AU697671B2 - A catalyst composition - Google Patents

Description

AUSTRALIA

Patents Act COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: Name of Applicant: Mobil Oil Corporation Actual Inventor(s): Frederick Yip-Kwai Lo Thomas Edward Nowlin Ronald Steven Shinomoto Pradeep Pandurang Shirodkar Address for Service: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: A CATALYST COMPOSITION coo.: Our Ref: 518187 POF Code: 1462/278160 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): r ~a i I 1A A CATALYST COMPOSITION This application is a divisional application of accepted patent application 57492/94, the entire contents of which are herein incorporated by reference.

The invention relates to a catalyst composition. The invention is particularly concerned with improvements in low pressure fluid bed gas phase systems for the polymerization and copolymerization of ethylene, undertaken in the presence of catalyst comprising metallocenes of transition metals. The invention aims to eliminate reactor fouling and to maintain the continuous operation of the distributor plate in the fluid bed gas phase reactor undertaken in the presence of catalysts comprising metallocenes of transition metals.

Polytheylene is produced commercially in a gas phase reaction in the absence of solvents by employing selected chromium and titanium-containing catalysts under specific operating conditions in a fluid bed process. The products of the early production processes exhibited medium-to-broad molecular weight distribution. To be commercially useful in the gas phase fluid bed process, the catalyst must exhibit high activity, with concomittant high catalyst productivity, because gas phase process systems do not include catalyst residue removal procedures. Accordingly, catalyst residue in the polymer product must be so 20 small that it can be left in the polymer without causing any undue problems in the fabrication and/or to the ultimate consumer. To this end, the patent literature is replete with developments of new catalysts, of high activity, with corresponding high productivity values.

The use of metallocene compounds of transition metals as catalysts for S 25 polymerisation and copolymerization of ethylene is one of those developments.

Metallocenes can be described by the empirical formula CpmMAnBp. These compounds in combination with methylalumoxane (MAO) have been used to produce olefin polymers and copolymers, such as ethylene and propylene homopolymers, ethylene-butene and ethylene-hexene copolymers, see US- A-4542199 and US-A-4404344. Unlike traditional titanium- and vanadium-based 0 Ziegler-Natta catalysts, a metallocene, e.g. a zirconocene catalyst, free of titanium- and vanadium-components produce resins with very narrow molecular C:\WINWORDANELLE\SPECI82842.DOC I I F-6938-L -2weight distributions (determined as MFR(I 21 /1 2 of 15 to 18, versus MFR of 25 to 30 for titanium-based catalysts) and with homogeneous short-chaip branching distributions.

When traditional titanium-based and vanadium-based catalysts are used to copolymerize ethylene and higher alphaolefins, the olefin is incorporated in polymer chains nonuniformly, and most of the olefin resides in the shortest polymer chains. With zirconocene catalyst, however, the branching distribution is essentially independent of chain length. LLDPE resins produced with zirconocene catalysts have superior properties. These resins can be used to make films with significantly better clarity and impact strength.

Extractables of such resins are lower and the balance of properties in the films between the machine and transverse directions is excellent.

More recently, as exemplified in US-A-5032562, metallocene catalysts containing a second transition metal, such as titanium have been developed which produce bimodal molecular weight distribution products, having a high molecular weight component and a relatively lower molecular weight component. The development of a catalyst which can produce bimodal products in a single reactor is significant per se. That development also provides a commercial alternative to processes which require two reactors to produce bimodal production with production of one 25 of the molecular weight components in a first reactor and transfer of that component to a second reactor and completion of the polymerization with production of the other component of different molecular weight.

Methylalumoxane (MAO) is used as co-catalyst with metallocene' catalysts. The class of alumoxanes comprises S• oligomeric linear and/or cyclic alkylalumoxanes represented by .the formula: R-(Al(R)-O)n-AlR 2 for oligomeric, linear alumoxanes and for oligomeric cyclic alumoxane o 35 wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C 1

-C

8 alkyl group and preferably methyl.

Methylalumoxane is commonly produced by reacting F-6938-L -3trimethylaluminum with water or with hydrated inorganic salts, such as CuSO 4 5H 2 0 or Al 2 (S0 4 3 .5H 2 0. Methylalumoxane can be also generated in situ in polymerization reactors by adding to them trimethylaluminum and water or water-containing inorganic salts.

MAO is a mixture of oligomers with a very wide distribution of molecular weights and usually with an average molecular weight of about 1200. MAO is typically kept in solution in toluene.

While the MAO solutions remain liquid at fluid bed reactor temperatures, the MAO itself is a solid at room temperature.

Most of the experiments reported in the literature relating to methylalumoxane used as a cocatalyst with metallocene catalysts are undertaken in a slurry or solution process, rather than in a gas phase fluid bed reactor process.

It was found that the metallocene catalyst must contact the MAO cocatalyst while MAO is in solution in order for the catalyst to be activated in the fluid bed reactor. Moreover, it was discovered that extensive reactor fouling results when MAO solutions are fed directly into the gas phase reactor in large enough quantities to provide this liquid contact. The fouling occurs because the MAO solution forms a liquid film on the interior walls of the reactor.

The catalyst is activated when it comes into contact with this liquid film, and the activated catalyst reacts with ethylene to form a polymer coating which grows larger in size 25 until the reactor is fouled. In addition, since substantially all of the activation takes place on the walls, the MAO is not uniformly distributed to the catalyst particles. The resulting non-homogeneous polymerization gives low catalyst activity and poor product properties.

I-

3A The problems invoked by the use of an alumoxane, particularly methylalumoxane, in catalyst production are addressed by the present invention.

In one aspect the present invention provides a catalyst composition which comprises a catalyst precursor and a cocatalyst free of alumoxane, which catalyst is effective to produce polymers and copolymers of ethylene, the improvement comprising a precursor, effective to produce bimodal molecular weight distribution product with said cocatalyst, wherein said precursor comprises particles wherein the particles comprise silica, having a pore volume of 0.5 to 5.0 cc/gram; containing reactive hydroxyl groups, ranging form 0.1 to 3.0 mmols/gram silica; and Mg, provided as an organomagnesium compound, in an amount to provide a Mg:OH molar ratio of from 0.5:1 to 4:1, wherein the organomagnesium compound has the formula R"a Mg R'b where R" and R' are the same or different C2-C 8 alkyl groups, and a and b are each 0,1 or 2, providing that a b is equal to the valence of Mg; and wherein the organomagnesium compound is reacted with said hydroxyl groups, and thereafter contacted with a non-metallocene transition metal compound, which is supported on said silica; 20 wherein the silica is impregnated with an activated metallocene compound, wherein the metallocene compound has the formula CprnMAnBp wherein Cp is a cyclopentadienyl or a substituted cyclopentadienyl group; m is 1 or 2; 25 M is zirconium or hafnium; and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group providing that m+n+p is equal to the valence of the metal M.

