Metal complexes containing bridging heteroatom for olefin-polymerization-process

• US 6,646,071 B1
• Filed: 09/06/2001
• Issued: 11/11/2003
• Est. Priority Date: 05/13/1999
• Status: Expired due to Term

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Nickias, Peter N., Klosin, Jerzy
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): RABAGO, ROBERTO
• Application Number:
  US09/936,120
• Time in Patent Office: 796 Days
• Field of Search: 502/155, 502/152, 502/103, 526/161, 526/172, 526/943, 526/126, 526/127, 556/52, 556/11
• US Class Current: 526/127
• CPC Class Codes: C07F 17/00 Metallocenes
• 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 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• 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

Metal complexes comprising an oxygen, sulfur, or nitrogen containing bridging group which are useful as catalyst components for the polymerization of olefins.

Claims

1. A metal complex corresponding to the formula:

where M is Ti, which is in the +2, +3 or +4 formal oxidation state;

R^A independently each occurrence is hydrogen, R^B or T′

R^B_j;

j is 1 or 2, and when j is 1, T′

is oxygen or sulfur and when j is 2, T′

is nitrogen or phosphorus,

R^B independently each occurrence is a group having from 1 to 80 atoms not counting hydrogen, which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, or hydrocarbylsilyl-substituted hydrocarbyl, or two R^B groups are joined together forming a divalent ligand group;

R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms;

X is an anionic or dianionic ligand group having up to 60 atoms;

X′

independently each occurrence is a Lewis base ligand having up to 20 atoms;

p is a number from 0, 1 or two;

q is zero, 1 or 2.

2. The complex of claim 1, corresponding to the formula:

where R^A, R*, M, X, X′

, and q are as previously defined in claim 1, and

p is 0, 1 or 2.

3. The metal complex of claim 2 wherein:

R^A independently each occurrence is hydrogen, alkyl, aryl, aralkyl, alkoxy, dihydrocarbylamino, or hydrocarbyleneamino, said R^A group having from 1 to 20 nonhydrogen atoms;

X groups are halide, alkyl, cycloalkyl, aryl, aralkyl or cycloalkadienyl groups, said X having from 1 to 20 atoms other than hydrogen;

X′

groups are selected from the group consisting of carbon monoxide, trimethylphosphine, triethylphosphine, triphenylphosphine, bis(1,2-dimethylphosphino)ethane, P(OR^c)₃, wherein R^c is hydrocarbyl, silyl and combinations thereof, ethers, pyridine, bipyridine, tetramethylethylenediamine, triethylamine, olefins, of and conjugated dienes having from 4 to 20 carbon atoms.

4. The metal complex of claim 3 wherein R^A independently each occurrence is hydrogen, or alkyl.

5. A metal complex according to claim 3 corresponding to the formula:

where, R^A, R*, M, X, X′

, p and q are as previously defined in claim 3.

6. The metal complex of claim 1 corresponding to the formula:

where R^A, T′

R^B_j, R*, M, X, X′

, p and q are as previously defined in claim 1.

7. A catalyst composition for olefin polymerization comprising:

(A) a catalyst component comprising a metal complex of claim 1; and

(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1;

10,000 to 100;

1;

or optionally catalyst component (A) is activated by use of an activating technique.

8. A process for polymerizing olefins comprising contacting one or more C_2-20 α

-olefins under polymerization conditions with a catalyst composition of claim 7.

9. A metal complex according to claim 1 selected from the group consisting of:

dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η

)-1H-inden-1-yloxy)silanaminato(1-)-titanium,

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η

))-1H-inden-1-yloxy)silanaminato(1-)dimethyl-titanium,

dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η

)-1H-inden-2-yloxy)silanaminato(2-)-titanium,

(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η

)-1H-inden-2-yloxy)silanaminato(2-)-dimethyl-titanium, and

dichloro(N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η

)-2-methyl-1H-inden-1-yloxy)silanaminato(1-)-titanium.

10. A catalyst composition for olefin polymerization comprising:

(A) a catalyst component comprising a metal complex of claim 2; and

(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1;

10,000 to 100;

1;

or optionally catalyst component (A) is activated by use of an activating technique.

11. A catalyst composition for olefin polymerization comprising:

(A) a catalyst component comprising a metal complex of claim 3; and

(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1;

10,000 to 100;

1;

or optionally catalyst component (A) is activated by use of an activating technique.

12. A catalyst composition for olefin polymerization comprising:

(A) a catalyst component comprising a metal complex of claim 4; and

(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1;

10,000 to 100;

1;

or optionally catalyst component (A) is activated by use of an activating technique.

13. A catalyst composition for olefin polymerization comprising:

(A) a catalyst component comprising a metal complex of claim 5; and

(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1;

10,000 to 100;

1;

or optionally catalyst component (A) is activated by use of an activating technique.

14. A catalyst composition for olefin polymerization comprising:

(A) a catalyst component comprising a metal complex of claim 6; and

(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1;

10,000 to 100;

1;

or optionally catalyst component (A) is activated by use of an activating technique.

15. A catalyst composition for olefin polymerization comprising:

(A) a catalyst component comprising a metal complex of claim 9; and

(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1;

10,000 to 100;

1;

or optionally catalyst component (A) is activated by use of an activating technique.

16. A process for polymerizing olefins comprising contacting one or more C_2-20 α

-olefins under polymerization conditions with a catalyst composition of claim 10.

17. A process for polymerizing olefins comprising contacting one or more C_2-20 α

-olefins under polymerization conditions with a catalyst composition of claim 11.

18. A process for polymerizing olefins comprising contacting one or more C_2-20 α

-olefins under polymerization conditions with a catalyst composition of claim 13.

19. A process for polymerizing olefins comprising contacting one or more C_2-20 α

-olefins under polymerization conditions with a catalyst composition of claim 14.

20. A process for polymerizing olefins comprising contacting one or more C_2-20 α

-olefins under polymerization conditions with a catalyst composition of claim 15.