SU564302A1 - Method for obtaining polyhydric alcohols - Google Patents

Description

(54) METHOD FOR OBTAINING MULTIHEAD ALCOHOLS

one

The invention relates to the preparation of alcohols, in particular, to a process for the preparation of polyatomic alcohols of the total foumula

RT RI:

jj I

Hi ((j-eH-R,

he he he he

where T is R - hydrogen or methyl,

used in the production of polyesters and polyurethanes.

The purpose of the invention is to expand the assimilation of polyhydric alcohols and the raw material base, simplifying the process technology and

an increase in the yield of the target product is achieved by the fact that the corresponding diene hydrocarbon, for example, divinyl, piperylene, isoprene, hydrochloride, is eluted by an aqueous solution of hydrogen peroxide (H.O.), preferably 30%, at a temperature of 0-70 ° C and pressure 0 -7 MPa in the presence of a catalyst based on compounds of tungsten or molybdenum and a non-ionic emulsifier.

Tungsten acid or its sodium, potassium, ammonium, calcium, magnesium, and other salts, or complex salts of tungstic acid, or heteropolyacids of tungsten or molybdenum, such as silicon wolfram, phosphomolybolybramide, silicon molybdenum, phosphorovov, and one of phosphorovov, are used as the catalyst. salts of tungsten or molybdenum.

The amount of catalyst is preferably 0.1-3% by weight of the reaction mass,

Esters of higher fatty alcohols with polyethylene glycols or polypropylene glycols are used as nonionic emulsifiers.

The yield of the target products in the calculation of the diene hydrocarbon and hydrogen peroxide b-81 and 69-72%, respectively. Conversion of diene hydrocarbon 98-1OO

Claims (3)

Synthesized polyhydric alcohols can be used in the production of polyesters and polyurethanes, and the coatings based on them are highly elastic and resistant to pacTpecKH. The process is carried out in one stage, using available raw materials, at low pressure and temperature at high speeds. The resulting products, if necessary, can be further purified, for example by crystallization. Example 1. In a glass reactor with a capacity of 1 l, 16 5.0 g of piperylene (purity 93.6%), 580, 30% HjO, 5.0 g of fresh calcium tungsten and 2 ml of emulsifier, which are a mixture of hot esters of primary alcohols Cg C, - (OP-7). The reaction is carried out for 4 hours at 44 ° C and vigorous stirring. - At the end of the reaction, the concentration of sPz in the aqueous layer is 0.6%, and may-: The ly layer disappears almost completely. The aqueous layer is extracted several times with perylene, after which water and diols are distilled off at a temperature of up to 160 ° C and a pressure of 0.5 mm, Hg. The remaining product {272 g) is a clear, slightly yellowish, viscous mass that dissolves well in water and does not dissolve in ether and acetone. According to the data of the JC spectra and the NMR spectra (solution in oxide | deuterium), the resulting product was identified as 1,2,3,4 tetraoxypentane (pentanetrol 1,2,3,4), mol. weight. 133137; d ° 1.4588; in the temperature range of 60-80 ° C, the product becomes liquid. The data for determining the hydroxyl number correspond to the content of pentantyletal in the obtained product 92.0%. The yield per reacted piperylene 81.0%. The yield, calculated on the reacted hydrogen peroxide, is 72.0%. Example 2. 60 g Hg. 12.5 g of butadiene -1.3 and 0.5 of tungsten sodium are loaded into an autoclave with a capacity of 0, 2 liters and 0.4 ml of an emulsifier, which is a mixture of alkyl phenyl ethers of curling fatty alcohols, is added. The reaction is carried out at 55-60 ° C in 4 hours. The isolated target product is a clear, slightly yellowish liquid containing 96.5% erythritol. The yield of polyhydric alcohol is 60.0% in the calculation for the initial diene. Example 3. Interaction of 60 g of 30% HgOg and 14.5 g of isoprene in the presence of 1, O of sodium tungstate and 0.3 m of a liquid non-ionic emulsifier, which is a mixture of polyoxyethylenegol, primary spiroc esters; S-, p. It is carried out at 6 ° C for 5 hours. The separated aqueous layer is processable; ne 1a) lich: ether, the water is distilled off and 2-methylbutanetrol -1,2, 3,4 is obtained in a yield of 63.0% based on the starting diene. The resulting product is a transparent yellowish viscous mass, well soluble in water, difficult to dissolve in alcohol, not soluble in ether and acetone, m.p. 75-90 ° C; a pier weight 133; (° 1.4450. Found,% C 42.3; H 10.2,; qH, 2a; Calculated,% C 44.1 ;; H 8.8. EXAMPLE 4. From 40.0 g of dimethylbutadiene - 1, 3 (purity 96.5%) and 118.0 g of 30% H 50-5 2 ° C in the presence of 0.2 g of molybdenum acetylacetonate and 0.3 ml of emulsifier (see Example 1) after separation 52, O g of a slightly yellow, transparent pasty substance, identified as 2.3 dimethylbutanetrol, soluble in water, not soluble in ether and acetone, mp 35-55 ° C; mol. weight 14 & : csiy 1.4340. The yield of the target product based on the starting diene and hydrogen peroxide is 78.5 and 69%, respectively. Found:%: C 50.8; H 11.0. 1 OQ, Calculated,% C 4.8; H 9.3. Example p 5. Using 19.5 g of hexadiene — 2.4 (purity 99, 0%) and, 55.5 g 30%, at 50-52 ° C in the presence of 0.2 g of tungsten acetylacetonate and 0.5 g of OP-7 receive the target DU1CT, which is isolated as in Example 1. The output hexanetrol - 2,3,4,5 (solid pasty substance) in the calculation of the original diene and hydrogen peroxide 75,0 and 7О, О%, respectively. Claims 1. A method for producing polyatomic pies of a common formula, Ri-CH-cJ-d-dH-Bg he he he where TG is hydrogen or methyl, characterized in that expanding the range of polyhydric alcohols and raw materials, simplifying the process technology ,; and increasing the yield of the target product, the corresponding diene hydrocarbon is treated with an aqueous solution of hydrogen peroxide at a temperature of 0-7 ° C, a pressure of 0-7 atm, in the presence of a catalyst based on tungsten or molybdenum compounds and a non-ionic emulsifier. 2. The method according to p. 1, about tl and h and y. y and y with the fact that as a catalyst using tungstic acid or its salts, or heteropolyacids containing -. tungsten ennf molybdenum, or salts of tungsten, ma or molybdenum.  3. The method according to paragraphs. 1 and 2, I differ by the fact that the catalyst is taken in an amount of 0–3–3% by weight of the reaction mass.