DE1469132B - Process for the production of thread from acrylic film copolymers precipitated from 1224506 - Google Patents

Description

The invention relates to a method for producing threads by spinning acrylonitrile copolymers. The threads produced by the process according to the invention are characterized by a high whiteness and excellent discoloration resistance and can be easily mixed with basic Coloring dyes.

Acrylonitrile polymers that have an acrylonitrile content of about 85% or more are usually made from aqueous solutions or dispersions of the monomers prepared by using a persulfate as a catalyst, such as sodium or potassium persulfate, used, which by a sulfoxy reducing agent such as sodium or Potassium metabisulfite, is activated. The amount ratio of activator to catalyst is usually a maximum of 2 parts by weight of activator per part by weight of catalyst. This is how the USA. Patent describes 2,486,241 a process for the production of, among other things, also suitable for spinning into fibers Homopolymers and copolymers of acrylonitrile in aqueous dispersion, in which the peroxy catalyst in amounts of 0.1 to 10 and the sulfoxy activator in amounts of 0.001 to 5 percent by weight, based on the monomers, are added should. In almost all of the exemplary embodiments of the patent, the amount of activator is less than the amount of catalyst; only in one example is the activator used in excess over the catalyst, and the weight ratio in this case is 1.7.

A very similar process is known from US Pat. No. 2,462,354, according to which the amount of catalyst 0.01 to 5 and the amount of activator should be 0.001 to 5 percent by weight of the monomers and according to the examples of these, the amount of catalyst usually exceeds the amount of activator, while in two cases the weight ratio of activator to catalyst is about 2: 1. From these Both patents therefore freely give the teaching, the polymerization or copolymerization of the acrylonitrile should normally be carried out with an excess of catalyst over activator, at most but do not use a higher ratio of activator to catalyst than about 2: 1.

The same ratio of activator to catalyst can also be found in US Pat. No. 2,628,223, the catalyst concentrations from 0.3 to 0.75 percent by weight and activator concentrations from 0.6 recommends up to 1.5 percent by weight and in all of their exemplary embodiments with a weight ratio of sulfoxy activator to peroxy catalyst of exactly 2: 1 works. Also in this patent is mentions that the acrylonitrile polymers produced according to it are suitable for Yprspinning into threads.

U.S. Patents 2,629,712 and 2,743,263 describe processes for preparing acrylonitrile polymers in aqueous dispersion and indicate that these polymers for spinning to be shiny, colorless threads are suitable, which is to be achieved in that the polymerization in the presence an oxygen acid of phosphorus or an organic sulfonic acid is carried out. The applicable Amounts of activator and catalyst are given on a molar basis: The ratio of Activator to catalyst should be in the range from 0.5: 1 to 7: 1. Since in the embodiments of in both patents almost all of them were sodium bisulfite as the activator and ammonium persulfate as the catalyst is used, the above information gives a maximum weight ratio of activator to 3.15: 1 catalyst; in the exemplary embodiments of the two patents, however, none higher activator to catalyst weight ratios than 2: 1 were used.

Now, although these ratios of activator to catalyst are satisfactory with regard to the polymer yield, but the polymers do not have that

ίο Whiteness that you choose for the manufacture of threads might wish, and are not sufficiently resistant to discoloration even when heated.

For the production of threads, the acrylonitrile polymer is in an organic solvent, such as Ν, Ν-dimethylformamide, dissolved. For this purpose, a dispersion of the polymer in the solvent is heated for a while to get a homogeneous solution. This solution is also used when filtering and spinning is kept at an elevated temperature. If now the polymer is not stain resistant is, then one obtains threads, the color of which can be yellowish white to light brown, and so far there is none ' practically feasible method known to make such discolored textiles permanently white. Man occasionally uses a bleaching treatment, but this does not result in a permanent white, Instead, the bleached textile material becomes dark again when exposed to ultraviolet light.

U.S. Patents 2,629,712 and 2,743,263 discussed above refer to the production of acrylonitrile polymers from, which can be spun into colorless threads; however, there is a need for threads to be able to spin acrylonitrile polymers, which have an even higher whiteness and a higher resistance exhibit against exposure to ultraviolet rays.

The invention is based on the object of a process for the production of threads from acrylonitrile polymers to make available that have a particularly high whiteness and high resistance to have ultraviolet rays, do not need to be bleached and contain many active sites the basic dyes can be permanently bound.

The method according to the invention for the production of threads by spinning a solution of acrylonitrile copolymers is characterized in that copolymers of acrylonitrile are used, by copolymerizing at least 85 percent by weight of acrylonitrile together with a or more ethylenically unsaturated sulfonates copolymerizable with acrylonitrile in the presence a redox system in which the weight ratio of sulfoxy activator to peroxy catalyst is at least 10: 1 have been obtained.

Preference is given to using copolymers which, in addition to acrylonitrile units, contain styrene sulfonate units contain. According to a further preferred embodiment of the invention, copolymers are used made of acrylonitrile, styrene sulfonate and methyl acrylate.

A particularly preferred embodiment of the invention is the use of copolymers, the 85 to 99% polymerized acrylonitrile and

6g in addition, per kilogram of polymer, at least 40 milliequivalents of sulfur in the form of ionizable sulfur Contain sulfonic acid or sulfuric acid groups.

