DE10214139C2 - Process for the preparation of emulsions of hydroxamic acid functional organopolysiloxane - Google Patents

Description

The invention relates to a method for producing Functional emulsions of hydroxy acid amide Organopolysiloxane, in which an amino functional Organopolysiloxane with a lactone in the presence of an emulsifier and a water phase is implemented.

JP-A 63-139106 describes a process for the production of Organopolysiloxanes containing sugar residues Organopolysiloxanes having aminoalkyl groups with a Lactone of an aldonic or uronic acid in a solution of a low molecular weight alcohol such. B. ethanol. When implementing water is excluded because the presence of water affects the basic catalyzed hydrolysis of the lactone promotes and thus suppresses the desired amide formation. The sugar residues Organopolysiloxanes containing are in the form of emulsions used in cosmetic compositions such as shampoos.

The invention relates to a process for the preparation of (E) emulsions of hydroxamic acid-functional organopolysiloxane, which comprises at least one unit of the general formula (I)

T _a R _b SiO _{4-ab / 2} (I),

has in which
T is a group of the general formula (II)

-R ¹ - [NR ² (CH ₂ ) _c ] _d NR ³ -CO- (CR ⁴ ₂ ) _e - (CR ⁵ OH) _f -CR ⁶ ₂ OH (II),

means
in which an (A) organopolysiloxane which has at least one unit of the general formula (III)

Q _a R _b SiO _{4-ab / 2} (III),

has in which
Q is a group of the general formula (IV)

-R ¹ - [NR ² (CH ₂ ) _c ] _d NR ³ -H (IV),

means with a (B) lactone of the general formula (V)

is reacted in the presence of (C) emulsifier and (D) a water phase, wherein
R are identical or different, monovalent, optionally fluorine, chlorine or bromine substituted C ₁ to C ₁₈ hydrocarbon radicals, hydrogen atoms, C ₁ to C ₁₂ alkoxy, hydroxy or alkyl glycol radicals,
R ^{1 is} a divalent C ₁ to C ₁₈ hydrocarbon radical,
R ² and R ^{3 represent} a hydrogen atom or an optionally fluorine, chlorine or bromine substituted C ₁ to C ₁₈ hydrocarbon radical,
R ⁴ , R ⁵ and R ^{6 represent} a hydrogen atom or an optionally hydroxy, fluorine, chlorine or bromine substituted C ₁ to C ₁₈ hydrocarbon radical,
a the values 1, 2 or 3,
b the values 0, 1 or 2,
c the values 0, 1, 2 or 3, 4, 5 or 6,
d the values 0, 1, 2, 3 or 4,
e the values 0, 1, 2, 3 or 4 and
f is 1, 2, 3, 4, 5 or 6.

The reaction of the aminosiloxane (A) with lactone (B) to Hydroxy acid amide functional organopolysiloxane takes place in Presence of water, i.e. during and / or after Emulsification of the aminosiloxane (A) instead. Lactone (B) reacts not with water, but almost exclusively with the Amino groups of the organopolysiloxane (A). A loss of lactone (B) can hardly be determined by hydrolysis. The implementation usually runs sufficiently at normal pressure fast and therefore does not require any special catalysts Accelerate the reaction.

Performing the implementation during emulsification, simplifies the manufacturing process of hydroxy acid amide functional emulsions (E) containing organopolysiloxane, because no longer two process steps, namely amide formation and subsequent emulsification are necessary.

The hydroxy acid amide functional organopolysiloxane containing emulsions (E) are much better in incorporate aqueous systems as the 100% from the usual Process obtained using alcohol as a solvent Product. This is also due to the progressive amide formation increasing viscosity of the organopolysiloxane (A) Dilution effects during emulsification compensated. Emulsification problems and unsatisfactory particle size and insufficient shear stability due to the too high viscosity do not occur.  

When performing the implementation after the emulsification can even smaller particle sizes can be achieved because of the relative low-viscosity amino-functional organopolysiloxanes (A) very can be emulsified in fine particles. The well-known emulsions or microemulsions of amino-functional organopolysiloxanes (A), which have good storage stability, for example application to the desired level of hydroxy acid amide be implemented. The diluted emulsion and preferably the concentrate can be implemented. A suitable one Process for the production of fine particles Organopolysiloxane emulsions are known, for example, from EP A-442 098. There, the emulsion with an im Organopolysiloxane (A) soluble emulsifier in 2 steps prepared, with a concentrate obtained in the first step which is diluted with water in the second step.

