CN114736322A - Magnetic snowman-shaped asymmetric Janus particle and preparation method thereof - Google Patents
Magnetic snowman-shaped asymmetric Janus particle and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
Abstract
The invention relates to a magnetic snowman-shaped asymmetric Janus particle and a preparation method thereof.
Description
Technical Field
The invention relates to a magnetic snowman-shaped asymmetric Janus particle and a preparation method thereof.
Background
The Janus particle is composed of two asymmetric parts, the Janus particle is different in composition structure and composition components, and the specific material compounds multiple materials together, so that the functional composition is realized, and the Janus particle is applied to multiple fields. For amphiphilic Janus particles, the amphiphilic Janus particles have the amphiphilicity of a small molecular surfactant and the Pickering effect of a solid particle emulsifier, and can well emulsify immiscible oil and water phases to form stable emulsion (Walther A,
AHE.Chem.Rev.2013,113,5194-5261；Liang FX,Liu B,Cao Z,Yang ZZ.Langmuir,2018,34,4123-4131)。
the preparation methods of the Janus particles are various, and comprise a two-dimensional interface protection method, a three-dimensional interface protection method, a sputtering spraying method and the like, all of which can prepare Janus materials with definite and partitioned structures, but the methods have no universality, more importantly, the yield of samples is very limited, and the development of the Janus particles is greatly limited. Emulsion polymerization phase separation techniques provide the possibility of bulk preparation of Janus particles. The emulsion polymerization can realize large-scale material preparation, and provides a foundation for the industrial application of Janus materials.
Disclosure of Invention
Problems to be solved by the invention
In view of the above problems in the prior art, the present invention provides a magnetic snowman-shaped asymmetric Janus particle with a definite structure, in which two parts of different compositions are precisely partitioned, and the composition is adjustable, so as to have different Janus balance. Another technical problem to be solved by the invention is to provide the preparation method of the magnetic snowman-shaped asymmetric Janus particles, which is simple in process, easy in raw material obtaining, easy in industrial production and capable of realizing ton-level batch production.
Means for solving the problems
The preparation method of the invention successfully prepares the snowman-shaped Janus particles by using the polymer hollow spheres as templates and utilizing a seeded emulsion polymerization induced phase separation technology, and obtains the magnetic snowman-shaped asymmetric Janus particles through a subsequent magnetization process.
Specifically, the present invention solves the technical problems to be solved by the present invention by the following technical solutions.
[1] A magnetic snowman-shaped asymmetric Janus particle is characterized by comprising a hydrophilic part and a hydrophilic oil part which respectively form two spheres of the snowman-shaped particle, wherein the hydrophilic part comprises polymer composite microspheres subjected to hydrophilic modification and magnetic nanoparticles attached to the surfaces of the polymer composite microspheres, and the lipophilic part comprises silicon dioxide subjected to hydrophobic modification.
[2] The Janus particle as recited in [1], wherein the Janus particle has a size of 450-1000 nm.
[3] The Janus particle of [1], wherein the particle size ratio of the hydrophilic portion to the lipophilic portion is from 10/1 to 10/10; wherein the particle size of the hydrophilic part is 440-500 nm.
[4] The Janus particle as claimed in [1], wherein the polymer composite microsphere is a composite microsphere of polystyrene and other polymer, wherein the other polymer is formed by polymerizing a raw material composition comprising one or more monomers selected from olefins, esters with double bonds and amides with double bonds, and optionally a crosslinking agent; the olefinic monomer is preferably one or more selected from optionally halogenated alkenes, styrene and its derivatives, and acrylonitrile; the double-bond ester monomer is preferably one or more selected from vinyl acetate, alkyl (meth) acrylate and derivatives thereof; the double-bond amide-based monomer is preferably a monomer having a (meth) acrylamide group.
[5] The Janus particle of [1], wherein the polymer composite microsphere is hollow.
[6] The Janus particle of [1], wherein the surface of the polymer composite microsphere is entirely covered with the magnetic nanoparticle.
[7] The Janus particle as recited in [1], wherein the magnetic nanoparticles have a particle size of 10-30nm, and the magnetic nanoparticles are preferably ferroferric oxide nanoparticles.
[8] The Janus particle of [1], wherein a hydrophobic group and/or a segment is attached to the surface of silica in the lipophilic portion.
[9] A method for producing magnetic snowman-shaped asymmetric Janus particles according to any one of [1] to [8], comprising the steps of:
preparing a seed emulsion: adding an oil/water emulsion containing a monomer, a cross-linking agent and an initiator into a dispersion liquid of a Polystyrene (PS) hollow sphere template, and heating and polymerizing to obtain a polymer composite seed emulsion;
preparation of snowman-like Janus granules: adding an emulsion containing a silane coupling agent monomer containing double bonds, an initiator and a surfactant into the polymer composite seed emulsion for swelling, and then heating for polymerization to induce phase separation to prepare snowman-shaped Janus particles;
hydrophobic modification: hydrophobically modifying a silica portion of the snowman-like Janus particles;
hydrophilic modification: carrying out hydrophilic modification on the snowman-shaped Janus particles subjected to hydrophobic modification to obtain amphiphilic snowman-shaped Janus particles;
magnetization: and attaching magnetic nanoparticles to the surfaces of the amphiphilic snowman-shaped Janus particles to obtain the magnetic snowman-shaped asymmetric Janus particles.
[10] The method according to [9], wherein in the step of preparing the seed emulsion, the content of the monomer in the oil/water emulsion is 5% -20%; the content of the cross-linking agent is 3-10%; the molar ratio of the cross-linking agent to the monomer is 10/1-1/10, the mass concentration of the initiator is 0.2-10.0 per mill, and the mass concentration of the surfactant is 1.2-20 per mill; the mass ratio of the total amount of the monomers and the cross-linking agent to the polystyrene hollow sphere template is 5/1-5/5.
[11] The method according to [9], wherein the double bond-containing silane coupling agent monomer is one or more selected from the group consisting of 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (methacryloyloxy) propyltrichlorosilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, 3-alkenylbutyltrimethoxysilane, 3-alkenylbutyltriethoxysilane, 3-alkenylbutyltrichlorosilane, and any combination thereof.