In another aspect the present invention provides a catalyst composition, which contains activated metallocene compound, and which obviates feeding alumoxane 30 solutions to a polymerization reactor, wherein the catalyst composition comprises a cocatalyst which is a monomeric trialkylaluminum, free of oligomeric or polymeric C.\WINWORDUANELLEUSPECIi82842.DOC L r 4 reaction products of trialkylaluminum and water, and a catalyst precursor, wherein the catalyst precursor comprises particles wherein the particles comprise silica, having a pore volume of 0.5 to 5.0 cc/gram; containing reactive hydroxyl groups, ranging from 0.1 to 3.0 mmols/gram silica; and Mg, provided as an organomagnesium compound, in an amount to provide a Mg:OH molar ratio of from 0.5:1 to 4:1, wherein the organomagnesium compound has the formula R"a Mg R'b where R" and R' are the same or different C2-C8 alkyl groups, and a and b are each 0,1 or 2, providing that a b is equal to the valence of Mg; and wherein the organomagnesium compound is reacted with said hydroxyl groups, and thereafter contacted with a non-metallocene transition metal compound, which is supported on said silica; wherein the silica is impregnated with an activated metallocene compound, wherein the metallocene compound has the formula CpmMAnBp wherein Cp is a cyclopentadienyl or a substituted cyclopentadienyl group; m is 1 or 2; M is zirconium or hafnium; and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, providing that m n p is equal to the valence of the metal M.

The metallocene compound may be selected from the group consisting of bis(cyclopentadienyl) metal dihalides, bis(cyclopenta-dienyl) metal hydridohalides, bis(cyclopentadienyl) metal monoalkyl monohalides, bis(cyclopentadienyl) metal 20 dialkyls and bis(indenyl)metal dihalides, wherein the halide groups are chlorine e and the alkyl groups are C 1

-C

6 alkyls.

.More preferably the metallocene compound is selected from the group consisting of bis(cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis a.

(cyclopentadienyl)hafnium dimethyl, bis(cyclopentadienyl)zirconium hydridochloride, bis(cyclopentadienyl) hafnium hydridochloride, bis (pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl) hafnium dichloride, bis(n-butylcyclopentadienyl) zirconium dichloride, cyclopentadienyl-zirconium trichloride, bis(indenyl)zirconium dichloride, bis 5, 6, 7-tetrahydro-l-indenyl) zirconium dichloride, and ethylene [bis(4, 5, 6, 7 tetrahydro-1-indenyl)] zirconium dichloride.

C:\WINWORDUANELLE\SPECIMa82842,DOC l--r -s ,d It is preferred that the metallocene is activated with alumoxane and the molar ratio of alumoxane, expressed as alumininum, to metallocene ranges from to 500.

Preferably the impregnated silica particles are heated to remove any solvent from the pores, under temperature conditions effective to prevent crosslinking of the alumoxane.

Desirably the temperature ranges from above 30°C to below The impregnated silica particles preferably exceed a particle size of 1 micron.

The impregnated silica particles are preferably sieved to isolate particles characterized by a particle size of 1-200 microns.

The silica preferably contains reactive hydroxyl groups in an amount ranging from 0.1 to 3.0 mmols/g carrier, and preferably the reactive hydroxyl groups are reacted with an organomagnesium compound, so that the Mg:OH molar ratio ranges from 0.9:1 to 4:1 wherein the organomagnesium compound has the formula R"a Mg R'b where R" and R' are the same or different C 2 -C8 alkyl groups, and a and b are each 0, 1 or 2, providing that a b is equal to the valence of Mg; and, after the reactive hydroxyl groups are reacted but prior to said contacting of step a non-metallocene transition metal is preferably added 20 to the slurry.

Both R" and R' are suitably n-butyl groups.

too*.: .o The non-metallocene compound is preferably a tetravalent titanium o• Scompound, which is desirably provided in an amount which is sufficient to provide a metallocene:Ti ratio of 0.01 to 0.50.

25 According to a further aspect of the invention there is provided a fluid bed 4* gas phase reactor process for producing resins, under polymerization conditions effective to form said resins comprising pressures ranging from 100 to 350 psi (690 to 2400 KPa), at temperatures ranging from 30°C to 1150C, in the presence of a catalyst, wherein the catalyst comprises an alumoxane, and wherein the 30 fluidized bed comprises a composition as described above, said process comprising introducing a feed polymerizable to form said resins; and introducing C:\WINWORDIANELLE\SPECI682842 DOC

II

6 as cocatalyst a monomeric trialkylaluminum, free of oligomeric or polymeric reaction products of trialkylaluminum and water.

Reference is now made to the accompany drawings, in which: Figure 1 is a schematic drawing of a fluid bed reactor for gas phase polymerization of ethylene.

Figure 2 is a gel permeation chromatograph of the product of Example 2.

Figure 3 is a gel permeation chromatograph of a bimodal product produced in two reactors.

Figure 4 is a gel permeation chromatograph of the product of Example 4.

Ethylene polymers, as well as copolymers of ethylene with one or more C 3

C

0 o alpha-olefins, can be produced in accordance with the invention. Thus, copolymers having two nomomeric untils are possible as well as terpolymers having three monomeric units. Particular examples of such polymers include ethylene/1-butene copolymers, ethylene/1-hexene copolymers and ethylene/4methyl-1-pentene copolymers.

Hydrogen may be used as a chain transfer agent in the polymerization reaction of the present invention. The ratio of hydrogen/ethylene employed will vary between about 0 to about 2.0 moles of hydrogen per mole of ethylene in the gas phase. Any gas inert to the catalyst and reactants can also be present in the 20 gas stream.

Ethylene/1-butene and ethylene/1-hexene copolymers are the most preferred copolymers polymerized in the process of and with the catalyst of this invention. The ethylene copolymers produced in accordance with the present invention preferably contain at least about 80 percent by weight of ethylene units.

The cocatalyst of this invention can also be used with the catalyst precursor of this invention to polymerize propylene and other alpha-olefins and to copolymerize them. The structure of alpha-olefin polymers prepared with the cocatlyst and the catalyst precursor of this invention depends on the structure of the cyclopentadienyl ligands attached to the metal atom in the catalyst precursor molecule. The cocatalyst compositions of this invention can also be used with the catalyst precursors of this invention to polymerize cyclo-olefins such as cyclopentene.

