RU2605554C1 - Polycondensation monomer - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a novel chemical compound, specifically to 2,2-di-[4,4′{1′1′-dichloro-2′-(4′′-oxyphenyl)ethylenyl}phenylcarbonate]propane as a polycondensation monomer of formula:

. Compound is obtained by reacting bischloroformate of 4,4′-dioxydiphenylpropane with 1,1-dichloro-2,2-di(4-oxyphenyl)ethylene in 1,2-dichloroethane.

EFFECT: in practical use the proposed monomer enables to obtain polyesters with good molecular weight values, high fire- and heat-resistance, which retain good dielectric properties in wide temperature and frequency range, are easily soluble in common organic solvents and can be processed into articles using conventional technological methods.

1 cl, 1 tbl, 5 ex

Description

The invention relates to a new chemical compound, specifically to 2,2-di- [4,4 ′ {1′1′-dichloro-2 ′ - (4 ″ - hydroxyphenyl) ethylenyl} phenyl carbonate] propane of the formula:

as a monomer for polycondensation.

Known compounds that are used as monomers for the synthesis of polyesters:

1. Monomers for polycondensation / Ed. V.V. Korshak. - M: Mir, 1976 .-- 626 p.

2. Borukaev T., Haraev A., Shaov A. Monomers for polycondensation. Palmarium Academic Publishing, 2014 .-- 92 p.

3. Plate N.A., Slivinsky E.V. Fundamentals of chemistry and technology of monomers. - M.: Science, MAIK "Science / Interperiodica", 2002. - 696 p.

Closer to the proposed in structure and properties is RF patent No. 2401826 "Monomer for polycondensation". Authors: Kharaev A.M., Bazheva R.Ch., Olkhovaya G.G. and other publ. 10/20/2010. Bull. No. 29.

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

The problem is solved by obtaining a compound by reacting 4,4′-dioxiphenylpropane bischloroformate with 1,1-dichloro-2,2-di (4-hydroxyphenyl) ethylene in 1,2-dichloroethane.

Example 1. Obtaining 2,2-di- [4,4 ′ {1′1′-dichloro-2 ′ - (4 ″ - hydroxyphenyl) ethylenyl} phenyl carbonate] propane

14.0570 g (0.05 mol) of 1,1-dichloro-2,2-di (4-hydroxyphenyl) ethylene, 100 ml of 1,2-dichloroethane, 1, 4 are introduced into a 200 ml two-necked flask equipped with a stirrer. ml of triethylamine. After complete dissolution of 1,1-dichloro-2,2-di (4-hydroxyphenyl) ethylene with 8.83 g (0.025 mol) of 4,4′-dioxiphenylpropane bichloroformate, the reaction is carried out at a temperature of 25 ° C for 1 h. The resulting mass diluted precipitated in propanol-2. 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 light brown in color 95-97%; softening temperature 83-85 ° 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 = 842.5428; elemental composition,%: C = 64.15 / 65.00; H = 3.83 /; 3.79, Cl = 8.42 / 8.4 (calculated in the numerator, found in the denominator). The content of hydroxyl groups is 4.04 / 4.08 (calculated in the numerator, found in the denominator).

In the IR spectra, absorption bands were found in the region, cm ^-1 : 1770 (C = O); 1190 (C-O-C); 1495, 1600 ( _{CC aroma} ); 980 (> C = CCl ₂ group); 3600-3300 (OH).

Example 2. Obtaining polyethyrylate (PEA-1)

To a solution of 8.4254 g (0.01 mol) 2,2-di- [4,4 ′ {1′1′-dichloro-2 ′ - (4 ″ - hydroxyphenyl) ethylenyl} phenyl carbonate] propane in 50 ml 1 , 2-dichloroethane, 2.8 ml of triethylamine are added. With vigorous stirring, 2.0303 g of terephthalic acid dichloride is added to this mixture. The reaction is carried out at a temperature of 25 ° C for 1 hour.

The polymer solution was diluted with 50 ml of 1,2-dichloroethane and precipitated with a 10-fold excess of propanol-2. The precipitated polymer is filtered off, washed twice with propanol-2, then with distilled water until the filtrate reacts negatively with chlorine ions and dried under vacuum at 70 ° C for 24 hours. The polymer yield is quantitative.

Polyetherylate is a light yellow fiber, the reduced viscosity is 1.0-1.2 dl / g (for a solution of 0.5 g / dl in chloroform). The onset temperature of decomposition in air is 380 ° C.

Example 3. Obtaining polyethyrylate (PEA-2)

To a solution of 8.4254 g (0.01 mol) 2,2-di- [4,4 ′ {1′1′-dichloro-2 ′ - (4 ″ - hydroxyphenyl) ethylenyl} phenyl carbonate] propane in 50 ml 1 , 2-dichloroethane, 2.8 ml of triethylamine are added. With vigorous stirring, 2.0303 g of isophthalic acid dichloride is added to this mixture. The reaction is carried out at a temperature of 25 ° C for 1 hour.

The polymer solution is diluted with 50 ml of 1,2-dichloroethane and a 10-fold excess of propanol-2 is precipitated. The precipitated polymer is filtered off, washed twice with propanol-2, then with distilled water until the filtrate reacts negatively with chlorine ions 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 0.9-1.1 dl / g (for a solution of 0.5 g / dl in chloroform). The temperature of the onset of decomposition in air is 370 ° C.

Example 4. Obtaining polyethyrylate (PEA-3)

To a solution of 8.4254 g (0.01 mol) 2,2-di- [4,4 ′ {1′1′-dichloro-2 ′ - (4 ″ - hydroxyphenyl) ethylenyl} phenyl carbonate] propane in 50 ml 1 , 2-dichloroethane, 2.8 ml of triethylamine are added. 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.

The polymer solution is diluted with 50 ml of 1,2-dichloroethane and a 10-fold excess of propanol-2 is precipitated. The precipitated polymer is filtered off, washed twice with propanol-2, then with distilled water until the filtrate reacts negatively with chlorine ions 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 0.9-1.3 dl / g (for a solution of 0.5 g / dl in chloroform). The onset temperature of decomposition in air is 380 ° C.

Example 5. Obtaining polyester carbonate (PEC)

To a solution of 8.0738 g (0.01 mol) of 2,2-di- [4,4 ′ {1′1′-dichloro-2 ′ - (4 ″ - hydroxyphenyl) ethylenyl} phenyl carbonate] propane in 30 ml 1 , 2-dichloroethane, 2.8 ml of triethylamine are added. With vigorous stirring, 3.5320 g of bisphenol A bischloroformate A is added to this mixture. The reaction is carried out at a temperature of 25 ° C. for 1 hour.

The polymer solution is diluted with 50 ml of 1,2-dichloroethane and a 10-fold excess of propanol-2 is precipitated. The precipitated polymer is filtered off, washed twice with propanol-2, then with distilled water until the filtrate reacts negatively with chlorine ions and dried under vacuum at 70 ° C for 24 hours. The polymer yield is quantitative. Polyester carbonate is a light yellow fiber with a reduced viscosity of 0.8-0.9 dl / g (for a solution of 0.5 g / dl in chloroform). The temperature at which decomposition begins in air is 350 ° C.

The structures 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, 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.

Claims (1)

Chemical compound of the formula:

as a monomer for polycondensation.