Patented June 10, 1952 2,599,974

UNITED STATES PATENT oFFICE 2,599,974 POLYMERC COMPOUNDS CONDENSED FROM EPICHLORHYDRIN AND A BI FUNCTIONAL AMNO COMPOUND, AND METHOD OF PRODUCTION Albert Stanley Carpenter, Sutton Coldfield, Bir mingham, and Eric R. Wallsgrove, Coventry, England, assignors to Courtaulds Limited, Lon don, England, a British company No Drawing. Application February 15, 1950, Se rial No. 144,373. In Great Britain March 2, 1949 12 Claims. (C. 260-42) This invention relates to the production of or a saturated heterocyclic ring structure con polymeric compounds and to the production from taining 5 carbon and one nitrogen atoms. AC Such compounds of threads, fibres, filaments and cording to the invention, the epichlorhydrin and the like, hereinafter generally referred to as the bifunctional compound are heated together 'threads.' with an alkali in an amount which is at least It is known that epichlorhydrin may be re substantially the chemical equivalent of the acted with aliphatic, aromatic or heterocyclic chlorine content of the epichlorhydrin used. Secondary amines to produce non-polymeric In accordance with further embodiments of products; for example British Patent Specifica the present invention, the bifunctional secondary tion No. 275,622 describes the reaction of O amino compound as defined is partly replaced, epichlorhydrin and secondary amines to form for example by a dihydric phenol as used in ap a-tertiaryaminoepihydrins which are then re plication Serial No. 124,944 or by a mono acted with bases to form unsymmetrically sub hydroxy benzoic acid such as parahydroxy stituted diaminopropanols. benzoic acid whereby mixed polymeric products The specification of application Serial No. 5 are obtained. 124,944, filed 1 November 1949 describes a process The present invention therefore also includes for the production of thermoplastic resins by a process for the production of mixed polymeric heating Substantially equimolecular proportions products which comprises heating together of epichlorhydrin and at least one aromatic epichlorhydrin, a bifunctional compound having dihydroxy compound in which the hydroxyl 20 a secondary amine group as one of its functional groupS are phenolic and the carbon atoms linked groups and as the other functional group a group to the hydroxyl groups are separated by at least chosen from the class consisting of Secondary one other carbon atom, together with a quantity amine groups and hydroxyl groups, the functional of an alkali such that the ratio of the number groups being separated by at least four carbon of molecules of alkali to the number of mole 25 atoms, said compounds containing either a cules of the dihydroxy compound is at least 1.0, benzene ring or a saturated heterocyclic ring the heating being continued until a fibre-forming structure containing five carbon and one nitrogen resinous product is obtained. atoms, an aromatic dihydroxy compound in French Specification No. 933,219 describes the which the hydroxyl groups are phenolic and the production of resinous products suitable for use 30 carbon atoms linked to the hydroxyl groupS are as anion-active agents by condensing at least 2 separated by at least one other carbon atom, and mols of an alpha-chloro, beta, gamma-epoxy an alkali in an amount which is at least the Compound Such as epichlorhydrin with one mol chemical equivalent of the chlorine content of of a polyalkylene polyamine, preferably in the the epichlorhydrin used, the combined propor presence of a strong alkali. 35 tions of the said bifunctional compound and the The object of the present invention is to pro said aromatic dihydroxy compound used being duce a novel class of polymeric compounds which substantially the equimolecular equivalent of are in general suitable for the production of the epichlorhydrin used. threads. The invention also includes a process for the In accordance with the present invention, a 40 production of mixed polymeric products which proceSS for the production of polymeric com comprises heating together epichlorhydrin, a pounds comprises heating together, in substan monohydroxy benzoic acid, a bifunctional Com tially equimolecular proportion, epichlorhydrin pound having a secondary amine group as One and a bifunctional compound having as one of of its functional groups and as the other func its functional groups a secondary amine group 45 tional group a group chosen from the class con sisting of secondary amine groups and hydroxyl and as the other functional group a secondary amine group or a hydroxyl group. The func groups the functional groups being separated by tional groups of these bifunctional compounds at least four carbon atoms, said compounds con are separated by at least 4 carbon atoms, and taining either a benzene ring or a saturated the compounds contain either a benzene ring 50 heterocyclic ring structure containing five car

