KR100887267B1 - Method for the discontinuous production of silicone emulsions - Google Patents

Abstract

The present invention relates to a discontinuous process for producing an aqueous emulsion (E) comprising an organosilicon compound (A), an emulsifier (B) and water. According to the invention, a high viscosity preemulsion (V) is prepared by shearing from an organosilicon compound (A), an emulsifier (B) and water, which is further diluted with water. The method of the present invention is characterized in that pressure and temperature can be adjusted.

Description

Discontinuous manufacturing method of silicone emulsion {METHOD FOR THE DISCONTINUOUS PRODUCTION OF SILICONE EMULSIONS}

The present invention relates to a batch production process of an aqueous emulsion comprising an organosilicon compound, an emulsifier and water.

Silicone emulsions are commercially available as milky macroemulsions in the form of water-in-oil (w / o) or oil-in-water (o / w) emulsions and are opaque to clear microemulsions. These are one or more water-insoluble silanes, silicone oils, silicone resins or silicone elastomers or mixtures thereof, mixtures of one or more emulsifiers and water. For the preparation of emulsions, these components are mixed with one another and, for example, narrow gaps such as rotor-stator systems, colloid mills, microchannels, membranes, high pressure homogenizers, jet nozzles, or the like. Dispersion is carried out using high and low temperature mechanical shears that can be generated by ultrasound. Homogenizers and methods are described, for example, in the keyword "emulsion" in Ullmann's Encyclopedia of Industrial Chemistry, CD-ROM edition 2003, Wiley-VCH Verlag.

The silicone component of the emulsion can be prepared in an upstream reaction outside the emulsification unit and then dispersed in the emulsification unit. Alternatively, the silicone component of the emulsion can be prepared in the emulsification unit itself (field preparation). The property of in situ preparation is that the chemical reaction takes place immediately before, during or immediately after the preparation of the emulsion.

All reactions customary in silicone chemistry, particularly those which lead to an increase in molecular weight, can be used for in situ preparation or polymerization of the silicone component, for example chain extension or equilibrium, polymerization, condensation or polyaddition.

Emulsion polymerization of polysiloxanes having terminal OH groups using acidic catalysts, for example acidic surfactants, is described in US Pat. No. 6,140,414, US Pat. No. 5,726,270 or US Pat. In US Pat. No. 5,504,150, phosphazene is used as an acidic catalyst. Base catalyzed emulsion polymerization of cyclic polysiloxanes or polysiloxanes having terminal OH groups is described, for example, in US Pat. No. 6,201,063.

The polyaddition or hydrosilylation reactions in emulsions are described, for example, in DE '198' 56 '075, US' 6 '057' 386, EP '1' 135 '429 or EP' 780 '422.

Polymerization reactions of emulsions inducing branched liquid polysiloxanes are described, for example, in DE # 199 60x291, and reactions inducing branched elastomeric polysiloxanes are described, for example, in WO # 00/34359.

In the preparation of silicone emulsions using shearing, for example, the silicone or silicone mixture is first mixed with one or more emulsifiers and a small amount of water and then exposed to high shear forces, for example in a rotor-stator mixer with narrow line. W / o emulsions with very high viscosity are formed in a so-called "stiff phase". The viscosity of these steels depends heavily on the shear. This phase is then slowly diluted with water to the turning point. At the turning point, the w / o emulsion becomes an o / w emulsion. Formation of the steel phase and dilution with water to the desired final concentration of the emulsion determines the quality of the emulsion. The quality of an emulsion means, in particular, particle size, particle size distribution, storage safety, and resistance of the emulsion to heating and / or cooling, vibration, pH changes, changes in salt content, and the like.

The preparation of the abovementioned silicone emulsions using shearing can be carried out batchwise or continuously. Batch preparation is described, for example, in EP 579 # 458A.

The present invention relates to a batch production method of an aqueous emulsion (E) comprising an organosilicon compound (A), an emulsifier (B) and water, wherein a high viscosity preemulsion (V) is prepared from an organosilicon compound (A), an emulsifier (B). ) And water, the preemulsion (V) is diluted with additional water and the pressure and temperature are adjusted during the manufacturing process.

