KR101147254B1 - Oval-Shaped Monodisperse Hybrid Particles Having Alignment Upon Magnetic Field and Manufacturing Method Thereof - Google Patents

Abstract

The present invention relates to an ellipsoidal hybrid particle which can be arranged and driven according to the magnetic force control in response to the orientation of the magnetic force, and a method for manufacturing the same. The magnetic inorganic metal is introduced into an ellipsoidal particle having the same size distribution as the conventional spherical particle. Is characteristic. Each of the particles can be arranged and driven in the shape desired by the operator by controlling the magnetic force.

Description

Oval-Shaped Monodisperse Hybrid Particles Having Alignment Upon Magnetic Field and Manufacturing Method Thereof}

The present invention relates to a method for producing an ellipsoid hybrid particle capable of driving each individual three-dimensionally independent of the magnetic field by introducing an inorganic material having a magnetic on the surface of the ellipsoid monodisperse polymer particles.

Unlike spherical polymer particles, monodisperse hybrid particles have properties of inorganic materials such as conductivity and magnetism and elasticity of polymers, and thus have been applied to conductive balls, medical particles, magnetic toners, and the like. And since it can be manufactured in nano size, it can be used as a self-driven catalyst by coating gold, silver, etc., and it can be applied not only to organic pigments, paints, inks and cosmetics that have high hiding power, but also to military equipment for autism. It is possible.

Several methods have been proposed in the meantime to produce such hybrid particles. European Patent No. 522,856 discloses a method for preparing a polymer having inorganic oxide particles dispersed in a polymer matrix, and pulverizing or crushing the same, to produce hybrid particles. The problem is that the size is not constant.

Australian patent 704,376 also discloses an aqueous suspension polymerization process comprising polymerizing a dispersed organic phase comprising monomers, inorganic magnetic powders and dispersants. In the polymerization process, a dispersant may react with a monomer to prepare spherical polymer particles in which a covalent bond is formed in the resin and inorganic particles are dispersed in the polymer particles. However, since the inorganic particles are dispersed in the monomer to polymerize, it is difficult to obtain particles having a high monodispersity and a desired size.

Existing magnetic hybrid particles have been produced, and since the basic shape is irregular or spherical, the particles are driven independently by magnetism, or the magnetic arrangement is not independent. Therefore, there has been a demand for a hybrid material capable of three-dimensional driving and arrangement independent of the shape desired by the driver, but until now, a method of manufacturing such a hybrid particle is not known.

Accordingly, the present inventors have completed the present invention by discovering that the magnetic particles of the ellipsoid have orientation to the magnetic field as a result of the study of adding new properties to the properties of the particles. That is, an object of the present invention is to provide monodisperse polymer particles having self-orientation and a method for producing the same.

The present invention relates to ellipsoid hybrid particles in which inorganic particles having magnetic properties are introduced using ellipsoidal monodisperse polymer particles as a support. The ellipsoid hybrid particles can be driven independently of each other with respect to the magnetic field, and also can be a three-dimensional space arrangement rather than a two-dimensional planar arrangement.

In addition, the present invention, after the addition of the radical polymerization monomer, the dispersion stabilizer, the crosslinking agent and the initiator into the solvent, the dispersion polymerization at elevated temperature and stirring, but the amount of the crosslinking agent is added to 100% by weight of the total solvent, radical polymerization monomer, dispersion stabilizer, crosslinking agent and initiator 1 step of preparing the ellipsoidal monodisperse polymer particles of 0.01 to 5% by weight, 2 steps of introducing the magnetic inorganic particles into the prepared polymer particles, and 3 to wash and dry the ellipsoidal monodisperse polymer particles into which the magnetic inorganic particles are introduced. The present invention relates to a method for producing an ellipsoid hybrid particle incorporating an inorganic particle having magnetic properties.

The ellipsoid hybrid particles of the present invention, unlike the previously known spherical magnetic hybrid particles, are capable of independently driving each particle with respect to a magnetic field, and are capable of three-dimensional spatial arrangement rather than two-dimensional planar arrangement. These driving and arrangement characteristics have the advantage that the arrangement of particles can be easily adjusted to the desired shape by using the magnetic characteristics. In addition, since it can be manufactured by the same process as the conventional method for producing spherical hybrid particles, it can be said that the ripple effect is large in that it can produce high functional hybrid particles without additional process improvement and addition.

