US5902866A
Expired / Lapsed
US
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Azaborolinyl metal complexes as olefin polymerization catalysts
Assignee: Equistar Chemicals LP
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Filing: 1996-11-13
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Granted: 1999-05-11
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Expires: 2016-11-13
Abstract
Abstract Disclosed is a catalyst having the general formula ##STR1## where L is a ligand having the formula ##STR2## L' is L, Cp, Cp*, indenyle fluorenyl, NR 2 , OR, or halogen, L can be bridged to L; X is halogen, NR 2 , OR, or alkyl from C 1 to C 12 , M is zirconium or hafnium, R is alkyl from C 1 to C 12 or aryl from C 6 to C 12 , R 1 is R, alkaryl from C 6 to C 12 , aralkyl from C 6 to C 12 , hydrogen, or Si(R) 3 , R 2 is R 1 , halogen, COR, COOR, SOR, or SOOR, R 3 is R 2 , OR, N(R) 2 , SR, or a fused ring system, Cp is cyclopentadienyl, Cp* is pentamethylcyclopentadienyl, n is 0 to 3, and L B is an optional Lewis base. Also disclosed is a method of making a poly-α-olefin comprising polymerizing an α-olefin monomer using a catalyst such as that described above where M can be titanium, zirconium, or hafnium.
Inventors
- 👤 Sandor Nagy
- 👤 Ramesh Krishnamurti
- 👤 Bradley P. Etherton
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 14:44
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/16; B01J31/18; B01J31/1805; B01J31/02; B01J31/12; B01J31/14; B01J31/143; B01J31/22; B01J31/2282; B01J31/2295; C; C07; C07F; C07F17/00; C08; C08F; C08F10/00; B01J2531/00; B01J2531/02; B01J2531/0225; B01J2531/0236; B01J2531/40; B01J2531/46; B01J2531/48; B01J2531/49; C08F110/00; C08F110/02; C08F210/00; C08F210/16; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65908; C08F4/65912; C08F4/6592
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
182 words
A method of making a poly-α-olefin comprising polymerizing an α-olefin monomer under polymerizing conditions in the presence of; (A) a catalyst having the general formula ##STR9## where L is a ligand having the formula ##STR10## L' is cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, fluorenyl, NR 2 , OR, or halogen, L' can be bridged to L, X is halogen, NR 2 , OR, or alkyl from C 1 to C 12 , M is zirconium, titanium, or hafnium, R is alkyl from C 1 to C 12 or aryl from C 6 to C 12 , R 1 is R, Si(R) 3 , or R 4 , R 4 is alkaryl from C 6 to C 12 , aralkyl from C 6 to C 12 , or hydrogen, R 2 is R, R 4 , halogen, COR, COOR, SOR, or SOOR, R 3 is R 2 , Si(R) 3 , OR, N(R) 2 , SR, or a fused ring system, n is 0 to 3, and L B is an optional Lewis base; and (B) about 0.01 to about 100,000 moles of an alumoxane cocatalyst.
Claim 2
Independent Claim
182 words
A method of making a poly-α-olefin comprising polymerizing an α-olefin monomer under polymerizing conditions in the presence of; (A) a catalyst having the general formula ##STR9## where L is a ligand having the formula ##STR10## L' is cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, fluorenyl, NR 2 , OR, or halogen, L' can be bridged to L, X is halogen, NR 2 , OR, or alkyl from C 1 to C 12 , M is zirconium, titanium, or hafnium, R is alkyl from C 1 to C 12 or aryl from C 6 to C 12 , R 1 is R, Si(R) 3 , or R 4 , R 4 is alkaryl from C 6 to C 12 , aralkyl from C 6 to C 12 , or hydrogen, R 2 is R, R 4 , halogen, COR, COOR, SOR, or SOOR, R 3 is R 2 , Si(R) 3 , OR, N(R) 2 , SR, or a fused ring system, n is 0 to 3, and L B is an optional Lewis base; and (B) about 0.01 to about 100,000 moles of an alumoxane cocatalyst.