The adjustment of pressure and temperature in the individual process steps, in particular in the preparation of the preemulsion (V), is crucial to the quality of the emulsion (E) and can be substantially improved by controlling the quality of the prepared emulsion (E). This control leads to a clearer product with smaller particle size in the case of microemulsions. In the case of macroemulsions, substantially smaller particle sizes and improved storage and dilution stability are achieved. Using temperature control, the particle size can be controlled. This effect is maintained by pressure regulation.

The method is described in the embodiment with reference to FIG. 1. An emulsifier (B) and some water are introduced into the container 1 and mixed. For mixing, the vessel 1 preferably comprises at least one stirrer. When a shear mixer 4, for example a rotor-stator homogenizer, and a positive transport pump 5, which can be, for example, a gear pump, a rotary piston pump or a rotary shaft pump, are operated, the emulsifier / water mixture (EW) Circulates, circulates through the pipe 8 and flows back to the vessel. The organosilicon compound (A) is metered into the vessel 1 via a pipe 2 or 3. Preferably, the organosilicon compound (A) is introduced slowly through the pipe (3) directly into the shear mixer (4) where it is mixed with the emulsifier / water mixture (EW), the mixture being passed through the pipe (8) to the vessel (1). Is recycled to). During this process, high viscosity preemulsions (V) are prepared. Dilution of the preemulsion (V) is carried out with the addition of additional water to the shear and shear mixers 4. The addition of water is preferably carried out through the pipe 3 and the mixture is circulated constantly through the pipe 8 by pumping. Additive (Z) can be added via pipe (2) or (3), emulsion (E) can be adjusted to the desired final concentration and removed through pipe (6). It is also possible for the emulsion (E) to be diluted during removal through the pipe (6), for example using an inline mixer or in a downstream mixing tank, before filling the final product into a transport or sales container.

It is particularly advantageous to use an additional pump 5 installed behind the shear mixer 4 in the flow direction in order to adjust the circulation rate of the mixture and the pressure before and after the pump 5 and in the desired range. Since the preemulsion (V) is exposed to shear for a longer time at a lower circulation rate in the shear mixer (4), energy is thus injected for a longer time, and the temperature of the preemulsion (V) becomes higher at a lower circulation rate. Through the interaction of circulation rate, pressure control and temperature, the droplet size and droplet size distribution of the preemulsion (V) and emulsion (E) can be efficiently controlled. This is very advantageous in the quality of the emulsion, since the fine splitting properties and the narrow distribution of droplet sizes lead to an increase in the stability of the emulsion (E).

The pressure in the range from 0.5 to 10 barbar and the temperature control at 5 to 120 ° C. can be carried out, for example, via the circulation speed of the pump 5 and can be determined at the measuring point 7. Preference is given to a pressure of 1.0 to 8 bar and a temperature of 8 to 100 ° C. Particular preference is given to pressures of 1.5 to 6 kPa and temperatures of 10 to 80 ° C.

Depending on the preemulsion (V) and its viscosity, the pressure and temperature values before and after the pump (5) are different. Usually, when the viscosity of the preemulsion (V) increases, the pressure and temperature also increase.

During the whole process, the total pressure of the system in the apparatus is preferably between 0 and 6 Pabar absolute pressure, preferably between 0.05 and 2 Pabar and in particular between 0.1 and 1.5 Pabar.

In one preferred embodiment,

In the first step, the emulsifier (B) is mixed with water to obtain an emulsifier / water mixture (EW),

In the second step, organosilicon compound (A) is added to the emulsifier / water mixture (EW) and a high viscosity preemulsion (V) is prepared by shearing.

Then, in the third step, the preemulsion (V) is diluted with water.

In the process of preparing the preemulsion (V), in particular in the first step, preferably up to 50%, particularly preferably up to 25%, in particular up to 10% of the total amount of water injected into the emulsion (E) is used. The viscosity of the preemulsion (V) at 25 ° C. is preferably from 40 kPa to 5 kPa 000 mPa · s, in particular from 50 kPa to 1 k000 kPa mPa · s.

In the second step, optionally one or more organosilicon compounds or mixtures thereof are added as organosilicon compounds (A) and energy is introduced, in particular by shear, to break up the droplets. Shearing in the second step is carried out using a shear mixer, for example a rotor-stator homogenizer. If necessary, the added organosilicon compounds (A) can be reacted with each other or with additional substances. For this purpose, all conventional reactions in silicone chemistry, in particular reactions which lead to an increase in molecular weight, can be used, for example chain extension or equilibrium, polymerization, condensation or polyaddition. On-site preparation using this process, in particular emulsions of high molecular weight liquid, elastomeric, gel-like or solid organosilicon compounds (A) is obtainable.

