Patent GB-990603-A (GB)
Title: New amides and process for their manufacture, and use
IPC: C08G59/54
Filed: 1963-05-01
Abstract: Carboxylic amides containing at least two amino groups are prepared by a process comprising (1) reacting an aliphatic monocarboxylic acid containing at least one epoxy group and at least 12 carbon atoms (or an ester of such an acid with a monohydric or polyhydric alcohol) with an alcohol or a phenol so as to split the epoxy group(s) and simultaneously etherify the alcohol or phenol, and (2) reacting the intermediate product so obtained with an aliphatic diamine or polyamine containing at least two primary or secondary amino groups. Examples are given in which (1) an epoxidized vegetable oil or (Example 2) epoxidized oleic acid is reacted with bisphenol-A and the product is further reacted with triethylenetetramine, (3) epoxidized soybean oil (prepared by treating a mixture of the oil and formic acid with hydrogen peroxide) is reacted with m-chlorophenol or (Example 4) with p-tert.-butylphenol or (Example 5) with m-butanol or (Example 6) with allyl alcohol and the product is further reacted with triethylenetetramine.  Other aliphatic acids or esters which may be used include 9,10-epoxypalmitic acid, 9,10,12,13-diepoxystearic acid (or epoxidized linolenic acid) and epoxidized tung oil fatty acid and esters of such acids with, e.g., methanol, hexanol, ethylene glycol, 1,2,4-hexanetriol and glycerol.  Other alcohols or phenols which may be used include methanol, stearyl alcohol, ethylene glycol, triethylene glycol, pentanediol-1,5, the bis-b -hydroxyethyl ether of bisphenol-A or of tetrachloro - bisphenol - A, phenol, guaiacol, a  - and b  - naphthol, monochlorophenols p - octylphenol, hydroquinone, bis - (p - hydroxyphenyl)-phenylmethane and resoles and novolaks produced from phenols and formaldehyde. Other diamines or polyamines which may be used include N-hydroxyethylethylene diamine, N - hydroxypropyl - tetramethylene diamine, N,N,N11 - tri(hydroxypropyl) - triethylenetetramine, N - hydroxy - ethyl - propylene diamine, hexamethylene diamine and cyanoethylated polyamines such as are obtainable from acrylonitrile and ethylene diamine.  None of these lists is exhaustive.  The products are useful as curing agents for epoxy resins (see Division C3).ALSO:As curing agents for epoxy resins, use is made of carboxylic amides containing at least two amino groups prepared by a process comprising (1) reacting an aliphatic monocarboxylic acid containing at least one epoxy group and at least 12 carbon atoms (or an ester of such an acid with a monohydric or polyhydric alcohol) with an alcohol or a phenol so as to split the epoxy group(s) and simultaneously etherify the alcohol or phenol, and (2) reacting the intermediate product so obtained with an aliphatic diamine or polyamine containing at least two primary or secondary amino groups.  Examples are given in which (1) an epoxidized vegetable oil or (Example 2) epoxidized oleic acid is reacted with bisphenol-A and the product is further reacted with triethylenetetramine, (3) epoxidized soybean oil is reacted with m-chlorophenol or (Example 4) with p-tert.-butylphenol or (Example 5 with n-butanol or (Example 6) with allyl alcohol and the product is further reacted with triethylenetetramine.  Other aliphatic acids or esters which may be used include 9,10epoxypalmitic acid, 9,10,12,13-diepoxystearic acid (or epoxidized linolenic acid) and epoxidized tung oil fatty acid and esters of such acids with, e.g., methanol, hexanol, ethylene glycol, 1,2,4-hexanetriol and glycerol. Other alcohols or phenols which may be used include methanol, stearyl alcohol, ethylene glycol, triethylene glycol, pentanediol-1,5, the bis-BETA-hydroxyethyl ether of bisphenol-A or of tetrachloro-bisphenol-A, phenol, guaiacol, a - and BETA-naphthol, monochlorophenols, p-octylphenol, hydroquinone, bis - (p - hydroxyphenyl) - phenylmethane and resoles and novolaks produced from phenols and formaldehyde.  Other diamines or polyamines which may be used include N-hydroxy-ethylethylene diamine, N - hydroxypropyl-tetramethylene diamine, N,N,N11 - tri - (hydroxypropyl) - triethylenetetramine, N - hydroxyethyl-propylene diamine, hexamethylene diamine and cyanoethylated polyamines such as are obtainable from acrylonitrile and ethylene diamine.  None of these lists is exhaustive. Compositions may be prepared comprising epoxy compounds having an epoxide equivalent greater than 1 and amides prepared as described above. The epoxy compounds in such compositions may be (1) alicyclic polyepoxides, e.g. vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, diethylene glycol-bis-(3,4-epoxycyclohexanecarboxylate) or 3,4 - epoxy-hexahydrobenzal - 3,4 -epoxycyclohexane - 1, 1-dimethanol, or alkylene polyepoxides, e.g. butadiene dioxide or epoxidized copolymers of butadiene with styrene or vinyl acetate, (2) polyglycidyl esters obtainable by reacting a dicarboxylic acid, e.g. succinic, adipic, phthalic or terephthalic acid, with epichlorohydrin or dichlorohydrin in the presence of an alkali, (3) basic polyepoxy compounds obtainable by reacting a primary or secondary aliphatic or aromatic amine, e.g. 4,41-diaminodiphenylmethane or 4,41-diaminodiphenyl sulphone, with epichlorohydrin in the presence of an alkali and (4) polyglycidyl ethers obtainable by etherifying a dihydric or polyhydric alcohol or diphenol, e.g. triethylene glycol, 2,4,6-hexanetriol, resorcinol, 1,4-dihydroxynaphthalene or bis-(p-hydroxyphenyl)-dimethylmethane None of the lists of compounds is exhaustive.  The compositions may contain conventional additives, a number of which are specified.  Examples are given in which the products of Examples 1-6 above are made into lacquers by mixing them with a product prepared by condensing bis-(p-hydroxyphenyl) dimethylmethane with at least two mols. of epichlorohydrin in the presence of aqueous sodium hydroxide solution, and the lacquers are dried or cured on glass plates or aluminium sheets under specified conditions.