WO2018141405A1

WO2018141405A1 - Emulsions containing amino acid-functional siloxanes

Info

Publication number: WO2018141405A1
Application number: PCT/EP2017/052426
Authority: WO
Inventors: Elke Fritz-Langhals; Richard Weidner; Sotirios KNEISSL
Original assignee: Wacker Chemie Ag
Priority date: 2017-02-03
Filing date: 2017-02-03
Publication date: 2018-08-09

Abstract

The invention relates to thickened emulsions containing 1) 100 parts by weight water (W), 2) maximum 20 parts by weight of a silicone polymer (P) containing amino acid groups, 3) maximum 30 parts by weight of a liquid (F) consisting of one or more compounds (V), the liquid (F) having a miscibility gap with water (W).

Description

Amino acid-functional siloxanes containing emulsions

The invention relates to emulsions containing amino acid functional siloxanes.

Emulsions play an important role in the art. They consist of two immiscible phases, an oil and a water phase. In order to achieve a stable finely divided distribution of the two phases, emulsifiers are used.

It is also desirable to have a thickening, i. an increase in viscosity of the emulsion, as this can simplify the application. Particularly interesting are stable emulsions. Applications are mainly in the field of cosmetic products, cleaning agents, wall and printing inks or in building materials.

Known thickening agents include e.g. pectins,

Cellulose ethers, polyvinyl alcohol and silicates.

Emulsions of high water content are of particular interest in the art. The active ingredients contained in the oil phase can then be applied more uniformly and thus often more sparingly due to the high dilution.

Silicone-based thickening emulsifiers are of particular interest because these polymers are very stable and chemically inert. Emulsions containing amine-functional silicones in combination with acetic acid are known. For example, EP 0442098 A2 describes organopolysiloxane emulsions which comprise siloxanes containing ammonium acetate groups, an emulsifier and water. These are from

Disadvantage that during storage by volatilization of the

Acetic acid can increase the pH. This is particularly disadvantageous in cosmetic applications. In addition, the effect is limited to a narrow pH range.

Amino acid-functional siloxanes have also been used in emulsions, but no formulations are known which lead to thickened emulsions.

DE 10036532 A1 describes the formulation of 0.13 parts by weight of a sarcosine-functional siloxane in 100 parts by weight of water in the presence of 0.42 parts by weight of a detergent, which, however, is a solution.

EP 2231753 describes emulsions which in each case contain from 42 to 45 parts by weight of amino acid-functional siloxane and from 10 to 12 parts by weight of non-silicone-based emulsifiers in 100 parts by weight of water.

The object of the present invention is to provide thickened emulsions using silicones containing small amounts of amino acid moieties.

The invention relates to thickened emulsions containing

1) 100 parts by weight of water (W),

2) at most 20 parts by weight of a silicone polymer containing amino acid groups (P)

3) at most 30 parts by weight of a liquid (F) consisting of one or more compounds (V), wherein the liquid (F) with water (W) has a miscibility gap. Surprisingly, it has now been found that containing significantly lower proportions of the amino acid groups

Silicone polymer (P) can be prepared based on the amount of water strongly thickened emulsions. The reduction in the proportion of amino acid-modified silicone means a significant increase in efficiency, resulting in new applications.

The silicone polymer (P) preferably contains at least one siloxane unit of the general formula I and no or at least one unit of the general formula II

wherein

R ¹ and R ² are independently hydrogen or a straight, branched or cyclic saturated or unsatu- rated alkyl group having 1 to 20 carbon atoms or aryl group or aralkyl group, wherein individual non-adjacent methylene units by groups -O-, -CO-, -COO -, -OCO- or -OCOO-, -S- or NR ^X or by an oxyalkylene group of the general formula (-O-CH ₂ -CHR ³ -) _d may be replaced, R ^{3 is} hydrogen or alkyl,

R ^{x is} hydrogen or a C ₁ -C ₁₀ -hydrocarbon radical which is unsubstituted or substituted by substituents selected from -CN and halogen,

