Patent GB-900506-A (GB)
Title: Esters containing epoxide groups, their production and their uses
Inventor: WEBB REGINALD FRANCIS
IPC: C07D303/16
Filed: 1959-12-23
Abstract: Hardenable compositions comprise esters of the formula <FORM:0900506/IV(a)/1> and one or more hardeners therefor, such as amines or amides, e.g. mono-, di- and tributylamine, p-phenylenediamine, bis(p-aminophenyl)methane, ethylenediamine, N:N-diethylethylenediamine, diethylenetriamine, tetra(hydroxyethyl)-diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylamine, diethylamine, triethanolamine, Mannich bases, piperidine, guanidine, phenyl guanidine and diphenyl guanidine, dicyandiamide, aniline-formaldehyde resins, polymers of amino-styrenes, polyamides, e.g. from aliphatic polyamines and di- or tri-merised unsaturated fatty acids, isocyanates, isothiocyanates, resorcinol, hydroquinone, bis(4-hydroxyphenyl)-dimethylmethane and quinone, phenol-aldehyde resins, oil-modified phenolaldehyde resins, reaction products of aluminium alkoxides or phenolates with tautomeric reacting compounds of the acetoacetic ester type, Friedel-Crafts catalysts, e.g. AlCl3, SbCl5, SnCl4, ZnCl2, BF3 and the complexes with organic compounds, and phosphoric acid.  Preferred hardeners are polybasic carboxylic acids and their anhydrides, e.g. phthalic anhydride, methylenedimethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydrides hexahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride or endomethylenetetrahydrophthalic anhydride or their mixtures, or maleic or succinic anhydrides.  Accelerators such as tertiary amines and polyhydroxy compounds such as hexanetriol and glycerol may be present in some cases.  The hardenable mixtures may contain a proportion of the epoxy esters in which one or both of the epoxy groups are hydrolysed to hydroxyl groups, and/or other polyhydroxy compounds such as hexanetriol.  Other epoxides, e.g. mono- or polyglycidyl ethers of mono- or polyalcohols such as butyl alcohol, butane-1:4-diol or glycerine, or mono or polyphenols, e.g. resorcinol, bis(4-hydroxyphenol) dimethylmethane or Novolaks; polyglycidyl esters of polycarboxylic esters, such as phthalic acid, or aminopolyepoxides obtained by dehydrohalogenation of products from epichlorhydrin and amines such as n-butylamine, aniline or 4:41-di-(monomethylamine)-diphenylmethane, may also be present.  The compositions may also contain asphalt, bitumen, glass fibres, mica, quartz, powder, cellulose, kaolin, kieselguhr or metal powder.  In an example the novel epoxy-carbonate ester is hardened with phthalic anhydride and tris(dimethylaminomethyl)phenol.ALSO:The invention comprises compounds of the formula <FORM:0900506/IV (b)/1> which may be made by epoxidation of a compound of the formula <FORM:0900506/IV (b)/2> The epoxidation may be effected by treatment with organic peracids, e.g. peracetic, perbenzoic, peradipic or monoperphthalic acid, or by treatment in a first stage with hypochlorous acid and in a second stage with an HCl-eliminating agent, e.g. a strong alkali. Preferably peracetic acid is used at 0-40 DEG C.  In addition to the di-epoxide, completely or partially hydrolysed epoxides arise from side reactions.  The unsaturated ester starting material may be made by reaction of phosgene, in the presence of a tertiary base, with dehydronorborneol.  The Provisional Specificagives general formulae in which the above compounds may be substituted on the ring carbon atoms by halogen, alkoxy or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residues.