Patent GB-943924-A (GB)
Title: Mixtures of esters containing epoxide groups, their production and their uses
Inventor: HUMPHREYS KEITH WOOD
IPC: C07D303/16
Filed: 1960-04-05
Abstract: The invention comprises a mixture of isomeric compounds conforming to the general formula: <FORM:0943924/C2/1> wherein n is 2, 3 or 4 and Z stands for that residue of an organic compound having n carboxyl groups which remains after removal of the hydroxyl groups from such carboxyl groups, the said residue optionally containing one or more epoxide groups or n is 1, and Z stands for a cycloaliphatic carboxylic acid to which is fused an epoxide group.  The mixture of esters are made by epoxidising the corresponding ethylenically unsaturated compound with a peracid, such as peracetic, perbenzoic, peradipic or monoperphthalic acid. Starting materials containing halohydrin groups may also be used, such groupings being epoxidised by treatment with dehydrohalogenating agents, such as potassium hydroxide or sodium hydroxide. When the starting material contains both double bonds and halohydrin groups, the double bonds are preferably epoxidised first.  The mixtures of isomeric esters used as starting materials are made by esterification of mixtures of isomeric hydroxydicyclopentadienes with either a monocarboxylic acid containing at least one epoxide or epoxidisable group or a dicarboxylic acid which may or may not contain epoxide or epoxidisable groups, or a functional derivative thereof such as an anhydride, acid halide or ester, if necessary in the presence of an esterification catalyst, e.g. toluene-p-sulphonic acid. Many suitable carboxylic acids are specified. Examples describe the preparation of bis-di-hydrodicyclopentadieny succinates, maleates, phthalates, D 4-tetrahydrophthalates, adipates, tetrahydrobenzoates, 2 : 5 - endomethylene -D 3-tetrahydrobenzoates, sebacates, methyl - endomethylene - tetrahydrophthalates, hexachloro-3, 6-endomethylenetetrahydrophthalates, of tris-dihydrodicyclopentadienyl trimellitates, and of dihydrocyclopentadienyl oleates and esters of fatty acids of tall oil, corn oil, cottonseed, castor oil, soya, tung oil, rapeseed, olive oil, groundnut oil, linseed oil, sunflower oil, dimerised fatty acids or lactic acid dihydrodicyclopentadienyl ether. Specification 943,925 is referred to.ALSO:A curable composition comprises a mixture of isomeric esters conforming to the general formula: <FORM:0943924/C3/1> wherein n is 1, 2, 3 or 4 and z stands for that residue of an organic compound having n carboxylic groups which remain after removal of the hydroxyl groups from such carboxyl groups, the said residue optionally containing one or more epoxide groups and, where n is 1, containing at least one epoxide or epoxidisable group, together with one or more hardeners therefor. Suitable hardeners are amines, amides, isocyanates, isothiocyanates, polyhydric phenols, phenol-aldehyde resins, reaction products of aluminium alkoxides or phenolates with tautomeric reacting compounds of the acetoacetic ester type, Friedel-Crafts catalyst, e.g. AlCl3, SbCl5, SnCl4, ZnCl2, BF3 and their complexes with organic compounds and phosphoric acids. The preferred hardeners are polybasic carboxylic acids and their anhydrides.  Accelerators such as tertiary amines and polyhydroxy compounds may be present.  The compositions preferably also contain a proportion of the above mixed esters in which some or all of the epoxide groups are hydrolysed to hydroxyl groups, and/or contain other polyhydroxy-compounds promoting cross-linking, such as hexanetriol.  Other epoxides may be present, such as mono- or poly-glycidyl ethers of mono- or poly-alcohols or mono- or polyphenols, polyglycidyl esters of polycarboxylic acids, or amino polyepoxides or mixtures of isomeric 4-oxatetracyclo (6:2:1:02, 7 03, 5) hendecanes as described in Specification 943,925.  Fillers, plasticizers or colouring agents may also be added.  Detailed examples are given.