KR101238827B1 - Method of preparing thermally-stable core-shell block copolymer-nanocomposite and thermally-stable core-shell block copolymer-nanocomposite made by the same - Google Patents
Method of preparing thermally-stable core-shell block copolymer-nanocomposite and thermally-stable core-shell block copolymer-nanocomposite made by the same Download PDFInfo
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Abstract
The present invention relates to core-shell nanoparticles having excellent thermal stability and a method of manufacturing the same, and in particular, a block made through reversible addition-fragmentation chain transfer polymerization (RAFT), which is one of living free radical methods. A method of preparing a nanoshell block copolymer composite having a core shell structure having excellent thermal stability, by introducing a photocrosslinking group into a copolymer and reacting it with nanoparticles, and then irradiating with light to form a shell around the nanoparticles. And it relates to a nanoparticle block copolymer composite having a core shell structure excellent heat safety prepared thereby.
Description
The present invention relates to core-shell nanoparticles having excellent thermal stability and a method of manufacturing the same, and in particular, a block made through reversible addition-fragmentation chain transfer polymerization (RAFT), which is one of living free radical methods. A method of preparing a nanoshell block copolymer composite having a core shell structure having excellent thermal stability, by introducing a photocrosslinking group into a copolymer and reacting it with nanoparticles, and then irradiating with light to form a shell around the nanoparticles. And it relates to a nanoparticle block copolymer composite having a core shell structure excellent heat safety prepared thereby.
Nanoparticles refer to particles having a size of about 1 nm to about 100 nm. Nanoparticles have a relatively large surface area compared to the volume of the particles, which exhibits electrical, optical and magnetic properties that are different from those of bulk materials. Recently, optical devices, light emitting devices, metal catalysts and the like manufactured by applying the properties of such nanoparticles are widely distributed in the market.
The biggest problem in using such nanoparticles in various devices is the aggregation of nanoparticles. Since the aggregation of such nanoparticles degrades the electrical, optical, and magnetic properties of the nanoparticles, which in turn lowers the quality of the device, efforts to prevent the aggregation of such nanoparticles and to disperse them in a solvent are continuously progressed.
Polymer-nanoparticle hybrids have attracted great interest in many applications, including optical bandgap materials, nanostructured solar cells, light emitting diodes, and storage devices. In addition, the properties of most polymers, such as mechanical strength, conductivity, and rheological properties, can be greatly improved by introducing nanoparticles into the polymer chain. For these applications it is basically necessary to mix the nanoparticles with the polymer while completely dispersing the nanoparticles into the polymer chain. A good strategy to increase dispersion is to commercialize the shell of the polymer into the nucleus of the inorganic nanoparticles to change the interface between the nanoparticle surface and the polymer chain. Several studies have involved careful selection of polymer chains in homopolymers, random copolymers, block copolymers, and mixtures of other polymers, so that not only the dispersion of nanoparticles, but also the precise location within the composite controls the nature of the interface between nanoparticles and polymer chains. It has been shown that you can.
Gold nanoparticles, among others, have received considerable academic interest for their applications in a wide range of applications, ranging from catalysts, sensors, biopharmaceuticals, and precise sizing capabilities ranging from 1 to 100 nm. Another advantage of gold nanoparticles is that the terminal thiol groups can be controlled and controlled by the easy grafting of the areal density of the polymer on the surface of the gold nanoparticles. In addition, the ability to absorb light in the visible region, as well as the strong contrast of gold nanoparticles and polymers in electron microscopy, makes a model study of the effect of gold nanoparticles suitable. Despite these advantages, the biggest obstacle to the study of thiol-based ligands that stabilized gold nanoparticles was the reversibility of the gold-thiol bonds, which caused the ligand to fall off at temperatures above 60 ° C. This serious limitation limited most of the applications mentioned above.
