WO2001018095A1 - Procede d'emulsification sans broyage de silicones thermosensibles - Google Patents
Procede d'emulsification sans broyage de silicones thermosensibles Download PDFInfo
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- WO2001018095A1 WO2001018095A1 PCT/FR2000/002338 FR0002338W WO0118095A1 WO 2001018095 A1 WO2001018095 A1 WO 2001018095A1 FR 0002338 W FR0002338 W FR 0002338W WO 0118095 A1 WO0118095 A1 WO 0118095A1
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- C—CHEMISTRY; METALLURGY
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08J2383/04—Polysiloxanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/924—Significant dispersive or manipulative operation or step in making or stabilizing colloid system
- Y10S516/928—Mixing combined with non-mixing operation or step, successively or simultaneously, e.g. heating, cooling, ph change, ageing, milling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/924—Significant dispersive or manipulative operation or step in making or stabilizing colloid system
- Y10S516/929—Specified combination of agitation steps, e.g. mixing to make subcombination composition followed by homogenization
Definitions
- the present invention relates to a process for emulsifying, without grinding, a silicone in water.
- the most common emulsification methods used in the art are methods involving the mixing of an aqueous phase and an oily phase with grinding, i.e. under high shear. Highly shear conditions are, for example, generated by agitation in a colloid mill.
- the major drawback of these methods is that they make it difficult, if not impossible, to produce heat-sensitive formulations in the form of emulsions.
- thermosensitive formulation a formulation comprising one or more thermosensitive constituents.
- thermosensitive constituent is a compound sensitive to temperature by nature or made sensitive to temperature due to its association with other compounds present in the formulation.
- direct emulsification processes and inversion emulsification processes.
- the direct emulsification processes for obtaining oil-in-water type emulsions are processes in which the emulsion is, throughout its preparation and as soon as it is formed, a direct emulsion, that is to say a oil in water emulsion.
- the inversion emulsification processes for obtaining oil-in-water emulsions involve the prior formation of a water-in-oil emulsion (commonly known as a reverse emulsion), then the inversion of this emulsion, which is obtained an oil in water emulsion.
- the processes by direct emulsification are not suitable for the preparation, on an industrial scale, of emulsions highly concentrated in oil.
- the oily phase must be added slowly to the aqueous phase, which is not desirable from the point of view of execution times.
- the method of the invention aims to solve all of these problems by allowing the emulsification of viscous or weakly viscous oils, possibly in the presence of one or more heat-sensitive constituents, with control of the particle size and the polydispersity.
- the emulsions obtained by this process can be very concentrated in oil and have a very high weight ratio of oil to surfactant, for example greater than 9/1.
- the process of the invention which is a process of emulsification, without grinding, of a silicone in water, comprises the steps consisting in: a) preparing a primary oil-in-water type emulsion comprising said surfactant and said silicone under a shear of less than 100 s "1 by adding an aqueous phase to an oily phase comprising said silicone, the proportion of oily phase in the primary emulsion being less than the maximum proportion pm ax above which the addition of the aqueous phase to the oily phase does not allow the preparation of an oil-in-water type emulsion, and the weight ratio of the surfactant to water in the primary emulsion being such that a mixture in the same ratio of water and surfactant leads to an organized phase excluding an inverse phase; b) enriching the emulsion thus prepared with an oily enrichment phase comprising said silicone by mixing, under a cisa less than 100 s "1 , from said emulsion to said oily enrichment phase,
- the silicones emulsifiable by the process of the invention are, for example, oils, gums or polyorganosiloxane resins.
- radicals R are identical or different and represent:
- R aliphatic or aromatic hydrocarbon radicals R, mention may be made of the groups:
- alkyl preferably C1-C10 alkyl optionally halogenated, such as methyl, ethyl, octyl, trifluoropropyl;
- alkoxyalkylene preferably C 2 -C10, more preferably C C ⁇ , such as -CH ⁇ CHrO-CHa; -CH ⁇ CH ⁇ O-CHa; • alkenyls, preferably C 2 -C 10 alkenyls, such as vinyl, allyl, hexenyl, decenyl, decadienyl;
- alkenyloxyalkoxyalkyl such as - (Chbk-OCH ⁇ CHz-O-CH ⁇ Ch in which the alkyl parts are preferably C 1 - C 10 and the alkenyl parts are preferably in ;
- aryls preferably C 6 -C 1 3 , such as phenyl.
- polar organic groups R there may be mentioned the groups:
- alkyl is meant a hydrocarbon chain preferably in C1-C10, better still in Ci-Ce; examples of these groups are - (CH 2 ) 3 -OH; - (CH 2 ) 4N (CH 2 CH 2 OH) 2; - (CH 2 ) 3 -N (CH 2 CH 2 OH) -CH 2 -CH 2 - N (CH 2 CH 2 OH) 2 :
- aminofunctional such as alkyl substituted by one or more amino or aminoalkylamino groups where alkyl is as defined above; examples are - (CH 2 ) 3 -NH 2 ; (CH 2 ) 3 -NH- (CH 2 ) 2 NH 2 ;
- amidofunctional such as alkyl substituted by one or more acylamino groups and optionally interrupted by one or more bivalent alkyl-CO-N ⁇ groups where alkyl is as defined above and acyl represents alkylcarbonyl; an example is the group - (CH 2 ) 3-N (COCH 3 ) - (CH 2 ) 2 NH (COCH3); • carboxyfunctionals such as carboxyalkyl optionally interrupted by one or more oxygen or sulfur atoms where alkyl is as defined above; an example is the group -CH 2 -CH 2 -S-CH 2 -COOH.
