US3901868A
Expired / Lapsed
US
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Process for producing butadiene polymers
Assignee: Ube Corp
•
Filing: 1974-09-20
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Granted: 1975-08-26
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Expires: 1994-09-20
Abstract
Abstract A butadiene polymer consisting essentially of syndiotactic 1,2polybutadiene is produced by the successive steps of: (A) preparing a catalyst component solution by dissolving, in an inert organic solvent containing 1,3-butadiene, a cobalt compound, soluble in the organic solvent, such as (i) cobaltBeta -diketone complex, (ii) cobalt- Beta -keto-acid ester complex, (iii) cobalt salt of organic carboxylic acid and (iv) halogenated cobalt-ligand compound complex, and an organoaluminum commpound, (B) preparing a catalyst composition by mixing the catalyst component solution with an alcohol, ketone or aldehyde compound and carbon disulfide; (C) providing a polymerization mixture containing desired amounts of 1,3-butadiene, the catalyst composition and an inert organic solvent, and (D) polymerizing 1,3-butadiene at a temperature of -20* to 80*C.
Inventors
- 👤 Haruo Ueno
- 👤 Kyohei Oizumi
- 👤 Hideo Ishikawa
- 👤 Hisawaki Hamada
- 👤 Hideyuki Aikawa
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 05:05
CPC Classifications
C; C08; C08F; C08F136/00; C08F136/02; C08F136/04; C08F136/06
Claims Analysis
Total Claims: 47
Claim 1
Independent Claim
219 words
A PROCESS FOR PRODUCTING A BUTADIENE POLYMER COMPOSED ESSENTIALLY OF 1,2-STRUCTURE, COMPRISING THE STEPS OF: A. PREPARING A CATALYST COMPONENT SOLUTION BY DISSOLVING, IN AN INERT ORGANIC SLOVENT CONTAINING 1,3-BUTADIENE, (A) AT LEAST ONE COBALT COMPOUND SELECTED FROM THE GROUP CONSISTING OF (I) B-DIKETONE COMPLEXES OF COBALT, (II) B-KETOACID ESTER COMPLEXES OF COBALT, (III) COBALT SALTS OF ORGANIC CARBOXYLIC ACIDS HAVING 6 TO 15 CARBON ATOMS, AND (IV) COMPLEXES OF HALOGENATED COBALT COMPOUNDS OF THE FORMULA COXN, WHEREIN X REPERSENTS A HALOGEN ATOM AND N REPRESENTS 2 OR 3, WITH AN ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF TERTIARY AMINES ALCOHOLS, TERTIARY PHOSPHINES, KETONES AND N, N-DIALKY-AMIDES, AND (B) AT LEAST ONE ORGANOALUMINUM COMPOUND OF THE FORMULA AIR3, WHEREIN R REPRESENTS A HYDROCARBON RADICAL OF 1 TO 6 CARBON ATOMS: B. PREPARING A CATALYST COMPOSITION BY MIXING SAID CATALYST COMPONENT SOLUTION WITH (C) AT LEAST ONE ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALCOHOL COMPOUNDS HAVING 1 TO 25 CARBON ATOMS, KETONE COMPOUNDS HAVING 3 TO 20 CARBON ATOMS AND ALDEHYDE COMPOUNDS HAVING 1 TO 20 CARBON ATOMS AND (D) CARBON DISULFIDE: C. PROVIDING A POLYMERIZATION MIXTURE CONTAINING DESIRED AMOUNTS OF 1,3- BUTADIENE, SAID CATALYST COMPOSITION AND AN INERT ORGANIC SOLVENT, AND: D. POLYMERIZING SAID 1,3-BUTADIENE IN SAID POLYMERIZATION MIXTURE AT A TEMPERATURE OFF -20* TO 80*C.
