SI20193A - Device and method for producing silicone emulsions - Google Patents

Abstract

The invention relates to a device for producing a silicone and/or silane emulsion consisting of an active component containing silicone and/or silane, and an aqueous phase. Said device comprises a first mixing station for the emulsion components which are delivered by pumps (P1, P2, P3) from reservoirs (VA, VB, VC), and is characterised in that said first mixing station has a mixing device (M1) wherein nozzles (2, 4) mix a jet of the active agent (1) with the aqueous phase (3) to produce a preliminary emulsion. The invention also relates to a method for producing fine-particle, stable silicone emulsions, especially for producing oil-in-water emulsions containing as little emulsifier as possible, and to emulsions produced according to said method.

Description

Device and process for preparing silicone emulsions

The invention relates to a device and method for the preparation of stable silicone emulsions with fine particles, in particular for the preparation of oil-in-water emulsions with the lowest content of emulsifiers.

A number of methods are known for emulsifying insoluble silicones or. of silanes in water. Thus, in general, before actual homogenization or in silicone in which the emulsifier is finely distributed, small amounts of water are slowly introduced, resulting in a water-to-oil emulsion, which is inverted by subsequent dilution with water before being homogenized in a special shear force device. into the fine particle emulsion, either the silicone is slowly introduced into the aqueous emulsifier with stirring, before the resulting emulsion with the coarse particles is subjected to actual homogenization.

Initially, the blended mixture may already be a sufficiently stable emulsion, depending on the type of process and the substance, the emulsifier concentration, the mixing energy input, and especially the time invested. As a rule, however, these emulsions, which are referred to as pre-emulsions, are coarse particles and, due to their lack of stability, must be immediately brought into actual homogenization. Homogeneous devices and processes are described in Ullmamis Encyclopedia of Industrial Chemistry Vol A9 Edition 1987, p. 309 to 310. The preparation of the pre-emulsion takes place in the mixing units and is a time-determining step, depending on the type of subsequently connected homogenizable machine.

Further procedures for the preparation of silicone emulsions are known from EP-A-043 091 and EP-A-0 579 458. In process EP-A-043 091, a small amount of water is supplied with the entire emulsifier to produce a high-viscosity paste or . gel, which is then translated by dilution into a final emulsion.

Preparation of pre-emulsion by classical methods with the addition of siloxanes and / or siloxanes becomes problematic. of silanes to excess water / emulsifier phase, especially when using silicon compounds which may exist from both monomemic, linear and resinous, optionally lower molecular siloxanes or organic compounds of dilute structures, provided that they can in principle react with the aqueous phase. These include e.g. alkylalkoxysilanes, resins bearing alkoxy groups, and optionally mixtures of the two.

A further problem is that the preparation of the pre-emulsion according to known procedures is particularly time-consuming. The influx of the siloxane component into the aqueous phase is controlled by stirring, i.e. so that it achieves optimum mixing. This does not allow for quick additions.

In doing so, the first molecules of the active substance are hit by an enormous excess of water, which only approaches the desired concentrations over time and produces an unstable pre-emulsion with coarse particles, which must be fed into the homogenizer as quickly as possible.

During addition, in the case of water-sensitive components, they are only insufficiently protected from the aqueous phase, even in the case of a buffer phase, so that the corresponding components can react with each other. This may cause the subsequent homogenization due to the condensation process followed by the formation of viscosity in the coarse emulsion particles obtained, making it difficult or difficult. to make the pre-emulsion so labile that they can no longer feed into the homogenizer. Other disadvantages can be counteracted by a strong increase in emulsifiability (in the range of 5%), leading to undesirable results in many applications and environmental burden.

They further lead e.g. in the case of alkylalkoxysiloxanes, the hydrolysis and condensation reaction during emulsification is generally ineffective in use and therefore renders the emulsion obtained inapplicable.

If pre-emulsion is prepared via a paste or a paste. gels, which are then diluted in a special procedure, can be prepared in such cases where the emulsifier content is not significant, emulsions with low average particle sizes are prepared without any information on their distribution.

Since these are a series of silicone substances which, at least at the required amounts of emulsifiers, give pastes only insufficiently, these processes are limited in their breadth of use. Further, a range of emulsions such as e.g. anti-foaming emulsions poor emulsifier (<5%) and concurrent poor (<20%) emulsion are not sufficiently prepared by this procedure. Thus, in the EP 0 579 458 process, very large particle emulsions in the range of 3-60 pm are obtained with high time consumption (see examples there).

It is an object of the present invention to provide a fast-running and therefore economical process that has no drawbacks described and allows the preparation of fine-particle emulsions having narrow particle size distributions, low emulsifier content and low to high active substance concentrations, as well as a device , we accept this process.

In doing so, water-sensitive active substances should lead to stable and, above all, effective emulsions over one year.

Specifically, in order to achieve high reproducibility, the ab initio emulsifier amount required for a particular planar coating of the active substance particles was targeted to contact the active substance and to direct mechanical energy. This presupposes a process with mathematically exact descriptive emulsifiers. Devices which are strongly influenced by the dwell time (eg mixing units, etc.) are not suitable.

Finally, the energy to be introduced should cover a wide area - hitherto accessible only by several devices of different construction - area. In this way, emulsions can be prepared in the same device, which must be protected against high energy intake - e.g. anti-foaming emulsions as well as emulsions that require a multiple of the energy made available by conventional homogenizers.

We were able to solve this task with a device consisting of a plant from pump and nozzle tanks, which is hereinafter referred to as a mixing station. Particularly advantageous sessions were shown when a nozzle disperser was subsequently connected to this mixer as described for the preparation of pharmaceutical or cosmetic dispersions (Bayer AG / EP 0 101 007).

The object of the invention is therefore a device for the preparation of silicone, silane or silicone / silane emulsions from an effective component containing silicones and / or silanes and aqueous phases (components), with the first mixing station for the emulsion components supplied via pumps Pl, P2, P3 from reservoirs (VA, VB, VC), at wherein the first mixing station has a mixing device Ml in which nozzles 2, 4 mix the jet of the active substance with aqueous phase 3 into the pre-emulsion (see FIGS. 1 and 2).

