Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution

• US 5,032,562 A
• Filed: 12/27/1989
• Issued: 07/16/1991
• Est. Priority Date: 12/27/1989
• Status: Expired due to Term

• Current Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Original Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Inventors: Lo, Frederick Y., Shirodkar, Pradeep P., Nowlin, Thomas E.
• Primary Examiner(s): Garvin, Patrick P.
• Assistant Examiner(s): PEEBLES, BRENT
• Application Number:
  US07/457,432
• Time in Patent Office: 566 Days
• Field of Search: 502/113, 502/115, 502/117, 502/120, 502/125, 502/127, 502/104, 502/111
• US Class Current: 502/111
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 4/63904 in combination with another component of C08F4/62
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65925 two cyclopentadienyl rings being mutually non-bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

There is disclosed a supported olefin polymerization catalyst composition comprising a precursor and a catalyst activator. The precursor comprises a magnesium compound, e.g., dibutylmagnesium, a cyclopentadienyl group-containing zirconium compound, and a titanium and/or a vanadium compound, e.g., TiCl₄, and an organic compound, e.g., an alcohol. The catalyst activator is a mixture of a conventional Ziegler/Natta co-catalyst and a zirconium sites activator, e.g., methylaluminumoxane. The catalyst is used in the presence of small amounts of hydrogen to produce polymers having multimodal molecular weight distribution in a single reactor.

Claims

1. An olefin polymerization catalyst precursor composition supported on a porous carrier which has active OH groups comprising a magnesium compound, a zirconium compound, and TiCl₄, wherein the magnesium compound has the formula:

space="preserve" listing-type="equation">Mg(OR).sub.2, R.sup.1.sub.m MgR.sup.2.sub.n or R.sup.3.sub.k MgX.sub.(2-k)

where R, R¹, R², and R³ each are each alkyl groups, X is a halogen, m and n are each 0, 1 or 2, providing that m+n equals the valence of Mg, and k is 0, 1, or 2; and

wherein the zirconium compound has the formula

space="preserve" listing-type="equation">Cp.sub.m ZrY.sub.n X.sub.(2-m)

wherein Cp is cyclopentadienyl, m is 1, 2 or 3, Y and X are each the same or different halogen, a C₁ -C₆ alkyl or hydrogen and n is 0 or 1, which is produced by impregnating a reaction product of said carrier and said magnesium compound with said zirconium compound;

wherein the reaction product is treated with said titanium compound prior to impregnating.

2. A precursor composition of claim 1 which has a Ti:

Zr molar ratio of about 1;

1 to about 50;

1.

3. A precursor composition of claim 2 which has a Ti:

Zr molar ratio of about 10;

1 to about 20;

1.

4. A precursor composition of claim 1 which additionally comprises at least one organic compound which is:

an alcohol of the formula R--OH;

ketone of the formula RCO--R;

an ester of the formula RCOOR;

an acid of the formula RCOOH;

or an organic silicate of the formula Si(OR)₄, where R for each of the organic compounds is the same or different linear, branched, or a cyclic alkyl group of 1-12 carbon atoms.

5. A precursor of claim 4 wherein the organic compound is an alcohol.

6. A precursor of claim 4 wherein the organic compound is butanol.

7. A catalyst composition comprising the precursor of claim 1 and a catalyst activator which is a mixture of a co-catalyst containing at least one compound of the elements of Group IB, IIA, IIIB, or IVB of the Periodic Chart of the Elements and a zirconium sites activator which is an aluminoxane of the formula ##STR7## for a linear aluminoxane, where n is 0 to 50 and/or ##STR8## for a cyclic aluminoxane, wherein m is an integer from 3 to 50, and R for both the linear and the cyclic aluminoxane is the same or different linear, branched or cyclic C₁ -C₁₂ alkyl group.

8. A catalyst composition of claim 7 wherein the co-catalyst is a Group IIIB metal alkyl or dialkyhalide having 1 to 20 carbon atoms per alkyl radical.

9. A catalyst composition of claim 8 wherein the co-catalyst is a trialkylaluminum compound having 1 to 6 carbon atoms per alkyl radical.

