WO1996018610A1

WO1996018610A1 - Amphiphilic compounds with at least two hydrophilic and at least two hydrophobic groups based on esters

Info

Publication number: WO1996018610A1
Application number: PCT/EP1995/003583
Authority: WO
Inventors: Klaus Kwetkat; Wulf Ruback
Original assignee: HÜLS Aktiengesellschaft
Priority date: 1994-12-17
Filing date: 1995-09-12
Publication date: 1996-06-20
Also published as: ZA9510680B; AU3566195A; DE4445133A1

Abstract

The invention concerns amphiphilic compounds of general formula (I) with at least two hydrophilic and at least two hydrophobic groups based on esters. The amphiphilic compounds according to the present invention are mostly surface-active and can be used as emulsifiers, demulsifiers, detergents, dispergents and hydrotropic agents in industry and homes in fields such as metal machiring, ore extraction, surface refinement, washing and cleaning, cosmetics, medicine and food processing and preparation.

Description

Amphiphilic compounds with at least two hydrophilic and at least two hydrophobic groups based on esters

The invention relates to amphiphilic compounds with at least two hydrophilic and at least two hydrophobic groups based on esters.

A wide variety of anionic, cationic, nonionic and zwitterionic compounds are known as amphiphilic substances. The vast majority of these substances consist of a hydrophilic head group and at least one hydrophobic part.

In the case of amphiphilic substances, there are ecological reasons, e.g. B. bezüg¬ Lich the reduction in packaging and transportation, the need to achieve ever greater effect per mass of substance used. Since optimization by mixing amphiphilic substances only continues to a very limited extent, new amphiphilic substances with a higher degree of efficiency are required. In particular, substances with lower critical micelle formation concentrations and / or lower surface and interfacial tensions have to be found in order to be able to significantly reduce the amount of active substance used.

The first approaches in this direction by doubling part of the structure (hydrophilic head group, hydrophobic group) are already known. For example, cationic surface-active compounds can be obtained by adding long-chain alkyl halides to permethylated alkylenediamines [R. Zana, M. Benrraou, R. Rueff, Langmuir, (1991) 1072; R. Zana, Y. Talmon, Nature, 362 (1993) 228; E. Alami, G. Beinert, P. Marie, R. Zana, Langmuir, 9 (1993) 1465].

Anionic surface-active compounds with at least two hydrophilic and at least two hydrophobic groups have hitherto been produced only on the basis of diglycidyl ethers (US Pat. No. 5,160,450, JP 01,304,033, JP 4,124,165). However, diglycidyl ethers are considered toxicologically unsafe and are quite expensive. In addition, epichlorohydrin is used for their production, which leads to large amounts of residues, so that these compounds are no longer appropriate from an ecotoxicological as well as an economical point of view. It was therefore the task of finding amphiphilic compounds which have at least two hydrophilic and at least two hydrophobic groups, the amphiphilic compounds having a very high degree of effectiveness, based on the amount used, and which are also made from readily available raw materials which are not technically large Accidental by-products can be produced.

The object is achieved according to the invention by amphiphilic di- or oligoesters, the base of which can be prepared from di-, oligo- or polyols and fatty acids or fatty acid methyl esters. The corresponding di- or oligoesters can be sulfonated. Conversely, sulfonated fatty acid methyl esters can also be transesterified with di-, oligo- or polyols and then neutralized.

The amphiphilic compounds according to the invention are compounds of the general formula I.

1 2 3 where R, R, R, M and M 'in formula I have the meanings described below: R and R independently of one another represent an unbranched or branched, saturated or unsaturated hydrocarbon radical having 1 to 22, preferably 6 to 18 carbon atoms.

1 3 The substituents R and R are in particular the radicals methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n -

Undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-

Heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-uneicosyl, n-docosyl and their branched-chain isomers and the corresponding mono-, di- or tri-unsaturated radicals.

R means a spacer consisting of an unbranched or branched

Chain with 2 to 100 carbon atoms, the 0 to 20 oxygen, 0 to 20

Contains nitrogen, 0 to 4 sulfur and 0 to 3 phosphorus atoms and the 0 to 20 functional side groups, such as B. hydroxyl, carbonyl, carboxyl, amino and / or acylamino groups, and / or 0 to 4 cycles which are isolated or fused.

