DE102007037345A1 - Quaternary ammonium-containing organosilicon compounds and their preparation - Google Patents

Abstract

Quaternary ammonium-containing organosilicon compounds (1) containing at least one Si-bonded group G of the general formula, $ F1 wherein Y is a bivalent organic radical having 1 to 100 carbon atoms, which may contain one or more ether oxygen atoms and / or one or more hydroxy groups , R <SUP> 1 </ SUP> is a monovalent organic radical having 1 to 30 C atoms, R <SUP> 2 </ SUP> is a methyl or ethyl radical, A is a monovalent organic radical having at least four carbon atoms substituted with at least two hydroxy groups, means L <SUP> - </ SUP> counterion to the positive charge on the quaternized nitrogen group selected from anions of inorganic or organic acids HL.

Description

The The invention relates to quaternary ammonium groups Organosilicon compounds and their preparation.

US 3,389,160 (corresponding DE 1 493 384 B ) describes siloxanes with lateral quaternary ammonium groups, which are obtained by the reaction of corresponding epoxyalkylsiloxanes with secondary amines and subsequent quaternization of the obtained tert. Amine groups can be prepared with alkylating agents such as methyl chloride.

The synthesis of α, ω-quaternary ammonium siloxanes is out EP 017 121 B known. In this case, the α, ω-Epoxisiloxanvorstufen tert with salts. Amines implemented. The use of further alkylating agents is not necessary since the quaternary ammonium groups are formed directly.

Similar polymers claimed the US 5,235,082 (corresponding EP 606 159 B ). These are accessible in the either α, ω-Halogenalkylsiloxane with tert. Amines are reacted or α, ω-tert. Aminosiloxanes are quaternized with alkylating agents. The ammonium groups each contain 2 N-linked methyl groups.

The preparation of polysiloxanes containing repeating units of siloxane blocks and isolated quaternary nitrogen atoms is disclosed in U.S. Pat US 6,730,766 (corresponding EP 1 288 246 A ). In this case, α, ω-epoxy siloxanes are reacted with secondary amines. The epoxy groups are used for two-stage alkylation; first to the stage of tert. Amines, then to the quaternary ammonium ion.

The implementation of structurally identical Epoxisiloxane with ditert. Amines is in US 4,833,225 (corresponding EP 282 720 B1 ). The products are linear polymers in which siloxane blocks repeat alternately with organic blocks. These each contain two quaternary ammonium groups which are attached to the siloxane via ring-opened epoxy structures.

To very similar polymers comes US 4,533,714 , Here are ditert. Amines reacted with α, ω-haloalkylsiloxanes, whereby alternating copolymers of siloxanes and organic diammonium groups are obtained.

US 7,041,767 (corresponding WO 02/10259 ) also discloses alternating copolymers composed of siloxane and organic diammonium groups. The chain ends are made of tert. Amine groups, so that the total chain length of the copolymer can be adjusted by the amount of these functions.

Another approach is in US 2006/128880 A (corresponding WO 2004/044306 ). α, ω-Diepoxisiloxanes are reacted with amines containing one tertiary and one secondary in the same molecule. In two subsequent stages, all basic amine groups are first alkylated, then the resulting polyquaternary siloxane is equilibrated with a hydrolyzate of aminoalkylsilane. The final product contains multiple quaternary ammonium groups as well as prim. and / or sec. Amino groups bound to the same siloxane skeleton.

Aminofunctional siloxanes which additionally contain polyhydroxy groups are made US 6,958,410 known. This class of polymers is available by reacting commercial aminosiloxanes with hydroxylactones (partially). Quaternary ammonium siloxanes can not be obtained by this method.

WO 2006/018327 also describes, among other compounds, polysaccharides which are simultaneously substituted with sulfonate and ammonium groups attached to the polysaccharide via siloxane chains. The siloxane chains are therefore substituted differently at their ends, which means considerable manufacturing effort and prone to instability in the presence of these highly polar groups.

