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US4123387A Expired / Lapsed US ⏱️ 0.0 years remaining

Catalysts for polymerization of olefins

Assignee: Sumitomo Chemical Co Ltd
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Filing: 1977-03-14
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Granted: 1978-10-31
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Expires: 1997-03-14
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Abstract

Abstract A solid catalyst for olefin polymerization which is obtained by the catalytic treatment of a titanium trichloride composition with a mixture of a halogenated hydrocarbon and an ether, the composition being produced by subjecting a solid reduction product, which is obtained by reduction of titanium tetrachloride with an organo-aluminum compound, to heat treatment or to catalytic treatment with a specific organo-aluminum compound, aluminum halide, an ether and the like. In the polymerization of an olefin, combined catalyst systems of this solid catalyst and organo-aluminum compounds as activators can be used for efficient production of olefin polymers having a high crystallinity.

Inventors

  • 👤 Akinobu Shiga
  • 👤 Yoshiharu Fukui
  • 👤 Kazuhiro Matsumura
  • 👤 Toshio Sasaki
  • 👤 Masahisa Ohkawa

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-31 13:12
CPC Classifications
C; C08; C08F; C08F10/00

Claims Analysis

Total Claims: 23
Claim 1
Independent Claim 608 words
In a method for the production of a solid catalyst for olefin polymerization comprising preparing a titanium trichloride composition by reducing tetrachloride with an organo-aluminum compound of the formula: R.sub.n A X.sub.3-n wherein R is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom or a hydrogen atom, and n satisfies the relationship 1 ≦ n ≦ 3, at a temperature of about -100° to about 60° C. to obtain a solid reduction product, and then treating the resulting solid reduction product by one of the following methods, (a), (b), (c), (d), (e) or (f): (a) heat-treating the solid reduction product at about 100° to about 180° C. in the absence of or presence of an inert solvent, (b) catalytically treating the solid reduction product with an aluminum compound of the formula: R".sub.p A X.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1 = p 1.5, and, optionally, further catalytically treating the resulting product with an ether, (c) catalytically treating the solid reduction product with an ether and then with an aluminum compound of the formula: R".sub.p A X.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1 ≦ p < 1.5, and, optionally, further catalytically treating the resulting product with an ether, (d) catalytically treating the solid reduction product with an ether and then with an aluminum compound of the formula: R".sub.p A X.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1 ≦ p < 1.5, in the presence of an organo-halogen compound of the formula: R'''X wherein R''' is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, and X is a halogen atom, and, optionally, further catalytically treating the resulting product with an ether, (e) catalytically treating the solid reduction product with an ether and then with an aluminum halide of the formula: AlX.sub.3 wherein X is a halogen atom, dissolved in an aromatic hydrocarbon in the presence of a hydrogen halide of the formula: HX wherein X is a halogen atom, and, optionally, further catalytically treating the resulting product with an ether, (f) catalytically treating the solid reduction product with an ether and then with titanium tetrachloride; the improvement comprising treating the thus produced titanium trichloride composition at a temperature of from about 0° to about 150° C. with a mixture of a halogenated hydrocarbon (1) represented by the formula CH.sub.q X.sub.4-q wherein X is a halogen atom and q is an integer satisfying the relationship 0 ≦ q < 4, and an ether (2) represented by the formula R.sub.3 --O--R.sub.4 wherein R 3 and R 4 , which may be the same or different, each is an alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 10 carbon atoms, wherein the amounts of the halogenated hydrocarbon and ether used in the catalytic treating of the titanium trichloride composition are about 0.001 to about 1.0 and about 0.001 to about 5 times on a molar basis to the amount of the titanium trichloride contained in the titanium trichloride composition, respectively.
Claim 2
Dependent Claim 608 words
In a method for the production of a solid catalyst for olefin polymerization comprising preparing a titanium trichloride composition by reducing tetrachloride with an organo-aluminum compound of the formula: R.sub.n A X.sub.3-n wherein R is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom or a hydrogen atom, and n satisfies the relationship 1 ≦ n ≦ 3, at a temperature of about -100° to about 60° C. to obtain a solid reduction product, and then treating the resulting solid reduction product by one of the following methods, (a), (b), (c), (d), (e) or (f): (a) heat-treating the solid reduction product at about 100° to about 180° C. in the absence of or presence of an inert solvent, (b) catalytically treating the solid reduction product with an aluminum compound of the formula: R".sub.p A X.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1 = p 1.5, and, optionally, further catalytically treating the resulting product with an ether, (c) catalytically treating the solid reduction product with an ether and then with an aluminum compound of the formula: R".sub.p A X.