DE1669564A1 - Process for the production of dyestuff-affine threads, fibers and the like. made of polyacrylonitrile and its mixtures with other polymers - Google Patents

Description

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Vor-jT & Jir-.an siir -i * erpt silling dyes off affine ariels, pasers Lira dgl c,?: Us polyacrylonitrile and its LIi sell lindane with miJerer polymers.

The Jrfindurg relates to a process for the i-erstellurg dye pffin-ar F ", en, fibers and the like _0, in particular from _'olyacrylnitril, .crylnitrilcopolymeren, polyvinyl chloride, polyvinyl chloride so-C-IL jriortöjii;.! Ie from binary mixtures is rerannten Polymers with one another or with other polymers that are produced from a solution of an organic solvent by the barrel spinning process ₀

It is known that the threads and fibers spun from the polymers and copolymers mentioned, due to their hydrophobic character, are unsatisfactory in their dyeability, especially in deep shades, and that in numerous cases their fastness properties are low despite good dye absorption. are end. The high demands on the dyeing ability of man-made fibers have led to a large number of ^; /oiicht"c'-ili.'^en to prevent or remedy this 1.x r <- · -e 1 ζ ce ? i { hrt _β

Special dyeing processes such as high-temperature dyeing or special types of dye such as metal coriplex dye have been developed, and the use of such processes as spin and gel dyeing has been proposed. Oil31 methods for modifying: / iKlenbil'ior'derj polymers are known, dj.3 on the Sin- füi'rur.r Γη: · .bf; tofTaffiner groups, in particular acidic or busirichei'ntur, by copolymerization or . Graft copolyrrifj. ·: · ■!.: .- ■ t. ' iori based. The ionomer containing sf.iuro - "urktioriGlle groups used for this purpose includes:? ° n £ or, / lr: äu: re, i./rt! Acrylaic acid, chloroacrylic acid, itaconic acid, j .. '. · '>'. Λ urriall.ylnulf oi; ot, iiatriumniethallylsulfonat, liatriuwntyroli.ulf'rj'i · t ua, while as basic groups ent-Ji-. ¹ ti (Ao I.ionor / ioro ^' - vinylpyridine, 2-methyl - ¹ 5 ~ Vinylpyridlri,

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H-yinylimidazole acrylamide, methacrylamide and others : rv :. Find, - - " \

Finally, it is also known to increase and equalize the dye uptake of the fibrous materials obtained by adding dyes of higher molecular components to the spinning solution. Such substances include, for example, subsequently alkylated condensation products of dichloroethane with polyfunctional amines, condensation products of m-phenylenediamines, hexamethylenediamine and Formaldehyde, poly ~ p-ethylamino methylstyrene, polyvinyl-3,5-diaminotriasine, polytriazoles obtained from debaoic acid hydrazide, etc., which increase the affinity for acid dyes by adding "thread-forming binary or ternary copolymers of acrylonitrile with small amounts of styrene -, ethylene, allyl or!, Lethallylsulphonic acid or their ammonium or alkali salts for spinning solubility - an improvement in the affinity for basic dyes has been achieved. ■.

The. The methods listed above are not universal applicable, and its implementation is therefore - to special Fiber types and shades, limited, before only abs.r is the application in the inverse number of cases with considerable Associated costs.

For example, high-temperature dyeing requires: Use especially their dyeing machines and makes considerable: \ nrequirements at. the thermostability of the fibers to be dyed. The use of special types of dye, such as Letal 1- ■ complex dyes, is because of the high; Price theoer Substances costly and therefore only in-a few Cases carried out »

High color fastness is achieved by means of spin dyeing, she has; however, the disadvantage of high dye consumption and = makes high demands on the uniformity of the substance dosage and, if necessary

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rr the · ; ' ^f erb £ -toff dispersion level to avoid fluctuations in ■■ '31 -bton Heit. ": 'ehend-st zn...

