CS256714B1 - Nitrogen derivatives of acrylic acid esters - Google Patents

Abstract

The solution describes nitrogen derivatives of acrylic acid esters of the general formula, where R1 represents a residue derived from diethylamine, diethanolamine, imidazole, piperidine, morpholine, pyrrolidine and R2 is ethyl or hydroxymethyl. By neutralization with formic or acetic acid, they can be converted into the corresponding hydrophilic salts. The compounds are suitable as raw materials for the production of polymers.

Description

The invention relates to nitrogenous derivatives of acrylic esters and their salts with formic and acetic acid.

Acrylates containing a nitrogen atom in their structure are known and have found significant industrial application. They can be prepared by treating an appropriate nitrogen derivative with an acrylating agent such as acrylic acid or a halide, anhydride or ester thereof. In addition to the most commonly used dialkylaminoctanols, various amidophenols (Cs. AO No. 162 957), aryldiethanolamines (Cs. AO No. 169 255), diazonium salts (Cs. AO No. 202 778) are used.

A variety of unsaturated derivatives can be prepared using the karyloylating agent (Jap. Pat. Nos. 55-31141, 55-31142, EP No. 0 084 227, British Pat. No. 2,035,296, 2,086,917).

These procedures are based on the condensation of the acryloying agent with the corresponding du-silicate derivative, which requires removal of either the water, alcohol, acid or salt of the respective halide to yield a pure product, which is further complicated by poor monomer stability.

These problems are substantially eliminated in the preparation of the compounds of the invention whose synthesis is based on the addition of active amine hydrogen to the acrylate group.

The present invention provides nitrogenous derivatives of acrylic acid esters of the general formula

O O

II II

CH2 = CHCOCH2-C (CHaOCCH2CH2R1) z

Where R2 represents

or “N, a

R 2 -C 2 H 5 or CH 2 OH and salts thereof with formic and acetic acid.

The preparation of these compounds can be carried out by treating pentaeritritol triacrylate or trimethylolpropane triacrylate in a molar ratio of 2: 1 with diethylamine, diethanolamine, imidazole, piperidine, morpholine and pyrrolidine. Neutralizing acids can be converted, if desired, to hydrophilic salts which provide opalescent to clear solutions in water. The course of the addition can be most accurately determined by determining the content of unsaturated acrylate bonds. The raw materials used for the synthesis are commercially available, which makes it possible to expand the range of acrylate monomers in a simple and unobtrusive manner.

The invention is further elucidated by way of examples.

Example 1

Preparation of compounds of formula

CH 2 = CHCOOCH 2 (C 2 H 5) C (CH 2 OOCCH 2 CH 2 R 1) 2

The flask was charged with 40 g of a 50% solution of trimethylolpropane triacrylate in methanol. While stirring, the amine was added as a 50% solution in methanol and the batch temperature was maintained at 50 ° C for 1 hour. The alcohol was removed in vacuo. The amounts of amine solutions and product properties are shown in Table 1.

258714

5 6 Table 1 amine weighed (G) amine number (mg KOH / g) n _D ²⁰ acrylic equivalent (mol / 100 g) di- 19.8 253.2 1.4650 0.2267 diethanolamine 28.4 220.9 1.4947 .2006 imidazole 18.4 517.6 1.5132 .2320 piperidine 23.0 239.8 1.4858 .2152 morpholino 23.6 238.7 1.4881 .2133 pyrrolidine 19.2 5.2 * 25 1.48512 .2288

EXAMPLE 2 A flask was charged with 40 g of a 50% solution of pentaeritritol trisacrylate in methyl. Preparation of Compounds of Formula Cohols and following the procedure of Example 1, the amine in methyl alcohol. Amine solution amount

CH 2 = CHC500CH 2 (HOCH 2) The C- properties of the products are shown in Table (CH 2 OOCCH 2 CH 2 R 1) 2 2.

Table 2 amine charge (g) amine number n _o ²⁰ acrylic (mg KOH / g) equivalent (mol / 100 g)

di- 19.6 diethanolamine 28.2 imidazole 18.2 piperidine 22.8 morpholino 23.4 pyrrolidine 19.1

252.1 1.4753 .2254 220.2 1.5023 0.2002 515.9 1.5140 .2311 240.2 1.4952 0.2126 237.1 1.4947 .2134 254.3 1.4944 .2271

Aqueous solutions of the prepared compounds can be prepared by homogenizing 5 g of the respective product with 1.4 g of acetic acid or 1.1 g of formic acid and adding it to water.

The compounds prepared are suitable as raw materials for the production of polymers.

Claims (2)

Nitrogen derivatives of acrylic esters of general formula O O II II CH2 —CKCOCH2 —C (CH2OCCH2CH2Ri) 2 I R2 I will invent where it represents C _{z) 2,} N s CH _Z CH _Z OH N. IN.. or R2-C2II5 or CH2OH and their salts with formic and acetic acid. Severography, n. p. Race 7, Most Price 2,40 Kčs