[12] The production method according to [9], characterized in that the hydrophobic modification is performed by reacting a silicon hydroxyl group of a silica surface with a silane coupling agent; the silane coupling agent is preferably one or more selected from the group consisting of ethyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, hexadecyltrimethoxysilane, n-octadecyltriethoxysilane, dicyclopentyldimethoxysilane, trimethoxy (2-phenylethyl) silane, phenyltrimethoxysilane, dimethoxydiphenylsilane, allyltrimethoxysilane, 7-octenyltrichlorosilane, vinyltriisopropenoxysilane, dimethyloctadecylchlorosilane, and 1H,1H,2H, 2H-perfluorodecaalkyltrichlorosilane.
[13]According to [9]]The preparation method is characterized in that the hydrophilic modification is carried out by carrying out solvent treatment on the hydrophobically modified snowman-shaped Janus particles, and the solvent is water, concentrated sulfuric acid, dilute sulfuric acid, SO3The aqueous solution of (3), the aqueous solution of chlorosulfonic acid, NaOH or the aqueous solution of KOH, is preferably concentrated sulfuric acid.
[14] The preparation method according to the item [9], characterized in that in the magnetization step, the amphiphilic snowman-shaped Janus particles are dispersed into an aqueous solution in which ferrous ions and ferric ions are dissolved, and ammonia water is added after adsorption to form ferroferric oxide nanoparticles attached to one side of the polymer composite microspheres of the amphiphilic snowman-shaped Janus particles, so that the magnetic snowman-shaped asymmetric Janus particles are obtained.
[15] The production method according to [14], characterized in that the aqueous solution is produced by dissolving a divalent iron salt and a trivalent iron salt in water, the divalent iron salt being preferably ferrous sulfate, ferrous nitrate and/or ferrous chloride, and the trivalent iron salt being preferably ferric sulfate, ferric chloride and/or ferric nitrate; the molar ratio of the ferrous ions to the ferric ions in the aqueous solution is 0.8: 1-1.2: 1, preferably 1: 1.
ADVANTAGEOUS EFFECTS OF INVENTION
The magnetic snowman-shaped asymmetric Janus particles are uniform in size distribution, two parts with different compositions are accurately partitioned, the emulsifying performance is excellent, the emulsified oil-water emulsion is very stable and limited by an interface formed by assembling the magnetic snowman-shaped asymmetric Janus particles, liquid drops can be controlled by an external magnetic field, the movement of the liquid drops is realized, and a formed magnetic liquid drop model provides a new strategy for industrial deep oil removal.
The preparation method of the magnetic snowman-shaped asymmetric Janus particle is simple in process, raw materials are easy to obtain, industrial production is easy, and ton-level batch production can be realized.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
< terms and definitions >
In the present specification, the term "snowman-like" refers to a three-dimensional structure formed by two spheres (or approximate spheres) of the same or different sizes stacked together in a partially overlapping manner.
In the present specification, the "size" described for the snowman-like particles means a size corresponding to the height direction of the snowman, i.e., the longest point between two points of the boundary of the snowman, which can be measured by an electron scanning microscope photograph; "size" as described for other particles refers to the particle size of the corresponding particle; the "size" described for each particle population refers to the average size of the particles comprised by that particle population.
In the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
As used herein, the term "optional" or "optional" is used to indicate that certain substances, components, performance steps, application conditions, and the like are used or not used.
In the present specification, the unit names used are all international standard unit names, and the "%" used means weight or mass% content, if not specifically stated.
In the present specification, the term "particle diameter" as used herein means an "average particle diameter" if not specifically stated, and can be measured by a commercially available particle sizer or an electron scanning microscope.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< magnetic snowman-like asymmetric Janus particle >
One of the objects of the present invention is to provide a magnetic snowman-shaped asymmetric Janus particle comprising a hydrophilic part and a hydrophilic part which respectively constitute two spheres of the snowman-shaped particle, wherein the hydrophilic part comprises a polymer composite microsphere modified by hydrophilicity and a magnetic nanoparticle attached to the surface of the polymer composite microsphere, and the lipophilic part comprises silicon dioxide modified by hydrophobicity.
In a preferred embodiment, the hydrophilic moiety consists of the hydrophilically modified polymer composite microsphere and magnetic nanoparticles attached to the surface of the polymer composite microsphere.
In a preferred embodiment, the lipophilic portion consists of hydrophobically modified silica.
The size of the magnetic snowman-shaped asymmetric Janus particle is in the range of 450-1000nm, preferably 450-800nm, and more preferably 500-700 nm.
The particle size ratio of the hydrophilic portion to the lipophilic portion is in the range of 10/1-10/10, preferably in the range of 8/1-2/1, more preferably in the range of 6/1-4/1. Wherein the particle size of the hydrophilic part is 440-500 nm.
Preferably, the magnetic nanoparticles in the hydrophilic part are spherical or approximately spherical, with a particle size of 10-30 nm. The magnetic nanoparticles may also be spread on the polymer surface in the form of a coating. Preferably, the surface of the polymer composite microsphere is entirely covered with the magnetic nanoparticles. Most preferably, the magnetic nanoparticles are ferroferric oxide nanoparticles.
The present invention is not particularly limited with respect to the polymer forming the polymer composite microsphere. In a preferred embodiment, the polymer composite microspheres are composite microspheres of polystyrene and other polymers, wherein the polystyrene and/or other polymers are optionally crosslinked, and at least part of molecular chains of the other polymers are interpenetrated between at least part of molecular chains of the polystyrene, thereby forming a composite structure part of the two polymers.
Thus, in one embodiment, the polymeric composite microspheres have a substantially uniform polymer network structure formed by interpenetrating molecular chains of the polystyrene and the other polymer. In one embodiment, the polymer composite microsphere includes a polymer network structure layer formed by interpenetrating molecular chains of the polystyrene and the other polymer layer outside the layer. In one embodiment, the polymer composite microsphere sequentially comprises the polystyrene layer, a polymer network structure layer formed by mutually interpenetration of molecular chains of the polystyrene and the other polymer, and the other polymer layer from inside to outside.
