KR20060102368A - Polymer macroparticle of which surface is modified by mesoparticle and nanoparticle, nanoparticle-polymer composite using the same, and preparation thereof - Google Patents

Abstract

According to the present invention, a composite of nanoparticles-mesoparticles-macroparticles is attached to mesoparticles and nanoparticles on the surface of the polymer macroparticles by mechanical means selected from impact striking means, drop mixing means, and high speed spraying means. By forming the structure and optionally heat-treating the nanoparticles or mesoparticles to the macroparticle surface, polymer macroparticles surface-modified with mesoparticles and nanoparticles can be produced simply and easily. In addition, nanoparticle-polymer composites can be provided from polymer macroparticles surface-modified with mesoparticles and nanoparticles.

Nanoparticles, Mesoparticles, Macroparticles, Polymers, Impact Strike, Composites

Description

POLYMER MACROPARTICLE OF WHICH SURFACE IS MODIFIED BY MESOPARTICLE AND NANOPARTICLE, NANOPARTICLE-POLYMER COMPOSITE USING THE SAME, AND PREPARATION THEREOF}

1 is an explanatory diagram conceptually showing the shape of a nanoparticle-mesoparticle-macroparticle composite prepared according to the present invention,

Figure 2 is an explanatory view conceptually showing the shape of the composite material of a multi-layer structure manufactured according to the present invention.

The present invention relates to a polymer macroparticles surface-modified with nanoparticles and mesoparticles, nanoparticle-polymer composites using the same and a method for producing the same. More particularly, the present invention relates to polymer macroparticles having a surface modified by attaching nanoparticles and mesoparticles, nanoparticle-polymer composite materials obtained by kneading these macroparticles, and a method of manufacturing the same.

Until now, many studies have been conducted to develop nanoparticle-polymer complexes and methods for preparing the same.

Conventional systems for incorporating and dispersing nanoparticles into a polymer matrix are satisfactory due to changes in the state of the nanoparticles due to the high surface energy of the nanoparticles and particle size changes due to the secondary aggregation of the nanoparticles and thus phase separation from the matrix material. It does not exhibit the unique composite material properties.

Systems for mixing nanoparticles and monomers and polymerizing them [eg. Polym. Composites 1996, 7, 125, J. Appl. Polym. Sci. 1995, 55, 371, J. Appl. Polym. Sci. 1996, 60, 323] undergoes two steps: polymerisation of monomers in the presence of nanoparticles and reduction of metal ions dispersed in this polymerized matrix, since metallization and reduction occur separately. It has been accompanied with a problem that is not well dispersed in the polymer matrix.

A system for preparing nanoparticles from nanoparticle precursors after mixing the nanoparticle precursors with the polymer [eg. Chem. Commun., 1997, 1081; Korean Patent No. 10-0379250; In Korean Patent Publication No. 2330-0082064, the nanoparticle precursor is reduced by UV or gamma ray to form nanoparticles in the polymer, but the nanoparticle precursor must be uniformly mixed with the polymer. Limited.

Nanoparticles of transition metals such as gold (Au), silver (Ag), palladium (Pd), platinum (Pt), etc., are in the form of agglomerated powders or are sensitive to the atmosphere and tend to be irreversibly agglomerated. Agglomeration results in a separation process that cannot narrow the particle size distribution and prevents the easy formation of essential soft thin films, such as magnetic recording applications. In addition, nanoparticle aggregates reduce chemically active surface areas for catalysis and the like and greatly limit solubility.