Recent studies have shown that the stability of gold-thiol bonds has been enhanced by crosslinking the polymer micelle shells surrounding the gold nanoparticles or by introducing two or more thiol-based anchoring groups at the polymer chain ends. However, these methods are still unstable due to lack of thermal stability and have the disadvantage of requiring multi-step synthesis. Recent studies have shown the synthesis of stable gold nanoparticles surrounded by polymers by the formation of copolymers consisting of monomers and crosslinkable functional groups. Dong, HC; Zhu, M. Z; Yoon, JA; Gao, HF; Jin, RC; Matyjaszewski, K. Journal of the american chemical Society 2008, 130 , 12852.] However, this study has limited the degree of control through a single step process and the thermal stability of the manufactured nanoparticles is maintained at only 110 ° C.
The present invention provides a method for producing a nanoshell block copolymer composite having a high thermal stability coreshell structure that does not dissociate bonds even at high temperature in order to solve the above problems, and a nanoshell having a coreshell structure excellent thermal safety prepared thereby It is an object to provide a block copolymer composite.
In addition, an object of the present invention is to provide a film in which the nanoparticle block copolymer composite having a core shell structure excellent in thermal stability is dispersed.
In addition, an object of the present invention is to provide a matrix in which the nanoparticle block copolymer composite having a core shell structure excellent in thermal stability is dispersed.
The present invention for the above purpose
i) reacting the vinyl aromatic monomer A, the initiator and the chain transfer agent to perform a reversible addition-breaking chain transfer polymerization reaction;
ii) synthesizing the block copolymer by polymerizing a monomer B and an initiator represented by the following Formula (1) to the polymer obtained in step i);
(In the above formula (1), Y represents an alkyl group having 1 to 10 carbon atoms which may include a hydroxy group or a carboxy group, and Z represents a halogen atom).
iii) stopping the polymerization reaction by adding a polymerization terminator to the block copolymer produced in step ii);
iv) replacing the halogen atom of the block copolymer with a photocrosslinking group; And
v) dissolving the block copolymer in which the photocrosslinking group is introduced into an ultraviolet light-permeable solvent;
vi) preparing a nanoparticle aqueous solution and adding the aqueous nanoparticle solution to a UV-permeable solvent in which the block copolymer into which the photocrosslinking group is introduced is prepared to prepare a nanoparticle block copolymer composite; And
vii) irradiating the aqueous solution of the nanoparticle block copolymer composite prepared in step vi) with ultraviolet light to crosslink the photocrosslinking group; providing a method of manufacturing a nanoshell block copolymer composite having a high thermal stability core shell structure do.
In the present invention, the vinyl monomer A in step i) is styrene; Divinylbenzene; Ethyl vinyl benzene; Paramethylstyrene; Fluorostyrenes; Vinylpyridine; Vinyl chloride; Acrylonitrile; Methacrylonitrile; Butyl acrylate; 2-ethylhexylethyl acrylate; Glycidyl acrylate; N, N'-dimethylaminoethyl acrylate; Butyl methacrylate; 2-ethylhexylethyl methacrylate; Methyl methacrylate; 2-hydroxyethyl methacrylate; Glycidyl methacrylate; Polyethylene glycol diacrylate; 1,3-butylene glycol diacrylate; 1,6-hexanediacrylate; Ethylene glycol dimethacrylate; Diethylene glycol dimethacrylate; Triethylene glycol dimethacrylate; Polyethylene glycol dimethacrylate; And it is selected from the group consisting of 1,3-butylene glycol dimethacrylate, the vinyl monomer A in step i) is preferably styrene.
In the present invention, the monomer B in the step ii) is p-chloromethylstyrene provides a method for producing a nanoshell block copolymer composite having a good thermal stability core shell structure.
In the present invention, the monomer A and the monomer B in the step ii) is a nanoshell block having excellent thermal stability core shell structure that the monomer B is polymerized in a ratio of 30 to 50 parts by weight per 100 parts by weight of the monomer A. Provided are methods for preparing the copolymer composite.
In the present invention, the chain transfer agent in step i) is a dithio ester type represented by the following general formula (2), preferably of the excellent core shell structure of excellent thermal stability, characterized in that the methyl ester benzyldithiol It provides a method for producing a nanoparticle block copolymer composite.
