Patent GB-954195-A (GB)
Title: Improved resinous compositions
Inventor: WATKINS NATHANIEL L
IPC: C08G63/87
Filed: 1960-04-04
Abstract: N, N1-Bis-1, 2-alkyleneamides of formula: <FORM:0954195/C2/1> where R is an organic radical, preferably an alkylene radical having 4-40 carbon atoms or a 1:3-or 1:4-phenylene radical; and R1 and R11 are hydrogen atoms or alkyl radicals, preferably containing 1-8 carbon atoms, made by reacting a 1, 2-alkylene imine with a dichloride of a dicarboxylic acid in the presence of a hydrogen chloride acceptor (e.g. an alkali metal carbonate or bicarbonate). 5-cyano-3-thiapentyl acrylate is made by (1) reacting the sodium derivative of 2-mercapto ethanol with beta-chloropropionitrile in the presence of ethanol to produce 5-cyano-3-thiapentyl alcohol and (b) reacting this product with acrylyl chloride in the presence of benzene and triethylamine.ALSO:Elastomers are made by curing low molecular weight polymers having an average of more than two and less than 15 carboxyl groups per molecule with a minor amount of a poly-N-alkylene amide of formula: <FORM:0954195/C3/1> where R is an organic radical, R1 and R11 are hydrogen atoms or alkyl radicals and n is at least two.  The low molecular weight polymers have a molecular weight of 700-10,000, an acid content between about 0.1 and about 3 milli-equivalents per gram and a viscosity of less than 10,000 poises at 25 DEG C., and are substantially free from hydroxyl groups.  Specified polymers are (a) branched polyesters obtained by reacting a diol, a dicarboxylic acid and a tri-or higher functional polyol or polycarboxylic acid, (h) branched polyester obtained by reacting a polycarboxylic acid with a hydroxycarboxylic acid or an aminocarboxylic acid, (c) dianhydride extended polyesters, (d) dianhydride extended polyether glycols, (e) anhydride extended branched polyether glycols and (f) acrylic addition polymers. Fillers e.g. calcium carbonate, iron oxide, titanium dioxide, carbon black or silica may be added.  Specified polyesters are obtained by reacting (1) 2, 2-dimethyl-1, 3-propanediol, succinic acid and glycerol; (2) diethylene glycol, adipic acid and trimethylol propane; (3) neopentyl glycol, diglycolic acid and trimethylol propane; (4) diethylene glycol, adipic acid and glycerol; (5) polyethylene glycol, thiadipropionic acid and trimethylol propane; (6) diethylene glycol, polyethylene glycol, oxydipropionic acid and trimethylolethane; (7) 2,2-bis-4-(2-hydroxypropoxy phenyl-propane, a zelaic acid and trimethylol propane; (8) diethylene glycol, diglycolic acid and mannitol; (9) propylene glycol, sebacic acid, isophthalic acid and pentaerythritol; (10) 3-methyl-3-azopentanediol-1, 5, azelaic acid and trimethylol propane; (11) neopentyl glycol, sebacic acid and trimethylol propane (12) neopentyl glycol, isosebacic acid and trimethylol propane; (13) diethylene glycol, adipic acid and trimeric acid; (14) polyethylene glycol, adipic acid and citric acid; (15) di-1, 4-(2-hydroxypropoxy) benzene, fumaric acid, sebacic acid and citric acid; (16) propylene glycol, 1, 4-butylene glycol, adipic acid and 1, 2, 4, 5-benzenetetracarboxylic acid; (17) polyethylene glycol, maleic acid and 1, 2, 4, 5-benzenetetracarboxylic acid; (18) 2, 2-diethyl-1, 3-propanediol, diglysolic acid and 1, 2, 4, 5-benzenetetracarboxylic acid; (19) 1, 2, 4, 5-benzenetetracarboxylic acid and 12-hydroxystearic acid, N-methyl-b -alanine or g -methyl-e -caprolactone; (20) polyacrylic acid and hydracrylic acid or N-methyl=omega-amino-undecainoc acid; (21) polymethacrylic acid and N-methyl-6-aminocaproic acid; (22) poly (diethylene glycol adipate) and pyromellitic dianhydride; (23) poly (1, 4-butylene glycol diglycolate) and 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride; (24) poly (polypropylene glycol isophthalate) and cyclohexanetetracarboxylic dianhydride; (25) first diethylene glycol and adipic acid, secondly trimethylol ethane and succinic acid and mixing the resulting esters.  Specified carboxyl-terminated polyethers are the reaction products of (26) polybutylene glycol and pyromellitic dianhydride; (27) polypropylene glycol and 1, 4, 5, 8-naphthalenetetracarboxylic dianhydride; (28) poly (3-methyl-1, 4-butylene glycol) and cyclohexane-1, 2, 4, 5-tetracarboxylic dianhydride; (29) oxypropylated ethylene diamine and glutaconic anhydride; (30) oxyethylated/oxypropylated pentaerythritol and maleic anhydride; (31) oxyethylated/oxypropylated glycerine and succinic anhydride; (32) oxyethylated/oxypropylated ethylene diamine and succinic anhydride. Specified addition copolymers are those of (33) acrylic acid and butadiene; (34) partially hydrolysed copolymer of maleic anhydride and butyl acrylate; (35) butyl acrylate, 2-cyanoethyl acrylate and acrylic acid; (36) methacrylic acid and butadiene; (37) acrylic acid and isoprene; (38) methacrylic acid and isoprene; (39) cinnamic acid and butadiene; (40) crotonic acid and butadiene; (41) acrylic acid and methoxyethyl acrylate; (42) acrylic acid, acrylonitrile and butadiene; (43) 5-cyano-3-thiapentyl acrylate and acrylic acid. Copolymer (33) is made by heating the monomers in aqueous medium in the presence of sodium lauryl sulphate, sodium sulphate, potassium persulphate and tertiary dodecyl mercaptan. Copolymers (41) and (43) are made by heating the monomers in the presence of tertiary dodecyl mercaptan and tertiary butyl peroxide. The compositions of polymers and curing agents may be used for sealing joints, coating metals (e.g. the insides of fuel tanks) or for coating fabric. Fabric treating compositions are described comprising a polyester, a curing agent, a filler (e.g. silica, butyl alcohol treated silica or titanium dioxide), an antioxidant (e.g. dibetanaphthyl p-phenylene diamine or a phenol-formaldehyde condensate) and, possibly, a solvent (e.g. acetone and toluene).ALSO:Fabrics are given an elastomeric coating by treating them with a composition of a low molecular weight polymer containing free carboxyl groups and a poly-N-alkyleneamide of formula <FORM:0954195/B1-B2/1> (where R is an organic radical, R1 and R11 are hydrogen atoms or alkyl radicals and n is at least two) and then curing the composition.  In examples (1) a composition of a diethylene glycol/trimethylol propane/adipic acid polyester, N,N1-bis-1,2-ethyleneisosebacamide, silica filler and symmetrical di-beta-naphthyl p-phenylene diamine antioxidant is knife-coated on to woven cloths of polyethylene, nylon or glass and the coated cloth heated to 250  DEG F.; (6) a composition of the same polyester and curing agent, butyl alcohol treated silica, titanium dioxide and phenol-formaldehyde antioxidant is coated on to woven glass cloth which is then heated to 300  DEG F.; (31) a composition of a neopentyl glycol/sebacic acid/trimethylol propane polyester, N,N1-bis-1,2-ethyleneisophthalamide, silica filler and, possibly, a solvent, e.g. acetone plus toluene, is coated on to cleaned glass fabric which is then heated to 350  DEG F.