Patent GB-975707-A (GB)
Title: Isocyanurate polymers and processes for their preparation
IPC: C08G73/06
Filed: 1961-09-19
Abstract: Isocyanate polymers comprising units of the formula <FORM:0975707/C1/1> in which n is at least 1, R is an allyl or substituted allyl group and Z is alkylene, vinylene, phenylene, dialkylene oxy, diphenylene oxy, or a derivative of one of these groups, are prepared by reacting in an inert liquid at 60 DEG  to 150 DEG C., XCH2ZCH2X (in which X is a halogen atom) with at least an equimolar amount of a cationic salt of isocyanuric acid and of RX, or with at least an equimolar amount of a cationic salt of a compound of formula <FORM:0975707/C1/2> When n=1, the free valencies on N atoms in the rings are satisfied by R groups.  If desired a portion of the R groups in the polymers may be other than allyl provided they are non-reactive in the polymer-forming reaction and with allyl halides and isocyanurate nuclei, e.g. they may be b -hydroxy-ethyl, benzyl, xylyl, alkyl, methoxycarbonyl methyl or cyanomethyl.  In examples polymers are formed from (1) tri-sodium cyanurate, allyl chloride and a , a 1-dichloro-p-xylene. (2) and (4) tri-sodium cyanurate, allyl chloride and 1, 4-dichlorobutene-2.  (3) tri-sodium cyanurate, 1,4-dichlorobutene-2 and a mixture of allyl chloride and chloroacetonitrile. (5) tri-sodium cyanurate, allyl chloride and a mixture of 1,4-dichlorobutene-2 and a , a 1-dichloro-p-xylene. (9) trisodium cyanurate, allyl chloride and 1,4-dichloro-butane.  (10) trisodium cyanurate, allyl chloride and bis(2-chloroethyl) ether. (11) trisodium cyanurate, allyl chloride and 1,2-dichloroethane. Production of polymers having the following recurring units is also referred to:- <FORM:0975707/C1/3> In Example 7 the polymer of Example 4 was cured with tert-butyl perbenzoate together, if desired, with chopped glass fibre wet with triallyl isocyanurate.  Example 8 describes the curing of the polymer of Example 1 with 2,5-dimethylerane-2,5-dihydroperoxide. There are statements that all the polymers of the examples may be cured, e.g. with tert. butyl hydroperoxide or tert. butyl perbenzoate.ALSO:Thermoplastic curable polymers comprising units of the formula <FORM:0975707/C3/1> in which R is an allyl or substituted allyl group, Z is alkylene, vinylene, phenylene, dialkylene oxy, diphenylene oxy or a derivation of one of those groups, and n is a least one, are prepared by reacting, in an inert liquid at 60 DEG  to 150 DEG C. XCH2ZCH2X (in whic X is a halogen atom) with at least an equimolar amount of a cationic salt of isocyanuric acid and of RX, or with at least an equimolar amount of a cationic salt of a compound of formula <FORM:0975707/C3/2> when n=1, the free valencies on N atoms in the rings are satisfied by R groups. If desired a portion of the R groups in the polymers may be other than allyl, provided they are non-reactive in the polymerforming reaction and with allyl halides and isocyanurate nuclei, e.g. they may be b -hydroxy-ethyl, benzyl, xylyl, alkyl, methoxycarbonylmethyl or cyanomethyl.  Suitable solvents for the reaction are dialkyl formamides with two to five carbon atoms, N-alkyl pyrrolidones or piperidones.  The polymers may be cured if desired together with styrene or polyallylisocyanurate by heating with a curing agent, e.g. a peroxide or azo free radical initiator. Conventional additives may be incorporated in the curable mixtures.  In examples polymers are formed from (1) tri-sodium cyanurate, allyl chloride and a ,a 1-dichloro-p-xylene; (2) and (4) tri-sodium cyanurate, allyl chloride and 1,4-dichlorobutene-2; (3) tri-sodium cyanurate, 1,4-dichlorobutene-2 and a mixture of allyl chloride an chloroacetonitrile; (5) tri-sodium cyanurate, allyl chloride and a mixture of 1,4-dichlorobutene-2 an a ,a 1-dichloro-p-xylene; (9) tri-sodium cyanurate, allyl chloride and 1,4-dichlorobutane; (10) tri-sodium cyanurate, allyl chloride and bis(2-chloroethyl)ether; (11) tri-sodium cyanurate, allyl chloride and 1,2-dichloroethane. Production of polymers having the following recurring units is also referred to:- <FORM:0975707/C3/3> In Example 7 the polymer of Example 4 was cured with tert.-butyl perbenzoate together, if desired, with chopped glass fibre wet with triallyl isocyanurate.  Example describes the curing of the polymer of Example 1 with 2,5-dimethylhexane-2, 5-dihydroperoxide. There are statements that all the polymers of the examples may be cured, e.g. with tert.-butyl hydroperoxide or tert.-butyl perbenzoate.