US5418200A Expired / Lapsed US ⏱️ 0.0 years remaining

Cyclopentadienyl group 6B metal α-olefin polymerization catalysts and process for polymerizing α-olefins

Assignee: Chevron Phillips Chemical Co LP

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Filing: 1992-10-20

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Granted: 1995-05-23

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Expires: 2012-10-20

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Abstract

Abstract Disclosed is a catalyst system for the homopolymerization and copolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a cyclopentadienyl Group 6b metal hydrocarbyl compound in which the metal has an oxidation state of +3, said Group 6b metal compound being supported on an inorganic support. The catalyst system may also contain a Group 2 or Group 3 metal alkyl compound.

Inventors

👤 Michael J. Carney
👤 David L. Beach

Bibliographic Details

Application Number —

Jurisdiction US

Data Source google_patents

Last Synchronized 2026-11-01 12:12

CPC Classifications

C; C08; C08F; C08F10/00; C08F110/00; C08F110/02; C08F2420/00; C08F2420/03; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/639; C08F4/63908; C08F4/63912; Y; Y10; Y10S; Y10S526/00; Y10S526/943

Claims Analysis

Total Claims: 57

Claim 1

Independent Claim 42 words

A catalyst system for the homopolymerization or copolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a cyclopentadienyl chromium hydrocarbyl compound in which the chromium has an oxidation state of +3, said chromium compound being supported on an inorganic support.

Claim 2

Dependent Claim 42 words

Claim 3

Dependent Claim 15 words

The catalyst system of claim 1 wherein the hydrocarbyl is sigma bonded to the chromium.

Claim 4

Dependent Claim 119 words

The catalyst system of claim 1 wherein the chromium compound has the formula: (C.sub.5 (R').sub.5).sub.a CrX.sub.b (L) (I) [(C.sub.5 (R').sub.5).sub.a CrX.sub.b ].sub.c (II) or [(C.sub.5 (R').sub.5).sub.a CrX.sub.b (L).sub.m ].sup.+ [A].sup.- (III) wherein (C 5 (R') 5 ) is a cyclopentadienyl or substituted cyclopentadienyl ring; R' is at each independent occurrence hydrogen, a hydrocarbyl radical having 1-20 carbon atoms, or adjacent R' groups may together form one or more rings; X is a hydrocarbyl radical having 1-20 carbon atoms; a=1 or 2, b=1 or 2 where a+b=3; c=1 or 2 with the proviso that when c=2 then X is alkyl; L is at each independent occurrence a sigma donor stabilizing ligand; m=1 to 2 inclusive; and A is an anion.

Claim 5

Dependent Claim 16 words

The catalyst system of claim 3 wherein the chromium compound has the formula: (C.sub.5 (R').sub.5)CrX.sub.2 L

Claim 6

Dependent Claim 14 words

The catalyst system of claim 4 wherein (C 5 (R') 5 ) is pentamethylcyclopentadienyl.

Claim 7

Dependent Claim 25 words

The catalyst system of claim 4 wherein X is selected from the group consisting of methyl, benzyl and trimethylsilylmethyl, and L contains oxygen or nitrogen.

Claim 8

Dependent Claim 15 words

The catalyst system of claim 4 wherein L is tetrahydrofuran, pyridine, N,N-dimethylaminopyridine, dimethylphenylphosphine, or 3,5-lutidine.

Claim 9

Dependent Claim 16 words

The catalyst system of claim 3 wherein the chromium compound has the formula: [C.sub.5 (R').sub.5)CrX.sub.2 ].sub.c

Claim 10

Dependent Claim 14 words

The catalyst system of claim 8 wherein (C 5 (R') 5 ) is pentamethylcyclopentadienyl.

Claim 11

Dependent Claim 19 words

The catalyst system of claim 8 wherein X is selected from the group consisting of methyl, benzyl and trimethylsilylmethyl.

Claim 12

Dependent Claim 8 words

The catalyst system of claim 8 wherein c=2.

Claim 13

Dependent Claim 17 words

The catalyst system of claim 3 wherein the chromium compound has the formula: [C.sub.5 (R').sub.5)CrXL.sub.2 ].sup.+ A.sup.-

Claim 14

Dependent Claim 14 words

The catalyst system of claim 12 wherein (C 5 (R') 5 ) is pentamethylcyclopentadienyl.