Hydrophilic siloxanes, each containing at least one polyether group and at the same time at least one quaternary nitrogen atom, are made US 6,242,554 (corresponding EP 1 000 959 A ) known. They are by the reaction of a corresponding Epoxivorstufe with a tert. obtained organic amine. The Epoxivorstufe here is an asymmetric organopolysiloxane having an epoxy group at one end and a polyether groups at the other end, a synthetically very complicated silicone macromer to be prepared.

According to DE 43 18 536 A For example, highly surface-active polymers can be prepared by attaching NH-functional carbohydrates to epoxysiloxanes by ring-opening. The copolymers used as wetting agents contain no cationic charges and hence no quaternary nitrogen.

It The task consisted of quaternary ammonium groups To provide organosilicon compounds containing (micro) emulsions form, which are stable even in the alkaline range (alkali-tolerant). Furthermore, the object was a process for the preparation of quaternary ammonium-containing organosilicon compounds provide that is simple, without using consuming to produce Siliconmacromere.

The Task is solved by the invention.

wobei
Y ein zweiwertiger organischer Rest mit 1 bis 100 C-Atomen, vorzugsweise mit 1 bis 12 C-Atomen, der ein oder mehrere Ethersauerstoffatome und/oder ein oder mehrere Hydroxygruppen enthalten kann, vorzugsweise einen ringgeöffneten Epoxidrest enthält, bedeutet,
R¹ ein einwertiger organischer Rest mit 1 bis 30 C-Atomen, vorzugsweise ein organischer Rest mit 1 bis 18 C-Atomen, der C-, H- und O-Atome enthält, bevorzugt ein Kohlenwasserstoffrest mit 1 bis 18 C-Atomen, bedeutet
R² ein Methyl- oder Ethylrest, bevorzugt ein Methylrest bedeutet,
A ein einwertiger organischer Rest mit mindestens 4 Kohlenstoffatomen, der mit mindestens 2 Hydroxygruppen, vorzugsweise mit mindestens 3 Hydroxygruppen substituiert ist, bedeutet,
L^– Gegenion zu der positiven Ladung an der quaternierten Stickstoffgruppe ausgewählt aus Anionen von anorganischen oder organischen Säuren HL bedeutet.The invention relates to quaternary ammonium-containing organosilicon compounds (1) containing at least one Si-bonded group G of the general formula

in which
Y is a divalent organic radical having 1 to 100 C atoms, preferably having 1 to 12 C atoms, which may contain one or more ether oxygen atoms and / or one or more hydroxyl groups, preferably contains a ring-opened epoxide radical,
R ^{1 is} a monovalent organic radical having 1 to 30 carbon atoms, preferably an organic radical having 1 to 18 carbon atoms, which contains C, H and O atoms, preferably a hydrocarbon radical having 1 to 18 carbon atoms
R ^{2 is} a methyl or ethyl radical, preferably a methyl radical,
A is a monovalent organic radical having at least 4 carbon atoms which is substituted by at least 2 hydroxyl groups, preferably by at least 3 hydroxyl groups,
L ^- counterion to the positive charge on the quaternized nitrogen group selected from anions of inorganic or organic acids HL.

The invention further provides a process for the preparation of the quaternary ammonium-containing organosilicon compounds, by organic amino compounds (2) of the general formula NR ¹ R ² A (II) or their ammonium salts HN ⁺ R ¹ R ² AL ^- ,
wherein R ¹ , R ² , A and L ^{- have} the meaning given above,
with organosilicon compounds (3) which contain at least one Si-bonded radical X which contains a group E which alkylates the N atom in the amino compound of the formula (II), preferably in the presence of inorganic or organic acids HL,
be implemented.

The Organosilicon compounds according to the invention (1) can be linear, branched, cyclic or resinous Structures with a variety of tri- and / or tetrafunctional ones Have siloxane units. The organosilicon compounds (1) have preferably at least two siloxane units, preferably at least ten siloxane units per molecule.

