RU2382054C2 - Unsaturated aromatic oligoesters - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: aromatic oligoesters can be used as oligomers for production of polycondensed polymers. Described are aromatic oligoesters of formula:

, where n=1-20. The method of producing said oligomers involves reacting 4,4'-dioxydiphenylpropane with 1,1-dichloro-2,2-di(4-chlorophenyl)ethylene in an aprotic dipolar solvent - dimethyl sulfoxide at 150°C in an inert gas atmosphere for 3 hours.

EFFECT: obtaining block-copolyesters with high values of reduced viscosity and molecular weight, thermal stability, heat resistance and improved deformation-strength properties.

1 cl, 4 ex

Description

The invention relates to macromolecular compounds, in particular to aromatic oligoesters, which can be further used as oligomers for polycondensation.

Oligomers based on various dioxo compounds and 4,4′-dichlorodiphenylsulfone, 4,4′-dichlorodiphenylketone and other halogen-containing monomers are known [1-3]. However, polymers based on them are characterized by low values of mechanical and thermal properties.

Closer to those proposed in structure and properties are oligosulfones based on 4,4′-dioxidiphenylpropane and 4,4′-dichlorodiphenylsulfone [4]. However, polymers based on them have insufficiently high physicochemical properties.

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

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

as oligomers for the preparation of block copolymers, where n = 1-20, synthesized by the reaction of 4,4'-dioxiphenylpropane with 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene in dimethyl sulfoxide in two stages.

Example 1. The synthesis of oligoester with a degree of condensation 1

To a 150 ml three-necked flask equipped with a stirrer, a reflux condenser with a Dean-Stark trap, a gas bubbler and a thermometer, 2.28293 g (0.01 mol) of 4,4′-dioxiphenylpropane, 20 ml of dimethyl sulfoxide (DMSO) are added and 40 ml of toluene. With stirring, nitrogen is passed and the temperature is raised to 70 ° C. After complete dissolution of the 4,4′-dioxiphenylpropane, 1.96 ml of 10.16 N are added. (0.02 mol) of 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 1.59016 g (0.005 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 10 ml of DMSO and precipitated into acidified distilled water. The precipitate is filtered off and washed with distilled water until the filtrate reacts negatively with chlorine ions. The resulting oligoester 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 94-95 ° 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 = 701.6878; elemental composition,%: C = 75.32 / 75.45; H = 5.42 / 5.31; O = 9.13 / 9.20 (calculated in the numerator, found in the denominator). The content of hydroxyl groups is 4.848 / 4.842 (calculated in the numerator, found in the denominator). In the IR spectra, absorption bands were found in the region, cm ^-1 : 920-940 (ether linkage), 980 (> С = CCl ₂ group), 3600-3300 (hydroxyl group).

Block copolyesters with a yield of 96-97% and reduced viscosity of 1.30-1.47 dl / g were obtained by the method of acceptor-catalytic polycondensation based on the proposed oligoester and dichlorohydrides of iso- and terephthalic acids. As an organic solvent used is 1,2-dichloroethane.

Example 2. Synthesis of oligoester with a degree of condensation of 5

The synthesis is carried out according to example 1. The starting components are taken in the following amounts: 2.73952 g (0.012 mol) of 4,4′-dioxiphenylpropane, 2.36 ml of 10.16 N. (0.024 mol) sodium hydroxide solution, 20 ml DMSO, 40 ml toluene and 3.18032 g (0.01 mol) 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene. The yield of the target product is a light brown color of 97-98%. Softening point 100-104 ° 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 = 2595.2782; elemental composition,%: C = 74.05 / 74.27; H = 4.86 / 4.71; O = 7.40 / 7.47 (calculated in the numerator, found in the denominator). The content of hydroxyl groups is 1.311 / 1.306 (calculated in the numerator, found in the denominator). In the IR spectra, absorption bands were found in the region, cm ^-1 : 920-940 (ether bond), 980 (> C = CCl ₂ group), 3600-3300 (hydroxyl group).

Block copolyesters with a yield of 96-98% and reduced viscosity of 1.05-1.25 dl / g were obtained by the method of acceptor-catalytic polycondensation based on the proposed oligoester and dichlorohydrides of iso- and terephthalic acids. As an organic solvent used is 1,2-dichloroethane.

