Patent GB-966698-A (GB)
Title: A method of curing polyepoxide compounds
IPC: C08G59/42
Filed: 1960-10-06
Abstract: Polyepoxides are cured by a chlorinated tetrahydrophthalic acid of formula: <FORM:0966698/C3/1> where X and Y are hydrogen, halogen or alkyl groups containing 1-3 carbon atoms, or by an anhydride thereof, or by a derivative thereof obtained by reacting one or both of the carboxylic groups with one or more further compounds and/or by epoxidation of the double bond. Specified derivatives are (a) acid esters or hydroxyacid esters obtained from the acid and glycols, glycerol, trimethylol propane or pentaerythritol; (b) amino-amides obtained by reacting the acid with an excess of a polyamine which amino-amide may be used in admixture with alkali metal hydroxides or phenolates; (c) amides, imides, sulphoacids, amino acids or amine salts of the acid; (d) polyesters obtained by the reaction of the acids with glycols or higher polyhydric alcohols (e.g. glycerol, hexanetriol, pentaerythritol or trimethylol propane) and, possibly other polycarboxylic acids (e.g. maleic, itaconic, citraconic, dimethylmaleic, fumaric muconic, adipic, carbic or ortho-, iso- or terephthalic acid) and oils or their fatty acids, which polyesters may be used in admixture with amines; (e) polyamides obtained by reacting the acids with polyamines (e.g. polymethylene diamines or polyalkylene polyamines) and possibly other polycarboxylic acids (e.g. aliphatic dicarboxylic acids, iso- or tere-phthalic acids, or polymerized fatty acids) or aromatic diamines; (f) polyesteramides obtained by reacting the acid, another saturated or unsaturated polycarboxylic acid and a polyamine, amino-alcohol or amino-acid and, possibly, a polymerized fatty acid; or (g) salts of the polyamides or polyesteramides with acetic acid, which acid is liberated or neutralized at the curing temperatures.  Specified polyepoxides are (i) epoxide resins obtained by reacting polyhydric phenols, phenolic resins, polyhydric alcohols, aromatic sulphonamides or polyamides with epihalohydrins or glycerol dihalohydrins; (ii) reaction products of these epoxide resins with fatty acids and, possibly, an unsaturated monomer; (iii) glycidyl ethers or esters; (iv) di(2,3-epoxybutyl)adipate or terephthalate, di(2,3-epoxycyclohexylmethyl-phthalate and 2,3-epoxybutyl-3,4-epoxy pentoate; (v) epoxidized soyabeam-, linseed- and dehydrated castor oil; (vi) epoxidized polybutadiene and butadiene-styrene or -acrylonitrile copolymers; (vii) epoxidized 2,2-bis(cyclohexenyl propane) and 2,6-octadiene.  The curable mixture may also include a thermosetting resin, a thermoplastic resin, a natural or synthetic rubber, a natural resin possibly mixed with a fatty oil or a pitch, a plasticizer (e.g. an ester of an organic or inorganic acid), a solvent (e.g. a hydrocarbon, chlorinated hydrocarbon, ester, ether, alcohol or ketone), a reactive solvent comprising an ethylenically unsaturated monomer or a saturated or unsaturated monoepoxide, a filler (e.g. sawdust, textile materials, glass fibres, asbestos, mica, cement, talc or a metal powder), an agent producing thixotropy (e.g. titanium oxide, zinc oxide, a natural silicate, chalk, or a mixture of polyester or polyesteramide with polyvinyl chloride, polyvinylidene chloride, chlorinated rubber or polychloroprene), or (if substances containing halogen are added) the normal stabilizers. The storage life of reaction mixtures containing amines may be increased by cyanoethylation of the amines with unsaturated nitriles. Examples (1)-(10) disclose composition of a bisphenol-A/epichlorhydrin resin together with (1) phenyl glycidyl ether, 4-chloro-1,2,3,6-tetrahydrophthali anhydride and, possibly, micronized asbestos; (2) a eutectic mixture of 4-chloro-1,2,3,6-tetrahydrophthalic anhydride and phthalic anhydride; (3) toluene, butanol, ethylene glycol monoethyl ether, butanol a butylated melamine-formaldehyde condensate and 4-chloro-4,5-epoxy-1,2,3,6-tetrahydrophthalic acid; (4) toluene butanol, ethylene glycol monoethyl ether, xylene, a resol etherified with butanol, and an acid ester obtained from 2,4-dichloro-1,2,3,6-tetrahydrophthalic acid and 1,4-butylene glycol; (5) an amino-amide obtained from 4-chloro-1,2-dimethyl-1,2,3,6-tetrahydrophthalic acid and diethylene triamine; (6) an unsaturated polyester obtained by condensing 4-chloro-1,2,3,6-tetrahydrophthalic acid, maleic anhydride and ethylene glycol, styrene, hydroquinone, diethylene triamine, cumene hydroperoxide and cobalt naphthenate; (7) a polyester obtained from 4-chloro-1, 2, 3, 6 - tetrahydrophthalic anhydride, adipic acid and diethylene glycol, polyvinyl butyrol and dicyandiamide; (8) an alkyd resin obtained by reacting 4-chloro-1,2,3,6-tetrahydrophthalic acid, glycerol and linseed oil, polyvinyl acetate and 4-chloro-1,2,3,6-tetrahydrophthalic acid diamide; (9) a polyamide obtained by reacting 4-chloro-1,2,3,6-tetrahydrophthalic acid, dimerized linseed oil acid and diethylene triamine together with dibutyl phthalate, or butanol and toluene or water and lauryl sulphate (as emulsifying agent); (10) as in Example (9) but using instead of the polyamide a polysteramide obtained by reacting 4-chloro-1,2,3,6-tetrahydrophthalic acid, dimerized linseed oil acids, diethylene glycol and tetraethylene pentamine.  The compositions of Examples (9) and (10) may be foamed by adding blowing agents or polyisocyanates. Further examples disclose compositions containing (11) a soya fatty acid modified bis-phenol A/epichlorhydrin resin, xylene, butanol, a butylated melamine-formaldehyde resin and 4-chloro-1,2,3,6-tetrahydrophthalic acid; (12) hydroquinone-bis-glycidyl ether, butanol, a butylated melamine-formaldehyde resin, xylene, petroleum lacquer and a silicone alkyd resin obtained by reacting the reaction product of dimethyl terephthalate, adipic acid and 4-chloro-1,2,3,6-tetrahydrophthalic acid with the reaction product of propylene glycol, glycerol and the hydrolysis product of methylphenyl triethoxy silane; (13) a soya fatty acid modified bis-phenol A/epichlorhydrin resin, a polyamide resin obtained from dimerized soya fatty acids, 4-chloro-1,2,3,6-tetrahydrophthalic acid and ethylene diamine, an alkyd resin obtained from glycerol, 4-chloro-1,2,3,6-tetrahydrophthalic anhydride and linseed oil, lacquer petroleum, pigments and siccatives.  Uses: adhesives, binding agents for laminated material casting resins and coating compositions.