RU2537392C1 - Aromatic block-copolyesters - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to block-copolyesters. Described are aromatic block-copolyesters of formula

where

n=1-20; m=20-50; z=2-50.

EFFECT: obtaining high-strength, heat- and fire-resistant block-copolyesters.

1 tbl, 6 ex

Description

The invention relates to macromolecular compounds, in particular to aromatic block copolymers, which may find application as structural and film materials.

Various block copolymers are known:

- Mikitaev A.K., Kharaev A.M., Shustov G.B. Synthesis and some properties of block copolyisulfonarylates. High mole. Connection - 1984., A, No. 1. T.26. - p. 75-78.

- Charaev A.M., A.K. Mikitaev, G. B. Sustov Ungesattigte aromatische Polyester auf der Basis von Chloralderivaten als Konstruktions- und Folienwerkstoff. Acta Polymerica 39 (1988) Nr. 5, pp. 228-236.

- 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.

- Ozden S., Charaev A.M., Shaov A.H. High impact thermally stable blok copolyethers. J. Mater. Sci. - 2001. - 36. - P.4479-4484.

- Kharaev A.M., Mikitaev A.K., Chaika A.A., Barokova E.B. Modified flame retardant aromatic polyesters. // Chemical industry today, No. 8, 2006, S.24-28.

These polymers are characterized by low thermal and mechanical characteristics.

The closest to the proposed structure and properties are block copolymers based on various oligoketones: 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.

However, these block copolymers have low thermal and fire resistance, as well as deformation and strength properties. The objective of the invention is to provide high-strength heat and flame retardant block copolyesters. The problem is solved by obtaining block copolyesters of the following structure:

Where

;

,

;

,

n is 1-20; m = 20-50; z = 2-50,

the interaction of equimolar amounts of oligoketone of the formula

where n = 1-20,

and bisphenol A with 1,1-dichloro-2,2-di (4-carboxyphenyl) ethylene dichloride or 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene.

The structure of the obtained block copolyesters is confirmed by the results of elemental analysis, IR spectroscopy, and turbidimetric titration.

The proposed block copolyesters exhibit high mechanical strength, thermal and fire resistance.

Synthesis of block copolyesters based on 1,1-dichloro-2,2-di (4-carboxyphenyl) ethylene dichlorohydride acceptor-catalytic polycondensation

Example 1

6.3478 g (0.01 mol) of oligoketone OK-1D, 2.2829 g (0.01 mol) of bisphenol A, 100 ml of dichloroethane, 5.6 ml (0.04 mol) of triethylamine are charged into a three-necked flask with stirring 7.4812 (0.02 mol) of 1,1-dichloro-2,2- (4-carboxyphenyl) ethylene dichloride was added. The reaction is carried out at room conditions for 1 hour. The resulting thick polymer solution is diluted with 100 ml of dichloroethane and precipitated in isopropyl alcohol. The block copolyester is filtered off, washed with water from traces of triethylamine hydrochloride and dried in vacuum at 80 ° C for 48 hours. Yield 95-98%, reduced viscosity 0.8-1.0 dl / g.

Example 2

4.2932 g (0.001 mol) of oligoketone OK-10D, 0.22829 g (0.001 mol) of bisphenol A, 50 ml of dichloroethane, 0.56 ml (0.04 mol) of triethylamine are charged into a three-necked flask, and 0.7481 is added with stirring (0.002 mol) of 1,1-dichloro-2,2- (4-carboxyphenyl) ethylene dichloride. The reaction is carried out at room conditions for 1 hour. The resulting polymer solution is diluted with 50 ml of dichloroethane and precipitated in isopropyl alcohol. The block copolyester is filtered off, washed with water from traces of triethylamine hydrochloride and dried in vacuum at 100 ° C for 48 hours. Yield 96-98%, reduced viscosity 0.6-0.7 dl / g.

Example 3

8.3584 g (0.001 mol) of oligoketone OK-20D, 0.22829 g (0.001 mol) of bisphenol A, 50 ml of dichloroethane, 0.56 ml (0.04 mol) of triethylamine are charged into a three-necked flask, and 0.7481 is added with stirring (0.002 mol) of 1,1-dichloro-2,2- (4-carboxyphenyl) ethylene dichloride. The reaction is carried out at room conditions for 1 hour. The resulting polymer solution is diluted with 50 ml of dichloroethane and precipitated in isopropyl alcohol. The block copolyester is filtered off, washed with water from traces of triethylamine hydrochloride and dried in vacuum at 100 ° C for 48 hours. Yield 95-97%, reduced viscosity 0.5-0.6 dl / g.

