DD289532A5 - PROCESS FOR THE PREPARATION OF NEW SILOXIDE-MODIFIED SULFOBETAIN-SULPHONES - Google Patents

Abstract

The invention relates to a process for the preparation of novel siloxane-modified sulfobetaine sulfones. According to the invention, in aqueous, aqueous / alcoholic or alcoholic solution, 3-sulfinomethyl-4-sulfomethylpyrrolidinium-betaines with unsupported esters or amides, e.g. B. reacted with * and or * at 60 to 110C. The new siloxane-modified sulfobetaine sulfones of the general formula I with XO or NH can be used as multifunctional surfactants, for example in aqueous and non-aqueous emulsion and microemulsion systems. Formula I a {sulfobetaine; sulfone; Sulfobetainsulfon; siloxane-modified sulfomethylpyrrolidinium betaine sulfone; sulfinic; maleic; maleic acid amide; surfactant}

Description

R _f - X - CO - CH - CH - O ₁

^z ib

in which

^R i = Ru - C C -CHj-, where R "= H or H

a methylol radical and ρ Siein straight-chain, branched-chain and / or cyclic methyl or

Arylsiloxanyl radical having 1 to 20 Si atoms or a straight-chain and / or branched-chain methyl and / or arylpolysiloxanyl radical having 20 to 700 Si atoms,

, CH -.CH-, where ^ Si is a straight line

2 »^

is a chain, branched-chain and / or cyclic methyl or arylsiloxanyl radical having 1 to 20 Si atoms or a straight-chain and / or branched-chain methyl and / or arylpolysiloxanyl radical having 20 to 700 Si atoms,

X = O or NH,

Y = COO ", COOH, COO-alkyl or H, Z = YoderHorCHa, Rj = H ₁ CH ₃ .

R ₃ = H, an alkyl radical of 1 to the C atoms. Alkylaminocarbonylmethyl radical to M18 to 18C atoms in the alkyl chain or aminocarbonylmethyl radical

mean, characterized.

For the R, radical representative siloxane-modified raw materials which can be converted by acylation into the unsaturated intermediates on which the invention is based are, for example:

- (2) 3-siloxane-modified propylamines and

- siloxane-modified alkenols or alkenediols.

Characteristic of the known state of the art

Sulfobetaine sulfones are not yet known. A variety of anionic, nonionic and amphoteric Tonside are known, which have been prepared in the search for new properties of surfactant molecules by ever new combinations of hydrophilic Grjppen with hydrophobic moiety. An effective change in the property profile of the surfactants is thus no longer achievable.

Therefore, it is attempted to improve the application possibilities by combining various known surfactants. However, decisive progress can only be achieved by synthesizing completely new surfactants by incorporating specific functional groups or additional chemical functions (WERDELMANN, Welt-Tensid-Kongress 1984, Konqreßberichte I, p. 9, Kürle Druck and Verlag Gelnhausen 1384). However, suitable methods are lacking in order to inexpensively produce such polyfunctional products with costs which are justifiable in the surfactant synthesis.

Object of the invention

It is an object of the invention to make accessible by developing a new synthesis method surfactants, which by combining several different functional groups in the hydrophilic Molokülbereich new, application technology favorable properties are inexpensively in a technically simple manner without waste products and depending on the choice of the synthesis building blocks total zwitterionic , zwitterionic / anionic, zwitterionic / nonionic.

Explanation of the essence of the invention

To achieve the goal of the invention, the object is to produce multifunctional surfactants on a new synthetic route, in the cost-effective overall process in simple synthetic steps based on proven Tensidrohstoffe and intermediates new structures to be obtained with a previously unknown property picture and the synthesis to be developed according to the new synthesis principle a varied range of different products for different application areas result as well as an extensive combinability of the new products with known surfactants should be given.