In a preferred embodiment of the apparatus of the invention, the first mixing station is coupled to a high-pressure homogenizer, wherein the high-pressure homogenizer receives a pre-emulsion exiting the mixing station.

The subject of the invention is further a process for the preparation of aqueous silicone and / or silane emulsions with a fine particle distribution, comprising the preparation of a pre-emulsion by injection of a silicone and / or silane component into an aqueous phase containing the emulsifier in a mixing station and homogenized in high pressure homogenizer as well as emulsions of silicone compounds and / or silanes obtainable by this process.

In particular, the invention relates to a process for the preparation of aqueous silicone and / or silane emulsions with fine particles having a U ₉₀ value below 1.2 (i.e., with a narrow particle distribution), comprising preparing a pre-emulsion by injecting a silicone and / or silane component into aqueous emulsifier-containing phase in the mixing station, maintaining a pressure difference, depending on the nozzle dimensions, of not more than 10 bar between the two streams at an absolute pressure drop below 100 bar and homogenization of the pre-emulsion.

The present invention is explained in more detail by the accompanying drawings and examples.

In doing so, they show:

FIG. 1 mixing station;

FIG. 2 is a schematic representation of a device according to the invention with a high pressure homogenizer;

FIG. 3 arrangement of nozzle dispersant nozzles;

FIG. 4 high pressure homogenizer;

FIG. 5, 6, 7 and 8 the differential and integral particle size distribution of Examples 10, 9, 18 and 19.

In the apparatus of the invention, the known pressure drop (Δρ) ', the known content and surface requirement of the emulsifier, the known nozzle diameter (D) * give the known boundary stresses

STR D plane (γ), known viscosity (η) of the dispersion phase and known number of flow rates (n) to calculate the expected average particle size (d) using the following formula:

d = k A (Δρ) ⁰ ' ⁶ A η ⁰ ' ⁴⁹⁵ A γ ° ' ³⁶⁵ AD ⁰ ' ¹⁶⁵ A n ^{0 '36} k = constant (concerning emulsifier content / surface need).

The core of the mixing station is the arrangement of the nozzles in the mixing apparatus Ml, the dimensions of which depend on the consistency of the two phases to be combined, their concentrations relative to each other, the selected pressure drop and flow rate.

FIG. 1 shows a possible embodiment. In this case, for example. the silicone oil 1 is injected through the first nozzle 2 into the aqueous phase 3 and then intensively stirred and homogenized in the second nozzle 4. In the subsequently connected STR-D nozzle disperser, the final fma distribution expires. The STR-D nozzle dispersant can be directly connected or in batch mode only after preparation of the entire pre-emulsion 5.

The nozzle arrangement of FIG. 1 is preferably applied via two pumps P1, P3 with a pressure difference of 2-3 bar, so that, in the case where the emulsifier coating speed permits, the aqueous emulsifier solution and the silicone together are led to the final emulsion concentration and directly homogenized via a STR-D nozzle dispersant. in one or at most three aisles.

As a rule, the number of transitions depends on the type and content of the emulsifier. Emulsifiers in the 3% range - except for exceptions - need only one pass.

In the case of emulsifiers which coat the surfaces of the particles of certain silicone agents only relatively slowly, the process can be modified to operate with any deficit of water containing the total amount of emulsifier. In this case, the resulting more concentrated emulsion can be led back into the aqueous emulsifier solution and thus into

again, it is fed into the nozzle and into the effluent to form a circuit. If the circuit is maintained for a few minutes after reaching the association, it depends on the concentration and type of emulsifier as well as the silicone to be emulsified. Through a further nozzle and pump, a residue of water can be added to the circuit, optionally mixed with further additives, e.g. thickened or canned agents before bringing this pre-emulsion to the STR-D nozzle dispersant.

FIG. 4 shows a STR-D nozzle disperser used as a high-pressure homogenizer 6. A STR-D nozzle dispersant consists in detail of a pump 14, optionally a pulsation damper 16 and a nozzle arrangement 18, which is illustrated in detail in FIG. 3. The two-stage arrangement of 18 nozzles has a first Nozzle 10 as well as a second nozzle 12 attached to it, by means of which the pre-emulsion is homogenized 5. Each nozzle 10, 12 consists of a cartridge 11 in a pipe 9, each cartridge 11 having a cylindrical section 13 projecting opposite the direction of the pre-emulsion flow 5 with two opposite capillary holes 15. The cylindrical section 13 forms a ring space 17 in the tube 9, the pre-emulsion 5 flows through the tube 9 into the ring space 17 and thence through the capillary holes 15 v. intermediate chamber 20. As the capillary bores 15 are facing opposite, the emulsion jets protruding inside the cylindrical section 13. This results in a particularly good dispersion. The emulsion flows from the intermediate chamber 20 into the second annulus 22 of the second nozzle 12 and returns there through the capillary holes 24 of the second nozzle

12. A homogenized emulsion 25 exits through the outlet 26 from a STR-D nozzle dispersant.

The proposed process also allows the ratio of total-emulsifier containing active substance-containing ducts to be selected immediately to form gels and pastes. The prerequisite is that forced-transport pumps are selected and have a consistent trap consistency.

The advantage of the presented procedure is that it is practically continuous to work, consumes less time and has excellent reproducibility. It produces stable emulsions having a mean particle size of 0.5 to 3% for emulsifier contents at values <1 pm. For stability and for many applications, the particle size distribution in the narrower range than in conventional processes is important.

There are also some rare cases where less stable emulsions are obtained, in which both the particle size and their distribution do not play any decisive role, so that, for cost or other reasons, we give up the following homogenization after passing through the mixing station. In such cases, the lack of stability of these emulsions can be compensated for by a substantial increase in the emulsion viscosity by the addition of a neutral thickener. Due to the frequent poor processing of such emulsions, however, we generally try to bypass this method of preparation.

