Patent EP0351392A2 successfully refreshed from Google Patents.
EP0351392A2
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Process and catalyst for producing syndiotactic polyolefins
Assignee: Fina Technology Inc
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Filing: 1989-05-31
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Granted: —
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Expires: 2009-05-31
Abstract
Abstract The invention provides a metallocene catalyst for use in preparing syndiotactic polyolefins. The catalyst comprises a bridged metallocene in which one of the cyclopentadienyl rings is substituted in a substantially different manner from the other ring. It was discovered that this type of catalyst is highly syndiospecific, and it also produces a polymer with a novel microstructure. The invention further includes the use of one or more of the catalysts in a polymerization process. The catalyst is generally described by the formula R˝(CpR n )(CpR′ m )MeQ k wherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R n and R′ m is the same or different and is a hydrocarbyl radicals having 1-20 carbon atoms; R˝ is a structural bridge between the two 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; 0 ≦ k ≦ 3; 0 ≦ n ≦ 4; 1 ≦ m ≦ 4; and wherein R′ m is selected such that (CpR′ m ) is a sterically different ring than (CpR n ).
Inventors
- 👤 John A. Ewen
- 👤 Abbas Razavi
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-10-25 14:42
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/42; C08F4/72; C08F4/74; C08F110/00; C08F110/04; C08F110/06; C07; C07F; C07F17/00; C08F10/00; C08F4/44; C08F4/60; C08F4/62; C08F4/622; C08F4/64; C08F4/639; C08F4/63912; C08F4/6392; C08F4/63922; C08F4/63927; Y; Y10; Y10S; Y10S526/00; Y10S526/943
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
143 words
A metallocene catalyst for use in preparing syndiotactic polyolefins, said catalyst described by the formula R˝(CpR n )(CpR′ m )MeQ k wherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R n is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ m is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; 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; 0 ≦ k ≦ 3; 0 ≦ n ≦ 4; 1 ≦ m ≦ 4; and wherein R′ m is selected such that (CpR′ m ) is a sterically different ring than (CpR n ).
Claim 2
Dependent Claim
143 words
A metallocene catalyst for use in preparing syndiotactic polyolefins, said catalyst described by the formula R˝(CpR n )(CpR′ m )MeQ k wherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R n is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ m is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; 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; 0 ≦ k ≦ 3; 0 ≦ n ≦ 4; 1 ≦ m ≦ 4; and wherein R′ m is selected such that (CpR′ m ) is a sterically different ring than (CpR n ).
Claim 3
Dependent Claim
21 words
The catalyst of Claim 1 wherein R′ m is selected such that (CpR′ m ) forms a fluorenyl or indenyl radical.
Claim 4
Dependent Claim
12 words
The catalyst of Claim 1 wherein Me is titanium, zirconium or hafnium.
Claim 5
Dependent Claim
46 words
The catalyst of Claim 1 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 6
Dependent Claim
18 words
The catalyst of Claim 1 wherein R˝ is a methyl, ethyl, isopropyl, cyclopropyl, dimethylsilyl, methylene or ethylene radical.
Claim 7
Dependent Claim
9 words
The catalyst of Claim 1 wherein n is 0.
Claim 8
Dependent Claim
15 words
The catalyst of Claim 1 wherein R˝(CpR n )(CpR′ m ) forms an isopropyl(cyclopentadienyl-1-fluorenyl) radical.
Claim 9
Dependent Claim
44 words
The catalyst of Claim 1 wherein R m is selected such that (CpR′ m ) forms a fluorenyl, indenyl, tetra-, tri-, or di-alkyl substituted cyclopentadienyl radical and R n is selected such that (CpR n ) forms an alkyl substituted or unsubstituted cyclopentadienyl radical.
Claim 10
Dependent Claim
22 words
The catalyst of Claim 1 further comprising an aluminum compound selected from the group consisting of alumoxanes, alkyl aluminums and mixtures thereof.
