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    • 专利摘要:
    the present invention relates to a process for the preparation of solid microcapsules (20), comprising the steps of: a) adding under stirring a composition c1 comprising at least one active material to a liquid composition c2 crosslinkable, wherein the active material is not is an additive to be used in the lubricants, fuels or bitumen industries or in muds or drilling muds, or an additive to be used in the exploration / production of oil, the composition c1 and composition c2 are immiscible with each other, so that a first emulsion is obtained, said first emulsion comprising drops (1) of composition c1 dispersed in composition c2, b) adding under stirring the first emulsion obtained in step a) to a liquid composition c3, composition c3 and composition c2 being immiscible with each other, so that a second emulsion is obtained, said second emulsion comprising droplets (5) dispersed in composition c3, c) loading the second emulsion obtained in step b) to to a mixer which applies a homogeneous controlled shear rate to the second emulsion, the shear rate being from 1,000 s -1 to 100,000 s -1 , such that a third emulsion is obtained, said third emulsion comprising drops (10) dispersed in composition c3 and d) crosslinking the droplets (10) obtained in step c), so that solid microcapsules (20) dispersed in composition c3 are obtained.
    公开号:BR112018005107B1
    申请号:R112018005107-1
    申请日:2016-09-16
    公开日:2021-06-22
    发明作者:Jamie WALTERS；Damien DEMOULIN；Jérôme Bibette
    申请人:Calyxia；
    IPC主号:
    专利说明:

    Field of Invention
    [001] The present invention relates to a method for the production of solid microcapsules and for the microcapsules obtained by said method. Background of the Invention
    [002] The problem of isolating an active material from the surrounding environment in order to improve the performance of an active material is a relatively new area for a number of industries. In most non-bio industries, performance losses associated with factors such as hydrolysis, thermal degradation, oxidation and cross-reactivity are resolved by increasing the concentration of active material to achieve the desired level of performance, which increases the cost, and also presents additional problems associated with the product formed from such unwanted reactions.
    [003] However, in a number of industries, including chemical, painting, agrochemical, it is necessary to isolate an active material from the surrounding environment so as to protect the material from hydrolysis, thermal degradation, oxidation, reactivity cross-linking and other methods that may reduce material performance.
    [004] Thus, it is sometimes advantageous to encapsulate an active material in microcapsules.
    [005] In addition, many applications require that the microcapsules so produced have a small size and/or a narrow size range (ie good sized monodispersity) in order to have greater control over their overall performance to improve its dispersion, and to produce more uniform coatings.
    [006] In recent years, a large number of encapsulation methods have been developed and reported in the literature, including spray drying, solvent evaporation, interfacial polymerization, and centrifugal extrusion, among many others. However, for industrial scale encapsulation methods, emulsification methods, for example batch emulsification methods, dominate because they are able to meet large volumes needed for industrial requirements. Such methods make use of a step of forming an emulsion of a hydrophobic oil or wax phase, dispersed in a continuous aqueous phase (or, alternatively, an emulsion of an aqueous phase, dispersed in a continuous hydrophobic oil or wax phase. ). These two phases are emulsified using a homogenizer or a stirred vessel equipped with baffles, and which are stabilized using surfactants or emulsifiers. Alternatively, a reaction at the interface between the two phases is used to form a polymer shell.
    [007] However, the industrial scale emulsification methods described above produce emulsions, and subsequently microcapsules, which are polydispersed and/or very large (size above 10 µm mean).
    [008] In addition, said methods require water to form one of the phases described above, and surfactants or emulsifiers to stabilize the emulsion, which can react with the encapsulated active material and/or provide the contaminants in each phase and therefore , decrease the performance of the active material.
    [009] Another limitation of these methods is that, depending on the viscosity of the emulsion and the chemical nature of the encapsulated active material, the dimensions of the emulsion droplet, and subsequently the microcapsules, can vary significantly. Invention Summary
    [0010] The purpose of the present invention is thus to provide a method for the production of monodisperse microcapsules encapsulating an active material, namely, monodisperse microcapsules having an average size of less than 5 µm, at the same time having a method in which the dimensions of the microcapsules can be precisely controlled and adjusted.
    [0011] Another objective of the present invention is to provide a method of eliminating the water requirement in the manufacturing process, which can negatively affect the active material.
    [0012] Another objective of the present invention is to provide a method of eliminating the requirement for surfactant or emulsifier in the manufacturing process, which can negatively affect the active material and its surrounding environment.
    [0013] Thus, the present invention relates to a method for producing microcapsules, in which regardless of the chemical properties of the active material encapsulated in microcapsules, the microcapsule diameter, shell thickness, chemical functionality and / or trigger release can be easily adjusted to meet application requirements.
    [0014] Furthermore, the present invention relates to a method for the production of microcapsules, which can be carried out in the absence of water.
    [0015] Furthermore, the present invention relates to method for the production of microcapsules, which can be carried out in the absence of surfactant and / or emulsifier.
    [0016] The present invention relates to an industrial scale method for producing populations of solid monodisperse microcapsules, with an average size preferably below 5 µm, using a double emulsion technique.
    [0017] An object of the present invention is thus a method for the preparation of solid microcapsules, comprising the steps of: a) adding under stirring a composition C1 comprising at least one active material to a crosslinkable liquid composition C2, in that the active material is not an additive to be used in the lubricant, fuel or bitumen industries, or in drilling muds or muds, or an additive to be used in oil exploration / production, the composition C1 and composition C2 being immiscible one with the other, so that a first emulsion is obtained, said first emulsion comprising drops of composition C1 dispersed in composition C2,
    [0018] b) add under stirring the first emulsion obtained in step a) to a liquid C3 composition,
    [0019] composition C3 and composition C2 being immiscible with each other, so that a second emulsion is obtained, said second emulsion comprising droplets dispersed in composition C3,
    [0020] c) loading the second emulsion obtained in step b) into a mixer that applies a homogeneous controlled shear rate for said second emulsion, with said shear speed being from 1,000 s-1 to 100,000 s-1 ,
    [0021] so that a third emulsion is obtained, said third emulsion comprises droplets dispersed in composition C3, and
    [0022] d) crosslinking the droplets obtained in step c), so that the solid microcapsules dispersed in composition C3 are obtained.
    [0023] The method of the invention implements a controlled homogeneous high shear (over 1000 s-1) mixing step that uniformly subjects the second emulsion droplets to a high shear rate, which fragments the droplets of the polydisperse population of the second emulsion in a monodisperse population of double emulsion droplets (third).
    [0024] The middle phase of the third emulsion (composition C2) is then polymerized to form a solid shell, minimizing any coalescence and growth.
    [0025] The present invention solves a double emulsion method to create microcapsules, which can be prepared in the absence of water, surfactant and / or an emulsifier, which can negatively interact with the encapsulated active material and / or induce contaminants into the surrounding medium (composition C3).
    [0026] The method of the invention can be a continuous process or a batch process for preparing solid microcapsules.
    [0027] According to one embodiment, the method of the invention is a batch method. STEP a)
    [0028] During step a), a composition C1 is added to a crosslinkable liquid composition C2, said addition to be carried out under stirring, which means that composition C2 is stirred, typically mechanically, while composition C1 is added, so as to emulsify the mixture of composition C1 and composition C2.
    [0029] The addition of composition C1 to composition C2 is typically carried out dropwise. During step a), composition C1 is at a temperature between 0 °C and 100 °C, preferably between 10 °C and 80 °C and more preferably from 15 °C to 60 °C. a), the composition is C2 at a temperature between 0°C and 100°C, preferably between 10°C and 80°C and more preferably from 15°C to 60°C.
    [0030] Under the conditions of addition of step a), composition C1 and composition C2 are immiscible with each other, which means that the amount (by mass) of composition C1 capable of being solubilized in composition C2 is less than or equal to 5%, preferably 1%, preferably 0.5%, relative to the total mass of composition C2, and that the amount (by mass) of composition C2 capable of being solubilized in composition C1 is less than or equal to 5%, preferably 1%, preferably 0.5%, relative to the total mass of composition C1.
