DE1643409A1 - New surface-active N-acyl-N-alkyl-polyglycerylamines and processes for their production - Google Patents

Description

Henkel & Cie GmbH 4000, Düsseldorf, September 22, 1969

Patent department at Henkelstrasse 67

Dr. Nä / pü
D 3 * 56

Subject: German patent application P 16 43 409.6

"New, surfactant N-acyl-N-alkyl-polyglycerylamines as well as process for their production "

The invention relates to new N-acyl-N-alkyl-polyglycerylamines the general formula

R ₁ - N - CO - R ₀

PgI - ■

wherein R, an aliphatic radical optionally interrupted by ether oxygen atoms and having 1 to 30 carbon atoms, Rp the hydrocarbon radical containing 1 to 29 carbon atoms an aliphatic carboxylic acid and PgI is a polyglyceryl radical.

If at least one of the two radicals R or R _{n contains} 8 to 30, preferably 10 to 20 carbon atoms and the other 1 to 4 carbon atoms, these compounds can be used as water-soluble surfactants. However, if the compounds contain a radical R with 8 to 30, preferably 12 to 26 carbon atoms and a radical R with 7 to 29, preferably 11 to 25 carbon atoms, the water solubility of the compounds is often already reduced; the compounds are then, for example, as oil-soluble emulsifiers and as textile auxiliaries and - provided that the sum of the in R, and

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2 Sep.

existing carbon atoms is 23 to 39 and preferably 27 to 35 - useful as a softening agent.

The water solubility of the compounds is not only dependent on the length of the two radicals R 1 and R p, but also on the length of the polyglyceryl residue. This usually has the following constitution:

OH

0-CH ₂ -CH-C

OH

-O-CH -CH-CH -OH, OH

where η is one of the integers from 0 to X ^, preferably from O to 8 means. Ether bridges, over which the glyceryl residues with each other are linked, can in some cases form a central carbon atom of a glyceryl radical to lead. It is quite possible that e.g. about. 15 ^ of the total existing ether compounds lead to the central carbon atoms, i.e. linked via <lie secondary hydroxyl groups became.

The invention further relates to a process for the preparation of N.-acyl-N-alkyl-polyglycerylamines of the constitution indicated above. The method is characterized in that ₁ -NHg glycidätherr polyglycerol "converted to a first Verfahrensstufe'Amine R by reacting with polyglycerol-l ^ -chlorhydrinen or with glycerol or in the secondary amines R ₁ -NH-PGI and this in a

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second "process stage with halides, anhydrides or Acylated esters of a carboxylic acid Rp-COOH. · ■■ -. · '■

The alkyl radicals present in the primary amines used as starting materials can be linked to the amine nitrogen atom via a primary / secondary or tertiary carbon atom. For the production of the λ polyglycerylamines, for example, methyl, ethyl, i ^ and n Propylamine, primary, secondary or tertiary butylamine and the corresponding pentyl, hexyl and heptyl amines are suitable. This and higher amines atoms with 8 to J> 0 _u carbon saturated or unsaturated, straight or branched, be of synthetic or natural origin. r

For the production of surface-active N-acyl-N-alkyl polyglycerylamines are the octyl, decyl, lauryl, myristyl, cetyl, Stearyl, oleyl, arachyl or dehenyl amines of particular Meaning. Such amines are obtained in many cases from the corresponding Fatty acids by converting them into amides and reducing those obtainable therefrom by dehydration Nitriles,

Often times int it is not necessary to produce the To use N-acyl-K-alkyl-polyglycerylamines chemical individuals, but one can also use homologous or isomeric

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Use mixtures, especially mixtures of homologues, such as those obtained from fatty acids of natural origin

receives. These fatty acids can have been obtained from the fats of plant, land or marine animals, for example from coconut fat, palm oil, linseed oil, cottonseed oil, Peanut oil, rapeseed oil, etc., from lard, tallow, from fish or whale oils or from fractions of the in these Fatty acids contained in fats. Many of the fatty acids found in the fats mentioned are more or less strong unsaturated; It is preferred to process largely saturated fatty acids, for example those with an iodine number of at most 50 and preferably those with iodine numbers below

For carrying out the process according to the invention as starting materials Usable .polyglycerols fall .zJB. at the glycerine distillate as a residue. In addition, polyglycerols are obtained by alkaline polycondensation of «Glycerine or through the gradual accumulation of glycide onto glycerine, diglycerine, triglycerine, etc.

