DE3018201A1 - METHOD FOR REFINING THE RAW CONDENSATION PRODUCT FROM AMINOALKYLALKANOLAMINES AND FATTY ACIDS, AND IF NECESSARY FOR THE FOLLOWING DETERMINATION OF AMPHOTENSIDE WITH INCREASED STORAGE STABILITY - Google Patents

Abstract

1. A process for purifying the crude condensation product of aminoalkyl alkanolamines corresponding to the following general formula H2 N-(CH2 )2 -NH-(CH2 )n -OH in which n is the number 2 or 3, and C6 -C22 fatty acids and, if desired, for subsequently alkylating and, optionally, quaternizing the purified condensation product to form amphoteric surfactants having improved stability in storage, characterized in that the crude condensation product of fatty acids and aminoalkyl alkanolamines is subjected to alkaline hydrolysis at temperatures in the range from 70 to 100 degrees C.

Description

FROM KREISLER SCHÖNWALD EISHOLD FUES FROM KREISLER KELLER SELTING WERNER

PATENT LAWYERS

Dr.-Ing. by Kreisler + 1973

_{DR 1} -IrIg-K-SChonWaId ₁ KoIn

Dr.-Ing. K. W. Eishold, Bad Soden

Dr. J. F. Fues, Cologne

Dipl.-Chem. Alek von Kreisler, Cologne

Dipl.-Chem. Carola Keller, Cologne

Dipl.-Ing. G. Selting, Cologne

Dr. H.-K. Werner, Cologne

DEICHMANNHAUS AT THE HAÜPTBAHNHOF

D-5000 COLOGNE 1

May 12, 1980

Henkel KGaA, Henkelstrasse 67, 4000 Düsseldorf

Process for refining the crude condensation product from aminoalkylalkanolamines and fatty acids and, if desired, to the subsequent Production of amphoteric surfactants with increased storage stability "■■" .. "■"

130047/0198

Telephone: (02 21) 1310 41 - Telex: 868 2307 dopa d - Telegram: Dompatent Cologne

uu I ι y

An important process for the production of amphoteric surfactants starts with condensation products of N-monosubstituted alkylenediamines from which in a further reaction with alkylating agents', for example sodium chloroacetate, alkylated will. Products based on N-aminoethyethanolamine and Fatty acids play a major role as skin-friendly surfactants.

The process for the preparation of such compounds is basically from US Patents 2,528,378, 2,528,379 and 2 52 8 380 known. While it was previously assumed that alkylation or quaternization products in this reaction des imidazolines, it has now been proven that they are predominantly alkylation or quaternization products is about aminoamides which are formed by hydrolysis of the imidazoline intermediate in an aqueous medium, see for example DE-AS 1 084 414 in this regard.

The basic procedure for the production of these surfactants is such that about 1 mole of fatty acid or fatty acid mixture with one mole of an aminoalkylalkanolamine - in particular aminoethylethanolamine - with a gradual increase in Temperature, finally in a vacuum, are condensed. This condensation product is then with varying amounts of a Alkylating agents, for example sodium chloroacetate, usually in an aqueous alkaline solution in the amphoteric surfactant convicted. Details on these process steps can be found in the literature cited, compare further on this Dr. K. Lindner "Tenside-Textile Auxiliaries-Washing Raw Materials" Wissenschaftliche Verlags GmbH, Stuttgart 1964, pages 1041/1042 and »the original literature cited here and DE-OS 27 52 116, published European patent application 001,006 and U.S. Patents 2,773,068 and 3,408,361.

