US4640906A
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Catalyst for the polymerization of olefins
Assignee: Toho Titanium Co Ltd
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Filing: 1985-11-01
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Granted: 1987-02-03
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Expires: 2005-11-01
Abstract
Abstract A catalyst for the polymerization of olefins which comprises: (1) a solid catalyst component, (2) a piperidine derivative and (3) an organoaluminum compound, characterized in that the solid catalyst component (A) has been prepared by mixing (a) a dialkoxymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) a titanium tetrahalide to effect reaction, as well as the solid catalyst component and a process for preparing same. The catalyst maintains a high polymerization activity combined with stereospecific performance over a prolonged polymerization time and scarcely incurs any problem of corrosion and odor in the resultant polymer.
Inventors
- 👤 Minoru Terano
- 👤 Yasushi Yokoyama
- 👤 Masuo Inoue
- 👤 Katsuyoshi Miyoshi
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 04:58
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 40
Claim 1
Independent Claim
126 words
A catalyst for the polymerization of olefins which consists essentially of: (A) a solid catalyst component, (B) a piperidine disubstituted or tetrasubstituted derivative of the general formula: ##STR4## wherein R 1 , R 2 , R 3 and R 4 each stands for a hydrogen atom or an alkyl group with the proviso that at least one of R 1 and R 2 and/or at least one of R 3 and R 4 is an alkyl group; and (C) an organoaluminum compound, wherein the solid catalyst component (A) has been prepared by mixing (a) a dialkoxymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) titanium tetrahalide to effect reaction.
Claim 2
Dependent Claim
126 words
A catalyst for the polymerization of olefins which consists essentially of: (A) a solid catalyst component, (B) a piperidine disubstituted or tetrasubstituted derivative of the general formula: ##STR4## wherein R 1 , R 2 , R 3 and R 4 each stands for a hydrogen atom or an alkyl group with the proviso that at least one of R 1 and R 2 and/or at least one of R 3 and R 4 is an alkyl group; and (C) an organoaluminum compound, wherein the solid catalyst component (A) has been prepared by mixing (a) a dialkoxymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) titanium tetrahalide to effect reaction.
Claim 3
Dependent Claim
16 words
The catalyst according to claim 1, wherein the disubstituted or tetrasubstituted piperidine is 2,6-dialkylpiperidine or 2,2,6,6-tetraalkylpiperidine.
Claim 4
Dependent Claim
44 words
The catalyst according to claim 1, wherein the organoaluminum compound is of the general formula: ##STR5## a C 1 -C 8 alkyl group, Q and Q' may be the same or different and each represents R or X, and X is a halogen atom.
Claim 5
Dependent Claim
13 words
The catalyst according to claim 3, wherein the organoaluminum compound is a trialkylaluminum.
Claim 6
Dependent Claim
26 words
The catalyst according to claim 1, wherein the organoaluminum compound is used in an amount of 1-1000 mols per titanium atom in the solid catalyst component.
Claim 7
Dependent Claim
24 words
The catalyst according to claim 1, wherein the piperidine derivative is used in an amount of 0.005-1.0 mol per mol of the organoaluminum compound.
Claim 8
Dependent Claim
62 words
A solid catalyst component for catalysts utilizable for the polymerization of olefins which has been prepared by a process consisting essentially of mixing (a) a dialkoxymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) a titanium tetrahalide thereby effecting reaction to obtain a solid matter.
Claim 9
Dependent Claim
62 words
A solid catalyst component for catalysts utilizable for the polymerization of olefins which has been prepared by a process consisting essentially of mixing (a) a dialkoxymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) a titanium tetrahalide thereby effecting reaction to obtain a solid matter.
Claim 10
Dependent Claim
20 words
The solid catalyst component according to claim 7, wherein the solid matter has further been treated with the titanium tetrahalide.
Claim 11
Dependent Claim
38 words
The solid catalyst component according to claim 7, wherein the dialkoxymagnesium is of the general formula: A--Mg--A' (I) wherein A and A' may be the same or different and each represents a C 1 -C 8 alkoxy group.