- radicals R ′ there may be mentioned the groups:
- alkoxy preferably C1-C10, better still Ci-Ce, such as methoxy, ethoxy, octyloxy;
- aminofunctional such as alkyl or aryl substituted by amino, alkyl preferably being Ci-Ce and aryl denoting a cyclic aromatic group preferably C 6 -C 13 hydrocarbon such as phenyl; examples are ethylamino, phenylamino;
- amidofunctional such as alkylcarbonylamino where alkyl is preferably Ci-Ce; examples are methylacetamido.
- D units mention may be made of: (CH 3 ) 2 SiO;
- oils, gums or resins contain reactive and / or polar radicals R (such as H, OH, vinyl, allyl, hexenyl, aminoalkyls, etc.), the latter generally do not represent more than 2% of the weight of the oil or gum and not more than 10% of the weight of the resin.
- R reactive and / or polar radicals
- Polydimethylsiloxane and ⁇ , ⁇ -bis (hydroxy) polydimethylsiloxane oils as well as polydimethylsiloxane, polyphenylmethylsiloxane and ⁇ , ⁇ -bis (hydroxy) polydimethylsiloxane gums are well known commercial products.
- silanol functions are also commercial products.
- oils and gums ⁇ , ⁇ - bis (trimethyl) polydimethylsiloxanes; ⁇ , ⁇ - bis (hydroxy) polydimethylsiloxane oils and gums; hydroxylated polydimethylsiloxane resins of type DT or MDT as well as their mixtures in any proportions.
- the emulsifiable silicones according to the process of the invention have very variable viscosities. We distinguish those of high viscosity, whose viscosity is greater than 1000 mPa.s, for example greater than 3000 mPa.s, preferably greater than 5000 mPa.s and can reach values greater than 10000 mPa.s and for example 500000 mPa.s, those of low viscosity whose viscosity is less than 1000 mPa.s, and preferably between 1 and 1000 mPa.s, for example between 20 and 1000 mPa.s.
- the values of the viscosities are the values of the dynamic viscosities measured at 25 ° C. using a BROOKFIELD viscometer according to the indications of standard AFNOR NFT 76102.
- polydimethylsiloxane oils are those in which the polydimethylsiloxane chain is blocked at its two ends by a (CH 3 ) 3 SiO ⁇ / 2 or (CH 3 ) 2 (OH) SiO ⁇ 2 group with a dynamic viscosity of 20 mPa.s , 350 mPa.s, 750 mPa.s, 80,000 mPa.s or 135,000 mPa.s.
- Preferred examples of polymethylsiloxane resins are: - a hydroxylated polymethylsiloxane resin of MDT type having 0.5% by weight of hydroxyl groups and consisting of 62% by weight of CH ⁇ iO ⁇ units, 24% by weight of (CH 3 ) units 2SiO ⁇ / 2 and 14% by weight of units (CH 3 ) 3 SiO ⁇ 2 ; and - A DT type hydroxylated polymethylsiloxane resin having 2.2% by weight of hydroxyl groups and consisting of 69% by weight of CH 3 Si ⁇ 3/2 units and 31% by weight of (CH 3 ) 2Si ⁇ 2 / 2 units.
- the temperature remains below 80 ° C, preferably below 60 ° C, better still below 35 ° C, for example between 15 and 35 ° C.
- the emulsification goes through stages of mixing the different phases involved. It is during these mixing steps that the shear must remain less than 100 s ⁇ 1 . This essential characteristic makes it possible to distinguish the process of the invention from a process with grinding.
- mixers with counter-rotating stirring for example trimix from the company Rayneri
- planetary mixers or mixers with central stirring of anchor type. or butterfly for example mixers with counter-rotating stirring (for example trimix from the company Rayneri), planetary mixers or mixers with central stirring of anchor type. or butterfly.
- surfactant which can be used for emulsification is not critical according to the invention.
- non-ionic, cationic, anionic or even zwitterionic surfactants can be used.
- anionic surfactants are:
- R represents an alkyl radical in C8-C20, preferably in Cio-Ci ⁇
- R' an alkyl radical in C ⁇ -C 6 , preferably in C1-C3 and M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ).
