US2356079A - Animalizing of cellulosic materials - Google Patents

Description

Patented Aug. 15, 1944 UNITED STATES PATENT OFFICE ANIMALIZING F CELLULOSIC MATERIALS Johannes Nelles, Leverkusen-Schlebusch, Otto Bayer and Wilhelm Tischbein, Leverkusen -I.G.- Werk, and Fritz Baehren, Dormagen, Kasino, Germany, assignors, by mesne assignments, to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application March 29, 1940, Se-

rial No. 326,656. In Germany March- 31, 1939 6 Claims.

I fabrics can be prepared from cotton on the one hand and natural silk on the other hand or from cellulosic staple fibers on the one hand and linen on the other hand and the like. Such composite fabrics or threads are not capable of yielding tone in tone dyeings by means of acid wool dyestufis.

It is an object of this invention to do away with these disadvantages and to incorporate with these cellulosic materials a so called animalizing agent, which serves to improve the affinity of such cellulosic materials towards acid wool dyestuffs. Another object of our invention resides in the preparation of composite fabrics prepared from cellu losic materials on the one hand and wool or silk on the other hand which are capable of yielding tone in tone dyelngs by means of acid wool dyestuffs.

With these and other objects in view, our invention comprises the incorporation within cellulosic materials of certain polymeric products which for brevitys sake will be defined as polyureas or polyurethanes. These expressions are intended to define such high molecular synthetic polymeric products as contain recurring or NH.COO- groups'in the molecule. Such products'can be prepared by causing compounds containing several NCO groups to react upon compounds containing several amino groups having exchangeable hydrogen atoms or with compounds containing several hydroxy groups. Processes for preparing such products are disclosed in detail in application Ser. No. 239,456 to/Rinke, Schild and Siefken, filed November 8, 1938. As a matter offact, these polymeric products may also contain urea besides urethane groups in case there has been employed as starting'material a compound containing hydroxy groups besides amino groups or a mixture of polyamines and converted into cellulose threads, staple fibers, films and So on. Moreover, the incorporation within cellulosic materials of the said polymeric products can be effected by immersing yarns made from cotton or from regenerated cellulose within a solution of the animalizing agent. For the purpose of incorporating our animalizing agents within cellulose spinning solutions we prefer to convert the same into an aqueous ,suspension or emulsion, if desired, with the aid of solvents and/or emulsifying agents. Our animalizing agents are generally insoluble or difiicultly soluble in acids so that they are not materially dissolved out by the washing operations following the precipitation process.

In general, an amount of up to about 20% of our animalizing agents (calculated on the weight of cellulosic material) is sufficient to exhibit the desired result. We prefer to work with such polyureas or polyurethanes as have amino nitrogen atoms in addition to the nitrogens which are connected with the CO-groups. This applies in the first line to the polyurethanes. The content of amino nitrogen atoms of such products is preferably about 1 to about 5% by weight of the polymeric product, The presence of such amino nitrogen atoms brings about an increase of the animalizing efiect so that such products are generally emp'loyed'in an amount of about 3% to about 10% by weight (calculated on the weight of the cellulosic material). In order to prevent any inconvenience in the course of the spinning operations, the size of particles of the polymeric products must be chosen between about 0.1 and about 10 a.

' The preferred animalizing agents are the polyureas and among those such compounds as contain aromatic and/or cycloaliphatic radicals. Such compounds are generally capable of being pulverized so as to be converted into a finely distributed state. In this case as well as in the case of other polyureas and of polyurethanes the amino nitrogen atoms can be introduced into the molecule in various ways. One method of preparing such compounds consists in the start 1 'ing from the mixture of a minor proportion of polyhydroxy compounds. The said polymeric products are preferably incorporated within the spinnin solutions of cuprammonium or viscose cellulose, the said solutions being subsequently -a polyisocyanate and a preponderant amount of a polyamine. In accordance with another process we start from such amines as contain tertiary nitrogen atoms in addition to the primary or secondary ones.

A preferred species of our animalizing agents is represented by the products of the interaction of an aromatic diisocyanate or acycloaliphatic diisocyanat with at least one aliphatic pclyamine.

