CS256198B1 - A tenside based on alkylenoxidated fatty acid alkanolamides - Google Patents

Abstract

The substance belongs to the class of non-ionic surfactants based on alkylene-oxidized alkanolamides of fatty acids. The fatty acids are of vegetable origin from rapeseed oil, which has a low content of erucic acid. The surfactant consists of derivatives of alkanolamides of fatty acids with alkylene oxide with a number of bonded alkylene oxides of 4 to 25 moles per mole of alkanolamide and reaction by-products, which mainly form polyglycols.

Description

256198

BACKGROUND OF THE INVENTION The present invention relates to a low erucic acid alkylene oxidized fatty acid alkanolamide surfactant having a degree of alkylene oxidation of 4 to 25 moles of alkylene oxide per mole of alkanolamide.

Higher fatty acid alkanolamides, as a raw material for the production of their alkylene oxide derivatives, have been known for many years. The first condensation products of higher fatty acids with alkanolamines were prepared by Kritchevsky (U.S. Pat. No. 2,089,212, U.S. Pat. No. 2,984,608). The aminoalcohols used are monoethanolamine, diethanolamine, triethanol-amine, monoisopropanolamine, diisopropanol-amine, triisopropanolamine, or mixtures thereof and other amine alcohols, respectively. Of the higher fatty acids, stearic, oleic, coconut and tall oil acids are most commonly used. The synthesis of alkanolamium fatty acids was studied by several authors (M. Ranný: Food Industry 12/1961), no. 8, pp. 399-404; M. Ranný - M. Nig-rin - J. Prachár: Food Industry (13 // 1962), No. 5, pp. 255 to 259 and (1963) No. 3, p. 155 to 160). It has been shown that by-products of the alcohol and the higher fatty acid are by-products. E.g. fatty acid monoethanolamide esters are formed when it is derived from monoethanolamine. In addition to the diethanolamine fatty acid reaction, diethanolamine fatty acid esters, diethanolamine fatty acid monoesters and fatty acid diethanolamide diesters are also present in addition to the diethanolamidastic acid component. The average content of the major fatty acid monoethanolamide component is 92-94% (Schick: Nonionic Surfactants, Marcel Dek-Ker, Inc. New York-1967).

Alkylene oxidation of alkanolamides of fatty acids is carried out in a conventional manner, most commonly using an alkaline catalyst at 130-160 ° C and working under a nitrogen atmosphere. Alkylene oxidation of fatty acid alkanolamides in comparison with alkylene oxidation reactions of fatty alcohols, alkylphenols, and chemical acids is less well understood. This is probably due to problems with the analysis mixture when the fatty acid alkanolamide alone is already a relatively complex multi-substance mixture. In addition, in the alkylene oxidation reactions, re-esterification and reamidation reactions and free polyethylene glycols are carried out in addition to polyaddition reactions. An industrially prepared alkylene oxide-based alkanolamide surfactant surfactant is therefore a diverse mixture of substances.

According to the use of the starting aminoalkyl of a higher fatty acid and of the alkylene oxide, as well as the molar ratio of the alkanolamide of the higher fatty acid to the alkylene oxide, nonionic surfactants with various surface-active and physico-chemical properties are formed. Rapeseed oil acids are also the raw material for the preparation of alkanolamium fatty acids. The fatty acids of the rapeseed oil, the so-called classical variety, have the following average composition - given in bv. No. 1. [I. Souček: Food Industry, Vol. 34, No. 1 (1983), pp. 1-3):

Table 1 Name of acid Number of atoms Number of double. Mol. wt. Wt. % carbon in g / mol. palmitic acid 16 0 256,4 7 stearic acid 18 0 284,5 1 oleic acid 18 1 282,5 13 linoleic acid 18 2 280,4 14 linolenic acid 18 3 278,4 8 erucic acid 22 1 338,6 47 indeed acids 14 to 20 - max. 312.5 10

The erucic acid content (13,14-docosine carboxylic acid) is high in these varieties. The oxyethylated alkanolamides prepared from the acids contained in the classic rape seed variety are pasty to waxy high viscosity substances. Pasty to waxy substances are difficult to transport and dispense. The musiasa was transported in tankers with the possibility of heating. When heated, steam consumption adversely affects the economy and, in addition, the elevated temperature adversely affects the quality of the alkylene oxide alkanolamide fatty acids, particularly deterioration. In addition, from the food industry caused by the negative attitude of health workers and justified by the physiological effects of erucic acid, the most recent time passes for oilseed rape, which contains a reduced content of eric acid and a classical type with an acidic content. about 47 wt. becomes difficult.

