WO1991004963A1

WO1991004963A1 - Salts of sulphonated esters of dicarboxylic acids with unsaturated fatty alcohols or alkoxylates, process for their manufacture and their use as surfactants

Info

Publication number: WO1991004963A1
Application number: PCT/EP1990/001590
Authority: WO
Inventors: Ansgar Behler
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1989-09-28
Filing date: 1990-09-19
Publication date: 1991-04-18
Also published as: DE3932492A1

Abstract

Salts of sulphonated esters of dicarboxylic acids with unsaturated fatty alcohols or with addition reaction products of ethylene oxide and/or propylene oxide with unsaturated fatty alcohols, obtained by sulphonation of dicarboxylic acid esters of general formula (I): R1O-(CmH2mO)n-CO-A-CO-(OCpH2p)q-OR2, where A is a vinylene or ethylene group; R1 is a straight-chain alkenyl group with 16 to 22 carbon atoms; R2 is hydrogen, an alkyl group with 1 to 22 carbon atoms or a straight-chain alkenyl group with 16 to 22 carbon atoms; n and q are each numbers ranging from 0 to 20; m and p are each the number 2 and/or 3, with sulphur trioxide in a molar ratio of sulphur trioxide to the double bonds present in the alkenyl groups of 0.5 to 1.8:1, in particular 0.6 to 1.5:1, and neutralization of the sulphonation products with bases. Said compounds have attractive surfactant properties.

Description

Salts of sulfonated esters of dicarboxylic acids with unsaturated fatty alcohols or alkoxylates, processes for their preparation and their use as surface-active agents.

The invention relates to salts of sulfonated esters of dicarboxylic acids with unsaturated fatty alcohols or with addition products of ethylene oxide and / or propylene oxide onto unsaturated fatty alcohols, obtainable by sulfonation of dicarboxylic acid esters of the general formula I

R ¹ 0- (C _m H _2m O) n-CO-A-CO- (OCpH2p) _q -OR ² (I)

in the

A is a vinylene or an ethylene group,

R ^{1 is} a straight-chain alkenyl group with 16 to 22 carbon atoms,

R ^{2 is} hydrogen, an alkyl group with 1 to 22 carbon atoms or a straight-chain alkenyl group with 16 to 22 carbon atoms,

n and q each have numbers in the range from 0 to 20 and and p each the numbers 2 and / or 3

mean

with sulfur trioxide in the molar ratio of sulfur trioxide to double bonds present in the alkenyl groups from 0.5 to 1.8: 1, in particular 0.6 to 1.5: 1, and neutralization of the sulfonation products with bases.

The compounds of the invention, hereinafter referred to as dicarboxylic acid ester sulfonates, have interesting surface-active properties and their properties as surface-active agents can be adapted to the respective requirements by varying the number of ethyleneoxy and / or propyleneoxy units contained in them.

The dicarboxylic acid ester sulfonates of the invention are half or full esters of maleic or fumaric acid (A = -CH = CH-) or succinic acid (A = -CH2-CH2-) which are mixed with at least one mole of a monounsaturated fatty alcohol with 16 up to 22 carbon atoms of the formula R --- 0H are esterified. Typical examples of such monounsaturated fatty alcohols are palmitoleyl alcohol, oleyl alcohol, elaidyl alcohol, gadoleyl alcohol, arachidone alcohol, eruca alcohol and brassidyl alcohol, which, as is common in fat chemistry, are often used in the form of their technical mixtures with other, saturated and / or unsaturated fatty alcohols; the technical mixtures of these fatty alcohols are in turn accessible from natural renewable raw materials, in particular animal or vegetable fats and oils. The technical fatty alcohol mixtures used to produce the starting compounds of the general formula I can also additionally contain small amounts of polyunsaturated fatty alcohols such as linoleyl alcohol or linolenyl alcohol, the residues of which then appear in the starting compounds do not interfere with the preparation of the dicarboxylic acid ester sulfonates of the invention.

Instead of the unsaturated fatty alcohols explained above, the corresponding addition products of ethylene oxide and / or propylene oxide (in the case of a random or block distribution of the propyleneoxy units in the case of mixed addition products) can also be used for esterification with the aforementioned dicarboxylic acids; the aforementioned adducts can contain up to 20 ethyleneoxy and / or propyleneoxy units.