According to the invention this object is achieved by reacting 3-sulfinic acid-methyl-4-sulfomethyl-pyrrolidiniumbetainen of the general formula II, wherein R ₂ and R _{3 have the} above meanings,

with esters and amides of the general formulas IIIa and 1Mb

R ₁ -X-CO-CH = CH-Y-IHa

R ₁ -X-CO-CH = CH-Z IHb

to Sulfobetainsulfonen the formulas I a and I b solved. The substances described by the general formulas III a and III b with the above meanings of the substituents X, Y, Z and Ri include esters or half esters of maleic and fumaric acid, mono-N-alkylamides of maleic and fumaric acid and esters and amides of acrylic or methacrylic acid.

The reaction succeeds easily and in mostly quantitative yields, if the Sulfobetainsulfinsäuren of formula H in the aqueous, aqueous / alcoholic or alcoholic solution of the components of the formol Hl a and III b heated for 0.5 to 2 hours with constant stirring and reflux. In aqueous / alcoholic solution, the progress of the reaction can be followed by the general resolution of the sulfinic acid. A generally applicable method for tracking the reaction is

the repeated determination of the titer of the reaction solution against bromate / bromide in hydrochloric acid solution, the decrease of which directly indicates the consumption of the sulfinic acid. The Sulfobetainsulfonlösung obtained contains the isomeric mixture of the formulas I a and I b and can be concentrated to isolate the product.

In some cases, the application effect achievable by using diosurfactant multifunctional surfactants is further enhanced when using mixtures of multifunctional surfactants, e.g. when applied in aqueous and non-aqueous emulsion and microemulsion systems.

According to the invention can be achieved with advantage to mixtures of different Sulfobetainsulfone, if these same in a "one-pot process" by the simultaneous and simultaneous reaction of maleic mono-N-alkylamides and maleic acid half-alkyl esters.

The 3-sulfinic acid methyl-4-sulfomethyl-pyrrolidinium betaines used as starting materials are accessible in a simple manner according to DD-PS 225.128.

Exemplary embodiments

example 1

Reaction of ₂ -dimethyl-S-sulfinic acid methyl -sulfomethyl-pyrrolidinium-betaine (formula II with R ₂ = R ₃ = CH 3, prepared according to DD-PS 225,128) with maleic acid mono-N-3 (2) - (1,1 , 1,3,5,5,5-heptamethyl-trisiloxanyl) propylamide to the sulfobetaine sulfone of the formulas Ia and Ib with:

Ri = [(CH ₃ I ₃ SiO) ₂ (CH ₃ ) SiC ₃ H ₆ -; X = NH; Y = Z = COO "; R ₂ = R ₃ = CH ₃ .

In a three-necked flask provided with stirrer, thermometer and reflux condenser, 0.1 mol (9.8 g) of maleic anhydride in 50 ml toluene are initially introduced with stirring, 0.1 mol (28.1 g) of N-3 (2) - (1,1, 1,3,5,5,5-heptamethyltrisiloxanyl) -propylamine and the mixture was held at 40 ° C for 2 hours. After formation of the siloxane-modified maleic acid mono-alkylamide, the toluene is distilled off, the residue is mixed with 100 ml of methanol and 30 ml of water and 0.1 mol (32.5 g, 83%) of 1,1-dimethyl-3-sulfinic acid-methyl-4-sulfomethyl- pyrrolidiniurn-betaine registered. The mixture is stirred for 3 hours at reflux (7O ⁰ C). The reaction mixture is adjusted to a pH of 7.5 with ammonia. After filtration, the solvent is removed on a rotary evaporator. A reddish, amorphous-crystalline product is obtained, which is readily soluble in water,

Example 2

Reaction of ₂ -dimethyl-S-sulfinic acid methyl -sulfomethyl-pyrrolidinium-betaine (formula II: R ₂ = R ₃ = CH ₃ ) with maleic acid mono-3 (2) - (1, 1, 1, 3, 5, 5,5-heptamethyl-trisiloxanyl) prop (2) enyl ester to the sulfobetaine sulfone of the formulas Ia and Ib with:

Ri = [(CH ₃ ) JSiO] ₂ (CH ₃ ) SiC ₃ H ₄ -; χ = 0, Y = Z = C00 ", R ₂ ⁼ R ₃ - CH ₃ .