    [0031] Thus, when it comes into contact with composition C2 under agitation, composition C1 is dispersed in the form of droplets (also called individual droplets).
    [0032] The immiscibility between composition C1 and composition C2 also prevents the active material to migrate from composition C1 to composition C2.
    [0033] After the addition of composition C1, composition C2 is stirred in order to form a liquid/liquid emulsion (also called first emulsion, or C1 -in-C2 emulsion, or C1 emulsion / C2) comprising droplets of composition C1 ( individual drops) dispersed in composition C2.
    [0034] Figure 1 schematically represents the method of the invention and, in particular, schematically represents droplets 1 obtained in step a), adding composition from C1 to C2 composition.
    [0035] In order to implement step a), any type of stirrer generally used to make the emulsions can be used, such as a suspended stirrer (mixing speed from 100 rpm to 2000 rpm), rotor-stator mixer (speed of mixing from 100 rpm to 5,000 rpm), or colloidal mill (mixing speed from 1,000 rpm, to 10,000 rpm). Alternatively, ultrasonic homogenizer, membrane homogenizer or high pressure homogenizer can also be used.
    [0036] Composition C1 comprises at least one active material, which is not an additive to be used in the lubricant, fuel or bitumen industries, or in drilling muds or muds, or an additive to be used in oil exploration / production.
    [0037] According to an embodiment of the invention, composition C1 is a liquid monophasic composition, which means that the active material is in pure form or is solubilized in composition C1.
    [0038] According to a variant of this embodiment, the active material is solubilized in composition C1.
    [0039] According to this variant, composition C1 can consist of a solution of the active material in an organic solvent, or a mixture of organic solvents.
    [0040] According to this variant, composition C1 can also consist of a solution of the active material in an aqueous phase, which comprises water and organic solvents, eventually hydrophilic.
    [0041] According to this embodiment, the content of active material in composition C1 is typically comprised between 1% and 99%, preferably from 5% to 95%, preferably from 10% to 90%, from 20% to 80% , from 30% to 70%, or between 40% and 60%, by weight relative to the total weight of composition C1.
    [0042] According to another variant of this embodiment, the active material is present in a pure form in composition C1, which means that composition C1 consists of the active material.
    [0043] According to another embodiment of the invention, composition C1 is a biphasic composition, which means that the active material is dispersed, either in a liquid form or a solid form, in C1 the composition and is not fully solubilized in C1 composition.
    [0044] According to a variant of said embodiment, the active material is dispersed in the form of solid particles in composition C1.
    [0045] According to this variant, composition C1 may consist of a dispersion of solid particles of the active material in an organic solvent, or a mixture of organic solvents.
    [0046] According to this variant, composition C1 can also be constituted by a dispersion of solid particles of the active material in an aqueous phase, which comprises water and organic solvents, eventually hydrophilic.
    [0047] According to another variant of this embodiment, the active material is dispersed in the form of liquid droplets in composition C1.
    [0048] According to this variant, composition C1 can consist of an emulsion of droplets of active material dispersed in an organic solvent, or a mixture of organic solvents.
    [0049] According to this variant, composition C1 can also be constituted by an emulsion of droplets of active material dispersed in an aqueous phase, comprising water and organic solvents, possibly hydrophilic.
    [0050] According to this embodiment, the content of active material in composition C1 is typically comprised between 1% and 99%, preferably from 5% to 95%, preferably from 10% to 90%, from 20% to 80% , from 30% to 70%, or between 40% and 60%, by weight relative to the total weight of composition C1.
    [0051] When the active material is in the form of particles in composition C1, it is preferably in the form of nanoparticles, either spherical or non-spherical, which can have a size ranging from 1 nm to 1000 nm.
    [0052] According to an embodiment, the active material is selected from the group consisting of:
    [0053] - crosslinkers, hardeners, organic catalysts and metal-based catalysts (for example organo-complexes and inorgano-complexes of platinum, palladium, titanium, molybdenum, copper, or zinc) for the polymerization of elastomer formulations, formulations rubber, paint formulations, coating formulations, adhesive formulations, or sealant formulations; - dyes, dyes, pigments for paints, personal care products, elastomer formulations, rubber formulations, paint formulations, coating formulations, adhesive formulations, sealant formulations, or paper formulations; - fragrances for detergents, household cleaning products, personal care products, textile products (so-called smart fabrics), coating formulations. Fragrances useful for the invention are any of the compounds belonging to the list of standards published and updated by the Fragrance Association International (IFRA); - aromas, flavors, vitamins, amino acids, proteins, essential lipids, probiotics, antioxidants, preservatives for food and food products; - softeners and conditioners for detergents and personal care products. Compounds useful for the invention include, but are not limited to those listed in US 6,335,315 and US 5,877,145; - bioactive compounds, such as vitamins, enzymes, proteins, plant extracts, moisturizers, disinfectants, antibacterial agents, sun protection agents, drugs, for personal care products, textile products (so-called smart fabrics). These compounds include, but are not limited to, vitamin A, vitamin B, vitamin C, vitamin D, vitamin E, aminobenzoic acid para, alpha hydroxy acid, camphor, ceramides, ellagic acid, glycerin, glycine, glycolic acid, hyaluronic acid, hydroquinone, isopropyl, isostearate, isopropyl palmitate, oxybenzone, panthenol, proline, retinol, retinol palmitate, salicylic acid, sorbic acid, sorbitol, triclosan, tyrosine; and - fertilizers, herbicides, insecticides, pesticides, fungicides, repellents and disinfectants for agrochemicals.
    Insecticides useful for the invention include, but are not limited to: O,O-diethylO-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate, O,O-diethyl S-2-ethylthioethyl phosphorodithioate, S- chloromethyl O,O-diethyl phosphorodithioate, O-ethyl S,S-dipropyl phosphorodithioate, O,O-diethyl S-ethylthiomethyl phosphorodithioate, S-terthiobutylthiomethyl O,O-diethyl phosphorodithioate, O,O-diethyl-O-4-methylsulfinylphenyl phosphorothioate , O-(4-bromo-2-chlorophenyl) O-ethyl-S-propyl phosphorodithioate, S-1,2-di(ethoxycarbonyl)ethyl O,O-dimethylphosphorodithioate, O,O,O',O'-tetraethyl- S,S'-methylene di(phosphorodithioate), O-(4-bromo-2,5-dichlorophenyl)O,O-diethyl phosphorothioate, S-4-chlorophenylthiomethylO,O-diethyl phosphorodithioate, O-2,5-dichloro- 4-(methylthio)phenylO,O-diethyl phosphorodithioate, O-4-cyanophenyl O,O-dimethyl phosphorothioate, O,O-dimethyl O-2-methylthioethyl phosphorothioate, O,O-diethyl O-2-ethylthioethyl phosphorothioate, O- 2,4-dichlorophenyl O,O-diethyl phosphorothioate, O-2,4-dichlorophenyl O-ethyl phenylphosphorothioate, 1,3-di(methoxycarbonyl)-1-propen-2-yldimethylf osphate, 2-chloro-1-(2,4-dichlorophenyl)vinyl diethylphosphate, O,O-dimethyl-O-4-nitro-m-tolyl phosphorothioate, O,O-dimethyl-O-4-methylthio-m-tolyl phosphorothioate, O-(5-chloro-1-isopropyl-1,2,4-triazol-3-yl)O,O-diethylphosphorothioate, S-2-isopropylthioethyl O,O-dimethyl phosphorodithioate, 4-(methylthio)phenyl dipropylphosphate , 1,2-dibromo-2,2-dichloroethyl dimethylphosphate, O,O-diethyl-alpha-cyanobenzylidene aminooxyphosphorothioate, O,O-diethyl O-4-nitrophenyl phosphorothioate, O-2-diethylamino-6-methylpyrimidin-4 -yl O,O-diethyl phosphorothioate, O-2-diethylamino-6-methylpyrimidin-4-yl O,O-dimethyl phosphorothioate, O,O,O',O'-tetraethyldithiopyrophosphate, O,O,O',O' -tetramethyl-O,O'-thiodi-p-phenylenediphosphorothioate, S,S'-(1,4-dioxane-2,3-diyl)O,O,O',O'-tetraethyl di(phosphorodithioate), S- 2-ethylthioethyl-O,O-dimethylphosphorodithioate, 3-phenoxybenzyl-(+-)-cis-trancrisanthemate, pyrethrins-2-(2-butoxyethoxy)erylthiocyanate isobornyl-thiocyanoacetate, carbondisulfide2-(4-terthio-butylphenoxy)cyclohexyl prop-2 -inylsulfide, 4-6-dinitro-6-octylphenylcrote nates, ethyl 4,4'-dichlorobenzylate, O,O-diethyl-O-1-phenyl-1,2,4-triazol-3-ylphosphorothioate, O-ethyl O-2,4,5-trichlorophenyl ethylphosphonothioate, (+ -)-3-allyI-2-methyl-4-oxocyclopent-2-enyl-(+)-cis,trans-chrysanthemate, and (+-)-3-allyl-2-methyl-4-oxocyclopent-2-enyl -(+)-trans-chisanthemate.