Claim 12
Dependent Claim
19 words
The solid catalyst component according to claim 7, wherein the dialkoxymagnesium is diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, di-n-butoxymagnesium, di-secbutoxymagnesium, and di-tert-butoxymagnesium.
Claim 13
Dependent Claim
47 words
A solid catalyst component according to claim 7, wherein the diester is a phthalic diester of the general formula: ##STR6## wherein R and R' may be the same or different and each represents a C 1 -C 8 alkyl group which may be branched at any position.
Claim 14
Dependent Claim
60 words
The solid catalyst component according to claim 11, wherein the diester is dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl isobutyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, propyl butyl phthalate, propyl isobutyl phthalate, propyl amyl phthalate or butyl amyl phthalate.
Claim 15
Dependent Claim
21 words
The solid catalyst component according to claim 7, wherein the halogenated hydrocarbon is a normally liquid halogenated, aromatic or aliphatic hydrocarbon.
Claim 16
Dependent Claim
35 words
The solid catalyst component according to claim 13, wherein the halogenated hydrocarbon is propyl chloride, butyl chloride, butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, methylene chloride, dichloroethane, dichloropropane, dichlorobenzene, chloroform, trichloroethylene, trichloroethane or carbon tetrachloride.
Claim 17
Dependent Claim
16 words
The solid catalyst component according to claim 7, wherein the titanium tetrahalide is TiCl 4 .
Claim 18
Dependent Claim
60 words
A process for the preparation of a solid catalyst component utilizable for the polymerization of olefins which consists essentially of mixing (a) a dialkoxymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) a titanium tetrahalide thereby effecting reaction to obtain a solid matter.
Claim 19
Dependent Claim
60 words
A process for the preparation of a solid catalyst component utilizable for the polymerization of olefins which consists essentially of mixing (a) a dialkoxymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) a titanium tetrahalide thereby effecting reaction to obtain a solid matter.
Claim 20
Dependent Claim
17 words
The process according to claim 16, wherein the solid matter is further treated with the titanium tetrahalide.
Claim 21
Dependent Claim
36 words
The process according to claim 16, wherein the dialkoxymagnesium is of the general formula: A--Mg--A' (I) wherein A and A' may be the same or different and each represents a C 1 -C 8 alkoxy group.
Claim 22
Dependent Claim
17 words
The process according to claim 18, wherein the dialkoxymagnesium is diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, di-n-butoxymagnesium, di-sec-butoxymagnesium or di-tert-butoxymagnesium.
Claim 23
Dependent Claim
46 words
The process according to claim 16, wherein the diester is a phthalic diester of the general formula: ##STR7## wherein R and R' may be the same or different and each represents a C 1 -C 8 alkyl group which may be branched at any desired position.
Claim 24
Dependent Claim
57 words
The process according to claim 20, wherein the diester dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl isobutyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, propyl butyl phthalate, propyl isobutyl phthalate, propyl amyl phthalate or butyl amyl phthalate.
Claim 25
Dependent Claim
19 words
The process according to claim 16, wherein the halogenated hydrocarbon is a normally liquid halogenated aromatic or aliphatic hydrocarbon.
Claim 26
Dependent Claim
33 words
The process according to claim 22, wherein the halogenated hydrocarbon is propyl chloride, butyl chloride, butyl bromide, propyl iodide, chlorobenzene, benzyl chloride, methylene chloride, dichloroethane, dichloropropane, dichlorobenzene, chloroform, trichloroethylene, trichloroethane or carbon tetrachloride.
Claim 27
Dependent Claim
14 words
The process according to claim 16, wherein the titanium tetrahalide is TiCl 4 .
Claim 28
Dependent Claim
41 words
The process according to claim 16, wherein the temperature at the reaction between the suspension and the titanium tetrahalide and the temperature at the treatment of the solid matter with further titanium tetrahalide are commonly within the range of 90°-130° C.
