WO2015138160A1 - Particules creuses de silice fonctionnalisées ayant une faible porosité à l'aide de précurseurs de silice à base d'eau - Google Patents

Particules creuses de silice fonctionnalisées ayant une faible porosité à l'aide de précurseurs de silice à base d'eau Download PDF

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WO2015138160A1
WO2015138160A1 PCT/US2015/017909 US2015017909W WO2015138160A1 WO 2015138160 A1 WO2015138160 A1 WO 2015138160A1 US 2015017909 W US2015017909 W US 2015017909W WO 2015138160 A1 WO2015138160 A1 WO 2015138160A1
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particle
functionalized
silica
hollow silica
silica particle
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PCT/US2015/017909
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Jelena LASIO
Hau-Nan LEE
Anilkumar Raghavanpillai
Devin T. WHIPPLE
Ma Helen CATIVO
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E I Du Pont De Nemours And Company
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • C09C1/3054—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/203—Exchange of core-forming material by diffusion through the capsule wall
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/149—Coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate

Definitions

  • the present disclosure relates to functionalized hollow silica particles. More particularly, the disclosure relates to functionalized silica particles with substantially impervious silica shells.
  • Nano core/shell particles are submicroscopic colloidal systems composed of a solid or liquid core surrounded by a thin polymer or inorganic shell. This solid or liquid core is removed to form hollow nanospheres.
  • Such core/shell systems may be prepared by deposition of the shell material onto a template particle, wherein the shell material can be either organic, inorganic, or hybrid. The selective removal of the core (template) material without disturbing the shell generates hollow particles.
  • the core (template) material without disturbing the shell generates hollow particles.
  • the disclosure provides functionalized hollow silica nanospheres, and allows for control of the porosity and surface area of the silica shells, providing access to substantially impervious hollow particles with tunable surface properties.
  • the surface properties of the particles are tuned through grafting with a variety of functionalized alkoxysilanes.
  • the functionalized hollow silica particle comprises:
  • a core/shell silica particle comprising a template core particle and a silica treatment, more typically a coating, wherein the core/shell silica particle has an outer surface; and wherein the silica treatment is prepared using a water-based silica precursor;
  • a functionalized surface on the core-shell silica particle wherein the functionalized surface is prepared using sulfonic acid, phosphonic esters, carboxylic acid, amines, epoxides, boronic acids or quarternary amines, and wherein the template core particle is removed before or after functional ization.
  • the template core particle from the core/shell silica particle may be removed before or after functionalization, more typically before
  • core removal is at low temperatures so no harm is done to the functionalized surface if core removal is achieved after
  • acid- or base-labile core materials that can be removed by hydrolysis can be removed before or after functionalization.
  • the silica treatment is substantially impervious.
  • substantially impervious we mean the surface area and porosity of the silica shell, typically walls, has to be tuned. Whether the silica shell is adequate can be determined by comparing the surface area of the particles with calculated surface area of a smooth sphere of the same diameter.
  • the shell substantially impervious if its surface area does not surpass about 130% of the calculated surface area of a smooth sphere of the same dimensions, i.e., it is about 30% or less higher than the surface of the core/shell silica particle compared to the calculated surface area of a smooth sphere of the same diameter, more typically about 125% of the smooth sphere surface area, and still more typically about 120% of the smooth sphere surface area of the same dimensions.
  • Addition of various amounts of the silica precursor will lead to more or less porous silica layers, which can lead to control of the porosity and surface area of the particles.
  • the silica precursor may be added in stages to modulate the porosity of the particles as well as their surface.
  • calcination at temperatures higher than about 500 °C may decrease the porosity and surface area of the particles without increasing the thickness of the wall.
  • the process for preparing the core/shell silica particle comprising a template core particle and a silica treatment comprises: a) providing a template core particle, more typically prepared using emulsion polymerization;
  • a water-based silica precursor such as sodium silicate, potassium silicate, ammonium silicate or pre-formed silicic acid, more typically sodium silicate or potassium silicate;
  • Figure 1 shows the process for making hollow silica particles, as described in Examples 3 and 5.
  • Figure 2 shows TEM images of hollow silica particles obtained by a procedure described in Example 3.
  • Figure 3 shows functionalization of hollow silica particles
