US2263730A - Method for improving textile material - Google Patents

Description

Patented a... 1941 METHOD FOR IMPROVING TEXTILE Winlrid Hentrlch, Dusseldori-Reisholr, Richard Hueter, Dessau-Rosslau-in-Anhalt, and Heinl- Joachim Engelbrecht, Dessau-in-Anhalt, Germany, assignors, by mesne assignments, to. Heberlcin Patent Corporation, New York, N. Y., a corporation or New York No Drawing. Application February 19, 1938, Se-

rial No. 191,494. 193'! 9 Claims.

. higher molecular alkyl groups. The impregnations obtained in this way are fast to a slight washing with soap as well as to the action of fat-solvents such as benzine or the like.

Now it has been found that analogous effects are obtainable in a very easy and advantageous manner by impregnating the textile material with a carbodiimide compound containing at least one higher molecular aliphatic radical having no less than 10 carbon atoms.

The substances found-valuable are carbodiimide compounds containing at least one higher molecular aliphatic radical having no less than 10 carbon atoms. The carbodiimide radical may be combined directly or through any suitable atoms or atomic groups with one or several higher molecular alkyl radicals.

It is of course not necessary that the alkyl radical be of a homogeneous nature. The alkyl radical will vary according to the nature of the of a diiferent chain-length. The chain length varies according to the initial'applied material.

Compared with the substances hitherto suggested and particularly with the esters of isocyanic acid and isothiocyanic. acid the diphenyl-carbodi-imides oiler-the advantage of being easily accessible. For instance it would be sufllcient to treat with carbon disulflde and an aniline which may be alkylated in the nucleus ("alkyP containing no less than 10 C atoms) and to separate hydrogen sulfide fromthe reaction product according to the well-known Unsymmetrical mono-substituted dial'Yl-varbodi imides are obtainable in the same way fromthe unsymmetrical thio-carbamides. The unsymmetrical thio-carbamides are produced according to the well-known method by the reaction of phenyl-mustard oil upon alkyl-substituted anianiline and obtained according to the method of Germany February 19,

lines or the like. The course of reaction is quite smooth. In a similar way the phenyl-carbodiimides are developed from phenyl-isocyanic acid esters by heating to higher temperatures. 'The action of the substances will not be impaired if the higher molecular alkyl residue is not substituted directly in the nucleus as itmay be bound indirectly, to the phenyl nucleus by means of another atom or another atom grouping. As an example from carbon disulflde and alkyl-ethers of the amide-phenols, which after the de-sulfurization with lead-carbonate result as high molecular alkoxyl-phenyl-carbodi-imides'. .Those substances are applied preferably in indifferent solvents such the like. a

In the further development of this invention it has also been found that the effect produced by diaryl-carbodi-imide derivatives, can likewise be obtained with difiereritly substituted carbodiimides, provided theycontain at least one alkylresidue with no less than 10 C atoms. Thus for example, aryl-alkyl-carbodiimides. are produced with one or several alkyl-substituents containing no less than 10 C atoms, which alkyl substituents may bebound on the aromatic nucleus as well as i on the not otherwise substituted nitrogen atom. The higher molecular dialkyl-carbodiimides are also useful in the same above described sense. Derivatives of cyanamide may be designated by the formula HN=C=N.R, where R contains an alkyl residue of not lessthan ten carbon atoms. These substancesmay also be employed in our process as they are in fact carbodiimide derivatlves.

The preparation of said substances is performed by well known methods. that is, by de- 4 sulfurization of the corresponding thio-carbamides with lead-oxide. lead-carbonate or mercuric oxide. The reaction follows in most cases in a practically quantitative yield. Only the mere aliphatic thio-carbamides offer some difflculties in the de-sulfurizing according to this method, as a substitution of the sulfur atonr by oxygen often takes place,- so that carbamide-de- Y rivatives are simultaneously developed, The

carbodiimides' are applicable either after'separating those indifierent by-products or mixed with such accompanying bodies.

Example 1 1.4 kgs. of cetyl-aniline (containing octadecy'lthere may-be cited the substances obtainable as benzol, benzine, chlorinated hydrocarbons or the treatment of textiles with high molecular mother-solution.

