Patent GB-1002183-A (GB)
Title: New halogen-containing glycidyl ethers
IPC: C07D303/22
Filed: 1961-09-13
Abstract: Curable compositions comprise glycidyl ethers of the general formula <FORM:1002183/C3/1> wherein n is 1 or 2, and A represents a cycloaliphatic residue with n free valencies which contains at least one grouping of the formula <FORM:1002183/C3/2> where Hal represents halogen, and a curing agent for epoxy resins. Many suitable curing agents are specified, these being unsubstituted or substituted amines, amides, isocyanates, isothiocyanates, phosphoric acid, polybasic carboxylic acids and their anhydrides, polyhydric phenols, quinone, phenolaldehyde resins, reaction products of aluminium alcoholates or phenolates with tautomers of the type of acetoacetic acid esters, Friedel-Crafts catalysts, metal fluoborates and boroxines.  The curable ethers, or their mixtures with curing agents, can be admixed at any stage prior to curing with flame-proofing agents, fillers, extenders, softening agents or colouring matter. The above ethers can also be used as modifying agents for known epoxy resins.  Examples are given. Specification 905,048 is referred to.ALSO:The invention comprises halogenated glycidyl ethers of the general formula <FORM:1002183/C2/1> wherein n is 1 or 2 and A represents a cycloaliphatic radical which contains at least one group <FORM:1002183/C2/2> where Hal represents halogen.  Preferred ethers are those of the general formula <FORM:1002183/C2/3> whre Hal1 represents chlorine or bromine, R1 and R2 are each hydrogen or together represent -CH2-, and R3 represents a hydrogen atom or a methyl group.  The compounds may be prepared by: (A) adding halogen on to the double bond or bonds of a glycidyl or glycerol monohalohydrin ether of a cycloaliphatic mono- or polyhydric alcohol which contains at least one -CH=CH-group, and, if the starting material was a glycerol monohalohydrin ether, dehydrohalogenating the halohydrin groups; or (B) reacting, in known manner, a cycloaliphatic mono- or polyhydric alcohol containing at least one group <FORM:1002183/C2/4> with an epihalohydrin and then dehydrohalogenating the halohydrin groups.  The halogen is preferably bromine or chlorine and the halogenation of the double bond is preferably carried out in a solvent such as benzene or carbon tetrachloride at a temperature of 0-25 DEG  C. The elimination of hydrogen halide in the case of halohydrins is carried out with solid alkali or aqueous alkali solution.  Specified alcohols whose glycidyl or glycerol monochlorohydrin ethers may be used are cyclohex-3-en-1-o1, D 3-tetrahydrobenzyl alcohol, 6-methyl-D 3-tetrahydrobenzyl alcohol, 2,5-endomethylene-D 3-tetrahydrobenzyl alcohol, D 3-cyclohexene-1,1-dimethanol, 6 - methyl - D 3 - cyclohexene - 1,1 - dimethanol, 2,5 - endomethylene - D 3 - cyclohexene - 1,1 - dimethanol and dihydrodicyclopentadien -8-o1. Examples are given of both types of preparation.  The halogenated glycidyl ethers react with conventional curing agents for epoxy resins (see Division C3).  Specification 905,045 is referred to.ALSO:Example 8 describes coating an aluminium sheet with a lacquer solution containing 3,4-dibromo-cyclohexane-1,1-dimethanol-bis(glycidyl) ether, butanol, ethylene glycol monomethyl ether, xylene and a polyamide resin obtained by condensing dimerized unsaturated plant fatty acids with diethylenetriamine.  The coated sheet is then dried and cured.  In Example 9, oak panels are brushed with a mixture of the above diglycidyl ether, triethylene-tetramine and tris-(1,2,4-dimethylaminomethyl)-phenol.  A glass fibre fabric is then interposed and, after gelling, another coat of the mixture is applied to the sandwich.  In Example 11, a 12-ply glass fibre laminate is covered with a mixture of the above diglycidyl ether, bis-(4-hydroxyphenyl)-dimethylmethane and triethylenetetramine and is then cured.  Specification 905,045 is referred to.