Preferred organosilicon compounds having quaternary ammonium groups (1) are organopolysiloxanes of the general formula G _g R _3-g SiO (SiR ₂ O) ₁ (SiRGO) _k SiR _3-g G _g (III), where G has the meaning given above,
R denotes a monovalent hydrocarbon radical having 1 to 18 C atoms,
g is 0 or 1,
k is 0 or an integer from 1 to 30, preferably 1 to 5, and
l is 0 or an integer from 1 to 1000, preferably 20 to 600,
with the proviso that at least one residue G per molecule is included.

Preferably Y is an SiC-bonded radical.

Prefers Y is a divalent hydrocarbon radical having 1 to 12 C atoms, which contains a ring-opened epoxy radical and additionally one or more ether oxygen atoms and / or May contain hydroxyl groups.

Examples of radicals Y which contain a ring-opened epoxide radical are in WO 2004/044306 (incorporated by reference) on page 19 (see R ⁴ =), in US 6,242,554 B1 (incorporated by reference), column 2, lines 46-65 and in WO 97/32917 A1 (incorporated by reference), page 3, lines 9-14 described.

The Silicon compounds (1) contain the bivalent organic Rest Y as a linking group between quaternary N atoms the reacted organic amino compounds (2) and Si atoms the reacted silicon compounds (3).

(N)-CH₂-(Si) Examples of the radical Y are: (N) -CH ₂ C ₆ H ₄ - (Si) (N) -CH ₂ C ₆ H ₄ -CH ₂ CH ₂ - (Si) (N) -CH ₂ CH = CH- (Si) (N) -CH ₂ CHOHCH ₂ OCH ₂ CH ₂ CH ₂ - (Si) (N) -CH (CH ₂ OH) CH ₂ OCH ₂ CH ₂ CH ₂ - (Si) (N) -CH ₂ CHOHCH ₂ CH ₂ CH ₂ CH ₂ - (Si) (N) -CH (CH ₂ OH) CH ₂ CH ₂ CH ₂ CH ₂ - (Si)

(N) -CH ₂ - (Si)

Examples R radicals are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl, such as n-hexyl, heptyl, such as the n-heptyl, octyl, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical, Nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl radical, Dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as n-octadecyl radical; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, Cycloheptyl and methylcyclohexyl radicals; Alkenyl radicals, such as the vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl and 4-pentenyl; Alkynyl radicals, such as the ethynyl, propargyl and 1-propynyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.

Examples of R ¹ are linear or branched or cyclic alkyl radicals having 1 to 18 carbon atoms, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso Butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl, such as the n-hexyl, heptyl, such as the n-heptyl, octyl, such as n-octyl and iso-octyl such as 2,2,4-trimethylpentyl, nonyl such as n-nonyl, decyl such as n-decyl, dodecyl such as n-dodecyl, and octadecyl such as n-octadecyl ; and cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals.

Examples of C, H and O-containing organic radicals R ¹ are alkanol radicals such as 2-hydroxyethyl and 2-hydroxypropyl, alkanol ether radicals such as 2-methoxyethyl, 2-butoxyethyl and 2-methoxypropyl.

Preferably, R ^{1 is} the methyl or ethyl radical, more preferably the methyl radical.

The structure of A is composed of the structural elements -B- (Z) _n ,
where n is an integer from 1 to 10, preferably 1 or 2, preferably 1,
B is an (n + 1) -valent (ie polyvalent) organic radical, in the function n groups Z (ie one or more groups Z), preferably one or two groups Z, preferably a group Z, with the quaternary To connect nitrogen atom (s). Preferably, the radical B is therefore bivalent or trivalent, preferably bivalent.