3 4

Persulfates, especially potassium or ammonium acid groups, may be present. In the following

persulfate, are the preferred catalysts used Description refers to the expression »milliequi-

Ren. In connection with the persulfates, valente sulfur / kg polymer allows «only on those

Sodium metabisulfite as an activator an excellent sulfur, which is in the form of ionizable sulfonic acid or

Control of the polymerization and the whiteness content 5 sulfuric acid groups is included.

of the polymer. For the ratio of activator to catalyst

Mixed polymers from which white yarns of good quality are made, according to the invention, no upper limit; All-discoloration resistance and good dyeability, however, reduce proportions of more than basic dyes to bright, deep tones about 2000: 1 the yield of polymer too much,
Can be obtained in the following way: The invention by spinning this poly are prepared: The filaments produced are subjected to the interpolymers or copolymers, a mixture of monomeric compounds, yarns and fibers are white products that are at least 85, preferably 90 ° / o acrylonitrile, whiteness when exposed to ultraviolet light and one or more other ethylenically unsaturated remains unchanged. Since the term "white" has a monomer and a sufficient amount of ethy-15 relative meaning and an object in the lenunsaturated sulfonate monomer, preferably generally only is regarded as white when in the form of an alkali salt, in addition not an object of higher whiteness To create comparison sulfonate groups and the total content of the object is perceived, it is advisable to clearly define this bound sulfur in the form of an ionizable expression. To determine sulfonic and sulfuric acid groups to at least 20 of the “fiber color value”, first 40 milliequivalents per kilogram of mixed polymer are produced by placing a sample in them for 30 minutes. The polymerization takes place in attendance dendem deionized water washes containing 0.1 ° / ₀ standardize a persulfate as a catalyst and a reduction pieces of a nonionic surfactant entzierenden Sulfoxyverbindung as an activator, wherein the holding. The samples are then rinsed twice in the deionization ratio of activator to catalyst on over about 25 tem water, squeezed off and spun, kept 6: 1. The amount of catalyst needed to remove any excess liquid. Is used Dargewöhnlich lies in the size on the sample is allowed to at room temperature on the order of 0.05 to 1.0 ° / ₀ of the total dry in the air. About 2 g of the thus obtained dry reaction mass containing monomers. Sample are carded to with a hand roller

So that the mixed polymer produced in this way lies parallel to the fibers, creating a flat structure

can be stained by basic dyes, it may arise from staple fibers of about 7.5 x 15 cm in size,

No less than 40 kilograms and should preferably which is folded lengthwise once. The Re-

between 40 and 90 milliequivalents bound flexion ratio of the samples is

Sulfur (in the form of ionizable sulfones or a green and blue filter in a colorimeter

Sulfuric acid groups) and must be free of 35 of the type »Colormaster Differential Colorimeter

strongly basic groups, such as Quaternary Ammonium Model IV «. The filter sets of this device

compounds, pyridine or amines. The mixed are with the standard reflective panels from the manufacturer

In addition, polymerisat may not be less or calibrated reflective plates from the National Bureau per kilogram

less than 10 milliequivalents of sulfur in the form of ionizing standards. On each side of the samples

containing sulfonic groups, with the sulfur at 4 °, two readings are made. To the second

Central carbon atoms in the polymer measurement are compared to their position in the sample

chain is tied. The ionizable sulfone or first measurement rotated 90 °. From the mean

Sulfuric acid groups are usually in the form of the four readings then being the fiber color values

hydrolyzable salts, but can also be calculated as free using the following formula:

^ ", Reflection ratio green - reflection ratio blue

Fiber color value = x 100.

Reflectance ratio green

Here "reflection ratio green" means that with a very good score and much whiter than the best up to

Polyacrylonitrile fibers are known from the green filter and the "blue reflection ratio". Under "white"

the reflection ratio measured with the blue filter. Fibers within the meaning of the present invention are therefore

To be understood from a number of different "white" samples of fibers with a color value below 6,
combed staple fiber samples are now 55 As mentioned above, bleached acrylonitrile

the color measurements carried out: fibers again after exposure to ultraviolet light

Fiber color value dark. To show this phenomenon, pro

"White" cellulose acetate fibers of the trade 3.5 to 4 ^{ben a} ! F known acrylonitrile copolymers and the

"White" nylon fibers from trade 4 to 6 | ^{whites made in accordance with the} present invention

»White« polyester fibers (Dacron) of the ^{Han- 6o} I? ^se ™ (fiber color value below 6) compared.

.1 4 to 6 fiber color values are determined prior to the action of the

"White"'polyacrylonitrile fibers of trade'. '. 8 to 18 ^UV . ^and ™ f- 20 hours of exposure to UV die

»White« polyacrylonitrile fibers according to the present fadeometer. 32 is made,

gender invention ^averages 1.4 to 6 · ^{A "Pr} ° ^{Be d} ^ ran F, ^{aser" is with}

65 acidified sodium hypochlorite solution

The above values show that bleaching according to the invention, which corresponds to industrial bleaching, is adequate manufactured fibers when compared with others finally treated with sodium bisulphite as antichloro, white synthetic fibers for whiteness then rinsed and dried.

