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US4153767A
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Method of producing 1,2-polybutadiene
Assignee: Ube Corp
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Filing: 1977-11-22
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Granted: 1979-05-08
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Expires: 1997-11-22
Abstract
Abstract Butadiene polymers containing 70% or more of 1,2-structure and a relatively low melting point are produced by polymerizing 1,3-butadiene in the presence of a catalyst which has been prepared by admixing (A) an organic solvent solution containing 1,3-butadiene, a cobalt compound and an organoaluminium compound; (B) an amide compound of the formula (2) or (3): <IMAGE> (2) or <IMAGE> (3) wherein R1, R2 and R3 are respectively an H atom, aliphatic hydrocarbon radical of 1 to 7 carbon atoms or aromatic hydrocarbon radical of 6 or 7 carbon atoms, R3 is H or an aliphatic hydrocarbon radical of 1 to 3 carbon atoms and n is 2 to 5, and; (C) carbon disulfide.
Inventors
- 👤 Haruo Ueno
- 👤 Kyohei Oizumi
- 👤 Hideo Ishikawa
- 👤 Kohei Nakajima
- 👤 Nobuhiro Tsujimoto
- 👤 Osamu Kimura
- 👤 Hideyuki Aikawa
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 13:09
CPC Classifications
C; C08; C08F; C08F136/00; C08F136/02; C08F136/04; C08F136/06
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
101 words
A process for producing 1,2-polybutadiene comprising polymerizing 1,3-butadiene in the presence of a catalyst which has been prepared by admixing: (A) a catalyst component solution prepared by dissolving, in an organic solvent containing at least a portion of 1,3-butadiene to be polymerized, (a) at least one cobalt compound which is soluble in said organic solvent and (b) at least one organoaluminum compound of the formula (1) AIR.sub.3 ( 1) wherein R represents an aliphatic hydrocarbon radical having 1 to 6 carbon atoms, an alicyclic hydrocarbon radical having 3 to 6 carbon atoms or phenyl radical; (B) N,N-dimethylformamide and; (C) carbon disulfide.
Claim 2
Dependent Claim
101 words
A process for producing 1,2-polybutadiene comprising polymerizing 1,3-butadiene in the presence of a catalyst which has been prepared by admixing: (A) a catalyst component solution prepared by dissolving, in an organic solvent containing at least a portion of 1,3-butadiene to be polymerized, (a) at least one cobalt compound which is soluble in said organic solvent and (b) at least one organoaluminum compound of the formula (1) AIR.sub.3 ( 1) wherein R represents an aliphatic hydrocarbon radical having 1 to 6 carbon atoms, an alicyclic hydrocarbon radical having 3 to 6 carbon atoms or phenyl radical; (B) N,N-dimethylformamide and; (C) carbon disulfide.
Claim 3
Dependent Claim
76 words
A process as claimed in claim 1, wherein said cobalt compound is selected from β-diketone complexes of cobalt, β-ketoester complexes of cobalt, cobalt salts of organic carboxylic acids having 6 to 15 carbon atoms and halogenated cobalt complexes of the formula (6) CoX.sub.l.Y.sub.m ( 6) wherein X represents a halogen atom, Y represent a ligand of the cobalt atom, l represents an integer of 2 or 3 and m represents an integer of 1 to 4.
Claim 4
Dependent Claim
71 words
A process as claimed in claim 2, wherein said β-diketone complexes of cobalt have been prepared by using, as a ligand of the cobalt atom, a β-diketone of the formula (4) ##STR7## wherein R 5 and R 8 represent an aliphatic hydrocarbon radical having 1 to 3 carbon atoms, respectively, and R 6 and R 7 represent a hydrogen atom or aliphatic hydrocarbon radical having 1 to 3 carbon atoms, respectively.
Claim 5
Dependent Claim
23 words
A process as claimed in claim 3, wherein said β-diketone complex of cobalt is selected from cobalt (II) acetylacetonate and cobalt (III) acetylacetonate.
Claim 6
Dependent Claim
71 words
A process as claimed in claim 2, wherein said β-ketoester complexes of cobalt have been prepared by using, as a ligand of the cobalt atom, a ketoester of the formula (5) ##STR8## wherein R 5 and R 8 represent an aliphatic hydrocarbon radical having 1 to 3 carbon atoms, respectively, and R 6 and R 7 represent a hydrogen atom or aliphatic hydrocarbon radical having 1 to 3 carbon atoms, respectively.
Claim 7
Dependent Claim
19 words
A process as claimed in claim 5, wherein said ketoester complex of cobalt is a cobalt-acetoacetic ethyl ester complex.
Claim 8
Dependent Claim
25 words
A process as claimed in claim 2, wherein said cobalt salt of organic carboxylic acid is selected from cobalt octoate, cobalt naphthenate and cobalt benzoate.
Claim 9
Dependent Claim
25 words
A process as claimed in claim 2, wherein said ligand in said halogenated cobalt complexes is selected from tertiary amines, alcohols, tertiary phosphines and N,N-dialkylamides.