Among the above emulsions, again, few high-viscosity emulsions are found in which a high-viscosity agent is responsible, e.g. an organic nature that we cannot relinquish.

In such cases, it would, of course, be uneconomical for such emulsions to be further emulsified in a STR-D nozzle disperser, since, if essentially to maintain the current state of the emulsion, the nozzle disperser could not significantly contribute to the required process conditions. improving the physical properties of the emulsion.

It is recommended that the pre-emulsion leaving the mixing station be homogenized at a higher pressure in the second mixing station, e.g. up to 100 bar.

This method is also recommended when it is necessary to emulsify Si compounds that can be easily emulsified with emulsifiers having sufficient velocity in coating the particle surfaces. In this case, we can cancel the jam.

However, in order to minimize apparatus costs, it is preferable to transport the pre-emulsion to a tank previously connected to the first mixing station and from there through the same mixing station under the other pressure conditions to the desired emulsion state.

The subject of the invention is further a process for the preparation of aqueous silicone and / or silane emulsions with fine to coarse particles in the range of about 0.4 to 5.0 pm with a U ₉₀ value above 1.1 (i.e. with a wider particle distribution) which Only slight shear forces or emulsification are required. they are stabilized by a thickener comprising the preparation of a pre-emulsion by injecting a silicone and / or silane component into an aqueous phase containing the emulsifier in a mixing station, maintaining a pressure difference of nozzle dimensions of not more than 10 bar at absolute pressure drop below 80 bar, homogenization of the pre-emulsion in a subsequently connected mixing station or displaced temporarily in the same mixing station at an absolute pressure drop of up to 100 bar.

The embodiment is illustrated in FIG. 2 in which they mean

VA: Active substance container

UK: Residual water tank (+ accessories)

VC: puff container / intermediate container

VE: tank / intermediate container

VD: puff container

Pl, P2: pumps (optional with forced transport)

P3, P4, P5: pumps

Ml: active substance / water agitator

STR-D: Nozzle Disperser.

In the active substance VA- »P1-» M1- »VA circuit, inject the aqueous phase at low pressure via VC-> P3-> M1 and after completion of adding VA-> P1-» M1- »VA circuits to a higher pressure, with Ml serves as a subsequently connected homogenizer. The emulsion can be withdrawn from Ml. Of course, the condition that the emulsifiers have a sufficiently high particle coating rate is a feature that also depends on the acceptability of the active ingredient to adhere to these emulsifiers.

Examples of the silicone and silane components are silicone compounds having a conventional composition:

(CH3) 3SiO [(CH ₃ ) ₂ SiO] 5o.5ooSi (CH ₃ > _i

HO (CH3) ₂ SiO [(CH3) ₂ SiO] ₃ QoSi (CK ₃ ) ₂ OH (CH ₃ ) ₃ SiO [(CH3) (H) SiO] ₃ oSi (CH ₃ ) 3 (CH ₃ ) ₃ Si ( 0) in (OCH ₃ ) og;

organoalkoxysilanes, their hydrolysates, e.g. :

CH ₃ (CH ₂ ) ₇ Si (OEt) ₃

CH ₃ (CH ₂ ) ₃ Si (OEt) 3

CH ₃ (CH ₂ ) ui ₃ (CH ₃ ) Si (OMe) ₂

CH ₃ (CH ₂ ) ₇ Si (OEt) ₂ O (OEt) ₂ Si (CH ₂ ) 7CH3

CH 3 (CH _{2) 3} St (OEt) ₂ [0 (EtO) Si (CH ₂₎ 3CH3] o-5 OSi (OEt) ₂ (CH _{2) 3} CH _3;

linear polyorganosiloxanes with and / or free of silicon-functional bound groups such as hydrogen, alkoxy, polyether or. hydroxy groups, with and / or non-organically functionally bound groups such as polyethers, amines or halogens, respectively. pseudo halogens, eg:

(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] jo-jooSi (CH ₃ ) ₃ HO (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] iooSi (CH ₃ ) ₂ OH (CH ₃ ) ₃ SiO [(CH ₃ ) (H) SLO] soSi (CH ₃ ) ₃ (CH ₃ ) 3SiO [(CH3) CH ₂ = CHSiO] ₃ [(CH ₃ ) ₂ SiO] 5o.jooSi (CH ₃ ) ₃ (CH3) ₃ SiO [CH ₃ (OCH ₂ CH ₂ ) sO (CH ₂ ) 3 (CH ₃ ) SiO] 3 [(CH ₃ ) ₂ SiO] ₆ ooSi (CH 3) ₃ branched polyorganosiloxanes with and / or without bound silicon functional groups, such as hydrogen, alkoxy, polyether or. hydroxy groups, with and / or non-organically functionally bound groups such as polyethers, amines or halogens, respectively. pseudo halogens, eg:

CH ₃ Si {[(CH ₃ ) ₂ SiO] ₅₀ OSi (CH ₃ ) 3} 3

CH ₃ SifKCHjhSiOjgoOSiCCIDiCH ^ CHjJs

CH ₃ SHKC ^ SiOJsoOSiCCftji (CH ₂ ) ₃ (OCH ₂ CH ₂ ) gOCH ₃ } 3

H ₂ N (CH ₂ ) ₃ Si {C (CH ₃ ) ₂ SiO] _in OSi (CH 3)} ₃ ;

silicone resins with aryl, alkyl, organofunctionally modified alkyl groups, alkoxy functional resins, with or without diluent, eg:

(CH3) ujSiiOt.42 (CH ₃ ) o. ₈ (C _l2 H ₂ 5) OASIA (0) _l (OCH _{3) 1} (SI0 ₂₎ io [(CH _{3) 3} SiO vjoj SI0 ₂ [(CH ₃₎ CH ₂ = CHSiO] oj [O _w Si (CH ₃ ) ₃ ], _but mixtures of the above components with each other or with insoluble additives of mineral or organic kind.

Emulsifiers are intended to be ionic and non-ionic emulsifiers, as is customary in silicone emulsification, respectively. mixtures thereof.