2 The spacer R means in particular

♦ unbranched or branched alkylene chains of the formula II as the base body

with a = 2 to 18, preferably a = 2 to 6;

♦ as a base body straight or branched alkenylene of the formula III -C _b H _2.-CH = CH-C _c H _2c - (III) + c b - 2 to 16, wherein b and c are each greater than zero;

♦ as the base unbranched or branched alkynylene chains of the formula IV -C _d H _2d -C * CC _e H _2e - (IV) with d + e = 2 to 16, where d and e are each greater than zero, and with the base bodies according to Fortnein II to IV the spacer can additionally contain 1 to 4 carbonyl, carboxyl, amino or acylamino groups at any point in the chain;

♦ Alicyclene according to the formula VC _f H _2f -cyclo C ₆ H _{1 £)} -C ₈ H _2g - (V) with f and g are each independently 1 to 6

or according to formula VI

-3 (4), 8 (9) -di (methylene) tricyclo [5.2.1.0 ^{2 '6} ] decane (VI);

♦ unsubstituted or substituted aromatics according to formula VII

-C. H . -C R.- _C (C .H. _C-C R _Λ). -C. H- . - (VII) h 2h 6 4 i 2ι 6 4'j- j ₂ 2j ₂

or according to formula VIII

- ^C h ^H ^2h-C .θV ^_C. ^H 2 _. - ^{(V, II)} with h, j, j. and j ₂ , independently of one another, are each 0 to 8 and i = 0 to 8 and with R, independently of one another, each H or C. to C _c alkyl; O

♦ a chain with functional side groups, in particular hydroxyl, carbonyl, carboxyl, amino and / or acylamino groups. 2

The spacer R further contains 0 to 20, preferably 1 to 12, oxygen and / or nitrogen atoms, 0 to 4 sulfur and 0 to 3 phosphorus atoms, at least one of the heteroatoms occurring at least once.

2 R therefore continues to have particular meaning

♦ a compound according to formula IX

-CH -.- CR -ZC R -CH ,, .- (IX) k 2k xyxy 1 21 with k and 1 equal and independently of each other 0 to 8, x = 6 and y = 4 or x and Z - 0, ¹ , S0 ₂

or according to formula IXa

-CH ₂ -CH (0CH ₂ CH (0X) -R ¹ ) -CH ₂ - or an isomer (IXa) with X = S0-M

or 2,2'-methylene-bis- (1,3-dioxolane-5-methylene) - or acetals, in particular diacetals from dialdehydes and di-, oligo- or polyols, where R denotes a hydrocarbon radical with 1 to 22 carbon atoms ,

♦ a compound according to formula X

-C H. - (0C H.) (C, H, 0) -C H. - (X) m 2 n 2n p 36 qr 2r with m = 1 to 4, n = 2 to 4, p = 1 to 20, preferably p = 1 to 4, q = 1 to 4 and r = 1 to 4, mixed alkoxide units also being able to occur and the sequence of the alkoxide units then being arbitrary,

♦ a compound according to the formula XI -C H. (RNC H.) ₊ -CH - (XI) r 2r s 2s tu 2u

or according to formula XII

- [C H. [RN-C (0) -NR] -C H_] - (XII) r 2 t u 2u w

or according to formula XIII

- [CH [RNC (0) C H_ C (0) NR] -CH "] - (XIII) ^L r 2r v 2v tu 2u w

or according to formula XIV - [C _r H _2r [RN-C (0) -CH = CH-C (0) -NR] .- C _u H _2u ] _w - (XIV)

or according to formula XV

- [C H. [RNC (0) CRC (0) NR] ₊ -CH „] - (XV) r 2r xy ' ^J tu 2u w with r = 2 to 4, s = 2 to 4, t - 1 to 20, preferably t = 1 to 4, u = 2 to 4, v = 0 to 12, w = 1 to 6, x = 6 and y = 4 or x = 10 and y = 6 or x = 14 and y = 8 with R the same independently of one another H or C.- to C _fi alkyl and with M, M '* alkali, ammonium, alkanolammonium or * alkaline earth.

The amphiphilic compounds according to the invention are usually characterized by extremely low critical micelle formation concentrations (CMC) and very low surface and interfacial tensions (e.g. against paraffin), which is due to their special structure - at least two hydrophilic groups and at least two hydrophobic groups - must be returned. In addition, most of them have a rather high hydrophilic suspending capacity, which is about halfway between that of conventional surfactants and that of pentasodium tripolyphosphate. Some of these connections are extremely fast wetting agents.

