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US4461883A
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Process for producing conjugated diene polymer using a solubilized lanthanum carboxylate catalyst
Assignee: JSR Corp
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Filing: 1982-06-14
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Granted: 1984-07-24
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Expires: 2002-06-14
Abstract
Abstract A process for producing a conjugated diene polymer, characterized by polymerizing at least one conjugated diene with a catalyst consisting of (A) a reaction product of a Lewis base and a carboxylate of a rare earth element of the lanthanum series represented by Ln(R 1 CO 2 ) 3 wherein Ln is a rare earth element of the lanthanum series having an atomic number of 57 to 71 and R 1 is a hydrocarbon substituent having 1 to 20 carbon atoms, (B) an organic aluminum compound represented by AlR 2 R 3 R 4 wherein R 2 , R 3 and R 4 , which may be identical or different, represent hydrogen atoms or hydrocarbon substituents having 1 to 8 carbon atoms, excluding the case where all of R 2 , R 3 and R 4 are hydrogen atoms at the same time, and (C) an (alkyl)aluminum halide represented by AlX n R 5 3-n wherein X is Cl, Br, F or I; R 5 is a hydrocarbon substituent having 1 to 8 carbon atoms; and n has a value of 1, 1.5, 2 or 3, or consisting of these (A), (B) and (C) components and (D) a conjugated diene. A polymer obtained by said process has a high cis-1,4-configuration content and is excellent in physical properties of vulcanizate.
Inventors
- 👤 Yasumasa Takeuchi
- 👤 Mitsuhiko Sakakibara
- 👤 Tooru Shibata
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 10:31
CPC Classifications
C; C08; C08F; C08F36/00; C08F36/02; C08F36/04
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
235 words
A process for producing a conjugated diene polymer, characterized by polymerizing at least one conjugated diene in a hydrocarbon solvent by using a catalyst consisting of (A) a reaction product of a Lewis base wherein the Lewis base is acetylacetone, tetrahydrofuran, pyridine, N,N'-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound or a monohydric or dihydric C 1-10 alcohol, and a carboxylate of a rare earth element in the lanthanum series represented by the formula Ln(R 1 CO 2 ) 3 wherein Ln is a rare earth element in the lanthanum series having an atomic number of 57 to 71 and R 1 is a hydrocarbon substituent have 1 to 20 carbon atoms, (B) an organic aluminum compound represented by the formula AlR 2 R 3 R 4 where R 2 , R 3 and R 4 , which may be identical or different, represent hydrogen atoms or hydrocarbon substituents having 1 to 8 carbon atoms, excluding the case where all R 2 , R 3 and R 4 are hydrogen atoms at the same time, and (C) an (alkyl)aluminum halide represented by the formula AlX n R 3 3-n wherein X is Cl, Br, F or I; R 5 is an alkyl group having 1 to 8 carbon atoms; and n is a value of 1, 1.5, 2 or 3, or consisting of the (A), (B) and (C) constituents and (D) a conjugated diene.
Claim 2
Dependent Claim
235 words
A process for producing a conjugated diene polymer, characterized by polymerizing at least one conjugated diene in a hydrocarbon solvent by using a catalyst consisting of (A) a reaction product of a Lewis base wherein the Lewis base is acetylacetone, tetrahydrofuran, pyridine, N,N'-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound or a monohydric or dihydric C 1-10 alcohol, and a carboxylate of a rare earth element in the lanthanum series represented by the formula Ln(R 1 CO 2 ) 3 wherein Ln is a rare earth element in the lanthanum series having an atomic number of 57 to 71 and R 1 is a hydrocarbon substituent have 1 to 20 carbon atoms, (B) an organic aluminum compound represented by the formula AlR 2 R 3 R 4 where R 2 , R 3 and R 4 , which may be identical or different, represent hydrogen atoms or hydrocarbon substituents having 1 to 8 carbon atoms, excluding the case where all R 2 , R 3 and R 4 are hydrogen atoms at the same time, and (C) an (alkyl)aluminum halide represented by the formula AlX n R 3 3-n wherein X is Cl, Br, F or I; R 5 is an alkyl group having 1 to 8 carbon atoms; and n is a value of 1, 1.5, 2 or 3, or consisting of the (A), (B) and (C) constituents and (D) a conjugated diene.
Claim 3
Dependent Claim
21 words
A process according to claim 1, wherein the rare earth element in the lanthanum series is cerium, praseodymium, neodymium or gadolinium.
Claim 4
Dependent Claim
17 words
A process according to claim 1, wherein the rare earth element in the lanthanum series is neodymium.
Claim 5
Dependent Claim
52 words
A process according to claim 1, wherein R 1 CO 2 is the residue of acetic acid, propionic acid, isobutyric acid, n-valeric acid, isovaleric acid, pivalic acid, n-hexanoic acid, 3,3-dimethylbutyric acid, n-heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, naphthenic acid, stearic acid, lauric acid, palmitic acid or oleic acid.
Claim 6
Dependent Claim
28 words
A process according to claim 3, wherein R 1 CO 2 is the residue of octanoic acid, 2-ethylhexanoic acid, benzoic acid, naphthenic acid, oleic acid or stearic acid.
Claim 7
Dependent Claim
20 words
A process according to claim 1, wherein the polymerization is effected at a temperature of -30° C. to 120° C.