X is a radical of the general formula which carries at least one amino acid unit and is bonded via a carbon atom to the silicon atom

-Y-NR ⁴ - (CH ₂ ) _e -CR ⁵ R ⁶ -COOM, mean,

M is hydrogen, metal or an ammonium radical NR ¹⁰ ₄ ⁺ ,

R ^{10 are} independently hydrogen or C ₁ -C ₁₂ alkyl, aryl or aralkyl,

R ^{4 is} hydrogen or a linear, branched or cyclic saturated or unsaturated alkyl group having 1 to 20 C atoms or aryl group or aralkyl group, with individual non-adjacent methylene units being represented by groups -O-, -CO-, -COO-, -OCO- or - OCOO-, -S- or NR ^X or may be replaced by an oxyalkylene group of the general formula (-O-CH ₂ -CHR ³ -) _d ,

R ⁵ and R ^{6 are} independently hydrogen or linear,

branched or cyclic saturated or unsaturated alkyl groups having 1 to 20 C atoms or aryl groups or aralkyl groups, wherein individual non-adjacent methylene units represented by groups -O-, -CO-, -COO-, -OCO- or -OCOO-, -S- or NR ^X may be replaced, where R ⁵ or R ^{6 may be} connected to R ⁴ ,

Y is a carbon atom to the organosilicon bond, linear, branched, cyclic, saturated or mono- or polyunsaturated C associated _x to C ₁ oo alkylene radical may be replaced in the individual carbon atoms are replaced by oxygen, nitrogen or sulfur atoms, and with non-adjacent hydroxyl groups may be substituted, mean

a is 0, 1, 2 or 3,

b the values 0, 1 or 2,

c is 1, 2 or 3

d integer values from 1 to 100,

b + c the values 1, 2, 3 or 4, and

e have integer values 0 to 50. The amino acid moieties - Y - NR ⁴ - (CH ₂ ) _e - CR ⁵ R ⁶ - COOM

can exist in different protonation states.

Carboxylic acid groups may be present as a free carboxylic acid or as a carboxylate salt or as mixtures of these. The amino moiety may be present both as a free amino group or in protonated form as an ammonium moiety or as a mixture thereof.

R ¹ and R ² independently of one another preferably denote hydrogen or an unbranched, branched or cyclic saturated or unsaturated alkyl group having 1 to 6 C atoms or a benzyl or phenyl group, where non-adjacent methylene units may be replaced by nitrogen atoms or oxygen atoms, or by a Oxyalkylene group of the general formula (-O-CH ₂ -CHR ³ -) _d may be replaced.

Preferably, the radicals R ³ mean hydrogen or

Methyl, especially methyl.

R ^{x is} preferably hydrogen or an unsubstituted C ₁ -C ₆ -hydrocarbon radical.

Preferably, M is alkali metal or alkaline earth metal,

particularly preferably alkali metal, particularly particularly preferably sodium or potassium, or an ammonium radical.

R ¹⁰ preferably denotes hydrogen or C ₁ -C ₄ -alkyl, in particular methyl, ethyl, n-propyl.

R ⁴ is preferably hydrogen or a linear, branched or cyclic saturated or unsaturated alkyl group having 1 to 10 carbon atoms or a benzyl or phenyl group, wherein non-adjacent methylene units may be replaced by nitrogen atoms or oxygen atoms, or by a Oxyalkylene group of the general formula (-O-CH ₂ -CHR ³ -) _d . R ⁴ particularly preferably represents a C ₁ -C _e alkyl group, wherein methylene units by oxyalkylene groups of the general

Formula -O- (CH ₂ -CHR ³ -) _d may be replaced, in particular methyl. Preferably, the radicals R ³ mean hydrogen or

Methyl, especially methyl.