On the other hand, conventionally, solidification prevention of solid particles, prevention of discoloration change, improvement of dispersibility, improvement of fluidity, improvement of catalytic effect, control of digestion and absorption, improvement of magnetic properties, improvement of color tone, improvement of light resistance, usefulness (high price) For the purpose of saving materials, various surface modifications have been performed by electrochemical methods, physical adsorption methods, chemical adsorption methods, vacuum deposition methods, electrostatic deposition methods, coating methods of dissolved materials, special spray drying methods, and fluid coating methods. In particular, when the surface of the solid particles is surface-modified as solid particles, that is, the surface of the powder is powdered, or when the surface of the solid particles is surface-modified as a suspension of fine particles of various substances and the dissolution of various substances, as a melt Although a variety of well-known mixer-type or ball-mill stirrers were used for a long time (several hours to several tens of hours), the electrostatic phenomena, gentle drying phenomena, and mechanochemical phenomena caused by the agitation were melted and modified. The adhesion of the particles or the film forming material to the particles is insufficient or the force applied to the parent particles is not uniform, so that the formation of the film is not uniform. Therefore, the powder after modification is mixed, kneaded, dispersed, In the case of processing such as pasting, the operation conditions are expressed by simple dropping of the particles or segregation of components. In addition to the jaehan, is the cause of the maximum dispersion occurs in the quality of the product after processing.

For example, in Korean Patent No. 90-001366, impact impact means is applied to the surface of the large particles (parent particles) constituting the powder to other solid particles (own particles) or liquid bodies having a relatively smaller size than the large particles. The method of immobilizing is disclosed. However, when the nanoparticles (subparticles) are to be attached to the surface of the macroparticles (parent particles) described above, since the nanoparticles (subparticles) adhere to the surfaces of the macroparticles (parent particles), significant aggregation occurs. It is difficult to produce nanoparticle-polymer composites in which particles are dispersed without aggregation.

Therefore, the present inventors have diligently studied to attach nanoparticles to the surface of polymer macroparticles without aggregation, and as a result, mesoparticles and / or smaller than macroparticles on the surface of macroparticles by mechanical means such as impact striking means, and / or By attaching nanoparticles smaller in size than mesoparticles simultaneously, sequentially, or alternately, the surface area can be increased while limiting the size of the macroparticles, thereby preventing excessive aggregation of nanoparticles attached to the surface of the macroparticles. to provide.

Another object of the present invention is to provide a nanoparticle-polymer composite prepared by kneading the surface modified polymer macroparticles described above.

One object of the present invention is to fix the mesoparticles and nanoparticles on the surface of the polymer macroparticles by using mechanical means such as impact striking means, drop mixing means, high-speed spray means, surface with nanoparticles It is to provide a modified polymer and a method of making the same.

Another object of the present invention is to provide a nanoparticle-polymer composite using the polymer surface-modified with the obtained nanoparticles.

The present invention is explained in more detail below.

In the present invention, there are no limitations on the kind of polymer used as the polymer macroparticles, but specific examples are as follows: polyethylene-based resins such as low density polyethylene resin (LDPE), ultra low density polyethylene resin (LLDPE), High density polyethylene (HDPE), ethylene-vinylacetate resin (EVA), copolymers thereof, and the like; Polystyrene-based resins such as HIPS, GPPS, SAN and the like; Polypropylene-based resins such as HOMO PP, RANDOM PP, copolymers thereof; Transparent or general ABS (acrylonitrile-butadiene-styrene terpolymer); -Rigid PVC; Engineering plastics such as nylon, PRT, PET, POM (acetal), PC, urethane, powder resin, PMMA, PES, etc.

In the present invention, the size of the macroparticles is 100 ~ 500 ㎛, the size of the meso particles 1 ~ 10 ㎛, the size of the nanoparticles is 5 ~ 500 nm. Crushing the polymer particles can be done using a common mill.

The mesoparticles may be similar or identical to the material of the macroparticles or nanoparticles. Specifically mention may be made of polymer filler materials, such as polymers identical or similar to macroparticles, silica, titania, alumina, calcium carbonate and the like.

The nanoparticles are not particularly limited, and may be made of metal, inorganic, organic, or a composite material thereof, and specifically, mention may be made of transition metal, gold, or silver.

The mesoparticles and nanoparticles described above may be supplied in powder form, but may be supplied in the form of a colloidal solution. In the case of the colloidal form, it can be applied to the surface of the macroparticle by spraying in the form of microdroplets.

