Patent GB-676785-A (GB)
Title: Improvements in polymeric materials and in processes for their production
Inventor: FISHER JAMES WOTHERSPOON
IPC: C08G73/08
Filed: 1949-07-11
Abstract: Linear poly-sulphone-1,2,4-triazoles or 4-amino-1,2,4-triazoles are made by any of the methods described in Specifications 612,609, 613,020, 654,273 or 674,747, (a) using as dicarboxylic acids sulphone dicarboxylic acids, or (b) using thia-dicarboxylic acids and oxidizing the resulting polythioethertriazoles to the corresponding polysulphonetriazoles with hydrogen peroxide in a reaction medium comprising a lower fatty acid of a high concentration.  Specified acids are sulphone-g ,g 1-dibutyric acid, sulphone-d ,d 1-divaleric acid, sulphone-e ,e 1-dicaproic acid, sulphone-3,31-diheptoic acid, and 7-thiatredecane-1,13-dicarboxylic acid, 5-thiaazelaic acid, 5 - thia - nonane - 1,9 - dicarboxylic acid, dibenzyl-thioether-4,41-dicarboxylic acid, a ,o  - bis - (phenyl - thio) - alkane - 4,41-dicarboxylic acids, e.g. a ,b -bis-(phenyl-thio)-ethane-4,41- dicarboxylic acid, and diphenylthioether-4,41-dicarboxylic acid.  Preferably there are not less than three carbon atoms between sulphone and carboxyl groups or between two adjacent sulphone groups where there are more than one in the acid, and the carbon atoms are preferably comprised by methylene groups.  In examples: (1) the hydrazine salt of the sulphone acid obtained by oxidizing 7-thiatredecane-1,13-dicarboxylic acid was heated with hydrazine under pressure to 260 DEG  C. and finally under reduced pressure at 240 DEG  C. to give a fibre forming polymer melting at 212 DEG  C. and intrinsic viscosity 0.43 which would be increased by further heating under high vacuum; (2) the methyl ester of 7-thiatredecane-dicarboxylic acid was converted to the dihydrazide by refluxing with excess hydrazine in methanol and the dihydrazide heated with hydrazine under pressure at 240 DEG  C.  The resulting polythioether - aminotriazole, soluble in cresol and formic acid, and melting at 180 DEG  C., was then oxidized with hydrogen peroxide in a mixture of formic and acetic acids.  The polymer was refluxed with caustic alkali to remove possible formyl groups on the exocyclic amino groups, the final product melting at 207 DEG  C. and being soluble in cresol and formic acid; (3) the dihydrazide of sulphone-bis-valeric acid, derived from the methyl ester as in (2) was heated with aqueous hydrazine under pressure to 230 DEG  C. to give a fibre-forming polymer melting at 220-225 DEG  C. and soluble in cresol and formic acid; (4) thiodivaleric acid was heated with excess aqueous hydrazine under pressure to 220 DEG  C. to give a fibre-forming polythioether-aminotriazole melting at 150-155 DEG  C. and soluble in cresol and formic acid.  This polymer was then oxidized to the sulphone polymer with hydrogen peroxide in a mixture of formic and acetic acids.  The polymer, after refluxing with caustic alkali, was fibre-forming and melted at 209 DEG  C.; (5) sulphone-bis-butyricd ihydrazide obtained from the methyl ester as before, was heated with excess hydrazine under pressure to 200 DEG C. to give a polymer melting at 259 DEG  C.; (6) thiodibutyric acid in methanol was mixed with hydrazine in methanol and the hydrazine salt precipitated with ether.  The salt was heated under nitrogen at 170-175 DEG  C. to give the polyhydrazide which was then heated with hydrazine under pressure at 200 DEG  C.  The resulting polythioetheraminotriazole, melting at 160-165 DEG  C. was then oxidized with hydrogen peroxide in acetic acid to give the sulphone polymer which melted at 230-235 DEG  C. and was insoluble in methanol.  The fibres produced from the polymer of example (1) had good cold-drawing properties.  The first Provisional Specification refers also to sulphone diacetic, sulphone-a -a 1-dipropionic, sulphone-a -a 1-isobutyric, toluene-2,4-bis-(sulphone acetic), benzene-1,3-bis-(sulphone - a  - propionic), benzene - 1,3 - bis-(sulphone - a  - butyric) and toluene - 2,4 - bis-(sulphone-a -butyric) acids.ALSO:Thia-dicarboxylic acids for use in the preparation of linear triazole polymers (see Group IV (a)), are prepared by treating an alkali metal sulphide with a lactone or halogenated carboxylic acid, ester or nitrile, followed by hydrolysis, if necessary.  The halogenated nitriles may be formed by reacting halogenated hydrocarbons (e.g. dichlorohexane and dichlorobutane), with sodium cyanide.  The sulphone compounds, which may also be used in the preparation of polymers, may be produced from the corresponding thia compounds by oxidation with hydrogen peroxide in formic acid solution.  The sulphone esters and nitriles may be hydrolysed to the free acids.  Specified halogenated carboxylic acids are g -halogen butyric, d -halogen valeric, e -halogen caproic and 3-halogen heptoic acids.  g -butyrolactone is referred to. Alternatively sulphone-d .d 1-divaleric acid may be produced by adding two mols. of butadiene nitrile to hydrogen sulphide as in example 6 of Specification 598,309, followed by reduction and hydrolysis of the product as in example 1 of the same Specification, and finally oxidation to the sulphone.  Thia acids referred to are 7-thiatredecane - 1.13 - dicarboxylic, 5 - thia - azelaic, 5 - thia - nonane - 1.9 - dicarboxylic, dibenzylthioether - 4.41 - dicarboxylic, a  : b  - bis-(phenylthio) ethane-4.41-dicarboxylic and diphenylthioether - 4.41 - dicarboxylic acids.  Sulphone acids referred to are sulphone-.g .g 1-dibutyric, sulphone - d .d 1 - divaleric, sulphone - e .e 1 - dicaproic and sulphone-3.31-diheptoic acids.  In examples: (1) 1.6-dichlorohexane was reacted with sodium cyanide to give 7-chloroheptanonitrile which was then reacted with sodium sulphide to give 7-thiatredecane-1.13-dicarboxylic acid dinitrile.  This was hydrolysed with caustic potash, acidified, and the resulting acid oxidized to the corresponding sulphone acid with hydrogen peroxide in formic acid.  The hydrazine salt of the sulphone acid was then formed; (2) the free thia acid of (1) was converted to the methyl ester with methanol and sulphuric acid, and the ester converted to the dihydrazide with excess hydrazine; (3) sulphone - d .d 1 - divaleric acid was prepared by oxidation of thio-bis-valeric acid obtained from 1.4-dichlorobutane by the method of example (1). The sulphone acid was converted to the dihydrazide via the methyl ester, as in example (2); (5) sodium sulphide was reacted with g -butyrolactone and the product acidified to give thio-bis-butyric acid which was then oxidized to the sulphone acid.  The sulphone acid was converted to the methyl ester and then to the dihydrazide; (6) thiodibutyric acid was converted to the hydrazine salt.  The first Provisional Specification refers also to sulphone diacetic, sulphone-a .a 1-dipropionic, sulphone-a .a 1-isobutyric, toluene-2.4-bis-(sulphone acetic), benzene-1.3-bis-(sulphone-a -propionic), benzene - 1.3 - bis - (sulphone - a  - butyric) and toluene - 2.4 - bis - (sulphone - a  - butyric) acids.