If the anhydrides of maleic or succinic acid are reacted with the aforementioned unsaturated fatty alcohols of the formula R --- 0H or the adducts of ethylene oxide and / or propylene oxide, the first step is to obtain those for the preparation of the dicarboxylic acid ester sulfonates Corresponding half esters of maleic or succinic acid of the general formula I suitable for the invention (A = vinylene or ethylene; g = 0; R ² = H). The free carboxyl function of these half-esters can also be esterified with alcohols of the formula R ² -0H, specifically with monoalkanols having 1 to 22 carbon atoms, for example methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, tetradecanol , Hexadecanol, Octadecanol, Eicosanol and Docosanol, which are also of natural or synthetic origin and can be used in the form of their technical mixtures. However, the esterification of the free carboxyl group of the half esters can also be carried out with the abovementioned unsaturated fatty alcohols R1_0H, so that ultimately full esters of maleic or succinic acid are obtained which each have two unsaturated fatty alcohol residues and are also suitable for the preparation of the dicarboxylic acid ester sulfonates of the invention . Instead of the monoalkanols or fatty alcohols mentioned, addition products of ethylene oxide and / or propylene oxide onto the monoalkanols or fatty alcohols can also be converted here the free carboxyl function of the half esters can be used in an ester function.

According to a preferred embodiment of the invention, the dicarboxylic acid ester sulfonates are obtainable from dicarboxylic acid esters of the general formula I which are derived from maleic or fumaric acid, ie in the general formula I A is a vinylene group and R-, R ² , m, n , p and q are as defined above.

Also preferred are dicarboxylic acid ester sulfonates, obtainable by sulfonating dicarboxylic acid esters of the general formula I in which m and p each have the number 2 and n and q each have numbers in the range from 0 to 10, in particular from

0 to 5, and A, R and R ^{2 are} as defined above. Preferred dicarboxylic acids thus have the general formula

1 residues of fatty alcohols or fatty alcohol ethoxylates, it being possible for the fatty alcohol ethoxylates to contain 1 to 10, in particular 1 to 5, ethylene oxide units.

According to a further advantageous embodiment of the invention, the radical R- of the dicarboxylic acid esters of the general formula I and optionally also the radical R ^{2 are derived} from oleyl alcohol.

According to a further advantageous embodiment of the invention, the sulfonated dicarboxylic esters of the general formula I are used with aqueous bases, for example with LiOH, sodium hydroxide solution, potassium hydroxide solution, ammonia, mono-C 1 -C 4 -alkylamines, di-C 1 -C 4 -alkylamines , Tri-C4-C4-alkylamines, mono- Cι-C4-hydroxyalkylamines, di-Cι-C4-hydroxyalkylamines, tri- Cι-C4-hydroxyalkylamines, Mg (OH) 2 _/ Ca (OH) 2 _/ Sr (0H) 2nd and Ba (OH) 2 neutralized; the use of aqueous sodium hydroxide solution is preferred. The neutralization should be carried out gently, ie with short reaction times and not too high reaction temperatures and while maintaining a pH in the range from about 6 to 8, if necessary with constant addition of the bases, so that the ester bonds are not cleaved at the same time as the neutralization.

The exact structure of the dicarboxylic acid ester sulfonates of the invention has not yet been conclusively clarified; presumably they have the general formula II

R3θ- (C _m H _2m 0) _n -C0-A-C0- (0C _p H _2p ) _g -0R ⁴ (II)

on, in which, n, p, q and A are as defined above,

R3 is a group of the formula purple or Illb

CH ₃ - (CH ₂ ) _x -CH (OH) - (CH2) y-CH (Sθ3M) - (CH2) _z -CH ₂ - (IHa)

respectively.

CH ₃ - (CH2) _x -CH (Sθ3M) - (CH2) y-CH (OH) - (CH2) _z -CH ₂ - (Illb)

means

in the

x and y numbers in the range from 0 to 18,

y the number 0, 1 or 2 and

M is a cation equivalent, the sum of x + y + z giving a number in the range from 14 to 18,

or a residue formed by splitting off a molecule of water from the group of the general formula lilac or Illb,

and R ⁴ is defined as R ³ or hydrogen, a cation equivalent or an alkyl group with 1 to 22 carbon atoms means, with the condition that R ⁴ is a cation equivalent only if q = 0. Cation equivalent is to be understood as the cationic remainder of the bases used for neutralization, for example according to the list above.