These polyglycerols can be converted into polyglycerol 1,2-monochlorohydrins in a manner known per se for further processing on the products according to the invention, for example by direct esterification with gaseous hydrogen chloride, the water formed during the reaction advantageously being removed continuously. Ea has proven to be expedient here,

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in the presence of e.g. 2 to 4 carbon atoms containing carboxylic acids "bzv; * their anhydrides, especially in the presence of Acetic acid to work. -

The polyglycerol-1,2-monochlorohydrins are also catalytic by means of Addition of epichlorohydrin to glycerine or to

Polyglycerols accessible in the presence of Lewis acids.

Boron trifluoride diethyl { ätherat proven to be useful, whereby it is advantageous in the presence of inert solvents, such as diethyl ether,

Dioxane, or tetrahydrofuran, works. * ~ *

Finally, polyglycerol-monochlorohydrins are also

v by the addition of hypochlorous acid to glycerol or

Polyglycerol allyl ether available.

The glycerine or polyglycerine glycidate which can also be used for the production of the products according to the invention can be used e.g. by splitting off hydrogen chloride from polyglycerin-1,2-monochlorohydrins produce. In practice, the treatment of monochlorohydrins with sodium hydroxide, Sodium aluminate or sodium carbonate powder in inert Solvents particularly proven. Another possibility for the production of such glycidyl ethers is oxidation of glycerine or polyglycerine allyl ethers with peroxy compounds, especially with performic acid, feracetic acid or benzoic acid. BATH ORIGINAL

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In one way of producing the N-alkyl-polyglycerylamines the primary amines with the polyglycerin-1,2-monochlorohydrins in the presence of acceptors for the hydrogen chloride formed in the reaction and preferably in Reacted presence of suitable solvents. The solvents used include ethers, containing 1 to 4 carbon atoms Alcohols or ethereal alcohols, water or mixtures of Water with the alcohols mentioned in question. Suitable acceptors for the hydrogen chloride are the alkali hydroxides, Alkali alcoholates, alkali carbonates and tertiary amines, such as triethylamine or pyridine. So much for the named acceptors are in the pure state / est, they are advantageously used as solutions in one of the solvents mentioned.

The reaction takes place in the temperature range from 0 to 100 ° C, the reaction being carried out many times at room temperature or slightly elevated, lying in the range from J50 to 50 ° C Temperatures begins and it comes to an end by post-heating to higher temperatures.

The formed alkali chloride or Amln chlorohydrate is depending on the type and amount of solvent, precipitated during the reaction or by means of an aqueous liquid from the others; Separated reactants.

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Another way of preparing the N-alkylpolyglyeerylamines the primary amines are converted with glycerol or polyglycerol glycidyl ethers. One works then advantageously in the presence of inert solvents such as diethyl ether, dioxane or tetrahydrofuran, starts the reaction by gradually warming it up and completes it with further heating up to the boiling point of the solvent.

The N-alkyl-polyglyeerylamines formed are heavy volatile, so that they cannot be purified by distillation unless you do this under high vacuum working short path distillation apparatus used. However, the process products can be separated by other common separation processes, such as extraction, Dialysis, partition chromatography or ion exchange chromatography clean. In this way one obtains color- ( loose substances that, depending on the type of alkyl radical R and the length of the polyglyceryl residue are obtained as colorless viscous oils, pastes or solids.

The N-alkyl-polyglycerylamines obtained in the described method can be obtained by acylation with carboxylic acids, carboxylic acid anhydrides, carboxylic acid halides or carboxylic acid esters into the corresponding N-alkyl-N-acyl-polyglyceryl-

transfer amines. Especially has acylation with

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Carboxylic acid methyl esters at 150 to 160 ° C without addition proven of solvents.

About the purification of the N-acyl-N-alkyl-polyglycerylamines thus obtained this applies to the N-alkyl-polyglyeerylamines said. The properties and areas of application of the products according to the invention are determined by the length and the Characteristics of the alkyl, acyl and polyglyceryl radicals determined. The water solubility of the products increases with the number of glyceryl residues present and falls with the length of the alkyl and acyl residues.