CA\WNWORDUANELLE'SPECMI682842.DOC i II 7 The catalyst of the invention exhibits high activity for polymerization of ethylene and higher alpha-olefins and allows the synthesis of ethylene polymers and copolymers with a broad molecular weight distribution and generally, bimodal molecular weight distribution with a relatively high molecular weight component and with a relatively lower molecular weight component in the resin blend. The molecular weight distribution of the bimodal resin, expressed as MFR, is about 110 to about 140. The catalyst of the invention comprises two transition metal compounds, only one of the transition metal compounds being a metallocene.

The Fluid Bed Reactor A fluidized bed reaction system which can be used in the practice of the process according to one aspect of the invention is shown in Fig. 1. With reference thereto, the reactor 10 consists of a reaction zone 12, a velocity reduction zone 14 and the distributor plate 20. Although fouling can occur in all of the cold areas (areas in a reactor at a temperature which is less than the temperature at which any component, in the gas phase reactor is liquid rather than gaseous) distributor plate fouling is the one most easily detected, since it results in a 0 0* o°.0 00 °ot C:\WINWORDJANELLE\SPECIB82842.DOC

I

F-6938-L 8 rapid increase in the pressure drop across the distributor plate due to flow restriction. Such flow restrictions also result in changing fluidization patterns and contribute to reactor wall fouling. The lowest temperature in the reactor loop is in the reactor inlet beneath the distributor plate. Other areas representing the coldest sections in the fluid bed reactor system include the cooler and piping between the cooler and the bottom head.

The reaction zone 12 comprises a bed of growing polymer particles and a mMnor amount of catalyst particles fluidized by the continuous flow of polymerizable and modifying gaseous components. To maintain a viable fluidized bed, the mass gas flow rate through the bed must be above the minimum flow required for fluidization, and preferably from about 1.5 to about 10 times Gmf and more preferably from about 3 to about 6 times Gmf. Gmf is used in the accepted form as the abbreviation for the minimum mass gas flow required to achieve fluidization, C. Y. Wen and Y. H. Yu, "Mechanics of Fluidization", Chemical Engineering Progress Symposium Series, Vol. 62, p. 100-111 (1966). The distribution plate 20 serves the purpose of diffusing recycle gas through the bed at a rate sufficient to maintain fluidization at the base of the bed. Fluidization is achieved by a high rate of gas recycle to and through the bed, typically in the order of about 50 times the rate of feed of 25 make-up gas.

Make-up gas is fed to the bed at a rate equal to the rate at which particulate polymer product is formed by reaction. The composition of the make-up gas is determined by a gas analyzer 16 positioned above the bed. The composition of the make-up gas 30 is continuously adjusted to maintain an essentially steady state gaseous composition within the reaction zone.

The portion of the gas stream which does not react in the bed (the recycle gas) passes a velocity reduction zone 14 where entrained particles are given an opportunity to drop back into the bed. The unreacted gas stream then passes through a cyclone 22, through a filter 24, through a compressor 25, through a heat exchanger 26, and is then returned to the bed. The distribution I' a' Y F-6938-L 9 plate 20 serves the purpose of diffusing recycle gas through the bed at a rate sufficient to maintain fluidization. The plate may be a screen, slotted plate, perforated plate, a plata of the bubble cap type, and the like. The elements of the plate may all be stationary, or the plate may be of the mobile type disclosed in US-A-3298792.

Conditions in the fluid bed reactor for the gas phase polymerization and copolymerization of ethylene It is essential to operate the fluid bed reactor at a temperature below the sintering temperature of the polymer particles. For the production of ethylene copolymers in the process of the present invention an operating temperature of about 30°C to 115°C is preferred,, and a temperature of about 75°C to 95°C is most preferred. Temperatures of about 75°C to are used to prepare products having a density of about 0.91 to 0.92, and temperatures of about 80 0 C to 100 0 C are used to prepare products having a density of about 0.92 to 0.94, and temperatures of about 90C to 115°C are used to prepare products having a density of about 0.94 to 0.96.

The fluid bed reactor is operated at pressures of up to about 1000 psi (6.9 MPa), and is preferably operated at a pressure of from about 150 to 350 psi (1 Mpa to 2.4 MPa), with operation at the higher pressures in such ranges favoring heat 25 transfer since an increase in pressure increases the unit volume heat capacity of the gas.

."The partially or completely activated catalyst is injected into the bed at a point above the distribution plate at a rate equal to its consumption. Since the catalysts used in the 30 practice of this invention are highly active, injection of the fully activated catalyst into the area below the distribution plate may cause polymerization to begin there and eventually cause plugging of the distribution plate. Injection into the bed, instead, aids in distributing the catalyst throughout the bed and precludes the formation of localized spots of high catalyst concentration.

The production rate of polymer in the bed is controlled by the rate of catalyst injection. Since any change in the rate of cntalyst injection changes the rate of generation of the heat of reaction, the temperature of the recycle gas is adjusted to accommodate the change in rate of heat generation.

Complete instrumentation of both the fluidized bed and the recycle gas cooling system is, of course, necessary to detect any temperature change in the bed so as to enable the operator to make a suitable adjustment in the temperature of the recycle gas.

Since the rate of heat generation is directly related to product formation, a measurement of the temperature rise of the gas across the reactor (the difference between inlet gas temperature and exit gas temperature) is determinative of the rate of particulate polymer formation at a constant gas velocity.

Under a given set of operating conditions, the fluidized bed is maintained at essentially a constant height by withdrawing a portion of the bed as product at a rate equal to the rate of formation of the particulate polymer product.

Catalyst Composition Catalysts which contain two transition metals, one in the form of a metallocene and one transition metal in the form of a non-metaliocene, have an activity of at least about 2,000 g polymer/g catalyst or about 100 kg polymer/g of transition metals.

The catalysts used in the invention comprise a cocatalyst such as an aluminum alkyl compound, preferably a trialkyl aluminum free of alumoxane, and a catalyst precursor comprising a carrier, an activated metallocene and a nonmetallocene transition metal source.

The carrier material is a solid, particulate, porous, preferably inorganic material, such as an oxide of silicon and/or of aluminum. The carrier material is preferably used in the form of a dry powder preferably having an average particle size of from about 1 micron to about 250 microns, more preferably about I to 200 microns, most preferably from about 10 microns to about 150 microns. If necessary, the treated carrier material may be sieved to ensure that the particles of the ultimate carrier-catalyst containing composition has material is also porous and has a mesh size of greater than 150 mesh.

:WINWIVORDUANELLESPEECI82842.DOC

I

11 The surface area of the carrier may preferably be at least about 3 m 2 /g, and more preferably is at least about 50 m 2 /g up to about 350 m 2 The carrier material should preferably be dry, that is, free of absorbed water. Drying of the carrier material can be effected by heating at about 100°C to about 1000oC, preferably at about 600C. When the carrier is silica, it is heated to at least 200°C, preferably about 200°C to about 850°C and most preferably at about 6000C.

