DE1518731A1 - Process for the production of cold water soluble etherification products of galactomannans and glucomannans - Google Patents

Description

Process for the production of etherification products soluble in cold water of galactomannans and glucomannans -.-.-.-.-.-.-.-.-.-. ~, -.-.-.-.-.-.-.-. ~, ~. ~. ~. ~. ~. ~ It is known to be made from locust bean gum and similar galactomannan gums obtained by reaction with d-halogenated fatty acids or their salts Xther can be, whose courtship represent substances soluble in water. you will be widely used as a thickening agent because of its swellability. This Xther however, still have some drawbacks.

The products are in fact, because they are the alkali salts, very weaker Deals with acids, cannot be stored indefinitely; they already lose from the carbonic acid the air's ability to swell.

Attempts have also been made by adding an excess of base to prevent this decomposition. The associated excessive alkalinity of the products however, it only led to it no longer being universal as a print thickener are usable. Alkali-sensitive dyes can therefore be mixed with carboxymethylated Galactomannans do not print with success.

The high alkalinity limits the usability of those containing carboxyl groups Etherification products are also used as a stabilizer for emulsions.

It has now been found that carbohydrates of the galactomannan type can be used and glucomannans, as they are e.g. B. in the kernels of carob, in guar or in Tamarind seeds occur with B-haloethanesulphonic acid or halo-methanesulphonic acid or their alkali or ammonium salts in an aqueous or alcoholic / aqueous medium Can etherify in the presence of alkaline reactants, with cold water soluble Products are created that do not have the disadvantages described.

It is known to ethereal starch and cellulose in a similar manner. However, because between starch and cellulose on the one hand and carbohydrates of the type the galactomannans, on the other hand, were fundamentally different from each other expect, that the etherification of the latter leads to products, which with minimal alkalinity such a high degree of copiousness and speed result. Also the products are made by etherification of cellulose and starch with B-haloethanesulphonic acid are so unlikely to be advantageous was that the implementation with the said galactomannans and glucomannans too improved products.

Another advantage of the new method is that through the special choice of polysaccharides makes the etherification conditions much milder can be chosen and that the galactomannans and glucomannans without special Pretreatment with the ß-haloethanesulphonic acids and halomethanesulphonic acids or let their salts react, in order to achieve sufficient solubility in cold water of the reaction products, a lower degree of etherification is sufficient than with cellulose or strong.

As halomethanesulfonic acids and B-haloethanesulfonic acids come Consider chloromethanesulphonic acid, bromoethanesulphonic acid, ß-chloroethanesulphonic acid and B-bromoethanesulphonic acid and its alkali and ammonium salts, as they are according to processes which are not the subject of this application, for example by implementing g of Alkyl halides with sodium sulfite, can be prepared as solvents In addition to aqueous salt solutions, water-soluble organic solvents are used, for example Acetone and alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol : as well as butyl alcohols.

The alkaline reactants are, for example, useful Hydroxides and carbonates of the alkali and alkaline earth metals as well as ammonia, primary, secondary and tertiary amines and quaternary ammonium hydroxides.

Their low alkalinity makes those made by this new process Sulphonic acid ethers are extremely useful for a wide variety of purposes, in particular they are suitable for all areas of the textile industry, e.g. B. as a finishing agent, as a sizing agent and as a printing thickener.

After dissolving in cold water, they thicken very quickly of very high yield. Moreover, they are more stable in aqueous solution against salts and alkalis and can be used in textile printing with the greatest advantage insert.

They bring about a better distribution of the dyes in the printing paste and thus push the disadvantageous dye aggregation, especially during printing of dye pigments back.

Their ability to coagulate with borax is remarkable.

They can also be used to stabilize emulsions and Dispersions, as surfactants and as additives promoting dirt-carrying capacity Detergents are used.

The parts mentioned in the examples are parts by weight.

Example li A mixture of 25 parts of locust bean gum, 12 parts Sodium salt of B-chloroethanesulfonic acid (56-58 percent in a mixture with sodium chloride) and 65 parts 80 percent. Isopropyl alcohol is heated to 40-80 ° C and then at the same temperature while stirring slowly with 15 parts over a period of 2 hours a 50 percent Sodium hydroxide solution added. The reaction product is filtered off with 70 percent Aqueous isopropyl alcohol and washed at room temperature in the air dried.

