DE2524125A1 - Acrylonitrile vinylchloride copolymer yarns with improved dyeability - by incorporating copolymer contg chlorine and sulphur oxyacid gps - Google Patents

Abstract

Dry spun modacrylic yarns with improved dyeing characteristics and adequate dimensional stability under dyeing conditions, comprise an acrylonitrile-vinyl chloride copolymer and a copolymer contg. Cl and sulphonic acid groups of sulphuric acid ester groups. The yarns can be uniformly dyed in deep shades with the usual basic dyes. Shades such as maine blue are obtd. within reasonable dyeing periods with recourse to ecologically critical auxiliaries and are fast to light.

Description

It is modaciyl threads with improved coloristic properties got the coloristic properties of synthetic fibers through the incorporation of color-affine Improve groups.

For this purpose, e.g. the fiber raw material is modified through use special starter systems or through the incorporation of comonomers with color affinity Groups or one used as fiber raw material polymer mixtures in which one Component that contains color-affine groups in increased concentrations. After Japanese Patent 35-22478 / 1960 can be achieved, for example, by using a Redox system based on ammonium persulfate, dihydroxymaleic acid and iron (II) sulfate, that formed during the copolymerization as end groups -SO3- or -O-SO3- groups will.

Such end groups give the fiber raw material a specific fish Affinity to basic dyes. It is disadvantageous for this procedure that there are only relatively small amounts of color-affine groups in the fiber raw material can incorporate and a dyeability with basic dyes in deep shades not possible. In addition, cause slight fluctuations in the manufacturing conditions of the fiber raw material, i.e. e.g. at. the polymerization, big changes in the Molecular weight distribution and thus due to the changed number of end groups also great changes in dyeing behavior.

Furthermore, it is known from Canadian patent specification 704 778, according to the procedure of a polymerization in an aqueous emulsion of acrylonitrile, Vinyl chloride and compounds such as N-acryloyldimethyltaurine, such starting polymers for modacrylic fibers and modacrylic threads to produce the improved coloristic Have properties. Disadvantageous for the procedure of the Canadian patent specification 704 778 is that the conversion in the copolymerization is only up to 50% of the used comonomers can lead. The easily soluble in water, non-volatile Comonomers containing sulfonic acid groups can after the copolymerization in In contrast to the highly volatile and only slightly or only sparingly soluble in water Comonomers vinyl chloride or acrylonitrile only in a very complex procedure be recovered from the reaction medium. The rate of incorporation of the comonomers, such as Acryloyldimethyltaurine and methacryloyltaurine are under the reaction conditions Canadian Patent 704 778, especially because of the low conversion in the copolymerization, depending on the conversion, and a fiber raw material with constant coloristic characteristic data is only possible with the application of a complex steering and control to produce the reaction procedure.

It is also known from US Pat. No. 3,113,122, the affinity of colors to improve acrylic or modacrylic threads by adding copolymers. To This procedure mixes the actual fiber raw material, which is at least Contains 35% copolymerized acrylonitrile, with up to 20% of a copolymer from 60 - 95% 2-cyanoethyl (meth) acrylate and 5 - 40, a C1 to C12 alkyl acrylate or C1 to C12 alkyl methacrylates. Disadvantageous for that after this procedure obtained fiber material is that just the pulling speed of dyes is generally increased by an additive, which under the dyeing conditions acts as a plasticizer and thus loosens the structure of the fibers. An increase the dye saturation is not achieved by such a measure, i.

you can achieve the maximum depth of color relatively quickly, but do not increase the maximum amount of dye that can be absorbed by the addition, because As is well known, the maximum absorbable amount of basic or of acidic dyes due to the total number of acceptor groups present set. For basic dyes then determine the concentrations of acidic ones Groups in the fiber raw material the maximum dye absorption. By acting as a plasticizer Additions to the fiber raw material are also used, especially in the case of modacrylic threads and fibers causes the dimensional stability of the resulting thread and fibers, in particular is greatly reduced under the conditions of the dyeing process. Good dimensional stability but under dyeing conditions is absolutely necessary for many purposes.

