SU413773A1 - The method of obtaining sulfolanolic esters of acrylic or methacrylic acid - Google Patents

Description

one

The invention relates to a process for the preparation of sulfur-containing monomers, in particular acrylic or methacrylic acid sulfolanol esters.

Sulfolanol esters of acrylic or methacrylic acids can be used as monomers for homo- and copolymerization, as well as intermediates for organic synthesis.

Sulfolanol esters of acrylic or methacrylic acids are not described in the literature and are valuable in that, having a sulfolane ring in its composition, makes it possible to obtain polymers with a number of useful properties (for example, high dielectric properties) that can be enhanced or modified by introducing various substituents in the original monomer.

A known method for the preparation of methacrylic acid esters containing sulfur, for example alkylthioethylthioethylthiol methacrylates, by reacting alkylthioethylthioethylthiol mercaptans with methacrylic acid chlorohydride in the presence of an aqueous alkali solution after cooling.

In order to obtain new monomers with new properties, a method has been proposed for the preparation of sulfolane esters of acrylic or methacrylic acid, which consists of

interactions of oxysulfolanols with acrylic or methacrylic acid chlorides at 20-90 C.

Target products are obtained with 80-95% yield.

Example 1. A mixture of 3 g (0.018 mol) of 3-hydroxy-4-methoxytetrahydro-thiofuefdoxide — 1.1 and 10 g (0.095 mol) of methyryl acid chloride was stirred at 65–70 ° C until the evolution of HC1 ceased (5–8 hours). By the end of the reaction, the temperature rises to 85 ° C. Excess acid chloride

methacrylic water-jet acid is distilled off in a pump vacuum, hydroquinone is added and the oil pump is distilled in a vacuum. 3.8 g (91% j 3-a-methacryloxy-4-methoxytetrahydrothiofenioxide-1, 1, t.kip. 178 ° C (1 mm Hg) are obtained; t. Il. (From methanol).

Calculated,%: C 46.1; H 6.0; S 13.7.

Sen.LOZZ.

Found %: C 46.1; H 6.0; S 13.7.

Example 2. A mixture of 1.5 g (0.0083 mol) of 3-hydroxy-4-ethoxytetrahydro-1DCoxide-1.1 and 4 g (0.038 mol) of methacrylic acid chloride, etc., is stirred at 65 ° C for 9 hours. The excess methacrylic acid acid chloride is distilled off in vacuo, the residue is recrystallized from methanol. 1.6 g (80%) of 3 a-methacryloxy-4-ethoxytetrahydrothiofenioxide-1, 1 are obtained; m.p. 69-71 ° C.

Calculated,%: C 48.4; H 6.5; S 12.9.

CioHieOsS.

Found,%: C 48.4; H 6.5; S 12.9.

Example 3. Under the conditions of example 1, of 5.9 g of 3-hydroxy-2,3-dihydrothiophene-dioxide-1.1, 8.2 g of 3-a "riyloxy-2,3-lT; igidrothiofendioxide-1, 1; 1; m.p. 160 ° С (1 mm of mercury); m.p. 53-55 ° C.

Calculated,%: C 44.7; H 4.3; S 17.0.

C7H804S.

Found,%: C 44.6; H 4.2; S 17.0.

Example 4. Under the conditions of example 1, out of 23.2 g (0.17 mol) of 3-hydroxytetrahydrothiophene oxide-1, 1, 32 g (95%) of 3-a-methacryloxytetrahydrothiofendioxide were obtained - 1.1; m.p. 155 ° С (1 mm of mercury, st.); m.p. 38-39 ° C (from methanol).

Calculated,%: C 47.0; H 5.9; S 15.7.

C8Hi204S.

Found,%: C 47.0; H 6.0; S 15.8.

Example 5. Under the conditions of example 2, 2.5 g (0.01 mol) of 3-hydroxy-4- (1-thioheptyl) -tetrahydrothiofenioxide-1, 1 give 2.7 g (85%) of 3-acryloxy-4 - (1 - thioheptyl) - tetrahydrothiophene-1, 1; m.p. .

Calculated,%; C, 51.0; H 7.2; S 20.9.

Ci3H22O4S2.

Found,%: C 51.0; H 7.1; S 20.9.

Subject invention

The method of producing sulfolanol esters of acrylic or methacrylic acids, which is based on the fact that the oxysulfolanols are reacted with acrylic or methacrylic acid chlorides at 20-90 ° C, followed by isolation of the target products by known methods.