As ionic emulsifiers, they are suitable with respect to the active ingredient e.g.

alkyl sulfonates having 8 to 18 C atoms, with or without ethylene or. propylene oxide units;

sulfate esters, such as e.g. CH ₃ (CH ₂ ) 6CH ₂ O (C ₂ H ₄ O) 6. ₁₉ SO ₃ H;

alkylarylsulfonates such as e.g. dodecylbenzenesulfonate;

quartemes of ammonium compounds such as e.g. dodecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxides, resp. their salts.

However, non-ionic emulsifiers with a HLB value in the range of v are preferred

from 10 to 16. In the case of mixtures of this range, these may exist from a combination of emulsifiers with an HLB value of between 2.7 and 18.7.

Ethylene oxide adducts to fatty alcohols, alkylphenols, triglycerides or sugars are suitable as non-ionic emulsifiers; polyethylene oxidesorbitanlavrates, -palmitates, -stearates; ethylenoxide adducts to alkylamines; and polyvinyl alcohols (such as Mowiol), in particular ethoxide adducts on tridecyl alcohol, ethoxide adducts on sorbitan monooleates (Tween® products from ICI), sorbitan monooleates and mixtures thereof.

The average particle diameter - also referred to as particle size in the text - is calculated from the volume average obtained from the total volume of all emulsion particles divided by the number of particles.

v

The numerical value of the width of the particle size distribution is calculated by ignoring the given particle size of particles with smallest diameters up to 10% by weight of particle size (d 10) and particles with largest diameters up to 10% by weight of particle size (d90). the difference between the diameters of the remaining largest particles and the remaining smallest particles is divided by the diameter of that particle (d50) which is greater than 50% by weight of all particles and less than 50% by weight of all particles. We call this numerical value hereafter U ₉₀ :

Uon = d90 - part of d50 (see Figs. 5, 6, 7 and 8).

Average particle sizes were measured by Frauenhofer removal, ultracentrifugation or photometry using Mie theory. The distribution curves were measured using an ultracentrifuge.

The apparatus (Fig. 2), shown in the appendix in the schematic flow chart, provides flexibility to the active ingredient, emulsifier and their concentrations of tailor made process adjustments.

Thus, e.g. in the case of easily emulsifiable products, the emulsifier is fast and in favorable concentration, the active ingredient (from VA) with the water / emulsifier mixture (from VC) is led together in the desired ratio in Ml and the resulting pre-emulsion is directed directly or through a buffer tank (VD) into a disperser with nozzles STR-D, homogenized in one pass and then led to a filling station.

This method of operation requires reliable steering or. synchronization of pumps with each other. If this is to be waived and the exact emulsifier / active ingredient ratio is not necessarily required in the Ml control, we can - nevertheless, to provide the required concentration of the active ingredient in the emulsion, supply the active ingredient via M1 to the calculated water / emulsifier deficit, the resulting pre-emulsion is fluidly returned water / emulsifier (VC) mixtures and in the Ml circuit are again run together with the active substance. If the entire active ingredient is consumed, pre-emulsion is passed through the Ml nozzle with the addition of residual water (from VB) over the final concentration M1-> VC- »M1, as described above, and homogenized as above.

In the case of difficult-to-emulsify agents, slow emulsifiers or very low concentrations of emulsifiers, pre-emulsions via VC and Ml in a circle may be pre-emulsified several times before being fed to STR-D before proceeding as above.

If the paste or gel, and the active ingredient is suitable for this purpose, with any water deficit (from VC) - but with the whole emulsifier - it can be combined together in Ml, the resulting emulsion as above can be led back to VC and with its content always sprayed again with Ml with the active ingredient . This produces a highly viscous pre-emulsion, which, depending on the selected conditions, may have the consistency of a paste or a paste. gel.

Depending on the purpose of use, this can be processed as such or further processed as described below.

Before homogenizing it above in STR-D, it is guided through Ml, where the remaining water (from VB) is injected, optionally by thickening and other conventional additives, to achieve the calculated composition.

If more than one pass through STR-D is required, it can be run again via VE- + STR-D in a circle before the emulsion is filled.

However, if you want more discrete passages, you can from the buffer tank. VD is emulsified via STR-D in the 1st gateway to the wind farm, then from there in the 2nd gateway via the STR-D again into the VDs, etc.

In the following cases, all data refer to the mass, unless otherwise stated.

Let's use the following abbreviations:

Me- -ch ₃ Et -c ₂ h ₃ Octeo C ₈ H ₁₇ Si (OE) ₃ V pre-emulsion.

The tables now state only the time required for the preparation of the pre-emulsion, since the preparations of aqueous emulsifiers are practically identical in the cases of the invention and in the cases of the non-invention. The actual homogenism rate was also not included in the consideration of time, since it depends to a large extent on the capacity of the comparative emulsifying apparatus.

In the tables, the examples according to the invention are printed in bold, comparative examples in italics.

Examples

A. Resin emulsions

Example 1 (Comparative Example)

238.7 g of distilled water is heated in a 2 liter container at 60 ° C and 55 g of the molten mixture - corresponding to 2.50% by total batch - of POE-stearyl alcohol and POE-cetyl alcohol with a total HLB value of 15 is added with stirring, 5.

After cooling to 40 ° C for 1 hour, add 1447.6 g of Isopar® G - solution with 80% resin of average composition (CHsjijgSiiOi ^ and with a viscosity of 1620 mPaAs at a stirring speed of 250 - 400 rpm. At a speed of ~ 400 rpm, 458.7 g of an aqueous solution of 1.76 g of carboxymethylcellulose (Walocel CRT 5000 GA) were added with stirring for 25 minutes and stirred for another 40 minutes.

The pre-emulsion is homogenized at a pressure drop ΔΡ = 250 bar in a six-pass classical high-pressure Gaulin homogenizer. The results are listed in Table 1.

Example 2 (Comparative Example)

Example 1 was repeated with a total emulsifier content of 3.00%. The results are listed in Table 1.

