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US4357448A
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Two step process for polymerizing ethylene
Assignee: NISSAKN CHEMCICAL INDUSTRIES Ltd 7-1 3-CHOME KANDA-NISHIKI-CHO CHIYODA-KU TOKYO
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Filing: 1980-05-20
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Granted: 1982-11-02
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Expires: 2000-05-20
Abstract
Abstract Ethylene or a mixture of ethylene and a small amount of another α-olefin or diene is polymerized in two successive steps under different hydrogen partial pressures by polymerizing 30 to 70 wt. % of the ethylene or ethylene mixture to be polymerized in the presence of hydrogen at a molar ratio of ethylene or ethylene mixture to hydrogen of 1:1-8 in the first step and polymerizing the residual ethylene or the ethylene mixture at a molar ratio of ethylene to hydrogen of 1:0-0.3 in the second step, in the presence of the specific catalyst system comprising an organoaluminum compound (C) and a specific solid catalytic component (B) obtained by reacting a titanium or vanadium halogen-containing compound with a reaction product (A) obtained by reacting a Grignard reagent with a hydropoly-siloxane having the formula ##EQU1## (R 1 represents an alkyl, aryl, aralkyl, alkoxy, or aryloxy group as a monovalent organic group; a is 0,1 or 2; b is 1, 2 or 3; and a+b≦3) or a silicon compound containing an organic group and hydroxyl group in the presence or absence of an aluminum-alkoxide, aluminum alkoxy-halide halide or a reaction product obtained by reacting the aluminum compound with water.
Inventors
- 👤 Kazumi Tsubaki
- 👤 Hiroshi Morinaga
- 👤 Yoshiho Matsuo
- 👤 Takeshi Iwabuchi
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 10:02
CPC Classifications
C; C08; C08F; C08F10/00; C08F10/02; C08F210/00; C08F210/16; C08F110/00; C08F110/02; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/52; Y10; Y10S; Y10S526/00; Y10S526/905
Claims Analysis
Total Claims: 9
Claim 1
Independent Claim
265 words
In a process for polymerizing ethylene alone or ethylene in admixture with a small amount of another α-olefin or conjugated diolefin in two successive polymerization steps, the improvement comprising: polymerizing 30 to 70 wt.% of said ethylene or ethylene mixture in the presence of hydrogen at a molar ratio of ethylene or ethylene mixture to hydrogen of 1:1-8 in the gaseous phase of the polymerization system in the first step and polymerizing the residual amount of said ethylene or ethylene mixture in the second step at an ethylene or ethylene mixture:hydrogen molar ratio of 1:0-0.3 in the gaseous phase of the polymerization system, wherein the catalyst in each of said polymerization steps comprises the combination of (1) an organoaluminum compound (C) selected from the group consisting of organometallic compounds sufficient for preparing Ziegler type catalysts and (2) a specific solid catalyst component (B) obtained by reacting (II) a titanium or vanadium halogen containing compound with a reaction product (A) obtained by reacting (I) a Grignard reagent with a silicon compound selected from the group consisting of a hydropolysiloxane having the formula: ##EQU4## wherein R' is a monovalent alkyl, aryl, aralkyl, alkoxy or aryloxy group, a is 0,1 or 2,b is 1, 2 or 3 and a+b≦3 and a silicon compound including the formula R n 2 Si(OH) 4-n wherein R 2 represents a C 1 -C 18 monovalent hydrocarbon moiety and n is 1, 2 or 3, said reacting (II) being in the presence or absence of an aluminum alkoxide, an aluminum alkoxyhalide or the reaction product obtained by reacting an alkoxyaluminum compound with water.
