RU2751105C1 - Diallyl ether of 4-chlorophthalic acid as a monomer for production of thermosetting polymers of increased fire resistance and method for its production - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the production of a new chlorine-containing organic compound – di(1,2-propenyl carboxylate)4-chloro-benzene as a monomer for the synthesis of thermosetting polymers, as well as a method for its preparation. Allyl ether of 4-chlorophthalic acid is claimed as a monomer for the production of thermosetting polymers, as well as a method for obtaining diallyl ether of 4-chlorophthalic acid by treating 4-chlorophthalic acid with allybromide at molar ratios of components 1:4÷1:10 at temperatures of 40-50°C. The object of the invention is to expand the range of monomers with reactive terminal allyl groups and polymers obtained on their basis with a predetermined set of necessary properties, operating under the influence of various external conditions.

EFFECT: invention makes it possible to obtain thermosetting polymers with high values of fire, heat and thermal resistance, maintaining good dielectric characteristics in a wide range of temperatures and frequencies, well soluble in conventional organic solvents and processed on existing serial technological equipment.

2 cl, 1 tbl, 4 ex

Description

The invention relates to new chemical compounds, namely to chlorine-containing diallyl ester of phthalic acid, which can be used as a monomer to obtain thermosetting polymers with increased fire resistance. The technical result is to expand the range of monomers with reactive end groups that enter into polymer synthesis reactions.

The invention relates to a new chemical compound, specifically to di (1,2-propenyl carboxylate) 4-chloro-benzene.

as a monomer for the production of thermosetting polymers.

Known chlorine esters of carboxylic acids exhibiting plasticizing properties [Ed. Testimonial USSR No. 525662. Chlorine-containing esters of carboxylic acids exhibiting plasticizing properties. Publ. 08/25/76. Bull. No. 31].

The proposed compounds exhibit a plasticizing effect with respect to polyvinyl chloride.

Known diallyl esters of iso- and terephthalic acids, and methods for their preparation, which are used as monomers for the synthesis of thermosetting polymers:

Auth. Testimonial USSR No. 420612. Method of producing diallyl esters of phthalic acids. Publ. 03/25/74. Bull. No. 11.

Auth. Testimonial USSR No. 491612. A method of obtaining diallyl ester of isophthalic acid. Publ. 11/15/75. Bull. No. 42.

The disadvantages of these monomers are insufficiently high values of fire resistance and mechanical properties of thermosetting polymers obtained on their basis.

It was not possible to find a description and method for the preparation of diallyl ester of 4-chlorophthalic acid in the available literature.

Closer to the proposed structure and properties is, ed. wit. USSR No. 1520063. A method of obtaining diallyl esters of phthalic acids. Publ. 09/22/86. Bull. No. 41.

This source proposes a method for producing diallyl esters of phthalic acid, in particular, diallyl ester of orthophthalic acid (analog) of the formula:

According to the inventor's certificate, the production of esters is carried out by the reaction of alkali metal salts of ortho-, iso-, and terephthalic acids with allyl chloride at 40-50 ° C in the presence of copper monochloride and sodium bicarbonate using waste water.

The disadvantages of the method for producing ethers are the multistage nature, the use of a large assortment of reagents, a relatively low yield of reaction products, and low fire resistance of thermosetting plastics obtained on their basis.

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

The problem is solved by obtaining a new chlorine-containing diallyl ether - di (1,2-propenyl carboxylate) 4-chlorobenzene by the interaction of 4-chlorophthalic acid with allyl bromide in the presence of an alkali solution.

The invention is illustrated by the following examples.

Example 1

In a three-necked flask equipped with a stirrer, thermometer and reflux condenser, load 5.0145 g (0.025 mol) of 4-chlorophthalic acid, 50 ml of 96% ethanol, 3.65 g (0.0505 mol) sodium hydroxide in the form of 14, 5 n. solution. Stirring is switched on, and the temperature is increased to 50 ° C, 12.1 g (0.1 mol) of allyl bromide are added. Maintain at a temperature of 50 ° C for 60 minutes. After that, the contents of the flask are cooled to 40 ° C, the stirrer is removed, a direct condenser is connected, and a mixture of allyl bromide, water and alcohol is distilled off under reduced pressure.

The contents of the flask - an oily liquid diluted with 50 ml of chloroform and washed with distilled water until a negative reaction of the wash water for bromine ions, and a neutral reaction for phenolphthalein. Thereafter, chloroform was distilled off at 45 ° C under reduced pressure.

6.17 g (88%) of a light yellow liquid, di (1,6-carboxy-2,3-propene) 4-chlorobenzene, are obtained.

From the results of elemental analysis, functional analysis, thin layer chromatography, IR spectroscopy, a diallyl ester of 4-chlorophthalic acid is formed of the formula:

Calculated molecular weight of the product = 280.6466 g / mol; elemental composition,%: C = 59.92 / 59.18; H = 4.67 / 4.25; O = 22.8 / 22.75; Сl = 12.63 / 12.35 (calculated in the numerator, found in the denominator).

The IR spectra revealed absorption bands in the region, cm ^-1 : 1080-1067 (C _arom -Cl); 3070 (stretching vibrations of CH = groups), 1650 (stretching vibrations of -CH = CH ₂ groups); 1730-1720 (stretching vibrations -C = O ester group).

Example 2

According to example 1, only the amount of allyl bromide in the reaction mixture is 18.15 g (0.15 mol). The reaction product yield is 6.27 g (89.4%).

Example 3

According to example 1, only the amount of allyl bromide in the reaction mixture is 24.2 g (0.2 mol). The reaction product yield is 6.35 g (90.5%).

Example 4

In example 1, only the amount of allyl bromide in the reaction mixture is 30.3 g (0.25 mol). The reaction product yield is 6.5 g (92%).

The synthesized diallyl ester of 4-chlorophthalic acid is cured with peroxide curing agents of unsaturated compounds. The proposed connection has a liquid state of aggregation, which makes it possible to obtain on its basis potting compounds, plasticizers with increased fire resistance and other important performance characteristics.

The table shows some properties of the polymers obtained according to example 4 and the analogue, cured with dibenzoyl peroxide.

Table

Cured polymer based Properties of ^{Cured Thermosetting Polymers ⃰} Self-extinguishing time, sec σ _res., kgf / cm ² T _2%, ° C Following example 4 2-3 780-800 310-320 Analogue 9-10 700-730 275-280

σ _res. - breaking stress at static bending;

T _2% is the temperature of 2% weight loss in air.

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

Claims (4)

1. Diallyl ester of 4-chlorophthalic acid of the formula:

as a monomer for the production of thermosetting polymers. 2. A method for producing diallyl ester of 4-chlorophthalic acid according to claim 1, characterized in that it is obtained by treating 4-chlorophthalic acid with allybromide at molar ratios of components 1: 4 ÷ 1: 10 at temperatures of 40-50 ° C.