In one embodiment, the other polymer may also be an optionally crosslinked polystyrene.
The other polymers described above are formed by polymerizing a feedstock composition comprising one or more monomers selected from olefins, double-bonded esters, and double-bonded amides, and optionally a crosslinking agent.
The olefin monomer may be one or more selected from optionally halogenated alkenes, styrene and its derivatives, and acrylonitrile; examples of the optionally halogenated alkene include, but are not limited to, vinyl chloride, 1, 3-dichloropropene, butene, 4-chloro-1-butene, 1, 3-butadiene, and the like; the derivatives of styrene include styrene substituted at the ortho, meta and/or para positions with a substituent selected from the group consisting of an optionally halogenated alkyl group having 1 to 15 carbon atoms, an alkoxy group, an alkenyl group and an optionally halogenated aryl group having 6 to 40 carbon atoms, wherein the alkyl group, the alkoxy group, the alkenyl group may be further substituted with an aryl group. Specific examples of styrene and its derivatives include, but are not limited to, styrene, p-methylstyrene, α -methylstyrene, p-methoxystyrene, 4-chloromethylstyrene, 4-tert-butylstyrene, divinylbenzene, 4-vinylbiphenyl.
The double-bond ester monomer is formed by esterifying acid and alcohol, wherein at least one of the acid and the alcohol contains a double bond in the molecular structure, and can be, for example, alkyl ester of unsaturated acid, unsaturated alcohol ester of saturated acid or unsaturated alcohol ester of unsaturated acid. Specifically, the double-bond ester monomer may be one or more selected from vinyl acetate and alkyl (meth) acrylate and derivatives thereof; the alkyl (meth) acrylate is preferably (meth) acrylic acid C1-C12Specific examples of the alkyl ester of (meth) acrylic acid and its derivatives include, but are not limited to, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, 2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester, oligoethyleneglycolmethylether methacrylate (OEGMA), polyethyleneglycol methyl ether acrylate, t-butyl methacrylate, n-butyl acrylate, n-butyl methacrylate, ethyl cyanoacrylate.
The double-bond amide-based monomer may be a monomer having a (meth) acrylamide group, preferably (meth) acrylamide and a derivative thereof, preferably a (meth) acrylamide having a substituent selected from the group consisting of an optionally halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an optionally halogenated aryl group having 6 to 40 carbon atoms on the N atom, wherein the alkyl group, the alkoxy group and the alkenyl group may be further substituted with an aryl group. Specific examples of the derivatives of the (meth) acrylamide include, but are not limited to, N-phenylacrylamide, N-phenylmethylacrylamide, N-benzylacrylamide, N- (4-chlorophenyl) acrylamide, N-t-butylacrylamide, N-dodecylacrylamide, N-octadecylacrylamide, N-diethylacrylamide, N-dibutylacrylamide.
Examples of such crosslinking agents include, but are not limited to, divinylbenzene, Ethylene Glycol Dimethacrylate (EGDMA), trimethylolpropane triacrylate, diethyl 1, 4-benzenediacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, glycerol dimethacrylate and ethylene glycol dimethacrylate, and combinations thereof.
In a preferred embodiment, the polymeric composite microspheres are hollow.
The silica in the lipophilic portion is formed by polymerization and further hydrolysis of a double bond-containing silane coupling agent.
The surface of the silica in the lipophilic portion is attached with hydrophobic groups and/or segments. The linkage may be by covalent, hydrogen, coordination and intermolecular forces, preferably by covalent bonding.
The present invention is not particularly limited with respect to specific hydrophobic groups and/or segments, including but not limited to one or more of unsubstituted or optionally halogenated alkyl, alkoxy, alkenyl, aryl, arylalkyl. The alkyl group and the alkyl moiety in the alkoxy and arylalkyl groups are preferably linear, branched or cyclic alkyl groups having 1 to 30C atoms, the alkenyl group is preferably a linear or branched alkenyl group having 2 to 30C atoms, and the aryl group is preferably a monocyclic or fused ring aryl group having 6 to 40C atoms.
Specifically, examples of the hydrophobic group and/or segment include unsubstituted or optionally halogenated methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups, and alkoxy and alkenyl groups corresponding to these alkyl groups, and phenyl, benzyl, phenethyl, phenylpropyl, phenylbutyl and the like. The alkoxy group corresponding to the alkyl group means a group formed by inserting-O-at a position where the alkyl group is bonded to another group, and the alkenyl group corresponding to the alkyl group means a group formed by replacing an arbitrary carbon-carbon single bond in the alkyl group with a carbon-carbon double bond. Preferred hydrophobic groups are alkyl and alkoxy groups having 6 to 20C atoms, particularly preferably n-octyl and n-octadecyl.
< method for producing magnetic snowman-shaped asymmetric Janus particle >
One of the objects of the present invention is to provide a method for producing magnetic snowmobile asymmetric Janus particles of the present invention by a one-step seeded emulsion polymerization induced phase separation method.
In a specific embodiment, the preparation method of the present invention comprises the steps of:
preparing a seed emulsion: adding an oil/water emulsion containing a monomer, a cross-linking agent and an initiator into a dispersion liquid of a Polystyrene (PS) hollow sphere template, and heating and polymerizing to obtain a polymer composite seed emulsion;
preparation of snowman-like Janus granules: adding an emulsion containing a silane coupling agent monomer containing double bonds and a surfactant into the polymer composite seed emulsion for swelling, and then heating for polymerization to induce phase separation to prepare snowman-shaped Janus particles;
hydrophobic modification: hydrophobically modifying a silica portion of the snowman-shaped Janus particle;
hydrophilic modification: carrying out hydrophilic modification on the snowman-shaped Janus particles subjected to hydrophobic modification to obtain amphiphilic snowman-shaped Janus particles;
magnetization: and attaching magnetic nanoparticles to the surfaces of the amphiphilic snowman-shaped Janus particles to obtain the magnetic snowman-shaped asymmetric Janus particles.