Examples of the hydrocarbon radicals R, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl , tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl; Hexyl radicals, such as the n-hexyl radical; Heptyl residues, such as the n-heptyl residue; Octyl radicals, 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; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals such as the phenyl and naphthyl radicals; Alkaryl groups such as o-, m-, p-tolyl groups, xylyl groups and ethylphenyl groups; Aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.

The hydrocarbon radicals R, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ optionally contain an aliphatic double bond. Examples are alkenyl radicals, such as vinyl, allyl, 5-hexen-1-yl, E-4-hexen-1-yl, Z-4-hexen-1-yl, 2- (3-cyclohexenyl) ethyl and cyclododeca-4,8-dienyl. Preferred residues with an aliphatic double bond are the vinyl, allyl and 5-hexen-1-yl residues.

However, preferably contain at most 1% of the Hydrocarbon residues R a double bond.

The alkoxy radicals R are bonded via an oxygen atom alkyl radicals described above. The examples of Alkyl radicals also apply in full to the alkoxy radicals.

The alkylglycol radicals R preferably have the general formula (VI)

-R ⁷ - [O (CHR ⁸ ) _m ] _n OR ⁹ (VI),

on in the
R ^{7 has} the meanings of R ¹ ,
R ^{8 has} the meanings of R ² and
R ^{9 is} a radical R ⁸ or a group of the general formula -CO-R ¹⁰ , where R ^{10 is} a radical R ⁸ or OR ⁸ ,
m the meanings of d and
n is a value from 1 to 100, in particular from 1 to 10.

R is in particular a methyl, phenyl, C ₁ - to C ₃ - alkoxy or hydroxy radical or a radical of the general formula (VI).

R ² and R ^{3 are} preferably hydrogen atom or C ₁ - to C ₆ -alkyl radicals, in particular a hydrogen atom or a methyl radical.

R ⁴ , R ⁵ and R ⁶ are preferably hydrogen atoms or C ₁ - to C ₆ -alkyl radicals, in particular methyl or ethyl radicals, which can each have a hydroxyl group on one or more carbon atoms. Preferred examples of R ⁴ , R ⁵ and R ⁶ are -CH ₂ OH, -H, -CH ₃ , -CH = CH ₂ .

Examples of the divalent radicals R ¹ are saturated straight-chain or branched-chain or cyclic alkylene radicals, in particular C ₁ - to C ₈ -alkylene radicals such as the methylene and ethylene radical and propylene, butylene, pentylene, hexylene, 2-methylpropylene, Cyclohexylene and octadecylene radicals or unsaturated alkylene or arylene radicals such as the hexenylene radical and phenylene radicals, the n-propylene radical and the 2-methylpropylene radical being particularly preferred.

R ¹ is preferably a divalent C ₂ to C ₆ hydrocarbon radical.

In a preferred embodiment mean
R ¹ C ₁ to C ₈ alkylene radicals,
R ² and R ^{3 are} hydrogen atoms,
c the values 0, 1, 2, 3 or 4 and
d the values 0 or 1.

All siloxane compounds are suitable as aminosiloxane (A), the at least one unit of the general formula (III) contain. Aminosiloxane oils are preferred. The amine number [mmol N / g substance] of the aminosiloxane oils is preferably 0.05 to 3.0, in particular 0.05 to 2.0, particularly preferably 0.1 to 2.0.  

The viscosity of the amine oil (A) is preferably 5 to 50,000 mPa.s, in particular 10 to 10,000 mPa.s, particularly preferably 20 up to 5000 mPa.s.

The structure of the aminosiloxane (A) can be linear or branched his. The silicon atom bearing the functional group Q can at the chain end (M unit, a + b = 3), in the chain (D unit, a + b = 2), or as a branch point (T unit, a = 1) his.

The functional groups Q on the aminosiloxane (A) used can be partially neutralized, for example as acetate. This can, based on aminosiloxane (A), during the implementation Acetic acid in the molar ratio of primary amine: acetic acid = 1: 0 to 1: 2, preferably 10: 1 to 1: 1, particularly preferably 5: 1 to 2: 1 available.