    Fungicides useful for the invention include, but are not limited to: copper naphthenate, 5-ethoxy-3-trichloromethyl-1, 2,4-thiadiazole, and O-ethyl S, S-diphenyl phosphorodithioate.
    Repellents useful for the invention include, but are not limited to: 6-butoxycarbonyl-2,3-dihydro-2,2-di-methylpyran-4-one, N,N-diethyl-m-toluamide, dibutylphthalate, dibutylsuccinate, 1,5a,6,9,9a,9b-hexahydro-4a(4H)-dibenzofurancarboxaldehyde, and dipropylpyridine-2,5-dicarboxylate.
    [0057] Herbicides useful for the invention include, but are not limited to:
    [0058] 2-(1,2-dimethylpropylamino)-4-ethyl-amino-6-methylthio-1,3,5-triazine-2-ethyl-5-methyl-5-(2-methylbenzyloxy)-1,3 -dioxane,
    [0059] S-ethyl-N-cyclohexyl-N-ethylthiocarbamate,
    [0060] S-2,3-dichloroallyl-diisopropylthiocarbamate,
    [0061] S-propyl butylethylthiocarbaxate,
    [0062] diisopropylthiocarbamate S-2,3,3-trichloroallyl,
    [0063] S-ethyl dipropylthiocarbamate,
    [0064] S-4-chlorobenzyl diethylthiocarbamate,
    [0065] S-ethyl diisobutylthiocarbamate,
    [0066] S-benzyl-di secbutylthiocarbamate,
    [0067] S-propyl dipropylthiocarbamate,
    [0068] S-ethylhexahydro-1H-azepino-1-carbothioate,
    [0069] N,N-diallylchloroacetamide,
    [0070] N-butoxymethyl-alpha-chloro-2',6'-diethylacetanilide,
    [0071] S-(0,0-diisopropyl-phosphorodithioate) ester
    [0072] N-(2-mercaptoethyl) benzenesulfonamide,
    [0073] N-alpha-chloro-6'-ethyl (2-methoxy-1-methyl]ethyl)-acetamide,
    [0074] N-benzyl-N isopropyltrimethylacetamide, and
    2-chloroallyl diethyldithiocarbamate.
    [0076] The active material can also be an active known in the art as Phase Change Material (PCM) capable of absorbing and releasing heat in case of phase change, to energy storage materials.
    [0077] PCM and its applications are described for example in "A Review on Phase Change Energy Storage: Materials and Applications", Farid et al, Conversion and Management 2004, 45 (9-10), 1597-1615 Energy .
    [0078] Examples of PCM include, but are not limited to: molten salts of aluminum phosphate, ammonium carbonate, ammonium chloride, cesium carbonate, cesium sulfate, calcium citrate, calcium chloride, calcium hydroxide, calcium oxide, calcium phosphate, calcium saccharate, calcium sulfate, cerium carbonate phosphaten phosphaten lithium iron, lithium sulfate, magnesium chloride, magnesium sulfate, manganese chloride, manganese nitrate, manganese sulfate, acetate potassium, potassium carbonate, potassium chloride, potassium phosphate, rubidium carbonate, rubidium sulfate, disodium tetraborate, sodium acetate, sodium bicarbonate, sodium bisulfate, sodium citrate, sodium chloride, sodium hydroxide, nitrate sodium, sodium percarbonate, sodium persulfate, sodium phosphate, sodium propionate, sodium selenite, sodium silicate, sodium sulfate, sodium tellurate, sodium thiosulfate, strontium hydrophosphate, zinc acetate, zinc chloride, sodium thiosulfate, and mixtures thereof; organic compounds such as saturated paraffinic hydrocarbons, polyethylene glycols, waxes and mixtures thereof.
    [0079] The active material can also be selected from waste materials defined as hazardous, toxic or harmful to humanity or the environment and, as such, require total containment for handling and storage.
    [0080] Examples of such waste materials include, but are not limited to toxic heavy metals, and radioactive compounds.
    [0081] Composition C2 is a liquid composition that can be cross-linked, which means that it is a composition capable of polymerizing (cross-linking), to obtain a solid material, which will be from the polymerized shell of the solid microcapsules of the invention.
    [0082] Composition C2 is typically a prepolymer formulation capable of polymerizing into a solid material.
    [0083] According to an embodiment of the invention, composition C2 comprises at least one monomer or a polymer, at least one crosslinking agent and at least one polymerization initiator.
    [0084] According to this embodiment, the composition C2 typically comprises from 50% to 95% by weight of monomer or polymer, or mixture of monomers or polymers, with respect to the total weight of composition C2.
    [0085] According to this embodiment, composition C2 typically comprises from 1% to 20% by weight of crosslinker or mixture of crosslinkers, relative to the total weight of composition C2.
    [0086] According to this embodiment, composition C2 typically comprises from 0.1% to 5% by weight of initiator or mixture of initiators, relative to the total weight of composition C2.
    [0087] By "monomer or polymer" is meant any building block suitable for the formation of a solid material by polymerization, either alone or in combination with other monomers or polymers.
    [0088] Monomers can be selected from monomers bearing at least one reactive function selected from the group consisting of methyl acrylate; methacrylate; vinyl ether; N-vinyl ether; mercaptoester; thiolen; siloxane; epoxy; oxetane; urethane; isocyanate and peroxide.
    [0089] Notably, monomers can be selected from monomers bearing at least one of the above reactive functions and additionally having one or more functions selected from the group consisting of primary, secondary and tertiary alkylamine; quaternary amine; sulfate; sulfonate; phosphate; phosphonate; hydroxyl; methyl carboxylate; and halogen.
    [0090] The polymers can be selected from polyethers, polyesters, polyurethanes, polyureas, polyethylene glycols, polypropylene glycols, polyamides, polyacetals, polyimides, polyolefins, polysulfides, and polydimethylsiloxanes, said polymers bearing at least one selected reactive function from the group consisting of methyl acrylate; methacrylate; vinyl ether; N-vinyl ether; mercaptoester; thiolen; siloxane; epoxy; oxetane; urethane; isocyanate; and peroxide.