Claim 2
Dependent Claim
219 words
A PROCESS FOR PRODUCTING A BUTADIENE POLYMER COMPOSED ESSENTIALLY OF 1,2-STRUCTURE, COMPRISING THE STEPS OF: A. PREPARING A CATALYST COMPONENT SOLUTION BY DISSOLVING, IN AN INERT ORGANIC SLOVENT CONTAINING 1,3-BUTADIENE, (A) AT LEAST ONE COBALT COMPOUND SELECTED FROM THE GROUP CONSISTING OF (I) B-DIKETONE COMPLEXES OF COBALT, (II) B-KETOACID ESTER COMPLEXES OF COBALT, (III) COBALT SALTS OF ORGANIC CARBOXYLIC ACIDS HAVING 6 TO 15 CARBON ATOMS, AND (IV) COMPLEXES OF HALOGENATED COBALT COMPOUNDS OF THE FORMULA COXN, WHEREIN X REPERSENTS A HALOGEN ATOM AND N REPRESENTS 2 OR 3, WITH AN ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF TERTIARY AMINES ALCOHOLS, TERTIARY PHOSPHINES, KETONES AND N, N-DIALKY-AMIDES, AND (B) AT LEAST ONE ORGANOALUMINUM COMPOUND OF THE FORMULA AIR3, WHEREIN R REPRESENTS A HYDROCARBON RADICAL OF 1 TO 6 CARBON ATOMS: B. PREPARING A CATALYST COMPOSITION BY MIXING SAID CATALYST COMPONENT SOLUTION WITH (C) AT LEAST ONE ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALCOHOL COMPOUNDS HAVING 1 TO 25 CARBON ATOMS, KETONE COMPOUNDS HAVING 3 TO 20 CARBON ATOMS AND ALDEHYDE COMPOUNDS HAVING 1 TO 20 CARBON ATOMS AND (D) CARBON DISULFIDE: C. PROVIDING A POLYMERIZATION MIXTURE CONTAINING DESIRED AMOUNTS OF 1,3- BUTADIENE, SAID CATALYST COMPOSITION AND AN INERT ORGANIC SOLVENT, AND: D. POLYMERIZING SAID 1,3-BUTADIENE IN SAID POLYMERIZATION MIXTURE AT A TEMPERATURE OFF -20* TO 80*C.
Claim 3
Dependent Claim
37 words
A process as claimed in claim 1, wherein said catalyst component solution is prepared by firstly dissolving said cobalt compound into said inert organic solvent containing 1,3-butadiene and secondly dissolving said organoaluminum compound into the above solution.
Claim 4
Dependent Claim
64 words
A process as claimed in claim 1, wherein said catalyst composition contains 0.0005 to 1.0% by mole of said cobalt compound, 0.001 to 10% by mole of said organoaluminum compound, 0.5 to 5,000% by mole of said alcohol, ketone or aldehyde and 0.0005 to 2% by mole of said carbon disulfide, based on the amount by mole of said 1,3-butadiene in said polymerization mixture.
Claim 5
Dependent Claim
60 words
A process as claimed in claim 3, wherein said cobalt compound is in an amount of 0.001 to 0.5% by mole, said organoaluminum compound in 0.03 to 5% by mole, said alcohol, ketone or aldehyde in 1 to 1,000% by mole and said carbon disulfide in 0.001 to 1% by mole, based on the amount by mole of said 1,3-butadiene.
Claim 6
Dependent Claim
21 words
A process as claimed in claim 1, wherein said catalyst component solution is prepared at a temperature of 10* to 50*C.
Claim 7
Dependent Claim
38 words
A process as claimed in claim 1, wherein said catalyst component solution is prepared by using an inert organic solvent containing at least 100% by mole of 1,3-butadiene based on the amount by mole of said cobalt compound.
Claim 8
Dependent Claim
29 words
A process as claimed in claim 6, wherein the amount of said 1,3-butadiene is at least 500% by mole based on the amount by mole of said cobalt compound.
Claim 9
Dependent Claim
31 words
A process as claimed in claim 1, wherein the ratio by mole of the amount of said organoaluminum compound to said cobalt compound is in a range from 0.1 to 500.
Claim 10
Dependent Claim
28 words
A process as claimed in claim 8, wherein said ratio by mole of the amount of said organoaluminum compound to said cobalt compound is from 0.5 to 100.
Claim 11
Dependent Claim
20 words
A process as claimed in claim 1, wherein said catalyst composition is prepared at a temperature of 10* to 50*C.
Claim 12
Dependent Claim
34 words
A process as claimed in claim 1, wherein the ratio by mole of the amount of said alcohol, ketone or aldehyde compound to said organoaluminum compound is in a range from 5 to 25,000.
Claim 13
Dependent Claim
31 words
A process as claimed in claim 11, wherein the ratio by mole of the amount of said alcohol, ketone or aldehyde compound to said organoaluminum compound is from 10 to 5,000.