The lactone (B) used is in particular the Aldonolactone, d. H. the lactones of the sugar acids belonging monocarboxylic acids by oxidation of the Aldehyde group of aldoses to the carboxy group are formed. Preferred aldonolactones are lactones of mono- and Disaccharides, especially the D-glucono-δ-lactone.

Any of the emulsifiers (C) for the production of Organopolysiloxane emulsions used emulsifiers especially those that differ from the lactone (B) behave inertly.

The following are particularly suitable as anionic emulsifiers:

• 1. Alkyl sulfates, especially those with a chain length of 8 up to 18 carbon atoms, alkyl and alkaryl ether sulfates with 8 to 18 carbon atoms Atoms in the hydrophobic residue and 1 to 40 ethylene oxide (EO) - or Propylene oxide (PO) units.
• 2. sulfonates, especially alkyl sulfonates with 8 to 18 carbon atoms, Alkylarylsulfonates with 8 to 18 carbon atoms, taurides, esters and Half ester of sulfosuccinic acid with monohydric alcohols or alkylphenols with 4 to 15 carbon atoms; if necessary these alcohols or alkylphenols also with 1 to 40 EO units be ethoxylated.
• 3. Alkali and ammonium salts of carboxylic acids with 8 to 20 C- Atoms in the alkyl, aryl, alkaryl or aralkyl radical.
• 4. partial phosphoric acid esters and their alkali and ammonium salts, especially alkyl and alkaryl phosphates with 8 to 20 carbon atoms in organic radical, alkyl ether or alkaryl ether phosphates with 8 up to 20 carbon atoms in the alkyl or alkaryl radical and 1 to 40 EO Units.

The following are particularly suitable as nonionic emulsifiers:

• 1. polyvinyl alcohol, which still contains 5 to 50%, preferably 8 to 20% Has vinyl acetate units with a degree of polymerization from 500 to 3000. Natural polymers such as carageen gum, Alginates, proteins or the like as stabilizers.
• 2. Alkyl polyglycol ethers, preferably those with 5 to 40 EO units and alkyl residues from 8 to 20 carbon atoms.  
• 3. alkylaryl polyglycol ethers, preferably those with 8 to 40 EO units and 8 to 20 carbon atoms in the alkyl and Aryl radicals.
• 4. ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those with 8 to 40 EO or PO units.
• 5. Addition products of alkylamines with alkyl radicals from 8 to 22 carbon atoms with ethylene oxide or propylene oxide.
• 6. Fatty acids with 6 to 24 carbon atoms.
• 7. Alkyl polyglycosides of the general formula R * -O-Zo, in which R * a linear or branched, saturated or unsaturated Alkyl radical with an average of 8-24 carbon atoms and Zo one Oligoglycoside residue with on average o = 1-10 hexose or Pentose units or mixtures thereof.
• 8. Natural products and their derivatives, such as lecithin, lanolin, Saponins, cellulose; Cellulose alkyl ether and Carboxyalkyl celluloses, the alkyl groups of which each have up to 4 Have carbon atoms.
• 9. linear organo (poly) siloxanes containing polar groups, in particular those with alkoxy groups with up to 24 carbon atoms and / or up to 40 EO and / or PO groups.

The following are particularly suitable as cationic emulsifiers:

• 1. Salts of primary, secondary and tertiary fatty amines with 8 to 24 carbon atoms with acetic acid, sulfuric acid,  Hydrochloric acid and phosphoric acids.
• 2. Quaternary alkyl and alkylbenzene ammonium salts, in particular those whose alkyl group has 6 to 24 carbon atoms have, especially the halides, sulfates, phosphates and Acetates.
• 3. Alkylpyridinium, alkylimidazolinium and Alkyloxazolinium salts, especially those whose alkyl chain has up to 18 carbon atoms, especially the halides, sulfates, Phosphates and acetates.

The following are particularly suitable as ampholytic emulsifiers:

• 1. Long-chain substituted amino acids, such as N-alkyl-di- (aminoethyl) glycine or N-alkyl-2-aminopropionic acid salts.
• 2. betaines, such as N- (3-acylamidopropyl) -N: N- dimethylammonium salts with a C8-C18 acyl radical and alkyl imidazolium betaines.

In addition to the emulsifiers (C), surfactants can be used become.