The steps of the method of manufacturing the magnetic snowman-like asymmetric Janus particles of the present invention will be described in detail below.
< preparation of seed emulsion >
The monomers and the crosslinking agent used in this step are the above-mentioned monomers and crosslinking agents for forming other polymers in the polymer composite microsphere.
The initiator used in the present step is not particularly limited and may be appropriately selected as needed. In one embodiment, the initiator is one or more selected from the group consisting of azo-type initiators, examples of which include, but are not limited to, azobisisobutyronitrile, azobisisoheptonitrile, and the like, and peroxide initiators, examples of which include, but are not limited to, dibenzoyl peroxide, lauroyl peroxide, N-dimethylaniline, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, and the like.
In a preferred embodiment, the monomer, crosslinker, initiator and water are combined and the oil/water emulsion is formed by the action of the surfactant. The surfactant in the present invention is not particularly limited, and may be appropriately selected as needed. Specifically, the surfactant may be one of a cationic surfactant, an anionic surfactant, a nonionic surfactant, or any combination thereof. Examples of cationic surfactants include, but are not limited to, N-dimethyloctadecyl amine hydrochloride, octadecyl amine hydrochloride, dioctadecyl amine hydrochloride, dodecyltrimethyl ammonium bromide, octadecyltrimethyl ammonium chloride, hexadecyltrimethyl ammonium chloride, and like amine salts. Examples of the anionic surfactant include, but are not limited to, sodium lauryl sulfate, sodium lauryl alcohol polyoxyethylene ether sulfate, sodium lauryl sulfate, sodium secondary alkyl sulfonate, ammonium lauryl sulfate, sodium fatty alcohol isethionate, dodecylbenzene sulfonic acid, sodium dodecylbenzene sulfonate and like sulfonates, and phosphate ester salts such as lauryl phosphate triethanolamine, lauryl phosphate, potassium lauryl phosphate and like salts. Examples of nonionic surfactants include, but are not limited to, tween 80, span 80, octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, dodecylphenol polyoxyethylene ether, hydroxysynthol polyoxyethylene ether, and the like.
In the oil/water emulsion, the content of the monomer is 5 to 20 percent; the content of the cross-linking agent is 3-10%; the molar ratio of crosslinker to monomer is from 10/1 to 1/10, preferably from 8/2 to 2/8, more preferably from 7/3 to 3/7, and most preferably from 6/4 to 6/10; the mass concentration of the initiator is 0.2-10.0 per mill, the mass concentration of the surfactant is 1.2-20 per mill, and the balance is water.
In the step, the mass ratio of the total amount of the monomers and the cross-linking agent to the polystyrene hollow sphere template is 5/1-5/5.
In a preferred embodiment, the monomer, the cross-linking agent, the initiator and the water are mixed, under the action of the surfactant, an oil/water emulsion is formed through shearing and stirring, the oil/water emulsion is added into the dispersion liquid of the Polystyrene (PS) hollow sphere template, and after swelling and oxygen elimination, the polymer composite seed emulsion is obtained through polymerization at elevated temperature. The dispersion liquid of the Polystyrene (PS) hollow sphere template consists of hollow spheres and water, the particle size of the polymer hollow spheres is 433nm +/-5 nm, and the solid content of the polymer hollow spheres reaches 30%.
In the step, the polymerization temperature of the temperature-rising polymerization is 60-90 ℃, and preferably 70-75 ℃; the polymerization time is from 1 to 30 hours, preferably 5 hours.
< preparation of snowman-like Janus particles >
In this step, a silane coupling agent containing a double bond and a seed in the polymer composite seed emulsion are subjected to polymerization reaction, polymerization-induced phase separation occurs, and the polymerized silane coupling agent is hydrolyzed, thereby forming a silica part, resulting in snowman-shaped Janus particles including an unmodified polymer composite microsphere part and a silica part which respectively constitute two spheres of snowman-shaped particles.
In one embodiment, the emulsion of this step is comprised of a double bond containing silane coupling agent, an initiator, a surfactant, and water.
The double bond-containing silane coupling agent is not particularly limited and may be appropriately selected as needed. In a preferred embodiment, the double bond-containing silane coupling agent is one selected from the group consisting of 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (methacryloyloxy) propyltrichlorosilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, 3-alkenylbutyltrimethoxysilane, 3-alkenylbutyltriethoxysilane, 3-alkenylbutyltrichlorosilane, or any combination thereof.
The surfactant used in this step may be selected accordingly from the surfactants described for the < preparation of seed emulsion > step.
The initiator in this step is a hydrophilic initiator such as potassium persulfate, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisdiisopropylimidazoline, or the like.
In the emulsion, the content of the double-bond-containing silane coupling agent is 5-30%; the content of the initiator is 0.5-10.0 per mill; the content of the surfactant is 0.5-20 per mill; the balance being water.
In the step, the polymerization temperature is 60-90 ℃, preferably 70-75 ℃; the polymerization time is from 1 to 40 hours, preferably from 3 to 5 hours.
In one embodiment, the method further comprises the following steps: after polymerization, the obtained snowman-like Janus particles were washed with ethanol and water and dried to obtain solid particles thereof.
< hydrophobic modification >
The hydrophobic modification is performed by reacting silicon hydroxyl groups of the silica surface with a silane coupling agent. Specifically, it is carried out by dispersing or dissolving the obtained snowman-like Janus particles in a solvent simultaneously with a silane coupling agent.
The silane coupling agent used in this step is a silane coupling agent having a hydrophobic group and/or segment, and any silane coupling agent that has a hydrophobic group and/or segment and can react with the silicon hydroxyl group on the silica surface can be used in the present invention. Preferably, the silane coupling agent used in this step is one or more selected from the group consisting of ethyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, hexadecyltrimethoxysilane, n-octadecyltriethoxysilane, dicyclopentyldimethoxysilane, trimethoxy (2-phenylethyl) silane, phenyltrimethoxysilane, dimethoxydiphenylsilane, allyltrimethoxysilane, 7-octenyltrichlorosilane, vinyltriisopropenoxysilane, dimethyloctadecylchlorosilane and 1H,1H,2H, 2H-perfluorodecaalkyltrichlorosilane.
