DE1094454B - Process for the preparation of polyester amides by reacting carboxylic acid anhydrides with basic ethylene imines substituted on the nitrogen atom - Google Patents

Description

GERMAN

It is known that the alkyleneimines and their derivatives are very reactive substances. One has Among other things, ethyleneimine or its derivatives are reacted with dicarboxylic acids or their chlorides. However, only mixtures of non-determinable compounds that are necessary for a technical Use are of no interest.

From German patent specification 711 408 and the corresponding US Pat. No. 2,382,185 it is known to produce nitrogen-containing condensation products by an alkyleneimine or a polymeric alkyleneimine with long-chain carboxylic acids or of course occurring fatty acid mixtures or cyclic carboxylic acids or their anhydrides or esters.

However, these known processes give products which cannot be used industrially. For example, when succinic anhydride is reacted with N-cyclohexylethyleneimine, only a brown-colored mass is obtained, which softens at 66.degree. Is replaced in this case by N-Cyclohexyläthylenimin N-Phenyläthylenimin, we obtain a yellow-brown-colored mass which softens already at 61 ⁰ C. Finally, the reaction of maleic anhydride with N-methylethyleneimine is so violent that it can hardly be carried out on an industrial scale. A dark-colored, crumbly reaction product is formed.

Surprisingly, it has now been found that industrially valuable polyester amides are obtained when substituted at the nitrogen atom, reacting a basic reaction Äthylenimine at temperatures between -20 and + 150 ⁰ C and phthalic anhydride. According to the method of the invention, polyester amides are obtained which are colored only slightly yellowish in contrast to the known products, and in general only at temperatures over 100 ⁰ C to soften. Ethyleneimines which are substituted on the nitrogen atom by an alkyl, cycloalkyl, aryl or aralkyl radical may be mentioned as examples of suitable basic ethylene imines which are substituted on the nitrogen atom. The ethyleneimines substituted on the nitrogen atom are z. B. can be prepared by reacting N-substituted / ϊ-chloroethyl urethanes in organic solvents with alkali metal hydroxide.

Basically reacting compounds which have several on the nitrogen atom can also be used for the reaction contain substituted, basic reacting ethyleneimine radicals. Such substances are z. B. Connections of the general formula

Method of manufacture
of polyester amides by implementation

of carboxylic acid anhydrides
with substituted on the nitrogen atom,
Ethylenimmune with a basic reaction

Applicant:

Aniline & Soda Factory in Baden.

Corporation,

Ludwigshafen / Rhine

Dr. Hans-Georg Trieschmann, Dr. Wolfgang Arend,

Ludwigshafen / Rhine,

and Lothar Reuter, Ludwigshafen / Rhein-Oppau,
have been named as inventors

In the process of the invention, compounds containing only one ethyleneimine group are formed contain linear, high molecular weight, solid polyester amides. So you get z. B. in the implementation of Phthalic anhydride with N-butylethyleneimine a light yellow colored Polyester amide soluble in methanol, butanol or tetrahydrofuran and the following repeating basic unit

O O

-CH ₂ -CH ₂ -NC CO

H ₉ C ₄

HX ₁

.CH,

CHg

in which R _{1 represents} an alkylene or cycloalkylene radical.

in the chain contains. Compounds containing two ethyleneimine groups give with phthalic anhydride highly cross-linked, sparingly soluble polyester amides.

The reaction proceeds at temperatures between -20 and +150 ⁰ C without the addition of catalysts. Since the exothermic reaction often progresses very quickly, intensive cooling of the reaction mixture is sometimes necessary. However, in order to dissipate the heat better, it is also possible to add inert solvents as diluents, such as aromatic, hydroaromatic or chlorinated hydrocarbons, to the reaction mixture. Water or compounds containing hydroxyl groups should not be present during the reaction.

In the process of the invention, polyester amides are produced in practically quanti-

009 677/464

relative yields. It is particularly noteworthy that no polyethyleneimines are formed.

In general, the reaction is carried out with approximately equimolecular amounts of the starting materials. However, it is also possible to work with an excess of one of the starting compounds by the length of the chain to regulate the polyester amides.

The polyester amides obtained by the process of the invention are available as paints, adhesives and Can be used commercially for the coating of textiles, paper or artificial leather.

The parts mentioned in the examples below are parts by weight.

example 1

A solution of 99 parts of N-butylethyleneimine in 500 parts of benzene is refluxed. To this mixture is added at the boiling point in the course of a Hour a solution of 148 parts of phthalic anhydride in 1500 parts of benzene. 2 hours after adding the phthalic anhydride the mixture is allowed to cool. The polyester amide formed has failed and has in the lower part of the vessel. Now the benzene comes first with no mechanical separation of the two layers distilled off at normal pressure and then in vacuo. 239 parts of a light yellow color remain in the flask Polyesteramide, which is readily soluble in tetrahydrofuran. It softens at 132 ° C and has the molecular weight 11600.

Example 2

11.9 parts of N-phenylethyleneimine in 20 parts of xylene given. The reaction mixture is then refluxed for a further 3 hours. After this Evaporation of the xylene under reduced pressure gives 26 parts of polyesteramide which softens at 130.5 ° C and has a molecular weight of 9200.

If 10 parts of succinic anhydride are used instead of phthalic anhydride, one obtains under otherwise the same conditions as a yellow-brown colored mass, ίο which softens already at 61 ° C.

Example 4

A solution of 22.8 parts of N-methylethyleneimine in 22 parts of toluene is added to a solution of 43.5 parts of phthalic anhydride in 40 parts of toluene with stirring at 100 ^{° C.} The reaction mixture is then kept at a temperature between 100 and 120 ° C. for 3 hours. After evaporation of the solvent under reduced pressure, 45 parts of a yellowish polyesteramide are obtained which softens at 116.3 ° C. and dissolves in tetrahydrofuran. It has a molecular weight of 7500. If 33.3 parts of maleic anhydride dissolved in 40 parts of toluene are used instead of the phthalic anhydride, the reaction mixture immediately turns dark when this solution is added and boils up very violently. Under otherwise identical reaction conditions, 41 parts of a dark brown, crumbly reaction product are then obtained which begins to decompose before it softens.

The solution of 12.5 parts is added to the boiling solution of 14.5 parts of phthalic anhydride in 15 parts of xylene Given N-Cyclohexyläthylenimin in 20 parts of xylene. The reaction mixture is then refluxed for a further 3 hours. After evaporation of xylene under reduced pressure, 26.5 parts of yellowish polyester amide are obtained, which has a softening point of 160 ° C and has a molecular weight of 10,500.

If 10 parts of succinic anhydride are used instead of phthalic anhydride, one obtains under otherwise the same conditions as a brown-colored mass, which softens at 66 ° C.

Example 3

To the boiling solution of 14.5 parts of phthalic anhydride in 15 parts of xylene, a solution of

Claims (2)

Patent claims: 1. A process for the preparation of polyester amides by reaction of carboxylic anhydrides with substituted on the nitrogen atom, basically reacting Äthyleniminen, characterized in that reacting the Äthylenimine at temperatures between -20 and + 15O ⁰ C and phthalic anhydride. 2. The method according to claim 1, characterized in that the reaction is carried out in the presence of performs indifferent solvents. Considered publications:
German Patent No. 711408;
U.S. Patent No. 2,382,185. © 009 677/464 11.60