SI20193A - Device and method for producing silicone emulsions - Google Patents
Device and method for producing silicone emulsions Download PDFInfo
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- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
- B01F23/45—Mixing liquids with liquids; Emulsifying using flow mixing
- B01F23/451—Mixing liquids with liquids; Emulsifying using flow mixing by injecting one liquid into another
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
- B01F25/3121—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof with additional mixing means other than injector mixers, e.g. screens, baffles or rotating elements
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
- B01F25/3124—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof characterised by the place of introduction of the main flow
- B01F25/31243—Eductor or eductor-type venturi, i.e. the main flow being injected through the venturi with high speed in the form of a jet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/40—Static mixers
- B01F25/45—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads
- B01F25/452—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces
- B01F25/4521—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through orifices in elements, e.g. flat plates or cylinders, which obstruct the whole diameter of the tube
- B01F25/45211—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through orifices in elements, e.g. flat plates or cylinders, which obstruct the whole diameter of the tube the elements being cylinders or cones which obstruct the whole diameter of the tube, the flow changing from axial in radial and again in axial
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/834—Mixing in several steps, e.g. successive steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
- B01F23/41—Emulsifying
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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Abstract
Description
Naprava in postopek za pripravo silikonskih emulzijDevice and process for preparing silicone emulsions
Izum se nanaša na napravo in na postopek za pripravo stabilnih silikonskih emulzij s finimi delci, zlasti za pripravo emulzij olje-v-vodi s kar najbolj zmanjšano vsebnostjo emulgatorjev.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.
Znana je vrsta postopkov za emulgiranje netopnih silikonov oz. silanov v vodi. Tako na splošno pred dejanskim homogeniziranjem bodisi v silikon, v katerem je emulgator fino porazdeljen, počasi uvajajo majhne količine vode, tako da nastane emulzija vodav-olju, ki jo invertirajo s sledečim razredčenjem z vodo, preden jo homogenizirajo v specialni napravi ob učinku strižnih sil v emulzijo s finimi delci, bodisi silikon počasi vnesejo v vodno emulgatorsko zmes ob mešanju, preden nastalo emulzijo ž grobimi delci podvržejo dejanskemu homogeniziranju.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.
V začetku zmešana zmes lahko glede na vrsto postopka in učinkovine, koncentracijo emulgatorja, vneseno mešalno energijo in predvsem investiran čas že predstavlja zadosti stabilno emulzijo. Praviloma pa so te emulzije, ki jih označujejo kot predemulzije, z grobimi delci in jih je treba zaradi pomanjkljive stabilnosti takoj dovesti v dejansko homogeniziranje. Homogenizime naprave in postopki so opisani v Ullmamis Encyclopedia of Industrial Chemistry Vol A9 Edition 1987, str. 309 do 310. Priprava pred-emulzije poteče v mešalnih agregatih in je glede na vrsto naknadno priključenega homogenizimega stroja časovno določujoča stopnja.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.
Nadaljnji postopki za pripravo silikonskih emulzij so znani iz EP-A-043 091 in EP-A-0 579 458. V postopku EP-A-043 091 dovedejo malo vode s celotnim emulgatorjem popolno količino silikona, tako da nastane visoko -viskozna pasta oz. gel, ki ga nato prevedejo z razredčenjem v končno emulzijo.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.
Problematična postane priprava pred-emulzije po klasičnih postopkih z dodatkom siloksanov oz. silanov k prebitni fazi vode/emulgatorja, zlasti pri uporabi silicijevih spojin, ki lahko obstoje tako iz monomemih, linearnih kot tudi smolastih, po želji z nižje molekulskimi siloksani ali organskimi spojinami razredčenih struktur, če te lahko v principu reagirajo z vodno fazo. Sem spadajo npr. alkilalkoksisilani, smole, ki nosijo alkoksi skupine, kot tudi po želji zmesi obeh.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.
Nadaljnji problem obstoji v tem, da je priprava pred-emulzije po znanih postopkih posebej časovno zahtevna. Dotok siloksanske komponente v vodno fazo poteka kontrolirano ob mešanju, t.j. tako, da doseže optimalno premešanje. To ne dopušča hitrega dodajanja.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.
Pri tem zadenejo prve molekule učinkovine na ogromen prebitek vode, ki se šele v teku časa približa želenim koncentracijam in daje nestabilno pred-emulzijo z grobimi delci, ki jo je treba kar najhitreje dovajati v homogenizator.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.
Med dodajanjem so v primeru za vodo občutljivih komponent le-te le nezadostno zaščitene pred vodno fazo, tudi v primeru njenega zapufranja, tako da lahko pride do reakcije ustreznih komponent med seboj. To lahko povzroči, da je sledeče homogeniziranje zaradi kondenzacijskega postopka, ki mu sledi nastanek viskoznosti v dobljenih grobih emulzijskih delcih, oteženo oz. da postane pred-emulzija tako labilna, daje sploh ne morejo več dovajati v homogenizator. Tej pomanjkljivosti se lahko sicer zoperstavijo z močnim zvišanjem emulgatoija (v območju 5%), vodi pa do neželenih rezultatov pri mnogih uporabah in do obremenitve okolja.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.
Nadalje vodijo npr. v primeru alkilalkoksisiloksanov hidrolizne in kondenzacijske reakcije med emulgiranjem praviloma do neučinkovitosti pri uporabi in torej do neuporabnosti dobljene emulzije.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.
Če pred-emulzijo pripravijo preko paste oz. gela, ki ga nato v specialnem postopku razredčijo, se dajo v takih primerih, v katerih niso pomembne vsebnosti emulgatorja, pripraviti emulzije z nizkimi povprečnimi velikostmi delcev, pri čemer pa ni nobenih podatkov o njihovi porazdelitvi.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.
Ker gre za vrsto silikonskih učinkovin, ki vsaj pri zahtevanih količinah emulgatorjev dajejo paste le v nezadostni meri, so ti postopki omejeni v svoji Širini uporabe. Nadalje se vrsta emulzij, kot so npr. emulzije antipenilcev oz. z emulgatorjem revne (< 5%) in istočasno z učinkovino revne (< 20%) emulzije, po tem postopku ne dajo zadovoljivo pripraviti. Tako dobijo pri postopku po EP 0 579 458 ob veliki porabi časa (glej tamkajšnje primere) emulzije z zelo velikimi delci v območju od 3-60 pm.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).
Naloga predloženega izuma je bila zato, da zagotovimo hitro potekajoč in torej gospodaren postopek, ki nima opisanih pomanjkljivosti in omogoča pripravo emulzij s finimi delci, ki imajo ozke porazdelitve velikosti delcev, z nizkimi vsebnostmi emulgatorja ter z nizkimi do visokimi koncentracijami učinkovine, kot tudi napravo, primemo za ta postopek.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.
Pri tem naj bi za vodo občutljive učinkovine vodile do - tudi preko enega leta stabilnih in predvsem učinkovitih emulzij.In doing so, water-sensitive active substances should lead to stable and, above all, effective emulsions over one year.
