DE2038410A1 - High molecular weight dye condensation products - Google Patents

Description

VEB CHEMIEKOHBIMT BIITBBFELD Bitterfeld, April 30, 1970

4 * 04 * 20/1504

Inventor: Prof. Dr _# Dr, h, c. Friedrich Wolf, Leipzig Dr. Gerhard Wolterj Wolfen Dipl.-Chem. Fritz Kleine, Leipzig

High molecular dye condensation products

The invention relates to new condensation products from organic Dyes and condensable synthetic resins or their preliminary products as well as a process for the production of the high molecular weight dye condensation products

Products made from organic dyes and synthetic resins are known based on formaldehyde-urea or melamine · There are also products made from organic dyes and polymers Plastics such as alkyd resins, polyvinyl chloride or polymeric ethaoryl acid esters, known · Auoh are already Adsorption products of ionic dyes on pocjr-n Exchangeable heart resins have been described

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All known compounds have the disadvantage that the used Dyes only in dissolved form or as adsorbates present on the surface of the obtained ifod products * Solohe Compounds are therefore found in many paints and plastics only an insufficient migration coherence, what under attributable to the lack of covalent bonds between the dye and the high molecular weight carrier is·

The object of the invention is to eliminate the deficiencies mentioned with the aim of dye condensation products develop which have covalent bonds between the dyes and the polymeric carrier and are sufficient Show migration fastness

The disadvantages mentioned are eliminated, and the stated The aim is achieved by the invention

The new high molecular weight dye condensation products according to the invention are polycondensates based on ketones ^ Formaldehyde and organic dyes with condensable groups · The ones in these polycondensates The dyes contained can belong to different classes The following dyes can advantageously be used:

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Azo dyes, phthalocyanine dyes, azine dyes, Thiazine dyes, oxazine dyes, xanthene dyes, Acridine dyes, triphenylmethane dyes, stilbene dyes} anthraquinone dyes.

They can be used individually or in a mixture with one another. Depending on the scope of disposal and the possible combinations, the selection j is made

of the dyes from the different classes when using mixtures according to the resistance to temperature and light.

For the production of the polycondensates according to the invention, use is made of organic dyes that contain iodine or Have bromine or groups capable of condensation from the series of unsubstituted or substituted amines, unsubstituted or substituted Carboxamides or sulfonic acid amides or carboxylic acid ' hydrazide, the carboxylic acids or their esters with alcohols, the formami dins, the hydrazino verb! ndungen or dear Mercaptans. The dyes must therefore contain the following groupings, where E is any substituent and E ^ mean any hydrocarbon radical: -Ij - Brj -MH ₂ J -HHE; -COIIH ₂ J

- CONHEj - SO ₂ NH ₂ J - SO ₂ NHEj - CONHNH ₂ J

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- OQHHNEH; - COOH; - COOE ₁ ; - C 1 _H ;

- MHlTH ₂ J - SH.

Substances with other groupings can be used if these groups are capable of condensation. Azo dyes which, in ortho position to the azo group, are hydroxy, Have amino or carboxy groups, can optionally also before the condensation reaction is carried out ~ duroh treatment with cobalt: or compounds that donate odor are converted into metal complex dyes.

The new dye condensation products are polycondensates of various molecular sizes with a molecular weight above about 3,000. They represent fine powders with a particle size of about 0.002 mm to 0.15 mm. * ■ '■ ..

fe One can produce condensates in water and the most organic solvents are insoluble; san but can also produce condensates that have a certain solubility in organic solvents, in particular in cyclohexanone, in glycols, in caprolaotam and preferably in dimethyl sulfoxide and dimethylformamide. This results in a wide range of applications for the dye condensation products according to the invention. Among other things, they can be used as

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Pigments can be used, or the Γslets are placed P oducts to the spinning masses for synthetic fibers, as a result of which completely wet-fast and through-dyed fibers are obtained.

As pigments, the condensates for "coloring plastics, such as polystyrene, polyethylene, polyvinyl chloride or rubber, suitable · »Vegen the pure, luminous shades recommends using it for printing, in particular for illustration print or poster print, and in luminous luminescent colors

The dye condensation products according to the invention are prepared by reacting the abovementioned ones organic dyes with the polymers of ketones and formaldehyde at a stage in which these polymers are still sufficiently condensable. By choosing the time of condensation I the dye with the preformed synthetic resin can be used to determine the physical properties of the end product targeted control · The lower the fondness level of the The synthetic resin, the higher the degree of solubility becomes the end products in organic reading center "

As a result, the condensation of the dye with the Synthetic resin carried out when this ") nor" h is liquid "

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The point in time of the condensation of the coloring matter with the synthetic resin can be _{shifted so far forward 9} that the reaction is practically carried out as a one-step process to the beginning by combining all reaction components, i.e. ketone, formaldehyde and coloring matter, the polycondensation using the known condensation agents setsst in Sang * Preferably the condensation is carried using alkalisohen won agents or thermally "Especially the latter working method duroh polycondensation from the beginning Parbstoffkondensationsprodukt © be obtained which have good solubility in organic solvents QibeageMiraten ''

Suitable ketones are all those which give solid polycondensates with formaldehyde, such as aoetone ₉ M @ th.yl ~ ethyl ketone, methyl propyl ketone, ethyl ketone, bipropyl ketone, cyclohexanone, lethyloyclohexanone or mixtures thereof p-cresol, to be replaced

TUR the Surohführung polycondensation of Parb- is ■ used toff in dissolved form _¥ unless he nioht in a de; solves another reection pariner. The choice of solvent is based on the losui-xgr.premogen for the dye and the compatibility of the

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with the other Heakt'on partners. The dyes go with covalent bonds η das (Sesamtm lectile of the inventive polycondensation products.

