Patent GB-779815-A (GB)
Title: Manufacture of fibres and other structures based on polyvinyl alcohol
IPC: D01F6/14
Filed: 1953-09-03
Abstract: Filaments, films and other shaped articles are obtained by extruding an aqueous solution containing polyvinyl alcohol, or a derivative thereof containing a substantial proportion of unsubstituted alcoholic hydroxyl groups, and an essentially linear polymer with reactive hydrogen at an amide nitrogen into an aqueous precipitation bath, and the shaped articles formed are subjected to the action of a reactive carbonyl compound at an elevated temperature in the presence of a compound of acid reaction.  The process may be modified by incorporating in the aqueous polyvinyl alcohol solution a polymerizable vinyl monomer containing an amide group and extruding the solution into an aqueous precipitation bath in the presence of a substance which causes polymerization of the monomer.  The process may also be modified by using a polyvinyl alcohol derivative containing amide groups as well as hydroxyl groups, the addition of another linear polymer with amide groups being omitted if desired. Preferably polyvinyl alcohol which is substantially free from acyl groups is used, but also suitable are derivatives in which the hydroxyl groups are partially substituted to such an extent that the solubility in water or predominantly aqueous liquids such as dilute aqueous solutions of methanol, acetone, tetrahydrofurane, or dioxane, is maintained.  Polyvinyl alcohol may be used in which some of the hydroxyl groups have been converted into acetals by reaction with aldehydes or ketones, e.g. formaldehyde, methoxyacetaldehyde, glyoxylic acid, dimethylamino acetaldehyde, or morpholino-acetone. Water-soluble, hydrolysed copolymers of vinyl acetate and vinyl chloride, acrylic acid, acrylamide, or itaconamide, may be used.  The synthetic linear polymer containing amide groups may be a vinyl polymer containing amide groups in side chains or a condensation polymer containing, in the main molecular chain or in lateral substituents, amide groups with reactive hydrogen, provided these compounds are soluble in water or in preponderantly aqueous liquids or soluble with formation of salts with the aid of acid or basic groups.  There may be used polyacrylamide, polymethacrylic methylamide, polyalpha-chloracrylamide, partially hydrolysed polyacrylonitrile; basic copolymers of acrylamide with basic esters, such as acrylic acid-gamma-dimethyl aminopropyl ester, or quaternary compounds of such basic copolymers, such as reaction products with dimethyl sulphate, ethylene chlorhydrin, or sodium chloroacetate; reaction products of copolymers of maleic anhydride with primary-secondary or primary-tertiary diamines such as asym.-dimethyl ethylene diamine; or a copolymer amidated with g -dimethylamino-propylamine and obtained from 1 mol. of maleic acid-N-methylimide and 1 mol. of vinylmethyl ether.  Amongst the amide containing condensation polymers there may be used (1) basic polyamides obtained from dicarboxylic acids or their esters and di-primary polyamines such as diethylene triamine and N-methyl-N-di-g -aminopropylamine; (2) basic polyurethanes such as the reaction products of hexamethylene di - isocyanate with N - methyl - di - [b - hydroxy - ethyl]-amine; (3) basic polyureas such as those obtained from hexamethylene di-isocyanate and N - methyl - N - di - [g  - amino - propyl] - amine; (4) polyisothioureas; (5) polyguanidines; (6) linear polyureas with lateral carbamyl groups; (7) water- or alkali-soluble linear polysulphonamides, e.g. the reaction product of tetramethylene disulphochloride and tetramethylene diamine.  A vinyl monomer containing an amide group may be incorporated in an aqueous polyvinyl alcohol spinning solution and polymerization may be effected in situ by addition of a catalyst, e.g. ammonium persulphate.  In the aqueous spinning solution, either the polyvinyl alcohol or the amide containing linear polymer may be present in the greater proportion.  The precipitating bath may be a dilute solution of sodium, magnesium, or ammonium sulphate, and it may be neutral, acidic, or alkaline in reaction.  It may contain a hardening agent such as formaldehyde.  For alkaline precipitation baths there may be used aqueous solutions of ammonia, sodium carbonate, sodium phosphate, or sodium borate, with or without other salts.  The precipitation bath may be used at raised temperatures, e.g. 60-110 DEG  C.  The freshly formed filaments may be rinsed with cold water which may contain formaldehyde, alkali-metal acetates, or anionic or cationicactive substances.  The filaments or other articles may be treated with solutions of salts such as those of barium, zinc, cadmium, or copper, particularly when the amide-containing polymer contains carboxyl groups, in order to render them less sensitive to water. They may be treated with organic bases or salts thereof, e.g. dodecylguanidine, for rendering dyeings with substantive dyes fast to water and washing or for fixing tanning agents.  For hardening the filaments, or other articles there may be used formaldehyde, glyoxal, acrolein, furfural, succinic acid dialdehyde, glyoxal bisulphite, dimethylol urea, tetramethylol-acetylene diureine, polymethylol melamines, or a  b -dichloro dioxane.  The acidic substance for catalyzing the acetalization may be hydrochloric, sulphuric, aminosulphuric, perchloric, trichloracetic, or benzene sulphonic acid.  The acidic bath may contain an addition of sodium or ammonium chloride or sulphate or a surface-active acid such as octyl sulphuric acid or tert.-butyl benzene sulphonic acid. Filaments may be subjected to stretching before or during the hardening treatment. The hardening may be effected in one or more stages and if desired at a temperature which is gradually increased to 100 DEG  C.  Stretching may be carried out while the filaments are passing through a hot liquid or through a hot air current between heated rolls, or while they are being subjected to infrared radiation.  After the stretching and hardening, the threads may be rendered shrink-resistant by heating them, e.g. at 110-210 DEG  C., with or without tension and they may finally be treated in boiling water containing urea.  Fibres may be crimped mechanically before or after being cut to staple length and they may be heated in dry or moist state to set the crimp. The filaments may be dyed in a hot bath with acid dyes, e.g. chrome complex dyes, and chrome developed dyes.  In an example, a spinning solution containing 12 per cent of polyvinyl alcohol and 1.2 per cent of polyacrylamide is extruded into a solution of 45 per cent ammonium sulphate at 55 DEG  C.  The thread obtained is washed with ammonium acetate solution and then dried, twisted, and at 155 DEG  C. stretched to 260 per cent of the initial length.  After further twisting, the thread is treated on a yielding support with a solution of formaldehyde, sodium chloride, and hydrochloric acid at 50-70 DEG C.  The thread shrinks about 16 per cent.  It is dried at low temperature and then heated without tension for 20 minutes at 120 DEG C., this causing a further small reduction in length.  Finally the thread is made to shrink further by treating it with boiling water. The total shrinkage is about 30 per cent calculated on the length after stretching.  Many other examples are given in the Specification.  In one example, the spinning solution is an aqueous solution of a highly viscous polyvinyl alcohol containing 10 per cent of acrylamide in the macromolecule, obtained by de-esterification of the corresponding copolymer of vinyl acetate and acrylamide.  In another example, a solution in aqueous methanol of a polyvinyl acetate, which has been hydrolysed to the extent of 75 per cent and a copolymer of 1 mol. of caprolactam, 1 mol, of adipic acid, and 1 mol. of butane-diol-bis-g . aminopropyl ether is extruded into potassium acetate solution to form a narrow band which, after stretching and washing, is hardened with formaldehyde in presence of hydrochloric acid and sodium chloride.