The amphiphilic compounds according to this invention are particularly suitable as emulsifiers, demulsifiers, detergents, dispersants and hydrotropes in industry and in the home, for example in the fields of metalworking, ore extraction, surface finishing, washing and cleaning, cosmetics, medicine and food processing and preparation.

Here they can be combined with all common anionic, nonionic, cationic and ampholytic surface-active substances. Examples of nonionic surface-active substances which can be used for a combination include fatty acid glycerides, fatty acid polyglycerides, fatty acid esters, ethoxylates of higher alcohols, polyoxyethylene fatty acid glycerides, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene-dericinoleedirate, or urethane oil derivatives, or polyoxyethylene-dericin derivative or di-urethane oil derivatives , Polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, alkanolamines, alkyl amine oxides, derivatives of protein hydrolyzates, hydroxy mixed ethers, alkyl polyglycosides and alkyl glucamides. Examples of anionic surface-active substances that can be used for combinations are soaps, ether carboxylic acids and their salts, alkyl sulfonates, o-olefin sulfonates, sulfonates of higher fatty acid esters, higher alcohol sulfates, alcohol ether sulfates, hydroxymixed ether sulfates, salts of phosphate esters, taurides, isethionates , linear alkylbenzenesulfonates, cumene sulfonates, alkylarylsulfonates, sulfates of polyoxyethylene fatty acid ide and salts of acylamino acids.

Examples of cationic common surface-active substances that can be used for combinations include aikyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylam onium salts, alkylpyridine salts, alkylisoquinolinium salts, benzethonium chlorides and cationic acylamino acid derivatives.

Examples of ampholytic surface-active substances that can be used for combinations include amino acids, betaines, sulfobetaines, imidazoline derivatives, soybean lipids and lecithin.

In addition, the amphiphilic compounds according to the invention can also be combined with one another.

Common additives can also be added to the amphiphilic compounds according to the invention. Such additives are specially selected for a formulation and usually include inorganic salts such as sodium chloride and sulfate, as well as builders, hydrotropics, UV absorbers, plasticizers, chelating agents, viscosity modifiers and fragrances.

The abovementioned compounds can be prepared from di-, oligo- or polyols and at least twice the equivalent of sulfonated fatty acid methyl esters or by at least double sulfonation of the di-, oligo- or polyester and with aqueous alkali or alkaline earth metal hydroxides or aqueous ammonia or neutralize alkanols. If necessary, the products are bleached in aqueous solution with hydrogen peroxide (0.1 to 2.0%, based on solids).

Claims

Claims:

1. Amphiphilic compounds of the general formula I

1 3 in which R and R independently of one another have a hydrocarbon radical

1 to 22 carbon atoms, 2 R are a spacer and M and M 'are alkali, ammonium, alkanolammonium or alkaline earth.

2. Amphiphilic compounds according to claim 1, characterized in that

1 3 that the hydrocarbon radicals R and R are unbranched or branched, saturated or unsaturated,

2 the spacer R is an unbranched or branched chain with 2 to 100 carbon atoms, each containing 0 to 20 oxygen and 0 to 20 nitrogen and 0 to 4 sulfur and 0 to 3 phosphorus atoms and the 0 to 20 functional side groups and / or has 0 to 4 cycles that are isolated or fused.

3. Amphiphilic compounds according to one of claims 1 or 2, characterized in that

1 3 that the hydrocarbon radicals R and R in formula I independently contain 6 to 18 carbon atoms.

4. Amphiphilic compounds according to one of claims 1 to 3, characterized in that R is a spacer which has as its base an unbranched or branched alkylene chain of the formula II

, preferably a = 2 to 6, or an unbranched or branched alkenylene chain of the formula III

-C _b H _2b -CH * CH-C _c H _2c - (III) with b + c = 2 to 16, where b and c are each greater than zero,

or an unbranched or branched alkynylene chain of the formula IV

- ^C d ^H 2d- ^C " ^C - ^C e ^H 2e- ^(IV) with d + e = 2 to 16, where d and e are each greater than zero, and where the basic bodies according to formulas II to IV the spacer additionally contains, independently of one another, 0 to 4 carbonyl, amino or acylamino groups at any point in the chain.

