Patent GB-870365-A (GB)
Title: Improvements in or relating to the preparation of epoxyethers
IPC: C08G59/30
Filed: 1959-03-16
Abstract: The invention comprises epoxy ethers of the formula: <FORM:0870365/IV (a)/1> where one X is an epoxyalkyl radical and the other is a halohydroxy-substituted alkyl radical or epoxyalkyl radical, Y is a halogen atom, R is hydrogen or an alkyl group, and n is at least 2.  They are prepared by treating a haloepoxy-alkane with a condensation catalyst in the presence of water and dehydrohalogenating the resulting polymer with an alkaline material. The preferred polymers are those having the formula: <FORM:0870365/IV (a)/2> where n is 4 to 20, obtained from epichlorhydrin.  Other haloepoxy alkanes which may be used are epibromohydrin, 1, 4-dichloro-2,3-epoxybutane and 1-chloro-2,3-epoxypentane. Condensation catalysts include acids, salts such as tin tetrachloride, and boron trifluoride complexes.  At least 4 mols of haloepoxyalkane should be used per mol of water.  The epoxy compound and the catalyst may be added in portions throughout the reaction.  Temperatures of 30 DEG  to 150 DEG C. are generally used. Suitable dehydrohalogenating compounds are sodium and potassium hydroxides, carbonates and bicarbonates; hydroxides and oxides of magnesium, zinc, lead, iron and aluminium; and aluminates, silicates and zincates of alkali metals.  The dehydrohalogenation may be effected in organic solvents or, except in the case of aluminates, silicates and zincates, in water.  The polyethers range from fluid liquids to semi-solids, soluble in most solvents, e.g. ketone alcohols and hydrocarbons.  Higher molecular weight products may be obtained by reaction with polyhydric alcohols or phenols, e.g. resorcinol, catechol, hydroquinone, methyl resorcinol, 2,2-bis(4-hydroxyphenyl) propane.  These products may be provided with further epoxy groups by reacting with epoxy-forming material and again dehydrohalogenating.  All the products may be polymerized alone or with up to 95% of other polyepoxides such as glycidyl polyethers of polyhydric phenols or alcohols, polyethers obtained by reacting alkane polyols with epichlorhydrin and dehydrohalogenating, polymers of unsaturated epoxides and the reaction products of polyhydric compounds with polyepoxides.  Curing agents which may be employed in the polymerization include carboxylic acids and anhydrides; polyisocyanates; Friedel-Crafts metal halides and their complexes with amines, ethers, anhydrides, ketones and diazonium salts; phosphoric acid and its partial esters; amines; and salts such as the fluoborates of nickel, zinc, copper, sellenium, magnesium, tin and aluminium, potassium persulphate and perchlorate, cupric sulphate, phosphate and phosphite, magnesium arsenate and sulphate, cadmium arsenate and silicate, ferrous sulphate and silicate, manganese hypophosphite, and nickel phosphate and chlorate.  The epoxy materials and curing agents may be mixed with solvents and other film-forming materials and driers to produce coating compositions. Film-forming materials incude drying oils, cellulose derivatives and vinyl and vinylidene chloride, methyl methacrylate and diallyl phthalate polymers.  The compositions of epoxy ethers and curing agents may also be used for castings and pottings, and, with the addition of fillers, as adhesives.  The epoxy ethers are also useful as stabilizers for halogen-containing polymers, particularly polyvinyl halides, if desired together with other stabilizers such as urea and thiourea and as secondary plasticizers in combination with, for example, dioctyl phthalate.ALSO:The invention comprises epoxy ethers of the formula: p   <FORM:0870365/IV (b)/1> where one X is an epoxyalkyl radical and the other is a halohydroxy-substituted alkyl or epoxyalkyl radical, Y is a halogen atom, R is hydrogen or an alkyl group, and n is at least 2.  They are prepared by treating a haloepoxy-alkane with a condensation catalyst in the presence of water and dehydrohalogenating the resulting polymer with an alkaline material.  The preferred polymers are those having the formula: <FORM:0870365/IV (b)/2> where n is 4 to 20, obtained from epichlorhydrin.  Other haloepoxy alkanes which may be used are epibromohydrin, 1,4-dichloro-2,3-epoxybutane and 1-chloro-2,3-epoxypentane. Condensation catalysts include acids, salts such as tin tetrachloride, and boron trifluoride complexes.  At least 4 mols of haloepoxyalkane should be used per mol of water.  The epoxy compound and the catalyst may be added in portions throughout the reaction.  Temperatures of 30 DEG  to 150 DEG C. are generally used. Suitable dehydrohalogenating compounds are sodium and potassium hydroxide, carbonates and bicarbonates; hydroxides and oxides of magnesium, zinc, lead, iron and aluminium; and aluminates, silicates and zincates of alkali metals.  The dehydrohalogenation may be effected in organic solvents or, except in the case of aluminates, silicates and zincates, in water.  The polyethers range from fluid liquids to semi-solids, soluble in most solvents. Higher molecular weight products may be obtained by further reactions (see Group IV(a)).