RU2497841C1 - Unsaturated block copolyester sulphones - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to high-molecular weight compounds, particularly aromatic block copolyesters. Described are unsaturated block copolyester sulphones of formula:

, where

n=1-20; z=2-100.

EFFECT: block copolyesters with improved thermal and mechanical properties as well as fire-resistance.

1 tbl, 13 ex

Description

The invention relates to macromolecular compounds, in particular to aromatic polyesters of block structure, which can be used as structural and film materials with enhanced performance characteristics.

Aromatic block copolyesters based on various oligomers are known. The main disadvantage of such polymers is their low fire resistance: Synthesis and some properties of block copolyisulfonarylates. Mikitaev A.K., Shustov G.B., Kharaev A.M. // High. Comp., 1984, 1A, T.26. - S. 75-78.

Synthesis and some properties of block copolyisulfonarylates based on oligosulfonophenolphthaleins. Kharaev A.M., Mikitaev A.K., Kunizhev B.I. // High. Comp., 1984, 14B, T.26. - S.271-274.

Closer to the structure and properties expected are aromatic block copolyesters based on diane and phenolphthalein oligosulfones and 1,1-dichloro-2,2-di (4-carboxyphenyl) ethylene dichloride: Ungesattigte aromatische Polyester auf der Basis von Chloralderivaten als Konstru und Folienwerkstoff. A.K. Mikitaev, A.M. Charaev, G. B. Sustov // Acta Polymerica. 39 (1988) Nr. 5. S.228-236.

However, polymers based on them have insufficiently high physicochemical properties.

The objective of the invention is the creation of block copolyesters with increased thermal and mechanical characteristics, as well as fire resistance, withstanding the effects of various external conditions.

The problem is solved by obtaining new unsaturated block copolyesters of the general formula:

;

;

where R =

;

;

n is 1-20; z = 2-100

The reaction is carried out by reacting oligosulfones of varying degrees of condensation based on 1,1-dichloro-2,2-di (4-hydroxyphenyl) ethylene and 4,4′-dichlorodiphenylsulfone with an equimolar mixture of iso- and terephthalic acid dichlorides, 1,1-dichloro-dichloride 2,2-di (4-carboxyphenyl) ethylene or 4,4′-difluorobenzophenone.

Synthesis of block copolyesters based on oligosulfones of varying degrees of condensation and an equimolar mixture of iso- and terephthalic acid dichlorides.

Example 1. In a two-necked conical flask with a capacity of 250 ml, equipped with a mechanical stirrer, load 7.7652 g (0.01 mol) of oligosulfone with a degree of condensation of n = 1 and 100 ml of 1,2-dichloroethane. After the formation of a homogeneous solution, 2.82 ml (0.02 mol) of triethylamine are added and, while stirring, an equimolar mixture of iso- and terephthalic acid dichloids in the amount of 2.03 g (0.01 mol) is added to the reaction flask. The reaction is carried out at room temperature for 1 hour. Then the reaction mass is diluted with 100 ml of 1,2-dichloroethane and the polymer is precipitated in isopropanol. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed. Some properties of the obtained block copolyester are given in the table.

Example 2. In a two-necked conical flask with a capacity of 250 ml, equipped with a mechanical stirrer, load 27.58 g (0.01 mol) of oligosulfone with a degree of condensation of n = 5 and 150 ml of 1,2-dichloroethane. After the formation of a homogeneous solution, 2.82 ml (0.02 mol) of triethylamine are added and, while stirring, an equimolar mixture of iso- and terephthalic acid dichloids in the amount of 2.03 g (0.01 mol) is added to the reaction flask. The reaction is carried out at room temperature for 1 hour. Then the reaction mass is diluted with 100 ml of 1,2-dichloroethane and the polymer is precipitated in isopropanol. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed. Some properties of the obtained block copolyester are given in the table.

Example 3. In a two-neck conical flask with a capacity of 250 ml, equipped with a mechanical stirrer, load 52.35 g (0.01 mol) of oligosulfone with a degree of condensation of n = 10 and 200 ml of 1,2-dichloroethane. After the formation of a homogeneous solution, 2.82 ml (0.02 mol) of triethylamine are added and, while stirring, an equimolar mixture of iso- and terephthalic acid dichloids in the amount of 2.03 g (0.01 mol) is added to the reaction flask. The reaction is carried out at room temperature for 1 hour. Then the reaction mass is diluted with 100 ml of 1,2-dichloroethane and the polymer is precipitated in isopropanol. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed. Some properties of the obtained block copolyester are given in the table.