In this process, the pressure is preferably controlled by the speed of the shear mixer and the circulation speed of the pump. Temperature control is preferably carried out using the temperature of the raw material, the speed of the shear mixer and the circulation rate of the pump.

The addition of the emulsion components to the emulsified container is preferably carried out directly in the region where the high shear occurs using a shear mixer.

In the third step, first, water is added very slowly to the high viscosity preemulsion (V), for example from 0.004% / sec to 0.1% / sec, in particular from 0.008% / sec to 0.05% / sec, relative to the total amount of the final emulsion. At a rate, for example at 0.015% / sec, preferably using shear. If water is well received by the emulsion, the rate of addition is further increased.

In or after the third step, other additives (Z), such as emulsifiers, thickeners, biocides and water-soluble or dispersible silicones, polysiloxanes or silanes and pH or acid or alkalis for pH adjustment, may also be mixed so that the solids content reaches the desired value. Adjusted.

Preferably, water and emulsifier (B) are first introduced into an emulsifying container, for example a mixing vessel. Complete mixing is preferably carried out using a conventional mixing tool, in particular a wall-channeling stirrer, or by circulating the contents of the emulsified container by pumping.

The emulsion (E) preferably has an organosilicon compound (A) content of at least 1% by weight to 99% by weight, particularly preferably 1 to 75% by weight, in particular 9 to 80% by weight. The average particle size measured by the photoacid is in the range of 0.001 to 100 μm, preferably 0.002 to 1 μm. The pH may vary from 1 to 14, preferably 2 to 10, particularly preferably 3 to 9.

All silicones, siloxanes, polysiloxanes or silanes and mixtures, solutions or dispersions thereof can be used as organosilicon compounds (A) in the process. Examples of (A) include linear organopolysiloxanes and silicone resins. By silicone resin is meant a product comprising mono- and di-functional silicon units as well as tri- and tetra-functional silicon units.

The organosilicon compound (A) is preferably a liquid at 25 ° C., and preferably has a viscosity of 0.5 to 100 μm 000 mPa · s, preferably 0.5 to 500 μm mPa · s, in particular 2 to 80 μm mPa · s. Have

The organosilicon compound (A) is reacted in the process to give another organosilicon compound (A) (field preparation). The organosilicon compound (A) thus prepared may be liquid, elastomer or solid at 25 ° C.

Examples of organosilicon compounds are organosilicon compounds comprising units of formula (I):

A _a R _b SiX _c O _{[4- (a + b + c)] / 2} (I)

In the formula,

R is a hydrogen atom, or a monovalent, divalent or trivalent hydrocarbon radical having 1 to 200 carbon atoms, which is halogen, amine, amide, ammonium, mercapto, acrylate, urethane, urea, carboxy or malein It is a mid group,

X is a chlorine atom, the formula -O ^- is a radical (wherein the proton and / or organic or inorganic ionic substances may be present in order to make up an electric charge), the formula -OR ¹ or a radical of the formula II of:

-(R ² ) _h- [OCH ₂ CH ₂ ] _e [OC ₃ H ₆ ] _f [OC ₄ H ₈ ) ₄ ] _g OR ³ (II)

In the formula,

R ¹ is a hydrogen atom or a hydrocarbon radical having 1 to 200 carbon atoms, which may be interrupted by one or more identical or different heteroatoms selected from O, S, N and P,

R ² is a divalent hydrocarbon radical having 1 to 200 carbon atoms, which are of the formula —C (O) —, —C (O) O—, —C (O) NR ¹ , —NR ^{1 —} , —N ⁺ May be interrupted by one or more groups of HR ^1- , -O-, -S- and / or substituted by F, Cl or Br,

R ³ means R ¹ , or A radical of the formula -C (O) R ¹ or -Si (R ¹ ) ₃ ,

A is a radical of formula IV:

R ⁴ (B) _z (IV)

In the formula,

R ⁴ is a divalent, trivalent or tetravalent hydrocarbon radical having 1 to 200 carbon atoms, which are of the formula —C (O) —, —C (O) O—, —C (O) NR ⁵ , —NR ^5- , -N ⁺ HR ^5- , -N ⁺ R ⁵ R ^5- , -O-, -S-,-(HO) P (O)-or-(NaO) P (O)- May be interrupted and / or substituted with F, Cl or Br,

