US2628886A

US2628886A - Production of artificial fibers of polymeric materials

Info

Publication number: US2628886A
Application number: US220732A
Authority: US
Inventors: Bamford Clement Henry; Hanby William Edward; Happey Frank
Original assignee: Courtaulds PLC
Current assignee: Akzo Nobel UK PLC
Priority date: 1950-05-12
Filing date: 1951-04-12
Publication date: 1953-02-17
Anticipated expiration: 1970-02-17
Also published as: FR1037034A; GB692433A; NL76193C; DE926270C

Description

Patented Feb. 17 1953 PRODUCTION OF ARTIFICIAL FIBERS OF POLYMERIC MATERIALS Clement Henry Bamford and William Edward Hanby, Maidenhead, and Frank Happey, Bingley, England, assignors to Courtaulds Limited, London, England, a British company No Drawing. Application April 12, 1951, Serial No. 220,732. In Great Britain May 12, 1950 7 Claims.

This invention relates to the production of artificial fibres of polymeric compounds and particularly to the production of fibres of synthetic polypeptides by polymerising anhydrocarboxyamino-acids having the general formula:

,a lower aliphatic carboxylic acid, a halogen-subsstituted lower aliphatic acid or mixtures of these compounds. 'lcified are meta-cresol, formic acid, dichloracetic Examples of suitable solvents speacid and trichloracetic acid. It'is stated ,in the specification of application Serial No. 159,391 filed May 1, 1950, or its continuation-in-part Serial :No. 221,144, filed April 18, 1951, that fibres ob tained using formic acid as solvent generally have a ,8 configuration whereas fibres obtained using phenols, dichloracetic acid and trichloracetic acid as solvents have generally an a configuration, A number of polypeptide fibres having an a configuration tend to swell or even dissolve in benzene, carbon tetrachloride and similar nonpolar organic liquids some of which find use as dry-cleaning agents.

The object of the present invention is toreduoe V the tendency for these polypeptide fibres to dissolve or swell in non-polar organic liquids.

According to the present invention, a process for the production of synthetic polypeptide fibres comprises extruding through a jet into aisetting medium a solution of the polypeptide in a solvent giving an a configuration, for example, metacresol, dichloracetic acid or trichloracetic acid and then treating the resultant thread with a bath comprising at least one aliphatic monocarboxylic acid containing from one tosix- .'c'arbon atoms per molecule or a like acid containing on the a carbon atom a bromine, phenyl or mercaptan group, so that at least part of the fibresis converted into the [3 configuration. Examples of 'suitablemonocarboxylic acids are formic acid,

, 2 glacial acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-caproic acid, iso-caproic acid and crotonic acid. Examples of -a-SllbStll7llt6d acids which may be used are bromoacetic acid, phenylacetic acid, a-bromo propionic acid, a. bromo butyric acid, a bromo-n-valeric acid and thioglycollic acid. Formic acid is the preferred acid. The extruded fibres While in the a form may be stretched before being treated with the acid in accordance with the invention.

The polypeptide solutions may be wet spun, or they may be dry spun, for example into hot air. Suitable coagulant liquids for use in the invention are water, ethyl alcohol, methyl alcohol and aqueous alcohols as described in the specification of application Serial No. 159,391.

The treatment according to the invention may be eiiected by immersing the fibres for a short time, for example, from 1 to 3 minutes in a liquid acid at ordinary temperatures although in some cases a shorter time is effective; if the particular acid is solid at ordinary temperatures, such acid may be used in the form of an aqueous or alcoholic solution. When formic acid is used the acid bath may consist of 100 per cent formic acid or aqueous or alcoholic solutions of formic acid containing at least 75 per cent by volume of formic acid.

' The present invention is illustrated by the following examples in which percentages are by weight unless otherwise stated.

Example 1 A copolymer of DL-p-phenylalanine and DL- leucine was prepared as described in the specification of application Serial No. 159,392 as follows: 60 millimols of anhydrocarboxy-DL-leucine and 60 millimols of anhydrocarboxy-DL-fi-phenylalanine were dissolved in approximately three times their total weight of nitro-benzene. 0.15 millimol of sarcosine dimethylamide in benzene solution was added as initiator and the mixture was allowed to stand for 3 days at centrigrade. At the end of this time polymerisation was substantially completed and evolution of carbon dioxide had substantially ceased. The polymer was precipitated by adding petroleum ether, the

precipitate was filtered ofi, washed with petroleum ether and dried.

The cep'olyrn'er obtained, which was soluble in benzene and in carbon tetrachloride, was dissolved in trichloracetic acid containing 10 per cent of water to form ,al5 per cent solution and "the solution was extruded'into abath of water "at ordinary temperature (20 centigrade). 'The fibres so produced, which had an a configuration, were withdrawn from the bath of water, passed through a bath of formic acid at 20 centigrade, and dried at 100 centigrade.

The fibres obtained had a B. configuration and were no longer soluble in benzene or carbon tetrachloride.

Example 2 A polymeric DL-p-phenylalanine,produced as described in Example 2 of the specification of ape plication Serial No. 159,391 was dissolved in metacresol to form a 15 per cent solution and the solu-' tion was extruded into a bath of ethyl alcohol at 20 centigrade. The fibres so produced, which had an a configuration, were withdrawn from the alcohol bath, passed through a bath of formic acid at 20 centigrade containing about 2 per cent by volume of water, and dried at 100 centigrade.

The fibres obtained had a 13 configuration.

