DE4436066A1 - fatty substances - Google Patents

Abstract

The invention concerns novel fats of formula (I), in which R<1> stands for a linear or branched alkyl group with eight carbon atoms, provided that the portion of free octanol is less than 5 wt %. The octylpropylene-glycolethers and the sulphates, ethoxylates and ether sulphates derived therefrom are distinguished by improved properties on application.

Description

Field of the invention

The invention relates to new fatty substances, a method for Production of fatty substances by propoxylation of octanol and then separating free fatty alcohol, method for the preparation of surface-active derivatives of this fat substances and the use of fatty substances and their derivatives for the preparation of surfactants.

State of the art

Modern washing, rinsing and cleaning agents are constantly being used growing demands. In addition to special ecotoxic Ecological compatibility is a special need for an ever better performance. This counts For example, the reliable avoidance of turbidity or the crystal formation with longer storage time and low Temperatures. Another point, especially for Pul Ver- and extrudate detergent is correct, the improvement tion of the dissolution rate and thus the Einspülvermö gens in the washing machine. In the field of liquid washing Medium products are desired, the least possible water  contained and yet low viscosity. The development always new surfactants is not a solution. Rather the expert will try to do it by intelligent mixing Exploit synergies between known surfactants or be to optimize existing products and their manufacturing processes.

From DE-C1 4243643 (Henkel), for example, new Mischethertypen the formula C _8-10 + (PO) _1.2-1.7 + (EO) _7-9- butyl ether are known, which are compared to very similar known types characterize an improved network effect.

In DE-A1 4237178 (Henkel) is proposed, the cold behavior of precursors for the production of liquid detergents by the addition of nonionic surfactants of formula C _6-10 + (PO) _0.5-3 + (EO) _4-10 and C _12-20 (EO) _4-10 .

From WO 94/11487 (Unilever) is finally the use of undecyl alcohol to improve the performance of al kylsulfathaltigen powder detergents known.

In view of the problems described in the use of anionic and nonionic surfactants offer this font However, at best partial solutions. Still exists a need for a doctrine that helps both the problem of cold stability with nonionic surfactants, the problem of crystallization tendency of alkyl ether sulfa the problem of unsatisfactory dermatological ver tolerability of concentrated alkyl sulfate pastes, as well same time the problem of insufficient water solubility of alkyl sulfate-containing detergent powders or extrudates can solve.

The complex object of the invention has been a Solution for the mentioned variety of problems len.

Description of the invention

The invention relates to fatty substances of the formula (I),

in the R¹ for a linear or branched alkyl radical with 8 Carbon atoms, with the proviso that the proportion of free octanol less than 5, preferably less than 1 wt .-% be wearing.

Surprisingly, it has been found that the inventive Fatty substances have an advantageous cold behavior. In Mixture of octyl propylene glycol ether with other anioni and / or nonionic surfactants becomes a lower Viscosity (liquid products) and an increased resolution Segeschwindigkeit and detergency (solid products) observed; In addition, an improvement in dermatological properties be noted what the possibility of production highly concentrated, powerful and yet as irritating makes it possible to classify products.

The invention includes the knowledge that these over striking properties both to the selected chemical  Composition as well as the distillative treatment are bound. This is how products show a longer alkyl chain and / or a higher Propoxylierungsgrades despite Nachbe treatment as well as improved cold stability Octylpropylenglycolether, in their preparation to the Ab separation of the free octanol after the propoxylation ver was canceled.

The inventive idea further includes the knowledge that the improved performance characteristics not limited solely to the octyl propylene glycol ethers are, but also in the typical secondary products as in For example, the sulfates, ethoxylates and ether sulfates he stay abreast. Octyl propylene glycol ethers also help interesting chemical intermediates.

Another object of the invention relates to a method for the preparation of fatty substances of the formula (I),

in the R¹ for a linear or branched alkyl radical with 8 Carbon atoms, which is characterized in that octanol in a conventional manner with propylene oxide ver ethers and then the proportion of unreacted Alko distillative to a value less than 5, preferably less than 1% by weight depleted.  