13O047 / 019S

ι. The quality of the amphoteric surfactants obtained and in particular their storage stability is decisively influenced by the

J purity of the obtained in the first .Kondensationsstufe

i imidazoline derivative determined. The reaction between fat

I 5 acids and aminoalkylalkanolamines not only run in

; Direction towards the formation of the desired imidazoline diva—

I tes, multiple side reactions complicate the reaction

j happen. The importance of this aspect is only in the last

Time has been re-emphasized, see E. G. Lomax

'10 "New and improved balanced amphoterics," Manufacturing. Chemist and Aerosol News, Volume 50, No. 8 _r August 1979, pages 39 and 41. It is described here, for example / that the j undesired side reactions in the stage of imidazoline formation can be suppressed by an excess of aminoethylethanolamine , but this excess; must be removed by distillation at the end of the reaction. * Excess aminoethylethanolamine can, however, cause new difficulties due to cyclization to pi-perazine. The purity of the first stage of the reaction! 20 nen imidazoline has a decisive influence on the storage, ι stability of the amphoteric surfactants obtained by subsequent alkylation or their aqueous solutions. Even minor impurities lead to the separation of a solid phase after a shorter or longer storage time, be it in the form of cloudiness or precipitation. Such products are useless for practical use or at least for only. j limited value. ·. . .

The invention is based on the object in the context of Her-30 position of the class of amphoteric surfactants described here. To create improvements, in particular in an increased Storage stability of the amphoteric surfactants are marked.

The invention aims to be as simple as possible by including a simple cleaning step on the primary obtained condensate of aminoalkylalkanolamine and fatty acid Eliminate any disturbing by-products present here. the

Liu II 'J

^: .. ^:: - ^: 3Q182Q1

The aim of the invention is to make costly detours customary up to now for obtaining a condensation product as pure as possible from this first process stage superfluous.
5

The teaching of the invention is based on the surprising finding that the crude condensation product of fatty acids and aminoalkylalkanolamines converted to a refined product by simple alkaline hydrolysis can be, the amphoteric surfactants improved in the subsequent alkylation and optionally quaternization with increased storage stability in particular.

The invention accordingly relates to a process for refining the crude condensation product from aminoalkylalkanolamines the general formula

H ₂ N- (CH ₂ ) _m -NH- (CH ₂ ) _n -OH

and fatty acids with 6 to 22 carbon atoms and if desired for the subsequent alkylation and optionally quaternization of the purified condensation product to form amphoteric surfactants increased storage stability, this process being characterized in that the crude coridation product from fatty acids and aminoalkylalkanolamines subjected to alkaline hydrolysis.

In the method according to the invention, the in this alkaline hydrolysis amount of alkali used on the amount of diamide present in the crude condensate general formula

R-CO-NH- (CH ₂ ) _m -N-CO-R

(CH ₂ ) _n -OH
35

Voted. In particular, the amount of alkali in this process step is such that it is preferred

130047/0198

in at least an approximately equimolar amount to the diamide in the crude Condensation product is present.

The invention is based on the finding that the Content of disruptive by-products in the finished surfactant can be drastically reduced if the fatty acid / amine condensation product an alkaline pretreatment in an aqueous medium before a further reaction with alkylating agents undergoes. As has been shown by means of experiments, diamide formed in particular in the course of the reaction is through aqueous lye on the text. Amide group quantitatively into the Monoamide of the primary amino group and fatty acid split. The fatty acid forms in the cleaning treatment of the present invention Soap that can remain in the reaction mixture.

j It is actually extremely astonishing that the ■ so far only with comparatively expensive cleaning

stride to overcome difficulties regarding the . 20 Storage stability of the amphoteric obtained in the last stage

side by the inventive intermediate treatment besei ¹ - are Untitled. However, it must be taken into account here that

the alkylation and optionally quaternization of the in ι

first stage obtained reaction product - with for example.

^! 25 se sodium chloroacetate - takes place in an aqueous alkaline medium, with process conditions relating to temperature

; and . Alkali did be chosen "that with the terms of the intermediate step according to the invention are at least comparable. It was not to be expected that the invention provided separate alkaline hydrolysis of the crude condensation product from the first process stage could give better results than a corresponding one aqueous-alkaline treatment in the course of the alkylation or quaternization of the condensation product.

130047/0198

- 7th

The alkaline pretreatment according to the invention, however, gives products that last longer even after dilution stay clear than 6 months. Costly purification steps such as recovery of the excess amine or distillation

₍ 5 of the imidazoline are no longer required.

