DE1930986A1 - Acrylonitrile polymer fiber material and process for its production - Google Patents

Description

Dipl.-Ing. Reinhold Kramer

PATENT ADVERTISER 69/87 ^ 0 19 3098

8OOO Munich 12

Maria-BIrnbaum-Strasse 1 Telephone SO OS 63

Mitsubishi Kayon Company Limited, Tokyo / Japan

Fiber material made from an acrylonitrile polymer and its method of manufacture

(Claimed priority:
June 19, 1965 Japan 42354/68)

The invention relates to a fiber material made of an acrylonitrile polymer, which improved heat setting spatial stability, excellent resistance to abrasion and excellent dyeing ability. The invention also relates to a method for producing said material.

The conventional laser materials made from an acrylonitrile polymer consist mainly of a copolymer of acrylonitrile and an unsaturated ethylene compound such as Methyl acrylate, vinyl acetate or methyl methacrylate.

SÖS881 / 14SÖ ^{r 2} "

93 0 98 6

In the production of these known fiber materials from a The acrylonitrile copolymer in question becomes the acrylonitrile polymer dissolved in a suitable solvent, the resulting spinning solution for the formation of filaments through a spinneret in atmospheric air or in a coagulation liquid bath squeezed out; and "the filaments formed are washed, drawn and subjected to a helaxing treatment. The fibers made of an acrylonitrile polymer have a pleasant wool-like feel, are extremely lightfast and white excellent dyeability. However, they have the disadvantage poor heat setting and poor spatial Stability on. Furthermore, they have poor wrinkle recovery and do not tolerate treatment in hot liquid,

Extensive tests have now shown that the aforementioned disadvantages of the usual fibers made of an acrylonitrile polymer can not be avoided by post-treatment of the fibers, but that, in order to achieve an improvement, the basic properties of the copolymer must change.

To eliminate the disadvantages mentioned, according to this invention, a fiber material is created from an acrylonitrile polymer whose Young's modulus in water of 90 ^° G has a value of at least 1.5 g / d, whose F value (as defined below) is at most 2, Is 0 and its color absorption capacity for ζχί ei hour of dyeing in a 5 percent by weight of a dye-containing bath at 100 ⁰ C is at least 70%.

900881/1480 " ³ "'

Such a fiber material made of an acrylonitrile polymer can be prepared according to the invention in that a polymer mixture, consisting of 50 to 95 parts of an acrylonitrile methacrylonitrile copolymer with a maximum of 40 percent by weight, preferably a maximum of 30 percent by weight methacrylonitrile and 50 to 5 parts of an acrylonitrile copolymer at 95 to 50 percent by weight Acrylonitrile and a comonomer is spun, the comonomer having the crystallinity of the resulting copolymer reduced by high polymerization with acrylonitrile (the comonomer in question is referred to below as the "decrystallization monomer" designated).

The fiber material obtained in this way from an acrylonitrile polymer shows an improved thermal setting compared to the known fiber materials made of an acrylonitrile polymer and better spatial stability. In particular, its mechanical properties are intact when hot, wet extremely improved compared to those of conventional fiber materials. It should be particularly pointed out that that the fiber material according to the invention consists of an acrylonitrile polymer a better resistance to abrasion, i.e. a higher abrasion resistance, and an excellent one Has dyeability.

Details of the invention emerge from the following Description on the basis of the drawing,

4 90 98 8 1 / U 6 = 0

8AO ORIGINAL

■ Fig. 1 shows an X-ray diagram of polyacrylonitrile,

2 shows an X-ray diagram of polyacrylonitrile and acrylonitrile-vinyl acetate copolymers,

3 shows an X-ray diagram of polyacrylonitrile and acrylonitrile methacrylonitrile copolymers,

Fig. 4 shows the temperature dependence of the viscoelastic ^ 'Behavior of polyacrylonitrile and acrylonitrile methacrylonitrile copolymers,

Fig. 5 shows the temperature dependence on the tangent of the dynamic loss angle of polyacrylonitrile and acrylonitrile methacrylonitrile copolymers,

Fig. 6 shows the temperature dependence of the viscoelastic Behavior of polyacrylonitrile and acrylonitrile vinyl acetate copolymers,

™ Fig. 7 shows the temperature-humidity ε-state during the Fiber relaxation, which is carried out at the same time as the drying process. ·.

The experiments have shown that polymerisation leads to formation suitable monomers with acrylonitrile can be divided into two groups. One group is made up of the monomers formed, which form isomorphic copolymers, which by copolymerization with acrylonitrile form a considerable Have crystallinity. In the other group are found

- 5 - ■■■ 90 98 81 / U 60

those monomers which, when copolymerized with acrylonitrile, cause a decrease in the crystallinity of the copolymer.

