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Patent US4330650A successfully refreshed from Google Patents.
US4330650A
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Catalyst for polymerization of olefins
Assignee: Asahi Kasei Corp
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Filing: 1980-03-28
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Granted: 1982-05-18
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Expires: 2000-03-28
Abstract
Abstract Catalysts for polymerization of olefin which comprise a solid catalyst component (A) and an organometallic compound with a heterocyclic carboxylic acid ester (B), wherein the solid catalyst component (A) is obtained by reacting or/and grinding a special magnesium compound (1), a titanium halide (2) and a carboxylic acid ester (3); and the heterocyclic carboxylic acid ester is N-, S- or O-containing heterocyclic compound, and processes for polymerization of olefin employing such a catalyst.
Inventors
- 👤 Hisaya Sakurai
- 👤 Hideo Morita
- 👤 Masayoshi Miya
- 👤 Katsuhiko Takaya
- 👤 Haruyuki Yoneda
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 07:52
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 13
Claim 1
Independent Claim
360 words
In a process for the polymerization of olefins comprising contacting the olefins with a catalyst comprising a magnesium compound, a titanium compound, an electron donor, and an organometallic compound, wherein a solid (1) obtained by reacting one mole of (i) an organomagnesium component of the formula M.sub.α Mg.sub.β R.sup.1.sub.p R.sup.2.sub.q X.sub.r wherein α, p, q and r each independently≧0, β>0, p+q+r=mα+2β M is Al, Zn, B or Be, m is the valence of M, R 1 and R 2 are the same or different hydrocarbon groups having 1-20 carbon atoms, and X is a halogen atom, or of the reaction product of M.sub.α Mg.sub.β R 1 p R 2 q X r with an electron donor, with 0.01 to 100 moles of (ii) a chlorosilane compound containing Si--H bonds and of the formula H.sub.a SiCl.sub.b R.sup.3.sub.4-(a+b) wherein 0<a≦2, b>0, a+b≦4, and R 3 is a hydrocarbon group having 1-20 carbon atoms, is used as a catalyst raw material, a solid catalyst component (A) is obtained by reacting and/or grinding said solid (1), a titanium compound (2) selected from a tetravalent titanium compound containing at least one halogen atom and/or a halide of trivalent titanium, and a carboxylic acid ester (3) and said catalyst component (A) is used with a component (B) which includes an organometallic compound and a carboxylic acid ester (3), the improvement wherein said last-mentioned carboxylic acid ester (3) of component (B) is a nitrogen-, sulfur- and/or oxygen-containing heterocyclic carboxylic acid ester selected from the group consisting of pyrrol-carboxylic acid esters, indole-carboxylic acid esters, carbazole-carboxylic acid esters, oxazole-carboxylic acid esters, thiazole-carboxylic acid esters, imidazole-carboxylic acid esters, pyrazole-carboxylic acid esters, pyridine-carboxylic acid esters, phenanthridinecarboxylic acid esters, anthrazoline-carboxylic acid esters, phenanthroline-carboxylic acid esters, naphthylidine-carboxylic acid esters, oxadine-carboxylic acid esters, thiazine-carboxylic acid esters, pyridazine-carboxylic acid esters, pyrimidine-carboxylic acid esters, pyrazine-carboxylic acid esters, thianaphthene carboxylic acid esters, isothianaphthene carboxylic acid esters, benzothiophene carboxylic acid esters, phenoxathiin carboxylic acid esters, benzothiane carboxylic acid esters, thiaxanthene carboxylic acid esters, thioindoxyl carboxylic acid esters, furan carboxylic acid esters, dihydrofuran carboxylic acid esters, benzofuran carboxylic acid esters, coumaran carboxylic acid esters, pyran carboxylic acid esters, pyrone carboxylic acid esters, coumalic acid esters, and isocoumalic acid esters.
