DE1669563A1 - Process for the production of threads, fibers and the like. from polyacrylonitrile or acrylonitrile copolymers and their mixtures with other polymers - Google Patents

Description

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VBB man-made fiber plant
"Friedrich Engels"
GDR 1832. Premnitz

Process for the production of threads, fibers and the like. From Polyacrylonitrile or acrylonitrile copolymers and their Blends with other polymers.

The invention relates to a process for the production of filaments, fibers and the like, i. Polyacrylonitrile or acrylonitrile copolymers and mixtures thereof with other polymers, which are obtained from a common solution in an organic solvent, in particular dimethylformamide, according to any of the usual spinning methods.

It is known that the threads, fibers and the like made of polyacrylonitrile. With regard to such properties as Colorability, whiteness, thermal resistance, dimensional stability and other high demands are made and numerous methods and procedures have been developed to improve these Aim at properties.

A copolymerization of acrylonitrile with suitable monomers such as acrylic acid, methacrylic acid, itaoonic acid, Sodium allyl sulfonate, sodium styrene sulfonate, 2-vinylpyridine, 2-methyl-5-vinylpyridine, methacrylamide and others an improvement the staining power and partly also the hydrophilicity achieved been. An advantageous modification of the properties is also through a graft copolymerization of the polyacrylonitrile or Copolymers of acrylonitrile with reactive monomers such as vinyl acetate, acrylic acid ester ^ sodium styrene sulfonate, N-vinyl-3-niorpholinone, 2-vinylpyridine, N-vinylpyrrolidone and others succeded.

New documents (Art 7 § ι Abe. A No. ι sentence
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Finally, it has also been proposed to use polyacrylonitrile or acrylonitrile copolymers in a mixture with one or more others Process polymers from a common solvent into molded articles. For this purpose one has, for example Combinations of polyacrylonitrile or copolymers of acrylonitrile with linear or cyclic vinyl polymers or -c © polymers, cellulose acetate, polyester, polyamide, polyurethane or mixtures of different aeryl nitrile copolymers used.

The methods listed above are not universally applicable, and their implementation is significant with either Associated costs or considerable technical difficulties. So has the copolymerization or graft polymerization with other monomers have the disadvantage that these monomers often Difficult to manufacture and therefore expensive. Furthermore, it can be associated with a considerable loss of monomers, since in the copolymerization and graft copolymerization reactions, complete conversion of the monomers is only achieved in a few cases is achievable and the unconverted portions are lost. Due to the sometimes considerable differences in activity of the monomers in the copolymerization is the batchwise or continuous addition of the more reactive monomer to the initially charged less reactive comonomers for the purpose of achieving homogeneous copolymers are usually unavoidable, whereby the overall process procedurally complicated. In addition, the improvement in certain properties achieved by copolymerization, such as, for example, the dyeability, often a deterioration in the thermal stability or the freezing temperature is accompanied. The general application of the process for the production of moldings from the common solution of a Polymer mixture are limited by the fact that the vast majority of the for the production of threads, fibers and the like. The polymers used are either incompatible with one another or only slightly incompatible with one another and are incompatible as a result of a combination Moldings made from polymers have poor mechanical properties. Therefore it is only under certain conditions such as by using special solvents or

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Additions to the spinning solution or suitable modification of the polymers It is possible to produce moldings with good properties from the joint solution of a polymer mixture. These conditions are not generally valid and must be processed in each case Polymer combination to be adjusted.

The purpose of the invention is to determine the utility properties of threads, fibers and the like. Which, with the participation of polyacrylonitrile or acrylonitrile copolymers are produced to improve.

The invention is based on the object of the production process to be designed so that threads, fibers and the like with good properties from a common solution of a polymer mixture can be produced.

It has surprisingly been found that a mixture of polyacrylonitrile or acrylonitrile copolymers and one Polycarbonate in an organic solvent, such as dimethylformamide, threads in a manner known per se, Produce fibers and the like with very good mechanical properties can when the molecular weight of the polycarbonate is 10,000 to 40,000, preferably 20,000 to 30,000, and one a mixing ratio of 1OGtO to 80t20, preferably 99s1 to 95 * 5. It is not absolutely necessary that to dissolve both polymers together, special one can also start from separate solutions of both components and then they Mix homogeneously immediately before processing. The polysarboxylates used according to the invention are are condensation products of phosgene or coblenic acid esters which are easily accessible industrially by known processes 2,2 bis (4-hydroxyphenyl) alkanes or their aromatic compounds or cyclic homologues or their derivatives «Ss is, however possible and even advantageous to use, in the context of the invention, instead of the simple polycarbonates, products which in substance, suspension or solution in an inert organic solvent using sulfuric acid ^ chlorosulfonic acid or sulfur trioxide were sulfonated in a known manner and desan sulfur content 1 Ms 15% by weight, but preferably 4 fcis 8 wt .- #, is ;.