Polyacrylonitrile includes a paracrystalline area and an amorphous area. An X-ray diagram of a polyacrylonitrile obtained by normal complete polymerization is shown in FIG. 1. Here the diffraction curve of the amorphous area is shown in dashed lines. From Pig. 2 it can be seen that an increase in the content of the vinyl acetate structural unit in the copolymer leads to an extremely strong reduction in the crystallinity and that even the paracrystalline structure is completely lost if the proportion of vinyl acetate exceeds 20%.

As Dekristallisationsmonomer example, Vinylester such as vinyl acetate, vinyl chloroacetate, vinyl stearate and vinyl propionate or acids such as acrylic acid, "L-chloroacrylic acid, oL-bromoacrylic acid and methacrylic acid, or acrylates or methacrylates such as methyl acrylate, methoxy acrylate, ethyl methacrylate, butyl methacrylate, Mebhylmethacrylat, ithylacrylat, ot-Ghloräthyl- ^ acrylate and chloromethyl acrylate or vinyl ethers such as acrylamide, methacrylamide, alkyl substitutes of the amides mentioned, methyl vinyl ketone, N-vinyl saximide, N-vinyl phthalimide, methyl enmaloneeter, methylenglutaric acid nitrile, H-vinylcarbazole and vinylfuran or vinylpyridine such as 2-vinylpyridine, 4-vinylpyridine and 2- -5-vinylpyridine or vinylimidazole such as 1-vinylimidazole and

- 6 909881 / ueo

- ο - -

alkyl substitutes 1-vinylimidazole, II-vinylpyrrolidone, vinylbenzenesulfonate, Methaci'yl sulfonic acid, acrylic sulfonic acid and balze of the acids mentioned are used.

In general, the fiber materials currently produced from an acrylonitrile polymer contain copolymers with the monomers listed above. On the other hand, a copolymer of acrylonitrile and methacrylonitrile has completely "different properties than a copolymer that contains acrylonitrile and a decrystallization monomer. The copolymer of acrylonitrile and Iialihaci'ylnitz'il retains its paracrystalline structure, so that there is only a surprisingly small decrease in the This shows that the methacrylonitrile structural units form mixed crystals with the acrylonitrile structural unit in the copolymer, Fig. 3 shows that only a small difference can be found between the diffraction curves of the acrylonitrile methacrylonitrile copolymer and the polyacrylonitrile and that no remarkable decrease in the Crystallinity is present in the copolymers. If one compares FIG. 2 and FIG. 3, one can readily see that methacrylonitrile plays a completely different role in the copolymers than vinyl acetate. FIG. 2 shows that the acrylonitrile-vinyl acetate copolymer amorphous, as soon as the proportion of vinyl acetate exceeds 14%. In contrast, FIG. 3 shows that the crystal structure of the acrylonitrile methacrylonitrile copolymer is retained, even if the methacrylonitrile content increases to 24 % .

'. - 7-90 988 1 / USC

The characteristic properties of the structural methacrylonitrile unit in the copolymer are not only evident in the crystallinity of the polymer, but also in the temperature dependence of the dynamic modulus of elasticity (E ¹ ), the dynamic loss modulus (E ") and the dynamic loss actuator (tg-4).

If one compares the temperature dependencies of the dynamic modulus of elasticity (E ¹ ) and the dynamic loss modulus (E ") of the Acx ^ ylnitrilmethacrylnitrilcopolymers with those of the polyacrylonitrile in J? If.;. 4-, one sees that the temperature dependence of the dynamic visco-elastic behavior of the Copolymers with a proportion of methacrylonitrile of 12.5 percent by weight is almost the same as that of the polyacrylonitrile,! Furthermore, it can be seen from! '' Fig. 5i that the lower temperature absorption peak of the loss factor (tg 4) of the acrylonitrile methacrylonitrile copolymer is shifted towards a * higher temperature compared to that of polyacrylonitrile. It is assumed that the above-mentioned special properties of the acrylonitrile methacrylic copolymer are a consequence of the methacrylonitrile structural unit in the copolymer, through which isomorphic paracrystals are formed, and are also caused by the higher transformation temperature of methacrylonitrile into the glass state, through the molecular chain movements can be prevented in the paracrystals. From Fig. 6. It can be seen that the values of the dynamic modulus of elasticity (E ¹ ) and the dynamic loss modulus (E ") of the acrylonitrile vinyl acetate copolymer increase rapidly with increasing

- 8 909881 / U6Q

Vinyl ac et at ant eil in the copolymer "at a temperature above 100 ⁰ C decrease.