    [0091] Examples of such polymers include, but are not limited to: 2-(1-naphthyloxy) ethyl acrylate, 2-(2-naphthyloxy) ethyl acrylate, 2-(2-naphthyloxy) ethyl methacrylate, sorbitol dimethacrylate , acrylamide, 2-propeneamide, 2-(1-naphthyloxy) ethanol, 2-(2-naphthyloxy) ethanol, 1-chloro-2,3-epoxypropane, poly(n-butyl-isocyanate), poly(vinyl carbazole N- ), poly (N-vinyl-pyrrolidone), poly (p-benzamide), poly (p-chlorostyrene), poly (p-methyl styrene), poly (p-phenylene oxide), poly (p-phenylene sulfide) , N-(methacryloxyethyl)succinimide, polybenzimidazole, polybutadiene, butylene terephthalate, polychloral, polychloro trifluoroethylene, polyetherimide, polyetherketone, polyether sulfone, polyhydridosylsesquioxane, poly(isophthalamide m-phenylene), methyl 2-acrylamido-2-methoxyacetate, acid 2-acrylamido-2-methylpropanesulfonic acid, mono-butyl maleate, butyl methacrylate, N-tert-butylmethacrylamide, Nn-butylmethacrylamide, cyclohexylmethacrylamide, m-xylenebisacrylamide 2,3-dim ethyl-1,3-butadiene, N,N-methacrylate, dimethylmethacrylamide, n-butyl, cyclohexyl methacrylate, isobutyl methacrylate, 4-cyclohexylstyrene, cyclol acrylate, cyclol methacrylate, diethyl ethoxymethylenemalonate, 2,2.2 methacrylate -trifluoroethyl, 1,1,1-trimethylolpropane trimethylolpropane, methacrylate, N,N-dimethylanilin, dihydrazide, isophthalic dihydrazine, isophthalic acid, dimethyl benzylketal, epichlorohydrin, ethyl-3,3-diethoxyacrylate, ethyl-3,3-dimethylacrylate , ethyl vinylketone, ethyl vinyl ketone, penten-3-one, diallyl formaldehyde acetal, fumaronitrile, glyceryl triacrylate propoxy, glyceryl trimethacrylale, glycidoxypropyltrimethoxysilane, glycidyl acrylate, n-heptyl acrylate, n-heptyl acrylic acid ester, n-heptyl, 3-hydroxypropionitrile, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-(methacryloxyethyl)phthalimide, 1, 9-nonanediol diacrylate, 1, 9-nonanediol dimethacrylate, N-(n-propyl)acrylamide , ortho acid -phthalic, iso-phthalic acid, 1, 4-benzenedicarboxylic acid, 1, 3-benzenedicarboxylic acid, phthalic acid, mono-2-acryloxyethyl ester, terephthalic acid, phthalic anhydride, polyethylene glycol diacrylate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate , isopropyl acrylate, sorbitol pentaacrylate, vinyl bromoacetate, polychloroprene, poly(di-n-hexyl silylene), poly(di-n-propyl siloxane), polydimethyl silylene, polydiphenyl siloxane, vinyl propionate, vinyl triacetoxysilane, vinyl tris-tert-butoxysilane, vinyl butyral, vinyl alcohol, vinyl acetate, ethylene-co-vinyl acetate, bisphenol-A polysulfone, 1,3-dioxepane, 1,3-dioxolane, 1,4-phenylene-vinylene, poly(2,6-dimethyl-1 A-phenylene oxide), poly(4-hydroxy acid), poly(4-methyl-pentene-1), poly(4-vinylpyridine), polymethylacrylonitrile, polymethylphenylsiloxane, polymethylsilmethylene, Polymethylsilsesquioxane, poly (phenylsilsesquioxane), poly (pyromellitimide-1 0.4-diff). nyl ether), tetrahydrofuran, polythiophene, poly(trimethylene oxide), polyacrylonitrile, sulfone ether, ethylene-co-vinyl acetate, ethylene propylene perfluoroelastomer, poly(perfluoralkoxyl alkan), poly(styrene-acrylonitrile).
    [0092] By "crosslinking agent" is meant any compound that carries at least two reactive functions suitable for the crosslinking of a monomer or a polymer, or a mixture of monomers or polymers, when polymerized.
    [0093] The crosslinking agent can be selected from molecules that support at least two functions selected from the group consisting of methyl acrylate; methacrylate; vinyl ether; N-vinyl ether; mercaptoester; thiolen; siloxane; epoxy; oxetane; urethane; isocyanate; and peroxide.
    [0094] By "initiator" is meant any compound capable of fragmenting when excited by an energy source.
    [0095] Preferably, composition C2 is a liquid photocross-crosslinkable composition and the initiator is thus a photoinitiator for polymerization.
    [0096] The initiator can be selected from the group consisting of:
    [0097] - α-hydroxyketones, such as 2-hydroxy-2-methyl-1-phenyl-1-propanone;
    - α-aminoketones, such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1;
    [0099] - α-dicarbonyl derivatives, such as benzyldimethyl ketal;
    [00100] - acylphosphine oxides, such as bis-acylphosphine oxide;
    [00101] - aromatic ketones, such as benzophenone;
    [00102] - phenylglyoxylates, such as phenyl glyoxylic acid methyl ester;
    [00103] - oxime esters such as methyl [1-(4-phenylsulfanylbenzoyl)heptylideneamino]benzoate;
    [00104] - sulfonium salts,
    [00105] - iodonium salts, and
    [00106] - oxime sulfonates.
    [00107] According to a variant of the invention, composition C2 may also comprise an additional monomer or polymer capable of improving the properties of the Shell microcapsules and/or to provide the shell microcapsules with new properties, such as to make the shell microcapsules responds to an external trigger.
    [00108] Such additional monomer or polymer may be a monomer or a polymer containing a pH-sensitive group, a temperature-sensitive group, a UV-sensitive group or an IV-sensitive group.
    These additional monomers or polymers can induce the rupture of the solid microcapsules and the subsequent release of their contents, when stimulated by a pH, a temperature, a UV or an external IR trigger.
    [00110] The additional monomer or polymer may be selected from monomers or polymers containing at least one reactive function selected from the group consisting of methyl acrylate; methacrylate; vinyl ether; N-vinyl ether; mercaptoester; thiolen; siloxane; epoxy; oxetane; urethane; isocyanate; and peroxide; and also having any of the following groups:
    - a hydrophobic group such as a fluorinated group, for example trifluoroethyl methacrylate, trifluoroethyl acrylate, tetrafluoropropyl methacrylate, pentafluoropropyl acrylate, hexafluorobutyl acrylate, or fluorophenyl isocyanate;
    [00112] - a pH sensitive group, such as a primary, secondary or tertiary amine, carboxylic acid, phosphate, sulfate, nitrate, carbonate or;
    [00113] - a UV-sensitive or UV-cleavable group (also called photochromic group), such as azobenzene, spiropyran, 2-diazo-1, 2-naphthoquinone, o-nitrobenzyl, thiol, or 6-nitro-veratroyloxycarbonyl, for example poly(ethylene oxide)-block-poly (2-nitrobenzylmethacrylate), and other block copolymers, as described, for example, in Liu et al, Polymer Chemistry 2013, 4, 3431-3443.;
    [00114] -. An IR-sensitive or IV-cleavable group such as o-nitrobenzyl or 2-diazo-1,2-naphthoquinone, for example polymers described in Liu et al, Polymer Chemistry 2013, 4, 3431-3443; and
    [00115] - a temperature sensitive group such as poly(N-isopropylacrylamide).
    [00116] Alternatively, the composition may also comprise C2 bearing nanoparticles on its surface, at least one reactive function selected from the group consisting of methyl acrylate; methacrylate; vinyl ether; N-vinyl ether; mercaptoester; thiolen; siloxane; epoxy; oxetane; urethane; isocyanate; and peroxide. These nanoparticles can generate heat when stimulated by an external electromagnetic field, inducing the rupture of solid microcapsules and the subsequent release of their contents.
    [00117] Suitable nanoparticles can be selected from among gold, silver, and titanium dioxide nanoparticles (which react to an IR field) and iron oxide nanoparticles (which react to a magnetic field).
    [00118] According to one embodiment, the viscosity of composition C2 at 25°C is from 500 mPa.s to 100,000 mPa.s.
    Preferably, the viscosity of the composition of C2 at 25 °C is 1000 mPa.s to 50 000 mPa.s, preferably from 5 000 mPa.s to 25 000 mPa.s, for example from 10 000 mPa.s mPa.s to 20 000 mPa.s.
    [00120] Preferably, the viscosity of composition C2 is greater than the viscosity of composition C1.
    [00121] According to this embodiment, regardless of the viscosity of the material or active chemical properties, the kinetic destabilization of the first emulsion droplets is significantly slow, which allows the envelope of the microcapsules to be polymerized during step d), providing thermodynamic stabilization before kinetic destabilization may arise.
