CS253437B1 - Tenzide with low frothiness and pleasent aroma - Google Patents

Abstract

The present invention relates to a nonionic surfactant which is prepared by alkylene oxidation of terpene alcohols linalool and dihydrolinalool and / or mixtures thereof. The surfactant has a low foaming and, in both concentrated and diluted form, has a pleasant odor. The surfactant can be used in the cosmetic industry and in the preparation of household chemistry.

Description

The invention relates to a low sudsing and pleasant fragrance surfactant prepared by alkylene oxide oxidation of terpenic alcohols and / or mixtures thereof.

The synthesis of vitamin A, vitamin E for the pharmaceutical industry and fragrances for the cosmetics industry is based on raw materials such as linalool, citral, citronelol, geraniol, nerol, pseudojonone and some other derivatives thereof. These are terpenic alcohols, aldehydes and ketones, characterized by a pleasant fragrance. The starting material of vitamins and fragrances is dehydrolinalool (3,7-dimethyl-3-ol-6-ene-1-octine). From the dehydrolinalool by hydrogenation on catalysts, in particular palladium, the alcohols linalool (2,6-dimethyl-2,7-octadien-6-ol) and dihydrolinalool (2,6-dimethyl-2-octen-6-ol) are obtained. Allyl rearrangement of linalool produces other fragrances nerol and geraniol. Geraniol alcohol is a major component of rose oil. It is a mixture of isomeric alcohols differing in the double bond position. The structural isomer of geraniol is linalool, contained in lavender oil (O. Červinka, V. Dedek, M. Ferles: Organic Chemistry, SNTL Prague 1969).

The hydrogenation of dehydrolinalool to linalool is very sensitive to hydrogenation conditions. Although all optimal reaction conditions have been found (Lindlar catalyst, low temperature, minimum hydrogen pressure, hydrogenation proceeds to the second stage on dihydrolinalool. The hydrogenation reaction mixture contains 5-20% by weight dihydrolinalool and 80-95% by weight of the solvent. Fractionation of the crude mixture removes linalool at the top of the column as the main component of rectification and remains in the digester a mixture of linalool and dihydrolinalool containing 20 to 70% by weight of dihydrolinalool.

Fractionation is difficult already because the products are of an oily consistency, high boiling point and a small difference between the boiling points of the two components. Linalool has a boiling point at 101.3 kPa of 198-199 ° C and at 1.32 kPa of 79.8 ° C.

Dihydrolinalool has a boiling point at 101.3 kPa of 201-202 ° C and at 1.86 kPa of 89-90 ° C (Handbook of Chemistry and Physies, Cleveland, USA - 1964; Chemisches Zentralblatt, 1966) to avoid darkening and decomposition Since linalool and dihydrolinalool have a difference in boiling point of the pure components of only about 4 ° C, high-efficiency distillation equipment is required for their separation, which increases the operating costs of their production.

Effectively evaluating the linalool fraction containing 20 to 70 wt. dihydrolinalool was the aim of this work. It has been found that alkylene oxide oxidation of linalool, dihydrolinalool and / or mixtures thereof provides nonionic surfactants having low foaming and pleasant odor.

The present invention provides a low sudsing and pleasant fragrance surfactant based on alkyl polyglycol ethers of the formula:

X

I

O (CH - CH2 O) _n H

CH 3 - C = CH-CH2-CH2-C-Y

CH3 CH3 where

X is H or CH 3

Y is —CH = CH2, —CH2 — CH3 n is an integer from 2 to 60, prepared by alkylene oxidation of terpenic alcohols of linalool, dihydrolinalool and / or mixtures thereof. When in the general formula Y is —CH = CH2, it is an alkylene oxide oxidized linalool, when Y is - CH2 --CH3 it is a dihydrolinalool. Also, terpene alcohols may be a mixture of isomeric alcohols differing in the position of the double bond or hydroxyl group (geraniol, nerol, citronellol). The starting materials may not have qualitative properties and may also be of a technical nature and may also contain by-products, whether from the production of starting materials or by-products of the reaction, or they may contain the substances I represent! a combination of these provinces.

The alkylene oxide products are liquid, pasty to solid, depending on the degree and type of alkylene oxide bound. When methyloxyran is used in the preparation of the surfactant, the products have a liquid oily consistency. The use of oxirane produces products ranging from liquid to solid, depending on the amount of oxirane bound. The resulting nonionic surfactants can be further treated by sulphation, phosphatation or combined with other surfactants coated with additives depending on the application for which they are intended. The products are characterized by a pleasant odor and surface-active properties in concentrated form as well as in their aqueous solution.

A further advantage of the low-foaming surfactant and the pleasant fragrance is that, in addition to reducing the surface tension of the water, they exhibit wettability and surfactants containing methyloxirane have good antifoaming performance. Further advantages are evident from the examples.