2,599,974, 3 4. bon and one nitrogen atoms; and an alkali in using alpha- or beta-glycerol dichlorhydrin, or an amount which is at least the chemical equiva a mixture of both, with one molar equivalent of lent of the chlorine content of the epichlorhydrin caustic alkali, in place of the epichlorhydrin. In used, the combined proportions of the Said bi this case, the caustic alkali used to react with the functional compound and the monohydroxy glycerol chlorhydrin is additional to the alkali benzoic-acid. used being substantially the equi required to effect the reaction according to the molecular equivalent of the epichlorhydrin used. invention. In making mixed polymeric products accord The polymers obtained according to the inven ing to the invention the bifunctional secondary tion are in general thermoplastic products of high amino compound as defined preferably forms at 10 : molecular weight which can usually be drawn least 10 per cent of the mixture which is re ... or melt-spun- to form threads generally capable acted with the epichlorhydrin, and the alkali. of being cold-drawn. Suitable secondary amino bifunctional com The invention is illustrated by the following pounds for use in the present invention are 4,4'- Examples in which the parts are by weight: dipiperidyl - - - - Eacample 1 C-C - CEC / / . . . . 10.1 parts (1 mol) of epichlorhydrin, a boiling N CH-ce NH solution of 18.4 parts (1 mol) of 4,4', dipiperidyl Yoh-off, CH-CH in 160 parts of ethyl alcohol and a cold solution of 20 4.55 parts (1.04 mol) of caustic soda in 20 parts para-methylaminophenol and other N-alkyl of water were mixed together and heated for 3 Substituted amino phenols, and bis-4,4'-(N- hours under a reflux condenser. At the end of methylaminophenyl) methane, H3C-HN this time a finely-divided precipitate had formed; the pasty mass was poured into twice its volume 25. of-water, filtered and the precipitate was Washed three times with hot-water -and-dried at 100 Suitable dihydric phenols for use in making -centigrade. mixed polymeric products are hydroquinone, The polymer-obtained had an intrinsic viscosity resorcinol and 3.3' or 4,4' dihydroxy diphenyls. in a 1 per cent solution in meta, cresol of 0.42 and The process according to the invention for 30. when heated was capable of being drawn into making polymeric products may be effected in a fibreS. single stage reaction by heating the epichlorhy - Eacample - 2 drin, the bifunctional secondary-amino com A product consisting of the mixed stereoisoners pound and the alkali together, preferably under of 1:4 bis (2:3 epoxypropoxy)benzene (otherwise a reflux condenser, until a resinous polymer sepa 35 known as hydroquinone bis-glycidyl-ether) was rates. A two-stage reaction may also be used, prepared from 1 mol of hydroquinone, 2 mols of for example by first reacting the epichlorhydrin epichlorhydrin and 2 mols of caustic soda by the with from 50 to 100 per cent of the bifunctional method described by Werner and Farenhorst compound as defined and then heating the prod 40 (Receuil des Travaux Chimique de Pays-Bas. uct with the alkali and any remaining bifunc vol. 67 (1948), pages 438 to 441) and 12 parts of tional compound until a resinous polymer sepa this product, 9.15 parts of 4,4'-dipiperidyl, 0.25 rates; in an alternative two-stage reaction, One part of caustic soda (as catalyst) and 80 parts of mol of the bifunctional compound may be first ethyl alcohol were mixed and heated under a re reacted with two mols of epichlorhydrin and its flux condenser for 14 hours, at the end of which equivalent of alkali to form a di-epoxide com 45 - time a finely-divided cream-coloured Solid had pound which is then heated with a further mol separated. This solid was filtered off, washed of the bifunctional compound containing a small with ethyl alcohol and then with water and proportion of an alkali catalyst. finally dried first at 100° centigrade and then in Mixed polymeric products may be prepared ac a vacuum desiccator. COrding to the invention by heating the four re actants as defined together, preferably under a Eacample 3 -reflux condenser, until a resinous mixed polymer 17.2 parts