DE4224362A1 - Ether-carboxylic acid salt surfactant prepn - by Williamson synthesis with organic halide treatment of prod to remove starting material and improve foaming and cleaning power - Google Patents

Abstract

Prepn. of ether-carboxylic acid salts with reduced residual polyglycol ether content comprises: (a) reacting a fatty alcohol polyglycol ether of formula (II) R10(CH2CHR2O)nH with a halo-carboxylic acid salt of formula (III) X(CH2)mCOOY in presence of base; and (b) treating the obtd. crude (I) R10(CH2CHR2O)m(CH2)mCOOY with an organic halide (IV) in presence of base: R1 = 6-22C aliphatic hydrocarbyl contg. 0-3 double bonds; R2 = H or Me; n = 1-20; X = Cl or Br; Y = alkali metal or ammonium; m = 1 or 2. (III) is sodium chloroacetate (IIIa). Mol. ratios are (II):(III) = 1:0.95-1.2, (II) base = 1:0.9-1.2, (II):(IV) = 1:0.1-0.5 and (IV): base = 1:0.95-2. The base is an alkali metal hydroxide. Reaction is at 40-120 deg. C. (IV) is a 1-8C alkyl or benzyl chloride or bromide. USE/ADVANTAGE - (I) are anionic surfactants with good detergent and esp. dermatological properties. The use of (I) obtd. by the process is claimed for prodn. of washing, rinsing and cleaning agents or hair- and body-care prods. Compsns. generally contain 1-50 (pref. 5-30) wt. % (I). The obtd. (I) are (almost) completely free of (II), and have improved foaming and cleaning power.

Description

Field of the Invention

The invention relates to a method for producing Ether carboxylic acid salts with reduced residual polyglycol ether content at which one fatty alcohol polyglycol ether with halogen implemented carboxylic acid salts and the raw reaction products post-treated organic halides and the use of products for the production of surfactants.

State of the art

The class of ether carboxylic acids is about ionic surfactants, which have good detergent properties and have special dermatological compatibility. An overview of the properties and possible applications of ether carboxylic acids in detergents and cleaning agents by Stroink in Seifen-Öle-Fette-Wwachs 115, 235 (1989) ben.  

According to Gerhardt et al. essentially three different procedures can be distinguished [Surfactants Surf. Det. 29, 169 (1992)]:

The introduction of carboxyl groups in alcohols or etherals kohole can for example by adding acrylonitrile and subsequent saponification. With regard to the be preferred use of ether carboxylic acids in preparations that contact with human skin, however, is the presence of nitrile inevitable in this process traces in the product undesirable.

A second way of producing ether carboxylic acids consists in a catalytic oxidation of the terminal Hy droxyl group of the fatty alcohol ethoxylates used in Presence of transition metal catalysts with inorganic Oxidizing agents or air can take place. With regard the technical effort involved in separating the Kataly sators and the processing of the resulting dilute aq other solutions, this procedure comes for one technical use only to a limited extent.

The technical production of ether carboxylic acids takes place there usually according to the classic method of a mode fished WILLIAMSON synthesis, in which fatty alcohol poly glycol ether in the presence of basic compounds with sodium reacted chloroacetate. There is a disadvantage to this method in that the degrees of implementation are not entirely satisfactory are and the ether carboxylic acids always contain no have reacted starting materials, which is disadvantageous  on the application properties of the products affects.

The object of the invention was therefore to improve tes process for the preparation of ether carboxylic acid salts develop that is free from the disadvantages described.

Description of the invention

The invention relates to a method for producing of ether carboxylic acid salts with reduced residual polyglycol ether content at which one

• a) fatty alcohol polyglycol ether of the formula (I) in which R ^{1 represents} a linear or branched, aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R ^{2 stands} for hydrogen or a methyl group and n stands for numbers from 1 to 20, in the presence of basic Reacts compounds with halocarboxylic acid salts of the formula (II), X- (CH₂) _m COOY (II) in which X is chlorine or bromine, Y is an alkali metal or ammonium and m is 1 or 2 and
• b) then the crude ether carboxylic acid salt in the presence basic compounds with organic halides treated.

Surprisingly, it was found that ether carboxylic acid Resalt with improved application properties can be preserved if one contains the in the raw products Proportion of free fatty alcohol polyglycol ethers through a End group closure with organic halides reduced.

