RU2680596C1 - Unsaturated aromatic polyester - Google Patents

Abstract

FIELD: chemical industry.SUBSTANCE: present invention relates to unsaturated aromatic polyetherketones, which can be used as structural and film materials. Described unsaturated aromatic polyetherketone formula,where z = 30–70.EFFECT: technical result is to obtain unsaturated aromatic polyether ketones, which have high heat and heat resistance, as well as high mechanical characteristics.1 cl, 2 ex

Description

The invention relates to macromolecular compounds, in particular, to unsaturated aromatic polyether ketones, which can be used as structural and film materials with enhanced performance characteristics.

Unsaturated aromatic polyether ketones based on monomers containing a dichloroethylene group are known

1. Kharaev A., Shaov A., Bazheva R. The Synthesis And Stabilization Of Polymer's (monograph). LAMBERT Academic Publishing. Saarbrucken, Germany. 2013, p. 300.

2. A. Kharaev, R. Bazheva, M. Istepanov Aromatic oligo- and polyetherketones based on chloral derivatives (monograph). Palmarium Academic Publishing. Saarbrucken, Germany. 2013, p. 116.

3. RF patent No. 2493178 "Unsaturated block copolyether ethers". Authors: Kharaev A.M., Bazheva R.Ch., Begieva MB Publ. 09/20. 2013. Bull. No. 26.

4. RF patent No. 2497839 "Fire-resistant block copolyether ethers". Authors: Kharaev A.M., Bazheva R.Ch., Kazancheva F.K. Publ. 11/10/2013. Bull. No. 31.

5. Kharaev A.M., Bazheva R.Ch., Kharaeva R.A. Synthesis and properties of unsaturated block copolyester ethers // Plastic Mases. M., 2016. No. 1-2. - S. 24-28.

In structure and properties, closer to the proposed polyetherketone are aromatic polyesters based on unsaturated oligoesters with a dichloroethylene group and 4,4'-dichlorodiphenylketone (or 4,4'-dichlorodiphenyl sulfone) [RF Patent No. 2556231 “Aromatic polyesters”. Authors: Kharaev A.M., Bazheva R.Ch., Kharaeva R.A. publ. 10.07. 2015. Bull. No. 19].

However, these polyesters have low performance indicators.

The objective of the invention is the creation of polyetherketone with high thermal and mechanical characteristics, as well as fire resistance, resistant to various environmental conditions.

The problem is solved by obtaining a new halogen-containing unsaturated aromatic polyetherketone of the formula:

where z = 30-70

the interaction of the monomer 2,2-di- [4,4 '{1'1'-dichloro-2' - (4 "-oxyphenyl) ethylenyl} phenyl carbonate] propane structure [RF Patent No. 2605554" Monomer for polycondensation ". Authors: Bazheva R.Ch., Bazhev A.Z., Kharaev AM et al. Publish. December 20, 2016. Bull. No. 35.]

with 4,4'-dichlorodiphenylketone or 4,4'-difluorodiphenylketone. The proposed polyetherketone is characterized by increased indicators of heat, thermal, fire resistance, as well as mechanical characteristics.

Example 1. Synthesis of polyetherketone based on 4,4'-dichlorodiphenyl ketone

8.4254 g (0.01 mol) of 2,2-di- [4,4 '{1'1'-dichloro-) are charged into a 200 ml three-necked conical flask equipped with a mechanical stirrer, a Dean-Stark trap, and a reflux condenser. 2 '- (4 "-oxyphenyl) ethylenyl} -phenyl carbonate] propane, 50 ml of dimethyl sulfoxide, 30 ml of toluene and with stirring and passing an inert gas raise the temperature of the reaction mass to 80 ° C. After complete dissolution of the monomer add 2.05 ml 9, 77 N NaOH solution, the temperature is raised to 140 ° C. and the azeotropic water-toluene mixture is distilled off, the reaction mixture is cooled to 80 ° C. 2.5111 g (0.01 mol) are added ) 4,4'-dichlorodiphenylketone. The synthesis was carried out at 170 ° C for 6 hours. The polymer solution was diluted with 50 ml of dimethyl sulfoxide, precipitated in distilled water, the polymer was filtered off, washed repeatedly with water until the chlorine ions were negatively reacted. The polymer was dried at 120 ° C. under vacuum for 24 hours. The yield of polyetherketone is 95-96%. The reduced viscosity of a 0.5% solution in chloroform is 0.9-1.1 dl / g. Thermal oxidative stability: 2% loss - 410-412 ° C; 50% loss - 607-609 ° C. Tensile strength - 73-75 MPa. Relative elongation is 22-24%. Fire resistance: KI = 37.5-38.0%. Glass transition temperature - 183-185 ° С. The pour point is 375-377 ° C.

Example 2. Synthesis of polyetherketone based on 4,4'-difluorodiphenyl ketone

In a three-necked 250 ml conical flask equipped with a mechanical stirrer, a Dean-Stark trap, a reflux condenser, 8.4254 g (0.01 mol) of 2,2-di- [4,4 '{1'1'-dichloro- 2 '- (4 "-oxyphenyl) ethylenyl} -phenyl carbonate] propane, 50 ml of dimethyl sulfoxide, 30 ml of toluene and with stirring and passing an inert gas raise the temperature of the reaction mass to 80 ° C. After complete dissolution of the monomer add 2.05 ml 9, 77 n of NaOH solution, the temperature is raised to 140 ° C. and the azeotropic water-toluene mixture is distilled off, the reaction mixture is cooled to 80 ° C., 2.18203 g (0.01 mo b) 4,4'-difluorodiphenylketone and the reaction is carried out at 170 ° C for 6 hours.The polymer solution is diluted with 100 ml of dimethyl sulfoxide, precipitated in distilled water, the polymer is filtered off, washed many times with water. The polymer is dried at 120 ° C under vacuum for 24 hours. The yield of polyetherketone is 97-98%. The reduced viscosity of a 0.5% solution in chloroform is 1.4-1.5 dl / g Thermal oxidative stability: 2% loss - 413-415 ° C; 10% loss - 610-612 ° C. Tensile strength - 78-80 MPa. Relative elongation is 25-26%. Fire resistance: KI = 37.0%. Glass transition temperature - 190-192 ° С. The pour point is 380-383 ° C.

The structure of polyetherketone is confirmed by elemental analysis and IR spectroscopy.

Aromatic polyetherketone is stable in dilute solutions of mineral acids and alkalis.

The technical result of the invention consists in expanding the range of self-extinguishing aromatic polyetherketones with high heat and heat resistance, as well as high rates of mechanical characteristics.

Claims (3)

Unsaturated Aromatic Polyester Ketone Formula

, where z = 30-70.