Example 4. In a two-necked conical flask with a capacity of 500 ml, equipped with a mechanical stirrer, load 101.89 g (0.01 mol) of oligosulfone with a degree of condensation of n = 20 and 250 ml of 1,2-dichloroethane. After the formation of a homogeneous solution, 2.82 ml (0.02 mol) of triethylamine are added and, while stirring, an equimolar mixture of iso- and terephthalic acid dichloids in the amount of 2.03 g (0.01 mol) is added to the reaction flask. The reaction is carried out at room temperature for 1 hour. Then the reaction mass is diluted with 100 ml of 1,2-dichloroethane and the polymer is precipitated in isopropanol. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed. Some properties of the obtained block copolyester are given in the table.

Synthesis of block copolyesters based on oligosulfones of varying degrees of condensation and 1,1-dichloro-2,2-di (4-carboxyphenyl) ethylene dichloride

Example 5. In a two-necked conical flask with a capacity of 250 ml, equipped with a mechanical stirrer, load 7.7652 g (0.01 mol) of oligosulfone with a degree of condensation of n = 1 and 100 ml of 1,2-dichloroethane. After the formation of a homogeneous solution, 2.82 ml (0.02 mol) of triethylamine is added and, with stirring, 1,1-dichloro-2,2-di (4-carboxyphenyl) ethylene dichloride in the amount of 3.74 g (0, 01 mol). The reaction is carried out at room temperature for 1 hour. Then the reaction mass is diluted with 100 ml of 1,2-dichloroethane and the polymer is precipitated in isopropanol. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed. Some properties of the obtained block copolyester are given in the table.

Example 6. In a two-necked conical flask with a capacity of 250 ml, equipped with a mechanical stirrer, load 27.58 g (0.01 mol) of oligosulfone with a degree of condensation of n = 5 and 150 ml of 1,2-dichloroethane. After the formation of a homogeneous solution, 2.82 ml (0.02 mol) of triethylamine are added and, with stirring, 1,1-dichloro-2,2-di (4-carboxyphenyl) ethylene dichloride in the amount of 3.74 g (0, 01 mol). The reaction is carried out at room temperature for 1 hour. Then the reaction mass is diluted with 100 ml of 1,2-dichloroethane and the polymer is precipitated in isopropanol. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed. Some properties of the obtained block copolyester are given in the table.

Example 7. In a two-necked conical flask with a capacity of 250 ml, equipped with a mechanical stirrer, load 52.35 g (0.01 mol) of oligosulfone with a degree of condensation of n = 10 and 200 ml of 1,2-dichloroethane. After the formation of a homogeneous solution, 2.82 ml (0.02 mol) of triethylamine is added and, with stirring, 1,1-dichloro-2,2-di (4-carboxyphenyl) ethylene dichloride in the amount of 3.74 g (0, 01 mol). The reaction is carried out at room temperature for 1 hour. Then the reaction mass is diluted with 100 ml of 1,2-dichloroethane and the polymer is precipitated in isopropanol. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed. Some properties of the obtained block copolyester are given in the table.

Example 8. In a 500 ml two-necked conical flask equipped with a mechanical stirrer, 101.89 g (0.01 mol) of oligosulfone with a condensation degree of n = 20 and 250 ml of 1,2-dichloroethane are charged. After the formation of a homogeneous solution, 2.82 ml (0.02 mol) of triethylamine are added and, with stirring, 1,1-dichloro-2,2-di (4-carboxyphenyl) ethylene dichlohydride 3.74 g (0.01 mol) is added to the reaction flask. ) The reaction is carried out at room temperature for 1 hour. Then the reaction mass is diluted with 100 ml of 1,2-dichloroethane and the polymer is precipitated in isopropanol. The precipitate formed is filtered off and washed with distilled water until the chlorine ions are completely removed. Some properties of the obtained block copolyester are given in the table.

