DE19641278C1 - New ester-quat compounds with high viscosity in aqueous solution - Google Patents

Abstract

New ester-quats (I) (i.e. quaternised fatty acid triethanolamine ester salts) are prepared by esterifying mixtures of triethanolamine (II) and diethanolamine (III) in weight ratio 75:35 to 95:5 with fatty acids (IV) and quaternising the reaction products conventionally with alkylating agents. The preparation process is claimed, as well as the product.

Description

Field of the Invention

The invention relates to new ester quats with improved rheological behavior based on defined alkanolamine mixtures, a process for their preparation and their use for Manufacture of anti-aging agents and cosmetic preparations.

State of the art

Quaternized fatty acid triethanolamine is generally referred to as "esterquats" understood ester salts. These are known substances that are used according to the relevant Me can obtain methods of preparative organic chemistry. In this context, be on the International patent application WO 91/01295 (Henkel), according to which one triethanolamine in Presence of hypophosphorous acid partially esterified with fatty acids, air passes through and on finally quaternized with dimethyl sulfate or ethylene oxide. From German patent DE-C1 43 08 794 (Henkel) is also known a process for the preparation of solid ester quats, in which the Quaternization of triethanolamine esters in the presence of suitable dispersants, preferably Fatty alcohols. Overviews on this topic are, for example, by R. Puchta et al. in Tens. Surf. Det., 30, 186 (1993), M. Brock in Tens. Surf. Det. 30, 394 (1993), R. Lagerman et al. in J. Am. Oil. Chem. Soc., 71, 97 (1994) and I. Shapiro in Cosm. Toil. 109, 77 (1994). The esterquats are usually marketed as alcoholic concentrates and then diluted to the application concentration. The problem is that the Lö Solutions are usually too thin, so that thickening for the required viscosity build-up agents such as ethoxylated polyglycerol esters are added.

Apart from the fact that the additivation of the esterquats with further technical effort and Ko Most connected, the use of such thickeners is not always desired, so that there is a high level of interest in the market for esterquats which are used in aqueous dilution without use of viscosity regulators show a sufficiently high and constant viscosity. The task the invention has been to meet this need.  

Description of the invention

The subject of are ester quats which are obtained by using mixtures of triethanolamine (TEA) and diethanolamine (DEA) in a weight ratio of 75:35 to 95: 5 esterified with fatty acids and the Reaction products then quaternized in a manner known per se with alkylating agents.

Surprisingly, it was found that the esterquats according to the invention based on TEA / DEA mixture conditions in aqueous dilution show a much higher viscosity than conventional ones Products based on pure triethanolamine.

Another object of the invention relates to a process for the preparation of ester quats, in which mixtures of triethanolamine and diethanolamine in a weight ratio of 75:35 to 95: 5 Fatty acids esterified and the reaction products then with Alky in a conventional manner quaternizing agents.

Alkanolamine mixtures

The alkanolamine mixtures to be used in the sense of the invention can be technical triethanol amine and technical diethanolamine in a weight ratio of 75:25 to 95: 5 and preferably 80:20 up to 90:10 included.

Fatty acids

Fatty acids are usually used to produce the new ester quats according to the invention sets that follow the formula (I),

R1 COOH (I)

in the R¹CO for an aliphatic, saturated and / or unsaturated acyl radical with 6 to 22 carbons atoms of matter stands. Typical examples are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, Lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearin acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachin acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, the z. B. at the pressure splitting of natural fats and oils or in the reduction of aldehydes from the Roelen's oxosynthesis occur. Fatty acids with 12 to 18 carbon are preferred  atoms such as partially hardened palm and / or tallow fatty acids used, which have an iodine number have in the range of 0.5 to 50.

Esterification

The esterification can be carried out in a manner known per se, i.e. H. in the presence of hypophosphorous acid or their salts and optionally reducing agents such as sodium borohydride are carried out. in the in general, the alkanolamines and the fatty acids in a molar ratio of 1: 1.1 to 1: 2.4 set, preferably the ratio is in the range 1: 1.4 to 1: 1.9. The reaction is common performed at temperatures in the range of 120 to 180 ° C. If desired, the reaction the mixture can then be bleached by adding hydrogen peroxide.