Wherein R ⁵ is a hydrogen atom or a hydrocarbon radical having 1 to 200 carbon atoms per radical, which are of the formula —C (O) —, —C (O) O—, —C (O) NR ⁵ —, — NR ^5- , -N ⁺ HR ^5- , -N ⁺ R ⁵ R ^5- , -O- or -S- may be interrupted and / or substituted with F, Cl or Br,

B stands for R ^5, or _{^{-COO -, -SO 3 -, -OPO}} 3 H y (2-y) -, -N + R 5 R 5 R 5, -P + R 5 R 5 R 5, - NR ⁵ R ⁵ , -OH, -SH, F, Cl, Br, -C (O) H, -COOH, -SO ₃ H, -C ₆ H ₄ -OH and -C _m F _{2m +1} ,

Is a radical selected from

Where x is an integer from 1-20,

y is 0 or 1,

z is 1, 2 or 3, depending on the valence of R ⁴ ,

h is 0 or 1,

m is an integer from 1-20,

a, b and c each have a value of 0, 1, 2, 3 or 4 and the sum of a + b + c is 4 or less,

e, f and g are each an integer of 0-200, except that the sum of e + f + g > 1.

In the case of silane, the value of a + b + c in formula (I) is 4 and in the case of siloxane, the units of formula (I) have an average (a + b + c) value of 0 to 3.99.

Preferred polyorganosiloxanes are those consisting of 10 to 50 000 000, preferably 20 to 20 000 000, particularly preferably 50 to 10 000 000 units of formula (I).

To supplement the charges of the radicals A, R and X , protons and / or organic or inorganic ionic substances, for example alkali metals, alkaline earth metals or ammonium ions, halides, sulfates, phosphates, carboxylates, sulfos Nate or phosphonate ions may optionally be present. In addition, the organosilicon compounds may optionally comprise units of the formulas (V) and (VI):

In the formula,

A ² is a trivalent hydrocarbon radical having 1 to 200 carbon atoms, which are of the formula —C (O) —, —C (O) O—, —C (O) NR ⁵ , —NR ⁵ —, —N ^{+ May} be interrupted by a radical of HR ^5- , -N ⁺ R ⁵ R ^5- , -O-, -S-, -N- or -N ⁺ R ⁵ -and / or substituted with F, Cl or Br and ,

A ¹ is a divalent radical R ² ,

i and k have values of 0, 1, 2 or 3, respectively, provided that i + k ≤ 3

R and X are as mentioned above.

The aforementioned hydrocarbon radicals R, R ¹ , R ² , R ³ , R ⁴ , R ^{5 ,} A ¹ and A ² are It may be saturated, unsaturated, linear, cyclic, aromatic or non-aromatic.

Examples of hydrocarbon radicals R include alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl or tert Pentyl radicals; Hexyl radicals such as the n-hexyl radical; Heptyl radicals such as the n-heptyl radical; Octyl radicals such as the n-octyl radical, and isooctyl radicals such as the 2,2,4-tri-methyl-pentyl 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; Octadecyl radicals such as the n-octadecyl radical; Cycloalkyl radicals such as cyclopentyl, cyclohexyl or cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals such as the phenyl, naphthyl, anthryl and phenanthryl radicals; Alkali radicals such as o-, m-, p-tolyl radicals; Xylyl radicals and ethylphenyl radicals; And aralkyl radicals such as benzyl radicals and α- and β-phenyl radicals. Hydrogen atoms or methyl, ethyl, octyl and phenyl radicals are preferred, and hydrogen atoms or methyl and ethyl radicals are particularly preferred.

Examples of halogenated radicals R include haloalkyl radicals such as 3,3,3-trifluoro-n-propyl radicals, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radicals, heptafluoro Isopropyl radicals, and haloaryl radicals such as o-, m- and p-chlorophenyl radicals.

As an example of the radical R ¹ There are examples mentioned for the alkyl radicals R and the methoxyethyl and ethoxyethyl radicals, the radicals R ¹ being preferably alkyl radicals having from 1 to 50 carbon atoms, which are oxygen atoms, particularly preferably methyl and It may be interrupted by ethyl radicals.

Organic or inorganic materials for replenishing charge for X = -O ^- include alkali metal and alkaline earth metal ions, ammonium and phosphonium ions and monovalent, divalent or trivalent metal ions, preferably alkali metal ions, in particular Preferably there are Na ⁺ and K ⁺ .

