Patent GB-873016-A (GB)
Title: Improvements in or relating to polyepoxy ethers of polyhydric phenols
IPC: C07D303/24
Filed: 1959-07-20
Abstract: Monomeric polyethers of a polyhydric phenol (which has been produced by reacting a phenol with a hydroxy-carbonyl compound) and an epoxy-substituted monohydric alcohol may be self-cured by the mere application of heat or may be cured in the presence of conventional epoxy curing agents.  They may also be copolymerized with other poly-epoxide materials 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 are 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 resin is accelerated at temperatures of 100 DEG -200 DEG C. The resin may be mixed with fillers, reactive diluents, pigments, plasticizers, phenolic resins, urea and melamine resins, polysulphide resins and polyvinyl resins.  In Examples, (1) a polyglycidyl ether of 1, 2-dihydroxy-3, 3-bis (hydroxyphenyl) propane is self-cured at 150 DEG C. for 6 heated with diethylene triamine at 125 DEG  for hours; several hours; (2) added to a 50/50 mixture of alcohol and water and cured with condensation product of the glycidyl ether of 2, 2-bis (4-hydroxyphenyl) propane and diethylene triamine; (4) the polyglycidyl ether of 1, 2-dihydroxy-3, 3-bis (hydroxyphenyl) butane is self-cured at 150 DEG C.; (5) the polyglycidyl ether of 1, 2-di-hydroxy-3, 3-bis (hydroxyphenyl) hexane is self-cured at 150 DEG C. or cured with 2, 6-diaminopyridine at 160 DEG C.; (6) the polyglycidyl ether of 1, 2-di-hydroxy-4, 4-bis (hydroxyphenyl) pentane is self-cured; polyglycidyl ethers of polyphenols from glyceraldehyde and resorcinol or o-cresol are also specified; (9) The resins described in (1), (4), (5) and (6) are heated with m-phenylene-diamine and diglycidyl ether of 2, 2-bis (4-hydroxyphenyl) propane, diglycidyl ester of dimerized fatty acids, diglycidyl ester of isophthalic acid, epoxidized soyabean oil, vinyl cyclohexene diepoxide or polyglycidyl 1, 1, 2, 2-tetra (hydroxyphenyl) ethane; (10) the glycidyl ether of (1) is dissolved in xylene and cured with soyabean oil fatty acid; (11) the polyethers of (1), (4), (5) and (6) are cured with hexahydrophthalic anhydride. In Example (3) an acetone solution of the polyglycidyl ether of (1) is mixed with a catalyst solution of 2, 6-diaminopyridine in water and acetone and is used to impregnate glass cloth to form a laminate (see Group VIII).ALSO:The invention comprises a monomeric polyether of a polyhydric phenol (produced by reacting a phenol with a hydroxy-substituted carbonylic compound) and an epoxy-substituted monohydric alcohol, preferably an aliphatic or cycloaliphatic alcohol containing from 3 to 15 carbon atoms in the molecule.  The polyethers are preferably obtained by reacting the polyhydric phenol with an epoxyhalo-substituted alkane or a dihalohydroxy-substituted alkane in 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 is added, and the mixture is heated to reflux.  Water is removed by azeotropic distillation with the epichlorohydrin.  The polyhydric phenol is obtained by mixing a substantial excess of a phenol with a hydroxy-substituted carbonylic compound, introducing a small amount of hyrogen chloride, allowing to react for several days and removing unreacted phenol, e.g. by distillation.  Mercaptans such as ethyl mercaptan may be added to improve the yield.  The phenols may contain halogen, alkoxy or hydrocarbon radicals.  Preferred phenols 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 hydroxy-substituted carbonylic compounds are aliphatic or cycloaliphatic compounds having at least one, preferably two or more, hydroxy groups, and at least one carbonyl group, preferably the di and trihydroxy-substituted aliphatic monoaldehydes and monoketones containing not more than 12 carbon atoms.