Patent GB-969041-A (GB)
Title: Esters containing both epoxide and oxetane groups, their production and their uses
Inventor: STARK BERNARD PETER
IPC: C08G59/20
Filed: 1961-10-11
Abstract: The invention comprises esters of formula: <FORM:0969041/C1/1> wherein R is an alkyl group, preferably methyl or ethyl, Z the residue of an organic carboxylic acid having n carboxyl groups and at least one epoxide group but no other functional group after the removal of hydroxyl groups, and n is an integer from 1 to 4, which are prepared by heating a hydroxy-oxetane. <FORM:0969041/C1/2> with an ester [R1O-]nZ in which R1 is a hydrocarbon residue, in the presence of a transesterification catalyst, e.g. tetrabutyl titanate, zinc or cadmium acetate, dibutyl tin oxide, alkali metals and their hydroxides and alkoxides, quaternary ammonium hydroxides and quaternary ammonium containing ion-exchange resins. A solvent such as dioxan, toluene or chlorine containing aromatic hydrocarbons may be present and the alcohol formed removed by distillation and the products are liquid or readily fusible compounds which may be hardened e.g. by treatment with a dicarboxylic acid anhydride to clean light-coloured resins. The preferred oxetane of Formula II is 3-ethyl -3- hydroxymethyl -1- oxacyclobutane and the ester [R1O-]n Z that of an epoxidised 1, 2, 3, 6-tetrahydrobenzoic or D 4-tetrahydrophthalic acid or a glycidic acid, e.g. methyl 3,4-epoxy-1, 2, 3, 6-tetrahydrobenzoate ethyl b -phenyl -b -methyl-glycidate, di-n-propyl 7-oxabicyclo [4, 1, 01, 6] heptanedicarboxylate, and epoxidised fatty acids, of such as soyabean, tung, sesame, sunflower, rapeseed, peanut, olive, castor, coconut, animal, tallow, fish and tall oils. The esters may be polymerized with Friedel Crafts catalysts or cross-linked and hardened by bis-n-poly-functional compounds and may be used in resinous compositions (see Division C3).ALSO:Compositions comprising esters of formula <FORM:0969041/C3/1> wherein n is 1 to 4, Z is the residue of an organic carboxylic acid originally with n carboxyl groups and at least one epoxide group but no other functional group, that remains after the removal of hydroxyl groups from such carboxyl groups; and R is an alkyl preferably a methyl or ethyl group (see Division C2) may be polymerized with Friedel Crafts catalysts or cross-linked or hardened by bis or polyfunctional compounds such as e.g. phthalic acid, adipic acid, methylendomethylenetetrahydrophthalic; endomethylenetetrahydrophthalic, dodecenylsuccinic, tetrahydrophthalic, hexahydrophthalic, maleic, succinic, and hexachloroendomethylenetetrahydrophthalic anhydrides or mixtures thereof. The mixtures may also contain proportions of alcohols <FORM:0969041/C3/2> from which the esters are prepared, and partial esters of formula <FORM:0969041/C3/3> Accelerators such as t-amines and toluene-p-sulphonic acid may be present together with other hardenable resins e.g. 2,6-dioxaspiro (3,3) heptane, the reaction products of alkali metal salts of bis-phenols with 3-halomethyl -3- alkyl -1- oxacyclobutanes, di- or poly-glycidyl ethers of di- or polyalcohols or di- or polyphenols such as bis (4-hydroxyphenyl) dimethyl-methane, polyglycidyl esters of polycarboxylic acids, aminopolyepoxides, and fillers, such as asphalt, bitumen, glass fibres, mica, quartz powder, cellulose, kaolin, silica, kieselguhr or metal powder. The compositions may be used in the form of solutions or emulsions as textile auxiliaries, laminating resins, varnishes, lacquers, dipping or coating resins, moulding compositions or adhesives. Examples describe the hardening of esters obtained from methyl 3,4-epoxy 1,2,3, 6- tetrahydrobenzoate and 3-ethyl -3- hydroxymethyl -1- oxacyclobutanes and maleic anhydride, and di-n-propyl 7-oxabicyclo (4,1,01,6) heptanedi carboxylate and 3-ethyl -3- hydroxymethyl -1-oxacyclobutane with phthalic anhydride.