Posebna želja je bila, med drugim za dosego visoke reproducibilnosti, ab initio emulgatorske količine, potrebne za določeno ploskovno oblaganje delcev učinkovin, ciljano spraviti v kontakt z učinkovino in na to naravnati mehansko energijo. To predpostavlja postopek z matematično ekzaktno opisljivimi emulgimimi napravami. Naprave, ki so podvržene močnemu vplivu zadrževalnega časa (npr. mešalni agregati itd.), niso primerne.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.
Končno naj bi energija, ki jo je treba vnesti, pokrivala široko - doslej dosegljivo le z več napravami različne konstrukcije - območje. Tako lahko v isti napravi pripravimo emulzije, ki jih je treba ščititi pred visokim vnosom energije - npr. emulzije antipenilcev kot tudi emulzije, ki potrebujejo večkratnik energije, ki jo dajo na razpolago klasični homogenizatorji.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.
Postavljeno nalogo smo lahko rešili z napravo, ki obstoji iz postrojenja iz rezervoarjev črpalk in šob, ki jo v nadaljevanju označujemo kot mešalno postajo. Posebno ugodno seje izkazalo, kadar smo tej mešalni postoji priključili naknadno dispergator s šobami, kot je bil opisan za pripravo farmacevtskih ali kozmetičnih disperzij (Bayer AG / EP 0 101 007).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).
Predmet izuma je torej naprava za pripravo silikonske, silanske oz. silikonsko/silanske emulzije iz učinkovite komponente, ki vsebuje silikone in/ali silane, in vodne faze (komponente), s prvo mešalno postajo za emulzijske komponente, dovedene preko črpalk Pl, P2, P3 iz rezervoarjev (VA, VB, VC), pri kateri ima prva mešalna postaja mešalno napravo Ml, v kateri šobi 2, 4 pomešata curek učinkovine z vodno fazo 3 v pred-emulzijo (glej sl. 1 in 2).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).
V prednostni izvedbeni obliki naprave v smislu izuma je prva mešalna postaja povezana z visokotlačnim homogenizatorjem, pri čemer visokotlačni homogenizator dobi pred-emulzijo, ki izstopa iz mešalne postaje.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.
Predmet izuma je nadalje postopek za pripravo vodnih silikonskih in/ali silanskih emulzij s finimi delci z ozko porazdelitvijo delcev, ki obsega pripravo pred-emulzije z injiciranjem silikonske in/ali silanske komponente v vodno fazo, ki vsebuje emulgator, v mešalni postaji in homogeniziranje v visokotlačnem homogenizatorju, kot tudi emulzije iz silikonskih spojin in/ali silanov, ki se jih da dobiti po tem postopku.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.
Zlasti se izum nanaša na postopek za pripravo vodnih silikonskih in/ali silanskih emulzij s finimi delci z vrednostjo U90 pod 1,2 (t.j. z ozko porazdelitvijo delcev), ki obsega pripravo pred-emulzije z injiciranjem silikonske in/ali silanske komponente v vodno fazo, ki vsebuje emulgator, v mešalni postaji, pri čemer vzdržujemo tlačno razliko, odvisno od dimenzij šob, največ 10 bar med obema tokovoma pri absolutnem padcu tlaka pod 100 bar in homogeniziranje pred-emulzije.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.
Predloženi izum natančneje pojasnjujejo priložene slike in primeri.The present invention is explained in more detail by the accompanying drawings and examples.
Pri tem prikazujejo:In doing so, they show:
sl. 1 mešalno postajo;FIG. 1 mixing station;
sl. 2 shematsko predstavitev naprave v smislu izuma z visokotlačnim homogenizatorjem;FIG. 2 is a schematic representation of a device according to the invention with a high pressure homogenizer;
sl. 3 razporeditev šob dispergatorja s šobami;FIG. 3 arrangement of nozzle dispersant nozzles;
sl. 4 visokotlačni homogenizator;FIG. 4 high pressure homogenizer;
sl. 5, 6, 7 in 8 diferancialno in integralno porazdelitev velikosti delcev iz primerov 10, 9, 18 in 19.FIG. 5, 6, 7 and 8 the differential and integral particle size distribution of Examples 10, 9, 18 and 19.
Pri napravi v smislu izuma se da pri znanem padcu tlaka (Δρ) ' , znani vsebnosti in površinski potrebi emulgatorja, znanem premeru šob (D) * , znani napetosti mejnihIn 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 ploskev (γ), znani viskoznosti (η) disperzne faze in znanem številu pretokov (n) izračunati pričakovano povprečno velikost delcev (d), in sicer po naslednji formuli: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 η0’495 A γ°’365 A D0’165 A n0’36 k = konstanta (ki zadeva vsebnost emulgatorja/površinsko potrebo).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).
Jedro mešalne postaje je razporeditev šob v mešalni napravi Ml, katere dimenzije so odvisne od konsistence obeh faz, ki jih je treba združiti, njihovih koncentracij glede druga na drugo, izbranega padca tlaka in pretoka.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.
Sl. 1 kaže možno izvedbeno obliko. Pri tem npr. silikonsko olje 1 skozi prvo šobo 2 injiciramo v vodno fazo 3 in takoj nato v drugi šobi 4 intenzivno premešamo in homogeniziramo. V naknadno priključenem dispergatorju s šobami STR-D poteče potem dokončna fma porazdelitev. Dispergator s šobami STR-D je lahko neposredno priključen ali pa pri šaržnem načinu šele po pripravi celotne pred-emulzije 5.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.
Razporeditev šob po sl. 1 obremenimo prednostno preko dveh črpalk Pl, P3 s tlačno razliko 2-3 bar tako, da v primeru - kjer to dopušča hitrost oblaganja emulgatorja vodno emulgatorsko raztopino in silikon skupaj vodimo v končni emulzij ski koncentraciji in direktno homogeniziramo preko dispergatorja s šobami STR-D v enem ali največ treh prehodih.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.
Število prehodov je praviloma odvisno od vrste in vsebnosti emulgatorja. Pri vsebnostih emulgatorjev v območju 3% - če ne upoštevamo izjem - je potreben le en prehod.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.
Če gre za emulgatorje, ki površine nastalih delcev določenih silikonskih učinkovin obložijo le relativno počasi, lahko postopek tako modificiramo, da delamo s poljubnim deficitom vode, ki vsebuje celotno količino emulgatorja. V tem primeru dobljeno bolj koncentrirano emulzijo lahko vodimo nazaj v vodno emulgatorsko raztopino in s to vIn 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
spet dovajamo v šobo in v učinkovino, ki priteka, tako da nastane krogotok. Ce po doseženem združenju vzdržujemo krogotok še nekaj minut, je odvisno od koncentracije in vrste emulgatorja kot tudi silikona, ki ga je treba emulgirati. Preko nadaljnje šobe in črpalke lahko dodamo v krogotok ostanek vode, ki je po želji pomešana z nadaljnjimi dodatki, npr. zagostili ali konzervimimi sredstvi, preden to pred-emulzijo dovedemo v dispergator s šobami STR-D.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.
