DE2060572A1 - Process for reducing the dye affinity of fiber materials made of polyacrylonitrile - Google Patents

Description

2060572 FARBENFABRIKEN BAYER AG

LEVERKUS E N-Bayerwerk P.tent department Β / Ρ] 8. Ö82.197 ·

Method of reducing dye affinity of fiber materials made of polyacrylonitrile

The invention relates to a method for reducing the dye affinity of polyacrylonitrile or acrylonitrile-containing substances Fiber materials made from mixed polymers; the procedure consists in making the fiber materials treated with aqueous baths before dyeing or printed with aqueous printing pastes containing such basic nitrogen atoms containing polyethers or their quaternization products contained in the condensation of N-2-hydroxyalkylamines the formula

HO-CH-CH ₀ -N-- CH ₀ - CH - OH (I)

Rj R Rp

in the

R ₁ and R ₂ independently of one another are hydrogen or one

Ο ,, - C.-alkyl radical and R stands for a C ₁ -C ₁ a -alkyl, cycloalkyl, aralkyl or aryl radical or one of the hydroxyalkyl groups -CH ₂ -CH-OH or

"1

-CH ₂ -CH-OH means, with the proviso that

E ₂

the amount of N-2-hydroxyalkylamines in which R represents a hydroxyalkyl group, no more than 20 percent by weight of the hydroxyalkylates used amounts to,

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optionally by co-condensation with polyols of the formula

/ "" Aj- (OH) _n

in the

A is the remainder of an aliphatic, cycloaliphatic

table, araliphatic or aromatic

Polyol means and

η eats a number from 2 to 4,

can be obtained.

Pur R are for example:

as Cj-C ^ -alkyl radicals the methyl, ethyl, propyl, n-butyl, \ sec-butyl, 2-ethylbexyl, decyl and dodecyl radical; as cycloalkyl create especially the cyclohexyl radicals and cyclobexyl radicals substituted by Cj-C.alkyl groups, such as methylcyclohexyl, ethylcyclobexyl, butylcyclohexyl, dimethylcyclohexyl and diethylcyclohexyl radicals;

as aralkyl radicals, in particular the benzyl and methylbenzyl radicals; as aryl radicals, especially the phenyl and C .j-C, alkyl groups substituted aryl radicals, such as cresyl-, IyIyI-, Ethylphenyl and tert-butylphenyl radical.

Pur R ₁ and R "may be mentioned as C 1-4 alkyl radicals of the methyl, ethyl, propyl, η-butyl and sec-butyl radical.

As polyols with the N-2-hydroxyalkylamines of the formula I can optionally be co-condensed, are mentioned: aliphatic polyols, e.g. B. diols, such as ethylene glycol, propylene glycol, Butylene glycol, diethylene glycol, triethylene glycol, Tetraethylene glycol;

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Triols such as glycerol, trimethylolethane, trimethylolpropane; Tetraols such as pentaerythritol;

Cycloaliphatic diols such as 1,4-dioxycyclohexane; araliphatic diols, such as 1,4-bis-methylolbenzene, 1,4-diß-hydroxyethoxy-benzene, 4,4'-di-ß-hydroxyethoxydiphenyl ether, 4,4'-di-ß-hydroxyethoxydiphenyl sulfide, 4,4'-di-B-hydroxyethoxybenzophenone, 2,2-bis- (4-ß-hydroxyethoxyphenyl) propane.

It was proven expedient to measure the amount of condensed water Polyols should not be higher than 25 percent by weight, based on the weight of the polyether.

The average molecular weight to be used according to the invention Polyether should be between 500 and 20,000, preferably 1,000 to 15,000.

The polyethers to be used according to the invention are linear or slightly branched polyethers. Linear polyethers are made by known processes by condensation of N-2-Hydroxyalkylamtnen of the formula I, in which R as indicated above for an alkyl, cycloalkyl, aralkyl or aryl radical, in the presence of acidic catalysts, eg Η, ΡΟ ,, elevated temperatures, e.g. B. 150-280 ⁰ C obtained. In order to obtain branched polyethers, the diols containing tertiary amino groups are condensed together with triols containing tertiary amino groups, ie N-2-hydroxyalkylamines of the formula I in which R is one of the β-hydroxyalkyl groups indicated. In order to avoid crosslinking, however, the amount of triplets in the condensation mixture should not be more than 20 percent by weight, preferably 2-15 percent by weight.