In a three-necked flask equipped with stirrer, thermometer and reflux condenser, place 14.1 g (0.05 mol) of 3 (2) - (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) prop (2) enol and 4.9 g (0.05 mol) of maleic anhydride and slowly heated to 110 ° C with stirring. After 15 minutes, the solution is completely clear and is slowly cooled within 2 hours with stirring. The ester is dissolved in 55 ml of methanol and 25 ml of water. With stirring, 0.05 mol (17 g, 80%) of 1,1-dimethyl-3-sulfinic acid-methyl-4-sulfoinethyl-pyrrolidinium-betaine in the solution and heated at reflux (75 ° C). After 1 hour, 15 ml of water are added again and stirred for a further two hours at reflux. After completion of the reaction is neutralized with technical 33% sodium hydroxide solution. The resulting product is water-soluble and foams strongly.

Example 3

Reaction of ii-dimethyl-S-sulfinic methyl-sulfomethyl-pyrrolidinium-betaine (formula II: R ₂ = R ₃ = CH ₂ ) with polysiloxane-modified maleic acid mono-N-alkylamide to give the corresponding sulfobetaine sulfone of the general formulas Ia and Ib, where

[Ri] _n = (CH _{3) 3} Si [(O-Si (CH _{3) 2)} ,. _M OSi (CH ₃ ) (C ₃ H _e -)] nOSi (CH ₃ ) ₃ (M ~ 2 470 g / mol)

X = NH,

Y = Z = COO ',

R ₂ = R ₃ = CH ₃ .

In a three-necked flask equipped with stirrer, thermometer and reflux condenser, 0.1 mol (9.8 g) of maleic anhydride are dissolved in 200 ml of dichloromethane while stirring, 23.2 g of polysiloxanylpropylamine (-NH: maleic anhydride = 1: 1) are added and the mixture is stirred at reflux for 15 minutes. After distilling off the dichloromethane, the maleic acid monoamide is dissolved in

Dissolved 50ml of methanol and 25ml of water and added with stirring with 0.1 mol (32.5 g, 83% lg) of 1,1-dimethyl-3-sulfi.isäuremethyl-4-sulfomethyl-pyrrolidinium-betaine. After 45 minutes of heating under reflux the reaction mixture is clear. After 3 hours, the sulfobetaination reaction to the corresponding sulfobetaine sulfone is complete. The anshließende neutralization may preferably be carried out with ammonia solution, sodium hydroxide or potassium hydroxide solution. The neutralized products formed are water-soluble and strongly foaming.

Example 4

Reaction of i-aminocarbonyl-1-methyl-S-sulfinetromethylsulfonylpyrrolidinium betaine (Formula II: with R ₂ = CH ₃ ; R ₃ --CH ₂ CO NH) with a polysiloxane-modified maleic acid mono-N-alkylamide to the corresponding sulfobetaine sulfone of the general formulas I a and I b, where

(M ~ 2470g / mol)

(R.) _n = (CH; ,), Sl [(O-Si (CH3) ₁ ), _lH OSI (CH3) (C) χ = ΝΗ, Y = Ζ = COO " R ₂ = CH ₃ and R ₃ = -CH ₂ CO NH.

The implementation of the reaction is carried out as described in Example 3. For better dissolution behavior, in this example 25 ml of n-butanol are added to the methanol / water mixture. The sulfobetaine obtained after neutralization o.g. Formula is very soluble in water and shows good foaming power.