The structural element Z preferably contains at least two hydroxyl groups which are each bonded to different carbon atoms. Z preferably contains 2 to 12 C atoms, preferably Z contains 3 to 12 C atoms and 2 to 10 hydroxy groups. Preferably Z is radicals which are derived from hydroxycarboxylic acids or oxidized mono- or disaccharides which contain at least two hydroxyl groups. Z is particularly preferably radicals which are derived from oxidized monosaccharides of the formulas HIGH ₂ - (CHOH) _d -CO- O = CH- (CHOH) _d -CO- HO ₂ C- (CHOH) _d -CO- where d is 2, 3, 4, 5, 6, 7, 8, 9 and 10.

These Z residues are derived from their underlying carboxylic acids by the absence of the hydroxy group of the carboxyl part, which in these special cases when linking from Z with B to an amide or ester with a hydrogen atom B formally forms one mole of condensation water.

Examples for the radicals Z underlying carboxylic acids are glyceric acid, mevalonic acid, gluconic acid, Mannoic acid, 2-ketogulonic acid, galactaric acid, Glucaric acid, isosaccharic acid as well as with theirs cyclic structures the glucuronic acid, galacturonic acid and quinic acid.

Preferably the radical B is an organic radical having 2 to 20 C atoms, preferably a hydrocarbon radical having 2 to 10 C atoms, one or more Contains oxygen or nitrogen atoms and by a Esterification or amidation via ester or amide groups is associated with the (or the) remainder (s) Z.

Examples of the polyvalent organic radical B are (N) -CH ₂ CH ₂ O- (Z) (N) -CH ₂ CH (CH ₃ ) O- (Z) (N) -CH ₂ CH ₂ NH- (Z) (N) -CH ₂ CH ₂ CH ₂ NH- (Z) (N) -CH ₂ CH ₂ CH ₂ N (- (Z)) CH ₂ CH ₂ CH ₂ NH- (Z) where (N) the bond to the N atom in the formula (I) or (II) and (Z) the bond to the radical Z means.

The Linking of the structural elements B and Z can in principle be carried out by any chemical reaction, preferably by Esterification or amidation. Due to the simple implementation the amidation is particularly preferred. Here are preferred the lactones (5) of the polyhydroxy acids underlying the Z radicals used, which are usually in high yields with prim. as well as with sec. React amino groups. Therefore, they contain the residues B organic compounds (4) preferably at least one prim. Amino group.

Examples of these organic compounds (4) are amines such as
2-Dimethylaminoethylamine
3-dimethylaminopropylamine
Bis (3-aminopropyl) methylamine
3- (3-dimethylaminopropylamino) propylamine
3-dimethylaminopropyl-methylamine
2-dimethylaminoethanol
1-dimethylamino-2-propanol

Preferred compound (4) contain one NH ₂ and one NMe ₂ group (Me = methyl radical) per molecule. Examples of compounds (5) which are reacted with the organic amines (4) in a pre-reaction to the organic amino compounds (2) are the lactones glucaric acid-1,4-lactone, glucono-1,5-lactone, glucurono-6, 3-lactone, galactono-1,4-lactone, mannonic acid-1,4-lactone, gulonic acid-1,4-lactone, ascorbic acid and gluco-ascorbic acid.

Preferably in the preparation of the amino compound (2), Compound (5) in amounts of from 0.8 to 1.2 moles per mole of prim. and sec. amino group used in connection (4).

The reaction of (4) with (5) is preferably carried out at temperatures of 40 to 100 ° C., preferably 40 to 70 ° C., either undiluted or else mixed by solvents such as lower alcohols. The reaction of prim. Amine with the lactone group is spontaneous and usually requires no catalyst. Since the viscosity of the compounds (2) is usually very high, a dilution with polar low molecular weight substances such as lower alcohols, eg. As ethanol, be advantageous, with about 50 to 80% solution is preferred. The reaction can also be carried out in the presence of further additives such as acids, especially if the compounds (2) in the form of ammonium salts HN ⁺ R ¹ R ² A L ^- to be obtained. For this purpose, organic acids, preferably C ₁ to C ₁₈ carboxylic acids, preferably acetic acid and / or inorganic acids, such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, can then be used as acids.

