US2157294A

US2157294A - Mercerizing lyes and a process for their manufacture

Info

Publication number: US2157294A
Application number: US119528A
Authority: US
Inventors: Lier Heinrich
Original assignee: FIRM OF CHEMICAL WORKS FORMERL
Current assignee: FIRM OF CHEMICAL WORKS FORMERL; FIRM OF CHEMICAL WORKS FORMERLY SANDOZ
Priority date: 1936-01-09
Filing date: 1937-01-07
Publication date: 1939-05-09
Anticipated expiration: 1956-05-09
Also published as: CH201259A; DE722258C; GB488620A; CH204116A; CH201260A

Description

' lye and impart thereto a powerful wetting-out- Patented May 9, 1939 IVIERCERIZING LYES AND A PROCESS FOR THEIR MANUFACTURE Heinrich Lier, Basel, Switzerland, assignor to the firm of Chemical Works Formerly Sandoz,

Basel, Switzerland No Drawing. Application January 7, 1937, Se-

rial No. 119,528. 1936 In Switzerland January 9,

8 Claims. (01. 8-427) The present invention relates to a process for improving the wetting-out properties of alkaline lyes of at least 18 B. and to such improved lyes and is based on the use of naphthenic acids as such or in combination with emulsifying agents of non-phenolic character or with aminoor ether alcohols.

Until now it has only been known that naphthenic acids which are a by-product in the manufacture of petrol can be used in dilute alkaline solutions the specific gravity of which is not higher than 1 B. It has always been thought that these acids cannot be used in concentrated lyes because of their poor solubility.

The present invention resides on the observation that naphthenic acids can very well be used alone as wetting agents in concentrated alkaline lyes say from 18 B. upwards, if their molecular weight or their acid number is adapted to the concentration of the lye.

According to the present invention concentrated alkaline lyes possessing excellent Wettingout power are prepared by adding thereto small quantities of selected fractions of naphthenic acids, whereby the selection is so made that th quotient acid number of the naphthenic acid fraction content in percent of alkali in the lye must be a number between and 25. This mathematical expression means that for lyes of lower concentration fractions of naphthenic acids with a low acid number are used, whereas for concentrated lyes naphthenic acids possessing a high acid number will be employed. Instead of the expression acid number it is also possible to say molecular weight, as a low acid number of a fraction indicates high molecular naphthenic acids, and a high acid number indicates low molecular acids. It the acid number is adapted to the concentration of the lye by following the above mathematical rule, the naphthenic acid fraction will generally be clearly soluble in the and penetrating action for raw cellulosic fibres. Such a lye will then be of great advantage for the treatment of cellulosic material, for instance for the mercerisation of raw unbowked cotton or the alkalisation of raw paper pulp in the manufacture of rayon.

The acid number of naphthenic acids varies between 250 and 500 and if the above rule is followed, it will be clear that for sodium hydroxide lyes of 30 B. and upwards, naphthenic acid fractions possessing the acid number 380 and upr ups.

wards will be preferably used. For caustic soda lyes of about 26-30 B. fractions with the acid number of about 360-380 are preferable. For more dilute lyes say of 22-26 B. fractions with the acid number of about 320-360 are suitable. If dilute lyes, say of 18-22" B., are used, then the corresponding acid number of the naphthenic acidfractions will be of 250-320.

It has further been observed that the wettingout power of naphthenic acids can be increased if the above quotient increases in value by adding t ereto a small amount of aminoor ether alcoho s. In the case the quotient sinks, then the activity of the naphthenic acids can be increased by adding theretma certain amount of emulsifying agents of a nonphenolic character.

This means that when naphthenic acid fractions of low molecular weight are used in rather dilute alkaline lyes, they obtain the property of emulsifying therein substances like aminoor ether alcohols, which then increase the wettingout power of alkaline lyes. For instance if naphthenic acid fractions with the acid number 380 and upwards are used in lyes of say 22-28 B., it is indicated to add to the naphthenic acids a small amount of aminoor ether alcohols and to use such mixtures as wetting agent, which will then increase the wetting-out properties of alkaline lyes much stronger than if the naphthenic acids fractions are used alone.-

In case that naphthenic acids of high molecular weight or of low acid number are used in concentrated alkaline lyes, it happens that they are no more completely soluble therein and instead of clear solutions, muddy alkaline lyes are obtained. In such a case it has been observed that. it is possible to increase the wetting-out power of naphthenic acid and to prepare clear soluble mixr tures by adding to the naphthenic acid fraction a certain amount of emulsifying agents of generally acid character or belonging to the glucoside type containing at least four aliphatic hydroxy For instance if a naphthenic acid fraction with the acid number 384 is used alone in lyes of 30-34" B., a muddy lye is obtained because the naphthenic acids are no more clearly soluble in such lyes. But if to such naphthenic acids a certain amount of an emulsifying agent like butylsulphate is added; then the mixtures thereby obtained become clearly soluble in lyes of such concentration and impart thereto a verypowerful wetting-out action.

As ether alcohols saturated and unsaturated compounds of thealiphatic, cycloaliphatic, aralian ether linkage at least one aliphatic hydroxy group, such as the ethers of glycol, glycerine and polyvalent alcohols, the acetalsv derived from polyvalent alcohols and ketones or aldehydes can 5 be used. As amino alcohols compounds containing one. or more nitrogen atoms and one or more oxalkyl groups in the molecule are suitable for improving the wetting-out properties of the fractions of naphthenic acids. In case that the" use of an emulsifying agent is indicated, derivatives are used which belong to the class of sulphonic acids of alkylated aromatic compounds, aliphatic and heterocyclic sulphonic acids with at least three carbon atoms in the molecule, the sulphuric esters of aliphatic alcohols with 2 to 12 carbon atoms possessing straight or ramified carbon chains, the sulphuric acid esters of etherand amino alcohols, aliphatic saturated or unsaturated monocarboxylic acids with 3 to 12 carbon atoms and with straight ramified carbon chains, which chains can eventually contain oxygen bridges; such cids are for example isobutyric acid, isovaleri nic acid, isocapronic acid, isobutylacetic acid, isoamyl acetic acid, methylisobutyl acetic acid, methylisoamyl acetic acid, ethylpropyl acetic acid, dipropyl acetic acid, 1:3- dimethyl valerianic acid, 3-n1ethyl capronic acid, lziii-dimethyl capronic acid, S-methyl-capryl acid 30 naphthenic acid fractions with aminoor ether alcohols in the case that the quotient acid number of the naphthenic acid fraction content in percent of alkali in the lye acid number of the naphthenic acid fraction content in percent of alkali in the lye is a number lower than 15.

Still another object of the present invention are the alkaline lyes of 18 B. and more containing suitable fractions of naph'thenic acidin mixture with aminoor ether alcohols or in mixture with emulsifying agents of an'acid character and the process of treating cellulosic material, especially the mercerizing process of cellulosic fibres with the said lyes.

The following first table and examples show how the present invention can practically be carried out, the parts-being by weight, or where especially indicated by volume:

Table I Degrees Cc. Percent Percent Percent 25. 5 32 10 4. 6 l1. l6. 4 15. 45 24. 5 31 10 8. 0 16. 4 20. 8 16. 1 23. 5 30 10 9.2 17. 0 20. 8 16. 76 21. 5 28 10 9. 3 16. 5 l9. 4 l8. 3 18. 7 25 10 v 9. 3 14. 7 16. 7 21. 07 23. 5 30 7. 5 6. 3 l4. 2 l9. 2 16. 34 40 23.5 30 5 r 21.0 16.55

384 g g: g (7) 19. 2 21. 6 17. 0

. 19. 130 140 Roumanian 011- 358 19 5 5 21 6 86 gm 26 5 .13. 4 19.6 21. (i 130-140 American origin. 384 18. 7 25 5 9. 2 15. 2 17. 0 130-440 American origin- 384 18. 7 25 7. 5 11. 4 17. 0 l8. 6 20. 53 140-150 356 18. 7 25 3 10. 0 l5. 4 17. 7 4 5 18.7 25 5 14. 9 20. 3 22. 0 19. 0

etc. (see British Patent No. 414,485), the glycosido-compounds obtainable fromsugars and aliphatic. alcohols or ether alcohols.

One object of the present invention is therefore a process for improving the wetting-out power of. alkaline lyes of a concentration superior to 18 B. by adding thereto fractions of naphthenic acid selected in such a manner that the quotient acid number of the naphflienic acid fraction content in percent of alkali in the lye is a number between and 25.

Another object of the. present invention is. a process for improving the wetting-out action of alkaline lyes by adding to concentrated lyes naphthenic acid fractions with a high acid numher, and to more dilute lyes,-fractions with a lower acid number.

Still another object of the presentinvention are the improved alkaline solutions of 18 B. and more containing suitable fractions of naphthenic acids.

Still another object of .the present invention is the process for improving the wetting-out action of alkaline lyes by adding thereto mixtures of Column 1 of this table gives the boiling point of the naphthenic acid fraction.

Column 2 of this table gives the acid number of the naphthenic acid fraction.

Column 3 of this table gives the content of free alkali in the lye.

Column 4 of this table of the"lye-in B.

Column 5 of this table gives the addition of naphthenic acid in cc. per liter lye.

Column 6 of this'table gives the shrinkage of raw cotton yarn after 5 seconds.

Column 7 of this table gives the shrinkage of raw cotton yarn after 10 seconds.

Column 8 of this table gives the shrinkage of raw cotton yarn after 15 seconds.

Column 9 of this table gives the quotient.

The following second table shows the action. in lyes of diiferent concentration, of mixtures of a naphthenic acid fraction of the acid number 384 and boiling point 130-140" C. with other compounds increasing its wetting-out properties in comparison to the action of the naphthenic acid fraction "itself.

gives the concentration Column 1 of this table indicates the quantity of naphthenic acid added to 1 liter lye.

Column 2 of this table indicates the quantity of 55% aqueous solution of the sodium salt of the n-butylsulphuric acid.

Column 3 of this table indicates the concentration of the lye.

Column 4 of this table indicates the content 25 of the lye on free alkali in Column 5 of this table indicates the quotient.

Column 6 of this table indicates the shrinkage of a raw cotton yarn after 15 seconds treatment.

Column 7 of this table indicates the nature of 30 the lye.

The following Table III shows the action of the same naphthenic acid fraction as above in mixture with the acetals obtained from glycerine and technical methylcyclohexanones.

with 1 cc. of di-(oxethyl)-n-buty1amine.

35 Table III Per- 46 Ce. Cc. Degrees cent 95:5 7.5 22.5 17.0 23.4 Littlemuddy.

25:5 7.5 26 21.55 17.3 23.3 Clear.

7.6 000. 25 18.71 20.53 18.6 Clear. 30:10 7.5 25 13.71 20.53 23.6 Do.

7.5 000. 0 20 14.3 26.8 6.2 Clear. 30120 7.5 20 14.3 25.3 11.2 Do.

50 Column 1 of this table indicates the quantity of naphthenic acid added to the lye.

. Column 2 of this table indicates the ratio of mixture of naphthenic acids with the acetals.

Column 3 of this table indicates the quantity 55 of the mixture added to the lye.

Column 4 of this table indicates the concentration of the 'lye.

- Column 5 of this table indicates the content of the lye on free alkali in Column 6 of this table indicates the quotient.

Column 7 of this table indicates the shrinkage of a raw cotton yarn after seconds treatment. Column 8 of this table indicates the natureof the lye.

Lyes possessing excellent wetting-out power may further be prepared by using following mixtures:

1. Mix 5 cc. of naphthenic acids of acid number 356 with 7 cc. of a 49% aqueous solution of the sodium salt of the butoxyethane sulphonic acid (CI-1;CHz-CHz-CH:OCH2CH2SO3N8.) and add this mixture to a liter of lye of 28 B.

of a raw cotton yarn after 15 seconds immersion reaches 23.8%.

2. Mix 4.5 cc. of raw naphthenic acids of acid number 291 with 10.5 cc. of isovalerianic acid and add this mixture to a liter of'lye of 30 B. Instead of isovalerianic acid, methylisobutyl acetic acid can be used, and mixed with naphthenic acid of acid number 331.

31 Mix 2.31 parts of naphthenic acids of acid number 359 with 5.39 parts'of isoamyl glucoside and add this mixture to a liter of lye of 35 B.

4. Add to a liter of lye of 35 B. a mixture of 5 cc. of naphthenic acids of acid number 389 with 12 cc. of n-propylsulphate. Clear lye with good wetting action will be obtained.

5. Add to a liter of lye of 23 B. a mixture of 9 cc. of naphthenic acids of acid number 356 Clear lye with good wetting-out action will be obtained.

By replacing the aboveamine by monooxethylisoamylamine or by di-(oxethyl) -isoamylamine, active wetting-out agents will be obtained.

6. Add toa liter of lye of 25 B. 5'cc. of a mixture consisting of 92 parts of naphthenic acids with acid number 384 and 8 parts of diethyleneglycolmonobutylether or of 95 parts of naphthenic acids and 5 parts of glycerine-a-isoamylether.

Clear lyes with good wetting-out action will be 3 obtained.

'7. Add to a liter of lye of 32 B. a mixture of 5 cc. of naphthenic acids of acid number 384 with 3.5 cc. of the concentrated aqueous solution of the sodium salt of a high sulphonated ricinoleic acid. Clear and stable lyes will be obtained.

What I claim is:

1. The phenol-free alkaline lyes of 18 B. and more, possessing good wetting out properties and containing a wetting-capacity increasing agent consisting of such fractions of naphthenic acids that the quotient acid number of the naphthenic acid fraction content in percent of the alkali in the lye is a number between 15-25.

2. The phenol-free alkaline lyes of B. and more, possessing good wetting-out properties and containing a wetting capacity increasing agent consisting of such fractions of naphthenic acids, the acid number of which is 380 and more and the quotient acid number of the naphthenic acid fraction content in percent of the alkali in the lye is a number between 15-25.

3. The phenol-free alkaline lyes of 26-30 B., possessing good wetting-out properties and containing a wetting capacity increasing agent consisting of such fractions of naphthenic acids, the acid number of which is 360-380 and the quotient acid number of the naphthenic acid fraction content in percent of'the alkali in the lye is a number between 15-25.

4. The phenol-free alkaline lyes of 18-26 B., possessing good wetting-out properties and containing a wetting capacity increasing agent consisting of such fractions of naphthenic acids, the acid number of which is 250-360 and the quotient acid of the naphthenic acid fraction content in percent of the alkali in the lye is a number between 15-25.

5. A process for the alkaline treatment of cellulosic material, comprising subjecting the cellulosic material to a treatment with a phenol free alkaline lye of 18 B. and more containing a wetting capacity increasing agent consisting of such fractions of naphthenic acids that the quotient acid number of the naphthenic acid fraction content in percent of the alkali in the lye is a number between 15-25.

6. A process for the alkaline treatment of cellulosic material, comprising subjecting the cellulosic material to a treatmentwith phenolfree' alkaline lyes of 30 B. and more, containa wetting capacity increasing agent consisting of which is 3 menace cellulosic material to a treatment with phenoliree alkaline lyes of 26-30 Ba, containing a wetting capacity increasing agent consisting of fractions of gaphthenic acids, the acid number 0-380 and the quotient acid number of the naphthenic acid fraction content in percent of the alkali in the lye is a number between 15-25. 8. A process for the alkaline treatment of cellulosic material, comprising subjecting the c'ellulosic material-to a treatment with phenolfree alkaline lyes of 18-26 B., containing a wetting capacity increasing agent consisting of fractions\ of naphthenic acids, the acid number of which is 250-360 and the quotient is a number between 15-25.