EP0284708A1
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Metallocene catalyst systems for olefin polymerization having a silicon hydrocarbyl bridge.
Assignee: Fina Technology Inc
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Filing: 1987-09-21
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Granted: —
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Expires: 2007-09-21
Abstract
Abstract The present invention provides a method for varying the melting points and molecular weights of polyolefins by changing the structure of the catalyst used in the polymerization. The catalysts that are useful in the present invention are chiral, stereorigid metallocene catalyst of the formula Rʺ(C₅Rʹ m )₂MeQ. The catalysts include a bridge structure between the (C₅Rʹ m ) groups and may contain substituents on the groups. It has been discovered that the melting points and molecular weights of the polymers produced by such catalysts are influenced by the bridge and substituents added to the (C₅Rʹ m ) groups. Thus, the present invention provides a method for varying the melting points of the polymer product and a method of varying the molecular weights of the product by changing the components and structure of the metallocene catalysts. The present invention also provides a process for polymerizing olefins in which the melting points and/or molecular weights of the product may be controlled. Also included in the invention is the discovery that the melting points of the products are controlled by the number of inversions in the xylene insoluble fraction of the polymer.
Inventors
- 👤 John A. Ewen
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-02 10:25
CPC Classifications
C; C08; C08F; C08F10/00; C07; C07F; C07F17/00; C08F110/00; C08F110/04; C08F110/06; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F110/02; C08F4/639; C08F4/63912; C08F4/6392; C08F4/63922; C08F4/63927; C08F4/659; C08F4/65912; Y; Y10; Y10S; Y10S526/00; Y10S526/943
Claims Analysis
Total Claims: 43
Claim 1
Independent Claim
200 words
In a process for the polymerization of olefins, a method for controlling the melting point of a polyolefin, said method comprising: (a) controlling the number of inversions in the chain of the xylene insoluble fraction of the polyolefin during the polymerization of olefin monomer; (b) contacting an organoaluminum compound with a metallocene catalyst described by the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ acts to bridge the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal as designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3; and (c) contacting an olefin monomer with said catalyst and said aluminum compound either simultaneously with or after step (b).
Claim 2
Dependent Claim
200 words
In a process for the polymerization of olefins, a method for controlling the melting point of a polyolefin, said method comprising: (a) controlling the number of inversions in the chain of the xylene insoluble fraction of the polyolefin during the polymerization of olefin monomer; (b) contacting an organoaluminum compound with a metallocene catalyst described by the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ acts to bridge the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal as designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3; and (c) contacting an olefin monomer with said catalyst and said aluminum compound either simultaneously with or after step (b).
Claim 3
Dependent Claim
186 words
A polyolefin produced by the process comprising: (a) controlling the number of inversions in the chain of the xylene insoluble fraction of the polyolefin during the polymerization of olefin monomer; (b) contacting an organoaluminum compound with a metallocene catalyst described by the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ acts to bridge the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkylene, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal as designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3; and (c) contacting an olefin monomer with said catalyst and said aluminum compound either simultaneously with or after step (b).
Claim 4
Dependent Claim
186 words
A polyolefin produced by the process comprising: (a) controlling the number of inversions in the chain of the xylene insoluble fraction of the polyolefin during the polymerization of olefin monomer; (b) contacting an organoaluminum compound with a metallocene catalyst described by the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ acts to bridge the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkylene, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal as designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3; and (c) contacting an olefin monomer with said catalyst and said aluminum compound either simultaneously with or after step (b).
Claim 5
Dependent Claim
219 words
A process for the polymerization of olefins comprising: (a) contacting an organoaluminum compound with a metallocene catalyst described by the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ acts to bridge the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal as designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3; (b) contacting an olefin monomer with the metallocene catalyst and the organoaluminum compound either simultaneously with or after (a); and (c) withdrawing a polymer product, wherein the process provides control of the melting point of the polymer product by controlling the number of inversions in the xylene insoluble fraction of the polymer during polymerization, and the melting point of the polymers may be varied by varying the Rʹ or Rʺ groups on the metallocene catalyst.