Example 2: A mixture of 25 parts of guar flour, 12 parts of sodium salt of B-chlorathanesulfonic acid (56-58 percent. In a mixture with sodium chloride) and 65 parts 80 percent Isopropyl alcohol is heated to 40-80 ° C and then at 40 ° C below Stir slowly within 2 hours with 15 parts of a 50 percent. Caustic soda offset. The reaction mixture is allowed to react for a further 1/2 hour and is filtered then off, washes with 70 percent. aqueous alcohol after and dries the reaction product in a vacuum at 40 ° C.

Example 3: A mixture of 25 parts of locust bean gum, 65 parts 95 percent n-Butanol and 15 parts of sodium hydroxide solution (50 percent) are heated to 40-80 ° C and then slowly with stirring within 2 hours with a solution of 15 parts of sodium ß-bromoethanesulfonic acid are added to 15 parts of water. The reaction = ' product is neutralized with hydrochloric acid} filtered off, with 70 percent. aqueous alcohol washed and dried.

Example 4: A mixture of 25 parts of tamarind seed meal, 65 parts 95 percent n-Butanol and 15 parts of sodium hydroxide solution (50 percent) are heated to 40-80 ° C and then at the same temperature while stirring within 2 hours and after with a solution of 15 parts of sodium B-bromoethanesulfonate in 15 parts Water added. The reaction product is filtered off after a further 30 minutes, with 70 percent washed aqueous alcohol and dried in vacuo at room temperature.

Example 5: A mixture of 25 parts of locust bean gum, 5 to 10 parts of soda ash, 12 parts of ß-chloroethanesulfonic acid sodium and the formation amount of water or a mixture of alcohol and water necessary for a kneadable mass, is treated in a kneader at 40-60 ° C for two hours, then neutralized, dried and optionally ground.

Example 6: A mixture of 25 parts of guar flour, 5 to 10 parts of soda ash, 12 parts of ß-Chloräthansulfonsaurem sodium and to form a kneadable mass necessary amount of water or mixture of alcohol and water is at 40-60 ° C Treated for two hours in a kneader, then neutralized and dried or dried without neutralization and optionally ground.

Example 7: A mixture of 25 parts of locust bean gum and 65 parts Share 95 percent Isopropanol is warmed to 40-80.degree. Then, while stirring at the same temperature within 2 hours the solution of 10 to 11 parts Sodium chloromethanesulfonic acid in 15 parts of water and 15 parts of a 50 percent. Sodium hydroxide solution added slowly. It is then left to react for a further 30 minutes. That The reaction product is then filtered off, with 70 percent. washed with aqueous alcohol and dried.

Example 8: A mixture of 25 parts of guar flour and 65 parts of 95 percent Isopropanol is heated to 40-80 ° C. Then with stirring at the same temperature within 2 hours, the solution of 10 to 11 parts of Chlormethansulfonsaurem Sodium in 15 parts of water and 15 parts of a 50 percent. Sodium hydroxide solution added slowly. After 30 minutes of post-reaction, the reaction product is filtered off, with 70 percent. washed with aqueous alcohol and dried.

Example 9: A mixture of 25 parts of locust bean gum, 12 parts ß-Chloräthansulfonsaurem sodium (56-58 percent.) And 100 parts of a 5 percent. Sodium chloride solution is applied to a drying roller in a thin layer and at a roller temperature dried from 100-150 ° C. After passing through the drying zone, the product is scraped off and crushed.

Claims (4)

Claims: 1) Process for the production of cold water soluble Inheritance products of carbohydrates from the group of galactomannans and glucomannans, how they z. B. occur in the kernels of carob, in guar or in tamarind seeds, characterized in that the carbohydrates with halogen methanesulfonic acids or ß-Halogenethanesulfonic acids or their salts in aqueous or alcoholic / aqueous Medium can be etherified in the presence of alkaline reactants. 2) Method according to claim 1), characterized in that the halogen methanesulfonic acids or halogenethanesulphonic acids chloromethanesulphonic acid, bromomethanesulphonic acid, B-chloroethanesulphonic acid, B-bromoethanesulfonic acid or its salts are used. 3) Method according to claim l), characterized in that in Presence of water-soluble organic solvents, especially aliphatic Alcohols or acetone will work. 4) Method according to claim 1), characterized in that in aqueous Salt solutions is used as a solvent.