Synthesis of block copolyesters based on oligosulfones of varying degrees of condensation and 4,4′-difluorobenzophenone

Example 9. In a three-necked 250 ml flask equipped with a mechanical stirrer, a Dean-Stark trap, a reflux condenser, an inert gas bubbler, 7.7652 g (0.01 mol) of oligosulfone with a condensation degree of n = 1, 50 ml of dimethyl sulfoxide are charged 50 ml of toluene and 2.04 ml (9.8 N) of NaOH solution. The temperature of the reaction mixture 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 toluene, the reaction mass is cooled to 70-80 ° C, 2.18203 g (0.01 mol) of 4,4′-difluorobenzophenone are added. The reaction is carried out for 3 hours at 170-180 ° C. The reaction mass is diluted with 50 ml of dimethyl sulfoxide and precipitated in distilled water. The resulting polymer is washed with distilled water and dried to constant weight.

Example 10. In a three-necked flask with a capacity of 250 ml, equipped with a mechanical stirrer, Dean-Stark trap, reflux condenser, bubbler for an inert gas, 7.7652 g (0.01 mol) of oligosulfone with a degree of condensation n = 1, 20 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 the distillation of all the water, 4.364 g (0.02 mol) of 4,4′-difluorobenzophenone is added to the reaction mass, and the reaction is carried out at the boiling point of the solvent (oil bath temperature ~ 180 ° C) for 3 hours. The resulting polymer is 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.

Example 11. In a three-necked flask with a capacity of 250 ml, equipped with a mechanical stirrer, Dean-Stark trap, reflux condenser, inert gas bubbler, 27.58 g (0.01 mol) of oligosulfone with a degree of condensation n = 5, 30 ml of dimethylacetamide, 30 are charged 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 0.06 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, 4.364 g (0.02 mol) of 4,4′-difluorobenzophenone is added to the reaction mass and the reaction is carried out at the boiling point of the solvent (oil bath temperature - 180 ° C) for 3 hours.

The resulting polymer is 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.

Example 12. In a three-necked flask with a capacity of 250 ml, equipped with a mechanical stirrer, a Dean-Stark trap, a reflux condenser, an inert gas bubbler, 52.35 g (0.01 mol) of oligosulfone with a degree of condensation n = 10, 50 ml of dimethylacetamide, 50 were charged 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 the distillation of all the water, 4.364 g (0.02 mol) of 4,4′-difluorobenzophenone is added to the reaction mass and the reaction is carried out at the boiling point of the solvent (oil bath temperature - 180 ° C) for 3 hours. The resulting polymer is 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.

Example 13. In a three-necked flask with a capacity of 250 ml, equipped with a mechanical stirrer, a Dean-Stark trap, a reflux condenser, an inert gas bubbler, 101.89 g (0.01 mol) of oligosulfone with a degree of condensation n = 20, 100 ml of dimethylacetamide, 100 were charged 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 the distillation of all the water, 4.364 g (0.02 mol) of 4,4′-difluorobenzophenone is added to the reaction mass, and the reaction is carried out at the boiling point of the solvent (oil bath temperature ~ 180 ° C) for 3 hours. The resulting polymer is 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.

Table Some properties of block copolyesters BSP by examples η _pref, dl / g T _c, ° C T _tech, ° C TGA, ° C KI,% σ _p, MPa ε _p, % 2% 10% fifty% one 0.95 171 310 405 455 570 43.0 94.0 5.8 2 0.86 196 315 408 459 572 41.0 90.5 5,4 3 0.69 203 317 410 462 574 40,0 86.3 5,0 four 0.67 210 320 418 471 577 40,0 85,4 4.3 5 1.13 185 324 410 476 590 46.0 97.0 6.3 6 1.10 199 330 412 480 594 46.0 96.0 6.1 7 1,02 213 336 416 491 599 45.5 96.5 6.0 8 0.94 220 340 420 490 603 46.0 95.3 5.8 9 1.40 184 320 404 450 560 42.0 91.0 10,4 10 1.20 183 320 400 450 547 42.0 90.0 10.0 eleven 1,04 180 325 407 460 545 40.5 91.0 12,4 12 0.95 186 333 410 465 540 40,0 84,4 13.3 13 0.90 184 330 410 460 535 39.7 80.0 13.7 Analogue 0.41-1.60 175-260 210-320 330-400 400-450 500-535 30-37 57-84 11-30

The technical result of the invention is to obtain polyesters with high oxygen index values (high fire resistance), high mechanical and thermal properties. The synthesized block copolymers are highly soluble in chlorinated hydrocarbons and are easily processed by solution irrigation.

Claims (1)

Unsaturated block copolyethersulfones of the formula:

Where

;

;

n is 1-20; z = 2-100.