US2471039A - Manufacture of improved fibrous materials and the materials thus obtained - Google Patents

Description

in theisaid solutions. derivedirom sulfonic acid amides containing a :saturated aliphatic hydrocarbon radical of at least 8 carbon atoms. sulfamides are readily soluble in the alkaline Patented May 24, 1949 UNITED STATES iFllCE 'MANUFACTURE OF IMPROVED FIBROUS IVIATERIl-KLS AND TI-IE'MATERIALS THUS OBTAINED Ludwig Orthner, Gerhard Balle, and Heinz Scliil'd, Frankfort-on-the-Main,Max-Otto Scliiirmann, Dorma'gen, "andKarl Brodersen and Matthias 'Quaedvlieg, -Dessau, Germany; vested in --the Attorney General. of the United' 'states .No Drawing. iApplication February 2.6, 1941,.Serial'N0."38.0,6?'2. In Germany February.21,.1940

- Section 1, PubliczLaw 690, -August-8f194'6 5 Patent: expires February 21,1960

(Cl. v1061(i5) '7 Claims. ,1

The *present :invention ."relates to a process of manufacturing' artificial tfibrous materials and to the materials thus obtained. It is an object of the invention toiprepare fibers having an agreeable, soft handle. :Itiswa-iurther objectof the invention'to impart tothefibers a-soft and elastic feel stable .to' thenisualwashing operations. The

:invention especially relates to the process of improving artificial fibrous materials which com- :prises incorporating in the aqueous spinning solution alkali compounds of sulfonic acid amides containing a saturated aliphatic hydrocarbon radical of at least Bcarbonatoms. In the manu- .1 facture of improved artificial filaments from aqueous solutions, e. g. cellulose spinning solutions, such as viscose-or cuprammonlum solutions .of cellulose or protein spinning solutions,

alkali compounds'are added which are soluble The alkali compounds are In general the said spinningsolutions; only in the cases the molecuilar weight of the sulfamide is extremely high,

there is not'obtained :a clear solution in alkaline fluids, but a suspension or emulsion is formed which may be stabilized bythe: addition of the usual dispersing agents "and which is likewise suitable for the ipresent process. Furthermore, mixtures :of sulfamides may be used, forinstance mixtures of compounds of high molecular weight and of compounds of lower'molecular weight. The aqueous spinning solutions containing alkali compounds of sulfonic ':acid amides having .a saturated aliphatic hydrocarbon radical of at least '8' carbon atoms are spun in the usual way into a known spinning'ba'th containing for instance sulfuric acid and Glauberistsalt.

-Su1famides of high molecular weight and. their alkali compounds may beipreparedin different ways: by transformation of alcohols of high molecular weight into halogen compounds, reaction of theha'logen compounds with sodium 'sulfite to form-sulfonic acids andtransformation of said acids or their alkali metal saltsinto the corresponding sulfo'chlor-i'des or sulfobromides, for instance with phosphoruspentachloride, and transformation of the -=sulfochlorides with ammanufacture r of artificial 'tfibers 'suitably :by the .sulfonamides.

:simultaneous action :of chlorine xdioxide on saturated aliphatic .hydrocarbons having at least 8- carbon atoms with ammonia, .or amines lor:hydroayamines. lBythe :selection ethylamine, butylamine, -.d"ode'cylamine, cyclohexylamine, aniline, furthermore: hydroxyamines,

such as aethanolamine,;.propanolamine, .butanolamine or oxethylaniline, into z-the corresponding At 'this synthesis rthere may likewise :be started from alcohols of high :molecular weight as they are, for;instance, cbtainedbythe reduction of fats and,oils ofltatty-acids .or the like.

'Sulfamides of hi ghimolecular weight are'ob- .tained in a technically;especially-simple manner :by the reaction of sulfochlorides formed by the and :sulfur of .the hydrocarbons -'or hydrocarbon mixtures serving .as starting :'material, the effect attainable-with'th'e sulfa-mides-may'sbe variedtola large extent.