The dosage of the silane coupling agent is 1-100% of the snowman-shaped Janus particles.
The solvent used in this step is selected from ethanol, benzene, toluene, xylene, pentane, hexane, octane, cyclohexane, tetrahydrofuran, dioxane, diethyl ether, anisole, diphenyl ether, N-hexane, N-dimethylformamide, 1, 4-dimethyl sulfoxide, N-methylpyrrolidone, acetone, cyclohexanone, epoxyacetone, chlorobenzene, dichlorobenzene, dichloromethane, trichloromethane and carbon tetrachloride.
The temperature of the hydrophobic modification is 30-90 ℃; the reaction time is 1-30h, preferably 24 h.
< hydrophilic modification >
In the production method of the present invention, the hydrophilic modification is performed by treating the hydrophobically modified snowman-like Janus particles with a solvent. In a specific embodiment, the hydrophobically modified snowman-shaped Janus particles are dispersed in a solvent and treated with the solvent to obtain hydrophilic groups, thereby obtaining the hydrophilically modified amphiphilic snowman-shaped Janus particles.
The solvent may be water, concentrated sulfuric acid, dilute sulfuric acid, SO3Aqueous solution of (3), sulfuric chloride acid, aqueous solution of NaOH, aqueous solution of KOH, etc.
In a preferred embodiment, the solvent is concentrated sulfuric acid, and the hydrophilic modification is performed by sulfonating the hydrophobically modified snowman-like Janus particles with concentrated sulfuric acid. Specifically, molecular chains with styrene structural units contained in the polymer composite microspheres in the hydrophobically modified snowman-shaped Janus particles are subjected to sulfonation reaction under the action of concentrated sulfuric acid, and sulfonic acid groups are formed on the surfaces of the molecular chains, so that the polymer composite microspheres have hydrophilic characteristics.
In one embodiment, the sulfonation treatment is carried out for a period of 5 to 60min, preferably 20 to 40 min.
Preferably, the step further comprises repeatedly washing the obtained amphiphilic snowman-shaped Janus particles with water and freeze-drying to obtain solid particles thereof.
< magnetization >
In the preparation method of the present invention, the magnetization is performed by attaching magnetic nanoparticles to the surface of the gemini snowy human-like Janus particles. In a specific embodiment, the amphiphilic snowman-shaped Janus particles are dispersed into an aqueous solution in which ferrous ions and ferric ions are dissolved, and after adsorption is carried out by utilizing charge interaction between the ferric ions and anionic groups carried by hydrophilic parts of the particles, ammonia water is added to form ferroferric oxide nanoparticles which are attached to one side of polymer composite microspheres of the amphiphilic snowman-shaped Janus particles, so that the magnetic snowman-shaped asymmetric Janus particles are obtained.
In a specific embodiment, the aqueous solution is prepared by simultaneously dissolving a ferrous salt and a ferric salt in water, so that a sulfonic acid group, a ferrous ion and a ferric ion in a polymer composite microsphere part of the amphiphilic snowman-shaped Janus particles are adsorbed by charge interaction, and then are crystallized under the action of ammonia water, thereby forming the ferroferric oxide nanoparticles attached to the surface of the polymer composite microsphere part.
Examples of the divalent iron salt that can be used for preparing the aqueous solution include ferrous sulfate, ferrous nitrate, ferrous chloride, and the like, and examples of the trivalent iron salt include ferric sulfate, ferric chloride, ferric nitrate, and the like. The molar ratio of the ferrous ions to the ferric ions in the aqueous solution is 0.8: 1-1.2: 1, preferably 1: 1. The total concentration of ferrous and ferric ions in the aqueous solution is 0.1-1mol/L, preferably 0.3-0.7mol/L, more preferably 0.5 mol/L.
By the preparation method, the structure of the hydrophilic part of the magnetic snowman-shaped asymmetric Janus particle is adjustable, and the content of the magnetic particle is controllable; the size ratio of the inorganic part to the polymer is adjustable, and the hydrophobic degree is controllable. The preparation method is simple, the fine structure of the product is clear, and batch production can be realized.
In a preferred embodiment, the preparation process of the present invention comprises the steps of:
mixing a monomer, a cross-linking agent, an initiator, a surfactant and water, forming an oil/water emulsion by shearing and stirring, adding the obtained oil/water emulsion into a dispersion liquid of a Polystyrene (PS) hollow sphere template, swelling and removing oxygen, and heating for polymerization to obtain a polymer composite seed emulsion;
preparing a double-bond-containing silane coupling agent monomer, an initiator, a surfactant and water into emulsion; adding the polymer composite seed emulsion into the obtained polymer composite seed emulsion for swelling, heating for polymerization to induce phase separation, preparing snowman-shaped Janus particles, washing with ethanol and water, and drying to obtain solid particles;
dispersing the obtained snowman-shaped Janus particles in a solvent, and dissolving a silane coupling agent in the solvent to obtain hydrophobically modified snowman-shaped Janus particles;
dispersing the obtained hydrophobically modified snowman-shaped Janus particles in a solvent, and treating the solvent to obtain amphiphilic snowman-shaped Janus particles;
dispersing the obtained amphiphilic snowman-shaped Janus particles in an aqueous solution in which ferrous ions and ferric ions are dissolved, adsorbing, and adding ammonia water to form ferroferric oxide nanoparticles attached to one side of the polymer composite microspheres of the amphiphilic snowman-shaped Janus particles, so that the magnetic snowman-shaped asymmetric Janus particles are obtained.