1 is a scanning electron microscope (SEM) photograph of elliptical monodisperse polymer particles synthesized by dispersion polymerization obtained in step 1 of Example 1. FIG.
2 is a SEM photograph of the monodisperse magnetic directional hybrid particles obtained in Example 1. FIG.
3 is an optical micrograph of the monodisperse magnetic directional hybrid particles obtained in Example 1. FIG.
4 is a transmission electron microscope (TEM) photograph showing a cross section of the monodisperse magnetic directional hybrid particles obtained in Example 1. FIG.
5 is an optical micrograph and a picture showing the arrangement and driving characteristics of the self-directed hybrid particles in Example 1.

The present invention relates to ellipsoid hybrid particles in which inorganic particles having magnetic properties are introduced using ellipsoidal monodisperse polymer particles as a support. The ellipsoid hybrid particles are capable of independent driving of the particles with respect to the magnetic field, and can also be arranged in three-dimensional space rather than in two-dimensional plane arrangement. Preferably, the ellipsoidal monodisperse polymer particles have a long axis / short axis ratio of 1.3 to 5. If the ratio is less than 1.3, it may be similar to a spherical shape, and the arrangement and driving characteristics, which are characteristics of an ellipsoid, may not appear. When the ratio exceeds 5, there may be a problem of deterioration of driving ability. The inorganic particles in the ellipsoid hybrid particles are preferably 5 to 80% by weight. If it is less than 5% by weight, there may be a problem that the arrangement and driving characteristics due to the lack of magnetism, the property of the polymer particles disappear when it exceeds 80% by weight.

The ellipsoid hybrid particles were charged with a radical polymerization monomer, a dispersion stabilizer, a crosslinking agent and an initiator in a solvent, and then dispersed and polymerized under elevated temperature and stirring, but the total weight of the crosslinking agent was 100 wt% in total. 0.01 to 5% by weight of the ellipsoidal monodisperse polymer particles prepared in step 1, the step of introducing the magnetic inorganic particles into the prepared polymer particles and the ellipsoidal monodisperse polymer particles in which the magnetic inorganic particles are introduced and washed and dried It can be prepared including three steps.

The first step is a step of preparing the ellipsoidal polymer particles serving as a support through dispersion polymerization, mixing a radical polymerization monomer, a dispersion stabilizer, a crosslinking agent and an initiator in a reactor in a solvent and then carrying out dispersion polymerization by heating and stirring. . In particular, by limiting the input weight of the crosslinking agent as described above, it becomes possible to produce monodisperse particles of an ellipsoid which is not spherical.

The second step is a step of introducing magnetic inorganic particles into the surface of the polymer particles by a method such as co-precipitation method, electroless plating method or acid treatment adsorption method to produce magnetic hybrid particles, and the method of introducing magnetic inorganic particles is not particularly limited. No.

The third step is to remove the inorganic material that has not been adsorbed in the process of introducing the magnetic inorganic material to the surface of the polymer particles through a washing process to obtain powder particles through a drying process, only the magnetic hybrid particles to the final product through this process Obtained.

Hereinafter, the components used in the present invention will be described in detail.

(1) radically polymerizable monomers

The radically polymerizable monomer which can be used for producing the monodisperse polymer crosslinked particles of the present invention is not particularly limited. Specific radical polymerizable monomers that can be used include styrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene, m-ethylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, aromatic vinyl monomers such as m-chloromethyl styrene, styrene sulfonic acid, pt-butoxy styrene, mt-butoxy styrene, fluoro styrene, alpha methyl styrene, vinyl toluene and chloro styrene; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylic Rate, fluoroethyl acrylate, trifluoroethyl methacrylate, pentafluoropropyl methacrylate, fluoroethyl methacrylate, hexafluorobutyl (meth) acrylate, hexafluoroisopropyl methacrylate, perfluoroalkyl acrylate (Meth) acrylate monomers such as octafluorophenyl methacrylate; And vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ether, allyl butyl ether, allyl glycidyl ether, (meth) acrylic acid, unsaturated carboxylic acids such as maleic acid, alkyl (meth) acrylamide, (meth) acrylonitrile One or more compounds selected from the group consisting of vinyl cyanide monomers may be used. In the present invention, (meth) acrylate means methacrylate or acrylate.