Claim 3
Dependent Claim
12 words
A method according to claim 1 wherein L' is cyclopentadienyl or pentamethylcyclopentadienyl.
Claim 4
Dependent Claim
10 words
A method according to claim 1 wherein X is halogen.
Claim 5
Dependent Claim
10 words
A method according to claim 1 wherein M is titanium.
Claim 6
Dependent Claim
10 words
A method according to claim 1 wherein M is zirconium.
Claim 7
Dependent Claim
17 words
A method according to claim 1 wherein R is alkyl from C 1 to C 4 .
Claim 8
Dependent Claim
19 words
A method according to claim 1 wherein R 1 is alkyl from C 3 to C 12 or aryl.
Claim 9
Dependent Claim
11 words
A method according to claim 1 wherein R 2 is t-butyl.
Claim 10
Dependent Claim
13 words
A method according to claim 1 wherein R 3 is hydrogen or methyl.
Claim 11
Dependent Claim
11 words
A method according to claim 1 wherein said cocatalyst is methylaluminoxane.
Claim 12
Independent Claim
208 words
A method of making a poly-α-olefin comprising polymerizing an α-olefin monomer under polymerizing conditions in the presence of: (A) a catalyst having the general formula ##STR11## where L is a ligand having the formula ##STR12## L' is cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, fluorenyl, NR 2 , OR, or halogen, L' can be bridged to L, X is halogen, NR 2 , OR, or alkyl from C 1 to C 12 , M is zirconium, titanium, or hafnium, R is alkyl from C 1 to C 12 or aryl from C 6 to C 12 , R 1 is R, Si(R) 3 , or R 4 , R 4 is alkaryl from C 6 to C 12 , aralkyl from C 6 to C 12 , or hydrogen, R 2 is R, R 4 , halogen, COR, COOR, SOR, or SOOR, R 3 is R 2 , Si(R) 3 , OR, N(R) 2 , SR, or a fused ring system, n is 0 to 3, and L B is an optional Lewis base, and (B) a cocatalyst of an acid salt comprising a non-nucleophilic compound containing a bulky ligand attached to a boron or aluminum atom in an amount of about 0.01 to about 1,000 moles per mole of said catalyst.
Claim 13
Independent Claim
208 words
A method of making a poly-α-olefin comprising polymerizing an α-olefin monomer under polymerizing conditions in the presence of: (A) a catalyst having the general formula ##STR11## where L is a ligand having the formula ##STR12## L' is cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, fluorenyl, NR 2 , OR, or halogen, L' can be bridged to L, X is halogen, NR 2 , OR, or alkyl from C 1 to C 12 , M is zirconium, titanium, or hafnium, R is alkyl from C 1 to C 12 or aryl from C 6 to C 12 , R 1 is R, Si(R) 3 , or R 4 , R 4 is alkaryl from C 6 to C 12 , aralkyl from C 6 to C 12 , or hydrogen, R 2 is R, R 4 , halogen, COR, COOR, SOR, or SOOR, R 3 is R 2 , Si(R) 3 , OR, N(R) 2 , SR, or a fused ring system, n is 0 to 3, and L B is an optional Lewis base, and (B) a cocatalyst of an acid salt comprising a non-nucleophilic compound containing a bulky ligand attached to a boron or aluminum atom in an amount of about 0.01 to about 1,000 moles per mole of said catalyst.
Claim 14
Dependent Claim
35 words
A method according to claim 11 wherein said acid salt is selected from the group consisting of lithium tatrakis(pentafluorophenyl) borate, lithium tetrakis(pentafluorophenyl) aluminate, anilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tatrakis(pentafluorophenyl) borate, trityl tetrakis(pentafluorophenyl) borate, and mixtures thereof.