In a particularly preferred embodiment, the preparation process of the invention comprises the following steps:
mechanically stirring a mixture of polystyrene hollow sphere dispersion liquid, styrene, divinylbenzene, azodiisobutyronitrile, sodium dodecyl sulfate and water to obtain emulsion, and polymerizing after swelling and oxygen gas exhaust to obtain polymer composite seed emulsion;
dropwise adding an emulsion containing 3- (methacryloyloxy) propyl trimethoxysilane into the obtained polymer composite seed emulsion, swelling the seed emulsion, heating for polymerization to induce phase separation, and obtaining polymer-silicon dioxide composite snowman-shaped Janus particles;
repeatedly washing the obtained polymer-silicon dioxide composite snowman-shaped Janus particles with ethanol and water, freeze-drying, dispersing dry powder into ethanol, and modifying with n-octyl triethoxysilane to obtain hydrophobically modified snowman-shaped Janus particles;
dispersing the obtained hydrophobically modified snowy Janus particles into concentrated sulfuric acid, keeping the sulfonation process for 30min, then repeatedly washing with water and freeze-drying to obtain amphiphilic snowy Janus particles with one side of the polymer being hydrophilically modified;
dispersing the obtained amphiphilic snowman-shaped Janus particles in an aqueous solution in which divalent and trivalent iron ions are dissolved, adsorbing, and adding ammonia water to form ferroferric oxide nanoparticles attached to one side of the polymer composite microspheres of the amphiphilic snowman-shaped Janus particles, so that the magnetic snowman-shaped asymmetric Janus particles are obtained.
In the above-described particularly preferred embodiment, PS/PDVB-Fe is prepared3O4@SiO2the-C8 snowman-like Janus particles have the following effects:
(1) the particle size distribution is uniform, and the particle size is adjustable in the range of 450-1000 nm.
(2)SiO2-C8 and PS/PDVB-Fe3O4The two parts are strictly partitioned, and the size ratio is adjustable.
(3) The magnetic snowman-shaped asymmetric Janus particle can be prepared in batch by a one-pot method, and the structure is accurate and controllable; other properties can also be obtained by subsequent chemical modification of the particles as desired.
(4) The method has simple process, easily obtained raw materials, and easy industrial production.
Examples
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it is to be understood that various changes or modifications may be made by those skilled in the art after reading the present disclosure, and such equivalents may fall within the scope of the present disclosure.
Unless otherwise specified, the percentages in the following examples are by mass.
Example 1: PS/PDVB-Fe3O4@SiO2Preparation of-C8 magnetic snowman asymmetric Janus particles
1g of styrene, 0.6g of divinylbenzene, 0.05g of sodium dodecyl sulfate, 0.02g of azobisisobutyronitrile and 10mL of water were emulsified at high speed to obtain an emulsion. And mixing the emulsion and 1g of polystyrene hollow sphere dispersion liquid for swelling, and carrying out polymerization reaction for 8 hours at the temperature of 70 ℃ under the stirring speed of 300rpm/min to prepare the seed emulsion. Emulsifying 3- (methacryloyloxy) propyltrimethoxysilane 1g, sodium dodecyl sulfate 0.04g, potassium persulfate 0.01g and water 10mL into emulsion, dripping the seed emulsion into the emulsion, and stirring for 5 h. Carrying out polymerization reaction for 24 hours at the temperature of 70 ℃ under the stirring speed of 300rpm/min to prepare PDVB/PS @ SiO2Composite snowman-like Janus particle emulsions. The solids content was 15% and the size of the snowman-like Janus particles was 450 nm.
The snowman-shaped Janus particles obtained above were dispersed in ethanol and hydrophobically modified by adding 0.1g of n-octyltriethoxysilane. The hydrophobically modified particles were dispersed in 10ml of concentrated sulfuric acid and sulfonated for 30min to hydrophilically modify the polymer fraction. Dispersing the obtained amphiphilic Janus particles into 20ml of dissolved Fe2+And Fe3+Adsorbing in 0.5mol/L aqueous solution, adding ammonia water to obtain magnetic Fe3O4Particle-compounded magnetic snowman-shaped asymmetric Janus particle PS/PDVB-Fe3O4@SiO2-C8。
Example 2: PS/PDVB-Fe3O4@SiO2Preparation of-C18 magnetic snowman asymmetric Janus particles
An emulsion was obtained by high-speed emulsification of 0.6g of divinylbenzene, 1g of styrene, 0.05g of sodium dodecylsulfate, 0.02g of azobisisobutyronitrile and 10mL of water. And mixing the emulsion and 1g of polystyrene hollow sphere dispersion liquid for swelling, and carrying out polymerization reaction for 8 hours at the temperature of 70 ℃ under the stirring speed of 300rpm/min to prepare the seed emulsion. Emulsifying 3- (methacryloyloxy) propyl trimethoxysilane 1.2g, sodium dodecyl sulfate 0.04g, potassium persulfate 0.01g and water 10mL into emulsion, dripping the seed emulsion into the emulsion, and stirring for 5 h. Stirring at 300rpm/min, and polymerizing at 70 deg.CThe synthesis reaction is carried out for 24 hours to prepare PDVB/PS @ SiO2Composite snowman-like Janus particle emulsion. The solids content was 15% and the size of the snowman-like Janus particles was 600 nm.
The snowman-shaped Janus particles obtained above were dispersed in ethanol and hydrophobically modified by the addition of 0.1g of n-octadecyl triethoxy silane. The hydrophobically modified particles were dispersed in 10ml of concentrated sulfuric acid and sulfonated for 30min to hydrophilically modify the polymer fraction. Dispersing the obtained amphiphilic Janus particles into 20ml of dissolved Fe2+And Fe3+Adsorbing in 0.5mol/L water solution, adding ammonia water to obtain magnetic Fe3O4Particle-compounded magnetic snowman-shaped asymmetric Janus particle PS/PDVB-Fe3O4@SiO2-C18。
Example 3: PS/PDVB/PVBC-Fe3O4@SiO2Preparation of-C18 magnetic snowman asymmetric Janus particles
1.2g of divinylbenzene, 1g of 4-chloromethyl styrene, 0.05g of sodium dodecyl sulfate, 0.02g of azodiisobutyronitrile and 10mL of water are emulsified at high speed to obtain emulsion. And mixing the emulsion and 1g of polystyrene hollow sphere dispersion liquid for swelling, and carrying out polymerization reaction for 8 hours at the temperature of 70 ℃ under the stirring speed of 300rpm/min to prepare the seed emulsion. Emulsifying 3- (methacryloyloxy) propyltrimethoxysilane 1g, sodium dodecyl sulfate 0.04g, potassium persulfate 0.01g and water 10mL into emulsion, dripping the seed emulsion into the emulsion, and stirring for 5 h. Carrying out polymerization reaction for 24 hours at the temperature of 70 ℃ under the stirring speed of 300rpm/min to prepare PS/PDVB/PVBC @ SiO2Composite snowman-like Janus particle emulsions. The solids content was 15% and the size of the snowman-like Janus particles was 500 nm.
