EP0712440A1

EP0712440A1 - Process for preparing water-free nitrogenated compounds

Info

Publication number: EP0712440A1
Application number: EP94926144A
Authority: EP
Inventors: Bernd Fabry; Wilfried Rähse; Johann Friedrich Fues; Oriol Ponsati Obiols; Nuria Bonastre; Joaquim Bigorra Llosas; Ester Prat Queralt
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-08-11
Filing date: 1994-08-03
Publication date: 1996-05-22
Also published as: JPH09501706A; KR960704021A; DE4326975A1; WO1995004810A1; CN1129012A

Abstract

In order to produce water-free nitrogenated compounds with an improved solubility or dispersibility in cold water, aqueous and/or alcoholic solutions or dispersions of quaternary ammonium compounds, quaternary esters or fatty acid amines are spray dried in the presence of overheated steam.

Description

Manufacturing process

of anhydrous nitrogenous compounds

Field of the Invention

The invention relates to a process for the preparation of anhydrous nitrogen-containing compounds with improved cold water solubility or dispersibility, in which aqueous or alcoholic solutions of quaternary ammonium compounds, ester quats or fatty acid amides are subjected to superheated steam drying, and the use of the dried material for the production of surface-active agents.

State of the art

For the treatment of textile fibers, yarns or fabrics, a large number of compounds or mixtures of substances are proposed which impart the desired properties to the textiles treated therewith or which are components of agents for textile care. Depending on the type of active ingredients used, the processing properties, the wearing properties of the textiles and their care can be improved become. Quaternary ammonium compounds (QAC), such as, for example, distaeryldimethylammonium chloride (DSDMAC) or increasingly quaternized fatty acid triethanolamine ester salts, so-called "esterquats", are generally suitable as active ingredients for this. Overviews are available for example from O.Ponsati in CR CED Congress, Barcelona, 1992, p.167 and R.Puchta et al. published in CR CED Congress, Sitges, 1993, p.59. Finally, fatty acid amides can also be used as further feedstocks.

QAV and esterquats can only be dewatered using conventional methods and are also not very water-soluble. They are therefore usually commercially available as dilute aqueous solutions or dispersions or alcoholic concentrates. The technical problems of drying fatty acid amides are less, so that flaky goods are common commercial products. Although the problem of inadequate cold water dispersibility applies to all three classes of nitrogen-containing compounds mentioned, a whole series of possible solutions to problems are known from the prior art, particularly for fatty acid amides:

For example, US Pat. No. 2,340,881 describes aqueous dispersions of condensation products, prepared from a hydroxyalkyl polyamine and a fatty acid glyceride, which improve the lubricity and the softness of the textiles treated therewith. The US 34 54 494 relates to fatty acid condensation products with an addition of dispersing polyglycol ethers. The German patent DE-PS 19 22 046 describes detergents with a Content of fatty acid condensation products which contain fatty acid glycerides with a dispersing action; in the German patent DE-PS 19 22 047 these substances are also described as textile softeners for liquid laundry aftertreatment agents in particular. These and similar agents can be dispersed in water by placing them in hot water and usually applying high shear forces, or by dispersing the condensation product, which has still been melted, in water. Because of the effort required, the manufacturer usually carries out the dispersion and supplies the user with the dispersions, which is associated with the storage and transport of considerable amounts of water and is therefore not economically viable. According to the teaching of German patent applications DE-A1 3530 302, DE-A1 37 30 792, DE-A1 39 01 820 and DE-A1 41 11 648 (Henkel), the dispersibility of such substances can be increased by adding suitable dispersion accelerators, for example glucose, Improve sorbitol, mannitol, pentaerythritol, alkyl polyglucosides, sorbitan esters, gelatin and unsaturated fatty alcohols and fatty acids. Products that contain mixtures of highly ethoxylated tallow alcohols and 1,2-propylene glycol as dispersion accelerators are also established on the market.

Further options, for example to obtain ester quats with improved solubility or dispersibility in cold water, are the skillful selection of the fatty acid component and the use of emulsifiers or dispersants (e.g. fatty alcohols or nonionic surfactants) as solvents instead of isopropyl alcohol in the alkoxylation and are the subject of previously unpublished patent applications . Nevertheless, it is observed time and again in practice that nitrogen-containing compounds produced by the methods of the prior art cannot be dissolved or dispersed, or can only be insufficiently dispersed. This uncertainty with regard to product quality represents a considerable economic disadvantage which limits the usability of the substances mentioned, for example as a sought-after textile treatment agent. Another problem is that even those prior art products that have satisfactory solubility or dispersibility often lose irreversibly when stored in air.

The object of the invention was therefore to provide a new process for the preparation of anhydrous nitrogen-containing compounds with improved cold water solubility or dispersibility and storage stability, which is free from the disadvantages described.