Alkylation

The alkylation of the fatty acid alkanolamine esters can be carried out in a manner known per se. For this purpose, the ester is introduced and with the alkylating agent - which is usually in equimolar Amounts or slight deficit - stirred at elevated temperatures (40 to 95 ° C). The Reaction can be carried out in alcoholic solution, for example in isopropyl alcohol, it is however, it is also possible in the presence of inert emulsifiers or dispersants, for example fatty alcohol fetch or alkyl polyglucosides and the like to work. The selection depends on the intended use of the esterquats. Especially for the production of esterquats for the Use in the areas of hair care and skin care is working in the absence of lower alcohol len and the use of suitable emulsifiers or dispersants clearly preferred. After Completion of the reaction can unreacted alkylating agent by adding a small amount Amino acid, preferably glycine, are destroyed. This comes together as an alkylating agent menhang alkyl halides, dialkyl sulfates and ethylene oxide - the latter in the presence of dialkyl phosphates - into consideration. The invention preferably relates to methylquaternized ester quats in the form their chlorides and especially methyl sulfate salts and ester quat salts containing 1 to 5 moles of ethylene oxide quaternized. However, the alkylation is preferably carried out using dimethyl sulfate.  

Industrial applicability

The new ester quats according to the invention show a significantly higher viscosity in aqueous dilution kosität as comparable known products based on pure triethanolamine. Another The invention therefore relates to the use of the new ester quats for the production of Anti-aging agents for pre-treatment and after-treatment of laundry as well as cosmetic preparations such as for example hair shampoos, hair rinses, creams, lotions and the like, in which the substances in amounts of 1 to 50, preferably 5 to 35% by weight, based on the composition, may be present can.

Examples General manufacturing example

513 g (1.9 mol) of partially hardened C _16/18 tallow fatty acid (iodine number = 40), 1 mol of alkanolamine mixture and 1.4 g of 50% by weight hypophosphorous were in a 1 l three-necked flask with stirrer, internal thermometer and distillation attachment Given acid. The reaction mixture was heated at a reduced pressure of 40 mbar to a temperature of 160 ° C. over a period of 4 hours until the acid number was below 5. The crude tallow fatty acid triethanolamine ester was then cooled, the reaction mixture relaxed and 0.4 g of hydrogen peroxide added. A mixture of 45 g (0.072 mol) of the ester in 105 g of isopropyl alcohol was then placed in a 500 ml three-necked flask equipped with a stirrer, dropping funnel and reflux condenser and heated to 45 ° C. with stirring. 8.5 g (0.067 mol) of dimethyl sulfate were added dropwise within 2 h. After the addition was complete, the mixture was stirred at 60 ° C. for a further 2 h. The mixture was obtained as a light-colored oil in practically quantitative yield.

Assessment of viscosity in aqueous dilution

The various esterquats were then mixed with water to a concentration of 5.15 or Diluted 30 wt .-% and the viscosity according to Brookfield immediately or after storage (4 weeks, 40 ° C) in an RVT viscometer (20 ° C, spindle 1.10 rpm). The results are summarized in Table 1 quantified. Examples B3 to B5 are according to the invention, examples B1, B2 and B6 are used for Comparison. It can be seen that only in a defined mixing range of tri- and diethanolamine Esterquats with the desired rheological profile can be obtained.

Table 1

Viscosity of various ester quats in aqueous solution

Claims (8)

1. Esterquats, obtainable by mixing mixtures of triethanolamine and diethanolamine in Weight ratio 75: 35 to 95: 5 esterified with fatty acids and the reaction products then quaternized with alkylating agents in a manner known per se. 2. Process for the preparation of esterquats, characterized in that mixtures of Triethanolamine and diethanolamine in a weight ratio of 75: 35 to 95: 5 esterified with fatty acids and the reaction products are then qua in a manner known per se with alkylating agents terniert. 3. The method according to claim 2, characterized in that one of fatty acids of formula (I) puts, R¹COOH (I) in the R¹CO for an aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 Carbon atoms. 4. Process according to claims 2 and 3, characterized in that fatty acids with 12th uses up to 18 carbon atoms which have an iodine number in the range from 0.5 to 50. 5. Process according to claims 2 to 4, characterized in that the alkanolamines and uses the fatty acids in a molar ratio of 1: 1.1 to 1: 2.4. 6. Process according to claims 2 to 5, characterized in that the alkylation with Performs dimethyl sulfate. 7. Use of ester quats according to claim 1 for the production of finishing agents. 8. Use of esterquats according to claim 1 for the production of cosmetic preparations.