Linearer,elastischer Kunststoff

摘要

1,157,945. Elastomeric polymers. J. R. GEIGY A.G. 18 Oct., 1967 [19 Oct., 1966], No. 47472/67. Heading C3R. Polymers are prepared by first condensing a bis-hydrazide: H 2 N.NH.A.NH.NH 2 (I), where A is a divalent acyl radical of a polybasic carboxylic acid which may contain aliphatic, carbocyclic or heterocyclic substituents, with a bisacid halide: Hal.CO(O) r X(O) r CO.Hal (II) in which Hal represents a halogen atom, X is a divalent linear aliphatic hydrocarbon radical which is a residue of a compound: H(O) r X(O) r H which has M.W. 400-5000 and m.p. <70‹ C. ; X may be interrupted by O, S and CO.O radicals but every two interrupting members are separated from each other by at least two chain carbon atoms; r is 0 or 1. I and II are reacted at a molar ratio from 3:1 to 1À2:1 at - 20‹ to 100‹ C. The resultant intermediate condensate has the formula where n is a whole or fractional number having an average value between 0À5 and 5. This is subsequently reacted with a chain extender which may be a bifunction acyl halide Y(COCl) 2 or anhydride Y(CO.OCO) or a diisocyanate: R(NCO) 2 . Y may be: (a) a straight-chain alkylene radical containing up to 12 carbon atoms, a C 5-8 cycloalkylene radical, phenylene, diphenylene, naphthylene, phenylene-E-phenylene where E is O, S, SO 2 , an alkylidene radical containing up to 8 carbon atoms, cycloalkylidine of 5 to 7 carbon atoms; the carbon atoms of the above may be substituted by C 1-6 alkyl radicals or by F, Cl or COOH; (b) -O-R1-O- where R1 is a C 2-12 alkylene radical or methylenecyclohexylene-methylene; (c) 1,4-piperazinediyl; or (d) -NH-R-NH- where R is C 2-12 alkylene,α,α1-xylylene, C 1-6 alkyl-α,α1-xylylene, halogeno-α,α1-xylylene (halogeno = F or Cl), cyclohexylene or methylene - cyclohexylenemethylene. The resultant polymer has the general formula in which Z is -CO.(O) r .X(O) r CO- (III) and -CO.Y.CO -(IV). The polymer contains from 0À5 to 5 radicals III per radical IV, which are statistically distributed over the whole polymer. In preferred and exemplified polymers A is a radical: in which Q is H, OH, C 1-6 alkoxy, C 1-6 alkyl, C 5-8 cycloalkyl, phenyl which may be substituted by C 1-6 alkyl, alkoxy radicals or by F, Cl, Br or COOH or a grouping M 1 and M 2 independently represent H, C 1-8 alkyl radicals, benzyl, phenyl, C 3-12 alkenyl, cyclohexyl or N,N-di (C 1-6 alkyl)-amino-C 1-6 alkyl or taken together form a heterocyclic ring with the N atom. In an example (1) the bischloroformate of polytetramethylene glycol is first reacted with 2,4-dihydrazino-6-dipropylamino-s-triazine in solution in hexamethyl phosphoric acid triamide. After reacting for ¢ hour the mixture is cooled to 5-10‹ C. and the prepolymer chain extended with adipic acid dichloride. An elastomer is obtained on precipitating the mixture in water. In other examples similar prepolymers are reacted with diisocyanates, e.g. hexamethylene diisocyanate.