DE1292309B - Process for the aftertreatment of wet-spun threads made of acrylonitrile polymers - Google Patents

Description

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In the production of Acrylonitrilpolymerisat- temperatures are required and solutions help after the wet spinning process, acrylics will be that are too viscous to be easy to use as a vernitrile polymer solution through a spinneret into one. According to the German Spun coagulating bath in which the solvent Auslegeschrift 1 069 818 is therefore a process for extracted from the solution and the polymer in 5 making deformable solutions from acrylic mold to be precipitated by threads. The Koagulier- nitrilpolymerisaten provided in which at one bath consisting of an aqueous, monomeric or poly- temperature between 10 and 45 ° C polyacrylonitrile can consist of more glycol-containing solution, or copolymers of at least 85% acrylic can be kept so that there is a desired nitrile and up to 15% of a vinyl compound in one Contains amount of solvent. The coagulated io aqueous saline solution is dissolved, taking this Threads are drawn from the coagulating bath and solution, based on the total weight of salts and stretched. The threads are generally based on a water in it, at least 30%, however Subject to washing process by z. B. less than required to dissolve the polymer Passes a water bath or sprinkles it with water. borrowed amount of zinc chloride and 5 to 25% calcium purpose this washing, which has coagulated filaments 15 or magnesium chloride or nitrate and which of residual solvent as much as possible to total concentration of the salts in this aqueous to free. In addition, the filaments are usually solution at least 55 percent by weight. at provided with equipment and e.g. B. with one of these methods, the zinc chloride is a solvent Finishing mass impregnated to make them antistatic, while the calcium and magnesium chloride to impart lubricating or soft properties, or form nitrate nonsolvents.

to their processing in the following work- In the German Auslegeschrift 1 069 818 is

were included like spinning, twisting, winding, slips of paper, and finally a procedure reported To facilitate carding, stretching or weaving. what acrylonitrile and its mixtures with others

It is known that textile materials, the threads in aqueous zinc chloride, bromide or monomers or fibers made of acrylonitrile polymers contain 25 iodide to be polymerized. It will be there in comparison to threads or fibers from other found that those from such polymers geMaterialien have the disadvantage that they have inferior properties due to spun products common dyeing processes are not satisfactory.

can be colored. Many aids were found in the German Auslegeschrift 1 069 818

suggested to the color penetration and on- 30 known method will not solve the problem of Right maintenance of the coloring in acrylonitrile polymer - increasing the dyeability of threads or fibers to promote threads or fibers. addressed from acrylonitrile polymers.

A disadvantage of using threads or threads. The object of the invention is to provide one

Fibers made in solvents such as Ν, Ν-dimethyl process for post-treatment of threads or Acetamide-dissolved acrylonitrile polymers wet 35 fibers made from acrylonitrile polymers to be spun into are, it consists in the fact that they are more dyeable and less expensive to the touch, more often and more cheaply have a corrosive effect on metal. This creates a corrosive effect on what is considerable in textile processing Difficulties and increased costs of making metal used equipment, during the handling of the threads or fibers The method according to the invention for after-

when spinning, twisting or carding. 40 handling of wet-spun threads made of acrylic

Various means have been proposed to make nitrile polymers characterized in that the properties of threads or fibers made of acrylic- you can use the freshly spun threads with a To influence nitrile polymers and give them z. B. Impregnated mixture of zinc oxide and water does not impart corrosive properties, however, and the water by drying the impregnated These remedies were not very effective as their threads were removed.

use various disadvantages, e.g. B. one after- It can be proceeded in such a way that one

Partial influence on the color or the handle of the zinc oxide mixes with water and the acrylonitrile threads, brought with it. polymer threads immersed in it or through the

From the German Auslegeschrift 1 013 831 it is obtained during a sufficient mixture also known to lead solutions of polymers on the 50 period so that they are jmprä-based with the mixture be gnosed by polyacrylonitrile in a solvent. Then the water becomes tin evaporated in the form of one or more tin (II) salts, the threads being dry and with zinc oxide to be absorbed, leaving behind after conventional spinning or impregnation. It was found that Pour objects such as threads, fibers, horsehair onto the threads treated in this way or with a higher level of dye Films are obtained which would take in terms of the 55 or dyeing speed at basic Coloring should be significantly improved. The be dyes have. When comparing colorations showed Known tin-containing products should also include those treated with zinc oxide no longer show yellowing. Threads also take up or

The problem of better dyeability and dyeing speeds with disperse dyes Prevention of corrosion is included in the known 60.