As ß-Hydroxyalkylaaine of the formula I, through their condensation obtained the polyether to be used according to the invention are, for example, the N-di- (2-hydroxyalkyl) -

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i - 'i'Vlcl · - tj' j.- · P-.> ·] ..- ■;. ·. ■. ■ ;. :. ^: -,; 'ir'nj: .f! .f: »j' ¹ JHrUiJ AIk ν! <: UOX i · ΐ ^{^;!} 'i ι * ϊ'.π -;> ίί ι) hVi ii: · -. . · ■ · ^; ■ '■;'! : .pija I i f.:>!u, a ra J; r-ba '; i.? c!) e Π'-ι -i r -! - v _i;:; ii Tfin Λ '_{; ί} -;,;, · -.,, - -' r hi "|;

] - · Κ I3i; ·· ί. '■ -Ii \ ^ι · Λ / <^ i ■ -s i. ^! ) .v "'; · -N -" m 1:.> 7 .; a'.niu, j '. Jf -Bi '· / -' ■ h, yd foy.yJ- ¹ J- (Ij ^ -I - (i jf --ι) ρ i, _ _· j j ii fiv,> - ^ i-. ^[: "■ · -I'i ■ hyd] · ι · / -; y-bu!, Y] - (t j / ^r -» '> !, ijv. "' - 'ι -Μ ·, t, ?, · Hi t '■ (. ■ · ■ iv'.. _i:: ->, ^ !, | i; '|) h; Ojíř ojv / J -ι ·] i η.. N ₁ W-

]) 7 ·, wiy; ί ι j / .. Jv-S- '' ··! i ^:! -y 1 a ^r ii ■ ι-, i <, U-Bi. '·· ■ * {"--hydr oxy al hy> _ } ■ -oyoj (, Ik'jc vi.' * '■ -. j -; ti, i, N ⁱ .. ^·;! Ij -) '? tj oxyjithv ι) "N ~ b' n, _t ylatnin N, IJ'J '^ · ■■ -i' ·. ■ i: ydi · - xj at, j Ii ■ · ('- · - "thylbour,;,; ij-awi.n _T W, NJi: -.';-(Γ-:)>^; fr 'JiVH i '· Ν j j - ; ii J ■ η, fv, N-lii ..; - /.-'-iiydro>.yskr>ropy] ~ (127 ™ ani J in, U - ] .i-.f ; -l, · - (: - hyd: nyyiiih y :.) -J-raei iiy Iani Ii n, N, Ii-BIs - (,> hyJroxyathy ^.: i ™ '} - t. · .. /'<, -buty J.atiilln.

ΑΊ i ^r ' Vfjrt :: etf'r <>. R z> :, he: -; ito'i limp der / orzwe i gten Polyather mJ.tYerwfiii'Ieiei;' ¹ Ir it: j. ·, Neieu 1 ucbeisotnierci Triäthanolaaiin, Tri iisopropaiiola-in η; j »· ■ Tr i Im; Ι .. · ^; called ddI ami η.

E'i has ni '.- l) ge:. · -J / i i., Ήΰ diu Quattirniernngaprfjdukte der * inventun ^ sff? Iuaß: -u vrirvnudeniien Polyäthe? often a "stronger downward " .nnc der> - 'a / i>; j! of faf fi titt-ät be f rken than the ToIyiHhür. The Qu. * t <:] · η? ^; : - !; ii / _!;]; rudukt e habcjn uicli alR beaoudero wi rk.uugtr '. ■] 1 b ·. ·. I * '■; - Hch iu <iJ utj / -:;: strongly acidic groups, aufwoi-.lendpjm.' \ V yj ni '·. · ' Vi-. ^] ■ ~ nvi Hi ^r -'- ^> ! IjoJ.y ^t J ⁱ eri na.te erwi eß (Hi.

