Patent GB-894037-A (GB)
Title: Hardenable compositions comprising epoxide compounds and cyclic ethers or thioethers
IPC: C08G75/12
Filed: 1959-03-23
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 of formula <FORM:0894037/IV (a)/1> in which R1-4 each represent hydrogen, halogen hydroxyl, nitro, aldehyde, acetyl, carboxyl, ester, nitrile, ether or aliphatic, cycloaliphatic, araliphatic or aromatic substituents or R1 and R2 and/or R3 and R4 are together members of a cyclic system, A1 represents two hydrogen atoms or monovalent substituents (as for R1-4) or a carbon-to-carbon bond, A2 represents a monovalent substituent and a hydrogen atom or two monovalent substituents 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-(monomethyl-amino)-diphenylmethane and epichlorohydrin; polyglycidyl esters obtained by the alkali-catalyzed reaction of epichlorohydrin or dichlorohydrin with aliphatic or aromatic dicarboxylic acids (many specified); and polyglycidyl ethers obtained by the alkali-catalyzed reaction of epichlorohydrin or dichlorhydrin with glycols, trihydric alcohols, di- and polyhydric phenols or novolacs (many specified). Cyclic ethers and thioethers specified include thiophene and furan-and numerous derivatives of thiophene, furan, tetrahydrothiophene, dihydrofuran and tetrahydrofuran. Specified catalysts include boron trifluoride, aluminium chloride, ferric chloride, zinc chloride, antimony trichloride, antimony pentachloride, tin tetrachloride and numerous metal fluoborates; 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 or tetrahydrofuran.  A particularly useful catalyst is boron trifluoride complexed either with water or with a nitrogenous base, e.g. ammonia, ethylamine, ethylene diamine, monoethanolamine, trithanolamine, 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, glycerol monostearate and tricresyl phosphate; active diluents, e.g. styrene, cresyl glycide, butyl glycide, methacrylic glycide, tetrahydrofuran and mono- or advantageously polyfunctional compounds containing hydroxyl, ketone, aldehyde or carboxyl groups especially polyhydric alcohols, polyglycols (polypropylene glycol in Example 7) and polyesters having terminal hydroxyl or carboxyl groups; accelerators, e.g. styrene oxide and organic peroxides; and hydroperoxides such as 1-hydroxycyclohexane hydroperoxide; and extenders and fillers, e.g. asphalt, bitumen, glass fibres, mica, quartz meal, asbestos powder, kaolin and finely divided silica acid.  The main components of the exemplified compositions are epoxy compounds an alkali-catalyzed condensate of 4:41-dihydroxydiphenyldimethyl methane and epichlorohydrin, containing 5,2 epoxy equivalents per kg. of resin; a phenol novolak polyglycidyl ether prepared from phenol, formaldehyde and epichlorohydrin and diluted with 2:4:6-hexanetriol-triglycidyl ether; 3:4-epoxy-6-methyl-cyclohexyl-methyl - 3:4-epoxy-6-methyl-cyclohexane carboxylate; and alkali-catalyzed condensate of aniline and epichlorohydrin, containing 6,7 gram equivalents of epoxy group per kg; 1:4-butanediol diglycidyl ether; and 1-vinyl cyclohexene-3-dioxide: cyclic ethers and thioethers tetrahydrofurfuryl alcohol, 2-methyl-tetrahydrofuran, 2:5-dimethyl-tetrahydrofuran, tetrahydrofurfuryl chloride, furfuryl alcohol, furfural, 2-methyl furan, 3-methylthiophene, 2-acetylthiophene, a -thiophene aldehyde, 2:3-benzo-thiophene, 2-benzoylthiophene, furan, thiophene and the monoester obtained by reacting maleic anhydride and tetrahydrofurfuryl alcohol.  Uses: rapidly hardening adhesives, laminating resins, lacquer coatings, cast resins and moulding compositions.  Specifications 887,529 and 888,149 are referred to.