Example 5

Reaction of i-dodecyl-S-suifinsäuremethyl ^ -Sulfornethyl-pyrrolidinium-botain (formula II: R ₂ = H; R ₃ = C ₁₂ H ₂₆ ) with a polysiloxane-modified maleic acid mono-N-alkyla-mid to the corresponding SulfoL./ .ainsulfone of the general formulas Ia and Ib, where

[R ₁ ] ,, = (CH ₃ I ₃ Si [OSi (CH ₃ I ₂ ) L ₆₃ OSi (CH ₃ ) C (CH ₂ -) = CH (CH ₂ -)] n OSi (CH ₃ ) ₃ (Vl ~ 2470g / mol)

X = NH,

Y = Z = COO ",

R ₂ = H and R ₃ = C ₁₂ H ₂₅ .

The reaction is carried out as described in Example 3. Here, in addition, in order to achieve a better solution behavior in the reaction, added to the solvent methanol / water mixture 35ml η-amyl alcohol and 45ml n-butanol. The obtained after neutralization with 33% technical sodium hydroxide sodium salt of the corresponding Sulfobetainsulfons is sparingly soluble in water, but good in a water / alcohol mixture in the weight ratio 1: 1.

Example 6

Reaction of 1,1-dimethyl-3-sulfinic acid-methyl-4-sulfomethylpyrrolidinium betaine (formula II: R ₂ = R ₃ = CH ₃ ) with 2- (1,1,1 "3,5,5,5- Heptamethyl-trisiloxanyl) but (2) en-1,4-diyl-bis (mono-maleate) to the corresponding sulfobetaine sulfone of the general formulas Ia and Ib, where

Ri = [(CH ₃ I ₃ SiO) ₂ (CH ₃ ) SiC (CH ₂ -IC = CH (CH ₂ -); X = O;

Y = Z = COO ";

R ₂ = R ₃ = CH ₃ .

The reaction of the 2- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) but (2) en-1,4-diol (31 g = 0.1 mol) with maleic anhydride (19.6 g = 0.2 mol) is carried out as described in Example 2. The addition of the i.i-dimethyl-S-sulfinic acid methyl-sulfomothylpyrrolidinium-betaine (68 g = 0.2 mol 80%) to the maleic acid monoester is carried out as described in the following. The product obtained is very soluble in water and has surfactant properties.

Example 7

Reaction of 1,1-dimethyl-3-sulfinic acid-methyl-4-sulfomethyl-pyrrolidinium-betaine (formula I: R ₂ = R ₃ = CH ₃ ) with a polysiloxane-modified maleic acid monoalkylaster to give the corresponding sulfobetaine sulfone of the general formulas I a and Ib, in which

[R,] _n = {CHjkSiJOSilCHshVsjOSilCHa) C (CHr -) = CH (CHR -)] NOSi (CH _{3) 3} (M ~ 2470 g / mol)

X = 0,

Y = Z = COO ",

R ₂ = R ₃ = CH ₃ .

In a provided with stirrer, thermometer and reflux condenser three-necked flask 25 g (0.05 mol) of the polysiloxane-modified alcohol component and 9.8 g (0.1 mol) of maleic anhydride are introduced and heated with stirring (11O ⁰ C). The resulting ester is dissolved in 80 ml of methanol and 40 ml of water. To this solution are added 34 g (0.1 mol = 80% g) of dimethyl 2-dimethyl-S-sulfinate-sulfomethyl-pyrrolidinium-betaln and the solution is heated to reflux. After completion of the reaction is adjusted to a pH of 7 with potassium hydroxide solution. The polysiloxane-modified sulfobetaine sulfone obtained has surfactant properties.

Examples

Reaction of II-dimethyl-S-sulfinic acid methyl-sulfomethyl-pyrrolidinium-betaine (formula II: R ₂ = Ra = CH ₃ ) with maleic mono-N-3- (triethoxysilyl) propylamide to give the corresponding sulfobetaine sulfone of the formulas Ia and Ib , in which

R ₁ = O _v , Si C ₃ H ₈ -,

X = NH,

Y = Z = COO ",

R ₂ = R ₃ = CH ₃ .