In particular, the radically polymerizable monomer is preferably a (meth) acrylate monomer or an aromatic vinyl monomer capable of forming a copolymer thereof.

The amount of the radical polymerizable monomer added in the first step may be 1 to 50% by weight, preferably 5 to 20% by weight based on 100% by weight of the total of the radically polymerizable monomer, the initiator, the crosslinking agent, the dispersion stabilizer and the solvent. have.

(2) crosslinking agent (polyfunctional crosslinking monomer)

The polyfunctional crosslinking monomers that drive the elliptical growth of the particles include divinylbenzene, 1,4-divinyloxybutane, divinylsulphone, diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, tri Allyl compounds such as allyl trimellitate, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, 1,3-butanediol Methacrylate, 1,6-hexanediol dimethacrylate, pentaaryl tritol tetra (meth) acrylate, pentaaryl tritol tri (meth) acrylate, pentaaryl tritol di (meth) acrylate, Trimethylolpropane, tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaaryltritolpenta (meth) acrylate, glycerol tri (meth) acrylate and allyl One or more compounds selected from the group consisting of (meth) acrylates can be used.

The multifunctional crosslinking monomer added in the second step is 0.01 to 5% by weight, preferably 0.2 to 0.5% by weight, based on the total amount of the radically polymerizable monomer and the polyfunctional crosslinking monomer in total, and is preferably 0.2 to 0.5% by weight. The shape of the particles is determined.

(3) initiator

Examples of the initiator include benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, t-butylperoxy-2-ethylhexanoate and t-hexyl peroxy-2. Peroxides such as ethylhexanoate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; Azo reaction initiators, such as 2,2'- azobisisobutyronitrile, 2,2'- azobis2, 4- dimethylvaleronitrile, and 2,2'- azobis 2-methylisobutyronitrile, and ammonium One or more compounds selected from the group consisting of sulfate-based reaction initiators such as persulfate, potassium persulfate, sodium persulfate, ammonium bisulfate, and sodium bisulfate may be used.

The amount of the initiator added may be 0.05 to 10% by weight, preferably 0.1 to 3% by weight, based on 100% by weight of the total amount of the radical polymerizable monomer, the crosslinking agent, the initiator, the dispersion stabilizer, and the solvent.

(4) dispersion stabilizers

Examples of the dispersion stabilizer include cellulose derivatives such as methyl cellulose, ethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl methyl ether, polyacrylic acid, polyvinylacetate, polyvinylpyrrolidone, vinylpyrrolidone and vinyl acetate. One or more compounds selected from the group consisting of copolymers may be used, and preferably polyvinylpyrrolidone and polyvinyl alcohol may be used. The amount of the dispersion stabilizer used in the first step may be 0.5 to 15% by weight, preferably 1 to 6% by weight, based on 100% by weight of the total amount of the radical polymerizable monomer, the crosslinking agent, the initiator, the dispersion stabilizer and the solvent. .

(5) inorganic particles

As the magnetic inorganic particles introduced into the surface of the elliptic polymer particles in the second step, paramagnetic inorganic materials such as iron oxide, nickel, cobalt, chromium, platinum, manganese, aluminum and the like, and diamagnetic inorganic materials such as bismuth, antimony, gold and silver This may be used, and the kind thereof is not particularly limited.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are merely to illustrate the present invention, but it should be understood that the present invention is not limited thereto.

Example  One

Step 1: preparing elliptical polymer particles

In a 300 ml three-neck separate reactor equipped with a stirrer, 100 g of methanol and 1 g of polyvinylpyrrolidone K-90 were added thereto to prepare a reaction solvent. 0.1 g of 2,2'-azobisisobutyronitrile, 10 g of methyl methacrylate, and 0.05 g of allyl methacrylate were added to the reactor and polymerized at 200 rpm for 12 hours at a temperature of 60 ° C to shorten 21 microns of short axis of 7 microns. Dispersion ellipsoid particles were prepared. The particles were analyzed by SEM and shown in FIG. 1. It was confirmed that particles of ellipsoid of the same size and shape were prepared.