(In the formula (2), R is
In the present invention, the initiator in step i) and ii) is one or two or more selected from oxygen, hydroperoxide, perester, percarbonate, peroxide, persulfate and azo system. It provides a nanoshell manufacturing method of the core shell structure excellent thermal stability.
In the present invention, the photocrosslinking group in step iv) is an amine group, an azido group, a hydroxyl group, a carboxyl group, a sulfhydryl group, and a carbo. The present invention provides a method for preparing nanoparticles having a core shell structure having excellent thermal stability, which is a hydrate (carbohydrate) and derivatives thereof.
In the present invention, the UV-permeable solvent in the step v) is a dioxane or chloroform provides a method of producing a nanoshell block copolymer composite having excellent thermal stability core shell structure.
In the present invention, in step vii), the nanoshell block of the core shell structure having excellent thermal stability is characterized in that crosslinking of the optical crosslinking is performed by irradiating light having a wavelength of 200 nm to 350 nm for 1 minute to 60 minutes. Provided are methods for preparing the coalesced composites.
In the present invention, the nanoparticles in step vi) are Zn, Cd, Hg, Pb, Sn, Ge, Ga, In, Tl, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Any one selected from the group consisting of Y, Zr, Nb, Mo, Tc, Pd, Ag, Au, and Pt, preferably Au is a core-shell nanoparticle block air having excellent thermal stability, characterized in that Au Provided are methods for preparing the coalesced composites.
In the present invention, the block copolymer provides a method for producing a nanoparticle block copolymer composite having a core shell structure having excellent thermal stability, characterized in that the total molecular weight is 1000g / mol-3000g / mol.
The present invention provides a nanoshell block copolymer composite having a core shell structure excellent in thermal stability produced by the production method of the present invention.
In addition, the present invention provides a film including the nanoparticle block copolymer composite having a core shell structure excellent in thermal stability produced by the production method of the present invention.
In addition, the present invention provides a matrix comprising a nanoshell block copolymer composite having a core shell structure excellent in thermal stability prepared by the production method of the present invention.
Hereinafter, the present invention will be described in detail.
The present invention prepares block copolymers using the reversible addition split chain transfer polymerization method.
Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) is one of the living free radical methods. Living free radical polymerization, which is attracting attention recently, is considered to be an important tool for synthesizing polymers with various reactors and high dimensional structures because a relatively narrow molecular weight distribution can be obtained under much milder conditions than ion polymerization. have. There are three types of living radical polymerizations known to date: nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible addition fragmentation chain transfer polymerization (RAFT).
Among these, RAFT (reversible addition-breaking chain transfer polymerization method) generates stable free radicals by an initiator, and the chain transfer agent binds to and ends with a chain where radicals exist by using a chain transfer agent as a chain end stopper. As the reaction occurs reversibly, the growth reaction proceeds in such a way that the monomers are added and stretched. The chain transfer agent is used to control the reactivity of radicals to synthesize polymers of desired molecular weight and low molecular weight distribution. The reaction mechanism of the block copolymer prepared by the reversible addition-break chain transfer polymerization method is as follows.
Vinyl monomer A in the step i) used in the present invention can be used as long as the radical initiation, which is used in general dispersion polymerization, emulsion polymerization or suspension polymerization and the like. Preferably aromatic vinyl compounds; Cyan vinyl compound; Acrylate compound; Methacrylate type compounds; Diacrylate type compound; And dimethacrylate type compound etc. can be used together 1 type (s) or 2 or more types. Specifically, styrene; Divinylbenzene; Ethyl vinyl benzene; Paramethylstyrene; Fluorostyrenes; Vinylpyridine; Vinyl chloride; Acrylonitrile; Methacrylonitrile; Butyl acrylate; 2-ethylhexylethyl acrylate; Glycidyl acrylate; N, N'-dimethylaminoethyl acrylate; Butyl methacrylate; 2-ethylhexylethyl methacrylate; Methyl methacrylate; 2-hydroxyethyl methacrylate; Glycidyl methacrylate; Polyethylene glycol diacrylate; 1,3-butylene glycol diacrylate; 1,6-hexanediacrylate; Ethylene glycol dimethacrylate; Diethylene glycol dimethacrylate; Triethylene glycol dimethacrylate; Polyethylene glycol dimethacrylate; And 1,3-butylene glycol dimethacrylate, and preferably styrene, but is not necessarily limited thereto. At this time, the surface shape of the particles to be produced will vary depending on the type of monomer used.