Γ; · "yi ^ '.' Vu ^: <! I in; '<-. · '' J η ar HJol) beb;: av 1. ο r way ν d-T'cb Ih; ο:>. T r. FU "; · - ^■:; <· RcliRuen '< a IJ ο in / ^; LV oho] or A V »ai? .. ■ pr-t.ii} ' ¹ )!.: - cb < ^: ι f, o J. ■; -1 e π f-fj '·>!. · Bu.-jjjendi er ton rolyäthf? R rait bt? K · KDf (H ¹ / ilky I i'; j uUf-ini?: J tt (3l ■ !, like Di η · - * ΐ hylnu] fat or Dietliyl -, "Ui ί at; Jj-ToJ '■) (. ■ _t . u I i ο η fj! ium a I ky j» intert !,;. . B. p-Tol uo];? Ulf onijaiirf! Iif? Tl..y] e; 5i: ov; M.] t \ 'i \ v, ilot'. <MUlüü,?.} L. He thy Ij ad id or Äthyl brorni ■ ;; Chlornc β taoiio, Ha] o / ?. "roarbou ^r · - j ^; i> alzeu, Un lop, encaibon- ~ snureeMti -.- rn, Α1] υ <.ν: ³ . \ - ΐ + οποη or I'.en ^ yl t> U] orid.

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ORIGINAL & 'J t / G / 1 Q ϋ 8

■ V '? O b Ci ο /

Here 0.J is not erf'jL-uurliüu, ien Polyicher completely to quaterriteron, but it is 'iii.; Ra Lchöiid, 20 bie 8Ü ' Jo of the basic nitrogen atoms quaternize the Polyüttuira au.

The quantities in which the substances used in the present invention are eyed by Vurböhandiungsbädarn; tzb, can fluctuate within wide limits, i'n -.iLLgeinn inen has sLch oln Zuaats: from 0, ü05 - 1 '/>, voraug uoLaf) 0.01 - 0, ij jt, percent by weight, based on the (rewicut Λα a i ^ itse ^ materiaiien, proven t.

The pretreatment of the PasermateriaLi ·. is carried out in the same way that "nan da."; MaLürLaL Ln an aqueous liquor heated to about 40 ⁰ G, which contains the polyethylene to be used, and its pH value by adding acids, e.g. formic acid or acetic acid , was inhaled to 4 to 7, then the temperature of the treatment abado «in the course of about 30 minutes to 90-10O ⁰ O and the bath is left at that temperature for 15-90 minutes. The temperature of the liquor is then cooled by inflow water is gradually lowered to about 50 ⁰ C, After brief rinsing with cold water da3 material is dewatered and dried.

Another embodiment of the method according to the invention is characterized in that the polyacrylonitrile Pasermaterialien, printed with aqueous pastes containing according to the invention to be used Polyfcther and optionally wetting agents and thickeners and attenuates then 5 bia 10 minutes at about 100 ⁰ C.

Suitable acrylonitrile-containing copolymers are, for example those made of acrylonitrile and vinyl chloride, vinylidene chloride, vinyl acetate, vinyl chloroacetate, vinyl alcohol, acrylic

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BATH

S 2OGiIbV /

and methacrylic acid, AcryL- and Mn thacryLiiaurnestorn, I, T-DiacyLoxy-2-methylenpr.opanen _f AlLyLchLorace bat, müiohpo Ly raerL-3baren SuIfonateti, phosphonates and DLaulfouiinLdan, or basic vinyl compounds, vinyl pyramid, vinyl pyramid ViriyLpyriinidin, provided that the outside of the co-monotners is no longer air. ? 0 percent by weight. The fiber materials can be in any processing state, e.g. B. as SpLnnkabaL, Faden, FLooke, Katnrazug, yarn, fabric or GewLrk.

The polyethers to be used according to the invention considerably reduce the dye affinity of the polyacrylonitrile fiber materials compared to basic dyes. The basic dyes can belong to a differently keyed% uten groups; for example the piphenylmethane, triphenylmethane or rhodamine dyes, the azo or anthraquinone dyes containing onium groups, and also the triazine, oxazine, methine and azomethine dyes.

