DE1122710B - Process for the production of polythioethers - Google Patents

Description

Process for the preparation of polythioethers It is known ethylene oxides to be converted into polyethers with the help of alkaline catalysts.

Also adducts of styrene oxide and alkylene oxides, which are used of alkaline solutions as catalysts and with the use of glycols as starting agents have been described (U.S. Patent 2,641,614). Mixed polymerizations are also known which are carried out with vinyl and vinylidene halides have been carried out in the presence of 0.1 to 250 / o styrene oxide (US Pat 2 422 637). Finally, it is also known in the case of the polyaddition of styrene oxide To use boron trifluoride as a catalyst (US Pat. No. 2,792,375). To these methods are oily to viscous substances with a molecular weight from around 400 to 700 can only be obtained if special measures are taken (freezing).

It has now been found that polythioethers can be produced if one styrene sulfide or styrene sulfide substituted in the core or in the side chain using a basic or acidic catalyst, especially one of the Lewis acid type, or of a substance that is under the prevailing conditions To form acids or acidic reacting substances in at least catalytic amounts able to react with itself.

The styrene sulfide that is used for the process according to the invention can be substituted in the core or in the side chain by short alkyl groups be.

In the context of this invention, preferred basic catalysts can be used Alkali metals, alkali hydroxides, sodium amide and pyridine can be used. Under These catalysts, the triethylphosphine is particularly to be emphasized because with this an immediate onset of polymerization can be achieved.

Of the acidic catalysts or of those belonging to the group belong to the Lewis acids, which are preferably used in the context of this invention, boron trifluoride is particularly advantageous as an etherate, iron (111) chloride, Aluminum chloride, zinc chloride, sulfuric acid and naphthalenesulfonic acid are possible. Tetranitromethane can also be used as a catalyst.

Instead of the above-mentioned acidic catalysts, these can also be used Substances are used that are acids or acidic reacting under the reaction conditions Can form substances in at least catalytic amounts. This includes in particular in addition to oxygen, oxidizing agents such as organic, peroxidic compounds, for example Benzoyl peroxide, acetyl peroxide, cumene hydroperoxide. However, the above will be acidic catalysts are also preferred over these.

The substances which can be used as catalysts can be used in amounts of 0.1 up to 100in, based on styrene fullfide, be present in the polyaddition. In general but amounts of up to about 5 ovo are sufficient. The polyaddition according to the invention can be carried out either as a solvent or as a precipitation polyaddition. Benzene is preferably used as the solvent, but can be used with good All other inert solvents such as aliphatic and aromatic solvents are also successful and hydroaromatic hydrocarbons, for example toluene, xylene, decalin, Pentane, hexane, etc., can be used individually or in admixture with one another.

The precipitation polyaddition can be carried out with the best results in petroleum ether will. The use of an inert protective gas is advantageous in all cases, like nitrogen.

The reaction generally lasts for several days at room temperature. However, it can be accelerated so much by increasing the temperature that it is finished in a few hours, for example.

Expediently, temperatures of 90 ° C. should not be exceeded here will. Particularly good results are achieved when using freshly distilled styrene sulfide is used as a starting component.

The resulting polyethers, which in most cases are colorless, clear and are solid to highly viscous and slightly yellowish, have molecular weights the between 1000 and 2000. They are not as brittle as the polyethers, very much stable and only disintegrate at high temperatures. You can fall out a benzene-methanol mixture (1:10).

The polyethers obtainable by the process according to the invention have compared to known products, e.g. B. the polyethers made of styrene oxide, an improved Elasticity and stability.

The polyethers according to the invention can be used for the production of textile auxiliaries or dyes can be used.

Some test results are given in the table below. The experiments were all carried out in sealed ampoules in a thermostat using nitrogen as the protective gas. The molecular weights were determined by the Rast's camphor method No. Catalyst temperature reaction time molecular Type l quantity weight 1 BF3 etherate 1 ° / e 200 C 10 days 1655 colorless, solid 2 FeCl3 1 O / o 200 C 10 days - yellowish 3 AIC13 1 O / o 200 C 10 days 1750 colorless, clear 4 ZnCl2 1 O / o 200 C 10 days 1437 colorless, highly viscous 5 ZnC / CH3OH 1% 200 C 10 days 1837 colorless, highly viscous 6 H2SO4 / diethyl ether 1% 20 ° C 10 days 1640 yellowish, clear, solid 7 naphthalene - 10 / o 500 C 15 hours - colorless, clear sulfonic acid 8 Tetranitromethane 10 / o 500 C 15 hours - yellowish, clear, highly viscous 9 K 20/0 200 C 10 days 1118 solid, yellow 10 KOH 20 / o 200 C 10 days - viscous, yellow 11 AFTER, 28 / o 200 C 10 days 1495 viscous, yellowish 12 triethylphosphine 20/0 200 C immediately 1650 viscous 13 pyridine 20 / o 200 C 10 days 1646 viscous, yellow 14 Benzoyl peroxide 10 / o 500 C 24 hours - colorless, clear

Claims (3)

PATENT CLAIMS: 1. Process for the production of polythioethers, characterized in that one styrene sulfide in the core or in the side chain may be substituted using a basic or an acidic catalyst or a compound that is acidic or acidic under the polymerization conditions capable of forming reactive compounds in at least a catalytic amount. 2. The method according to claim 1, characterized in that as A Lewis acid, sulfuric acid or benzoyl peroxide catalyst is used. 3. The method according to claim 1 or 2, characterized in that the catalyst in amounts of 0.1 to 100 / o, based on styrene sulfide or its Derivative, used. References considered: U.S. Patent No. 2,792 376, 2,792,375.