| 摘要 |
Production of stable, modified, unsaturated cycloaliphatic epoxy resins by reacting liquid cycloaliphatic diepoxides with half-esters of unsaturated dicarboxylic acids and unsaturated mono-alcohols, hydroxy-(cyclo)alkyl vinyl ethers, alkoxylated hydroxyalkyl (meth)acrylates or hydroxyl-containing reaction products, e.g. from glycidyl versatate and (meth)acrylic acid. A process for the production of stable liquid or semi-solid modified cycloaliphatic epoxy resins (MCE) (A) and/or fusible and/or soluble and/or dispersible solid MCE (B) with more than one epoxide group. At least one second hydroxyl group and at least one ester linkage per average mol. wt., optionally with a fluorine content of 0.01-3 wt% and a silicon content of 0.01-10 wt%. The process involves reacting liquid cycloaliphatic diepoxides (CDE) with (I) half-esters of unsaturated dicarboxylic acids (or anhydrides) (UDCA) and unsaturated mono-alcohols based on 2-10C olefins and/or (II) half-esters of UDCA with hydroxy-(cyclo)alkyl vinyl ethers and/or (III) half-esters of UDCA with hydroxyalkyl (meth)acrylates containing polyoxyalkylene units and/or reaction products with a sec. OH group from the reaction of glycidyl versatate (e.g. Cardura E10 (RTM)) with (meth)acrylic acid and/or products with an OH group from the reaction of caprolactone with hydroxyalkyl (meth)acrylates (optionally in presence of fluorine-containing acids or anhydrides) and/or dicarboxylic acid half-esters of fluorine-containing monohydric alcohols and diacids or their anhydrides and/or perfluoro-acids of formula F(CF2)nCOOH in which n = 5-21 and/or organosilicon compounds with group(s) which can react with epoxide, at elevated temperature, optionally in presence of organic solvent and/or inert gas and/or catalysts for the epoxide/carboxyl reaction and/or polymerisation inhibitors and using 0.02-0.49 equivalents of the modifier per epoxide group, to give MCE as described but with at least two olefinic double bonds connected to one another via ester linkages and also via one or more methylene and/or alkyl, cycloalkyl, alkylaryl-aryl or aralkyl groups. An Independent claim is also included for a process for the production of (A) and (B) with epoxide, sec. OH groups and ester linkages as above and also with at least one olefinic double bond, by reacting liquid CDE with (IV and V) half-esters of saturated diacids with hydroxy compounds as listed in sections (II) and (III) under conditions as above. |
