RU2816458C1 - Diglycidyl ester of 3,4,5,6-tetrachlorophthalic acid as monomer for production of epoxy polymers - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the use of diglycidyl ester of 3,4,5,6-tetrachlorophthalic acid of the formula

as a monomer for production of epoxy polymers.

EFFECT: expansion of the range of monomers with reactive end groups that enter into polymer synthesis reactions.

1 cl, 1 tbl, 4 ex

Description

The invention relates to chemical compounds, namely to chlorine-containing diglycidyl ether, which can be used as a monomer for the production of epoxy polymers. The technical result is an expansion of the range of monomers with reactive end groups that enter into polymer synthesis reactions.

The use of diglycidyl ester of 3,4,5,6-tetrachlorophthalic acid is proposed

as a monomer for the production of epoxy polymers.

Chlorine-containing epoxy compounds are known, which are used as monomers for the synthesis of epoxy polymers:

1. Pat. Japan No. 15540, ser. 2, Sat. 12-68, publ. 1964.

2. Pat. US No. 3399174, cl. 260-47, publ. 1968.

3. Auto. date USSR No. 684044, C 08G 59/00. Publ. 09/05/79. Bulletin No. 33.

4. Auto. date USSR No. 1219595, C 08G 59/06. Publ. 03/23/86. Bulletin No. 11.

5. Auto. date USSR No. 1126571, C 07D 303/28. Publ. 03/23/86. Bulletin No. 11. 11/30/84. Bulletin No. 44.

The disadvantages of these monomers are the insufficiently high fire resistance and mechanical properties of the epoxy polymers obtained from them.

Closer to those proposed in structure and properties is [6] Pat. RF No. 2757583, C07D 303/44, C08G 59/24. Diglycidyl ester of 4-chlorophthalic acid as a monomer for the production of epoxy polymers. Publ. 10/19/2021. Bulletin No. 29. This source suggests using 4-chlorophthalic acid diglycidyl ester as a monomer to produce epoxy polymers. Although the fire resistance and mechanical properties of the resulting polymers are quite high, they do not have high heat resistance.

The objective of the invention is to expand the range of monomers with reactive end epoxy groups and polymers obtained on their basis with a predetermined set of necessary properties and operating under various extreme conditions.

The problem is solved by obtaining chlorine-containing diepoxide - di[1,2-carboxy-(2,3-epoxy-propane)]3,4,5,6-tetrachloro-benzene by reacting 3,4,5,6-tetrachlorophthalic acid with epichlorohydrin (ECH ) in the presence of a base solution.

Example 1

15.195 g (0.05 mol) of 3,4,5,6-tetrachlorophthalic acid, 18.5 g (0.2 mol) of epichlorohydrin are charged into a three-neck flask equipped with a stirrer, thermometer and reflux condenser. Turn on the stirring and raise the temperature to 65 °C, hold for 45 minutes, add 4.4 g (0.11 mol) of sodium hydroxide in the form of 12.6 N. solution. The temperature rises to 82 °C due to the exothermic reaction. Maintain at this temperature for 90 minutes. After this, the contents of the flask are cooled to 50 °C, the stirrer is removed, a direct cooler is connected, and epichlorohydrin is distilled off under reduced pressure. The contents of the flask are diluted with 150 ml of chloroform and washed with distilled water until the wash water reacts negatively to chlorine ions and is neutral to phenolphthalein. After this, chloroform is distilled off at 70 °C, first at atmospheric pressure, then at reduced pressure. 19.22 g (92.4%) of light yellow powder - diepoxide - di[1,2-carboxy-(2,3-epoxy-propane)]3,4,5,6-tetrachlorobenzene - are obtained. Melting point - 92-94 °C. From the results of elemental analysis, functional analysis, thin layer chromatography, and IR spectroscopy, 3,4,5,6-tetrachlorophthalic acid diglycidyl ester is formed with the formula:

Calculated molecular weight of product = 416.04 g/mol; elemental composition,%:

C = 40.42/40.56; H = 2.42/2.48; O = 23.07/22.75; Сl = 34.09/35.12 (calculated in the numerator, found in the denominator). The content of epoxy groups (%) is 20.6/18.4 (calculated in the numerator, found in the denominator).

In the IR spectra, absorption bands were detected in the region, cm ^-1 : 1076-1063 (C _arom -Cl); 915, 885 (epoxy group); 1730-1710 (ester group).

Example 2

According to example 1, only the amount of epichlorohydrin in the reaction mixture is 37.0 g (0.4 mol). The yield of the reaction product is 19.45 g (93.5%). The content of epoxy groups (%) is 20.6/18.8 (calculated in the numerator, found in the denominator).

Example 3

According to example 1, only the amount of epichlorohydrin in the reaction mixture is 46.25 g (0.5 mol). The yield of the reaction product is 19.72 g (94.7%). The content of epoxy groups (%) is 20.6/18.9 (calculated in the numerator, found in the denominator).

Example 4

According to example 1, only the amount of epichlorohydrin in the reaction mixture is 55.5 g (0.6 mol). The yield of the reaction product is 19.8 g (95.2%). The content of epoxy groups (%) is 20.6/20.1 (calculated in the numerator, found in the denominator).

The synthesized diglycidyl ester of 3,4,5,6-tetrachlorophthalic acid is cured with known amine and anhydride hardeners.

In table Table 1 shows some properties of epoxy polymers obtained from the monomer obtained according to example 4.

Table 1 Epoxy resin Properties of cured epoxy resins Self-extinguishing time, sec σ _resolution, kgf/cm ² T _2%, °C According to example 4 0-1 890-900 435-445 Analogue 1-2 850-880 400-420 σ _res. - breaking stress during static bending;
T _2% - temperature of 2% mass loss in air.

With the applied use of the proposed diglycidyl ester of 3,4,5,6-tetrachlorophthalic acid, polymers with increased values of fire, heat and heat resistance are obtained, retaining good dielectric properties over a wide range of temperatures and frequencies, are easily soluble in conventional organic solvents and can be processed into products using conventional technological methods.

Claims (3)

Application of 3,4,5,6-tetrachlorophthalic acid diglycidyl ester of the formula as a monomer for the production of epoxy polymers.