Preferably, R ⁵ is hydrogen and R ⁶ is hydrogen or a linear, branched or cyclic saturated or unsaturated alkyl group having 1 to 10 carbon atoms or aryl group, or

Aralkyl group, wherein individual non-adjacent methylene units may be replaced by groups -O-, -CO-, -COO-, -OCO- or -OCOO-, -S- or NR ^X. In particular, R ^{5 is} hydrogen and R ^{6 is} -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CHOH-CH ₃ , -CH ₂ -SS-CH ₂ -CH (NH ₂ ) COOH, -CH ₂ -CH ₂ -CONH ₂ , -CH ₂ CONH ₂ , CH ₂ -CH ₂ -COOH, CH ₂ -COOH, -CH ₂ -CH ₂ -CH ₂ -NH-CO-NH ₂ , -CH ₂ -CH ₂ -CH ₂ -CH ₂ - NH ₂ , -CH ₂ -CH ₂ -CH ₂ -NH ₂ , -CH ₂ -CH ₂ -CH ₂ -NH-C (= NH) -NH ₂ , and -CH ₂ - (4- Imidazolyl), -CH ₂ - (3-indolyl).

When R ^{4 is} connected to R ⁵ or to R ⁶ , the radicals are preferably linked via an alkylene radical, in particular with 1 to 6 carbon atoms. Y is preferably a linear or branched, saturated C ₁ to C ₂₀ alkylene radical in which individual carbon atoms may be replaced by oxygen, nitrogen or sulfur atoms.

Y is particularly preferably a grouping

(Z) e - CR ⁷ (OH) - CR ⁸ R ⁹

Z is a via a carbon atom to the Organosili- ciumverbindung linked linear, branched, cyclic, saturated or mono- or polyunsaturated C ₁ to C ₁₀₀ Alkylene radical in which individual carbon atoms may be replaced by oxygen atoms. Z particularly preferably denotes an oxyalkylene radical of the general formula

-CH ₂ -CH ₂ -CH ₂ -O- (CHs-CHR ^ -O) _f -CH ₂ , in which the radicals R ¹¹ independently of one another are hydrogen or alkyl, in particular methyl, and f is a value of 0 to 100, preferably 0 to 50 and more preferably 0 assumes.

The radicals R ⁷ , R ⁸ and R ⁹ independently of one another preferably denote hydrogen or a linear C ₁ to C ₆ alkyl group, particularly preferably hydrogen or a linear C ₁ to C ₃ alkyl group.

The radicals R ⁸ and R ⁹ may also be connected to one another via alkylene radicals or oxygen and to the Z grouping. d and f are each independently of one another preferably 0 to 50, particularly preferably 0 to 10, particularly preferably 0 to 5 and very particularly preferably the values 0 to 3. e is preferably 0 to 10, particularly preferably 0 to 5 and very particularly preferably 0 to 3.

The liquid (F) is preferably an organic liquid which is liquid at 20 ° C and 0.1 MPa.

The compounds (V) contained in the liquid (F) are preferably selected from siloxanes, ethers, esters, amines,

Nitriles, hydrocarbons and mixtures thereof. Preferably, the compounds (V) are liquid at 20 ° C and 0.1 MPa.

The siloxanes are linear, branched or cyclic siloxanes or mixtures thereof.

Examples of linear siloxanes are hexamethyldisiloxane,

Octamethyltrisiloxane, decamethyltetrasiloxane, their higher homologs and mixtures thereof. Examples of cyclic siloxanes are hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D6), their higher homologs and mixtures thereof. Examples of branched siloxanes are Me ₃ Si-O-SiMe (OSiMe ₃ ) -O-SiMe ₃ and (Me ₃ SiO) ₄ Si.

Examples of ethers are methyl tert. butyl ether, diethyl ether, diphenyl ether, diisopropyl ether, tetrahydrofuran, dioxane and ethylene glycol diethyl ether.

Examples of esters are ethyl acetate and butyl acetate.

Examples of amines are triethylamine and tributylamine.