Claim 10
Dependent Claim
22 words
A process as claimed in claim 8, wherein said tertiary amine is selected from pyridine, triethyl amine, tributyl amine and dimethyl aniline.
Claim 11
Dependent Claim
18 words
A process as claimed in claim 8, wherein said alcohol is selected from methyl alcohol and ethyl alcohol.
Claim 12
Dependent Claim
19 words
A process as claimed in claim 8, wherein said tertiary phosphine is selected from triphenyl phosphine and tributyl phosphine.
Claim 13
Dependent Claim
17 words
A process as claimed in claim 8, wherein said N,N-dialkylamide is selected from N,N-dimethylformamide, N,N-dimethylacetamide and N,N-diethylformamide.
Claim 14
Dependent Claim
31 words
A process as claimed in claim 8, wherein said halogenated cobalt complex is selected from a complex of cobalt chloride with pyridine and a complex of cobalt chloride with ethyl alcohol.
Claim 15
Dependent Claim
18 words
A process as claimed in claim 1, wherein said organoaluminium compound is selected from trimethylaluminium, triethylaluminium and triphenylaluminium.
Claim 16
Dependent Claim
37 words
A process as claimed in claim 1, wherein said organic solvent is selected from aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated compounds of the above-mentioned hydrocarbon compounds and mixtures of two or more of the above-mentioned compounds.
Claim 17
Dependent Claim
25 words
A process as claimed in claim 1, wherein said organic solvent consists of at least one selected from benzene, toluene, xylene, n-hexane, n-heptane, cyclohexane, chlorobenzene.
Claim 18
Dependent Claim
16 words
A process as claimed in claim 1, wherein said 1,3-butadiene is polymerized in an organic solvent.
Claim 19
Dependent Claim
23 words
A process as claimed in claim 17, wherein said organic solvent is the same as the organic solvent used for preparing the catalyst.
Claim 20
Dependent Claim
19 words
A process as claimed in claim 1, wherein said catalyst component solution is aged for at least 30 seconds.
Claim 21
Dependent Claim
33 words
A process as claimed in claim 1, wherein the amount of said 1,3-butadiene to be dissolved in said catalyst component solution is at least 1 mole per mole of said cobalt compound used.
Claim 22
Dependent Claim
20 words
A process as claimed in claim 1, wherein said organic solvent contains the entire amount of 1,3-butadiene to be polymerized.
Claim 23
Dependent Claim
22 words
A process as claimed in claim 1, wherein said catalyst has been prepared at a temperature of from 10° to 50° C.
Claim 24
Dependent Claim
33 words
A process as claimed in claim 1, wherein said cobalt compound is used in an amount of from 0.0001 to 1% by mole based on the entire amount of 1,3-butadiene to be polymerized.
Claim 25
Dependent Claim
33 words
A process as claimed in claim 1, wherein said organoaluminium compound is used in an amount of from 0.001 to 10% by mole based on the entire amount of 1,3-butadiene to be polymerized.
Claim 26
Dependent Claim
34 words
A process as claimed in claim 1, wherein said carbon disulfide is used in an amount of from 0.0005 to 2% by mole based on the entire amount of said 1,3-butadiene to be polymerized.
Claim 27
Dependent Claim
30 words
A process as claimed in claim 1, wherein the ratio by mole of said organoaluminium compound to said cobalt compound (Al/Co) is in a range of from 0.1 to 30.
Claim 28
Dependent Claim
17 words
A process as claimed in claim 1, wherein the resultant 1,2-polybutadiene contains at least 70% of 1,2-structure.
Claim 29
Dependent Claim
14 words
A process as claimed in claim 27, wherein said 1,2-structure is a syndiotactic 1,2-structure.
Claim 30
Dependent Claim
21 words
A process as claimed in claim 1, wherein the resultant 1,2-polybutadiene has a melting point of from 70° to 200° C.
Claim 31
Dependent Claim
22 words
A process as claimed in claim 1, wherein said polymerization is carried out at a temperature of from -20° to 80° C.
Claim 32
Dependent Claim
18 words
A process as claimed in claim 1, wherein said polymerization is carried out in a solution polymerization system.
Claim 33
Dependent Claim
28 words
A process as claimed in claim 31, wherein the concentration of 1,3-butadiene in the solution polymerization system is in a range of from 3 to 50% by weight.
Claim 34
Dependent Claim
18 words
A process as claimed in claim 1, wherein said polymerization is carried out in a bulk polymerization system.
Claim 35
Dependent Claim
33 words
A process as claimed in claim 1, wherein the amount of N,N-dimethylformamide is in a range of from 0.1 to 40% by mole based on the entire amount of 1,3-butadiene to be polymerized.
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) | 1982-05-07 | 1982-11-06 | 1983-05-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-05-07 | 1986-11-06 | 1987-05-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-05-07 | 1990-11-06 | 1991-05-08 | $7700.00 | Window Closed / Lapsed |