    [00122] Thus, the relatively high viscosity of composition C2 ensures the stability of the first emulsion obtained in step a).
    [00123] This embodiment solves the limitation associated with the large variation in the properties of microcapsules that usually occurs when the active material for the encapsulation varies.
    [00124] Preferably, there is a low interfacial tension between composition C1 and composition C2. Suitable interfacial tensions typically range from 0 mN/m up to 50 mN/m, preferably from 0 mN/m up to 20 mN/m.
    [00125] The low interfacial tension between composition C1 and composition C2 also advantageously ensures the stability of the first emulsion obtained in step a).
    [00126] According to one embodiment, the composition volume of C1 to composition ratio volume C2 is from 1:10 to 10:1.
    [00127] Preferably, said ratio is from 1:3 to 5:1, preferably from 1:2 to 4:1.
    [00128] The said proportion can be adapted according to these intervals in order to control the thickness of the resulting microcapsule polymerized shell. Step b)
    [00129] During step b), the first emulsion obtained in step a) is added to a liquid composition C3, said addition to be carried out under stirring, which means that the composition C3 is stirred, typically mechanically, while the first Emulsion is added so as to emulsify the mixture of composition C1, composition C2, and composition C3.
    [00130] The addition of the first emulsion with composition C3 is typically carried out dropwise.
    [00131] During step b), the first emulsion is at a temperature typically comprised between 15 °C to 30 °C. During step b), the composition is C3, at a temperature typically comprised between 15 °C to 30 °C. °C
    [00132] Under the conditions of addition of step b), composition C2 and composition C3 are immiscible with each other, which means that the amount (by mass) of composition C2 capable of being solubilized in composition C3 is less than or equal to 5%, preferably 1%, preferably 0.5%, relative to the total mass of composition C3, and that the amount (by mass) of composition C3 capable of being solubilized in composition C2 is less than or equal to 5%, of preferably 1%, preferably 0.5%, relative to the total mass of composition C2.
    [00133] Thus, when it comes into contact with the C3 composition under stirring, the first emulsion (C1 -in-C2 or C1 / C2) is dispersed in the form of droplets (also called double droplets), the dispersion of these droplets of emulsion in the first continuous phase C3 to be called the second emulsion.
    [00134] Typically, a double drop formed during step b) corresponds to a single drop of composition C1, as described above, surrounded by a shell of composition C2 which encapsulates said totally single drop.
    [00135] The double droplet formed during step b) may also comprise at least two individual drops of composition C1, as described above, said individual droplets being surrounded by a shell of composition C2 which fully encapsulates said individual droplets.
    Thus, said double droplets comprise a core consisting of one or more individual droplets of composition C1, and a layer of composition C2 around said core.
    [00137] The resulting second emulsion is generally a polydispersed double emulsion (C1 -in-C2-C3-in emulsion or C1 / C2 / C3 emulsion), which means that the double droplets do not have a sharp size distribution in said second emulsion.
    [00138] Figure 1 schematically represents the method of the invention and, in particular, schematically represents polydispersed droplets 5 obtained in step b), by adding in composition C3 the first emulsion of 1 droplets dispersed in composition C2.
    [00139] The immiscibility of composition C2 with composition C3 prevents the composition layer of C2 from mixing with composition C3 and thus ensures the stability of the second emulsion.
    [00140] The immiscibility of composition C2 with composition C3 also prevents the active material in composition C1 to migrate from the core of the composition C3 droplets.
    [00141] In order to implement step b), any type of stirrer commonly used to make the emulsions can be used, such as a suspended stirrer (mixing speed 100 to 2000 rpm), rotor-stator mixer (mixing speed 100-5 000 rpm), or colloidal mill (mixing speed 1000 and 10 000 rpm). Alternatively, ultrasonic homogenizer, membrane homogenizer or high pressure homogenizer can also be used.
    [00142] According to one embodiment, composition C3 is a hydrophobic phase.
    [00143] According to said embodiment, composition C3 typically comprises an elastomer or resin formulation, a paint, a coating, a sealant, an adhesive, or a hydrocarbon oil (such as paraffinic oil, naphthenic oil , vegetable oil, mineral oil, castor oil, corn oil, peanut oil, jojoba oil, alkyl adipates, alkyl palmitates, the alkyl oxystearates oils, glycerol triacetates, or isopropyl myristates).
    [00144] According to another embodiment, composition C3 is a hydrophilic phase.
    [00145] According to said embodiment, composition C3 is typically an aqueous composition comprising a thickening agent, such as dextran, alginate, cellulose and cellulose derivatives (such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, cetyl), guar gum, xanthan gum, gelatin, starch, agar, collagen hydrolyzed carrageenan, hyaluronic acid, pectin, acrylate polymers and copolymers, polyacrylic acid, carbero, polyacrylamide, polyvinylpyrrolidone, or polyvinyl acetate.
    [00146] According to one embodiment, the viscosity of composition C3 at 25°C is higher than the viscosity at the temperature of 25°C of the first emulsion obtained in step a).
    [00147] Composition C3 typically has a viscosity at a temperature of 25°C from 500 mPa.s to 100,000 mPa.s. Preferably, the viscosity of composition C3 at 25°C is from 1000 mPa.s to 50,000 mPa.s, preferably from 5,000 mPa.s to 25,000 mPa.s, for example from 10,000 mPa.s to 20 000 mPa.s.
    [00148] According to this embodiment, given the higher viscosity of the continuous phase (composition C3) compared to the first emulsion, the kinetic destabilization of the double emulsion droplets (second) is significantly slow, providing thermodynamic stabilization before kinetic destabilization can to emerge.
    [00149] Thus, the relatively high viscosity of composition C3 ensures the stability of the second emulsion obtained in step b).
    [00150] Preferably, there is a low interfacial tension between the C2 composition and C3 composition.
    [00151] The low interfacial tension between composition C2 and composition C3 also guarantees the stability of the second emulsion obtained in step b).
    [00152] According to an embodiment, during step b), the volume of the first emulsion to the volume of composition ratio C3 is from 1:10 to 10:1.
    [00153] Preferably, said ratio is from 1: 9 to 3: 1, preferably from 1: 8 to 1:1, for example from 1: 6 to 1: 2.
    [00154] Said proportion can be adapted according to these intervals, in order to control the total content of active material encapsulated in the resulting population of polymerized microcapsules. Step c)
    [00155] In step c), the second emulsion obtained in step b), which consists of polydispersed droplets dispersed in a continuous phase, is cut in a mixer, which applies a homogeneous controlled shear rate, comprising 1000 s-1 at 100,000 s-1 .
    [00156] Surprisingly, the inventors found that this emulsification process creates, through a fragmentation mechanism, a double emulsion with a better size range, i.e. a double emulsion consisting of double monodisperse droplets (also called third emulsion) .
    [00157] In a mixing device, the shear rate is said to be homogeneous and controlled when, regardless of the variation in time of the shear rate, it passes through a maximum value that is the same for all parts of the emulsion, in a given instant that may differ from one point in the emulsion to another. The exact configuration of the mixing device is not essential according to the invention, since, on leaving this device, the entire emulsion was subjected to the same maximum shear. Suitable mixers for carrying out step c) are notably described in US5938581.
    [00158] The second emulsion can be subjected to homogeneous controlled shear when circulated through a cell formed by:
    [00159] - two concentric rotating cylinders (also called Couette-geometry mixer),
    [00160] - two parallel rotating discs, or
    [00161] - two parallel oscillating plates.
    [00162] The shear rate applied to the second emulsion is formed from 1000 s-1 to 100 000 s-1 preferably from 1000 s-1 to 50 000 s-1 preferably from 2000 s -1 20 000 s-1.