The initiator in step i) used in the present invention has a property of initiating radical decomposition and addition polymerization of monomers in the presence of heat and a reducing substance. As the initiator, known fat-soluble or water-soluble initiators are used. Preferably, one or a mixture of two or more selected from oxygen, hydroperoxide, perester, percarbonate, peroxide, persulfate and azo initiator may be used. For example, acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate; Benzoyl peroxide; 2,2'-azobisisobutyronitrile;Azobis-2,4-dimethylvaleronitrile; Azobis (4-methoxy-2,4-dimethylvaleronitrile); Di-isopropyl peroxydicarbonate; Di-2-ethylhexyl peroxydicarbonate; Dioctoxyethyl peroxydicarbonate; α-cumyl peroxyneodecanate; t-butyl peroxy neodecanate, etc. can be used.
The use of various chain transfer agents in reversible addition- splitting chain transfer polymerization allows the molecular weight to be arbitrarily controlled and a very narrow molecular weight distribution can be obtained. The chain transfer agent in step i) used in the present invention is dithioester, or dithiocarbamate, xanthaite, benzyl dithio, represented by the following formula (2): Benzoate, cumyl dithiobenzoate, 1-phenylethyl dithio benzoate, S- (thiobenzoyl) thioglycolic acid, preferably methyl ester benzyldithiol. However, the present invention is not limited thereto.
(In the formula (2), R is
Next, in step ii), a block copolymer is synthesized by polymerizing a monomer B and an initiator represented by the following formula (1) to the polymer obtained in step i). The monomer B in step ii) used in the present invention is p-chloromethyl styrene, and 30 to 50 parts by weight is added per 100 parts by weight of the vinyl aromatic monomer A.
Thereafter, step iii) is added to stop the polymerization reaction by adding a polymerization terminator to the block copolymer produced in step ii). The polymerization terminator may be an alcohol having 1 to 20 carbon atoms, alkyl or cycloalkyl monoether having 2 to 20 carbon atoms, ammonia, water, alkyl or aryl amine, and mixtures thereof, but is not limited thereto.
Iv) substituting a halogen atom of the block copolymer with a photocrosslinking group; And v) dissolving the block copolymer into which the photocrosslinking group is introduced into an ultraviolet-transmissive solvent; vi) preparing a nanoparticle aqueous solution and adding the aqueous nanoparticle solution to a UV-permeable solvent in which the block copolymer into which the photocrosslinking group is introduced is prepared to prepare a nanoparticle block copolymer composite; And vii) irradiating the nanoparticle block copolymer composite aqueous solution prepared in step vi) with ultraviolet light to crosslink the photocrosslinking group.
A bond formed as a bridge between atoms and atoms in a chain is called a crosslink. Among them, a bond by light is called a photocrosslink. The photocrosslinking group in step iv) is an amine group, an azido group, a hydroxyl group, a carboxyl group, a sulfhydryl group, a carbohydrate, It is preferably a derivative thereof, and more preferably, it may be an azido group, but is not necessarily limited thereto. Photocrosslinking groups, which serve as intermolecular linkages for photocrosslinking, form bonds through free radicals induced by UV irradiation. For example, when azido groups are exposed to light, they provide free radicals to the polymer through decomposition of the azido groups, and crosslinking occurs at the starting point.
The block copolymer synthesized by the above steps is preferably a total molecular weight of 1000g / mol-3000g / mol. However, since the molecular weight of the core-shell nanoparticles is higher, the dispersibility in the solvent of the nanoparticles is lowered, so that the molecular weight of the core-shell nanoparticles is greater than 1000 g / mol, which is a minimum molecular weight containing at least two or more blocks required for the block copolymer, but does not exceed 3000 g / mol. desirable.
As the UV-permeable solvent used in step v), preferably, an organic solvent capable of dissolving the vinyl monomer and water are mixed and used as a cosolvent. The organic solvent that can be used is preferably one or two or more selected from alcohols, ether alcohols, ketones and phenyls. For example, methanol; ethanol; Isopropyl alcohol; Butyl alcohol; Octyl alcohol; Benzyl alcohol; Cyclohexanol; Ethylene glycol; Glinerol; Diethylene glycol; Methyl cellosolve; Cellosolves; Butyl cellosolve; Isopropyl cellosolve; Ethylene glycol monomethyl ether; Ethylene glycol monoethyl ether; Diethylene glycol monomethyl ether; Diethylene glycol monoethyl ether; Acetone; Methyl ethyl ketone; Methyl isobutyl ketone; Chlorobenzene; benzene; Toluene or the like may be used, and preferably dioxane or chloroform.
In step vi), the nanoparticle aqueous solution is prepared, and the nanoparticle aqueous solution is prepared by adding the aqueous nanoparticle solution to a UV-permeable solvent in which the block copolymer into which the photocrosslinking group is introduced is dissolved.
The nanoparticles are Zn, Cd, Hg, Pb, Sn, Ge, Ga, In, Tl, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, It may be any one of Tc, Pd, Ag, Pt, but is not necessarily limited thereto. The metal nanoparticles may preferably be gold (Au) because gold (Au) nanoparticles have an excellent ability to precisely control the size from 1 to 100 nm in catalysts, sensors, biopharmaceuticals, in a wide range of applications. Gold nanoparticles are suitable for nanoparticle synthesis because the terminal thiol groups can control and adjust the polymer ligand areal density of the surface of gold nanoparticles through simple grafting.
Au salts include gold chloride, gold bromide, gold iodide, gold sulfide, chloroauric acid, gold sodium thiomalate hydrate sodium thiomalate hydrate, gold hydroxide, gold cyanide, chlorotriethyl phosphine gold, chlorotrimethylphosphine gold and chlorotriphenylphosphine gold (chlorotriphenylphosphine gold) and the like can be selected from the group consisting of one or more, and are not limited to these.
Reducing agents for reducing Au ions include sodium borohydride, ethylene oxide, sodium citrate, thiocyanate, and ascorbic acid. It is not limited to these.
The aqueous solution of the block copolymer having the photocrosslinked group prepared in the above step is mixed with the gold nanoparticle aqueous solution and stirred to obtain a gold nanoparticle block copolymer composite in which thiol groups of the block copolymer are adsorbed with the gold nanoparticles. Can be. In this case, the gold nanoparticle block copolymer composite preferably contains gold nanoparticles in an amount of 0.0001 to 0.1% by weight based on the weight of the gold nanoparticle block copolymer composite.
Thereafter, in step vii), the photocrosslinking group is photocrosslinked by irradiating ultraviolet light to the aqueous nanoparticle block copolymer composite solution prepared in step vi). In this case, in order to cause photocrosslinking, ultraviolet rays having a wavelength of 200 nm to 350 nm may be irradiated for 1 to 60 minutes. This is because the photosensitivity of the polymer is more sensitive in the ultraviolet region of 200nm-300nm.
Next, the film or matrix material containing the nanoparticle block copolymer composite of the present invention is obtained by dispersing the nanoshell block copolymer composite of the coreshell structure of the present invention using a solvent as a dispersion medium.
In the present invention, a method for forming a core-shell nanoparticle block copolymer composite by dispersing the nanoparticle block copolymer composite in a solvent, coating it on a substrate and irradiating with ultraviolet light to form a core-shell structure, pre-cured core shell structure All methods of dispersing the nanoparticle block copolymer composites are possible.
Gold nanoparticle block copolymer composite of the core shell structure according to the present invention is improved thermal stability and dispersibility as the bond between the gold nanoparticles and the block copolymer is protected by a cross-linked shell.
1 is a schematic diagram showing a synthesis process of a block copolymer according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing the synthesis process of the gold nanoparticle block copolymer composite according to an embodiment of the present invention.
