or greater ethylene). The more ethylene input to a reactor in a given unit of time, the greater will be the amount of ethylene based copolymer product obtained in that same unit of time. Yet, polymers are designed for a variety of end services and this design constraint dictates the molar percentage of incorporated .alpha.-olefin which must be obtained in the targeted copolymer product. The "catalyst reactive ratio (r.sub.1)" of a catalyst system defines the property of the system of assimilating an ethylene monomer into a polymer molecule chain in preference to a particular .alpha.-olefin comonomer. The larger the r.sub.1 number, the greater the preference of the catalyst system for incorporating an ethylene monomer rather than a .alpha.-olefin monomer. Thus, to achieve a targeted .alpha.-olefin monomer incorporation (C.sub..alpha.) in the product polymer, the higher the r.sub.1 value of a catalyst system, the larger must be the C.sub..alpha. /C.sub.2 molar ratio of monomers used in the reactor, and as the C.sub..alpha. /C.sub.2 ratio increases the lower is the production capacity of the reactor.

To achieve a desired level of .alpha.-olefin monomer incorporation in a copolymer product, as can be seen, it is often desired to have a catalyst system which can achieve a low molar ratio of C.sub..alpha. /C.sub.2, i.e., a catalyst system with a low r.sub.1 is desired. For example, with reference to 1-butene, the catalyst systems of this invention wherein the titanium metal compound has a tetramethyl substitute cyclopentadienyl ligand generally exhibit an r.sub.1 value of 6 or less, and typically of 5 or less. Thus, with catalyst systems of this invention an .alpha.-olefin incorporation of greater than 20wt. % can be achieved at a C.sub..alpha. /C.sub.2 ratio of 2.0 or less, and typically of about 1.6.

In addition to the benefits of increased reactor productivity which, for a copolymer of a targeted .alpha.-olefin incorporation level, which a catalyst system of lower r.sub.1 values allows, other significant additional benefits ensue from a low r.sub.1 value. Recovery of unreacted monomer, particularly .alpha.-olefin monomer for later reuse adds significantly to production cost. By use of the catalyst systems identified by this invention, the cost of unreacted .alpha.-olefin monomer recovery may be reduced significantly since a smaller quantity of .alpha.-olefin monomer can be used to achieve the same target level of .alpha.-olefin incorporation.

Further, since it is the ratio of C.sub..alpha. /C.sub.2 in the medium wherein polymerization occurs which is critical (i.e., liquid phase, gas phase, or super critical fluid phase, etc.) the low r.sub.1 values for the catalyst systems of this invention permit the catalyst systems to be used in a wider variety of polymerization procedures than was heretofore believed to be practically possible. Praticularily within this range of possibilities is that of the gas phase polymerization of an ethylene .alpha.-olefin copolymer of a greater than heretofore believed possible level of .alpha.-olefin incorporation.

Without limiting in any way the scope of the invention, one means for carrying out the process of the present invention for production of a copolymer is as follows: in a stirred-tank reactor liquid .alpha.-olefin monomer is introduced, such as 1-butene. The catalyst system is introduced via nozzles in 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 is well known in the art. The reactor contains a liquid phase composed substantially of liquid .alpha.-olefin comonomer, 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 .alpha.-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 .alpha.-olefin comonomer in the reactor, which is controlled by manipulating the relative feed rates of these components to the reactor.

As before noted, a catalyst system wherein the Group IV B transition metal component is titanium has the ability to incorporate high contents of .alpha.-olefin comonomers. Accordingly, the selection of the titanium metal component to have the cyclopentadienyl group to be tetramethyl substituted and to have an amido group bridged through its nitrogen atom to the cyclopentadienyl ring wherein the nitrogen of the amido group is bonded through a 1.degree. or 2.degree. carbon atom to an aliphatic or allcyclic hydrocarbyl group, most preferably an alicyclic hydrocarbyl group is another parameter which may be utilized as a control over the .alpha.-olefin content of the ethylene-.alpha.-olefin copolymer within a reasonable ratio of ethylene to .alpha.-olefin comonomer. For reasons already explained, in the production of an ethylene-.alpha.-olefin copolymer a molar ratio of ethylene to .alpha.-olefin of 2.0 or less is preferred, and a ratio of 1.6 or less is more preferred.

In the examples which illustrate the practice of the invention the analytical techniques described below were employed for the analysis of the resulting polyolefin products. 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 on-line light scattering photometer. The system was used at 135.degree. 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 editor, Marcel Dekker. 1981, p. 207, 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 polyisoprenes (an alternating ethylene-propylene copolymer) demonstrated that such corrections 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.

The following examples are intended to illustrate specific embodiments of the invention and are not intended to limit the scope of the invention.