Step 2: Preparation of Magnetic Hybrid Particles

1 g of the elliptic polymer particles prepared above was dispersed in 50 g of distilled water solution in which 0.3 g of tin chloride and 0.7 g of hydrochloric acid were dissolved, and ultrasonic wave was applied at 200 W for 1 hour, followed by washing with distilled water several times. 1 g of the pore particles adsorbed with tin ions were dispersed again in 40 g of distilled water solution containing 0.003 g of palladium chloride and 1.7 g of hydrochloric acid, and ultrasonic wave was applied at 200 W for 1 hour, followed by washing 5 times using distilled water. 1 g of pore particles adsorbed on the surface and internal pores of the tin and palladium ions were dispersed in 50 g of an ionic nickel plating solution having a pH of 11 and stirred at 55 ° C. for 12 hours at 200 rpm to obtain nickel on the surface of the ellipse particles. Introduced magnetic hybrid particles were prepared.

Step 3: cleaning the magnetic hybrid particles

The nickel-coated hybrid particles dispersed in the plating solution prepared above were placed in a 100 ml plastic bottle for centrifugation and centrifuged at 1000 rpm for 1 minute to separate the plating liquid and the hybrid particles, and then 50 g of distilled water in a plastic container containing only the hybrid particles. After dispersing the hybrid particles in the washing solution, and centrifuged for 1 minute at 1000rpm again. The distilled water was added and washed three times to remove the plating liquid remaining in the remaining amount and the nickel fine powder remaining in the plating liquid without being coated on the polymer particles. The washed hybrid particles were dried for 1 hour at 80 ° C. nitrogen atmosphere to obtain powdered self-directed hybrid particles. The scanning microscope, the optical microscope, and the transmission electron microscope photograph of this ellipsoid hybrid particle were shown to FIG. 2, FIG. 3, and FIG.

Example  2

The same procedure as in Example 1 was carried out except that iron oxide (magnetite) was used instead of nickel as the magnetic inorganic material introduced into the polymer particles.

Example  3

The same procedure as in Example 1 was conducted except that iron oxide (maghemite) was used instead of nickel as the magnetic inorganic material introduced into the polymer particles.

Example  4

The procedure was the same as in Example 1 except that cobalt was used instead of nickel as the magnetic inorganic material introduced into the polymer particles.

Example  5

The size of the polymer support of the hybrid particles was proceeded in the same manner as in Example 1, except that particles having a long axis of 5.1 microns and a single axis of 3 microns were used.

Comparative example  One

The procedure was the same as in Example 1 except that the polymer particles of the ellipse were not hybridized without preparing a magnetic inorganic material.

Comparative example  2

The form of the polymer support of the hybrid particles was carried out in the same manner as in Example 1 except for using elliptical to spherical 10 micron particles.

Comparative example  3

The inorganic material introduced into the hybrid particles was carried out in the same manner as in Example 1 except that carbon black was used.

Experimental Example

It was intended to confirm the array driveability and the direction driveability of the particles prepared in Examples 1 to 5 and Comparative Examples 1 to 3.

A magnetic field was generated through a rare earth magnet having 2000 G (Gauss), and the particles were dispersed in ethylene glycol and dispersed between laminated transparent PET films, and then a magnetic field was generated around the film to drive the arrangement of the particles under an optical microscope. And confirming the direction driveability is shown in Table 1 below.

Long shaft length (㎛) Long axis / short drive
(1 = spherical) Inorganic particles Mineral
Remaining weight (% by weight) Array driveability Directional driveability Example 1 20 3 nickel 21 O O Example 2 20 3 Magnetite 18 O O Example 3 20 3 Maghemite 14 O O Example 4 20 3 cobalt 12 O O Example 5 5 1.7 nickel 28 O O Comparative Example 1 20 3 none 0 X X Comparative Example 2 10 One nickel 23 O X Comparative Example 3 20 3 Carbon black 16 X X

From the results of Table 1, in the case of using the magnetic hybrid particles having an elliptic form according to the present invention, it can be seen that the characteristics of the array driveability and the direction driveability in accordance with the control of the artificial magnetic field, both of which are not elliptical The spherical hybrid particles exhibited characteristics that were arranged according to the magnetic field, but it was confirmed that there was no direction driving ability to drive the magnetic directions. A graph and a description of confirming such three-dimensional driving are shown in FIG. 4. As shown in FIG. 4, when the magnetic field was applied in the horizontal direction, the horizontal direction was uniformly arranged, but when the magnetic field was applied in the vertical direction, the alignment was performed in the vertical direction.