    [00163] During step c), the second emulsion is introduced into the mixer and is then subjected to a shear force which results in the formation of a third emulsion. Said third emulsion is chemically the same as the second emulsion, but consisting of double monodisperse droplets, whereas the second emulsion consisted of polydisperse double droplets. The third emulsion typically comprises a double droplet dispersion comprising a core consisting of one or more individual droplets of composition C1, and a layer of composition C2 surrounding said core, said double droplets being dispersed in composition C3.
    [00164] The difference between the second emulsion and the third emulsion is the variation in the size of the double droplets: the droplets of the second emulsion are polydisperse in size while the emulsion droplets are the third monodisperse, thanks to the fragmentation mechanism described above.
    [00165] Preferably, the second emulsion is introduced into the mixer continuously, which means that the amount of double emulsion introduced into the mixer inlet is the same as the amount of third emulsion outlet from the mixer outlet.
    [00166] Since the droplet size of the third emulsion subsequently corresponds to the size of the solid microcapsules after polymerization, it is possible to adjust the microcapsule size and reservoir thickness by adjusting the shear rate during step c) with a strong correlation between decreasing droplet size and increasing shear velocity.
    [00167] This allows the resulting dimensions of the microcapsules to be adapted by varying the shear rate applied during step c).
    [00168] According to a preferred embodiment, the mixer implemented in step c) is a Couette-geometry mixer, comprising two concentric cylinders, an outer cylinder of inner radius R 0 and an inner cylinder of outer radius R, the cylinder outer to be fixed and the inner cylinder to be rotating with an angular velocity o.
    [00169] A Couette-geometry mixer suitable for the method of the invention can be purchased from TSR Company France.
    [00170] According to one embodiment, the angular velocity w of the inner rotating cylinder of the Couette-geometry mixer is more than or equal to 30 rad.s 1 .
    [00171] For example, the angular velocity w of the inner cylinder rotation is about 70 rad.s-1.
    [00172] The dimensions of the fixed outer cylinder of the Couette-Geometry mixer can be chosen to modulate the difference (d = R0 - R1) between the inner cylinder and the fixed outer rotating cylinder.
    [00173] According to one embodiment, the interval d = R0 - R, between the two concentric cylinders of the Couette-geometry mixer is from 50 μm to 1000 μm, preferably from 100 μm to 500 μm, for example from 200 µm to 400 µm.
    [00174] For example, the gap d between the two concentric cylinders is 100 µm.
    [00175] According to the embodiment of the invention, the implementation of a Couette-geometry mixer, during step c), the second emulsion is introduced into the inlet of the mixer, typically by means of a pump, and is directed to the space between the two concentric cylinders, the outer cylinder being fixed and the inner cylinder was rotating at an angular velocity w.
    [00176] The second emulsion is then subjected to a shear force which results in the formation of a third emulsion at the outlet of the mixer. Said third emulsion is chemically the same as the second emulsion, but consisting of double monodisperse droplets, whereas the second emulsion consisted of polydisperse double droplets. The third emulsion typically comprises a double droplet dispersion comprising a core consisting of one or more individual droplets of composition C1, and a layer of composition C2 surrounding said core, said double droplets being dispersed in composition C3.
    [00177] The difference between the second emulsion and the third emulsion is the variation in the size of the double droplets: the droplets of the second emulsion are polydisperse in size while the emulsion droplets are the third monodisperse, thanks to the fragmentation mechanism described above.
    [00178] Preferably, the second emulsion is introduced into the mixer inlet continuously, which means that the amount of double emulsion introduced into the mixer inlet, is the same as the amount of third emulsion outlet from the mixer outlet .
    [00179] When the double emulsion is in the space between the two cylinders, the y shear rate applied to said emulsion is given by the following equation:
    where w is the angular velocity of rotation of the inner cylinder, R0 is the inner radius of the fixed outer cylinder, and Ri is the outer radius of the rotating inner cylinder.
    [00180] The parameters of the Couette-geometry mixer (ie the angular velocity and the gap between the cylinders) is adjusted so that the y cutting speed is 1 000 s-1 20 000 s-1 .
    [00181] Since the droplet size of the third emulsion subsequently corresponds to the size of the solid microcapsules after polymerization, it is possible to adjust the microcapsule size and shell thickness by adjusting the shear rate during step c), with a strong correlation between decreasing drop size and increasing shear rate.
    [00182] This allows the resulting dimensions of the microcapsules to be adjusted by varying either the angular velocity of the rotating cylinder, or the inner radius of the fixed outer cylinder, or both.
    [00183] Figure 1 schematically represents the method of the invention and, in particular, schematically represents monodisperse droplets 10 obtained in step c).
    [00184] Figure 2 schematically represents a Couette-geometry mixer suitable for the preferred embodiment of the method of the invention and, in particular, schematically represents the polydispersed droplets 5 of the second emulsion to be introduced into the inlet 50, in the space between the cylinder inner rotatable 55 of outer radius Ri, and outer cylinder 60 fixes inner radius R0, thus providing the monodisperse droplets 10 from the third emulsion outlet through outlet 65. Step d)
    [00185] During step d), the double droplets of the third emulsion are crosslinked to provide microcapsules that encapsulate the active material.
    [00186] More particularly, the reservoir of these double droplets consisting of the crosslinkable composition C2 is crosslinked and thus converted into a viscoelastic polymeric shell matrix, encapsulating and protecting the active material from release, in the absence of a mechanical trigger.
    [00187] The mechanical properties of the polymerized shell of the microcapsules can be adapted by modifying the proportion of monomer or polymer to crosslinking agent within the initial C2 composition.
    [00188] The composition obtained after step d), comprising the microcapsules of the invention dispersed in composition C3, is ready-to-use and does not need to be washed or does not need any post-treatment.
    [00189] Solid microcapsules obtained according to the method of the invention have a mean diameter (as measured by image analysis of optical microscopy images or transmission electron microscopy images), preferably comprised between 0.1 µm to 10 µm preferably from 0.2 µm to 5 µm.
    [00190] The thickness of the polymerized shell of solid microcapsules obtained according to the method of the invention is typically between 10 nm and 2.5 μm, preferably between 100 nm to 1000 nm.
    [00191] According to an embodiment, during step d), the crosslinking is carried out by subjecting the double droplets obtained in step c) to a light source, preferably a UV light source, capable of initiating the crosslinking of composition C2 .
    [00192] Preferably, the UV light source emits in the range of 100 nm - 400 nm.
    [00193] The double droplets obtained in step c) are typically subjected to a light source for 1 minute to 15 minutes.
    [00194] According to this embodiment, the cross-linkable composition C2 is photocross-crosslinkable and the polymerization is initiated so-photo.
    [00195] Figure 1 schematically represents the method of the invention and, in particular, schematically represents polymerized monodisperse microcapsules 20 obtained in step d), after polymerization of the shell of composition C2.
    [00196] The method of the invention allows great versatility and thus is suitable for the encapsulation of various active materials, regardless of their viscosity or chemical properties.
    [00197] The method of the invention allows its adaptation to the shell thickness and/or the size of the microcapsules, adjusting the proportion of composition C1 over composition C2 in step a), and/or the shear rate applied by the Couette mixer -geometry in step c).
    [00198] The method of the invention allows the adaptation of the total content of active material in the resulting composition, obtained after step d), adjusting the proportion of the first emulsion over composition C3 in step b).
    [00199] The method of the invention allows for the adaptation of the mechanical sensitivity, flexibility, and/or fragility of solid microcapsules (particularly the shell) by adjusting the cross-linking agent content in the C2 composition. Microcapsules and composition
    [00200] The method of the invention allows the preparation of solid microcapsules, comprising a core consisting of the composition C1 comprising an active material, said core being encapsulated by a shell solid (polymerized or crosslinked) of polymerized composition C2.
    [00201] The core of the microcapsules can consist of a single drop or several drops of composition C1.
    [00202] The core of the microcapsules can be a liquid, aqueous or oily solution, a liquid/liquid emulsion, or a dispersion of (nano) particles in a liquid composition.
    The microcapsules of the invention are dispersed in a continuous liquid C3 composition.
    [00204] The method of the invention allows the preparation of solid monodisperse microcapsules, thanks to the specific fragmentation mechanism described above in step c).