All procedures were performed under an inert atmosphere of helium or nitrogen. Solvent choices are often optional, for example, in most cases either pentane or 30-60 petroleum ether can be interchanged. The lithiated amides were prepared from the corresponding amines and either n-BuLi or MeLi. Published methods for preparing LiHC.sub.5 Me.sub.4 include C. M. Fendrick et al. Organometallics, 3, 819 (1984) and F. H. Kohler and K. H. Doll, Z. Naturforich, 376, 144 (1982). Other lithiated substituted cyclopentadienyl compounds are typically prepared from the corresponding cyclopentadienyl ligand and n-BuLi or MeLi, or by reaction of MeLi with the proper fulvene. TiCl.sub.4, ZrCl.sub.4 and HfCl.sub.4 were purchased from either Aldrich Chemical Company or Cerac. TiCl.sub.4 was typically used in its etherate form. The etherate, TiCl.sub.4 .cndot.2Et.sub.2 O, can be prepared by gingerly adding TiCl.sub.4 to diethylether. Amines, silanes, substituted and unsubstituted cyclopentadienyl compounds or precursors, and lithium reagents were purchased from Aldrich Chemical Company or Petrarch Systems. Methylalumoxane was supplied by either Sherring or Ethyl Corp.

Further, since the full disclosure of U.S. application Ser. No. 581,841 has been incorporated herein, the Examples hereof are identified by designations which are consistent with the Example designations of the incorporated application. Examples of the incorporated application relating to the Zr or Hf metal classes of a monocyclopentadienyl transition metal catalyst system are not here repeated (which are Examples A to L) for sake of brevity. Accordingly, not verbatim repeated herein (but incorporated) are Examples A to L, and certain other double letter designated Examples of the incorporated patent. Set forth verbatim herein as repeats of Examples of the incorporated application are Examples AT, FT, IT, JT, 40-47, 53-58, 58, 67 and 70.

Compound AT: Part 1. MePhSiCl.sub.2 (14.9 g, 0.078 mol) was diluted with 250 ml of thf. Me.sub.4 HC.sub.5 Li (10.0 g, 0.078 mol) was slowly added as a solid. The reaction solution was allowed to stir overnight. The solvent was removed via a vacuum to a cold trap held at -196.degree. C. Petroleum ether was added to precipitate out the LiCl. The mixture was filtered through Celite and the pentane was removed from the filtrate. MePhSi(Me.sub.4 C.sub.5 H)Cl (20.8 g, 0.075 mol) was isolated as a yellow viscous liquid.

Part 2. LiHN-t-Bu (4.28 g, 0.054 mol) was dissolved in .about.100 ml of thf. MePhSi(C.sub.5 Me.sub.4 H)Cl (15.0 g, 0.054 mol) was added dropwise. The yellow solution was allowed to stir overnight. The solvent was removed in vacuo. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through Celite, and the filtrate was evaporated. MePhSi(C.sub.5 Me.sub.4 H)(NH-t-Bu) (16.6 g, 0.053 mol) was recovered as an extremely viscous liquid.

Part 3. MePhSi(C.sub.5 Me.sub.4 H)(NH-t-Bu) (17.2 g, 0.055 mol) was diluted with .about.20 ml of ether. n-BuLi (60 ml in hexane, 0.096 mol, 1.6M) was slowly added and the reaction mixture was allowed to stir for .about.3 hours. The solvent was removed in vacuo to yield 15.5 g (0.48 mol) of a pale tan solid formulated as Li.sub.2 [MePhSi(C.sub.5 Me.sub.4)(N-t-Bu)].

Part 4. Li.sub.2 [MePhSi(C.sub.5 Me.sub.4)(N-t-Bu)] (8.75 g, 0.027 mol) was suspended in .about.125 ml of cold ether (.about.-30.degree.). TiCl.sub.4 .cndot.2Et.sub.2 O (9.1 g, 0.027 mol) was slowly added. The reaction was allowed to stir for several hours prior to removing the ether via vacuum. A mixture of toluene and dichloromethane was then added to solubilize the product. The mixture was filtered through Celite to remove the LiCl. The solvent was largely removed via vacuum and petroleum ether was added. The mixture was cooled to maximize product precipitation. The crude product was filtered off and redissolved in toluene. The toluene insolubles were filtered off. The toluene was then reduced in volume and petroleum ether was added. The mixture was cooled to maximize precipitation prior to filtering off 3.34 g (7.76 mmol) of the yellow solid MePhSi(C.sub.5 Me.sub.4)(N-t-Bu)TiCl.sub.2.

Compound FT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared as described in Example BT for the preparation of compound BT, Part 1.

Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (5.19 g, 0.024 mol) was slowly added to a solution of LiHNC.sub.6 H.sub.11 (2.52 g, 0.024 mol) in .about.125 ml of thf. The solution was allowed to stir for several hours. The thf was removed via vacuum and petroleum ether was added to precipitate the LiCl which was filtered off. The solvent was removed from the filtrate via vacuum yielding 6.3 g (0.023 mol) of the yellow liquid, Me.sub.2 Si(C.sub.5 Me.sub.4 H)(HNC.sub.6 H.sub.11).

Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(HNC.sub.6 H.sub.11) (6.3 g, 0.023 mol) was diluted with .about.100 ml of ether. MeLi (33 ml, 1.4M in ether, 0.046 mol) was slowly added and the mixture was allowed to stir for 0.5 hours prior to filtering off the white solid. The solid was washed with ether and vacuum dried. Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.6 H.sub.11)] was isolated in a 5.4 g (0.019 mol) yield.