Claim 11
Dependent Claim
17 words
The catalyst of Claim 9 comprising an isolated complex of the metallocene catalyst and the aluminum compound.
Claim 12
Dependent Claim
175 words
A process for polymerizing an olefin monomer to form a syndiotactic polyolefin, said process comprising: a) selecting a metallocene catalyst described by the formula R˝(CpR n )(CpR′ m )MeQ k wherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R n is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ m is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; 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; 0 ≦ k ≦ 3; 0 ≦ n ≦ 4; 1 ≦ m ≦ 4; and wherein R′ m is selected such that (CpR′ m ) is a sterically different ring than (CpR n ); and b) introducing the catalyst into a polymerization reaction zone containing an olefin monomer and maintaining the reaction zone under polymerization reaction conditions.
Claim 13
Dependent Claim
175 words
A process for polymerizing an olefin monomer to form a syndiotactic polyolefin, said process comprising: a) selecting a metallocene catalyst described by the formula R˝(CpR n )(CpR′ m )MeQ k wherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R n is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ m is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; 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; 0 ≦ k ≦ 3; 0 ≦ n ≦ 4; 1 ≦ m ≦ 4; and wherein R′ m is selected such that (CpR′ m ) is a sterically different ring than (CpR n ); and b) introducing the catalyst into a polymerization reaction zone containing an olefin monomer and maintaining the reaction zone under polymerization reaction conditions.
Claim 14
Dependent Claim
21 words
The process of Claim 11 wherein R′ m is selected such that (CpR′ m ) forms a fluorenyl or indenyl radical.
Claim 15
Dependent Claim
12 words
The process of Claim 11 wherein Me is titanium, zirconium or hafnium.
Claim 16
Dependent Claim
46 words
The process of Claim 11 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 17
Dependent Claim
19 words
The process of Claim 11 wherein R˝ is a methyl, ethyl, ethylene, isopropyl, cyclopropyl, dimethylsilyl or a methylene radical.
Claim 18
Dependent Claim
9 words
The process of Claim 11 wherein n is 0.
Claim 19
Dependent Claim
16 words
The process of Claim 11 wherein R˝ (CpR n )(CpR′ m ) forms an isopropyl(cyclopentadienyl-1-florenyl) radical.
Claim 20
Dependent Claim
44 words
The process of Claim 11 wherein R m is selected such that (CpR′ m ) forms a fluorenyl, indenyl, tetra-, tri, or di-alkyl substituted cyclopentadienyl radical and R n is selected such that (CpR n ) forms an alkyl substituted or unsubstituted cyclopentadienyl radical.
Claim 21
Dependent Claim
22 words
The process of Claim 11 further comprising an aluminum compound selected from the group consisting of alumoxanes, alkyl aluminums and mixtures thereof.
Claim 22
Dependent Claim
17 words
The process of Claim 19 comprising an isolated complex of the metallocene catalyst and the aluminum compound.
Claim 23
Dependent Claim
34 words
The process of Claim 11 further comprising prepolymerizing the catalyst prior to introducing it into the reaction zone, said step of prepolymerizing including contacting the catalyst with an olefin monomer and an aluminum compound.
Claim 24
Dependent Claim
10 words
The polymer produced by the polymerization process of Claim 11.
Claim 25
Dependent Claim
178 words
A process for producing syndiotactic polyolefins having a broad molecular weight distribution, said process comprising a) utilizing at least two different metallocene catalysts described by the formula R˝(CpR n )(CpR′ m )MeQ k wherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R n is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ m is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; R˝ is a structural bridge between the two 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; 0 ≦ k ≦ 3; 0 ≦ n ≦ 4; 1 ≦ m ≦ 4; wherein R′ m is selected such that (CpR′ m ) is a sterically different ring than (CpR n ), and b) introducing the catalyst into a polymerization reaction zone containing an olefin monomer and maintaining the reaction zone under polymerization reaction conditions.