Example 3

Increase the same batch as in Example 1 - but with 2.2% emulsifier - by a factor of 2.7273. 645.0 g of distilled water is heated in VC (see Appendix Fig. 2) to 50 ° C and 133 g of the molten mixture - correspondingly 2.20% over the entire batch - of POE-cetyl alcohol with full value are added with stirring. HLB 15.5 and push through P3 with 3 bar through Ml (nozzle diameter 2.1 / 1.0 mm) in VC and for 30 s lead in a circle over P3 through Ml in VC. In this circuit, 3948 g of the same resin as in Example 1 from VA was injected over 17 minutes via Pl with 5 bar in Ml. Then maintain the circuit for 10 minutes, then inject an aqueous solution of 4.8 g of carboxymethylcellulose (Walocel CRT 5000 GA) in 1264.2 g of water into the circuit from Ml for 9 minutes. After the addition is complete, the circuit is maintained for another 40 minutes before the pre-emulsion at a pressure drop of ΔΡ = 250 bar in a STR-D nozzle disperser (nozzle diameter: 0.2828 mm) is homogenized in three passes. The results are listed in Table 1.

Example 4

Example 3 was repeated with a total emulsifier content of 2.5%. The results are listed in Table 1.

Example 5

Example 3 was repeated with a total emulsifier content of 2.8%. The results are listed in Table 1.

Example 6

Example 3 was repeated with a total emulsifier content of 3.0%. The results are listed in Table 1.

Table 1

Stability [months] are o - IT o - 9 < > 6 and - Q © > 6 > 6 Prim ³ © - > 6 > 6 4 n o - <r © © > r θ ' • r, θ ' θ ' - o - 0.5 > r θ ' 0.5 0.5 0.5 Particle size 0 [gm] SO > 5,000 2,106 th most common 0.634 0,589 th most common io 5,000 2,453 th most common 0.660 0.593 t ΤΓ li (U β > 5,000 2,550 th most common 0.653 0.642 1 ^ε 1 sep- » > 5,000 2,915 th most common 2,143 th most common 1,617 th most common CM > 5,000 4,760 th most common 4,487 th most common 4,390 th most common 4,202 th most common 4,068 th most common 3,989 th most common - > 5,000 4,954 th most common 4,687 th most common 4,423 th most common 4,343 th most common 4,216 th most common 4,094 th most common Passage no. are > CM rr ψ io > CM rT Im 4) 'Τ p > CM rr 'Mr. Oh > IM CM rr φ ci > - CM rr r · ir SO - > l — M CM rr rf »R SO

B. Resin / silane emulsions (water sensitive)

Example 7 (Comparative Example) g of emulsifier mixture - corresponding to 1% by weight of the total batch - of ethoxylated sorbitan monolaurate and ethoxylated oleyl alcohol with a total HLB value of 15.3 was mixed in a 4 liter mixing vessel with 816.22 g of water and 2. 18 g of diethanolamine and stirred for 2 hours at 80 ° C to form a clear solution. To the cooled solution was added 65 minutes at a stirring speed of 700 rpm 1359.6 g of a mixture of 49.2% octyltriethoxysilane and 50.8% resin with the composition (CH ₃ ) o _{> 8} (Ci 2 H 25) o _> 2Si (0) ₁ ( OCH ₃ ) i. After the addition is complete, stir for another 30 minutes at 550 rpm. After 30 minutes, take a sample to determine the particle size. The two-pass pre-emulsion is homogenized at a pressure drop ΔΡ = 250 bar in a classical Gaulin type homogenizer. The results are listed in Table 2.

Example 8

The batch from Example 7 is doubled. 44 g of the emulsifier mixture - corresponding to 1% by weight of the total batch - of ethoxylated sorbitan monolaurate and ethoxylated oleyl alcohol with a total HLB value of 15.3 are mixed in VC (see Fig. 2) with 1632.44 g of water and 4.36 g of diethanolamine and stirred at 80 ° C for 2 hours to give a clear solution. After cooling, pump for 1 minute at 3 bar in circle VC P3 -> Ml -> VC. Injected from this VA from Pl via Pl and through Ml (nozzle diameter 2.1 / 1.0 mm) for 3.5 minutes 2719.2 g of a mixture of 49.2% octyltriethoxysilane and 50.8% resin with composition (CH ₃ ) o, 8 (C ₁₂ H25) o _> 2Si (0) and (OCH ₃ ) and at 5 bar. After the addition is complete, maintain the upper circuit for another 15 minutes at 3 bar. The particle size determination sample was taken after 5 and 15 minutes. The two-pass pre-emulsion is homogenized at a pressure drop ΔΡ = 100 bar. The results are listed in Table 2.

Example 9 (Comparative Example) g of emulsifier mixture - corresponding to 1% by weight of the total batch - of ethoxylated sorbitan monolaurate and ethoxylated oleyl alcohol with a total HLB value of 15.3 was mixed in a 4 liter mixing vessel with 163.2 g of water and 2, 18 g of diethanolamine and stirred for 2 hours at 80 ° C to form a clear solution. To the cooled solution was added 65 minutes at a stirring speed of 700 rpm 1359.6 g of a mixture of 49.2% octyltriethoxysilane and 50.8% resin with the composition (CH ₃ ) o, 8 (Ci ₂ H ₂ 5) o, ₂ Si (0) and (OCH ₃ ) i. After the addition is complete, the mixture is further stirred for 15 minutes at 550 rpm to form a more viscous paste. At the previous mixing speed, 653.0 g of water was added for 30 minutes and stirred until the particle size had dropped below 5 pm (45 minutes). The pre-emulsion is homogenized in 2 passages at a pressure drop ΔΡ = 200 bar in a classical Gaulin type homogenizer. The results are listed in Table 2.