  • Figure 4 shows the scheme for converting the phosphonate ester- functionalized silica from Figure 3, Example 7 into phosphonic acid- functionalized silica particles through hydrolysis of phosphonic ester groups, as described in Example 8.
  • Figure 5 shows functionalization of hollow silica particles with (3- glycydoxypropyl)trimethoxysilane, as described in Examples 9 and 10.
  • Figure 6 shows the process for further functionalization of the epoxy silyl- funtionalized silica with glycine, to generate carboxyl group-functionalized silica particles through an amine linkage, as described in Example 9.
  • Figure 7 shows the process for further functionalization of the epoxy silyl- funtionalized silica with thioglycolic acid, to generate carboxyl group- functionalized silica particles through a thioether linkage, as described in Example 10.
  • Figure 8 shows the process for functionalization of hollow silica particles with (diethoxyphosphoryl)methyl-2-((triethoxysilyl)ethyl)carbamate, as described in Example 1 1 .
  • Figure 9 shows the TEM image of sample described in Example 5.
  • a process is provided for preparing the hollow inorganic particles, typically hollow silica, through intermediacy of template particles, onto which the shell material is deposited, to generate core/shell particles.
  • the process of silica deposition is such that it allows tuning of the surface area and porosity of the silica shells, thereby allowing for synthesis of impervious core/shell particles.
  • the core material is removed to generate hollow particles.
  • the resulting hollow particles are then functionalized with a variety of alkoxysilanes to generate functionalized hollow particles, with tunable porosity and surface area.
  • the particles, such as template particles, described herein are between about 100 to about 900nm in size, more typically between about 100 and about 600nm, and still more typically between about 150 and about 300nm.
  • the disclosure describes the process for hollow silica particles with tunable porosity and surface area, as well as the functional group on the hollow particles' surface. Particles of about 50 to about 100nm in size may be used provided they do not have a surfactant layer on the outer surface of the particle.
  • the functionalized hollow silica particle comprises:
  • a core/shell silica particle comprising a template core particle and a silica treatment, more typically a coating, wherein the core/shell silica particle has an outer surface; and wherein the silica treatment is prepared using a water-based silica precursor;
  • a functionalized surface on the core/shell silica particle wherein the functionalized surface is prepared using sulfonic acid, phosphonic esters, carboxylic acid, amines, epoxides, boronic acids or quarternary amines, and wherein the template core particle is removed before or after functionalization.
  • the template core particle may be removed before or after functionalization, more typically before functionalization. If removed after functionalization, it is important the core removal does not damage the functionalized surface. For example, with a-methyl styrene core removal is at low temperatures so no harm is done to the functionalized surface if core removal is achieved after functionalization. Also acid- or base-labile core materials that can be removed by hydrolysis can be removed before or after functionalization.
  • the core/shell silica particle comprising a template core particle and a silica treatment, typically a coating, is prepared by a process comprising: (a) providing a template core particle, more typically prepared using emulsion polymerization;
  • a water-based silica precursor such as sodium silicate, potassium silicate, ammonium silicate or pre-formed silicic acid, more typically sodium silicate or potassium silicate;
  • the template particle or core is prepared using typically an organic monomer which is polymerized to generate template particles, or dispersed in water to generate template particles of the appropriate size.
  • Some monomes for the template include styrene, methyl methacrylate, polyacrylic acid, a-methylstyrene, lactic acid, formaldehyde, or copolymers like Surlyn® (copolymer of ethylene and methacrylic acid) more typically styrene, methyl methacrylate, ⁇ -methylstyrene, Surlyn®, and still more typically methyl methacrylate, styrene, or polyacrylic acid.
  • Surlyn® copolymer of ethylene and methacrylic acid
  • a group of two monomers can be chosen for a copolymerization, such as a variety of diacids and dialcohols for polyester polymers (like polyethylene terephthalate, PET), diacids and diamides for various polyamides (like Nylon 6,6, or other Nylons), etc.
  • the particle size of the template is tunable, and the particle size distribution of the template particles achieved is narrow, which is advantageous.
  • preparation of the template particle or core by emulsion polymerization is achieved by emulsification of the water-insoluble monomer or a mixture of in water, and polymerized using radical polymerization conditions.
  • Radical initiators such as potassium- or ammonium persulfate, and 2,2-azobis(2- methylpropionamidine) hydrochloride (AIBA) can be used.
  • Surfactant can also typically be used.
  • suitable surfactants include sodium dodecylsulfate (SDS), cetyltrimethylammonium bromide (CTAB), poly-(vinylpyrrolidinone) PVP, etc.
  • silyl group-containing monomers such as 3-(trimethoxysilyl)propylmethacrylate can be used, in order to facilitate the silica deposition in the subsequent step.
