DE2148347A1 - PROCESS FOR THE MANUFACTURING OF PIGMENT PREPARATIONS FOR THE DARKING OF POLYACRYLNITRILE - Google Patents

Description

FARBWERKE HOECHST AG. formerly Master Lucius & Brüning

File number: HOE 71 / F 255

Date: September 27, 1971 Dr.Ot / cv

Process for the production of pigment preparations for the dope coloring of polyacrylonitrile

It has long been known to use polyacrylonitrile fibers to color basic dyestuffs from aqueous solutions «However, the use of pigments wins for this Purpose due to the better fastness properties of the pigments and the more efficient and cheaper working methods Coloring is becoming more and more important. It is necessary to disperse the pigments very finely in the spinning mass, so that an optimum of color strength and levelness of the color is achieved and technical problems such as clogging the filter or the spinneret and thread breaks due to coarse agglomerates are excluded. In the German patent specification 1 225 858 describes a process in which pigments with polyvinyl acetate or a predominantly from Polyvinyl acetate existing copolymer or polymer mixture grind in a double trough kneader or in an attritor mill and then added to the spinning solutions,

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The use of polyvinyl acetate, which serves to stabilize the pigment dispersion, and a reagglomeration of the pigment is intended to prevent, but can lead to changes in the physical properties of the fiber material.

In the GDR patent 62 443 a process for the production of pigment preparations is described, which do not have the properties the Paser-impairing substances contain »The pigment preparations are there by the separated or joint aqueous bead milling of pigment and polymer and subsequent joint flocculation obtained.

Another possibility for the production of powdery pigment preparations with the desired properties is kneading the pigment with a highly viscous paste made of polymer and solvent and then removing it of the solvent by evaporation

For immediate consumption one can also use pigment dispersions by bead milling the pigment in the appropriate Prepare spinning solvent and stabilize the dispersion with polymer solution.

All of the methods listed here for making Pigment preparations or for the fine distribution of pigments for polyacrylonitrile spunbond dyeing have the disadvantage that they are caused by the use of grinding and kneading devices are technically very complex.

The present invention relates to a process for the production of pigment preparations for dyeing the dope of polyacrylonitrile and its modifications, which is characterized in that one in the production or Formation of the pigments polyacrylonitrile ^ in or mixed polymers, produced by the dispersion polymerization process, added as a carrier material and the pigments in the usual way.

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The production of such pigment preparations takes place in the way that in the production or formation of the pigments they are mixed with the required amount of the polyacrylonitrile pure or mixed polymer is stirred up and the pigment treated in this way is worked up in the usual manner. That Pure polyacrylonitrile or mixed polymer is advantageously used turn out to be in the form of its moist press cake, as it is obtained in dispersion polymerization.

It is not necessary here to through the press cake Dispersion, for example pearl milling, to bring into a dispersion form, the particle size of which corresponds to the pigment fineness is equivalent to. If necessary, an additional use of small amounts of surface-active auxiliaries has been found to achieve optimal pigment preparations as advantageous. Both nonionic alkoxylated alkylphenols are used for this purpose or fatty alcohols, as well as special cationic or anionic auxiliaries in embossing. With a number of Pigments, for the production or formation of which already require surfactants, do not need to be further added surface-active substances Preparation tools

Both pure polyacrylonitrile and copolymers which, in addition to acrylonitrile, are suitable as carrier material or several other copolymerizable monoolefinic ^ Contain monomers. Suitable copolymerizable monoolefins Connections are described in German Auslegeschrift 1 292 310, for example.

The amount of carrier material added is 20 to 80, preferably 30 to 60, by weight based on the finished preparation.

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The time of preparation is "different for the individual pigments, as it depends on the type of production" or depends on the formation. The preparation of azo pigments is carried out in such a way that the aqueous press cake of the polyacrylonitrile is in front. or after the coupling admits. In the case of pigments which, after the coupling reaction has ended, are formed by heating to temperatures of up to 100 ^° C. and / or above, the polyacrylonitrile can also be added before or after heating. The additional use of surface-active auxiliaries is not necessary here. The preparation is separated, as in the production of the pure pigment, by suction, washing and drying and subsequent grinding. Pigments, which are subjected to salt grinding for the purpose of distributing the powder, are prepared by adding water and the required polyacrylonitrile press cake as well as small amounts of surface-active auxiliaries and introduces the pigment-salt mixture with stirring. The salt extraction is expediently carried out at elevated temperature (60-80 ⁰ C). The preparation is worked up analogously to the azo pigment preparations described above.

