Improvements in or relating to nitrogen-containing polymers

摘要

Elastomeric polymers are made by reacting a hydrazine of the formula (X and X1 each being hydrogen or a hydrocarbon radical) with at least one macro intermediate being a homopolymer or copolymer of melting point above 60 DEG C., having at least two groups which include the structure -C = O and are capable of undergoing with hydrazine a reaction involving a hydrogen atom on each nitrogen atom thereof but no other groups which would react with the hydrazine under the reaction conditions employed, a total functionality of at least two and a molecular weight such that the residues of the macro intermediate in the immediate high polymeric reaction product have a molecular weight of 700 to 8,000, the hydrazine and the macro intermediate being employed in such proportions that the immediate high polymeric reaction product contains at least 60% by weight of residues of the macro intermediate. Specified hydrazines are phenyl, ethyl, methyl and N,N-dimethyl hydrazine. Specified macro intermediates are polyethers, polyether thioethers, polyesters, polyamides, polyureas, polyurethanes, polyolefines, polysulphonamides and polysiloxanes and include those made by polymerising dihalodialkyl silanes in the presence of a monobromoalkyl- or monobromoaryl-dialkyl halosilane and converting the products to nitriles which are reduced to amines or hydrolised to acids and the dicarboxylic acids made by oxidising with nitric acid polyisobutylene or isobutylenebutadiene copolymers; suitable reactive end groups, which may be introduced by reaction of the macro intermediate with monomeric difunctional molecules, being acid halide, haloformate, carboxyl, ester, ketone and isocyanate groups. The polymers may be modified by the inclusion in the reaction mixture of compounds having active hydrogen atoms, e.g. ethylene and propylene diamine. The polymers may be cured, e.g. with polyisocyanates to form vulcanised elastomers or they may be formed into films or filaments, e.g. by dry spinning from solvents such as N,N-dimethyl formamide, N,N-diethyl acetamide, tetramethylene sulphone, formic acid and 1 : 1 : 2-trichloroethane-formic acid mixtures. In the Examples, polymers are made by reacting hydrazine or hydrazine hydrate with : (I) a methylene-bis(4-phenyl isocyanate) modified reaction product of poly(tetramethylene oxide) glycol and 4-methyl-m-phenylene diisocyanate ; (II) a polyether diester made by reacting poly(tetramethylene oxide) glycol with terephthaloyl chloride; (III) a solution made by adding a poly(tetra methylene oxide) glycol-4-methyl-mphenylene diisocyanate reaction product to a solution of p,p1-methylene-diphenylisocyanate in dimethyl formamide by extruding the solution into hydrazine hydrate to form filaments ; (IV) a solution in N,N-dimethyl formamide of a reaction product of poly(tetramethylene oxide) glycol and 4-methyl-m-phenylene diisocyanate modified by reaction with methylene bis (4phenyl isocyanate) by extruding the solution into hydrazine hydrate to produce fibres which are immersed in boiling water ; (V) a polyether diurethane having isocyanate end groups made by reacting poly(tetramethylene oxide) glycol with methylene bis (4-phenyl isocyanate) a solution of the product being passed through a 5 hole spinneret to produce filaments which are exposed to heated air ; (VI) a methylene bis (4-phenyl isocyanate) modified adipic acid (propylene glycol) ethylene glycol polyester, the product being cast from solution as films which are immersed in boiling water ; (VIII) a methylene bis (4-phenyl isocyanate) modified adipic acid/propylene glycol polyester, the products being extruded through a multi-fil spinneret into a water bath to produce filaments which are immersed in boiling water ; (X) and (XI) a polymer made by reacting poly(tetramethylene oxide) glycol with 4-methyl-m-phenylene diisocyanate, the resultant polymer being cured by reaction with 1,3-bis (3-isocyanato-p-tolyl) urea ; (XII) a 4-methyl-m-phenylene diisocyanate modified poly(alkylene oxide sulphide) glycol made by reacting thiodiglycol and 1 : 4-butanediol, the resultant polymer being cured by reaction with 1 : 3-bis-(3-cyanato-p-tolyl) urea ; XIII) a polymer made by reacting a polyester derived from 2,2-dimethyl-1 : 3-propane diol and sebacyl chloride, the resultant polymer being melt spun through a monofil spinneret and (XVII) a polyurethane made from N,N-diisobutyl hexamethylene diamine and the bischloroformate of 2 : 2-dimethyl-1,3-propane diol modified by reaction with methylene-bis (4-phenyl isocyanate), the products being cast as a film. In the remaining Examples, (VII) a polymer as in Ex. (VI) is spun from solution in N,N-dimethyl formamide through a multifil spinneret into water ; (IX) a polymer as in Ex. (I) is dry spun to form filaments which are drawn at room temperature ; (XIV) a polymer as in Ex. (V) is spun through a single spinneret hole to produce filaments which are immersed in boiling water ; (XV) a polymer as in Ex. (IX) is spun as described in Ex. (XIV) and in XVI), a polymer as in Ex. (V) is spun as in Ex. (XIII). Specification 849,156 is referred to.ALSO:Example XII describes the preparation of poly (tetramethylene oxide/ethylene sulphide) glycol of molecular weight 965 by refluxing thiodiglycol and 1 : 4-butanediol in the presence of benzene and p-toluene-sulphonic acid whilst allowing water formed to evaporate off. The purification of the product is also described. Specification 849,156 is referred to.