Examples of amino compounds (2) are those of the formulas NR ¹ R ² -CH ₂ CH ₂ OZ NR ¹ R ² -CH ₂ CH (CH ₃ ) OZ NR ¹ R ² -CH ₂ CH ₂ NH-Z NR ¹ R ² -CH ₂ CH ₂ CH ₂ NH-Z NR ¹ R ² -CH ₂ CH ₂ CH ₂ N (-Z) CH ₂ CH ₂ CH ₂ NH-Z wherein R ¹ , R ² and Z have the meaning given above.

at the reaction of the organic amino compounds (2) to the inventive Silicon compounds (1) is the tert. Amino group in formula (II) alkylated by the silicon compounds (3) and thus in the inventive converted to quaternary ammonium compounds.

When Compounds (3) can generally all silicon compounds are used, which per molecule at least one, preferably at least contain two Si-bonded radicals X, each having an alkylating group E included.

Preferably X is a monovalent Si-bonded organic radical of 1 to 100 C atoms, preferably 1 to 12 C atoms, which is an alkylating Group E contains. The radical X may be one or more ether oxygen atoms and / or hydroxyl groups.

Preferably X is an SiC-bonded radical.

Prefers the alkylating group E is an epoxy group, preferably in terminal position of the Si-bonded radical X.

Prefers X is a hydrocarbon radical having 1 to 12 C atoms, which is a Contains epoxy group and the additional one or contain a plurality of ether oxygen atoms and / or hydroxyl groups can.

Especially preferably X is an epoxyalkyl such as 5,6-epoxyhexyl, 7,8-epoxyoctyl, 11,12-epoxydodecyl or the 2- (epoxycyclohexyl) ethyl group or Glycidoxypropyl.

Further examples of radicals X with alkylating groups E are
3,4-Epoxycyclohexylethyl- (Si)
2- (3,4-epoxy-4-methylcyclohexyl) -2-methylethyl (Si)
4-chloromethylphenyl (Si)
4-Chlormethylphenylethyl- (Si)
4-Brommethylphenylethyl- (Si)
3-bromo-1-propenyl (Si)
p-Tosylmethyl- (Si)

polymers Silicon compounds (3) can be linear, branched, cyclic or resinous structures with a variety of tri- and / or have tetrafunctional siloxane units.

The Organosilicon compounds (3) preferably have at least two Siloxane units, preferably at least ten siloxane units per Molecule up.

Preferred organosilicon compounds (3) are organopolysiloxanes of the general formula X _g R _3-g SiO (SiR ₂ O) ₁ (SiRXO) _k SiR _3-g X _g (III), where X has the meaning given above,
R denotes a monovalent hydrocarbon radical having 1 to 18 C atoms,
g is 0 or 1,
k is 0 or an integer from 1 to 30, preferably 1 to 5, and
l is 0 or an integer from 1 to 1000, preferably 20 to 600,
with the proviso that at least one radical X per molecule is included.

Prefers contain the organosilicon compounds (3) alkylating Groups E, in particular epoxy groups, in a concentration of approx. 0.1 m equ./g to approx. 4 m equ./g silicon compounds (3).

The Reaction of the compounds (2) with (3) is preferably carried out at a temperature of 20 ° C to about 150 ° C, preferably from 50 ° C to about 120 ° C.

The Reaction can occur under pressure of the surrounding atmosphere (approx. 1020 hPa) or at higher or lower pressures be performed.

at the method according to the invention the molar ratio of alkylating groups E in (3) to basic nitrogen in (2) preferably about 0.1: 1 to 3: 1, preferably 0.1: 1 to 2: 1, being more of a higher molar ratio is applied when the basic nitrogen is secondary Nature is, since this only to the tert. Nitrogen are alkylated got to.