As a starting material for the production of ether carboxylic acid Ren come addition products of ethylene and / or propy lenoxide to linear or branched primary alcohols in Be dress. Typical examples are adducts of average 1 to 20 moles of ethylene and / or propylene oxide on Capronalko hol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, isotridecyl alcohol, cetyl alcohol, palmoleyl alcohol, Stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol hol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and Erucyl alcohol and their technical mixtures. The alkylene Oxide adducts can be both conventional and have a narrow homolog distribution.

Fatty alcohol polyglycol ethers of the formula (I) are preferably used in which R ^{1 is} an alkyl radical having 12 to 18 carbon atoms, R ^{2 is} hydrogen and n is a number from 2 to 7.

Among halocarboxylic acid salts are the alkali or ammoni salts of bromoacetic acid and chloro or bromopropionic acid  to understand. Because of the easy accessibility is the one preferred sodium chloroacet. Usually they can Fatty alcohol polyglycol ether and the halocarboxylic acid salts in molar ratio of 1: 0.95 to 1: 1.2, preferably 1: 1.0 up to 1: 1.1 can be used.

Those to be used in the sense of the method according to the invention organic halides of the following formula (III),

R³-Z (III)

in which R ^{3 represents} an alkyl radical having 1 to 8 carbon atoms or a benzyl radical and Z represents chloride or bromide.

Typical examples of this are methyl chloride, methyl bromide, Ethyl chloride, ethyl bromide, propyl chloride, propyl bromide, pen tyl chloride, n-octyl chloride and 2-ethylhexyl chloride. Because of Their accessibility is the use of n-butyl chloride and benzyl chloride for the end group closure before moves. The fatty alcohol polyglycol ethers and the organic Ha In this case, logenides can be used in a molar ratio of 1: 0.1 to 1: 0.5, preferably 1: 0.2 to 1: 0.3 can be used. Basically, the molar amount of organic halo genid the residual content of unreacted fatty alcohol polygly colether must at least match; an excess favors naturally the completeness of the end group closure, usually requires an additional step during the processing of the products, in which the unreacted Halide is separated off by distillation.  

As basic compounds that both implement the Polyglycol ether with the halocarboxylic acids, as well later end group closure unreacted starting pro Catalyze the product with the organic halides Alkali metal hydroxides into consideration. Typical examples are Sodium hydroxide and especially potassium hydroxide, the above preferably in solid form, for example as scales or Semolina can be used.

Usually the fatty alcohol polyglycol ethers and basic compounds in a molar ratio of 1: 0.95 to 1: 1.2, preferably 1: 1.0 to 1: 1.1 and the organic Halides and the basic compounds in molar ver Ratio of 1: 0.95 to 1: 2, preferably 1: 1.0 to 1: 1.2 be used.

The entire reaction can take place at temperatures from 40 to 120 ° C be carried out, focusing on the condensation of Polyglycol ether and halocarboxylic acid range from 40 to 80 ° C has proven to be optimal. With regard to short reak on the one hand and negligible education desired olefinic by-products, on the other hand, has a temperature for the end group closure in the 2nd stage range from 60 to 100 ° C has proven to be particularly advantageous. The reaction time of the overall reaction can be 1 to 24, preferably 5 to 15 hours.

After the implementation, it is recommended to use the basic Neutralize the catalyst. By adding water separation into an aqueous salt phase and an organic one Phase reached in which the valuable product is contained. Shares  of unreacted halides can by distillation in Water jet vacuum can be removed. For further cleaning the ether obtainable by the process according to the invention carboxylic acid salts, it is also beneficial to use the products in Filter in the presence of a filter aid.

Industrial applicability

The ethers obtainable by the process according to the invention carboxylic acid salts have and are low hydroxyl numbers practically free of fatty alcohol polyglycol ethers. Against They show a verb about state of the art products increased foaming and cleaning ability.

Another object of the invention therefore relates to the Ver use of those obtainable by the process according to the invention Ether carboxylic acid salts for the production of surface active Mit tel, in particular washing, rinsing and cleaning agents, and Products for hair and body care in which they are in quantities from 1 to 50, preferably 5 to 30 wt .-% - based on the Means - may be included.