Claim 2
Dependent Claim
265 words
In a process for polymerizing ethylene alone or ethylene in admixture with a small amount of another α-olefin or conjugated diolefin in two successive polymerization steps, the improvement comprising: polymerizing 30 to 70 wt.% of said ethylene or ethylene mixture in the presence of hydrogen at a molar ratio of ethylene or ethylene mixture to hydrogen of 1:1-8 in the gaseous phase of the polymerization system in the first step and polymerizing the residual amount of said ethylene or ethylene mixture in the second step at an ethylene or ethylene mixture:hydrogen molar ratio of 1:0-0.3 in the gaseous phase of the polymerization system, wherein the catalyst in each of said polymerization steps comprises the combination of (1) an organoaluminum compound (C) selected from the group consisting of organometallic compounds sufficient for preparing Ziegler type catalysts and (2) a specific solid catalyst component (B) obtained by reacting (II) a titanium or vanadium halogen containing compound with a reaction product (A) obtained by reacting (I) a Grignard reagent with a silicon compound selected from the group consisting of a hydropolysiloxane having the formula: ##EQU4## wherein R' is a monovalent alkyl, aryl, aralkyl, alkoxy or aryloxy group, a is 0,1 or 2,b is 1, 2 or 3 and a+b≦3 and a silicon compound including the formula R n 2 Si(OH) 4-n wherein R 2 represents a C 1 -C 18 monovalent hydrocarbon moiety and n is 1, 2 or 3, said reacting (II) being in the presence or absence of an aluminum alkoxide, an aluminum alkoxyhalide or the reaction product obtained by reacting an alkoxyaluminum compound with water.
Claim 3
Dependent Claim
78 words
The process according to claim 1 wherein the first polymerization step is conducted at a temperature of 50° to 110° C. under a total pressure of from 1 to 50 kg/cm 2 in an inert solvent such that a slurry of the polymer product is formed and wherein the second polymerization step is conducted at a temperature from 50° to 110° C. under a total pressure of from 1 to B 50 kg/cm 2 in an inert solvent.
Claim 4
Dependent Claim
34 words
The process according to claim 1, wherein said ethylene mixture contains less than 10 mole % of another olefin selected from the group consisting of propylene, butene-1, hexene-1, and 4-methyl-pentene-1, or a conjugated diene.
Claim 5
Dependent Claim
57 words
The process according to claim 1, wherein the silicon compound is a silane having at least one organic group and at least one hydroxyl group of the formula: R.sub.n.sup.2 Si(OH).sub.4-n (II) wherein R 2 represents a C 1 -C 18 monovalent hydrocarbon moiety, n is 1, 2 or 3 or is a polysiloxane condensate of silane (II).
Claim 6
Dependent Claim
67 words
The process according to claim 1, wherein the titanium halogen-containing compound is a compound having the formula TiX.sub.n (OR.sup.5).sub.4-n wherein X represents a halogen atom, R 5 represents a C 1 -C 18 hydrocarbon moiety and n is a value from 1 to 4, and the vanadium halogen-containing compound is a compound having the formula VX.sub.n (OR.sup.5).sub.4-n wherein X, R 5 and n are as defined above.
Claim 7
Dependent Claim
60 words
The process according to claim 1, wherein in the first step of the polymerization reaction, the amount of solid catalyst component (B) is present in the range of 0.001-1 gram per 1 liter of the reaction medium and wherein the amount of the organometallic compound (C) is in the range of 0.1-50 millimole per 1 liter of the reaction medium.
Claim 8
Dependent Claim
50 words
The process according to claim 1, wherein the amount of said titanium or vanadium in solid catalyst component (B) is in the range of 1 to 120 mg. per 1 gram of solid catalyst component (B) in the absence of said aluminum alkoxide, said aluminum oxyhalide or said reaction product.
Claim 9
Dependent Claim
16 words
The process according to claim 1, wherein said vanadium halogen containing compound is: VCl.sub.4 or VOCl.sub.3
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) | 1985-11-01 | 1986-05-03 | 1986-11-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-11-01 | 1990-05-03 | 1990-11-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-11-01 | 1994-05-03 | 1994-11-02 | $7700.00 | Window Closed / Lapsed |