The alkaline hydrolytic treatment according to the invention

takes place preferably at temperatures of about 70 to 100 ^° C., in particular in the temperature range from 80 to 90 ^° C. Particularly suitable alkalis are alkali hydroxides, especially sodium hydroxide. The amount of alkali is preferably in the range of about 1 to 3 times the eauimolar alkali requirement, based on the diamide present in the crude condensation product. In particular, with alkali levels in the area

'15 of 1 to 2 equivalents, based on diamide, worked.

· ■ ·

The crude condensation product becomes alkaline according to the invention Hydrolysis expediently suspended in an amount of water that is 0.5 to 10 times, especially the

1 to 5 times the crude condensation product. ^: The aqueous alkaline hydrolysis is carried out until practically complete elimination of the diamide present as a by-product. The diamide content of the crude product and its decrease in the treatment according to the invention can be determined in a known manner, for example by working with ion exchangers.

; As aminoalkylalkanolamines of the general formula

H ₉ N- (CH ₉ ) -NH- (CH ₀ ) -OH

b L · » JIl £ Xl

: In particular, those compounds are used in which m has the value from 2 to 6 and η the value from 2 or 3

! sen. The meaning of m is preferably 2, 3 or 6, the preferred meaning for η is 2. The most important starting amine of the type in question in practice is aminoethylethanolamine. The fatty acids related to the condensation have carbon numbers in the range from 6 to 22, the range from 8 to 18 carbon atoms being of particular importance

130047/0198

Has. The carboxylic acids can be present as pure components or as mixtures. You can do this natural and / or of synthetic origin.

The condensation product pretreated in the context of the invention by the alkaline hydrolysis is then converted into the finished amphoteric surfactant in a manner known per se. Here, too, the details of the extensive prior art cited apply again. The pretreatment according to the invention [ ! 10 proves to be valuable not only for the manufacturer. treatment of the so-called imidazolinium surfactants, it is a lot; ■ more versatile. Clear and storable pro—

ι products are also preserved with the implementation of the alkaline

treated amine condensation products with alkylating agents; 15 parts of the type of chlorohydroxypropanesulfonic acid, des

Propane sultone as well as in the alkylation with vinylogous' · compounds such as acrylic acid or acrylate ^comprising: subsequent saponification and Z-acrylamido ^ -methylpropan-: sulfonic acid or the corresponding alkali metal salts. 20th

The amphoteric surfactants can, depending on the structure and extent of the Reaction in the second reaction stage and alkylated if necessary have quaternized nitrogen. In a further embodiment, the invention includes manufacture such amphoteric surfactants using a condensation precursor , which treated according to the alkali, calcium hydrolytic process of the invention described has been.

In the following examples, the percentages relate to% by weight. The diamide content is determined as follows: The condensation product is sent as an alcoholic solution over a strongly acidic ion exchanger. The eluate w ± rd evaporated and the remaining residue related to the weight. By determining the S.Z. and des The amount of diamide can be calculated from the total nitrogen.

130047/0198 I COPY

- '- 301820

example 1

j Condensation products of fatty acids with aminoethylethanol- ' amln

j 5 1.1 Molar ratio_2_i_l

In a three-necked flask equipped with a stirrer, nitrogen flow, Thermometer and distillation attachment were 208 g (1 mol) coconut fatty acid C8 / 18 with 104 g (1 mol)

; 10 aminoethylethanolamine mixed and slowly heated to 200 ° C

; heated; Duration approx. 6 hours. After distilling off a total of 20 g of amine-containing water, approx. 290 g of a

i get slowly solidifying, yellow mass, the following

de key figures showed:

i 15

S.Z. 2.8

N _K 9.5%
j

^N titr. ⁴ ' ^7%
• 20th

Diamide content (determined via ion exchanger) 16.1 %

(= 0.04 mol / 100 g). A UV spectrosc. Examination at ^: 230 mm showed an imidazoline content of 8.0%.

j 25 1.2 Molverhälntis_1._i_1. _i 1. '

; As described under 1.1, 208 g (1 mol) of coconut

j fatty acid with 114.5 g (1.1 mol) aminoethylethanolamine

condensed.

