Supported polymerization catalyst

• US 4,701,432 A
• Filed: 06/09/1986
• Issued: 10/20/1987
• Est. Priority Date: 11/15/1985
• Status: Expired due to Term

• Current Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Welborn, Howard C. Jr.
• Primary Examiner(s): Garvin, Patrick P.
• Application Number:
  US06/871,962
• Time in Patent Office: 498 Days
• Field of Search: 502/103, 502/113, 502/114, 502/115, 502/116, 502/117, 502/118, 502/120, 502/121, 502/123, 502/129, 502/132
• US Class Current: 502/113
• 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 210/08 Butenes
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/01 High molecular weight, e.g. >800,000 Da.
• CPC Class Codes: C08F 2500/04 Broad molecular weight distribution, i.e. Mw/Mn > 6
• CPC Class Codes: C08F 4/6228 with an aluminoxane, i.e. a compound containing an Al-O-Al- group
• CPC Class Codes: C08F 4/65904 in combination with another component of C08F4/64
• 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 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

An olefin polymerization catalyst comprising (a) a supported transition metal containing component comprising the support treated with at least one metallocene and at least one non-metallocene transition metal compound, and a cocatalyst comprising an alumoxane and an organometallic compound of a metal of Groups IA, IIA, IIB, or IIIA of the Periodic Table.

Claims

1. An olefin polymerization supported catalyst component comprising a support treated with at least one metallocene of a Group IVB or VB metal and at least one non-metallocene compound of a Group IVB, VB, or VI transition metal.

2. The olefin polymerization supported catalyst component of claim 1 wherein the (a) metallocene is represented by the formulas:

space="preserve" listing-type="equation">(Cp).sub.m MR.sub.n X.sub.q (I)

space="preserve" listing-type="equation">C.sub.5 R'"'"'.sub.k).sub.g R".sub.s (C.sub.5 R'"'"'.sub.k)MQ.sub.3-g and (II)

space="preserve" listing-type="equation">R".sub.s (C.sub.5 R'"'"'.sub.k).sub.2 MQ'"'"' (III)

wherein Cp is a cyclopentadienyl ring, M is a Group IVB or VB transition metal, X is a halogen, R is hydride, a hydrocarby or hydrocarboxy group having from 1 to 20 carbon atoms, m=1-3, n=0-3 and the sum of m+n +q is sufficient to saturate M, (C₅ R'"'"'_k) is a cyclopentadienyl or an alkyl substituted cyclopentadienyl;

each R'"'"' is the same or different and is hydrogen or a hydrocarbyl radical selected from alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals containing from 1 to 20 carbon atoms, or two carbon atoms are joined together to form a C₄ -C₆ ring, R" is a C₁ -C₄ alkylene radical, a dialkyl germanium or silicon or an alkyl phosphine or amine radical bridging two (C₅ R'"'"'_k) rings;

Q is a hydrocarbyl radical selected from aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radicals having from 1-20 carbon atoms, hydrocarboxy radical having from 1-20 carbon atoms or halogen and can be the same or different from each other Q'"'"' is an alkylidiene radical having from 1 to about 20 carbon atoms;

s is O or 1;

g is 0,1, or 2;

s is O when g is O;

k is 4 is when s is 1 and k is 5 when s is O; and

M is defined as above, and,

(b) the non-metallocene transition compound metal is represented by the formulas;

TrX'"'"'_4-g (OR'"'"')_q, TrX'"'"'_4-q R²_q, VOX'"'"'₃ and VO(OR")₃ wherein Tr is a Group IVB or Group VB metal, Q is O or a number equal to or less than 4, X'"'"' is a halogen, R¹ is an alkyl group, aryl group, or cycloalkyl group having from 1 to 20 carbon atoms, and R² is an alkyl group, aryl group, aralkyl group having from 1 to 20 carbon atoms.

3. The olefin polymerization supported catalyst component of claim 2 wherein the support is silica.

4. The olefin polymerization supported catalyst component of claim 2 wherein the metallocene is selected from titanium, zirconium, hafnium or vanadium metallocenes or mixtures thereof.