Sl. 4 prikazuje dispergator s šobami STR-D, ki ga uporabimo kot visokotlačni homogenizator 6. Dispergator s šobami STR-D obstoji podrobno iz črpalke 14, po želji pulzacijskega dušilca 16 in razporeditve 18 šob, ki je podrobno predstavljena na sl. 3. Dvostopenjska razporeditev 18 šob ima prvo Šobo 10 kot tudi za njo priključeno drugo šobo 12, s pomočjo katere homogeniziramo pred-emulzijo 5. Vsaka šoba 10, 12 obstoji iz vložka 11 v cevi 9, pri čemer ima vsak vložek 11 cilindričen odsek 13, ki štrli nasproti smeri toka pred-emulzije 5, z dvema nasproti ležečima kapilarnima izvrtinama 15. Cilindrični odsek 13 tvori obročni prostor 17 v cevi 9, pri čemer predemulzija 5 struja skozi cev 9 v obročni prostor 17 in od tam skozi kapilarne izvrtine 15 v vmesno komoro 20. Ker si kapilarni izvrtini 15 stojita nasproti, se izstopajoči emulzijski curki zaletavajo v notranjosti cilindričnega odseka 13. S tem dosežemo posebno dobro dispergiranje. Emulzija struja iz vmesne komore 20 v drugi obročni prostor 22 druge šobe 12 in stopa tam ponovno skozi kapilarne izvrtine 24 druge šobeFIG. 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. Homogenizirana emulzija 25 izstopa skozi iztok 26 iz dispergatorja s šobami STR-D.12. A homogenized emulsion 25 exits through the outlet 26 from a STR-D nozzle dispersant.
Predloženi postopek omogoča tudi, da lahko razmerje -celoten emulgator vsebujočevode proti učinkovini takoj izberemo, da nastanejo tudi geli in paste. Predpogoj je, da so izbrane črpalke s prisilnim transportom in obvladajo konsistenco past.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.
Prednost predloženega postopka je, da lahko praktično kontinuimo dela, porabi manj časa in ima izvrstno reproducibilnost. Daje stabilne emulzije, katerih srednje velikosti delcev so, pri emulgatorskih vsebnostih v območju od 0,5 - 3%, pri vrednostih < 1 pm. Pri tem je za stabilnost in za mnoge uporabe važna porazdelitev velikosti delcev v ožjem območju kot pri klasičnih postopkih.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.
Obstaja pa tudi nekaj redkih primerov, kjer dobimo manj stabilne emulzije, pri katerih tako velikost delcev kot tudi njihova porazdelitev ne igra nobene odločilne vloge, tako da se iz stroškovnih ali drugih razlogov po prehodu skozi mešalno postajo odpovemo sledečemu homogeniziranju. Pomanjkljivost stabilnosti teh emulzij lahko v takih primerih kompenziramo z bistvenim povečanjem emulzijske viskoznosti z dodatkom nevtralnega zagostila. Zaradi pogoste slabe nadaljnje predelovalnosti takih emulzij pa praviloma poskušamo obiti to metodo priprave.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.
Med gornjimi emulzijami ponovno najdemo malo emulzij z visoko viskoznostjo, pri katerih je za to odgovorna visokoviskozna učinkovina, npr. organske narave, ki se ji ne moremo odpovedati.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.
V takih primerih bi bilo seveda negospodarno, da bi take emulzije naknadno dodatno emulgirali v dispergatorju s šobami STR-D, ker - če naj bi v bistvu zadržali sedanje stanje emulzije - dispergator s šobami ob za to potrebnih pogojih postopka ne bi mogel znatno prispevati k izboljšanju fizikalnih lastnosti emulzije.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.
Pri tem se priporoča, da bi pred-emulzijo, ki zapušča mešalno postajo, v drugi mešalni postaji homogenizirali z višjim tlakom, npr. do 100 bar.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.
Ta metoda je prav tako priporočljiva, kadar je treba emulgirati Si spojine, ki se jih da zlahka emulgirati z emulgatorji, ki imajo zadostno hitrost pri oblaganju površin delcev. V tem primeru se lahko odpovedemo zagostilu.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.
Da bi minimizirali aparativne izdatke, pa je prednostno, da pred-emulzijo transportiramo v rezervoar, predhodno priključen prvi mešalni postaji, in od tam preko iste mešalne postaje ob drugih tlačnih pogojih spravimo v želeno emulzijsko stanje.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.
Predmet izuma je torej nadalje postopek za pripravo vodnih silikonskih in/ali silanskih emulzij s finimi do grobimi delci v območju od okoli 0,4 do 5,0 pm z vrednostjo U90 nad 1,1 (t.j. s širšo porazdelitvijo delcev), ki za emulgiranje potrebujejo le neznatne strižne sile oz. jih stabiliziramo z zagostilom, ki obsega pripravo pred-emulzije z injiciranjem silikonske in/ali silanske komponente v vodno fazo, ki vsebuje emulgator, v mešalni postaji, pri čemer vzdržujemo tlačno razliko, odvisno od dimenzij šob, največ 10 bar med obema tokovoma pri absolutnem padcu tlaka pod 80 bar, homogeniziranje pred-emulzije v naknadno priključeni mešalni postaji ali časovno premaknjeno v isti mešalni postaji pri absolutnem padcu tlaka do 100 bar.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.
Izvedbena oblika je razvidna s sl. 2, v kateri pomenijoThe embodiment is illustrated in FIG. 2 in which they mean
VA: posoda za učinkovinoVA: Active substance container
VB: posoda za preostalo vodo (+ dodatke)UK: Residual water tank (+ accessories)
VC: puffska posoda/vmesna posodaVC: puff container / intermediate container
VE: rezervoar/vmesna posodaVE: tank / intermediate container
VD: puffska posodaVD: puff container
Pl, P2: črpalki (po želji s prisilnim transportom)Pl, P2: pumps (optional with forced transport)
P3, P4, P5: črpalkeP3, P4, P5: pumps
Ml: mešalna šoba učinkovina/vodaMl: active substance / water agitator
STR-D: dispergator s šobami.STR-D: Nozzle Disperser.
V krogotoku učinkovine VA-»P1-»M1-»VA injiciramo vodno fazo pri nizkem tlaku preko VC->P3->M1 in po končanem dodajanju krogotok VA->P1-»M1-»VA priključimo na višji tlak, pri čemer Ml služi kot naknadno priključen homogenizator. Emulzijo lahko odvzemamo za Ml. Seveda je pogoj, da imajo emulgatorji zadosti visoko hitrost oblaganja delcev, lastnost, ki je odvisna tudi od akceptance učinkovine, da te emulgatorje adirajo.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.
