DE1126611B - Process for the production of unsaturated nitrogen-containing macromolecular polycondensation products - Google Patents

Description

Process for the preparation of unsaturated nitrogen-containing macromolecular Polycondensation products It is known that in the implementation of aliphatic Obtains dihalogen compounds with amines oligomeric amines. So from 1,2Die chloroethane with aqueous ammonia at 110 to 140 ° C and at 25 to 30 atmospheres in addition to ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine and further condensed bases.

If one uses aliphatic dihalides, in which the two halogen atoms separated by four, five or six atomic members, with amines to form preferably nitrogen heterocycles.

It is also known that anhydrous ammonia can be mixed with dihalohydrocarbons can convert to insoluble condensation products.

However, relatively low molecular weight products are obtained.

It has now been found that macromolecular polycondensation products are obtained when halobutenes of the formula in which R denotes hydrogen atoms, alkyl, aryl or aralkyl radicals, X denotes identical or different halogen atoms and Y denotes a halogen atom or cyano, aryl, alkoxy or phenoxy radicals, with ammonia, primary amines or with amino compounds which have at least two alkylatable Have hydrogen atoms on the nitrogen atom, or reacts with their alkali salts in the presence of water or organic solvents.

The reaction takes place in aqueous suspension or in organic Solvents, e.g. B. in alcohols, at temperatures between about 0 and 100 C, expediently at room temperature.

Due to the presence of the radical Y in the 3-position of the halobutene the halogen atoms get a different mobility, so that the implementation with the amino compound probably proceeds in two stages. This is how it becomes possible, beyond low degrees of condensation to form highly condensed substances reach.

The unsubstituted and substituted halobutenes can be used as halobutenes 1,3,4-trihalobutene-2, such as 1, 3,4-trichlorobutene-2, 1, 3,4-tribromobutene-2, 1,4Die bromine - 3 - chlorobutene - 2, 1,4 - dichloro - 3 - bromobutene - 2, 1,3,4-trichloropentene-2, or the corresponding 3-substituted cyano, methyl, methoxy or phenoxy compounds, such as B. 1,4-dichloro-3-cyano- butene-2, 1, 4-dibromo-3-methoxybutene-2, 1,4-dichloro-3-phenoxybutene-2 and 1,4-dibromo-3-methylpentene-2 can be used.

In addition to ammonia, amino compounds such as primary amines such as methylamine, Ethylamine, hydrazine, hydroxylamine, cyanamide and other amino compounds are used which have at least two more alkylatable hydrogen atoms, for example unsubstituted or N-substituted alkylenediamines or melamines. These connections can be used as free amines. It is useful to bind the to be split off hydrogen halide an equivalent amount of the same or one to add other, weaker basic amine during the reaction.

The compounds can also be in the form of their alkali compounds, such as B. unsubstituted or substituted sodium amide or sodium sulfanilamide, used for implementation.

The degree of condensation of the macromolecular amines depends on the reaction conditions away.

Longer reaction times and elevated temperatures result in products with a higher degree of condensation. The low molecular weight products dissolve to Partly in water or in dilute acid and can be salted out with salt solutions or precipitate with alkalis. Those precipitated from the aqueous solution with alkalis macromolecular amines are rubber-like substances that can condense afterwards and solidify in the process. The high molecular weight products are infusible and insoluble in water.

From 1,3,4-trichlorobutene-2, for example, at 20 hours Action of excess ammonia in methanolic solution in addition to ammonium chloride produce a high molecular weight amine that dissolves in water. That from this solution precipitated rubber-like product solidifies to a hard plastic after days. If methylamine is reacted with 1,3,4-trichlorobutene-2 in the presence of ammonia, so you get products that remain elastic.

The substances obtainable by this process can be used for textile and paper finishing, as coating raw materials, as adhesives or as ion exchangers be used.

The parts mentioned in the examples are parts by weight.

Example 1 2000 parts of methanol are mixed with ammonia gas at room temperature saturated. 1120 parts of 1,3,4-trichlorobutene-2 are added at 5 to 10 ° C. At a At a temperature below 203 C, ammonia gas is passed in. The reaction mixture is stirred at 15 to 20 ° C. for 20 hours. Then ammonia and methanol distilled off in vacuo at 20 to 30 C. The residue is three times with 1300 Parts of water washed out, whereupon it dissolves cloudy in 4000 parts of water. By Acidification to Pn 3, the macromolecular amine hydrochloride solution becomes clear, and thus further condensation to insoluble products is avoided at the same time. To the Cleaning can be done by salting out this solution with concentrated saline and redissolve the precipitated product in water. With alkalis, e.g. B. with soda, Sodium hydroxide solution or ammonia becomes the macromolecular solution from the aqueous solution obtained Amine precipitated as a rubber-like, initially elastic mass, which precipitated after a few days hardens completely.

Example 2 To 155 parts of methylamine, dissolved in 120 parts of methanol, 800 parts of trichlorobutene are added at 5 to 10 ° C. The reaction mixture is stirred first 3 hours at 15 to 200 C and then another 20 hours with the introduction of gaseous ammonia. Working up is carried out as described in Example 1.

With alkalis, products are obtained from the aqueous polyamine solution, which do not become hard, but remain flexible.

Example 3 160 parts of 1, 3,4-trichlorobutene-2 are mixed with 300 parts stirred concentrated aqueous ammonia for 20 hours. Most of the excess Ammonia is distilled off in vacuo.

The small amounts of ammonia remaining in the reaction mixture are neutralized with dilute hydrochloric acid. The reaction mixture is, as in Example 1 described, worked up. One receives from the aqueous polyamine solution a rubber-like product that hardens after a few days.

Claims (1)

PATENT CLAIM: Process for the preparation of unsaturated nitrogen-containing macromolecular polycondensation products, characterized in that halobutenes of the formula in which R denotes hydrogen atoms, alkyl, aryl or aralkyl radicals, X denotes identical or different halogen atoms and Y denotes a halogen atom or cyano, aryl, alkoxy or phenoxy radicals, with ammonia, primary amines or with amino compounds which have at least two alkylatable Have hydrogen atoms on the nitrogen atom, or reacts with their alkali salts in the presence of water or organic solvents. References considered: U.S. Patent No. 2268 620.