Claim 29
Dependent Claim
39 words
The process according to claim 16, wherein the time for the reaction between the suspension and the titanium tetrahalide and the time for the treatment of the solid matter with further titanium tetrahalide are commonly at least 30 minutes.
Claim 30
Dependent Claim
28 words
The process according to claim 16, wherein 0.1-1 g of the diester and at least 1 g of the titanium tetrahalide are used per gram of the dialkoxymagnesium.
Claim 31
Dependent Claim
60 words
The solid catalyst component according to claim 12, wherein the diester is dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamly phthalate, diisodmyl phthalade, methyl ethyl, phtholate, methyl propyl phthalate, methyl butyl phthalate, methyl isobutyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, propyl butyl phthalate, propyl isobutyl phthalate, propyl amyl phthalate or butyl amyl phthalate.
Claim 32
Dependent Claim
25 words
The solid catalyst component according to claim 9, wherein A and A' are identical with each other or are C 2 -C 4 alkoxy groups.
Claim 33
Dependent Claim
25 words
The solid catalyst component according to claim 11, wherein R and R' are C 2 -C 5 alkyl groups or are branched at any position.
Claim 34
Dependent Claim
21 words
The catalyst according to claim 1, wherein the alkyl group of the piperdine is a C 1 -C 8 alkyl group.
Claim 35
Dependent Claim
125 words
A catalyst for the polymerization of olefins which consists of: (A) a solid catalyst component, (B) a piperidine disubstituted or tetrasubstituted derivative of the general formula: ##STR8## wherein R 1 , R 2 , R 3 and R 4 each stands for a hydrogen atom or an alkyl group with the proviso that at least one of R 1 and R 2 and/or at least one of R 3 and R 4 is an alkyl group; and (C) an organoaluminum compound, wherein the solid catalyst component (A) has been prepared by mixing (a) a dialkoxymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) titanium tetrahalide to effect reaction.
Claim 36
Dependent Claim
125 words
A catalyst for the polymerization of olefins which consists of: (A) a solid catalyst component, (B) a piperidine disubstituted or tetrasubstituted derivative of the general formula: ##STR8## wherein R 1 , R 2 , R 3 and R 4 each stands for a hydrogen atom or an alkyl group with the proviso that at least one of R 1 and R 2 and/or at least one of R 3 and R 4 is an alkyl group; and (C) an organoaluminum compound, wherein the solid catalyst component (A) has been prepared by mixing (a) a dialkoxymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) titanium tetrahalide to effect reaction.
Claim 37
Dependent Claim
61 words
A solid catalyst component for catalysts utilizable for the polymerization of olefins which has been prepared by a process consisting of mixing (a) a dialkozymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) a titanium tetrahalide thereby effecting reaction to obtain a solid matter.
Claim 38
Dependent Claim
61 words
A solid catalyst component for catalysts utilizable for the polymerization of olefins which has been prepared by a process consisting of mixing (a) a dialkozymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) a titanium tetrahalide thereby effecting reaction to obtain a solid matter.
Claim 39
Dependent Claim
58 words
A process for the preparation of a solid catalyst component utilizable for the polymerization of olefins which consists of mixing (a) a dialkozymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) titanium tetrahalide thereby effecting reaction to obtain a solid matter.
Claim 40
Dependent Claim
58 words
A process for the preparation of a solid catalyst component utilizable for the polymerization of olefins which consists of mixing (a) a dialkozymagnesium and (b) a diester of an aromatic dicarboxylic acid with (c) a halogenated hydrocarbon to form a suspension and thereafter adding the suspension to (d) titanium tetrahalide thereby effecting reaction to obtain a solid matter.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1990-02-02 | 1990-08-04 | 1991-02-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-02-02 | 1994-08-04 | 1995-02-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-02-02 | 1998-08-04 | 1999-02-03 | $7700.00 | Window Closed / Lapsed |