It has now been found that modacrylic threads with improved coloristic Properties and sufficient dimensional stability from acrylonitrile / vinyl chloride copolymers can be obtained when polymer mixtures of at least one acrylonitrile / vinyl chloride copolymer and a chlorine-containing copolymer containing sulfonic acid groups or sulfuric acid ester groups contains, spun.

The invention therefore relates to dry-spun modacrylic threads with improved coloring properties and under Coloring condition more sufficient Dimensional stability from polymer mixtures which are characterized in that they consist of at least one acrylonitrile-vinyl chloride copolymer and one chlorine and copolymers containing sulfonic acid or sulfuric acid ester groups.

The invention also relates to a method of production of modacrylic threads with improved coloristic properties and under dyeing conditions Sufficient dimensional stability from polymer mixtures using a dry spinning process, which is characterized in that polymer mixtures of at least one acrylonitrile / Vinyl chloride copolymer and a chlorine and sulfonic acid groups or sulfuric acid ester groups containing copolymer spun.

At least one component of these blends is made from a copolymer Acrylonitrile and vinyl chloride with 30 to 70% by weight, preferably 40 to 65% by weight vinyl chloride. Particularly useful products contain 55 to 65 percent by weight vinyl chloride. Next to the Acrylonitrile / vinyl chloride copolymer contains the polymer mixture from which the invention Modacrylic threads are obtained, as a component a linear, chlorine-containing copolymer, the sulfonic acid or sulfuric acid half-ester groups, which either via the Incorporation of a corresponding comonomer bound to the polymer chain via major valences, or which were introduced into a suitable polymer by a polymer-analogous reaction.

Copolymers containing chlorine and sulfonic or sulfuric ester groups contain and with those within the meaning of the invention a useful technical effect is achieved you e.g. if you follow the procedure a solution polymerization at temperatures of 35 to 850 C, the reaction in solvents, such as dimethylformamide, dimethylacetamide or dimethyl sulfoxide. The copolymerization is carried out so that the comonomers used in a concentration of 20 - 40% using radical formers, such as azodiisobutyronitrile, or peroxides, such as benzoyl peroxide, polymerized. Starter systems have proven particularly effective In this solution polymerization, redox systems based on persulfate and oxalic acid or based on persulfate and tetravalent compounds of sulfur. Likewise can Redox systems are used as starter systems that use hydroperoxides as oxidizing agents, such as tert-butyl hydroperoxide or H2O2 and as reducing agents sulfinic acids or Contain amines.

The composition of the polymer, sulfo groups or sulfuric acid groups containing additive depends on various criteria.

On the one hand it is necessary that the fiber raw material, i.

the acrylonitrile-vinyl chloride copolymer compatible with the additive is so that homogeneous spinning solutions can be obtained. Second is a minimum salary of chlorine in the polymer additive is required to ensure the flammability of the modacrylic threads to keep it low.

It has been shown that when using vinyl chloride or vinylidene chloride good results achieved with contents of 10 to 40% by weight of chlorine-containing comonomer will.

However, copolymerized proportions of from 15 to are preferably chosen 35 96 Vinyl chloride or vinylidene chloride in the color-affine copolymer.

A good technical effect in terms of compatibility achieved in general, if the sulfur content in these polymers is at least 0.6% by weight. However, polymers with more than 1.0% sulfur content are preferred used. Particularly useful results are achieved when the blend component on the one hand has the highest possible content of sulfur and on the other hand with the or are compatible with the other components of the polymer mixture, so that usable spinning solutions can be obtained from the mixture. The technical Results corresponding to requirements are obtained if the copolymers 1.5 to 5% by weight of sulfur.

Polymers or copolymers with higher sulfur contents are in in most cases incompatible with vinyl chloride / acrylonitrile copolymers and are only suitable as polymeric color additives in special cases.

To ensure optimal compatibility of the polymeric additive with an affinity for color to ensure with the fiber raw material, it is advantageous to use copolymers, which as additional components compounds such as acrylonitrile, acrylic acid esters, e.g.

