US3846389A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Production of alternating copolymers of conjugated dienes and conjugated polar vinyl monomers
Assignee: Individual
•
Filing: 1972-03-28
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Granted: 1974-11-05
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Expires: 1992-03-28
Abstract
Abstract Novel alternating copolymers of conjugated dienes and conjugated polar vinyl monomers, wherein the conjugated diene unit is connected in a trans-1,4 form and the conjugated polar vinyl monomer unit and the conjugated diene unit are bonded alternately, are produced efficiently by copolyermizing these monomers in a non-aqueous medium at rather low temperature by using a catalyst system prepared by admixing a selected transition metal compound and an organoaluminum halide in the presence of the polar vinyl monomer or another selected Lewis base. The alternating copolymer here obtained has a regular structure, on this account, for example, the butadiene/acrylonitrile elastic alternating copolymer can be oriented and crystallized under a highly stretched condition.
Inventors
- 👤 J Furukawa
- 👤 Y Iseda
- 👤 N Kataoka
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 15:10
CPC Classifications
C; C08; C08F; C08F236/00; C08F236/02; C08F236/04; C08L; C08L21/00
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
187 words
A METHOD OF PRODUCING ALTERNATING COPOLYMERS OF CONJUGATED DIENES AND CONJUGATED POLAR VINYL MONOMERS, WHEREIN THE CONJUGATED DIENE UNIT AND THE CONJUGATED POLAR VINYL MONOMER UNIT ARE BONDED ALTERNATELY, WHICH COMPRISES COPOLYMERIZING A CONJUGATED DIENE HAVING 4 TO 10 CARBON ATOMS AND A CONJUGATED POLAR VINYL MONOMER SELECTED FROM THE GROUP CONSISTING OF METHYL ACRYLATE, ETHYL ACRYLATE, PROPYL ACRYLATE, BUTYL ACRYLATE, METHYL METHACRYALTE, AND ETHYL METHACRYLATE, THE MOLAR RATIO OF SAID CONJUGATED DIENE TO SAID POLAR VINYL MONOMER BEING 1:10 TO 10:1, AT A TEMPERATURE OF -78*C TO 50*C, UNDER THE MONOMER GAS WITH OR WITHOUT AN INERT GAS, AT A PRESSURE FROM ONE DETERMINED BY VAPOR PRESSURE IN THE REACTION SYSTEM TO 50 ATM., IN A NON-AQUEOUS MEDIUM IN THE PRESENCE OF A CATALYST PREPARED FROM A COMPONENT (A): AT LEAST ONE TRANSITION METAL COMPOUND SOLUBLE IN THE MONOMER SOLUTION SELECTED FROM THE GROUP CONSISTING OF HALIDES, ALCOXIDES, ACETYLACETONATES, AND SALTS OF CARBOXYLIC ACIDS OF METALS AND OXY-METALS OF THE GROUP IV-B AND V-B IN THE PERIODIC TABLE AND A COMPONENT (B): AN ALUMINUM-CONTAINING COMPONENT SELECTED FROM THE GROUP CONSISTING ALUMINUM COMPOUNDS HAVING THE GENERAL FORMULAE
Claim 2
Independent Claim
187 words
A METHOD OF PRODUCING ALTERNATING COPOLYMERS OF CONJUGATED DIENES AND CONJUGATED POLAR VINYL MONOMERS, WHEREIN THE CONJUGATED DIENE UNIT AND THE CONJUGATED POLAR VINYL MONOMER UNIT ARE BONDED ALTERNATELY, WHICH COMPRISES COPOLYMERIZING A CONJUGATED DIENE HAVING 4 TO 10 CARBON ATOMS AND A CONJUGATED POLAR VINYL MONOMER SELECTED FROM THE GROUP CONSISTING OF METHYL ACRYLATE, ETHYL ACRYLATE, PROPYL ACRYLATE, BUTYL ACRYLATE, METHYL METHACRYALTE, AND ETHYL METHACRYLATE, THE MOLAR RATIO OF SAID CONJUGATED DIENE TO SAID POLAR VINYL MONOMER BEING 1:10 TO 10:1, AT A TEMPERATURE OF -78*C TO 50*C, UNDER THE MONOMER GAS WITH OR WITHOUT AN INERT GAS, AT A PRESSURE FROM ONE DETERMINED BY VAPOR PRESSURE IN THE REACTION SYSTEM TO 50 ATM., IN A NON-AQUEOUS MEDIUM IN THE PRESENCE OF A CATALYST PREPARED FROM A COMPONENT (A): AT LEAST ONE TRANSITION METAL COMPOUND SOLUBLE IN THE MONOMER SOLUTION SELECTED FROM THE GROUP CONSISTING OF HALIDES, ALCOXIDES, ACETYLACETONATES, AND SALTS OF CARBOXYLIC ACIDS OF METALS AND OXY-METALS OF THE GROUP IV-B AND V-B IN THE PERIODIC TABLE AND A COMPONENT (B): AN ALUMINUM-CONTAINING COMPONENT SELECTED FROM THE GROUP CONSISTING ALUMINUM COMPOUNDS HAVING THE GENERAL FORMULAE
Claim 3
Dependent Claim
14 words
The method as claimed in claim 1, wherein butadiene and methyl acrylate are copolymerized.
