RU2413713C2 - Polycondensation monomer - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a chemical compound of formula

as a polycondensation monomer.

EFFECT: invention enables to obtain a monomer use of which enables to obtain polyesters with good molecular weight values, high fire- and thermal stability, retain good dielectric properties in a wide temperature and frequency range, easily dissolve in common organic solvents and can be processed into articles using conventional methods.

5 ex, 1 tbl

Description

The invention relates to a new chemical compound, specifically to 1,1-dichloro-2,2-di-4 [4 '{1'1'-dichloro-2' - (4 '' - hydroxy-3``, 5 '' -dibromophenyl) ethylenyl} 2 ', 6'-dibromophenoxyphenyl] ethylene of the formula

as a monomer for polycondensation.

The compound 1,1-dichloro-2,2-di (3,5-dibromo-n-hydroxyphenyl) ethylene is known

which is used as a monomer for the synthesis of polyesters [1].

The polymers obtained on its basis are distinguished by high fire resistance, good deformation and strength properties, heat and heat resistance [2-4].

The objective of the invention is to expand the range of monomers with reactive end groups that enter into the polycondensation reaction to obtain polymers with a predetermined set of necessary properties and working under various external conditions.

The problem is solved by obtaining a compound by the interaction of 1,1-dichloro-2,2-di (3,5-dibromo-n-hydroxyphenyl) ethylene with 1,1-dichloro-2,2-di (n-chlorophenyl) ethylene in dimethyl sulfoxide in an inert atmosphere.

Example 1. Obtaining 1,1-dichloro-2,2-di-4 [4 '{1'1'-dichloro-2' - (4 "- hydroxy-3", 5 "- dibromophenyl) ethylene} 2 ', 6'-dibromophenoxyphenyl] ethylene.

29.8362 g (0.05 mol) of 1,1-dichloro-2,2-di (3, 5-dibromo-n-hydroxyphenyl) ethylene, 100 ml of dimethyl sulfoxide (DMSO) and 30 ml of toluene. With stirring, nitrogen is passed and the temperature is raised to 70 ° C. After complete dissolution of 1,1-dichloro-2,2-di (3,5-dibromo-n-hydroxyphenyl) ethylene, 6.33 ml of 15.81 N are added. (0.1 mol) sodium hydroxide solution. The temperature was raised to 130-140 ° C and the azeotropic toluene-water mixture was distilled off. The reaction mass is cooled to 70-80 ° C and 7.9508 g (0.025 mol) of 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene are added. The temperature was raised to 150 ° C and the synthesis was carried out for 3 hours. The resulting mass was diluted with 50 ml of DMSO and precipitated in acidified distilled water. The precipitate is filtered off and washed with distilled water until the filtrate reacts negatively with chlorine ions. The resulting monomer is dried at 80 ° C. under vacuum for 24 hours.

The yield of the target product is a light brown color of 97-98%; softening temperature 96-97 ° C; the content of the basic substance is not less than 99.9%; allowed as an impurity sodium chloride in an amount of not more than 0.05-0.1%; molecular weight 1446.6239; elemental composition,%: C = 34.87 / 34.80; H = 1.81 / 1.82; O = 4.42 / 4.43; Cl = 14.70 / 14.69 (calculated in the numerator, found in the denominator). The content of hydroxyl groups is 2.35 / 2.34 (calculated in the numerator, found in the denominator). Absorption bands were detected in the IR spectra in the region, cm ^-1 : 920-940 (ether bond), 980 (> С = CCl ₂ group), 680-690 (-Ar-Br) 3600-3300 (hydroxyl group) .

Example 2. Obtaining polyethyrylate (PEA).

To the solution, 14.4662 g (0.01 mol) 1,1-dichloro-2,2-di-4 [4 '{1'1'-dichloro-2' - (4 '' - hydroxy-3 '', 5 '' - dibromophenyl) ethylenyl} 2 ', 6'-dibromophenoxyphenyl] ethylene, 2.8 ml of triethylamine are added in 50 ml of 1,2-dichloroethane. With vigorous stirring, 2.0303 g of an equimolar mixture of dichlorohydrides of tere- and isophthalic acids is added to this mixture. The reaction is carried out at a temperature of 25 ° C for 1 hour.

Then the polymer solution is diluted with 50 ml of 1,2-dichloroethane and poured into a 10-fold excess of isopropyl alcohol. The precipitated polymer is filtered off, washed twice with isopropyl alcohol, then with distilled water until the filtrate reacts negatively with chlorions and dried under vacuum at 70 ° C for 24 hours. The polymer yield is quantitative. Polyetherylate is a light yellow fiber with a reduced viscosity of 0.6-0.7 dl / g (for a solution of 0.5 g / dl in chloroform). The decomposition temperature in air is 370 ° C.