Primeri za silikonsko in silansko komponento so silikonske spojine z običajno sestavo:Examples of the silicone and silane components are silicone compounds having a conventional composition:
(CH3)3SiO[(CH3)2SiO]5o.5ooSi(CH3>i (CH3) 3SiO [(CH 3 ) 2 SiO] 5o.5ooSi (CH 3 > i
HO(CH3)2SiO[(CH3)2SiO]3QoSi(CK3)2OH (CH3)3SiO[(CH3)(H)SiO]3oSi(CH3)3 (CH3)3Si(0)u(OCH3)o.g;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;
organoalkoksisilani, njihovi hidrolizati, npr. :organoalkoxysilanes, their hydrolysates, e.g. :
CH3(CH2)7Si(OEt)3 CH 3 (CH 2 ) 7 Si (OEt) 3
CH3(CH2)3Si(OEt)3CH 3 (CH 2 ) 3 Si (OEt) 3
CH3(CH2)u.i3(CH3)Si(OMe)2 CH 3 (CH 2 ) ui 3 (CH 3 ) Si (OMe) 2
CH3(CH2)7Si(OEt)2O(OEt)2Si(CH2)7CH3CH 3 (CH 2 ) 7 Si (OEt) 2 O (OEt) 2 Si (CH 2 ) 7CH3
CH3(CH2)3St(OEt)2[0(EtO)Si(CH2)3CH3]o-5 OSi(OEt)2(CH2)3CH3;CH 3 (CH 2) 3 St (OEt) 2 [0 (EtO) Si (CH 2) 3CH3] o-5 OSi (OEt) 2 (CH 2) 3 CH 3;
'l linearni poliorganosiloksani z in/ali brez silicijevo funkcionalnimi vezanimi skupinami, kot so vodik, alkoksi, polietrske oz. hidroksi skupine, z in/ali brez organo funkcionalno vezanimi skupinami, kot so polietri, amini ali halogeni oz. psevdo halogeni, npr.: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:
(CH3)3SiO[(CH3)2SiO]jo-jooSi(CH3)3 HO(CH3)2SiO[(CH3)2SiO]iooSi(CH3)2OH (CH3)3SiO[(CH3)(H)SLO]soSi(CH3)3 (CH3)3SiO[(CH3)CH2=CHSiO]3 [(CH3)2SiO]5o.jooSi(CH3)3 (CH3)3SiO[CH3(OCH2CH2)sO(CH2)3(CH3)SiO]3[(CH3)2SiO]6ooSi(CH3)3 razvejeni poliorganosiloksani z in/ali brez vezanimi silicijevo funkcionalnimi skupinami, kot so vodik, alkoksi, polietrske oz. hidroksi skupine, z in/ali brez organo funkcionalno vezanimi skupinami, kot so polietri, amini ali halogeni oz. psevdo halogeni, npr.:(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:
CH3 Si{[(CH3)2SiO]50OSi(CH3)3}3CH 3 Si {[(CH 3 ) 2 SiO] 50 OSi (CH 3 ) 3} 3
CH3 SifKCHjhSiOjgoOSiCCIDiCH^CHjJsCH 3 SifKCHjhSiOjgoOSiCCIDiCH ^ CHjJs
CH3 SHKC^SiOJsoOSiCCftji (CH2)3(OCH2CH2)gOCH3}3CH 3 SHKC ^ SiOJsoOSiCCftji (CH 2 ) 3 (OCH 2 CH 2 ) gOCH 3 } 3
H2N(CH2)3Si{C(CH3)2SiO]uOSi(CH3)}3;H 2 N (CH 2 ) 3 Si {C (CH 3 ) 2 SiO] in OSi (CH 3)} 3 ;
silikonske smole z arilnimi, alkilnimi, organofunkcionalno modificiranimi alkilnimi skupinami, alkoksifunkcionalne smole, z ali brez razredčila, npr.:silicone resins with aryl, alkyl, organofunctionally modified alkyl groups, alkoxy functional resins, with or without diluent, eg:
(CH3)ujSiiOt.42 (CH3)o.8 (Cl2H25)oaSi(0)l(OCH3)1 (Si02)io[(CH3)3SiO vjoj Si02[(CH3)CH2=CHSiO]oj[OwSi(CH3)3],a zmesi gornjih komponent med seboj ali z netopnimi dodatki mineralne ali organske vrste.(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.
Z emulgatorji so mišljeni ionski in neionski emulgatorji, kot so običajni v silikonskem emulgiranju, oz. njihove zmesi.Emulsifiers are intended to be ionic and non-ionic emulsifiers, as is customary in silicone emulsification, respectively. mixtures thereof.
Kot ionski emulgatorji so primerni glede na učinkovino npr.As ionic emulsifiers, they are suitable with respect to the active ingredient e.g.
alkilsulfonati z 8 do 18 C-atomi z ali brez etilen- oz. propilenoksidnih enot;alkyl sulfonates having 8 to 18 C atoms, with or without ethylene or. propylene oxide units;
sulfatni estri, kot npr. CH3(CH2)6CH2O(C2H4O)6.i9SO3H;sulfate esters, such as e.g. CH 3 (CH 2 ) 6CH 2 O (C 2 H 4 O) 6. 19 SO 3 H;
alkilarilsulfonati, kot npr. dodecilbenzensulfonat;alkylarylsulfonates such as e.g. dodecylbenzenesulfonate;
kvarteme amonijeve spojine, kot npr. dodeciltrimetilamonijev hidroksid, oktildimetilbenzilamonijevi hidroksidi oz. njihove soli.quartemes of ammonium compounds such as e.g. dodecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxides, resp. their salts.
Vsekakor pa so prednostni neionski emulgatorji, katerih vrednost HLB je v območju vHowever, non-ionic emulsifiers with a HLB value in the range of v are preferred
od 10 do 16. Ce gre za zmesi tega območja, lahko te obstoje iz kombinacije emulgatorjev z vrednostjo HLB med 2,7 in 18,7.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.
Kot neionski emulgatorji so primerni etilenoksidni adukti na maščobne alkohole, alkilfenole, trigliceride ali sladkorje; polietilenoksidsorbitanlavrati, -palmitati, -stearati; etilenoksidni adukti na alkilamine; in polivinilalkoholi (kot Mowiol), zlasti etoksidni adukti na tridecilalkohol, etoksidni adukti na sorbitan monooleate (Tween® produkti od ICI), sorbitan monooleati in njihove zmesi.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.
Povprečni premer delcev - v tekstu označen tudi kot velikost delcev - preračunamo iz volumskega povprečja, ki ga dobimo iz celotnega volumna vseh delcev emulzije, deljeno s številom delcev.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.
vv
Številčno vrednost širine porazdelitve velikosti delcev izračunamo tako, da od dane količine delcev delcev z najmanjšimi premeri do količine 10 mas.% količine delcev (d 10) in delcev z naj večjimi premeri do količine 10 mas.% količine delcev (d90) ne upoštevamo in razliko premerov preostalih največjih delcev in preostalih najmanjših delcev delimo s premerom tistega delca (d50), kije večji kot 50 mas.% vseh delcev in manjši kot 50 mas.% vseh delcev. To številčno vrednost imenujemo v nadaljevanju U90: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 - dio d50 (glej sl. 5, 6, 7 in 8).Uon = d90 - part of d50 (see Figs. 5, 6, 7 and 8).
Povprečne velikosti delcev smo merili s Frauenhoferjevim uklonom, ultracentrifugiranjem ali s fotometrijo s pomočjo Mie-teorije. Porazdelitvene krivulje smo merili s pomočjo ultracentrifuge.Average particle sizes were measured by Frauenhofer removal, ultracentrifugation or photometry using Mie theory. The distribution curves were measured using an ultracentrifuge.
Aparatura (sl. 2), prikazana v prilogi v shematski tehnološki shemi, omogoča fleksibilno na učinkovino, emulgator in njihove koncentracije prikrojene prilagoditve postopka.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.