There may berstar-ted from hydrocarbons or from "mixtures of hydrocarbons which are obwta-ined tby iractionating.petroleum or fromprodducts whichare ohtained 'by the hydrogenation of carbon or thereduction ofecarbon monoxide. I'Ihese technical productsmaybe freed from any unsaturated portions which may be ,present, by .zihydrogenation or refining. rmayzbe reacted with chlorine and sulfur dioxide The hydrocarbons with exposure ato aultraviolet .rays. .The hydro- :carbons 'may be used in- BXOESS,';S0 that only a :part is 1transformed:..into rproducts containing chlorine,'sulfuriandlxoxygen. "The excess of the :hy'drocarbon may she separatedimmediately or after the 'rea'ction with ammonia or amines.

Sulfamides which are kl-useful .JfOr n'the rpresent process may also besobtaine'd for'instance as'follows: carboxylic acids haVing an aliphatic hydrocarbon 'radical of at least 8:.carbon atoms are caused to react --..with sulfamides containing amino groups, for instanceby the condensation "of lauric acid with *meta aminobenzeneesulfamide 0r beta-aminoethane-sulfamide.

The sulfamides herein described may be incorporated in the spinning solutions zused for the -addition of :an alkalinesolutionnf the zsuliamide to :the :spinning ssolution,:- foriinstance ;a viscose solution 1 or the ;solution :of sccel-lulose :in copper primarymasesf h as methylamine, 1-60 .oxiderzarld ammonia. nuringssa-id:operationthe solubility or distributability in alkali may be enhanced by the simultaneous use of dispersing agents, such as alcohol-sulfonates, condensation products of carboxylic acids of high molecular weight and amino-sulfonic acids or hydroxy-sulfonic acids or amino-carboxylic acids or hydroxycarboxylic acids, aromatic sulfonic acids, for instance alkyl-naphthalenesulfoni acids, condensation products from ethylene-oxide and alcohols of high molecular weight, carboxylic acids of high molecular weight, alkylphenols, alkylcyclohexanols and others. The sulfamide may be added to the spinning solution in any desired phase of its preparation. The alkaline solutions of the sulfamides may also be incorporated without any diificulty to the spinning solutions for casein fibers. The spinning solutions to which the sulfamide has been added are worked up in the usual manner in the usual devices. During the formation or the after-treatment of the threads in the usual acid precipitating bath the sulfamide is separated from its alkaline solution and finely and uniformly subdivided in the thread. During the preparation of casein fibers while simultaneously using sulfamides a reaction of the sulfamide with the formaldehyde moreover probably occurs during the usual hardening operation; a good fixing in the fiber of the substance added is thus attained.

The artificial fibers thus obtained are distinguished by a soft and elastic feel. Owing to the insolubility of the sulfamides in alkali carbonates the incorporated substance imparting softness is not removed from the fiber by the usual washing operations when washing liquids containing sodium carbonate are used. According to the present process artificial fibers are obtained which contain the softening agent not only at the surface; on the contrary, the product imparting softness is uniformly subdivided also in the interior of the fiber. The good subdivision is attained by the fact that the product is present in the spinning solution in the form of a molecular or colloidal solution. If the fiber is formed in the acid spinning bath it is uniformly precipitated in an insoluble form. The softening effect produced is, therefore, more stable than in those cases where the fibers are treated with water-soluble softening agents which are absorbed by the fiber. In that case salts of amines of high molecular weight are frequently used. The free amines are, as is known, insoluble in alkaline spinning solutions and can, therefore, not be incorporated in the same manner as the alkali metal compounds of sulfamides. Furthermore, quaternary ammonium compounds of high molecular weight or other water soluble bodies are used as softening agents. If the compounds Of said kind are already used on spinning it is found that the effect produced is not very resistant to washing operations owing to the solubility in water of the compounds.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weight:

1. 4000 parts of a viscose solution containing about 5 per cent of cellulose are mixed with a solution in 2N-caustic soda solution of a sulfamide obtained by the simultaneous action of chlorine and sulfur dioxide on a benzine fraction mainly containing saturated aliphatic hydrocarbons and boiling between 240 C. and 340 C. formed by reduction of carbon monoxide and a subsequent reaction of the aliphatic sulfochlorides formed with ammonia. The solution is spun in known manner into an acid precipitating bath. The fibers obtained are after-treated in the usual manner and dried and are distinguished by an excellent softness and suppleness.