In the case of naphthalenetetracarboxylic acid, dioxazine, quinacridone or phthalocyanine pigments, the preparation takes place also in the manufacturing or formation process, e.g. in the formation of the pigment grain or the desired Crystal modification by heating in aqueous or solvent-based systems or during the hydrolysis of Salts or salt-like addition compounds, as well as in the redissolution of the pigments.

In this way, preparations are obtained with contents of $ 20 to $ 80, preferably $ 40-70, pigment.

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The process is suitable for the preparation of inorganic and organic pigments, which are used in purely aqueous * Systems produced or "formed, for example azo pigments, perylenetetracarboxylic acid or haphthalenetetracarboxylic acid pigments, Dioxazines, phthalocyanines, quinacridones, indigoids, anthraquinone dyes, iron oxide and Titanium dioxide pigments.

The pulverulent preparations according to the invention are particularly suitable for dyeing polyacrylonitrile fibers and their modifications. You can simply stir in the respective spinning solvent, for example Dimethylformamide, dimethyl sulfoxide or dimethylacetamide, disperse, the pigment particle size in the suspension obtained being 0.02-2 µm. The advantage of this Process compared to already known methods is that the primary grain accumulating during production or formation of the pigment is protected and retained in the preparation, while the methods mentioned at the beginning The pigment agglomerates resulting from the isolation and drying are broken down again using complex methods Need to become. The pigment and the preparation are therefore produced in one operation without additional equipment.

In the following examples, parts mean parts by weight and percent means percent by weight.

Example 1

101.2 parts of 3.3 ^l -dichloro-4,4'-diamino-diphenyl are stirred with approx. 250 parts of water and 195 parts of hydrochloric acid (37% ) and mixed with 138 parts of sodium nitrite solution (40 %) diazotized at 0-10 ⁰ C. 240 parts of 2,5-dimethoxy-4-chloro

* or aqueous containing organic solvents

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acetoacetanilide are dissolved at 25 ⁰ C in 800 parts of water and 109 parts of sodium hydroxide j2 (33 $) and the solution with stirring at 5-14 ⁰ C to a mixture of 1000 parts of water, 684 parts of glacial acetic acid and 4 parts of a 20 moles of ethylene oxide allowed to run in oxethylated stearyl alcohol. In this suspension of the coupling component is slowly added the solution of the, diazotized 3,3'-dichloro-4,4 ^l -diamino-diphenyl and then 618 parts of an aqueous press cake (36.7 f <>) of polyacrylonitrile, as in the Production by the dispersion polymerization process is obtained (referred to in the following examples as PÄC press cake). The mixture is stirred for 1 hour at room temperature and heated to 85 ⁰ C. iTach 15 minutes of heating at 85 ⁰ C is filtered, the residue washed with water and dried at 6O ⁰ C. In this way, 567 parts of a yellow pigment preparation with 60 # pigment are obtained, which can be dispersed into the spinning solvent simply by stirring. By introducing the dispersion into the spinning mass and then shaping it into threads, brilliant stains which are fast to rubbing and are highly transparent are obtained.

Similar good products are obtained by using the PAC press cake prior to the precipitation of the coupling component in the mixture of water, glacial acetic acid and emulsifier or the same after precipitation to the suspension of 2,5-dimethoxy-4-chloroacetoacetanilide gives and carries out the coupling reaction.

Example 2

40.8 parts of 4-amino-benzamide are dissolved in 1,600 parts water and 88.5 parts of hydrochloric acid (37 ° i) and diazotized at 12 ⁰ C with 52 parts Uatriumnitritlösung (40 fo). 6 parts of glacial acetic acid, 13.6 parts, are added to the diazonium salt solution

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crystallized sodium acetate and 3 parts of a stearyl alcohol oxyethylated with 20 moles of ethylene oxide.