Claim 14
Dependent Claim
16 words
A process as claimed in claim 1, wherein said polymerization temperature is from 5* to 50*C.
Claim 15
Dependent Claim
31 words
A process as claimed in claim 1, wherein said 1,3-butadiene to be polymerized is in an amount of 2 to 30% based on said inert organic solvent in said polymerization mixture.
Claim 16
Dependent Claim
32 words
A process as claimed in claim 1, wherein said catalyst composition further contains water in a ratio by mole of 0.01 to 5,000 to the amount by mole of said cobalt compound.
Claim 17
Dependent Claim
140 words
A process as claimed in claim 1, wherein said catalyst component solution is prepared by firstly dissolving said orgaNoaluminum compound in said inert organic solvent containing 1,3-butadiene and secondly dissolving said cobalt compound in the above-prepared solution, and said catalyst component solution contains water, said organoaluminum compound and said cobalt compound in a ratio by mole percentage of a : b : c, said proportion a, b and c being on or within a figure defined, in a triangular coordinate system having three ordinates respectively presenting the mole percentages of said water, organoaluminum compound and cobalt compound, by coordinates A (a 49.8, b 50 and c 0.2), B (a 0, b 99.8 and c 0.2), C (a 0, b 25 and c 75), D (a 20, b 25 and c 55) and E (a 20, b 55 and c 25).
Claim 18
Dependent Claim
30 words
A process as claimed in claim 16, wherein said inert organic solvent contains no or at most 500 p.p.m. of water based on the weight of said inert organic solvent.
Claim 19
Dependent Claim
26 words
A process as claimed in claim 17, wherein said amount of water is at most 200 p.p.m. based on the weight of said inert organic solvent.
Claim 20
Dependent Claim
44 words
A process as claimed in claim 1, wherein said inert organic solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated alicyclic hydrocarbons, and mixtures of two or more of the above-mentioned compounds.
Claim 21
Dependent Claim
26 words
A process as claimed in claim 19, wherein said polymerization mixture further contains the same inert organic solvent as that used in said catalyst component solution.
Claim 22
Dependent Claim
21 words
A process as claimed in claim 1, wherein said Beta -diketone complex of cobalt has a diketone group of the formula:
Claim 23
Dependent Claim
23 words
A process as claimed in claim 1, wherein said Beta -diketone complex of cobalt is either cobalt (II) acetylacetonate or cobalt (III) acetylacetonate.
Claim 24
Dependent Claim
24 words
A process as claimed in claim 1, wherein said Beta -keto-acid ester complex of cobalt has a Beta -keto-acid ester group of the formula:
Claim 25
Dependent Claim
22 words
A process as claimed in claim 1, wherein said Beta -keto-acid ester complex of cobalt is a cobalt-acetacetic acid ethyl ester complex.
Claim 26
Dependent Claim
18 words
A process as claimed in claim 1, wherein said cobalt salt is either cobalt octoate or cobalt naphthenate.
Claim 27
Dependent Claim
26 words
A process as claimed in claim 1, wherein said complex of halogenated cobalt compound is either a complex of cobalt chloride with pyridine or ethyl alcohol.
Claim 28
Dependent Claim
22 words
A process as claimed in claim 1, said organoaluminum compound is selected from the group consisting of trimethylaluminum, triethylaluminum, tributylaluminum and triphenylaluminum.
Claim 29
Dependent Claim
31 words
A process as claimed in claim 1, wherein said alcohol is selected from the group consisting of monohydric alcohols, polyhydric alcohols and polyhydric alcohol derivatives having at least one hydroxyl radical.
Claim 30
Dependent Claim
31 words
A process as claimed in claim 28, wherein said monohydric alcohol is selected from the group consisting of saturated aliphatic alcohols, unsaturated aliphatic alcohols, alicyclic alcohols, aromatic alcohols and heterocyclic alcohols.
Claim 31
Dependent Claim
67 words
A process as claimed in claim 29, wherein said saturAted aliphatic alcohol is selected from the group consisting of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tertbutyl alcohol, isobutyl alcohol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, n-hexyl alcohol, 2-ethylbutyl alcohol, n-heptyl alcohol, 2-heptyl alcohol, n-octyl alcohol, 2-octyl alcohol, 2-ethylhexyl alcohol, capryl alcohol, nonyl alcohol, n-decyl alcohol, lauryl alcohol and 4-methylpentanol-2.