The Preparation of Octylpropylene Glycol Ethers ("Octanol + 1PO") takes place in a conventional manner, preferably by order Substitution of 1 mole of 2-ethylhexanol and in particular n-octanol with 1 mole of propylene oxide in the presence of alkaline catalysts (For example, sodium methylate) at 120 to 180 ° C in a pressure vessel under autogenous pressure. Instead of the preferred n-octanol can also be technical octyl alcohol, as he as for example Flow in the fractionation of coconut fatty alcohol is obtained be used.

Fatty alcohol sulphates

Another object of the invention relates to a method for the preparation of fatty substances of the formula (II),

in the R¹ for a linear or branched alkyl radical with 8 Carbon atoms and X for an alkali and / or alkaline earth metal tall, ammonium, alkylammonium, alkanolammonium or glucammo It is clear that it is distinguished by the fact that one

• a) octanol in a conventional manner with propylene oxide ver etherified,
• b) the proportion of unreacted alcohol by distillation until depleted to a value less than 5% by weight,
• c) the Octylpropylenglycolether in a conventional manner sulfated and finally  
• d) neutralized with bases.

The sulfation of octyl propylene glycol ethers can be used in the Fatty acid lower alkyl esters known manner [J. Falbe (ed.), "Surfactants in consumer products", Springer Verlag, Berlin- Heidelberg, 1987, p. 61], whereby reactors which are after working the falling film principle, are preferred. As Sulfiermit tel come chlorosulfonic acid and especially gaseous Sulfur trioxide into consideration. The latter is usually with an inert gas, preferably air or nitrogen diluted and in the form of a gas mixture containing the sulfonating agent in a concentration of 1 to 8, in particular 2 to 5 vol .-% contains, used.

The molar ratio of ether to sulfating agent may be 1: 0.9 to 1: 1.3 and preferably 1: 0.95 to 1: 1.05 be. Usually the sulfation is at Tem temperatures of 20 to 50 ° C carried out. In terms of Viscosity of the starting materials on the one hand and the color quality on the other hand, it has the resulting sulfation products proved to be optimal, the reaction in a temperature range of 25 to 35 ° C perform.

The acid sulfonation products obtained in the sulfation are stirred into aqueous bases, neutralized and adjusted to a pH of 6.5 to 8.5. Suitable bases for the neutralization are alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C _2-4 -alkanolamines, for example mono -, di- and triethanolamine and primary, secondary or tertiary C _1-4 alkyl amines and Gluca mine into consideration. The neutralization bases are preferably used in the form of 5 to 55% strength by weight aqueous solutions, with 5 to 25% strength by weight aqueous sodium hydroxide solutions being preferred.

The sulfation products can after neutralization in an known manner by the addition of hydrogen peroxide or Bleached sodium hypochlorite solution. In doing so, based on the solids content in the solution of the sulphate tion products, 0.2 to 2 wt .-% hydrogen peroxide, calculated as 100% substance, or equivalent amounts of sodium hypo chlorite used. The pH of the solutions may be below Ver use of suitable buffering agents, e.g. B. with sodium phosphate or citric acid are kept constant. To stabilize tion against bacterial attack is also recommended a Kon Serving, z. With formaldehyde solution, p-hydroxybenzoate, Sorbic acid or other known preservatives.

fatty alcohol ethoxylates

Another object of the invention relates to a method for the preparation of fatty substances of the formula (III),

in the R¹ for a linear or branched alkyl radical with 8 Carbon atoms and n stands for numbers from 1 to 10, the characterized by the fact that one

• a) octanol in a conventional manner with propylene oxide etherified,
• b) optionally the proportion of unreacted alcohol distillative to a value less than 5 wt .-% abrei chert and
• c) the Octylpropylenglycolether in a conventional manner reacts with on average 1 to 10 moles of ethylene oxide.

The ethoxylation of Octylpropylenglycolether can in Gegen wart acidic, but preferably alkaline catalysts such as sodium methylate, potassium hydroxide and the same take place. Are products with a restricted Ho mologenverteilung desired, offers the use of Stontium or barium salts and in particular calcined or hydrotalcites hydrophobicized with fatty acids. Übli The reaction may be carried out at temperatures in the range of 120 to 150 and preferably 140 to 160 ° C and an autoge NEN pressure in the range of 1 to 5 bar performed. To new tralization of basic catalysts is the products in the Usually phosphoric acid or lactic acid added.

