WO1996004318A1

WO1996004318A1 - Polymerization catalyst systems, their production and use

Info

Publication number: WO1996004318A1
Application number: PCT/US1995/009663
Authority: WO
Inventors: Main Chang
Original assignee: Exxon Chemical Patents Inc.
Priority date: 1994-08-05
Filing date: 1995-08-01
Publication date: 1996-02-15

Abstract

This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for supporting the catalyst of the invention includes a washing step and provides for a supported bulky ligand transition metal catalyst which when utilized in a polymerization process substantially reduces the reactor fouling and sheeting particularly in a slurry phase polymerization process.

Description

- 1

POLYMERIZATION CATALYST SYSTEMS. THEIR PRODUCTION AND USE

INVENTOR: Main Chang

FIELD OF THE INVENTION

This invention relates to catalysts, catalyst systems, and to methods for their production and use in olefin polymerization. In particular this invention relates to a process for preparing a supported transition metal catalyst system for use in gas phase, slurry phase or liquid/solution phase olefin polymerization with improved reactor operability. BACKGROUND OF THE INVENTION

In many polymerization processes, particularly a slurry phase or gas phase process, it is desirable to use a supported catalyst. Generally these catalyst systems include a metallocene and alumoxane supported on a carrier such as silica. For example, U.S. Patent No. 4,937,217 generally describes combining in solution a mixture of trimethylaluminum and triethylaluminum with an undehydrated silica. A metallocene is then added and thereafter the mixture is dried to form a free flowing powder. Similarly, U.S. Patent Nos. 4,912,075, 4,935,397, and 4,937,301 generally describe the addition of trimethylaluminum to an undehydrated silica to which is then added a metallocene to form a dry supported catalyst. U.S. Patent No. 4,914,253 describes adding trimethylaluminum to undehydrated silica, adding a metallocene, and then drying the catalyst. U.S. Patent Nos. 4,808,561, 4,897,455 and 4,701,432 describe techniques to form a supported catalyst where the inert carrier, typically silica, is calcined and contacted with a metallocene(s) and a activator/cocatalyst component. U.S. Patent No. 5,238,892 describes forming a dry supported catalyst by mixing a metallocene with an alkyl aluminum then adding undehydrated silica. U.S. Patent No, 5,240,894 generally describes making a supported metallocene/alumoxane catalyst system by forming a metallocene/alumoxane reaction solution, adding a porous carrier, then evaporating the resulting slurry to remove residual solvent from the carrier. Finally, U.S. Patent Nos. 5,008,228, 5,086,025 and 5,147,949 generally describe a process which involves forming a dry supported catalyst by the addition of trimethylaluminum to a water impregnated silica to form alumoxane within the silica pores and then adding the metallocene. While these supported catalysts are useful, it would be desirable to have a catalyst system that provides improved reactor operability. When catalyst systems such as those described above are used, particularly in a slurry or gas phase polymerization process, there is sometimes a tendency for the reactor to foul. During some gas phase polymerization processes, fines within the reactor accumulate and stick to the walls of the reactor, the recycling lines, and cooling systems. This phenomenon, often referred to as "fouling" or "sheeting," results in many problems including poor heat transfer during the polymerization process. Polymer particles that adhere to the walls of the reactor continue to polymerize and typically fuse together and form chunks which disrupt polymer discharge and at worst cause shutdown of the reactor.

It would be highly desirable to have an improved polymerization catalyst that would significantly reduce fouling and thereby enhance reactor operability. SUMMARY OF THE INVENTION This invention generally relates to a new polymerization catalyst system and to methods for its manufacture and use in polymerization. In one embodiment, the invention is a new method for producing a supported transition metal catalyst system made by contacting a water containing support material with an organometallic compound and at least one metallocene compound. The solid product is then recovered by drying. At some point in the process, before and/or after metallocene addition, organometallic compound is washed from the support. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION Introduction This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for forming the catalyst system involves supporting a metallocene compound and an organometallic compound on a support material containing water.