Tako lahko npr. v ugodnem primeru, ko gre za produkte, ki se dajo zlahka emulgirati, je emulgator hiter in je v ugodni koncentraciji, učinkovino (iz VA) z zmesjo vode/emulgatorja (iz VC) v želenem razmerju vodimo skupaj v Ml in nastalo predemulzijo vodimo direktno ali preko pufrske posode (VD) v dispergator s šobami STR-D, v enem prehodu homogeniziramo in nato vodimo v polnilno postajo.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.
Ta način postopka zahteva zanesljivo krmiljenje oz. sinhronizacijo črpalk med seboj. Če naj se temu odpovemo in točno razmerje emulgatorja/učinkovine pri skupnem vodenju v Ml ni nujno potrebno, lahko - da bi kljub temu zagotovili zahtevano koncentracijo učinkovine v emulziji, učinkovino dovajamo preko M1 k izračunanemu deficitu vode/emulgatorja, nastalo pred-emulzijo tekoče vračamo zmesi vode/emulgatorja (po VC) in v krogotoku preko Ml spet vodimo skupaj z učinkovino. Če je celotna učinkovina porabljena, pred-emulzijo spravimo preko šobe Ml z dodatkom preostale vode (iz VB) preko podobnega, kot zgoraj opisanega krogotoka M1->VC-»M1, do končne koncentracije in kot zgoraj homogeniziramo.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.
V primeru učinkovin, ki se dajo težko emulgirati, počasnih emulgatorjev ali zelo majhnih koncentracij emulgatorjev lahko pred dovodom v STR-D nekajkrat predemulgiramo preko VC in Ml v krogu, preden postopamo kot zgoraj.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.
Če je pomembna pasta oz. gel in je učinkovina za to primerna, jo lahko s poljubnim deficitom vode (iz VC) - vendar s celotnim emulgatorjem - skupaj vodimo v Ml, nastalo emulzijo kot zgoraj vodimo nazaj v VC in z vsebnostjo le-te vedno spet razpršujemo preko Ml z učinkovino. Pri tem nastane visoko viskozna pred-emulzija, ki ima lahko glede na izbrane razmere konsistenco paste oz. gela.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.
To lahko - glede na namen uporabe - polnimo kot tako ali nadalje obdelamo, kot je opisano v nadaljevanju.Depending on the purpose of use, this can be processed as such or further processed as described below.
Preden jo homogeniziramo zgoraj v STR-D, jo vodimo preko Ml, kjer preostalo vodo (iz VB), po želji z zagostilom in drugimi običajnimi dodatki injiciramo, tako da dosežemo izračunano sestavo.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.
Če je potreben več kot en prehod skozi STR-D, lahko še enkrat vodimo preko VE-+STR-D v krogu, preden emulzijo polnimo.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.
Če pa želimo več diskretnih prehodov, lahko iz pufrske posode. VD emulgiramo preko STR-D v 1. prehodu v VE, po koncu od tam v 2. prehodu preko STR-D spet v VD itd.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.
V naslednjih primerih se nanašajo vsi podatki, če ni drugače navedeno, na maso.In the following cases, all data refer to the mass, unless otherwise stated.
Uporabimo naslednje okrajšave:Let's use the following abbreviations:
V tabelah je sedaj naveden le potreben čas za pripravo pred-emulzije, ker so priprave vodnih emulgatorskih zmesi pri primerih v smislu izuma in pri primerih, ki niso v smislu izuma, praktično enake. Dejanska homogenizima stopnja prav tako ni bila vključena v upoštevanje časa, ker je v najširši meri odvisna od kapacitete primerjalnih emulgimih aparatov.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.
V tabelah so primeri v smislu izuma tiskani krepko, primerjalni primeri kurzivno.In the tables, the examples according to the invention are printed in bold, comparative examples in italics.
PrimeriExamples
A. Smolne emulzijeA. Resin emulsions
Primer 1 (Primerjalni primer)Example 1 (Comparative Example)
238,7 g destilirane vode segrejemo v 2-litrski posodi na 60 °C in ob mešanju dodamo 55 g staljene zmesi - ki ustreza 2,50% glede na celotno šaržo - iz POE-stearilalkohola in POE-cetilalkohola s celotno vrednostjo HLB 15,5.238.7 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.
Po ohlajenju na 40 °C v 1 uri dodamo 1447,6 g Isopar® G - raztopine z 80% smole s povprečno sestavo (CHsjijgSiiOi ^ in z viskoznostjo 1620 mPaAs pri mešalni hitrosti 250 - 400 obr/min. Mešamo še 10 minut z mešalno hitrostjo ~ 400 obr/min. V 25 minutah dodamo ob mešanju 458,7 g vodne raztopine 1,76 g karboksimetilceluloze (Walocel CRT 5000 GA). Mešamo še 40 minut.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.
Pred-emulzijo homogeniziramo pri padcu tlaka ΔΡ = 250 bar v klasičnem visokotlačnem homogenizatorju tipa Gaulin v šestih prehodih. Rezultati so navedeni v tabeli 1.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.
Primer 2 (Primerjalni primer)Example 2 (Comparative Example)
Primer 1 ponovimo s celotno vsebnostjo emulgatorja 3,00%. Rezultati so navedeni v tabeli 1.Example 1 was repeated with a total emulsifier content of 3.00%. The results are listed in Table 1.
Primer 3Example 3
Enako šaržo kot v primeru 1 - vendar z 2,2 % emulgatorske zmesi - povečamo za faktor 2,7273. 645,0 g destilirane vode segrejemo v VC (glej dodatek sl. 2) na 50 °C in ob mešanju dodamo 133 g staljene zmesi - ustrezno 2,20% glede na celotno šaržo - iz POE-sterarilalkohola in POE-cetilalkohola s celotno vrednostjo HLB 15,5 in potisnemo preko P3 s 3 bar skozi Ml (premer šob 2,1/1,0 mm) v VC in 30 s vodimo v krogu preko P3 skozi Ml v VC. V tem krogotoku 17 minut injiciramo 3948 g iste smole kot v primeru 1 iz VA preko Pl s 5 bar v Ml. Nato vzdržujemo krogotok 10 minut, nato iz VB preko Ml 9 minut injiciramo vodno raztopino 4,8 g karboksimetilceluloze (Walocel CRT 5000 GA) v 1264,2 g vode v krogotok. Po končanem dodajanju vzdržujemo krogotok še 40 minut, preden pred-emulzijo pri padcu tlaka ΔΡ = 250 bar v dispergatorju s šobami STR-D (premer šob: 0,2828 mm) homogeniziramo v treh prehodih. Rezultati so navedeni v tabeli 1.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.
Primer 4Example 4
Primer 3 ponovimo s celotno emulgatorsko vsebnostjo 2,5%. Rezultati so navedeni v tabeli 1.Example 3 was repeated with a total emulsifier content of 2.5%. The results are listed in Table 1.
Primer 5Example 5
Primer 3 ponovimo s celotno emulgatorsko vsebnostjo 2,8%. Rezultati so navedeni v tabeli 1.Example 3 was repeated with a total emulsifier content of 2.8%. The results are listed in Table 1.
Primer 6Example 6
Primer 3 ponovimo s celotno emulgatorsko vsebnostjo 3,0%. Rezultati so navedeni v tabeli 1.Example 3 was repeated with a total emulsifier content of 3.0%. The results are listed in Table 1.