Methyl acrylate and ethyl acrylate, acrylamides, e.g. Acrylamide, N-methylacrylamide, N-tert-butyl aylamide and N, N-dimethylacrylamide, methacrylic acid ester, such as.

Methacrylic acid methyl and ethyl esters, methacrylic acid amides, e.g. Methacrylamide, N-methyl methacrylamide and N, N-dimethyl methacrylamide, vinyl ester, such as vinyl acetate or styrene. Preferably the polymeric color additives as ternary copolymers of vinyl chloride and / or vinylidene chloride, Acrylonitrile and a sulfonic acid or sulfuric acid half ester group containing Comonomer used.

Comonomers containing sulfo groups or sulfuric acid ester groups are for example allylsulfonic acid, methallylsulfonic acid, styrene sulfonic acid, N-acryloyltaurine, N-methacryloyltaurine, N-acryloyldimethyltaurine or N-methacryloyldimethyltaurine, Vinyl sulfonic acid and the sulfuric acid half-esters of allyl alcohol are also suitable, Methallyl alcohol and other ethylenically unsaturated ones.

Compounds containing hydroxyl groups, such as the sulfuric acid half-ester of ethylene glycol acrylate or of ethylene glycol methacrylate.

The molecular weights of the polymeric color additives can vary widely Limits vary and are not critical for the effect according to the invention; However, since the mutual compatibility of polymers in blends in some cases depends on the molecular weight of the components of the mixture, it is necessary the components not only in terms of sulfur content, but also in terms of molecular weight to vote. Polymers with a molecular weight between 500 and 500,000. Preference is given to copolymers with medium molecular weights used from 2000 to 200,000. In many cases it was found to be polymeric Color additives suitable copolymers with relatively high sulfur contents, e.g. 2% by weight, are then compatible with acrylonitrile / vinyl chloride copolymers if the polymeric Color additives have molecular weights between 1,000 and 50,000, with decreasing molecular weight of the polymeric color additive improves its compatibility in many cases.

The improvement of the coloristic properties according to the invention of modacrylic threads can be achieved by adding the Staining additives in such amounts to the fiber raw material that the total sulfur content in the polymer mixture between 0.1 and 1 total%. To level dyeings with basic dyes too achieve, it is advantageous to set a sulfur content of 0.2 to 0.8%. With regard to the lightfastness of the colorations, sulfur contents are between 0.25 and 0.5% particularly advantageous.

The coloristic properties of modacrylic threads and modacrylic fibers are generally determined by the total fiber number SF and by the drawing speed V as parameters (as described in "Textilindustrie" 71, 9/1969, pp. 603-608 are) defined for dyeing with basic dyes. High fiber numbers mean thereby a high concentration of dye acceptor groups in the fiber raw material. Height Draw speeds mean that the given acceptor groups rapidly with dye molecules be satiated.

The modacrylic threads according to the invention can be mixed with the usual basic ones Dye any dyes in deep shades.

Shades like navy blue or black are used in favorable coloring times obtained without using ecologically critical dyeing auxiliaries. It was Surprisingly that in the modacrylic threads according to the invention, the light fastness of Coloration compared with the light fastness of coloration from modacrylic threads made from unmodified fiber raw material are considerably improved. By the invention Procedure, i.e. by combining a fiber raw material with a polymer Additive that contains color-affine groups, i.e.

A "polymeric color additive" will not only make an improvement in that Applicability of basic dyes achieved, but also an improvement in the lightfastness of the colorations achieved.

The threads with the improved coloristic properties are made according to a dry spinning process by spinning the solutions of polymer mixtures obtain. While modacrylic threads are usually produced by spinning solutions of the Fiber raw materials are spun in acetone, cyclohexanone or acetonitrile, the method according to the invention is better suited for the production of modacrylic fibers and modacrylic threads from solutions of the polymer mixtures in solvents such as them are suitable for the production of acrylic threads; such solvents are dimethylformamide, Dimethylacetamide, dimethyl sulfoxide, ethylene glycol carbonate, hexamethylphosphoric acid triamide, Tetramethylurea and the concentrated solutions of inorganic salts, e.g.