That also has the I .vchtsil oine.s high ϊΉ-rb st off consumption Piping for GsI coloring »

Jie copolymerization or graft copolymerization with forbstoxxaiTiBeii IIonomeren has Each part that these JLonoRiex'-efi nieist difficult to manufacture and therefore expensive tir .-. I iu fill α izcrj-y further onorneren to a considerable loss of J ", since in the copolymer In only a few cases, a complete conversion of the monomer can be achieved and the non-transferring components are lost The batchwise or continuous addition of the more reactive monomer to the submitted, less reactive comonomer is usually unavoidable in order to achieve homogeneous copolymers, which complicates the overall process from a technical point of view reach and the necessary stability of the dispersion is only possible with additional expenditure. Insofar as the use of a polymer which is soluble in the spinning solution and contains groups with an affinity for dye has already been proposed, the synthesis of these products causes difficulties and considerable costs *

The purpose of the invention is to circumvent the old difficulties associated with the use of known dyeing processes to reduce the amount of work necessary for a good dyeing of the man-made fibers, -.

The invention is based on the round of reference, the dye affinity of manufactured according to the Haßsplnn method To improve threads, fibers and the like so that with basic

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Dyes real and deep shades in an extensive range Color palette can be generated »'

According to the invention, this is done by filament-forming spinning solutions prepared in the usual way Polymers, such as polyacrylonitrile, acrylonitrile copolymers, Polyvinyl chloride, chlorinated polyvinyl chloride or binary mixtures of the components mentioned add high molecular weight, dye affinity, acidic group-containing components with one another or with another polymer, which do not disperse in the solutions, but be dissolved in them.

The components used according to the invention are polymers containing aromatic cores, in particular binary and ternary copolymers of styrene and its Derivatives in bulk, suspension or solution in an inert organic solvent by sulfuric acid, chlorosulfonic acid or sulfur trioxide in known Way are sulfonated, or. To sulfonate groups in the aromatic nucleus containing monomers, such as styrene sulfonic acid and its derivatives, which with ".olefinically unsaturated, polymerizable compounds, such as J3, acrylic acid or methacrylic acid esters are copolymerized.

It has proven to be useful to adjust the degree of suIfonieruhgsgrad to keep the components to be used according to the invention so high that even a small addition of sulfonate for the spinning solution of the thread-forming polymer causes a significant improvement in the ability to be dyed, and on the other hand set it so low that a good solubility of the sulfonate in the preparation of the spinning solution Solvents used, such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide and the like, ensured .is, '

It has been found that the polymer or polymer mixture together with 1 - 10% by weight of a 1 - 15% by weight - <o,

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preferably 4-8 wt _o -% sulfur as sulfonate group-containing copolymers of styrene jnif in particular, acrylonitrile and / or acrylic or methacrylic acid ester in dimethylformamide, dimethylacetamide or dimethylsulfoxide, and can solve spun in a conventional manner. The spinning solution can also be mixed with the separately prepared solution of a polymeric sulfonate and then spun in the usual way ₀

This method has the advantage that the in small Quantities of added components are completely and evenly incorporated into the finished thread and there are dyestuff-affine act and not, as is the case, for example, with a dispersed dye-affine component of Pall, if the degree of dispersion is not uniform, some of the spinning solution is lost in the course of the filtration. The nature of the components used according to the invention conditioned their participation in the thread formation and thus an advantageous effect on the physical textile fiber properties, such as tear resistance and thermal stability. These components also have the advantage that they are made from technically easily accessible products and their use the application of basic dyes as well conventional dyeing process with very good dyeing and color fastness guaranteed.

The invention is illustrated by the following examples:

Example 1.