Examples of nitriles are acetonitrile, propionitrile, butyronitrile and benzonitrile.

The hydrocarbons may be linear, branched, cyclic, aliphatic or aromatic.

Examples of hydrocarbons are pentane, hexane, heptane and their higher homologues, 2-methylpentane, cyclohexane,

Methylcyclohexane, toluene, dimethylbenzene, cumene, fcert-butylbenzene and chlorobenzene. The emulsions of the invention contain based on 100

Parts by weight of water (W), preferably at least 0.05 part by weight and not more than 20 parts by weight of a silicone polymer (P) containing amino acid groups, and at least 1

Part by weight and not more than 30 parts by weight of liquid (F).

More preferably, the emulsions contain, based on 100 parts by weight of water (W), at least 0.1 part by weight and at most 10 parts by weight of a silicone polymer (P) containing amino acid moieties and at least 2 parts by weight and at most 20 parts by weight of the liquid (F).

The silicone polymers (P) used in the emulsions can be prepared in a manner known to those skilled in the art. For example, the following reactions can be used for the attachment of the amino acids:

(a) Addition of the amino groups in amino acids to epoxyfunctional siloxanes,

(b) addition of thiol group-containing amino acids to vinylsiloxanes,

(c) Nucleophilic substitution of chloroalkyl-functional siloxanes with the amino group of amino acids

(d) reaction of anhydride-functional siloxanes with

Amino acids.

Preference is given to the linking type mentioned under (a), in which the amino group of the amino acid is added to an epoxide group present in the silicone polymer. It can also be a double addition, i. E. per existing

Amino group may be bound to two silicone radicals. If an amino acid contains more than one basic nitrogen-containing group, it can react in the same way so that a maximum of 2 siloxane residues per amino group present can be bound.

The arrangement of the siloxane or the amino acid units to each other can be different, as in the

The following example structures show:

The emulsions may contain other polymers. These may form homogeneous or inhomogeneous mixtures, they may be covalently bound or not bound to the polymer (P)

available.

The emulsions contain these further polymers preferably in proportions of at least 0.01 and at most 50 parts by weight, more preferably in amounts of at least 0.1 and

at most 20 parts by weight, in particular in at least 1 and at most 10 parts by weight, each based on 100 parts by weight of water.

The silicone-containing polymer (P) may contain blocks of siloxane units of the general formula I and none or at least one unit of the general formula II and organic blocks through which the blocks of siloxane units

to be interrupted. The organic blocks may be linked to the blocks of siloxane units, for example via urea moieties, urethane moieties or ester groups. The proportion of organic blocks is preferred

at least 2 and at most 100 parts by weight, particularly preferably at most 30 parts by weight, in particular at most 10 parts by weight per 100 parts by weight of siloxane units of the general formula I and II. The emulsions may contain further substances which are present either as solids or dissolved. As solids, for example, highly disperse silica, silicates or zeolites or inorganic and organic salts, for example NaCl, ammonium chloride, potassium chloride in proportions of preferably at least 0.01 wt .-% to at most 30 wt .-%, particularly preferably 0.1 wt. % to a maximum of 10% by weight,

more preferably 1 wt .-% to at most 5 wt .-% based on 100 parts by weight of water may be present.

The silicone-containing polymer (P) is used to prepare the

Emulsion preferably dissolved in the liquid (F) or

water is added and water is then added in several steps and the mixture is mechanically agitated, e.g. by stirring or shaking.

The emulsions according to the invention are preferably added

Temperatures of at least -20 ° C and at most + 100 ° C, more preferably of at least 0 ° C and at most 60 ° C, most preferably of at least + 10 ° C and + 40 ° C.

produced.

Another object of the invention is the use of the emulsions.

The emulsions are preferably used in cosmetic

Products, in cleaning agents, wall paints, printing inks,

Building materials, in non-combustible hydrous gels,

For example, for firefighting or to protect against fire.