, til the development of hydrogen-sulfide ceases completely. While still warm the cetyl-phenyl-B thio-carbamide forms crystals of the lamellar shape. After sucking off the liquid and drying the crystals 6 kgs. of toluol are brought in without previously cleaning the crystals. In order to convert into the di-(cetyl-phenyl) carbodiimide 1.4 kgs. of lead-carbonate are brought into the toluol-solution at 100 C. while being stirred. The stirring is continued at this temperature until a sample filtered ofi results after evaporating as awax-like residue solid at roomtemperature and free of sulfur. Then by filtration the leaf-sulfide is separated oil. The thus obtained solution can be applied directly as For impregnating-purposes it is diluted with benzol, benzine or the like up, to A2 to 1%.

With a solution diluted in the aforesaid manner light fibers are treated at room-temperature for approximatelylO minutes, and heavy fibers up to half an hour. Then they are squeezed out and dried at 80-100 C., whereupon one continues heating for 1 to 2 hours at 110125 C.

Fibers of artificial silk get particularly water- Example 2 1.2 kgs. of hexa-decyl-p-amidophenol ether, 4.5 kgs. of carbonic disulfide and 0.015 kg. of sulfurpowder are heated to a slight boiling until the development of hydrogen-sulfide ceases completely. After cooling one sucks off the remaining liquid and the deposit is washed out with spirit. 'The thus resulting hexa-decoxy-phenylthio-carbamide (boiling point 139.5 C.) in the form of colourless lamellar crystals is dissolved without further purification in 5 kgs. of toluol, and treated with an excessof lead-carbonate (1 kg.) at about 100 C. while being stirred for 30 to 40 minutes. The thus formed lead-sulfide is filtered off. The approximately 18-20% solution if evaporated leaves, at room temperature, a solid waxlike substance.- Instead of evaporating it may be diluted for use with benzine or benzol to the desired-proportion for use.

, 0.25% of fatty acid, no diminution of those properties could be observed. Mixed fibers consisting of wool and cotton and treated in the same way became likewise strongly water-repellent. This impregnation also proved fast to washing with benzine.

' Example 3 A mixture of 0.67 kg. of phenyl-mustardoil and 1.6 kgs. of cetyl-p-amido-phenyl ether is dissolved in 6 kgs. of benzohand kept boiling under a reflux condenser for 2 hours. Then with mechanical stirring it is treated with lead-carbonate (about 2.8 kgs.) until a sample filtered off leaves hexadecoxy-allyl-thiocarbamide a residue free of sulfur, whereupon the mixture is filtered.

The effects obtained with a dilution of the filtrate containing 1% of solid substance, in treating viscose-silk, cotton materials or woolen-fibers are, after drying and subsequent treatment at a temperature up to 120 C., in exact accordance with those described in Example 2.

Example 4 To produce a dilauryl-carbodiimide suitable for the purpose of the present invention we avail ourselves of monolauryl-amine (technical. boiling point 0.8 mm. :96.5 to 97.5 C.). By treatment with carbon disulfide it changes over into lauryl-dithio-carbamide-acid lauryl-amine, which when heated up to 1l0-120 C. forms di-laurylthio-carbamide (boiling point, after re-crystallization from alcohol, 80.5"). This is now converted into dilauryl-carbodiimide by further treatment with an excess of ten times the weight of mercuric oxide at a temperature of -120" C. The isolation of the carbodiimide (yellowish oil slowly solidifying when kept at room temperature) is obtained by dissolving it in cold benzol from the reaction-mixture. For the impregnation we takea 0.5-1%-solution in benzol. The material is. agitated in this solution for 10 minutes at 20-30 C., whereupon it is centrifuged and dried. By heating the material for 1 hour up to 110-120 the fixation of the impregnation will occur. This impregnation imparts to woolen cloths, mixed fibers and artificial silk materials the property of water-repelling to asurprisingly high degree. This impregnation proved fast to a. mild soap-washing as well as to benzine-washing.

Example 5 A mixture of 2' kgs. of hexadecyl-p-amidophenol ether, 1 kg. of allyl-mustard -oil and 4 kgs. of toluol are heated to 100 C. for 5 hours, whereupon the solvent is removed by distilling. After cooling the residue is stirred with ether and the liquid sucked off. The thus resulting (boiling point 965) in the form of light powder is treated in 5 kgs. of toluol with an excess of lead-carbonate under vigorous stirring and at a temperature of approximately 100 C. The thus formed leadsuliide is filtered off and the solution is applicable for the impregnation after dilution to the desired degree.