The above-mentioned disadvantages are eliminated by a novel surfactant based on alkylenoxidated fatty acid alkanolamides of vegetable origin, characterized in that it consists of 70 to 90 wt. alkylene oxide fatty acid alkanolamide derivatives of 256198 alkylenoxidation with 4 to 25 moles of alkylene oxide per mole of alkanolamide, in which the acids have a length of alkyl chain characterized by a number of carbon atoms, Cm to C0, with mole. weight of max. 312.5 and 3 to 5 wt. alkanolamide fatty acid derivatives with an alkylene oxide having an alkylene oxidation degree of 4 to 25 moles of alkylene oxide per mole of alkanolamide, in which the acids have an alkyl chain length characterized by a number of carbon atoms with one mole double bond. max weight of 350 and the remainder being reaction by-products, especially polyglycols.

The oil from oil-free rape has the following central fatty acid content - listed in Table 2 [J. Souček: Food Industry, Vol. 34, No. 1 (1983), p.

Table 2 Acid Name

Number of carbon atoms

Number of double bonds

Mol. weight g / mol.

Wt. palmitic acid 16 0 256,4 6 stearic acid 18 0 284,5 2 oleic acid 18 1 282,5 55 linoleic acid 18 2 280,4 22 linolenic acid 18 1 3 278,4 10 erucic acid 22 1 338,6 5 indeed acids 14 to 20 - max 312.5 -

Alkylene oxidation of alkanolamides prepared from non-oilseed rape produces liquid products with good surfactant properties, good dispensing handling and good detergent effects. Oxypropylation produces the products that can be used to prepare the defoamers. The term alkylene oxidation refers to oxyethylation and / or oxypropylation. The products are unsafe. Up to now, the use of a starting vegetable province feedstock based on rapeseed oil with a low erucic acid content on surfactant preparation has not been described in the literature.

For more clarity, we provide examples of translations. Example 1

1120 g of rapeseed fatty acid mono-ethanolamide are added to a stainless steel autoclave of 2.5 dm @ 3 equipped with a duplicator and the mixer, with the starting acids having the following composition (given in% by weight) according to gas chromatography analysis. ): palmitic acid 5.9 stearic acid 2.3 oleic acid 54.8 linoleic acid 21.3 linolenic acid 8.0 erucic acid 5.0 indeed Cm to C20 2.7

Average moles the rapeseed fatty acid monoethanolamide weight is 345. Further, 10 g of COH catalyst are added to the autoclave. 600 g of ethylene oxide (4.2 moles of ethylene oxide per mole of fatty acid alkanolamide) are successively fed to the thus prepared feedstock with nitrogen at a temperature of 125 to 145 ° C and a pressure of max. The obtained liquid product having a bound ethylene oxide of 35.0% by weight. (determined by hydriodic acid cleavage) at 9 ° C, has a density of 978.2 kg. m-3, viscosity 160.4 mPa. s and refractive index 1.4749. 89.9% by weight of the product are derivatives of alkanolamide fatty acids with ethylene oxide, in which the acids have a length of alkyl chain characterized by a number of carbon atoms Cm to Co with moles. weight of max. 312.5 and 4.8 wt. they form derivatives of fatty acid alkanolamides with ethylene oxide, in which the acids have a length of alkyl chain characterized by the number of carbon atoms C22 by a single double bond by mole. hmotnostimax. 350 and 5.3 wt. they form polyethylene glycols. The resulting product was determined to be desensitizing at 60 ° C and 90 ° C. The results of the washing efficiency are given in Example 9, Tab. No. 1. Example 2

