US3876595A
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Process for producing olefinic copolymers
Assignee: Sumitomo Chemical Co Ltd
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Filing: 1973-02-26
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Granted: 1975-04-08
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Expires: 1993-02-26
Abstract
Abstract Wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are hydrogen atoms, hydrocarbon radicals having one to 20 carbon atoms, halogen atoms, or halogenated hydrocarbon radicals having one to 20 carbon atoms and containing at least one halogen atom as substituent, provided that R.sub.1, R.sub.2, and R.sub.4 have as a whole at least one halogen atom, with a coordinated catalyst comprising an organoaluminum compound of the formula, A1R''.sub.n X.sub.3.sub.-n, wherein R'' is a hydrocarbon radical having 1 to 20 carbon atoms, X is a halogen atom, and n is any number of from 1.5 to 3, and a transition metal compound selected from the group consisting of vanadium compounds and titanium compounds, the molar ratio of said organoaluminum compound to said transition metal compound being from 5 : 1 to 0.5 : 1. The rate of vulcanization of the said quadripolymer is freely controllable by varying the non-conjugated diene content thereof. A halogen-containing, sulfur-curable, normally amorphous quadripolymer is produced by contacting a mixture of (1) ethylene, (2) an .alpha.-olefin having the formula, R-CH=CH.sub.2 wherein R is a hydrocarbon radical having one to 20 carbon atoms, (3) a hydrocarbon compound having a plurality of non-conjugated unsaturated bonds capable of polymerizing with a coordinated catalyst, and (4) a halogenated norbornene compound represented by the formula,
Inventors
- 👤 Masatoshi Ogura
- 👤 Keisaku Yamamoto
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 19:32
CPC Classifications
C; C08; C08L; C08L21/00; C08F; C08F210/00; C08K; C08K3/00; C08K3/02; C08K3/04; C08K3/06; C08K3/18; C08K3/20; C08K3/22; C08K5/00; C08K5/0008; C08K5/0025; C08K5/04; C08K5/09; C08L23/00; C08L23/02; C08L23/16; C08L23/18; C08L23/20; C08L23/22; C08L53/00; C08L53/02; C08L2312/00; C08L2666/00; C08L2666/02; C08L2666/04
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
65 words
A PROCESS FOR PRODUCING A HALOGEN-CONTAINING, SULFURCURABLE, NORMALLY AMORPHOUS GUADRIPOLYMER, WHICH COMPRISES CONTACTING A MIXTURE COMPRISING (1) ETHYLENE, (2) AN A-OLEFIN OF THE FORMULA R-CH=CH2 WHEREIN R IS A HYDROCARBON RADICAL HAVING 1 TO 20 CARBON ATOMS, (3) A HYDROCARBON COMPOUND HAVING A PLURALITY OF NON-CONJUGATED UNSATURATED BONDS CAPABLE OF POLYMERIZING WITH A COORDINATED CATALYST, AND (4) A HALOGENATED NORBORNENE COMPOUND REPRESENTED BY THE FORMULA,
Claim 2
Dependent Claim
65 words
A PROCESS FOR PRODUCING A HALOGEN-CONTAINING, SULFURCURABLE, NORMALLY AMORPHOUS GUADRIPOLYMER, WHICH COMPRISES CONTACTING A MIXTURE COMPRISING (1) ETHYLENE, (2) AN A-OLEFIN OF THE FORMULA R-CH=CH2 WHEREIN R IS A HYDROCARBON RADICAL HAVING 1 TO 20 CARBON ATOMS, (3) A HYDROCARBON COMPOUND HAVING A PLURALITY OF NON-CONJUGATED UNSATURATED BONDS CAPABLE OF POLYMERIZING WITH A COORDINATED CATALYST, AND (4) A HALOGENATED NORBORNENE COMPOUND REPRESENTED BY THE FORMULA,
Claim 3
Dependent Claim
25 words
A process according to claim 1, wherein the mixture of monomers is contacted with the coordinated catalyst at a temperature of from -78.degree. to 120.degree.C.
Claim 4
Dependent Claim
25 words
A process according to claim 1, wherein the mixture of monomers is contacted with the coordinated catalyst at a temperature of from 20.degree. to 70.degree.C.
Claim 5
Dependent Claim
26 words
A process according to claim 1, wherein R of the .alpha.-olefin is an alkyl, aryl, aralkyl, alkylaryl, or cycloalkyl group having one to 20 carbon atoms.
Claim 6
Dependent Claim
29 words
A process according to claim 1, wherein the .alpha.-olefin is propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, 5-methylnonene-1, 5,5-dimethyloctene-1, 4-methylhexene-1, 4-methylheptene-1, 6-methylheptene-1, 5,6,6-trimethylheptene-1, styrene, 4-phenylheptene-1, or 4-cyclohexylhexene-1.
Claim 7
Dependent Claim
13 words
A process according to claim 1, wherein the 2-olefin is propylene or butene-1.
Claim 8
Dependent Claim
46 words
A process according to claim 1, wherein the hydrocarbon compound having a plurality of non-conjugated unsaturated bonds is a non-conjugated polyene selected from the group consisting of dicylopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-(1''-butenyl)-2-norbornene, 5-(2''-butenyl)-2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatriene, 6-methyl-4,7,8,9-tetrahydroindene, 2,2''-dicyclopentenyl, trans-1,2-divinylcyclobutane, 1,4-hexadiene, 1,6-octadiene, and 6-methyl-1,5-heptadiene.
