Patent GB-901696-A (GB)
Title: Hardenable compositions comprising epoxide compounds and cyclic ethers or thioethers
IPC: C08G59/40
Filed: 1959-04-08
Abstract: Hardenable compositions suitable for use in adhesives, laminating resins, lacquer coatings, casting resins and moulding compositions, comprise (1) an epoxy compound which has an epoxy equivalency greater than 1, (2) a Friedel Crafts catalyst, including boron trifluoride, or a metal fluoborate and (3) a cyclic ether or thioether containing 1 or 2 monovalent residues of the formula <FORM:0901696/IV(a)/1> in which R1-5 each represents a hydrogen atom, a lower alkyl radical, a lower hydroxy alkyl radical, a lower methoxy alkyl radical, a phenyl radical, a carboxyl group or an acyl radical, or any two residues R1-5 together form fused benzene rings, A1 and A2 each represent a carbon to carbon bond or two hydrogen atoms, and Z represents oxygen or sulphur-with the proviso that if A1 and A2 simultaneously represent a carbon-to-carbon bond, at least one of the radicals R1-5 must not be a hydrogen atom.  Specified epoxy compounds include butadiene dioxide, 1:2:5:6-diepoxy-hexane, 1:2:4:5-diepoxy-cyclohexane methyl-9:10:12:13-diepoxy stearate; the dimethyl ester of 6:7:10:11-diepoxy-hexadecane-1:16-dicarboxylic acid; diethylene glycol bis-(3:4-epoxy-cyclohexane carboxylate), 3:4 - epoxy - cyclohexyl - methyl - 3:4-epoxy-cyclohexane carboxylate; the alkali-catalyzed reaction products of aniline or 4:41-di-(monomethylamine)-diphenylmethane with epichlorhydrin; polyglycidyl esters obtained by the alkali-catalyzed reaction of epichlorhydrin or dichlorhydrin with aliphatic or aromatic dicarboxylic acids (many specified); and polyglycidyl ethers obtained by the alkali-catalyzed reaction of epichlorhydrin or dichlorhydrin with glycols, trihydric alcohols, di- or polyhydric phenols or phenol novolacs (many specified). The cyclic ethers and thioethers may have only one movovalent residue of the above formula and may be tetrahydrothiopyran, dihydropyran and tetrahydropyran and simple substitution products of these compounds and of thiopyran and pyran (many specified). Alternatively, the cyclic ethers and thioethers may have two residues of the above formula linked by a divalent hydrocarbon radical, e.g. the diester of maleic acid and 2-hydroxymethyl-tetrahydropyran.  Specified catalysts include, in addition to boron trifluoride and numerous fluoborates, aluminium chloride, ferric chloride, zinc chloride, antimony pentachloride and tin tetrachloride.  The catalyst may be used in the form of a complex, e.g. with water, alcohols, ethers, ketones, carboxylic acids or their anhydrides, amines, amides, sulphides, tetrahydrofuran or tetrahydrofurfuryl alcohol.  When boron trifluoride is the catalyst, it is advantageously used in the form of a stable complex with water or a nitrogenous base, e.g. ammonia, ethylamine, ethylene diamine, monoethanolamine, triethanolamine, piperidine, urea, hexamethylene tetramine, trimethylamine, pyridine and especially aromatic amines such as aniline, toluidine and Schiff's bases of such amines. Additional components of the compositions may be plasticizers, e.g. dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and triphenyl phosphite; active diluents, e.g. styrene, cresyl glycide, butyl glycide, epoxidized cardanol, tetrahydrofuran, tetrahydrofurfuryl alcohol, ditetrahydrofurfuryl phthalate, methacrylic acid glycidyl ester, and mono- or advantageously poly-functional compounds containing hydroxyl, ketone, aldehyde or carboxyl groups such as dihydric or polyhydric alcohols (pentane diol in Example 5), polyglycols and polyesters containing terminal hydroxyl or carboxyl groups; accelerators, e.g. styrene oxide and organic peroxides; pigments, extenders and fillers, e.g. titanium dioxide, asphalt, bitumen, glass fibres, mica, quartz meal, kaolin and finely divided silicic acid.  The main components of the exemplified compositions are epoxy compounds an alkali catalyzed condensate of 4:41-dihydroxy diphenyl dimethylmethane and epichlorohydrin; 1:4-butanediol diglycidyl ether; a phenol novolac polyglycidyl ether used with 1:4-butanediol diglycidyl ether; 1-vinyl-cyclohexene-3-dioxide; 3:4-epoxy-6-methyl-cyclohexylmethyl-3:4-epoxy-6-methyl-cyclohexane carboxylate cyclic ethers and thioethers tetrahydropyran, dihydropyran, 2-hydroxymethyl-tetrahydropyran, the diester of maleic acid and 2-hydroxymethyl-tetrahydropyran and 2:4-dimethyl-2-methoxymethyl-dihydropyran.  Specifications 887,529, 888,149, 894,037 and 894,038 are referred to.