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Examples

Some of the amines R, -NH ₂ used as starting material were prepared by amidating fatty acid mixtures of natural origin, converting the amides into the nitriles and reducing the nitriles to the amines. During the reduction, some of the unsaturated nitriles present in the starting material were saturated, so that the amines obtained had a higher degree of saturation than the fatty acid mixtures from which they were derived. those made from coconut oil have a JZ of about 5 · The radicals R ₂ -CO-, on the other hand, correspond to the starting fatty acids in terms of the degree of saturation.

The following substances were used as polyglycerine chlorohydrins:

a) a diglycerol-1,2-chlorohydrin produced by reacting glycerol with epichlorohydrin with the following key figures: OHZ = 900 (calculated 912), chlorine content = 19.56 fo (calculated 19.25 #)

b) a polyglycerol-1,2-chlorohydrin produced from technical polyglycerol (OHN = 1 102) by esterification with hydrogen chloride with the following key figures:

OHZ »799, chlorine content = £ 10.8

c) a polyglycerol-1,2-chlorohydrin obtained by reacting technical polyglycerol (OHN = 1 090) with epichlorohydrin with the following parameters: OHN = 850, chlorine content = 8.4 %.

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Furthermore, a glycerol-glycidyl ether obtained from the above-mentioned diglycerol-1,2-chlorohydrin by elimination of HC! With an epoxy oxygen content of 10.0 % (calculated 10.8 %) was available .

ι ϊ

For the preparation of the N-alkyl-polyglycerylamines a Solution of equimolecular amounts of polyglycerol-1,2-chlorohydrin and amine in ethanol mixed with the calculated amount of 40 # strength sodium hydroxide solution and refluxed for several hours heated. The water-containing ethanol was then distilled off in vacuo and the solid residue obtained was then removed suspended in water and dialyzed to remove the salt components. This remained after the water had been distilled off Amine mostly as a waxy substance.

To prepare the N-alkyl-N-acyl-polyglycerylamins equimolecular amounts of the amine obtained by the above procedure and the Carbonsäuremethylesters used for acylation under a nitrogen atmosphere at normal pressure were heated at I50 ⁰ C, until no methanol distilled off more. The reaction proceeded practically quantitatively, so that further work-up was unnecessary and the resulting residue, which was mostly waxy in the cold, was the desired product.

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The following substances were produced according to the above regulations:

example 1

a) ί N-Oetadecyl-polyglycerylamine Reaction approach:

154.7 g polyglycerin-1,2-chlorohydrin (6.2 % Cl)

73 grams of oetadecylamine 2JO g of ethanol, 27.8 g of 40% NaOH

Process product:

Yield: 145 g / N = 1.75 %

b): N-caproyl-N-oetadecyl-polyglycerylamine Reaction preparation:

40.1 g of N-octadecyl-polyglycerylamine 5 * 5 g of methyl caprylate

Process product:

Yield: 44 g; N = 1.6 % (calc .: 1.5.1) OHZ =

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Example 2

a): N-Octadecyl-polyglyeerylamine Reaction approach:

7 e polyglycerin-l ^ -chlorohydrin (6.2 # Cl) 73 g octadecylamine 2 ^ 0 g ethanol 27.8 g of 40% NaOH

Process product: Yield: 145 g; N = 1.75 %

b): N-lauroyl-N-octadecyl-polyglycerylamine ^u

Reaction approach:

40.1 g of N-octadecyl-polyglycerylamine

10.7 g methyl laurate r *

Process product:

Yield: 4 g; N = 1.55 % (calc .: 1.4; 5 %) OHZ =

Beis p iel

a): N-octadecyl-polyglycerylamine reaction mixture:

154.7 g polyglycerol-1,2-chlorohydrin (6.2 % Cl) ■ 73 g octadecylamine 230 g ethanol

27.8 g 4Q # NaOH process product:

Yield: 1 ^ 5 g; N = 1.75 %

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Oo ς -., Ν »,; ■■■ ■■ -.