Fiber color value 20 hours from ultra
purple untreated
sample light Unbleached acrylic nitrile staple fiber 9.0 known type 12.6 Bleached polyacrylonitrile Staple fiber better known 11.1 Art 5.7 Unbleached white poly- acrylonitrile staple fiber 4.3 according to the invention ... 5.8

These figures prove that chemically bleached polyacrylonitrile fibers under the action of ultraviolet Light ^ darken, while untreated samples become whiter.

Another test for the final whiteness of the fibers and the discoloration resistance of the polymer under the action of heat is referred to here as "color value (heated)". This test is going on Samples of the polymer carried out and allows to predict the degree of whiteness required for the finished threads, Yarns and fibers can be expected. A comparison of the "color values (heated)" of the polymer with the "color values" of the polymer is also interesting insofar as it determines the color stability of polymer samples shows when heated. Both tests are explained below.

The "color value" is determined as follows: First, a standard solution is created, e.g. For example, a 5.8 ° / _o solution of the polymer in pure dimethylaminfreiem N, N-dimethylformamide forth and the optical density of the solution determined at 400 ηιμ compared with a sample of the pure solvent. A Beckman spectrophotometer, model DU is used for this. The optical density, multiplied by 100, is the "color value" of the polymer. Since the color of the solution of the polymer can increase several times with prolonged heating, e.g. B. from 5 to 25, the "color value (heated)" is also determined. For this purpose, a sample of a 25 ° / _o solution of the polymer in dimethylformamide is heated for 4 hours at 100 ° C. A sample of this solution is then diluted to the standard concentration (5.8%) of polymer and the optical density of the solution is again determined. The "color value (heated)" of the polymer is a useful measure of the actual fiber color values if the temperature and duration of the heating in the test correspond to the temperature and residence time of the polymer in the solution before spinning. A low "color value (heated)" does not indicate a low starting value for the color value of the polymer as much as the greater resistance to maintaining the initial whiteness. It allows a prediction of the final whiteness of the threads, yarns and fibers.

Therefore there is a direct relationship between the "color value (heated)" and the "fiber color value". For example, from a polymer that has a "color value (heated") of about 6, according to the usual With the technique of dry spinning, a fiber can be produced which has a fiber color value of 2. When the color value (heated) of the polymer is 12 or 13, with normal preparation of the solution and Dry spinning the same a fiber color value of about 6 can be achieved. The color values (heated) of the polymer can be used with sufficient accuracy to predict the fiber color values that will occur with normal Treatment and spinning of the polymer can be achieved as illustrated in Example 4.

A valuable statement about the improved dyeability of the fibers with basic dyes is given by

ίο Number of milliequivalents available ionizable Sulfon and sulfuric acid groups per kilogram of polymer; 1 milliequivalent is 0.032 g Sulfur. This value can be determined in a number of ways; preferably work as follows:

Prepare a l ° / _o solution of the polymer in dimethylformamide forth. This solution is passed through an ion exchange column, the acid a dehydrated mixture of strong and contains highly basic ion exchange resins wherein the cation exchanger is present ₀ to 100 ° / in the free acid form and the anion exchanger to be 100% in the basic hydroxyl form. The resin can be dehydrated by washing it with acetone and then displacing it with dimethylformamide. A suitable mixed resin bed consists of Amberlite MB-3 from Röhm & Haas. The flow rate is such that the solution is in contact with the resin for no less than 3 minutes. The solution is then passed through a column containing a strongly acidic sulfonate type resin, e.g. B. the resin IR 120 Rohm & Haas, which is present to 100 ° / ₀ in the free acid form. Here, too, the contact time is no less than 3 minutes. These treatment steps remove all ionizable impurities from the solution and effect a complete conversion of the ionizable acidic sites into the corresponding free acids. Aliquots of the dimethylformamide solution flowing off are taken to determine the polymer content and to determine the polymer acidity present in the solution. The titration of the free polymer acidity is carried out directly in the dimethylformamide. B. 0.005 n-potassium hydroxide titrated and the end point determined either with the help of a color indicator or potentiometrically. The free acids of alkyl sulfates and alkyl and aryl sulfonates are titrated as strong acids in the dimethylformamide solution, while carboxylic acids are titrated as weak acids and, if present, can be determined separately. The results of the acidity determination are expressed as the number of milliequivalents / kg of dry polymer. It has been found that there is a mathematical relationship between the total content of ionizable sulfonate and sulfate end groups in the polymer chain and the intrinsic viscosity if the polymerization conditions are kept constant with the exception that changes in the starting system in order to change the intrinsic viscosity or the Molecular weight can be made. If this relationship is known, the total acidity of a polymer can be used to calculate the proportion which has entered the polymer chain as a result of interpolymerization of the ethylene-unsaturated sulfonate comonomer.