Claim 6
Dependent Claim
219 words
A process for the polymerization of olefins comprising: (a) contacting an organoaluminum compound with a metallocene catalyst described by the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ acts to bridge the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal as designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3; (b) contacting an olefin monomer with the metallocene catalyst and the organoaluminum compound either simultaneously with or after (a); and (c) withdrawing a polymer product, wherein the process provides control of the melting point of the polymer product by controlling the number of inversions in the xylene insoluble fraction of the polymer during polymerization, and the melting point of the polymers may be varied by varying the Rʹ or Rʺ groups on the metallocene catalyst.
Claim 7
Dependent Claim
12 words
The process of Claim 3 wherein the metallocene catalyst is a zirconocene.
Claim 8
Dependent Claim
12 words
The process of Claim 3 wherein the metallocene catalyst is a titanocene.
Claim 9
Dependent Claim
18 words
The process of Claim 3 wherein the Rʺ bridge of the metallocene catalyst is an alkyl silicon compound.
Claim 10
Dependent Claim
12 words
The process of Claim 3 wherein the organoaluminum compound is an alumoxane.
Claim 11
Dependent Claim
11 words
The process of Claim 3 wherein the olefin monomer is propylene.
Claim 12
Dependent Claim
25 words
The process of Claim 3 wherein the number of inversions in the xylene insoluble fraction are controlled by the Rʺ group in the metallocene catalyst.
Claim 13
Dependent Claim
26 words
The process of Claim 3 wherein the number of inversions in the xylene insoluble fraction are controlled by the Rʹ groups attached to the cyclopentadienyl rings.
Claim 14
Independent Claim
31 words
A method for controlling the melting point of an olefinic polymer in the presence of a chiral, stereorigid metallocene catalyst having an interannular bridge, comprising varying the structure of said bridge.
Claim 15
Independent Claim
31 words
A method for controlling the melting point of an olefinic polymer in the presence of a chiral, stereorigid metallocene catalyst having an interannular bridge, comprising varying the structure of said bridge.
Claim 16
Dependent Claim
137 words
The method of Claim 11 wherein the metallocene catalyst is described by the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ is a bridge between the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3.
Claim 17
Dependent Claim
19 words
The method of Claim 12 wherein the Rʺ bridge is varied to include a silicon atom in the bridge.
Claim 18
Dependent Claim
17 words
The method of Claim 12 wherein the Rʺ bridge is varied to include an alkyl silicone compound.
Claim 19
Dependent Claim
16 words
The method of Claim 12 wherein the Rʺ bridge is changed to include an alkylene compound.
Claim 20
Dependent Claim
20 words
The method of Claim 12 wherein the metallocene catalyst is selected from the group consisting of titanocene, zirconocene, and hafnocene.
Claim 21
Dependent Claim
11 words
The method of Claim 12 wherein the olefin monomer is propylene.
Claim 22
Dependent Claim
20 words
The method of Claim 12 further comprising changing the Rʹ group attached to the cyclopentadienyl rings in the metallocene catalyst.
Claim 23
Independent Claim
31 words
A method for controlling the molecular weight of an olefinic polymer produced in the presence of a chiral, stereorigid metallocene catalyst having interannular bridges comprising varying the structure of said bridge.
Claim 24
Independent Claim
31 words
A method for controlling the molecular weight of an olefinic polymer produced in the presence of a chiral, stereorigid metallocene catalyst having interannular bridges comprising varying the structure of said bridge.
Claim 25
Dependent Claim
135 words
The method of Claim 19 wherein said metallocene catalyst is described by: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ is a bridge between the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3.
Claim 26
Dependent Claim
20 words
The method of Claim 19 wherein the metallocene catalyst is selected from the group consisting of titanocene, zirconocene, and hafnocene.