5. The olefin polymerization supported catalyst component of claim 4 wherein the metallocene is selected from titanium or zirconium metallocenes or mixtures thereof.

6. The olefin polymerization supported catalyst component of claim 2 wherein the non-metallocene transition metal compound is selected from TiCl₄, TiBr₄, Ti(OC₄ H₉)₂ Cl₂, VCl₄, VOCl₃, and ZrCl₄.

7. The olefin polymerization supported catalyst component of claim 2 wherein the at least one metallocene is selected from bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium dimethyl, bis(methylcyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium methyl chloride, bis(methylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium methyl chloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium methyl chloride, bis(n-butylcyclopentadienyl)zirconium dimethyl, biscyclopentadieny.1)titanium diphenyl, bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)titanium methyl chloride, bis(cyclopentadienyl)titanium dimethyl, bis(methylcyclopentadienyl)titanium diphenyl, bis(methylcyclopentadienyl)titanium dichloride, bis(methylcyclopentadienyl)titanium diphenyl, bis(methylcyclopentadienyl)titanium methyl chloride, bis(methylcyclopentadienyl)titanium dimethyl, bis(pentamethylcyclopentadienyl)titanium dichloride, bis(pentamethylcyclopentadienyl)titanium diphenyl, bis(pentamethylcyclopentadienyl)titanium methyl chloride, bis(pentamethylcyclopentadienyl)titanium dimethyl, bis(n-butylcyclopentadie)titanium diphenyl, bis(n-butylcyclopentadienyl)titanium dichloride and mixtures thereof.

8. The olefin polymerization supported catalyst component in accordance with claim 7 wherein the metallocene is selected from bis{methylcyclopentadien)zirconium dichloride, bis(n-butylcyclopentadieyl)zirconium dichloride, bis(pentamethylyclopentadienyl)zirconium dichloride, bis{cyclopentadieny)titanium diphenyl, and bis(metylcyclopentadien)titanium diphenyl.

9. The olefin polymerization supported catalyst component in accordance with claim 2 wherein the molar ratio of the metallocene to the non-metallocene transition metal containing compound is in the range of 10 moles metallocene compound per mole of non-metallocene transition metal compound to about 0.1 moles metallocene compound per mole of non-metallocene transition metal compound.

10. An olefin polymerization supported catalyst system comprising

I. a cocatalyst comprising

(a) an alumoxane, and

(b) an organometallic compoound of a metal of Groups IA, IIA, IIB, and IIIA of the Perodic Table, and

II. a supported catalyst component of comprising a support treated with at least one metallocene of a Group IVB or VB metal and at least one non-metallocene compound of a Group IVB, VB, or VIB transition metal compound.

11. An olefin polymerization supported catalyst system as in claim 10 wherein the

(a) metallocene is represented by the formulas:

space="preserve" listing-type="equation">(Cp).sub.m MR.sub.n X.sub.q (I)

space="preserve" listing-type="equation">(C.sub.5 R'"'"'.sub.k).sub.g R".sub.s (C.sub.5 R'"'"'.sub.k)MQ.sub.3-g and (II)

space="preserve" listing-type="equation">R".sub.s (C.sub.5 R'"'"'.sub.k).sub.2 MQ'"'"' (III)

wherein Cp is a cyclopentadienyl ring, M is a Group IVB or VB transition metal, X is a halogen, R is a hydride, a hydrocarbyl or hydrocarboxy group having from 1 to 20 carbon atoms, m=1-3, n=0-3, q=0-3 and the sum of m +n +q is sufficient to saturate M, (C₅ R'"'"'_k) is a cyclopentadienyl or an alkyl substituted cyclopentadienyl;

each R'"'"' is the same or different and is hydrogen or a hydrocarb.yl radical selected from alkyl, alkenyl aryl, alkylalyl or arylalky.1 radicals containing from 1 to 20 carbon atoms, or two carbon atoms are joined together to form a C₄ -C₆ ring, R" is a C₁ -C₄ alkylene radical, a dialkyl germanium or silicon or an alkyl phosphine or amine radical bridging two (C₅ R'"'"'_k) rings;