In a three-necked flask equipped with stirrer, thermometer and reflux condenser, 0.05 mol (11 g) of 3- (triethoxysilyl) propylamine are heated with 0.05 mol (4.9 g) of maleic anhydride in 50 ml of toluene at 40 ° C. with stirring. After 1 hour amide formation is complete. The solvent is removed and the residue is dissolved in 100 ml of water. Subsequently, to the solution 0.05 mol (17g = 80%) of 1 J-dimethyl-3 sulfinsäuremethyM-sulfornethyl-pyrrolidinium betain added. It is then heated under reflux for 2 hours. After the reaction is neutralized with sodium hydroxide solution. The product obtained can be used for the hydrophobization of metallic surfaces.

Example 9

Reaction of i-dodecyl-S-suifinsäuremethyl ^ -sulfomethyl-pyrrolidinium-betaine (formula II: R ₂ = H and R ₃ = C ₁₂ H ₂₆ ) with maleic acid mono-N-3- (triethoxysilyl) propylamide to Sulfobetainsulfon the general Formoln I a and I b, where

R ₁ = (C ₄ H ₉ O) _n (C ₂ H ₆ O) ₃ -OSiC ₃ He-, X = NH,

Y = Z = COO-,

R ₂ = H and R ₃ = C ₁₂ H ₂ S.

The reaction is carried out as described in Example 8. Instead of 100ml of water is worked with 100ml n-butanol. Working in n-butanol leads to partial transesterification of the triethoxysilyl group. The resulting product consists of a mixture of ethoxy and n-butoxy group on Si atom. The product obtained is well suited as a primer on metallic surfaces.

Example 10

Reaction of i-coconut fattyaminocarbonylmethyM-methyl-S-sulfinic acid methyl -sulfomethylpyrrolidinium betaine (formula II: R ₂ = CH ₃ and R ₃ = C ₁₃ Hj ₇ NHC (O) CH ₂ -) with a polysiloxane-modified maleic acid mono- N-alkylamide to the corresponding sulfobetaine sulfone of the general formulas Ia and Ib, wherein

[R ₁ J _n = (CH 3) ssfsfOSKCHaWLHOSilCHaHCaHHlnOSifCH (M ~ 2470g / mol)

X = NH,

Y = Z = COO ",

R ₂ = CH ₃ and R ₃ = C ₁₃ H ₂₇ NHC (O) CH 2 -.

The reaction is carried out as described in Example 3. Instead of a methanol / water mixture is worked here with a n-butanol / water mixture. The product obtained is soluble after neutralization with technical 33% sodium hydroxide solution in a water / ethanol mixture in a weight ratio 1: 1. The product is particularly suitable for the emulsification of silicone oils from the group of dimethylpolysiloxanes.

Example 11

Silicone oils are difficult to incorporate into surfactant systems (emulsions, dispersions, surfactant formulations). With the synthesis to produce siloxane-modified sulfobetaine sulfones, a possibility has been created to find good emulsifiers or dispersants for siloxane compounds. On the basis of microemulsion examples which contain partially or completely dimethylpolysiloxanes as the organic phase, the particular surfactant properties which could not be predicted in any way are clarified.

A premix emulsion system having the following composition:

3% by weight of methylaminomethane-bisphosphonic acid,

6% by weight alkanesulfonate (C-9 to C-IB alkyl chain mixture),

6 wt% of nonionic surfactant (oxethylated fatty alcohol mixture of chain length C-9 to C-18 with an average

EO Gehaltvon10EO-Einhoiten,

- 3Gev .'.-% xylene blended,

4% by weight of n-butanol,

- 3Gew .-% n-octanol.