In the most preferred embodiment, the carrier is silica (with at least some active hydroxyl groups) which, prior to the use thereof in the first catalyst synthesis step, has been dehydrated by fluidizing it with nitrogen and heating at about 600°C for about 16 hours to achieve a surface hydroxyl group concentration of about 0.7 millimoles per gram (mmols/g). The silica of the most preferred embodiment is a high surface area, amorphous silica (surface area 300 m 2 pore volume of 1.65 cm 3 and it is a material marketed under the tradenames of Davison 952 or Davison 955 by the Davison Chemical Divison of W R Grace and Company. The silica is in the form of spherical particles, eg, as obtained by a spray-drying process.

The metallocene is preferably activated with an alumoxane. The class of alumoxanes useful for this invention comprises oligomeric linear and/or cyclic alkylalumoxanes represented by the formula: R-(A1(R)-0)n-A1 R 2 for oligomeric, linear alumoxanes and for oligomeric cyclic alumoxane wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C1-C alkyl group and preferably methyl. MAO is a mixture of oligomers with a very wide distribution of molecular weights and usually with an average molecular 4. weight of about 1200. MAO is typically kept in solution in toluene. While the MAO solutions remain liquid at fluid bed reactor temperatures, the MAO itself is a solid.

To form catalysts of the invention, all catalyst precursor components can be dissolved with alumoxane and impregnated into the carrier. In a unique process, the carrier material is impregnated with a solid alumoxane, preferably methylalumoxane, in a process described below.

C:\WINWORDUANELLESPECM%082842.D0C i I- I 12 Although the alumoxane can be impregnated into the carrier at any stage of the process of catalyst preparation, the preferred stage of alumoxane incorporation will depend on the ultimate catalyst sought to be synthesized. The volume of the solution comprising a solid alumoxane and a solvent therefor can vary, depending on the catalyst sought to be produced. In a preferred embodiment, one of the controlling factors in the alumoxane incorporation into the carrier material catalyst synthesis is the pore volume of the silica. In this preferred embodiment, the process of impregnating the carrier material is by infusion of the alumoxane solution, without forming a slurry of the carrier material, such as silica, in the alumoxane solution. The volume of the solution of the alumoxane is sufficient to fill the pores of the carrier material without forming a slurry in which the volume of the solution exceeds the pore volume of the silica; accordingly and preferably, the maximum volume of the alumoxane solution is, does not exceed, the total pore volume of the carrier material sample. That maximum volume of the alumoxane solution ensures that no slurry of silica is formed.

Accordingly, if the pore volume of the carrier material is 1.65 cm 3 then the volume of alumoxane will be equal to or less than 1.65 cm 3 /g of carrier material. As a result of this proviso, the impregnated carrier material will appear dry immediately following impregnation although the pores of the carrier will be filled with inter alia solvent.

4 4 4e 4 9 0a 4 C:\WINWORDUJANELLE\SPEC82842.DOC Ir 13 Solvent may be removed from the alumoxane impregnated pores of the carrier material by heating and/or under a positive pressure induced by an inert gas, such as nitrogen. If employed, the conditions in this step are controlled to reduce, if not to eliminate, agglomeration of impregnated carrier particles and/or crosslinking of the alumoxane. In this step, solvent can be removed by evaporation effected at relatively low elevated temperatures of above about and below about 50°C to obviate aglomeration of catalyst particles and crosslinking of the alumoxane. Although solvent can be removed by evaporation at relatively higher temperatures than that defined by the range about 40°C and below about 50°C, very short heating times schedules must be employed to obviate agglomeration of catalyst particulars and crosslinking of the alumoxane.

In a preferred embodiment, the metallocene is added to the solution of the alumoxane prior to impregnating the carrier with the solution. The mole ratio of alumoxane provided aluminum, expressed as Al, to metallocene metal expressed as M (e.g Zr), ranges from 50 to 500, preferably 75 to 300, and most preferably 100 to 200. An added advantage of the present invention is that this AI:Zr ratio can be directly controlled. In a preferred embodiment the alumoxane and metallocene compound are mixed together at a temperature of about 20*C to 0 C, for 0.1 to 6.0 hours, prior to use in the infusion step. The solvent for the metallocene and alumoxane can be appropriate solvents, such as aromatic hydrocarbons, halogenated aromatic hydrocarbons, ethers, cyclic ethers or esters, preferably it is toluene.

The metallocene compound has the formula CpmMAnBp in which Cp is an unsubstituted or substituted cyclopentadienyl group, M is zirconium or hafnium and A and B belong to the group including a halogen atom, hydrogen or an alkyl group. In the above formula of the metallocene compound, the preferred transition metal atom M is zirconium. In the above formula of C:A\WNWROUANELLELSPECI828422DOC F-6938-L 14 the metallocene compound, the Cp group is an unsubstituted, a mono- or a polysubstituted cyclopentadienyl group. The substituents on the cyclopentadienyl group may be straight-chain

C

1

-C

6 alkyl groups. The cyclopentadienyl group may also be a part of a bicyclic or a tricyclic moiety such as indenyl, tetrahydroindenyl, fluorenyl or a partially hydrogenated fluorenyl group, as well as a part of a substituted bicyclic or tricyclic moiety. In the case when m in the above formula of the metallocene compound is equal to 2, the cyclopentadienyl groups can be also bridged by polymethylene or dialkylsilane groups, such as -CH 2 -CH2-CH 2

-CR

1

R

2 and -CR 1

R

2

-CR

1

R

2 where R 1 and

R

2 are short alkyl groups or hydrogen, -Si(CH 3 2 Si(CH 3 )2-CH 2

CH

2 -Si(CH 3 2 and similar bridge groups. If the A and B substituents in the above formula of the metallocene compound are halogen atoms, they belong to the group of fluorine, chlorine, bromine or iodine. If the substituents A and B in the above formula of the metallocene compound are alkyl groups, they are preferably straight-chain or branched C 1

-C

8 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl or n-octyl.

