RU2585281C1 - Aromatic block copolyester ketones - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to aromatic block copolyester ketones of formula:

where

n, m and z are equal to 1-20, 20-50 and 2-50, respectively.

EFFECT: data block-copolymers can be used as high-strength, heat-and heat resistant structural and film materials.

1 cl, 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 oligoketones and block copolymers based on them are known:

- 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. - pp. 485-490.

- Ozden S., Kharayev A.M., Shaov A.Kh., Bazheva R.Ch. The synthesis of blok copolyetheketones on 4,4′-dichlodiphenylketone, phenolphthaleine and bisphenol A and investigation of their properties. / J. of Applied Polymer Science. 2008. V. 107, I. 4, P. 2459-2465.

- Kharaev A., Shaov A., Bazheva R. The Synthesis and Stabilization of Polymers (Monograph). Saarbrucken, Deutschland / Germany: Palmarium Academic Publishing. ISBN-13: 2013.978-3-659-48590-9.

- RF patent 2493178, publ. 09/20/13, bull. No. 26. Kharaev A.M., Bazheva R.Ch., Begieva M.B. Unsaturated block copolyether ether ketones.

- RF patent 2327680, publ. 06/27/2008, bull. 18. Kharaev A.M., Bazheva R.Ch., Istepanova O.L. and others. Aromatic oligoester for polycondensation.

- RF patent 2497839, publ. 11/10/2013, bull. 31. Kharaev A.M., Bazheva R.Ch., Kazancheva F.K. Fire-resistant block copolyether ether ketones.

These polymers are characterized by low deformation-strength characteristics.

Closer copolymers according to the patent of the Russian Federation No. 2537392 by A. Haraev, A. Bedanokova, R. Ch. Bazhevoy, MB Begieva, N. I. Mashukova are closer to those proposed in structure and properties. Aromatic block copolyesters. Publ. 01/10/2015. Bull. No. 1.

However, these block copolymers have low indicators of heat and heat resistance, as well as deformation and strength properties.

The objective of the invention is the creation of high-strength heat-resistant 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 copolyester ethers exhibit high mechanical strength, heat and heat resistance.

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

Example 1

8.1485 g (0.01 mol) of oligoketone OK-1F, 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 a temperature of 20-25 ° C for 1 h. The resulting 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 0.6-0.8 dl / g.

Example 2

5.288 g (0.001 mol) of oligoketone OK-10F, 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 (0.002) are added with stirring mole) 1,1-dichloro-2,2- (4-carboxyphenyl) ethylene dichloride. The reaction is carried out at a temperature of 20-25 ° C for 1 h. 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

10.2488 g (0.001 mol) of oligoketone OK-20F, 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 a temperature of 20-25 ° C for 1 h. 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, 8.1485 g (0.01 mol) of oligoketone are charged into a 200 ml three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap, a reflux condenser, an inert gas bubbler. OK-1F, 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 distilling off 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 was diluted with dimethylacetamide, 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, reduced viscosity is 0.9-1.0 dl / g.

Example 5

0.2283 g (0.001 mol) of bisphenol A, 5.2838 g (0.001 mol) of oligoketone OK-10F, are loaded into a 200-ml three-necked flask equipped with a mechanical stirrer, Dean-Stark trap, reflux condenser, inert gas bubbler. 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 the completion of water distillation, 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) in within 6 hours. The resulting polymer was diluted with dimethylacetamide, 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 0.8-0.9 dl / g.

Example 6

0.2283 g (0.001 mol) of bisphenol A, 10.2488 g (0.001 mol) of oligoketone OK-20F, are loaded into a 200-ml three-necked flask equipped with a mechanical stirrer, Dean-Stark trap, reflux condenser, inert gas bubbler. 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 the completion of water distillation, 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) in within 6 hours. The resulting polymer was diluted with dimethiacetamide, precipitated 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.

The table shows some properties of block copolyester ethers.

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

Claims (1)

Aromatic block copolyetherketones of the formula

Where

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