DE1237322B - Process for the production of water-insoluble polysulfonic acids from acrolein polymers or copolymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German KL: 39 c- 25/01

Number: 1237 322

File number: D 43752IV d / 39 c

Filing date: February 28, 1964

Opened on: March 23, 1967

It has been found a process for producing water polysulfonic by reacting acrolein polymers or -Mischpolymerisate with hydrogen sulfide in a strongly acidic aqueous medium to sulfur-containing polymers and the ererhaltenen products, preferably in an aqueous medium at temperatures between about 20 and 100 ⁰ C in a oxidized in a known manner, e.g. B. by means of hydrogen peroxide, nitric acid, oxygen or peracids, optionally reacting the hydrogen sulfide reaction products with aldehydes, preferably with formaldehyde, in an alkaline medium before the oxidation. It is surprising that water-insoluble products are formed even with high contents of sulfonic acid groups. With the help of this process, therefore, aliphatic, water-insoluble polysulfonic acids are easily accessible. The strongly acidic products produced according to the invention are distinguished by a large internal surface area, and they can therefore be used with advantage as acidic catalysts even at higher temperatures. They also split neutral salts, such as. B. sodium chloride, so that they can also be used as ion exchangers. Since the starting material, namely the acrolein polymers and copolymers, can be varied in many ways, the polymers can be adapted to the various purposes of use.

example 1

100 g of polyacrolein [relative viscosity 1.2 dissolved in H ₂ SO ₃ (10%)] are suspended in 1000 qcm of concentrated hydrochloric acid by stirring.

Hydrogen sulfide is passed into this suspension. After 8 hours, a product with a sulfur content of 31.5% is obtained. It is filtered off with suction, washed and, without drying, admixed with 700 ecm 15% hydrogen peroxide while stirring. The reaction temperature between 30 and 6O ⁰ C is maintained by cooling. The use of higher and lower temperatures is possible. After 2 hours the reaction subsides and after about 5 hours it has ended. Yield 145 g, sulfur content 16.5%. Products with a higher or lower sulfur content can be prepared by changing the reaction time and the pressure during the reaction with hydrogen sulfide.

Process for the production of water-insoluble
Polysulfonic acids from acrolein polymers
or copolymers

Applicant:

Dynamit Nobel Aktiengesellschaft,
Troisdorf (district of Cologne)

Named as inventor:

Dr. Robert Büning, Oberlar

Example 2

100 g of polyacrolein (relative viscosity 3.5) are, as described in Example 1, with H ₂ S to form a product

with a sulfur content of 25.3%. 50 g of this product are suspended in 250 cc of 40 ° / ₀ formalin at 75 ⁰ C, and within one hour this is allowed 5 g NaOH in 30 cc of H ₂ O is added dropwise. The product thus prepared with a sulfur content of 20.5% is oxidized with hydrogen peroxide in the manner described in Example 1. The end product absorbs about twice the amount of water as the product according to Example 1, without changing into a gel-like state.

Example 3

100 g of a copolymer of acrolein and vinyl ether with a content of 15% vinyl ethyl ether (relative viscosity 1.8) are suspended in 1000 ecm concentrated hydrochloric acid with stirring, and then hydrogen sulfide is introduced. After a reaction time of 6 hours at 20 ° C., the product becomes Sucked off and washed, in order to then be oxidized according to Example 1. Yield 125 g, sulfur content 10.5%.

Claims (1)

Claim: Process for the production of water-insoluble polysulfonic acids from acrolein polymers or / - - ■ "- ■ 709 520/431 3 4 -Mixed polymers, thereby marked- about 20 and 100 ° C in a manner known per se draws that the polymers are oxidized with sulfur, optionally before the oxy- Hydrogen in a strongly acidic aqueous medium dation the hydrogen sulfide reaction products reacts and the products obtained, preferably with aldehydes, preferably with formaldehyde, in in an aqueous medium, at temperatures between 5 alkaline medium. 709 520/431 3.67 © Bundesdruckerei Berlin