Patent GB-918510-A (GB)
Title: New epoxy derivatives and process for their production
IPC: C08G59/26
Filed: 1961-03-27
Abstract: Curable mixtures contain epoxy compounds of the formula <FORM:0918510/IV(a)/1> where R1 and R2 each represents a hydrogen or halogen atom or an alkyl or alkoxy group or both together from a condensed aromatic ring; X1 and X2 each represents a hydrogen atom or a methyl group, Y the residue of a dihydric alcohol containing at least one epoxide group; y=1 or 2; p=1, 2 or 3; n is an integer from 1 to 4, preferably 1 or 2; and z represents a hydrogen atom, an aliphatic residue with n free valencies, or an araliphatic residue joined to the remainder of the molecule via n free valencies attached to aliphatic carbon atoms, together with a curing agent for epoxy resins.  Curing agents include amines or amides, aniline-, urea- or melamine-formaldehyde resins, polymers of aminostyrenes, polyamides, isocyanates, isothiocyanates, polyhydric phenols, phenol-aldehyde resins, reaction products of aluminium alcoholates or phenolates with tantomeric compounds such as acetoacetic ester, Friedel-Crafts catalysts and organic complexes thereof, phosphoric acid and, preferably, polycarboxylic acids and anhydrides thereof.  An accelerator such as a tert-amine or strong Lewis base and a polyhydroxyl compound may be present.  The curable mixtures may also contain the above acetals in which the epoxide groups have been wholly or partially hydrolysed.  Active diluents or modifying agents such as mono or polyglycidyl ethers of mono or polyalcohols or phenols, polyglycidyl esters of polycarboxylic acids, and aminopolyepoxides, may also be present.  Fillers, extenders, plasticizers, and colouring matter, can also be added.  In examples curable compositions are described containing an acid anhydride, e.g. phthalic anhydride and epoxy compounds obtained by epoxidation of the reaction product of (a) phenol, p-cresol or bisphenol A and the acetal from acrolein and 1:1-bis-[hydroxymethyl]-cyclohexene-3, (b) phenol and the acetal from (i) acrolein and 1:1-bis(hydroxymethyl)-6-methylcyclohexene, (ii) acrolein and 1:1-bis/hydroxymethyl - 2:5 - endomethylenecyclohexene - 3, (iii) methacrolein or crotonic aldehyde and 1:1-bis(hydroxymethyl)-cyclohexene-3, (c) p-chlorophenol, and -naphthol or hydroquinone, and the acetal from acrolein and 1:1-bis(hydroxymethyl)-cyclohexene-3.  In a further example, a sodium alcoholate derived from 2:4-dihydroxy-3-hydroxymethylpentane is added to a mixture of the epoxidized product of phenol and the acetal from acrolein and 1:1-bis(hydroxymethyl)-cyclohene-3, and the mixture is cured.ALSO:The invention comprises epoxy compounds of the general formula <FORM:0918510/IV (b)/1> where R1 and R2 each represent a hydrogen or halogen atom, or an alkyl or alkoxy group, or together represent a condensed aromatic ring, X1 and X2 each represents a hydrogen atom or a methyl group; Y represents the residue of a dihydric alcohol that contains at least one epoxide group; y = 1 or 2; p = 1, 2 or 3; and n is an integer from 1 to 4, advantageously 1 or 2; and Z represents a hydrogen atom, an aliphatic residue having n free valencies, or an araliphatic residue joined to the remainder of the molecule via n free valencies attached to aliphatic carbon atoms. The new compounds may be made by epoxidation of the corresponding acetal wherein Y contains an epoxidisable group, which may be a carbon-carbon double bond, (in which case epoxidation may be effected with an organic peracid or by treatment with HOCl followed by a strong alkali) or a halohydrin group (which can be epoxidised by treatment with a dehydrohalogenating agent).  The acetal starting materials may be made by reacting a phenol of the formula <FORM:0918510/IV (b)/2> <FORM:0918510/IV (b)/3> in a mol ratio of 1 to n.p.  Suitable mono, di and polyphenols are specified.  The above unsaturated acetals are made by reacting crotonic aldehyde, methacrolein or acrolein with an epoxidisable or unsaturated diol Y1(OH)2 in the presence of an acid catalyst.  Specifie unsaturated diols are butene-(2)-diol-1 : 4, glycerol monoallyl ether, butanetriol-(1 : 2 : 4)-monoallyl ether and 1 : 1-bis(hydroxymethyl)-cyclohexene-(3) and halogen, alkoxy or hydrocarbon substituted derivatives thereof.  Detailed examples are given.