The snowman-shaped Janus particles obtained above were dispersed in ethanol and hydrophobically modified by the addition of 0.1g of n-octadecyl triethoxy silane. The hydrophobically modified particles were dispersed in 10ml of concentrated sulfuric acid and sulfonated for 30min to hydrophilically modify the polymer fraction. Dispersing the obtained amphiphilic Janus particles in 20ml dissolved with Fe2+And Fe3+Adsorbing in 0.5mol/L aqueous solution, adding ammonia water to obtain magnetic Fe3O4Particle-compounded magnetic snowman-shaped asymmetric Janus particle PS/PDVB/PVBC-Fe3O4@SiO2-C18。
Example 4: PS/PDVB/PVBC-Fe3O4@SiO2Preparation of-C8 magnetic snowman asymmetric Janus particles
1.2g of divinylbenzene, 1g of 4-chloromethyl styrene, 0.05g of sodium dodecyl sulfate, 0.02g of azodiisobutyronitrile and 10mL of water are emulsified at high speed to obtain emulsion. And mixing the emulsion with 1g of polystyrene hollow sphere dispersion liquid for swelling, and carrying out polymerization reaction for 8 hours at the temperature of 70 ℃ under the stirring speed of 300rpm/min to prepare the seed emulsion. Emulsifying 3- (methacryloyloxy) propyl trimethoxysilane 1.2g, sodium dodecyl sulfate 0.04g, potassium persulfate 0.01g and water 10mL into emulsion, dripping the seed emulsion into the emulsion, and stirring for 5 h. Carrying out polymerization reaction for 24 hours at the temperature of 70 ℃ under the stirring speed of 300rpm/min to prepare PS/PDVB/PVBC @ SiO2Composite snowman-like Janus particle emulsions. The solids content was 15% and the size of the snowman-like Janus particles was 660 nm.
The snowman-shaped Janus particles obtained above were dispersed in ethanol and hydrophobically modified by adding 0.1g of n-octyltriethoxysilane. The hydrophobically modified particles were dispersed in 10ml of concentrated sulfuric acid and sulfonated for 30min to hydrophilically modify the polymer fraction. Dispersing the obtained amphiphilic Janus particles in 20ml dissolved with Fe2+And Fe3+Adsorbing in 0.5mol/L water solution, adding ammonia water to obtain magnetic Fe3O4Particle-compounded magnetic snowman-shaped asymmetric Janus particle PS/PDVB/PVBC-Fe3O4@SiO2-C8。
Example 5: PS/PMMA/PEGDMA-Fe3O4@SiO2Preparation of-C18 magnetic snowman asymmetric Janus particles
1g of styrene, 1.2g of ethylene glycol dimethacrylate, 1g of methyl methacrylate, 0.05g of sodium dodecyl sulfate, 0.02g of azobisisobutyronitrile and 10mL of water are emulsified at a high speed to obtain an emulsion. Mixing the emulsion with 1g polystyrene hollow sphere dispersion liquid for swelling, stirring at 300rpm/min, and performing polymerization reaction at 70 deg.C for 8h to obtain the final productA sub-emulsion. Emulsifying 3- (methacryloyloxy) propyltrimethoxysilane 1g, sodium dodecyl sulfate 0.04g, potassium persulfate 0.01g and water 10mL into emulsion, dripping the seed emulsion into the emulsion, and stirring for 5 h. Carrying out polymerization reaction for 24 hours at the temperature of 70 ℃ under the stirring speed of 300rpm/min to prepare PS/PMMA/PEGDMA @ SiO2Composite snowman-like Janus particle emulsions. The solids content was 15% and the size of the snowman-like Janus particles was 500 nm.
The snowman-shaped Janus particles obtained above were dispersed in ethanol and hydrophobically modified by the addition of 0.1g of n-octadecyl triethoxy silane. The hydrophobically modified particles were dispersed in 10ml of concentrated sulfuric acid and sulfonated for 30min to hydrophilically modify the polymer fraction. Dispersing the obtained amphiphilic Janus particles into 20ml of dissolved Fe2+And Fe3+Adsorbing in 0.5mol/L water solution, adding ammonia water to obtain magnetic Fe3O4Particle compounded magnetic snowman-shaped asymmetric Janus particle PS/PMMA/PEGDMA-Fe3O4@SiO2-C18。
Industrial applicability
The magnetic snowman-shaped asymmetric Janus particle can be used as an emulsifier for industrial deep oil removal.
Claims (15)
1. A magnetic snowman-shaped asymmetric Janus particle is characterized by comprising a hydrophilic part and a hydrophilic oil part which respectively form two spheres of the snowman-shaped particle, wherein the hydrophilic part comprises polymer composite microspheres subjected to hydrophilic modification and magnetic nanoparticles attached to the surfaces of the polymer composite microspheres, and the lipophilic part comprises silicon dioxide subjected to hydrophobic modification.
2. The Janus particle of claim 1 wherein the Janus particle is 450-1000nm in size.
3. The Janus particle of claim 1 wherein the particle size ratio of the hydrophilic portion to the lipophilic portion is from 10/1 to 10/10; wherein the particle size of the hydrophilic part is 440-500 nm.
