US4176219A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for the production of 1,2-polybutadiene with regulated molecular weight
Assignee: JSR Corp
•
Filing: 1978-05-30
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Granted: 1979-11-27
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Expires: 1998-05-30
Abstract
Abstract In the production of 1,2-polybutadiene by contacting 1,3-butadiene with a catalyst composed of (A) a cobalt compound, (B) an organic phosphine compound, (C) trialkylaluminum and (D) water in an amount of 0.25 to 1.5 moles per mole of said trialkylaluminum, the addition of (E) at least one compound selected from the group consisting of allyl halides, alkyl-substituted allyl halides, benzyl halides, alkyl-substituted benzyl halides, and tertiary aliphatic halides to the reaction system enables the molecular weight of the objective 1,2-polybutadiene to be regulated to any desired value without causing any change in microstructure and degree of crystallization of the product and also without deteriorating so much the polymerization activity.
Inventors
- 👤 Kenya Makino
- 👤 Tsunezo Ishikawa
- 👤 Koei Komatsu
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 20:07
CPC Classifications
C; C08; C08F; C08F136/00; C08F136/02; C08F136/04; C08F136/06
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
130 words
A process for producing 1,2-polybutadiene with a regulated molecular weight which comprises contacting 1,3-butadiene with a catalyst composed of (A) a cobalt compound selected from the group consisting of cobalt chloride, cobalt bromide, cobalt iodide, cobalt naphthenate, cobalt octanoate, cobalt trisacetylacetonate, cobalt bisacetylacetonate and cobalt carbonyl, (B) an organic phosphine compound selected from the group consisting of triethylphosphine, triisopropylphosphine, a tri-n-butylphosphine, triphenylphosphine, tri-m-phenylphosphine, tri-m-xylylphosphine, and tri-m-tolylphosphine, (C) a trialkylaluminum and (D) water in an amount of 0.55 to 1.5 moles per mole of said trialkylaluminum in the presence of (E) at least one compound selected from the group consisting of allyl halides, alkyl-substituted allyl halides, benzyl halides, alkyl-substituted benzyl halides, and tertiary aliphatic halides, in an amount of 0.01 to 10 moles of component (E) per mole of component (C).
Claim 2
Dependent Claim
130 words
A process for producing 1,2-polybutadiene with a regulated molecular weight which comprises contacting 1,3-butadiene with a catalyst composed of (A) a cobalt compound selected from the group consisting of cobalt chloride, cobalt bromide, cobalt iodide, cobalt naphthenate, cobalt octanoate, cobalt trisacetylacetonate, cobalt bisacetylacetonate and cobalt carbonyl, (B) an organic phosphine compound selected from the group consisting of triethylphosphine, triisopropylphosphine, a tri-n-butylphosphine, triphenylphosphine, tri-m-phenylphosphine, tri-m-xylylphosphine, and tri-m-tolylphosphine, (C) a trialkylaluminum and (D) water in an amount of 0.55 to 1.5 moles per mole of said trialkylaluminum in the presence of (E) at least one compound selected from the group consisting of allyl halides, alkyl-substituted allyl halides, benzyl halides, alkyl-substituted benzyl halides, and tertiary aliphatic halides, in an amount of 0.01 to 10 moles of component (E) per mole of component (C).
Claim 3
Dependent Claim
22 words
The process according to claim 1, wherein the amount of component (E) is 0.1 to 3 moles per mole of component (C).
Claim 4
Dependent Claim
23 words
The process according to claim 1, wherein 1,3-butadiene is contacted with the catalyst at a temperature ranging from -40° C. to 100° C.
Claim 5
Dependent Claim
28 words
The process according to any one of claims 1, 2 or 3, wherein components (A) and (B) are used in the form of a complex with each other.
Claim 6
Dependent Claim
35 words
The process according to claim 4, wherein the complex is a bis(triphenylphosphine) complex of cobalt chloride or bromide, a bis(tri-m-xylylphosphine) complex of cobalt chloride or bromide or a bis(tri-m-tolylphosphine) complex of cobalt chloride or bromide.
Claim 7
Dependent Claim
21 words
The process according to any one of claims 1, 2 or 3, wherein component (C) is trimethylaluminum, triethylaluminum, triisobutylaluminum or trihexylaluminum.