The inventive method is preferably in Presence of an inorganic or organic acid HL carried out. Examples of inorganic acids are hydrochloric acid, sulfuric acid, nitric acid, Phosphoric acid, with hydrochloric acid being preferred.

Examples of organic acids are C ₁ -C ₁₈ -carboxylic acids, such as formic acid, acetic acid, propionic acid, lauric acid, myristylic acid, 2-ethylhexanoic acid, toluenesulfonic acid, methylsulfuric acid, trifluoroacetic acid, perfluorooctanoic acid, trifluoromethanesulfonic acid.

The anion L ^{- of} the inorganic or organic acid is therefore the counterion to the positive La at the quaternary nitrogen group in the organosilicon compound (1) according to the invention.

to better handling is the invention Process preferably in the presence of organic solvents carried out. Examples of organic solvents are ethanol, diethylene glycol monobutyl ether, propylene glycol, dipropylene glycol monomethyl ether.

To the reaction, the solvents - preferably distillatively - removed. Is with a mixture of Solvents worked, preferably with a mixture from a low boiler (solvent with a boiling point preferably below 100 ° C, such as ethanol) and a high boiler (Solvent with a boiling point of preferably over 150 ° C, such as diethylene glycol monobutyl ether) is preferred Low boilers removed and the high boiler as a viscosity regulator in the organosilicon compound of the invention (1) leave.

With the organosilicon compounds of the invention (1) can obtain aqueous (micro) emulsions become.

object The invention therefore emulsions containing quaternary Ammonium-containing organosilicon compounds (1) and water

The emulsions according to the invention have the advantage that they are stable even in the alkaline range.

Example 1:

20.4 g of 3-dimethylaminopropylamine are diluted with 56 g of ethanol and partially neutralized with 12.0 g of acetic acid. In this Mixture is added with moderate stirring 35.6 g of gluconolactone. In a slightly exothermic reaction that achieves Mixture about 55 ° C and is becoming increasingly clear. The temperature is held at 50 ° C for two hours while which completely dissolves the lactone. you receives a yellowish solution of 3-diethylammonium propylgluconamide in ethanol containing 1.62 m equ. Nitrogen base per g solution.

42.6 g of this solution are in 140 g about 60 ° C warm α, ω-bis (glycidoxypropyl) polydimethylsiloxane with one with a concentration of epoxy groups of 0.49 m equ./g dosed and catalysed with 1 ml of 25% hydrochloric acid. to For better handling, 41 g of diethylene glycol monobutyl ether are added. The mixture is then stirred well at 100 ° C for 2 hours, cooled to 60 ° C and freed from ethanol in vacuo. It 202 g of a clear, yellowish silicone oil are obtained containing quaternary nitrogen of 0.34 m equ./g Solution.

In 40 g of this solution are slowly 60 g of deionized water stirred in, whereupon a pale yellowish, clear microemulsion receives.

With the quaternary ammonium groups of the invention having polysiloxane becomes a spontaneous formation in a simple manner achieved a (micro) emulsions.

Example 2:

Similarly as in Example 1 42.6 g of there prepared as a precursor solution of the basic Gluconsäureamids in a preheated solution of 245 g of a methyl-terminated copolymer of dimethylsiloxy and Glycidoxypropylmethyl siloxane units having a concentration of epoxy groups of 0.28 m Equ./g and a viscosity of 540 mm ² / s (25 ° C) in 72 g Diethylenglycolmonobutylether. After catalysis with 1 ml of 25% hydrochloric acid, the strongly turbid mixture is allowed to react for 3 hours at 100 ° C. and for a further hour at 120 ° C. Ethanol is removed at 60 ° C in vacuo, whereupon 359 g of a slightly cloudy silicone oil with 0.18 m equ. quaternary nitrogen per g of solution.

Out 40 g of this solution and the same amount of deionized Water can be made by simply stirring with a Spatel produce a weakly colored microemulsion.

