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WO2015138164A1 - Procédé de préparation de nanosphères polymères et hybrides polymère/silice creuses à surface fonctionnalisée - Google Patents

Procédé de préparation de nanosphères polymères et hybrides polymère/silice creuses à surface fonctionnalisée Download PDF

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Publication number
WO2015138164A1
WO2015138164A1 PCT/US2015/017916 US2015017916W WO2015138164A1 WO 2015138164 A1 WO2015138164 A1 WO 2015138164A1 US 2015017916 W US2015017916 W US 2015017916W WO 2015138164 A1 WO2015138164 A1 WO 2015138164A1
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WO
WIPO (PCT)
Prior art keywords
polymeric
acrylic
styrenic monomer
mixture
methacrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2015/017916
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English (en)
Inventor
Hau-Nan LEE
Stephanie A. BERNARD
Jelena LASIO
Andrew Jay Duncan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of WO2015138164A1 publication Critical patent/WO2015138164A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0279—Porous; Hollow
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • A61K8/8117—Homopolymers or copolymers of aromatic olefines, e.g. polystyrene; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/614—By macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present disclosure relates to a process for making surface functionalized polymeric or polymeric/silica hybrid hollow nanospheres, more particularly to a preparation process for making surface
  • Nanospheres 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.
  • core- shell systems may be prepared from micro or miniemulsions via polymerization reaction at the interface of the droplets, the so-called interfacial polymerization reaction. Interfacial polymerization occurs at the interface of two immiscible phases, for example, oil and water, and a thin shell is formed. In the formation of the shell, the monomers are in either oil or water phase to participate in the reaction.
  • a microemulsion or miniemulsion is first prepared, either water in oil or oil in water, wherein in the former nanocapsules with an aqueous core suspended in oil are formed and in the latter nanocapsules with an oily core suspended in water are formed.
  • Existing processes for the preparation of surface functionalized polymeric or polymeric/silica hybrid hollow particles either require a multi-step polymerization or grafting process, or use a sacrificial polymer or inorganic hard template.
  • the disclosure provides a process for the synthesis of surface functionalized polymeric or polymeric/silica hybrid hollow nanospheres.
  • the surface properties of the particles are tuned through copolymerization with a variety of functionalized acrylic or styrenic monomer.
  • the disclosure provides a process for preparing a surface functionalized polymeric and polymeric/silica hybrid hollow nanospheres comprising:
  • non- reactive solvent we mean that the solvent does not substantially react, more typically does not react, with any of the other components added to the reaction.
  • Figure 1 is the structure of the resulting particles from Example 1 that was analyzed using transmission electron microscopy.
  • Figure 2 is the structure of the resulting particles from Example 2 that was analyzed using transmission electron microscopy.
  • Figure 3 is the structure of the resulting particles from Example 3 that was analyzed using transmission electron microscopy.
  • Figure 4 is the structure of the resulting particles from Example 4 that was analyzed using transmission electron microscopy.
  • the disclosure relates to a process for preparing a surface
  • polymeric or polymeric/silica hybrid hollow nanospheres are useful as hiding or opacifying agents in coating and molding compositions. They are also useful as drug delivery systems in the pharmaceutical and medical industries; in food, personal care and cosmetics; and agriculture.
  • the disclosure describes the process for surface functionalized polymeric and polymeric/silica hybrid hollow nanospheres with tunable functional group on the hollow particles' surface.
