Patent GB-1033275-A (GB)
Title: High molecular polyester amides
Inventor: UGI IVAR
IPC: C08F8/28
Filed: 1963-04-04
Abstract: A process for making polyesteramides comprises reacting (a) a carboxyl group containing polymer having a molecular weight of between 300 and 200,000 and having a carboxyl group content of from 1 to 2%, with (b) an isonitrile of at least 7 carbon atoms and having at least 1, preferably 2 or 3 isonitrile groups and with (c) an aldehyde and/or ketone, at least two of the components (a), (b) and (c) being at least difunctional with respect to the defined functional groups.  Specified components (a) are the copolymers of acrylic or methacrylic acid or maleic acid semi-esters with monovinyl or monovinylidene compounds or conjugated aliphatic dienes having from 4 to 6 carbon atoms; polyesters derived from saturated aliphatic diols or triols and saturated or unsaturated aliphatic or aromatic di- or tri-carboxylic acids, the polyesters optionally containing residues of monoalcohols, monocarboxylic acids, phosphoric acid, tetra or higher polyols, amino alcohols or polyisocyanates; polycarboxylic acids; polyamide carboxylic acids; polycarboxylic acids made by the polymerization or copolymerization of acrylic acid or maleic acid semi-esters; compounds made by complete or partial saponification of high molecular weight ester, amide, cyclic anhydride or nitrile group-containing compounds; polycondensation products of form aldehyde and phenol carboxylic acids and carboxylic acid esters which split-off alcohol under the reaction contions. Specified isonitriles are monocyclic aromatic diisonitriles, diisonitriles of diphenyl alkanes, cycloaliphatic mono- or diisonitriles having 4 to 6 carbon atoms and diisonitriles of aliphatic saturated hydrocarbons having from 2 to 10 carbon atoms. Specified carbonyl compounds are saturated aliphatic aldehydes having from 1 to 12 carbon atoms and 1 or 2 carbonyl groups, monocyclic aromatic aldehydes having 1 or 2 aldehyde groups, aliphatic saturated monoketones having 3 to 10 carbon atoms, saturated aliphatic-aromatic monoketones having at least 8 carbon atoms, aromatic-aromatic monoketones and cyclic monoketones having at least 5 and up to 10 carbon atoms.  Many suitable reactants are exemplified. The products of the process of the invention may be cross-linked or vulcanized with sulphur, formaldehyde, hexamethylene tetramine, polyepoxides, resols or peroxides.  Foamed products may be made, specified foaming agents being air and petroleum ether.  The examples (in which isocyanide A is 3:31:5:51-tetraethyl - 4:41 - diphenylmethane - di - isocyanide, isocyanide B is 1:4-cyclohexane diisocyanide and isocyanide, (C) is a mixture of 1 - methyl - 3:5 - diethyl - 2:4 - phenylene diisocyanide and 1 - methyl - 3:5 - diethyl2:6-phenylene diisocyanide describe the preparation of polyesteramides from:  (1) a polyester derived from adipic acid and ethylene glycol modified by succinic anhydride, terephthalic dialdehyde and 1-methyl-3:5-diethyl-2:4-phenylene diisocyanate; (2) the modified polyester of (1), terephthalic dialdehyde, 2:4-toluvlene diisocyanate and 3:31:5:51-tetraethyl diphenyl methane-4:41-diisocyanide; (3) a polyester as in (1) modified by 1:2:4-benzene-tricarboxylic anhydride, a polyester as in (1), hydroxypivalinic aldehyde, 1 - methyl-3:5 - diethyl - 2:4 - phenylene diisocyanide and 4:41-diphenyl methane diisocyanate; (4) a copolymer of methylmethacrylate with acrylic acid, isonitrile (A) and cyclohexanone; (5) a copolymer as in (4), cyclohexanone and isonitrile (B); (6) a copolymer as in (4), cyclohexanone and isonitrile (C); (7) a copolymer as in (4), cyclohexanone, acetone and isonitrile (C); (8) a copolymer of cyclohexyl methacrylate, dodecylmethacrylate and methacrylic acid, isonitrile (B) and benzophenone; (9) a copolymer as in (8), isonitrile (B) and heptyl aldehyde; (10) a copolymer as in (8), heptyl aldehyde and isonitrile (C); (11) a copolymer of acrylonitrile, butadiene and acrylic acid, isonitrile (B) and acetophenone; (12) a copolymer of actylonitrile and acrylic acid; isonitrile (B) and cyclohexane; (13) as in (12) with addition of benzhydrazide; (14) a copolymer of acrylic acid, vinyl acetate and vinyl chloride, isonitrile (C) and isobutyraldehyde; (15) a copolymer of acrylic acid and vinyl acetate, isonitrile (C) and benzaldehyde; (16) the reaction product of succinic anhydride with saponified ethylene-vinyl acetate copolymer, isonitrile (B) and cyclohexanone; (17) a copolymer of styrene, methacrylic acid and butylacrylate, isonitrile (C) and formaldehyde; (18) as in (17) but with the addition of cyclohexanone; (19) a copolymer of vinyl acetate, acrylamide and acrylic acid, isonitrile (C), dioxane and glutardialdehyde; (20) a copolymer of acrylic acid, hydroxypropyl methacrylate, isonitrile (A) and cinnamic aldehyde; (21) an alternating copolymer of isoprene and maleic acid-cyclohexyl semi-ester, isonitrile (C) and cyclohexanone; (22) the copolymer of (21), cyclohexanone and isonitrile (B); (23) a copolymer of vinylidene chloride, methyl methacrylate and methacrylic acid, isonitrile (B) and ethylamyl ketone; (24) a pyromellitic acid anhydride modified adipic acid-ethylene glycol polyester, 3:31:5:51 - tetraethyl diphenyl methane-4:41 - diisocyanide and benzophenone; (25) reaction product of linseed oil, trimethylol propane and 1:2:4-benzene tricarboxylic acid anhydride, 1:4 - hexane - diisocyanide, cyclohexanone and manganese naphthenate; (26) a copolymer of styrene, butyl acrylate and acrylic acid and isonitrile (C); (27) as in (26) with the addition of hydrazine; (28) a copolymer of styrene, acrylic acid butyl ester and methacrylic acid and isonitrile (C); (29) a copolymer of methacrylic acid dodecyl ester, styrene and methacrylic acid, methyl ethyl ketone, isonitrile (B) and cyclohexanone; (30) a trifunctional isonitrile mixture made by reacting citric acid, isonitrile (C) and cyclohexanone, a copolymer of methacrylic acid dodecylester, styrene and methacrylic acid and cyclohexanone; (31) as in (30) but replacing isonitrile (C) with isonitrile (A); (32) as in (30) with the addition of stearylamine and (33) a copolymer of styrene, acrylic acid, butyl acetate and acrylonitrile, acetone, cyclohexanone and isonitrile (C).ALSO:In Example (33) a solution in ethyl acetate and acetone of a polyesteramide made by reacting a mixture of 1-methyl 3.5-diethyl-2.4-phenylene diisocyanide, cyclohexanone and a copolymer of acrylic acid, styrene, butyl acrylate and acrylonitrile is cast as a coating on to an iron shed and dried at room temperature or maintained for 5 minutes at 120 DEG C.