Tabela 1Table 1
B. Emulzije smole/silana (v vodi občutljiv)B. Resin / silane emulsions (water sensitive)
Primer 7 (Primerjalni primer) g emulgatorske zmesi - ki ustreza 1 mas.% glede na celotno šaržo - iz etoksiliranega sorbitanmonolavrata in etoksiliranega oleilalkohola s celotno HLB vrednostjo 15,3 pomešamo v 4-litrski mešalni posodi z 816,22 g vode in 2,18 g dietanolamina in mešamo 2 uri pri 80 °C, pri čemer nastane bistra raztopina. K ohlajeni raztopini dodajamo 65 minut pri mešalni hitrosti 700 obr/min 1359,6 g zmesi iz 49,2% oktiltrietoksisilana in 50,8% smole s sestavo (CH3)o>8(Ci2H25)o>2Si(0)1(OCH3)i. Po končanem dodajanju mešamo še 30 minut pri 550 obr/min. Po 30 minutah odvzamemo vzorec za določitev velikosti delcev. Predemulzijo v dveh prehodih homogeniziramo pri padcu tlaka ΔΡ = 250 bar v klasičnem homogenizatorju tipa Gaulin. Rezultati so navedeni v tabeli 2.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.
Primer 8Example 8
Šaržo iz primera 7 podvojimo. 44 g emulgatorske zmesi - ki ustreza 1 mas.% glede na celotno šaržo - iz etoksiliranega sorbitanmonolavrata in etoksiliranega oleilalkohola s celotno HLB vrednostjo 15,3 pomešamo v VC (glej sl. 2) s 1632,44 g vode in 4,36 g dietanolamina in mešamo 2 uri pri 80 °C, pri čemer nastane bistra raztopina. Po ohlajenju črpamo 1 minuto pri 3 bar v krogu VC P3 -> Ml -> VC. V ta krogotok injiciramo iz VA preko Pl in skozi Ml (premer šob 2,1/1,0 mm) 3,5 minut 2719,2 g zmesi iz 49,2% oktiltrietoksisilana in 50,8% smole s sestavo (CH3)o,8(C12H25)o>2Si(0)i(OCH3)i pri 5 bar. Po končanem dodajanju vzdržujemo gornji krogotok še 15 minut pri 3 bar. Vzorec za določitev velikosti delcev odvzamemo po 5 in 15 minutah. Pred-emulzijo v dveh prehodih homogeniziramo pri padcu tlaka ΔΡ = 100 bar. Rezultati so navedeni v tabeli 2.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.
Primer 9 (Primerjalni primer) g emulgatorske zmesi - ki ustreza 1 mas.% glede na celotno šaržo - iz etoksiliranega sorbitanmonolavrata in etoksiliranega oleilalkohola s celotno HLB vrednostjo 15,3 pomešamo v 4-litrski mešalni posodi s 163,2 g vode in 2,18 g dietanolamina in mešamo 2 uri pri 80 °C, pri čemer nastane bistra raztopina. K ohlajeni raztopini dodajamo 65 minut pri mešalni hitrosti 700 obr/min 1359,6 g zmesi iz 49,2% oktiltrietoksisilana in 50,8% smole s sestavo (CH3)o,8(Ci2H25)o,2Si(0)i(OCH3)i. Po končanem dodajanju nadalje mešamo 15 minut pri 550 obr/min, pri čemer nastane bolj viskozna pasta. Pri prejšnji mešalni hitrosti dodajamo 30 minut 653,0 g vode in še toliko časa mešamo, dokler velikost delcev ne pade pod 5 pm (45 minut). Pred-emulzijo homogeniziramo v 2 prehodih pri padcu tlaka ΔΡ = 200 bar v klasičnem homogenizatorju tipa Gaulin. Rezultati so navedeni v tabeli 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.
Primer 10Example 10
Šaržo iz primera 9 potrojimo. 66 g emulgatorske zmesi - ki ustreza 1 mas.% glede na celotno Šaržo - iz etoksiliranega sorbitanmonolavrata in etoksiliranega oleilalkohola s celotno HLB vrednostjo 15,3 pomešamo v VC (glej sl. 2) s 489,60 g vode in 6,54 g dietanolamina in mešamo 2 uri pri 80 °C, pri čemer nastane bistra raztopina. Po ohlajenju črpamo 1 minuto pri 3 bar v krogu VC -> P3 -> Ml -> VC. V ta krogotok injiciramo iz VA preko Pl in skozi Ml (premer šob 2,1/1,0 mm) 5 minut 4078,8 g zmesi iz 49,2% oktiltrietoksisilana in 50,8% smole s sestavo (CH3)oi8(Ci2H25)o(2Si(0)i(OCH3)i pri 5 bar. Po končanem dodajanju vzdržujemo gornji krogotok še 4 minute pri 3 bar. Nato iz VB 10 minut injiciramo v gornji krogotok 1959 g vode preko Ml. Po končanem dodajanju vode pred-emulzijo še 1 minuto predhomogeniziramo v krogotoku, odvzamemo vzorec za določitev velikosti delcev in v dveh prehodih homogeniziramo pri padcu tlaka ΔΡ = 100 bar v dispergatorju s šobami. Rezultati so navedeni v tabeli 2.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.
Tabela 2Table 2
>N μCS χλ> N μCS χλ
U •M ><Z>In • M> <Z>
C —C -
O' >O '>
ΌΌ
CU *CU *
C •θ' bC • θ 'b
‘C cu'C cu
Primer 11 g emulgatorske zmesi - ki ustreza 0,64 mas.% glede na celotno šaržo - iz etoksiliranega sorbitanmonolavrata in etoksiliranega oleilalkohola s celotno HLB vrednostjo 15,3 pomešamo v VC (glej sl. 2) s 390,83 g vode in 3,17 g dietanolamina in mešamo 2 uri pri 80 °C, pri čemer nastane bistra raztopina. Po ohlajenju črpamo 1 minuto pri 3 bar v krogu VC -> P3 -> Ml -> VC. V ta krogotok injiciramo iz VA preko Pl in skozi Ml (premer šob 1,8/0,9 mm) 3 minute pri 5 bar 1980 g zmesi iz 49,2% oktiltrietoksisilana in 50,8% smole s sestavo (CH3)oXCi2H25)o,2Si(0)i(OCH3)i. Po končanem dodajanju vzdržujemo gornji krogotok še 2 minuti pri 3 bar. Nato iz VB 13 minut injiciramo v gornji krogotok 2594 g vode preko Ml. Po končanem dodajanju vode pred-emulzijo še 4 minute pred-homogeniziramo v krogotoku, odvzamemo vzorec za določitev velikosti delcev in v 2 prehodih homogeniziramo pri padcu tlaka ΔΡ = 95 bar v dispergatorju s šobami. Rezultati so navedeni v tabeli 3.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.