Part 4. Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.6 H.sub.11)] (2.57 g, 8.90 mmol) was suspended in .about.50 ml of cold ether. TiCl.sub.4 .cndot.2Et.sub.2 O (3.0 g, 8.9 mmol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and a mixture of toluene and dichloromethane was added. The mixture was filtered through Celite to remove the LiCl byproduct. The solvent was removed from the filtrate and a small portion of toluene was added followed by petroleum ether. The mixture was chilled in order to maximize precipitation. A brown solid was filtered off which was initially dissolved in hot toluene, filtered through Celite, and reduced in volume. Petroleum ether was then added. After refrigeration, an olive green solid was filtered off. This solid was recrystallized twice from dichloromethane and petroleum ether to give a final yield of 0.94 g (2.4 mmol) of the pale olive green solid, Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.6 H.sub.11)TiCl.

Compound IT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared as described in Example BT for the preparation of Compound BT, part 1.

Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (10.0 g, 0.047 mol) was slowly added to a suspension of LiHN-t-Bu (3.68 g, 0.047 mol, .about.100 ml thf). The mixture was stirred overnight. The thf was then removed via a vacuum to a cold trap held at -196.degree. C. Petroleum ether was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(NH-t-Bu) (11.14 g, 0.044 mol) was isolated as a pale yellow liquid.

Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(NH-t-Bu) (11.14 g, 0.044 mol) was diluted with .about.100 ml of ether. MeLi (1.4M,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, [Me.sub.2 Si(C.sub.5 Me.sub.4)(N-t-Bu)]Li.sub.2, was washed with several small portions of ether, then vacuum dried.

Part 4. [Me.sub.2 Si(C.sub.5 Me.sub.4)(N-t-Bu)Li.sub.2 (6.6 g, 0.025 mol) was suspended in cold ether. TiCl.sub.4 .cndot.2Et.sub.2 O (8.4 g, 0.025 mol) was slowly added and the resulting mixture was allowed to stir overnight. The ether was removed via a vacuum to a cold trap held at -196.degree. C. Methylene chloride was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was significantly reduced in volume and petroleum ether was added to precipitate out the product. This mixture was refrigerated prior to filtration in order to maximize precipitation. Me.sub.2 Si(C.sub.5 Me.sub.4)(N-t-Bu)TiCl.sub.2 was isolated (2.1 g, 5.7 mmol).

Compound JT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared as described in Example BT for the preparation of Compound BT, Part 1.

Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (8.0 g, 0.037 mol) was slowly added to a suspension of LiHNC.sub.12 H.sub.23 (C.sub.12 H.sub.23 =cyclododecyl, 7.0 g, 0.037 mol, .about.80 ml thf). The mixture was stirred overnight. The thf was then removed via a vacuum to a cold trap held at -196.degree. C. Petroleum ether and toluene was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(NHC.sub.12 H.sub.23) (11.8 g, 0.033 mol) was isolated as a pale yellow liquid.

Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(NHC.sub.12 H.sub.23) (11.9 g, 0.033 mol) was diluted with .about.150 ml of ether. MeLi (1.4M, 47 ml, 0.066 mol) was slowly added. The mixture was allowed to stir for 2 hours after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, [Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.23)]Li.sub.2, was washed with several small portions of ether, then vacuum dried to yield 11.1 g (0.030 mol) of product.

Part 4. [Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.23)]Li.sub.2 (3.0 g, 0.008 mol) was suspended in cold ether. TiCl.sub.4 .cndot.2Et.sub.2 O (2.7 g, 0.008 mol) was slowly added and the resulting mixture was allowed to stir overnight. The ether was removed via a vacuum to a cold trap held at -196.degree. C. Methylene chloride was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was significantly reduced in volume and petroleum ether was added to precipitate out the product. This mixture was refrigerated prior to filtration in order to maximize precipitation. The solid collected was recrystallized from methylene chloride and Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.23)TiCl.sub.2 was isolated (1.0 g, 2.1 mmol).

Compound KT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared as described in Example A for the preparation of compound A, Part 1.

Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (6.0 g, 0.0279 mol) was diluted in 200 ml of thf. LiHNC.sub.12 H.sub.25 (C.sub.12 H.sub.25 =n-dodecyl, 5.33 g, 0.0279 ml) was slowly added and the mixture was allowed to stir for 3 hours. The thf was removed in vacuo and 200 ml ether was added.

To this solution, MeLi (1.4M, 34 ml, 0.0476 mol) was slowly added. Upon completion of the reaction, a small amount of TiCl.sub.4 .cndot.2Et.sub.2 O was added to scavenge the excess MeLi. The solution was then cooled to -30.degree. C. and an additional 7.75 g (0.030 mol) of TiCl.sub.4 .cndot.2Et.sub.2 O was added. The mixture was allowed to stir overnight. The solvent was removed and pentane was added. The resulting mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and chilled to induce crystalization of the product. Filtration yielded 4.2 g (0.0087 mol) Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.25)TiCl.sub.2.

Compound LT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared as described in Example A for the preparation of compound A, Part 1.

Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (12.0 g, 0.056 mol) was diluted with 300 ml of thf. LiHNC.sub.8 H.sub.15 (C.sub.8 H.sub.15 =cyclooctyl, 742 g, 0.056 mol) was slowly added and the mixture was allowed to stir overnight. The reaction product, Me.sub.2 Si(C.sub.5 Me.sub.4 H)(HNC.sub.8 H.sub.15) was not isolated. The thf was removed and 300 ml of diethyl ether was added. MeLi (1.12M, 105 ml, 0.118 mol) was slowly added to form the dilithiated salt, Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.8 H.sub.15)]. This mixture was cooled to -30.degree. C., and TiCl.sub.4 .cndot.2Et.sub.2 O (19.14 g, 0.057 mol) was slowly added. The resulting mixture was allowed to stir overnight. The ether was removed in vacuo, and pentane was added to solubilize the product. The mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and chilled to -40.degree. C. to induce crystallization of the product. Filtration yielded 7.9 g (0.019 mol) of Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.8 H.sub.15)TiCl.sub.2.

Compound MT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared as described in Example A for the preparation of compound A, Part 1.

Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (6.0 g, 0.028 mol) was diluted with 150 ml of thf. LiHNC.sub.8 H.sub.17 (C.sub.8 H.sub.17 =n-octyl, 3.7 g, 0.030 mol) was slowly added. The mixture was allowed to stir overnight. The reaction product, Me.sub.2 Si(C.sub.5 Me.sub.4 H(HNC.sub.8 H.sub.17) was not isolated prior to adding MeLi (2.1M, 35 ml, 0.074 mol) to give Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.8 H.sub.17)]. The solvent was removed via vacuum and replaced with diethyl ether, then cooled to -30.degree. C. TiCl.sub.4 .cndot.2Et.sub.2 O (8.46 g, 0.025 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed in vacuo and methylene chloride was used to solubilize the product. The solvent mixture was filtered through Celite to remove the LiCl. The filtrate was evaporated down to dryness and pentane was added. The pentane soluble fraction was cooled to -40.degree. C. to induce crystallization of the product. After filtration, Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.8 H.sub.17)TiCl.sub.2 was isolated (1.8 g, 0.0042 mol).

Compound NT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared as described in Example A for the preparation of compound A, Part 1.

Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (6.0 g, 0.028 mol) was diluted in 150 ml of thf. LiHNC.sub.6 H.sub.13 (C.sub.6 H.sub.13 =n-hexyl, 2.99 g, 0.028 mol) was slowly added. The mixture was allowed to stir overnight. The thf was removed via vacuum and replaced with diethyl ether. The reaction product Me.sub.2 Si(C.sub.5 Me.sub.4 H)(HNC.sub.6 H.sub.13) was not isolated prior to adding MeLi (1.4M, 45 Ml, 0.063 mol) to give Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.6 H.sub.13)]. The resulting mixture was then cooled to -30.degree. C. TiCl.sub.4 .cndot.2Et.sub.2 (8.6 g, 0.025 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed in vacuo and pentane was used to solubilize the product. The solvent mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and cooled to -40.degree. C. to induce crystallization of the product. While crystalline material appeared in the flask at -40.degree. C., upon slight warming, it dissolved back into solution and therefore could not be isolated by filtration. Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.6 H.sub.13)TiCl.sub.2 was isolated in an oil form by removing the solvent from the above solution. (4.0 g, 0.010 mol).

Compound OT: Part 1. MePhSi(C.sub.5 Me.sub.4 H)Cl was prepared as described in Example AT for the preparation of compound AT, Part 1.

Part 2. MePhSi(C.sub.5 Me.sub.4 H)Cl (6.0 g. 0.022 mol) was diluted with ether. LiHN-s-Bu (1.7 g, 0.022 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed and a mixture of toluene and petroleum ether was added. This mixture was filtered through Celite to remove the LiCl. The solvent was removed via vacuum leaving behind the viscous liquid, MePhSi(C.sub.5 Me.sub.4 H)(HN-s-Bu). To this liquid which was diluted with ether, 28 ml (0.039 mol 1.4M in ether) MeLi was slowly added. After stirring overnight, a small portion of TiCl.sub.4 .cndot.2Et.sub.2 O (total of 5.86 g, 0.017 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum, dichloromethane was added and the mixture was filtered through Celite. The filtrate was evaporated down producing a brown solid. Petroleum ether was added and the mixture was filtered. The brown solid remaining on the filter stick was discarded and the filtrate was reduced in volume and refrigerated to maximize precipitation. After filtration and washing with cold aliquots of petroleum ether, a dark mustard yellow solid was isolated and identified as MePhSi(C.sub.5 Me.sub.4)(N-s-Bu)TiCl.sub.2 (2.1 g, 4.9 mmol).

Compound PT: Part 1. MePhSi(C.sub.5 Me.sub.4 H)Cl was prepared as described in Example AT for the preparation of compound AT, Part 1.