In the following there is given a list of diisocyanates and hydroxy or amino compounds which have proved to be suitable for the preparation of our animalizing agents:

. Diisocyanates Example 2 A polyurea is pr pared in the usual manner from 236 parts of 2.4'diphenylenediisocyanate, 96.7, parts of N.N.N"-trimethyldiethylenetriamine and 67.3 parts of N.N'.N.N-tetramethyltriethylenetetramine in the presence of chloroform. This product is emulsified in water as described in Example 1 and then incorporated within a cuprammonium cellulose solution. The resulting textiles yield even dyeings with acid wool dyestuffs regardless as to whether the said fibers are employed alone or in admixture with Polyhydroxy compounds including those containing tertiary nitrogen atoms:

Di- (fl-hydroxylethyl) -alkylamines 1.4-butyleneglycol As examples for compounds containing hydroxy groups besides amino groups there may be mentioned ethanolamine and higher homologues thereof.

The following acid wool dyestuffs have been employed in the examples unless otherwise stated:

(a) Chromium complexes of the azo dyestuff from diazotized 1.2.4-aminonaphthol sulfonic acid and 1.8-naphtholsulfonic acid,

(b) Chromium complexes of the azo dyestufl from diazotized 6 -nitro-2-aminophenol-i-sulfonic acid and 2.4-dihydroxyquinoline;

(c) The azo dyestuffs from diazotized aniline (or homologues thereof) and the product of the condensation of 2-naphthol-6-sulfonic acid chloride with l.8-amidonaphthol-4.6-disulfonic acid.

(d) The azo dyestuff prepared fromdiazotized a-aminodiphenylsulfone and 2.8-6-amidonaphtholsulfonic acid.

((2) Products of the interaction of 1-amino-4- bromoanthraquinone-2-sulfonic acid and aromatic amines.

(j) Azodyestuifs from diazotized aminobenzoyl- 'ethyl-a-naphthylamine and lebenzoylamino-iinaphthol-4.6-disulfonic acid;

(g) S'ulfonic acids of the products of the condensation of 2-methyl-3-hydroxyquinoline-4- carboxylic acid with phthalic acid.

The following examples illustrate the invention without, however, limiting it thereto, the parts being by weight.

Example 1 A polyurethane which has been prepared from 1.6-hexamethylenediisocyanate and di-(fi-hydroxyethyl) -butylamine is dissolved in cyclohexanone. The solution is emulsified in water with the aid of a product of the condensation of oleylalcohol and ethyleneoxide. This emulsion is incorporated within a cuprammonium cellulose wool.

Example 3 A polymeric product containing urea groups besides urethane groups is prepared in the usual manner from 236 parts of 2.4'-diphenylenediisocyanate, 48.3 parts of N.N'.N"-trimethyldiethylenetriamine, 33.7 parts of N.N'.N.N'-tetramethyltriethylenetetramine and 201 parts of a compound of the following formula in the presence of pyridine. The resulting product can easily be pulverized and is soluble in a dilute caustic soda but insoluble in dilute acid.

An alkaline solution of the said polymeric product is incorporated in an amount of about 8% (calculated upon the cellulose) within a cuprammonium or a viscose cellulose solution. The threads are spun therefrom in the usual manner. They are capable of being dyed by acid wool dyestuffs, the dyeings being distinguished by excellent fastness properties.

Example 4 236 parts of 2.4-diphenylenediisocyanate are caused to react upon 45.5 parts of triethylenetetramine and 97.5 parts of N.N.N".N"-tetramethyltriethylenetetramine in the presence of pyridine. The resulting product which is not capable of beingmolten or of being dissolved is converted into an aqueous suspension, the size of particles of which is about 1-5 a. This suspension is incorporated within a cuprammonium cellulose solution so as to contain 10% of the polyurea (calculated upon the cellulose). The threads or fibers which are obtainable therefrom are capable of being directly dyed by means of various kinds of acid wool dyestuffs, the dyeings showing excellent fastness properties.