Example 3. Synthesis of oligoester with a degree of condensation of 10

The synthesis is carried out according to example 1. The starting components are taken in the following amounts: 2.51123 g (0.011 mol) of 4,4′-dioxiphenylpropane, 2.16 ml of 10.16 N. (0.024 mol) sodium hydroxide solution, 20 ml DMSO, 40 ml toluene and 3.18032 g (0.01 mol) 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene. The yield of the target product is brown 97-98%. Softening point 114-117 ° 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 = 4962.2662; elemental composition,%: C = 73.85 / 74.03; H = 4.76 / 4.65; O = 7.10 / 7.17 (calculated in the numerator, found in the denominator). The content of hydroxyl groups is 0.685 / 0.680 (calculated in the numerator, found in the denominator). In the IR spectra, absorption bands were found in the region, cm ^-1 : 920-940 (ether linkage), 980 (> С = CCl ₂ group), 3600-3300 (hydroxyl group).

Using acceptor-catalytic polycondensation based on the proposed oligoester and dichlorohydrides of iso - and terephthalic acids, block copolyesters were obtained with a yield of 96-98% and reduced viscosity of 1.0-1.2 dl / g. As an organic solvent used is 1,2-dichloroethane.

Example 4. Synthesis of oligoester with a degree of condensation of 20

The synthesis is carried out according to example 1. The starting components are taken in the following amounts: 2.39708 g (0.0105 mol) of 4,4′-dioxiphenylpropane, 2.067 ml of 10.16 N. (0.02 mol) sodium hydroxide solution, 20 ml DMSO, 40 ml toluene and 3.18032 g (0.01 mol) 1,1-dichloro-2,2-di (4-chlorophenyl) ethylene. The yield of the target product is brown 95-96%. Softening point 120-125 ° 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 = 9696.2422; elemental composition,%: C = 73.73 / 73.97; H = 4.70 / 4.74; O = 6.93 / 6.81 (calculated in the numerator, found in the denominator). The content of hydroxyl groups is 0.351 / 0.347 (calculated in the numerator, found in the denominator). In the IR spectra, absorption bands were found in the region, cm ^-1 : 920-940 (ether linkage), 980 (> С = CCl ₂ group), 3600-3300 (hydroxyl group).

Using acceptor-catalytic polycondensation based on the proposed oligoester and dichlorohydrides of iso- and terephthalic acids, block copolyesters with a yield of 96-98% and reduced viscosity of 0.77-0.85 dl / g were obtained. As an organic solvent used is 1,2-dichloroethane.

The technical result of the invention is to expand the range of oligomers capable of entering into a polycondensation reaction to obtain block copolyesters with high mechanical and thermal properties.

The proposed oligomers are highly active in acceptor-catalytic polycondensation reactions, as evidenced by the formation of high molecular weight block copolyesters. The block copolymers synthesized based on them are highly soluble in chlorinated hydrocarbons and are easily processed by solution irrigation.

In the practical use of the proposed oligomers, block copolyesters are obtained with good values of molecular weight, increased fire, heat and heat resistance, retain good dielectric properties in a wide range of temperatures and frequencies, and are heat-structured with an increase in many operational characteristics.

LITERATURE

1. Kharaev A.M., Mikitaev A.K., Shustov G.B. et al. Synthesis and some properties of block copolyisulfonarylates based on oligosulfonophenolphthaleins. - Vysokomol. Comp., 1984, T. 26B, No. 4, S. 271-274.

2. Chiang T.C., Ng S. - L. Polymer communications. Polysulphonearylate block copolymers. - Polymer, 1981, v. 22, No. 1, p. 3-5.

3. Patent GB 1078234 A, 08/09/1967.

4. Mikitaev A.K., Shustov G. B., Kharaev A.M. et al. Synthesis and some properties of block copolyisulfonarylates. - Vysokomol. Comp., 1984, T. 26A, No. 1, pp. 75-78.

Claims (1)

Unsaturated aromatic oligoesters of the general formula

where n = 1-20 as oligomers to obtain block copolyesters.