Synthesis of block copolyesters based on 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene by high temperature polycondensation

Example 4

2.2829 g (0.01 mol) of bisphenol A, 6.3478 g (0.01 mol) of oligoketone OK are charged into a 200-ml three-necked flask equipped with a mechanical stirrer, Dean-Stark trap, reflux condenser, inert gas bubbler. -1D, 40 ml of dimethylacetamide, 30 ml of chlorobenzene, a mixture of K ₂ CO ₃ and Na ₂ CO ₃ in a ratio of 1.0: 0.3 in the amount of 0.026 mol. The reaction mass is heated to 140 ° C and water is distilled off under nitrogen stream as an azeotropic mixture with chlorobenzene. After the completion of the distillation of all the water, 6.3606 g (0.02 mol) of 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene is added to the reaction mass, and the reaction is carried out at the boiling point of the solvent (oil bath temperature ~ 180 ° C) within 6 hours. The resulting polymer is diluted, precipitated in distilled water, acidified with oxalic acid to destroy phenolate groups, and washed from low molecular weight products. The polymers are dried at a temperature of 100-120 ° C for 24 hours and at 150 ° C for 24 hours. The product yield is 95-98% of theoretical, the reduced viscosity is 1.0-1.1 dl / g.

Example 5

0.2283 g (0.001 mol) of bisphenol A, 4.2932 g (0.001 mol) of OK-10D oligoketone, 40 ml of dimethylacetamide, 30 ml of chlorobenzene, a mixture of K ₂ CO ₃ and Na ₂ CO ₃ in a ratio of 1.0: 0.3 in an amount of 0.026 mol. The reaction mass is heated to 140 ° C and water is distilled off under nitrogen stream as an azeotropic mixture with chlorobenzene. After all water has been distilled off, 0.6361 g (0.002 mol) of 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene is added to the reaction mass and the reaction is carried out at the boiling point of the solvent (oil bath temperature ~ 180 ° C) within 6 hours. The resulting polymer is diluted, precipitated in distilled water, acidified with oxalic acid to destroy phenolate groups, and washed from low molecular weight products. The polymers are dried at a temperature of 100-120 ° C for 24 hours and at 150 ° C for 24 hours. The product yield is 95-98% of theoretical, the reduced viscosity is 0.9-1.1 dl / g.

Example 6

0.2283 g (0.001 mol) of bisphenol A, 8.3584 g (0.001 mol) of oligoketone OK-20D, 40 ml of dimethylacetamide, 30 ml of chlorobenzene, a mixture of K ₂ CO ₃ and Na ₂ CO ₃ in a ratio of 1.0: 0.3 in an amount of 0.026 mol. The reaction mass is heated to 140 ° C and water is distilled off under nitrogen stream as an azeotropic mixture with chlorobenzene. After all water has been distilled off, 0.6361 g (0.002 mol) of 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene is added to the reaction mass and the reaction is carried out at the boiling point of the solvent (oil bath temperature ~ 180 ° C) within 6 hours. The resulting polymer is diluted, planted in distilled water and washed from low molecular weight products. The polymers are dried at a temperature of 100-120 ° C for 24 hours and at 150 ° C for 24 hours. The product yield is 95-98% of theoretical, the reduced viscosity is 0.7-0.8 dl / g.

Below are some properties of block copolyesters.

Table Examples T _tech , ° C σ, MPa ε,% TGA, 10% KI,% one 254 72,4 19.5 453 36.5 2 247 78.1 16,4 461 32,0 3 240 88.5 11,2 479 30.5 four 235 76.6 14.1 487 33,4 5 230 80.3 13.7 499 32,0 6 217 86.9 13.0 511 31.6

The technical result of the invention is to obtain high-strength, heat- and fire-resistant block copolyesters for structural and film purposes.

Claims (1)

Aromatic block copolyesters of the formula

;

.
n is 1-20; m = 20-50; z = 2-50.