Suitable metallocene compounds include bis(cyclopentadienyl)metal dihalides, bis(cyclopentadienyl)metal hydridohalides, bis(cyclopentadienyl)metal monoalkyl monohalides, bis(cyclopentadienyl)metal dialkyls and 25 bis(indenyl)metal dihalides wherein the metal is zirconium or hafnium, halide groups are preferably chlorine and the alkyl groups are C 1

-C

6 alkyls. Illustrative, but non-limiting examples of metallocenes include bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)hafnium dichloride, 30 bis(cyclopentad i eny zirconium dimethyl bis (cyclopentadienyl) hafnium dimethyl, O bis(cyclopentadienyl) zirconium hydridochloride, bis(cyclopentadienyl)hafnium hydridochloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, Poo. 35 bis (pentamethylcyclopentadienyl) hafnium dichloride, bis(nbutylcyclopentadienyl)zirconium dichloride, cyclopentadienylzirconium trichloride, bis(indenyl)zirconium dichloride, bis(4, 5, 6, 7-tetrahydro-l-indenyl)zirconium dichloride, and ethylene-[bis(4, 5, 6, 7-tetrahydro-l-indenyl)] zirconium dichloride.

The metallocene compounds utilized within the embodiment of this art can be used as cyrstalline solids, as solutions in aromatic hydrocarbons or in a supported form.

As stated above, the alumoxane can be impregnated into the carrier at any stage of the process of catalyst preparation. The catalyst contains two transition metals components, one of which is a metallocene, and one of which is nonmetallocene (free of unsubstituted or substituted cyclopentadienyl groups) and the impregnation of the alumoxane in accordance with the unique method described above is preferably undertaken after hydroxyl groups of the carrier material are reacted with an organomagnesium compound and the nonmetallocene transition metal compound. In this embodiment, the amount of A1, provided by alumoxane, is sufficient to provide an A1:transition metal (provided by metallocene) mole ratio ranging from 50 to 500, preferably 100 to 300. The carrier material, having said (OH) groups, is slurried in a non-polar solvent and the resulting slurry is contacted with at least one organomagnesium composition having the empirical formula below. The slurry of the carrier material in the solvent is prepared by introducing the carrier into the solvent, preferably while stirring, and heating the mixture to about 25°C to about 70°C, preferably to about 400C to about 600C. Temperatures here are critical with respect to the nonmetallocene transition metal which is subsequently added; that is temperatures in this slurry of about 90 0 C results in deactivation of the transition metal added subsequently. The slurry is then contacted with the aforementioned organomagnesium composition, while the heating is continued at the aforementioned temperature.

The organomagnesium composition has the empirical formula R"a Mg R'b ***where R" and R' are the same of different C2-C12 alkyl groups, preferably C4-C10 alkyl groups, more preferably C4-C8 normal alkyl groups, and most preferably both R" and R' are n-butyl CAMWNWRDUANELLESPECfl882842,00C L I--Lr F-6938-L 16 groups, and a andb are each 0, 1 or 2, providing thata b is equal to the valence of Mg.

Suitable non-polar solvents are materials in which all of the reactants used herein, the organomaghesium composition, and the transition metal compound, are at least partially soluble and which are liquid at reaction temperatures.

Preferred non-polar solvents are alkanes, such as hexane, nheptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene and ethylbenzene, may also be employed. The most preferred non-polar solvent is cyclopentane. Prior to use, the non-polar solvent should be purified, such as by percolation through silica gel and/or molecular sieves, to remove traces of water, oxygen, polar compounds, and other materials capable of adversely affecting catalyst activity.

In the most preferred embodiment of the synthesis of this catalyst it is important to add only such an amount of the organomagnesium composition that will be deposited physically or chemically onto the support since any excess of the organomagnesium composition in the solution may react with other synthesis chemicals and precipitate outside of the support. The .carrier drying temperature affects the number of sites on the carrier available for the organomagnesium composition the 25 higher the drying temperature the lower the number of sites.

*Thus, the exact molar ratio of the organomagnesium composition to the hydroxyl groups on the carrier will vary and must be determined on a case-by-case basis to assure that only so much .4 of the organomagnesium composition is added to the solution as will be deposited onto the support without leaving any excess of the organomagnesium composition in the solution.

SFurthermore, it is believed that the molar amount of the organomagnesium composition deposited onto the support is greater than the molar content of the hydroxyl groups on the support. Thus, the mola ratios given below are intended only as an approximate guideline and the exact amount of the organomagnesium composition in this embodiment must be I I-21iI F-6938-L 17 controlled by the functional limitation discussed above, i.e., it must not be greater than that which can be deposited onto the support. If greater than that amount is added to the solvent, the excess may react with the non-metallocene transition metal compound, thereby forming a precipitate outside of the support which is detrimental in the synthesis of our catalyst and must be avoided. The amount of the organomagnesium composition which is not greater than that deposited onto the support can be determined in any conventional manner, by adding the organomagnesium composition to the slurry of the carrier in the solvent, while stirring the slurry, until the organomagnesium composition is detected as a solution in the solvent.

For example, for the silica carrier heated at about 6000C, the amount of the organomagnesium composition added to the slurry is such that the molar ratio of Mg to the hydroxyl groups (OH) on the solid carrier is about 0.5:1 to about 4:1, preferably about 0.8:1 to about 3:1, more preferably about 0.9:1 to about 2:1 and most preferably about 1:1. The organcimagnesium composition dissolves in the non-polar solvent to form a solution from which the organomagnesium composition is deposited onto the carrier.

It is also possible to add such an amount of the organomagesium composition which is in excess of that which will be deposited onto the support, and then remove, eg. by filtration and washing, any excess of the organomagnesium composition. However, this alternative is less desirable than the most preferred embodiment described above.

After the addition of the organomagnesium composition to the slurry is completed, the slurry is contacted with a non- 30 metallocene transition metal compound, free of substituted or unsubstituted cyclopentadienyl groups. The slurry temperature must be maintained at about 25°C to about 70 0 C, preferably to .*about 40C to about 60°C. As noted above, temperatures in this slurry of about 80 0 C or greater result in deactivation of the non-metallocene transition metal. Suitable non-metallocene transition metal compounds used herein are compounds of metals of Groups IVA, and VA, of the Periodic Chart of the Elements,

II-

F-6938-L 18 as published by the Fisher Scientific Company, Catalog No. 702-10, 1978, providing that such compounds are soluble in the non-polar solvents. Non-limiting examples of such compounds are titanium and vanadium halides, titanium tetrachloride, TiCl 4 vanadium tetrachloride, VCl 4 vanadium oxytrichloride, VOCl 3 titanium and vanadium alkoxides, wherein the alkoxide moiety has a branched or unbranched alkyl radical of 1 to about carbon atoms, preferably 1 to about 6 carbon atoms. The preferred transition metal compounds are titanium compounds, preferably tetravalent titanium compounds. The most preferred titanium compound is titanium tetrachloride. The amount of titanium or vanadium, in non-metallocene form ranges from a Ti/Mg molar ratio of 0.5 to 2.0, preferably from 0.75 to 1.50.

