Patent GB-873017-A (GB)
Title: Improvements in or relating to polyepoxy ethers of epoxy-substituted polyhydric phenols
IPC: C08G59/06
Filed: 1959-07-20
Abstract: Monomeric polyethers of an epoxy-substituted polynuclear polyhydric phenol and an epoxysubstituted monohydric alcohol (wherein the polyhydric phenol is obtained by condensing a phenol with an epoxy-substituted carboylic compound or the corresponding chlorohydrin substituted carboxylic compound in the presence of alkaline material), may be cured with conventional epoxy-curing agents or may be copolymerized with other poly-epoxides such as glycidyl polyethers of polyhydric phenols or alcohols, e.g. bisphenol, resorcinol, glycerol or sorbitol and polymers from unsaturated epoxides, e.g. poly (allyl glycidyl ether).  Examples of curing agents include oxalic acid, phthalic anhydride, Friedel Crafts metal halides and complexes thereof with ethers, ketones, diazonium salts; phosphonic acid and partial esters thereof; amino compounds, dicyandiamide and melamine, and salts of inorganic acids.  Many examples of such agents are specified.  Cure of the resins is accelerated at 100 DEG -200 DEG C.  The resin may be mixed with fillers, reactive diluents, pigments, phenolic resins, urea and melamine resins, polysulphide resins and polyvinyl resins.  In Examples (1) a polyglycidyl ether of 1, 2-epoxy-3, 3-bis (4-hydroxyphenyl) propane and (3) the polyglycidyl ether of 1, 2-epoxy-3, 3-bis (hydroxyphenyl) butane are cured with m-phenylene diamine; (4) the glycidyl ether of 1, 2-epoxy-3, 3-bis (hydroxyphenyl) hexane is cured with 2, 6-diamino-pyridine; (5) the polyglycidyl ether of 1, 2-epoxy-4, 4-bis (hydroxyphenyl) pentane is cured with tetrahydrophthalic anhydride; (9) the polyethers of (1), (4), (5) and (6) a polyether in which the polyhydric phenol is obtained from resorcinol and glycidaldehyde, are heated with m-phenylene diamine and several polyepoxides viz. the diglycidyl ether of bisphenol A, the diglycidyl esters of dimerized fatty acids and of isophthalic acid, epoxidized soyabean oil, vinyl cyclohexenedioxide and the polyglycidyl ether of 1, 1, 2, 2-tetrakis (hydroxyphenyl) ethane; (10) the polyether of (1) is dissolved in xylene, soyabean oil fatty acid is added and the mixture is heated to form a coating; (11) the polyethers of (1), (4), (5) and (6) are cured by heating with hexahydrophthalic anhydride.  In Example (2) an acetone solution of the polyglycidyl ether of (1) was mixed with an aqueous acetone solution of 2, 6-diaminopyridine and used to impregnate glass cloth to form a laminate (see Group VIII).ALSO:The invention comprises a monomeric polyether of an epoxy-substituted polyhydric polynuclear phenol (which has been produced by condensing a phenol with (i) an epoxy-substituted carbonylic compound or (ii) the corresponding chlorohydrin-substituted carbonylic compound in the presence of alkaline material) and an epoxy-substituted monohydric alcohol, preferably an epoxy-substituted aliphatic or cycloaliphatic alcohol containing from 3 to 18 carbon atoms in the molecule.  The polyethers may be obtained by reacting the polyhydric phenol with an epoxy-halo-substituted alkane or a dihalo-hydroxy-substituted alkane in an alkaline medium.  For example, the polyhydric phenol may be added to 2 to 10 moles of epichlorohydrin per phenolic hydroxyl group, an alkali metal hydroxide such as sodium or potassium hydroxide is added, and the mixture is heated to reflux. Water is removed azeotropically with epichlorohydrin.  The polyethers may also be made by first forming an ether of the appropriate olefinically unsaturated alcohol and epoxidizing the product, for example with peracetic acid in chloroform solution. The polyhydric phenol is obtained from a monohydric or polyhydric phenol which may contain halogen atoms, alkoxy radicals or hydrocarbon groups.  Preferred are monohydric phenols containing 6 to 12 carbon atoms, and di or trihydric phenols containing a single aromatic ring or rings joined through an alkylene group and containing not more than 25 carbon atoms.  The epoxy-substituted carbonylic compounds are aliphatic or cycloaliphatic compounds having at least one oxirane group and at least one carbonyl group, preferred are the monoepoxy and diepoxy aliphatic monoaldehydes and monoketones containing not more than 12 carbon atoms per molecule.  The chlorohydrin derivatives used are those which give the epoxy-substituted compounds on treatment with alkaline materials.  Examples describe the polyglycidyl ethers of 1,2-epoxy-3,3-bis(4-hydroxyphenyl) propane, 1,2-epoxy-3,3-bis(hydroxyphenyl) butane, 1,2-epoxy-3,3-bis(hydroxyphenyl) hexane, 1,2-epoxy-4,4-bis(hydroxyphenyl) pentane and similar ethers in which the polyhydric phenol is obtained from glycidaldehyde and resorcinol, glycidaldehyde and o-cresol, and 1,2-epoxy-3-ketobutane with resorcinol.  The products may be used for making epoxy resins (see Group IV(a)) and laminates (see Group VIII).