CS231147B1 - Processing method of polymere materials with hydroxyesther bond esp of technical rubbor - Google Patents

Abstract

The purpose of the invention is to improve the technology production of polymeric materials with hydroxyester technical ties rubber or bleached epoxy resins. The improvement lies in shortening Reeds needed for cross-linking and temperature reduction sieving. To the reaction mixture formed by organic carboxyl compounds, in particular carboxyl, telechelic polymers, and epoxides, catalytic is added combination, consisting of multinucleated chromium complexes of organic aliphatic monocarboxylic acids the number of c-atoms 4 or aromatic and z organic electron donor compounds, in particular tertiary amines, by weight ratio of both components 5 to 95 to 60: 40. This catalytic combination is added in from 0.2 to 6 parts by weight per 100 parts of the reaction mixture. After homogenization the material crosslinks in the future product at 100-160 ° C. Like the electron donor compound is preferably use a chromium-miscible liquid a complex such as quinoline.

Description

The purpose of the invention is to improve the technology for the production of polymeric materials with hydroxyester bonds, in particular for the production of technical rubber or fusible epoxy resins. The improvement consists in shortening the Reindeer required to sulfur and lower the sieve temperature. To the reaction mixture consisting of organic carboxylic compounds, in particular carboxyl, terminated with telechelic polymers, and epoxides, a catalytic combination consisting of a multinuclear chromium complex of organic monocarboxylic acids aliphatic having 4 or aromatic atoms and organic electron donor compounds, in particular tertiary amines, is added. in a weight ratio of Both Components 5 with 95 to 60:40.

This catalyst combination is added in an amount of 0.2 to 6 parts by weight per 100 parts of the reaction mixture. After homogenization, the material crosslinks in the shape of a future product at a temperature of 100 to 160 ° 0. As an electron donor compound, it is advantageous to use a liquid which is miscible with the chromium complex, for example quinoline.

.231 147

231 147

The invention provides a process for the production of polymeric materials and hydroxyester linkages, in particular technical rubber or elasticized epoxy resins, from organic carboxyl compounds, in particular from telechelic polymers terminated with carboxyl functional groups.

The technique of treating carboxyl-terminated telechelic polymers, among which liquid rubbers occupy the dominant position, is currently not sufficiently developed. Due to the specific physical and chemical properties of these materials, processing processes known as Liquid Injection Molding - LIM and Reaction Injection Molding - RIM appear to be promising. The relatively long reaction times of the carboxyl functional groups with the crosslinking and modifying polyepoxide components prevent the efficient use of these investment-intensive technologies.

Shortening of vulcanization times is usually achieved by using basic catalysts, usually tertiary amines. In basic catalysis, it is often insufficient to accelerate the reaction of carboxyl functional groups with epoxide - formation of substituted hydroxy steres, and, in addition, the undesired side-chain etherification reactions are simultaneously accelerated.

Simultaneous enhancement of the catalytic effect and selectivity of the reaction can be achieved by the use of trivalent trivalent catalysts. Its organic complex (AMC-2) is commercially available and its catalytic activity can be blocked, if necessary, by electron donating agents such as alcohols, amines, amides. Odstraněníρ removal of these reagents - for example by evaporation in paint applications - the catalyst efficiency is restored.

- 1232 147

Other known catalysts are polynuclear chromium complexes of substituted salicylic acid. Their catalytic activity is relatively high, but their preparation according to AO 194 148 is relatively expensive and demanding and exhibits a certain induction period in the reaction.

Organic chromium complexes prepared by melting chromium salts with organic acids can also be used to catalyze epoxy carboxylic compounds. However, the catalytic activity of these complexes is greatly reduced in the polar environment. When used in a non-polar environment, the disadvantage is that the complex in powder consistency has only limited solubility in this medium and thus the catalytic activity is reduced again.

Said shortcomings of the known processes for the catalysis of the reaction of carboxylic compounds with epoxides are overcome by the process for the production of polymeric materials with hydroxyester bonds, in particular technical rubber or the flexible epoxy resins according to the invention. SUMMARY OF THE INVENTION The present invention is characterized in that a catalytic combination consisting of polynuclear chromic complexes of organic monocarboxylic acids aliphatic having a number of C-atoms in the chain of> 4 or aromatic and organic electron-donor compounds, in particular tertiary amines, is added to the mixture of carboxylic compounds with epoxides.

at a weight ratio of both components of 5:95, 60:40 and dosed in an amount of 0.202 6 parts by weight per 100 parts of the reaction mixture, after which the homogenized material is cross-linked in the shape of the product at 100 ° C & 160 ° C.

In this way, technical rubber products can be obtained from the prepared mixture of carboxyl-terminated telechelic polymer or oligomer and polyepoxide compound from 0.5 to 10 minutes at a temperature of 150 ° C. «The catalysis used here strongly prefers the formation of hydroxyester bonds over other usually .

As the agent capable of accelerating the reaction catalyzed by chromium complexes, for example, triethylenediamine, but preferably quinoline, can also be used as a solvent for the chromium catalyst; it is poorly soluble in non-polar environments.

231 147

The individual components can be mixed into the mixture sequentially or simultaneously. The latter is advantageous especially when the components form a liquid mixture.

For the production of monolithic technical rubber, it is necessary to use in the catalyst mixture those electron donors whose boiling point exceeds the selected strengthening temperature. The condition does not apply to the production of porous materials. The method is also suitable for solution applications.