Claim 15

Dependent Claim 15 words

The catalyst system of claim 12 wherein X is selected from methyl, benzyl and trimethylsilylmethyl.

Claim 16

Dependent Claim 12 words

The catalyst system of claim 12 wherein L contains oxygen or nitrogen.

Claim 17

Dependent Claim 17 words

The catalyst system of claim 15 wherein L is selected from tetrahydrofuran, pyridine, N,N-dimethylaminopyridine, dimethylphenylphosphine, or 3,5-lutidine.

Claim 18

Dependent Claim 114 words

The catalyst system of claim 3 wherein the chromium compound is selected from Cp*Cr(CH 3 ) 2 (THF) [Cp*Cr(CH 3 ) 2 ] 2 [Cp*Cr(THF) 2 CH 3 ]+[BPh 4 ] - Cp*Cr(Bzyl) 2 (THF) Cp*Cr(TMSM) 2 Cp*Cr(CH 3 ) 2 (Pyr) Cp*Cr(TMSM) 2 (Pyr) Cp*Cr(Bzyl) 2 (Pyr) Cp*Cr(CH 3 ) 2 (DMAP) Cp*Cr(CH 3 ) 2 (PMe 2 Ph) Cp*Cr(CH 3 ) 2 (3,5-lutidine) CpCr(CH 3 ) 2 (Pyr) CpCr(CH 3 ) 3 (PMe 2 Ph) CpCr(CH 3 ) 2 (DMAP) where Cp* is pentamethylcyclopentadienyl, THF is tetrahydrofuran, Ph is phenyl, Bzyl is benzyl, TMSM is trimethylsilylmethyl, Pyr is pyridine, DMAP is N,N-dimethylaminopyridine, PMe 2 Ph is dimethylphenylphosphine, and Cp is unsubstituted cyclopentadienyl.

Claim 19

Dependent Claim 18 words

The catalyst system of claim 1 wherein the support is an inorganic metal oxide or inorganic metal phosphate.

Claim 20

Dependent Claim 27 words

The catalyst system of claim 18 wherein the support is selected from the group consisting of alumina, silica, silica-alumina, aluminum phosphate, zirconium phosphate, and alumina aluminum phosphate.

Claim 21

Dependent Claim 19 words

The catalyst system of claim 17 wherein the support is selected from silica, aluminum phosphate and alumina aluminum phosphate.

Claim 22

Dependent Claim 13 words

The catalyst system of claim 20 wherein the support is alumina aluminum phosphate.

Claim 23

Dependent Claim 27 words

The catalyst system of claim 17 wherein the support is selected from the group consisting of alumina, silica, silica-alumina, aluminum phosphate, zirconium phosphate, and alumina aluminum phosphate.

Claim 24

Dependent Claim 19 words

The catalyst system of claim 22 wherein the support is selected from silica, aluminum phosphate and alumina aluminum phosphate.

Claim 25

Dependent Claim 13 words

The catalyst system of claim 23 wherein the support is alumina aluminum phosphate.

Claim 26

Dependent Claim 51 words

Claim 27

Dependent Claim 51 words

Claim 28

Dependent Claim 15 words

The catalyst system of claim 25 wherein the hydrocarbyl is sigma bonded to the chromium.

Claim 29

Dependent Claim 103 words

The catalyst system of claim 25 wherein the chromium compound is selected from Cp*Cr(CH 3 ) 2 (THF) [Cp*Cr(CH 3 ) 2 ] 2 [Cp*Cr(THF) 2 CH 3 ]+[BPh 4 ] - Cp*Cr(Bzyl) 2 (THF) or Cp*Cr(TMSM) 2 , Cp*Cr(CH 3 ) 2 (Pyr) Cp*Cr(TMSM) 2 (Pyr) Cp*Cr(Bzyl) 2 (Pyr) Cp*Cr(CH 3 ) 2 (DMAP) Cp*Cr(CH 3 ) 2 (PMe 2 Ph) Cp*Cr(CH 3 ) 2 (3,5-lutidine) CpCr(CH 3 ) 2 (Pyr) CpCr(CH 3 ) 3 (PMe 2 Ph) CpCr(CH 3 ) 2 (DMAP) the support is silica or alumina aluminum phosphate, and the alkylaluminum compound is an aluminoxane or a trialkylaluminum compound.