The following are particularly suitable as surfactants:

• A) nonionic surfactants, in particular
  • 1. Oxalkylates, ie reaction products of ethylene oxide and / or propylene oxide
    • a) linear and branched, primary and secondary alcohols with 12 to 18 carbon atoms,
    • b) alkylphenols whose alkyl chains have up to 14 C atoms;
    • c) fatty acids with up to 24 carbon atoms;
    • d) fatty acid ethanolamides, fatty acid glycerol esters and fatty amines, the alkyl group of which each has up to 24 carbon atoms;
  • 2. esters of fatty acids each having up to 24 carbon atoms with polyhydroxy compounds, in particular with glycerol, diglycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, mannitol and sucrose;
• B) cationic surfactants, in particular
  • 1. quaternary ammonium compounds in which the nitrogen atom of the ammonium group is bonded to alkyl, alkaryl, alkylene hydroxy, alkylene alkoxy and alkylene amino groups each having up to 24 carbon atoms;
  • 2. imidazolinium salts which carry alkyl, aralkyl and / or alkylene hydroxy groups with up to 24 carbon atoms on C and / or N atoms and whose anion is halide, sulfate, phosphate or acetate;
• C) anionic surfactants, in particular
  • 1. Carboxylates, especially alkali metal or ammonium salts of fatty acids with up to 24 carbon atoms, of their (poly) oxyalkylene esters, the alkyleneoxy units being ethyleneoxy and / or propyleneoxy units, their amides with sarcosinic acid and / or oligopeptides;
  • 2. sulfonates, especially alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkanesulfonates, olefinsulfonates, @ sulfofatty acid esters, alkyl sulfosuccinates, alkoxy-, acyloxy-acylaminoalkanesulfonates, the hydrocarbon chain of which each has up to 30 carbon atoms;
  • 3. sulfates, especially primary and secondary alkyl sulfates and salts of the sulfuric acid half-esters of alkyl or alkylaryl oligoglycol ethers, the alkyl chain of which each has up to 24 carbon atoms;
  • 4. phosphonates and phosphates, especially alkali and / or ammonium salts of these compounds, which have alkyl and / or alkaryl groups with up to 24 carbon atoms;
• D) amphoteric surfactants, in particular
  • 1. aminocarboxylic acids with up to 18 carbon atoms, especially the β-aminocarboxylic acids;
• E) surfactants with heteroatoms in the hydrophobic radical, in particular
  • 1. liquid, pasty or waxy block copolymers of propylene oxide and ethylene oxide, in particular those with molar masses of 1000 to 5000 g / mol;
  • 2. silicone surfactants, especially polymethylsiloxanes with ethyleneoxy, propyleneoxy, alkoxy and ammonium groups;
  • 3. Fluorosurfactants, in particular fluoroalkane carboxylic acids, such as perfluoroalkane carboxylic acids, fluoroalkane sulfonic acids, in particular perfluoroalkane carboxylic acids, the alkyl radical of the acids mentioned each having up to 24 carbon atoms.

In addition to emulsifiers (C) and optionally surfactants, known solubilizers, such as butyl diglycol become.

The proportion of emulsifiers (C), based on the sum Organopolysiloxane (A), lactone (B), emulsifier (C) and Water phase (D) is preferably up to 30 percent by mass, in particular 1-20%, particularly preferably 2-15%.

The content of the organopolysiloxane (A), based on the sum Organopolysiloxane (A), lactone (B), emulsifier (C) and water phase (D) is preferably 5-70%, especially 5-50%, especially preferably 10-40%.

The implementation of the organopolysiloxane (A) with lactone (B) takes place preferably by adding the lactone (B) to the aqueous Emulsion formulation of the organopolysiloxane (A) with increased Temperature instead. Temperatures of 40-90 ° C. are preferred, particularly preferably 50-80 ° C. In the implementation lies preferably an emulsion with an average particle size of <1 µm in diameter, preferably less than 500 nm, particularly preferably <200 nm before.

The emulsions (E) can be used for different purposes and Dispersion formulations common additives,  preferably contained in smaller amounts, such as. B. alcohols, Perfume oils, preservatives, thickeners, etc.

All of the above symbols of the above formulas have theirs Meanings each independently.

In the following examples, unless otherwise different indicated, all quantities and percentages by weight related, all pressures 0.10 MPa (abs.) and all temperatures 20 ° C.

