Patent GB-813865-A (GB)
Title: Polyepoxy polyethers, their polymers and derivatives
IPC: C08G59/06
Filed: 1956-12-12
Abstract: A polyepoxy polyether of a glycidol and a polyhydric alcohol having in the molecule at least one benzene ring substituted with 3 or 4 alkyl side chains or a phenol having the formula <FORM:0813865/IV (a)/1> wherein R is an alkyl radical containing up to 8 C atoms, X is an alkylene radical containing up to 6 C atoms and R1 is a phenol of formula <FORM:0813865/IV (a)/2> in which one A is the free bond of the phenol radical and the other As and R2s are hydrogen, halogen and/or alkyl radicals having up to 8 C atoms is obtained by reacting the respective alcohol or phenol with a halo-epoxy substituted alkane.  The polyethers are cured to hard infusible resins by heating them with the usual curing agents for epoxy resins, e.g. carboxylic acids and their anhydrides, Friedel-Crafts catalysts, phosphoric acids and partial esters thereof, polyamines, and salts of inorganic acids, e.g. zinc fluoborate, potassium persulphate, magnesium perchlorate.  They also may be esterified with drying oil fatty acids or reacted with methyolol ureas or melamines or diisocyanates.  They may be used as stabilizing agents for vinyl compounds.  The alcohols have the formulae <FORM:0813865/IV (a)/3> wherein Y is a monovalent hydrocarbon radical, X is a bivalent organic radical which is substituted with up to 4 hydroxy groups, R is hydrogen or an alkyl radical, n is 3 or 4 and m is 0 or an integer up to 50.  Examples are 1,4-bis-(beta - hydroxyethoxy - methyl) tetramethylbenzene and 1,3 - bis - (4 - hydroxybutoxymethyl) tetrahexyl benzene.  Examples of the phenols are 1,4-bis-(4-hydroxyphenyl) methyl tetramethylbenzene and 1,3-bis-1-(2-hydroxy-5-chlorphenyl) methyl tetraoctylbenzene. The polyether polyepoxides may be also obtained by heating the polyalcohols with polyepoxides.  Higher molecular weight products may be obtained by further treatment with polyhydric phenols.  In Example (1) glycerol chlorhydrin was reacted with 1,4-bis-(hydroxymethyl) tetramethylbenzene and the product epoxidized by treatment with alkali; the diglycidyl ether obtained was heated with diethylene triamine or a mixture of tetrahydrophthalic anhydride and benzyldimethylamine to give a hard tough casting.  The diglycidyl ether of formula <FORM:0813865/IV (a)/4> was converted to a tough hard resin by heating with diethylene triamine at 100 DEG  C.  (8) The diglycidyl ether of Example (1) was mixed with the diglycidyl ether of resorcinol and one of the following curing agents: (a) triethylene tetramine, (b) m-phenylene diamine, (c) di (aminophenyl) sulphone.ALSO:Di- or polyepoxypolyethers are obtained by reacting an epoxy halo alkane, a dihalo-hydroxy alkane, or a monohalo-polyhydroxy alkane with a polyhydric alcohol of formula <FORM:0813865/IV (b)/1> or <FORM:0813865/IV (b)/2> wherein Y is a monovalent hydrocarbon radical, X is a bivalent organic radical, R is hydrogen or a hydrocarbon radical, n is 3 or 4 and m is 0 or an integer up to 50; or (2) a polyhydric phenol having the formula <FORM:0813865/IV (b)/3> where R is an alkyl radical containing up to 8 C atoms, X is an alkylene radical containing up to 6 carbon atoms and R1 is as shown <FORM:0813865/IV (b)/4> in which one A is the free bond of the phenol radical and the other As and R2s are hydrogen, halogen and/or alkyl radicals each having up to 8 C atoms.  Examples of (1) are 1,4-bis-(beta-hydroxyethoxy - methyl) tetramethylbenzene 1,4 - bis-(2,6 - dihydroxyhexyloxymethyl) tetramethylbenzene 1,3 - bis - (4 - hydroxybutoxymethyl) tetrahexylbenzene.  Examples of (1) are 1,4-bis-[(4-hydroxyphenyl) methyl] tetramethyl benzene 1,4 - bis-[(4 - hydroxyphenyl) ethyl] tetraisopropylbenzene 1,4 - bis - [(2 - hydroxy - 4 - tert. butylphenyl) ethyl] tetramethylbenzene 1,3 - bis-[(4 - hydroxyphenyl) methyl] tetramethylbenzene 1,3 - bis - [(2,3 - dihydroxyphenyl) methyl] tetramethylbenzene 1,3 - bis - [1 - (2 - hydroxy - 5 - chlorophenyl) methyl] tetraoctylbenzene.  If necessary, the reaction is followed by dehydrohalogenation.  The epoxy ethers of the poly (alkyl) benzene substituted phenols are obtained by reacting the phenol with an epoxyhalo-substituted alkane or dihalohydroxy substituted alkane in an alkaline medium, e.g. an alkali metal hydroxide.  In examples (i) glycerol monochlorohydrin was reacted with 1 : 4 bis-(hydroxymethyl) tetramethylbenzene and the product epoxidized by treatment with alkali; (ii) as (i) but using 1 : 4-bis-(hydroxymethyl) 2 - ethyl - 3 : 5 : 6 - trimethyl benzene, 1 : 3 bis-(hydroxymethyl) tetramethyl benzene and 1 : 4 bis-(hydroxymethyl) tetraethyl benzene; (iii), (iv), (v), (vi) epichlorohydrin was reacted with 1 : 4 bis-(hydroxyphenylmethyl) tetramethyl benzene, 1 : 4 bis - (2 - hydroxy - 5 - chlorophenyl) methyl] tetramethyl benzene, 1 : 4 bis-[(2 - hydroxy - 3 - tert. - butyl 5 - methylphenyl) methyl] tetramethyl benzene, 1 : 4 bis-[(2 - hydroxy - 3 - tert. - butyl - 5 - ethylphenyl) methyl] tetramethyl benzene and 1 : 4 bis-(betahydroxy ethoxymethyl) tetramethyl benzene to give the corresponding diglycidyl ethers.