Part 2. MePhSi(C.sub.5 Me.sub.4 H)Cl (6.0 G, 0.022 mol) was diluted with either. LiHN-n-Bu (1.7 g, 0.022 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and a mixture of toluene and petroleum ether was added. This was filtered through Celite to remove the LiCl. The solvent was removed from the filtrate leaving behind a viscous yellow liquid which was diluted with ether. To this, 28 ml of MeLi (1.4M in ether, 0.038 mol) was added and the mixture was allowed to stir overnight. A small portion of TiCl.sub.4 .cndot.2Et.sub.2 O (total of 5.7 g, 0.017 mol) was slowly added. In spite of the slow addition, the highly exothermic reaction bumped, thus some product loss occurred at this point in the reaction. The remaining mixture was stirred overnight. The solvent was then removed via vacuum. Dichloromethane was added and the mixture was filtered through Celite to remove the LiCl. The solvent was removed and petroleum ether was added. The mixture was refrigerated to maximize precipitation. Filtration produced a yellow-brown solid which was recrystallized from petroleum ether. The final filtration produced 2.0 g (4.6 mmol) of MePhSi(Me.sub.4 C.sub.5)(N-n-Bu)TiCl.sub.2.

Compound OT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared as described in Example A for the preparation of compound A, Part 1.

Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (9.0 g, 0.042 mol) was diluted in ether. LiHn-s-Bu (3.31 g, 0.042 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether was added. This mixture was filtered through Celite to remove the LiCl. The solvent was removed from the filtrate leaving behind the pale yellow liquid, Me.sub.2 Si(C.sub.5 Me.sub.4 H(HN-s-Bu) (10.0 g, 0.040 mol).

Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H)(HN-s-Bu) (10.0 g, 0.040 mol) was diluted with ether. MeLi (58 ml, 1.4M in ether, 0.081 mol) was added and the mixture was allowed to stir overnight. The solvent was reduced in volume and the white solid was filtered off and washed with small portions of ether. Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4)(N-s-Bu)] (10.1 g, 0.038 mol) was isolated after vacuum drying.

Part 4. Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4)(N-s-Bu)] (7.0 g, 0.027 mol) was suspended in cold ether. TiCl.sub.4 .cndot.2Et.sub.2 O (8.98 g, 0.027 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and dichloromethane was added. The mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and petroleum ether was added. This mixture was refrigerated to maximize precipitation prior to filtering off the olive green solid. The solid was recrystallized from dichloromethane and petroleum ether yielding 2.4 g (6.5 mmol) of the yellow solid, Me.sub.2 Si(C.sub.5 Me.sub.4)(N-s-Bu)TiCl.sub.2.

Compound RT: Part 1. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl was prepared as described in Example A for the preparation of compound A, Part 1.

Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (8.0 g, 0.037 mol) was diluted with ether. LiHN-n-Bu (2.95 g, 0.037 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether was added. The mixture was filtered through Celite to remove the LiCl. The solvent was removed from the filtrate leaving behind the yellow liquid, Me.sub.2 Si(C.sub.5 Me.sub.4 H)(HN-n-Bu) (8.6 g, 0.034 mol).

Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H (HN-n-Bu) (8.6 g, 0.034 mol) was diluted with ether. MeLi (50 ml, 1.4M in ether, 0.070 mol) was slowly added and the mixture was allowed to stir for two hours. The solvent was removed leaving behind 10.2 g (0.035 mol) of the yellow solid, Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4 (N-n-Bu)].cndot.1/3Et.sub.2 O.

Part 4. Li.sub.2 [Me.sub.2 Si(C.sub.5 Me.sub.4)(N-n-Bu)].cndot.1/3Et.sub.2 O (6.0 g, 0.021 mol) was suspended in cold ether. TiCl.sub.4 .cndot.2Et.sub.2 O (7.04 g, 0.0212 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed and dichloromethane was added. The mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and petroleum ether was added. The mixture was refrigerated to maximize precipitation prior to filtering off a mixture of dark powder and yellow crystals. The material was redissolved in a mixture of dichloromethane and toluene. A small portion of petroleum ether was added and the brown precipitate was filtered off and discarded. The filtrate was reduced in volume, additional petroleum ether was added and the mixture was placed back in the refrigerator. Later, 3.65 g of the maize yellow solid, Me.sub.2 Si(C.sub.5 Me.sub.4)(N-n-Bu)TiCl.sub.2 was filtered off.

Compound ST: Part 1. Me.sub.2 SiCl.sub.2 (210 ml, 1.25 mol) was diluted with a mixture of ether and thf. LiMeC.sub.5 H.sub.4 (25 g, 0.29 mol) was slowly added, and the resulting mixture was allowed to stir for a few hours, after which time the solvent was removed in vacuo. Pentane was added to precipitate the LiCl, and the mixture was filtered through Celite. The pentane was removed from the filtrate leaving behind a pale yellow liquid, Me.sub.2 Si(Me.sub.5 H.sub.4)Cl.