It is believed that by reducing the mole ratio of the metal of the organometallic compound to the water content of the support material, the catalyst system's tendency to foul during polymerization is reduced, however, as a consequence of reducing this mole ratio, the catalyst activity is reduced. It has been discovered that a catalyst with less fouling tendency can be produced using a wide range of metal to water ratios if the supported organometallic compound is washed prior to use. This method results in a commercially useful supported catalyst system with both high activity and a reduced tendency for sheeting or fouling.

Catalyst Components

Metallocene catalysts are typically bulky ligand transition metal compounds represented by the formula:

[L]_mM[A]_n where L is a bulky ligand; A is at least one halogen leaving group; M is a transition metal; and m and n are such that the total ligand valency corresponds to the transition metal valency. Preferably the catalyst is four co-ordinate such that the compound is ionizable to a 1⁺ charge state.

The ligands L and A may be bridged to each other. The metallocene compound may be full-sandwich compounds having two or more ligands, L, which may be cyclopentadienyl ligands or cyclopentadiene derived ligands. Alternatively the metallocene compound may be of the half-sandwich type having one ligand, L, which is a cyclopentadienyl ligand or cyclopentadienyl derived ligand.

The metallocene compounds contain a multiplicity of bonded atoms, preferably carbon atoms, forming a group which can be cyclic. The bulky ligand can be a cyclopentadienyl ligand or cyclopentadienyl derived ligand or any other ligand capable of η-5 bonding to the transition metal. One or more bulky ligands may be π-bonded to the transition metal atom. The transition metal atom may be a Group 4, 5 or 6 transition metal and/or a transition metal from the lanthanide or actinide series. Other ligands may be bonded to the transition metal, such as at least one halogen which serves as a leaving group. Non-limiting examples of metallocene catalysts and catalyst systems are discussed in for example, U.S. Patent Nos. 4,530,914, 4,952,716, 5,124,418, 4,808,561, 4, 897,455, 5,278,119, and 5,304,614 all of which are herein fully incorporated by reference. Further examples may be found in the disclosures of EP-A- 0129368, EP-A-0520732, EP- A- 0420436, WO 91/04257 WO 92/00333, WO 93/08221, and WO 93/08199 which are all fully incorporated herein by reference. Various forms of metallocenes may be used in the polymerization process of this invention. Examples of the development of metallocene catalysts may be found in the disclosures of U.S. Patent Nos. 4,871,705, 4,937,299, 5, 324,800, 5,017,714 5,120,867, and EP-A-0 129 368 published July 26, 1989 all of which are fully incorporated herein by reference. These publications teach metallocene structure and describe alumoxane as the cocatalyst. There are a variety of well known methods for preparing alumoxane such as those described in U.S. Patent 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,248,801, 5,235,081, 5,157,137, 5,103,031, and EP-A-0561476, EP-B1- 0279586, EP-A-0594218, and WO 94/10180, all of which are incorporated herein by reference. The metallocene catalyst component can be a monocyclopentadienyl heteroatom containing compound which is typically activated by either an alumoxane, an ionic activator, a Lewis acid, or a combination thereof to form an active catalyst system. These types of catalyst systems are described in, for example, PCT International Publication WO 92/00333, WO 94/07928, and WO 91/ 04257, and WO 94/03506, U.S. Patent Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,264,405 and 5,227,440 and EP-A-0 420 436, all of which are fully incorporated herein by reference. In addition, the metallocene catalysts useful in this invention can include non-cyclopentadienyl catalyst components such as boroles or carbollides in combination with a transition metal. Also useful may be those catalyst systems described in U.S. Patent Nos. 5,064,802, 5,149,819,

5,243,001, 5,239,022, 5,276,208, 5,296,434, 5,321,106, and 5,304,614, and PCT publications WO 93/08221 and WO 93/08199 published April 29, 1993 all of which are herein incorporated by reference.

The preferred transition metal components are those of Group 4, particularly, zirconium, titanium and hafnium. The transition metal may be in any oxidation state, preferably +3 or +4 or a mixture thereof. All of the catalyst systems of the invention may be prepolymerized or used in conjunction with an additive or scavenging component.

