Patent GB-851936-A (GB)
Title: Improvements in or relating to polymeric products
IPC: C08G18/10
Filed: 1957-07-17
Abstract: The invention comprises, as new substances, polymeric compounds of molecular weight at least 750 consisting essentially of more than two structural units of formula -R-N=C=N-(in which R is an organic bivalent or polyvalent radical) and obtainable by the intermolecular condensation of more than two molecules of organic di and poly-isocyanates with the elimination of carbon dioxide. Such compounds are obtained by contacting an organic di- or polyisocyanate with a catalyst consisting of a substituted phospholine of the formula:  <FORM:0851936/IV(a)/1> or a substituted phospholidine of formula:  <FORM:0851936/IV(a)/2> wherein R is lower alkyl and phenyl radical, R1 is a hydrogen atom or a lower alkyl or lower alkenyl radical, a, b, c and d each represent a hydrogen or halogen atom or a lower alkyl, lower alkenyl, phenyl or cyclohexyl group or represent polymethylene groups which, together with two adjacent carbon atoms in the heterocyclic ring, form a cyclo-aliphatic ring, and X is an oxygen or sulphur atom.  The reaction may be effected in a solvent such as benzene, toluene, xylene, decahydronaphthalene, acetonitrile, nitromethane, 2-nitropropane, N-nitrosodimethylamine, methyl amyl ketone or anisole, at temperatures up to 300 DEG C. and preferably at 100 DEG -200 DEG C.  As polyisocyanates there can be used tolylene, phenylene, methylene di (p-phenylene), 4,-chloro-1, 3-phenylene, 4, 41-biphenylene, 1, 5-naphthylene, polymethylene, 3, 31-dimethoxy-4, 41-biphenylene, cyclohexylene, 4, 41-methylene dicyclohexylene, 1, 5-tetrahydronaphthalene diisocyanates, m-(1-isocyanatoethyl)-phenyl isocyanate, 2, 4, 6-tri-isocyanato-toluene and pisocyanatophenyl-2, 4-diisocyanotophenyl ether.  Mixtures can be used.  Also suitable are polymers containing isocyanate groups, such as the reaction products of excess polyisocyanate with polymers containing terminal hydroxy, amino or carboxyl groups.  Specified are polyisocyanate reaction products of polyalkylene ether glycols, polyalkylenearylene ether glycols, polyalkylene ether-thioether glycols, polyalkylene arylene ether thioether glycols, polyester glycols and polyhydrocarbon glycols.  A reaction product of 3 mols of a diisocyanate with one mol of castor oil or one mol of a polyester of trimethylol propane, polytetramethylene ether glycol and adipic acid or of 4, 41-isopropylidene-diphenol with excess methylene di (p-phenylene) diisocyanate can also be used) The products can be formed as foams or elastomers (fibres, films, sheets) or be formed into coating compositions.  The products, if linear, can be used with peroxides such as dicumyl or benzoyl peroxide.  Polymers having -CH=CH2 terminated side chains (obtained from a mixture of an isocyanate-terminated reaction p  product of diisocyanate and polyalkylene ether glycol and isocyanate-terminated reaction product of a glycol containing a side chain unsaturated group) can be cured with sulphur.  The products can also be reacted with ammonia or mono amines to give a linear polymer containing a plurality of guanidine linkages or with a diamine to give a cross-linked product containing guanidine linkages.  The guanidine polymers are suitable for making films and fibres.  The polymers can be compounded with carbon black, clay, silica, talc, zinc and magnesium oxides, calcium and magnesium carbonate, titanium dioxide, plasticisers and organic and inorganic colouring agents.  In typical Examples (1) 2, 4-tolylene diisocyanate is heated at 100 DEG C. with 3-methyl-1-phenyl-3-phospholine.  The poly (2, 4-tolylenecarbodiimide) produced is moulded at 250 DEG -300 DEG C. 5-tert-butyl-2-methyl-1, 3-phenylene diisocyanate, 4, 41-oxydiphenylene diisocyanate, 2, 4, 6-trimethyl-1, 3-phenylene diisocyanate and durylene diisocyanate may be polymerized similarly; (12) polytetramethylene ether glycol is reacted with 2, 4-tolylene diisocyanate in a 2 : 1 molar ratio and the hydroxy-terminated polymer obtained is reacted with excess methylene-di (p-phenylene) diisocyanate.  The product is (A) heated in xylene with 3-methyl-1-phenyl-3-phospholine to give a spinnable solution of polymer; (B) mixed with methylene di (p-phenylene) diisocyanate and heated with 1-ethyl-3-methyl-phospholine 1-oxide to give a polymer; or (C) the solution of polymer used in spinning in (A) is wet spun into a precipitating bath of bis (4-aminocyclohexyl) methane in hexane, cross-linking taking place by reaction of the carbodiimide linkages with the amine to form guanidine groups; (25) a mixture of isocyanate terminated polymers from 2, 4-tolylene diisocyanate and polytetramethylene glycol and 3-allyloxy-1, 2-propanedial, respectively is heated with 3-methyl-1-phenyl-3-phospholine 1-oxide. The product containing carbodiimide linkages and side chain allyloxymethyl groups is compounded with carbon black, 2, 21-dithiobisbenzothiazole, mercaptobenzthiazole, sulphur and zinc p-methoxydithiocarbamlate and moulded under heat and pressure; (27) a poly (2, 4-tolylenecarbodiimide) solution is poured into (A) aniline solution; (B) tert butylamine solution. The polyguanidine product of (B) is purified by solution in dilute hydrochloric acid and precipitation by ammonia and dissolved in dilute sulphuric acid to give a poly (guanidinium sulphate) solution.  Specification 797,863 is referred to.ALSO:The invention comprises, as new substances, polymeric compounds (which may be cellular) of molecular weight at least 750 consisting essentially of more than two structural units of the formula-R-N=C=N-(in which R is an organic bivalent or polyvalent radical) and obtainable by the intermolecular condensation of more than two molecules of organic di-and polyisocyanates with the elimination of carbon dioxide.  Such compounds are obtained by contacting an organic di-or poly-isocyanate with a catalyst consisting of a substituted phospholine of the formula <FORM:0851936/V/1> and <FORM:0851936/V/2> or a substituted phospholidine of formula <FORM:0851936/V/3> and <FORM:0851936/V/4> Included in di- and polyisoyanates are reaction products of polyisocyanates with polyethers and polyesters.  The products can be reacted with ammonia or amines to give polymers containing guanidine linkages or can be cured with peroxides or (where CH=CH2 groups are present) with sulphur.  Specification 797,863 is referred to.