Patent GB-620116-A (GB)
Title: Improvements in or relating to the manufacture of nitrogen-containing linear polymers
IPC: C08G18/80
Filed: 1939-01-23
Abstract: Nitrogen-containing linear polymers are produced by reacting a di-isocyanate or a di-urethane with a bifunctional reagent containing as one reactive function a hydroxy or carboxy group and as the other a hydroxy, carboxy or amino group.  Suitable reactants mentioned are o -amino-caproic acid, o -amino-caprylic acid, o -amino-nonanoic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, hexahydroterephthalic acid, trimethylene glycol, tetramethylene glycol, ethanolamine, the propanolamines and the butanolamines. The two urethane or isocyanate groups of the other component of the reaction mixture may be joined by a polymethylene chain which may be interrupted by an oxygen, sulphur or other atom. The complementary reactive radicals in the reaction mixture should be present in substantially equivalent proportions if filament- or film-forming polymers are required.  Reaction is effected by heating above 100 DEG  C. with reduced pressure if desired in the later stages.  Removal of volatile by-products may be assisted by passing an inert gas through the mixture.  The reaction may be performed in presence of a solvent for the reagents.  The products may be formed into shaped articles.  The di-urethanes may be produced from the corresponding diamines and a carbonate, e.g. phenyl carbonate; or from the corresponding di-isocyanate or di-carbonyl chloride with a hydroxy compound, e.g. a volatile phenol; or from the appropriate diazide and a hydroxy compound.  Samples have been furnished under Sect. 2(5) of polymers prepared from (1) and (2) octamethylene di-urethane and ethanolamine; (3) hexamethylene diphenyl urethane and hexamethylene glycol; (4) m-toluylene diphenyl urethane and hexamethylene glycol; (5) tetramethylene di-isocyanate and hexamethylene glycol; (6) hexamethylene di-isocyanate and hexamethylene glycol; (7) hexamethylene di-isocyanate and 1.4-butylene glycol; (8) hexamethylene di-isocyanate and decamethylene glycol; (9) m-toluylene di-isocyanate and hexamethylene glycol; (10) tetramethylene di-isocyanate and p-hydroxybenzoic acid; (11) tetramethylene di-isocyanate and lactic acid; (12) tetramethylene di-isocyanate and sebacic acid; (13) hexamethylene di-isocyanate and -aminocaproic acid; (14) hexamethylene di-isocyanate and aminopivalic acid.  The urethanes used for the samples were obtained from the corresponding di-isocyanate and phenol.  Tetramethylene di-isocyanate was made by the Curtius process from adipic dihydrazide.ALSO:Nitrogen-containing linear polymers are produced by reacting a di-isocyanate or a diurethane with a bifunctional reagent containing as one reaction function a hydroxy or carboxy group and as the other a hydroxy, carboxy or amino group. Suitable reactants mentioned are o -amino-caproic acid, o -amino-caprylic acid, o -amino-nonanoic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, hexahydroterephthalic acid, trimethylene glycol, tetramethylene glycol, ethanolamine, the propanolamines and the butanolamines. The two methane or isocyanate groups of the other component of the reaction mixture may be joined by a polymethylene chain which may be interrupted by an oxygen, sulphur or other atom.  The complementary reaction radicals in the reaction mixture should be present in substantially equivalent proportions if filament- or film-forming polymers are required.  Reaction is effected by heating above 100 DEG C. with reduced pressure if desired in the later stages.  Removal of volatile by-products may be assisted by passing an inert gas through the mixture.  The reaction may be performed in presence of a solvent for the reagents.  The products may be formed into shaped articles. The diurethanes may be produced from the corresponding diamines and a carbonate, e.g. phenyl carbonate; or from the corresponding di-isocyanate or dicarbamyl chloride with a hydroxy compound, e.g. a volatile phenol; or from the appropriate diazide and a hydroxy compound. Samples have been furnished under Sect. 2(5) of polymers prepared from 1- and 2-octamethylene diurethane and ethanolamine; (3) hexamethylene diphenyl urethane and hexamethylene glycol; (4) m-toluylene diphenyl urethane and hexamethylene glycol; (5) tetramethylene di-isocyanate and hexamethylene glycol; (6) hexamethylene di-isocyanate and hexamethylene glycol; (7) hexamethylene di-isocyanate and 1.4-butylene glycol; (8) hexamethylene di-isocyanate and decamethylene glycol; (9) m-toluylene di-isocyanate and hexamethylene glycol; (10) tetramethylene di-isocyanate and p-hydroxybenzoic acid; (11) tetramethylene di-isocyanate and lactic acid; (12) tetramethylene di-isocyanate and sebacic acid; (13) hexamethylene di-isocyanate and b -aminocaproic acid; (14) hexamethylene di-isocyanate and aminopivalic acid. The urethanes used for the samples were obtained from the corresponding di-isocyanates and phenol. Tetramethylene di-isocyanate was made by the Curtius process from adipic dihydrazide.