As used herein the term "metallocene" is defined to contain one or more unsubstituted or substituted cyclopentadienyl or cyclopentadienyl moiety in combination with a transition metal. In one embodiment the metallocene catalyst component is represented by the general formula (Cp)mMRnR'p wherein at least one Cp is an unsubstituted or, preferably, a substituted cyclopentadienyl ring, even more preferably a monosubstituted cyclopentadienyl ring; M is a Group 4, 5 or 6 transition metal; R and R' are independently selected halogen, hydrocarbyl group, or hydrocarboxyl groups having 1-20 carbon atoms; m = 1-3, n = 0-3, p = 0-3; and the sum of m + n + p equals the oxidation state of Me.

In another embodiment the metallocene catalyst component is represented by the formulas: (C5R^,m)pR"s(C5R'm)MQ3-p-χ and

R^R'π^MO: wherein M is a Group 4, 5, or 6 transition metal; C5R'_m is a substituted cyclopentadienyl; each R', which can be the same or different, is hydrogen, alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two carbon atoms joined together to form a part of a C4 to C20 ring; R" is one or more or a combination of a carbon, a germanium, a silicon, a phosphorous or a nitrogen atom containing radical bridging two (C5R'_m) rings, or bridging one (^R'm) ring back to M; when p = 0 and x = 1 otherwise "x" is always equal to 0; each Q, which can be the same or different, is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms, or alkoxide, or Q is a halogen; Q' is an alkylidene radical having from 1-20 carbon atoms; s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2, and when s is 1, m is 4 and p is 1.

The term "carrier" or "support" as used herein are interchangeable and can be any support material, preferably a porous support material, capable of containing water, absorbed or adsorbed, such as talc, inorganic oxides, inorganic chlorides, and resinous support materials such as polyolefin or polymeric compounds or other organic support materials.

The preferred support materials are inorganic oxide materials which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal oxides. Particularly preferred catalyst support materials include silica, alumina, silica-alumina, and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like. Additional suitable support materials include finely divided polyolefins, such as polyethylene or polymeric compounds and inorganic compounds such as magnesium dichloride and the like. The support material preferably has a water content in the range of from about 3 weight percent to about 27 weight percent based on the total weight of the support material and water contained therein, preferably in the range of from about 7 weight percent to about 15 weight percent, and most preferably in the range of from about 9 weight percent to about 14 weight percent. The amount of water contained within the support material can be measured by techniques well known in the art. For the purposes of this patent specification and the appended claims the weight percent water is measured by determining the weight loss of the support material which has been heated and held at a temperature of 1000°C for 16 hours. This procedure is known as "Loss on Ignition" (LOI) and is measured in weight percent of weight lost based on the initial weight of the support material.

Hereinafter, for the purposes of this patent specification and the appended claims, the support material used to make the catalyst system contains water. This support may be formed by adding or removing the desired quantity of water from, for example, commercially available silica (Davidson 948).

It is preferred that the support material have a surface area in the range of from about 10 to about 700 m^/g, pore volume in the range of from about 0.1 to about 4.5 cc/g, and average particle size in the range of from about 10 to about 500 μm. More preferably, the surface area is in the range of from about 50 to about 500 m^/g, pore volume of from about 0.5 to about 4.0 cc/g, and average particle size of from about 20 to about 200 μm. Most preferably the surface area range is from about 100 to about 400 m^/g, pore volume from about 0.8 to about 3.5 cc/g, and average particle size is from about 30 to about 150 μm Method of Producing the Activator

In one preferred method of making the catalyst system of the invention, the support material is first contacted with a component capable of forming an activator for the metallocene catalyst component. In one embodiment, the preferred activator component is an organometallic compound of Group 1, 2, 3 and 4 organometallic alkyls, alkoxides, and halides. The preferred organometallic compounds are lithium alkyls, magnesium alkyls, magnesium alkyl halides, aluminum alkyls, silicon alkyl, silicon alkoxides and silicon alkyl halides More preferred organometallic compounds are aluminum alkyls and magnesium alkyls The most preferred organometallic compounds are aluminum alkyls, for example, triethylaluminum (TEAL), trimethylaluminum (TMAL), tri-isobutylaluminum (TLBAL) and tri-n-hexylaluminum (TNHAL) and the like