  • the reaction temperature is kept between about 25 and about 100°C, more typically about 45 to about 90°C, still more typically about 55°C to about 75°C.
  • the template particle or core may be inorganic, for example calcium carbonate, or other inorganic particles onto which silica can be deposited.
  • the template particle or core is then coated with a shell material to generate a core/shell particle.
  • a water-based silica precursor is used to generate a silica treatment or shell.
  • water-based silica precursors include sodium silicate, potassium silicate, ammonium silicate or pre-formed silicic acid, more typically sodium silicate or potassium silicate.
  • organic siloxanes the reaction is typically done in a dilute ethanol/water ammonia solution, with or without sonication.
  • the suspension of template particles in a dilute ethanol/water ammonia solution is treated with a water-based silica precursor, such as sodium- or potassium silicate, the template particles are suspended in water, and the silicate agent is added either drop-wise, over a period of time, or all at once.
  • the pH is maintained at about 2 to about 10, more typically about 5 to about 9 to form a silica layer on the recyclable template particle and the reaction times are held between about 1 to about 24 hours, more typically about 1 .5 to about 18 hours, still more typically about 2 to about 12 hours. This results in the deposition of a silica treatment or shell on the recyclable template particle or core.
  • the core/shell particles are separated or removed from the aqueous solution by centrifugation or filtration, more typically by
  • silica shells typically, surface area and porosity of the silica walls have to be tuned. Whether the silica shell is adequate can be determined by comparing the surface area of the particles with calculated surface area of a smooth sphere of the same diameter. Typically, we consider the shell impervious if its surface doesn't surpass about 130% of the calculated surface area of a smooth sphere of the same dimensions, i.e., it is about 30% or less higher than the surface of the core/shell silica particle prior to functionalization, more typically about 125% of the smooth sphere surface area, and still more typically about 120% of the smooth sphere surface area of the same dimensions.
  • silica precursor Addition of various amounts of the silica precursor will lead to more or less porous silica layers, which can lead to control of the porosity and surface area of the particles. Further, the silica precursor may be added in stages to modulate the porosity of the particles as well as their surface. Lastly, calcination at temperatures higher than about 500°C can decrease the porosity and surface area of the particles without increasing the thickness of the wall.
  • the core may then be removed before or after grafting of a variety of alkoxysilanes onto the surface of the silica particles to form hollow silica particles having a functionalized surface.
  • removal of the template may be achieved through calcination, namely heating the material to about 300 to about 800 °C, more typically about 400 C to about 600 °C, and most typically about 450 to about 550 °C.
  • CaCO3/silica core/shell particles hollow particles are typically obtained through reaction with acid. If the core is made of recyclable material, it may be recycled either through thermal depolymerization, or acid- or base hydrolysis.
  • core materials made out of poly-(a- methylstyrene), PMMA, various polyamides, as well as styrene are depolymerized at increased temperatures, with the temperatures of depolymerization varying with the polymer used.
  • temperature ranges include about 250 to about 450°C, more typically about 275 to about 400°C, still more typically from about 290 to about 325°C, to generate hollow particles as well as core monomer.
  • poly(methylmethacrylate)@silica core/shell particles can be heated above around about 300°C to generate methyl methacrylate monomer and hollow silica particles.
  • poly(a- methylstyrene)@silica can be heated to about above 60°C to generate hollow silica particles and a-methylstyrene monomer.
  • acid- or base-labile core materials can be hydrolyzed instead of thermally depolymerized to generate hollow particles with possibility of monomer recycling.
  • Polymers such as Delrin® (polyacetal), poly(lactic acid), as well as other polyesters can be depolymerized through acid hydrolysis.
  • treating polyacetal@silica with acid should generate hollow silica as well as aldehyde monomer that can be recycled in template particle synthesis.
  • polyesters or polyamides from core/shell particles can be recycled in the same fashion to generate diacid/dialcohol (diacid/diamine) monomer couples as well as hydroxylic or amino acids as monomers (like in the case of polylactic acid, for example).
  • the core is calcium carbonate, it is removed by acid treatment, which generates hollow particles.
  • the functionalized surface on the silica particle may be prepared using sulfonic acid, phosphonic esters, carboxylic acids, amines, epoxides, boronic acids, quaternary amines, etc. Grafting of a variety of alkoxysilanes onto the surface of the hollow silica particles provides functionalized hollow silica particles.
  • a large spectrum of functionalities can be introduced onto the silica surface, for example silyl phosphonates, phosphonic acids, amines, alcohols, epoxides, carboxylic acids, thiols, thioethers, carbamates, isocyanates, quarternary ammonium ions, etc.
