SU891702A1 - Method of producing polymers - Google Patents

Description

(54) METHOD FOR OBTAINING POLYMERS

one

This invention relates to the field of polymers / namely, to a process for the preparation of polymers having surface-active and antioxidant properties. Such polymers can be used in the medical, food and cosmetic industry as substances, delaying oxidation of organic compounds. with oxygen, and as surface-active substances, stabilizing dispersions at the same time from delamination and oxidation by oxygen.

A known method for the preparation of compounds with antioxidant properties of D-l.

The disadvantage of this method is that these compounds are not surfactants 20 and are not soluble in water.

The closest in technical essence and achievable results is the method of producing polymers — 25 polyethylene glycol ethers by reacting polyethylene glycols with an alkylating agent when heated. Benzyl chloroyl C2J is used as the alkylating agent. thirty

i The disadvantage of this method is the absence. of the polymers having antioxidant properties.

The purpose of the invention is the preparation of polymers possessing surface-active and anti-acid®I properties.

The goal is achieved by the fact that according to the method of producing polymers by reacting polyethylene glycols with an alkylating agent, when heated, 3.5-di-tert-butyl-4-hydroxybenzylacetate is used as the alkylating agent and the interaction is carried out in bulk or in an organic aprotic solvent molar ratio of 3,5-di-tert-butyl-4-hydroxybenzyl acetate and polyethylene glycol 0.5: 1-3: 1, respectively, in the presence of 0.05-0.5 mol of a strong organic acid per mol of 3,5-di-tert -butyl-4-hydroxybenzyl acetate at BS-OO S.

The reaction is carried out in sealed ampoules or under an inert gas (argon, nitrogen) to prevent oxidation, dp separating polymers from unreacted polyethylene glycol, the latter is extracted with a hot saturated aqueous solution of sodium chloride, in which the polymers are insoluble, or

gel chromatography is used in an aqueous solution in which the polymers are eluted in the form of micelles.

To separate the polymers from an excess of the starting acetate and from aromatic by-products, the polymers are washed with saturated carbon or precipitated with saturated hydrocarbons from the benzene solution.

Polymers are well soluble in benzene, toluene, carbon tetrachloride, chloroform, ethyl acetate, dioxane, acetone, in alcohols, dimethylformamide, dimethyl sulfoxide.

As strong organic acids, p-toluenesulfonic acid, trifluoroacetic acid in t are used. PRI me R 1. 2.78 g {10.0 mmol) 3,5-and-tert-butyl-4-hydroxybenzylacetate (acetate) and 17.2 g (57.3 mmol) of polyethylene glycol with a molecular weight of 300 (PEG-300) is dissolved in 23 ml of abs. dioxane, g (1,2) p-toluenesulfonic acid is added and heated in a sealed ampoule for 7 hours at. 4 ml of a saturated aqueous solution of MaNSO3 are added, and 100 ml of water, the mixture is extracted successively with hexane (3 x 25 ml) and benzene (3 x 25 ml). The benzene extract is evaporated to dryness. 2.54 g of polymer are obtained. . & 47%. The content of 3,5-di .tret-butyl-4-oxybenzyl group (A) is 42% by weight.

Example 2, 2.78 g (10.0 mmol of acetate and 2.8 ml (20 mmol) of PEG-300 are dissolved in 25 ml of abs. Acetonitrile, 0.156 ml (2.0 mmol) of trifluoroacetic acid is added, heated to This is taken 7 hours at 80 ° C. The mixture is evaporated to dryness, the residue is chromatographed on silica gel with a gradient from CCfj to CHCI and acetone.Faccinate containing dimer (control by thin layer chromatography) are combined and evaporated to dryness. 70g (50%). And 42 wt.%.

6-10 M carotene concentration, toluene,.

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3,5-di-tert-butyl-4-hydroxybenzyl group, mol / lp and r e mep, 3. 5.56 g (20.0 mmol acetate, 5.94 g (9.90 mmol) PEG-BOO and 0.08 ml (1 mmol) of trifluoroacetic acid is heated in a sealed ampoule for 4 hours at. The mixture is twice evaporated in vacuo with benzene, the syrup is washed with hexane (.5 x 50 ml) and dissolved in 10 ml of water containing 0.08 g NaHCOj, and chromatographic on Sephadex G-25 (cm, 9 cm,

280 mp). The first 120 ml

Vn

water,

the eluate is combined and evaporated to dryness, the residue is washed with hot hexane (5 x 50 ml; and dried. Yield 2.4 g (26%). HA 10 wt.%.

Example 4. 56 g (200 mmol) of acetate, 132 g (66 mmol) of PEG-2000 and 7.6 ml (100 kmol) of trifluoroacetic acid are heated in a sealed ampoule for 4 hours at .- Poured into 100 ° C heated saturated aqueous a solution of sodium chloride (350 ml) in a mixture of 20 ml of a saturated aqueous solution of NaHCOj, the aqueous layer was separated, the organic layer was dissolved in 350 ml of benzene, filtered through cotton wool, and a volume of 2 liters of hexane was added. The precipitated precipitate is separated, washed four times with hexane, then washed four times with a hot saturated aqueous solution of sodium chloride, dissolved in benzene, dried over anhydrous sodium sulfate, and the polymer precipitated with hexane.

yield 33 g (23%). GAS 5.3 wt.%.

Example 5. About 50 g of polymer with A 5.3 wt.% (Example 4) are treated with the saliva of 2.5-ml of hot saturated aqueous NaCl and 2.5 ml of hot p-butane. The organic layer is washed three times with 2.5 ml of saturated aqueous NaCI, evaporated to dryness and the residue is precipitated with hexane from benzene. Get 0.20 g of polymer, just

; And 13%.

Claims (2)

The properties of the polymers are given in the table. The critical micelle concentration of polymers in water is (2-8) .10-3 mol / L. Thus, carrying out the process according to the proposed method allows to obtain polymers, possessing surface-active and anti-thioxide and jibHbEMH properties. DETAILED DESCRIPTION OF THE INVENTION A method for producing polymers by reacting polyethylene glycols with an apicalizing agent by heating, characterized in that, in order to obtain polymers having surface-active and anti-oxidative properties, 3,5-di-tert-butyl-4 is used as alkylaryl agent -oxybenzylamine and the interaction is carried out in bulk or in an organic aprotonic solvent at a molar ratio of 3,5-di-tert-butyl-4-hydroxybenzyl cdetate and polyethylene glycol 0.5 1-3: 1, respectively, in the presence of 0.05-Q, 5 mo a strong organic acid per 1 mol of 3-5-di-tert-butyl-oxybenzylacetate at 60-100 0. Sources of information taken in. attention during examination 1.Ershov V.V., et al. Spatially obstructed phenols, m., Chemistry, 1972, p. 157. 2.Ed. M.J. Sckic, Mace I Oekker Hohionis surfactants, 1966, Acad. Press, N, Y ,, p. 411-412 (prototype).