In this case, a depletion of the proportion of free, non-propoxylated octanol before ethoxylation only then required if 1 mol octanol + 1PO with less than 7 mol Ethylene oxide is to be implemented. In all other cases, So at higher degrees of ethoxylation, the undesirable Proportion of free octanol by the subsequent reaction with  Ethylene oxide lowered below the required limit. These Restriction also applies then the ethoxylates are followed ßend be sulfated.

fatty alcohol

Another object of the invention relates to a method for the preparation of fatty substances of the formula (IV),

in the R¹ for a linear or branched alkyl radical with 8 Carbon atoms, n for numbers from 1 to 10 and X for a Alkali and / or alkaline earth metal, ammonium, alkylammonium, Alkanolammonium or glucammonium stands, which is characterized distinguishes that one

• a) octanol in a conventional manner with propylene oxide ver etherified,
• b) optionally the proportion of unreacted alcohol distillative to a value less than 5 wt .-% abrei chert,
• c) the Octylpropylenglycolether in a conventional manner with an average of 1 to 10 moles of ethylene oxide,
• d) the resulting octylpropylene glycol (poly) ethylene glycol colether sulfated in a conventional manner and after all
• e) neutralized with bases.

The ether sulfates are prepared analogously to the teaching of Chapter "Fatty alcohol sulfates" and "fatty alcohol ethoxylates".

Industrial Applicability

Octyl propylene glycol ether after separation of free Octanol on a particularly beneficial cold behavior. you allow the production of low-viscosity liquid detergents telkonzentrate and improve the dissolution rate of alkyl sulphate powder detergents. Also derivatives of these Ethers, in particular sulfates, ethoxylates and ether sulfates, the collectively subsumed under the term "fatty substances", show alone, but especially in mixture with others Surfactants have interesting surface-active properties such as for example, a reduced tendency to crystallize or an improved dermatological compatibility.

Another object of the invention finally relates the use of said fatty substances for the production of surfactants such as powder wash medium, liquid detergents, hand dishwashing detergents, hand washing pastes, all-purpose cleaners, mechanical means Bottle cleaning and degreasing agents for metallober areas.

In preferred embodiments of the invention, the Oc tylpropylenglycolether and their sulfates, ethoxylates and / or Ether sulfates with anionic surfactants of the fat type alcohol sulfates ("alkyl sulfates") and / or fatty alcohol ethers fate ("ether sulfates") and nonionic surfactants of the type  the fatty alcohol polyglycol ether, mixed ether and alkyl oligoglu coside be mixed. The mixtures can be known th methods of the prior art. For the case of a mixture of an Octylpropylenglycolsulfats or ether sulphate with another fatty alcohol sulphate or ether sulfate offers a cosulfation of the starting substances.

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

Examples I. Production Examples Example H1

• a) In a 500 ml steel autoclave, 256 g (2 mol) submitted n-octanol and with 4 g of sodium methylate - ent 1 wt .-% based on the final product - in the form a 30 wt .-% solution in methanol. The Reactor was sealed, alternating three times with N₂ rinsed and evacuated. Subsequently, the Reakti heated to 140 ° C and 116 g (2 mol) of Propy lenoxid pressed in portions, the pressure is not increase above 1.5 bar. After the end of the encore, the Stirred for 30 min, cooled, relaxed and the crude ether with lactic acid to a pH of 7.5 set. The yield was 370 g and was convenient quantitatively.
• b) The crude octyl propylene glycol ether was added to a distill transferred lationsapparatur and unreacted octanol at a bottom temperature of about 90 ° C and a ver reduced pressure of about 20 mbar distilled off. there 20 g of octanol were recovered. The distillation Residue had a residual octanol content of 0.9 Wt .-% on.