Claim 26
Dependent Claim
178 words
A process for producing syndiotactic polyolefins having a broad molecular weight distribution, said process comprising a) utilizing at least two different metallocene catalysts described by the formula R˝(CpR n )(CpR′ m )MeQ k wherein each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R n is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ m is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; R˝ is a structural bridge between the two 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; 0 ≦ k ≦ 3; 0 ≦ n ≦ 4; 1 ≦ m ≦ 4; wherein R′ m is selected such that (CpR′ m ) is a sterically different ring than (CpR n ), and b) introducing the catalyst into a polymerization reaction zone containing an olefin monomer and maintaining the reaction zone under polymerization reaction conditions.
Claim 27
Dependent Claim
46 words
The process of Claim 11 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 28
Dependent Claim
19 words
The process of Claim 23 wherein R˝ is a methyl, ethyl, ethylene, isopropyl, cyclopropyl, dimethylsilyl or a methylene radical.
Claim 29
Dependent Claim
9 words
The process of Claim 23 wherein n is 0.
Claim 30
Dependent Claim
16 words
The process of Claim 23 wherein R˝ (CpR n )(CpR′ m ) forms an isopropyl(cyclopentadienyl-1-florenyl) radical.
Claim 31
Dependent Claim
44 words
The process of Claim 23 wherein R m is selected such that (CpR′ m ) forms a fluorenyl, indenyl, tetra-, tri, or di-alkyl substituted cyclopentadienyl radical and R n is selected such that (CpR n ) forms an alkyl substituted or unsubstituted cyclopentadienyl radical.
Claim 32
Dependent Claim
22 words
The process of Claim 23 further comprising an aluminum compound selected from the group consisting of alumoxanes, alkyl aluminums and mixtures thereof.
Claim 33
Dependent Claim
17 words
The process of Claim 29 comprising an isolated complex of the metallocene catalyst and the aluminum compound.
Claim 34
Dependent Claim
34 words
The process of Claim 23 further comprising prepolymerizing the catalyst prior to introducing it into the reaction zone, said step of prepolymerizing including contacting the catalyst with an olefin monomer and an aluminum compound.
Claim 35
Dependent Claim
10 words
The polymer produced by the polymerization process of Claim 23.
Claim 36
Dependent Claim
109 words
A process for preparing a bridged metallocene catalyst comprising: a) contacting a cyclopentadiene or substituted cyclopentadiene with fulvene or a substituted fulvene under reaction conditions sufficient to produce a bridged dicyclopentadiene or substituted dicyclopentadiene, and b) contacting said bridged dicyclopentadiene or substituted dicyclopentadiene with a metal compound of the formula MeQ k under reaction conditions sufficient to complex the bridged dicyclopentadiene or substituted dicyclopentadiene with the metal compound to produce a bridged metallocene, wherein 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 and 0 ≦ k ≦ 4.
Claim 37
Dependent Claim
109 words
A process for preparing a bridged metallocene catalyst comprising: a) contacting a cyclopentadiene or substituted cyclopentadiene with fulvene or a substituted fulvene under reaction conditions sufficient to produce a bridged dicyclopentadiene or substituted dicyclopentadiene, and b) contacting said bridged dicyclopentadiene or substituted dicyclopentadiene with a metal compound of the formula MeQ k under reaction conditions sufficient to complex the bridged dicyclopentadiene or substituted dicyclopentadiene with the metal compound to produce a bridged metallocene, wherein 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 and 0 ≦ k ≦ 4.
Claim 38
Dependent Claim
17 words
The process of Claim 33 wherein the contacting of step (b) is performed in a chlorinated solvent.
Claim 39
Dependent Claim
16 words
The process of Claim 33 wherein the cyclopentadienyl rings of the dicyclopentadiene compound are sterically different.
References Cited (Backward Citations)
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