7 8

The colorability by basic dyes is and then centrifuged in order to remove the water, which is usually solid on the surface at widths below 20 milliequivalents of azi,
dity / kg polymer insufficient; sufficient, but for each liquor of 30 or fewer samples, 0.300 g of pure crystal violet as a powder (color index 681), values between 20 and 35 are not sufficient to achieve a strong color shade; 5 1 cm ^{3 of} a 15% strength aqueous solution of acetic acid, but above 40, a good color 1 cm ^{3 of} a 15% strength aqueous solution of sodium exercise with a deep shade can be achieved in an acceptable time. Very high acetate and water except for a total volume of sulfur values, eg 100 or more milliequivalents 1500 cm ³ used. The liquor is in a sulfur / kg polymer can in some cases be useful - stainless steel beakers, which are useful with reflux condenser, but in general values in the io and thermometer are provided with a bun range of 40 to 90 preferred. Senburner heated to boil the liquor vigorously

The dye capacity of the fiber samples is proportional to what the samples are added. After 60 minutes

tional of the number of milliequivalents of sulfur that after utes the samples are removed, thoroughly immersed in water

can be determined using the test described. As a white rinsed from room temperature, spun and at

The further measure of this capacity is the dye on taking 15 70 to 75 ° dried for 2 hours in a steam oven,

of the prepared according to the various examples. A portion of each colored sample of one

Fibers in percent dye at the saturation point weight of about 0.10 g is calculated on an analytical basis

specified; for this purpose, a basic dye, namely a balance, is weighed out and placed in a 100 cm ³ volumetric flask

borrowed crystal violet (color index 681). It's brought in. About 75 cm ^{3 of} pure y-butyro-

It is important that the fibers have sufficient dye capacity for lactone and that the fibers last for 5 to 10 minutes

to be deeply colored. It is heating in a water bath at 70 ° in solution. the

It is also important that the fibers have the ability, volumetric flask is now cooled and by adding

the dyes filled to the mark with pure butyrolactone at a manageable rate. This

so that the dyer does not stain the solution for a long time.

must in order to achieve the desired depth of color. 25 thins (usually about 20: 100) to make an optical

The coloring of fibers from acrylonitrile mixed density in the range from 0.1 to 0.6 to be obtained. These polymeric with basic dyes follows in the first solutions are in a Beckman spectral stage of the staining process (e.g. up to about 90 microphotometer (model DU) at 595 ΐημ without using grooves when boiling) a simple speed one Filters examined. It has been found that color equations (cf. Vickerstaff, "The Physical Chemicals in Butyrolactone up to an Optical Mistry of Dyeing", Interscience Publishers, NY, 1950, density of 1.0 obey Beer's law. P. 129 ). If one also uses the percentage of the dye, which plots 0.005 g loading of the fiber against the square root of the ^{undyed fiber in 25 cm 3 of} butyrolactone decolorizing time, a straight line is obtained. holds.

This makes it possible to obtain a percentage of the dye loading on the fiber for the sample under consideration

to determine a simple "rate constant", determined as follows:

which is expressed by the following relation: _. ,,. /.

Fiber weight (g) x 10

_{K =} dye content of the fiber in% ^L dilution factor -

] / Time (minutes) 4 ° = grams of dissolved fiber / liter of solution.

For the determination of the relative staining speed 2. Optical density (at 595 ΐημ) · 0.00406

Density of the obtained according to the various examples = g / l dye in solution,

The following test is applied to the threads:.

Take a staple fiber sample of approximately 0.12 g. 45 3. gßJ ^ rbstoa ^ VM

The carded sample is placed loosely in a bag of g / l fiber

introduced about 2.5 cm in diameter, which consists of a = percent dye on the fiber,
consists of a single layer of coarse cotton gauze; the ends of this bag are closed by a thread made of tree The invention is closed on the polymerisation of acrylic wool yarn. Control samples are made of an- 50 nitrile with a large number of other ethylene uneaten. Stainless steel tags of a saturated copolymerizable compound weight of about 5 g are attached about 5 cm from the bag bar, such as vinyl acetate, methyl vinyl ketone, acrylic acid, and numbered to identify the sample methyl ester / itaconic acid dimethyl ester → methacrylic acid. These tags also serve to keep the proputyl ester, butyl acrylate and maleic acid diethylben below the surface of the dye liquor. 55 ester, vinyl trimethyl acetate, methacrylonitrile, the tags are tied together for quick removal from styrene, vinyl ethylhexyl ether, octyl methacrylate, <x-Meder dye liquor; up to thylstyrene, 4-methoxystyrene, ethylene sulphonic acid, Al-30 individual samples can be dyed together in the liquor: lylsulphonic acid, methallyl sulphonic acid, halogenated Mowerden. ethylene compounds, N-vinyl compounds, etc.

Before dyeing, the pouches containing the rods can be used for 30 minutes at 70 to 80 ° merizable compounds, if desired, two or more mixed polyp fiber samples. Newly washed in a bath containing 1.0 g / l of a sulfotral monomer alone can be used to make nated lauryl alcohol or the like or a better surfactant as a result of opening up the polymer structure. For washing, to give dyeability, but the rinsing and dyeing are preferred, deionized water is used from those copolymers which have both a conductivity of not more than 1.0 · 10 ~ ^e Sie- a neutral modifier and a strongly mens / cm used. After washing, the acidic group will contain e.g. B. 85 to 95 ° / ₀ acrylic samples with a single change of the water rinsed nitrile, 14 to 4% acrylic acid methyl ester, vinyl acetate,

9 10

Methyl vinyl ketone, etc., and 0.1 to 5 ° / ₀ of a mixing sierbaren sulfonate monomers are many more

polymerizable sulfonates, such as sodium or Ka- compounds, which are preferably in the form of their

lium styrene sulfonate. Alkali or ammonium salts can be used

To be able to produce dyeable copolymers of acrylonitrile. Examples of such monomers are

that are resistant to discoloration, the 5 salts of allyloxyethylsulfonic acid, methallyloxy-

ratio of sulfoxy activator to persulfate catalyst in ethyl sulfonic acid, allyloxypropanol sulfonic acid, allyl