Following the procedure described in Example 1 and the composition of the starting oil fatty acids of Example 1, a surfactant with 6 moles of ethylene oxide was prepared such that 1120 g of rapeseed monoethanolamide were sequentially oxyethylated with 860 g of ethylene oxide. The resulting surfactant is a liquid having a refractive index of 1,442 at 30 ° C, a density of 997.3 kg. m ~ 3; viscosity 153 mPa. 89.3 wt. ethylene oxide fatty acid derivatives in which the acids have a length of alkyl chain characterized by carbon atoms of Cm to C20 with moles of ethylene oxide. massmax. 312.5 and 4.7 wt. they form ethylene oxide fatty acid derivatives of alkanolamides in which the acids have an alkyl chain length characterized by carbon atoms of C22 with a single double bond of 256198 by mol. weight of max. 350 and 6.0% by weight are polyethylene glycols. The resultant product was found to be desensitizing and the results are given in Example 9, Tab. 3. P ri 1 and d 3

Following the procedure described in Example 1 and the composition of the starting oil fatty acids of Example 1, a surfactant with 8 moles of ethylene oxide was prepared such that 345 g of rapeseed fatty acid monoethanolamide was oxyethylated with 355 g of ethylene oxide. The product formed is a liquid which is absorbed. 30 ° C refractive index 1 4738; density 1,013,3kg. rn <:; viscosity 158.7 mPa. 87.2 wt. The product of the alkanolamium fatty acid derivatives of ethylene oxide, of which may have a length of alkyl chain characterized by a number of C11 to C11 carbon atoms, with moles. weight max. 312.5 and 4.6% pot. they form derivatives of alkanol amines of fatty acids with ethylene oxide, in which the acids have an alkyl chain length characterized by the number of carbon atoms C22 with one double bond by mole. weight of max. 350 and 8.2 wt. form ethylene glycols. The resulting product was determined to be tardy and the results are given in Example 9, Table 3. Example 4

Following the procedure described in Example 1 and the composition of the rapeseed starting fatty acids and also according to Example 1, a surfactant with 12 moles of ethylene oxide is prepared so that 455 g of rapeseed fatty acid monoethanolamide are oxyethylated with 530 g of ethylene oxide. oxide. The resulting product is a liquid having a refractive index of 1 4731 at 30 ° C; density1 032.9 kg. m-3 and viscosity 166 mPa. p. wt. ethylene oxide fatty acid alkanolamide derivatives in which the acids have an alkyl chain length, characterized by carbon atoms of Cm to C20 with mole. massmax. 312.5 and 4.3 wt. they form ethylene oxide fatty acid derivatives of alkanolamides in which the acids have a length of the alkyl chain characterized by carbon atoms of C22 with one mole double bond. weight of max. 350 and 13.5% w / w of polyethylene glycols. The resulting product was determined to be tardy and the results are given in Example 9, Table 3. Example 5

Following the procedure described in Example 1 and the composition of the starting oil fatty acids of Example 1, a surfactant with 16 moles of ethylene oxide was prepared such that 345 g of rapeseed fatty acid monoethanolamide was oxyethylated with 705 g of ethylene oxide. The resulting product is a liquid having a refractive index of 1.4735 at 30 ° C; density1 049.0 kg. m-3; viscosity 214 mPa. 73.1. wt. ethylene oxide fatty acid alkanolamide derivatives in which the acids have a length of alkyl chain characterized by the number of carbon atoms C14 to C20 with mole. massmax. 312.5 and 3.8 wt. they form ethylene oxide fatty acid derivatives of alkanolamides in which the acids have an alkyl chain length characterized by carbon atoms Cž2 with one double mole bond. with a maximum weight of 350 and 23.1% by weight of polyethylene glycols. The resulting product was determined to be tardy and the results are presented in Example 9, Table 3. Example 6

Following the procedure described in Example 1 and the composition of the starting oil fatty acids also as in Example 1, a surfactant with 20 moles of ethylene oxide is prepared such that 345 g of rapeseed fatty acid monoethanolamide are oxyethylated with 880 g of ethylene oxide. The resulting product is a liquid having a refractive index of 1.4725 at 30 ° C; density1 056.7 kg. m ~ 3; viscosity 220 mPa. p. wt. ethylene oxide fatty acid alkanolamide derivatives in which the acids have a length of alkyl chain characterized by carbon atoms of C11 to C20 with mole. massmax. 312.5 and 3.7 wt. they form ethylene oxide fatty acid derivatives of alkanolamides in which the acids have an alkyl chain length characterized by carbon atoms of C22 and one double bond of moles. weight of max. 350 and 26.0% w / w of polyethylene glycols. The resulting product was determined to be tardy and the results are given in Example 9, Table 3. Example 7