Preferably the organometallic compound, when contacted with the water containing support material, forms an oxy-containing organometallic compound represented by the following general formula:

(R-Al-O)_n which is a cyclic compound and

R (R-A]-O)_n A1R which is a linear or non-cyclic compound and mixtures thereof including multi¬ dimensional structures In the general formula R is a C\ to C12 alkyl group such as for example methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, and n is an integer from about 1 to 20. The most preferred oxy containing organometallic compounds are alumoxanes, for example methyl alumoxane and/or ethylalumoxane In a preferred embodiment the support material is introduced to a solution of an organometallic compound at a temperature ranging from 0°C to 80°C. The temperature may optionally be maintained at a constant, preferably in the range of from about 0°C to about 45°C. The temperature used will depend on the quantity of the catalyst system of the invention being produced in a single batch.

The mole ratio of the organometallic metal to the water content of the support material, for example AI/H2O, is preferably in the range of from about 0.7 to about 1.5, preferably about 0.8 to about 1.3, and even more preferably in the range of from about 0.9 to about 1.3. As the support material is added to the organometallic compound, for example when the organometallic compound is TMAL, alumoxane, an activator, is generated predominantly inside the pores of the support material. Typically, however, excess metal and/or organometallic compound remains unreacted. The amount of excess organometallic compound naturally depends upon the initial ratio of organometallic compound to water described above. While not wishing to be bound by any particular theory, it is believed that this excess organometallic compound which fails to form activator, is at least partially responsible for reactor fouling.

It has been discovered that washing the activated support material reduces the amount of unreacted organometallic derived metal among the pores of the support. "Washing" is a process familiar to those skilled in the art and may be generally defined as any process by which a liquid is used to remove relatively loose components, particles, compounds, or elements from a solid material. For example, the washing process may be one involving successive slurrying and decantation as described below or the process may be involve continuous flow of fresh liquid over the solid.

The washing step may be performed either before or after metallocene addition or both before and after. Preferably, washing is accomplished by first allowing the support material to settle after reaction with the organometallic compound then decanting any supernatant. Next, the activated support is re- slurried in a suitable diluent such as a dry, oxygen-free aliphatic hydrocarbon. Finally, the support is again allowed to settle so that the supernatant is removed. This washing process can be repeated and can be performed at any stage or in a combination of stages prior to final drying as will be more fully described below. After washing, the organometallic compounds and/or metallocene compounds may be recovered from the diluent for future use or disposal. The diluent may be any hydrocarbon, preferably an inert hydrocarbon of which non-limiting examples include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane and mixtures thereof. Dry, oxygen free, aliphatic hydrocarbons such as isobutane, isopentane, hexane, and heptane are particularly preferred. Method of Producing the Catalyst System

Preferably the activator is formed as described above and then the metallocene catalyst component is added. The supported activator can be washed and or dried before introducing the metallocene component, it can then be slurried in a suitable solvent as is known in the art and the metallocene catalyst component added thereafter.

In a preferred embodiment, the metallocene catalyst component is added to a support material/alumoxane activator solution, and is then heated to complete the reaction between the metallocene catalyst component and the alumoxane. (The term "solution" as used herein includes a suspension, a slurry, or a mixture.) If the activator is washed prior to metallocene addition, the catalyst system may at this point be introduced into the reactor as a slurry or it can be dried to a free flowing powder without any further washing.

The washing step, regardless at what point in the process it is performed, may be repeated a number of times depending on the amount of organometallic compound originally used, the volume of diluent used, and the desired amount of metal removal. There should be less than about 10,000ppm of the metal of the organometallic compound extracted in a final wash using a diluent such as hexane. Preferably there will be less than about 7000ppm of the metal of the organometallic compound extracted in the final wash. More preferably there will be less than about 5000 ppm of the metal of the organometallic compound extracted in the final wash. Even more preferably there will be less than about 2000ppm of the metal of the organometallic compound extracted in the final wash. Ideally there will be less than about lOOOppm of the metal of the organomatallic compound extracted in the final wash. The quantity of metal is measured by atomic absorption techniques well known in the art such as by ICPES. In an alternative embodiment a porous support is contacted with a liquid comprising a metallocene catalyst and/or organometallic activator component, the total volume of the liquid being less than about four times the total pour volume of the porous support. The support is thereafter washed as described above. The catalyst system is then dried to remove excess liquid. Polymerization Process

