Patent GB-870958-A (GB)
Title: New diels-alder adducts containing epoxy groups and resins made therefrom
IPC: C07D303/24
Filed: 1959-07-03
Abstract: A composition of matter comprises, a Diels-Alder adduct of a diene containing at least one chlorine atom and a dienophilic compound which contains at least two epoxide groups and is known to be capable of combining with dienes in the Diels-Alder addition reaction (see Group IV(b)), and a hardening agent therefore of the kind conventional for epoxide resins.  Many dienes and dienophilic compounds especially polyglycidyl ethers and esters of unsaturated alcohols and acids are listed and specific adducts, prepared by reacting 2-butene-1, 4-diol-di-glycidyl ether with hexachloro- or 1, 1-dimethoxy-2, 3, 4, 5-tetrachloro-cyclopentadiene, or crude diglycidyl ether of 1, 1-bis-hydroxymethyl 1-cyclohex-3-ene hexachloro- or 1, 1-dimethoxy-2, 3, 4, 5-cyclopentadiene, are described.  The preparation of castings and adhesives for aluminium from compositions containing such adducts and such hardening agents as phthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride (Example 7), a mixture of hexahydrophthalic anhydride, tetrahydrophthalic anhydride and phthalic anhydride (Example 7), and triethylene tetramine (Example 8) is described.  Additional hardeners specified include mono-, di- and tributylamines, p-phenylene diamine, ethylene diamine, N, N-diethyl-ethylene diamine, diethylene triamine, diethylene tetramine, tetraethylene-pentamine, trimethyl amine, diethylamine, triethanolamine, Mannich bases, piperidine, piperazine, guanidine, diphenyl guanidine, phenyl diguanidine, dicyandiamide, aniline-, urea- and melamine-formaldehyde resins, polymers of aminostyrenes, polyamides of aliphatic polyamines with di- and tri-merized unsaturated fatty acids, isocyanates, isothiocyanates, polyhydric phenols, e.g. resorcinol, hydroquinone, phenol-aldehyde resins, quinone, reaction products of aluminium alcoholates or phenolates with acetoacetic ester, aluminium chloride, antimony pentachloride, SnCl4, ferric chloride, zinc chloride and boron tri-fluoride and their organic complexes, phosphoric acid, endomethylene tetrahydrophthalic anhydride, dodecenyl succinic, maleic and succinic and hexahydrophthalic anhydrides.  Other materials which may be employed in the compositions are asphalt, bitumen, glass fibres, mica, powdered quartz, cellulose, kaolin, finely divided silica and metal powder.  The compositions may be employed in the form of solutions or emulsions.  In Examples 7 and 8 there are disclosed mixtures of the epoxy compounds of the invention with a conventional epichlorhydrin/bis phenol A epoxy resin.ALSO:The invention comprises adducts of dienes containing at least one chlorine atom and dienophilic compounds which contain at least two epoxide groups and are known to be capable of combining with dienes in the Diels-Alder addition reaction.  The products may be converted to epoxy resins (see Group IV(a)).  Halogenated dienes specified for use as starting materials include halogen derivatives of butadiene, isoprene, 1-methyl butadiene, 2,3-dimethyl butadiene, 1-acetoxy butadiene, anthracene, furan, alkyl furans, coumalins, cyclohexadiene, 2,3-dimethyl cyclohexadiene, 1,11 dicyclohexenyl, cyclopentadienone, aryl cyclopentadienones and cyclopentadiene, especially 2-chloro-butadiene, tetrachloropentadienone, dimethoxytetrachlorocyclopentadiene and hexachlorocyclopentadiene. Dienophilic compounds specified include unsaturated ethers or esters containing at least two glycidyl groups of diglycidyl or polyglycidyl ethers of unsaturated dialcohols or polyalcohols such as 2-butene-1,4-diol. 1,1-bis-(hydroxymethyl)-cyclohex-3-ene, 1,1-bis-hydroxymethyl-6-methyl cyclohex-3-ene, 1,1-bis-(hydroxy methyl)-2,4,6-trimethyl-cyclohex-3-ene, 1,1-bis(hydroxymethyl)- 2,5-endomethylene-cyclohex-3-ene and 1,1-bis-(hydroxymethyl)-4-chloro-cyclohex-3-ene, diglycidyl and polyglycidyl esters of unsaturated dicarboxylic acids e.g. acetylene dicarboxylic acid, maleic acid and fumaric acid and in particular 2-butene-1,4-diglycidyl ether and fumaric acid diglycidyl ester. Examples are furnished in which tetrachloropentadiene is reacted with 2-butene-1,4-diol-diglycidyl ether; 1,1-dimethoxy 2,3,4,5-tetrachlorocyclopentadiene is reacted with 2-butene-1,4-diol-diglycidyl ether; and the crude diglycidyl ether of 1,1-bis(hydroxy methyl)-cyclohex-3-ene, obtained by reacting 1,1-bis(hydroxymethyl)-cyclohex-3-ene with epichlorhydrin in the presence of boron trifluoride and ether, is reacted with hexachlorocyclopentadiene or 1,1-dimethoxy-2,3,4, 5-cyclopentadiene.