98 parts of a polyacrylonitrile with a K value of 90 (according to Fikentscher) and 2 parts of a sulfonated styrene / acrylonitrile copolymer of the composition 70 % styrene and 30 % acrylonitrile with a sulfur content of 4.80 %, together in dimethylformamide at 70 ^° C. were used within

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Dissolved into a 16% spinning solution for 2 hours. The solutions were spun through a nozzle with 240 openings of 0.09 mm 'in a dimethylformamide / water pall bath of the composition 50 and 50' at a temperature of 15-1: 5 ° C. and the threads in 2 stages at one temperature verstreekt 1OO- ⁰ 1 C j G, washed with water and air - 98; dried at 20 C »The spun threads, which have a titer of 2.95 der, a strength of 2.86 g / den and an elongation of 21 % , can be dyed very well with ßasaeryl blue GL in deep shades. An 8> C colored fluff was completely taken off »

Example 2.

Of a 20% solution of a polyacrylonitrile having a K value 90 (after Pikentscher) in dimethylformamide and a 5 / ε-solution of a 6.78% sulfur-containing sulfonated styrene / acrylonitrile Gopolymerisates in dimethylformamide was prepared by mixing two 16% - ige spinning solutions produced »The ratio of the polymers of polyacrylonitrile to sulfonated], styrene / acrylonitrile copolymer was 90:10 in the first solution and 95 ί5 in the second. These spinning solutions were 0.09 through a nozzle with 240 openings mm in a dimethylformamide / water falling bath of the composition 50:50 at a temperature of 16-17 ⁰ C and the threads are drawn in 2 stages at a temperature of ^{98-100 0} C 1: 6, washed thoroughly with water and on the Air dried at 20 ^{0 G.} As a comparison, a 16% PAH solution was spun into threads under the same conditions. In Table 1 the textile physical values and in Table 2 the thermostability and the colorability values with Basacryl Blue GL are summarized _Λ Whiteness and thermostability are measured in a Zeiss leukometer against a BaSO standard »

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Tabel 1 0 0 Titer tensile strength
(den) (g / den) 2 , 68 Jl Elongation - Weii3 | , 6 1 fo completely moved out relationship
PAH / sulf.KQmpo 5 5 3.09 * 2 , 74 2Ο, · 5 52, t-3 7% totally moved out 100 ί 10 10 2.83 2 »65 .19.7 6B ₁ , 5 9 % almost completely off 95: 2 2.99 20.0 ■ 7I ₁ 90: relationship
PAK / sulf. Comp. Tabel 10.0: Tit he
(the) 95: 3.09 switch
) 90; 2.83 , 7 2.99 > 8 »5 Thermostability Colorability
30 '160 ° {%) • 26 51 51

drawn

Example 3., - .. ".-

Of 90 parts of polyvinyl chloride of K value 55 (according to Fikentscher) and 10 parts sulfonated styrene / acrylonitrile copolymer having a sulfur content of 8.1% was prepared by co-dissolving at 70 ⁰ G within 2 hours, a clear 16 fa-spinning solution ₀ 70 ⁰ C hot solution was in a .Oimethylformamid / water precipitation bath of composition 80: '20, as in example 2, spun into filaments of 1.95 g at a titer of 3.1 to a strength / den and have an elongation of $ 31 and completely take off a $ 5 bath of Basacryl Blue GL. A faner spun without the addition of sulfonate does not completely pull out a 2 % dye liquor.

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Claims (2)

Patent claims: 1, process for the production of 'dyes off affine threads, Fibers and the like made of polyacrylonitrile, acrylonitrile copolymer en, polyvinyl chloride, chlorinated polyvinyl chloride as well as from their binary mixtures with each other or with other fiber-forming polymers, characterized in that the polymer or polymer mixture together with 1-10 G-ew, - / 5 of a 1-15 Wt .- 'S, preferably 4-8 wt .- / 5 sulfur, as sulfonate groups, containing copolymers ^ of styrene with in particular acrylonitrile and / or acrylic or Fethacrylaäureester in dimethylformamide, dirnethylacetamide or Dimethylsulfoxid.gelöst and known per se Is spun wisely " 2. The method according to claim 1, characterized in that, the polymer or polymer mixture '.' and the one containing sulfonate groups Polymers dissolved separately and the result the. Solutions mixed homogeneously before spinning will" BATH ORIGMAt. 109829/1720