Of the dicarboxylic acid ester sulfonates of the general formula II disclosed here in connection with the general formulas lilac or Illb, those in which

R ^{3 is} the residue of a fatty alcohol with 18 carbon atoms of the formula lilac or Illb and

R ⁴ is defined as R ³ or is hydrogen, a cation equivalent or an alkyl group having 1 to 22 carbon atoms, with the condition that R ^{4 is} only a cation equivalent if q = 0,

m the number 2,

n is a number in the range from 0 to 10, in particular from 0 to 5,

x and z numbers in the range from 0 to 14,

y the numbers 0, 1 or 2,

where the sum of x + y + z = 14 and A and M are as defined above. Here too, the group R ³ and optionally the group R ^{4 are} preferably derived from a sulfonated oleyl radical.

The invention further relates to a process for the preparation of salts of sulfonated esters of dicarboxylic acids with unsaturated fatty alcohols or with addition products of ethylene oxide and / or propylene oxide onto unsaturated fatty alcohols, characterized by those described above Process features. The dicarboxylic acid ester sulfonates of the invention can be prepared largely analogously to a process for the production of monocarboxylic acid ester sulfonates known from DE-A 37 25 030.

Finally, the invention relates to the use of the salts of sulfonated esters of dicarboxylic acids with unsaturated fatty alcohols or with addition products of ethylene oxide and / or propylene oxide onto unsaturated fatty alcohols of the type explained above as surface-active agents.

The invention is explained in more detail below on the basis of preferred exemplary embodiments.

Example 1.

Maleic acid monooleylesulfonate sodium salt.

148.6 g (0.4 mol) of maleic acid monooleylester, obtained from maleic anhydride and a commercially available, technical oleyl alcohol (oleyl alcohol content: approx. 90%; iodine number = approx. 95) were heated to 55 ° C. in a laboratory stand reactor. 38.4 g of sulfur trioxide (0.48 mol; produced by heating 65% strength oleum, diluted with nitrogen to 5% by volume of SO 3 content) were then passed in within 30 minutes. Following the actual sulfonation reaction, the product was immediately neutralized with 25% sodium hydroxide solution. Since the product was subsequently acidified by hydrolysis of intermediate sulton groups, the pH was kept at a value of 7 by continuously adding sodium hydroxide solution.

Examples 2.

Example 1 was repeated, working with a molar ratio of sulfur trioxide to olefinic double bonds present in the starting material of 1.2: 1.

Example 3.

Analogous to the procedure described in Example 1, 154.8 g (0.25 mol) of a half ester of maleic acid with an adduct of 5 mol of ethylene oxide with an industrial oleyl alcohol of the composition given in Example 1 were mixed with 24.0 g (0.3 mol ) SO3 sulfonated at 45 ° C. Example 4.

Analogously to the manner described in Example 1, 138.9 g (0.13 mol) of a diester of maleic acid with an adduct of 5 mol of ethylene oxide with an industrial oleyl alcohol of the composition given in Example 1 were mixed with 22.0 g (0.275 mol) of sulfur trioxide implemented. The sulfonation product was neutralized as indicated in Example 1.

The most important structural features of the compounds obtained according to Examples 1 to 4, the most important process conditions and the characteristics of the reaction products are shown in Table 1.

Table 1

Key figures of the products

1.0 l, ² 2.2

55 45 75

20.1 17.8 24.3

⁴ , ⁴ 8.4 12.3 77.1 65.1 59.1 25.4 27.5 38.2

1.8 l, ² 1.6

1) surfactant 3) total sulfur

2) unsulfated substance 4) dry residue

Claims

1. Salts of sulfonated esters of dicarboxylic acids with unsaturated fatty alcohols or with addition products of ethylene oxide and / or propylene oxide onto unsaturated fatty alcohols, obtainable by sulfonation of dicarboxylic acid esters of the general formula I

RO- (C _m H _2m 0) _n -CO-A-CO- (OC _p H _2p ) q-OR ² (I)

in the

A is a vinylene or an ethylene group,

R- a straight-chain alkenyl group with 16 to 22 carbon atoms,

n and q each have numbers in the range from 0 to 20 and

m and p each have the numbers 2 and / or 3

mean, with sulfur trioxide in the molar ratio of sulfur trioxide to double bonds present in the alkenyl groups from 0.5 to 1.8: 1, in particular 0.6 to 1.5: 1, and neutralization of the sulfonation products with bases.