Claim 32
Dependent Claim
26 words
A process as claimed in claim 29, wherein said unsaturated aliphatic alcohol is selected from the group consisting of allyl alcohol, crotyl alcohol and propargyl alcohol.
Claim 33
Dependent Claim
24 words
A process as claimed in claim 29, wherein said alicyclic alcohol is selected from the group consisting of cyclopentanol, cyclohexanol, 2-methylcyclohexanol and Alpha -terpineol.
Claim 34
Dependent Claim
25 words
A process as claimed in claim 29, wherein said aromatic alcohol is selected from the group consisting of benzyl alcohol, cinnamyl alcohol and triphenyl carbinol.
Claim 35
Dependent Claim
18 words
A process as claimed in claim 29, wherein said heterocyclic alcohol is either furfuryl alcohol or tetrahydrofurfuryl alcohol.
Claim 36
Dependent Claim
34 words
A process as claimed in claim 28, wherein said polyhydric alcohol is selected from ethylene glycol, propylene glycol, 1,3-butane diol, 1,5-pentane diol, 1,6-hexane diol, 1,10-decane diol, glycerin, 1,1,1-tris-hydroxypropane, 1,2,6-hexane triol, pentaerythritol and trimethylol propane.
Claim 37
Dependent Claim
42 words
A process as claimed in claim 28, wherein said polyhydric alcohol derivative is selected from the group consisting of ethylene glycol monoalkyl ether, diethylene glycol, diethylene glycol monoalkyl ether, triethylene glycol, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether and diacetone alcohol.
Claim 38
Dependent Claim
27 words
A process as claimed in claim 1, wherein said ketone compound is selected from the group consisting of aliphatic ketones, alicyclic ketones, aromatic ketones and heterocyclic ketones.
Claim 39
Dependent Claim
39 words
A process as claimed in claim 37, wherein said aliphatic ketone is selected from the group consisting of acetone, acetylacetone, ethylmethyl ketone, methylpropyl ketone, iso-propylmethyl ketone, butylmethyl ketone, isobutylmethyl ketone, pinacolone, diethyl ketone, butyrone, di-isopropyl ketone and di-isobutyl ketone.
Claim 40
Dependent Claim
23 words
A process as claimed in claim 37, wherein said alicyclic ketone is selected from the group consisting of cyclobutanone, cyclopentanone, cyclohexanone and cyclododecanone.
Claim 41
Dependent Claim
27 words
A process as claimed in claim 37, wherein said aromatic ketone is selected from the group consisting of acetophenone, propiophenone, butylophenone, valerophenone, benzophenone, dibenzyl ketone and 2-aceto-naphthone.
Claim 42
Dependent Claim
16 words
A process as claimed in claim 39, wherein said heterocyclic ketone is either 3-acetothienone or 2-acetofuron.
Claim 43
Dependent Claim
26 words
A process as claimed in claim 1, wherein said aldehyde compound is selected from the group consisting of aliphatic aldehydes, aliphatic dialdehydes, aromatic aldehydes, heterocyclic aldehydes.
Claim 44
Dependent Claim
51 words
A process as claimed in claim 42, wherein said aliphatic aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, n-butyl aldehyde, isobutyl aldehyde, n-valeraldehyde, isovaleraldehyde, pivalic aldehyde, caproic aldehyde, heptaldehyde, caprylic aldehyde, pelargonaldehyde, capric aldehyde, undecyl aldehyde, lauric aldehyde, tridecyl aldehyde, mystic aldehyde, pentadecylaldehyde, palmitic aldehyde and stearic aldehyde.
Claim 45
Dependent Claim
16 words
A process as claimed in claim 42, wherein said aliphatic dialdehyde is either glyoxal or succindialdehyde.
Claim 46
Dependent Claim
35 words
A process as claimed in claim 42, wherein said aromatic aldehyde is selected from the group consisting of benzaldehyde, o- m- and p-tolualdehydes, salicyl aldehyde, Alpha - and Beta -naphthoaldehydes and o-, m- and p-anisaldehydes.
Claim 47
Dependent Claim
13 words
A process as claimed in claim 42, wherein said heterocyclic aldehyde is furfural.
References Cited (Backward Citations)
US3778424A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-08-25 | 1979-02-24 | 1979-08-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-08-25 | 1983-02-24 | 1983-08-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-08-25 | 1987-02-24 | 1987-08-26 | $7700.00 | Window Closed / Lapsed |