Example H2

In a 1-L sulfonation reactor with jacket cooling, 186 g (1 mol) Octylpropylenglycolether according to Example H1b) submitted and at 30 ° C with 84 g (1.05 mol) of gaseous sulfur trioxide implemented. The sulfur trioxide was prepared by heating from a expelled corresponding amount of 65% oleum, to a Concentration of 3 vol .-% diluted and within 25 min introduced into the starting product. After sulfation The acidic reaction mixture was in portions in aqueous 25 wt .-% pure Sodium hydroxide solution stirred and neutralized. The characteristics are summarized in Table 1:

Octylpropylenglycolsulfat sodium salt anionic surfactant 27% by weight Unsulfiertes 3% by weight sodium sulphate 1% by weight water 69% by weight Velcro Color 69

The anionic surfactant content (WAS) and the unsulfonated fractions (US) according to the DGF standard methods, Stuttgart 1950-1984, H-III-10 and G-II-6b determined. The determination of Klett color number was after 30 minutes of bleaching with 1 Wt .-% of a 35 wt .-% aqueous hydrogen peroxide solution. The measurement was carried out at a concentration of 5% by weight of anion  surfactant, pH = 7 and using a 1 cm round cuvette and a blue filter (400 to 465 nm).

Example H3

Analogously to Example H1b), 186 g (1 mol) of purified octyl propylene glycol ether in an autoclave submitted with 2.7 g Sodium methylate and 88 g (2 mol) of ethylene oxide puts. The octylpropylene glycol 2EO adduct was as colorless Obtained liquid in virtually quantitative yield.

Example H4

In a 500 ml steel autoclave 130 g (1 mol) of n-octa were added submitted nol and with 2.5 g of a 30 wt .-% solution of Sodium methylate in methanol. The reactor was ver closed and rinsed three times alternately with nitrogen and evacuated. Subsequently, the reaction mixture was heated to 140.degree heated and 58.4 g (1 mol) of propylene oxide in portions presses, the pressure did not rise above 1.5 bar. After this After the addition was stirred for 30 min and in the same Wei Added 394 g (9 mol) of ethylene oxide. After a stirring time of again 30 min, the reactor was cooled, ent spans and the basic catalyst by adding milk acid neutralized. The octyl + 1PO + 9EO adduct was in prak obtained quantitative quantitative yield.  

Example H5

Analogously to Example H2), 274 g (1 mol) of octylpropylene glycol 2EO adduct from Example H3) with 84 g of sulfur trioxide sulfa and then neutralized with sodium hydroxide solution. The Characteristics are summarized in Table 2:

Octylpropylenglycolsulfat-2 EO-sodium salt anionic surfactant 31% by weight Unsulfiertes 4% by weight sodium sulphate 1% by weight water 64% by weight Velcro Color 55

II. Application studies

To investigate the application properties of the Fats according to the invention were the following investigations carried out:

• (a) Determination of the cloud point of various Nio surfactants (Table 3);
• (b) Determination of Viscosity of Liquid Detergent Concentrates occurred (Table 4);  
• (c) dissolution rate of powder detergents. For this were each 10 g of various alkylsulfathaltiger Recipes dissolved in 100 ml of water (30 ° C, 16 ° d) or dispersed. After 30, 120 and 360 s the solutions became or dispersions filtered off, the residue dried and balanced (Table 5).

Table 3

Cold cloud point (KTP)

Table 4

Viscosity of liquid detergents (data as% by weight)

Table 5

Dissolution rate of powder detergents

(Data as wt .-%)

III. formulation Examples Example R1

70% by weight C _12/14 coconut fatty alcohol + 2EO sulfate sodium salt (Texapon® N70, Henkel KGaA, Dusseldorf / FRG)
30% by weight of n-octanol + 1PO / 2EO sulfate sodium salt

Compared to a pure Texapon® 70 is a 40% ver improved cold stability achieved.

Example R2

70% by weight C _12/14 coconut fatty alcohol + 2EO sulfate sodium salt (Texapon® N70, Henkel KGaA, Dusseldorf / FRG)
30% by weight of n-octanol + 1PO sulfate sodium salt

The surfactant compound can be classified as "irritant" and owns 25% better than pure Texapon® N70 Secured crystallization inhibition. The compound is suitable for the production of hand dishwashing detergents.

Examples R3 and R4

70% by weight of C _16/18 tallow alcohol sulfate sodium salt (Sulfopon® T55, Henkel KGaA, Dusseldorf / FRG)
30 wt .-% n-octanol + 1PO sulfate sodium salt or
14 wt .-% C _12/14 cocoalkyl sulfate sodium salt
56% by weight of C _16/18 tallow alcohol sulfate sodium salt
30% by weight of n-octanol + 1PO sulfate sodium salt

Compared to pure Sulfon® T55, a 35% and 25% respectively improved dissolution rate in cold water (20 ° C) reached. The compounds are suitable for example for Her setting of hand washing pastes.