C Ly OCH, ί ^ Οα

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b): N-myristoyl-N-octadecyl-polyglycerylamine Reaction approach:

4θ, 1 g of N-octadecyl-polyglycerylamine 12.1 g of methyl myristic acid

Process product:

Yield: kk g; N = 1.44 % (calc.:!, ?? ^) OHZ =

Example 4 -. -

a): N-octadecyl-polyglycerylamine Reaction approach:

154.7 g polyglycerol-l ^ -chlorohydrin (6.2 ^ Cl) 75 g octadecylamine
g of ethanol

27.8 g of 40% NaOH

Process product:

Yield: 1 ^ 5 gi N = 1.75 %

b): N-palmitoyl-N-octadeeyl-polyglycerylamine Reaction approach:

40.1 g N-octadecyl-polyglycerylamine 1 ^ * 5 g Pa.lmitic acid methyl ester

Process product:

Yield: 44 g; N = 1.27 % (calc .: 1.55 %) OHZ =

14 -4

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Example 5

a): N-cocoalkyl-polyglycerylamine reaction mixture:

80 g of polyglycerol-l ^ -chlorohydrin (10.8 % Cl) 49 g of coconut amine 20 g of ethanol 24.1 g of 40% NaOH

Process product:

Yield: 110 g; N = 4.04 %

b): N-tallow acyl-N-coconut-alkyl-polyglycerylamine Reaction approach:

54.5 g of N-cocoalkyl-polyglycerylamine 38 g of tallow fatty acid methyl ester

Process product:

Yield: 100 g; N = 2.8 % OHN =

Example 6

a): N-cocoalkyl-polyglycerylamine reaction mixture:

304 g polyglyceryl-1,2-chlorohydrin (11.7 # Gl)

203 g coconut amine

500 g of ethanol

100 g of 40% NaOH

Process product: 'Yield; N = 2.97

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b): N-tallow acyl-N-coconut-alkyl-polyglycerylamine Reaction approach:

404 g of N-cocoalkyl-polyglycerylamine 248 g of tallow fatty acid methyl ester

Process product:

Yield: 640 g; N = 1.73 %

Example 7

a): Diglyceryl-ethylamine ™

Reaction approach:

461 g diglycerol chlorohydrin 180 g ethylamine (50% solution) 104 g sodium hydroxide 900 ml of ethanol

250 ml water process product:

Yield: 390 g (quantitative)

b): N-diglyceryl-N-ethyl-lauric acid amide (

Reaction approach:

193 g biglyeeryl-ethylamine 214 g of methyl laurate Process product:

Yield: 336 g = 90 $ of theory

N = 2.16 # 0HZ = 468

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Example 8

a): Diglyceryl-ethylamine see Example 7a

b): N-diglyeeryl-N-ethyl-stearic acid amide Reaction approach:

192 g. Diglyceryl ethylamine 298 g of ethyl stearate

Process product:

Yield: 420 g = 92 $ of theory

N = $ 1.55 OHZ =

example 9 G Diglycerol chlorohydrin ε Dodecylamine G Sodium hydroxide a): Diglyceryl-dodecylaniine ml Ethanol •• Reaction approach: ml water IOI5 750 220 1800 500

Process product:

Yield: quantitative

b): N-diglyceryl-N-dodecyl-aeetamide Reaction approach:

234 g diglyceryl-dodecylamine 74 g of methyl acetate

Process product:

- Yield: 364 g - 97 $ of theory

N = 2.8; 5 # OHZ =

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Example 10

a): Diglyceryl-dodecylamine
see example 9a

b): N-diglyceryl-N-dodecyl-stearic acid amide Reaction batch ϊ

666 g diglyceryl dodecylamine 595 g stearic acid methyl ester

Process product: _ '

Yield: 1118 g = 92 # of theory

N = 1.75Ji OHT =

Example 11

a): Diglyceryl-tetradecylamine reaction mixture:

1015 g diglycerol chlorohydrin 854 g tetradecylarain 220 g sodium hydroxide 180 ml ethanol
500 ml of water

Process product:

Yield; quantitatively

to): N-diglyceryl-N-tetradecyl-palmitic acid amide Reaction approach:

722 g diglyceryl-tetrad.ecylamine 5 ^ 0 g of methyl palmitate

Process product;

Yield: quantitative

N «1.78 ^ OHZ = 215

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Example 12

a): Diglyceryl-hexadecylamine reaction mixture:

1015 ε Diglycerol chlorohydrin : quantitative 944 G Hexadecylamine . 220 s Sodium hydroxide l800 ml Ethanol 500 ml water Traversing resulting product: yield

b): N-diglyceryl-N-hexadecyl-lauric acid amide Reaction approach:

1045 g Diglyceryl hexadecylamine : 1390 g = 92 # d.Th. Diglycerol chlorohydrin 535 p Laurin's aureme thyle ster N = 1.80 # OHZ = 285 Octadecylamine Process product: Nat r iuirihydr ox id yield a): Dlgljrceryl-octadecylamine Ethanol Reaction approach: water Example 13 1015 g 1076 g 220 g I8OO ml 500 ml