As can be seen from the previous sections, this Acrylonitrile methacrylonitrile copolymer has excellent characteristic properties that differ from those of the copolymer differentiate between acrylonitrile and a monomer, for example with vinyl acetate, methyl acrylate or methyl methacrylate, previously used as components of acrylonitrile polymer fibers became. The fibers of the former copolymer are more promising than the conventional fibers made of one Acrylonitrile polymer. However, so far no fiber materials have been consisting of the acrylonitrile methacrylonitrile copolymer are used except for one in the United States patent 2 692 875 described case. In this patent it is proposed that to use a copolymer which contains methacrylonitrile in a proportion of 15 to 30 percent by weight. However, fiber materials made from the proposed copolymers have unpleasant disadvantages that make their practical use, prevent it. The elongation of the fiber is a maximum of 18%, and the force-elongation ratio of the fiber is so unbalanced that that it is unsuitable for practical use,

Various model tests were carried out according to the teaching of the USA patent performed around the disadvantages described above to be able to determine. It turned out, however, that the fiber material according to the US patent specification is still further serious

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Has disadvantages. In general, in practical use of synthetic fiber materials, strength and den- * · The ability of the fibers to work well must be well matched to one another, and the fiber material must also have good resistance against abrasion, good abrasion resistance and dyeability exhibit. In this context, the tests carried out by us have shown that according to the above-mentioned Patent specified method produced fibers have poorly coordinated properties. Your relative

poor elongation leads to difficulties in the subsequent process steps, such as when spinning the fiber to threads. They also have remarkably poor scrub resistance and extremely poor dyeability. Even if, for example, the fibers consist of a copolymer in which a small proportion of sodium benzene sulfonate is built in as a dye attachment point, the dyeability cannot be improved to a sufficient extent. In addition, the disadvantages described can hardly be reduced even then when the conditions for fiber relaxation are set differently. That means the fibers only difficult to relax. But it is the relaxation treatment Carried out under strict conditions, the fibers are then extremely strongly changed in color and damaged.

We have conducted further research with the aim of finding a Fiber material with good abrasion resistance and excellent Obtain dyeability while maintaining the excellent properties

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of the acrylonitrile methacrylonitrile copolymer in the hot, wet state should be preserved.

The fiber material made of an acrylonitrile polymer according to The present invention has over the conventional! fiber materials from an acrylonitrile polymer have some very excellent properties. The fiber material according to the invention from an acrylonitrile polymer can be produced by an acrylonitrile methacrylonitrile copolymer (first component) with a maximum of 40 percent by weight, preferably a maximum of 30 percent by weight Methacrylonitrile and an acrylonitrile copolymer (second component) with 95 "to 50 weight percent acrylonitrile and a decrystallization monomer in a common solvent and then dissolves the resulting spinning solution through a spinneret in squeezes out a coagulant «So far one knew in the trade still no fiber material made of an acrylonitrile polymer, which equally excellent properties in the hot and wet state, the same excellent spatial stability 'and such a good one Abrasion resistance and dyeability like that according to the invention Has fiber material.

, The fiber material according to the invention is made by mixing polymers made of 50 to 95 parts from an Acrylni trilmethacrylonitrile copolymer with a maximum of 40 percent by weight, preferably at most JO weight percent methacrylonitrile and to 50 to 5 parts of a 95 to 50 weight percent copolymer Acrylonitrile and a decrystallization monomer exist.

- 11 909881/14 60

The first-named polymer is preferably replaced by a copolymer formed, its specific viscosity between 0.13 and 0.18 and soft between 5 and 15 percent by weight methacrylonitrile contains, while the specific viscosity of the last-mentioned polymer is preferably in a range between 0.10 and 0.25. The specific viscosity is in Dimethylformamide at 25 ° C and a concentration of 0.1 g / / 100 ml determined. '

In addition, the polymers mentioned can be copolymerized with a suitable proportion of other acidic or basic monomers. As examples of the above-mentioned monomers are used as basic monomers .2-vinylpyridine, 4-vinylpyridine, ^2-methyl-5-n Vi ylpy ^r i <t: tt and 1-vinylimidazole and as acidic monomers ITatriuinmethasulfophenylmethaerylamid, Hatriumparasulfophenylmethacrylamid, Ή atriumparasulf ophenylmethallyläther , Sodium parasulfophenyl allyl ether, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, vinylbenzenesulfonic acid and salts of these acids.