- Mention may very particularly be made of methyl ester sulfonates whose radical R is C 14 -
- alkyl sulphates of formula ROSO3M where R represents a C10-C24, preferably C12-C20 alkyl or hydroxyalkyl radical and very particularly
- Ci 2 -C 18 , M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 6 units, preferably from 0.5 to 3 OE and / or OP units;
- RCONHROSO3M alkylamide sulfates of formula RCONHROSO3M where R represents an alkyl radical in C 2 -C 2 2, preferably in C6-C20, R 'an alkyl radical in C2-C 3 , M representing a hydrogen atom or a cation of same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 60 OE and or OP units;
- C8-C24 preferably C 14 -C 20 saturated or unsaturated fatty acids, C9-C20 alkylbenzenesulfonates, C 8 -C 22 primary or secondary alkylsulfonates, alkylglycerol sulfonates, polycarboxylic acids sulfones described in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, alkylisethionates, alkylsuccinamates and alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, sulfates of alkyl glycosides, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, di
- nonionic surfactants are: polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols in which the alkyl substituent is C 6 -C 12 and containing from 5 to 25 oxyalkyiene units; by way of example, mention may be made of the Triton X-45, X-114, X-100 or X-102 sold by Rohm & Haas Cy. ; - glucosamines, glucamides;
- amine oxides such as alkyl oxides C10-C1 8 dimethylamines, alkoxy oxides C 8 -C 2 2 ethyl dihydroxy ethylamines;
- amphoteric and zwitterionic surfactants are:
- betaine type such as betaines, sulfo-betaines, amidoalkyl betaines, sulfo-betaines, alkylsultaines, alkyltrimethylsulfobetaines,
- alkyl polyamines such as AMPHIONIC XL marketed by RHONE-POULENC, AMPHOLAC 7T / X and AMPHOLAC 7C / X marketed by BEROL NOBEL, and
- Nonionic surfactants are nonetheless preferred and more particularly nonionic surfactants of the fatty alcohol type with a linear or branched polyoxyalkylene chain resulting from the condensation of a fatty alcohol with a C2-C4 alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide.
- a C2-C4 alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide.
- ethoxylated isotridecyl alcohol More generally, the preferred nonionic surfactants are those in which the HLB is between 8 and 16, preferably between 10 and 15, better still between 12.5 and 15.
- HLB Hydrophilic Lipophilic Balance
- the method of the invention comprises at least steps a) and b), step a) consisting in preparing a direct primary emulsion of oil-in-water type including silicone and surfactant, this primary emulsion being enriched in step b) by an oily enrichment phase based on said silicone. It should be understood that by this enrichment step, the concentration of the resulting silicone emulsion increases while the concentration of the resulting emulsion in surfactant decreases.
- the primary emulsion, prepared by adding an aqueous phase to an oily phase, is a direct emulsion.
- direct emulsion is meant, according to the invention, any oil-in-water type emulsion.
- Reverse emulsions refer to any water-in-oil type emulsion.
- the aqueous phase essentially comprises water but preferably also the surfactant used for the emulsification.
- the process of the invention is not limited to the emulsification of a silicone, but can be used for the emulsification of several silicones, said and said silicones respectively being optionally mixed with one or more distinct organic oils of silicones, but compatible with them.
- the oily phase comprises one or more silicone compounds as defined above and optionally one or more constituents chosen from a silane, a siliceous filler or not, a solvent and / or a compatible or compatibilized additive with silicones.
- silicone oils for example octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane
- short polydimethylsiloxane oils viscosity less than 100 mPa.s
- ketones for example methyl ethyl ketone
- ethers for example diethyl ether
- esters for example isopropyl myristate, ethyl acetate
- certain chlorinated or chlorofluorinated solvents for example methylene chloride, chloroform
- highly branched paraffins for example white oils based on isoalkanes and cycloal
- the silanes can in particular be by-products of synthesis of said oils, gums or polyorganosiloxane resins used or crosslinking agents of said oils, gums or resins.
- Rb Si
- R and R ′ having the definition given above. They are in particular described in US-A-3,294 725; US-A-4 584 341; US-A-4 618 642; US-A-4 608 412; US-A-4 525 565; EP-A-340 120; EP-A-364 375; FR- A-1 248 826; FR-A-1 423 477; EP-A-387 157.
- They are generally present in amounts of the order of 0 to 10 parts by weight, preferably of the order of 0 to 5 parts by weight per 100 parts by weight of oil (s) and / or of gum (s) ) and / or polyorganosiloxane resin in the case of reaction by-products.
- silanes When their function as crosslinking agent for oils, gums or hydroxylated resins is sought, they are generally present in amounts of the order of 0.5 to 30 parts by weight, preferably of the order of 2 to 8 parts by weight per 100 parts by weight of oil (s) and / or gum (s) and / or resin (s).
- Said silanes can also be an additive for modulating the physiocochemical and adhesion properties, in particular silicone compositions of various applications obtained from aqueous emulsions prepared according to the process of the invention. Examples of such silanes are described in particular in EP-A-340 120.
- silanes Among this category of silanes, mention may be made of aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane; glycidoxypropyltrimethoxysilane. They are used in amounts up to 200%, generally of the order of 2 to 100% by weight of oil (s) and / or gum (s) and or resin (s).