Absence of a complexing agent behaves- thioethylsulphonic acid, allylthiopropanolsulphonic acid,

be moderately high. In the examples this is isopropenylbenzenesulfonic acid, vinylbromobenzene sulfonic acid

Ratio at least about 8: 1 and is often polyic acid, vinylfluorobenzenesulfonic acid, vinylmethylben-

higher, and the highest example is 91: 1. The highest io zolsulfonic acid, vinylethylbenzenesulfonic acid, isoprope

Whiteness and the lowest tendency to discolour nylisopropylbenzenesulfonic acid, vinyloxybenzenesulfone-

without the aid of a complexing agent acid, vinyl dichlorobenzene sulfonic acid, vinyl dioxybene

was at this upper limit of the activator-Kataly- zolsulfonsäure, Vinyltrioxybenzenesulfonsäure, Vinyl-

sator ratio achieved; the "color value (heated)" oxynaphthalene sulfonic acid, isopropenylnaphthalene sulfonic acid

is 6 and the fiber color value is 2.0, which corresponds to whitefonic acid, sulfodichlorovinylnaphthalene, allylbenzene sulfate

content of bleached cotton or even a fonsäure, methallylbenzenesulfonic acid, isopropenyl-

corresponds to an even higher whiteness. However, phenyl-n-butanesulfonic acid, vinylchlorophenylethane sulfonic acid

the ratio of activator to catalyst among fonsäure, vinyloxyphenylmethanesulfonsäure, vinyltri-

under certain conditions significantly below 8: 1 sin- oxyphenylethanesulphonic acid, isopropylethylene sulphonic acid

ken, e.g. B. 6: 1, and still to a 20 acid, acetylethylene sulfonic acid, naphthylethylene sulfonic acid

Polymer and to "fibers within the specified fonsäure, Diphenyloxyäthylenensulfonsäure, Propensul-

Limit. It is of course possible to use a higher fonsäure, Butensulfonäure, Hexensulfonäure, Me-.

Activator-catalyst ratio as 100: 1 to ethylpentensulfonic acid, methylbutensulfonic acid, tri-

turn, e.g. B. 200: 1 or even 2000: 1 and above, isobutylene sulfonic acid, diisobutylene sulfonic acid, etc.

to produce products of excellent whiteness and 25 salts of dibasic acids, e.g. of disulfonic

an extremely high resistance to discoloration acids, can also be used, e.g. B.

to obtain, but then the degree of conversion is low- salts of sulfobutene sulfonic acid, vinylbenzene disul-

rig and the use of such a ratio in fonsäure, vinylsulfophenylmethanesulfonsäure, allyl-

generally not economically viable. idensulfonic acid, etc.

Although the examples relate to the use of 30 In general, together with the polymer

certain persulfate catalysts and bisulfite-activatable sulfonate and acrylonitrile as third

Ren are limited, an ethylene-unsaturated monomer can also be used instead of an ethylene-unsaturated monomer

whose correspondingly acting compounds are used. Suitable monomers of this type are

will. The catalyst can be any water-soluble apart from those mentioned above, including methacrylic acid octyl,

Iiches derivative of persulphuric acid and in grain 35 -methoxyäthyl-, -phenyl-, -cyclohexyl- and -dimethyl-

Bination with a water-soluble oxidizable sulfamidoethyl ester and the corresponding ester of

Oxy compound can be used in which the Wer- Acrylic acid; Acrylamides and methacrylamides or

activity of a sulfur atom does not exceed 4 alkyl substitution products; unsaturated k

progresses, such as sodium bisulfite, sodium metabisulfite, clay, e.g. B. methyl vinyl ketone, phenyl vinyl ketone and

Sulfur dioxide, sodium hydrosulfite and other similar 40 methyl isopropenyl ketone; Vinyl carboxylates, such as

lich water-soluble salts. nyl formate, vinyl acetate, vinyl propionate, vinyl butyrate,

While the dye capacity of the fiber depends on the vinyl thiol acetate, vinyl benzoate, ester of ethylene, the presence of ionizable sulfonate and sulfate group- «, / 3-carboxylic acids, such as maleic acid, fumaric acid, pen, the speed of the dye citraconic acid, mesaconic acid, aconic acid, N-alkyl uptake largely on the amount and the struc- 45 maleimides, N-vinylcarbazole, N-vinylsuccin of the neutral imide, N-vinylphthalimide, vinyl ether, etc. polymerizable comonomer content contained in the copolymer. From the examples given it can be seen that the amount of sulfonate to be mixed-polymerized is generally in the range of the rate constant of dye uptake about 0.1 to 5.0%, which varies widely from its molecular weight, from a maximum of 50% and the number of sulfonate groups contained in it, K-value of 0.360 when the polymer is about 14 ° / ₀ depends. Up to 14% of the third monomer component containing methoxyethyl acrylate (Example 8) to can generally be present up to 14%, but at a minimum of 1.058, if the best results are achieved in the polymer when the acrylonitrile contains about 8% styrene (Example 7). When about the same content is kept above 90% and the third amount of neutral modifying agent is contained in the monomer component in an amount of no more than about 9% in the form of N-tert-butylacrylic acid amide (Example 4).

