DE881245C - Process for the production of fibers and threads by spinning polymerization products - Google Patents

Description

Process for the production of fibers and filaments by spinning Polymerization products For the manufacture of staple fibers for clothing The polyvinyl esters of organic acids generally come because of their inadequate quality mechanical and thermal properties not taken into account. The same applies to Polymers of vinyl derivatives of aromatic hydrocarbons, ffe. Apart from this, -that their character is unsuitable for clothing purposes, they have the disadvantage for this type of use, in the usual way for textiles not being able to be colored.

Polyvinyl chloride, practically cannot become dyeable fibers and threads to be spun. Threads or fibers made of Po.lyvinylacetat show a relative low softening point when heated, they are also sensitive to water. Even the copolymers of vinyl chloride and vinyl acetate are satisfactory in terms of their resistance to thermal stress not yet. Threads or fibers made from partially saponified organic polyvinyl esters are even more sensitive to water as threads made of polyvinyl acetate.

The condensation products behave much more favorably in this regard from the highly viscous stages of polyvinyl alcohol with aldehydes or hydroaromatic Ketones where the carbonyl compounds acetalarti.g on polyvinyl alcohol are bound. This body class, which because of its excellent mechanical Properties and their colorability with acetate silk dyes are already important Requirements for their application in the textile field are met, but shows that Disadvantage of most polyvinyl derivatives: a relatively low softening point, so that difficulties arise in practical use.

It has now been found that fibers and threads of high water resistance can be obtained and heat resistance when one uses the acetal-like condensation products for their production of aldehydes or Cych's ketones with saponified copolymers made of vinyl chloride and organic vinyl esters are used. Subject to the named copolymers the saponification under the same conditions, under .denen P @ olyvinyl alcohol obtained from polyvinyl acetate, according to patent specification 565 633, Example 2, so that remains Vinyl chloride portion of the copolymer unaffected, while the remainder of the organic Acids, e.g. B. the acetic acid residues, split off.

The acetalization of such a saponified copolymer, for example .according to patent specification 59-22: 233, offers no special features compared to the acetalization of pure polyvinyl alcohol. The acetalization can also be carried out without prior saponification, as in the case of polyvinyl acetate, in a single-bath process.

The technical effects that can be achieved in this way result from the following: Provided that the most viscous stages are used as starting materials, the acetalization of polyvinyl alcohol with acetaldehyde gives a podyvinylacetaldehyde acetal, which undergoes permanent deformation in water from 8o to 8-5 °. If you go from that Saponification product of a copolymer of 10 parts of vinyl chloride and 10 parts From vinyl acetate, a polyvinyl acetal is obtained, which only remains at 92 to 6 ° Undergoes deformations.

If the vinyl chloride content of the copolymer is increased to 25 % "in this way, acetalization after saponification results in products which only at io2 to io.5 ° soften to such an extent that they remain under mechanical stress Suffer deformations. So threads from this product are already boil-proof. Foils or compacts become in hot water due to their increased water resistance not tarnished.

While using the higher aldehydes acetals with lower E. The softening point is obtained, namely the softening points decrease under comparable conditions with increasing number of carbon atoms, give hydroaromatic ketones such as cyclohexanone and methylcyclohexanone, acetals with a strikingly high softening point, namely these are even higher than when acetaldehyde is used as an acetalizing agent. You can also produce mixed xeton-alde'hyd acetals by adding a part the hydroxyl groups are acetalized with cyclohexanone, the remainder with an aldehyde.

Mixed acetals with remarkable textile-technical properties is also obtained by combining some of the hydroxyl groups with a chloraldehyde, -like ß-chlorobutyral, dehyd, ß-chloropropionaldehyde or chloroacetaldehyde, the rest acetalized with a normal aldehyde or cyclic ketone. One (can, there proceed so that .man, the chloraldehyde with, the chlorine-free aldehyde together for Brings influence. The reactive chlorine atom of the acetals obtained in this way can subsequently be exchanged for amine groups, including in the staple fiber will.

Such polyvinyl acetals can be made with acidic wool dyes stain.

The spinning of these polyvinyl acetals can be carried out according to known methods Methods are done. If the products do not contain active chlorine, that can Threads are pulled from the fusible foot, with temperatures usually above 2oo ° required are. But you can also spin out of the solution, namely after the production of cellulose acetate silk conventional dry spinning processes or by the wet spinning process, spinning in water or aqueous solutions.

A particularly suitable solvent is tetrahydrofuran, which for the representatives of this body class has an excellent solvent power.

In the unstretched state, the threads tend to have a tensile strength of 8 to i i kg / qmm. After stretching by 2oo%, the tensile strength increases to 2.5 kg / qmm and is then higher than that of horsehair and sheep's wool. Examples i. A high molecular one Copolymer of 10 parts of vinyl chloride and parts of vinyl acetate is known in the art Way saponified and acetalized with as much cyclohexanone as the theoretical one Amount corresponds. After the reaction has ended, as much isdbutyrate dehyde is added corresponds to, as io%, of the cyclohexanone used.

The polyvinyl acetal will. isolated, freed from catalyst residues and dried.

The completely anhydrous product is made in an extruder 12a ° preheated, strongly compressed and from a spray head with circular bores pressed out, in which it is converted to the viscous state at 22o ° 2n.

The threads obtained with a circular cross-section are wound up and stretched in a known manner after cooling. When stretching around the zoo %, the original strength is increased by a factor of 2 '/ 2.

The threads can be colored with the dyes that are used for dyeing of cellulose acetate end application, under the same conditions. the Threads and yarns or fabrics made from them can be under the same conditions wash like wool without shrinking or reducing their tear resistance to become. In the same way one can find threads of the nature of horsehair produce.

2. A copolymer of 80 parts of vinyl acetate is used as the starting material and 2o parts of vinyl chloride, which after saponification of the acetate residues with an equimolar Mixture of propionaldehyde and ß-chlorobutyral, dehyd is acetalized.

The isolated, from catalyst residues and. The product freed from water is dissolved in five times the amount of tetrahydrofuran. This 20 per cent solution has a viscosity of 170 poises. It is filtered, freed from physically dissolved air by heating to the boiling point of the solvent and spun into a channel through which warm air flows in the manner customary for cellulose acetate. The processing of the web takes place in a known manner.

Treated to make the threads receptive to acidic dyes they are at 6o to 8o ° with a saturated aqueous solution of dimethylamine, with the fleet moving briskly. After two hours of treatment, it is rinsed out, Nachhehandelt with i ° acetic acid, rinsed and dried.

Treatment with the base does not adversely affect the Strength, as the acetal violin bases are completely resistant.

You can also add octadecylamine to the spinning solution and the implementation after spinning by heating the threads. In this case there is a follow-up treatment with soap or similar synthetic substances.

The product treated with octadecylamine shows a particularly soft one Handle and is highly water-repellent.

Claims (2)

PATENT CLAIMS: i. Process for the production of fibers and threads by spinning polymerization products, characterized in that the acetal-like condensation products of aldehydes or cyclic ketones with saponified, chlorine-containing copolymers of vinyl esters of organic acids and vinyl chloride are used. 2. The method according to claim i, characterized in that mixed acetals of chloraldehyde and other aldehydes or hydroaromatic ketones with saponified chlorine-containing Mischpolymeri.saten from vinyl esters of organic acids and vinyl chloride are used, either adding amines to the spinning mass and heating the spun threads or wherein the finished threads are aftertreated with amines. Cited references : U.S. Patent No. 1,939-422; German Patent No. 592 233; French Patent No. 767,093; British Patent Nos. 419 826, 482 216.