Claim 27
Dependent Claim
18 words
The method of Claim 19 wherein the bridge is changed to include a silicon atom in the bridge.
Claim 28
Dependent Claim
16 words
The method of Claim 19 wherein the bridge is changed to include an alkyl silicon compound.
Claim 29
Dependent Claim
13 words
The method of Claim 20 wherein the (C₅Rʹ m ) is an indene.
Claim 30
Dependent Claim
16 words
The method of Claim 20 wherein the Rʺ bridge is changed to include an alkylene compound.
Claim 31
Dependent Claim
11 words
The method of Claim 20 further comprising changing the Rʹ group.
Claim 32
Independent Claim
180 words
A method for varying the melting point of a polyolefin in the polymerization of an olefin monomer, said method comprising: (a) utilizing an organoaluminum compound, a metallocene catalyst and an olefin monomer in a polymerization reaction, said metallocene catalyst being stereorigid, chiral and described by the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ is a bridge between the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3; and (b) changing the Rʹ group on the cyclopentadienyl rings.
Claim 33
Independent Claim
180 words
A method for varying the melting point of a polyolefin in the polymerization of an olefin monomer, said method comprising: (a) utilizing an organoaluminum compound, a metallocene catalyst and an olefin monomer in a polymerization reaction, said metallocene catalyst being stereorigid, chiral and described by the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ is a bridge between the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3; and (b) changing the Rʹ group on the cyclopentadienyl rings.
Claim 34
Dependent Claim
12 words
The method of Claim 27 wherein Rʹ is changed to include hydrogen.
Claim 35
Dependent Claim
11 words
The method of Claim 27 wherein the metallocene catalyst is zirconocene.
Claim 36
Dependent Claim
11 words
The method of Claim 27 wherein the olefin monomer is propylene.
Claim 37
Dependent Claim
11 words
The method of Claim 27 wherein the metallocene catalyst is hafnocene.
Claim 38
Independent Claim
171 words
A method for varying the molecular weights of a polyolefin in the polymerization of an olefin monomer, said method comprising: (a) utilizing a metallocene catalyst, an organoaluminum compound and an olefin monomer, said catalyst being of the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ is a bridge between the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3; and (b) changing the Rʹ group on the cyclopentadienyl rings.
Claim 39
Independent Claim
171 words
A method for varying the molecular weights of a polyolefin in the polymerization of an olefin monomer, said method comprising: (a) utilizing a metallocene catalyst, an organoaluminum compound and an olefin monomer, said catalyst being of the formula: Rʺ(C₅Rʹ m )₂ Me Q p wherein (C₅Rʹ m ) is a cyclopentadienyl or substituted cyclopentadienyl; Rʹ is hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms, each Rʹ may be the same or different; Rʺ is an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine, and Rʺ is a bridge between the two (C₅Rʹ m ) rings; Q is a hydrocarbon radical such as an aryl, alkyl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a group 4b, 5b or 6b metal designated in the Periodic Table of Elements; O ≦ m ≦ 4; and O ≦ p ≦ 3; and (b) changing the Rʹ group on the cyclopentadienyl rings.
Claim 40
Dependent Claim
13 words
The method of Claim 32 wherein the Rʹ is changed to include hydrogen.
Claim 41
Dependent Claim
20 words
The method of Claim 32 wherein the metallocene catalyst is selected from the group consisting of titanocene, zirconocene, and hafnocene.
Claim 42
Dependent Claim
11 words
The method of Claim 32 wherein the olefin monomer is propylene.
Claim 43
Dependent Claim
12 words
The method of Claim 32 wherein the metallocene catalyst is a hafnocene.
References Cited (Backward Citations)
DE2608933A1
Cited
DE2608863A1
Cited
US4404344A
Cited
US4542199A
Cited
US4522982A
Cited
US4530914A
Cited
EP0128046B1
Cited
EP0129368B1
Cited
EP0185918A2
Cited
EP0197319A2
Cited
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