4. The Janus particle of claim 1, wherein the polymer composite microsphere is a composite microsphere of polystyrene and another polymer, wherein the other polymer is formed by polymerizing a raw material composition comprising one or more monomers selected from olefins, double-bonded esters and double-bonded amides, and optionally a crosslinking agent; the olefinic monomer is preferably one or more selected from optionally halogenated alkenes, styrene and its derivatives, and acrylonitrile; the double-bond ester monomer is preferably one or more selected from vinyl acetate, alkyl (meth) acrylate and derivatives thereof; the amide-based monomer having a double bond is preferably a monomer having a (meth) acrylamide group.
5. The Janus particle of claim 1 wherein the polymeric composite microspheres are hollow.
6. The Janus particle of claim 1 wherein the surface of the polymeric composite microsphere is entirely covered by the magnetic nanoparticle.
7. Janus particles as claimed in claim 1, wherein the magnetic nanoparticles have a particle size of 10-30nm, and are preferably ferroferric oxide nanoparticles.
8. The Janus particle of claim 1 wherein the silica surface in the lipophilic portion has attached hydrophobic groups and/or segments.
9. A method of making magnetic snowman asymmetric Janus particles as claimed in any one of claims 1 to 8 comprising the steps of:
preparing a seed emulsion: adding an oil/water emulsion containing a monomer, a cross-linking agent and an initiator into a dispersion liquid of a Polystyrene (PS) hollow sphere template, and heating and polymerizing to obtain a polymer composite seed emulsion;
preparation of snowman-like Janus granules: adding an emulsion containing a silane coupling agent monomer containing double bonds, an initiator and a surfactant into the polymer composite seed emulsion for swelling, and then heating for polymerization to induce phase separation to prepare snowman-shaped Janus particles;
hydrophobic modification: hydrophobically modifying a silica portion of the snowman-like Janus particles;
hydrophilic modification: carrying out hydrophilic modification on the snowman-shaped Janus particles subjected to hydrophobic modification to obtain amphiphilic snowman-shaped Janus particles;
magnetization: and attaching magnetic nanoparticles to the surfaces of the amphiphilic snowman-shaped Janus particles to obtain the magnetic snowman-shaped asymmetric Janus particles.
10. The method according to claim 9, wherein in the step of preparing the seed emulsion, the content of the monomer in the oil/water emulsion is 5% to 20%; the content of the cross-linking agent is 3-10%; the molar ratio of the cross-linking agent to the monomer is 10/1-1/10, the mass concentration of the initiator is 0.2-10.0 per mill, and the mass concentration of the surfactant is 1.2-20 per mill; the mass ratio of the total amount of the monomers and the cross-linking agent to the polystyrene hollow sphere template is 5/1-5/5.
11. The method according to claim 9, wherein the double bond-containing silane coupling agent monomer is one or more selected from the group consisting of 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (methacryloyloxy) propyltrichlorosilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, 3-alkenylbutyltrimethoxysilane, 3-alkenylbutyltriethoxysilane, 3-alkenylbutyltrichlorosilane, and any combination thereof.
12. The production method according to claim 9, characterized in that the hydrophobic modification is performed by reacting a silicon hydroxyl group of a silica surface with a silane coupling agent; the silane coupling agent is preferably one or more selected from the group consisting of ethyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, hexadecyltrimethoxysilane, n-octadecyltriethoxysilane, dicyclopentyldimethoxysilane, trimethoxy (2-phenylethyl) silane, phenyltrimethoxysilane, dimethoxydiphenylsilane, allyltrimethoxysilane, 7-octenyltrichlorosilane, vinyltriisopropenoxysilane, dimethyloctadecylchlorosilane, and 1H,1H,2H, 2H-perfluorodecaalkyltrichlorosilane.
13. The method of claim 9, wherein the hydrophilic modification is performed by treating hydrophobically modified snowman-shaped Janus particles with a solvent selected from the group consisting of water, concentrated sulfuric acid, dilute sulfuric acid, SO3The aqueous solution of (3), the aqueous solution of chlorosulfonic acid, NaOH or the aqueous solution of KOH, is preferably concentrated sulfuric acid.
14. The preparation method according to claim 9, wherein in the magnetization step, the amphiphilic snowman-shaped Janus particles are dispersed into an aqueous solution in which ferrous ions and ferric ions are dissolved, and ammonia water is added after adsorption to form ferroferric oxide nanoparticles attached to one side of the polymer composite microspheres of the amphiphilic snowman-shaped Janus particles, so that the magnetic snowman-shaped asymmetric Janus particles are obtained.
15. The method according to claim 14, wherein the aqueous solution is prepared by dissolving a ferrous salt, preferably ferrous sulfate, ferrous nitrate and/or ferrous chloride, and a ferric salt, preferably ferric sulfate, ferric chloride and/or ferric nitrate, in water; the molar ratio of the ferrous ions to the ferric ions in the aqueous solution is 0.8: 1-1.2: 1, preferably 1: 1.
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| KR20160047793A (en) * | 2014-10-23 | 2016-05-03 | 명지대학교 산학협력단 | Manufacturing method for janus particle, manufacturing method for antibacterial janus particles using the method and antibacterial janus particles |
| CN111643926A (en) * | 2020-05-28 | 2020-09-11 | 清华大学 | Extraction method based on magnetic Janus particles |
| CN111825926A (en) * | 2019-04-23 | 2020-10-27 | 中国科学院化学研究所 | Organic/inorganic hybrid three-component Janus particle and preparation method thereof |
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| US20120248020A1 (en) * | 2007-12-06 | 2012-10-04 | The Board Of Trustees Of The University Of Illinois | Chromatography devices and methods |
| KR20160047793A (en) * | 2014-10-23 | 2016-05-03 | 명지대학교 산학협력단 | Manufacturing method for janus particle, manufacturing method for antibacterial janus particles using the method and antibacterial janus particles |
| CN111825926A (en) * | 2019-04-23 | 2020-10-27 | 中国科学院化学研究所 | Organic/inorganic hybrid three-component Janus particle and preparation method thereof |
| CN111643926A (en) * | 2020-05-28 | 2020-09-11 | 清华大学 | Extraction method based on magnetic Janus particles |
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