Description of the invention

The invention relates to a process for the preparation of anhydrous nitrogen-containing compounds having improved solubility or dispersibility in cold water, in which aqueous and / or alcoholic solutions or dispersions of quaternized ammonium compounds, esterquats or fatty acid amides are subjected to spray drying in the presence of superheated steam. Surprisingly, it was found that the spray drying of the substances mentioned in the presence of superheated steam leads to a particularly advantageous grain structure which is free-flowing, low-dust and extremely water-soluble or water-dispersible. In particular, comparable dry products that are manufactured using conventional processes (rotary evaporators, spray drying) are significantly exceeded in their properties. Another advantage of the process according to the invention is that the drying can also be used to separate non-aqueous solvents without pluming and thus without any environmental pollution, since the process allows a completely closed procedure. The invention also includes the knowledge that drying also deodorises and purifies the nitrogen-containing compounds, since disturbing contaminants which are volatile in water vapor, such as traces of unreacted alkylating agents, alkyl ethers and odor carriers, are removed virtually quantitatively. The resulting dry material is very stable in storage and also meets the highest quality requirements, such as those desired for cosmetic products.

Quaternized ammonium compounds (QAV)

Suitable quaternized ammonium compounds are quaternized tetraalkylammonium salts of the formula (I)

in which R ¹ and R ² independently of one another are aliphatic alkyl radicals having 6 to 22 carbon atoms or benzyl radicals, R ^{3 is} an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, R ^{4 is} a methyl group and X is halide, alkyl sulfate or alkyl phosphate.

The substances of the formula (I) are preferably classic cationic surfactants which have two fatty alkyl radicals having 6 to 22, preferably 16 to 18, carbon atoms and two methyl groups. The most important example is distearyldimethylammonium chloride.

Esterguats

Substances of the formula (II) are suitable as quaternized fatty acid triethanolamine ester salts (esterquats),

C

in which R ⁵ CO represents an acyl radical having 6 to 22 carbon atoms, R ⁶ and R ⁷ independently of one another are hydrogen or R ¹ CO, R ^{8 represents} an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate.

These are known substances that can be obtained by the relevant methods of preparative organic chemistry. In this connection, reference is made to the international patent application WO 91/01 295 (Henkel), according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide.

Examples of the fatty acid component of the ester quats are caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as those used in Pressure splitting of natural fats and oils occur. _Ester quats based on technical C _12/18 coconut _fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids and C _16/18 fatty acid _cuts rich in elaidic acid are preferably used and dried.

The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm fatty acid (iodine number 0 to 40).

Fatty acid amides

Suitable fatty acid amides are compounds which follow the formula (III)

in which R ⁹ CO represents an aliphatic acyl radical with 8 to 22 carbon atoms and 0 and / or 1 to 3 double bonds, R ^{10 represents} hydrogen, a methyl, ethyl, hydroxyethyl or a - (CH ₂ ) _n -NHR ¹¹ - Group, R ¹¹ for hydrogen, a methyl, Ethyl or hydroxyethyl group, x stands for numbers from 2 to 4 and y for numbers from 1 to 4. Preference is given to the use of fatty acid amides of the formula (III) in which R ^{9 is} CO for a saturated and / or monounsaturated acyl radical having 16 to 18 carbon atoms, R ¹⁰ for a hydroxyethyl or

(CH ₂ ) ₂ NH ₂ group, R ^{11 is} hydrogen, x is 2 and y is 1 or 2.

In the production of the fatty acid amides, for example, the fatty acids or their esters and the polyvalent amines can be used in a molar ratio of 1: 1 to 2.5: 1, preferably 1.3: 1 to 1.7: 1. The components are heated over a period of 0.5 to 5, preferably 1 to 2 h to a temperature of 170 to 210, preferably 180 to 200 ° C. until the fatty acid or the fatty acid ester has been virtually completely reacted, and the mixture is then left to further React for 5 to 60, preferably 15 to 30, minutes at the reaction temperature. If the production of particularly light-colored products is desired, it is advisable to condense in the absence of atmospheric oxygen and, if appropriate, in the presence of a reducing agent, e.g. B. hypophosphorous acid to perform.

Following the condensation, the unreacted amino groups are neutralized with low molecular weight organic carboxylic acids, hydroxycarboxylic acids or inorganic acids, such as. As acetic acid, lactic acid or phosphoric acid, for example by mixing the melt of the fatty acid condensation product with the calculated amount of acid with salt formation or the amine salt by dissolving or dispersing the reaction product in the organic acid or Forms solution of organic acid in water. According to the invention, the acid used for salt formation can be used in amounts such as are required for 20 to 80, preferably 30 to 60, mol% neutralization.

Hot steam drying

The term "superheated steam drying" is to be understood as a special spray drying in the absence of atmospheric oxygen in the presence of superheated steam. The principle of this new technical method has been disclosed by the applicant in its German patent application DE-A1 40 30 688.

The process referred to as "superheated steam drying" or "steam drying" is based on the principle that condensation of the superheated steam on the cooler feed and release of the heat of condensation to the material to be dried spontaneously heats the aqueous drop to the boiling point of the water under working conditions at normal pressure So at temperatures of about 100 ° C takes place. This boiling temperature is maintained as a minimum temperature in the droplet during the entire drying period. A desired effect of the superheated steam drying of nitrogen-containing compounds can be seen in the fact that a dried material with a high inner surface is obtained which is particularly easy to dissolve or disperse in water.