Example 3 Example 4 Th cep ym r o -fi-p enylalanin an D .le e ne as used. i Example 1 w s dry sp n n hot air fr m a 30 p r nt sol on in meth n chloride. The resulting fibre was oriented by str n 200 p cent in Steam, passed t rou h a bath of formic acid containing per cent by volume of water, the bath being at 20 centigrade, and dried at 100 centigradei The fibres obtaine ha a is confi ura ion- Example 5 Fibres of the copolymer of DLepephenylalanine+DL-.1eucine prepared as described Example 1 were immersed for one minute in glacial acetic acid at 20 centigrade and then dried at 100 centigrade. The fibres obtained were insoluble in benzene whereas the fibres before treatment were readily soluble in benzene.

Examples 6 to 11 Fibres of the benzene soluble copolyiner described in Example 1 were immersed for 3 minutes in one of each of the following baths at 20 centimixture oi equal volumes of ethanol and water.

The fibres were then washed with ether and ried. T pr duc s obta ned in each examp e were insoluble in benzene.

. Examples 12 to 14 I F bres e he be zene-soluble eopolymer escr bed in Example l were immersed ter 1 minu e 4 in one of each of the following baths at 20 centigrade:

Example 12 n-butyric acid. Example 13 isobutyric acid, Example 14 n-caproic acid.

The fibres were then washed with ether and -dried. The products obtained in each example were insoluble benzene.

' Examples 15 to 17 A copolymer prepared from equimolecular proportions of 'DL-B-phenylalanine, DL-leucine and -benzyl-DL-glutamate was prepared by the method described in application Serial No. 159,392 using 1/800 roportion of carcosine dimethylamideas initiator. The product was spun I into fibres from benzene solution using petroleum ether as coagulant bath.

Samples of the fibres were then treated as follows:

Example l5 Immersed for 1 minute in formic acid and then dried directly at 100 centigrade.

Example 16 Immersed for 3 minutes in glacial acetic acid,

washed with ether and dried.

Example 17 Immersed for 1 minute in propionic acid and dried directly at 100 centigrade.

. of ti e not xe e n a t 3 i ut s in a at comprising at lea'st'onIacid chosen from the group consisting of. aliphatic. monocarboxyiic acids containing from one to, six carbon atoms per molecule and such acids containing on the a carbon atom a radical chosen from the group consisting of bromide, phenyl and mercaptan groups, so that at least part of the fibres is converted into the a configuration. i

v 2. A process forthe production of fibres from fibre-forming polypeptides obtained by polynierising alpha anhydrocarboxyamino-carboxylic acids comprising extruding through a jet into I a setting medium a solution of the polypeptide indichloroacetic acid andthen treating the resultant thread for a period of time not exceeding about 3 minutes in a bath comprising at least one acid chosen from the group consisting of aliphatic monocarboxylic acids containing from one to six carbon atoms per molecule and such acids containing on the carbon atom a radical cho en f om th r up Consisting o br id phenyl and mercaptan groups, so that at least part of the fibres is converted into the B-configuration.

3, A process for the production of fibres from fibre-forming polypeptides obtained by polymerising alpha anhydrocarboxyamino-carboxylic acids comprising extruding through a jet into' a setting medium a solution of the polypep id in t ieh ora e e ac d and en t e n theresultant thread for a period of time not ex ceeding about 3 minutes in a bath comprising at least one a d h s n ro e gro p n stin of al phatic nion ar e d cont nin from one to six carbon a ms pe molecu e an such acid en ainin on the a carb n stem radical chosen from the group consisting of bromide, phenyl and mercaptan groups, so that at least part of the fibres is converted into the e configuration.

4. A process for the production of fibres from fibre-forming polypeptides obtained by poly merising alpha anhydrocarboxyamino-carboxylic acids comprising extruding through a jet into a setting medium a solution of the polypeptidein a solvent given an a configuration and then treating the resultant thread for a period of time not exceeding about 3 minutes in a bath comprising formic acid so that at least part of the fibres is converted into the B configuration.

5. A process for the production of fibres from fibre-forming polypeptides obtained by polymerising alpha anhydrocarboxyamino-carboX- ylic acids comprising extruding through a jet into a setting medium a solution of the polypeptide in dichloracetic acid and then treating the resultant thread for a period of time not exceeding about 3 minutes in a bath comprising formic acid so that at least part of the fibres is converted into the ,8 configuration.

6. A process for the production of fibres from fibre-forming polypeptides obtained by polymerising alpha anhydrocarboxyamino-carboxylic acids comprising extruding through a jet into a setting medium a solution of the polypeptide in trichloracetic acid and then treating the resultant thread for a period of time not exceeding about 3 minutes in a bath comprising formic acid so that at least part of the fibres is converted into the ;& configuration.

7. A process for the production of fibres from fibre-forming polypeptides obtained by polymerising alpha anhydrocarboxyamino-carboxylic acids comprising extruding through a jet into a setting medium a solution of the polypeptide in a solvent giving an alpha configuration, stretching the resultant thread and then treating the resultant thread for a period of time not exceeding about 3 minutes in a bath comprising at least one acid chosen from the group consisting of aliphatic mono-carbo-xylic acids containing from one to six carbon atoms per molecule and such acids containing on the alpha carbon atom a radical chosen from the group consisting of bromide, phenyl and mercaptan groups, so that at least part of the fibres is converted into the beta configuration.

CLEMENT- HENRY BAMFORD. WILLIAM EDWARD HANBY. FRANK HAPPEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,318,704 Moncrieff et a1 May 11, 1943 2,516,162 Tullock July 25, 1950