Claim 30

Dependent Claim 13 words

The catalyst system of claim 27 wherein the support is alumina aluminum phosphate.

Claim 31

Dependent Claim 119 words

The catalyst system of claim 25 wherein the chromium compound has the formula: (C.sub.5 (R').sub.5).sub.a CrX.sub.b (L) (I) [(C.sub.5 (R').sub.5).sub.a CrX.sub.b ].sub.c (II) or [(C.sub.5 (R').sub.5).sub.a CrX.sub.b (L).sub.m ].sup.+ [A].sup.- (III) wherein (C 5 (R') 5 ) is a cyclopentadienyl or substituted cyclopentadienyl ring; R' is at each independent occurrence hydrogen, a hydrocarbyl radical having 1-20 carbon atoms, or adjacent R' groups may together form one or more rings; X is a hydrocarbyl radical having 1-20 carbon atoms; a=1 or 2, b=1 or 2 where a+b=3; c=1 or 2 with the proviso that when c=2 then X is alkyl; L is at each independent occurrence a sigma donor stabilizing ligand; m=1 to 2 inclusive; and A is an anion.

Claim 32

Dependent Claim 16 words

The catalyst system of claim 29 wherein the chromium compound has the formula: (C.sub.5 (R').sub.5)CrX.sub.2 L

Claim 33

Dependent Claim 14 words

The catalyst system of claim 30 wherein (C 5 (R') 5 ) is pentamethylcyclopentadienyl.

Claim 34

Dependent Claim 25 words

The catalyst system of claim 30 wherein X is selected from the group consisting of methyl, benzyl and trimethylsilylmethyl, and L contains oxygen or nitrogen.

Claim 35

Dependent Claim 15 words

The catalyst system of claim 30 wherein L is tetrahydrofuran, pyridine, N,N-dimethylaminopyridine, dimethylphenylphosphine, or 3,5-lutidine.

Claim 36

Dependent Claim 16 words

The catalyst system of claim 29 wherein the chromium compound has the formula: [C.sub.5 (R').sub.5)CrX.sub.2 ].sub.c

Claim 37

Dependent Claim 14 words

The catalyst system of claim 34 wherein (C 5 (R') 5 ) is pentamethylcyclopentadienyl.

Claim 38

Dependent Claim 19 words

The catalyst system of claim 34 wherein X is selected from the group consisting of methyl, benzyl and trimethylsilylmethyl.

Claim 39

Dependent Claim 8 words

The catalyst system of claim 34 wherein c=2.

Claim 40

Dependent Claim 17 words

The catalyst system of claim 29 wherein the chromium compound has the formula: [(C.sub.5 (R').sub.5)CrXL.sub.2 ].sup.+ A.sup.-

Claim 41

Dependent Claim 14 words

The catalyst system of claim 38 wherein (C 5 (R') 5 ) is pentamethylcyclopentadienyl.

Claim 42

Dependent Claim 15 words

The catalyst system of claim 38 wherein X is selected from methyl, benzyl and trimethylsilylmethyl.

Claim 43

Dependent Claim 12 words

The catalyst system of claim 38 wherein L contains oxygen or nitrogen.

Claim 44

Dependent Claim 17 words

The catalyst system of claim 41 wherein L is selected from tetrahydrofuran, pyridine, N,N-dimethylaminopyridine, dimethylphenylphosphine, or 3,5-lutidine.

