Method of production of polymers and copolymers of cycloalkene o

Details Method of production of polymers and copolymers of cycloalkene o Method of production of polymers and copolymers of cycloalkene o

1993-10-15

1995-10-03

Zitomer, Fred

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

502167, 526281, 526283, 526284, C08F 422, C08F 478

Patent

active

054553180

DESCRIPTION:

BRIEF SUMMARY
FIELD OF THE ART

The invention relates to metathetical polymerization of cycloalkenes of norbornene type by catalysts based on tungsten compounds during injection moulding by RIM (Reaction Injection Moulding) method.


STATE OF THE ART

U. S. Pat. No. 4,400,340 and U. S. Pat. NO. 4,426,502 disclose metathetical polymerization of cycloalkenes by ring opening by the action of a catalytic system containing transition metal. By mixing two streams, of which the first contains catalyst and the second the cocatalyst, cross-linked polymer is obtained containing double bonds in the chain. As catalytic components of the metathetically polymerizing system compounds based on halogenides and oxyhalogenides of tungsten, molybdenum, tantalum or rhenium and tetraalkylammonium salts of tungsten and molybdenum are used. Tungsten and molybdenum salts are preferred, especially WCl.sub.6 and WOCl.sub.4. But such halides of a transition metals, if added to the mixture of metathetically polymerized monomers, initiate very rapid cationic polymerization. Therefore, they must be in advance suspended in an inert solvent and solubilized by the addition of alcoholic and phenolic compound 5 (called also modifiers). Their activity is thereby decreased. As solvent benzene, toluene, chlorobenzene, dichlorobenzene, etc. are used.
Suitable phenolic compounds are phenol, halogenated phenols and alkylphenols, especially tert-butylphenol, tert-octylphenol and nonylphenol. Molar ratio [tungsten compound ]/[phenolic compound ] ranges from 1:1 to 1:3.
The phenolic component is added to the suspension of the tungsten compound in organic solvent. The reaction is carried under mixing and bubbling by a stream of inert gas to remove the HCl being formed . Alternatively, also phenolic salt can be used, e.g. Li- or Na- phenoxide and the formed inorganic compound is filtered off or centrifuged. All such operations have to be carried out in the absence of air and moisture to prevent deactivation of catalyst (U.S. Pat. Nos. 4,507,453, 4,469,809).
EP 304 900 discloses the use of 2, 6-dihalo- 4-alkylphenol, where the alkyl group contains 1 to 18 carbon atoms; especially suitable is 2, 6-dibromo-4-alkylphenol with 1 to 12 carbon atoms containing alkyl. The catalytic WCl.sub.6 and WOCl.sub.4 mixture shows high activity and polymerization proceeds very rapidly. A ratio of WCl.sub.6 to WOCl.sub.4 in the range from 9:1 to 1:3 is used.
To prevent premature reaction of the catalytic precursor with the monomer that forms the first component of the polymerization system, it is necessary to use an inhibitor. Inhibitors are chelating agents or Lewis bases e.g. acetylacetone, alkylesters, tetrahydrofuran, benzonitrile, etc. in the amount 1 to 5 mol/mol of the tungsten compound. As cocatalysts in the metathetical polymerization organometalic compounds are used, i.e. alkyls of metals of the Groups I-III of the periodic system, especially alkylcompounds of aluminium, tin, silicon and zinc. The cocatalyst is dissolved in the norbornene hydrocarbon and forms the second reaction solution.
EP 222 432 and EP 336 486 disclose polymerization of dicyclopentadiene by means of a catalytic system containing: ##STR1## where X is chlorine, R is alkyl group or hydrogen, R.sup.1 is alkylgroup with 1 to 10 hydrocarbon atoms or hydrogen, ##STR2## where M is tin or silicon, R.sup.2 is alkyl group containing 1-10 carbon atoms or phenyl. In contradiction to organoaluminium compounds, this compound is substantially less sensitive to the presence of oxygen. This means that it is not necessary to work with it in an inert atmosphere.
The polymer is obtained by blending two reaction solutions. One solution contains monomer, catalytic precursor and inhibitor and the other solution contains monomer and cocatalyst. As blending of both solutions results in instantaneous polymerization, which is not desirable in case of RIM equipment application, a so called modifier is added to the latter solution. Usually Lewis bases, e.g. ethers, esters, nitriles, etc. are used (EP 280 247). EP 259 215 describes po

REFERENCES:
patent: 3691095 (1972-09-01), Kroll et al.
patent: 4080491 (1978-03-01), Kobayashi
patent: 4882401 (1989-11-01), Bell
patent: 4883849 (1989-11-01), Matlack
patent: 5171776 (1992-12-01), Khasat
patent: 5268232 (1993-12-01), Khasat
Chemical Abstracts, vol. 93, No. 6, Aug. 1980, Columbus, Ohio, US; abstract o. 47280, T. T. Denisova et al. "activating effect of stable phenoxyl and piperidinoxyl radicals on the polymerisation of cyclopentene and cyclooctene with ring opening" p. 5; column 2; & Vysokomol. Soedin. Ser. B., vol. 22, No. 4, 1980, pp. 243-246.
Database WPIL, Derwent Publications Ltd., London, GB; AN 81-14958 & SU,A,733 714 (Sarat Univ Chem Inst and as USSR Chem Phys Inst) 18 May 1980.

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