Although as a rule only one polymer is used as the second component, the advantages of the er ~ can be used without reducing the advantages. According to the invention laser material, two or more polymers can also be used.

According to the present invention, one for the two components common solvent used as a solvent

= 12 -

90 9881 / 14S0

The following are possible: N, IT'-dimethylformamide, Ν, Ν'-dimethylacetaiiiia, N-formylpyrrolidone, IT-acetylpyrrolidone, cL-pyrrolidone, cL-piperidone, ε- aminocaprolactam, N-methylpyrrolidone, dimethylsulfoxydone, succinic acid sulphate, tetramethylsulfate , T'-butyrolactone, propiolactone, hexamethylphosphoramide, N-formylmorpholine, N-acetylmorpholine, propylene carbonate, highly concentrated aqueous solution of nitric acid, aqueous solution of sulfuric acid, aqueous solution of perchloric acid and concentrated aqueous solution of sodium thiocyanate or zinc chloride. Among the solvents listed above, the following are primarily used: IT, IT ¹ -dimethylformamide, Π, IT ¹ -dimethyl ac et amide, dimethyl sulfoxide, aqueous solution of nitric acid with a concentration above 50 % and aqueous solution of IT sodium thiocyanate.

Various methods such as JTaB-

³ * ^Z '■ * ■ - ■■:

Spinning process, dry spinning process, ITass extrusion dry spinning process (dry-jet xfet-methodj see example 3) and Spinning processes in which the materials are in the semi-molten and gel states are used. in case of a Spinning process in which the material is in the gel state, the acrylonitrile copolymers are mixed with a solvent mixture, which consists of an organic solvent and a liquid, which is no or only a bad solvent exists. The mixture obtained in this way is heated to the To dissolve copolymers. Then it is monitored with a monitored temperature " temperature in atmospheric air and while cooling deformed into filaments.

- 13 909881 / 14SQ

In the case of a spinning process using semi-molten materials, a mixture of 40 to 90 ° acrylonitrile copolymers and 10 "to 60 % of an organic solvent is heated and pressed through a spinneret.

Among the spinning processes listed above, the dry

3 2 1 4

Spinning process and the wet-express-dry-spinning process for Preference is given to the objects of the present invention.

The dry spinning process is preferably carried out in such a way that the copolymers of the aforementioned first and second components are dissolved in dimethylformamide in order to obtain a spinning solution with a concentration of the polymer between 15 and 35 percent by weight, the viscosity of which is at a temperature of 50 ° C is in the range from 500 to 2500 P, and that the spinning solution has a temperature between 8O ⁰ C and 170 ⁰ C, preferably between 110 ⁰ C and 140 ⁰ C, is extruded into atmospheric air, the temperature to a value between 8O ⁰ C and 300 ⁰ G, preferably between 150 ⁰ C and 240 ⁰ C is set. The draft ratio is preferably between 0.4 and 50, even better between 0.8 and 20. The filaments produced in this way are 1.5 to 7 times greater, in one or two stages, in a water bath a temperature above 60 ⁰ C stretched. The drawn filaments are then relaxed and dried at the same time or relaxed only after drying so that the fibers shrink by more than 7%,

- 14 909881/1460

The relaxation process becomes simultaneous with the drying process made, then the fibers are fed to the relaxation process in such a state that the water content of the drawn filaments 0.3 "to 10 times dry weight of filaments is. The treatment of the fibers is carried out in the loose state, taking into account the temperature and humidity ratios are chosen so that they are in one area which is defined by A, B, G, D, E and F (see Fig. 7) is. If the temperature and humidity are outside the surface area specified above, then the fibers can dried, but not relaxed; one therefore obtains practically hardly usable fibers. In such a. Fall can the fibers, however, still become practically usable fibers Well-matched properties can be improved if they are subjected to yet another relaxation treatment.

In the case of the fibers to a heat relaxation treatment are subjected to after the drying process, the drying is carried out at a temperature between 1OO ° C and 200 ⁰ C, while the relaxation process carried out in either the wet or in the dry state at a temperature between 80 ⁰ C and 280 ⁰ C. will shrink the fibers by more than 7%.