The following examples are intended to be the subject of the invention explain in more detail without restricting it.

Examples example 1

428 g (1 mol) of C _12/18 coconut oil alcohol-5 EO ether (Dehydol® LT5, sales product from Henkel KGaA, Dusseldorf / FRG) and 122 were placed in a 1 liter three-necked flask equipped with a stirrer, dropping funnel and reflux condenser g (1.05 mol) of sodium chloroacetate and stirred for 20 min at room temperature. 24 g (1.05 mol) of sodium hydroxide flakes were then added and the mixture was stirred at 40 ° C. for a further 7 h.

After completion of the reaction, the reaction mixture was 28 g (0.5 mol) potassium hydroxide flakes and 46 g (0.5 mol) Butyl chloride was added and the mixture was stirred at 80 ° C. for 7 h and then with neutralized aqueous sulfuric acid. After adding water divided the product into an aqueous salt phase and one organic value phase. The latter was used in a distillation apparatus transferred and excess butyl chloride in what separated by jet vacuum. Eventually the product was in Filtered in the presence of a filter aid (Celite®). It was an ether carboxylic acid salt with a hydroxyl number of 2.0 and obtained an acid number of 86.  

Example 2

Analogously to Example 1, 428 g of C _12/18 coconut _fatty alcohol 5 EO ether and 122 g of sodium chloroacetate were reacted. The reaction mixture was then stirred with 7 g (0.3 mol) of sodium hydroxide flakes and 38 g (0.3 mol) of benzyl chloride at 60 ° C. for 7 h. Working up was carried out analogously to Example 1. An ether carboxylic acid salt with a hydroxyl number of 2.4 and an acid number of 56 was obtained.

Comparative Example V1

Analogously to Example 1, 428 g of C _12/18 coconut _fatty alcohol 5 EO ether and 122 g of sodium chloroacetate were reacted. However, the mixture was worked up directly with organic halides without further end group capping. An ether carboxylic acid salt with a hydroxyl number of 8.1 was obtained.

Claims (11)

1. Process for the preparation of ether carboxylic acid salts with reduced residual polyglycol ether content, in which

• a) fatty alcohol polyglycol ether of the formula (I) in which R ^{1 represents} a linear or branched, aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R ^{2 represents} hydrogen or a methyl group and n represents numbers from 1 to 20, in the presence of basic compounds reacted with halocarboxylic acid salts of the formula (II), X- (CH₂) _m COOY (II) in which X is chlorine or bromine, Y is an alkali metal or ammonium and m is 1 or 2 and
• b) then the crude ether carboxylic acid salt is treated in the presence of basic compounds with organic halides.

2. The method according to claim 1, characterized in that fatty alcohol polyglycol ether of the formula (I) is used in which R ^{1 is} an alkyl radical having 12 to 18 carbon atoms, R ^{2 is} hydrogen and n is a number from 2 to 10. 3. The method according to claim 1, characterized in that one as the halogenated carboxylic acid salt sodium chloroacetate puts. 4. The method according to claim 1, characterized in that one the fatty alcohol polyglycol ether and the halogen car bonic acid salts in a molar ratio of 1: 0.95 to 1: 1.2 starts. 5. The method according to claim 1, characterized in that one uses organic halides of the formula (III), R³-Z (III) in the R ³ for an alkyl radical having 1 to 8 carbon atoms or a benzyl radical and Z for chloride or Bro mid stands. 6. The method according to claim 1, characterized in that one the fatty alcohol polyglycol ether and the organic Halides in a molar ratio of 1: 0.1 to 1: 0.5 starts. 7. The method according to claim 1, characterized in that alkali metal hydroxides as basic compounds starts.   8. The method according to claim 1, characterized in that one the fatty alcohol polyglycol ether and the basic Compounds in a molar ratio of 1: 0.95 to 1: 1.2 starts. 9. The method according to claim 1, characterized in that the organic halides and the basic ver Bonds in a molar ratio of 1: 0.95 to 1: 2 starts. 10. The method according to claim 1, characterized in that the reaction at temperatures from 40 to 120 ° C. carries out. 11. Use of ether carboxylic acid salts by the process according to claims 1 to 10 for the production of washing, Detergents and cleaning agents as well as products for hair and personal care.