Part 2. Me.sub.2 Si(MeC.sub.5 H.sub.4)Cl (10.0 g, 0.058 mol) was diluted with a mixture of ether and thf. To this, LiHNC.sub.12 H.sub.23 (11.0 g, 0.058 mol) was slowly added. The mixture was allowed to stir overnight. The solvent was removed via vacuum and toluene and pentane were added to precipitate the LiCl. The solvent was removed from the filtrate leaving behind a pale yellow liquid, Me.sub.2 Si(MeC.sub.5 H.sub.4)(HNC.sub.12 H.sub.23)(18.4 g, 0.058 mol).

Part 3. Me.sub.2 Si(MeC.sub.5 H.sub.4)(HNC.sub.12 H.sub.23) (18.4 g, 0.058 mol) was diluted in ether. MeLi (1.4M in ether, 82 ml, 0.115 mol) was slowly added. the reaction was allowed to stir for several hours before reducing the mixture in volume and then filtering off the white solid, Li.sub.2 [Me.sub.2 Si(MeC.sub.5 H.sub.3)(NC.sub.12 H.sub.23)] (14.3 g, 0.043 mol).

Part 4. Li.sub.2 [Me.sub.2 Si(MeC.sub.5 H.sub.3)(NC.sub.12 H.sub.23)] (7.7 g, 0.023 mol) was suspended in cold ether. TiCl.sub.4 .cndot.2Et.sub.2 (7.8 g, 0.023 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum. Dichloromethane was added and the mixture was filtered through Celite. The dichloromethane was reduced in volume and petroleum ether was added to maximize precipitation. This mixture was then refrigerated for a short period of time prior to filtering off a yellow/green solid identified as Me.sub.2 Si(MeC.sub.5 H.sub.3)(NC.sub.12 H.sub.23)TiCl.sub.2 (5.87 g, 0.013 mol).

Compound TT: Part 1. Me.sub.2 SiCl.sub.2 (7.5 ml, 0.062 mol) was diluted with .about.30 ml of thf. A t-BuH.sub.4 C.sub.5 Li solution (7.29 g, 0.057 mol.about.100 ml of thf) was slowly added, and the resulting mixture was allowed to stir overnight. The thf was removed in vacuo. Pentane was add to precipitate the LiCl, and the mixture was filtered through Celite. The pentane was removed from the filtrate leaving behind a pale yellow liquid, Me.sub.5 Si(t-BuC.sub.5 H.sub.4)Cl (10.4 g, 0.048 mol).

Part 2. Me.sub.2 Si(t-BuC.sub.5 H.sub.4)Cl (8.0 g, 0.037 mol) was diluted with thf. To this, LiHNC.sub.12 H.sub.23 (7.0 g, 0.037 mol) was slowly added. The mixture was allowed to stir overnight. The solvent was removed via vacuum and toluene was added to precipitate the LiCl. The toluene was removed from the filtrate leaving behind a pale yellow liquid, Me.sub.2 Si(t-BuC.sub.5 H.sub.4)(HNC.sub.12 H.sub.23) (12.7 g, 0.035 mol).

Part. 3 Me.sub.2 Si(t-BuC.sub.5 H.sub.4)(HCN.sub.12 H.sub.23) (12.7 g, 0.035 mol) was diluted with ether. To this, MeLi (1.4M in ether, 50 ml, 0.070 mol) was slowly added. This was allowed to stir for two hours prior to removing the solvent via vacuum. The product, Li.sub.2 [Me.sub.2 Si(t-Bu-C.sub.5 H.sub.3)(NC.sub.12 H.sub.23)] (11.1 g, 0.030 mol) was isolated.

Part 4. Li.sub.2 [Me.sub.2 Si(t-BuC.sub.5 H.sub.3)(NC.sub.12 H.sub.23)] (10.9 g, 0.029 mol) was suspended in cold ether. TiCl.sub.4 .cndot.2ET.sub.2 O (9.9 g, 0.029 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum. Dichloromethane was added and the mixture was filtered through Celite. The solvent was removed and pentane was added. The product is completely soluble in pentane. This solution was passed through a column containing a top layer of silica and a bottom layer of Celite. The filtrate was then evaporated down to an olive green colored solid identified as Me.sub.2 Si(t-BuC.sub.5 H.sub.3)(NC.sub.12 H.sub.23)TiCl.sub.2 (5.27 g, 0.011 mol).

Compound UT

Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.23)TiMe.sub.2 was prepared by adding a stoichiometric amount of MeLi (1.4M in ether) to Me.sub.2 Si(C.sub.5 Me.sub.4)(NC.sub.12 H.sub.23)TiCl.sub.2 (Compound JT from Example JT) suspended in ether. The white solid recrystallized from toluene and petroleum ether was isolated in a 57% yield.

Polymerization--Compound AT

The polymerization run was performed in a 12-liter autoclave reactor equipped with a paddle stirrer, an external water 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 or comonomers, 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 toluene, 5 ml of 1.0M MAO, 0.206 mg compound AT (0.2 ml of a 10.3 mg in 10 ml of toluene solution) into the reactor. The reactor was then heated to 80.degree. 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 and venting the system. The solvent was evaporated off of the polymer by a stream of nitrogen. Polyethylene was recovered (11.8 g, MW=279,700, MWD=2.676).