Following the procedure described in Example 1 and the composition of rapeseed fatty acids starting from Example 1, a surfactant with 8.7 moles of propylene oxide is prepared such that 345 g of rapeseed fatty acid monoethanolamide is propoxylated with 510 g of propylene oxide . The product formed is a liquid containing 60 wt. bound propylene oxide. 87.2% by wt. The product of the product is a propylene oxide alkanolamide fatty acid derivative in which the acids have a long chain alkyl characterized by carbon atoms of C14 to C20 with mole. massmax. 312.5 and 4.6 wt. they form propylene oxide fatty acid derivatives of alkanolamides in which the acids have the length of α-256198 10 of the keel characterized by carbon atoms of C22 with one mole of mole. masses of max. 350 and 8.2% w / w are polyglycols. Detoxification efficiency according to the method described in MS. AO236 099 is 67.6%. Example 8

By way of comparison, the surfactants are prepared according to Example 1 by oxyethylating rape fatty acid monoethanolamides with 4 to 20 moles of ethylene oxide, while the starting acids are derived from the so-called higher rape grade rape variety and have the following composition. in% by weight: palmitic acid 7.0 stearic acid 1.5 oleic acid 13.5 linoleic acid 14.0 linolenic acid 8.0 erucic acid 47.0 indeed C14 to C;

The content of free polyglycols is at the same level as the surfactants prepared according to Examples 1 to 6. The prepared polyesters are pasty to solid. Example 9

The efficacy of the samples prepared according to Examples 1 to 8 was determined, while the efficacy of the surfactants prepared by oxyethylation of monoethanol amides of fatty acids prepared from the so-called high erucic acid-grade rape variety with the samples prepared by oxyethylation of fatty acid monoethanolamides prepared from the novel low-fat repellents was compared. The erosion test was performed on a 100% cotton cotton fabric which was artificially soiled. Washing time 30 minutes, temperature 60 and 90 cc, distilled water. The detergent performance (0.75 g. &Lt; 1 &gt; tenside according to Example ++ 1.5 g of sodium sulfate) and potency in standard detergent (15) were tested. As a result of the washing efficiency, the optical remissions of the soiled tissue after washing are reported, with the flood remission of the textiles being 11.9%.

Table 3

Surfactant n Basic Detergent Efficiency in Standard. detergent efficiency

60 ° C 90 ° C 60 ° C 90 ° C

According to the invention Example 1 24.3 30.0 35.0 41.3 According to the invention Example 2 6 29.7 34.2 40.0 45.0 According to the invention Example 3 8 33.5 38.0 43.9 48, 3 According to the invention Example 4 12 37.2 41.8 47.6 52.0 According to the invention Example 5 16 37.9 42.0 48.0 52.9 According to the invention Example 6 20 35.1 39.3 45.5 50 , 3 Example 8 4 20.2 25.2 30.1 36.7 6 25.8 30.1 36.2 40.3 8 30.1 33.2 39.9 44.0 12 33.6 37, 1 42,9 47,0 16 35,2 39,1 45,8 49,5 20 36,0 39,0 46,3 50,0 where "n" means the number of moles of bound ethylene oxide per mole of monoethanolamide fatty acids of rapeseed oil. It can be seen from the results of the work efficiency that the surfactants prepared according to the invention are more effective than surfactants prepared from the so-called classic rape-based raw materials with high erucic acid content.

Claims (2)

SUBJECT A surfactant based on alkylene oxide fatty acid alkanolamides of vegetable oil, characterized in that it consists of 70 to 90 wt. fatty acid alkanolamide derivatives with alkylene oxide having an alkylene oxidation degree of 4 to 25 moles of alkylene oxide per mole of alkanolamide, in which the acids have an alkyl chain length characterized by &lt; / RTI &gt; the number of carbon atoms C 1 to C 20 with mol. weight max. 312.5 u INVENTION 3 to 5 wt. alkylene oxide fatty acid alkanolamide derivatives having an alkylene oxidation degree of 4 to 25 moles of alkylene oxide per mole of alkanolamide in which the acids have an alkyl chain length characterized by the number of C22 carbon atoms with one double bond per mole. weight max. 350 and the remainder being reaction by-products, in particular polyglycols.