  • the surface properties of the particles are tuned through copolymerization with a variety of functionalized acrylic or styrenic monomer.
  • These nanospheres have a particle size of about 5 nm to about 400 nm, more typically about 50 nm to about 300 nm, and still more typically about 50 nm to about 250 nm.
  • the solids concentration of these nanospheres dispersion is at least about 5% solids, more typically about 5 wt% to about 30 wt%, still more typically about 5 wt% to about 20 wt%.
  • the surface functionalized polymeric and polymeric/silica hybrid hollow nanospheres are prepared by a process comprising:
  • the non-reactive solvent may be an alkane, a hydrocarbon oil, aromatic hydrocarbon or halogenated hydrocarbon liquid, more typically alkane or hydrocarbon oil.
  • the at least one acrylic or styrenic monomer may be methyl methacrylate, methyl acrylate, n-butyl methacrylate, t-butyl methacrylate, t- butyl acrylate, ethyl glycol dimechacrylate, styrene or divinylbenzene; more typically methyl methacrylate or styrene.
  • the monomer is present in the amount of about 5 wt % to about 30 wt %, more typically about 5 wt% to about 20 wt%, based on the total weight of all components.
  • the at least one functionalized acrylic or styrenic monomer may be a monomer having one of the following formulas:
  • R H or Chb
  • X and Y are the functional groups that can be introduced onto the hollow particle surface.
  • a large spectrum of functionalities can be used, for example boronic acid, sulfonic acid, silyl phosphonates, phosphonic acids, amines, alcohols, epoxides, carboxylic acids, thiols, thioethers, carbamates, isocyanates, quarternary ammonium ions.
  • Suitable functionalized acrylic or styrenic monomers are glycidyl methacrylate, phosphoric acid 2-hydroxyethyl methacrylate ester, 4-vinylbenzenephosphonic acid, 4-vinylbenzeneboronic acid, 4- vinylbenzene sulfonic acid and salts or esters.
  • the functional groups can be located in the either inner or outer surface of the hollow spheres.
  • the functionalized acrylic or styrenic monomer is present in the amount of about 0.1 wt % to about 20 wt %, more typically about 1 wt% to about 12 wt%, still more typically about 2 wt% to about 8 wt% based on the total weight of all monomers.
  • Some suitable initiators include azo compounds such as 2,2'- azobisisobutyronitrile (AIBN) or 2,2'-azobis(2-methylpropionamide) dihydrochloride (AIBA); metal persulfate such as potassium persulfate (KPS) or sodium persulfate; more typically AIBN or KPS.
  • AIBN 2,2'- azobisisobutyronitrile
  • AIBA 2,2'-azobis(2-methylpropionamide) dihydrochloride
  • metal persulfate such as potassium persulfate (KPS) or sodium persulfate
  • the initiator is present in the amount of about 0.05 wt % to about 0.5 wt %, more typically about 0.1 wt% to about 0.3 wt%, based on the total weight of all components.
  • Suitable surfactants include cetyltrimethylammonium bromide (CTAB), lauryltrimethylammonium bromide, dodecyltrimethylammonium bromide, octyltrimethylammonium bromide, sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate (SDBS), dioctylsulfosuccinate , nonionic surfactants such as alkylphenol polyoxyethylene,
  • polyoxyethylene glycol alkyl ethers polyoxypropylene glycol alkyl ethers, octylphenol ethoxylates, or poloxamers, more typically SDS, SDBS or CTAB.
  • surfactants series include Triton X® manufactured by The Dow Chemical Company, Brij®
  • the surfactant concentration is about 0.001 wt % to about 5 wt %, more typically about 0.1 wt% to about 2 wt%, based on the total weight of all components.
  • a polymerizable silane may be needed if the
  • polymeric/silica hybrid hollow particles are desired.
  • suitable polymerizable silanes are allyltriethoxysilane, allyltrimethoxysilane, diethoxy(methyl)vinylsilane, dimethoxymethylvinylsilane,
  • triethoxyvinylsilane trimethoxy(7-octen-1 -yl)silane, 3-(trimethoxysilyl)- propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate, or