    [00205] An object of the present invention is also a series of solid microcapsules, the microcapsules being obtained by the method of the invention defined above, each microcapsule comprising the said:
    [00206] - a core comprising a composition comprising at least one active material as defined above, and
    [00207] - a cross-linked solid shell surrounding said core,
    [00208] in which the standard deviation of the microcapsule diameter distribution is less than 25% or less than 1 μm.
    The solid microcapsule series of the invention is a monodisperse population of microcapsules.
    [00210] The population of microcapsules can be visualized with an electron microscope or optical transmission microscope and subsequent images can be treated with image analysis software in order to extract the distribution of microcapsule diameters and thus determine the monodispersity of the microcapsule population.
    [00211] Alternatively, techniques based on light scattering, sieving or centrifugation can be used.
    [00212] According to one embodiment, the solid microcapsule series of the invention has a microcapsule shell thickness distribution standard deviation below 25% or below 300 nm.
    [00213] According to one embodiment, the series of solid microcapsules is characterized in that the average diameter D of solid microcapsules is less than or equal to 10 µm, preferably from 0.1 µm to 5 µm, more preferably from 0.3 µm to 1 µm.
    [00214] According to one embodiment, the solid microcapsules of the invention are free of surfactant.
    [00215] According to one embodiment, the solid microcapsules of the invention are water-free.
    [00216] The method of the invention allows the preparation of such microcapsules, namely monodisperse microcapsules, with an average size of less than 10 µm.
    [00217] The microcapsules of the invention, and the continuous phase in which they are dispersed, are advantageously free of any contaminant such as surfactant, emulsifier, or unreacted monomers.
    [00218] An object of the present invention is also a composition comprising a series of solid microcapsules, as defined above, said microcapsules being dispersed in a continuous liquid phase.
    [00219] Said continuous liquid phase typically corresponds to composition C3.
    [00220] An object of the present invention is also a composition comprising a series of solid microcapsules according to the invention.
    [00221] An object of the present invention is also a method for releasing an active material, comprising a step of applying a mechanical shear stress from a composition comprising a series of solid microcapsules as defined above. EXAMPLES Example 1 - Encapsulation Method Versatility
    [00222] The following materials have been successfully used as C1 composition:


    [00223] Composition C2 was made from: - 89% CN981 (Sartomer, Arkema), - 10% hexanediol diacrylate, - 1% Darocure 1 173.
    [00224] Composition C3 was ExxonMobil PAO 100.
    [00225] Step a) Composition C1 was added dropwise, under constant stirring, composition C2 until a ratio C1:C2 = 1:4 was reached. After this step, a C1 -in-C2 emulsion was formed.
    [00226] Step b) the C1-in-C2 emulsion was added dropwise, under constant stirring, the C3 composition until a ratio C1-in-C2:C3 = 1: 4 was reached. After this step, a C1 -in-C2-C3-double emulsion was formed.
    [00227] Step c) The double emulsion C1 -in-C2-in-C3 was passed through a Couette-geometry mixer with a flow rate of 8 ml/min and the rotation speed of 100 rpm, which corresponds to a shear rate of 2,083 s -1 . After this step, a monodisperse C1 double emulsion -in-C2-C3-was formed.
    [00228] NB: for the wax, steps a), b) and c) were carried out at 40°C.
    [00229] Step d) The resulting double monodisperse emulsion was subjected to UV irradiation to polymerize the microcapsules for 6 minutes using a Dymax Light Box 2000 ECE having an output light intensity of 0.1 W/cm 2 at 365 nm.
    [00230] Images of the resulting solid microcapsules were obtained with a JEOL JEM 201 transmission electron microscope and showed regular spherical shaped microcapsules.
    [00231] This example illustrates that a variety of materials, which have a wide range of viscosities and chemical properties, can be encapsulated according to the method of the invention. Example 2 - The robustness of the encapsulation method
    [00232] An image analysis (using Image J. software) was performed on TEM images of microcapsules fabricated in Example 1. The results (mean diameter and thickness of microcapsule distributions as well as standard deviations) are shown in the table below.

    [00233] This example illustrates that different materials can be encapsulated according to the invention with little variation in microcapsule size and shell thickness. Example 3 - Complete containment of microcapsules
    The two-component "Silgard 184 silicone elastomer" kit marketed by Dow Corning was used in this example. The two components, termed A and B, are respectively a siloxane monomer composition and a cross-linked siloxane composition. When mixed together in a weight ratio of A:B=10:1, these two components form a solid crosslinked elastomer within 24 hours at room temperature or within 2 hours at 90°C.
    [00235] Encapsulation was carried out with component B as composition C1 and component A as composition as C3.
    [00236] Composition C2 was made from: - 89% CN981 (Sartomer, Arkema) - 10% hexanediol diacrylate - 1% Darocure 1173 (photoinitiator) Manufacturing of Microcapsules:
    [00237] An overhead stirrer (Heidolph RZR 2021) equipped with a three-blade propeller was used to manufacture the emulsions. The mixing speed was set at 1000 rpm. All steps were carried out at room temperature.
    [00238] Step a) Composition C1 was added dropwise, under constant stirring, composition C2 until a ratio C1:C2 = 1:6 was reached. After this step, a C1 -in-C2 emulsion was formed.
    [00239] Step b) The C1-in-C2 emulsion was added dropwise, under constant stirring, the composition C3 until a ratio C1-in-C2:C3 = 1: 4 was reached. After this step, a Ci-in-C2-C3-double emulsion was formed.
    [00240] Step c) The double emulsion C1 -in-C2-in-C3 was passed through a Couette-geometry mixer with a flow rate of 8 ml/min and a rotation speed of 450 rpm, which corresponds to a shear rate of 9,373 s-1. After this step, a Ci-in-C2-in-C3 double monodisperse emulsion was formed.
    [00241] Step d) The resulting double monodisperse emulsion was subjected to UV irradiation to polymerize the microcapsules for 6 minutes using a Dymax Light Box 2000 ECE having an output light intensity of 0.1 p/cm2 at 365 nm.
    [00242] The mean diameter of the microcapsule distribution was 346 nm ± 80 nm and the mean shell thickness of the microcapsule distribution was 62 nm ± 19 nm. Stability of microcapsules:
    [00243] The viscosity of the microcapsule dispersion resulting from step d) was measured at 25°C with a HAAKE Rheostress™ 600 rheometer for 60 days.
    [00244] No variation in viscosity was observed, demonstrating the absence of leakage of component B from the capsules. Release triggered:
    [00245] After 60 days, the solid microcapsule dispersion was cut in a Couette-geometry mixer with a flow rate of 0.5 ml/min and a rotation speed of 680 rpm, which corresponds to a cutting speed of 17,200 s- 1, and then left at 90°C for 2 hours.
    [00246] It was then impossible to measure the viscosity of the cut microcapsule dispersion because it had polymerized into a solid elastomer. This demonstrates that the capsules were ruptured under shear and had released their contents.
    [00247] This example demonstrates the fabrication of microcapsules that contain a cross-linking agent and dispersed in a matrix that can be cross-linked. The resulting dispersion of microcapsules is stable for at least 60 days without polymerization. Shearing of this dispersion results in the rupture of the microcapsules and triggers polymerization. Example 4 - Comparison of different methods - Characterization of monodispersity
    [00248] Solid microcapsules were prepared using the following compositions of C1, C2, and C3:
    [00249] Composition C1: ExxonMobil PAO40 (polyalpha olefin with a viscosity of 892 mPa.s at 25 °C)
    [00250] - Composition C2: - 89% CN981 (Sartomer, Arkema) - 10% Hexanediol diacrylate - 1% Darocure 1 173 (photo-initiator)
    [00251] - Composition C3: ExxonMobil PAO100 (polyalpha olefin with a viscosity of 2989 mPa.s at 25 °C)
    [00252] An overhead stirrer (Heidolph RZR 2021) equipped with a three-blade propeller was used to manufacture the emulsions. The mixing speed was set at 1000 rpm. All steps were performed at 25°C.