- the siliceous or non-siliceous fillers can be reinforcing or semi-reinforcing: by way of example, there may be mentioned colloidal silicas, silica powders for combustion and precipitation, diatomaceous earths, ground quartz , natural calcium carbonate, hydrated alumina, magnesium hydroxide, carbon black, titanium dioxide, aluminum oxide, vermiculite, zinc oxide, mica, talc, iron oxide, barium sulfate, slaked lime; the particle size of these fillers is generally of the order of 0.001 to 300 ⁇ m; they are generally present in amounts up to 300%, preferably of the order of 3 to 100% by weight of oil (s) and / or gum (s) and / or resin (s) .
- the oily phase can also comprise the surfactant, when the latter has not been added to the aqueous phase.
- the surfactant necessary for the preparation of the primary emulsion is either present entirely in the aqueous phase, or entirely present in the oily phase, or else distributed, in any proportions, between these two phases.
- the surfactant is added separately and all at once to the oily phase maintained at rest, at the same time as the aqueous phase.
- all of the surfactant is contained in the aqueous phase before addition.
- the addition of the aqueous phase to the oily phase can be carried out in any way.
- a first way of proceeding consists in adding gradually or in small quantities the aqueous phase to the oily phase maintained with stirring, and for example drop by drop, the stirring being continued after completion of the addition until an emulsion is obtained.
- direct by inversion As a variant, it is possible to add all at once, to the oily phase at rest, the aqueous phase on the one hand, and, optionally the surfactant on the other hand (when the latter is not present entirely in the aqueous and oily phases), then keep the whole under agitation until a direct emulsion is obtained.
- the first condition to be observed concerns the relative proportion of water and surfactant present in the primary emulsion to be
- the weight ratio of water to the surfactant in the primary emulsion is such that a mixture of water and surfactant in this same ratio leads to an organized phase but not to a examples of organized phases are the micellar phase, the lamellar phase, the hexagonal phase and any mixture comprising two of these phases such as a mixture of lamellar phase and mice phase. llaire.
- the mixture of water and surfactant in said ratio leads to a micellar phase, to a lamellar phase or to a mixture of these two phases.
- the silicone present in the primary emulsion is highly viscous, it is advantageous for the mixture of water and surfactant in said ratio to lead to a lamellar phase.
- strongly viscous is meant more precisely a silicone with a viscosity greater than 1000 mPa.s, for example greater than 3000 mPa.s, preferably between 1000 and 500000 mPa.s, better still between 2000 and 300000 mPa. s.
- the silicone to be emulsified has a low viscosity (less than 1000 mPa.s, preferably between 1 and 1000 mPa.s, and better still between 20 and 1000 mPa.s)
- step a it is not necessary to form said organized phase beforehand in order to then add it to the oily phase, although this effectively corresponds to a preferred embodiment.
- the ratio of water to surfactant is such that if these two constituents were to be mixed in this same ratio, they would form said organized phase. It follows that the addition of an aqueous phase free of surfactant to the oily phase is another way of carrying out step a), the surfactant being added simultaneously to the oily phase, or else being previously mixed with said oily phase.
- test protocol is for example the following.
- This uses a mixer consisting of a paddle frame and a metal container (for example made of stainless steel), comprising an annular insulating part (for example made of Teflon®), as a wall, arranged in the bottom of the container, so that a measure of conductivity and therefore of the resistance of the solution contained in the container is possible.
- a metal container for example made of stainless steel
- an annular insulating part for example made of Teflon®
- the conductivity is sufficient to be measured.
- the conductivity is zero. In this way, it is easy to determine the maximum proportion of oil for which the formation of an oil-in-water emulsion is possible.
- a third variant consists in proceeding as in 1) otherwise that the oily phase poured into the mixing container contains all of the surfactant, the aqueous phase consisting exclusively of water.
- a fourth variant consists in proceeding as in 2) except that the oily phase poured into the mixing container contains all of the surfactant, the aqueous phase consisting exclusively of water.
- the weight ratio of the amount of water to the amount of surfactant corresponds to that fixed for the implementation of step a), as well as 'indicated above and that the shear is maintained below 100 s "1 , for example by fixing the speed of rotation of the frame blade around 400 rpm.
- the proportion p max of oil allowing a direct oil-in-water emulsion to be obtained is greater than 80%, generally greater than 90%.
- the proportion p max of oily phase is much lower, generally greater than 30%, and for example, greater than 40%.
- the proportion of oily phase in the primary emulsion must be equal to or less than pm ax .
- This proportion will be less than the proportion of oily phase present in the final emulsion obtained at the end of the process (at the end of step b), or, if appropriate, at the end of step c)) .
- the primary emulsion prepared in step a) comprises more than 15% by weight of oily phase, preferably more than 25% by weight, better still more than 30% by weight.
- the organic phase consists of one or more silicones.
- the size of the oily phase droplets dispersed in the aqueous continuous phase depends on many parameters and in particular on the type of organized phase constituted by the water + surfactant mixture, on the viscosity of the oily phase and, to a lesser extent, on the mode of addition selected.