Process product:

Yield: quantitative

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b): N-diglyeeryl-N-octadeeyl-lauric acid amide

Beaction approach:

l4O4ε diglyceryl-oetadecylamine 672 g of methyl laurate

Process product:

Yield: 1818 g = 96.5% of theory

N = 1.88 # OHZ =

Example 14

a): Diglyeeryl coconut alkylamine reaction mixture:

IOI5 g diglycerol chlorohydrin 777 g coconut alkylamine 220 g sodium hydroxide 1800 ml ethanol 500 ml water

Process product:

Yield: quantitative

b): N-diglyceryl-N-coconutalkyl tallow fatty acid amide

Reaction ζ:

664 g diglyceryl coconut alkylamine (

588 g of tallow fatty acid methyl ester

Process product:

Yield: 1184 g = 97 $ of theory

N = 1.72 ^ OHZ =

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• a): Diglyceryl tallow alkylamine.

1015 g diglycerol chlorohydrin

1052 grams of tallow alkylamine

220 g sodium hydroxide

1800 ml. Ethanol

500 ml of water

Process product:

Yield: quantitative

b): N-diglyceryl ~ N-tallow alkyl coconut fatty acid amide Reaction batch: 804 g diglyceryl tallow alkylamine 448 g coconut fatty acid methyl ester

Process product:

Yield: 1112 g = 92.5 $ d.Th .. N = 1.75 ^ OHZ =

Example 16

a): Diglyceryl tallow alkylamine see example 15a

b): N-diglyoeryl-N-tallow alkyl tallow fatty acid amide

Reaction approach: 804 g diglyceryl tallow alkylamine 588 g tallow fatty acid methyl ester

. Process product: Yield: 1207 B 93, -7 # 'd.! Fh.

N = 1.80 ^ OHZ = 228

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Claims (7)

Patent Department D Claims 1) New N-acyl-N-alkyl-polyglycerylamines of the general formula which can be used as surface-active substances R ₁ - N - CO - Rp '-. · PgI - - wherein R is an optionally replaced by ether oxygen atoms | interrupted aliphatic radical with 1 to JO carbon atoms, Rp is a hydrocarbon radical containing 1 to 29 carbon atoms an aliphatic. Carboxylic acid and PgI a polyglyceryl residue mean. 2) New chemical compounds according to claim .1), characterized in that the polyglyceryl radical contains 2 to 15, preferably 2 to 10 glyceryl radicals. _; jj>) Compounds useful as water-soluble surfactants according to claim 1) and 2), characterized, that the Radical R, 8 to 20 and preferably 12 to 18 carbon atoms and the remainder Rp contains 1 to 3 carbon atoms. 4). Compounds according to claim 1) and 2) which can be used as water-soluble surfactants, characterized in that the remainder R _{1 contains} 1 to 4 and the remainder R _{g contains} 7 to 1%, preferably 11 to 14 carbon atoms,. · '_ ■ N @ us 5) Compounds according to claim which can be used as oil-soluble, water-dispersible surface-active substances 1) and 2), characterized in that the grate R, 8 to 20, preferably 12 to 18 and the remainder Rp 7 to 19 * preferably Contains 11 to 17 carbon atoms. 6) As textile auxiliaries, in particular as textile softeners, useful compounds according to claim 5) * characterized in that in the radicals R .. and R _? it contains a total of 23 to, preferably 27 to 35, carbon atoms. 7) Process for the preparation of N-acyl ~ M-alkyl-polyglycerylami- Using the general formula ".. _, _ _. PgI. where R, an aliphatic radical optionally interrupted by ether oxygen atoms and having 1 to 5 carbon atoms, Rp a hydrocarbon radical of an aliphatic carboxylic acid containing 1 to 29 carbon atoms, and PgI a polyglyceryl radical, characterized in that amines R-NHp by reacting with ■ polyglycerin-l ^ S-chlorohydrins or with glycerin or polyglycerin glycidethers converted into the secondary amines R.-NH-Pgl and these in a second process stage with 109825/2137 Halides, anhydrides or »esters of a carboxylic acid Rg-COOH acylated Hen ke 1 & / ■ G ie . GmbH. (Dr. Haas). (Dr. Aiagel) 109825/2137