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The advantages of the process are that it can be used by common Deformation of polyacrylonitrile or acrylonitrile copolymer and polycarbonate due to the participation of the latter in the Structure formation of the shaped body, regardless of the low proportion in the mixture, succeeds in the advantageous properties of the To transfer polycarbonates to the polymer combination and thereby the properties of polyacrylonitrile or acrylonitrile polymers to improve. When using sulfonated polycarbonates, the result is due to the high affinity for the dye of the acidic sulfonate groups, in addition to the improvements mentioned, an increase in the staining ability of the moldings.

The invention is illustrated by the following examples:

Example 1.

A 16% solution of a polyacrylonitrile with a K value of 90 (according to Fikentscher) and an equally concentrated solution of a polycarbonate with a molecular weight of 30,000 in dimethylformamide were mixed in a ratio of 98-2 and fed through a nozzle with 240 openings with a diameter of 0.09 mm composed of 20 parts dimethylformamide and 80 parts of hexane triol coagulation bath having a temperature of 105 - 110 ⁰ C-spun, stretched at 98-100 ⁰ C in water, washed and dried at 20 ⁰ C in air. For comparison, a 16% polyacrylonitrile solution was spun into threads without the addition of polycarbonate. The physical textile values of the threads obtained are shown in Table I:

Table I. Ver
stretching
(%) Titer
(the) Tear
sturdiness
(κ / den) fracture
strain
(%) Schiingen
strength
(ς / den) White
salary
C%) relationship
PAN / poly
carbonate 600 3.04 2.60 42.2 2.15 59.0 10010 800 2.84 3.41 37.6 2.24 60.2 600 2.81 3.93 40.1 2.03 68.7 98t 2 800 3.20 4.01 35.8 1.91 68.3

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Example 2.

From 95 parts of a polyacrylonitrile with a K value of 90 and 5 parts of a polycarbonate having a molecular weight of 25,000 was prepared by co-dissolving in dimethylformamide with stirring over the course of A 16% spinning solution was prepared for 2 hours. Among the im The conditions described in Example 1 were spun into threads, the physical textile properties of which are shown in Table II are 2

'Table II

Ratio of titer tear-break-loop-white-PAN / poly-stretching (den) strength- elongation strength content carbonate (%) speed (%) (g / den) (%)

(g / den)

95: 5

600 3, 32 3 , 40 37 , 6 1 , 94 66 , 4 800 3, 51 3 , 82 33 , 2 1 , 83 65 ,8th

Example 3

From 95 parts of a polyacrylonitrile with a K value of 90 and 5 parts of a sulfonated polycarbonate with a sulfur content of 7.15% a solution was prepared and spun under the conditions described in Example 1. The threads obtained showed with a titer of 3.12 denier, a strength of 3.2 g / denier and an elongation at break of 32%. Dyeability, whiteness and Thermal resistance of the threads are along with the appropriate Values for filaments made of pure polyacrylonitrile illustrated in Table III »

Table III

relationship

PAN / sulfone.

Polycarbonate

Whiteness

OT

Thermostability (White content after treatment 30 'at 160 ⁰ C)

Can be stained with basaoryl blue GL

1OOiO
95i5

59.0 62.8

28.6
39.5

3% not undressed 7% completely undressed 9% almost completely undressed.

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Whitening and thermal stability were measured in a Zeiss leukometer measured against a BaSCV standard.

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Claims (3)

Patent claims: 1. Process for the production of from polyacrylonitrile or a Acrylonitrile copolymer and a further polymer consisting of threads, fibers and the like., Characterized in that the acrylonitrile polymer is a polycarbonate with a molecular weight of 10,000 to 40,000, preferably from 20,000 to 30,000, in a ratio of 100: 0 to 80:20, preferably from 99: 1 to 95: 5, is added so that both are together in one organic solvent, preferably dissolved in dimethylformamide, and the resulting solution in a manner known per se and way is spun. 2. The method according to claim 1, characterized in that the two polymers are dissolved separately and the solutions obtained be mixed homogeneously before spinning. 3. The method according to claim 1 and 2, characterized in that the polycarbonate used dye-affine groups, in particular contains sulfonate groups, and the sulfur content in this sulfonated polycarbonate is 1-15% by weight, preferably 4-8% by weight. New underground (απ.7§iAbi. 109820/2024