- the dispersed phase droplets have a volume average diameter of less than 50 ⁇ m, for example less than 10 ⁇ m, most often less than 1 ⁇ m.
- the oily phase has a high viscosity, greater than 1000 mPa.s (preferably greater than 2000 mPa.s), the finest particle size is obtained for a water / surfactant ratio defining a lamellar phase.
- oily phase has a low viscosity, less than 1000 mPa.s (for example between 1 and 1000 mPa.s, better still between 20 and
- the finest particle size is obtained for a water / surfactant ratio defining a biphasic mixture of lamellar phase and micellar phase.
- step b) the primary emulsion is enriched with an oily enrichment phase.
- the oily enrichment phase has the same composition as the oily phase used in step a) for the preparation of the direct primary emulsion. It being understood that the oily phase of step a) preferably consists of one or more silicones, the oily enrichment phase will also preferably consist of said same silicones.
- step b) to enrich the primary emulsion must not be excessive so as not to make it impossible to prepare a direct oil-in-water emulsion by mixing the primary emulsion with said oily enrichment phase.
- the amount of oily enrichment phase can represent from 25 to 100% of the amount of oily phase present in the direct emulsion to be enriched, preferably from 50 to 100%, better still from 75 to 100%.
- the protocol for mixing the primary emulsion and the oily phase under a shear of less than 100 s ⁇ 1 is not critical according to the invention.
- the oily phase can either be added to the emulsion (in one once or gradually), or add the emulsion to the oily phase (all at once or gradually).
- the mixture goes through the formation of a reverse water-in-oil type emulsion and its inversion, finally leading to a direct oil-in-water emulsion.
- a reverse water-in-oil type emulsion and its inversion finally leading to a direct oil-in-water emulsion.
- Step c) allows the subsequent enrichment of the direct emulsion by implementation, one or more times, of step b).
- the emulsions obtained by implementing the process of the invention are concentrated in oil, the weight ratio of oil to surfactant generally being greater than 9/1.
- the final emulsion although having the desired characteristics for the particle size distribution, is too concentrated in organic oil, it is possible to dilute the final emulsion by adding an aqueous dilution phase, the method of addition of this aqueous phase being arbitrary.
- the particle size of the emulsion is not modified by this dilution step. At the same time, this dilution stage makes it possible to further reduce the concentration of surfactant.
- the method of the invention further comprises a step of diluting the direct emulsion obtained, by addition of an aqueous dilution phase.
- the process of the invention is particularly advantageous insofar as it does not involve significant shearing or high temperatures.
- the direct heat-sensitive emulsions obtained according to the process of the invention comprising one or more heat-sensitive constituents are new and therefore form another object of the invention.
- emulsion mention may be made of those containing:
- a hydroxylated polymethylsiloxane resin of MDT type having 0.5% by weight of hydroxyl groups and consisting of 62% by weight of CH 3 Si ⁇ 3/2 units , 24% by weight of (CH 3 ) 2 SiO ⁇ / 2 units and 14% by weight of units (CH 3 ) 3 SiO ⁇ / 2 ; and - a DT type hydroxylated polymethylsiloxane resin having 2.2% by weight of hydroxyl groups and consisting of 69% by weight of CH 3 Si ⁇ 3/2 units and 31% by weight of (CH3) 2Si ⁇ 2 / 2- units
- the mixers used are, for example, static type mixers and the different phases are added to each other by joining in a single and convergent flow pipe.
- a particularly advantageous way of proceeding is to convey the different flows at a point of convergence by means of pipes of different diameters, so that:
- step a the flow of aqueous phase is surrounded by the flow of oily phase, at the point of convergence, and
- step b) the flow of primary emulsion is surrounded by the flow of oily enrichment phase, at the point of convergence.
- Figure 1 shows schematically the functional diagram of continuous implementation of a method according to the invention comprising two enrichment steps.
- Figure 1 very schematically shows a functional diagram for the continuous implementation of the method of the invention.
- the installation illustrated in FIG. 1 comprises a tank 1 for storing the starting aqueous phase comprising water and all of the surfactant, a dropping funnel 2 for storing the oily phase, three static mixers 3, 4 and 5, pumps 6, 7, 8, 9, 10 and 11, valves 12, 13 and 14, as well as pipes for the circulation of the various fluids.
- the oil stored in the bulb 2 is conveyed to the line 15 by opening the valve 12, via the line 16 under the action of the pump 6.
- the aqueous phase stored in the tank 1 is routed to line 15, via line 17 under the action of the pump 7.
- Line 15 ends at the static mixer 3.
- the emulsion leaving the mixer 3 is circulated to line 20 via the line 18 under the action of the pump 9.
- oil stored in the bulb 2 is conveyed to the line 20 by opening the valve 13 via the line 19 under the action of the pump 8.
- the pipe 20 opens into the static mixer 4.
- the emulsion is conveyed to the pipe 23 which opens into the mixer 5, and this via the pipe 22 under the action of the pump 11.