Examples of radicals X include methoxy or ethoxy radicals and radicals of formula (II), such as

There is.

Examples of radicals R ² are preferably linear or branched, substituted or unsubstituted hydrocarbon radicals having 2 to 10 carbon atoms, wherein saturated or unsaturated alkylene radicals are preferred, with ethylene or propylene radicals being particularly preferred.

Examples of radicals R ³ include those mentioned for alkyl radicals or aryl radicals R , and radicals of the formula —C (O) R ¹ or —Si (R ¹ ) ₃ , methyl, ethyl, propyl and butyl, trialkylsilyl And -C (O) -alkyl radicals are preferred, with methyl, butyl, -C (O) -CH ₃ trimethylsilyl radicals being particularly preferred.

Examples of R ⁴ are radicals of the formula:

Preferred radicals R ⁴ are those of the formula

A _{(CH 2) 3 -NH- (CH} 2) 2 - R 4 are particularly preferably - (CH _{2) 3} - and.

Examples of R ⁵ are the alkyl and aryl radicals mentioned above in the case of R and radicals of the formula:

Examples mentioned for the hydrogen atom and R are preferred, with hydrogen atoms and alkyl radicals being particularly preferred.

Examples of the radical _{B -COONa, -SO 3 Na, -COOH} , -SH and in particular _{-OH, -NH 2, -NH-CH} 3, -NH- (C 6 H 11) and -N- (CH _{2 -} CH = CH ₂ ) ₂ , -NH ₂ , -NH-CH ₃ and -NH- (C ₆ H ₁₁ ) are particularly preferred.

Examples of A ¹ are linear or branched, preferably divalent alkyl radicals having 2 to 20 carbon atoms, or radicals of the formula:

An example of A ² is N [(CH ₂ ) _3- ] ₃ .

Organosilicon compounds (A) may also be formed from the crude product during the process.

Preferred examples of the organosilicon compound (A) are linear trimethylsilyl- or hydroxydimethylsilyl-terminated polydimethylsiloxanes such as, for example,

96.5 mol% of _{(CH 3) 2 SiO 2/} 2 , and 3.5 mol% of _{(CH 3) 3 SiO 1/} 2 , or

96.5 mol% of _{(CH 3) 2 SiO 2/} 2 , and 3.5 mol% of (CH _{3) 2} (OH) containing SiO _1/2,

Oil having a viscosity of 50 μmPa · s;

98 mol% of (CH _{3) 2} SiO _2/2, and _{2 mol% (CH 3) 3} SiO 1/2 , or

98 mol% of _{(CH 3) 2 SiO 2/} 2 , and 2 mol% of (CH _{3) 2} (OH) containing SiO _1/2,

Oil having a viscosity of 100 μmPa · s;

99.2 mol% of _{(CH 3) 2 SiO 2/} 2 , and 0.8 mol% of _{(CH 3) 3 SiO 1/} 2 , or

99.2 mol% of _{(CH 3) 2 SiO 2/} 2 , and 0.8 mol% of (CH _{3) 2} (OH) containing SiO _1/2,

Oil having a viscosity of 1000 mPa · s;

99.63 mol% of _{(CH 3) 2 SiO 2/} 2 and 0.37 mol% of _{(CH 3) 3 SiO 1/} 2 , or

99.63 mol% of _{(CH 3) 2 SiO 2/} 2 and 0.37 mol% of (CH _{3) 2} (OH) containing SiO _1/2,

Oil having a viscosity of 12 500 μmPa · s;

99.81 mol% of _{(CH 3) 2 SiO 2/} 2 and 0.19 mol% of _{(CH 3) 3 SiO 1/} 2 , or

99.81 mol% of _{(CH 3) 2 SiO 2/} 2 and 0.19 mol% of (CH _{3) 2} (OH) containing SiO _1/2,

Oils having a viscosity of 100 000 mPa · s;

Examples of further preferred linear organosilicon compounds (A) include further terminal chemical groups, i.e. alkyl, alkenyl, aryl, amine, amide, ammonium, urethane, urea, carboxy, glycol, ether, ester, mercapto, fluorine in the chain Linear trimethylsilyl- or hydroxydimethylsilyl-terminated polydimethylsiloxanes which may include chemical groups such as furnaces or SiH functional groups.