Claim 8
Dependent Claim
67 words
A process according to claim 1 or 4, wherein the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-pentyl alcohol, isopentyl alcohol, 2-methyl-1-butyl alcohol, 2-methyl-2-butyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, isooctyl alcohol, 2-ethylhexyl alcohol, n-nonyl alcohol, n-decyl alcohol, 1,5-pentanediol, 1,6-hexanediol, allyl alcohol, crotyl alcohol, 3-hexen-1-ol, citronellol, cyclopentanol, cyclohexanol, salicyl alcohol, benzyl alcohol, phenethyl alcohol or cinnamyl alcohol.
Claim 9
Dependent Claim
20 words
A process according to claim 1 or 5, wherein the Lewis base is acetylacetone, methyl alcohol, ethyl alcohol or pyridine.
Claim 10
Dependent Claim
42 words
A process according to claim 1, wherein the organic aluminum compound represented by AlR 2 R 3 R 4 is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride or a mixture of two or more of them.
Claim 11
Dependent Claim
33 words
A process according to claim 1, wherein the organic aluminum compound represented by AlR 2 R 3 R 4 is triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride or a mixture of two or more of them.
Claim 12
Dependent Claim
97 words
A process according to claim 1, wherein the organic aluminum compound represented by AlR 2 R 3 R 4 is a mixture of (B') a tri-organic aluminum compound represented by AlR 2' 3 wherein R 2' is a C 1-8 hydrocarbon group and (B") an organic aluminum hydride represented by AlH m R 2' 3-m wherein R 2' is as defined above and m is a value of 1 or 2, in which mixture the (B')/(B") molar ratio is 95/5-25/75; the (B')+(B")/(A) molar ratio is at least 10; and the (C)/(A) molar ratio is 0.1/1 to 10/1.
Claim 13
Dependent Claim
58 words
A process according to claim 1, wherein the (alkyl)aluminum halide represented by AlX n R 5 3-n is dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diethylaluminum fluoride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, sesquimethylaluminum chloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, aluminum trichloride, aluminum tribromide, aluminum triiodide, aluminum trifluoride or a mixture thereof.
Claim 14
Dependent Claim
31 words
A process according to claim 1, wherein the carboxylate of a rare earth element and the Lewis base are reacted with each other in a molar ratio of 1:0.01 to 1:100.
Claim 15
Dependent Claim
31 words
A process according to claim 1, wherein the carboxylate of a rare earth element and the Lewis base are reacted with each other in a molar ratio of 1:0.05 to 1:50.
Claim 16
Dependent Claim
31 words
A process according to claim 1, wherein the carboxylate of a rare earth element and the Lewis base are reacted with each other in a molar ratio of 1:0.1 to 1:30.
Claim 17
Dependent Claim
34 words
A process according to claim 1, wherein the (B) constituent is used in a proportion of 2 to 300 moles per mole of the carboxylate of a rare earth element for the (A) constituent.
Claim 18
Dependent Claim
34 words
A process according to claim 1, wherein the (B) constituent is used in a proportion of 20 to 150 moles per mole of the carboxylate of a rare earth element for the (A) constituent.
Claim 19
Dependent Claim
36 words
A process according to claim 10 or 16, wherein the (C) constituent is used in a proportion of 0.5 to 10 moles per mole of the carboxylate of a rare earth element for the (A) constituent.
Claim 20
Dependent Claim
34 words
A process according to claim 17, wherein the (C) constituent is used in a proportion of 1 to 5 moles per mole of the carboxylate of a rare earth element for the (A) constituent.
Claim 21
Dependent Claim
38 words
A process according to claim 1, wherein the conjugated diene as the (D) constituent is used in a proportion of 100 moles or less per mole of the carboxylate of a rare earth element for the (A) constituent.
Claim 22
Dependent Claim
38 words
A process according to claim 1, wherein the conjugated diene as the (D) constituent is used in a proportion of 0.5 to 500 moles per mole of the carboxylate of a rare earth element for the (A) constituent.
Claim 23
Dependent Claim
40 words
A process according to claim 1 or 19, wherein the conjugated diene as the (D) constituent is used in a proportion of 2 to 100 moles per mole of the carboxylate of a rare earth element for the (A) constituent.
Claim 24
Dependent Claim
20 words
A process according to claim 1 or 20, wherein the conjugated diene is isoprene, butadiene, 1,3-pentadiene or a mixture thereof.
Claim 25
Dependent Claim
23 words
A process according to claim 1, wherein the hydrocarbon solvent is butane, n-pentane, isopentane, n-hexane, cyclohexane, cycloheptane, benzene, toluene or a mixture thereof.
Claim 26
Dependent Claim
30 words
A process according to claim 1 or 24, wherein the hydrocarbon solvent contains a substituted aromatic hydrocarbon having an active hydrogen, in a proportion of 80% by weight or less.
Claim 27
Dependent Claim
20 words
A process according to claim 25, wherein the proportion of the substituted aromatic hydrocarbon is 1 to 50% by weight.
Claim 28
Dependent Claim
19 words
A process according to claim 25, wherein the substituted aromatic hydrocarbon has an active hydrogen at the benzyl position.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-07-24 | 1988-01-23 | 1988-07-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-07-24 | 1992-01-23 | 1992-07-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-07-24 | 1996-01-23 | 1996-07-24 | $7700.00 | Window Closed / Lapsed |