A relaxation in the wet state is carried out preferably at a temperature between 80 ⁰ C and 160 ° C, during a relaxation in the dry state preferably takes place at a temperature between 120 ° C and 280- ⁰ C. Can be used as a heating medium

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heated air, steam, or a water bath can be used. Will If the fibers are at a temperature above an undesired discoloration occurs.

the fibers treated at a temperature above 280 ⁰ C, then

In the ITass spinning process, the copolymers are preferably dissolved in an organic solvent in order to produce a spinning solution with a concentration of the polymer between 10 and 30 percent by weight and a viscosity between 50 and 2000 P at 50.degree. This spinning solution is then squeezed into a coagulation bath consisting of the solvent, the squeeze-out ratio being selected between 0.3 and 10. The filaments produced in this way are stretched 1.5 to 10 times in a hot water bath. If a nitric acid diluted with water is used as the solvent, the copolymers are dissolved at a concentration of the solvent above 65% and a temperature below 5 ° C., preferably below ⁰ ° C., in order to obtain a spinning solution at which the concentration of the polymer is between 10 and 20 percent by weight. The spinning solution produced in this way is pressed into an aqueous nitric acid with a concentration below 40 percent by weight.

An aqueous sodium thioeyanate solution is used as the solvent for the copolymers, then you take a concentration of the solvent above 4-5%, do a spinning solution with a concentration of the polymer to produce between 8 and 15 percent by weight. This spinning solution is then converted into an aqueous one

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Squeezed sodium thiocyanate solution with a concentration of less than 15 % . After the pressing process, the filaments formed are stretched in a hot water bath.

Example 1 carried out for comparison

A solution of 800 parts of water, 2.00 parts of potassium persulfate and 2.32 parts of sodium bisulfite was kept at a temperature of 50 C held. This solution became a monomeric mixture 90 parts of acrylonitrile and 10 parts of methacrylonitrile dropwise added to achieve a copolymerization of both components. After two and a half hours, the polymer formed was filtered off, washed out with water and then dried *

The conversion was 82%. The specific viscosity of the polymer was 0.161 at C «0.1. The polymer had a powdery constitution of pure white color and contained approximately 12% methacrylonitrile as a structural unit. The polymer was dissolved in dimethylacetamide in order to obtain a spinning solution with a ^{polymer concentration of 2} % by weight. This spinning mass was pressed through a spinneret into an aqueous coagulation bath of 40% dimethyl ac et amide at 65.degree. The extrusion / pull ratio, by which one understands the ratio of the draw-off speed of the filaments to the extrusion speed of the spinning solution, was 0.41 and its maximum value was 0.6. After coagulation, the filaments were in

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a bath of boiling water in a stretching ratio of 5,

Then dried and then subjected to relaxation in a steam atmosphere of 3.5 kg / cm pressure, the fiber shrinkage by 28 % .

The fiber material obtained in this way has a tear strength of 2.0 g / d and an elongation of 23.5 % in the dry state. The characteristic properties of the fibers obtained are, however, well against each matched * niaht the knot breaking strength is namely only 0.4-1 g / d, the F value is 12 and the absorption capacity for basic dyes amounts to only 37 »^% t although the polymer 4 Contains 89 x 10 " ^ equivalents / g of strongly acidic groups.

As mentioned above, show the fibers produced according to the example described thus poor scrub resistance _t poor dyeability and a very low Enotenreißkraft. The fiber cannot be relaxed to a sufficient extent, even if the treatment is carried out in a steaming atmosphere with a pressure of 3.5 kg / cm.

Measurement of the B-value

A Pro "be that äuaech cutting a fiber cable zn 8 cia Iiänge herges% elit wiiiiäe ^ j was cleaned fiiit Deorlen bluing $ G colored

and soaped.

On an abrasion tester, 0.5 g of the sample was applied 2000 times

ο rubbed an ITyion cloth under a load of 100 g / cm and the · abraded fiber particles on the nylon cloth dissolved in dimethylformamide. A corresponding Fiber content of the sample without subjecting it to the scrubbing process, dissolved in dimethylformamide to form a second solution, liach The F-value can be measured by measuring the optical densities of both solutions determine according to the following equation:

F value «- £ p χ V

where 0 »optical density of the last-mentioned solution, G ^f » optical density of the first-mentioned solution, W β denotes the proportion of the non-abraded fiber material of the sample in mg. ■

Although the minimum F-value is envelope, fiber materials are considered With an F-value less than 2 as abrasion-resistant and useful in practice.