A similar effect is attained by using an aliphatic sulfamide prepared by the simultaneous action of chlorine and sulfur dioxide on a paraffine fraction boiling between 340 C. and 380 C. and a subsequent reaction with ammonia.

The viscose solutions may also be worked up by a process of spinning by stretching the filement.

2. kilograms of casein are caused to swell at 24 C. in 200 liters of water, a mixture of 23 liters of caustic soda solution of 35 per cent strength and 7'7 liters of water is added and the whole is then diluted with water so as to obtain 550-600 liters of a clear, alkaline casein solution. 5 kilograms of a mixture of sulfamides prepared by the simultaneous action of chlorine and sulfur dioxide on a mixture of parafiine wax formed during the benzine synthesis by the catalytic reduction of carbon monoxide and a subsequent reaction of the sulfochlorides obtained with ammonia is dissolved in 2N-caustic soda solution and the solution is added to the spinning solution. After the solution has been allowed to ripen in the usual manner it is spun into an acid precipitating bath. The filament formed is then hardened in the known manner with formaldehyde. The artificial fibers obtained are distinguished by an agreeable and soft feel.

3. 46 parts of sulfamide (obtained by the simultaneous action of chlorine and sulfur dioxide on a mixture of hydrogenated hydrocarbons by the reduction of carbon monoxide and boiling between 240 C. and 340 C. and a subsequent reaction of the sulfochlorides formed with ammonia) are stirred with 9.5 parts of ZN-caustic soda solution, while adding 4.6 parts of the product of the reaction between octadecyl alcohol and 10 mol of ethylene oxide. The whole is diluted with about 300 parts of cold water and stirred into 12,700 parts of a solution of 9 per cent strength of cellulose in copper oxide and ammonia. The solution is then spun by a process of spinning by stretching the filament so as to obtain artificial silk. The skeins are Washed as usual with acid and Water, then agitated for 5 minutes in water heated to 65, centrifuged and dried. The artificia1 silk thus obtained has a soft feel even without the usual after-treatment with softening agents.

4. 40 parts of a sulfamide (obtained by the simultaneous action of chlorine and sulfur dioxide on a parafiine fraction mainly containing saturated aliphatic hydrocarbons and boiling between 320 C. and 380 C. and a subsequent reaction of the aliphatic sulfochlorides formed with methylamine) are dissolved in 2N-caustic soda solution. The solution is stirred into 4000 parts of a viscose solution containing about 6 per cent of cellulose. The solution produced is spun in known manner into an acid precipitating bath. The fibers obtained are distinguished, after having been Worked up in the usual manner and dried, by a soft and supple feel.

A similar effect is attained by using an aliphatic sulfamide obtained by the simultaneous action of chlorine and sulfur dioxide on the parafline fraction named above and a subsequent reaction with aniline. The produce is suitably dissolved in lN-caustic soda solution.

5. 4000 parts of a viscose solution contain- ..ing about 6 per cent of cellulose are mixed with a solution in 2N-caustic soda solution of 8 parts of a sulfamide substantially containing 16 to 18 carbon atoms and obtained by the reaction of a mixture of cetyl alcohol and octadecyl alcohol with thionyl chloride so as to obtain the corresponding chlorides, reaction of the chlorides with sodium sulfite so as to obtain the corresponding sulfonic acid salts, transformation of the sulfonic acid salts with phosphorus pentachloride into the corresponding sulfonic acid chlorides and finally reaction of the sulfochlorides with ammonia to obtain the corresponding sulfamides. The solution is spun into an acid precipitating bath and worked up as usual. The fibers obtained have a very good softness and suppleness.

6. To 4000 parts of a viscose solution containing about 6 per cent of cellulose there is added an alkaline casein solution prepared by dissolving 40 parts of casein in the corresponding quantity of alkali lye. To the solution thus produced there are added 6 parts of a sulfamide obtained by the simultaneous action of chlorine and sulfur dioxide. on a benzine fraction containing saturated aliphatic hydrocarbons and boiling between 230 C. and 320 C. and the subsequent reaction of the sulfochlorides formed with ammonia. For said purpose the sulfamide is dissolved in 2N-caustic sod-a solution, while adding 1 per cent of an emulsifying agent, for instance the product of reaction of octadecyl alcohol and mol of ethylene oxide. The spinning solution formed is worked up in the usual manner to obtain fibers which after having been hardened with formaldehyde are distinguished by an agreeable and soft feel.