5. Amphiphilic compounds according to one of claims 1 to 3, characterized in

2 that R means a spacer consisting of

Alicycles according to formula V

-C _f H _2f -cyclo C ₆ H _1Q -C ₈ H - (V) with f and g are each independently 1 to 6

or according to formula VI

-3 (4), 8 (9) -di (methylene) tricyclo [5.2.1.0 ^2.6 ] decane (VI).

6. Amphiphilic compounds according to one of claims 1 to 3, characterized in

2 that R is a spacer which consists of unsubstituted or substituted aromatics according to the formula VII - ^c n ^H a - ^c Λ- < ^c.H2i -WV ^{2 (VU>} or according to the formula VIII

with h, j, J _! un j ₂ gec independently of one another each 0 to 8 and i = 0 to 8 and RR also independently of one another in each case H or C. to C _fi alkyl

7. Amphiphilic compounds according to one of claims 1 to 6, characterized in that

2 that the spacer R functional side groups, especially hydroxyl,

Carbonyl, carboxyl, amino and / or acylamino groups.

8. Amphiphilic compounds according to one of claims 1 to 6, characterized in that

2 that the spacer R contains 0 to 20, preferably 1 to 12, oxygen and / or nitrogen atoms, 0 to 4 sulfur atoms and 0 to 3 phosphorus atoms, at least one of the heteroatoms occurring at least once.

9. Amphiphilic compounds according to claim 8, characterized in that R is a spacer according to formula (IX)

-C.kH2 „.k-CxRy-Z-CxRy-C, 1H2 ₁ 1- ( ^x IX) 'with k and 1 are each independently 0 to 8, x = 6 and y = 4 or x - 10 and y Z = 0, CO, NH, NR ¹

or according to the formula IXa -CH ₂ -CH (0CH ₂ CH (0X) -R ¹ ) -CH ₂ - or an isomer (IXa) with X = S0-M, where R represents a hydrocarbon radical having 1 to 22 carbon atoms, means.

10. Amphiphilic compounds according to claim 8, characterized in that R is a spacer according to the formula X -CmH2.m- (CnH.2n0) p (C3, H _c 60) q-CH2_r- (X) with m = 1 to 4 , n = 2 to 4, p = 1 to 20, preferably p = 1 to 4, q = 1 to 4 and r = 1 to 4, where mixed alkoxide units can also occur and then the

The order of the alkoxide units is arbitrary, ₂ or that R 2,2'-methylene-bis- (1,3-dioxolane-5-methylene) -

2 or that R acetals, in particular diacetals from dialdehydes and di-,

Means oligo- or polyols.

11. Amphiphilic compounds according to claim 8, characterized in that

2 that R is a spacer according to formula XI

-C H. (RNC H „) ₊ -C H- - (XI) r 2r s 2s'tu 2u

or according to formula XII

- [C _r H _2r [RN-C (0) -NR] _t -C _u H _2u ] _w - (XII)

or according to the formula XIII - [C _r H _2r [RNC <0) C _v H _2v C (0) R] _t -C _u H _2u ] _w - (XIII)

or according to formula XIV

- [C _r H _2r [RN-C (0) -CH = CH-C (0) -NR] _t -C _u H _2u ] _w - (XIV)

or according to formula XV

- [C _r H _2r [RNC (0) C _χ R _y C (0) NR] .- C _u H _2u ] _w - (XV) with r = 2 to 4, s - 2 to 4, t = 1 to 20, preferably t = 1 to 4, u = 2 to 4, v = 0 to 12, w = 1 to 6, x = 6 and y = 4 or x = 10 and y ■ 6 or x = 14 and y = 8 where R is independently of one another H or C.- to C _fi alkyl.

12. Use of the amphiphilic compounds according to one of claims 1 to 11 as emulsifiers or demulsifiers.

13. Use of the amphiphilic compounds according to one of claims 1 to 11 as an aid in metalworking, ore extraction or surface treatment.

14. Use of the amphiphilic compounds according to one of claims 1 to 11 as textile auxiliaries or for cleaning and washing textiles.

15. Use of the amphiphilic compounds according to any one of claims 1 to 11 for cleaning hard surfaces.

16. Use of the amphiphilic compounds according to any one of claims 1 to 11 for the cleaning and washing of skin and hair.