Resin-like organosilicon compound (A), for example, the general formula _{CH 3 Si (OC 2 H 5} ) 0.8 (O) ethoxy resin in methyl with _1.1, for example, 80 mol% of CH ₃ SiO _3/2, and 20 the _{mol% (CH 3) 2 SiO} 2/2 including and of those having a molar mass of about 5000 g / mol, or _{98 mol% CH 3 SiO 3/} 2 , and 2 mol% of (CH _{3) 2} SiO _{2 And / 2} and having a molar mass of about 5000 g / mol.

When the organosilicon compound (A) itself acts as an emulsifier, the organosilicon compound (A) and the emulsifier (B) may be the same. It is then also possible to add separate emulsifiers (B).

Component (B) of the emulsion is preferably commercially available and currently studied emulsifiers such as, for example, sorbitan esters of fatty acids having 10 to 22 carbon atoms; Polyoxyethylene sorbitan esters of fatty acids having 10 to 22 carbon atoms and an ethylene oxide content of up to 35%; Polyoxyethylene sorbitol esters of fatty acids having 10 to 22 carbon atoms; Polyoxyethylene derivatives of phenols having 6 to 20 carbon atoms and up to 95% ethylene oxide content in the aromatic phase; Fatty amino- and amidobetaines having 10 to 22 carbon atoms; Polyoxyethylene condensates of fatty acids or fatty alcohols having 8 to 22 carbon atoms having an ethylene oxide content of up to 95%; Ionic emulsifiers such as alkylaryl sulfonates having 6 to 20 carbon atoms in the alkyl group; Fatty acid soaps having 8 to 22 carbon atoms; Fatty sulfates having 8 to 22 carbon atoms; Alkyl sulfonates having 10 to 22 carbon atoms; Alkali metal salts of dialkylsulfosuccinates; Fatty amine oxides having 10 to 22 carbon atoms; Fatty imidazolines having 6 to 20 carbon atoms; Fatty amidosulfobetaines having 10 to 22 carbon atoms; Quaternized emulsifiers such as fatty ammonium compounds having 10 to 22 carbon atoms; Fatty morpholine oxides having 10 to 22 carbon atoms; Alkali metal salts of carboxylated, ethoxylated alcohols having from 10 to 22 carbon atoms and up to 95% ethylene oxide; Ethylene oxide condensates of fatty acid monoesters having from 10 to 22 carbon atoms and up to 95% ethylene oxide; Mono- or diethanolamides of fatty acids having 10 to 22 carbon atoms; Phosphate esters; Organosilicon compounds (A) having units of formula (I) wherein X is a radical of formula (II) and c is at least 1).

As is well known in the field of emulsifiers, in the case of anionic emulsifiers the counter ions can be alkali metals, ammonia or substituted amines such as trimethylamine or triethanolamine. Usually, ammonium, sodium and potassium ions are preferred. In the case of cationic emulsifiers, the counter ions are halides, sulfates or methylsulfates. Chloride is the most industrially available compound.

The fatty structures mentioned above usually have half the lipid affinity of the emulsifier. Typical fatty groups are alkyl groups of natural or synthetic origin. Known unsaturated groups include oleyl, linoleyl, decenyl, hexadecenyl and dodecenyl radicals. Alkyl groups may be cyclic, linear or branched. Other possible emulsifiers include sorbitol monolaurate / ethylene oxide condensates; Sorbitol monomyristate / ethylene oxide condensates; Sorbitol monostearate / ethylene oxide condensates; Dodecylphenol / ethylene oxide condensates; Myristylphenol / ethylene oxide condensates; Octyl-phenyl / ethylene oxide condensates; Stearyl-phenol / ethylene oxide condensates; Lauryl alcohol / ethylene oxide condensates; Stearyl alcohol / ethylene oxide condensates; Decylaminobetaine; Coco-amidosulfobetaine; Oleamidobetaine; Coco-imidazoline; Cocosulfoimidazoline; Cetylimidazoline; 1-hydroxy-ethyl-2-heptadecenylimidazoline; n-coco-morpholine oxide; Decyldimethylamine oxide; Coco-amidodimethylamine oxide; Sorbitan tristearate with condensed ethylene oxide groups; Sorbitan trioleate with condensed ethylene oxide groups; Sodium or potassium dodecyl sulfate; Sodium or potassium stearyl sulfate; Sodium or potassium dodecylbenzenesulfonate; Sodium or potassium stearylsulfonate; Triethanolamine salt of dodecyl sulfate; Trimethyldodecylammonium chloride; Trimethylstearylammonium methosulfate; Sodium laurate; Sodium or potassium myristate.