Tabela 3Table 3
C. Emulzije silikonskega oljaC. Silicone oil emulsions
Primer 12Example 12
150 g staljene emulgatorske zmesi - ki ustreza 3 mas.% glede na celotno šaržo - iz etoksiliranega triglicerida in etoksiliranega tridecilalkohola s celotno HLB vrednostjo150 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 pomešamo v VC (glej sl. 2) s 1850 g vode pri 50 °C in črpamo 2 minuti pri 3 bar v krogu VC —» P3 —» Ml —» VC, ohladimo in v ta krogotok 18 minut injiciramo iz VA preko Pl s 5 bar 3000 g diorganopolisiloksana z viskoznostjo η = 350 mPaAs v Ml (premer šob 1,4/0,7 mm). Nato homogeniziramo pri padcu tlaka 250 bar v STR-D. Rezultati so navedeni v tabeli 4.13.5 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.
Primer 13Example 13
200 g staljene emulgatorske zmesi - ki ustreza 4 mas.% glede na celotno šaržo - iz etoksiliranega triglicerida in etoksiliranega tridecilalkohola s celotno HLB vrednostjo200 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 pomešamo v VC (glej sl. 2) s 1550 g vode pri 45 °C in črpamo 2 minuti pri 3 bar v krogu (premer šob 1,4/0,7 mm), ohladimo in v ta krogotok 5,5 minut injiciramo iz VA preko Pl pri 5 bar 1750 g diorganopolisiloksana z viskoznostjo η = 350 mPaAs v Ml (premer šob: 2,1/1,0 mm). Po končanem dodajanju črpamo še 5 minut pri 3 bar v krogotoku. Nato injiciramo 1500 g vode iz VB pri 5 bar 8 minut preko Ml. Po še 5 min krogotoka pri 3 bar homogeniziramo pri padcu tlaka 250 bar v STR-D. Rezultati so navedeni v tabeli 4.15.4 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.
Primer 14Example 14
180 g staljene emulgatorske zmesi - ki ustreza 4,5 mas.% glede na celotno šaržo - iz etoksiliranega triglicerida in etoksiliranega tridecilalkohola s celotno HLB vrednostjo180 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 pomešamo v VC (glej sl. 2) s 1240 g vode pri 50 °C in črpamo 1 minuto pri 3 bar v krogu VC -> P3 -» Ml -» VC, ohladimo in v ta krogotok 1,5 minute injiciramo iz VA preko Pl s 5 bar 800 g diorganopolisiloksana z viskoznostjo η = 350 mPaAs v Ml (premer šob: 2,1/1,0 mm). Po končanem dodajanju črpamo še 2 minuti pri 3 bar v krogotoku. Nato injiciramo 1780 g vode iz VB pri 5 bar 8,5 minut preko Ml in naknadno homogeniziramo 2 minuti pri 3 bar v istem krogotoku. Nato homogeniziramo pri padcu tlaka 200 bar v STR-D. Rezultati so navedeni v tabeli 4.15.4 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.
Primer 15 (Primerjalni primer) g staljene emulgatorske zmesi - ki ustreza 4,5 mas.% glede na celotno šaržo - iz etoksiliranega triglicerida in etoksiliranega tridecilalkohola s celotno HLB vrednostjoExample 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 pomešamo v mešalni posodi 620 g vode pri 50 °C in mešamo 3 minute, ohladimo in ob mešanju 13 minut preko kapalnika dodajamo 400 g diorganopolisiloksana z viskoznostjo η = 350 mPaAs. Po končanem dodajanju mešamo še 5 minut pri 400 obr/min, preden 27 minut pri 300 obr/min (močna tvorba pene) dodajamo 890 g vode. Pred-emulzijo homogeniziramo v 2 prehodih pri padcu tlaka ΔΡ = 200 bar v klasičnem homogenizatorju tipa Gaulin. Rezultati so navedem v tabeli 4.15.4 620 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.
Tabela 4Table 4
1} šarža 5000 g 2) šarža 5000 g 3) šarža 4000 g 4) šarža 2000 g 1} batch 5000 g 2) batch 5000 g 3) batch 4000 g 4) batch 2000 g
Primer 16Example 16
2800 g vode, 4,6 g 37% solne kisline, 5,25 g glicina, 51,3 g glicerina, 200 g alkilbenzilamonijevega bromida, 30 g etoksiliranega tridecilalkohola s HLB vrednostjo 11,4 in 22,6 g glikola predložimo v VC (glej sl. 2) in črpamo 30 sekund pri 3 bar v krogu VC -> P3 -> Ml -> VC. 2056 g organopolisiloksana, ki nosi vodik, z viskoznostjo η = 40 mPas pri 7 bar 100 sekund injiciramo iz VA preko Pl v Ml (premer šob: 1,8/0,9 mm) v gornji krogotok. Po končanem dodajanju črpamo predemulzijo v pufrsko posodo VD in rahlo časovno premaknjeno preko P4 homogeniziramo v enem prehodu v dispergatorju s šobami STR-D pri padcu tlaka ΔΡ = 250 bar. Rezultati so navedeni v tabeli 5.2800 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.
Tabela 5Table 5
D. Silikonska emulzija v mešalni postajiD. Silicone emulsion in a mixing station
Primer 17Example 17
Zmes iz 96,6 g etoksiliranega tridecilalkohola s HLB vrednostjo 11,4, 552,72 g polidimetilsiloksana z viskoznostjo η = 500 mPas, 994,84 g rafmata mineralnega olja z vrelnim območjem 382 do 432 °C in 691,04 g di-(2-etilheksil)-ftalata Črpamo iz predložke VA pri tlaku 3 bar najprej 1 minuto preko Ml (premer šob: 1,4/0,6 mm) v krogu VA -» Pl -» Ml -» VA. Nato raztopino iz 464,52 g vode in 0,28 g benzilalkoholmonohemiformala injiciramo 3 minute pri tlaku 3,5 - 4 bar preko VC P3 —» Ml v ta krogotok. Po končanem dodajanju vode še 3 minute črpamo pri tlaku 3 bar v krogu VA -»Pl -»Ml -» VA. Ta krogotok vzdržujemo še 10 minut s tlakom 12 bar. Nastane gosto tekoča stabilna emulzija. Rezultati so navedeni v tabeli 6.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.
Tabela 6Table 6
Primer 18 (v smislu izuma)Example 18 (In the Invention)
V raztopino iz 171,9 g etoksiliranega triglicerida s HLB vrednostjo 18,1 in 148,1 g etoksiliranega tridecilalkohola s HLB vrednostjo 11,4 v 800 g vode, ki se nahaja v krogotoku VC -» P3 -»Ml, injiciramo 2800 g polidimetilsiloksana z viskoznostjo η = 1000 mPas preko krogotoka učinkovine VA -» Pl -» Ml -» VA. Pri tem začetni absolutni tlak krogotoka učinkovine v 9 minutah naraste od 5 na 12 bar. Tlak krogotoka VC -» P3 -»Ml spremlja - vsakokrat za 2 bar nižji - ta porast. Po skupaj 12 minutah je dovajanje učinkovine končano in nastane viskozna bela pasta. To ob hlajenju še 14 minut črpamo v krogotoku VC -» P3 -» Ml pri 10 bar.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.
Nato pri 25 °C iz VB preko P2 injiciramo 4080 g vode s tlakom 12 bar okoli 5 minut. Pri tem se zmanjša tlak z naraščajočim razredčenjem v krogotoku VC -» P3 -» Ml naThen 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, pri čemer ima črpalka P2 spremljajoče za 2 bar višji tlak. Po končanem dodajanju vode se zviša tlak v krogotoku VC -» P3 -» Ml na 80 bar in emulzijo odvzamemo preko Ml iz mešalne postaje.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.