  • the grafting process includes mixing the grafting agent with silica particles, with or without the solvent, with optional heating of the material, in the temperature range about 25 to about 150°C, more typically about 60 to about 130°C, still more typically about 80 to about 120°C, with or without the application of vacuum, in order to remove the volatile byproducts, like water or alcohols.
  • the hollow silica particles may be functionalized with
  • the silica particles may be functionalized with diethyl [2- (triethoxysilyl)ethyl]phosphonate to generate phosphonate-functionalized silica particles. Then, in another embodiment, phosphonate ester functionality on the surface of the silica particles may be hydrolyzed to generate phosphonic acid-functionalized hollow silica particles. In another embodiment of the disclosure, silica particles may be treated with (3- glycidopropyl)trimethoxysilane, to generate epoxy functionality on the silica surface.
  • the epoxy silica may be then treated, in one embodiment of the disclosure, with glycine, to introduce carboxylic acid functionality through an amine linkage on the particle.
  • the epoxy silica may be treated with thioglycolic acid to introduce the carboxylic functionality through a thioether group.
  • inorganic hollow particle dispersions are useful as hiding or opacifying agents in coating and molding compositions. They are also useful as photonic band gap or thermal insulation materials.
  • Example 1 Polystyrene template particle synthesis To a 2L four-neck round bottom flask, equipped with a mechanical stirrer, thermometer, a reflux condenser, and a nitrogen inlet, was added styrene (18mL, 157.1 mmol), and 600mL of degassed water. Polyvinylpyrrolidinone, PVP (100mg) solution in 100mL of degassed water was then added. The resulting mixture was stirred at room temperature for 15min. The mixture was degassed by bubbling nitrogen for 20min.
  • Example 2 Preparation of PMMA recyclable template particle
  • methyl methacrylate 9g, 94.89mmol
  • 2- (methacryloxy)ethyltrimethylammonium chloride (0.125g of 80% aqueous solution, mmol
  • ethylene glycol dimethacrylate 0.4g, mmol
  • AIBA 0.1 g, mmol
  • Trimethoxysilyl propyl methacrylate 0.5 g 2.01 mmol
  • the mixture was degassed by purging N2 for 10min, and then heated to 70°C under nitrogen overnight, to generate a white slurry of PMMA particles.
  • Particle size analysis of the resulting suspension revealed particles with average particle size of 280nm.
  • Example 3 Preparation of PMMA silica core/shell particle, and its conversion to a hollow silica particle
  • Example 5 Preparation of a PMMA silica core/shell particle, and its conversion to a hollow particle
  • the material obtained in Example 4 (150ml_ of the suspension) was taken and concentrated in vacuo to remove acetone, until the weight of the mixture reached 100g.
  • the material was then transferred to a 1 L three neck round bottom flask, equipped with an overhead stirrer and pH probe inlet.
  • the pH of the mixture was adjusted to 9.5, and the mixture heated to 80°C.
  • sodium silicate (7.08 mL of 26.2% solution in water, diluted further to 20mL total volume)
  • HCI (2.01 mL, diluted to 20mL with water) were added to the flask over 5h.
  • Example 6 Preparation of PS/silica core/shell particle, and its conversion to a hollow silica particle
  • To a three-necked 250ml_ round bottom flask, equipped with an addition funnel and a reflux condenser is added 25ml_ of polystyrene slurry from Example 1 , following with sodium silicate solution (26.5 wt%, 4.72g).
  • the resulting mixture is heated to 80°C for three or more hours, and the solids are isolated by centrifugation.
  • the core/shell particles are placed inside a tube furnace and heated to 500°C to generate hollow silica particles.
  • Solid hollow particles (10g) are dispersed in 300ml_ dimethyl formamide (DMF). To this suspension is added a diethyl-(2- (triethoxysilyl)ethyl)phosphonate (10ml_, 31 .Ommol ), and the mixture heated to 120°C overnight. The resulting material is centrifuged to remove the DMF solvent, and washed with ethanol. The presence of grafting groups can be measured by TGA and ESCA.
  • DMF dimethyl formamide
  • Example 8 Phosphonic acid-functionalized particles To a 1 L round bottom flask, equipped with an addition funnel and a reflux condenser are added 25.6g of phosphonate ester-functionalized particles (Example 5) and 400ml_ dichloromethane, and the mixture is kept under nitrogen. To the mixture is added trimethylsilyl bromide (75ml_), dropwise, via an addition funnel. Upon addition, the mixture is heated to reflux for 18h. The mixture is then cooled to room temperature and the volatiles removed in vacuo. To the residue is then added 150ml_ of methanol, and 50ml_ of dichloromethane, and the mixture left stirring at room temperature overnight.
  • Example 10 Epoxide-functionalized hollow silica particles, followed by reaction with thioglycolic acid
  • Solid hollow particles (1g) are dispersed in dilute ammonia solution (7wt%, 20ml_), with sonication.
  • the resulting suspension is added to 30ml_ DMF, and the water was removed in vacuo.
  • To this suspension is added (diethoxyphosphoryl)methyl-2-((triethoxysilyl)ethyl)carbamate (1 g, 2.49mmol), and the mixture is then heated to 120 °C overnight.
  • the resulting material is centrifuged to remove the DMF solvent, and washed with ethanol.
  • the presence of grafting groups can be measured by TGA and ESCA.