It is also known that it is also possible to use an inorganic solid as the emulsifier (B). For example, as described in EP # 1017745XA or DE # 19742759XA, there is silica or bentonite.

Nonionic emulsifiers are preferred. Component (B) may consist of the emulsifier mentioned above or a mixture of two or more of the aforementioned emulsifiers and may be used in pure form or as a solution of one or more emulsifiers in water or an organic solvent.

The emulsifier (B) is used in each case in an amount of preferably 0.1 to 60% by weight, particularly preferably 1 to 30% by weight, based on the total weight of the organosilicon compound (A).

Examples of the silane include vinyl tris (methoxyethoxy) silane, tetraethoxysilane, anhydrous tetraethoxysilane, methyltriethoxysilane, anhydrous methyl-triethoxy-silane, aminoethylaminopropyltrimethoxysilane, Amino-ethylaminopropyl (methyl) dimethoxysilane.

All the above formulas have the meanings in each case independently of one another. In all formulas, the silicon atom is tetravalent.

In the examples below, all amounts and percentage data are based on weight unless otherwise noted, all temperatures are 20 ° C. and all pressures are 1.013 Pa (absolute pressure). All viscosities were measured at 25 ° C.

Example 1a (invention): aminofunctionality Polysiloxane  Clear Emulsion  Produce

8 EO on average (Arylpon 1.60% isotridecyl alcohol ethoxylate with IT 8), on average 5 EO (Lutensol 4.14% isotridecyl alcohol ethoxylate with TO 5), 0.2% acetic acid (80% concentration) and 3.93% demineralized water (temperature 12 ° C., temperature adjusted to +/- 2 K) are first injected into the vessel It was. The temperature of the mixing vessel was kept constant at 40 ° C., the homogenizer at 2000 rpm, and the stirrer and circulation pump were operated. Thereafter, 16.25% of the aminofunctional silicone oil (Wacker Finish WR 1300) was fed through pipe 3 at a rate of 1% / min relative to the final amount of emulsion at a temperature of 20 ° C. A thick phase formed. The pressure in the circulation pipe was about 4 bar and the temperature was 45 ° C. Then 70.5% demineralized water (12 ° C.) was metered starting at 0.02% / sec relative to the final amount of emulsion. Finally, 0.08% preservative (Kathon LXE) and 3.5% glycerol were weighed.

This produced a clear silicone emulsion having a particle size of 20 μs nm and a haze of 10 μm ppm. The emulsion remained stable for several months at a storage temperature of 50 ° C.

Comparative example 1 b (different from the present invention):

If a similar process condition as mentioned under Example 1 is chosen but the aminofunctional silicone oil is metered at room temperature (20 ° C.) and the mixer is not kept at constant temperature, it will result in a substantial temperature drop to about 30 ° C., but The pressure does not substantially change because no steel phase with high viscosity is formed, as in 1. The product produced had a substantially larger particle size of 42 nm and a haze of 23 ppm. Upon storage at 50 ° C., phase separation was observed after 3 weeks.

Example 2a (invention): polyvinyl With alcohol  Stabilized silicone resin Emulsion  Produce

A 35.3% polyvinyl alcohol solution (10% concentration) (25 ° C., temperature kept constant at +/− 2 K) was first injected into the container. Operation of the stirrer and circulation pump was started and the homogenizer was set to 2000 rpm. Container temperature was adjusted to 15 ° C. Then 48.4% of a mixture of silicone resin (80 mol% T units, 20 mol% D units, 20 ° C.) and OH-terminated polydimethylsiloxane with a viscosity of 30 mPa · s was added to the final amount of the emulsion. Feed through pipe 3 at an addition rate of 1% / min. The pressure in the circulation pipe was 2 bar and the temperature was below 37 ° C. 16.06% of demineralized water (12 ° C.) is then added, starting at 0.02% / sec relative to the final amount of emulsion, and 0.24% of preservative (Rocima). 523) was added to homogenize the mixture for 5 minutes. Using certain process parameters, an emulsion with one year of storage stability without phase separation at room temperature was prepared.