of para-methylamino phenol. Sul - Separates. Two-stage processes may also be phate, 9.25 parts of epichlorhydrin, 16 parts of lused. For example the bifunctional secondary 5 5 alcohol, 20 parts of water and 4.2 parts of caustic amino-compound as defined may be used in one soda (a slight excess over the - amount required stage.anda-dihydric phenol as defined or a mono to liberate the free para-methylamino phenol) hydroxybenzoic acid used...in the other stage; were mixed together in a vessel fitted with a ... thus 1 mol. of the dihydric phenol, 2 mols of stirrer and a condenser. The apparatus was -epichlorhydrin and 2 mols of alkali may be re 60 Swept out with oxygen-free nitrogen. The mix - acted together in the first stage to form an aro ture was then heated on a boiling Water bath natic bis-glycidyl ether, by the method described under reflux with stirring in an atmosphere of by Werner, and Farenhorst (Receuil des Travaux nitrogen for 45 minutes. A solution of 4 parts of Chimique de Pays-Bas, vol. 67 (1948), pages 438 caustic soda in 10 parts of -Water. was then intro to .441) and then, reacting the bis-glycidyl ether 65 duced slowly over a period of 1. hour down the With mol of the bifunctional secondary-amino ... condenser, the reaction mixture being heated un Compound to form a resinous mixed polymeric der reflux and Stirred throughout. When all the product. Alternatively, mixtures of the bifunc caustic Soda had been added the mixture was tional compound with a dihydric phenol as de heated under reflux for 3 hours. The product fined or with a hydroxybenzoic acid may be used 70 had separated as a plastic mass which was sep -in.both stages. arated, washed three times with boiling water The processes according to the invention are and dried. preferably effected in the presence of a diluent The product melted - at approximately 120° Such as aqueous alcohol. centigrade and when molten was readily drawn The epichlorhydrin may be formed in situ by 75 out into fibres. 2,599,974 Eacample 4 carbon atoms and (4) mixtures of any of said 13.6 parts (.82 mol) of 4,4'-dipiperidyl, 2.2 bifunctional amino compounds and a compound parts of hydroquinone (.2 mol), 9.25 parts of selected from the group consisting of (a) aro epichlorhydrin (1 mol), 4.4 parts of caustic soda, matic dihydroxy compounds in which the hy (1.1 mol), 80 parts of alcohol and 10 parts of droxyl groups are phenolic and the carbon atoms water were mixed and heated under reflux for 7 linked to the hydroxyl groups are separated by hours with continuous vigorous stirring. The at least One other carbon atom, and (b) mono product which separated Was a Wiscous maSS ad hydroxy benzoic acids; and an alkali in an hering to the sides of the vessel; 200 parts of amount which is at least the chemical equivalent water were added, the product separated, washed O of the chlorine content of the epichlorhydrin four times with boiling water and dried. The used. . product was a dark thermoplastic polymer. 6. A process as claimed in claim 5 in which the Eacample 5 bifunctional reactant is a mixture of Said bi functional amino compounds and an aromatic 15.4 parts (0.93 mol) of 4,4'-dipiperidyl, 1.38 15 dihydroxy compound in which the hydroxyl parts (0.1 mol) of para-hydroxy-benzoic acid, groups are phenolic and the carbon atoms linked 9.25 parts (1 mol) of epichlorhydrin, 4.4 parts to the hydroxyl groups are separated by at least (1.1 mol) of caustic Soda, 80 parts of alcohol and One other carbon atom. 10 parts of Water were mixed and heated under 7. A process as claimed in claim. 6, wherein reflux for six hours with vigorous stirring. The 20 the aromatic dihydroxy compound used is hydro reaction mixture was diluted with 500 parts of quinone. water, brought to the boil and filtered hot to sep 8. A process for the production of polymeric arate the product which was Washed twice With compounds which comprises heating together boiling Water and dried. epichlorhydrin, 4,4'-dipiperidyl and an aromatic The product was an off-white fibre-forming 25 dihydroxy compound in which the hydroxyl thermoplastic powder which Softened at 200 cen groups are phenolic and the carbon atoms linked tigrade. Its intrinsic viscosity in a 1 per cent to the hydroxyl groups are separated by at least solution in meta-cresol was 0.41. one other carbon atom and an alkaliin an amount The term "cyclic amino compound' is used in which is at least the chemical equivalent of the the claims to include compounds containing either 30 chlorine content of the