Working method not resolved. It has also been found that the invention

In the German Auslegeschrift 1069 818, proper treatment leads to threads that do not Among other things, it is described that aqueous solutions have a corrosive effect on metal and metal alloys Salts, such as the chlorides in particular, possess bro- genes with which they can be used during processing, Iodides, thiocyanates and nitrates of sodium, 65 tung z. B. come into contact with tissues Lithium, aluminum, calcium, zinc and cad can.

medium for dissolving acrylonitrile polymers. Under the name »Acrylonitrilpolymerisate«

are useful, but sometimes too high are polyacrylonitrile, copolymers and terpolymer

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Merisate of acrylonitrile and mixtures of poly- holds, conduct and then for the first time the impräacrylnitril and copolymers of acrylonitrile-gnosed filaments with the application of heat with other polymerizable monoolefinic fibers. The threads are through the finishing materials, as well as with mixtures of poly-bad performed in such a way that the on the acrylonitrile and such copolymers with 5 threads through the liquid applied first If amounts of other polymeric materials, deposited zinc oxide constituents do not wrestle completely. B, polystyrene, where e.g. B. Vinyl is washed.

acetate, vinylpyridine or alkyl-substituted vinyl- The threads that contain zinc oxide become pyridine suitable ,, with acrylonitrile mischpolymerisier- dries, preferably using bare monomers are, «heat. For example, the threads can be dried In the method of the invention, the will be done by subjecting them to a number of dry treatments the acrylonitrile polymer threads with kenwalzen or cylinders, zinc oxide after the wet spinning of the threads and in the impregnation of the threads is preferred Course of the aftertreatment of the freshly spun during the aftertreatment on the endless thread Threads, however, carried out before the beginning of the drying of the 15, however, this is for the. Process ge threads carried out. It is. care should be taken that the extent of the invention is not essential. For example The threads can also be dried in the presence of the zinc oxide after they have been stretched will. den, cut into staple fibers and in this form

From a solution of the acrylonitrile polymer. to be post-treated. The fiber fleece is used for this a suitable solvent, e.g. B. Ν, Ν-dimethyl ao continuously given on a flat conveyor belt

formamide, Ν, Ν-dimethylacetamide, / -butyrolactone, which the fibers are washed by spraying

Be able to use ethylene carbonate or an aqueous solution. Then the nonwoven fabric is placed under a

certain inorganic salts, by wet spinning a liquid finish mass with a shower

The threads obtained can be carried out in the coagulating bath with zinc oxide content. After that, the and / or dried after their removal from the coagulating fibers, e.g. B. in a common

bath can be stretched to a desired orien- radiation dryer.

to obtain a rating. The threads are washed, in general the application of the zinc

to free them from residual solvent, oxyds take place when the threads through a liquid

the washing operation being conducted in the various baths at atmospheric pressure, above 3a, other pressures can be used,

can. Before the threads are dried, room temperature is sufficient, however can

through a liquid bath that adds a finishing compound to either higher or lower temperatures.

contains, directed. As it is generally necessary to be applied.

is a finish on wet-spun. Acrylonitrile zinc oxide is applied to the acrylonitrile polymer threads polymer threads during the aftertreatment for 35 in an amount of at least 0.01 and up to

one or more purposes, e.g. slipping 0.40 ° / »and above, preferably in the range of.

of threads or reduction in development from 0.025 to 0.20 "Zo based on the weight of the

static electricity, is the zinc polymer, in the form of zinc oxide or other

oxide is preferably added to the finishing compound. Any zinc compounds applied, whereby it is desirable

Common thread finishing compound is applicable, 40 is worth, only the minimum amount of zinc oxide, which is necessary

and the selection of a special finishing compound is agile to achieve the desired effect,

not required to use the invention in a more suitable manner as excessive additions of zinc oxide

Way to carry out practical, there are only additional expenses.

When zinc oxide is incorporated into a finishing compound The concentration of zinc oxide in the

it preferably consists of an aqueous impregnation bath which can be varied considerably. the

Emulsion. The solids content of the finishing compound concentration depends, among other things, on the specific

In addition to zinc oxide, there is preferably an additional application process, the proportion of through

composition of about 20 to 50 percent by weight the threads absorbed liquid and given

a nonionic surface-active ester, from the composition of the finish,

15 to 35 ¹⁰ Za of a nonionic surface-active 50 baths with a content of 0.02 to 0.8% zinc

Polyethers, from 10 to 40% of a cationic oxide result in an incorporation of 0.01 to. 0.40%

surface-active quaternary ammonium compound zinc oxide, based on the weight of the dry

dung and from 5 to 25% of a substituted thread.