Mixtures of such non-metallocene transition metal compounds may also be used and generally no restrictions are imposed on the transition metal compounds which may be included. Any transition metal compound that may be used alone may also be used in conjunction with other transition metal compounds.

Incorporation of the alumoxane-metallocene can be directly to this slurry. Alternatively, 'and in accordance with the unique method of infusion of alumoxane into the pores of the carrier, descibed above, the carrier slurry can be stripped of solvent, after the addition of the non-metallocene transition metal compound, to form a free-flowing powder. The free flowing powder can then be impregnated by determining the pore volume of the carrier and providing an metallocenealumoxane solution in a volume equal to or less than that of the pore volume of the carrier, and recovering a dry catalyst precursor. The resulting free-flowing powder, referred to 30 herein as a catalyst precursor, is combined with an activator (sometimes referred as a cocatalyst). The cocatalyst can be a a trialkylaluminum, free of alumoxane. Preferably, trimethylaluminum (TMA) is the cocatalyst or activator. The amount of the TMA activator is sufficient to give an Al:Ti molar 35 ratio of about 10:1 to about 1000:1, preferably about 15:1 to about 300:1, and most preferably about 20:1 to about 100:1. The catalyst exhibits high activity for long periods of time in the 19 pilot plant, and exhibits little deactivation.

The catalyst precursor of this invention comprises an activated metallocene compound which is fed to the fluid bed reactor for gas phase polymerizations and copolymerizations of ethylene in particulate form. The cocatalyst or activator is fed to the fluid bed reactor for polymerizations and copolymerizations of ethylene in the absence of alumoxane solution.

The invention will now be exemplified by way of the following examples.

Example 1 The titanium component of the catalyst was prepared using a chemical impregnation technique. The zirconium component of the catalyst was prepared using a physical impregnation method. Solution To a 50 ml serum-bottle 0.140 grams of Cp 2 ZrCI 2 was transferred and then 10.2 grams of a methylalumoxane (13.2 wt. al) solution were added. The solution remained at room temperature for 60 minutes until the entire contents were transferred to the silica slurry described below.

Into a 100ml pear-flask equipped with a magnetic stirring bar, 3.0 grams of Davison 955 silica calcined at 600°C, was added followed by addition of about dry toluene. The flask was placed into a 59°C oil bath. Next, 2.9 ml of dibutylmagnesium (0.74 mmol/ml) was added to the silica/toluene slurry. The contents of the flask were stirred for 25 minutes. Then, 2.3 mis of a 0.94 molar a titanium tetrachloride solution in heptane was added to the flask. The slurry turned a dark brown color and stirring was continued for 25 minutes. Finally, the entire contents of solution was transferred into the catalyst preparation flask, and the slurry was allowed to stir for 10 minutes. After this time, all solvents were removed by evaporation under a nitrogen purge. Catalyst yield was 5.6 grams of a dark-brown free-flowing powder. The Al/Zr ratio was 104.

*oo.o oV C.WINWORDJANELLE'$PECM%2842.DOC F-6938-L Example 2 Ethylene/1-hexene copolymer was prepared with the catalyst of the foregoing example under polymerization conditions to produce high density polyethylene (HDPE), with a flow index (121) of about 6.

A 1.6 liter stainless steel autoclave, at about 500C, was filled with 0.750 liters of dry heptane, 0.030 liters of dry 1hexene and 4.0 mmols of trimethylaluminum (TMA) while under a slow nitrogen purge. The reactor was closed, the stirring rate was set at about 900 rpm, the internal temperature was increased to 85°C, and the internal pressure was raised from 7 psi to psi (48 KPa to 69 KPa) with hydrogen. Ethylene was introduced to maintain the reactor pressure at about 203 psi (1.4 MPa).

Next, 0.0639 grams of catalyst was introduced into the reactor with ethylene over pressure and the temperature was increased and held at 950C. The polymerization was continued for minutes, and then the ethylene supply was stopped and the reactor allowed to cool to room temperature. 78 grams of polyethylene were collected.

The molecular weight distribution (MWD) of the polymer was 0.

examined by Gel Permeation Chromatography (GPC), and the results clearly show that the polymer has a bimodal MWD (Figure Figure 3 shows the GPC chromatogram for a HDPE polymer prepared in tandem gas phase reactor. Comparison of the two GPC chromatograms clearly shows that the polymer prepared in a single reactor is essentially the same as the polymer prepared in two tandem reactors.

Presently, commercial samples of HDPE with a bimodal MWD are produced in a tandem reactor process. In that process, two reactors are run in series and the catalyst is exposed to ethylene polymerization conditions in one reactor, and the Sresulting polymer-catalyst particles are transferred to a second reactor for additional polymerization. One of the main process differences in the two different reactors, is that the amount of hydrogen is different in the two different reactors.

Relatively lower molecular weight product is produced in the reactor containing more hydrogen, because the hydrogen acts as 00 F-6938-L 21 a chain transfer agent; whereas relatively higher molecular weight product is produced in the reactor containing lesser relative amounts of hydrogen.

Example 3 This catalyst was prepared in two stages. 495 grams of Davison grade 955 silica, previously calcined with dry nitrogen for about 12 hours at 600 0 C, was added to a 2 gallon stainless steel autoclave under a slow nitrogen purge to eliminate oxygen and moisture from the catalyst preparation vessel, Then, liters of dry isopentane (IC5) was added to the autoclave and the silica/IC5 were slurried at about 100 rpm and the internal temperature was maintained at about 55-600C. Next, 469 ml of a 0.76 molar solution of dibutylmagnesium in heptane was added to the silica/IC5 slurry and stirring was continued for minutes. Next, 39.1 ml of neat titanium tetrachloride was diluted with about 40 ml of IC5 and this solution was added to the autoclave and stirring was continued for 60 minutes.

Finally, the solvents were removed with a nitrogen purge through S 20 a vent line and 497 grams of a brown free-flowing powder were obtained. Ti found was 2.62 wt%; Mg found was 1.33 wt% and Ti/Mg molar ratio was 492 grams of the product of the first stage was added to a 1.6 gallon glass catalyst preparation vessel fitted with a temperature jacket and an internal stirrer. The product of the first stage had an estimated pore volume of 1.5 cm 3 /g 738 cm 3 of pore volume). Then into a stainless steel Hoke bomb was added 13.93 grams of (BuCp) 2 ZrCl 2 (34.4 mmol Zr) and 717.5 ml of a methylalumoxane solution (3,444 mmol of Al) in toluene (4.8 30 Molar). Note: The total volume of the methylalumoxane/toluene solution is equal to or less than the total pore volume of the product of the first step. Next, the toluene solution containing the methylalumoxane and the zirconium compound were mixed and then the solution was added to the product of the first step in approximately 5 ml aliquots over 90 minutes; (during this time, the product of the first step remains completely dry and always consists of a free-flowing powder).