In the following examples, unless stated otherwise, all amounts and percentages are by weight and all temperatures are 20 ° C. All the above symbols of the above formulas each have their meanings independently of each other. In all formulas, the silicon atom is tetravalent. The viscosity measurements in the following examples were measured with a cone-plate viscometer from Anton-Parr with the following parameters: a) samples without water (Newton's fluids without structure viscosity): cone: CP50-1 / TG ( 50mm width, degrees and true gap

Surface), gap height with this cone 0,097mm referred to the cone point, T = 25 ° C.

1st section (pre-shear) 10 sec with a shear rate of 5 1 / s,

2nd section (waiting time): 5 s,

3rd section (measurement): 11 measuring points with a measuring point duration of 6 s and a linear shear stress profile of τ = 1 - 5 Pa, linear progression (Newton). b) Hydrous samples (pseudoplastic): Cones: CP25-1 / TG (25mm width, 1 degree and true gap surface)

Gap height with this cone amounts to 0,053mm related to the cone apex, T = 25 °.

1st section (pre-shear): 10 s with a shear rate of 20 1 / s,

2nd section (waiting time): 5 s,

3rd section (measurement): 50 measuring points with a measuring point duration of 6 s and a linear shear rate profile of 5-150 1 / s, non-linear course. example 1

310 mg terminal glutamic acid functionalized siloxane (α, ω-Glu, n = 54), formula:

prepared by reacting an α, ω-glycidoxypropyl-functionalized siloxane and glutamic acid in ethanol was dissolved in 3.01 g of silicone oil DM2 (linear oligodimethylsiloxane having an average chain length of 5 and a viscosity of about 2 μs). The viscosity of the solution was 3.80 mPa.s according to the Newton method.

The solution was added with shaking with water, forming turbid dispersions. The viscosities (r |) of the resulting samples were measured depending on the composition of the sample. The thickening of the emulsion increased sharply during the addition of water. Table 1 shows the viscosity values as a function of the composition of the sample at two different shear rates γ.

The parts by weight of siloxane (P) and liquid (F) given in Table 1 are each based on 100 parts by weight of water.

Table 1

Example 2

315 mg terminal lysine-functionalized siloxane (α, ω-Lys, = 54), formula:

prepared by reacting an α, ω-glycidoxypropyl-functionalized siloxane and lysine in methanol was dissolved in 3.10 g of silicone oil DM2 (linear oligodimethylsiloxane having an average chain length of 5 and a viscosity of about 2 μs).

The solution was added with shaking with water, forming turbid highly viscous dispersions. The viscosities (r |) of the resulting samples were determined as a function of Composition measured. The thickening of the emulsion increased sharply during the addition of water. Table 2 shows the

Viscosity values as a function of the composition of the sample at two different shear rates γ.

The parts by weight of siloxane (P) and liquid (F) given in Table 2 are each based on 100 parts by weight of water.

Table 2

Example 3

The preparation of the amino acid-functional siloxanes was carried out in each case by reacting the corresponding glycidoxy-functional silicones with the free amino acids or the amino acid sodium salts in methanol or in ethanol. α, ω-Glu, n = 54: see formula in Example 1, chain length n = 54;

α, ω-Glu-Na, n = 54: prepared analogously with glutamic acid disodium salt;

s-Glu, n = 150: analogously prepared siloxane with pendant glutamic acid groups and chain length n = 150 α, ω-Lys, n = 54: see formula in Example 2, chain length n = 54 α, ω-Lys-Na, n = 54 : prepared analogously with lysine sodium salt; α, ω-Ν-Me-Gly, n = 58 prepared analogously with N-methylglycine; α, ω-Ν-Me-Gly-K, n = 58 prepared analogously with N-methylglycine.

The amino acid-functional siloxanes (P) were dissolved or suspended in the liquid (F), and the mixture was then added with water in portions with stirring or shaking. This formed an emulsion, which at high

Water shares was stable.

Stable emulsions whose composition is listed in Table 3 were prepared from the siloxanes containing amino acid moieties.