In the present invention, the relative size of the macroparticles, mesoparticles or nanoparticles, based on their average particle size, the macroparticles and mesoparticles 20 to 100: 1, the meso particles and nanoparticles 20: It may be 1 to 100: 1, but can be adjusted as needed. For example, when the polymer macroparticles have an average particle size of 200 to 400 μm, the mesoparticles of calcium carbonate or another polymer may have an average particle size of 2 to 10 μm, and the silver nanoparticles have an average particle size of 40 to 200 nm. It may have a particle size.

In the present invention, the attachment of mesoparticles or nanoparticles to the surface of the macroparticles is achieved by mechanical means such as impact striking means, drop mixing means or high speed spraying means as well as electrostatic adsorption force between the particles. As the impact striking means, it may be desirable to use an impact striking means such as an impact crushing device equipped with a cutter that rotates at high speed. As an example of the impact striking means, a device disclosed in Korean Patent No. 1990-001366 or a commercially available device having a similar function (eg, HYBRI-DIC manufactured and sold by Dongmyung) can be mentioned. In the impact impact device mentioned, the mesoparticles / nanoparticles can be embedded or firmly fixed on the surface of the macroparticles since the impact operation is repeated several times in succession within a short time (seconds-minutes).

According to one embodiment of the present invention, a commercially available polymer chip is pulverized to an average particle size of 200 μm in an impact mill to produce polymer macroparticles, and carbonic acid having an average particle size of 2 μm is heated and circulated through the prepared macroparticles. A calcium solution and a silver nanoparticle colloidal solution having an average particle size of 20 nm are sprayed on the macroparticles sequentially, alternately or simultaneously, and the solvent is gradually removed. The macroparticles treated with mesoparticles / nanoparticles are introduced into the impact mill again and again, and the grinding and circulation are repeated to crush the agglomerated macroparticles again, and to reduce the amount of mesoparticles / nanoparticles applied to the macroparticles. Can be increased.

1 is an explanatory view conceptually showing the shape of the nanoparticle-mesoparticle-macroparticle composite prepared according to the present invention. Mesoparticles 2 attached to the macroparticles 1 significantly increase the surface area, and the nanoparticles 3 are dispersed on the surfaces of the macroparticles 1 and the mesoparticles 2.

Figure 2 is an explanatory view conceptually showing the shape of the composite material of a multi-layer structure manufactured according to the present invention. In the upper right box, the nanoparticles 1 attached between the macroparticles 1 and the mesoparticles 2 are only shown in the upper right box, where the mesoparticles and nanoparticles are sprayed simultaneously or alternately several times. It has been shown that a multi-layer structure can be formed on the macroparticle surface.

In the method of the present invention, it is preferable to adjust the grinding conditions, the circulation conditions and / or the working temperature to the polymer macroparticles to induce static electricity, it is possible to install an electrostatic device if necessary. Electrostatic-induced macroparticles can not only enhance the adsorption of mesoparticles / nanoparticles but also increase agglomeration between macroparticles, but the agglomerated macroparticles are pulverized by an impact mill in a repeated circulation process.

The mesoparticles used in the present invention are preferably made of the same or similar material as the macroparticles or made of a material that helps the macroparticles and the nanoparticles bind. In addition, mesoparticles and nanoparticles may be composed of a single component or multicomponent. That is, by using a colloidal solution of a mixture or a mixture containing silver nanoparticles and other metal or inorganic nanoparticles, aggregation of a target material to be dispersed without aggregation, for example, silver nanoparticles, may be suppressed as much as possible.

According to another embodiment of the present invention, generally, a commercially available polymer chip is pulverized to an average particle size of 200 μm to prepare polymer macroparticles, and the prepared macroparticles are treated under heating in a mixing apparatus such as a mixer to induce static electricity, Here, a calcium carbonate solution having an average particle size of 2 µm and a silver nanoparticle colloidal solution having an average particle size of 20 nm are sprayed on the macroparticles sequentially, alternately or simultaneously, to remove the solvent. Introduction of mesoparticles and nanoparticles is preferably carried out several times, but is not essential. Mixing devices such as mixers or kneaders may use a general mixer or kneader, but a drop-type mixing device such as a V-type mixer or an O type circulating grinding mixer is preferable.