epichlorhydrin used, the a benzene ring structure or a saturated heterocy combined proportions of said 4,4'-dipiperidyl clic ring structure consisting of five carbon atoms and said aromatic dihydroxy compound being and a single nitrogen atom. substantially the equimolecular equivalent of the What we claim is: epichlorhydrin used. 1. A process as claimed in claim 5, wherein the 35 9. A process as claimed in claim 5, wherein the epichlorhydrin is reacted with from 50 to 100 per bifunctional reactant used is a mixture of Said cent of the Said bifunctional compound and the bifunctional amino compounds and a mono product is heated with the alkali and up to 50 hydroxy benzoic acid. per cent of the bifunctional compound. 10. A process as claimed in claim 9, wherein 2. A process as claimed in claim 5, wherein the 40 the monohydroxy benzoic acid used is para bifunctional compound used is 4,4'-dipiperidyl. hydroxy benzoic acid. 3. A process as claimed in claim 5, wherein the 11. A process for the production of polymeric bifunctional compound used is para-methyl-ami compounds which comprises heating together nOphenol. epichlorhydrin, 4,4'-dipiperidyl, a monohydroxy 4. A process as claimed in claim 5, wherein the 45 benzoic acid, and an alkali in an amount which bifunctional reactant is a mixture of any of said is at least the chemical equivalent of the chlorine bifunctional amino compounds and an aromatic content of the epichlorhydrin used, the combined dihydroxy compound in which the hydroxyl proportions of the 4,4'-dipiperidyl and the mono groups are phenolic and the carbon atoms linked hydroxy benzoic acid being Substantially the to the hydroxyl groups are separated by at least 50 equimolecular equivalent of the epichlorhydrin One other carbon atom and wherein 1 mol of the used. aromatic dihydroxy compound is reacted with 2 12. A composition of matter comprising a poly mols of epichlorhydrin and 2 mols of alkali to meric compound obtained by heating together in form an aromatic bisglycidyl ether and the bis Substantially equimolecular proportions epichlor glycidyl ether so obtained is reacted with 1 mol 55 hydrin and a bifunctional reactant selected from of the Said bifunctional compound to form a the group consisting of (1) bifunctional amino resinous mixed polymeric product. Compounds containing a benzene ring, and in 5. A process for the production of polymeric which both functional groups are secondary compounds Which comprises heating together in amino groups separated by at least four carbon Substantially equimolecular proportions, ep 60 atoms, (2) bifunctional amino compounds con chlorhydrin and a bifunctional reactant selected taining a Saturated heterocyclic ring structure from the group consisting of (1) bifunctional having five carbon and One nitrogen atoms, and amino compounds containing a benzene ring and in which both functional groups are Secondary in which both functional groups are secondary amino groups separated by at least four carbon amino groupS and are separated by at least four 65 atoms, (3) bifunctional amino compounds COn carbon atoms, (2) bifunctional amino compounds taining a benzene ring, and in which one func COntaining a Saturated heterocyclic ring struc tional group is a secondary amine and One func ture having five carbon and one nitrogen atoms, tional group is an hydroxyl group, Said functional and in Which both functional groups are second groups being separated by at least four carbon alry amino groups separated by at least four car 70 atoms, and (4) mixtures of any of Said bi bon atoms, (3) bifunctional amino compounds functional amino compounds and a compound Containing a benzene ring, and in which one Selected from the group consisting of (a) aro functional group is a secondary amine and one matic dihydroxy compounds in which the hy functional group is an hydroxyl group, said func droxyl groups are phenolic and the carbon atoms tional groups being separated by at least four 75 linked to the hydroxyl groups are separated by at 2,599,974 least one other carbon atom and (b) ... mono- UNITED STATES PATENTS : hydroxy benzoic ... acids; and an alkali in an Number Name Date ...amount which is at least the chemical equivalent 2,500,600 Bradley------Mar. 14, 1950 of the chlorine content of the epichlorhydrin sww.www. - as as ava men - - - - y used. 5 FOREIGN PATENTS A. STANLEY CARPENER, Number Country Date E. R. WALLSGROVE. 124,294 Australia. ------May 19, 1947 REFERENCES CITED The following references are of record in the l0 file of this patent: