US1914321A - Production of assistants for the textile and related industries - Google Patents

Description

Patent ed June 13, 1933 v UNITED STATES PATENT OFFICE HANS IBELL'ER, or LUnwTesHArEN-on-THn-RHmE, AND HERMANN SCHUETTE, or

SCHAFT, OF FRANKFORT-ON-THE-MAIN, GERMANY PRODUOTIOIY OF ASSISTANTS FOR THE TEXTILE AND RELATED INI USTRIES No Drawing. Application filed June 15, 1931,Serib1 No. 544,696, and in Germany June as, 1930.

The present invention relates to the production of assistants for the textile and re-' lated industries and particularly of wetting,

cleansing and emulsifying agents.

A process for the production t wetting, cleansing and emulsifying agents has been elsewhere described according to which high.

7 molecular aliphatic olefines having a double linkage at the end of a chain of at least 8 carbon atoms, such as may be obtainedv for example from the corresponding monohydric aliphatic alcohols by splitting oil water, are

' sulphonated under energetic conditions.

We have now found that equally valuable products which may be employed in an ad vantageous manner as wetting, cleansing and emulsifying agents can be obtained by treating the olefinic mixtures obtainable from the oxidation products of a destructive oxidation of ditfieultly volatile, liquid or solid aliphatic hydrocarbons, i. e. aliphatic open chain or cycloaliphatic hydrocarbons, containing at least 8 carbon atoms and mixtures containing a preponderating quantity ofsuch hydrocarbons, or mixtures containing a preponderating quantity of the said olefines,'with.energetic sulphonating agents, such as oleum, chlorsulphonic acid or sulphur trioxide, or

with less energeticsulphonating agents such as concentrated sulphuric acid, under energetic conditions, i. e. at temperatures above 100 C. or while removing the water formed by means of dehydrating agents, such as acetic anhydride and/or by an extended period of working, until true sulphonic acids CSO OH) are formed. This aim is attained as soon as a sample remains soluble in water after boiling with an aqueous about 10 per cent hydrochloric acid solution.

The olefines employed as initial materials may be of aliphatic, cycloaliphatic or aliphatic-cycloaliphatic nature and usually 'contain olefines with one double linkage in the molecule in preponderating quantities; they may be obtained for example according to the process described in the application Ser. No. 47 8,550 filed by one of the present inventors together with another on August 28, 1930. Moreover, mixtures of olefines may be employed which contain olefinic compounds conlike.

taining hydroxy, carboxylic acid or carboxylic ester groups besides the double linkagis. Since the hydroxyl groups of the consti uents of the oxidation products are mainly contained in or near the centre of the chains, the "double linkages will not be in a final position of at least 50 per cent, or generally more, of tlfe olefinic constituents.

Such olefines, or mixtures containing them, can be obtained for example from the products of a destructive oxidation of liquid or solid paraffin or naphthene hydrocarbons, as for example paraiiin oil or wax, petroleums, benzines, middle oils, brown coal tar oils, Montan wax or other waxes, hydrogenation products of coals or tars, petroleums and the These oxidation products, which contain hydroxy, carboxylic or ester groups or several of such groups as for example in hydroxy-carboxylic acids, estolides, laetides or lactones are subjected to distillation whereby double linkages are formed in the molecule while water is split oft. As a rule, a splitting off of carboxylic and ester groups, when such are present, also takesv place during this distillation. The olefines employed for the sulphonation may be solid or liquid and may be employed in admixture with high molecular organic compounds containing more than 8 carbon atoms such as alcohols, carboxylic acids, hydroxy-carboxylic acids or esters of any origin. as such, separated for example by distillation, or in admixture with each other, or the whole of the mixture containing olefines or fractions of the same may be subject to the sulphona tion. i

The sulphonation of the olefines is preferably eitected while employing energetic sulphonating agents, as for example chlorsulphonic acid, oleum or sulphur trioxide, or

concentrated sulphuric acid either at temperatures above C. or in the presence of a dehydrating agent. It is often preferable in any caseto employ additions of de-- for example active carbon or diatomaceous' earth during the sulphonation. Solvents" or diluents such as chloroform, trichlorethylene, nitro-benzene, diethyl ether and the like may also be present during the sulphonation. In this manner, true sulphonic acids are obtained, that is compounds which when boiled with dilute aqueous mineral acids do not decompose with the splitting ofl" of sulphuric acid. The conditions of the sulphonation may also be selected so that a mixture of true sulphonic acids and sulphuric esters is obtained, for example a temperature of about 40 C. may be applied when working with oleum.

According to this invention, water-soluble sulphonic acids, or mixtures thereof with sulphuric esters, are obtained which may be employed as such. or in the form of their inorganic or organic salts as assistants in the textile, leather or paper industries, and in the production of polishing and cleansing preparations and, generally, as Wetting, emulsifying and cleansing agents. The said sulphonic acid compoundsmay be employed in acid, alkaline and neutral media and are especially suitable aswetting, cleansing and washing agents for textiles of all kinds and for raw fibres, for the preparation of dispersions, i. e. solutions, of solid or liquid dye-baths, oils, fats, Waxes, paraifins, organic solvents and other insoluble substances, especially in suspensions or emulsions, substances, as for example water, and as additions to mercerizing liquors,

carbonizing baths, liquids to be employed for dressing, and as softening agents and the like. The products may be employed alone or in admixture with other substances, such as inorganic or organic salts, soaps or the socalled substitutes for soaps as for example saponin, Turkey redoils, or sulphonic acids of aromatic monoor especially poly-nuclear compounds, further with glue, gelatines, gum arabic, vegetable mucilages or solvents. The sulphonic acids may also be employed for the preparation of drilling and lubricating oils, and as agents for working up leather and metal polishes.

,The following examples will further illustrate the nature of this invention, but the invention is not restricted to these examples. The parts are by weight.

Example 1 45 parts of chlorsulphonic acid are stirred at from about 30 to 40 G. into 100 parts of a liquid mixture of olefines, obtained from the fraction. of an oxidation product of hard paraffin wax, insoluble in petroleum ether,

destructive distillation, and having an iodine value of over 100. The whole is then stirred at room temperature until-the product has becomesoluble in water. Any hydrochloric acid gas still presentisexpelled by blowing air through the reaction mixture, the mixture dyestufi' pastes, dyestufli' powders,

carbon dioxide by:

is poured on to ice and the remainders of sulphonalting agent are removed by washing with a 10 per cent aqueous solution of Glaubers salt. After neutralizing with an aqueous dilute solution of an alkali, such as alkali metal hydroxide, ammonia or organic amines, such as mono-, di-, or triethanol amine, cyclohexyl ethanol amines or pyridine and the like, a solution is obtained which may be employed as such as washing or emulsify ing agent as well as the salts of the sulphonic acid which are obtained in a. solid form by evaporating the solution. The resulting products have an excellent washing, and emulsifying power. The sulphonic acids obtained cannot be saponified by boiling with aqueous mineral acid.

Example 2 first separated from the distillate by saponification with alkalies, and then the unsaturated hydrocarbons are separated from the unsaponifiable fraction in the usual manner, as for example by distillation. 100 parts of the olefines thus obtained are converted into true sulphonic acids by warming them. with a mixture of 30 parts of acetic anhydride and 30 parts of sulphuric acid monohydrate at about 35 C. After the reaction mixture has become soluble in water, which is the case after from about 5 to 6 hours, ice is added to the reaction mixture; it is then'diluted with water and-neutralized with alkaline sub-v stances as described in Example 1. A procluct having an excellent washing action is obtained. The sulphonic acids obtained cannot be saponified by boiling with aqueous mineral acid. a

Example 5 Soft paralfin wax is oxidized by blowing with air .at 160 C. for 6 hours and the acid constituents are removed from the oxidation product by washing'with about 25 per cent aqueous caustic soda solution. The unsaponiliable constituents are separated by centrifuging at about 20 G. into a liquid fraction consisting mainly of substances containing hydroxyl groups and a solid fraction mainly consisting of unattacked initial paraflin wax. The liquid fraction is heated to from 180 to 220 C. with a .few per cent its weight of agents removin water, such as zinc chloride, concentrated su phuric acid and the like acting agents, whereby mainly olefines are obtained in addition to unchanged hydroxyl compounds.

100 parts of the mixture thus obtained are vigorously stirred at 15 C. with 80 parts of oleum containing 23 per cent of sulphur trioxide. The temperature is then raised to from to 'C. and the mixture stirred for about 5 hours until a sample withdrawn is soluble in water. The reaction mixture is then poured on to ice and neutralized with. caustic soda solution. The product has excellent washing and emulsifying properties. The sulphonic acids obtained cannot be saponitied by boiling with aqueous mineral acid.

\Vhat we claim is 1. The process for the production of assistants for the textile and related industries which comprises acting with a sulphonating agent on 'olefinic mixtures, resulting from splitting off at least water from products of the liquid phase oxidation of difliculty volatile, aliphatic hydrocarbons, under such energetic reaction conditions as regards strength of sulphonating agent, reaction temperature and presence of dehydrating agents that a sample of the reaction product remains soluble in water after boiling with aqueous hydrochloric acid.

2. As new articles of manufacture assistants for the textile and related industries comprising sulphonic acid compounds of olefinic compound resulting from splitting off at least water from the hydroxyland carboxyl-bearing products 'of the liquid phase oxidation of difiicultly volatile, aliphatic hydrocarbons.

3. As new articles of manufacture assistants for the textile and related industries comprising sulphonic acid compounds of mixtures of olefines and other olefinic compounds resulting from plitting off at least Water from the hydroxyland carboxyl-bearing products of-th-e liquid phase oxidation of difficultly volatile aliphatic hydrocarbons.

4. As new articles of manufacture assistwater from the hydroxyl-, and carboxyl-bearing products of the liquid phase oxidation of a mineral from said olefines.

8. As new articles of manufacture assistants for the textile and related industries comprising alkali salts of sulphonic acid compounds of olefines, resulting from splitting ofi at least water from the hydroxyland carboxyl-bearing products of the liquid phase oxidation of a mineral middle oil.

9. As new articles of manufacture assistants for the textile and related industries comprising sulphonic acid compounds of olefin'es, resulting from splitting ofl at least water from the hydroxyland carboxyl-bearing products of the liquid phase oxidation of soft paraffin wax.

10. As new articles of manufacture assistants for the textile and related industries comprising alkali salts of sulphonic acid compounds of olefines', resulting from splitting oil at least water from the hydroxyland carboxyl-bearing products of the liquid phase oxidation of soft paraflin wax.

In testimony whereof we have hereunto set our hands.

- HANS BELLER.

HERMANN SCHUETTE.

ants for the textile and related industries comprising sulphonic acid compounds of olefines,

resulting from plitting 01f at least water from the hydroxyland carhoxyl-bearing products of the liquid phase oxidation of diflicultly volatile aliphatic hydrocarbons, and

sulphuric esters from said olefines.

5. As new articles of manufacture assistants for the textile and related industries compounds of olefines,

prising alkali salts of sulphonic acid comresulting from splitting off at least water from the hydroxyland carcarhoxyl-bearing products of the liquid phase oxidation of diflicultly volatile aliphatic hydrocarbons.

6. As new articles of manufacture assistants for the textile and related industries comprising sulphonic acid compounds of olefines, resulting from splitting oif at least water from the hydroxyland carboxyl-bearing products of the liquid phase oxidation of a mineral middle oil.

7. As new articles of manufacture assistants for the textile and related industries comprising sulphonic acid compounds of olefines, resulting from splitting oif at least middle oil and sulphuric esters