Patent GB-1108545-A (GB)
Title: Aromatic substituted polyoxyalkylene compounds and their preparation
IPC: C08G65/331
Filed: 1965-03-09
Abstract: The invention comprises polyethers of formula [Y-(B)c-Ar-O-(alk-O)n]mQ I wherein Y is a benzene ring functionally substituted by a hydroxy, glycidoxy, glyceroxy or alkenoyl glyceroxy group, which may also be substituted by one or two chlorine or bromine atoms or C1- 4 hydrocarbon groups; B is a sulphone group or one carbon atom of a C1- 13 alkylene or aralkylene group; c is 0 or 1; Ar is a phenylene group, a C1- 4 alkyl or alkenyl phenylene group, or a mono- or di-chloro or bromo phenylene group; alk is a C2- 4 alkylene group; Q is an unsubstituted m-valent C2- 6 alkylene group; m is 2 or 3, n is from about 2 to 20 and the product of m and n is not greater than about 50.  Compounds containing a hydroxyl group as the functional substituent on Y are prepared by firsty reacting a compound [HO(alk-O)n[mQ with an aryl sulphonyl chloride of formula ApSO2Cl wherein Ap is a substituted or non-substituted aryl group and an amine:-NR3, where R is C1- 6 alkyl, to produce a compound of formula [ApSO2O-(alk-O)n]mQ and then interacting this compound under substantially anhydrous conditions in an alkanolic medium with up to about 10 mole per cent excess (over the stoichiometric amount) of a phenolic compound: Y-(B)c-Ar-OH III wherein the functional substituent on Y is a hydroxy group, in the presence of a strong base in a molar amount intermediate between the amounts of compounds II and III. The hydroxy group on Y in the thus formed compounds may then be converted into the other possible substituents in conventional manner. For example, glycidoxy ethers may be prepared by reacting the thus formed phenolic compounds with epichlorhydrin, or the phenolic compounds may be reacted with, e.g. glycidyl acrylate or methacrylate to produce the acrylyl or methacrylyl glyceroxy derivatives.  Example 16 describes the curing with methylene bis aniline of the bis glycidoxy phenyl diphenyl methyl phenyl ether of a polyethylene glycol to give a cured resin.  Bisphenols of Formula (I) above (i.e. compounds in which m is 2 and the functional substituent on Y is a hydroxy group) may be reacted with formaldehyde to produce phenol formaldehyde resins. Example 12 describes the preparation of such a resin from the bis-(bis-phenol-A-ether) of a polyethylene glycol in the presence of n-BuOH, H2O, methanolic NaOH, lactic acid and glycerol.  Compounds of Formula I in which the functional substituent on Y is an alkenoyl glyceroxy group may be polymerized.  Example 18 describes the polymerization of various of such unsaturated monomers in which the functional group on Y is an acrylyl- or methacryl-glyceroxy group to produce thermoset resins.  The monomers, which are bis-(meth)acrylate esters. are polymerized in bulk in the presence of benzoyl peroxide and dimethyl-p-toluidine.ALSO:The invention comprises compounds of formula [Y-(B)c-Ar-O-(alk-O)n]mQ wherein Y is a benzene ring functionally substituted by a hydroxy, glycidoxy, glyceroxy or alkenoyl glyceroxy group and may also be substituted by one or two chlorine or bromine atoms or C1- 4 hydrocarbon groups; B is a sulphone group or one carbon atom of a C1- 13 alkylene or aralkylene group; c is 0, or 1; Ar is a phenylene group, an alkyl or alkenyl (C1- 4) phenylene group or a mono- or di-chloro or bromo phenylene group; alk is a C2- 4 alkylene group; Q is an unsubstituted m-valent C2- 6 alkylene group; m is 2 or 3, n is from about 2 to 20 and the product of m and n is not greater than about 50.  Compounds containing a hydroxyl group as the functional substituent on Y are prepared by firstly reacting a compound [HO(alk-O)n]mQ with an aryl sulphonyl chloride of formula ApSO2Cl in which Ap is a substituted or non-substituted aryl group and an amine NR3 in which R is C1- 6 alkyl or produce a compound of formula [ApSO2-O-(alk-O)n]mQ and then interacting this compound in an alkanolic medium under substantially anhydrous conditions and up to about 10 mole per cent excess over the stoichiometric amount of a phenolic compound Y-(B)c-Ar-OH wherein the functional substituent on Y is a hydroxy group, in the presence of a strong base in a molar amount intermediate between the amounts of the compounds II and III. The hydroxy group on Y in the thus formed compounds may then be converted in to the other possible substituents in conventional manner. For example, glycidoxy ethers may be prepared by reacting the thus formed phenolic compounds with epichlorhydrin, or the phenolic compounds may be reacted with e.g. glycidyl acrylate or methacrylate to produce the acrylyl and methacrylyl glyceroxy derivatives.