Example 10

The batch from Example 9 is tripled. 66 g of the emulsifier mixture - corresponding to 1% by weight over the entire batch - of ethoxylated sorbitan monolaurate and ethoxylated oleyl alcohol with a total HLB value of 15.3 were mixed in VC (see Fig. 2) with 489.60 g of water and 6.54 g of diethanolamine and stirred at 80 ° C for 2 hours to give a clear solution. After cooling, pump for 1 minute at 3 bar in circle VC -> P3 -> Ml -> VC. In this circuit, inject from VA via Pl and through Ml (nozzle diameter 2.1 / 1.0 mm) for 5 minutes 4078.8 g of a mixture of 49.2% octyltriethoxysilane and 50.8% resin with the composition (CH ₃ ) about _i8 (Ci ₂ H ₂₅ ) o ₍₂ Si (0) i (OCH ₃ ) i at 5 bar. After the addition is complete, maintain the upper circuit for another 4 minutes at 3 bar. Then inject from the UK for 10 minutes into the upper circuit 1959 g of water via Ml After the addition of water is completed, pre-emulsion is pre-homogenized in the circuit for 1 minute, the sample is determined to determine the particle size, and homogenized in two passes at a pressure drop of ΔΡ = 100 bar in the nozzle dispersant The results are listed in Table 2.

Table 2

Width of distribution U90 0 PP n «S © P H θ ' (U 1,75 • '-T £ 00 1.21 | 1.02 r- 2.03 d d Pre-emulsion takes time [min] © + n mer 1 ⁹ 110 'C 00 • K © d r- 95 Particle Size 0 [pm] © 4,371 th most common 0.632 0,583 O \ Si Oh 4,241 th most common 0.763 0.548 Prin 8 3,773 th most common 0.647 0.609 v. 0 Ci 0 1,766 th most common 0.707 Pressure drop ΔΡ [bar] © 3/5 100 -1 001 i ner 9 05 200 200 Prir ⁸ 3/5 100 001 d <o> 250 L. ------ 250 1 Passage no. 0 > PP d ω Os C d Prir 8 > PP d d d

> N μCS χλ

In • M> <Z>

C -

O '>

Ό

CU *

C • θ 'b

'C cu

Example 11 g of emulsifier mixture - corresponding to 0.64% by weight of the total batch - of ethoxylated sorbitan monolaurate and ethoxylated oleyl alcohol with a total HLB value of 15.3 were mixed in VC (see Fig. 2) with 390.83 g of water and 3, 17 g of diethanolamine and stirred for 2 hours at 80 ° C to form a clear solution. After cooling, pump for 1 minute at 3 bar in circle VC -> P3 -> Ml -> VC. Inject this into the circuit from VA via Pl and through Ml (nozzle diameter 1.8 / 0.9 mm) for 3 minutes at 5 bar 1980 g of a mixture of 49.2% octyltriethoxysilane and 50.8% resin with (CH3) oXCi ₂ composition. H25) o, 2Si (0) and (OCH ₃ ) i. After the addition is complete, maintain the upper circuit for 2 minutes at 3 bar. Then from the UK for 13 minutes, 2594 g of water were injected into the upper circuit via Ml. After the addition of water is completed, the pre-emulsion is pre-homogenized in the circuit for 4 minutes, the sample is determined to determine the particle size and homogenized in 2 passes at a pressure drop ΔΡ = 95 bar in the nozzle disperser. The results are listed in Table 3.

Table 3

Passage no. Fall pressure ΔΡ [bar] Size particles 0 [pm] Pre-emulsion takes time [min] Emulsifier content [%] Emulsion stability [months] V 3/5 4,326 th most common 25 0.64 - 1 95 0.621 > 6 2 95 0.611 > 6

C. Silicone oil emulsions

Example 12

150 g of molten emulsifier mixture - corresponding to 3% by weight of the total batch - of ethoxylated triglyceride and ethoxylated tridecyl alcohol with total HLB value

13.5 is mixed in VC (see Fig. 2) with 1850 g of water at 50 ° C and pumped for 2 minutes at 3 bar in a circle VC - »P3 -» Ml - »VC, cooled and injected into this circuit for 18 minutes via Pl with 5 bar 3000 g of diorganopolysiloxane with a viscosity η = 350 mPaAs in Ml (nozzle diameter 1.4 / 0.7 mm). It is then homogenized at a pressure drop of 250 bar in STR-D. The results are listed in Table 4.

Example 13

200 g of molten emulsifier mixture - corresponding to 4% by weight of the total batch - of ethoxylated triglyceride and ethoxylated tridecyl alcohol with total HLB value

15.4 is mixed in a VC (see Fig. 2) with 1550 g of water at 45 ° C and pumped for 2 minutes at 3 bar in a circle (nozzle diameter 1.4 / 0.7 mm), cooled and in this circuit 5.5 minutes injected from VA via Pl at 5 bar 1750 g of diorganopolysiloxane with a viscosity of η = 350 mPaAs in Ml (nozzle diameter: 2.1 / 1.0 mm). After the addition is complete, pump for another 5 minutes at 3 bar in the circuit. Then inject 1500 g of water from the UK at 5 bar for 8 minutes via Ml. After a further 5 min, a 3 bar cycle was homogenized at a pressure drop of 250 bar in STR-D. The results are listed in Table 4.

Example 14

180 g of molten emulsifier mixture - corresponding to 4.5% by weight of the total batch - of ethoxylated triglyceride and ethoxylated tridecyl alcohol with total HLB value

15.4 was mixed in VC (see Fig. 2) with 1240 g of water at 50 ° C and pumped for 1 minute at 3 bar in a circle VC -> P3 - »Ml -» VC, cooled and injected into this circuit for 1.5 minutes from VA via Pl with 5 bar 800 g of diorganopolysiloxane with a viscosity of η = 350 mPaAs in Ml (nozzle diameter: 2.1 / 1.0 mm). After the addition is complete, pump for another 2 minutes at 3 bar in the circuit. Subsequently, 1780 g of UK water was injected at 5 bar for 8.5 minutes via Ml and subsequently homogenized for 2 minutes at 3 bar in the same circuit. It is then homogenized at a pressure drop of 200 bar in STR-D. The results are listed in Table 4.