the rate of dye uptake more than the molded articles of the invention can three times as large as in the case of Example 7. Neutral also from mixtures of the above-described polymerisables Monoethylene-unsaturated compounds and copolymers with other polymers are bonds with regard to their effect on the Ge 60 or copolymers are produced. So can a speed of dye uptake very different - sulfonate-containing copolymer according to Erlich. Examples of polymerizable monomers, the finding with an acrylonitrile homopolymer or with are desirable from this point of view, a two-component polymer (z. B. from 95% Methyl acrylate, methyl methacrylate, acrylonitrile and 5% methyl acrylate) as well as with various methyl vinyl ketone, Methacrylic acid amide, N-tert-butyl-65 with which terpolymers are mixed. The amount of acrylamide, vinyl methoxyethyl ether, acrylic acid meth- copolymers prepared according to the invention in soloxyethyl ester etc. mixtures depends on their content of ionizing

In addition to the polymerizable sulfonate and sulfate groups mentioned in the examples and the composition

composition of the other polymers contained in the mixture. In general, such polymer blends to 5 are made up to 95 ° / ₀ of an inventively prepared copolymers.

The high degree of whiteness of the fibers or films according to the invention enables the application of luminous Colors even in pastel-like tones. The better retention of the original whiteness even when heated to higher temperatures, the acrylonitrile polymer fibers according to the invention make whole excellent for all types of fine textiles, such as shirt fabrics, fine jersey yarns, clothing fabrics and the like, especially for white or pastel-like fabrics Shades colored goods, suitable.

In the examples below, parts are always parts by weight, unless otherwise stated.

example 1

This experiment is carried out in a polymerization vessel equipped for continuous operation with an overflow under conditions such that the average residence time of the reactants in the polymerization vessel is 1 hour. At the beginning of the polymerization is half-filled with water which is acidified with sulfuric acid to a pH of 3.75, and heated to 45 ⁰ C. This temperature is kept constant throughout the course of the experiment. The reactants are added steadily at a constant rate, with enough water and acid to keep the residence time at one hour and the pH at 3.75. The reaction mixture also contains iron in an amount of 0.2 parts per million. The percentage of monomer feed (100 ° / ₀ acrylonitrile) is based on the total weight of the feed. The percentages in the table for catalyst and activator relate to the weight of the monomeric starting material contained in the charge.

It is carried out a continuous polymerization to copolymers of 93.5 ° / ₀ acrylonitrile, 6 ° / o Meth .acrylat and produce 0.5 ° / ₀ potassium styrenesulfonate. In all of these experiments, the temperature is kept constant at 45 ^° C. and the pH value is kept at about 3.5. The amounts of potassium persulfate catalyst and sodium bisulfite activator are varied as indicated in the table below. The "color value (heated)" is improved if the ratio of activator to catalyst is increased.

table

Ver
search Catal
goal
% Acti
vator
% Activator
to Kataly
sator M. »Color value
(heated) «des
Polymers 13th
14th
15th 1.08
0.15
0.075 1.83
5.5
7.0 1.7
37.0
93.0 1.20
1.59
1.47 17.7
7.0
6.0

Example 2

In a vehicle equipped for continuous operation of the polymerization vessel which is partially filled with water of 45 °, which was acidified with sulfuric acid to a fpH value of 3.6, is O, 5 ° / _O strength [aqueous sulfuric acid, 0.4 ° / ₀ strength aqueous potassium per-; , ° / _o aqueous sodium metabisulfite solution, 1, O ⁰ Z introduced sulphate solution 8.0 ₀ IgC aqueous Natriumstyrolsulfonatlösung and a mixture of acrylonitrile and methyl acrylate together with a quantity of water such that the residence time in the reaction vessel is 91 minutes when the uniform operation used has. The water contains so much iron that the ίο iron content in the reaction mixture is about 0.2 parts per million. The composition of the feed is as follows:

Parts by weight of acrylonitrile 2068

Methyl acrylate 132

Potassium persulfate 5.7

Sodium metabisulfite 88.0

Sodium styrene sulfonate .... 5.7

acidified with H ₂ SO ₄ to pH 3.6

Water 7700.6

The reaction mixture is kept at 45 ° under inert gas. The mixed polymer overflowing from the reaction mixture is washed free of catalyst, activator and unreacted monomeric constituents and then dried _{at 108 ° to a moisture content below 1 ° / 0.} There is achieved a 73 ° / ₀ by weight conversion of the monomeric components in the polymer; the inherent viscosity of the polymer is 1.45. The discoloration tendency of the mixed polymer, expressed as "color value (heated)", is 10.1.
A dispersion containing 29% polymer is produced from the dry copolymer and deionized dimethylformamide. This dispersion is kept at 55 ° for 8 to 16 hours and then heated to 80 ° until the polymer has dissolved. The homogeneous solution is then filtered at a temperature between 80 and 95 ° and, with further heating, fed to an evaporation spinning head from which it is pressed through a multi-hole spinning nozzle at about 140 °. The total residence time of the solution at a temperature of 80 ° or above is about 30 minutes and for temperatures above 100 ° no more than about 5 minutes. The thread bundle coming from the dry spinning cell is washed free of solvent with 98 ° hot water and then stretched four times in 98 ° hot water, crimped, cut into lengths of about 5 cm and ^{relaxed dry for 6 1} ₂ minutes at 127 °. The fiber color value is 4.8.