Nastane nizkoviskozna stabilna emulzija.A low-viscosity stable emulsion is formed.
Rezultati so navedeni v tabeli 7.The results are listed in Table 7.
Primer 19 (v smislu izuma)Example 19 (In the Invention)
V raztopino iz 171,9 g etoksiliranega triglicerida s HLB vrednostjo 18,1 in 148,1 g etoksiliranega tridecilalkohola s HLB vrednostjo 11,4 v 800 g vode, ki se nahaja v krogotoku VC -» P3 -»Ml, injiciramo 2800 g polidimetilsiloksana z viskoznostjo η = 350 mPas preko krogotoka učinkovine VA -»Pl -»Ml -» VA. Pri tem naraste začetni absolutni tlak krogotoka učinkovine v 6 minutah od 7 na 10 bar. Tlak krogotoka VC -» P3 -» Ml spremlja - vsakokrat za 2 bar nižji - ta porast. Po skupaj 6 minutah je dovajanje učinkovine končano in nastane viskozna bela pasta. To ob hlajenju še 20 minut črpamo v krogotoku VC -» P3 -» Ml pri 10 bar.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.
Nato pri 25 °C na VB preko P2 injiciramo 4080 g vode s tlakom 10 bar okoli 5 minut. Pri tem se zmanjša tlak z naraščajočim razredčenjem v krogotoku VC -» P3 -» Ml na 4 bar, pri čemer ima črpalka P2 spremljajoče za 2 bar višji tlak. Po končanem dodajanju vode se zviša tlak v krogotoku VC -» P3 -» Ml na 80 bar in emulzijo odvzamemo preko Ml iz mešalne postaje.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.
Nastane nizkoviskozna stabilna emulzija.A low-viscosity stable emulsion is formed.
Rezultati so navedeni v tabeli 7.The results are listed in Table 7.
Tabela 7Table 7
ZaFor
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DE19814267A DE19814267A1 (en) | 1997-09-25 | 1998-03-31 | Device and method for producing silicone emulsions |
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DE19933440A1 (en) * | 1999-07-16 | 2001-01-18 | Bayer Ag | Dispersing nozzle with variable throughput |
FR2820343A1 (en) * | 2001-02-02 | 2002-08-09 | Rhodia Chimie Sa | PROCESS FOR EMULSION OF A SILICONE OILY PHASE IN AQUEOUS PHASE, RESULTING EMULSION, AND APPLICATION TO THE PRODUCTION OF ANTI-MOIST EMULSIONS |
JP2006507921A (en) * | 2002-06-28 | 2006-03-09 | プレジデント・アンド・フェロウズ・オブ・ハーバード・カレッジ | Method and apparatus for fluid dispersion |
US7351749B2 (en) * | 2002-12-16 | 2008-04-01 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Process for manufacture of personal care products utilizing a concentrate water phase |
US7595195B2 (en) * | 2003-02-11 | 2009-09-29 | The Regents Of The University Of California | Microfluidic devices for controlled viscous shearing and formation of amphiphilic vesicles |
JP4777238B2 (en) | 2004-03-23 | 2011-09-21 | 独立行政法人科学技術振興機構 | Method and apparatus for generating microdroplets |
DE102004018283A1 (en) * | 2004-04-15 | 2005-11-03 | Wacker-Chemie Gmbh | Process for the continuous production of silicone emulsions |
DE102004023911A1 (en) | 2004-05-13 | 2005-12-01 | Wacker-Chemie Gmbh | Process for the discontinuous production of silicone emulsions |
DE102005004871A1 (en) * | 2005-02-03 | 2006-08-10 | Degussa Ag | Highly viscous aqueous emulsions of functional alkoxysilanes, their condensed oligomers, organopolysiloxanes, their preparation and their use for the surface treatment of inorganic materials |
EP1690886A1 (en) | 2005-02-12 | 2006-08-16 | Ciba Spezialitätenchemie Pfersee GmbH | Combination of amino-functional and acrylato-functional polyorganosiloxanes |
EP1787712A1 (en) * | 2005-11-17 | 2007-05-23 | Sika Technology AG | Mixing device for liquids |
JP5023902B2 (en) * | 2007-09-06 | 2012-09-12 | 株式会社日立プラントテクノロジー | Emulsifying device |
EP2145912A1 (en) | 2008-07-19 | 2010-01-20 | Momentive Performance Materials GmbH | Method of coating substrates |
EP2566608B1 (en) * | 2010-05-05 | 2018-07-11 | Basf Se | Method for producing fine particle suspensions by melt emulsification |
CN101921397B (en) * | 2010-08-24 | 2012-04-18 | 泸州北方化学工业有限公司 | Device and method for mixing and reacting halogenated silane with reaction medium |
DE102010056345B4 (en) * | 2010-12-29 | 2017-01-19 | Siegfried Zech | Process for the preparation of an oil-water emulsion |
CN102961987A (en) * | 2012-12-18 | 2013-03-13 | 江南大学 | Emulsification technology and emulsification equipment for premixed continuous high-viscosity silicone oil |
JP5972434B2 (en) * | 2015-07-24 | 2016-08-17 | 株式会社 美粒 | Emulsified dispersion manufacturing system |
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FR1486341A (en) * | 1965-07-12 | 1967-06-23 | Manton Gaulin Mfg Company | Improvements for obtaining dispersions of finely divided solids in a liquid vehicle |
DE3230289A1 (en) * | 1982-08-14 | 1984-02-16 | Bayer Ag, 5090 Leverkusen | PRODUCTION OF PHARMACEUTICAL OR COSMETIC DISPERSIONS |
DE3916465A1 (en) * | 1989-05-20 | 1990-11-22 | Bayer Ag | PRODUCTION OF SPHERICAL DISPERSIONS BY CRYSTALLIZATION OF EMULSIONS |
GB2233572B (en) * | 1989-07-10 | 1994-03-23 | Neptune Orient Lines Limited | Method and apparatus for producing layer-in-oil emulsions |
CA2050624C (en) * | 1990-09-06 | 1996-06-04 | Vladimir Vladimirowitsch Fissenko | Method and device for acting upon fluids by means of a shock wave |
DE4202973A1 (en) * | 1992-02-03 | 1993-08-05 | Bayer Ag | METHOD FOR THE CONTINUOUS PRODUCTION OF POLYURETHANE AND POLYURETHANE URBAN ELASTOMERS |
DE4309971A1 (en) * | 1993-03-26 | 1994-09-29 | Bayer Ag | Impregnation emulsion for mineral building materials |
ES2137401T3 (en) * | 1994-06-03 | 1999-12-16 | Bayer Ag | AQUEOUS EMULSIONS OF 2-COMPONENT POLYURETHANE VARNISH AND PROCEDURE FOR ITS MANUFACTURE. |
IL116709A (en) * | 1995-01-10 | 2000-02-29 | Procter & Gamble | Continuous process for the preparation of high internal phase emulsion |
DE19605674A1 (en) * | 1996-02-15 | 1997-08-21 | Wacker Chemie Gmbh | Self-priming building material coatings |
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