RU2556231C2 - Aromatic polyethers - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: claimed invention relates to aromatic polyethers of constructive and film purpose. Described are aromatic polyethers of formula

, where n = 2-20; z = 2-100; R =

,

.

EFFECT: obtaining aromatic polyethers with high indices of fire-, heat-, and thermal resistance and mechanical characteristics.

6 ex

Description

The invention relates to macromolecular compounds, namely to aromatic polyesters for structural and film purposes.

Aromatic polyesters are compounds that have increased fire, heat, heat resistance, as well as high deformation and strength properties.

Aromatic polyesters based on various oligomers are known.

1. Kharaev A.M., Mikitaev A.K., Kunizhev B.I. Synthesis and some properties of block copolyisulfonarylates. Navy. 1984, A1, pp. 75-78.

2. Mikitaev A.K., Kharaev A.M., Shustov G.B. Synthesis and some properties of block copolyisulfonarylates based on oligosulfonophenolphthaleins. High mole. conn. - 1984, BI, No. 14, t.26. - p. 271-274.

3. Kharaev A.M., Ozden S., Shaov A.H. Synthesis of blok copolyetherether ketones and investigations of their properties. J. Appl. Polym. Sci. - 2002. - Vol. 85. - Is.3. - pp. 485-490.

4. Ozden S., Charaev A.M., Shaov A.H. The synthesis of Polyetheretherketones and investigations of their properties. J. Mater. Sci. - 1999 .-- vol. 34. - P.2741-2744.

The main disadvantage of these polyesters is their low fire resistance. The structure and properties closer to the proposed invention are polyesters based on diane oligoesters and 4,4′-difluorodiphenyl ketone. [RF patent No. 2466151. Aromatic polyesters. Bull. No. 31, 2012]. However, the latter are characterized by low mechanical and thermal characteristics, as well as low oxygen index values.

The objective of the invention is the creation of polyesters with enhanced characteristics of fire, heat, heat resistance, as well as strength properties.

The problem is solved by obtaining aromatic polyesters of the following formula:

where n = 2-20; z is 2-100;

R =

,

,

the interaction of oligoesters of the formula:

with degrees of condensation n = 2-20 [Patent No. 2382756 of the Russian Federation] with 4,4′-dichlorodiphenylsulfone or 4,4′-difluorodiphenylketone in dimethyl sulfoxide. The proposed polyesters are characterized by high rates of fire, heat, heat resistance and strength properties.

Synthesis of polyesters based on 4,4′-difluorobenzophenone.

Example 1. In a three-necked conical flask with a capacity of 250 ml, equipped with a mechanical stirrer, a Dean-Stark trap, a reflux condenser, an inert gas feed barber, 13.3353 g (0.01 mol) of an oligoester with n = 2 with a molecular weight of 1333 was charged 5321, 50 ml of dimethyl sulfoxide, 50 ml of toluene and 2.04 ml of 9.8 N NaOH solution.

The temperature of the reaction mass is raised to 140 ° C and the synthesis is carried out under a stream of inert gas (nitrogen or argon) to completely remove traces of water. After distillation of the azeotropic toluene-water mixture, the reaction mass is cooled to 70-80 ° C, 2.18203 (0.01 mol) of 4,4′-difluorobenzophenone is added. The reaction is carried out at a temperature of 170-180 ° C for 6 hours. The reaction mass is diluted with 150 ml of dimethyl sulfoxide and precipitated in distilled water. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed and dried to constant weight.

The yield is 97%. Z = 40-60.

Example 2. The synthesis is carried out as in example 1, and as an oligoester is taken an oligomer with n = 10 (mol. Mass = 5543.6458).

The yield is 96%. Z = 5-10.

Example 3. The synthesis is carried out according to example 1, and as the oligoester is taken oligomer with n = 20 (mol. Mass = 10806,15).

The yield is 96%. Z = 3-6.

Synthesis of polyesters based on 4,4′-dichlorodiphenylsulfone.

Example 4. The synthesis is carried out as in example 1, only 4,4′-dichlorodiphenylsulfone in the amount of 2.8586 g (0.01 mol) is taken as the dihalide.

The yield is 98%. Z = 40-60.

Example 5. The synthesis is carried out according to example 4, and as the oligoester is taken oligomer with n = 10.

The yield is 97%. Z = 5-10.

Example 6. The synthesis is carried out as in example 4, and as the oligomer is taken oligoester with n = 20.

The yield is 97%. Z = 3-6.

Some properties of aromatic polyesters

Example η _ave. , dl / g T _Art ° C KI,% TGA, 2%, 0C σ _p. MPa % one 0.86 187 40,0 398 83.3 36.6 2 0.79 180 40.5 404 84.5 35,4 3 0.75 183 41.5 409 85.1 32.1 four 0.92 179 40.5 403 79.8 31.8 5 0.90 171 40.5 410 81.6 29.7 6 0.81 170 41.0 413 82,2 28.8

The structure of aromatic polyesters is confirmed by IR spectroscopy. The IR spectra have absorption bands corresponding to the dichloroethylene group, ether bonds, sulfonic and ketone groups, and there are no bands for hydroxyl groups. The results of turbidimetric titration confirm the proposed structure.

The technical result of the invention is to obtain aromatic polyesters with high rates of fire, heat, heat resistance and mechanical characteristics.

Claims (1)

Aromatic polyesters of the formula

where n = 2-20; z is 2-100;