- the oil stored in the tank 2 is conveyed to the mixer 5 by opening the valve 14 via the lines 21 and 23 under the action of the pump 10.
- the emulsions of oils and / or gums and / or resins obtained according to the process of the invention can be used for the preparation of compositions based on silicones adhering to surfaces made of various materials such as glass, concrete, wood, for the preparation of cosmetic products (for example shampoos, creams, conditioners, liquid soaps or other personal hygiene products), industrial or household cleaning products, household descaling products, surface polishing products (for example for car), waxing products (for example for shoes), for the softening treatment of textiles.
- cosmetic products for example shampoos, creams, conditioners, liquid soaps or other personal hygiene products
- household descaling products for example for car
- surface polishing products for example for car
- waxing products for example for shoes
- Step 1
- the whole is kept under stirring (200 rpm) until an oil-in-water emulsion is obtained, and more precisely less than a minute.
- the point of obtaining the oil-in-water emulsion is determined by conductimetry and more precisely by measuring the resistance of the emulsion. Agitation is continued for 5 minutes.
- the emulsion is observed under a microscope to check its appearance, its homogeneity and its particle size.
- the particle size distribution is determined with a laser granulometer.
- Median diameter 1.1 ⁇ m, the median diameter being such that 50% of the particles by volume have a diameter less than or equal to this median diameter.
- the emulsion obtained contains 71.7% by weight of oil.
- Step 2 Optionally, distilled water is added to the emulsion contained in the container, so as to maintain the water / surfactant ratio of 44/56.
- step 1 After homogenization of the medium with gentle stirring, the stirring is stopped and 20 g of the oil used in step 1 are added all at once to the emulsion. The whole is kept under stirring (200 rpm) for 5 minutes.
- the inversion is obtained from the first minute of agitation.
- the emulsion obtained at the end of this second step contains 84.5% by weight of oil.
- Step 5 During this last step, 45.3 g of distilled water are slowly charged with stirring (200 rpm).
- the agitation is continued for five minutes.
- the final emulsion contains 60% by weight of oil.
- the initial charge of the container consists of 10.43 g of distilled water and 13.27 g of the mixture of 15% water and 85% surfactant A, which leads to a water / surfactant ratio of 44 / 56;
- the silicone used is a polydimethylsiloxane oil, the polydimethylsiloxane chain of which is blocked at each of its ends by a pattern (CH 3 ) 3 SiO ⁇ / 2 and has a viscosity of 20 mPa.s at 25 ° C as measured at using a BROOKFIELD viscometer according to the indications of the AFNOR standard
- the process comprises eight additional stages (stages 5 to 12) during which one proceeds exactly as in stage 2 by addition of 20 g of oil; after step 4, the emulsion is transferred to a 1 1 reactor; in step 13, the procedure is carried out as in step 5 of example 1 above, diluting the emulsion by adding 91.6 g of distilled water.
- Examples 1 and 2 clearly show that the process of the invention makes it possible to reduce the polydispersite of the final emulsion while allowing the preparation of a finer emulsion (smaller diameter of the droplets of dispersed phase).
- FIG. 2 For the implementation of this exemplary embodiment, the installation of FIG. 2 was used.
- This installation includes a storage tank 30, a dropping funnel 31, two positive-displacement positive displacement gear pumps 32 and 33 and two static mixers 34 and 35 of the Sulzer SMX type DN 12 and DN 4, as well as pipes for circulation. different fluids.
- Tank 30 is initially loaded with 44% water and 56% of a mixture of 15% water and 85% surfactant A.
- the dropping funnel 31 is loaded with polydimethylsiloxane oil identical to that used in Example 1.
- the oil is brought, via line 37 by means of the pump 33 to line 38, into which it is introduced, by an injection nozzle (not shown), with a flow rate of 1.7 kg / hour. .
- the aqueous phase consisting of water and surfactant is brought up to line 38 through line 36 by means of pump 32.
- the rate of introduction of the aqueous phase into line 38 is 1 , 65 kg / h.
- the total liquid flow rate is 3.35 kg / h in the line 38.
- the line 38 opens into the mixer 34.
- the mixer 34 is connected to a mixer 35 located downstream.
- an oil-in-water emulsion containing 50% by weight of oil is recovered via line 40.
- Example 1 The particle size distribution of this emulsion is analyzed as in Example 1.
- v sp represents the specific surface expressed in m 2 / m 3 , namely the sum of the surfaces of the droplets of dispersed phase present in 1 m 3 of emulsion;
- D (0.9) being such that 90% of the particles by volume have a diameter less than or equal to the diameter D (0.9);
- D (0.1) being such that 10% of the particles by volume have a diameter less than or equal to the diameter D (0.1).
- the difference D (0.9) -D (0.1) is a measure of the polydispersite of the emulsion. The greater this difference, the greater the polydispersite. 2nd step
- the tank 30, emptied of the aqueous phase which it contained in the previous step, is charged with the emulsion withdrawn from the pipe 40 in the previous step.
- the emulsion is then introduced into line 38 with a flow rate of 2 kg / h from tank 30 via line 36.
