Patent GB-654331-A (GB)
Title: Adhesives
IPC: C08J5/06
Filed: 1948-11-10
Abstract: Compounds for use in preparing adhesives (see Group V), having the general formula R(NH COCR1R11COR111)n wherein R is an n-valent, aliphatic, including cyclo-aliphatic, aromatic, or aliphatic-aromatic or aliphatic-aromatic hydrocarbon radical, saturated or unsaturated, unsubstituted or substituted with a group or groups free from active hydrogen, R1 and R11 are hydrogen, X, COX1, or COOX11, the same or different, R111 is X111 or OX1111, wherein X, X1, X11, X111 and X1111 are monovalent aliphatic, including cycloaliphatic, aromatic or aliphatic-aromatic hydrocarbon radicals, saturated or unsaturated, substituted or unsubstituted, the same or different, and n is an integer from 2 to 5, are prepared by the interaction of compounds containing reactive methylene groups with polyisocyanates, or by the interaction of polyamines with ketenes, diketenes, substituted or unsubstituted acetacetic esters and homologues The compounds containing methylene groups may be acetoacetic esters, ethyl alpha-acetobutyrate, acetylacetone and malonic esters.  The polyisocyanates may be ethylene diisocyanates, butylene diisocyanates, hexamethylene diisocyanates, benzene di- and tri-isocyanates, toluene di- and tri-isocyanates, diphenyl-methane p : p1-diisocyanates, dicyclohexylmethane diisocyanates, chlorobenzene di- and tri-isocyanates, naphthalene di- and tri-isocyanates, stilbene diisocyanate, ditolylmethane p : p1-diisocyanates, dixylyl methane diisocyanates, diphenyl propane p : p1-diisocyanates, diphenylmethane 2 : 4 : 21 : 41-tetraisocyanate, trimethyl benzene triisocyanates, phenyltolylmethane triisocyanates, ditolylmethane triisocyanates and triphenylmethane triisocyanates.  Specified compounds are N : N1-bis - (acetoacetyl)-, N : N1 - bis - (carbethoxyacetobutyryl)-, N : N1 - bis - (alpha - (carbo - 2 - chloroethoxy) - acetoacetyl)-, N : N1 - bis - (alpha : alpha-dicarbethoxyacetyl)-, N : N1-bis-(diacetoacetyl) -, N : N1 - bis - (carbethoxyaceto, butyryl) -, N : N1 - bis - (carbethoxyacetyl) - N : N1 - bis - (carballyloxyacetoacetyl) -, N : N1-bis - (alpha - benzoylacetoacetyl) -, N : N1 - bis-(benzyloxyacetoacetyl)-, -hexamethylene diamines or -cyclohexyl diamines, or -diamino cyclohexylmethanes, or -chlorophenylene diamines, or toluylene diamines or -diamino diphenyl methanes; and similar N : N1 : N11-tris-(acetoacetyl)-, toluylene triamines or triaminophenylmethanes; and also N2 : N4 : N6-tris-(alpha-carbethoxyacetoacetyl)-toluene triamine, N : N - bis - (alpha - carbethoxyacetoacetyl) - 4 - chloro - m - phenylene diamine, N : N1 - bis - (alpha - carbethoxyacetoacetyl) - 1 : 6 - hexamethylene diamine, and N : N1-bis-(alpha - carbethoxyacetoacetyl) - 4 : 41 diamino dicyclohexylmethane.ALSO:An adhesive composition comprises, either in solution in a volatile organic liquid, or in aqueous dispersion, or admixed with a natural or synthetic rubber, a compound of the formula R(NHCOCR1R11COR111)n, wherein R is an n-valent, aliphatic, including cyclo-aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical, saturated or unsaturated, unsubstituted or substituted with a group or groups free from active hydrogen, R1 and R11 are hydrogen, X, COX1, or COOX11, the same or different, R111 is X111 or X1111, wherein X, X1, X11, X111 and X1111 are monovalent, aliphatic, including cycloaliphatic, aromatic or aliphatic-aromatic hydrocarbon radicals, saturated or unsaturated, substituted or unsubstituted, the same or different, and n is an integer from 2-5.  Compounds of this formula may be prepared by reacting compounds containing reactive methylene groups such as aceto-acetic esters, ethyl a -aceto-butyrate, acetyl acetone and malonic esters with polyisocyanates as described in Group IV (b). For bonding rubber to cellulose or to regenerated cellulose compounds in which R contains not more than 8n carbon atoms, R1 is hydrogen, and the hydrocarbon radicals in R11 and R111 each contain not more than 7 carbon atoms are preferred. Specified compounds are N : N1-bis-(acetoacetyl)-, N : N1-bis - (carbethoxyacetoacetyl)-, N : N1 - bis - (a  - (carbo - 2 - chlorethoxy) - acetoacetyl)-, N : N1 - bis - (a  : a  - dicarbethoxyacetyl)-N : N1 - bis - (diacetoacetyl)-, N : N1 - bis - (carbethoxyacetobutyryl)-, N : N1 - bis - (carbethoxyacetyl)-, N : N1 - bis - (carballyloxyacetoacetyl)-, N : N1 - bis - (carbethoxybenzoylacetyl)-, N : N1 - bis - (a  - benzoylacetoacetyl)-, N : N1 - bis - (benzyloxyacetoacetyl)-, -hexamethylene diamines, or -cyclohexyl diamines, or -diamino-cyclohexylmethanes, or -chlorophenylene diamines, or -toluylene diamines, or -diamino diphenyl - methanes; and similar N : N1 : N11 - tris - (acetoacetyl)-, toluylene triamines or triaminotriphenylmethanes.  Many examples are given in which in addition to some of the above compounds the following compounds are also used: N2 : N4 : N6 - tris - (a  - carbethoxyacetoacetyl) - toluene triamine, N : N1 - bis - (a  - carbethoxyacetoacetyl) - 4, chloro - m - phenylene diamine, N : N1 - bis - (a  - arbethoxyacetoacetyl) - 1 : 6 - hexamethylenediamine, N : N1 - bis - (a  - carbethoxyacetoacetyl) - 4 : 41 - diamino-dicyclohexyl-methane. The materials which may be bonded by the process include natural and synthetic rubbers such as polychloroprene, butadiene polymers and interpolymers, and olefine polysulphide rubbers; cellulose derivatives containing hydroxyl, amino or other active-hydrogen containing groups including acetate, propionate, butyrate or nitrate; cellulose ethers such as methyl or ethyl cellulose; carboxylated cellulose polyvinyl alcohol, or polyvinyl halides, polystyrene, polytetrafluoromethylene, polyethylene, alkyd resins; condensate of formaldehyde with phenols, amides, aldehydes, ketones, aromatic ethers, aromatic hydrocarbons, carbamates and amines; polyester amides, polyamides, ether resins, and polymeric derivatives of acrylic, methacrylic or fumaric acid.  These materials may be bonded to fibrous materials consisting of yarns, filaments, cords, and fabrics having a basis of regenerated cellulose, cellulose ethers, cellulose esters, cotton, linen, wool, nylon, or polyesters such as polyethylene terephthalate.