Patent GB-1082104-A (GB)
Title: Polyepoxides
IPC: C07D303/22
Filed: 1965-09-23
Abstract: Epoxy resins are prepared by treating an epoxide coupling reagent and, optionally, an epoxide polymerizing catalyst with novel polythioepoxides, preferably of formula <FORM:1082104/C3/1> where n is an integer of 2 or more; R is an n-valent organic radical, such that at least 2 of the sulphur atoms are no more than 6 carbon atoms away from each other or from a negative activating group; R is a hydrocarbon, hydrocarbon-ether or hydrocarbon-ester chain including at least 2 carbon atoms, which hydrocarbon chain may comprise a 5- or 6-membered carbocyclic ring, or an alkyl, aryl or halogen substituted derivative thereof; R2 and R3 are hydrogen, alkyl or halogen; R4, when not connected to R1, is hydrogen, halogen, alkyl, haloalkyl, aryl, haloaryl, alkyaryl or haloalkaryl, and, when connected to R1, is a hydrocarbon chain of 2 or 3 carbon atoms or an alkyl, aryl or halogen substituted derivative thereof, are prepared by reacting a polymercaptan R(SH)n with an olefinically unsaturated epoxide containing at least one vicinal epoxide group separated from an olefin group by at least one carbon, the olefin group being located in a 5 or 6-membered carbon ring or in a terminal position in an aliphatic hydrocarbon chain, the reaction product not containing the radical -S-CH2-S-. Specified negative activating groups are -C(O)O-, -OH, -S-, -O- and -CO-. Examples prepare resins from reaction products of 1,4-butanedithiol and various esters of polyhydric compounds with mercaptoacetic and b -mercaptopropionic acids with alkyl glycidyl ether, the glycidyl ether of 2-alkyl-phenol, vinyl-3,4-epoxycyclohexane, limonene monoxide or glycidyl acrylate. The polythioepoxides may be prepared, at least in part, in situ in the presence of the epoxide coupling agent. Examples use methylbicyclo-2,2,1-hept-5-ene-2,3-dicarboxylic anhydride, phthalic anhydride or maleic anhydride as coupling agents, and 2,4,6-tris(dimethylaminomethyl)phenol as catalyst, when used.  The mercaptoacetate of an allyl alcohol-styrene copolymer is prepared in Example 8 by conventional esterification and the mercaptoacetate of a phenol-formaldehyde resin similarly in Example 14.  The novel polythioepoxides described above may be used to stabilize vinyl chloride resin compositions.ALSO:Novel polythio - group containing polyepoxides, preferably of formula <FORM:1082104/C2/1> where n is an integer of 2 or more; R is an n-valent organic radical, such that at least 2 of the sulphur atoms are no more than 6 carbon atoms away from each other or from a negative activating group; R1 is a hydrocarbon, hydrocarbon-ether or hydrocarbon-ester chain including at least 2 carbon atoms, which hydrocarbon chain may comprise a 5- or 6-membered carbocyclic ring, or an alkyl, aryl or halogen substituted derivative thereof; R2 and R3 are hydrogen, alkyl or halogen; R4, when not connected to R1 is hydrogen, halogen, alkyl, haloalkyl, aryl, haloaryl, alkaryl or haloalkaryl, and, when connected to R1 is a hydrocarbon chain of 2 or 3 carbon atoms or an alkyl, aryl or halogen substituted derivative thereof, are prepared by reacting a polymercaptan R(SH)n with an olefinically unsaturated epoxide containing at least one vicinal epoxide group separated from an olefin group by at least one carbon, the olefin group being located in a 5- or 6-membered carbon ring or in a terminal position in an aliphatic hydrocarbon chain, the reaction product not containing the radical -S-CH2-S-.  Specified negative activating groups are -C(O)O-, -OH, -S-, -O-and -CO-.  Examples react 1,4-butanedithiol and various esters of polyhydric compounds with mercaptoacetic and b -mercaptopropionic acids with allyl glycidyl ether, the glycidyl ether of 2-allylphenol, vinyl-3,4-epoxycyclohexane, limonene monoxide, or glycidyl acrylate.  Conventional esterification is used to prepare, as starting materials, the completely esterified mercaptoacetate of triethylene glycol, 1,4 - butanediol, 1,1,1 - trimethylolpropane, glycerol, 1,1,1 - trimethylolethane, pentaery - thritol, hydroxylated castor oil and bisphenol A, the b  - mercaptopropionate of 1,1,1 - trimethylolpropane, mixed esters of pentaerythritol with mercaptoacetic acid and soya bean oil acids and of 1,1,1-trimethylolpropane with mercaptoacetic and dimerized soya bean oil acids, and the mercaptoethanol ester of adipic acid.