Polymerization--Compound AT

Using the same reactor design and general procedure as described in Example 40, 400 ml of toluene, 5.0 ml of 1.0M MAO, and 0.2 ml of a preactivated compound AT solution (10.3 mg of compound AT dissolved in 9.5 ml of toluene and 0.5 ml of 1.0M MAO) were added to the reactor. The reactor was heated to 80.degree. C., the ethylene was introduced (60 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 14.5 g of polyethylene was recovered (MW=406,100, MWD=2.486).

Polymerization--Compound AT

Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml of 1-hexene, 7.0 ml of 1.0M MAO, and 1.03 mg of compound AT (1.0 ml of 10.3 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80.degree. C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 48.6 g of an ethylene-1-hexene copolymer was recovered (MW 98,500, MWD=1.745, 117 SCB/1000C by .sup.13 C NMR).

Polymerization--Compound AT

Using the same reactor design and general procedure described in Example 40, 375 ml of toluene, 25 ml of 1-hexene, 7.0 ml of 1.0M MAO, and 1.03 mg of compound AT (1.0 ml of a 10.3 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80.degree. C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 29.2 g of an ethylene-1-hexene copolymer was recovered (MW=129,800, MWD=2.557, 53.0 SCB/1000C by .sup.13 C NMR).

Polymerization--Compound AT

Using the same reactor design and general procedure described in Example 40, 375 ml of toluene, 25 ml of 1-hexene, 7.0 ml of 1.0M MAO, and 1.03 mg of compound AT (1.0 ml of 10.3 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 50.degree. C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 15.0 g of an ethylene-1-hexene copolymer was recovered (MW=310,000, MWD=2.579, 47.2 SCB/1000C by .sup.13 C NMR).

Polymerization--Compound AT

Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml of propylene, 7.0 ml of 1.0M MAO, and 2.06 mg of compound AT (2.0 ml of a 10.3 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80.degree. C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 46.0 g of an ethylene-propylene copolymer was recovered (MW=110,200, MWD=5.489, 20 wt % ethylene by IR).

Polymerization--Compound AT

Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml of 1-butene, 7.0 ml of 1.0M MAO, and 1.03 mg of compound AT (1.0 ml of a 10.3 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80.degree. C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 35.1 g of an ethylene-1-butene copolymer was recovered (MW=94,400, MWD=2,405, 165 SCB/1000C by .sup.13 C NMR).

Polymerization--Compound AT

Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml of 1-octene, 7.0 ml of 1.0M MAO,and 1.04 mg of compound AT (1.0 ml of a 10.4 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80.degree. C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 30.6 g of an ethylene-1-octene copolymer was recovered (MW=73,100, MWD=2,552, 77.7 SCB/1000C by .sup.13 C NMR).

Polymerization--Compound AT

The polymerization was performed in a stirred 100 ml stainless steel autoclave which was equipped to perform polymerizations at temperatures up to 300.degree. C. and pressures up to 2500 bar. The reactor was evacuated, purged with nitrogen, purged with ethylene and heated to 200.degree. C. 1-hexene (75 ml) was added to the reactor under ethylene pressure. A stock solution of compound AT was prepared by dissolving 6.5 mg of compound AT in 12.5 ml of toluene. The test solution was prepared by adding 1.0 ml of the compound AT stock solution to 1.9 ml of 1.0M MAO solution, followed by 7.1 ml of toluene. The test solution (0.43 ml) was transferred by nitrogen pressure into a constant-volume injection tube. The autoclave was pressurized with ethylene to 1748 bar and was stirred at 1800 rpm. The test solution was injected into the autoclave with excess pressure, at which time a temperature rise of 16.degree. 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 to recover any polymer remaining within. These washings were combined with the polymer released when the reactor was vented. Precipitation of the polymer from the mixture by addition of acetone yielded 2.7 g of polymer (MW=64,000, MWD=3.16, 14.7 SCB/1000C by IR).

Polymerization--Compound AT

For this Example a stirred 1 L steel autoclave reaction vessel which was equipped to perform continuous Ziegler polymerization reactions at pressures to 2500 bar and temperatures up to 300.degree. C. was used. The reaction system was supplied with a thermocouple and pressure transducer to measure temperature and pressure continuously, and with means to supply continuously purified compressed ethylene and 1-butene (or propylene). Equipment for continuously introducing a measured flow of catalysts solution, and equipment for rapidly venting and quenching the reaction, and of collecting the polymer product were also a part of the reaction system. The polymerization was performed with a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent. The temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180.degree. C. The catalyst solution was prepared by mixing 0.888 g of solid compound AT with 0.67 L of a 30 wt % methylalumoxane solution in 4.3 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.56 L/hr which resulted in a temperature of 180.degree. C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer products was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 50,200, a molecular weight distribution of 2.36 and 60.1 SCB/1000C as measured by .sup.13 C NMR.