Carbamyl derivatives. The here preferred finish. After completion of the impregnation, the

mass is in US Pat. No. 2,735,790 55 excess liquid z. B. by pressing

wrote. removed, whereupon the fiber material is

However, it is not necessary that the zinc oxide be dried. Drying can be done by heating

To incorporate finishing mass. The same increased amount of zinc oxide-containing material, for example

dyeability and non-corrosive properties can allow a temperature of 185 to 245 ° C during a

can be obtained when the threads have passed through an after-60 time sufficient to dry the threads,

treatment bath, which only contains the zinc oxide, can be achieved.

until the threads are impregnated with zinc oxide. 1 shows schematically an apparatus used for

are committed. You can z. B. the threads first continuously carrying out an embodiment of the method

nuierlich by an aqueous bath, which zinc oxide rens can be used according to the invention,

contains, preferably 0.02 to 0.8%, and an- 65 With 10 is a cable made of stretched acrylonitrile

finally through a finishing bath, which denotes a polymer thread. This cable out

A small amount of zinc oxide, preferably 0.02 to 0.8%, is fed through a thread by means of guide rollers 11

based on the weight of the equipment bath, ent- container 12, which has a bath 13 with a

Contains zinc oxide suspension. After it has passed through the zinc oxide-containing bath over a sufficient distance the tow is removed therefrom and passed over a plurality of heated drying rollers 14 headed. After it has dried, the cable can be used for 10 further operations, such as Krausem, Cutting and bale packing can be subjected, or the cord can be collected in continuous form will. Additional bath liquid is added to container 12 through line 15 if necessary fed.

Fig. 2 is a graph comparing dye absorption when impregnated with zinc oxide Fibers and the same fibers that were not impregnated with zinc oxide shows. Is on the abscissa the boiling time in minutes and the ordinate is the dye absorbed by the fibers applied in percent. The dye used in this comparison was 8% blue dye C. I. Basic Blue 22 and 0.5% wetting agent. The diagram shows that the zinc oxide-containing Fibers show a higher absorption of dye.

In the examples below, parts and percentages are by weight.

example 1

(a) A copolymer was used to produce the threads to be post-treated according to the invention from 94% acrylonitrile and 6% vinyl acetate in a solvent made from 98% N, N-dimethylacetamide and 2% acetic acid dissolved and the polymer solution spun through a spinneret, which is poured into an aqueous, submerged a coagulating bath containing approximately 55% solvent and 45% water. The received Rope of thread, which had a total denier of 360,000, was passed through a hot water bath which moved in countercurrent to the cable, while at the same time an orientation stretch of about 525% was given.

(b) For the aftertreatment according to the invention, the cable was then continuously passed through a Bath containing a finishing compound and zinc oxide. The bath consisted of an aqueous emulsion with a content of 2.2% non-aqueous finishing compound and 0.25% zinc oxide. The finishing mass consisted of sorbitan monopalmitate, with about 200 moles of ethylene oxide condensed castor oil and a quaternary antistatic agent. The cable was then increased by a number of Drying rollers, which were heated from the inside with steam at an overpressure of 2.81 atmospheres, out. It the dried filaments were found to contain 0.27% zinc compounds calculated as zinc. The tow was crimped and cut into staple fibers. The fibers were made on a customary Carding machine. The fibers did not develop any corrosive effects on the metal this machine, even after prolonged contact with it.

(c) Comparison: threads were produced and aftertreated analogously to the manner described above. However, in this case the emulsion sizing bath did not contain zinc oxide. During carding Corrosion of the fibers due to contact of the fibers with the carding machine was observed.

Example 2

A tow of 480,000 from wet-spun filaments of the type described in Example 1, which had been stretched, was passed through a bath made of water and 0.13% zinc oxide, as zinc calculated, composed. The threads were then sprayed with water and passed through a Finishing bath, which contains 2.2% of the non-aqueous components described in Example 1 and 0.03% Zinc oxide calculated as zinc. The cable was dried by turning it around a number of Drying rolls was passed. The dried filaments contained 0.15% zinc compounds, as zinc calculated. The tow was crimped and cut into staple fibers. The fibers acted on one Common carding machine non-corrosive

Technical progress

The threads obtained according to Example 1, (a) and aftertreated according to Example 1, (b) were spun into yarn and this yarn was woven into a ribbon. For comparison, a section of yarn which had been produced from the fibers obtained according to Comparative Example 1, (c) was also worked into the woven tape.

A series of dyeing tests were carried out with this woven tape.