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  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
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  • Silicon Compounds (AREA)

Abstract

La présente invention concerne une particule creuse de silice fonctionnalisée comprenant : une particule de silice cœur/écorce comprenant une particule noyau matrice et un traitement à la silice, la particule de silice cœur/écorce ayant une surface extérieure; et le traitement à la silice étant préparé à l'aide d'un précurseur de silice à base d'eau; une surface fonctionnalisée sur la particule de silice cœur/écorce, la surface fonctionnalisée étant préparée à l'aide d'acide sulfonique, d'esters phosphoniques, d'acide carboxylique, d'amines, d'époxydes ou d'acides boroniques, et la particule noyau matrice étant retirée avant ou après la fonctionnalisation. Ces particules creuses minérales sont utiles en tant qu'agents de masquage ou agents opacifiants dans des compositions de revêtement et de moulage. Elles sont également utiles en tant que bande interdite photonique ou matériaux d'isolation thermique.
PCT/US2015/017909 2014-03-11 2015-02-27 Particules creuses de silice fonctionnalisées ayant une faible porosité à l'aide de précurseurs de silice à base d'eau WO2015138160A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201461950895P 2014-03-11 2014-03-11
US61/950,895 2014-03-11

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106219543A (zh) * 2016-07-12 2016-12-14 常州英中纳米科技有限公司 一种亚毫米级聚苯乙烯基球状活性炭及其制备方法与应用
WO2017085544A1 (fr) * 2015-11-20 2017-05-26 King Abdullah University Of Science And Technology Particules de silice creuses fonctionnalisées en surface et composites
CN107019802A (zh) * 2017-03-22 2017-08-08 南京邮电大学 一种柔性中空介孔有机氧化硅纳米囊材料及制备方法
WO2022209952A1 (fr) * 2021-03-31 2022-10-06 キヤノン株式会社 Particules et leur procédé de production

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080241474A1 (en) * 2005-06-02 2008-10-02 Asahi Glass Company Limited Process for producing dispersion of hollow fine sio2 particles, coating composition and substrate with antireflection coating film
WO2009088250A2 (fr) * 2008-01-10 2009-07-16 Industry-Academic Cooperation Foundation, Yonsei University Nanoparticules creuses de silice poreuse, procédé de confection des nanoparticules de silice, et vecteurs de médicaments et compositions pharmaceutiques comprenant ces nanoparticules de silice
US20120045515A1 (en) * 2009-02-04 2012-02-23 Ye Liu Hollow silica particle with a polymer thereon

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080241474A1 (en) * 2005-06-02 2008-10-02 Asahi Glass Company Limited Process for producing dispersion of hollow fine sio2 particles, coating composition and substrate with antireflection coating film
WO2009088250A2 (fr) * 2008-01-10 2009-07-16 Industry-Academic Cooperation Foundation, Yonsei University Nanoparticules creuses de silice poreuse, procédé de confection des nanoparticules de silice, et vecteurs de médicaments et compositions pharmaceutiques comprenant ces nanoparticules de silice
US20120045515A1 (en) * 2009-02-04 2012-02-23 Ye Liu Hollow silica particle with a polymer thereon

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017085544A1 (fr) * 2015-11-20 2017-05-26 King Abdullah University Of Science And Technology Particules de silice creuses fonctionnalisées en surface et composites
CN106219543A (zh) * 2016-07-12 2016-12-14 常州英中纳米科技有限公司 一种亚毫米级聚苯乙烯基球状活性炭及其制备方法与应用
CN107019802A (zh) * 2017-03-22 2017-08-08 南京邮电大学 一种柔性中空介孔有机氧化硅纳米囊材料及制备方法
WO2022209952A1 (fr) * 2021-03-31 2022-10-06 キヤノン株式会社 Particules et leur procédé de production

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