Example 15 (Comparative Example) g of molten emulsifier mixture - corresponding to 4.5% by weight of the total batch - of ethoxylated triglyceride and ethoxylated tridecyl alcohol with total HLB value

15.4 620 g of water at 50 ° C are mixed in a mixing vessel and stirred for 3 minutes, cooled and 400 g of diorganopolysiloxane with a viscosity of η = 350 mPaAs are added via dropper for 13 minutes. After complete addition, the mixture is stirred for another 5 minutes at 400 rpm, before 890 g of water is added for 27 minutes at 300 rpm (strong foam formation). The pre-emulsion is homogenized in 2 passages at a pressure drop ΔΡ = 200 bar in a classical Gaulin type homogenizer. The results are listed in Table 4.

Table 4

4— * C / 5 o * «« < 1 1 1 They are 7 ' <6 rO 3 ₌ _ ΤΤ 1 are are SO are ζ / 5 ο υ Ο c «J CZ2 d ζΛ ο £ • 1Η π tO SO are Oh are ¹ Λ Λ Λ A N 3 ω η are SO SO ΤΗ Λ Λ A Ό C0 <d> %] ro ί \ ro ro 03 * - » c Λ -τ ο © © Oh > ο ο Λ U. 4) Mr Rücker r, π ro ro d t > υ C ο ο C CU that ir, ir, ir, ir, D τ * ro ro ro ro Ο οι © © © © · · Η <1 are are are Ό Ό * -> > Η Λ : £> £ Tf Tf Ν ΤΗ 1— υ Mr Rücker > ο Mr Rücker <υ Ο <υ c 1) rO ω h 'FM ίο 3L fC ΤΗ 23.5 C-4 ο α. ro X ΤΗ ** s M > 'Oh ro Η ^- » Ι / - ') that They are Ό £ ** - 4 1 tn Ό that ro 3. «Ο * «O * r \ ro ' ro ' ro ' Q ro © ro X τΤ tr HT ro OS > U 1 r- Os X r-> ο ο ω £ »S ro «S © T o © ο 'C © n M t- Ο C- ΓΠ SO ro X r- Η-> τΗ ¹ os X l> t ο © © d © ο η © Os X > Υ · ^ 1 «S «S © »> · © ro that -> > cza m ττ > ro ro tr Τ3 Ο ϋ 3 ΗΜ c Λ υ At Γ, that > ro ro tr C, } “1 ι * ~ \ ro > tH ro rO

^1} batch 5000 g ²⁾ batch 5000 g ³⁾ batch 4000 g ⁴⁾ batch 2000 g

Example 16

2800 g of water, 4.6 g of 37% hydrochloric acid, 5.25 g of glycine, 51.3 g of glycerin, 200 g of alkylbenzylammonium bromide, 30 g of ethoxylated tridecylalcohol with an HLB value of 11.4 and 22.6 g of glycol are presented in VC ( see Fig. 2) and pump for 30 seconds at 3 bar in the VC -> P3 -> Ml -> VC circuit. 2056 g of hydrogen-bearing organopolysiloxane with a viscosity of η = 40 mPas at 7 bar for 100 seconds is injected from VA via Pl in Ml (nozzle diameter: 1.8 / 0.9 mm) into the upper circuit. After the addition is complete, the pre-emulsion is pumped into the VD buffer tank and slightly time-shifted via P4 is homogenized in one pass in a STR-D nozzle disperser at a pressure drop ΔΡ = 250 bar. The results are listed in Table 5.

Table 5

Example no. The passage no. Size particles 0 [pm] Time [min / sec] The whole emulsifying [min / sec] Stability [months] 15 V 2 * 10 1 0.368 4 * 40 > 6 6 * 50

D. Silicone emulsion in a mixing station

Example 17

Mixture of 96.6 g ethoxylated tridecyl alcohol with an HLB value of 11.4, 552.72 g polydimethylsiloxane with a viscosity η = 500 mPas, 994.84 g mineral oil rafmata with a boiling range of 382 to 432 ° C and 691.04 g di- ( 2-Ethylhexyl) -phthalate We pump from the VA template at a pressure of 3 bar for 1 minute first through Ml (nozzle diameter: 1.4 / 0.6 mm) in circle VA - »Pl -» Ml - »VA. Then a solution of 464.52 g of water and 0.28 g of benzyl alcohol-hemiformal was injected for 3 minutes at a pressure of 3.5 - 4 bar via VC P3 - "Ml into this circuit. After the addition of water is completed, pump for a further 3 minutes at a pressure of 3 bar in the circle VA - »Pl -» Ml - »VA. This circuit is maintained for a further 10 minutes at a pressure of 12 bar. A dense liquid stable emulsion is formed. The results are listed in Table 6.

Table 6

Example Time [min / sec] Particle size 0 [pm] Viscosity [mPas] Stability [months] 17 17 1,748 th most common 2670 > 6

Example 18 (In the Invention)

To the solution of 171.9 g ethoxylated triglyceride with HLB value 18.1 and 148.1 g ethoxylated tridecyl alcohol with HLB value 11.4 in 800 g water contained in the VC - »P3 -» Ml circuit, inject 2800 g polydimethylsiloxane with a viscosity of η = 1000 mPas across the active substance circuit VA - »Pl -» Ml - »VA. The initial absolute pressure of the active substance circuit rises from 5 to 12 bar in 9 minutes. Circuit pressure VC - »P3 -» Ml monitors - each time 2 bar lower - this increase. After a total of 12 minutes, the drug delivery is complete and a viscous white paste is formed. With cooling for 14 minutes, this is pumped into the VC - »P3 -» Ml circuit at 10 bar.

Then 4080 g of water at a pressure of 12 bar for about 5 minutes is injected at 25 ° C from VB via P2. This reduces the pressure with increasing dilution in the VC circuit - »P3 -» Ml at

4.5 bar, with pump P2 accompanied by 2 bar higher pressure. After the addition of water is completed, the pressure in the VC - »P3 -» Ml circuit is increased to 80 bar and the emulsion is withdrawn via Ml from the mixing station.

A low-viscosity stable emulsion is formed.

The results are listed in Table 7.