Example 3. Obtaining polyester carbonate (PEC).

To the solution, 14.4662 g (0.01 mol) 1,1-dichloro-2,2-di-4 [4 '{1'1'-dichloro-2' - (4 '' - hydroxy-3 '', 5 '' - dibromophenyl) ethylenyl} 2 ', 6'-dibromophenoxyphenyl] ethylene in 30 ml of 1,2-dichloroethane add 2.8 ml of triethylamine. With vigorous stirring, 3.5320 g (0.01 mol) of bisphenol A bischloroformate A is added to this mixture. The reaction is carried out at a temperature of 25 ° C. for 1 hour.

Then the polymer solution is diluted with 50 ml of 1,2-dichloroethane and poured into a 10-fold excess of isopropyl alcohol. The precipitated polymer is filtered off, washed twice with isopropyl alcohol, then with distilled water until the filtrate reacts negatively with chlorions and dried under vacuum at 80 ° C for 24 hours. The polymer yield is quantitative. Polyester carbonate is a light yellow fiber with a reduced viscosity of 0.5-0.6 dl / g (for a solution of 0.5 g / dl in chloroform). The decomposition temperature in air is 360 ° C.

Example 4. Obtaining polyethersulfone (PES).

To a three-necked conical flask equipped with a stirrer, a reflux condenser with a Dean-Stark trap, a bubbler and a thermometer, 14.4662 g (0.01 mol) of 1,1-dichloro-2,2-di-4 [4 '{1' 1'-dichloro-2 '- (4' '- hydroxy-3``, 5' '- dibromophenyl) ethylenyl} 2', 6'-dibromophenoxyphenyl] ethylene, 50 ml of dimethylacetamide, 30 ml of chlorobenzene and added while heating and stirring 1.122 g (0.02 mol) KOH. In a stream of nitrogen at a temperature of 130-140 ° C, water with chlorobenzene is distilled off. After the water and chlorobenzene were completely distilled off, 2.8717 g (0.01 mol) of 4,4'-dichlorodiphenyl sulfone were added to the reaction flask and the reaction was carried out at 170-180 ° C for 6 hours.

The reaction mass is cooled, diluted with 50 ml of dimethylacetamide, precipitated in isopropyl alcohol and washed ten times with hot distilled water and five times with hot isopropanol.

Polyethersulfone is a light brown powder. Yield 95-96%. η _ol = 0.5-0.6 dl / g. The decomposition temperature in air is 390 ° C.

Example 5. Obtaining polyetherketone (PECetone).

To a three-necked conical flask equipped with a stirrer, a reflux condenser with a Dean-Stark trap, a bubbler and a thermometer, 14.4662 g (0.01 mol) of 1,1-dichloro-2,2-di-4 [4 '{1'1'-dichloro-2'-(4''- hydroxy-3``, 5''- dibromophenyl) ethylenyl} 2', 6'-dibromophenoxyphenyl] ethylene, 1.8 g K ₂ CO ₃ , 50 ml dimethylacetamide, 30 ml of chlorobenzene and with stirring is heated to 130-140 ° C. In a stream of nitrogen at a temperature of 130-140 ° C, water with chlorobenzene is distilled off. After the water and chlorobenzene are completely distilled off, 2.1820 g (0.01 mol) of 4,4'-difluorodiphenylketone are introduced into the reaction flask and the reaction is carried out at 170-180 ° C for 6 hours.

The reaction mass is cooled, diluted with 50 ml of dimethylacetamide, precipitated in isopropyl alcohol and washed ten times with hot distilled water and five times with hot isopropanol.

Yield 95-96%. η _ol = 0.4-0.5 dl / g. The decomposition temperature in air is 400 ° C.

The properties of the obtained polymers are presented in the table.

In the practical use of the proposed monomer, polyesters are obtained with good molecular weights, increased fire, heat and heat resistance, which retain good dielectric properties in a wide range of temperatures and frequencies, are easily soluble in ordinary organic solvents and can be processed into products by conventional technological methods.

Literature

1. Kharaev A.M., Mikitaev A.K., Shustov G.B. Properties of unsaturated aromatic polyesters. Plastics. - 1988, No. 10, - p. 17-18.

2. Dobkowski Z., Krajewski Z. Synthesis of polycarbonates by interfacial method. - Polimery twrz. wielkoczastesteczk, 1970, 15, No. 8, P. 428-431.

3. Porejko S., Wielgosz. Synteza i wlasciwosci poliweglanow z chlorobisfenoli Cz.I. - Polymery twrz. wielkoczastesteczk, 1968, 13, No. 2, P. 55-59.

4. Pat. No. 48893 (Poland). The method of obtaining self-extinguishing thermoplastics. - RJH, 1967, 16. S. 255.

Claims (1)

Chemical compound of the formula

as a monomer for polycondensation.