The Farbabsörptionsfähigkeit of Fäsermaterials was measured by that the inked Probefäser for two hours in a dye bath containing 5 weight percent Deörleii Blue 3G at a Tempe "temperature of 1ÖÖ ^Ö C"

- 19 109881 / UBi

example 1

85 parts of an acrylonitrile methacrylonitrile copolymer (first component) with 12.5 percent by weight methacrylonitrile were mixed with a copolymer of acrylonitrile vinyl acetate sulfophenyl methacrylic ether (second component) which contained 90.5 percent by weight of acrylonitrile, 9 percent by weight of vinyl acetate and 0.5 percent by weight of sulfophenyl methacrylic ether. The first component contains 4.89 x 10 "^ equivalent / g of strongly acidic groups, and the second component contains 5 69 x lO? '' -. ⁵ equivalent / g of strongly acidic groups The specific viscosity of the first component was 0.162 and the second component 0.17.

3The mixture of the polymers listed above was dissolved in dimethylacetamide to prepare a spinning solution containing 23% polymer concentration to obtain strength, the specific viscosity is 4-75 P at 50 ⁰ C. The spinning solution produced in this way was pressed through a spinneret into an aqueous coagulation bath with 40 % dimethylacetamide at 52 ° C. The filaments thus obtained were placed in a boiling water bath in. Ratio 5 stretched, dried and, in the loose state, subjected to a relaxation treatment in a steam atmosphere of 3 »0 kg / cm in order to achieve a shrinkage of 16.3%.

The fiber material obtained in this way shows in the dry state an Eeißkraft of 2.77 g / <3 - ₅ an elongation of 29%, a knot tear

90988 1 / 1.4 SO. :

force of 2.30 g / d and a Young's modulus, the Vert of which in water at 90 ^° C. is 3.6 g / d. The dye absorption capacity of the fiber material is 98.2 % and its IT value is 0.5. Thus, the fiber material according to the invention has a greatly improved dyeability, an excellent abrasion resistance and a good behavior in hot and wet state at the same time.

Example 2

70 parts of an acrylonitrile methacrylonitrile copolymer with a specific viscosity of 0.162 and a content of 12.5 percent by weight Methacrylonitrile were with 30 parts of an acrylonitrile vinyl acetate sulfophenylmethallyl ether copolymer, Consists of .90.5 percent by weight acrylonitrile, 9 percent by weight vinyl acetate and 0.5 weight percent sulfophenyl methallyl ether mixed.

The mixture of the copolymers mentioned was dissolved in dimethylacetamide to form a spinning solution with a polymer concentration of 23.5 % . The spinning solution was pressed out through a spinneret into an aqueous coagulation bath with 40 % dim ethyl ac et amide at 52 ° C. under an extraction / pull ratio of 0.76. The filaments obtained were in a boiling water bath to 5 times their length (draw ratio

β 5) stretched, dried and in a steam atmosphere of 2.2 kg / cm Pressure in the loose state subjected to relaxation to a

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Achieve a shrinkage of 25%.

The fiber material obtained has a dry tensile strength of 3.0 g / d, a dry elongation of 34 %, a knot tensile strength of 2.4 g / e and a Young's modulus of 3.4-2 g / d in water of 90 G ^0, an F value of 0 and a dye absorption capacity of 98.8 ° / o on. Since the conventional fiber material made from an acrylonitrile polymer has a Young's modulus, the value of which is in the range between 0.5 and 0.65 g / d in water at 90 ⁰ O, it can be concluded that the fiber produced according to the invention has very excellent properties in hot water wet state, which are combined with a high scrub resistance and excellent dyeing ability.

Example 3

The spinning solution was prepared in the same way as described in Example 2 and pressed out through a spinneret which was arranged somewhat above the surface of the eoagulation bath. The filaments formed were then introduced into the coagulation bath, which contained 65 % dimethylacetamide at 33 ° C., the extrusion-pull ratio being 3-4-7. The coagulated filaments were then stretched in boiling water to 5 times their length (stretching ratio> 5), dried and subjected to relaxation in a completely relaxed state.

The process is subjected to a pressure of 2.2 kg / cm in a steam atmosphere.

- 22 9Q988t / Ußö '

In the dry state, the fiber material obtained has a hot strength of 2.97 ε / α-> an elongation of 32.4%, a note tear strength of 2.14 g / d, an IT value of 0, and an absorption capacity of 98 for basic dyes , 9 ° / ° and · a Young's modulus of 3> 3 c / d in water of 90 ⁰ G.

