Patent GB-917027-A (GB)
Title: New epoxides and processes for their preparation
IPC: C08G59/14
Filed: 1960-10-21
Abstract: Hardenable mixtures comprise a monoepoxide of formula:-<FORM:0917027/IV(a)/1> where R1 to R8 are H or substituents such as halogen atoms or an aliphatic, cycloaliphatic, arylaliphatic, or aromatic hydrocarbon residue, or R1 and R5 may be a methylene group, and X1 and X2 are hydrogen or methyl groups, and a curing agent with or without an accelerator, and if desired the mixture may contain a curable polyepoxide or epoxy resin such as:-epoxidized diolefines including dienes, cyclic dienes, unsaturated carboxylic acid esters, compounds with two cyclohexenyl groups, compounds from the dehydrohalogenation of rereaction products of primary and secondary amines with epichlorohydrin, polyglycidyl esters and polyglycidyl ethers. Specified curing agents are aliphatic and aromatic primary, secondary and tertiary, diamines, triamines, alcoholamines, Mannich bases, guanidines, piperidine, piperazine, formaldehyde-amine resins, amino-styrene polymers, polyamides, isocyanates, isothiocyanates, polyhydric phenols, quinone, phenol aldehyde resins, including oil-modified resins, reaction products of aluminium alcoholates or phenolates with compounds of the acetoacetic ester type, 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 alcoholate, or a polyhydroxy compound.  Other additives may include fillers, plasticizers, and colouring matter.  Suitable fillers and extenders are asphalt, bitumen, glass fibres, mica, quartz meal, cellulose, kaolin, finely-distributed silicic acid and metal powders.  The mixtures may be used as textile assistants, laminating resins, paints, lacquers, dipping resins, casting resins, coating compositions, putties, adhesives, pore fillers, moulding compositions and electrical insulators.  Examples are given of resins formed from (1) polyglycidyl ether prepared by reacting epichlorohydrin with bis[4-hydroxyphenyl]-dimethyl methane and the epoxide of the acetal from acrolein and 1:1-bis[hydroxymethyl]-cyclohexene-3 with phthalic anhydride as curing agent, and (2) a cycloaliphatic polyepoxide of given formula and (a) the epoxide of the acetal from crotonic aldehyde and bis-1:1-[hydroxymethyl]-cyclohexene-3 and (b) the epoxide from the acetal of crotonic aldehyde and 1:1-bis[hydroxymethyl]-6-methylcyclohexene-3 with sodium alcoholate as curing agent.ALSO:The invention comprises epoxides of formula <FORM:0917027/IV (b)/1> where R1 to R8 are H or substituents such as halogen atoms or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residues or R1 and R5 may be a methylene group, and X1 and X2 are H or Me.  The epoxides are made from the appropriate acetal diolefine by treatment with an epoxidising agent under conditions such that only the cycloolefinic double-bond is affected. The reagents used may be organic peracids e.g. peracetic and monoperphthalic acids. Preferably the R's are alkyl radicals of 1-4 C atoms.  The epoxides may be cross-linked or cured (see Group IV(a)). The acetals are made from appropriate aldehydes e.g. acrolein, methacrolein and crotonic aldehyde and alcohols such as 1,1-bis(hydroxymethyl)-cyclohexene-(3) and -6-methyl-, -2,4,6-trimethyl-, 2,5-endomethylene- and -4-chlorocyclohexenes-(3). During epoxide formation some of the product may be hydrolysed to yield alcohols.  Examples are provided of the preparation of epoxides from certain of the above specified reactants.