- the oil is introduced into line 38 with a flow rate of 2 kg / h by an injection nozzle (not shown), at the outlet of line 37.
- the total flow rate in line 38 is 4 kg / h.
- An emulsion containing 75% by weight of oil is recovered at the outlet of the mixer 35, via line 40.
- step 2 The procedure is exactly as in step 2.
- the emulsion resulting from step 2 is introduced into line 38 with a flow rate of 1.64 kg / h from the tank 30.
- the oil is introduced into line 38 from the pouring bulb 31, with a flow rate of 2 kg / h.
- the total flow in line 38 is 3.64 kg / h.
- the emulsion recovered through line 40 is 88% by weight of oil.
- the particle size distribution of this emulsion has the following characteristics:
- the emulsion is refined by reintroducing this emulsion into the mixers 34 and 35 with the manual piston of the main line pump, with a flow rate of 4 kg / h.
- the resulting final emulsion has the following characteristics:
- This example is implemented in the installation shown diagrammatically in FIG. 3.
- This installation includes:
- a stainless steel reactor 51 not stirred, containing polydimethylsiloxane oil, the polydimethylsiloxane chain of which is blocked at each of its ends by a (CH 3 ) 2 (OH) SiO ⁇ / 2 unit and having a dynamic viscosity of 135,000 mPa. s at 25 ° C, as measured using a BROOKFIELD viscometer according to the indications in AFNOR NFT 76102 standard; this reactor can withstand a pressure of 3 bars. This property makes it possible to force-feed the pump 53 located downstream of the reactor 51 on the pipe 57;
- the silicone oil is introduced into line 58 at a rate of 14 kg / h, from reactor 51 via line 57, by means of an injection nozzle (not shown) and via pump 53.
- the total flow rate in line 58 is 24 kg / h.
- Line 58 opens into mixer 54, which is connected to mixer 55 via line 59. From mixer 55, an oil-in-water emulsion containing 59% by weight of silicone oil is recovered through line 60.
- Example 3 The particle size distribution of this emulsion is characterized as in Example 3. Its characteristics are as follows: - Sauter diameter: 0.41 ⁇ m
- Step 2 The emulsion recovered at the end of line 60 is loaded into reactor 50b.
- This emulsion is introduced into line 58 with a flow rate of 15 kg / h from the reactor via line 56 by means of pump 52. Simultaneously, silicone oil from reactor 51 is introduced into line 58, with a flow rate of 15 kg / h.
- the total flow of liquid in line 58 is 30 kg / h.
- An emulsion of the oil-in-water type at 79% by weight of silicone oil, the particle size distribution of which has the following characteristics, is recovered, at the outlet of the mixer 55, via the line 60: - Sauter diameter: 0.47 ⁇ m
- This emulsion is then refined in the following manner. It is first loaded into reactor 50b and then reintroduced, alone, into line 58 with a flow rate of 30 l / h, in order to reduce the dispersity. The resulting emulsion contains 79% by weight of silicone oil and differs essentially from the previous one by the characteristics of its particle size distribution.
- the installation of Figure 3 further comprises a storage container of surfactant A, a positive displacement pump for the circulation of the mixture of 15% water and 85% surfactant A to line 58; and a line for conveying the mixture of 15% water and 85% of surfactant A to said line 58; the installation of FIG. 3 is modified, the mixers 54 and 55 being replaced by three mixers mounted in series, namely a type mixer
- Kenics consisting of 9 elements Kenics DN35, a Sulzer type mixer consisting of 12 Sulzer SMX DN50 elements and a Sulzer SMX DN25 type mixer.
- the emulsion recovered at the outlet of the mixers via line 60 is an oil-in-water emulsion with 89% oil.
