SU1065438A1 - Process for preparing block-polyamidoesters - Google Patents

Abstract

A method for producing a block of polyamide esters by polycondensation of a blocoligoether and an aromatic diamine with aromatic dicarboxylic acid dichlorohydride in an aqueous-organic medium, characterized in that, in order to simplify the technology for producing a high molecular weight polymer, it is used as a blogger patterner to use a patterner and a patterner and a developer will use a patterner by a designer and a developer will use a pattern and a developer will be able to use a patterner or a graphic designer who will use a designer and a designer who will use a patterner and a grouper who will use a patterner and a template will be used as a template for a grouper and a grouper will be used by a person who will work as a block patterner and a template will be used by a person who will work as a block patterner and a template will be used by a group in a group, and a template will be used by a group, and a template will be used by a group, and a template will be used by a group, a group will be used by a group and a group will be used as a template for a high molecular weight polymer.

Description

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CO 00 The invention relates to a block polyamide ester which can be used as a heat resistant polymer Zialov mat (films, fibers, plastic. The closest to the proposed method to the technical essence and the achieved effect is the method of obtaining polyamido esters by polycondensation method carried out in two stages: at the first stage, macrodichlorohydrin is obtained by reacting oligoether glycols with carboxylic acid dichloroanhydrides; at the second stage, macrodichloride anhydride is condensed with a diamine into an emulsion Organic Solvent-Salting System 111 system. However, this method of obtaining block polyamido esters with a rather long duration of the first stage (up to 2 hours), high temperature of the first stage (100-120 ° C, requires the use of an inert gas to remove the reaction gas the mass of hydrogen chloride released in the first stage of the process, the need to use a hydrogen chloride acceptor. The purpose of the invention is to simplify the synthesis of high molecular weight polyamido esters of the block structure. This goal is achieved by the fact that according to the method of producing the polyamide ester of a polycondensate oligo ester block and an aromatic mineral with dichlorohydride aromatic dicarboxylic acid in an aqueous-organic system, an oligoester with terminal amino groups is used as a block oligoether. Amino-terminated oligoether is obtained by saponification of oligoether with isocyanate-terminated groups with strong alkali for 3-60 minutes. This eliminates the need for using an inert gas flow and a hydrogen chloride acceptor, since the latter does not release. I. . The duration of the first stage of the oligoester mineshaft process at 10-30 C. After the time for the conversion of the terminal isocyanate groups to amino groups in the oligoester, the diamine is added to the reaction mass to further condense the latter and the oligoether with terminal amino groups with the dichloro hydrides, which are of the aromatic type, and the amino group with terminal amino groups with the dichlorine hydrides, which are of the aromatic type, and the amino group with terminal amino groups with the dichlorine are hydrides of the aromatic, and the oligoether with the terminal amino groups with the dichloro hydrides are charged to the aromatic group of the latter and the oligoether with the terminal amino groups with the dichlorine in the hydrides of the aromatic, and the oligoether with terminal amino groups with the dichlorine of the hydrides are of the aromatic tetrahydrofuran-water. According to the proposed method, the hydrochloric acid acceptor and the salting out agent are not required to be introduced into the organic water system, since their role is played by the alkali used in the first stage and formed during the saponification of hCO-Na-COj groups. Example 1. 2.610 g (mol% with respect to diamine)) oligoester with terminal isocyanate groups (based on polyoxypropylene glycol with mol lOOO) is washed in 25 ml of water in the presence of 3,000 g of sodium hydroxide for 5 minutes at 10 30 C with slow stirring. At the end of the saponification, 1.6 to 11 g (90 mol.%) Of m-phenylenedioylmine dissolved in 25 ml of water was added to the reaction solution. To a vigorously stirred aqueous solution of an oligoester, with terminal amino groups, m-phenylenediamine (m-FDAV and caustic sodium, are quickly added 1.720 g (50 mol.%) Of terehydrofuran dichloride and 1.720 g mol.%) Of isophthalic acid, dissolved in 50 ml of tetrahydrofura (THF). The reaction mass is stirred for 3 minutes and precipitated with water, the polymer precipitated is filtered off, washed with hot water until the chlorine ions disappear and dried at 100-110 ° C for 10 hours. The polymer yield is 96% of the theoretical. The reduced viscosity of the polymer solution in dimethylformamide with the addition of 5 wt.% Lithium chloride (Cs.-) is 0.68 dp / g. The duration of the synthesis is reduced compared with the current method from 30 to 5 minutes. Example 2. The polymer is prepared according to the procedure described in Example 1, except for the time of oligo ester saponification with terminal isocyanate groups, which is 15 minutes. The polymer yield 92% of theoretical. The reduced viscosity of the polymer solution is 1.00 dl / g. . Example 3. 5.220 g (20 mol.% By weight of diamine) of the oligoester with terminations and isocyanate groups are washed in 25 ml of WATER in the presence of caustic sodium in the amount of 3,000 g for 5 minutes at 10-30 ° C with slow drying. After the saponification time, 1.432 g (80 mol%) m-FDA, dissolved in 25 ml of water, is added to the reaction solution. To a vigorously stirred aqueous solution of an amino-terminated oligoester, m-FDA and sodium hydroxide, 1.720 g (50 mol.%) - dichlou terephrous anhydride and 1.720 g (50 mol.%) Of isophthalic acid, dissolved in 50 ml of THF, are quickly added. Polycondensation time 3 min. The reaction mass is precipitated with water, filtered off (from precipitated polymer, washed with hot water "until there are no chlorine ions, and dried at 100110 ° C for 10 hours.

The polymer yield 92% of theoretical. The reduced viscosity of the polymer solution in the form of naphthan formamide 9 with the addition of 5 wt.% UC1 0.48 dl / g. The duration of the synthesis is reduced compared with the existing method from 120 minutes to 5 minutes.

Example. 4. The polymer is obtained according to the procedure described in Example 3, except for the time from the addition of the oligoester to the ends of the isocyanate groups, which is 15 minutes. The polymer yield 94% of the theoretical. The reduced viscosity of the polymer solution in dimethylformamide with the addition of lithium chloride is 0.66 dp / g.

For example 5. Prlimer poluptstsot according to the method described in example 3, except for the saponification time, oligoester. With terminal isocyanate groups, which is 30 minutes. Polymer yield 95% of theoretical. The reduced viscosity of the polymer-dimethylformamide solution with the addition of 5 wt.% L (56 dl / g.

Example 6. The polymer is prepared according to the procedure described in Example 3, with the exception of the oligoester olysomer with the ends of isocyanate groups, which is 60 minutes. Polymer yield 93% of theoretical ..

The viscosity of the polymer solution in dimethylformamide with the addition of 5 wt.% UQu is 0.60 dp / g.

This method of producing a block polyacdioether leads to a simplification of the synthesis technology (the need to use an hydrogen chlorine acceptor on the second stage of ISO # eliminates), the duration of synthesis (by 0.08–1 h) and synthesis temperature (to 10–30 ° C) decrease,

Claims (1)

METHOD FOR PRODUCING BLOCK-POLYAMIDE ETHERS by polycondensation of block oligoester and aromatic diamine with aromatic dicarboxylic acid dichloride in an aqueous-organic medium, characterized in that, in order to simplify the technology for producing high molecular weight polymer, oligomers are used as block oligoesters.