Approx. 300 g of a slowly solidifying, yellow mass with the following key figures were obtained:

130047/0198

i copy

- 10 -

SZ 2,3
N _x , 10.2%

^N titr. ⁵ ' ⁶

Diamide content 10.7% (= 0.02 mol / 100 g) Imidazoline content 3.0%

! 10

15th

. 3. Molar ratio __1 _ £ _J _± 5

As described under 1.1, 208 g (1 mol) of coconut ■ fatty acid with 156 g (1.5 mol) of aminoethylethanolamine condensed with slow heating so that the content of free amine as high as possible during the reaction stayed. Reaction temp. up to 180 ° C, last at approx. 14 mbar. After the excess amine had been distilled off, approx. 270 g of residue remained with the following key figures:

N _x

20th

25th

titr.

10.3%
⁵ ' ^2%

30th

35

Diamide content 2.7% (= 0.006 mol / 100 g) Imidazoline content 96%

Example 2 '

Reactions with sodium chloroacetate

2.1 Without alkaline treatment

2.1.1. 90 g (0.3 mol, calculated from N.) of product Experiment 1.1 was dispersed with 148 g of water and 203 g (0.7 mol) of a freshly prepared one at 60 ° C. 40% sodium chloroacetate solution is added. When adding 56 g (0.7 mol) of 50% strength Sodium hydroxide solution rose the pH to 11.52. Man Stirred for 2 hours at this temperature and increased

/ I 3004 7/0 198
COPY,

then for 1 hour at 80 ° C .; the pH slowly fell to approx. 10. The approx. 40% strength product began after 2 days at R.T. to cloud over.

2. 1 .2. 80 g (0.32 mol, calculated from N.) of product

Li. L-jT

from Experiment 1.2 were dispersed with 134 g of water and at 60 ° C with 214 g (0.74 mol) of one freshly prepared 40% solution of sodium chloroacetate was added. It was then left at 60.degree 58.8 g (0.74 mol) of 50% sodium hydroxide solution run in,

the mixture was held for 2 hours at 60 ° C and then raised the temperature to 80 ⁰ C. the pH was adjusted to 11.5 on addition of the sodium hydroxide solution and fell nad

sam down to 10.1.

and sank after 1 hour of heating at 80 ° C for a long

A clear solution with a solids content of approx. 40% was obtained, but this already after 2 days at R.T. began to cloud over.

2.1.3 90 g (0.3 mol) of imidazoline from Experiment 1.3 were dispersed with 134 g of water for 1 hour at 60.degree and then with 203 g (0.7 mol) of a freshly prepared 40% sodium chloroacetate solution offset. Then 56 g (0.7 mol) of 50% Na

tron lye added. The pH rose to 11.6. It was 2 hours at this temp, and one Stirred at 80 ° C. for a further hour. After about 10 weeks of storage at R.T. the first showed up Cloudiness.

130047/0 1 98
COPY

2.2 With_alkaline_yorbehandlunc [

2.2.1 a) 90 g (0.3 mol, calculated from N.) Product: from Experiment 1.1, containing 0.035 mol of diamide, 'were dispersed in 148 g of water, with 1.2 g

50% NaOH (0.015 mol) were added and the mixture was stirred at 80-90 ° C. for 1 hour. Then the procedure was as! ^; under 2.1.1. described. ·;

The product is clearly obtained as under 2.1.1,

However, it also becomes cloudy after 6 days because not all of the diamide has been saponified.

b) The experiment was repeated with the addition of 4.8 g of 50% NaOH (0.06 mol).

As the analysis also showed, the diamide was saponified quantitatively to give the monoacyl product, which Product is still clear even after> 6 months. 20th

2.2.2 80 g (0.32 mol) of product from Experiment 1.2 were dispersed in 60 g of water, 4.8 g (0.06 mol)% of sodium hydroxide solution were added and the mixture was stirred at 80 ° C. for 1 hour.
25th

After further implementation, as described under 2.1.2, a surfactant was obtained, which even after> 6 Mon. is still clear.