The catalyst system of this invention is suited for the polymerization of monomers and/or comonomers in any polymerization or prepolymerization process, gas, slurry or solution phase process. In the preferred embodiment, the catalyst system is used in a gas phase or slurry phase polymerization process. Slurry or gas phase polymerization or copolymerization reactions may involve the polymerization or optionally prepolymerization of one or more of the alpha-olefin monomers having from 2 to 20 carbon atoms, preferably 2-12 carbon atoms. The invention is particularly well suited to the copolymerization reactions involving the polymerization of one or more of the monomers, for example alpha- olefin monomers of ethylene, propylene, butene-1, pentene-1, 4-methylpentene-l, hexene-1, octene-1, decene-1, and cyclic olefins such as styrene. Other monomers can include polar vinyl, diolefins such as dienes, norbornene, acetylene and aldehyde monomers. Preferably a copolymer of ethylene or propylene is produced. Preferably the comonomer is an alpha-olefin having from 3 to 15 carbon atoms, preferably 4 to 12 carbon atoms and most preferably 4 to 10 carbon atoms. In another embodiment ethylene is polymerized with at least two comonomers to form a terpolymer and the like. In an alternative embodiment of the process of the invention, the olefin(s) are prepolymerized in the presence of the catalyst system of the invention prior to the main polymerization. For details on prepolymerization see U.S. Patent No. 4,923,833 and 4,921,825 and EP-B-0279 863, published October 14, 1992 all of which are incorporated fully herein by reference.

While the novel catalyst system of this invention is effective in reducing reactor fouling, it is within the scope of this invention to also employ other methods of reducing fouling such as the use of antistatic agents or mechanical scrapers. Examples of antistatic agents are described in U.S. Patent No. 5,283,278, fully incorporated herein by reference. Other examples of antistatic agents include but are not limited to alcohol, thiol, silanol, ester, ketone, aldehyde, acid, amine, and ether compounds.

EXAMPLES In order to provide a better understanding ofthe present invention including representative advantages and limitations thereof, the following examples are offered. Example 1 Into a 1 liter flask equipped with mechanical stirrer, 220 ml of TMAL in heptane solution (15 wt%) and 90 ml of heptane were charged. The solution was cooled to about 50°F (10°C). A 40 g sample of silica gel (Davison D-948 with average particle size of 70 micron) which contained 12.5 wt% of water was slowly added into the flask over 70 minutes. The mole ratio TMAL/H2O was 1.13. 0.9 g of l-(n-l,3-BuMeCp)2ZrCl2 slurried in 20 ml of heptane was then added into the vessel. The mixture was allowed to react at 150°F (65.5°C) for 1 hour. At the end ofthe reaction, the slurry mixture was allowed to settle and the supernatant was decanted. 150ml of hexane was added to the mixture and the mixture was stirred for 10 min. The mixture was then allowed to settle and the supernatant decanted. This washing procedure was performed a total of four times. The amount of aluminum in the supernatant as measured by ICPES decreased substantially with each wash.

WashNo. Aj

1 7362ppm

2 5641ppm

3 2748ppm

4 1070ppm

After washing, the solid was dried by nitrogen purging. A free flowing solid was obtained at the end ofthe preparation.

Into a clean 2 liter autoclave, 800 ml of hexane and 20 ml of hexene-1 were charged. 2.0 ml of TEBAL in heptane solution (1.78 mmole Al) was charged into the autoclave. The reactor was heated to 70°C. 125 mg ofthe catalyst prepared above was then charged into the autoclave through a catalyst injection tube using pressurized ethylene. The autoclave was pressurized to a total pressure of 95psig

(655 kPag). The polymerization was allowed to proceed at 70°C for 30 minutes.