Claim 8
Dependent Claim
28 words
The process according to any one of claims 1, 2 or 3, wherein component (E) is selected from the group consisting of allyl halides and alkyl-substituted allyl halides.
Claim 9
Dependent Claim
30 words
The process according to claim 7, wherein component (E) is selected from the group consisting of allyl chloride, allyl bromide, allyl iodide, crotyl chloride, crotyl bromide, 1-bromo-2-butene, 1-chloro-2-butene and 1-bromo-2-methyl-2propene.
Claim 10
Dependent Claim
15 words
The process according to claim 7, wherein component (E) is allyl chloride or allyl bromide.
Claim 11
Dependent Claim
28 words
The process according to any one of claims 1, 2 or 3, wherein component (E) is selected from the group consisting of benzyl halides and alkyl-substituted benzyl halides.
Claim 12
Dependent Claim
33 words
The process according to claim 10, wherein component (E) is selected from the group consisting of benzyl chloride, benzyl bromide, benzyl iodide, p-methylbenzyl chloride, p-methylbenzyl bromide, o-methylbenzyl chloride, m-methylbenzyl chloride and p-tert-butylbenzyl chloride.
Claim 13
Dependent Claim
17 words
The process according to claim 10, wherein component (E) is benzyl chloride, benzyl bromide or p-methylbenzyl chloride.
Claim 14
Dependent Claim
25 words
The process according to any one of claims 1, 2 or 3, wherein component (E) is selected from the group consisting of tertiary aliphatic halides.
Claim 15
Dependent Claim
25 words
The process according to claim 13, wherein component (E) is selected from the group consisting of tert-butyl chloride, tert-butyl bromide, 2-chloro-2-methylbutane, 2-bromo-2-methylbutane, 2-chloro-2-methylpentane and 2-chloro-2-methylhexane.
Claim 16
Dependent Claim
15 words
The process according to claim 13, wherein component (E) is tert-butyl chloride or tert-butyl bromide.
Claim 17
Dependent Claim
31 words
The process according to any one of claims 1, 2 or 3, wherein the contact of 1,3-butadiene with the catalyst in the presence of component (E) is performed in a solvent.
Claim 18
Dependent Claim
16 words
The process according to claim 16, wherein the solvent is a hydrocarbon or a halogenated hydrocarbon.
Claim 19
Dependent Claim
16 words
The process according to claim 16, wherein the solvent is benzene, toluene, n-pentane, n-hexane or cyclohexane.
Claim 20
Dependent Claim
15 words
The process according to claim 16, wherein the solvent is methylene chloride, chloroform or chlorobenzene.
Claim 21
Dependent Claim
12 words
The process according to claim 16, wherein the solvent is methylene chloride.
Claim 22
Dependent Claim
26 words
The process according to claim 16, wherein the sequential order of addition to the solvent is component (D), butadiene, component (C), component (E) and component (A).
Claim 23
Dependent Claim
26 words
The process according to claim 16, wherein the sequential order of addition to the solvent is 1,3-butadiene, component (E), component (C), component (D) and component (A).
Claim 24
Dependent Claim
35 words
The process according to claim 16, wherein an aged mixture of component (C) and component (E) is added to a mixture of the solvent, 1,3-butadiene and component (D), and then component (A) is added thereto.
Claim 25
Dependent Claim
42 words
The process according to claim 16, wherein an aged mixture of component (E) and a part of component (C) is added to a mixture of the solvent, 1,3-butadiene and component (D), and then the remaining amount of component (C) is added thereto.
Claim 26
Dependent Claim
25 words
The process according to claim 1, wherein the amount of the organic phosphine compound is 0.2 to 50 mols per mol of the cobalt compound.
Claim 27
Dependent Claim
28 words
The process according to claim 1, wherein the amount of the catalyst used is 0.001 to 1 mmol in terms of the cobalt compound per mol of 1,3-butadiene.
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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) | 1982-11-26 | 1983-05-28 | 1983-11-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-11-26 | 1987-05-28 | 1987-11-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-11-26 | 1991-05-28 | 1991-11-27 | $7700.00 | Window Closed / Lapsed |