DE554781C - Process for the production of cellulose derivatives - Google Patents

Description

Process for the production of cellulose derivatives It has been found that brought into reactive form C ellulose, such as. B. pretreated with alkalis Cellulose, with those heterocyclic compounds which contain one or more C halogen groups included, such as B. Cvanur chloride, C_vanurbromid or other compounds of the triazine series, with at least one mobile halogen atom, dichloroquinazoline, dichlorophthalazine, Dichloromalein acid hydrazide. Tribrompy rimidine etc. can react with formation new cellulose derivatives, which in many cases are replaced by valuable dyeing agents Characteristics can distinguish. These new products may still be interchangeable Contain halogen atoms and are therefore reacted with compounds that at least one replaceable hydrogen bonded to nitrogen, oxygen or sulfur or contain metal atom.

The treatment of cellulose with alkalis can be in aqueous, more expedient take place in an alcoholic medium. -Get after this latter way of working after treatment with the heterocyclic halocene compound, products which, although there was a relatively small increase in weight, compared to direct Cotton dyes, vat and sulfur dyes are largely immunized and, on the other hand, show strong affinity for basic dyes. Opposite with haloids Celluloses immunized with stronger acids, the new products have the advantage of maintain their strength even after long periods of storage. Besides, those are so treated Textiles resistant to the saponifying effect of alkalis. In this regard they differ further advantageously from those immunized by acidylation Celluloses. If the products are then reacted with amines, it disappears the affinity for the basic dyes, and products are obtained which are can be characterized by a pronounced affinity for acidic dyes; the Immunity to direct, vat and sulfur dyes remains, however.

The procedure is suitable for both natural and regenerated Cellulose: this can also be mixed with suitable dyes,% vie z. B. vat dyes or alkali-proof nouns dyes, without being colored by the described Treatment a significant change in color takes place.

The following examples explain embodiments of the new process, whereby Quantities and concentration within wide limits can be varied. .

Example r The cotton is impregnated in 10% alcoholic caustic potash solution and the excess lye is removed by pressing or spinning. This will to .4o ° treated in a 3- to 4 ° 1oigen solution of cyanuric chloride in xylene for '/., Up to 2 hours at 25 in the presence of powdered chalk. After the reaction has ended, the system is rinsed warm, washed in water containing hydrochloric acid and rinsed again with warm water. Washing with water containing hydrochloric acid is unnecessary if a little dimethylaniline is added to the Xvlol instead of chalk powder as a weak neutralizing agent. The cellulose derivative obtained in this way is immune to substantive vat and acid dyes; however, it can be colored with basic dyes. Boiling with water does not change the coloring properties of the new product.

Is a cotton fabric with effect threads from the so available Yarn with vat dyes, e.g. B. Cibanonbroun GR, colored, the effect threads remain White. If you have the effect threads with a vat dye before the treatment with cyanuric chloride, like Cibanon blue RS, Cibav iolett B or Cibanon yellow G, colored, so you get blue, purple or yellow effects on a brown background.

Effects can also be achieved with other dyes. Has one z. B. the effect threads before treatment with cyanuric chloride with substantive dyes, like cotton yellow CH or direct real scarlet SE, dyed and then dyed the finished Cotton fabric with chlorine light blue 4GL, so you get red and yellow effects on a blue background. Example e The cotton is impregnated in 100% alcoholic Potash lye and squeezes out or flings. The goods are then heated in a solution of cyanuric bromide in xylene, corresponding to 5 parts of cyanuric bromide for 10 parts of cotton, in the presence of chalk powder for 1/2 to 2 hours at 7o to 8o °. One rinses as indicated in example i and receives a similar product.

Example 3 Artificial silk (for example viscose) is impregnated in 100% alcoholic potassium hydroxide solution, removes the. Excess of the latter by pressing or spin and treated in a solution of z to 5 parts of cyanuric chloride (on 10 parts cellulose) in 15o to 25o parts of xylene at ordinary temperature during 2 to 3 hours in the presence of a little chalk flour. This is how in example i flushed. A similar product is obtained.

Example q.

The cotton is impregnated in 10% alcoholic potassium hydroxide solution and squeezes or flings. The goods are then treated in a boiling manner Solution of dichloromaleic hydrazide in xylene, in the presence of some chalk powder, for 1 to 2 hours. Washing is carried out as in Example i and a similar product is obtained.