Example 3:

20.4 g of 3-dimethylaminopropylamine are diluted with 96 g of ethanol and heated to 50.degree. Nachei Nander be first added 40 g of lauric acid and then 35.6 g of gluconolactone. After a brief slight warming, the mixture is stirred well for 3 hours at 50 ° C, where it clears after about 20 minutes. The clear, yellowish solution contains 1.02 m equ. Nitrogen base per g.

40 g of this 50% ethanolic solution are in a 60 ° C preheated solution of 85 g of an α, ω-bis (glycidoxypropyl) polydimethylsiloxane with a concentration of epoxy groups of 0.49 m equ./g and 26 g Diethylenglycolmonobutylether dosed and with 1 ml of 25% hydrochloric acid catalyzed. The reaction mixture is at 100 ° C for one hour stirred, she clears up, then another hour at 120 ° C. At 60 ° C, the ethanol in vacuo away. This gives 130 g of a clear, reddish Solution of a quaternary ammonium group having Polysiloxane containing quaternary nitrogen of 0.31 m equ./g.

40 g of this solution are mixed with the same amount of deionized Turn the water into a clear microemulsion by stirring gently.

Comparative experiment according to DE 4318536 A :
The procedure of Example 1 is repeated with the modification that is used as the amino compound, an amino compound having a secondary amino group in place of the tertiary amino group according to the invention. Thus, the 20.4 g of 3-dimethylaminopropylamine are replaced by 17.6 g of 3-methylaminopropylamine, the amount of ethanol increased to 58.8 g, so that the obtained after the reaction with gluconolactone yellowish solution of Methylammoniumpropylgluconsäureamid also 1.62 meq. Nitrogen base per g of solution contains, but this time as a secondary amino compound. The second stage is carried out with the same amounts as in Example 1 under the same conditions.

The stirring of 40 g of the product solution obtained in 60 g of water gives a finely divided emulsion. The respectively weakly acidic emulsions from Example 1 and Comparative Experiment according to DE 4318536 A are adjusted to pH 8 with dilute sodium hydroxide solution to determine the alkali tolerance: While the emulsion according to the invention of Example 1 remains virtually unchanged, the comparison emulsion separates and separates out an oily mass.

Example 4:

• a) D-Glucurono-6,3-lacton
• b) D-(–)-Galactono-1,4-lacton
• c) L-Mannonsäure-gamma-lacton
• d) L-(+)-Gulonsäure-gamma-lacton

Example 1 is repeated analogously, in which the gluconolactone is replaced by other lactones according to the invention, and for the preparation of the quaternary ammonium polysiloxanes having the following lactones in each case prepared an ethanolic solution of Dimethylammoniumpropylzuckersäureamids same active ingredient content:

• a) D-glucurono-6,3-lactone
• b) D - (-) - galactono-1,4-lactone
• c) L-mannonic acid gamma-lactone
• d) L - (+) - gulonic acid gamma-lactone

As in Example 1, the respective ethanolic solutions reacted with the same Epoxisiloxanen, and from it aqueous Dilutions made. In all cases will be obtained yellowish, clear microemulsions.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - US 3389160 [0002]
• - DE 1493384 B [0002]
• EP 017121 B [0003]
• - US 5235082 [0004]
• - EP 606159 B [0004]
• - US 6730766 [0005]
• - EP 1288246 A [0005]
• - US 4833225 [0006]
• - EP 282720 B1 [0006]
• US 4533714 [0007]
• US 7041767 [0008]
• - WO 02/10259 [0008]
• - US 2006/128880 A [0009]
• - WO 2004/044306 [0009, 0022]
• - US 6958410 [0010]
• WO 2006/018327 [0011]
• - US 6242554 [0012]
• - EP 1000959 A [0012]
• - DE 4318536 A [0013, 0073, 0074]
• US 6242554 B1 [0022]
• WO 97/32917 A1 [0022]

Claims (10)