Example 4

85 parts of an acrylonitrile methacrylonitrile copolymer having a specific viscosity of 0.168 and containing 5 percent by weight methacrylonitrile were mixed with 15 parts of an acrylonitrile methyl acrylate sodium vinylbenzenesulfonate copolymer having a specific viscosity of 0.172, the latter containing 90 percent by weight of acrylonitrile, 9> 5 percent by weight of methyl acrylate and 0.5 percent by weight of methyl acrylate. The mixture of the copolymers listed above was dissolved in dimethylformamide to form a 30% spinning solution. The spinning solution prepared in this way was squeezed out through a spinneret into atmospheric air at an extrusion speed of 44.6 emv min. The spinning chamber was maintained at a temperature of 180 ⁰ C, and the spinneret used had 50 holes with a diameter of 0.1 mm. The countercurrent velocity of the gas was 1 m / sec. The withdrawal speed of the filaments was 200 m / min, and the draft ratio was 1.76 The filaments were stretched in boiling water to four times their length (stretch ratio = 4),

- 23 - ■ »09881 / U

dried and in a steam atmosphere of 2.5 kg / cm pressure in loose state subjected to relaxation.

In the dry state, the fiber material obtained has a tensile strength of 2.94 g / d, an elongation of 33%, a knot tensile strength of 2.4-2 g / d, an absorption capacity of basic dyes of 97> 6 % and a Young- module of the value of 3 »6 g / d in water at 9O ⁰ C.

Example 5

70 percent by weight of an acrylonitrile methacrylonitrile copolymer, which was prepared in the same manner as described in Example 2, was mixed with 30 percent by weight of an acrylonitrile / vinyl acetate sulfophenylmethallyl ether copolymer. 27 _} 5 parts of the copolymer mixture were dissolved in 72.5 parts of dimethylformamide to produce a spinning solution. The spinning solution was so stable that no gel formation could be detected after 4-8 hours. The copolymer mixture contains 5 ₅ ° 3 × 10 equivalents / g of strongly acidic groups. The spinning solution was kept at 120 ^° C. and pressed into atmospheric air at 180 ^° C. through a spinneret with 50 openings, each 0.15 mm in diameter. In the present case, the parallel flow speed of the inert gas was 0.8 m / sec and the withdrawal speed of the filaments was 300 m / min. l) the filaments were then washed out ^{with water at 90 ° C. for three minutes,}

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while they remained at their specified length, they were then stretched in boiling water to four times their length (stretching ratio «4). The wet filaments, which contained 0.6 times their dry weight of water, were dried in the loose state in atmospheric air at 140 ° C. and a relative humidity of 25 % . During this treatment, the pores in the fibers disappeared and the fibers were moderately relaxed.

In the dry state, the fiber obtained has a tensile strength of 2.70 g / d, an elongation of 36.4%, a knot tensile strength of 2.60 g / d, an absorption capacity of basic dyes of 72.0%, an F value of 0 and a Toung modulus of 3 »2 g / d in water of 90 ⁰ G,

ßtrickstoffe from the fibers produced in this way show a remarkable, worth improved spatial stability and a reduction in the tendency to pill if you combine them with conventional acrylic fibers compares manufactured products.

Example 6

85 parts of an acrylidtrilmetnacryliiitrilecopolymerB of a specific Viscous ditift of 0.162 and with 20 crew not fisproient meth- ^ Acrylonitrile were mixed with 15 parts of an acrylonitrile methyl acrylate sodium methallyl sulfonate a specific viscosity of

■ '. - 25 -

909881 / UeO

0.145 missing, the latter containing 89.3 percent by weight of acrylonitrile, 10 percent by weight of methyl acrylate and 0.76 percent by weight of sodium methallyl sulfonate. 178 ropes of the copolymer mixture were dissolved in 800 parts of an aqueous solution of nitric acid at -3 ° 0 to produce a spinning solution. The spinning solution was pressed through a spinneret with openings with a diameter of 0.09 mm into an aqueous solution of nitric acid with a concentration of 34 % at -3 ⁰ C with a withdrawal speed of 6 m / min. After the filaments had been washed out with water, they were stretched in a water bath at 98 ⁰ C, dried and in a steam atmosphere of

Subjected to relaxation at 2.5 kg / cm in the loose state.

The fiber material obtained has a Jj 'value ύοώ. 0, an absorption capacity of basic dyes of 98% and a Young's modulus of 2.8 g / d in water of 90 ^° C.

In addition, other fiber materials also became more similar Manufactured as described above, with the only difference that instead of the copolymer mixture, an aeryl nitrile methacrylonitrile copolymer was used. Such a fiber has an F value of 8 and an absorbency of more basic Dyes by 38% · You could therefore use it as an acrylonitrile polymer fiber not be used in trade.