Ammonium rhodanide or zinc chloride in water. Particularly good results are achieved when the polymer mixtures in dimethylformamide or in dimethylacetamide are dissolved and spun by a dry spinning process. The spinning solutions can both by dissolving the individual components with a subsequent mixing these solutions as well as by dissolving the premixed components at room temperature and / or at elevated temperatures. The solving process can be done in with Kettles equipped with stirrers, in loosening screws continuously or as a multi-stage process be performed. You can, for example, first of all polymer in a paste screw and solvents combine with each other and then in a dissolving screw or the actual spinning solution in a stirred kettle at elevated temperature produce. In some cases it is necessary to keep the spinning solutions on for a longer period of time handle elevated temperatures. It's beneficial though man Temperatures of 1000 C does not exceed, but temperatures are preferred not exceeded by 800; particularly good results are achieved when temperatures between 150 and 600 must be maintained during the dissolving process.

The concentration of the polymer mixture in the spinning solutions is in generally between 25 and 40 total%. Depending on the average molecular weight of the Components you get a favorable spinning process either with the larger or at the lower concentrations of the spinning solutions, however, one preferably chooses If possible, concentrations above 30% by weight. In most cases it is best to 35 - 38 goat solutions to spin. The viscosity of the spinning solutions should be between 700 and 6000 poise, measured at 200 C, preferably between 2500 and 4000 poise lie. The spinning solution is extracted from the release units used in each case via metering devices, such as dosing pumps and heating elements transported to the spinnerets, can it may be advantageous to use trace heating, if necessary, to ensure that that the temperature of the spinning solution is regulated in order to gel the spinning solutions to exclude. Good results are achieved when the spinning solutions Depending on the concentration and viscosity are maintained at temperatures between 20 and 500. A breakdown or gelation of the spinning solution does not occur even with a longer residence time. This The surprising effect is a particular advantage that is preferred according to the invention used solvents dimethylacetamide and dimethylformamide compared to those in general solvents used to dissolve halogen-containing copolymers, such as Cyclohexanone, acetonitrile and acetone. Have as metering devices themselves Gear pumps have proven particularly effective. About heating elements that range from 20 to 1400 C, the spinning solution is pumped through spinnerets, e.g. as cone nozzles or are attached as ring nozzles in heated spinning shafts. The heated spinning shafts are kept at temperatures between 130 to 1900 C, preferably 150 to 1700 C. and with a hot gas stream, preferably an air stream, the temperature of which is between 150 to 2200 C, the solvent is largely removed from the threads. Particularly advantageous spinning results are achieved. when you consider the supply air temperature selects so that temperatures of 170 to 2200 in the immediate vicinity of the nozzle are present. Depending on the number of holes in the spinneret, the diameter of the holes between 150 to 300 p should be chosen, and according to the amount of spinning solution delivered per time one obtains tow with a spinning titer of 400 to 5000 dtex. The resulting Spun material can still contain solvents and is made according to a procedure known per se stretched at elevated temperature and then washed, dried, if appropriate ruffled and cut. The dyeing with cationic dyes takes place after known procedure at elevated temperature in a weakly acidic medium. the Amounts of dye absorbed can easily be determined by a colorimetric measurement can be quantified.

EXAMPLES A) Example for the production of a polymeric coloring additive from acrylonitrile 'vinylidene chloride and N-acryloyl-dimethyltaurine.

The following solutions and mixtures are used: I 4325 g of dimethylformamide 175 g deionized water II 1000 g dimethylformamide 375 g N-acryloyl-dimethyltaurine (ADT) 132.5 g 2-methylamino-ethanol III 1250 g acrylonitrile 875 g vinylidene chloride IV 300 g dimethylformamide 6 g ammonium peroxydisulfate V 300 g dimethylformamide 7 g of oxalic acid In a 10 liter glass reaction vessel equipped with an ice-water-cooled The DMF / water mixture becomes a reflux condenser, a stirrer and a gas inlet tube (I) presented and flushed with nitrogen at 500.degree. After that they will be at 0 ° C ADT ammonium salt solution (II) obtained by neutralization and the monomer mixture (III) combined with the template. After setting the reaction temperature of 500 C the polymerization is started by adding the initiator solutions (IV) and (V).