Claim 15
Independent Claim
181 words
A method of making a poly-α-olefin comprising polymerizing an α-olefin monomer using a catalyst that has the general formula ##STR13## in the presence of about 0.01 to about 100,000 moles per mole of said catalyst of a co-catalyst selected from an alumoxane or an acid salt comprising a non-nucleophilic compound containing a bulky ligand attached to a boron or aluminum atom, where L is a ligand having the formula ##STR14## L' is cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, fluorenyl, NR 2 , OR, or halogen, L' can be bridged to L, R is alkyl from C 1 to C 12 or aryl from C 6 to C 12 , R 1 is R, Si(R) 3 , or R 4 , R 4 is alkaryl from C 6 to C 12 , aralkyl C 6 to C 12 , or hydrogen, R 2 is R, R 4 , halogen, COR, COOR, SOR, or SOOR, R 3 is R 2 , Si(R) 3 OR, N(R) 2 , SR, or a fused ring system, n is 0 to 3, and L B is an optional Lewis base.
Claim 16
Independent Claim
181 words
A method of making a poly-α-olefin comprising polymerizing an α-olefin monomer using a catalyst that has the general formula ##STR13## in the presence of about 0.01 to about 100,000 moles per mole of said catalyst of a co-catalyst selected from an alumoxane or an acid salt comprising a non-nucleophilic compound containing a bulky ligand attached to a boron or aluminum atom, where L is a ligand having the formula ##STR14## L' is cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, fluorenyl, NR 2 , OR, or halogen, L' can be bridged to L, R is alkyl from C 1 to C 12 or aryl from C 6 to C 12 , R 1 is R, Si(R) 3 , or R 4 , R 4 is alkaryl from C 6 to C 12 , aralkyl C 6 to C 12 , or hydrogen, R 2 is R, R 4 , halogen, COR, COOR, SOR, or SOOR, R 3 is R 2 , Si(R) 3 OR, N(R) 2 , SR, or a fused ring system, n is 0 to 3, and L B is an optional Lewis base.
Claim 17
Dependent Claim
22 words
A method according to claim 13 wherein L' is cyclopentadienyl and R 1 is alkyl from C 1 to C 12 .
Claim 18
Dependent Claim
16 words
A method according to claim 13 wherein said catalyst has been deposited onto a silica support.
Claim 19
Dependent Claim
16 words
A method according to claim 13 wherein L' is bridged to L and L' is Cp.
Claim 20
Dependent Claim
14 words
A method according to claim 16 wherein said bridge is methylene, ethylene, or dimethylsilyl.
Claim 21
Dependent Claim
15 words
A method according to claim 13 wherein said catalyst is (1-tert-butyl-2-methyl-η 5 -1,2-azaborolinyl) zirconium trichloride.
Claim 22
Dependent Claim
17 words
A method according to claim 13 herein said catalyst is η 5 -cyclopentadienyl)(-1-tert-butyl-2-methyl-η 5 -1,2-azaborolinyl) zirconium dichloride.
Claim 23
Independent Claim
85 words
A method of making polyethylene comprising polymerizing ethylene using a catalyst that has the general formula ##STR15## in the presence of about 0.01 to about 100,000 moles per mole of said catalyst of an organo aluminum cocatalyst, where L is a ligand having the formula ##STR16## where L' is cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, or fluorenyl, X is chlorine or methyl, R 1 is alkyl from C 1 to C 12 or aryl from C 6 to C 12 , and R 2 is t-butyl or trimethylsilyl.
Claim 24
Independent Claim
85 words
A method of making polyethylene comprising polymerizing ethylene using a catalyst that has the general formula ##STR15## in the presence of about 0.01 to about 100,000 moles per mole of said catalyst of an organo aluminum cocatalyst, where L is a ligand having the formula ##STR16## where L' is cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, or fluorenyl, X is chlorine or methyl, R 1 is alkyl from C 1 to C 12 or aryl from C 6 to C 12 , and R 2 is t-butyl or trimethylsilyl.
References Cited (Backward Citations)
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