The method according to the invention is of particular importance for the generation of color depth differences in colors or Printing of fiber materials made of polyacrylonitrile. This is because fiber materials pretreated according to the invention are dyed together with untreated polyacrylonitrile fiber materials in continuous or discontinuous operation, in this way, high-contrast bicolor dyeings are obtained, since the pretreated fiber material has a significantly lighter color as the non-pretreated fiber material. As by the treatment according to the invention at the same time with the lowering of the dye affinity for basic dyes a good dyeability of the polyacrylonitrile fiber materials by anionic dyes, such as those commonly used for dyeing natural and synthetic polyamide fibers is achieved, it is possible by using anionic dyes in addition to basic dyes To achieve dyes in the padding liquors or dye baths multicolor effects. Very appealing multicolor effects

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BATH ORIGINAL

■ ü 9 ü _t > fi / I fj u β

γ 2 Π rs O Li 7

lh:?, r: f'i \ ai eh ttU '.' h uar ·;!. ; 1 ^:: -. ^j J, "'verweH iuHf' von Diaper fli on» · - f;. r ^ alof fen beiti; KiH; < _: r; 'TP;.!'. π, -; ί? <> «3 wii Ji pretreated «! * Υηβ ti'ib ^ oano'olter Pol J '■ ι>.' i '''.' ^{! f} '! - "" i »ri hJ j en"> ii ^; bapiiJohun T'ari at ape orrdiol.-fiU, rhi din J); : - (r "i onr.'J'yl IH.of in, do ^r 's A ¹ Ji?." Solion duroh οι ρ ν> Ί v _<l:; ju · - ": <r-- . n'tciA] m-.v J ui'J ui? tv / iisj,. · =. ϊγϊ '"cn vorbsh: tulei i'M..: ■. Ov- ^ t- ■ ;. ■ <■■ '' Hi ¹ Lt '■ :; l ·' -.: · '7'Ί * · ιΐ for? Ri' · 1 ar; W>'R6llt.] J Ch ρΐ * ί ^; · β (:' Γΐ. ί.! 'iT "]; 1 (il; V (Γ, ■' Ij i nlilJPj / ϊ hew j T.i ', Ü Ii al: - · cälii" i] r} \ v uuvoi'behau'de! .ton ■>'. m. »J: w», ι. ·. -. "* 11. r-; 11 bevel r'.n'j 1; eria].

Before ie ti in dal J.eu1 ^ o'ien Ληπκη ii; ng P ij Γ 7 'i ^ OO zur Vorrolnriorun / i der Ani'ärbl; ar) << ri t von! "Olyacr ^ J tii tri.J ianermateria J inn bei-j'ihrieljerjtfn. Verl>iU'.iuu {i » ⁱ u ^ n;: bu (") inch oi.o erfitidun / rege-T «? Äß Ku vorwendeudfciti Polyätlrn: iureb ibir ·; E] ektralyt-Uneajpf indli ohkelt and ihi :(? Rilari; * -?. = Ϋυ Ληί'ϋι ih-irhei t diminish- <i (i effect au ». Er, soj l-eicui, that diieri" i And in accordance with the pretreatment germ?

Those given in the examples unj HerijteJ lun;!; 'Vt: r,' 'ct:] "i iten Parts are r, if not different; - anf (? {'El: et), weight ~ parts, parts by weight vr-rb-iltei). · 5: ο (;: υ Vo] uuunitellen like ^ to al. The specified I'arl ^ tofftrvj-nern beniohen sieve the information in Color Index, 2. / i.Jila^e, Volume 3 (19i; 6).

Production of the verv / on ΐ ·? ⁴ .'π? Polyether. Pol yether A

H- (O-CH ₂ -OHp-H-OHj, -OH ₀ - ;. ,, OU

1500 parts of di-ß-hydroxy & thylcycl-ohexylami η v / urdeu in Gegen was 15 parts of H, F0, 3 hours under nitrogen.