Table 3: Manufactured stable emulsions, parts by weight of components P and F based on 100 parts by weight of water. Abbreviations:

HMDS = hexamethyldisiloxane, DM2 = linear oligodimethylsiloxane with an average chain length of 5 and one

Viscosity of about 2 es, DM5 = linear oligodimethylsiloxane with an average chain length of 10 and a viscosity of about 5 es, D5 = decamethylcyclopentasiloxane, MTBE = methyl tert. butyl ether

Claims

claims

1. containing thickened emulsions

1) 100 parts by weight of water (W),

3) at most 30 parts by weight of a liquid (F) consisting of one or more compounds (V), wherein the liquid (F) with water (W) has a miscibility gap.

2. Thickened emulsions according to claim 1, wherein the

Silicone polymer (P) at least one siloxane unit of the general formula I and no or at least one unit of the general formula II

contains, in which

R ¹ and R ² independently of one another denote hydrogen or an unbranched, branched or cyclic saturated or unsaturated alkyl group having 1 to 20 C atoms or aryl group or aralkyl group, where individual non-adjacent methylene units are represented by -O-, -CO-, -COO-, -OCO- or -OCOO-, -S- or NR ^X or may be replaced by an oxyalkylene group of the general formula (-O-CH ₂ -CHR ³ -) _d ,

R ^{3 is} hydrogen or alkyl,

R ^{x is} hydrogen or a C ₁ -C ₁₀ -hydrocarbon radical which is unsubstituted or substituted by substituents selected from -CN and halogen, X is a radical of the general formula which carries at least one amino acid unit and is bonded via a carbon atom to the silicon atom

-Y - NR ⁴ - (CH ₂ ) _e - CR ⁵ R ⁶ - COOM, mean

M is hydrogen, metal or an ammonium radical NR ¹⁰ ₄ ⁺ ,

R ¹⁰ is independently hydrogen or C ₁ -C ₁₂ alkyl, aryl or aralkyl,

R ^{4 is} hydrogen or a linear, branched or cyclic saturated or unsaturated alkyl group having 1 to 20 C atoms or aryl group or aralkyl group, where individual non-adjacent methylene units are represented by groups -O-, -CO-, -COO-, -OCO- or - OCOO-, -S- or NR ^X or may be replaced by an oxyalkylene group of the general formula (-O-CH ₂ -CHR ³ -) _d ,

R ⁵ and R ^{6 are} independently hydrogen or linear,

branched or cyclic saturated or unsaturated alkyl groups having 1 to 20 C atoms or aryl groups or aralkyl groups, wherein individual non-adjacent methylene units represented by groups -O-, -CO-, -COO-, -OCO- or -OCOO-, -S- or NR ^X may be replaced, where R ⁵ or R ^{s may be} connected to R ⁴ ,

a is 0, 1, 2 or 3,

b the values 0, 1 or 2, c is 1, 2 or 3

d integer values from 1 to 100,

b + c the values 1, 2, 3 or 4, and

e have integer values 0 to 50.

3. Thickened emulsions according to claim 2, in which R ¹ and R ² independently of one another are an unbranched, branched or cyclic saturated or unsaturated alkyl group having 1 to 6 C atoms.

4. Thickened emulsions according to one or more of claims 2 or 3, wherein M is selected from sodium, potassium, and ammonium radical.

5. Thickened emulsions according to one or more of claims 2 to 4, in which e represents values of 0 to 5.

6. Thickened emulsions according to one or more of

preceding claims, wherein the compounds (V) are selected from siloxanes, ethers, esters, amines, nitriles, hydrocarbons and mixtures thereof.

7. Thickened emulsions according to one or more of

preceding claims, which in addition to silicone polymer (P) contain other polymers.

8. Use of the thickened emulsions according to one or

several of the preceding claims in cosmetic

Products, in cleaning agents, wall paints, printing inks, building materials or in non-flammable water-containing gels.