- 26 -909881 / USO

Example 7

10 parts one after the. Prepared in Example 6 given procedure Copolymerization mixture were in 90 parts of a aqueous solution of sodium thiocyanate to produce a Spinning solution dissolved. The solution was converted into an aqueous 10% Fe sodium thiocyanate solution of -2 ° G through a spinneret with 100 Pressed openings of 0.08 mm in diameter each. The received Filaments ^^ are sufficient in hot water washed, stretched in boiling water to 5 times its length (stretching ratio> 5), dried and in a steam atmosphere of 2.5 kg / cm pressure in a relaxed state of relaxation subject.

The fiber material obtained has an F value of 0.5, an absorption capacity of 98.2 % for basic dyes and a Xoung modulus of 2.7 g / d in water of 90 °.

10 claims
7 figures

90 9 881 / 14S0

Claims (10)

193698-6 69/8710 Patent claims / rl! Fiber material made from an acrylonitrile polymer, characterized in that the Paser has a Xoung Mqdul in water at 90 ⁰ C of at least 1.5 g / d, a P value (as defined in the description) of at most 2.0 and a color absorption capacity for two hours of dyeing in a bath containing 5 percent by weight of a dye ^{at 100 °} C. of at least? 0 % . 2. Fiber material according to claim 1, characterized in that it consists of 50 to 95 parts Acrylonitrile methacrylonitrile copolymers with a maximum of 40 percent by weight Methacrylonitrile and from 50 to 5 parts of an acrylonitrile copolymer with 5 to 50 percent by weight acrylonitrile and a decrystallization monomer (definition according to description) consists* 3. Easermaterial according to claim 2 _t characterized in that the AcrylnitrilmethacrylÄ nitrile copolymer has a specific viscosity from 0.15 to 0.18 and the acrylonitrile copolymer has a specific viscosity from 0.10 to 0.25. - 2 -90988 1 / UeO 4 .. A method for producing a fiber material according to one of claims 1 "to 3 _r dadurchgeke η η indicates that 50" to 95 parts of an acrylonitrile methacrylonitrile copolymer with a maximum of 40 percent by weight methacrylonitrile and 50 to 5 parts of an acrylonitrile copolymer with 95 "to 50 percent by weight acrylonitrile and a. decrystallization monomer. (as defined above) are dissolved in a solvent common to both copolymers, the resulting spinning solution for filament formation is pressed through a spinneret into a coagulation medium and the filaments formed are drawn and subjected to an after-treatment ^; 5. The method according to claim 4,. since you rch ge ken ζ n, _t ei ch n-.et in that the two common Oopolymeren Lösungsmittel.N, K'-dimethylformamide or N, N'-dimethyl-.acetamid or dimethyl sulfoxide or i ^ ^ ver -Buthyrolacton IEn- 6. The method according to claim 4j. dad u roh geke η η. «indicates that the copolymers are dissolved in N, N'-dimethylformamide to produce a spinning solution with a polymer content of 15 to 35% and a viscosity between 500" and 25QQ ρ at 5P ° C that , the spinning solution is gehalte.n at a temperature between 80 ° and 0 ... ⁰ 3QO Q is squeezed d.urch a spinneret in atmospheric air, wherein the .Verzugsverhältnis between 0.4 and 5Q is to, 90 98 8 1 / U 6 0-. 3Λ "Form, and that the generated" filaments to filaments to 1.5 to 7 »5 times in water at a temperature above 6O ⁰ C. be stretched. 7. The method according to claim 6, characterized in that the drawn filaments are then ^{dried at a temperature between 10O 0} C and 200 ⁰ C and subjected to a heat treatment in the loose state at a temperature between 8O ⁰ C and 280 ^{0 C,} to shrink them more than 7 %. 8. The method according to claim 4, characterized in that the copolymers are dissolved in an organic! Solvent to produce a spinning solution with a content of polymers between 10 and 30 % and a viscosity between 50 and 2500 P at 50 ⁰ C, that the resulting Spinning solution through, a spinneret into a coagulation bath from the solution mentioned with a draft ratio between 0.3 and 10 is pressed and that the filaments produced in this way are stretched in boiling water on their 1.5 to lOfauhe lungs. 9. The method according to claim 6 or 8, since you r c it | «- k e a η * ei cn η e t that the drawn filament at 0.3 to 10 times their dry weight ~ Speaking water content in loose conditions in atmospheric . Air are treated, "their temperature and their low-temperature. is in a range which is delimited by a line connecting the points A, B, C, D, E and S ¹ in FIG. 7. 10. The method according to claim 8, characterized in that the drawn filaments are dried at a temperature between 80 ° C and 200 ° 0 so that they shrink by more than 7%. ' 809881/1410