After 15 hours, the solids content of the solution is 24.0% by weight. achieved, corresponding to a conversion of 75%.

The polymer solution with a conversion of 75 becomes 96 after dilution A polymer of the following composition is obtained with water by adding electrolyte: 47.0 % By weight acrylonitrile 32.0% by weight vinylidene chloride 21.0% by weight N-acryloyl-dimethyltaurine (as the ammonium salt of 2-methylaminoethanol) (ADT salt) K value: 72 Yield: 1970 g Example B (comparative example): A copolymer of acrylonitrile / vinyl chloride, that contains the comonomers in a ratio of 42:58 and that has an intrinsic viscosity in DMF of 0.99 at 250 ° C., it is made into a paste with dimethylformamide at room temperature and brought into solution in a stirred kettle at 400.degree. C. over the course of 6 1/2 hours.

To remove glass bubbles one evacuates for 30 minutes and then has a spinning solution is present which has a viscosity of 2000 poise at 400.degree. Above a gear pump acting as a metering device is this solution through a ring nozzle trained spinneret promoted, which are arranged in a vertical spinning shaft and has 120 holes with a diameter of 0.15 mm. There are 38.4 per minute cm3 solution, and the threads are transported at a speed of 100 m / min. deducted. With a delay in the spinning shaft of 1: 5.5, the spinning process is at a shaft temperature of 145 - 1500 C and a supply air temperature of 180 ° C. The resulting threads are stretched five times in boiling water, then the material is treated at 1400 C and thereby shrunk by 25%.

Modacrylic threads are obtained which are characterized by the following parameters are: tensile strength 2.02 p / dtex elongation at break 40.3% when dyeing with basic dyes becomes a color saturation number SF of 1.2 and a drawing speed V of 0.76 found.

EXAMPLE 1: Proceed as in example B, but instead of the The vinyl chloride / acrylonitrile copolymer used there is a mixture according to the invention from this copolymer and the acrylonitrile / vinylidene chloride / acryloyldimethyltaurine terpolymer according to Example A in a mixing ratio of 92% by weight of copolymer and 8% by weight Terpolymer.

The following conditions were set for dry spinning: Temperature in the spinning shaft 151O C temperature of the supply air 1820 C temperature in the Spinneret 100 ° C Delivery rate 39.4 cm3 solution / min.

Take-off speed 100 m / min.

Shaft distortion 1: 5.2.

The further aftertreatment was carried out in the same way as in Example B. The threads obtained have the following parameters: Tear resistance 1.94 p / dtex elongation at break 38% When dyeing with basic dyes, a color saturation number is obtained SF of 3.3 and a pull rate V of 2.07 were found.

The parameters characteristic of the coloristic behavior are improved to an outstanding degree over the comparative example.

Example C (comparative example) A copolymer P of acrylonitrile / vinyl chloride in a weight ratio of 42.4: 57.6 is with a dissolving screw at 400 C. DMF made into a paste and then dissolved in a kettle for about 2 hours, so that the Solids content is 38% by weight. The heated to 700 C solution is in one 1600 C heated shaft pressed through a DUse and most of the solvent transported away with air heated to 1900 C. The resulting threads are with a speed of 200 m / min. withdrawn from the shaft. After stretching from 400 96 in boiling water, the threads are dried at 800 C under tension.

When dyeing with basic dyes, a total fiber number became SF of 1.3 and a pulling speed of 0.76 was determined.