A dye tape was made containing 8.0% C.I. Basic Blue 22 blue dye, 5.0% ammonium acetate and 0.5% wetting agent in 40 volumes of water, with all percentages are based on the weight of the fabric to be dyed. The sample to be colored was placed in the Dyebath introduced, and the temperature of the dyebath was slowly increased to boiling and held there for the periods of time given in Table I below. The percentage of absorbed dye and the percentage of bath depletion were determined for each colored tape certainly. The following results were obtained:

Table I.
Fibers treated with zinc oxide

Time % absorbed exhaustion at boiling point dye 0 25.8 10 2.1 40.2 20th 3.2 51.0 30th 4.1 58.8 40 4.7 65.5 50 5.2 71.7 60 5.7 76.8; 70 6.1 81.1 80 6.5 84.6 90 6.8 87.5 100 7.0

Control fibers (without zinc oxide)

Time ° / o more absorbed "/O at boiling point dye exhaustion 0 10 1.5 18.4 20th 2.2 27.0 30th 2.6 33.0 40 3.0 37.9 50 3.3 41.8 60 3.5 43.7 70 3.7 46.1 80 3.9 48.8 90 4.0 50.6 100 4.3 53.3

The above values show that acrylonitrile polymer fibers impregnated with zinc oxide faster dyeing or higher dyeing speed with basic dyes compared to as similar fibers that do not contain zinc oxide. About the relationship of the relative colorations To determine dyeing rates, respectively, the percentage of dye absorbed versus the Plotted the square root of time. From the slopes of the points connecting the plotted points Lines were calculated that the zinc oxide-containing fibers took up about 60% higher dye or dyeing speed than the fibers that are not impregnated with zinc oxide.

A number of comparative dyeings were made (both sample and control in the same dye bath colored) carried out for 90 minutes at the boiling point. Again all stains were carried out in a 40: 1 bath, with the percentages are based on the weight of the fabric. Belts with a standard construction, which were woven from spun yarn of the fibers according to Example 1, (a) and (b) or (c), used. The sample [Examples 1, (a) and (b)] and the control [Example 1, (c)] were visually tested Color depth classified using the international gray scale. The stains were with the following dyes carried out:

1. Selected basic dyes at 4.0% depth and dyes of the black type (see table II).

Dyes with

5% ammonium acetate,
0.5% wetting agent.

2. Two selected disperse dyes at 4% depth and navy blue type dyes (see Table II). Colorants with 0.5% wetting agent.

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Color depth values of the bands for these dyes are given in Table II below, in which is given a value of 5 for the deepest colored threads. The threads were given comparative values of 4 for slightly brighter, 3 for noticeably brighter, 2 for considerably brighter and 1 for much brighter given.

Table II

° / o dye

10 color depth
Sample control

Basic dyes

4.0% CI Basic Red 14 5 2 to 3

4.0% CI Basic Blue 21 5 2

Black type dyes
0.58% CI Basic Green 4

(CI 4200) 5 2 to 3

0.60% CI Basic Red 26 c
1.80% CI Basic Orange 21

(CI 48035)

Disperse dyes
4.0% CI Disperse Blue 3

(CI 61505) 5 4

4.0% CI Disperse Yellow 37 5 4

Navy blue type dyes
4.0% disperse dye
(Mixture)

It follows that the threads impregnated with zinc oxide are considerably deeper with basic ones Dyes and can be dyed deeper with disperse dyes than threads that do not contain zinc oxide, which indicates a higher dye uptake or dyeing speed.

It can thus be seen that the use of zinc oxide has several advantages. Containing zinc oxide Acrylonitrile polymer threads are practically non-corrosive to metal and can can therefore be handled on textile processing equipment without having to rely on this equipment Give cause for damage due to corrosion. In addition, those treated with zinc oxide show Threads have a higher dyeing speed with basic dyes than those not treated with zinc oxide Threads. Zinc oxide-containing threads are colored a little deeper with disperse dyes, which is a higher color Indicates staining or staining speed. Another advantage is that zinc oxide is a is a common chemical that is readily available in technical quantities at moderate prices. Zinc oxide can easily be incorporated into the finishing bath, which is used for the aftertreatment of wet-spun Acrylic thread is used. In addition, the quantities of zinc oxide used influence the stability of the common finishing solutions, to which they can be incorporated directly if desired, not disadvantageous. In addition, there are no operational hazards when using zinc oxide, and no major changes to the facility are required. The light stability of the with Zinc oxide treated threads and fibers are not reduced, but increased.

Claims (3)

Patent claims: 1. Process for the aftertreatment of wet-spun threads made of acrylonitrile polymers, characterized in that the freshly spun threads with a mixture 909515/1621 impregnated from zinc oxide and water and that Water removed by drying the impregnated threads. 2. The method according to claim 1, characterized in that an impregnation bath is used, containing 0.02 to 0.8% zinc oxide. 3. The method according to claim 1, characterized in that the threads are continuously by an aqueous bath containing 10 0.02 to 0.8% zinc oxide and then through a finishing bath consisting of a mixture of zinc oxide and an aqueous emulsion of a textile finishing agent, the zinc oxide in the mixture in an amount of 0.02 to 0.8%, based on weight of the finishing bath , and then drying the impregnated threads for the first time with the application of heat 1 sheet of drawings