The pH of this formulation is adjusted to 9.0 with ethanolamine; after the pH adjustment is done with water

100% by weight filled up. In the thus formed Vormikroemulsionssystem can up to 10Gew .-%, based on the

Total formulation, a xylene mixture are incorporated. The microemulsion formed forms a stable system. Attempting to replace part of the xylene (up to 1% by weight) with dimethylpolysiloxane will not produce a stable one

Systems.

Are 2Gew .-% alkanesulfonate and 2Gew .-% nonionic Tonsld by 4Gew .-% of Sulfobetainsulfons from Example 10th

replaced, so can be without difficulty 5Gew .-% dimethylpolysiloxane in o. g. Formulate a formulation and there is a stable microemulsion, which then contains 5 wt .-% dimethylpolysiloxane, which does not reach with other surfactant combinations

Instead of the sulfobetaine sulfone of Example 10, the sulfobetaine sulfone of Example 5 can also be used. in this connection

Then 6% by weight of the sulfobetaine sulfone according to Example 5 is used and the amount of alkanesulfonate and nonionic surfactant used is reduced to 4% by weight and the xylene addition is brought to 0% by weight. In such a formulation, up to 8% by weight of dimethylpolysiloxane can be stably incorporated into a microemulsion.

Claims (4)

1. A process for the preparation of novel siloxane-modified sulfobetaine sulfones of the general formella jndlb, R * - X - CO - CH - O ₁ SV y SOj Y - CH, I X N R ", - X - CO - CHj - CH - OjS - / - ^S0 3 ¹ Φ in which Ri = RC ₄ - C « C-CH ^ -, where R ^ = H or a methylol residue and £ Si is a straight-chain, branched-chain and / or is cyclic methyl or arylsiloxanyl radical having 1 to 20 Si atoms or a straight-chain and / or branched-chain methyl and / or arylpolysiloxanyl radical having 20 to 700 Si atoms, CII * "|" ^ H - CHr-, where j ^{si is a} S ^erad ~ H is a chain, branched-chain and / or cyclic methyl or arylsiloxanyl radical having 1 to 20 Si atoms or a straight-chain and / or branched-chain methyl and / or arylpolysiloxanyl radical having 20 to 700 Si atoms, X = O or NH, Y = COO ", COOH, COO-alkyl or H, Z = Y or H or CH ₃ , R2 = H ₇ CH _3, R ₃ = H, an alkyl radical with bis-SC atoms, alkylaminocarbonylomethyl radical having up to 18 C atoms in the alkyl chain or amincarbonylomethyl radical mean characterized geken / izeichnet that in aqueous, aqueous / alcoholic or alcoholic solution 3-Sulfinsäuremethyl-4-sulfornethyl-pyroldinium-betaine of the general formula II with unsaturated esters or amides of the general formulas III a and / or III b with the same meaning of Ru ₂ R, R ₃ , X, Y and Z as in the formulas I a and I b R ₁ -X-CO-CH = CH-Y purple R i -X-CO-CH = CH-Z-IHb be implemented in the temperature range of 60 to 100 ⁰ C. 2. The method according to claim , characterized in that mixtures of different compounds of the formula lh a are reacted with compounds of formula II. 3. The method according to claim 1, characterized in that mixtures of different compounds of formula III b are reacted with compounds of formula H. 4. The method according to claim 1, characterized in that mixtures of compounds of the formula IIIa are reacted with compounds of formula II b and with compounds of formula II. Field of application of the invention The invention relates to a process for the preparation of novel siloxane-modified sulfobetaine sulfones, which can be used as special surfactants due to further functional groups and whose property pattern allows new versatile applications. Thus, they are particularly suitable for use in nonaqueous systems, such as emulsions, microemulsions and suspensions and for hydrophobing metal surfaces.
The siloxane-modified sulfobetaine sulfones are represented by the general formulas I a and I b R ,, - X - CO - CH - O ₄ S - ^ y SO, *