Patent GB-938809-A (GB)
Title: New monoepoxides and process for their preparation
IPC: C08G59/14
Filed: 1960-10-21
Abstract: Hardenable mixtures comprise a monoepoxide of the formula <FORM:0938809/IV(a)/1> where R1 to R9 each represents hydrogen, halogen or a monovalent hydrocarbon substituent, inert to epoxidation, with the proviso that R1 and R5 may be joined together to form a methylene group, and Z is the hydrocarbon residue of a triol, with a curing agent for epoxy resins with or without an accelerator, and, if desired, the mixture may also contain curable polyepoxides, or epoxy resins, such as:-epoxidized diolefines, including dienes, cyclodienes, unsaturated compounds with two cyclohexenyl groups, compounds from the dehydrohalogenation of reaction products of primary and secondary amines with epichlorohydrin, and polyglycidylethers and -esters.  Mixtures of epoxides may be used as may epoxides containing hydrolysed by-products (see Group IV(b)).  The hydrocarbon substituent may be an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residue and is preferably an alkyl group of 1 to 4 carbon atoms. Specified curing agents are aliphatic and aromatic primary, secondary and tertiary amines, diamines, triamines, alcoholamines, Mannich bases, guanidines, piperidine, piperazine, formaldehydeamine resins, amino styrene polymers, polyamides, isocyanates, isothiocyanates, polyhydric phenols, quinone, phenol-aldehyde resins, including oil modified resins, reaction products of aluminium alcoholates with compounds of acetoacetic type esters, Friedel-Crafts catalysts, fluoroborates, boroxines, phosphoric acid, polycarboxylic acids and anhydrides thereof, and the accelerator used may be a tertiary amine, strong Lewis base, e.g. alkali metal alcoholates, or a polyhydroxy compound.  Other additives may include fillers, plasticizers, and colouring matter. Suitable extenders and fillers include asphalt, bitumen, glass fibres, mica, quartz meal, cellulose, kaolin, finely divided silicic acid and metal powders.  The mixtures may be used as textile assistants, laminating resins, paints, lacquers, coating compositions, pore fillers, putties, adhesives, moulding compositions and electrical insulators.  Examples are given of resins formed by reacting the epoxide of the acetal formed from \se3 tetrahydrobenzaldehyde and glycol with (1) polyglycidyl ethers from epichlorohydrin and bis-(4-methylphenyl)-di-methyl methane, and (2) a cyclo-aliphatic polyepoxide of given formula, using phthalic anhydride as the curing agent.ALSO:The invention comprises monoepoxides of formula <FORM:0938809/IV(a)/1> where R1 to R9 each represents hydrogen, halogen or a monovalent hydrocarbon substituent inert to epoxidation, with the proviso that R1 and R5 may be joined together to form a methylene group, and Z is the hydrocarbon residue of a trihydric alcohol.  The epoxides are made in the usual fashion from the corresponding olefinically unsaturated acetals.  The acetals may be made by treating a corresponding olefinic aldehyde with a triol Z(OH)3 or an epoxide OZ-OH.  Acetalisation may result in a mixture of isomers which may be epoxidised without separation. Epoxidation is preferably effected with organic peracids, hydrogen peroxide and succinic anhydride, or hypochlorous acid, and in the latter method the epoxide is formed from the reaction product on treatment with a base.  The hydrocarbon substituent may be an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residue and is preferably an alkyl group of 1 to 4 carbon atoms. Specified starting aldehydes are D 3-tetrahydrobenzaldehyde and its 2-, 4- and 6-methyl-, 4-chloro- and 2,5-endo-methylene derivatives. Specified triols are glycerol, trimethylol-ethane and -propane and 1,2,4-butane- and 1,2,6-hexane-triols.  During epoxidation some of the epoxide groups may be hydrolysed to hydroxyl groups. Preferred epoxides are derived from the acetal, or mixed acetals, obtained from glycerol and D 3-tetrahydrobenzaldehyde and its 6 preferred alkyl homologues.  The epoxide products may be cross linked to form epoxide resins (see Group IV(a)).  Examples are provided illustrating the preparation of the epoxides and the curing thereof.