The advantages of the process according to the invention are illustrated by the following examples.

Initially, the efficiency of the catalyst combination according to the invention in the catalysis of the reaction of epoxy resins with low molecular weight carboxylic acids was studied in a solution arrangement.

A solution was prepared containing 12.4 g of epoxy resin and 17.9 g of an equimolar portion of oleic acid in 68 ml of toluene. The solution was continuously stirred and heated to 76.5 ° C by boiling tetrachloromethane. The time loss of the carboxyl and epoxide groups was determined by titration and the course was approximated by the second order reaction kinetic equation. Chromium complex of butyric acid was used for catalysis and triethylenediamine was used as electron donor. The values are shown in the following table:

Table I

example C. amount of chromium component amount electron donor fg] rate constant ·, 1 1 0 5.03 2 1 1 23.7

Furthermore, the efficiency of the catalyst combination according to the invention in the catalysis of epoxy resins with carboxyl-terminated telechelic polymers was studied in detail.

acrylonitrile - number average molecular weight of IL

231 147

A mixture was prepared consisting of 1 kg of radical carboxyl-terminated liquid copolymers of butadiene · * 2934 g / mol, content of carboxyl ^{groups, and c} 0oOH 6.56 · Io * ⁴ mol of COOH / g, number average functionality f _n * 1.925 - 0.136 kg and aromatic epoxy resins - «481,5 g / mol} c _epoxy * 6, Ο44 · 1Ο ^ mol epoxy / gj? _{n 2} 2.91. A quinoline solution of the polynuclear chromic butyric acid complex was used for catalysis, in which the quinoline is both a medium and an electron donor. This solution was designated as solution A. Comparative experiments were performed with a solution of the same chromium complex in dioctyl phthalate, where dioctyl phthalate is only a medium to facilitate dispersion of the chromium catalyst · Comparative solution was designated as solution B ·

The catalysed mixture was immediately strengthened in the measuring chamber of the vulcameter. The experimentally determined vulcametric curve was mathematically modeled by a kinetic first-order equation with a delay (induction period). The following characteristics were evaluated by correlation analysis

- induction period t _Q & ύη]

- 1st order velocity constant k ^ [min J

- time of 95% module change t ^ [min ·]

The catalytic effects of the individual mixtures were evaluated using these characteristics. Was carried out:

-comparison of the effects of the catalytic combination according to the invention with the most efficient catalysis by the Or complex itself dissolved in the inactive solvent

- evaluating the ratio of the two components of the combination to the desired effect

-determining the appropriate reaction temperature range ·

The characteristics determined, depending on the individual parameters, are summarized in the following Tables II Ctf IV.

231 147

Table II - Comparison of the catalytic effect of solutions A and B at a vulcanization temperature of 14 ° C, where A - the catalyst combination according to the invention, B - the chromium catalyst solution in DOP and the chromium content in both A and B is 33% by weight

3říkl. C. content of solutions A-B fhmodZJ induction period t _Q fmin] speed constant time 95% of module change t ₉₅ [min] AND (B) AND Β And '- -' & 3 2 1.16 1.48 0,922 0.393 4.41 9.10 4 6 0.53 0.48 2,410 1,456 1.77 2.54 5 0.6 3.30 3.72 0.437 0.239 10.15 , 16.24 6 0.2 9.81 13.67 0.149 0.051 30.0 72.2

Table III - Effect of Catalyst Combination Composition on Catalysis Efficiency at a Total Content of 2 wt./00 d. Mixture and Cure Temperature 140 ° C

he shouted C. content of chromium catalysts [%] induction period t _Q [min] speed constant k ^ fmin] 95% module change time t ₉₅ fminj 7 60 1.36 0.579 6.53 8 5 5.77 0, 1 «3 24.2

Table IV - Dependence of catalysis on temperature at the total content of dw / d mixture and content of chromium component 33% by weight

he said. C. vulcanization temperature [° GJ induction period t _Q [min] rate constant © k ^ ^ nin ~ l] time 95% of module change t _§5 (min]. 9 100 ALIGN! 3.63 0.591 62.10 3 x / 140 1.16 0,922 4.41 LO 160 0.76 1,231 3.21

x / Note The corresponding values from example 3 are used »

SUBJECT OF THE INVENTION

231 147

Claims (2)

Process for the production of polymeric materials having hydroxyether bonds, in particular technical rubber or elasticized epoxy resins, from organic carboxylic compounds, in particular from carboxyl functional end telechelic polymers, characterized in that a catalytic combination consisting of epoxy-containing carboxylic compounds is added to the mixture of polynuclear chromium complexes of organic monocarboxylic acids aliphatic with a number of carbon atoms in the chain> 4, in particular butyric, isobutyric, oleic or aromatic, in particular diisopropylsalieylic acid, and organic electron-donor compounds such as amines, in particular tertiary, by weight No. 5,960: 40 and dosed in an amount of 0.26 parts by weight per 100 parts of the reaction mixture, then the resulting mixture after homogenization and molding force is at a temperature of 100 ° C to 60 ° C. 2. A process for the production of technical rubber according to claim 1, characterized in that the organic electron donor compound is a liquid which is readily miscible with the chromium complex, preferably quinoline. Printed by Moravian Printing Dukes, plant 12, Leninova 21, Olomouc