Example 5 The cotton is impregnated in 100% alcoholic strength Lye and squeezes out or spins. The goods pretreated in this way are then in a Solution of dichloroquinazoline in xylene heated to a gentle boil, Treated until the fiber is uniformly immune to direct dyes is. - Washing is carried out as in example i and a similar product is obtained.

Example 6 Bleached or unbleached cotton is impregnated in 15% potassium hydroxide solution, prepared by dissolving potassium hydroxide in a mixture from 2 parts of water and 1 part of alcohol. After pressing off the excess lye the material is treated in a solution of 5 parts of cyanuric chloride (to 10 parts Cotton), with frequent moving or changing, in order to achieve more even Exposure for 112 hours at room temperature. Some chalk flour can are expediently added. After rinsing in a little acetone (to remove excess Remove cyanuric chloride) and cold water, the yarn is immediately in an aqueous Solution of diethylethylenediamine aftertreated by keeping it at ordinary temperature Left in it for 12 to 24 hours. After rinsing and drying it becomes a cellulose derivative obtained which, in contrast to the product of example i, no longer has an affinity to the basic dyes, on the other hand dye with acidic wool dyes leaves. A similar result is obtained with ethylenediamine.

Example j One impregnates mercerized or non-mercerized Cotton in 15% aqueous sodium hydroxide solution and treated afterwards to the Pressing in a solution of cyanuric chloride in Zvlol at o to -io ° during i to z hours. After a short rinse in cold water, the aftertreatment is carried out in aqueous water Solution of piperazine. The properties of the product obtained are those of the product of Example 6 is similar.

Example S io parts of cotton are made according to the information in the example 6 treated with potassium hydroxide solution. After pressing is in a solution, which 5 to io parts of cyanuric chloride in zoo parts contains carbon tetrachloride, registered, the temperature rising to 6o to 65 °. After about 2 hours it will be 20 parts Aniline was added and left to stand for 2.4 hours. This is followed by rinsing and drying. A cellulose yarn is obtained whose affinity for the basic dyes is weaker is available as the yarns according to Example 1, 2, 4 or 5. In contrast, it has noticeable Affinity for acidic dyes.

The same effect can be achieved in the following way: io parts Cvanur chloride are dissolved in acetone and then in a mixture of ice and water and 10 parts of aniline. After brief stirring, the powdery reaction product, which from the secondary condensation product of i Mo1 cyanuric chloride and i mol Aniline is made up, suction filtered, washed with water and dried. One then resolves it in 20o to 300 parts -XvIol and add alkali cellulose to this solution, which in turn from 10 parts of cellulose either by treatment with 10% alcoholic potassium hydroxide solution or with 100% aqueous sodium hydroxide solution or with a mixture of 1 part 33 ° joiger 'Sodium hydroxide solution, 1 part alcohol and 1 / _ part water has been produced. One heats up 2 hours on 6o to Sun °, rinses and dries.

Example If the cellulose derivative produced according to example i or 2 is used After-treatment with an aqueous solution of sodium sulfate, the There is an affinity for basic dyes and immunity to cotton dyes obtain.

EXAMPLE 10 50 parts of linters are impregnated in 1/2% sodium hydroxide solution, the excess alkali is pressed off and this alkali cellulose is introduced into a solution of 30 to 50 parts of vanuric chloride in 1,000 parts of carbon tetrachloride at 25 to 30 °; the temperature rises fairly rapidly to 60 to 650. After two hours the product is suction filtered, washed and dried. The same treatment is repeated twice more. After the third treatment there was only a very slight increase in weight. The product is pure white and has gained 100 per cent in weight. It contains 11.7 per cent nitrogen and 4.5 per cent chlorine; compared to untreated cellulose, it no longer swells in the Ouellungs- and solvents customary for cellulose, such as conc. Salt solutions, copper oxide ammonia, etc. It does not reduce Fehling's solution, so it represents an undegraded cyanuric cellulose. With regard to dyes, it behaves analogously to the cellulose etherified with cyanuric chloride according to the previous examples.

Instead of linters, of course, all types of cellulose can be used also regenerated cellulose, hydro-, oxycellulose, etc.

Claims (1)

PATENT CLAIM: Process for the production of cellulose derivatives, characterized in that alkali cellulose is condensed with those heterocyclic compounds which contain one or more contain gene groups, whereupon the condensation product is optionally reacted with compounds which contain at least one replaceable hydrogen or metal atom bonded to nitrogen, oxygen or sulfur.