- the characteristics of the particle size distribution are as follows: Sauter diameter: 2.81 ⁇ m D (0.9) -D (0.1): 2.89 ⁇ m.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU70141/00A AU7014100A (en) | 1999-09-03 | 2000-08-18 | Method for emulsifying heat-sensitive silicone emulsion without grinding |
EP00958703A EP1232200A1 (fr) | 1999-09-03 | 2000-08-18 | Procede d'emulsification sans broyage de silicones thermosensibles |
CA002383874A CA2383874A1 (fr) | 1999-09-03 | 2000-08-18 | Procede d'emulsification sans broyage de silicones thermosensibles |
US10/069,659 US6660778B1 (en) | 1999-09-03 | 2000-08-18 | Method for emulsifying heat-sensitive silicones emulsion without grinding |
JP2001522313A JP2003508611A (ja) | 1999-09-03 | 2000-08-18 | 粉砕なしに感熱シリコーンを乳化する方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR99/11091 | 1999-09-03 | ||
FR9911091A FR2798133B1 (fr) | 1999-09-03 | 1999-09-03 | Procede d'emulsification sans broyage de silicones et emulsion thermosensible resultante |
Publications (1)
Publication Number | Publication Date |
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WO2001018095A1 true WO2001018095A1 (fr) | 2001-03-15 |
Family
ID=9549548
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2000/002338 WO2001018095A1 (fr) | 1999-09-03 | 2000-08-18 | Procede d'emulsification sans broyage de silicones thermosensibles |
Country Status (7)
Country | Link |
---|---|
US (1) | US6660778B1 (fr) |
EP (1) | EP1232200A1 (fr) |
JP (1) | JP2003508611A (fr) |
AU (1) | AU7014100A (fr) |
CA (1) | CA2383874A1 (fr) |
FR (1) | FR2798133B1 (fr) |
WO (1) | WO2001018095A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004043580A1 (fr) * | 2002-11-14 | 2004-05-27 | K.U.Leuven Research & Development | Procede de preparation d'emulsions |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7365030B2 (en) * | 2003-07-09 | 2008-04-29 | The Procter & Gamble Company | Process for making a wet wipe using a concentrated emulsion |
DE102004018283A1 (de) * | 2004-04-15 | 2005-11-03 | Wacker-Chemie Gmbh | Verfahren zur kontinuierlichen Herstellung von Silicon Emulsionen |
US7144148B2 (en) * | 2004-06-18 | 2006-12-05 | General Electric Company | Continuous manufacture of high internal phase ratio emulsions using relatively low-shear and low-temperature processing steps |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2333562A1 (fr) * | 1975-12-06 | 1977-07-01 | Pfersee Chem Fab | Procede pour l'obtention d'emulsions aqueuses, stables de substances insolubles dans l'eau |
FR2697025A1 (fr) * | 1992-10-20 | 1994-04-22 | Rhone Poulenc Chimie | Procédé de préparation d'émulsions aqueuses d'huiles et/ou de gommes et/ou de résines silicones. |
EP0771629A1 (fr) * | 1995-11-01 | 1997-05-07 | Dow Corning Toray Silicone Company Ltd. | Procédé continu d'émulsification pour gommes en organopolysiloxane |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0183285B1 (fr) * | 1984-09-28 | 1990-04-11 | Stamicarbon B.V. | Procédé de préparation en continu de solutions homogènes de polymères à poids moléculaire élevé |
DE3925846A1 (de) * | 1989-08-04 | 1991-02-14 | Huels Chemische Werke Ag | Emulgatoren zur herstellung von lagerstabilen, waessrigen polysiloxan- bzw. polysiloxan-paraffinoel-emulsionen |
EP0466236B1 (fr) * | 1990-07-11 | 1994-08-17 | Quest International B.V. | Emulsions parfumées structurées dans produits à usage corporel |
US5763505A (en) | 1992-10-20 | 1998-06-09 | Rhone Poulenc Chimie | Process for the preparation of aqueous emulsions of silicon oils and/or gums and/or resins |
JP3439860B2 (ja) * | 1995-01-24 | 2003-08-25 | 東レ・ダウコーニング・シリコーン株式会社 | オルガノポリシロキサンエマルジョンの連続的製造方法 |
-
1999
- 1999-09-03 FR FR9911091A patent/FR2798133B1/fr not_active Expired - Fee Related
-
2000
- 2000-08-18 WO PCT/FR2000/002338 patent/WO2001018095A1/fr not_active Application Discontinuation
- 2000-08-18 US US10/069,659 patent/US6660778B1/en not_active Expired - Fee Related
- 2000-08-18 JP JP2001522313A patent/JP2003508611A/ja active Pending
- 2000-08-18 EP EP00958703A patent/EP1232200A1/fr not_active Withdrawn
- 2000-08-18 CA CA002383874A patent/CA2383874A1/fr not_active Abandoned
- 2000-08-18 AU AU70141/00A patent/AU7014100A/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2333562A1 (fr) * | 1975-12-06 | 1977-07-01 | Pfersee Chem Fab | Procede pour l'obtention d'emulsions aqueuses, stables de substances insolubles dans l'eau |
FR2697025A1 (fr) * | 1992-10-20 | 1994-04-22 | Rhone Poulenc Chimie | Procédé de préparation d'émulsions aqueuses d'huiles et/ou de gommes et/ou de résines silicones. |
EP0771629A1 (fr) * | 1995-11-01 | 1997-05-07 | Dow Corning Toray Silicone Company Ltd. | Procédé continu d'émulsification pour gommes en organopolysiloxane |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004043580A1 (fr) * | 2002-11-14 | 2004-05-27 | K.U.Leuven Research & Development | Procede de preparation d'emulsions |
US7629390B2 (en) | 2002-11-14 | 2009-12-08 | K.U. Leuven Research & Development | Method for preparing emulsions |
Also Published As
Publication number | Publication date |
---|---|
FR2798133B1 (fr) | 2003-06-13 |
AU7014100A (en) | 2001-04-10 |
FR2798133A1 (fr) | 2001-03-09 |
JP2003508611A (ja) | 2003-03-04 |
EP1232200A1 (fr) | 2002-08-21 |
US6660778B1 (en) | 2003-12-09 |
CA2383874A1 (fr) | 2001-03-15 |
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