Patent GB-927615-A (GB)
Title: Improvements in and relating to epoxides
IPC: C08G59/24
Filed: 1961-05-29
Abstract: A curable composition comprises bis(3-oxatetracyclo[4.4.0.17,10.02.4]undec-8-yl) ether and an active organic hardener comprising a polycarboxylic acid, polycarboxylic acid anhydride, polyol, polycarboxy polyester, polythiol, polyisocyanate, polythioisocyanate, polyacyl halide, polyfunctional amine or a mixture thereof.  The curable compositions can be partially or fully cured by maintaining the temperature in the range of from 10 DEG  to 250 DEG C. for times varying from 10 minutes to 1 week.  Curing catalysts such as metal halide Lewis acids including boron trifluoride -amine or -ether complexes, strong mineral acids, saturated aliphatic hydrocarbon sulphonic acids and aromatic hydrocarbon sulphonic acids, alkali metal hydroxides, amines and trimethylammonium hydroxide.  When the catalyst and curable compositions are immiscible, the catalyst can be added as a solution in an inert normally-liquid organic medium such as an ether, ester or ketone.  There may also be added a minor amount relative to the organic hardener of a second organic hardener comprising a polycarboxylic acid, polycarboxylic acid anhydride, polyol, polycarboxy polyester, polythiol, polyisocyanate, polythioisocyanate, polyacyl halide, polyfunctional amine or a mixture thereof such that the ratio of reactive groups in the amount of second organic hardener to the reactive groups in the amount of first organic hardener is less than one.  One or more other polyepoxides may be present. Varnish compositions may be made by reacting the epoxy ether with polyols at a temperature in the range from 25 DEG  to 250 DEG C. for 0,5 to 10 hours followed by partial or essentially complete esterification of the product with an aliphatic monocarboxylic acid at elevated temperatures.  A homopolymer of bis(3-oxatetracyclo-[4.4.0.17,10.02,4]undec-8-yl) ether may be obtained by heating the monomeric ether at a temperature from 25 DEG to 250 DEG C. in the presence of a polymerization catalyst, such as a metal halide Lewis acid, a strong mineral acid, a saturated aliphatic or aromatic hydrocarbon sulphonic acid, an alkali metal hydroxide, or an amine.  Varnishes are obtained by reacting the epoxy ether with aliphatic monocarboxylic acids, at elevated temperatures, e.g. 100 DEG  to 200 DEG C., for from 0,5 to 10 hours followed by homopolymerizing the resulting reaction product with a catalyst such as those described above, preferably at a temperature in the range from 25 DEG  to 200 DEG C. Metallic salts of organic compounds, e.g. cobalt naphthenate and lead octanoate, may be added to the polymerized compositions to accelerate drying.ALSO:The invention comprises bis-(3-oxatetracyclo-[4,4,0,17,1002,4] undec-8-yl) ether <FORM:0927615/IV(a)/1> and the preparation thereof by reacting bis (tricyclo-[4,3,0,12,4]-7-decen-3-yl) ether with an organic peracid in an inert normally liquid organic solvent at a temperature in the range from 0 DEG C. to 100 DEG C. and recovering the ether product. The peracid may be, for example, peracetic, perpropionic or perbenzoic acid and suitable media are ethyl acetate, acetone and butyl acetate.  A detailed example is given and the preparation of bis(tricyclo[4,3,0,12,5]-7-decen-3-yl) ether by heating hydroxydihydrodicyclopentadiene with dicyclopentadiene in the presence of boron trifluoride-etherate is also exemplified. The epoxy ether may be reacted with aliphatic monocarboxylic acids, at elevated temperatures, e.g. 100 DEG  to 200 DEG C. to form products containing residual epoxy groups and free hydroxy groups.  The monocarboxylic acids are preferably unsaturated. Examples are given.  The products may be polymerised to form varnishes (see Group IV(a)).