US2288106A - Viscose spinning solution - Google Patents

Description

Patented June 30, 1942 OFFICE VISCOSE SPINNING SOLUTION Elmar Profit, Berlin-Lichterfelde, Germany, as-

signor to North New York, N. Y.,

American Rayon Corporation, a corporation of Delaware No Drawing. Application August 3, 1939, Serial No. 288,170. In Germany August 6, 1938 9 Claims. This invention relates to a method for improving the physical properties of textile structures such as filaments, threads, bands, staple fibres, and the like, made of viscose.

It is an object of the invention to improve certain of the physical properties of viscose structures of this type, including the wet and dry strengths and the wet and dry elongations as well as the dye afiinity thereof by introducing certain chemical agents, e. g. organic sulphur compounds into the solutions from which such artificial structures are spun and which agents are adapted to produce eiiects analogous to those which impart desirable characteristics to natural products such as animal hair, wool, and the like.

A further object of the invention is to provide a method which can be practised with relatively low cost materials readily obtainable on a large scale.

It is known that in organic animal products such as wool, the sulphur, especially in the keratin, -plays a very special and very unique role in that it functions to a certain extent as a connective and intermeshing bridging bond between the principal valence chains of the protein molecule.

-The quantity of sulphur which is necessary for forming these bridging bonds is relatively small and, as a rule, amounts to 2 to 4 per cent of the wool substance per se. It seems that the sulphur in this case is at least partially present in the form of disulphide bridging bonds.

ably to the good physical properties possessed by organic animal products, such-as 'wool, etc.

In accordance with the present invention it has been found that it-is also possible to produce an analogous effect in the case of artificial products such as viscose and hence to improve the physical properties of artificial silk, staple fibres and the like made therefrom, by adding certain sulphurcontaining compounds to the viscose. More specrfically, for example, organic compounds of a disulphide-like nature are added to the viscose and the viscose thus charged with sulphur com,- pounds is spun into artificial threads, bands, staple fibres, and the like. By this means it is possible very appreciably to improve the properties of the structures spun or otherwise obtained therefrom compared to those which are spun without the addition of such sulphur-containing compounds. The dry strength as well as the wet strength thereof is appreciably increased, whereas the elongation values thereof are not only not noticeably impaired but under proper conditions It is generally assumed that such bonds contribute appreciare actually improved. Furthermore, the dye affinity of the finished product, as a rule, is also improved. Another feature of the invention resides in the fact that the addition of the disulphidelike substances to the viscose also leads to the result that the wetting capacity of the threads thus obtained is less than is customarily the case, i. e. they are less hydrophilic than normal regenerated cellulose.

It is probable that an explanation for the improvement in the physical properties of the artificial structures may be predicated upon the fact that a chemical reaction occurs between the di sulphides and the cellulose, thus forming sulphur-contain'ing bridging bonds between 'the molecular chains and producing a sort of molecular intermeshing, that is, something similar to that inherent in keratin and also allegedly involved in the vulcanization of rubber.

The following have been-found to be suitable disulphide-like substances for theaforesaid purpose: higher aliphatic or cyclo-aliphatic disulphides, chlorinated higher aliphatic or cycloaliphatic disulphides which, for example, have taken on one mol of chlorine; and higher aliphatic or cyclo-aliphatic tetrasulphides, polysulphides, and the like. Such organic sulphur compounds are obtained, for example, by oxidation of the corresponding mercaptans and thioglycols. Exceptionally good results have been obtained with mixtures of substances of the type indicated, these being derived from petroleum (or the fractions thereof which boil above and secured .by the roundabout method of first producing the halogenation products and then the correspond ing mercaptans as set forth in my co-pending application Ser. No. 189,275, now U. S. Patent No. 2,231,594 of February 11, 1941, entitled Process for producing improving'products for pelts, furs, hairs, and textiles of all kinds, these substances furthermore being well suited for the process due to their exceptional cheapness and availability in adequate quantities. It is not necessary to purify or separate these substances or mixtures, which consist, as they do, of innumerable chemical compounds of the most varied nature and of disulphide-likecharacter, but on the contrary, the technical (crude) mixtures may even be used with advantage per se directly as produced. Such substances are preferably added to the viscose in quantities amounting to about 5 to 15 per cent of the cellulose content of the viscose.

Example I and which are obtained from petroleum indirectly by way of its chlorination products and by way of the mercaptans are intimately mixed with about 200 kg. of viscose possessing a cellulose content of about 7.2 per cent, the treated viscose being then spun into artificial silk in an acid bath containing zinc sulphate or other conventional spin baths. The physical properties of the artificial silk so obtained are better than those of artificial silk spun from viscose to which the disulphide or disulphide mixture has not been added as shown by the following results:

Strength Elongation Dry Wet Dry Wet Grams Grams Percent Percent Treated 204 105 22. l 38. 4 Untreated 174 78 20. 9 29. 4

Example II Elongation Amount of Strength per disulphide 100 denier 5 Disulphide (based on e a cellulose content) Dry Wet Dry Wet I. Petroleum disulphides containing about 1, Percent Grams Grams mol of chlorine. i 205 94 26. 4 39. Petroleum disulphides... 10 202 95 21. l 35. 6 Without addition of disulphides 0 174 78 20. 9 29. 4 II. Petroleum disulphides treated with nitric acid- 10. 3 181 i 92 19. 2 28. 7 Petroleum-bis-disulphides '1 containing 2 S2 groups- 10.3 173 1 89 23. 5 35.8 Without addition of disulphides L 0 160 85 18.0 26.3

It is also to be notedfihat the petroleum disulphides cause a more rapid maturing of viscose solutions.

I wish to emphasize that any organic disulphide may be used in my novel process provided it is capable of chemically reacting with regenerated cellulose. Modifications of my invention y will readily be recognized by those skilled in the art and I desire to include all modifications comin within the scope of the appended claims.

I claim:

l. A spinning solution for the manufacture of artificial silk comprising a viscose solution and ,a disulphide derived from a petroleum fraction having a boiling point above 120 C., said disulphide forming connective and intermeshing bridging bonds between the principal valence chains of the cellulose contained in said viscose solution.

2. A spinning solution for the manufacture of artificial silk comprising a viscose solution and above 120 C., said disulphide forming connective from a petroleum fraction having a boiling point 5 about 120 C., said disulphide forming connective and intermeshing bridging bonds between the principal valence chains of the cellulose contained in said viscose solution, and said percentage being based upon the cellulose content of said 0 viscose solution, said percentage being based upon the cellulose content of said viscose solution.

3. A spinning solution for the manufacture of artificial silk comprising a viscose solution and a disulphide derived from a halogenated petroleum fraction having a boiling point above 120 C., said disulphide forming connective and intermeshing bridging bonds between the principal valence chains of the cellulose contained in said viscose solution.

artificial silk comprising a viscose solution and a disulphide derived from a chlorinated petroleum fraction having a boiling point above 120 C., said disulphide forming connective and inter- 5 meshing bridging bonds between the principal valence chains of the cellulose contained in said viscose solution.

5. A spinning solution for the manufacture of artificial silk comprising a viscose solution and about 5 to 15% by weight of a disulphide derived from a halogenated petroleum fraction having a boiling point above 120 C., said disulphide forming connective and intermeshing bridging bonds between the principal valence chains of the cellulose contained in said viscose solution, and said percentage being based upon the cellulose content of said viscose solution.

6. A spinning solution for the manufacture of artificial silk comprising a viscose solution and about 5 to 15% by weight of a disulphide derived from a chlorinated petroleum fraction having a boiling point above 120 C., said disulphide forming connective and intermeshing bridging bonds between the principal valence chains of the cellulose contained in said viscose solution, and said percentage being based upon the cellulose content of said viscose solution.

'7. Regenerated cellulose containing a disulphide derived from a petroleum fraction having a boiling point above 120 C., said disulphide forming connective and intermeshing bridging bonds between the principal valence chains of ,said cellulose. 8. Riegenerated cellulose containing a disulphide derived from a halogenated petroleum fraction'having a boiling point above 120 C., said disulphide forming connective and intermeshing bridging bonds between the principal valence chains of said cellulose.

9. Regenerated cellulose containing a disulphide derived from a. chlorinated petroleum fraction having a boiling point above120 C., said disulphide forming connective and intermeshing bridging bonds between the principal valence chains of said cellulose.

ELMAR PROFFT.

4. A spinning solution for the manufacture of I CERTIFICATE OF CORRECTION. Patent No. 8 3%. June 50, 19M.

ELMAR PROFFT It is hereby certified that error appears in the printed Specification of the above numbered patentrequiring correction as follows: Page sec,- ond column, line 5-, claim for "above 120 0-, Said disulphide forming connective" read -about 5 to 1 zan weight of e disulphide derived-,-; line 5, same claim, for "about".read --above-; and line 10-, same clainl strike out the comma 'after "solution"; and that the said Letters Patent should be. read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signedend sealed this 1st day of September, A. D.. 1914.

. Henry'Ven Arsdale, (Seal) Acting Commissioner of Patents.