Patent GB-894038-A (GB)
Title: Hardenable compositions comprising epoxide compounds and cyclic ethers or thioethers
IPC: C08G75/12
Filed: 1959-03-26
Abstract: Hardenable compositions comprise (1) an epoxy compound with an epoxy equivalency greater than 1, (2) a Friedel-Crafts catalyst, including boron trifluoride, or a metal fluoborate, (3) a cyclic ether or thioether containing at least two monovalent residues of the formula <FORM:0894038/IV (a)/1> in which R1-3 represents hydrogen, A1 and A2 each represent two hydrogen atoms or a carbon-to-carbon bond, and Z represents oxygen or sulphur.  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 (monomethylamino)-diphenyl-methane and epichlorohydrin; 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-formaldehyde condensation products (many specified).  The preferred cyclic ethers and thioethers have the two monovalent residues linked through a divalent hydrocarbon radical and include the polyesters and especially the diesters of tetrahydrofurfuryl alcohol, a -thenyl alcohol or furfuryl alcohol and di- and polycarboxylic acids; the formals, acetals and ketals of tetrahydrofurfuryl alcohol, a -thenyl alcohol or furfuryl alcohol and aldehydes or ketones; the polyethers and especially diethers of tetrahydrofurfuryl alcohol, a -thenyl alcohol or furfuryl alcohol and di- or polyvalent alcohols; the di- or polyesters of thiophene-2-carboxylic acid or furane-2-carboxylic acid and di- or polyvalent alcohols; difurfuryl, difurfuryl acetone; difurfuryl-cyclohexanone, difurfuryl ether 1:5-difurfuryl pentane and 2:6-ditetrahydrofurfuryl cyclohexanol-(1).  Specified catalysts include, in addition to boron trifluoride and numerous fluoborates, aluminium trichloride, ferric chloride, zinc chloride, antimony trichloride and 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, tetrahydrofuran, tetrahydrofurfuryl alcohol and monofunctional or preferably polyfunctional compounds containing hydroxyl, ketone, aldehyde or carboxyl groups such as dihydric or polyhydric alcohols (butane diol-1:4 in Example 3), polyglycols and polyesters having terminal hydroxyl or carboxyl groups; accelerators, e.g. styrene oxide and organic peroxides and hydroperoxides such as hydroxycyclo-hexylhydroperoxide; and extenders, pigments and fillers, e.g. titanium dioxide, asphalt, bitumen, glass fibres, mica, quartz meal, kaolin and finely dispersed silicic acid.  The main components of the exemplified compositions are epoxy compounds an alkali catalyzed condensate of 4:41-dihydroxydiphenyl-dimethyl methane and epichlorohydrin, containing 5,1 or 4,6 epoxy equivalents per kg; a phenol novolac polyglycidyl ether used with diglycidyl ether of diethylene glycol; phthalic acid diglycidyl ester; an alkali catalyzed condensate of aniline and epichlorohydrin, containing 6,7 epoxy equivalents per kg; 3:4-epoxy-6-methylcyclohexylmethyl-3:4-epoxy-6-methyl cyclohexane carboxylate; 1:4-butanediol diglycidyl ether; and 1-vinyl-cyclohexene-3-dioxide cyclic ethers and thioethers ditetrahydro-furfuryl phthalate, ditetrahydrofurfuryl maleate, 2:6-ditetrahydrofurfuryl cyclohexanol-1, ditetrahydrofurfuryl formal, ditetrahydrofurfuryl-endomethylene-tetrahydro phthalate, the reaction product of trimellitic anhydride and tetrahydrofurfuryl alcohol. Uses: rapidly hardening adhesives, laminating resins, lacquer coatings, casting resins and moulding compositions. Specifications 887,529, 888,149 and 894,037 are referred to.