Example R5

90% by weight C _12/18 cocos / tallow alkyl sulfate-sodium salt mixture (Sulfopon® 1218 W, Henkel KGaA, Dusseldorf / FRG)
10% by weight of n-octanol + 1PO

The surfactant compound can be combined with 20 wt .-% zeolite A. - Based on the total mixture - to a dry powder granulate or extrude, compared to pure sulfo pon® 1218 W / zeolite powder has a 25% improvement in resolution speed in cold water (20 ° C) and at 10% improved washing performance. In addition, the powder is si significantly drier.  

Example R6

16% by weight of lauryl sulfate sodium salt (Texapon® NSO, Henkel KGaA, Dusseldorf)
13% by weight of C _8/16 -alkylpolyglucoside (Glucopon® 600 UP, Henkel KGaA, Dusseldorf)
12% by weight C _12/18 coconut _fatty alcohol + 7EO (Lorol® T7, Henkel KGaA, Dusseldorf)
8% by weight of n-octanol + 1PO / 8EO
8% by weight of C _12/18 coconut _fatty acid
5 wt .-% potassium hydroxide
8% by weight ethanol
30% by weight of deionized water

The surfactant compound has a very low viscosity (after Brookfield, RTV viscometer, 20 ° C, spindle 1, 10 rpm) about 300 mPas and can be used as a liquid detergent become. Replacing the n-octyl-1PO / 8EO adduct with Lorol® T7, however, is given a cut-resistant gel.

Example R7

80% by weight C _12/18 coconut _fatty alcohol + 10EO-butyl ether (Dehypon® LT 104, Henkel KGaA, Dusseldorf)
20% by weight of n-octanol + 1PO / 6EO

The surfactant compound is suitable as a low foaming wetting agent for the spray cleaning of body panels.

Claims (6)

1. fatty substances of the formula (I), in which R¹ is a linear or branched alkyl radical having 8 carbon atoms, with the proviso that the proportion of free octanol is less than 5 wt .-%. 2. Process for the preparation of fatty substances of the formula (I), in which R¹ is a linear or branched alkyl radical having 8 carbon atoms, characterized in that octanol is etherified in a conventional manner with Propy lenoxid and then de-enriched the proportion of unreacted alcohol by distillation to a value less than 5 wt .-%. 3. Process for the preparation of fatty substances of the formula (II), with 8 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, characterized in that

• a) octanol etherified in a conventional manner with propylene oxide,
• b) the fraction of unreacted alcohol is distilled off by distillation to a value of less than 5% by weight,
• c) sulfating the octyl propylene glycol ether in a conventional manner and finally
• d) neutralized with bases.

4. Process for the preparation of fatty substances of the formula (III), in which R¹ is a linear or branched alkyl radical having 8 carbon atoms and n is a number from 1 to 10, characterized in that

• a) octanol etherified in a conventional manner with propylene oxide,
• b) if appropriate, the fraction of unreacted alcohol is distilled off by distillation to a value of less than 5% by weight, and
• c) the octyl propylene glycol in a conventional manner with an average of 1 to 10 moles of ethylene oxide.

5. Process for the preparation of fatty substances of the formula (IV), in which R¹ is a linear or branched alkyl radical having 8 carbon atoms, n is a number from 1 to 10 and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, characterized in that

• a) octanol etherified in a conventional manner with propylene oxide,
• b) if appropriate de-enriching the fraction of unreacted alcohol to a value of less than 5% by weight,
• c) the octyl propylene glycol ether is reacted in a manner known per se with an average of from 1 to 10 mol of ethylene oxide,
• d) the resulting octyl-propylene glycol (poly) ethylene glycol ether in a conventional manner Sulfa benefits and finally
• e) neutralized with bases.

6. Use of fatty substances obtainable by the methods according to claims 2 to 5 for the production of powder detergents, liquid detergents, hand dishwashing detergents hand washing pastes, all-purpose cleaners, means for the machine bottle cleaning and means for Ent greasing of metal surfaces.