Claim 2
Dependent Claim
360 words
In a process for the polymerization of olefins comprising contacting the olefins with a catalyst comprising a magnesium compound, a titanium compound, an electron donor, and an organometallic compound, wherein a solid (1) obtained by reacting one mole of (i) an organomagnesium component of the formula M.sub.α Mg.sub.β R.sup.1.sub.p R.sup.2.sub.q X.sub.r wherein α, p, q and r each independently≧0, β>0, p+q+r=mα+2β M is Al, Zn, B or Be, m is the valence of M, R 1 and R 2 are the same or different hydrocarbon groups having 1-20 carbon atoms, and X is a halogen atom, or of the reaction product of M.sub.α Mg.sub.β R 1 p R 2 q X r with an electron donor, with 0.01 to 100 moles of (ii) a chlorosilane compound containing Si--H bonds and of the formula H.sub.a SiCl.sub.b R.sup.3.sub.4-(a+b) wherein 0<a≦2, b>0, a+b≦4, and R 3 is a hydrocarbon group having 1-20 carbon atoms, is used as a catalyst raw material, a solid catalyst component (A) is obtained by reacting and/or grinding said solid (1), a titanium compound (2) selected from a tetravalent titanium compound containing at least one halogen atom and/or a halide of trivalent titanium, and a carboxylic acid ester (3) and said catalyst component (A) is used with a component (B) which includes an organometallic compound and a carboxylic acid ester (3), the improvement wherein said last-mentioned carboxylic acid ester (3) of component (B) is a nitrogen-, sulfur- and/or oxygen-containing heterocyclic carboxylic acid ester selected from the group consisting of pyrrol-carboxylic acid esters, indole-carboxylic acid esters, carbazole-carboxylic acid esters, oxazole-carboxylic acid esters, thiazole-carboxylic acid esters, imidazole-carboxylic acid esters, pyrazole-carboxylic acid esters, pyridine-carboxylic acid esters, phenanthridinecarboxylic acid esters, anthrazoline-carboxylic acid esters, phenanthroline-carboxylic acid esters, naphthylidine-carboxylic acid esters, oxadine-carboxylic acid esters, thiazine-carboxylic acid esters, pyridazine-carboxylic acid esters, pyrimidine-carboxylic acid esters, pyrazine-carboxylic acid esters, thianaphthene carboxylic acid esters, isothianaphthene carboxylic acid esters, benzothiophene carboxylic acid esters, phenoxathiin carboxylic acid esters, benzothiane carboxylic acid esters, thiaxanthene carboxylic acid esters, thioindoxyl carboxylic acid esters, furan carboxylic acid esters, dihydrofuran carboxylic acid esters, benzofuran carboxylic acid esters, coumaran carboxylic acid esters, pyran carboxylic acid esters, pyrone carboxylic acid esters, coumalic acid esters, and isocoumalic acid esters.
Claim 3
Dependent Claim
24 words
A process for polymerizing olefins according to claim 1, wherein (3) of (B) is a lower alkyl ester of a nitrogen-containing heterocyclic carboxylic acid.
Claim 4
Dependent Claim
24 words
A process for polymerizing olefins according to claim 1, wherein (3) of (B) is a lower alkyl ester of a sulfur-containing heterocyclic carboxylic acid.
Claim 5
Dependent Claim
24 words
A process for polymerizing olefins according to claim 1, wherein (3) of (B) is a lower alkyl ester of an oxygen-containing heterocyclic carboxylic acid.
Claim 6
Dependent Claim
27 words
A process for polymerizing olefins according to claim 1, wherein solid catalyst component (A) is further treated with a halide of tetravalent titanium before combination with (B).
Claim 7
Dependent Claim
19 words
A process for polymerizing olefins according to claim 5, wherein the further treating tetravalent titanium halide is titanium tetrachloride.
Claim 8
Dependent Claim
25 words
A process for polymerizing olefins according to claim 1, wherein the organomagnesium component (i) is a hydrocarbon-soluble organomagnesium complex which corresponds to α>0 and r=0.
Claim 9
Dependent Claim
96 words
A process for polymerizing olefins according to claim 1, wherein the organomagnesium component (i) is a hydrocarbon-soluble organomagnesium compound wherein α=0, r=0, and (a) R 1 is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, and R 2 is a hydrocarbon group having 4 to 6 carbon atoms, or (b) R 1 is an alkyl group having 2 to 3 carbon atoms, and R 2 is an alkyl group having at least 4 carbon atoms, or (c) R 1 and R 2 both are alkyl groups having at least 6 carbon atoms.
Claim 10
Dependent Claim
24 words
A process for polymerizing olefins according to claim 1, wherein the organomagnesium component (i) is an organomagnesium halide wherein α=0, β=1, q=0 and r=1.
Claim 11
Dependent Claim
19 words
A process for polymerizing olefins according to claim 1, wherein α>0 and β/α is from about 0.5 to 10.
Claim 12
Dependent Claim
41 words
A process for polymerizing olefins according to claim 1, wherein carboxylic acid ester (3) of component (A) is reacted with the solid (1) in an amount of 0.001 to 50 mols per 1 mol of hydrocarbon group remaining in solid (1).
Claim 13
Dependent Claim
61 words
A process for polymerizing olefins according to claim 1, wherein the organometallic compound of component (B) is an organoaluminum compound represented by the general formula AlR 4 n Z 3-n , wherein R 4 is a hydrocarbon group having 1 to 20 carbon atoms; Z is hydrogen, halogen or an alkoxy, aryloxy or siloxy group; and n is 2 or 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) | 1985-05-17 | 1985-11-16 | 1986-05-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-05-17 | 1989-11-16 | 1990-05-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-05-17 | 1993-11-16 | 1994-05-18 | $7700.00 | Window Closed / Lapsed |