Example 19 (In the Invention)

To the solution of 171.9 g ethoxylated triglyceride with HLB value 18.1 and 148.1 g ethoxylated tridecyl alcohol with HLB value 11.4 in 800 g water contained in the VC - »P3 -» Ml circuit, inject 2800 g polydimethylsiloxane with a viscosity η = 350 mPas across the active substance VA - »Pl -» Ml - »VA circuit. This increases the initial absolute pressure of the active substance circuit within 6 minutes from 7 to 10 bar. Circuit pressure VC - »P3 -» Ml monitors - each time 2 bar lower - this increase. After a total of 6 minutes, the active substance is finished and a viscous white paste is formed. With cooling for 20 minutes, this is pumped into the VC circuit - »P3 -» Ml at 10 bar.

Then at 25 ° C in UK injected 4080 g of water at a pressure of 10 bar for about 5 minutes via P2. This decreases the pressure by increasing the dilution in the VC - »P3 -» Ml circuit to 4 bar, with the P2 pump accompanying 2 bar higher pressure. After the addition of water is completed, the pressure in the VC - »P3 -» Ml circuit is increased to 80 bar and the emulsion is withdrawn via Ml from the mixing station.

A low-viscosity stable emulsion is formed.

The results are listed in Table 7.

Table 7

Example no. Time [min / sec] Particle size 0 [gm] at ₉₀ Stability [months] 18 32 0.689 1,541 th most common > 6 19 32 0.531 1,168 th most common > 6

For

Claims (17)

Patent claims A device for preparing a silicone and / or silane emulsion from an effective component comprising silicones and / or silanes and from an aqueous phase with a first mixing station for the emulsion components delivered via pumps (Pl, P2, P3) from reservoirs (VA, VB, VC), characterized in that - the first mixing station has a mixing device (Ml) in which the jets (2, 4) of the active substance jet are mixed with the aqueous phase (3) into a pre-emulsion (5), - the distance of the nozzles (2, 4) from one another is 1 to 10 times, preferably 2- to 4 times the diameter of the other nozzle (4), - the diameter of the second subsequently connected nozzle (4) is about 2- to 3 times as large as the diameter of the first nozzle (2), and the mixing station is coupled to the nozzle disperser (6), the nozzle dispersant (6) receiving a pre-emulsion (5) projecting out of the mixing station, and - a pressure drop in the nozzle dispersant (STR-D) is between 100 and 1000 bar, preferably between 100 and 600 bar, and - is an intermediate vessel (VD) which serves as a buffer vessel connected to the mixing device (Ml) and that the dispersant (6) with the nozzles receives a pre-emulsion (5) via an intermediate vessel (VD). Device according to claim 1, characterized in that the mixing station has a pre-homogenisation device (VC, P3) in which the pre-emulsion can be pre-homogenized in one circuit. Apparatus according to one of Claims 1 to 2, characterized in that a dilution device (VB, P2) is installed in front of the mixing station and the nozzle disperser (6). Device according to one of Claims 1 to 3, characterized in that the mixing device (Ml) consists of two nozzles (2, 4) arranged one after the other. Apparatus according to claim 4, characterized in that the pressure difference between the nozzles (2, 4) of the mixing device (Ml) is between 1 and 10 bar, preferably between about 2 and 3 bar. Apparatus according to one of Claims 1 to 5, characterized in that the first nozzle (2) of the mixing device (Ml) injects a jet (1) of the active substance into the supplied aqueous phase (3) and that the second nozzle (4) is a jet (1) the active substances with the aqueous phase (3) are intensively mixed and homogenized. Device according to one of Claims 1 to 6, characterized in that the nozzle dispersant (STR-D) consists of several nozzles (10, 12) connected one after the other. Device according to one of Claims 1 to 7, characterized in that the absolute pressure drop in the mixing station is between 2 and 100 bar, in particular between 2 and 60 bar. Apparatus according to one of Claims 3 to 8, characterized in that the dilution device consists of a vessel (VB) containing residual water and optionally additives and a pump (P2) through which water can be added by means of a first nozzle ( 2) mixing devices (Ml) to the pre-emulsion. Apparatus according to one of Claims 1 to 9, characterized in that the nozzle dispersant (6) is connected to a reservoir (VE) from which the emulsion can be re-fed to the nozzle disperser (6). A process for the preparation of aqueous silicone and / or silane emulsions with fine particles having a U90 value of less than 1.2 using a device according to claim 1, characterized in that it comprises - preparing a pre-emulsion by injecting a silicone and / or silane component into an aqueous phase containing the emulsifier in a mixing station, maintaining a pressure difference of not more than 10 bar between the two streams at absolute pressures below 100 bar, and - homogenization of the pre-emulsion is effected by means of a nozzle dispersant, the value U _{90 being} determined by the following formula: Uqo = d90-dl0 d50 in which dlO or. d90 represent the diameters of the remaining smallest (d 10) and. of the remaining largest (d90) particles remaining after subtracting 10% by weight of the smallest particles (dlO) or. having a maximum (d90) diameter of a given particle quantity and a value of d50 corresponding to a particle diameter greater than 50% by weight of all particles and less than 50% by weight of all particles. Method according to claim 11, characterized in that the homogenization takes place in a nozzle disperser having a maximum pressure drop of up to 1000 bar. Method according to claim 12, characterized in that the pre-emulsion leaving the mixing station is led into a nozzle dispersant directly or through a buffer tank. A method according to claim 12, characterized in that the pre-emulsion in the mixing station is pre-homogenized in a circuit before being led into a nozzle dispersant. Process according to claim 13, characterized in that the pre-emulsion is homogenized with a water shortage in the mixing station in the circuit before being led to a nozzle dispersant, inverted therein if desired, and then diluted with water to the required concentration. Method according to claim 13, characterized in that the pre-emulsion is homogenized by a water shortage in the mixing station in the circuit, then brought to the required concentration via a subsequently connected dilution device with water before being fed to the nozzle dispersant. Process according to claim 14 or 15, characterized in that the dilution water contains a thickener.