SU895492A1 - Catalyst for oxyethylating fat alcohols c7-c8 - Google Patents

Description

The invention relates to catalysts for the oxyethylation of fatty alcohols in order to obtain non-ionic surfactants (nonionic surfactants). Non-ionic surfactants based on alcohols and ethylene oxide have found wide application in various areas of the national economy (the active base in synthetic detergents household and technical equipment, surfactants to increase the completeness of the release of oil from the subsoil, emulsifiers and demulsifiers in various technological processes, cosmetics components, etc.). The use of alkali metal hydroxides or alkoxides as catalysts for hydroxyethics is known. lysis of higher fatty acids 1, The disadvantage of these catalysts in addition to low activity requiring the use of high temperatures (150 iso c) is the wide on-mass distribution of molecules (MMPJ polymer homologues in the reaction products significantly (wider than the expected by the Poisson statistical formula). where n is the degree of ethoxylation, Xp is the molar fraction of the groups oxyethylated on p mol of oxyethylene (OE). This reduces the consumer properties of the products, since in the reaction mixture obtained by oxyethylation, The mole layer contains a large proportion of ballast products in the form of undeoxyethylated and peroxyethylated alcohols. It is also known to use boron trifluoride as a catalyst for oxyethylation of higher fatty alcohols 2. However, this catalyst causes dehydration of alcohols and oxyethylated alcohols and, therefore, degrades color and gives an additional amount of polyethylene glycols (PEG ). The aim of the invention is to increase the activity of the catalyst. This goal is achieved by using the complex compound of triphenyl phosphate and boron fluoride of the formula p-O-SeNK "e 1- | -F 8 as a catalyst for oxyethylation of fatty alcohols,. This complex compound of triphosphonate boron trifluoride is described in the literature and its structure has been proved, but its use as a catalyst is unknown. The process of hydroxyethylation of alcohols in the presence of this catalyst, whose components (triphenyl phosphite and boron trifluoride etherate) are added to the alcohol separately in a ratio of from 15: 1 to 2; 1 (mol) or prepared in advance, leads to products those with MMPs of polymer homologists are close to the statistical one calculated using the Rlaccon formula. If the catalyst is pretreated, then it loses its activity over time. Therefore, it is advisable to feed the components of the catalyst directly into the alcohols by feeding to 03. At the same time, the process proceeds at high speed over a wide range of temperatures from 40 to 120 ° C and is accompanied by a slight formation of polyethylene glycols. The invention is illustrated with the following examples. Example 1. A thermostated steel autoclave with a capacity of 0.3 liters, equipped with a stirrer, a thermocouple, a pressure gauge and a tube for introducing liquid hydroxy ethylene, is charged with 100 g (0.86 mol) of heptyl alcohol in the presence of 3.45 g of triphenylphosphite and 0.1 g Boron trifluoride etherate. A complex compound triphenylphosphite and boron trifluoride is formed, which catalyzes the process. Then, 7 g (1.68 mol) of liquid OE are fed into the reaction mixture at such a rate that the pressure in the autoclave does not exceed 0.5 atm. The temperature is maintained within the range of 5-55 ° C. After supplying the total amount of OE and reducing the pressure to O, the mixture is stirred for another 10 minutes at 50 ° C. Then it is cooled and the autoclave is opened. The reaction mixture is neutralized with triethylamine. 177.5,, 5 g (100) of a colorless product were obtained. The content of bound OE is 1, b7 mol. The product contains 13.4% free heptyl alcohol. PEGs not detected. The theoretical amount of free alcohol, as expected by the Poisson’s formula, in the oxyethylation of 1.7b mol 03 is 10.29. Example 2. The reaction of hydroxyethylation of octyl alcohol is carried out in the same autoclave at 110-120 ° C. Amount of burned) {; Amount of products: 100 g (0.7b mol) of octyl alcohol. 3, + 5 g of triphenyl phosphite, 0.1 boron trifluoride etherate, 101 g (2.29 mol) re. The yield is -0.55 g (1001), which contains 1.72% PEG and 3.12% free octyl alcohol. The content of the bound OE is 2.48 mol. The theoretical amount of free alcohol, as expected by the Poisson’s formula, in oxyethylation by 2.8 mol 03 is k ,. Example 3. In this autoclave under the conditions of example 1, oxyethylation of 100 g (0.86 mol) of heptyl alcohol was carried out in the presence of 3, 3 g of triphenylphosphite, 0.1 g of boron trifluoride etherate 117.68 (2.67 mole) OE. After the reaction, the autoclave is cooled, the reaction mixture is neutralized with triethylamine, and the product is discharged. 221.23 g (100%) of a colorless product are obtained. The product contains 1.10 / 0 PEG and 2.78% free heptyl alcohol and 2.78 moles of coupled OE. The theoretical amount of free alcohol expected by the Poisson’s formula in the oxyethylation by 2.78 moles is 2.95. Example 4. In the same autoclave, with SO-IOOC, oxyethylation of 100 g (0.86 mol) of heptyl alcohol was carried out in the presence of 3.5 g of triphenyl phosphite and 0.1 g of boron trifluoride etherate 2, G g (2.85 mol) OE, the autoclave is cooled, and the reaction mixture is neutralized with triethylamine. The product is discharged. 228.95 g (100%) of a colorless product are obtained. The product contains 0.83% PEG and 2.53% free heptyl alcohol. The expected theoretical amount of free alcohol predicted by the Poisson formula, when oxyethylation at 2.85 mol 03 is 2.71%. The content of PEG is determined by method 5 thin layer chromatography. The free alcohol content is determined by GLC. The content of bound OE is 2.85 mol, 10 895 6 The content of PEG in the reaction mixture is 0.85 °. The content of free heptanol 2 ,, For comparison, all the data obtained and the data published in the literature on the use of boron trifluoride as catalysts for ether etherate are tabulated.

Hydroxyethylation in the presence of a catalyst according to the invention

The use of the invention allows the production of nonionic surfactants with a close to theoretical molecular weight distribution of polymer homologues. invention formula

Use of triphenylphosphite complex compound and boron trifluoride of formula

BI5

P-O-CgHs

Hydroxyethylation in the presence of a known catalyst BF ",

As a catalyst for the oxyethylation of fatty alcohols.

Sources of information taken into account in the examination

1, Zimakov P, V, and others. Ethylene oxide, M, Khim, 1967.

2, US Patent No. 3372201, class 260-615, published in 1968,.

3, Arbuzov B, A, et al. Reactions of acyclic full esters of phosphorous acid with trifluoride ester

Bora, DAN SSSR, t, 216, 197, W, s, 793 (prototype),

Claims (1)

claims The use of a complex compound of triphenylphosphite and boron trifluoride of the formula e ₆ n ₅ o) p-0- " _in n ₅ w ^z .i_ _K I F as a catalyst for oxyetipation of fatty alcohols Su-Sd.