Artificial silk-satin, treated for 10 minutes with a 1% solution diluted with benzine and then dried for 2 hours at temperatures gradually rising to C., is of a soft handle. At the-same time this impregnation eliminates the water absorptive power. Thoseeifects could not be reduced even by washing several times in a'0.5%-solution of soap-flakes. The water repellant property remained after a washing with benzine.

Example 1 kg. of hexadecoxy-pphenyl-Inustard oil is 120-130 with vigorous stirring of '7 kgs. of

soluble in organic solvents like mass (mono-hexa-decoxy-p-phenyl-carbodiimide or hexa-decoxy-pphenyl-cyanamide). The product is suitable for impregnating wool,

cotton, mixed tissues and the like to render them water repellent. An artificial silk-satin impregnated for minutes with a 0.5-l%-solution in benzol and subsequently treated (as per Example 2) has a very remarkable water-repelling power which is fast to washing. In a similar way materia s of wool or mixed fibers can be impregnated to become water-repellent.

amide (boiling point 78 0.), is produced by converting octadecyl-amine with an equi-molecular amount of chloro-acetyl-chloride in the presence of pyridine, and 0.2 kg. of the mo'no-sodium-salt of cyanamide, .such mixture is heated up to dibutyl ether and a small amount of copper-bronze powder. After removal of sodium-chloride one filters oil? from the precipitated salt and the, solvent distilled off. The thus obtained residue is a waxlike mass solid at mom-temperature and is easily such as benzine, benzol etc. This mass dissolved in benzol is suitable for treatment of fibers in a manner similar to that of the preceding examples for providing water-repellence.

We claim:

l. The method for improving textile material characterized by impregnating the textile material by a carbodiimide compound containing at least one higher molecular alkyl radical having at least 10 carbon atoms, and heating the. impregnated material at temperatures above 100 C. to produce a reaction by the said compound to produce water-repellency in the fibre.

2. The method for improving textile, material characterized by impregnating the textile material by a carbodiimide compound containing at least one higher molecular hydrocarbon radical of the group consisting of alkyl, arallml, alkylaryl radicals having at least 10 carbon atoms in the 'alkyl portion thereof, and heating the impregnated material at a temperature between 105-l20 C. to produce a reaction produce water-repellency in the fibre.

3. The method for improving textile material characterized by impregnating the textile material by a carbodiimide compound containing at 'therein, and heating the by the said compound to g least one higher molecular alkyl radical having at least 10 carbon atoms, having at least one hetercatom in the a iphatic chain and heating the impregnated material to, produce a reaction by the said compound to produce water-repellency in the fibre.

4. The method for improving textile material characterized by impregnating the textile material by a carbodiimide compound containing at least one higher molecular aliphatic radical having no less than 10 carbon atoms and heating the impregnated material to produce a reaction by the said compound to produce water-repellency in the fibre.

- 5. The method for improving textile material characterized by impregnating the textilematerial by a diarylcarbodiimide having at least onealkyl radical in the compound containing no less than 10 carbon atoms and heating the impregnated material to produce a reaction bythe said compound to produce water-repellency in the fibre.

6. The method for improving textile material characterized by impregnating the textile material by a carbodiimide compound containing an alkyl-aryl radical having an oxygen atom in the hydrocarbon chain and at least 10 carbon atoms impregnated material to produce a reaction by the said compound to produce water-repellency in the fibre.

7. The method for improving textile material characterized by impregnating the textile material by a carbodiimide compound containing an aliphatic radical having an -+NHCO group carbon atoms.

. WINFRID HENTRICH. RICHARD HUETER. HEINZ-JOACEIM ENGELBRECHT.

CERTIFICATE OF CORRECTI'CYN, V 4 Patent No. 2,365,750. I November 25, 19L 1.

WINFRID HENTRICH, ET AL. V Y

' It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as fiollows: Page 1, first column, line 51, for the wordsfiepplied material read.-material applied-; line 50,"for diaryi -varbodi read diaryi-carhodipage 2, first column, line 17,4101- 1eafsu1fide" read "legi -sulfide"; page 5, first column, line 20; after "stirring" insert in the. preserijce j line "25, .after "solvent" insert -is--' and theft the aid LettersP'Zi-te nt' shouldbe read with this correction therein that the same meg: confornrto the record of the case in the Patent Office. 1 1 Signed and sealed this 15th day of Jarr'jary, A ."-'B..l9h.2.

n 1 Henry Van Arsdalle, O (Seal) e Acting Commissioner of Patents