Basically, it works in a closed system with a steam cycle that the vaporized Water content of the feed material is withdrawn, while the amount of energy given off in particular in the drying step is fed back into the circulating stream. While conventional spray drying always involves working at higher temperatures with the risk of partial charring of the material to be dried, the absence of atmospheric oxygen makes drying temperatures of 200 to 250 ° C readily possible. After the cleaning of the carried-along portions of the good, the partial steam stream which has been drawn off can advantageously be used as service steam for other uses.

In the course of hot steam drying, the anhydrous nitrogen-containing compounds are obtained as low-dust, free-flowing powders with a bulk density of at least 150 g / l.

Auxiliaries and additives

Drying with superheated steam can be carried out in the presence of further auxiliaries and additives, the amount used being 0.5 to 15, preferably 1 to 10% by weight, based on the solids content of the material to be dried.

Examples include dispersion accelerators such as addition products of an average of 1 mol of ethylene oxide and 2 mol of propylene oxide, 2 mol of ethylene oxide and 4 mol of propylene oxide, 5 mol of ethylene oxide and 1 mol of propylene oxide and 2 to 3 mol of propylene oxide with C _12/18 - coconut oil _alcohol , C _{16 / 18} - Taig fatty alcohol or C _16/18 palm fatty alcohol, monosaccharides of the aldose and ketose type, the polyhydroxy compounds derived therefrom by hydrogenation, pentaerythritol, trimethylolpropane, alkyl oligoglucosides, sorbitan esters, polysorbates as well as hydrophilic polymers based on carbohydrates or unsaturated alcohols or carboxylic acids.

Industrial applicability

The anhydrous nitrogen-containing compounds obtainable by the process according to the invention are free-flowing, low-dust and outstandingly water-soluble or water-dispersible. They are suitable for the production of surface-active agents, in particular fabric softeners, hair and fiber conditioners and antistatic agents, in which they can be present in amounts of 1 to 75, preferably 3 to 50% by weight, based on the agent.

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

Examples

Example 1 :

In a spray tower from NIRO ATOMIZER, a methylguaternized ditallow fatty acid triethanolamine ester in the form of the methyl sulfate salt (Dehyquart ^(R) AU-36, 80% by weight in isopropyl alcohol, Pulcra SA, Barcelona / ES) was dried with superheated steam. The process data are summarized in Tab. 1:

The product obtained had a dry matter content of 98.9% by weight and a bulk volume of 350 g / l. Examples 2 and 3

Analogously to Example 1, two further ester quats were based

C _12/18 palm _fatty acid and C _16/18 tallow fatty acid (partially hydrogenated) are subjected to hot steam drying. These products also had a dry matter content of 98.9% by weight and a bulk volume of 350 g / l.

Examples 4 to 6, comparative examples V1 and V2

To investigate the solubility, 10 g of the drying products according to the invention and two reference substances were dissolved or dispersed in 100 ml of water (30 ° C., 16 ° d). After 30, 120 and 300 s, the solutions or dispersions were filtered off, the residue was dried and weighed out. The results are summarized in Tab. 2:

Claims

1. A process for the preparation of anhydrous nitrogen-containing compounds with improved cold water solubility or dispersibility, in which aqueous and / or alcoholic solutions or dispersions of quaternized ammonium compounds, esterquats or fatty acid amides are subjected to spray drying in the presence of superheated steam.

2. The method according to claim 1, characterized in that one uses quaternized tetraalkylammonium salts of the formula (I),

3. The method according to claim 1, characterized in that quaternized fatty acid triethanolamine ester salts of the formula (II) are used. in which R ⁵ CO represents an acyl radical having 6 to 22 carbon atoms, R ⁶ and R ⁷ independently of one another are hydrogen or R ¹ CO, R ^{8 represents} an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate.

4. The method according to claim 1, characterized in that fatty acid amides of the formula (III) are used,

in the R ⁹ CO for an aliphatic acyl radical with 8 to 22 carbon atoms and 0 and / or 1 to 3 double bonds, R ¹⁰ for hydrogen, a methyl, ethyl, hydroxyethyl or a - (CH ₂ ) _n _NHR ¹¹ group , R ^{11 represents} hydrogen, a methyl, ethyl or hydroxyethyl group, x stands for numbers from 2 to 4 and y stands for numbers from 1 to 4.

5. Process according to claims 1 to 4, characterized in that the spray drying is carried out at temperatures in the range from 200 to 250 ° C.

6. The method according to claims 1 to 5, characterized in that the anhydrous nitrogen-containing compounds are obtained as low-dust, free-flowing powder with a bulk density of at least 150 g / l.

7. Process according to claims 1 to 6, characterized in that the drying is carried out with superheated steam in the presence of further auxiliaries and additives.

8. Use of anhydrous nitrogen-containing compounds by the process according to claims 1 to 7 for the production of surface-active agents.