99 parts of 2-Oxy-naphthoic acid-o-phenetidid are / dissolved in 2800 parts of V ater and _73} 5 parts of sodium hydroxide (33 $) and at 13-15 ° C to the diazonium salt solution allowed to run. After completion of the coupling reaction, 272 parts of the residue are added a PAC press cake (36 F °), stirred for one hour "at room temperature and the suspension heated to 98 ⁰ O. After 1 to 2 hours of heating at 98 ⁰ C is filtered off, with Y / ater and dried at 60 ⁰ C. one obtained 240 parts of a 60 percent pigment containing preparation with excellent dispersing properties.

Example 3

50.4 parts of 5-nitro-2-amino-anisole are stirred with 1200 parts water and 118 parts of hydrochloric acid (37 #) and diazotized at 0-10 ⁰ C with 51.8 parts of sodium nitrite solution (40 $),

105.3 parts of 5- (2'-hydroxy-3-naphthoylamino) -benzimidazolone ater are dissolved in 500 parts V / by the addition of 109 parts of sodium hydroxide solution (33 ^), while stirring at 5 ⁰ C and the diazonium salt solution into a mixture of 2700 parts V / water, 146.4 parts of sodium hydroxide solution (33 ^), 90 parts of glacial acetic acid and 18 parts of a 10 $ aqueous emulsion of a concentrate of 25 parts of sodium alkylsulfoamidoacetate ^{obtained by halosulfochlorination of a hydrocarbon fraction with boiling limits 180-330 0} O and run in from 75 parts of mineral oil.

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After the coupling reaction has ended, the pH is adjusted to slightly acidic with dilute sodium hydroxide solution and the suspension is heated ^{to 130 ° C. in an autoclave for 3 to 4 hours.} After cooling to 8O ⁰ C 291 parts of a 37.5 $ strength PAC filter cake are added with stirring and stirred for 1 hour at 8O ⁰ C. It is suctioned off, the residue is washed with water and dried at 6O ⁰ C. There are obtained 280 parts of a 60 follow pigment preparation which can be dispersed by simple stirring into the spinning solvent "

Example 4

In a stirred vessel, 408 parts of a 36.7 $ strength are suspended PAC filter cake in 1600 parts of water and 3 parts of sodium naphthenate and with stirring 937 "5 parts of a ground in a rolling or vibrating mill mixture of 16 io perylene (3, 4,9,10) tetracarboxylic acid bis (3 ', 5'-dimethyl anilide) and 84 io sodium sulfate. It is then ^{heated to 80 °} C. and stirred for about 30 minutes. The batch is filtered through a suction filter and washed salt-free ^{with approx. 10,000 parts of water at 80 ° C.} The presscake is dried at 6O ⁰ C milled in a circulating air cabinet and on a pin mill. The powder obtained contains 50 % pigment and can be easily and completely dispersed in the respective spinning solvent by simply stirring in with a dissolver.

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Example 5

If one replaces the ground pigment-salt mixture moves in Example 4 by an appropriately milled with sodium sulfate of 4.4 -7.7 ^{I I} -Tetrachlorthioindigo ', and as in Example 4, we obtain a pigment preparation with equally good performance properties.

Example 6

160 parts of a 37.5 $ PAC press cake and 6 parts of a nonylphenol oxyethylated with 15 mol of ethylene oxide are stirred in about 3000 parts of water / water. 359 parts of the ethanol-moist potassium addition compound of 8,17-dioxobis-benzimidazo (2,1-b: 2 ·, 1'-i) benzo (lmn) - (3,8) -phenanthrpline (CI. Vat Orange 7, No. 71 105) with a pigment content of $ 39 are added to the suspension, the potassium addition compound hydrolyzing to the pigment. The pH is then adjusted to 8 with 5N HCl and the mixture is then ^{stirred at a temperature of 60 °} C. for about 30 minutes. The mixture is filtered to batch off on a suction, washed neutral and dried in a circulating air oven at 6O ⁰ C. By grinding in a pin mill obtains a pulverulent pigment preparation with a pigment content of 60 fo.

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Claims (1)

- ίο - Claims 1 * Process for the production of pigment preparations for the Coloring of polyacrylonitrile pure and mixed polymers, characterized in that during the production or Forming the pigments Pure polyacrylonitrile or mixed polymers as carrier material and optionally surface-active Additive is added and the pigments are worked up in the usual way. 2, use of pigment preparations prepared according to claim 1 for k spinning mass dyeing of polyacrylonitrile, or their modifications. 309RfSZIIS7