Examples example 1

500 g of a 35% emulsion of an amino functional Polydimethylsiloxane (aminoethylaminopropyl functional, Amine oil viscosity 4000 mPa.s, amine number 0.14 mmolN / 100 g, 5% nonionic emulsifier) and 2.46 g of gluconolactone were added mixed thoroughly and stirred for 4 hours at 70 ° C. The Amine number of the product is 0.052, which is a conversion of 100% corresponds to primary amino groups.

Example 2

By adding nonionic emulsifier and acetic acid made of amino-functional polydimethylsiloxane (Aminoethylaminopropyl functional, amine oil viscosity 1000 mPa.s, Amine number 0.3 mmolN / 100 g) according to that in EP-A-442 098 described process in a first step a concentrate manufactured, which in a second step with water in transferred a microemulsion with a silicone content of 16% has been.

500 g of the microemulsion were mixed with 4.33 g of gluconolactone at 70 ° C Implemented 3 hours. The amine number of the product became 0.023  determines what sales based on primary amino groups corresponds to 96%.

Example 3

By adding nonionic emulsifier and acetic acid made of amino-functional polydimethylsiloxane (Aminoethylaminopropyl functional, amine oil viscosity 400 mPa.s, Amine number 0.65 mmolN / 100 g) according to that in EP-A-442 098 described process in a first step a concentrate manufactured, which in a second step with water in transferred a microemulsion with a silicone content of 16% has been.

300 g of the microemulsion were mixed with 5.35 g of gluconolactone at 60 ° C Implemented 4 hours. The amine number of the product became 0.052 determines what sales based on primary amino groups corresponds to 96%.

Claims (7)

1. A process for the preparation of (E) emulsions of hydroxamic acid-functional organopolysiloxane which comprises at least one unit of the general formula (I)
T _a R _b SiO _{4-ab / 2} (I),
has in which
T is a group of the general formula (II)
-R ¹ - [NR ² (CH ₂ ) _c ] _d NR ³ -CO- (CR ⁴ ₂ ) _e - (CR ⁵ OH) _f -CR ⁶ ₂ OH (II),
means
in which an (A) organopolysiloxane which has at least one unit of the general formula (III)
Q _a R _b SiO _{4-ab / 2} (III),
has in which
Q is a group of the general formula (IV)
-R ¹ - [NR ² (CH ₂ ) _c ] _d NR ³ -H (IV),
means with a (B) lactone of the general formula (V)
is reacted in the presence of (C) emulsifier and (D) a water phase, wherein
R are identical or different, monovalent, optionally fluorine, chlorine or bromine substituted C ₁ to C ₁₈ hydrocarbon radicals, hydrogen atoms, C ₁ to C ₁₂ alkoxy, hydroxy or alkyl glycol radicals,
R ^{1 is} a divalent C ₁ to C ₁₈ hydrocarbon radical,
R ² and R ^{3 represent} a hydrogen atom or an optionally fluorine, chlorine or bromine substituted C ₁ to C ₁₈ hydrocarbon radical,
R ⁴ , R ⁵ and R ^{6 represent} a hydrogen atom or an optionally hydroxy, fluorine, chlorine or bromine substituted C ₁ to C ₁₈ hydrocarbon radical,
a the values 1, 2 or 3,
b the values 0, 1 or 2,
c the values 0, 1, 2 or 3, 4, 5 or 6,
d the values 0, 1, 2, 3 or 4,
e the values 0, 1, 2, 3 or 4 and
f is 1, 2, 3, 4, 5 or 6. 2. The method according to claim 1, in which R ^{1 is} C ₁ to C ₈ alkylene radicals, R ² and R ^{3 are} hydrogen atoms, c is 0, 1, 2, 3 or 4 and d is 0 or 1. 3. The method according to claim 1 or 2, in which as aminosiloxane (A) Aminosiloxane oils with an amine number from 0.05 to 3.0 [mmolN / g substance] can be used. 4. The method according to claim 3, wherein the viscosity of the Amine oil (A) is preferably 5 to 50,000 mPa.s. 5. The method according to claim 1 to 4, in which as the lactone (B) Aldonolactones are used.   6. The method according to claim 1 to 5, wherein the content of Organopolysiloxane (A), based on the sum Organopolysiloxane (A), lactone (B), emulsifier (C) and Water phase (D) is 5-70%. 7. The method according to claim 1 to 6, wherein the temperature 40- Is 90 ° C.