Therefore, according to the manufacturing method of the present invention, it was confirmed that the self-directed hybrid particles capable of regular arrangement and three-dimensional driving according to the control of the magnetic field.

Claims (12)

delete delete delete A radical polymerizing monomer, a dispersion stabilizer, a crosslinking agent and an initiator are added to a solvent, and the weight of the crosslinking agent is 0.01 to 5 wt% based on 100% by weight of the total of the radical polymerizable monomer, the initiator, the crosslinking agent, the dispersion stabilizer and the solvent. 1 step of preparing the particles;
Step 2 of introducing the magnetic inorganic particles into the prepared polymer particles and
Three steps of washing and drying the ellipsoidal monodisperse polymer particles into which the magnetic inorganic particles are introduced
Method for producing an ellipsoidal hybrid particle incorporating inorganic particles having a magnetic property.
The method according to claim 4, wherein the radically polymerizable monomer is styrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene, m-ethylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, m-chloromethylstyrene, styrenesulfonic acid, pt-butoxystyrene, mt-butoxystyrene, fluorostyrene, alphamethylstyrene, vinyltoluene, chlorostyrene, methyl (meth) acrylate, ethyl (meth) acrylate , Butyl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, fluoroethyl acrylate, trifluoroethyl methacrylate , Pentafluoropropyl methacrylate, fluoroethyl methacrylate, hexafluorobutyl (meth) acrylate, hexafluoroisopropyl methacrylate, perfluoroalkyl acrylate, octafluorope Methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ether, allyl butyl ether, allyl glycidyl ether, (meth) acrylic acid, maleic acid, alkyl (meth) acrylamide and (meth) acrylonitrile Method for producing an ellipsoid hybrid particle, characterized in that at least one compound selected from the group consisting of.
The method for producing an ellipsoid hybrid particle according to claim 4, wherein an input weight of the radical polymerizable monomer is 1 to 50% by weight based on 100% by weight of the total of the radical polymerizable monomer, initiator, crosslinking agent, dispersion stabilizer and solvent. .
The method of claim 4, wherein the crosslinking agent is divinylbenzene, 1,4-divinyloxybutane, divinyl sulfone, diallyl phthalate, diallyl acrylamide, triallyl (iso) cyanurate, triallyl trimellitate, Hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, 1,3-butanediol methacrylate, 1,6-hexane Diol dimethacrylate, pentaaryl tritol tetra (meth) acrylate, pentaaryl tritol tri (meth) acrylate, pentaaryl tritol di (meth) acrylate, trimethylolpropane, tri (meth) acrylic Selected from the group consisting of latex, dipentaaryltritol hexa (meth) acrylate, dipentaaryltritolpenta (meth) acrylate, glycerol tri (meth) acrylate and allyl (meth) acrylate Method for producing an ellipsoid hybrid particle, characterized in that at least one compound.
The method of claim 4, wherein the initiator is benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t- butyl hydroperoxide, t- butyl peroxy-2-ethyl hexanoate, t -Hexyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,2'-azobisisobutyronitrile, 2,2'- Selected from the group consisting of azobis2,4-dimethylvaleronitrile, 2,2'-azobis2-methylisobutyronitrile, ammonium persulfate, potassium persulfate, sodium persulfate, ammonium bisulfate and sodium bisulfate Method for producing an ellipsoid hybrid particle, characterized in that at least one compound.
The method of claim 4, wherein the input weight of the initiator is 0.05 to 10% by weight based on 100% by weight of the total of the radically polymerizable monomer, the crosslinking agent, the initiator, the dispersion stabilizer and the solvent.
5. The dispersion stabilizer according to claim 4, wherein the dispersion stabilizer is methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl methyl ether, polyacrylic acid, polyvinylacetate, polyvinylpyrrolidone and vinylpyrrolidone-vinylacetate. Method for producing an ellipsoid hybrid particles, characterized in that at least one compound selected from the group consisting of copolymers.
The method of claim 4, wherein the input weight of the dispersion stabilizer is 0.5 to 15% by weight based on 100% by weight of the total amount of the radical polymerizable monomer, the crosslinking agent, the initiator, the dispersion stabilizer and the solvent.
The method of claim 4, wherein the magnetic inorganic particles are iron oxide, nickel, cobalt, chromium, platinum, manganese, aluminum, bismuth, antimony, gold or silver.

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