Claim 4
Dependent Claim
14 words
The method as claimed in claim 1, wherein butadiene and methyl methacrylate are copolymerized.
Claim 5
Dependent Claim
44 words
The method as claimed in claim 1, wherein the component (A) is compounds of vanadium and titanium, soluble in the mixed monomer solution. 5.. The method as claimed in claim 1, wherein the component (A) is vanadium compound soluble in the mixed monomer solution.
Claim 6
Dependent Claim
14 words
The method as claimed in claim 1, wherein the component (A) is vanadyl trichloride.
Claim 7
Dependent Claim
35 words
The method as claimed in claim 1, wherein the component (A) is a compound selected from the group consisting of vanadyl tribromide, vanadyl diacetylacetonate, tri-tert-butoxy vanadyl, di-tert-butoxy vanadyl chloride, tert-butoxy vanadyl dichloride, and vanadyl naphthenate.
Claim 8
Dependent Claim
33 words
The method as claimed in claim 1, wherein the component (B) is the compounds having the following formulae, RAlCl2 and R3Al2Br3 wherein R is an alkyl radical having 1 to 4 carbon atoms.
Claim 9
Dependent Claim
14 words
The method as claimed in claim 1, wherein the component (B) is ethylaluminum dichloride.
Claim 10
Dependent Claim
30 words
The method as claimed in claim 1, wherein the component (B) is an aluminum-containing compound selected from the group consisting of ethylaluminum sesquichloride, methylaluminum sesquichloride, ethylaluminum sesquibromide, and isobutylaluminum sesquibromide.
Claim 11
Dependent Claim
37 words
The method as claimed in claim 1, wherein the component (B) is a combination selected from the group consisting of triethylaluminum/aluminum trichloride, diethylaluminum chloride/aluminum trichloride, ethylaluminum dichloride/aluminum trichloride, ethylaluminum sesquichloride/ethylaluminum dichloride, triethylaluminum/aluminum tribromide, and ethyl-aluminum dichloride/aluminum tribromide.
Claim 12
Dependent Claim
15 words
The method as claimed in claim 1, wherein said basic organic compound is dimethyl aniline.
Claim 13
Dependent Claim
17 words
The method as claimed in claim 1, wherein the copolymerization is effected in the absence of solvent.
Claim 14
Dependent Claim
18 words
The method as claimed in claim 1, wherein the copolymerization is effected in carbon disulfide as a solvent.
Claim 15
Dependent Claim
17 words
The method as claimed in claim 1, wherein the copolymerization is effected in tetrachloroethane as a solvent.
Claim 16
Dependent Claim
17 words
The method as claimed in claim 1, wherein the copolymerization is effected in ethylene as a solvent.
Claim 17
Dependent Claim
31 words
The method as claimed in claim 1, wherein the transition metal atom in the component (A) is 1:200 to 1:3 g-atom based on 1 g-atom of Al in the component (B).
References Cited (Backward Citations)
US3773854A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1977-11-04 | 1978-05-06 | 1978-11-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1981-11-04 | 1982-05-06 | 1982-11-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1985-11-04 | 1986-05-06 | 1986-11-05 | $7700.00 | Window Closed / Lapsed |