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BATH ORIGINAL

220 - 23O ⁰ C condensed. Subsequently, the Reaktionsniischung was heated to remove volatiles for 1 hour under reduced pressure (12 ramHg) to 220 ⁰ C. The polyether obtained as a residue is a yellow, water-insoluble syrup (average molecular weight: 4460, OH number: 25).

Polyether B

The solution of 150 parts of polyether A in 200 parts by volume of methanol was boiling with 82 parts of dimethyl sulfate (0.75 mol of dimethyl sulfate per mol of basic amino group) offset. The reaction mixture was refluxed for 3 hours. Then the solvent was im Distilled off under vacuum. The quaternization product remains as a yellow, water-soluble syrup.

Polyether C

Polyether C was produced in the same way as polyether B, except that instead of 82 parts of dimethyl sulfate, only dimethyl sulfate was used for quaternization 54 parts of dimethyl sulfate (0.5 mole of dimethyl sulfate per mole of basic amino group) are used. The quaternization product remains as a yellow water soluble syrup.

Polyether D

Starting product:

First, 500 parts of N, N-di- (ß-hydroxyethyl) -N-cyclohexylamine were added in the presence of 7.5 parts Η, ΡΟ, analogous to the preparation of polyether A to a polyether with an OH number of 8.6, corresponding to an average molecular weight of 13 condensed. The polyether can be expressed by the formula

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H- (O-CH ₂ -CH ₂ -N-CH ₂ -CH ₂ ) _?? -0Η ^^

describe.

85 parts of this polyether were suspended in 80 parts by volume of methanol and 19 parts at the boiling point Dimethyl sulfate (0.3 mol of dimethyl sulfate per Λοί basic amino group) offset. After refluxing for two hours, the solvent was distilled off. Of the Quaternized polyether was in the form of a yellow water-soluble Get syrups.

Polyether E.

H- (0-CH ₂ -CH ₂ -N-CH ₂ -CH ₂₎ "-OH

1900 parts of N, N-di- (β-hydroxyethyl) -N-butylamine were _{condensed in the presence of 19 parts of H 5} PO ₅ under nitrogen at 200 ^° C. for 9 hours. The reaction mixture was then heated ^{to 200 °} C. under reduced pressure (12 mmHg) for 2 hours to remove the volatile constituents. The polyether obtained as residue is a water-insoluble, slightly reddish colored viscous oil (average molecular weight: 5000; OH number: 22).

Polyether

CH, CH,
ι ■> ι ->

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OU826 / 1008

700 parts of N, N-di- (ß-bydroxypropyl) -N-methylamine were in Presence of 10.5 parts Η, ΡΟ, under nitrogen for 6 hours

O JJ

condensed at 220 C. Subsequently, the reaction mixture was heated to remove volatiles for 1 hour under reduced pressure (12 mmHg) at 22O ⁰ C. The polyether obtained as a residue is a slightly reddish colored water-soluble oil (average molecular weight: 1340; OH number: 84).

Polyether G

Starting product:

First, 500 parts of N, N-di- (ß-hydroxyethyl) -N-cyclohexylamine were added in the presence of 7. »5 parts Η, ΡΟ, analogous to the preparation of polyether A to a polyether with an OH number of 14 corresponding to an average molecular weight of 8000 condensed. The polyether can be expressed by the formula

H- (O-CH ₀ -CH ₀ -N-CH ₀ -CH ₀ ) ^ - OH

describe.

The solution of 338 parts of this polyether in 400 parts by volume of methanol was boiled with 151 parts of methyl chloroformate added (0.8 mol of chloroformic acid ester per mol of basic amino group). After 3 hours

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heat to reflux temperature, the solvent was im Distilled off under vacuum. The quaternization product was obtained in the form of a water-soluble yellowish oil.

Polyether H

Starting product:

1800 parts of N, N-di (ß-bydroxyethyl) -N-cyclohexylamine, 200 parts of 2,2-di- / 4 "- (ß-hydroxyethoxy) -phenyl7-propane were Η, ΡΟ, 5 hours in the presence of 20 parts under nitrogen. ei 220-230 ⁰ C condensed then the reaction mixture of the devolatilization was.