The production process for the novel polycondensation products according to the invention is explained below using a few examples, without the invention Beiepi Ie su limit. |

example 1

Place 100 al 15% sodium hydroxide solution in a flask at 98 ⁰ ° C. 60 al of an 80 Higen acetone / formaldehyde condensate are added dropwise with vigorous stirring (in a ratio of alcohol to aldehyde of the above: 2 to 1: 4) , in the 2 g of bhodamine 6 GM are dissolved. The mixture is then stirred at the same temperature or the like. 30 minutes and then let to cool to 40 to 50 ⁰ C. It is suctioned off and washed with water to naoh sub i are colorless.

The filter cake is then dispersed in 200 μl of water and sown with a dilute acidic or acidic acid pH 5 to 2 adjusted. A bright red xondensate of particles 0.12 mm in diameter is obtained. Duron, the above-mentioned pH-Hertz correction, one achieves a blue-thou-blue and clearer parbon tone. laoh appropriate form

BATH

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The pigment colors the PVC and polyethylene immigration-resistant cement that has been retained in a bright blue-tinged red.

Beiepitl 2

If you proceed according to Example 1 and use the dye Aniline, coupled to carbamide / nomethylpyrasolone, eo one obtains a similar condensate, which after forming for Figment in PVC and polyethylene migratlonsfeste luminous greenish yellow tones "

Example 3

The procedure is as in Example 1, but using a mixture of Bhodamine 6 GDK and the dye from Example 2, we get 3e naoh. Mixing ratio of dyeings νου yellow over orange and soharlaoh to red »

Example 4

14 g of the dye it from Example 2 are dissolved in 170 ml of acetone and then diluted with 430 ml of 30 ml formalin. This solution is left in .160 ml of 5 # sodium hydroxide solution in this way; enter that with vigorous stirring under Rüokfluß di · temperature not exceeding 70 ⁰ C increases · Lan "can naohrt Nooh oa x 10 hours» crave, then sucks in SO! ⁰ C, wäeoht neutral to sum colorless and

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adjusts to pH 5 to 2 with dilute hydrochloric or acetic acid.

A yellow powder with a particle diameter of approx. 0.006 mm is obtained. This powder colors after formation PVG, polyethylene and rubber greenish yellow * Dissolves on the other hand, if it is in dimethylformamide and this solution is added to a polyacrylonitrile spinning mass, one obtains migration and wet fast greenish yellow colored PAN fibers

Example 5

If you proceed according to Example 4 using a 1: 2 misoh complex with chromium from the "two dyes 4 | 6-dinitro-2-aminophenol, coupled to 2-ifaphthol-6-sulfamide, and 4-nitro-2-arenophenol, coupled on 1-phenyl-3-methylpyrazolone (-5) -4'-sulfa- A inide as dyes, the result is a brown powder which gives plastics a reddish brown color and, in polyaorylnitrile fibers, gives strong brown colorations with excellent migration and wet smoothness.

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Claims (4)

- 10 - 4 «04.20 / 1504 ff a , t ,, e,., 4., - fr a ,,,, ft, s, Pr ₁₁ ft ο, ft, $, - 1 · High molecular weight dye condensation products from Polycondensates based on ketones, formaldehyde and organic dyes with condensable properties Groupings, 2. High molecular dye compensation products according to claim 1, characterized in ₉ that the organ! - see dyes azo dyes, hithalogyazine dyes, azine dyes, egg azine dyes $ oxazine? » dyes, xantfree dyes, aoride dyes, triphenylmetal dyes ₉ stilbene dyes, anthraconone dyes or emieeh © of these are " 3 · High molecular weight dye condensation products according to claim 1 and 2, characterized in that the organic dyes iodine or * bromine or; Groups capable of condensation have from the series "unsubstituted or substituted amines," unsubstituted or substituted, carbonic acid amides or sulfonic acid amides, hydrazides, carbonic acids or their%. #nsL _: iait alcohols ^ of the fonaamidine, the .gen or the mercaptans. - 11 - 4.04.20 / 1504 4. High molecular weight dye condensation products after Claim 1 to 3, characterized in that the ketones acetone, methyl ethyl ketone, methyl propyl ketone, Diethyl ketone, Dipropylketcn, cyclohexanone, methylcyclohexanone or mixtures with one another or with Bienoles are,. 5 »Process for the production of high molecular weight color. Substance condensation products, characterized that organic dyes which have condensable groups are polycondensed with ketones and formaldehyde or their liquid condensation products. 6 · The method of claim 5, characterized in _t DAB as organic dyes azo dyes, ShthaloEyaninfarbstoff ©, azine dyes, Thiazinfarbetof- | fe, oxazine dyes, xanthene dyes, aoridine dyes, triphenylmethane dyes, stilbene dyes, Anthraquinone dyes or mixtures thereof are used 7. Process according to claims 5 and 6, characterized in that organic dyes are used which contain death or bromine or groups capable of condensation 109846/1584 . ORIGINAL INSPECTSO - -12 - 4.04 20/1504 It is composed of the unsubstituted or substituted amines, the unsubstituted or unsubstituted substituted carboxamides or sulfonamides or carboxylic acid hydrazides, the carboxylic acids or their esters with alcohols, formamidine, hydrazino compounds or the mercaptans. 8 · Method according to Claim 5 »characterized by that as ketones acetone, methyl ethyl ketone, methyl propyl ketone, Diethyl ketone, dipropyl ketone, cyclohexanone, Methy! Cyclohexanone or mixtures with one another or used with phenols P / H 109846/1584