Patent GB-609792-A (GB)
Title: Improvements relating to the manufacture of highly polymeric esters
IPC: C08G63/685
Filed: 1946-03-22
Abstract: Polyesters capable of being formed into filaments having cold-drawing properties are prepared by reacting glycols of the series HO (CH2)n-OH, where n is in the range of 2 to 10, with N.N1-diphenyl-polymethylene diamine-4.41-dicarboxylic acids of the general formula <FORM:0609792/IV(a)/1> in which R is the group -NH-(CH2)m-NH-, where m is in the range of 2 to 10, or one of the groups <FORM:0609792/IV(a)/2> or with ester-forming derivatives of such acids preferably a low alkyl ester, e.g. methyl, ethyl, n-butyl, to form low polymeric esters, and further polymerizing these esters until filaments drawn from the molten product may be colddrawn. Acids specified are the 4,41-dicarboxylic acids of N,N1-diphenyl-ethylenediamine, -trimethylene diamine, -tetramethylene diamine, -hexamethylene diamine, -octamethyllene diamine, -decamethylene diamine, -piperazine, -tetrahydroglyoxaline, -ethylene trimethylene diamine.  The glycol may be ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene or decamethylene glycol in the proportions of 4 to 6 mols. per mol. of acid or 1 1/2 to 3 mols. per mol. of acid derivative.  The reaction between a glycol and an ester of the acids is carried out in the presence of an ester interchange catalyst such as lithium, sodium, potassium, calcium, magnesium (conveniently in the form of alcoholates, carbonates or borates), zinc, cadmium, manganese, iron, nickel, cobalt, tin, lead and bismuth or a mixture of a small amount of an alkali metal with one or more metals belonging to another group. The polymerization stage is carried out at a temperature above the boiling point of the glycol and preferably at a reduced pressure, e.g. 20-0.1 mm. of mercury, advantageously in the absence of oxygen and in a stream of inert gas, e.g. nitrogen.  In the examples, esters are prepared from (1) diethyl-N.N1-diphenylethylene diamine - 4.41 - dicarboxylate and ethylene glycol; (2) dimethyl-N.N1-diphenylethylene diamine-4.41-dicarboxylate and hexamethylene glycol; (3) diethyl-N.N1-diphenylethylene diamine-4.41-dicarboxylate and hexamethylene glycol; (4) decamethylene glycol and the acid of example (3); (5) diethyl-N.N1-diphenyltrimethylene diamine-4.41-dicarboxylate and hexamethylene glycol; (6) diethyl-N.N1-diphenylhexamethylene diamine-4.41-di-carboxylate and ethylene glycol; (7) diethyl-N.N1 - diphenyldecamethylene diamine - 4.41-dicarboxylate and ethylene glycol, (8) diethyl-N.N1 - diphenyldecamethylene - diamine-4 . 41 dicarboxylate and hexamethylene glycol; (9) diethyl-N.N1-diphenyldecamethylene diamine-4.41-dicarboxylate and decamethylene glycol; (10) diethyl - N.N1 - diphenyl piperazine - 4.41 - dicarboxylate and decamethylene glycol; (11) diethyl - N.N1 - diphenyltetrahydroglyoxaline - 4.41-dicarboxylic acid and decamethylene glycol; (12) diethyl - N.N1-diphenylethylene - trimethylene diamine-4.41-dicarboxylate and hexamethylene glycol.ALSO:Polyesters capable of being formed into filaments having cold drawing properties are prepared by reacting glycols of the series HO(CH2)n-OH, where n is in the range of 2 to 10, with N,N1 - diphenyl - polymethylene - diamine-4,41-dicarboxylic acids of the general formula <FORM:0609792/IV(b)/1> , in which R is the group -NH-(CH2)n-NH-, where m is in the range of 2 to 10, or one of the groups <FORM:0609792/IV(b)/2> , or with ester-forming derivatives of such acids preferably a low alkyl ester, e.g. methyl, ethyl or n-butyl, to form low polymeric esters; these esters are then further polymerized until filaments drawn from the molten product may be cold-drawn (see Group IV (a)).  Acids specified are the 4,41-dicarboxylic acids of N,N1-diphenylethylenediamine, -trimethylene diamine, -tetramethylene diamine, -hexamethylene diamine, -octamethylene diamine, -decamethylene diamine, -piperazine, -tetrahydroglyoxaline, -ethylene trimethylene diamine.  The glycol may be ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol or decamethylene glycol in the proportions of 4 to 6 mols, per mol. of acid or 1 1/2 to 3 mols. per mol. of acid derivative.  The reaction between a glycol and an ester of the acids is carried out in the presence of an ester interchange catalyst such as lithium, sodium, potassium, calcium, magnesium (conveniently in the form of alcoholates, carbonates or borates), zinc, cadmium, manganese, iron, nickel, cobalt, tin, lead and bismuth or a mixture of a small amount of an alkali metal with one or more metals belonging to another group.  In the examples, esters are prepared from (1) diethyl-N,N1-diphenylethylenediamine-4, 41-dicarboxylate and ethylene glycol; (2) dimethyl-N,N1-diphenylethylenediamine - 4,41 - dicarboxylate and hexamethylene glycol; (3) diethyl-N,N1-diphenyl ethylene diamine-4,41-dicarboxylate and hexamethylene glycol; (4) decamethylene glycol and the acid of example (3); (5) diethyl-N,N1-diphenyltrimethylenediamine-4, 41-dicarboxylate and hexamethylene glycol; (6) diethyl-N,N1 - diphenylhexamethylenediamine - 4,41 - dicarboxylate and ethylene glycol; (7) diethyl-N,N1-diphenyldecamethylenediamine-4, 41-dicarboxylate and ethylene glycol; (8) diethyl-N,N1 - diphenyldecamethylenediamine - 4,41-dicarboxylate and hexamethylene glycol; (9) diethyl-N,N1-diphenyldecamethylenediamine-4, 41-dicarboxylate and decamethylene glycol; (10) diethyl - N,N1 - diphenylpiperazine - 4,41 - dicarboxylate and decamethylene glycol; (11) diethyl - N,N1 - diphenyltetrahydroglyoxaline - 4,41 - dicarboxylic acid and decamethylene glycol; (12) diethyl - N,N1 - diphenylethylenetrimethylene diamine - 4,41 - dicarboxylate and hexamethylene glycol.