I I F-6938-L 22 Finally, nitrogen is purged through the glass vessel for about hours with the jacket temperature at about 45°C. Yield: 877 grams of a free-flowing powder. Ti found was 1.85 wt%; Zr found was 0.30 wt%.

Example 4 The catalyst described in Example 3 was examined in a pilot plant fluid bed gas phase reactor under the following conditions: ethylene 180 psi (1.2 Mpa) hydrogen/ethylene 0.005-0.008 hexene/ethylene 0.015 reactor temperature 95 0

C

The resin prepared at a productivity of about 1400 g polymer/g catalyst had the following characteristics: average particle size 0.017 inches (0.43 mm) resin metal content 13.0 ppm HLMI (121) 5.3 MFR (I21/I2.16) 113 Density 0.949 g/cm 3 The GPC curve of this product is in Figure 4 [solid line] and is compared to a commercially produced tandem unit in a two stage process, in which a different molecular weight component is made in each stage [dotted line in Figure 4.] Properties of films of the product of Example 4 [solid line in Figure 4] are compared to the commercially produced product [dotted line in Fig. 4] OxyChem L5005.

F-6938-L 23 Sample Ti/Zr 0x,=e o5005 121 5.3 MFR 113 160 Density 0.949 0.950 Throughput, lb/hr (kg/hr) 98 (44) 120 (54) Melt Pressure (at 120 lb/hr) psi 7550 6450 (MPa) (52) (44) FQR 15 Dart Drop, 1 mil.g 565 325 mil.g 410 420 MD Elmendorf Tear, 0.5 mil. g/mil 37 The results in the GPC curve of Figure 4 show that the Example 4 bimodal product (solid line] has a high molecular weight component with higher molecular weight than that produced in the tandem two reactor process. The film of Example 4 is substantially reduced in, if not free of, gel content. The film of the Example 4 product has improved dart impact.

Comparative Example 1 o54.5.

A zirconium catalyst was tested in a slurry reactor at 850C with 130 psi (900 KPa) ethylene partial pressure. A hexene/ethylene gas ratio of 0.03 was used. MAO/toluene solution (12 2 ml) was added to the ieactor. Productivity of 800 g resin/g catalyst/hr was measured.

S. Sa The same catalyst system was tested in the fluid bed reactor at 90 0 C with 200 psi (1.4 MPa) ethylene partial pressure. A 0.025 hexene to ethylene gas ratio was used. A feed rate of 150 to 200 cm 3 /hr of 2 wt% MAO/toluene solution was employed. The MAO solution was added below the distributor plate. Even at very high MAO/toluene feed rates, catalyst productivity was only 220 g resin/g catalyst/hr. In addition, the reactor had to be shut down due to a fouled plate only 18 hours after the MAO feed was started.

This example illustrates that it is inore effective to F-6938-L 24 activate zirconium catalysts prior to introduction into a gas phase reactor. It also illustrates the fouling problems experienced when MAO solutions are added to the gas-phase reactor.

Comparative Example 2 A titanium/zirconium mixed metal catalyst was tested in the fluid bed reactor. At 150 psi (1 MPa) ethylene partial pressure at 90 0 C a 0.04 hexene to ethylene gas ratio was employed, and a hydrogen to ethylene gas ratio was 0.045 A 2 wt% solution of MAO in toluene was added beneath the fluid bed distributor plate. Resin flow index and GPC curve analysis showed that the zirconium catalyst sites were active, and the Ti:Zr productivity ratio was 7:3. However, the reactor had to be shut down within 24 hours because the distributor plate had fouled.

Comparat-ve Example 3 The same titanium/zirconium catalyst used in Example 2 was tested in the fluid bed reactor. It was run at 90 0 C with 150 20 psi (1 MPa) ethylene partial pressure. A 0.03 hexene to o ethylene gas ratio was used and a hydrogen to ethylene ratio was 0.04 A solution of 2 wt% MAO in toluene was added directly into the bed at the rate of 200 cc/hr. The resin flow index and molecular weight distribution showed definitively that the zirconium sites were active with a Ti:Zr productivity ratio of 3:7. In the process of running this test, though, a very large chunk grew und the injection port causing a shutdown.

This example demonstrates that relative zirconocene catalyst activity is significantly higher when there is better 30 contact between the MAO/toluene droplets and the catalyst sites.

It also verifies that fouling also occurs when the MAO solution is added to the reactor directly into the fluid-bed of polymer.

Comparative Example 4 The catalyst used in examples 2 and 3 was re-run under the same conditions used in example 3. The MAO feed rate was the same as well. During this test, though, the MAO was dispersed ~II i P' '71 i 1 into a 10 Ib/hr (4.5 Kg/hr) ethylene gas stream using an ultrasonic atomizer. The atomizer dispersed the MAO solution into very small (40 micron) droplets.

Enough gas was used so that the toluene evaporated from the MAO. The gas flow rate was determined in an off-line test using toluene alone. The resin produced during this test showed no evidence of activity from the zirconium sites. In addition, there were no signs of reactor fouling after an extended period of running.

This example proves that it is the presence of liquid in the reactor that is responsible both for the activation of the zirconium and the fouling of the reactor.

Throughout the description and claims of this specification, the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended to exclude other additives or components or integers.

a 4« S 4 4 44. 4 MCC \WINWORODIMAALO'OOELETEPS5749294 COC

Claims (16)

1. In a catalyst composition which comprises a catalyst precursor and a cocatalyst free of alumoxane, which catalyst is effective to produce polymers and copolymers of ethylene, the improvement comprising a precursor, effective to produce bimodal molecular weight distribution product with said cocatalyst, wherein said precursor comprises particles wherein the particles comprise silica, having a pore volume of 0.5 to 5.0 cc/gram; containing reactive hydroxyl groups, ranging form 0.1 to 3.0 mmols/gram silica; and Mg, provided as an organomagnesium compound, in an amount to provide a Mg:OH molar ratio of from 0,5:1 to 4:1, wherein the organomagnesium compound has the formula R"a Mg R'b where R" and R' are the same or different C2-C8 alkyl groups, and a and b are each 0,1 or 2, providing that a b is equal to the valence of Mg; and wherein the organomagnesium compound is reacted with said hydroxyl groups, and thereafter contacted with a non-metallocene transition metal compound, which is supported on said silica; 9 wherein the silica is impregnated with an activated metallocene compound, wherein the metallocene compound has the formula CpmMAnBp wherein Cp is a cyclopentadienyl or a substituted cyclopentadienyl group; m is 1 or 2; M is zirconium or hafnium; and 25 each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group providing that m+n+p is equal to the valence of the metal M.