3 is a TEM image and particle size before and after heating after dispersing the gold nanoparticle block copolymer composite of the core shell structure and the gold nanoparticle polystyrene prepared in Comparative Example in dibutyl phthalate (DBP) according to an embodiment of the present invention It is a distribution graph.
4 is a TEM image and a particle size distribution graph before and after heating after dispersing a gold nanoparticle block copolymer composite of a core shell structure and a gold nanoparticle polystyrene prepared in a comparative example in a nanocomposite film according to an embodiment of the present invention. .
5 is a TEM image after the PS / PMMA (50:50) is heated for 48 hours at 180 ℃ according to an embodiment of the present invention.
6 is a TEM image of PS / PMMA (50:50) mixed with (a) 0.0wt% (b) 5.0wt% (c) 10wt% of photocrosslinked gold nanoparticles according to an embodiment of the present invention. And droplet size distribution graph.
Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the scope of the present invention is not limited by the following examples, and those skilled in the art to which the present invention pertains should be within the equivalent scope of the technical concept of the present invention and the claims to be described below. Of course, various modifications and variations are possible.
< Example One : Block copolymer Synthesis>
Figure 1 schematically shows the synthesis process of the block copolymer in Example 1.
< Example 1-1: Polymerization of Polystyrene Particles>
As monomer A, commercially available styrene was diluted with caustic soda solution to remove the polymerization inhibitor, followed by washing with water, and then refrigerated after pretreatment to separate only styrene.
10 g of the pretreated styrene and 0.05 g of N, N'-azobisisobutyronitrile (AIBN) as an initiator, 0.29 g of sodium dodecyl sulfate (SDS) and 0.06 g of methyl ester benzyldithiol as a chain transfer agent After emulsification at 900rpm for 30 minutes to form a micelle containing the reactants, the reaction was maintained in a three-necked flask for 24 hours while maintaining a nitrogen atmosphere at 80 ℃ to obtain an emulsion of polystyrene beads dispersed in water, water Was evaporated to obtain polymer beads in the solid state.
< Example 1-2: monomer Of B Stopping Addition and Polymerization Reaction>
To the styrene polymer obtained in Example 1-1, 10 g of p-chloromethylstyrene as monomer B and 0.05 g of N, N'-azobisisobutyronitrile (AIBN) were added as an initiator to synthesize a block copolymer, followed by polymerization. Hexylamine was added as a reaction terminator to terminate the polymerization reaction.
< Example 1-3: Optical bridge Introduction of group>
An azido group was introduced as a photocrosslinking group into the block copolymer obtained in Example 1-2. Specifically, the chloro group of the block copolymer synthesized in Example 1-2 was reacted with azido with sodium azide to introduce an azido group into the side chain. Subsequently, the prepared solution was put in an aqueous solution in which 1% of polyvinyl alcohol (average degree of saponification of 89%) was dissolved and emulsified at 6,000 rpm for 5 minutes using a mechanical homogenizer. Subsequently, the temperature of the reactor was increased to 70 ° C. and polymerized at 400 rpm for 10 hours, and then the porous polymer particles prepared through the filter paper were collected by filtration. The unreacted substance and the dispersion stabilizer were repeatedly washed with methanol, and then dried in a vacuum oven for 24 hours to obtain a powder form.
< Example 2: Preparation of Gold Nanoparticles Aqueous Solution>
Gold chloride was dissolved in water at 0.01% by weight based on the total weight to prepare an aqueous solution, and then sodium citrate was added at 0.01% by weight, and sodium borohydride was added at 0.00075% by weight. Was prepared.
Example 3 Preparation of Aqueous Composite Solution of Gold Nanoparticles and Block Copolymer
In the present invention, the synthesis process of the gold nanoparticle block copolymer composite of the core shell structure is schematically shown in FIG. 2.
First, the block copolymer made in Example 1 was dissolved in dioxane, a UV transparent solvent, and 30 parts by weight of an aqueous gold nanoparticle solution per 100 parts by weight of the block copolymer made in Example 1 was added for 6 hours. After the adsorption reaction was filtered through a filter paper to prepare a gold nanoparticles and block copolymer composite aqueous solution.