Polymerization--Compound AT

Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to propylene of 2.6 without the addition of a solvent. The temperature of a cleaned reactor containing ethylene and propylene was equilibrated at the desired reaction temperature of 140.degree. C. The catalyst solution was prepared by mixing 0.779 g of solid compound AT with 0.5 L of a 30 wt % methylalumoxane solution in 24.5 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.9 L/hr which resulted in a temperature of 140.degree. C. in the reactor. During this run, ethylene and propylene were pressured into the autoclave at a total pressure of 2200 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 2.3 kg/hr of an ethylene-propylene copolymer which had a weight average molecular weight of 102,700, a molecular weight distribution of 2.208 and a density of 0.863 g/cc.

Polymerization--Compound FT

Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent. The temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180.degree. C. The catalyst solution was prepared by mixing 0.859 g of solid FT with 30 wt % methylalumoxane solution and toluene such that the catalyst concentration was 0.162 g/L with an Al/M molar ratio of 1200. The preparation was done under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 1.15 L/hr which resulted in a temperature of 180.degree. C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 61,400, a molecular weight distribution of 2.607 and 104.8 SCB/1000C by .sup.13 C NMR.

Polymerization--Compound AT

Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 170.degree. C. The catalyst solution was prepared by mixing 0.925 g of solid compound AT with 2 L of a 10 wt % methylalumoxane solution in 8 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.28 L/hr which resulted in a temperature of 170.degree. C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.7 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 69,500, a molecular weight distribution of 2.049 and 35.7 SCB/1000C by .sup.13 C NMR.

Polymerization--Compound IT

Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180.degree. C. The catalyst solution was prepared by mixing 1.94 g of solid compound IT with 30 wt % methylalumoxane solution and toluene such that the catalyst concentration was 0.388 g/L and the Al/M molar ratio was 600. The preparation was done under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.42 L/hr which resulted in a temperature of 180.degree. C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 50,800, a molecular weight distribution of 2.467 and 69 SCB/1000C as measured by .sup.1 H NMR.

Polymerization--Compound JT

Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180.degree. C. The catalyst solution was prepared by mixing 1.78 g of solid compound JT with 30 wt % methylalumoxane solution and toluene such that the catalyst concentration was 0.318 g/L and the Al/M molar ratio was 1400. The preparation was done under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.55 L/hr which resulted in a temperature of 180.degree. C. in the reactor. During thus run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 72,600, a molecular weight distribution of 2.385 and 110 SCB/1000C as measured by .sup.1 H NMR.

Each of the compounds of Examples KT through TT were used to prepare an ethylene-1-butene copolymer. The polymerization reactions were carried out in the same reactor design as described in Example 54. With the sole exception of Example 83, all polymerizations were carried out using a molar ratio of 1-butene to ethylene of 1.6 without the addition of a solvent. In Example 83 a 1-butene to ethylene ratio of 2.0 was used. The temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180.degree. C.

The catalyst solution was prepared by mixing a specified amount of solid transition metal component with a 30 weight percent methylalumoxane solution and this catalyst solution was then further diluted in toluene under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate which resulted in the desired reactor temperature of 180.degree. C., which was the polymerization temperature for all examples. The reactor contents were stirred at 1000 rpm and a reactor mass flow rate of 40 kg/g was used for all examples. The reactor pressure was maintained at 1300 bar and no hydrogen was supplied to the reactor. Exact run conditions including catalyst preparation [transition metal component (TMC) and amount (g), methylalumoxane (MAO) volume used (L), total volume of catalyst solution (L) and concentration (g TMC/L) and (g MAO/L)], catalyst feed rate (L/hr), polymer production rate (kg polymer/hr), molar Al/M ratio, productivity (kg polymer/g catalyst) and polymer characteristics including weight average MW (Daltons), molecular weight distribution (MW/MN), melt index (10 g/minute at 190.degree. C.), weight percent comonomer (determined by .sup.1 H NMR or .sup.13 C NMR), and catalyst reactivity ratios (r.sub.1) are collected in Table 1.

By appropriate selection of (1) 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; (4) reaction temperature; and (5) reaction pressure, one may tailor the product polymer to the weight average molecular 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.

From the above examples, particularly as collected in Table 1, it appears that for a catalyst system wherein the group IV B transition metal component is a titanium species of the following structure: ##STR5## the nature of the R' group dramatically influence the catalytic properties of the system. For production of ethylene-.alpha.-olefin copolymers of greatest comonomer content, at a selected ethylene to .alpha.-olefin monomer ratio, R' is preferably a non-aromatic substituent, such as an alkyl or cycloalkyl substituent preferably bearing a primary or secondary carbon atom attached to the nitrogen atom.

Further, from the above data, the nature of the Cp ligand structure of a Ti metal component may be seen to influence the properties of the catalyst system. Those Cp ligands which are not too sterically hindered and which contain good electron donor groups, for example the Me.sub.4 C.sub.5 ligand, are preferred.

From the standpoint of having a catalyst system of high productivity which is capable of producing an ethylene-.alpha.-olefin copolymer of high molecular weight and high comonomer incorporation, the most preferred transition metal compound for the catalyst system is of the following structure: ##STR6## wherein R.sup.1 and R.sup.2 are alkyl radicals having 1 to 6 carbon atoms, each Q is chlorine or methyl, and R' is an aliphatic or alicyclichydrocarbyl having from 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms.

The resins that are prepared in 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 in the art may, 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.