^{Heated to 220 0} O for 1 hour under reduced pressure (12 nmHg). The polyether obtained as residue is a yellow syrup (average molecular weight: 8000; OH number: 14; content of basic amino groups: 5.16 equivalents / kg of polyether).

The solution of 300 parts of the polyether in 300 parts by volume of methanol was added dropwise to the boiling point 158 parts of dimethyl sulfate are added (0.8 mol of dimethyl sulfate per mole of basic amino group). The reaction mixture was

Heated to reflux temperature for 2 hours. The solvent was then distilled off in vacuo. The quaternization product remains as a slightly yellowish water-soluble syrup.

Polyether I.

Starting product 1:

1385 parts of N, N-di- (beta-hydroxypropyl) -N-methylamine were in the presence of 62 parts Η, ΡΟ 5 hours under nitrogen at 210 - 22O ⁰ C is condensed. The reaction mixture was then used to remove the volatile components

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Heated for 1 hour under reduced) pressure (12 mmHg) at 21O ⁰ C. The polyether obtained as residue is a slightly reddish, viscous water-soluble oil (average molecular weight: 1290; OH number: 86; content of basic amino groups: 7 equivalents / kg of polyether).

The polyether can be expressed by the formula

CH ₅ CH, HfOC-CHp -N-

describe.

Starting product 2:
710 parts of this polyether and 710 parts of N, N-di- (β-hydroxyethyl) -N-cyclohexylamine were _{condensed in the presence of 15 parts of H 5} PO ₅ ^{at 220 °} C. for 10 hours under nitrogen. Subsequently, the Reaktonsmiscbung was heated to remove the volatiles 3 hours under reduced pressure (12 mmHg) at 220 ⁰ C. The mixed polyether obtained as residue is a water-insoluble, orange-colored syrup (average molecular weight: 6150; OH number: 18; content of basic amino groups: 6.8 equivalents / kg of polyether).

The solution of 500 parts of the mixed polyether in 500 parts by volume of methanol was added dropwise at the boiling point * 128 parts of dimethyl sulfate are added (0.3 mol of dimethyl sulfate per mole of amino group). The reaction mixture became 6 Heated to reflux temperature for hours. The solvent was then distilled off in vacuo. The quaternization product remains as a water-soluble yellow syrup.

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Polyether K

Starting product:

360 parts of N ^ -di-ISS hydroxyäthyD-N-cyclohexylamine and 40! Peile triethanolamine were condensed ₅ 5 hours under nitrogen at 220 ⁰ C in the presence of 1.5 parts H ₅ PO. Subsequently, the Reaktionsmisehung was heated to remove volatiles for 1 hour under reduced pressure (12 mmHg) at 17O ⁰ C. The branched mixed polyether obtained as residue is a pale yellowish water-insoluble syrup (OH number: 108; content of basic amino groups: 6.3 equivalents / kg of polyether).

200 parts of the polyether were in 300 parts by volume Suspended methanol and treated with 79 parts of dimethyl sulfate at the boiling point (0.5 mol of dimethyl sulfate per mol Araino group). After refluxing for 3 hours the solvent was distilled off in vacuo. The quaternized polyether was in the form of a water soluble Get syrups.

example 1

Polyacrylonitrile yarn is treated in a dyeing apparatus in a liquor ratio of 1:30 with a liquor which contains 0.03 g of polyether A per liter. The bath is heated over 30 minutes from 40 to 100 ⁰ C and then gebalten 15 minutes this temperature. After a short rinse, the yarn is drained and dried.

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The pretreated yarn is made with non-pretreated polyacrylonitrile yarn processed into a carpet, which is placed on the reel runner in a plotting ratio of 1:40 in the usual way is colored with a plot that is in liters

0.3 g of dye No. 51 005, 0.2 g of glacial acetic acid and
0.25 g of natriam acetate

contains. A high-contrast, luminous light blue-dark blue coloration is obtained, because the pretreated yarn has a much lighter blue color than that which has not been pretreated.

An equally strong reduction in the dyeability of the Poly-P acrylonitrile yarn and therefore an equally high-contrast one Light blue-dark blue coloring was obtained when, instead of polyether A, 0.16 part of polyether E, 0.03 part of polyether P, 0.2 part of polyether G or 0.06 part of polyether H were used.