Claim 45

Dependent Claim 114 words

The catalyst system of claim 29 wherein the chromium compound is selected from Cp*Cr(CH 3 ) 2 (THF) [Cp*Cr(CH 3 ) 2 ] 2 [Cp*Cr(THF) 2 CH 3 ]+[BPh 4 ] - Cp*Cr(Bzyl) 2 (THF) Cp*Cr(TMSM) 2 Cp*Cr(CH 3 ) 2 (Pyr) Cp*Cr(TMSM) 2 (Pyr) Cp*Cr(Bzyl) 2 (Pyr) Cp*Cr(CH 3 ) 2 (DMAP) Cp*Cr(CH 3 ) 2 (PMe 2 Ph) Cp*Cr(CH 3 ) 2 (3,5-lutidine) CpCr(CH 3 ) 2 (Pyr) CpCr(CH 3 ) 3 (PMe 2 Ph) CpCr(CH 3 ) 2 (DMAP) where Cp* is pentamethylcyclopentadienyl, THF is tetrahydrofuran, Ph is phenyl, Bzyl is benzyl, TMSM is trimethylsilylmethyl, Pyr is pyr%dine, DMAP is N,N-dimethylaminopyridine, PMe 2 Ph is dimethylphenylphosphine, and Cp is unsubstituted cyclopentadienyl.

Claim 46

Dependent Claim 18 words

The catalyst system of claim 25 wherein the support is an inorganic metal oxide or inorganic metal phosphate.

Claim 47

Dependent Claim 27 words

The catalyst system of claim 44 wherein the support is selected from the group consisting of alumina, silica, silica-alumina, aluminum phosphate, zirconium phosphate, and alumina aluminum phosphate.

Claim 48

Dependent Claim 19 words

The catalyst system of claim 45 wherein the support is selected from silica, aluminum phosphate and alumina aluminum phosphate.

Claim 49

Dependent Claim 13 words

The catalyst system of claim 46 wherein the support is alumina aluminum phosphate.

Claim 50

Dependent Claim 20 words

The catalyst system of claim 25 wherein the Group 2 or Group 3 metal alkyl compound is an alkylaluminum compound.

Claim 51

Dependent Claim 25 words

The catalyst system of claim 48 wherein the alkylaluminum compound is selected from the group consisting of trialkylaluminum compounds, alkylaluminum alkoxides, alkylaluminum halides and aluminoxanes.

Claim 52

Dependent Claim 16 words

The catalyst system of claim 49 wherein the alkylaluminum compound is an aluminoxane or trialkylaluminum compound.

Claim 53

Dependent Claim 117 words

The catalyst system of claim 25 wherein the chromium compound is selected from Cp*Cr(CH 3 ) 2 (THF) [Cp*Cr(CH 3 ) 2 ] 2 [Cp*Cr(THF) 2 CH 3 ]+[BPh 4 ] - Cp*Cr(Bzyl) 2 (THF) or Cp*Cr(TMSM) 2 , Cp*Cr(CH 3 ) 2 (Pyr) Cp*Cr(TMSM) 2 (Pyr) Cp*Cr(Bzyl) 2 (Pyr) Cp*Cr(CH 3 ) 2 (DMAP) Cp*Cr(CH 3 ) 2 (PMe 2 Ph) Cp*Cr(CH 3 ) 2 (3,5-lutidine) CpCr(CH 3 ) 2 (Pyr) CpCr(CH 3 ) 3 (PMe 2 Ph) CpCr(CH 3 ) 2 (DMAP) the support is selected from the group consisting of alumina, silica, silica-alumina, aluminum phosphate, zirconium phosphate, and alumina aluminum phosphate, and the Group 2 or 3 metal alkyl compound is an alkylaluminum compound.

Claim 54

Dependent Claim 19 words

The catalyst system of claim 51 wherein the support is selected from silica, aluminum phosphate and alumina aluminum phosphate.

Claim 55

Dependent Claim 13 words

The catalyst system of claim 52 wherein the support is alumina aluminum phosphate.

Claim 56

Dependent Claim 25 words

The catalyst system of claim 51 wherein the alkylaluminum compound is selected from the group consisting of trialkylaluminum compounds, alkylaluminum alkoxides, alkylaluminum halides and aluminoxanes.

Claim 57

Dependent Claim 16 words

The catalyst system of claim 54 wherein the alkylaluminum compound is an aluminoxane or trialkylaluminum compound.

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USPTO Annuity & Maintenance Windows

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1998-05-22	1998-11-21	1999-05-23	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	2002-05-22	2002-11-21	2003-05-23	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2006-05-22	2006-11-21	2007-05-23	$7700.00	Window Closed / Lapsed

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