Quaternary ammonium-containing organosilicon compounds (1) containing at least one Si-bonded group G of the general formula

wherein Y is a bivalent organic radical having 1 to 100 carbon atoms, which may contain one or more ether oxygen atoms and / or one or more hydroxy groups, R ^{1 is} a monovalent organic radical having 1 to 30 carbon atoms, R ^{2 is} a methyl - or ethyl radical, A is a monovalent organic radical having at least 4 carbon atoms which is substituted by at least 2 hydroxyl groups. L ^- counterion to the positive charge on the quaternized nitrogen group selected from anions of inorganic or organic acids HL. Quaternary ammonium-containing organosilicon compounds (1) according to claim 1, characterized in that Y is a bivalent Hydrocarbon radical having 1 to 12 C atoms, one or more Ether oxygen atoms and / or one or more hydroxy groups can, and contains a ring-opened epoxy group. Quaternary ammonium-containing organosilicon compounds (1) according to claim 1 or 2, characterized in that A is a radical of the formula -B- (Z) _n , where n is 1 or 2, B is a di- or trivalent organic radical having 2 to 10 C atoms which contain one or more oxygen or nitrogen atoms and are linked to the (or the) radical Z by an esterification or amidation via an ester or amide group, and Z is an organic radical having 2 to 12 C atoms. Atoms derived from hydroxycarboxylic acids or oxidized mono- or disaccharides containing 2 to 10 hydroxy groups. Quaternary ammonium-containing organosilicon compounds (1) according to claim 1, 2 or 3, characterized in that Z is a radical selected from the group of the formulas HIGH ₂ - (CHOR) _d -CO- O = CH- (CHOH) _d -CO- HO ₂ C- (CHOR) _d -CO- where d is 2, 3, 4, 5, 6, 7, 8, 9 and 10. Quaternary ammonium-containing organosilicon compounds (1) according to one of claims 1 to 4, characterized in that they are organopolysiloxanes of the general formula G _g R _3-g SiO (SiR ₂ O) ₁ (SiRGO) _k SiR _3-g G _g (III), wherein G has the meaning given in claim 1, R is a monovalent hydrocarbon radical having 1 to 18 carbon atoms, g is 0 or 1, k is 0 or an integer from 1 to 30 and l is 0 or an integer of 1 to 1000, with the proviso that at least one remainder G per molecule is included. A process for the preparation of quaternary ammonium-containing organosilicon compounds (1) by adding organic amino compounds (2) of the general formula NR ¹ R ² A (II) or their ammonium salts HN ⁺ R ¹ R ² AL ^- wherein R ¹ , R ² , A and L ^{- have} the meaning given in claim 1, with organosilicon compounds (3) containing at least one Si-bonded organic radical X, which is a N-atom in the amino compound of the formula (II) alkylating group E contains, preferably in the presence of inorganic or organic acids HL, are reacted. Process for the preparation of quaternary Ammonium-containing organosilicon compounds (1), characterized in that X is an Si-bonded organic radical with 1 to 12 carbon atoms containing an epoxy group. Process for the preparation of quaternary Ammonium-containing organosilicon compounds (1), characterized characterized in that X is a Glycidoxypropylrest. Process for the preparation of quaternary ammonium-containing organosilicon compounds (1), characterized in that the amino compound (2) is selected from the group of the formulas NR ¹ R ² -CH ₂ CH ₂ OZ NR ¹ R ² -CH ₂ CH (CH ₃ ) OZ NR ¹ R ² -CH ₂ CH ₂ NH-Z NR ¹ R ² -CH ₂ CH ₂ CH ₂ NH-Z NR ¹ R ² -CH ₂ CH ₂ CH ₂ N (-Z) CH ₂ CH ₂ CH ₂ NH-Z are used, wherein R ¹ and R ^{2 have} the meaning given in claim 1, and Z has the meaning given in claim 3 or 4. Emulsions containing quaternary ammonium groups having organosilicon compounds (1) according to any one of claims 1 to 5 or produced according to one of claims 6 to 9 and water.