From experiments 2.1.1. - 2.1.3 as well as 2.2.1 and

2.2.2 can be seen:

j Also the use of a very pure imidazoline

j as a preliminary stage (2.1.3) does not lead to the quality

. 35 improvement, like even with diamond-rich

■ Raw materials (1.1 and 1.2) after alkaline preparation

action is achieved. Appropriately is

130047 /

an amount of caustic soda used that is equivalent, but preferably about twice as high as is required due to the diamide content.

Example 3

Reactions with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or Na salt
10

3.1 Without_alkaline_pre-treatment2

• 75.0 g (0.3 mol, calculated from N.) Product from ver

"Clti *

such 1.2 were suspended in 200 g of water, mixed with 80.6 g (0.39 mol) of AMPS and then with 31.2 g (0.39 mol) 50% caustic soda. The mixture was stirred at 80 ° C. for 4 hours.

The finished product is clear and fluid, shows

however, deposits already occur after 2 days. 20th

. 2 With_alkaline_pre-treatment.

75.0 g (0.3 mol) of product from Experiment 1.2 were suspended in 200 g of water and stirred with 4.8 g (0.06 mol) of 50% sodium hydroxide solution at 80-90 ° C. for 1 hour. Further implementation as under 3.1. The product is still completely clear even after y 6 months.

Example 4 Reactions with chlorohydroxypropanesulfonic acid or Na-Salz

4.1 0without_alkaline_pre-treatment2

75 g (0.3 mol) of product from Experiment 1.2 were dispersed in 200 ml of water, with 3.6 g (0.3 mol) of chlorohydroxypropanesulfonic acid added and in 30 min. At 80 C with 24.0 g (0.3 mol) of 50% sodium hydroxide solution. 4 hrs.

130047/0 198

3Q18201

tion at 50 ° C.

The end product is clear, but becomes cloudy after 3 days.

4.2 With_alkaline_pre-treatment2

The implementation was carried out as in 3.1, but before Addition of the chlorohydroxypropanesulfonic acid * 1 hour at 90 ° C after adding 4.8 g (0.06 mol) of 50% sodium hydroxide solution touched.

The product is still clear after more than 6 months.

* (Na-SaIz)

Example 5 . .

Reactions with acrylic acid

5.1 Without_alkaline_pre-treatment. .

75.0 g (0.3 mol) of product from experiment 1.1 were mixed with 21.6 g (0.3 mol) of acrylic acid and ^{stirred for 4 hours at 80 °} C. and then diluted with 145 g of water. The product becomes cloudy after 2 weeks.

5.2

j 75, Og (0.3 mol) of product from Experiment 1 .1 were "with

ί 4.8 g (0.06 mol) 50% sodium hydroxide solution for 1 hour at 80 ^° C.

stirred and then treated further as under 4.1.

- The product remains clear for> 6 months.

Claims (5)

Claims .1. Process for refining the crude condensation product V- / from aminoalkylalkanolamines of the general formula H ₀ N- (CH ₀ ) -NH- (CH ₀ ) -OH
Z 2 m 2. η and fatty acids with 6 to 22 carbon atoms and if desired for the subsequent alkylation and optionally quaternization of the purified condensation product to form amphoteric surfactants with increased storage stability, characterized in that the crude condensation product of fatty acids and Aminoalkylalkanolamines subjected to alkaline hydrolysis. 2. The method according to claim 1, characterized in that the amount of alkali used in the alkaline hydrolysis the amount of diamide present in the crude condensation product is adjusted and preferably at least is used approximately in an equimolar amount and in particular not more than about 3 molar amount. 3. The method according to claims 1 and 2, characterized in that that the alkaline hydrolytic treatment at temperatures of about 70 to 100 ° C and especially in the temperature range from 80 to 90 ° C. 4. Process according to Claims 1 to 3, characterized in that the general given with aminoalkylalkanolamines Formula is used in which m is a number from 2 to 6, in particular 2, 3 or 6 and η is the number 2 or 3. 5. The method according to claims 1 to 4, that it is carried out with pure fatty acids or any fatty acid mixtures of the specified C number range and in particular the range of C _3-18 . 13004770198
ORIGINAL INSPECTED