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1 ≦ p < 1.5, and, optionally, further catalytically treating the resulting product with an ether, (d) catalytically treating the solid reduction product with an ether and then with an aluminum compound of the formula: R".sub.p A X.sub.3-p wherein R" is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, X is a halogen atom, and p satisfies the relationship 1 ≦ p < 1.5, in the presence of an organo-halogen compound of the formula: R'''X wherein R''' is a straight or branched alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 18 carbon atoms, and X is a halogen atom, and, optionally, further catalytically treating the resulting product with an ether, (e) catalytically treating the solid reduction product with an ether and then with an aluminum halide of the formula: AlX.sub.3 wherein X is a halogen atom, dissolved in an aromatic hydrocarbon in the presence of a hydrogen halide of the formula: HX wherein X is a halogen atom, and, optionally, further catalytically treating the resulting product with an ether, (f) catalytically treating the solid reduction product with an ether and then with titanium tetrachloride; the improvement comprising treating the thus produced titanium trichloride composition at a temperature of from about 0° to about 150° C. with a mixture of a halogenated hydrocarbon (1) represented by the formula CH.sub.q X.sub.4-q wherein X is a halogen atom and q is an integer satisfying the relationship 0 ≦ q < 4, and an ether (2) represented by the formula R.sub.3 --O--R.sub.4 wherein R 3 and R 4 , which may be the same or different, each is an alkyl group, an alicyclic group or an aromatic hydrocarbon group, each having up to 10 carbon atoms, wherein the amounts of the halogenated hydrocarbon and ether used in the catalytic treating of the titanium trichloride composition are about 0.001 to about 1.0 and about 0.001 to about 5 times on a molar basis to the amount of the titanium trichloride contained in the titanium trichloride composition, respectively.
Claim 3
Dependent Claim 57 words
The method according to claim 1, wherein said ether used in method (b), (c), (d), (e) or (f) is represented by the general formula: R.sub.1 --O--R.sub.2 wherein R 1 and R 2 , which may be the same or different, each is an alkyl group or an aromatic hydrocarbon group, each having up to 10 carbon atoms.
Claim 4
Dependent Claim 24 words
The method according to claim 2, wherein said ether used in method (b), (c), (d), (e) or (f) is di-n-butyl ether or diisoamyl ether.
Claim 5
Dependent Claim 52 words
The method according to claim 2, wherein the amount of the ether used in the catalytic treatment of method (b), (c), (d), (e) or (f) is about 0.05 to about 3 times on a molar basis the amount of the titanium trichloride contained in the solid reduction product produced to be treated.
Claim 6
Dependent Claim 30 words
The method according to claim 4, wherein the amount of the ether used in method (b), (c), (d), (e) or (f) is 0.5 to 1.5 times on a molar basis.
Claim 7
Dependent Claim 31 words
The method according to claim 2, the treatment with the ether used in method (b), (c), (d), (e) or (f) is carried out at a temperature of 0° to 100° C.
Claim 8
Dependent Claim 25 words
The method according to claim 1, wherein said aluminum compound is represented by the general formula: R"AlX.sub.2 wherein R" and X are as defined above.
Claim 9
Dependent Claim 13 words
The method according to claim 1, wherein said aluminum halide is aluminum chloride.
Claim 10
Dependent Claim 20 words
The method according to claim 1, wherein R''' in said organo-halogen compound is an alkyl group or an aralkyl group.
Claim 11
Dependent Claim 39 words
The method according to claim 1, wherein the amount of the aluminum compound is about 0.1 to about 10 times on a molar basis the amount of the titanium trichloride contained in the solid reduction product to be treated.
Claim 12
Dependent Claim 22 words
The method according to claim 10, wherein the amount of the aluminum compound is 0.5 to 5 times on a molar basis.
Claim 13
Dependent Claim 27 words
The method according to claim 1, wherein the catalytic treating with the aluminum compound is at a temperature of from about room temperature to about 200° C.
Claim 14
Dependent Claim 14 words
The method according to claim 12, wherein the temperature is 50° to 180° C.
Claim 15
Dependent Claim 34 words
The method according to claim 1, wherein the concentration of the aluminum halide is about 1 to about 80% by weight based on the total amount of the aluminum halide and the aromatic hydrocarbon.
Claim 16
Dependent Claim 35 words
The method according to claim 14, wherein the amount of the aluminum halide is 0.5 to 5 times on a molar basis the amount of the titanium trichloride contained in the ether-treated solid reduction product.
Claim 17
Dependent Claim 26 words
The method according to claim 1, wherein the catalytic treating with the aluminum halide is at a temperature of from about -100° to about 200° C.
Claim 18
Dependent Claim 27 words
The method according to claim 1, wherein the catalytic treating with the titanium tetrachloride is at a temperature of from about room temperature to about 100° C.
Claim 19
Dependent Claim 25 words
The method according to claim 1, wherein said halogenated hydrocarbon is carbon tetrachloride, chloroform, methylene chloride, carbon tetrabromide, bromoform, methylene bromide or a combination thereof.
Claim 20
Dependent Claim 13 words
The method according to claim 18, wherein said halogenated hydrocarbon is carbon tetrachloride.
Claim 21
Dependent Claim 16 words
The method according to claim 1, wherein the ether (2) is di-n-butyl ether or diisoamyl ether.
Claim 22
Dependent Claim 31 words
The method according to claim 1, wherein the amounts of halogenated hydrocarbon (1) and the ether (2) are 0.003 to 1.0 and 0.003 to 1.5 times on a molar basis, respectively.
Claim 23
Dependent Claim 13 words
A catalyst for olefin polymerization produced according to the method of claim 1.

References Cited (Backward Citations)

US3354139A Cited
US3131171A Cited
US3530107A Cited
US3701763A Cited
US3769233A Cited
US3984350A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1981-10-30 1982-05-01 1982-10-31 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1985-10-30 1986-05-01 1986-10-31 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1989-10-30 1990-05-01 1990-10-31 $7700.00 Window Closed / Lapsed

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