After the polymerization, the polymer slurry was transferred into a evaporation dish. The surface ofthe autoclave wall and ofthe agitator were very clean. The product was recovered after letting the solvent evaporate. A total of 45 g of polymer was obtained.

Comparative Example 2

Example 1 was repeated except that 200ml ofthe TMA solution was used. The mole ratio of TMA H2O was dropped to 1.03. The polymerization step was repeated as in Example 1. After polymerization, the surface ofthe autoclave was inspected and the autoclave wall and agitator were clean. A total of 35g of polymer was obtained.

Comparative Example 3 Example 1 was repeated except that the washing steps after metallocene addition were deleted. The aluminum content ofthe supernatant following metallocene addition was measured at 17153 ppm. The solid catalyst was dried from this solution using nitrogen purging without any washing. The polymerization step was repeated as in Example 1. After polymerization, the surface ofthe autoclave wall and the agitator were coated with a thick layer of polymer and most ofthe polymer product was fused together. A total of 18g of polymer was obtained.

Example 4

Example 1 was repeated except that the washing steps were conducted before the metallocene addition. The polymerization step was repeated as in

Example 1. After polymerization, the surface ofthe autoclave wall and agitator were clean. A total of 25g of polymer was obtained.

While the present invention has been described and illustrated by reference to preferred embodiments, it will be appreciated by those of ordinary skill in the art that the invention lends itself to variations not necessarily illustrated herein.

Claims

CLAIMS I Claim:

1. A method of producing a supported catalyst system, said method comprising the steps of: contacting a water containing support material with an organometallic compound; adding at least one metallocene catalyst component; and washing the support material.

2. The method of claim 1 wherein the support material is at least one ofthe group consisting of inorganic oxides, inorganic chlorides, and polyolefins, preferably silica, alumina, and magnesia.

3. The method of claims 1 or 2 wherein the organometallic compound is selected from the group consisting of aluminum alkyls and magnesium alkyls, preferably TMAL, TIBAL, TEAL, and TNHAL.

4. The method of any ofthe preceding claims wherein the step of contacting the water containing support material with the organometallic compound is performed at a constant temperature in the range of from 0°C to 40°C.

5. The method of any ofthe preceding claims wherein the support material is washed after contact with the organometallic compound but before metallocene addition or wherein the support material is first contacted with the organometallic compound and then metallocene is added, and thereafter the support material is washed.

6. The method of any ofthe preceding claims wherein the support material is washed at least two times.

7. The method of any ofthe preceding claims wherein the water content of the support material is in the range of from 3 weight percent to 27 weight percent based on the total weight ofthe support material.

8. The method of any ofthe preceding claims wherein the content ofthe metal ofthe organometallic compound in the final wash is less than 2748 ppm, preferably less than 1070 ppm .

9. The method of any ofthe preceding claims wherein the mole ratio ofthe metal ofthe organometallic compound to the water content ofthe support material is in the range from 0.7 to 1.5.

10. The method of any ofthe preceding claims wherein the metallocene catalyst component is represented by the formulae: (C₅R'_m)pR^Hs(C5R'm)MQ3-p-χ and κ's(c₅R'_m)₂MQ' wherein M is a Group 4, 5, 6 transition metal; C5R'_m is an unsubstituted or substituted cyclopentadienyl; each R', which can be the same or different, is a hydrogen, alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms or two carbon atoms joined together to form a part of a C to C20 ring; R" is one or more of or a combination of a carbon, a germanium, a silicon, a phosphorous or a nitrogen atom containing radical bridging two (C5R'_m) rings, or bridging one (CsR'm) ring back to M; wherein when p = 0 and x = 1 otherwise "x" is always equal to 0; each Q, which can be the same or different, is an aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms or Q is a halogen; Q' is an alkylidene radical having from 1-20 carbon atoms; and wherein s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s is 1, m is 4 and p is 1.

11. A catalyst system produced by the method of any ofthe preceding claims.

12. A process of polymerizing olefins alone or in combination with one or more other olefins, said process comprising polymerizing in the presence ofthe catalyst system of claim 11.