Patent GB-928009-A (GB)
Title: Process for the preparation of halogenated glycidyl ethers
IPC: C08G59/14
Filed: 1961-09-13
Abstract: Compounds of the formula <FORM:0928009/IV(a)/1> where n is 1 or 2 and A represents an aliphatic residue with n free valencies which contains at least one grouping of the formula <FORM:0928009/IV(a)/2> in which the two residues Hal represent vicinal halogen atoms, especially chlorine or bromine atoms, and R1 and R2 each represents a hydrogen or halogen atom or an alkyl radical of 1 to 4 carbon atoms (see Group IV(b)) react with conventional curing agents for epoxy resins and can be cured in the cold or with heating.  Many basic and acidic curing agents are specified including amines, hydroxyamines, Mannich's bases, heterocyclic amines, guanidines, amides, dicyandiamide, formaldehyde resins of urea, melamine or aniline, polymers of aminostyrenes, polyamides, isocyanates, isothiocyanates, phosphoric acid, polybasic carboxylic acids and their anhydrides, polyhydric phenols, quinone, unmodified or oil-modified phenolaldehyde resins, reaction products of aluminium alcoholates or phenolates with acetoacetic acid-type tantomers, Friedel-Crafts catalysts, metal fluoborates and boroxines.  Flame-proofing agents, fillers, softening agents, colouring matter or extenders may be admixed with the halogenated glycidyl ethers at any stage prior to curing. The ethers may also be used as flame-proofing active diluents or modifying agents for other epoxy resins.  In Example 1 the diglycidyl ether of 2,3-dibromobutane-1,4-diol is cured in admixture with 30% of a polyglycidyl ether obtained by alkaline condensation of epichlorohydrin with 2,2-bis-(parahydroxyphenyl)-propane, 15% of trixylenyl phosphate, and diethylene triamine.ALSO:Halogenated glycidyl ethers of the general formula <FORM:0928009/IV(a)/1> wherein n is 1 or 2 and A represents an aliphatic radical having n free valencies which contains at least one group <FORM:0928009/IV(a)/2> where Hal represents halogen and R1 and R2 represent hydrogen or halogen atoms or alkyl radicals containing 1 to 4 carbon atoms are prepared by (i) adding halogen on to the double or triple bond or bonds of a glycidyl or glycerol monochlorohydrin ether of an aliphatic mono- or polyhydric alcohol which contains at least one group <FORM:0928009/IV(a)/3> or <FORM:0928009/IV(a)/4> and (ii) dehydrohalogenating the halohydrin groups (if any).  The halogen is preferably bromine or chlorine and the reaction is preferably carried out in a solvent such as carbon tetrachloride or benzene at a temperature of 0-25 DEG C.  The elimination of hydrogen halide in the case of halohydrins is preferably carried out with solid alkali or aqueous alkali solution.  Specified alcohols whose glycidyl or glycerol monochlorohydrin ethers may be used are allkyl, crotyl and propargyl alcohols, but-1-yn-3-ol, n-octadec-9-en-1-ol, but-2-en-1,4-diol and but-2-yn-1,4-diol.  The halogenated ethers react with conventional curing agents for epoxy resins (see Group IV(a)).  In examples: (1) a solution of bromine in carbon tetrachloride is added to a solution of but-2-en-1,4-diol-bis(a -monochlorohydrin) ether in carbon tetrachloride and 50% aqueous sodium hydroxide is added to yield, on purification, the digylcidyl ether of 2,3-dibromobutane-1,4-diol; (2) chlorine is passed into a solution of the diglycidyl ether of but-2-en-1,4-diol in benzene to give the diglycidyl ether of 2,3-dichloro-butane-1,4-diol; (3) chlorine is passed into a solution of but-2-yn-1,4-diol-bis-(a -monochlorohydrin) ether in benzene and then powdered sodium hydroxide is added to give, on purification, the diglycidyl ether of 2,2,3,3-tetrachlorobutane-1,4-diol.