Example 1

In a stainless steel autoclave under a nitrogen atmosphere at 135 + 5 ° C, max. 0.3 MPa and using an alkaline KOH catalyst, an oxyethylated mixture consisting of 75 wt. linalool and 25 wt. of dihydrolinalool in an amount of 155 g of a mixture (1 mole) and 155 g of oxoxane (3.5 mole). The amount of bound oxirane was 50% by weight. The resulting product of slurry consistency had a surface tension measured according to ČSN 1101 at a concentration of 1 g.l ^-1 in distilled water and a temperature of 20 ° C of 44.5 mNirf '.

The foaming was determined by the method described in art. AO 208 350 and 37.5%. Wettability by concentration of 1 gl ^-1 in sodium hydroxide solution with conc. 30 g. I ¹ according to the ON 66 6129 methodology was 166 seconds.

The product in concentrated form as well as diluted in aqueous solution showed a pleasant fragrance.

Example 2

A surfactant sample was prepared as in Example 1. 155 g of a mixture of linoleol and dihydrolinalool (1 mole) of 30 wt. % linolool and 70 wt. of dihydrolinalool was oxyethylated with 440 g of oxirane (10 mol). The total amount of bound oxirane was 74% by weight. The resulting pate consistency product had a surface tension of an aqueous solution of conc. 1 g ^-1 and a temperature of 20 ° C of 49.0 mNm ¹ . The foaming was 54.6%. The product in concentrated form as well as diluted in aqueous solution showed a pleasant aroma.

Example 3

A surfactant sample was prepared as in Example 1. 155 g of a mixture of linoleol and dihydrolinalool (1 mole) of the composition of Example 1 were oxyethylated with 880 g of oxirane (20 mole). The total amount of bound oxirane was 85.0 wt. The resulting pasty consistency product had a surface tension of an aqueous solution of conc. 1 g. I 'and ¹ 20 ° C 45.0 mNnr ^first The foaming was 44.0%. The product in concentrated form as well as diluted in aqueous solution showed a pleasant aroma.

Example 4

A surfactant sample was prepared as in Example 1. 154 g of linoleol (1 mol) were oxyethylated with 2640 g of oxirane (60 moles), and the total bound oxirane content was 95 percent by weight. The surface tension of the aqueous solution having a concentration of 1 g / ^l and a temperature of 20 ° C was 56.2 mNm ^-1 The product in concentrated form as well as diluted in aqueous solution showed a pleasant odor.

Example 5 as in Example 1. 154 g of linealool (1 mol) were oxypropylated with 1740 g of methyl oxirane (30 mol). The total bound methyloxirane content was 91.8% by weight. The resulting product was of a liquid consistency, insoluble in water. The surface tension of this concentrated product measured at 20 ° C was 35.7 mNm ^-1 . The surfactant formed has been shown to have antifoaming activity. The foaming efficiency determined according to the methodology described in Art. AO 208 350 was 78.3%. The product showed a pleasant fragrance.

Example 6

A surfactant sample was prepared as in Example 1. 156 g of dihydrolinalool (1 mol) were oxyethylated with 440 g of oxirane (10 mol) and then oxypropylated with 350 g of methyl oxirane (6 mol). The resulting product contains 46.5 wt. % bound oxirane and 37.0 wt. of bound methyloxirane was of a pate-like consistency well soluble in water. The foamability of the product was 12.5%. Surface tension of aqueous solution with conc. 1 g. . 1 ^_1 at 20 ° C was 41.8 ninmu ^first The product in concentrated form as well as diluted in aqueous solution showed a pleasant aroma.

Example 7

A surfactant sample was prepared as in Example 1. 156 g of dihydrolinalool (1 mol) were oxyethylated with 1100 g of oxirane (25 mgl). The resulting product containing 87.5 wt. The bound oxirane exhibited a good water-soluble waxy appearance. The foamability of the product was 50.9%, the surface tension of the aqueous solution at conc. 1 g ^-1 at 20 ° C was 51.0 mNm ^-1 . The product in concentrated form as well as diluted in aqueous solution showed a pleasant aroma.

Example 8

A surfactant sample was prepared as in Example 1. 156 g of dihydrolinalool (1 mol) were oxypropylated with 870 g of methyloxirane (15 mol). The resulting product containing 84.8% w / w. The bound methyloxirane was of liquid consistency and was insoluble in water. The surface tension of the concentrated product measured at 20 ° C was 35.7 mNm ¹ . The foaming efficiency determined according to the methodology described in Art. AO 208,350 was 83.3 percent. The product showed a pleasant aroma.

A surfactant sample was prepared by step

Claims (1)

Low-foaming surfactant with a pleasing formula based on alkyl polyglycol ethers of the general formula: X OF THE INVENTION where X is H or CH3 Y is —CH = CH2, —CH2 — CH3 n is an integer from 2 to 60, O (Ca = CH 2 O) _n H CH2-CH2-CH2-CH2-C-Y prepared by alkylene oxidation of the terpenic alcohols of linalool, dihydrolinalool and / or mixtures thereof. • CH3 CH3