Q is a hydrocarbyl radical selected from aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radicals having from 1-20 carbon atoms, hydrocarboxy radical having from 1-20 carbon atoms or halogen and can be the same or different from each other, Q'"'"' is an alkylidiene radical having from 1 to about 20 carbon atoms;

s is 0 or 1;

g is 0, 1, or 2;

s is 0 when g is 0;

k is 4 when s is 1 and k is 5 when s is 0; and

M is defined as above, and,

(b) the non-metallocene transition compound metal is represented by the formulas;

TrX'"'"'_4-q (OR'"'"')_q, TrX'"'"'_4-q R² _q, VOX'"'"'₃ and VO(OR'"'"')₃ wherein Tr is a Group Group VB - 28 metal, Q is 0 or a number equal to or less than 4, X'"'"' is a halogen. R¹ is an alkyl group, aryl group, or cycloalkyl group having from 1 to 20 carbon atoms, and R² is an alkyl group, aryl group, aralkyl group, having from 1 to 20 carbon atoms.

12. An olefin polymerization supported catalyst system as in claim 11 wherein the support is silica.

13. An olefin polymerization supported catalyst system as in claim 11 wherein the metallocene is selected from titanium, zirconium, hafnium or vanadium metallocenes or mixtures thereof.

14. An olefin polymerization supported catalyst system as om claim 13 wherein the metallocene is selected from titanium or zirconium metallocenes or mixtures thereof.

15. An olefin polymerization supported catalyst system as in claim 11 wherein the non-metallocene transition metal compound is selected from TiCl₄, TiBr₄, Ti(OC₄ H₉)₂ Cl₂, VCl₄, VOCl₃, and ZrCl₄.

16. An olefin polymerization supported catalyst system as in claim 11 wherein the at least one metallocene is selected from bis(clcopentadie)zirconium dichloride, bis(cyclopentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium dimethyl, bis(methylcyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium methyl chloride, bis(methylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium methyl chloride, bis(pentamethylcyclopentadieyl)zirconium dimethyl, bis(n-butylcyclopentadienyl}zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium methyl chloride, bis(n-butylcyclopentadienyl)zirconium dimethyl, bis{cyclopentadienyl)titanium diphenyl, bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)titanium methyl chloride, bis(cyclopentadienyl)titanium dimethyl, bis(meth.ylcyclopentadienyl)titanium diphenyl, bis(met-lcyclopentadieyl)titanium dichloride, bis(methylcyclopentadienyl)titanium diphenyl, bis(methylcyclopentadienyl)titanium methyl chloride, bis(methylcyclopentadienyl)titanium dimethyl, bis(pentamethylcyclopentadienyl)titanium dichloride, bispentametylcyclopentadienyl)titanium diphenyl, bis(pentamethylcyclopentadieyl}titanium methyl chloride, bis(pentamethylcyclopentadienyl)titanium dimet-1, bis(n-butylcyclopentadienyl)titanium diphenyl, bis(n-buylcyclopentadienyl)titanium dichloride and mixtures thereof.

17. An olefin polymerization supported catalyst system as in claim 16 wherein the metallocene is selected from bis(methylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(cyclopentadieyl)titanium diphenyl, and bis(methylcyclopentadienyl)titanium dipheyl.

18. An olefin polymerization supported catalyst system as in claim 11 wherein the molar ratio of the metallocene to the nonmetallocene transition metal containing compound is in the range of 10 moles metallocene compound per mole of non-metallocene transition metal compound to about 0.1 moles metallocene compound per mole of non-metallocene transition metal compound.

19. An olefin polymerization supported catalyst system as in claim 10 wherein the alumoxane to organometallic compound is in the range of 10 moles of alumoxane per mole of organometallic compound to 0.1 moles of alumoxance per mole of organometallic compound.

20. An olefin polymerzation catalyst system as in claim 10 wherein the alumoxane is methyl alumoxane and the organometallic compound is represented by the general formula R_n AlX_3-n wherein R is an alkyl group or an aryl group having from 1 to 18 carbon atoms, X is a halogen atom, an alkoxy group or a hydrogen atom, and n is in the range of 1 to 3.