Patent GB-865340-A (GB)
Title: Epoxy compounds
IPC: C07D303/24
Filed: 1959-07-21
Abstract: Epoxy resin compositions comprise epoxy ketals or acetals of the formula:- <FORM:0865340/IV (a)/1> in which m and n each represents 1 or 2, each of R1 to R9 and R11 to R91 represent a hydrogen atom, a halogen atom, an alkoxy group, an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radical, R10 and R101 each stands for an alkylene group, and each of X and Y is a hydrogen atom, an aliphatic, cycloaliphatic or aromatic hydrocarbon radical or a heterocyclic radical, or one of X or Y is as just defined and the other is a single bond or a divalent organic radical linked to another residue of the formula shown above after removal of X or Y, and hardeners for epoxy compounds.  Suitable hardeners are amines, e.g. monobutylamine, dibutylamine, tributylamine, p-phenylene diamine, bis-[p-aminophenyl]-methane, ethylene diamine, N, N-diethyl ethylene diamine, tetra-[hydroxyethyl]-diethylene-triamine, diethylene triamine, triethylene tetramine (Examples 13 and 14), tetraethylene pentamine, trimethylamine, diethylamine, triethanolamine, Mannich Bases, piperidine, piperazine, guanidine, diphenyl guanidine, phenyl diguanidine, dicyandiamide, aniline-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, polymers of amino-styrenes, polyamides from aliphatic polyamines and dimerized or trimerized unsaturated fatty acids, isocyanates, isothiocyanates, resorcinol, hydroquinone, quinone, phenol-aldehyde resins, oil-modified phenol-aldehyde resins, reaction products of aluminium alcoholates or phenolates with tautomeric compounds such as acetoacetic ester, Friedel-Crafts catalysts, e.g. AlCl3, Sb Cl3, Sn Cl4, Fe Cl3, Zn Cl2\t and BF3 and their organic complexes, phosphoric acid, and preferably polycarboxylic acids and their anhydrides, e.g. phthalic anhydride (Examples 9, 10, 11, 15 and 16), methyl endomethylene tetrahydrophthalic anhydride (Example 12), endomethylene tetrahydrophthalic anhydride tetrahydrophthalic anhydric (Example 11), or mixtures (Example 11), maleic or succinic anhydrides. Accelerators such as t-amines, e.g. tris-dimethyl-aminophenol (Example 12) and polyhydroxyl compounds, such as hexanetriol (Example 14) may be present.  Preferably 0,3 to 0,9 gram equivalent of anhydride group is used per gram equivalent of epoxide group.  The hardenable mixtures may contain a proportion of the acetals or ketals in which the epoxide groups are wholly or partially saponified. Other polyepoxides may be present such as monoglycidyl or polyglycidyl ethers of monoalcohols (e.g. butyl alcohol) or polyalcohols, monophenols or polyphenols, e.g. resorcinol, bis[4-hydroxyphenyl] dimethyl methane or condensation products of aldehydes with phenols, polyglycidyl esters of polycarboxylic acids, e.g. phthalic acid, or aminopolyepoxides such as those obtained by dehydrohalogenation of reaction products of epihalohydrins and primary or secondary amines such as n-butylamine, aniline or 4, 41-di-(monomethylamino)-diphenyl methane.  In Examples (10) and (11) there is also present a cycloaliphatic epoxide ester resin of the formula:- <FORM:0865340/IV (a)/2> Fillers such as asphalt, bitumen, glass fibres, mica, powdered quartz, cellulose, kaolin, finely divided silica or metal powders, can be present.  Uses: A wide variety of uses is mentioned, electrical insulation being particularly recommended, and the adhesion of aluminium sheets, casting in aluminium moulds, and films on glass plates being exemplified.ALSO:The invention comprises ketals and acetals containing epoxide groups of the general formula:  <FORM:0865340/IV (b)/1> in which m and n each represents 1 or 2, each of R1 to R9 and R11 to R91 represents a hydrogen atom, a halogen atom, an alkoxy group, an aliphatic, cycloaliphatic, araliphatic, or aromatic hydrocarbon radical, R10 and R101 each stands for an alkylene group, and each of X and Y is a hydrogen atom, an aliphatic, cycloaliphatic, or aromatic hydrocarbon radical or a heterocyclic radical, or one of X or Y is as just defined and the other is a single bond of a divalent organic radical linked to another residue of the formula shown above after removal of X or Y.  The novel compounds are made by epoxidation of the corresponding unsaturated compound by conventional methods, e.g. by means of peraretic, perbenzoic, peradipic or monoperphthalic acid, or by reacting with hypochlorous acid and then splitting off HCl with strong alkalis.  The hydroaromatic acetals and ketals used as p  starting compounds are made by acetalization of the unsaturated cyclic alcohols with an aldehyde or ketone of the formula X.CO.Y, e.g. by heating in the presence of an acid catalyst such as hydrochloric or p-toluene sulphonic acid.  The epoxidized acetals or ketals can be cross-linked or cured by addition of hardeners (see Group IV(a)).