Example3

In a polymerization vessel equipped for continuous operation, which is partly filled with water at 45 °, which has been brought to a pH of 3.6 with sulfuric acid, 0.4 ° aqueous potassium persulfate solution, 0.5 ° aqueous sulfur -So acid, S, O ° l ^ ge aqueous sodium metabisulfite solution, l, O% aqueous sodium styrene sulfonate solution and a mixture of acrylonitrile and methyl acrylate introduced together with such an amount of water that the residence time of the reactants in the polymerization vessel is 91 minutes as soon as the has started working steadily. The water contains so much iron that the iron content of the reaction mixture is about 0.2 parts per million. The co-

The loading composition is as follows:

Parts by weight

Acrylonitrile 2068

Methyl acrylate 132

Potassium persulfate, K ₂ S ₂ O ₈ 5.7

Sodium metabisulfite, Na ₂ S ₂ O ₅ 88

Sodium styrene sulfonate 5.7

water acidified to pH 3.6 with H ₂ SO _{4 7700.6}

An atmosphere of inert gas is maintained in the reaction vessel. The temperature will be on 45 ° held. The mixed polymer overflowing from the reaction vessel becomes the catalyst, the activator and the unreacted monomers washed out. The copolymer is then at 108 ° dried to a moisture content below 1 ° / o. A degree of conversion of Monomers in polymer of 73%; the inherent viscosity of the copolymer is 1.45. The thus obtained Copolymer is based on its content of total bound ionizable sulfonic acid and Sulfuric acid groups investigated. It contains 44.1 million equivalents Sulfur in the form of these groups per kilogram of dry polymer. In the chain contains 13 milliequivalents of sulfur per kilogram. The discoloration tendency of the mixed polymer, expressed as "color value (heated)" is 10.1.

So much dry copolymer is dispersed in deionized dimethylformamide that a dispersion of 29 ° / ₀ polymer is formed, which is kept at 55 ° for 8 to 16 hours. The dispersion is then converted into a homogeneous solution by heating to 80 °. The solution is filtered at a temperature between 80 and 95 ° and, with further heating, conveyed into a dry spinning head, from which it is spun through a multi-hole spinning nozzle at about 140 °. The total residence time of the solution at 80 ° or above is about 30 minutes and at a temperature above 100 ° no more than about 5 minutes. The thread bundle obtained from the dry spinning cell is washed free of solvent with 98 ° hot water and stretched fourfold in 98 ° hot water, crimped, cut into lengths of about 5 cm and relaxed dry for 6/2 minutes at 127 °. The fiber color value is 4.8. The fiber has a dye absorbency equivalent to 1.79% crystal violet and a staining rate constant (K) of 0.087.

Example4

As described in Example 3, the components given below are one for continuous Polymerization equipped reaction vessel supplied. The amount of water used is such that that the residence time of the reactants in the reaction vessel is 60 minutes. It will the following parts by weight of monomers and reagents are added:

Parts by weight

Acrylonitrile 2000

N-tert-butyl acrylic acid amide 200

K ₂ S ₂ O ₈ (catalyst) 5.7

Na ₂ S ₂ O ₅ (activator) 88

Sodium allyl sulfonate 7.0

with H ₂ SO ₄ up to pH 3.6

acidified water 7699.3

A temperature of 45 ° and an atmosphere of inert gas are maintained in the reaction vessel. The resulting polymer is freed from unreacted monomers and salts by washing and then dried. The dry polymer yield is 70% and its inherent viscosity is 1.51. This polymer contains 41.6 milliequivalents of sulfur as ionizable sulfonic acid and sulfuric acid groups. The "color value (heated)" is 11.2. The polymer is, as described in Example 3, spun and processed into crimped staple fibers. The fiber color value is 5.1; the dye capacity is 1.69% crystal violet and the rate constant (K) of staining is 0.191.

Eg game 5

As in the previous examples, a copolymer of acrylonitrile and methyl vinyl ketone is used and sodium methallyl sulfonate. The reactants are used in the following amounts :

Parts by weight

Acrylonitrile 2050

Methyl vinyl ketone 150

Sodium methallyl sulfonate ^! 11

K ₂ S ₂ O ₈ (catalyst) 7.1

Na ₂ S ₂ O ₅ (activator) 88

acidified to pH 3.6 with H ₂ SO ₄

Water 7693.9

The reaction mixture is kept at a temperature of 45 ° in the polymerization vessel; Dwell time: 90 minutes. Yield of washed, dried copolymer: 74%; Intrinsic viscosity: 1.4. This copolymer as well as those produced from this copolymer as described earlier Fibers have the following key figures:

Parts by weight

Sulfur 55 milliequivalents / kg

Color value (heated) 11.9

Dye capacity 2.24% crystal violet

Rate constant
(K) [of the staining process] 0.134

Fiber color value 5.8

Example 6

As described in the previous examples, a copolymer of acrylonitrile and vinyl acetate is used and ammonium vinyl sulfonate. The following respondents are used:

Parts by weight

Acrylonitrile 2090

Vinyl acetate 110

Vinyl sulfonic acid (ammonium salt) .. 12.4

K ₂ S ₂ O ₈ (catalyst) 4.8

Na ₂ S ₂ O ₅ (activator) 88

acidified to pH 3.4 with H ₂ SO ₄

Water 7694.8

Polymerization temperature: 48 °; Dwell time: 90 minutes. Intrinsic viscosity of the copolymer: 1.7; Degree of conversion: 70%. The key figures of the

60

65

The fibers spun from this copolymer are as follows:

Sulfur 45.8 milliequi-

valente / kg

Color value (heated) 10.7

Dye Capacity 1.86% Crystal Violet Rate Constant (K)

of staining 0.061

Fiber color value 4.7

Example 7

As described in the earlier examples, a copolymer of acrylonitrile, styrene and sodium styrene sulfonate is used manufactured. The feed consists of the following reaction participants:

Parts by weight

Acrylonitrile 2024

Styrene TT-. 176

Sodium styrene sulfonate 5.1

K ₂ S ₂ O ₈ (catalyst) 5.7

Na ₂ S ₂ O ₅ (activator) 88

water 7701.2 acidified with H ₂ SO _{4 to pH 3.6}

Polymerization temperature: 45 °; Dwell time: 90 minutes. Yield of copolymer: 70%; Intrinsic viscosity: 1.5. The copolymer contains 55 milliequivalents of sulfur and has a color value (heated) of 12.1. The fiber spun therefrom has a dye capacity of 2.24% crystal violet, a dyeing rate constant (K) of 0.058, and a fiber color value of 5.8.

Example 8

The composition of the feed stream, the polymerization conditions and the properties of the spun thread are the following:

Acrylonitrile 2805 parts by weight

Acrylic acid methyl ester 178.8 parts by weight

Potassium styrene sulfonate 16.2 parts by weight

Potassium persulfate 2.3 parts by weight

Sodium metabisulfite 210 parts by weight

with H ₂ SO ₄ to pH 3.5

acidified water 6787.7 parts by weight

Temperature 45 ° C

Degree of conversion 40%

Intrinsic viscosity 1.47

Sulfur 70.9 milliequi-

valente / kg

Color value (heated) 6

Fiber color value 2.0

Dye capacity 2.89% crystal

purple rate constant

(K) of staining 0.111

B e i s ρ i e 1 10

As described in the previous examples, a copolymer of acrylonitrile and Sodium Styrene Sulphonate made using the following feed:

3 °

35

As in the previous examples, a copolymer of acrylonitrile with methoxyethyl acrylate is used and sodium styrene sulfonate; Composition of the feed stream:

Parts by weight

Acrylonitrile 1700

Acrylic acid methoxyethyl ester 280

Sodium styrene sulfonate 20

Potassium persulfate 4.4

Sodium Metabilsulfite 80

acidified with H ₂ SO ₄ to pH 3.5

Water 7915.6

50

Residence time in the polymerization vessel: 45 minutes at 46 °. Degree of conversion: 57%; Inherent viscosity of the copolymer: 1.63. The other key figures are the following:

Sulfur 98 milliequi-

valente / kg

Color value (heated) 11.9

Fiber color value 5.7

Dye capacity 3.99% crystal violet

Staining rate constant (K) 0.360

Example 9

As described in Example 3, a copolymer of acrylonitrile becomes methyl acrylate and potassium styrene sulfonate made a fiber.

Parts by weight

Acrylonitrile 2178.0

Sodium styrene sulfonate 24.6

K ₂ S ₂ O ₈ (catalyst) 5.5

Na ₂ S ₂ O ₅ (activator) 88.0

acidified to pH 3.6 with H ₂ SO ₄

Water 7702.9

The polymerization is carried out at 48 ° and gives a degree of conversion of -62%. The inherent viscosity of the polymer is 1.5. The total sulfur content in the form of ionizable sulfonic acid and sulfuric acid groups is 100 milliequivalents / kg polymer, with 70 milliequivalents sulfur / kg polymer being contained in the chain. The color value (heated) of the polymer is 11. Fibers made from this copolymer by the method of Example 5 are characterized by a dye capacity corresponding to 4.06% crystal violet, a dyeing rate constant (K) of 0.076 and a fiber color value of 4.9.

Claims (4)

Patent claims: 1. Process for the production of threads by spinning a solution of acrylonitrile copolymers, characterized in that one copolymers of acrylonitrile used, composed by copolymerization of at least 85 percent by weight of acrylonitrile with one or more ethylenically unsaturated ones which are copolymerizable with acrylonitrile Sulfonates in the presence of a redox system in which the weight ratio of sulfoxy activator to peroxy catalyst is at least 10: 1, have been obtained. 2. The method according to claim 1, characterized 109 536/342 draws that copolymers are used which, in addition to acrylonitrile units, styrene sulfonate units contain. 3. The method according to claim 1 or 2, characterized in that copolymers from Acrylonitrile, styrene sulfonate and methyl acrylate are used. 4. The method according to claim 1, characterized in that copolymers are used, the 85 to 99% polymerized acrylonitrile and also at least per kilogram of polymer 40 milliequivalents of sulfur in the form of ionizable sulfonic acid or sulfuric acid groups contain.