US5225500A
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Process and catalyst for producing syndiotactic polyolefins
Assignee: Fina Technology Inc
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Filing: 1992-04-24
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Granted: 1993-07-06
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Expires: 2012-04-24
Abstract
Abstract Syndiospecific catalysts and processes for the syndiotactic propagation of a polymer chain derived from an ethylenically unsaturated monomer which contains 3 or more carbon atoms or is a substituted vinyl compound. The catalysts comprise an unbalanced metallocene cation, characterized by a cationic metallocene ligand having sterically dissimilar ring structures joined to a positively charged coordinating transition metal atom, and a stable noncoordinating counter anion for the metallocene cation. One of said ring structures is a substituted or unsubstituted cyclopentadienyl ring and the other of the ring structures is a substituted cyclopentadienyl group which is sterically different from the first cyclopentadienyl group. A structural bridge between cyclopentadienyl groups imparts stereorigidity to the catalyst. The catalyst is contacted with a C 3 + alpha olefin or other ethylenically unsaturated compound in a polymerization reaction zone and maintained in contact with the catalyst in the reaction zone under polymerization conditions to produce a syndiotactic polymer.
Inventors
- 👤 Michael J. Elder
- 👤 Abbas Razavi
- 👤 John A. Ewen
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 05:20
CPC Classifications
C; C08; C08F; C08F110/00; C08F110/04; C08F110/06; C07; C07F; C07F17/00; C08F10/00; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/639; C08F4/63912; Y; Y10; Y10S; Y10S526/00; Y10S526/943
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
204 words
A process for the syndiotactic propagation of a polymer chain derived from an ethylenically unsaturated monomer comprising: (a) providing a metallocene catalyst characterized by the formula: [R"(CpR n ) (CpR' m ) MeQ k ]+[P a ]- wherein: each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R' is the same or different and is ahydrocarbyl radical having 1-20 carbon atoms and is selected such that (CpR' m ) is a sterically different ring than (CpRn); R" is a structural bridge between the Cp rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b, or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen; P2 is a stable noncoordinating anion; n is from 0 to 4, m is from 1 to 4, k is from 0 to 2; and (b) contacting said catalyst in a polymerization reaction zone with an ethylenically unsaturated monomer which contains 3 or more carbon atoms or which is a substituted vinyl compound and maintaining said reaction zone under polymerization conditions to produce syndiospecific polymerization of said monomer.
Claim 2
Dependent Claim
204 words
A process for the syndiotactic propagation of a polymer chain derived from an ethylenically unsaturated monomer comprising: (a) providing a metallocene catalyst characterized by the formula: [R"(CpR n ) (CpR' m ) MeQ k ]+[P a ]- wherein: each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R' is the same or different and is ahydrocarbyl radical having 1-20 carbon atoms and is selected such that (CpR' m ) is a sterically different ring than (CpRn); R" is a structural bridge between the Cp rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b, or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen; P2 is a stable noncoordinating anion; n is from 0 to 4, m is from 1 to 4, k is from 0 to 2; and (b) contacting said catalyst in a polymerization reaction zone with an ethylenically unsaturated monomer which contains 3 or more carbon atoms or which is a substituted vinyl compound and maintaining said reaction zone under polymerization conditions to produce syndiospecific polymerization of said monomer.
Claim 3
Dependent Claim
16 words
The process of claim 1 wherein Me is titanium, zirconium or hafnium and K is 1.
Claim 4
Dependent Claim
11 words
The process of claim 2 wherein Q is a methyl group.
Claim 5
Independent Claim
14 words
The method of wherein said ethylenically unsaturated monomer is a C 3 + hydrocarbon.
Claim 6
Independent Claim
14 words
The method of wherein said ethylenically unsaturated monomer is a C 3 + hydrocarbon.
Claim 7
Dependent Claim
15 words
The method of claim 1 wherein said ethylenically unsaturated monomer is a vinyl aromatic compound.
Claim 8
Dependent Claim
12 words
The method of claim 5 wherein said vinyl aromatic compound is styrene.
Claim 9
Dependent Claim
15 words
The method of claim 1 wherein said ethylenically unsaturated monomer is a substituted vinyl compound.
Claim 10
Dependent Claim
13 words
The method of claim 7 wherein said substituted vinyl compound is vinyl chloride.
Claim 11
Dependent Claim
17 words
The method of claim 1 wherein said ethylenically unsaturated monomer is a C 3 + alpha olefin.
Claim 12
Dependent Claim
175 words
A process for the production of syndiotactic polypropylene, comprising: (a) providing a metallocene catalyst characterized by the formula [R"(CpR n )(CpR' m )MeQ k ]+[P2]- wherein: each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R' is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms and is selected such that the (CpR' m ) is a sterically different ring than (CpRn); R" is a structural bridge between the Cp rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b, or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen; P2 is a stable noncoordinating anion; n is from 0 to 4, m is from 1 to 4, k is from 0 to 2; and (b) contacting said catalyst with propylene is a polymerization reaction zone and maintaining said reaction zone under polymerization reaction conditions to produce syndiotactic polypropylene.
Claim 13
Dependent Claim
175 words
A process for the production of syndiotactic polypropylene, comprising: (a) providing a metallocene catalyst characterized by the formula [R"(CpR n )(CpR' m )MeQ k ]+[P2]- wherein: each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R' is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms and is selected such that the (CpR' m ) is a sterically different ring than (CpRn); R" is a structural bridge between the Cp rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b, or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen; P2 is a stable noncoordinating anion; n is from 0 to 4, m is from 1 to 4, k is from 0 to 2; and (b) contacting said catalyst with propylene is a polymerization reaction zone and maintaining said reaction zone under polymerization reaction conditions to produce syndiotactic polypropylene.
Claim 14
Dependent Claim
34 words
The process of claim 10, wherein said polymerization reaction is carried out under conditions in which any aluminoxane concentration is maintained at a level providing an Al/Me mole ratio of no more than 10.
Claim 15
Dependent Claim
18 words
The method of claim 11, wherein said polymerization process is carried out in the absence of added aluminoxane.
Claim 16
Dependent Claim
16 words
The process of claim 10, wherein Me is titanium, zirconium or hafnium and k is 1.
Claim 17
Dependent Claim
21 words
The process of claim 13, wherein R' m is selected such that (CpR' m ) forms a fluorenyl or indenyl radical.
Claim 18
Dependent Claim
46 words
The process of claim 13, wherein R" is selected from the group consisting of an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, and an aluminum hydrocarbyl radical.
Claim 19
Dependent Claim
18 words
The process of claim 13, wherein R" is a methyl, ethyl, isopropyl, cyclopropyl, dimethylsilyl, methylene or ethylene radical.
Claim 20
Dependent Claim
11 words
The process of claim 16, wherein Q is a methyl group.
Claim 21
Dependent Claim
19 words
The process of claim 17, wherein R' m is selected such that (CpR'm) forms a fluorenyl or indenyl radical.
Claim 22
Dependent Claim
12 words
The process of claim 18, wherein R"(CpRn)(CpR'm) forms an isopropylidene (cyclopentadienyl-1-fluorenyl) radical.
References Cited (Backward Citations)
US4752597A
Cited
US4849487A
Cited
EP0277004A1
Cited
EP0277003A1
Cited
US4794096A
Cited
US4931417A
Cited
US5132381A
Cited
US5036034A
Cited
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