    [00253] Step a): Composition C1 was added dropwise, under constant stirring, composition C2 until a ratio C1:C2 = 1: 4 was reached. After this step a C1 -in-C2 emulsion was formed. Step b): The C1 -in-C2 emulsion obtained then dropwise, step a) was added under constant stirring, the composition C3 until a ratio C1 -in-C2: C3 = 1: 4 was reached. After this step a C1 -in-C2-in-C3 double emulsion was formed.
    [00254] Mixing step: The double emulsion C1 -in-C2- C3 was then cut with different types of mixer:
    [00255] - an overhead stirrer (Heidolph RZR 2021) equipped with a three-blade propeller with a mixing speed of 1000 rpm,
    [00256] - an Ultra-Turrax T25 IKA mixer for 5 minutes at 24,000 rpm, or
    [00257] - a Couette-geometry mixer, with a flow rate of 8 ml/min and a rotation speed of 450 rpm, which corresponds to a cutting speed of 9373 s "1 (homogeneous high-shear mixture, which corresponds to the conditions of step c) of the method of the invention).
    [00258] Step d): The emulsions were then subjected to UV irradiation to polymerize the microcapsules for 6 minutes using a Dymax 2000 Light Box ECE having an output light intensity of 0.1 P/cm 2 at 365 nm. The series of solid microcapsules thus obtained were subsequently visualized with an Olympus microscope equipped with a 1X71 UPlanSApo 100x / 10.4 objective and with a JEOL JEM 201 transmission electron microscope. The resulting images were treated with Image J software. Extract the capsule diameter distribution.
    [00259] The distribution of the series of capsules is represented in Figure 3 (capsule diameter distribution) and Figure 4 (tank thickness distribution), in which "..." corresponds to the suspended agitator, the plot corresponds to the 'Ultra mixer' -Turrax, and the continuous weft corresponds to the Couette mixer- geometry.
    [00260] The series of solid microcapsules resulting from a mixing step performed in an overhead stirrer (standard emulsification) has an average diameter is 9.05 μm and the standard deviation of the distribution is 8.16 μm or 90% . The mean shield thickness is 2.32 µm and the standard deviation of the distribution is 2.01 µm or 87%.
    [00261] This result illustrates the fact that conventional mixers yield such solid capsules having very wide size distributions.
    [00262] The series of solid microcapsules resulting from a mixing step carried out in an IKA Ultraturrax T25 mixer, which provides high shear mixing heterogeneous, has an average diameter of 5.18 μm and a standard deviation of 4.35 μm or 84%. The mean shield thickness is 1 0.50 µm and the standard deviation of the distribution is a 0.38 µm or 92%.
    [00263] This result illustrates the fact that mixers such as the T25 IKA Ultra-Turrax allow to decrease the average size of capsules, because of the high shear applied to the double emulsion, but still produce very wide size distributions.
    [00264] On the other hand, the series of solid microcapsules obtained according to the method of the invention, which results from a mixing step carried out in a Couette-geometry mixer, has an average diameter of 0.13 μm and a standard deviation of 0.03 µm or 23%.
    [00265] This result demonstrates the importance of the Couette-geometry mixer to obtain both small capsule sizes and narrow distributions.
    权利要求:
    Claims (17)
    [0001]
    1. Process for the preparation of solid microcapsules (20) characterized in that it comprises the steps of: a) adding under stirring a C1 composition comprising at least one active material from a crosslinkable liquid C2 composition, wherein the material active is not an additive to be used in the lubricant, fuel or bitumen industries, or in drilling muds or silt, or an additive to be used in petroleum exploration / production, composition C1 and composition C2 being immiscible with each other , so that a first emulsion is obtained, said first emulsion comprising drops (1) of composition C1 dispersed in composition C2, b) adding under stirring the first emulsion obtained in step a) a liquid composition C3, composition C3 and composition C2 being immiscible with each other, so that a second emulsion is obtained, said second emulsion comprising drops (5) dispersed in composition C3, c) loading the second emulsion obtained in the eta pa b) in a mixer that applies a homogeneous controlled shear rate for said second emulsion, said shear speed being from 1,000 s-1 to 100,000 s-1, so that a third emulsion is obtained, said third emulsion comprising drops (10) dispersed in composition C3, and d) crosslinking the drops (10) obtained in step c), so that solid microcapsules (20) dispersed in composition C3 are obtained.
    [0002]
    2. Process according to claim 1, characterized in that the active material is solubilized in composition C1 or dispersed in the form of solid particles within composition C1.
    [0003]
    3. Process according to any one of claims 1 or 2, characterized in that composition C2 comprises at least one monomer or polymer, at least one crosslinking agent and at least one polymerization initiator.
    [0004]
    4. Process according to any one of claims 1 to 3, characterized in that the viscosity of the composition from C2 to 25°C is from 500 mPa.s to 100,000 mPa.s.
    [0005]
    5. Process according to any one of claims 1 to 4, characterized in that the viscosity of composition C2 is greater than the viscosity of composition C1.
    [0006]
    6. Process according to any one of claims 1 to 5, characterized in that during step a), the ratio of composition volume of C1 to composition volume C2 is from 1:10 to 10:1.
    [0007]
    7. Process according to any one of claims 1 to 6, characterized in that the viscosity of the composition C3 at 25°C is higher than the viscosity at a temperature of 25°C of the first emulsion obtained in step a) .
    [0008]
    8. Process according to any one of claims 1 to 7, characterized in that during step b), the ratio of the volume of the first emulsion to the volume of composition C3 is from 1:10 to 10:1.
    [0009]
    9. Process according to any one of claims 1 to 8, characterized in that the mixer used in step c) is a Couette-geometry mixer, which comprises two concentric cylinders, an outer cylinder with an inner radius R0 and an inner cylinder of outer radius R, the outer cylinder being fixed and the inner cylinder being rotatable with an angular velocity o.
    [0010]
    10. Process according to claim 9, characterized in that the angular velocity o of the inner cylinder is rotatable through what or equal to 30 rad.s-1.
    [0011]
    11. Process according to any one of claims 9 or 10, characterized in that the interval d = R0 - R, between the two concentric cylinders is from 50 μm to 1,000 μm.
    [0012]
    12. Process according to any one of claims 1 to 11, characterized in that during step d), the crosslinking is carried out by submitting the double drops (10) obtained in step c) to a light source, preferably , a UV light source, capable of initiating crosslinking of the C2 composition.
    [0013]
    13. A series of solid microcapsules (20), wherein the microcapsules (20) being obtained by the process as defined by any one of claims 1 to 12, each microcapsule (20) characterized in that it comprises: - a core comprising a a composition comprising at least one active material as defined in claim 1, and - a crosslinked shell solid surrounding said core, wherein the standard deviation of the microcapsule diameter distribution is less than 25% or below 1 µm.
    [0014]
    14. Series of solid microcapsules (20), according to claim 13, characterized in that the average diameter of the microcapsules (20) is less than or equal to 10 μm.
    [0015]
    15. Series of solid microcapsules (20) according to any one of claims 13 or 14, characterized in that each microcapsule (20) is free of surfactant and/or free of water.
    [0016]
    16. Composition characterized in that it comprises a series of solid microcapsules (20) as defined by any one of claims 13 to 15.
    [0017]
    17. Process for releasing an active material characterized in that it comprises a step of applying a mechanical shear stress to a composition comprising a series of solid microcapsules (20) as defined by any one of claims 13 to 15.
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    同族专利:
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    CN108348886A|2018-07-31|
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    WO2017046360A1|2017-03-23|
    US10807060B2|2020-10-20|
    MX2018003286A|2018-08-16|
    EP3349891B1|2021-04-21|
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    法律状态:
    2020-03-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/09/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP15306428.2A|EP3144058A1|2015-09-16|2015-09-16|Method for preparing microcapsules by double emulsion|
    EP15306428.2|2015-09-16|
    PCT/EP2016/072028|WO2017046360A1|2015-09-16|2016-09-16|Method for preparing microcapsules by double emulsion|
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