Patent GB-932144-A (GB)
Title: Epoxy ethers and curable and resinous compositions containing them
IPC: C08G65/26
Filed: 1961-05-16
Abstract: Epoxy ethers of the general formula <FORM:0932144/IV(a)/1> wherein X represents R-O- where R is (a) an epoxyalkyl radical, (b) an epoxycycloalkyl radical, (c) an epoxycycloalkylalkyl radical, (d) a 3-oxatricyclo[3,2,1,02,4]-oct-6-yl radical, or (e) a 3-oxatricyclo[3,2,1,02,4]-oct-6-yl alkyl radical, are homopolymerized by heating at 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 an aromatic sulphonic acid, an alkali metal hydroxide or an amine, or are cured using one or more organic hardeners comprising polycarboxylic acids, polycarboxylic acid anhydrides, polyols, polycarboxypolyesters, polythiols, polyisocyanates, polyisothiocyanates, polyacylhalide or polyfunctional amine at temperatures in the range 10 DEG  to 250 DEG C.  Polymerization catalysts as indicated above may be used to increase the cure rate, and may be added as a solution in an organic ether, ester or ketone.  Many examples of suitable hardeners are give.  Compositions comprising epoxy ether and an organic hardener may be dissolved in an inert normally liquid organic medium, for surface coatings which can be subsequently heat cured to scratch-resistant coatings.  Varnishes are obtained by reaction of the epoxy ether with aliphatic monocarboxylic acids, preferably unsaturated acids, at elevated temperatures, e.g. 100 DEG  to 200 DEG C., to produce a product containing epoxy groups and hydroxy groups which is then homopolymerized with a catalyst such as those described above, preferably at a temperature in the range 25 DEG  to 200 DEG C. The polymerized compositions may be used as modifiers for coating resins such as phenolformaldehyde resins, melamine-formaldehyde resins or alkyd resins.  Varnish compositions may also be obtained by reacting the epoxy ethers with polyols at a temperature in the range 25 DEG  to 250 DEG C. followed by partial or complete esterification with an aliphatic monocarboxylic acid at elevated temperatures. Thermoset resins may be prepared from curable compositions comprising an epoxy ether, a hardener and other polyepoxides.  Examples describe the use of 3-oxatetracyclo[4,4,0,17,1002,4] undec-8-y1 2,3-epoxypropyl ether in curable compositions with diethylene triamine, with phthalic anhydride, with adipic acid, with tetrahydrophthalic anhydride, with chlorendic anhydride, with toluene diisocyanate and BF3-piperidine, with maleic anhydride and trimethylolethane, with maleic anhydride and bisphenol A; the ether is homopolymerized with sulphuric acid; 3-oxatetracyclo[4,4,17,1002,4] undec-8-y1 6-methyl-3,4epoxycyclohexylmethyl ether is cured with phthalic anhydride; 3-oxatetracyclo[4,4,0,17,10,02,4] undec-8-yl 2,3-epoxybutyl ether is reacted with dehydrated castor oil acid and the product is polymerized in the presence of stannic chloride; 3-oxatetracyclo[4,4,17,10,02,4] undec-8-yl 3,4epoxycyclohexyl ether is reacted with soya bean oil acid and the product polymerized in the presence of BF3-ether complex.ALSO:The invention comprises epoxy ethers of the general formula <FORM:0932144/IV(a)/1> wherein X represents R-O- and R represents (a) a vic-epoxyalkyl radical, (b) a vicepoxycycloalkyl radical, (c) a vic-epoxycycloalkylalkyl radical, (d) a 3-oxatricyclo[3.2.1.02,4] oct-6-yl radical, and (e) a 3-oxatricyclo [3.2.1.02,4]oct-6-ylalkyl radical.  The epoxy ethers may be made by reacting a corresponding polyunsaturated ether with an organic peracid, e.g. perbenzoic, perpropionic or peracetic acid preferably in an inert normally liquid organic medium at a temperature in the range 0 DEG C. to 100 DEG C. for sufficient time to epoxidize all the double bonds.  The epoxy ether may be reacted with aliphatic monocarboxylic acids at elevated temperatures, e.g., 100 DEG  to 200 DEG C., to form a product containing epoxy groups and free OH groups which may be polymerized.  The epoxy ethers themselves may be polymerized or copolymerized (see Group IV(a)).  Examples of the preparation of the ethers are given.  The preparation of tricyclo[4.3.0.12,5]-7-decen-3-yl allyl ether from allyl alcohol and dicyclopentadiene is also described.