We claim:

1. The process of improving cellulose fibrous materials distinguished by a soft and agreeable feel without the usual treatment with softening agents which comprises incorporating with the aqueous cellulose spinning solution colloidal alkali compounds of a sulfonic acid amide obtained by the simultaneous action of chlorine and sulfur dioxide on a mixture of saturated aliphatic hydrocarbons boiling from 240 C.-340 C. formed by the reduction of carbon monoxide, and subsequent reaction with ammonia, said sulphonic acid amids being insoluble in alkali carbonates and being uniformly subdivided in the interior of the fiber.

2. The process of improving cellulose fibrous materials distinguished by a soft and agreeable feel without the usual treatment with softening agents which comprises incorporating with the aqueous cellulose spinning solution colloidal alkali compounds of a sulfonic acid amide obtained by the simultaneous action of chlorine and sulfur dioxide on a mixture of saturated aliphatic hydrocarbons boiling from 340 C.- 380 C. formed by the reduction of carbon monoxide, and subsequent reaction with ammonia, said sulphonic acid amids being insoluble in alkali carbonates and being uniformly subdivided in the interior of the fiber.

3. Cellulose fibrous materials distinguished by a soft and agreeable feel without the usual treatment with softening agents and having uniformly distributed therethrough a colloidal sulfonic acid amide being insoluble in alkali carbonates and obtained by the simultaneous action of chlo- '6 rine and sulfur dioxide on a mixture of saturated. aliphatic hydrocarbons boiling from 240 C.-340 C. formed by the reduction of carbon monoxide, and subsequent reaction with ammonia.

4. Cellulose fibrous materials distinguished by a soft and agreeable feel without the usual treatment with softening agents and having uniformly distributed therethrough a colloidal sulfonic acid amide being insoluble in alkali carbonates and obtained by the simultaneous action of chlorine and sulfur dioxide on a mixture of saturated aliphatic hydrocarbons boiling from 340 C.- 380 C. formed by the reduction of carbon monoxide, and subsequent reaction with ammonia.

5. The process of improving artificial fibrous materials distinguished With a soft and agreeable feel without the usual treatment with softening agents Which comprises incorporating with the aqueous spinning solution colloidal alkali compounds of sulfonic acid amides obtained by the simultaneous action of chlorine and sulfur dioxide upon saturated aliphatic hydrocarbons having at least 8 carbon atoms and subsequent amidation with a substance selected from the class consisting of ammonia and primary amines, said sulphonic acid amids being insoluble in alkali carbonates and bein uniformly subdivided in the interior of the fiber.

6. Artificial fibrous materials distinguished by a soft and agreeable feel without the usual treatment with softening agents and having uniformly distributed therethrough colloidal sulfonic acid amides being insoluble in alkali carbonates and obtained by the simultaneous action of chlorine and sulfur dioxide upon saturated aliphatic hydrocarbons having at least 8 carbon atoms and subsequent amidation with a substance selected from the class consisting of ammonia and primary amines.

7. The process as defined in claim 1 wherein 46 parts by weight of the sulfonic acid amide are incorporated in 12,700 parts by weight of a solution of 9 per cent strength of cellulose in copper oxide and ammonia.

LUDWIG ORTHNER. GERHARD BALLE.

HEINZ SCHILD. MAX-OTTO scHiiRMANN. KARL BRODERSEN. MATTHIAS QUAEDVLIEG.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,947,939 Hubert Feb. 20, 1934 2,002,613 Orthner et al May 28, 1935 2,047,066 Glietenberg July 7, 1936 2,069,804 Heckert Feb. 9, 1937 2,112,728 Morgenstern Mar. 29, 1938 2,142,934 Bruson Jan. 3, 1939 2,174,507 Tinker Sept. 26, 1939 2,197,800 Henke Apr. 23, 1940 2,213,360 Calcott Sept. 3, 1940 2,225,960 Orthner et al. Dec. 24, 1940 2,300,589 Nelles Nov. 3, 1942 2,316,242 Hentrich Apr. 13, 1943 2,335,592 Hill Nov. 30, 1943