Example 2 The copolymer P from Comparative Example C is with a polymeric, color-affine component X made from 50% by weight of N-tert.-butyl acrylic acid amide, 33 % By weight of vinylidene chloride and 17% by weight of ADf-SalL (K value: So) that the Weight ratio P: X = 95: 7. If one makes from this polymer mixture P + X according to the method described in Example C, according to the invention, produces threads, so under the same dyeing conditions as in example C the following characteristic results Key figures SF = 2.7 V = 1.6 Example 3 The copolymer described in Example C. P is 7% by weight - based on the total polymer weight - of a ternary color affinity Copolymer Y (K value: 57) mixed, which has the following composition 48 % By weight methyl acrylate 34% by weight vinylidene chloride 18% by weight ADT salt.

If one sets from the polymer mixture A + Y according to the invention Procedure in the manner described in Example C, threads are obtained the following values are obtained after staining as in Example C: 5F = 5.0 V = 2.0 example 4 Comparison of the light fastness values with and without dye additive.

A copolymer of 60% by weight of vinyl chloride and 40% by weight of acrylonitrile was mixed with 10% by weight, based on the polymer mixture, of an additive having the composition 48% by weight of acrylonitrile, 51.5% by weight of vinylidene chloride and 20.5% by weight of ADT salt and spun into threads as described in Example B, once with a yellow dye of the formula and on the other hand with a red pigment of the constitution were colored.

In a comparative experiment, the above copolymer, but without the addition of the additive, threads are spun and dyed in the same way.

The light fastness properties are listed in the following table.

Dye light fastness according to the invention. Comparison I> 6 4 - 5 II > 6 5 The light fastness test was carried out according to the determination of the light fastness of Dyeing and printing carried out with artificial daylight in accordance with DIN 54004.

Claims (15)

Claims 1.) Dry-spun modacrylic threads with improved dyeing properties and under coloring conditions sufficient dimensional stability from polymer mixtures, characterized in that it consists of at least one acrylonitrile-vinyl chloride copolymer and a copolymer containing chlorine and sulfonic acid or sulfuric acid ester groups exist. 2.) threads according to claim 1, characterized in that the acrylonitrile-vinyl chloride copolymer consists of 30 to 70% vinyl chloride. 3.) threads according to claims 1 and 2, characterized in that the copolymers containing chlorine and sulfonic acid groups or sulfuric acid ester groups Has a sulfur content of 0.6-5% by weight. 4.) threads according to claims 1-3, characterized in that the Copolymers containing chlorine and sulfonic acid groups or sulfuric acid ester groups has a chlorine content of 10 to 30% by weight. 5.) threads according to claims 1 to 4, characterized in that they have a total sulfur content of 0.1-1% by weight. 6.) Process for the production of dry-spun modacrylic threads with improved coloristic properties and more adequate under dyeing conditions Dimensional stability from polymer mixtures, characterized in that one polymer mixtures from at least an acrylonitrile / vinyl chloride copolymer and a chlorine and containing sulfonic acid groups or sulfuric acid ester groups Spun copolymer. 7.) The method according to claim 6, characterized in that the Spun polymer mixtures of dimethylformamide or dimethylacetamide. 8.) The method according to claim 6, characterized in that as Mixture component of the polymer mixture is a vinyl chloride / acrylonitrile copolymer used, which contains 30 to 70% vinyl chloride. 9.) The method according to claim 6, characterized in that as Mixture component of the polymer mixture is a vinyl chloride / acrylonitrile copolymer used, which contains 40 to 65% vinyl chloride. 1C.) Process according to Claims 6 to 9, characterized in that that as a component of the polymer mixture with affinity for color, a sulfonic acid group or Copolymer containing sulfuric acid ester groups and containing 0.6 to 5% sulfur, is used. 11.) Process according to claims 6 to 10, characterized in that that polymer solutions are spun in a concentration of 25 to 40. 12.) Method according to claims 6-11, characterized in that that the resulting threads at temperatures of 80 to 1000 C in a water bath around 2.5 to Can be stretched 8 times. 13.) method according to claims 6 to 11, characterized geennzeichret, that the threads are stretched at temperatures of @ 5 ° C. 14 .; Method according to claims 6 to 11, characterized in that that the threads are stretched 3.5 to 6 times. 15.) Process according to claims 6 to 14, characterized in that that the resulting threads are fixed at 110 to 1750 C.