Example 5 168 parts of l.6-hexamethylenediisocyanate are caused to react upon 77.4 parts of 1.6-hexamethylenediamine and 134.1 parts of dl-(y-hydroxypropyl) -1.5- naphthalenedisulfamide. The resulting product which contains urea groups besides urethane groups is incorporated in form of an. alkaline solution within a viscose cellulose solution in an amount of about 10% (calculated upon the cellulose). The resulting fibers (either silk or staple fibers) show an affinity towards acid wool dyestuffs resembling to that of wool itself.

Example 6 A pclyurea is prepared from 70.8 parts of 2.4-

diphenylenediisocyanate, 10;.4 parts of hexamethylenediamine and 30.4 parts or M-diaminopropylmethylamine in the presence of xylol. The resulting polyurea is finely distributed in water and then incorporated within a viscose cellulose or a cuprammonium cellulose spinning solution, the amount of the polyurea being about 6-7% (calculated upon the cellulose). The fibers which are obtainable therefrom yield excellent tone in tone dyeings with acid wool dyestuffs even in the case of mixed fibers with wool.

Example 7 70.8 parts of diphenylenediisocyanate are caused to react upon 44.9 parts of p.p'-di-(hydroxyethyl) -cyclohexylamine and 5.4 parts of 1.4- butyleneglycol in the presence of xylol. Cotton is immersed in a proportion of 1:20 in a percent solution of the resulting product in methylformamlde at 40-50 for 1 hour. After drying the resulting cotton is capable of being dyed (either alone or in admixture with wool) with various acid wool dyestuffs.

Example 8 Example 9 A polyurea is prepared in the manner described in Example 7 from 100 parts of p-cyclohexylenediisocyanate and 61.3 parts 01' p-cyclohexylenediamine. A cellulose spinning solution containing 10% of this polyurea yields fibers and threads of an excellent afiinity towards acid wool dyestuffs.

We claim:

1. Cellulose fibers having increased aflinity to acid wool dyestuifs and having deposited therein a synthetic polymer obtained by reacting an arcmatic diisocyanate and a mixture comprising N.N'.N"-trimethyldiethylenetrlamine and said synthetic polymer containing amino nitro gen atoms in addition to those connected to the 00 groups of the polymer in an amount of about one to about five percent by weight of the polymeric product.

2. Cellulose fibers having increased aflinity to "acid wool dyestuffs and having deposited therein a synthetic polymer obtained by reacting an aromatic diisocyanate and a mixture comprising N.N.N"-trimethyldiethylenetriamine, N. N N '.N' tetramethyltriethylenetetramine and N.N' di- (y-hydroxypropyl) -1.5-naphtha1enedisulfamide, said synthetic polymer containing amino nitrogen atoms in addition to those connected to the CO groups of the polymer in an amount of about one to about five per cent by weight of the polymeric product.

3. Cellulose fibers having increased aflinity to acid wool dyestuffs and having deposited therein a synthetic polymer obtained by reacting a diphenylene diisocyanate and a mixture comprising N.N.N -trimethyldiethylenetrlamine and N.N'.N".N"' tetramethyltriethylenetetramine, said synthetic polymer containing amino nitroen atoms in addition to those connected to the CO groups of the polymer in an amount of about one to about five percent by weight of the polymeric product.

4. Cellulose fibers having increased afiinity to acid wool dyestuffs and having deposited therein a ,synthetic polymer obtained by reacting a diphenylene diisocyanate and a mixture comprising N.N' .N' -trimethyldiethylenetriamine, N N .N".N"' tetramethyltriethylenetetramine' and N.N' di- -hydroxypropyl) -1.5-naphthalenedisulfamide, said synthetic polymer containing amino nitrogen atoms in addition to those connected to the CO groups of the polymer in an amount of about one to about five percent by weight of the polymeric product.

5. The products defined in claim 1, wherein the polymer is present in an amount of between about N.N'.N".N" tetramethyltriethylenetetramine,

3 and about 10% by weight calculated with respect to the weight of the cellulose material.

6. The products as defined in claim 1, wherein the polymer has a particle size ranging between about 0.1 to about 10 JOHANNES NELLES. OTTO BAYER. WILHELM 'I'ISCHBEIN. FRITZ BAEHREN.