  • the monomers to non-reactive solvent ratio is about 0.1 to about 6, more typically about 0.5 to about 3, still more typically about 0.5 to about 2; oil to water or water to oil ratio is about 0.01 to 0.55, more typically 0.05 to 0.25; and surfactant concentration is about 0.001 wt % to about 5 wt %, more typically 0.1 wt% to about 2 wt%, based on the total weight of all components.
  • the water phase comprises water and surfactant and the oil phase comprises at least one non-reactive solvent, at least one acrylic or styrenic monomer; at least one functional ized acrylic or styrenic monomer and the optional polymerizable silane.
  • the initiator may be considered to be in either the water phase or oil phase. It is important because the combination of monomers to non- reactive solvent ratio, oil to water ratio and surfactant level determine the particle size, hollow or non-hollow particle structure, and the shell thickness.
  • the mixture in step (a) may be prepared in any glass container or stainless steel reaction vessel .
  • the mixture of the above components is then sheared at an energy density of at least 10 ⁇ 6 J/m A 3, more typically about 10 ⁇ 7 J/m A 3 to about 5*10 ⁇ 8 J/m A 3, to form a mini-emulsion.
  • Some useful means for shearing include an ultrasonic disruptor, high speed blender, high pressure homogenizer, high shear disperser, membrane homogenizer or colloid mill, more typically an ultrasonic disruptor, high speed blender, or a high pressure homogenizer.
  • shearing occurs for a period of about 5 to about 120 minutes depending on amount of emulsion needed to be prepared and desired emulsion size range, more typically about 30 minutes to about 60 minutes.
  • shearing is accomplished at room temperature.
  • a defoamer may be needed to avoid foaming during emulsifying.
  • Some suitable defoamers include BASF Foamaster®, Dow Corning® 71 and 74 Antifoams.
  • the mini-emulsion formed in step (b) is then heated to at least about 50°C, more typically about 50°C to about 90°C; and still more typically about 60°C to about 80°C to form, in one step, a surface functionalized polymeric or polymeric/silica hybrid hollow nanosphere. Heating may be accomplished using hot plate, heating mantle or any other heating method.
  • the surface functional ized polymeric or polymeric/silica hybrid hollow nanospheres are useful as hiding or opacifying agents in coating and molding compositions. They are also useful as drug delivery systems in the pharmaceutical and medical industries; in food, personal care and cosmetics; and agriculture. EXAMPLES
  • dimethacrylate, 3.6 g of styrene, 1 .8 g of 4-vinylbenzene boronic acid and 0.798 g of AIBN was first prepared, and added to a water solution which contains 420.0 g of water, 0.9 g of CTAB and 0.5 g of defoamer
  • Example 2 An oily mixture which contained 5.0 g of hexadecane, 36.8 g of octane, 28.8 g of methyl methacrylate, 3.6 g of ethylene glycol
  • dimethacrylate, 3.6 g of styrene, 0.9 g of 4-vinylbenzene boronic acid and 0.798 g of AIBN was first prepared, and added to a water solution which contains 420.0 g of water, 0.9 g of CTAB and 0.5 g of defoamer
  • Example 4 An oily mixture which contained 6.0 g of hexadecane, 5.4 g of methyl methacrylate, 0.6 g of ethylene glycol dimethacrylate, 0.6 g of phosphoric acid 2-hydroxyethyl methacrylate ester and 0.133 g of AIBN was first prepared, and added to a water solution which contains 60.0 g of water and 0.05 g of sodium dodecylbenzene sulfonate. Miniemulsification was achieved by ultrasonicating the mixture for 60 s with a Branson sonifier W150 at 100% amplitude and then stopping for 30 s; and repeating this cycle 10 times.
  • the mixture was cooled in an ice-bath during homogenization. After forming a stable miniennulsion, the polymerization was started by heating to 70 °C for at least 16 hours.
  • the structure of the resulting particles was analyzed using transmission electron microscopy and shown in Figure 4.
  • the average particle size of the resulting hollow particles determined by dynamic light scattering is 229 nm with a polydispersity of 0.162.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Organic Chemistry (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Silicon Compounds (AREA)
  • Cosmetics (AREA)