Claim 9
Dependent Claim
27 words
A process according to claim 1, wherein the halogenated norbornene compound is 5-chloro-2-norbornene, 5-bromo-2-norbornene, 5-iodo-2-norbornene, 5,5-dichloro-2-norbornene, 5,6-dichloro-2-norbornene, 5,5,6-trichloro-2-norbornene, 5-chloro-6-methyl-2-norbornene, 5-chloromethyl-2-norbornene, 5-bromomethyl-2-norbornene, 5,6-dichloromethyl-2-norbornene, 5,6-dibromomethyl-2-norbornene, 5,5,6,6-tetrachloronorbornene, 5-(1'',2''-dichloroethyl)-2-norbornene, or 5-.omega.-chlorooctyl-6-octyl-2-norbornene.
Claim 10
Dependent Claim
14 words
A process according to claim 6, wherein the non-conjugated polyene is 5-ethylidene-2-norbornene or 5-isopropylidene-2-norbornene.
Claim 11
Dependent Claim
15 words
A process according to claim 9, wherein the halogenated norbornene compound is 5-chloromethyl-2-norbornene or 5-bromomethyl-2-norbornene.
Claim 12
Dependent Claim
27 words
A process according to claim 1, wherein R'' of the organoaluminum compound is an alkyl, aryl, aralkyl, alkylaryl, or cycloalkyl group having one to 20 carbon atoms.
Claim 13
Dependent Claim
53 words
A process according to claim 1, wherein the organoaluminum compound is ethylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquiiodide, methylaluminum sesquichloride, n-propylaluminum sesquichloride, isobutylaluminum sesquichloride, n-hexylaluminum sesquichloride, cyclohexylaluminum sesquichloride, 2-ethylhexylaluminum sesquichloride, laurylaluminum sesquichloride, diethylaluminum chloride, dimethylaluminum chloride, di-n-butylaluminum chloride, ethylpropenylaluminum chloride, dicyclopentadienylaluminum chloride, cyclohexylethylaluminum chloride, trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, triphenylaluminum, tricyclohexylaluminum, or tribenzylaluminum.
Claim 14
Dependent Claim
23 words
A process according to claim 1, wherein the organoaluminum compound is an ethylaluminum sesquihalide, a diethylaluminum halide, or a mixture of these compounds.
Claim 15
Dependent Claim
55 words
A process according to claim 1, wherein the transition metal compound is a tri- to pentavalent vanadium compound selected from the group consisting of vanadium halides, vanadyl halides, vanadium acetylacetonate, vanadyl acetylacetonate, vanadium haloacetylacetonates, vanadyl haloacetylacetonates, esters of orthovanadic acid containing a hydrocarbon radical of one to 20 carbon atoms, vanadyl haloalkoxides, cyclopentadienylvanadium, and halocyclopentadienylvanadiums.
Claim 16
Dependent Claim
52 words
A process according to claim 1, wherein the transition metal compound is vanadium tetrachloride, vanadium trichloride, vanadyl trichloride, vanadyl tribromide, vanadium triacetylacetonate, vanadyl acetylacetonate, vanadyl dichloroacetylacetonate, vanadyl monochlorodiacetylacetonate, ethyl orthovanadate, n-hexyl orthovanadate, cyclohexyl orthovanadate, phenyl orthovanadate, vanadyl diethoxymonochloride, vanadyl diethoxymonobromide, vanadyl di-n-octoxymonochloride, vanadyl monomethoxydichloride, vanadyl monoethoxydichloride, vanadyl monostearoxydichloride, dicyclopentadienylvanadium, or dicyclopentadienylvanadium dichloride.
Claim 17
Dependent Claim
22 words
A process according to claim 1, wherein the transition metal compound is vanadyl trichloride, vanadium tetrachloride, or an ester of orthovanadic acid.
Claim 18
Dependent Claim
17 words
A process according to claim 1, wherein the transition metal compound is titanium tetrachloride or titanium tetrabutoxide.
Claim 19
Dependent Claim
39 words
A process according to claim 1, wherein the catalyst contains as a third component an electrondonating compound selected from the group consisting of amines, cyclic nitrogen compounds, acid amides, ethers, esters, ketones, and compounds of the Group Vb elements.
Claim 20
Dependent Claim
44 words
A process according to claim 1, wherein the catalyst contains as a third component an oxidizing compound selected from the group consisting of halogens, sulfur, metal halides, oxygen, nitro compounds, nitroso compounds, nitrates, nitrites, N-oxides, P-oxides, azo compounds, sulfides, disulfides, quinones, and acid halides.
Claim 21
Dependent Claim
28 words
A process according to claim 1, wherein the molar ratio of the organoaluminum compound to the transition metal compound is from 5 : 1 to 2 : 1.
Claim 22
Dependent Claim
25 words
A process according to claim 1, wherein the concentration of the transition metal compound in a reaction medium is 0.01 to 50 millimoles per liter.
Claim 23
Dependent Claim
24 words
A process according to claim 1, wherein the concentration of the organoaluminum compound in a reaction medium is 0.05 to 100 millimoles per liter.
Claim 24
Dependent Claim
22 words
A process according to claim 1, wherein the proportion of the propylene in the monomer mixture is 50 to 98 mole percent.
References Cited (Backward Citations)
US3222330A
Cited
US3705138A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-04-07 | 1978-10-07 | 1979-04-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-04-07 | 1982-10-07 | 1983-04-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-04-07 | 1986-10-07 | 1987-04-08 | $7700.00 | Window Closed / Lapsed |