According to another embodiment of the present invention, the macroparticles treated with nanoparticles and mesoparticles are optionally heat treated to soften and melt all or part of the nanoparticles and mesoparticles, thereby fixing them on the surface of the macroparticles. It is possible to prevent the nanoparticles and the mesoparticles from being detached from the macroparticles in the impact grinding or circulation process. Furthermore, it is also possible to produce polymer particles having a multi-layer structure by forming a film on the surface of macroparticles treated with nanoparticles / mesoparticles through this heat treatment.

According to another embodiment of the present invention, it is possible to use an ultrasonic grinding device for preventing the aggregation of the nanoparticles on the macroparticles and for pulverizing the aggregated nanoparticles.

Another object of the present invention is to provide an apparatus for implementing the above-described method, comprising: an impact chamber provided with impact impact means; a supply port for supplying macroparticles to the impact chamber; A circulation passage communicating with the supply port, a meso particle supply port and a nano particle supply port provided in the circulation path, and in some cases, electrostatic means and ultrasonic grinding means for causing static electricity to the circulating macroparticles.

The nanoparticle-mesoparticle-macroparticle multilayer structure composite material thus prepared may be kneaded to prepare a nanoparticle-polymer composite material.

According to one preferred method of the invention, the macroparticles are polymer particles, the mesoparticles are inorganic or organic particles, and the nanoparticles are composed of inorganic or metal particles. For example, the macroparticles may be nylon 12, the mesoparticles may be titanium dioxide particles, the nanoparticles may be silver nanoparticles or silver or silica or titania particles supported thereon.

Although the present invention has been described in terms of preferred embodiments by way of example, the present invention is not limited to the above embodiments and those skilled in the art without departing from the spirit of the present invention. Various changes and modifications will be possible.

According to the present invention, there is provided a method for easily and easily preparing a nanoparticle-polymer composite material while preventing the problem of aggregate formation between nanoparticles, which is a problem of the existing composite material process.

Claims (7)

A macroparticle polymer surface-modified with mesoparticles and nanoparticles, wherein the mesoparticles and nanoparticles are attached to the surface of the polymer macroparticles to have a complex structure of nanoparticles-mesoparticle-macroparticles. The macroparticle polymer of claim 1, wherein the mesoparticles described above are polymer particles or inorganic particles, and the nanoparticles are inorganic or metal particles. The macroparticle polymer surface-modified with mesoparticles and nanoparticles according to claim 1, wherein the nanoparticles are silver nanoparticles or silver-supported inorganic particles. Mesoparticles and nanoparticles are attached to the surface of the polymer macroparticles by mechanical means selected from impact striking means, drop mixing means, and high speed spraying means to form a composite structure of nanoparticle-mesoparticle-macroparticles, A method of producing a macroparticle polymer surface-modified with mesoparticles and nanoparticles, characterized in that the nanoparticles or mesoparticles are adhered to the macroparticle surface by heat treatment in some cases. Mesoparticles and nanoparticles are attached to the surface of the polymer macroparticles so that the mesoparticles having a complex structure of nanoparticles-mesoparticles-macroparticles and the surface-modified macroparticle polymers are mixed and kneaded with any polymer. Characterized in that the nanoparticle-polymer composite material. Nanoparticle-polymer composite prepared according to the method of claim 5. An impact chamber provided with impact striking means, a supply port for supplying macroparticles to the impact chamber, a circulation passage communicating from the outlet of the impact chamber to the supply port, a meso particle supply port and a nano particle supply port provided in the circulation path, and the case Apparatus for producing surface-modified polymer macroparticles having a composite structure of nanoparticle-mesoparticle-macroparticles, comprising electrostatic means and ultrasonic grinding means for causing static electricity in the circulating macroparticles.

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