Abstract

Cette divulgation concerne un procédé de préparation de nanosphères polymères ou hybrides polymère/silice creuses à surface fonctionnalisée comprenant : la préparation d'un mélange comprenant de l'eau, au moins un solvant non réactif, au moins un monomère acrylique ou styrénique ; au moins un monomère acrylique ou styrénique fonctionnalisé ; un amorceur ; au moins un tensioactif ; et, éventuellement, un silane polymérisable si des particules hybrides polymère/silice creuses sont souhaitées ; et le cisaillement des composants du mélange à un cisaillement élevé ayant une densité d'énergie d'au moins 10^6 J/m^3 pour former une mini-émulsion ; et le chauffage à au moins environ 50 °C, plus typiquement entre environ 50 °C et environ 90 °C ; et encore plus typiquement entre environ 60 °C et environ 80 °C pour former, en une seule étape, une nanosphère polymère ou hybride polymère/silice creuse à surface fonctionnalisée.
PCT/US2015/017916 2014-03-11 2015-02-27 Procédé de préparation de nanosphères polymères et hybrides polymère/silice creuses à surface fonctionnalisée Ceased WO2015138164A1 (fr)

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US61/950,908 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
WO2017112516A1 (fr) * 2015-12-22 2017-06-29 Rohm And Haas Company Gouttelettes réparties dans un milieu aqueux
WO2017112515A1 (fr) * 2015-12-22 2017-06-29 Rohm And Haas Company Procédé de polymérisation en suspension de gouttelettes distribuées dans un milieu aqueux
CN108368207A (zh) * 2015-12-22 2018-08-03 罗门哈斯公司 分布于水性介质中的液滴
CN118667097A (zh) * 2024-07-01 2024-09-20 华南理工大学 一种聚甲基丙烯酸甲酯-二氧化硅复合中空微球及其制备方法和应用

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DE19852784A1 (de) * 1998-11-16 2000-05-18 Max Planck Gesellschaft Osmotische Stabilisierung von Mini- und Mikroemulsionen und deren Anwendung zur Herstellung von Nanohybridpartikeln
WO2002024756A2 (fr) * 2000-09-21 2002-03-28 Rohm And Haas Company Nanocomposites polymeres d'argile modifie de maniere hydrophobe
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CN101537333A (zh) * 2009-04-02 2009-09-23 浙江大学 可重分散亚微米聚合物中空胶囊及其制备方法
US20130209678A1 (en) * 2010-10-29 2013-08-15 Zhejiang University Method for preparing a porous anti-reflection thin film composed of hollow polymeric nanoparticles
CN103865010A (zh) * 2014-03-12 2014-06-18 合肥工业大学 聚硫密封剂用功能型无机/聚合物中空微球的制备方法

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DE19852784A1 (de) * 1998-11-16 2000-05-18 Max Planck Gesellschaft Osmotische Stabilisierung von Mini- und Mikroemulsionen und deren Anwendung zur Herstellung von Nanohybridpartikeln
WO2002024756A2 (fr) * 2000-09-21 2002-03-28 Rohm And Haas Company Nanocomposites polymeres d'argile modifie de maniere hydrophobe
EP1739116A1 (fr) * 2004-04-05 2007-01-03 Sekisui Chemical Co., Ltd. Particules fines creuses de résine, particules fines hybrides organiques/inorganiques et procédé pour la fabrication d"articiles en résine fine creuse
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US20130209678A1 (en) * 2010-10-29 2013-08-15 Zhejiang University Method for preparing a porous anti-reflection thin film composed of hollow polymeric nanoparticles
CN103865010A (zh) * 2014-03-12 2014-06-18 合肥工业大学 聚硫密封剂用功能型无机/聚合物中空微球的制备方法

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017112516A1 (fr) * 2015-12-22 2017-06-29 Rohm And Haas Company Gouttelettes réparties dans un milieu aqueux
WO2017112515A1 (fr) * 2015-12-22 2017-06-29 Rohm And Haas Company Procédé de polymérisation en suspension de gouttelettes distribuées dans un milieu aqueux
CN108368207A (zh) * 2015-12-22 2018-08-03 罗门哈斯公司 分布于水性介质中的液滴
CN108367255A (zh) * 2015-12-22 2018-08-03 罗门哈斯公司 分布在水介质中的液滴
CN108367254A (zh) * 2015-12-22 2018-08-03 罗门哈斯公司 悬浮聚合分布在水性介质中的液滴的方法
US10640580B2 (en) 2015-12-22 2020-05-05 Ddp Specialty Electronic Materials Us 8, Llc Method of suspension polymerization of droplets distributed in an aqueous medium
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RU2731490C2 (ru) * 2015-12-22 2020-09-03 Ром Энд Хаас Компани Способ суспензионной полимеризации капель, распределенных в водной среде
CN108367255B (zh) * 2015-12-22 2021-03-23 罗门哈斯公司 分布在水介质中的液滴
CN108368207B (zh) * 2015-12-22 2021-05-04 罗门哈斯公司 分布于水性介质中的液滴
CN108367254B (zh) * 2015-12-22 2021-08-24 罗门哈斯公司 悬浮聚合分布在水性介质中的液滴的方法
CN118667097A (zh) * 2024-07-01 2024-09-20 华南理工大学 一种聚甲基丙烯酸甲酯-二氧化硅复合中空微球及其制备方法和应用

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