Comparative example 2b (different from the present invention)

If the process parameters of Example 2 are not changed differently, the temperature of the polyvinyl alcohol solution according to the invention is not increased to 50 ° C. without monitoring otherwise, and the container is not cooled, the temperature in the circulation pipe is up to about 45 ° C. Rose. The product obtained showed substantial deposition of the silicone resin after only two weeks of storage at room temperature.

Example  3a (invention): In emulsion Hydrosilylation

1.7% of water (12 ° C.) and 3.2% of isotridecyl alcohol ethoxylate of General Formula C ₁₃ H ₂₇ O (C ₂ H ₄ O) ₁₀ H were injected into the container. The stirrer and circulation pump were operated and the homogenizer was set to 2000 rpm. Container temperature was adjusted to 15 ° C. 45% of a mixture of trivinylcyclohexane and HMe ₂ Si- (OSiMe ₂ ) _x -H (the molar ratio of C = C to SiH is 1.75) was metered through pipe (3) for 30 minutes at a temperature of 13 ° C. The components were mixed until a very high viscosity phase was formed. For very high viscosity phases the circulation rate was set high using pump 5, the temperature at measuring point 7 was set at 29 ° C. and the pressure in the circulation pipe at 2.7 bar.

Thereafter, 10 kppm of platinum (platinum-1,3-divinyl-1,1,3,3-tetra-methyl-disiloxane complex according to US 3,775,452) in the form of a Karstedt catalyst solution having a Pt content of 1.1% by weight was hydrotreated. Add as a reaction catalyst for the silylation reaction and immediately dilute the high viscosity phase with 50.1% distilled water, which is then metered through pipe (3) starting at an addition rate of 0.01% / sec relative to the final amount of emulsion, A milky white emulsion was obtained. The resulting homogeneous emulsion has an average particle size of 202 nm nm and a storage stability of 9 months or more.

The silicone polymer isolated from the emulsion by acetone addition had a viscosity of 14 Pa 550 mPa · s at 25 ° C.

Comparative example  3b (different from the present invention):

The experiment was carried out as described in Example 3a, but the emulsion raw material was weighed at 25 ° C. Emulsification was carried out without the pump (5). The temperature at measuring point 7 was 17 ° C. higher than at 3a. The resulting emulsion was heterogeneous and had coarse, rubber-like particles that accumulate at the top during the day. Thus the emulsion did not have sufficient storage stability. The particle size was 274 nm. The particle size distribution was maximum.

Effects of the Invention

As described above, by using the discontinuous manufacturing method of the emulsion of the present invention, it is possible to obtain a clear emulsion with improved quality, in particular because of the pressure and temperature can be controlled in the preparation of the pre-emulsion, in particular having an excellent storage stability Emulsions can be obtained.

Claims (8)

A batch production method of an aqueous emulsion (E) comprising an organosilicon compound (A), an emulsifier (B) and water, the viscosity of which is 40 000 to 5 at 25 ° C. from the organosilicon compound (A), the emulsifier (B) and water After preparing a preemulsion (V) of 000 mW 000 mPa · s, the preemulsion (V) was diluted with additional water, and the pressure was in the range of 0.5 bar to 10 bar, and the temperature was 5 ° C. to 80 ° C. during the production process. Aqueous emulsion, wherein the pressure is controlled through the speed of the shear mixer and the circulation rate of the pump, and the temperature is controlled through the temperature of the raw material, the speed of the shear mixer and the circulation rate of the pump. The batch production method of (E). 2. The emulsifier (B) is mixed with water in the first step to obtain an emulsifier / water mixture (EW), and in the second step, the organosilicon compound (A) is added to the emulsifier / water mixture (EW). And a pre-emulsion (V) having a viscosity of 40 000 to 5 000 000 000 mPa · s at 25 ° C. by shearing. The process for batch production of an aqueous emulsion (E) according to claim 1 or 2, wherein up to 25% of the total amount of water introduced into the emulsion (E) is used for the preparation of the preemulsion (V). delete delete delete The batch production method of an aqueous emulsion (E) according to claim 1 or 2, wherein the organosilicon compound (A) is reacted with each other or with an additional substance to obtain another organosilicon compound (A). The batch production method of an aqueous emulsion (E) according to claim 1 or 2, wherein the organosilicon compound (A) is a liquid at 25 ° C and has a viscosity of 0.5 to 100 000 000 mPa · s.