2. Salts of sulfonated esters according to claim 1, obtainable by sulfonation of dicarboxylic acid esters of the general formula I, in which A represents a vinylene group and R-, R ² , m, n, p and q are as defined above.

3. salts of sulfonated esters according to claim 1 or 2, obtainable by sulfonation of dicarboxylic acid esters of the general formula I, in which m and p each have the number 2 and n and q each have numbers in the range from 0 to 10, in particular from 0 to 5, mean, and A, R ¹ and R ^{2 are} as defined above.

4. Salts of sulfonated esters according to at least one of claims 1 to 3, obtainable by sulfonation of dicarboxylic acid esters of the general formula I in which R is an oleyl radical and A, R ² , m, n, p and q are as defined above.

5. Salts of sulfonated esters according to claim 4, obtainable by sulfonation of dicarboxylic acid esters of the general formula I in which R ¹ and R ^{2 are} oleyl radicals and A, m, n, p and q are as defined above.

6. Salts of sulfonated esters according to at least one of claims 1 to 4, obtainable by sulfonation of dicarboxylic acid esters of the general formula I, in which q is the number 0 and R ^{2 is} hydrogen and A, R ¹ , m and n are as defined above. Salts of sulfonated esters according to at least one of Claims 1 to 6, obtainable by neutralizing the sulfonation products with aqueous bases.

Process for the preparation of salts of sulfonated esters of dicarboxylic acids with unsaturated fatty alcohols or with addition products of ethylene oxide and / or propylene oxide onto unsaturated fatty alcohols, characterized by the sulfonation of dicarboxylic acid esters of the general formula I

R-0- (C _m H _2m 0) _n -CO-A-CO- (0C _p H _2p ) q-OR ² (I)

in the

A is a vinylene or ethylene group,

R-- a straight chain alkenyl group with 16 to 22 carbon atoms,

n and q each have numbers in the range from 0 to 20 and

m and p each have the numbers 2 and / or 3

mean,

with sulfur trioxide in the molar ratio of sulfur trioxide to double bonds present in the alkenyl groups from 0.5 to 1.8: 1, in particular 0.6 to 1.5: 1, and neutralization of the sulfonation products with bases. 9. The method according to claim 8, characterized by the sulfonation of dicarboxylic esters of the general formula I, in which A is a vinylene group and R--, R ² , m, n, p and q are as defined above.

10. The method according to claim 8 or 9, characterized by the sulfonation of dicarboxylic esters of the general formula I, in which m and p each represent the number 2 and n and q each represent numbers in the range from 0 to 10, in particular from 0 to 5, and A, R and R ^{2 are} as defined above.

11. The method according to at least one of claims 8 to 10, characterized by the sulfonation of dicarboxylic esters of the general formula I, in which R ^{1 is} an oleyl radical and A, R ² , m, n, p and q are as defined above.

12. The method according to at least one of claims 8 to 11, characterized by the sulfonation of dicarboxylic acid esters of the general formula I, in which R and R ² oleyl radicals and A, m, n, p and q are as defined above.

13. The method according to at least one of claims 8 to 12, characterized by the sulfonation of dicarboxylic esters of the general formula I, in which q is the number 0 and R ^{2 is} hydrogen and A, R-, m and n are as defined above.

14. The method according to at least one of claims 8 to 13, characterized by the neutralization of the sulfonation products with aqueous bases.

15. Use of salts of sulfonated esters of dicarboxylic acids with unsaturated fatty alcohols or with addition products of ethylene oxide and / or propylene oxide of unsaturated fatty alcohols according to at least one of claims 1 to 7 as surface-active agents.