An even greater reduction in the paraffin affinity of the polyacrylonitrile yarn and thus an even higher contrast On the other hand, light blue-dark blue coloring was achieved if, instead of polyether A, the same amount of polyether B, C, D, or K were used.

Measurements of the tensile strength and elongation at break on polyacrylonitrile thread treated with W polyether D gave the following values:

Titer (dtex) tear strength elongation at break

(p / dtex)

Untreated 571.0 1.59 24.3

Treated 588 1.50 24.5

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Example 2

Polyacrylonitrile yarn is treated in a yarn dyeing machine in a liquor ratio of 1:30 with a liquor which contains 0.06 parts of polyether I per liter. The bath is heated from 40 to 100 ^° C. within 30 minutes and then held at this temperature for 15 minutes. After a short rinse, the yarn is drained and dried.

This pre-treated yarn is knitted with yarn that has not been pre-treated. The knitted piece is in the liquor ratio 1:30 colored in the usual way with a liquor that is in liters

0.25 g of dye # 48 060, 0.2 g glacial acetic acid and 0.33 g sodium acetate

contains. A brilliant light yellow-dark yellow dyeing is obtained, since the pretreated yarn is much lighter Color than that which has not been pretreated.

Example 3

A carpet made of polyacrylonitrile fiber yarn is printed on a film printing machine with a printing paste, which in 1 000 g

3 g of polyether F
20 g of the polyglycol ether of the formula

-0-4-CH ₂ -CH ₂ -0-4 ^ -CH ₂ -CH ₂ -OCH ₂ -CH ₂ -CN

SO ₃ NH ₂ (CH ₂ -CH ₂ -OH) ₂ and

400 g of a 3.5 ige η solution of a commercially available Carob Gum Derivatives

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contains and then steams it for 5 to 10 minutes.

The carpet is then dyed with a liquor in the usual way on the reel runner in a liquor ratio of 1:40, those in the liter

0.25 g of the dye / 4 "-nitro-2-chloro-

aniline - > N-ethyl-N- (dimethylamino) -ethylaniline quaternized with (CH ₅ O) ₂ SO _2- /

0.2 g of glacial acetic acid and

0.25 g sodium acetate

contains. A very high-contrast light red-dark red print is achieved, because the printed areas are much lighter red than the unprinted areas,

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Claims (4)

Claims Process for reducing the parbatoff affinity of made of polyacrylonitrile or acrylonitrile-containing copolymers produced fiber materials, characterized in that the fiber materials with aqueous baths treated or printed with aqueous pastes containing such basic nitrogen atoms polyethers or their Contain quaternization products in the condensation of H-2-Hydroxyalkylaniinen of the formula HO - CH - CH ₂ - N - CH ₂ - CH - OH A IX XV ri ' in the R ₁ and Rp, independently of one another, denote hydrogen or a Cj-C ^ -alkyl radical and R represents a C ₁ -C ₁ , - alkyl, cycloalkyl, aralkyl or aryl radical or one of the hydroxyalkyl groups -CH ₀ -CH-OH or _{-CH 0} -CH-OH, with the R ₁ R ₂ Provided that the amount of N-2-hydroxyalkylamines, in which R stands for a hydroxyalkyl group, not more than 20 percent by weight of the hydroxyalkylamines used amounts to, optionally by co-condensation with polyols of the formula in the A is the remainder of an aliphatic, cycloaliphatic table ^, araliphatic or aromatic polyol means and Le A 13 427 - 17 - 09826/1008 α is a number from 2 to 4,
can be obtained. 2. The method according to claim 1, characterized in that such polyethers or their quaternization products ver applies, which have a molecular weight of 500 to 20,000. 3. The method according to claim 1, characterized in that one ver such polyethers or their quaternization products which have a molecular weight of 1,000 to 15,000. 4. Fiber materials made of polyacrylonitrile or acrylonitrile
W- containing copolymers treated according to the process according to claim 1 to 3. le A 13 427 - 18 - 09826/1008