2. The catalyst of claim 1, wherein the metallocene is activated with an alumoxane of the formula or wherein is R-(AI(R)-O)x-AIR 2 for oligomeric, linear alumoxanes and is for oligomeric cyclic alumoxane wherein x is 1-40, y is 3-40, and R is a Ci-C8 alkyl group and wherein the molar ratio of alumoxane, expressed as aluminum, to metallocene ranges from 50 to 500. C;WINWORDUANELLESPEC82B42.DOC 27

3. The catalyst of claim 2, wherein the alumoxane is methylalumoxane.

4. The catalyst of any one of claims 1-2, wherein the cocatalyst is trialkylaluminum. The catalyst of claim 4, wherein the cocatalyst is trimethylaluminum.

6. The catalyst of any one of claims 1-5, wherein the non-metallocene transition metal compound is a tetravalent titanium compound.

7. The catalyst of claim 6, wherein the tetravalent titanium compound is provided in an amount sufficient to provide a metallocene :Ti ratio of 0.01 to 0.50,

8. The catalyst of any one of claims 1-7, wherein the organomagnesium compound is dibutylmagnesium.

9. The catalyst of any one of claims 1-8, wherein the metallocene is selected from the group consisting of bis (cyclopentadienyl) metal dihalides, bis (cyclopentadienyl) metal hydridohalides, bis (cyclopentadienyl) metal monoalkyl monohalides, bis (cyclopentadienyl) metal dialkyls and bis (indenyl) metal dihalides wherein the metal is zirconium or hafnium, and the alkyl groups are C 1 C 6 alkyls. The process of claim 9, wherein the metallocene is selected from the group consisting of bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis 20 (cyclopentadienyl) hafnium dimethyl, bis (cyclopentadienyl) zirconium hydridochloride, bis (cyclopentadienyl) hafnium hydridochloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (n-butylcyclopentadienyl) ''zirconium dichloride, cyclopentadienylzirconium trichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydro-l-indenyl) zirconium dichloride, and ethylene- °o [bis(4,5,6,7-tetrahydro-1-indenyl)] zirconium dichloride.

11. A catalyst composition, which contains activated metallocene compound, and which obviates feeding alumoxane solutions to a polymerization reactor, .I wherein the catalyst composition comprises a cocatalyst which is a monomeric trialkylaluminum, free of oligomeric or polymeric reaction products of trialkylaluminum and water, and a catalyst precursor, C:\WNWORDUANELLESPECI82842,DOC 28 wherein the catalyst precursor comprises particles wherein the particles comprise silica, having a pore volume of 0.5 to cc/gram; containing reactive hydroxyl groups, ranging from 0.1 to mmols/gram silica; and Mg, provided as an organomagnesium compound, in an amount to provide a Mg:OH molar ratio of from 0.5:1 to 4:1, wherein the organomagnesium compound has the formula R"a Mg R'b where R" and R' are the same or different C2-C8 alkyl groups, and a and b are each 0,1 or 2, providing that a b is equal to the valence of Mg; and wherein the organomagnesium compound is reacted with said hydroxyl groups, and thereafter contacted with a non-metallocene transition metal compound, which is supported on said silica; wherein the silica is impregnated with an activated metallocene compound, wherein the metallocene compound has the formula CpmMAnBp wherein Cp is a cyclopentadienyl or a substituted cyclopentadienyl group; m is 1 or2; M is zirconium or hafnium; and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom and an alkyl group, providing that m n p is g equal to the valence of the metal M. 20 12. The catalyst of claim 11, wherein the metallocene is activated with an S" alumoxane of the formula or wherein is R-(AI(R)-O)x-AIR 2 for oligomeric, linear, alumoxanes and is for oligomeric cyclic alumoxane whetein x is 1-40, y is 3-40, and R is a CI-C8 alkyl group and V I wherein the molar ratio of alumoxane, expressed as aluminum, to metallocene ranges from 50 to 500. S13. The catalyst of claim 12, wherein the alumoxane is methylalumoxane.

14. The catalyst of any one of claims 11-13, wherein the cocatalyst is trialkylaluminum.

15. The catalyst of claim 14, wherein the cocatalyst is trimethylaluminum.

16. The catalyst of any one of claims 11-15, wherein the non-metallocene transition metal compound is a tetravalent titanium compound. C:\WNWORDUMANELL sPECMiZe242.DO -I I 29

17. The catalyst of claim 16, wherein the tetravalent titanium compound is provided in an amount sufficient to provide a metallocene:Ti ratio of 0.01 to 0.50.

18. The catalyst of any one of claims 11-17, wherein the organomagnesium compound is dibutylmagnesium.

19. The catalyst of any one of claim I11-18 wherein the metallocene is selected from the group consisting of bis (cyclopentadienyl) metal dihalides, bis (cyclopentadienyl) metal hydridohalides, bis (cyclopentadienyl) metal monoalkyl monohalides, bis (cyclopentadienyl) metal dialkyls and bis (indenyl) metal dihalides wherein the metal is zirconium or hafnium, and alkyl contains 1 to 6 carbon atoms. The catalyst of claim 19, wherein the metallocene is selected from the group consisting of bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) hafnium dimethyl, bis (cyclopentadienyl) zirconium hydridochloride, bis (cyclopentadienyl) hafnium hydridochloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (n-butylcyclopentadienyl) :zirconium dichloride, cyclopentadienylzirconium trichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, and ethylene- 6:*1 20 [bis(4,5,6,7-tetrahydro-1-indenyl)] zirconium dichloride. 0lt21. The catalyst of claim 20, wherein the metallocene is selected from the group consisting of bis (cyclopentadienyl) zirconium dichloride and bis- (butylcyclopentadienyl) zirconium dichioride.

22. The catalyst of any one of claims 11-21, wherein the activated metallocene compound is formed in a solution of an alumoxane and said metallocene compound, wherein the solution has a maximum volume which is equal to the total pore volume of said silica. M IYTED: 20 Iambexr 1998 MrS cRVOE FTIMaRICK Att2rqys far: MBT OIL CRECN A913~tJL C:\WNWORDUANELLEISPECM82842.DOC ABSTRACT A catalyst composition which comprises a catalyst precursor and a co-catalyst free of alumoxane. The catalyst precursor comprises particles comprising silica, an organomagnesium compound, an non-metallocene transition metal compound and an activated metallocene compound. The catalyst is effective to produce polymers and co-polymers of ethylene, the improvement residing in the precursor which is effective to produce a bimodal molecular weight distribution product with the co-catalyst. 0* e St. e S. 6 PS S. C:\WNWORDJANELLESPECMa82842A.DOC .i