Patent GB-1257976-A (GB)
IPC: C08G65/34
Filed: 1969-08-04
Abstract: 1,257,976. Polyethers grafted with acrylonitrile. FARBENFABRIKEN BAYER A.G. 4 Aug., 1969 [23 Aug., 1968; 2 Oct., 1968; 16 May, 1969], No. 38879/69. Heading C3G. [Also in Divisions D1-D2] A graft polymer comprises at least 50% by weight of graft polymerized acrylonitrile, optionally with up to 10% by weight of a graft polymerized comonomer, and, as graft substrate, from 5 to 40% by weight of a linear polyether containing tertiary nitrogen atoms or a derivative thereof which is quaternized on the nitrogen atoms, which polyether has the general formula Y 1 -D-Y 2  in which D represents (a) a radical of general formula in which R 1  represents hydrogen or a C 1  to C 3 - alkyl radical or a phenyl radical and Z represents or in which R 2  represents a C 1  to C 6 -alkyl or alkenyl or a cycloalkyl radical, R 3  represents a C 1  to C 4 - alkyl radical and A# represents a halide ion or or CH 3 SO 4 # or in which R 3  and A# together represent -(CH 2 ) 3 -SO 3 # or -(CH 2 ) 4 SO 3 # and n is a number from 10 to 80 or (b) a linear polyether without the terminal hydrogen atoms which has been obtained by cocondensation of 90 to 99À5% by weight of a diol of formula with either 10 to 0À5% by weight of a second diol of formula in which R 1  and R 2  are as defined above, R 4  represents one or more aromatic radicals which are attached to each other directly or via hetero atoms, or linear or branched alkylene groups, and R 5 , R 6 , R, and R 8  each represent hydrogen or a C 2  to C 6 -alkenyl radical, at least one of them being an alkenyl radical and x represents an integer of at least 2, or with 10 to 0À5% by weight of an aromatic dicarboxylic acid or an ester thereof having the formula  in which R 9  represents hydrogen or a C 1  to C 6 - alkyl radical, R 10  and R 11  represent hydrogen or C 3  to C 6 -aliphatic linear or branched radicals which contain a double bond, and R 10  and R 11  may be the same or different but at least one must contain a double bond, R 12  represents a carboxyalkyl, or carboalkoxyalkyl radical or a radical of formula in which R 9 , R 10  and R 11  are as defined above and R 13  represents a radical of formula -(CH 2 ) m -, and may be linear or branched and m has a value from 1 to 12, or represents a radical of formula -Ar-, -Ar-O-Ar-, -Ar-SO 2 -Ar-, or Ar-O-Ar-SO 2 -Ar-O-Arin which Ar represents an optionally substituted bivalent aromatic radical, or R 12  represents a radical of formula  in which R 14  has the same meaning as R 9  and may be the same as or different from R 9 , wherein Y 1  and Y 2  may be the same or different and represent hydrogen or a radical of formula in which R 15  is a C 2  to C 6 -alkenyl radical, 0 to 75 mol per cent of (Y 1 +Y 2 ) being said radical in the case of (a) and Y 1  and Y 2  representing hydrogen in the case of (b). The graft polymer is produced in dilute nitric acid at a pH of 1 to 6 and temperature of 0‹ to 90‹ C. in the presence of a free-radical catalyst. In the examples, acrylonitrile and methyl acrylate are grafted on to polyethers derived from (a) N,N-bis(betahydroxyethyl)cyclohexylamine, (b) said cyclohexylamine and 2,2-bis(3-allyl-4-betahydroxyethyl-phenyl)propane, (c) said cyclohexylamine and 1,2-bis(2-allyl-4-carboxyphenoxy)ethane, (d) bis(betahydroxypropyl)methylamine, (e) bis- (betahydroxyethyl)butylamine, (f) N,N-bis- (betahydroxyethyl)cyclohexylamine, the polyether being acylated with methacryloyl chloride to 50 or 75% conversion of the terminal hydroxyl groups, or unilaterally acylated and then quaternized with dimethyl sulphate. Films of the resulting graft polymers are dyed.