10. A catalyst composition of claim 9 wherein the co-catalyst is a trialkyaluminum compound having 1 to 4 carbon atoms per alkyl radical.

11. A catalyst composition of claim 10 wherein the co-catalyst is trimethylaluminum.

12. A catalyst composition of claim 11 wherein the aluminoxane is methylaluminoxane.

13. The precursor composition of claim 1, wherein the zirconium compound is admixed with an aluminoxane compound of the formula ##STR9## for a linear aluminoxane, where n is 0 to 50 and/or ##STR10## for a cyclic aluminoxane, wherein m is an integer from 3 to 50, and R for both the linear and the cyclic aluminoxane is the same or different linear, branched or cyclic C₁ -C₁₂ alkyl group.

14. The precursor composition of claim 1, wherein the zirconium compound is admixed with an aluminoxane compound of the formula ##STR11## for a linear aluminoxane, where n is 0 to 50 and/or ##STR12## for a cyclic aluminoxane, wherein m is an integer from 3 to 50, and R for both the linear and the cyclic aluminoxane is the same or different linear, branched or cyclic C₁ -C₁₂ alkyl group.

15. A method of synthesizing an olefin polymerization catalyst precursor composition comprising contacting a solid, porous carrier having reactive OH groups with a magnesium compound, a zirconium compound, and a compound selected from the group consisting of titanium compounds, vanadium compounds and mixtures thereof;

wherein the magnesium compound has the formula;

space="preserve" listing-type="equation">Mg(OR).sub.2, R.sub.m.sup.1 MgR.sub.n.sup.2, or R.sub.k.sup.3 MgX.sub.(2-k)

where R, R¹, R² and R³ are each alkyl groups, X is a halogen, k, m, and n are each 0, 1, or 2, providing that m+n equals the valence of Mg;

the zirconium compound has the formula Cp_m ZrY_n X.sub.(2-n)

wherein Cp is cyclopentadienyl, m is 1, 2 or 3, Y and X are each a halogen, a C₁ -C₆ alkyl or hydrogen, and n is 0 or 1;

the titanium compound is a titanium halide and the vanadium compound is a vanadium halide, a vanadium oxyhalide or mixtures thereof;

wherein the contacting is conducted in the presence of an organic solvent in the magnesium compound, the zirconium compound, the titanium compound, the vanadium compound, or mixtures of the titanium and vanadium compounds are soluble;

wherein the solid, porous carrier is contacted with the zirconium compound in the presence of an aluminoxane compound of the formula ##STR13## for a linear aluminoxane, where n is 0 to 50 and/or

space="preserve" listing-type="equation">(Al(R)--O).sub.m

for a cyclic aluminoxane, wherein m is an integer from 3 to 50, and R for both the linear and the cyclic aluminoxane is the same or different linear, branched or cyclic C₁ -C₁₂ alkyl group, which process comprises reacting said carrier with said magnesium compound and titanium compound and, subsequently, undertaking contacting with said zirconium compound.

16. A method of claim 15 wherein after the carrier is contacted with the magnesium compound but before it is contacted with the zirconium compound, the carrier is contacted with at least one organic compound, soluble in the organic solvent, which is:

an alcohol of the formula R--OH;

a ketone of the formula RCO--R;

an ester of the formula RCOOR;

an acid of the formula RCOOH;

or an organic silicate of the formula Si(OR)₄ where R for each of the organic compounds is the same or different linear, branched, or a cyclic alkyl group of 1-12 carbon atoms.

17. A method of claim 16 wherein the organic compound is an alcohol.

18. A method of claim 17 wherein the organic compound is butanol.

19. The process of claim 15, wherein the zirconium compound is admixed with an aluminoxane compound of the formula ##STR14## for a linear aluminoxane, where n is 0 to 50 and/or ##STR15## for a cyclic aluminoxane, wherein m is an integer from 3 to 50 and R for both the linear and the cyclic aluminoxane is the same or different linear, branched or cyclic C₁ -C₁₂ alkyl group.