Example 4 Preparation of Composite Aqueous Solution of Core Nanostructured Gold Nanoparticles and Block Copolymer >
The prepared gold nanoparticles and the block copolymer composite aqueous solution were irradiated with UV light at 254 nm for 1 hour using a UV flashlight to prepare a gold nanoparticle block copolymer composite having a core shell structure.
< Comparative example >
Without introducing azido groups, which are optical crosslinking groups, polystyrene polymerized using only styrene produced in Example 1-1 as a monomer was used as a comparative example. Gold nanoparticle polystyrene composite aqueous solution was prepared by reacting polystyrene having a thiol group at the polymerized terminal with gold nanoparticles.
Experimental Example 1 Thermal Stability Test
The gold nanoparticle block copolymer composite of the core shell structure made in Examples 1 to 3 was dispersed in dibutyl phthalate (DBP) which is a selective solvent for polystyrene and nonvolatile, and heated at 150 ° C., and a TEM photograph before heating. And (b) of FIG. 3 and particle size distribution are shown the TEM photograph after heating in FIG.
Gold nanoparticle polystyrene prepared in Comparative Example was also dispersed in dibutylphthalate (DBP), an optional solvent for nonvolatile polystyrene, and heated at 150 ° C., and TEM image and particle size distribution before heating were shown in FIG. ) And a photograph after heating is shown in Fig. 3C.
When the polystyrene gold nanoparticle composite aqueous solution of the comparative example without the photocrosslinked bond was heated, the nanoparticles were dissociated due to dissociation of the gold nanoparticle-thiol bond as shown in FIGS. 3A and 3C. It was found that the particles aggregated and precipitated with heating. In contrast, in the crosslinked embodiment of the present invention, since the gold nanoparticle-thiol bond is protected due to the shell made by the photocrosslinking bond, the photographs of (b) (before heating) and (d) (after heating) It can be seen that the color of the solution and the diameter of the gold nanoparticles (2.62nm and 2.71nm (Fig. 3 (b) and (d)), respectively) before and after heating did not change, so that the thermal stability was excellent.
It was found that the photocrosslinked bonding groups introduced into the side chains of the nanoparticles and the block copolymer of the present invention were successfully crosslinked by UV irradiation, and as a result, dissociation of the gold-thiol bond was completely suppressed by the presence of the crosslinked shell. Indicates.
<
Example
5: with gold nanoparticles
Block copolymer
Fabrication of Composite Films>
The gold nanoparticle block copolymer composite prepared in Examples 1 to 3 was 100 nm SiO 2 Films were prepared by spin coating onto a layered silicon substrate. The prepared film was irradiated with ultraviolet rays for 15 minutes in a vacuum state to generate photocrosslinked bonds.
Gold nanoparticle polystyrene prepared in the comparative example was also spin-coated on a silicon substrate having a SiO 2 layer of 100nm in the same process to prepare a film.
The prepared film was heated for 48 hours in a vacuum of 180 ° C, and the TEM test was performed after removing
4 (a) and 4 (c) show graphs of TEM images and particle size distribution before and after heating of a film obtained by dispersing the gold nanoparticle polystyrene polymer of Comparative Example, and FIGS. 4 (b) and 4 (d) show the present invention. The TEM image and particle size distribution graph of nanoparticles before and after heating of the film which disperse | distributed the gold nanoparticle block copolymer of an Example are shown.
In the case of the comparative example shows a clear degree of aggregation after heating as shown in Figure 4 (c), in the case of the embodiment of the present invention when dispersed and crosslinked in the film as shown in Figure 4 (b), (d) It can be seen that the size of the gold nanoparticles did not change before and after heating. These results indicate that the photocrosslinking of azido groups forms a thermally stable coreshell nanostructure in the film.
<
Example
6: with gold nanoparticles
Block copolymer
Preparation of Composite Matrix>
In order to examine the dispersibility of the gold nanoparticles and block copolymer particles in the polymer matrix according to the present invention, an experiment is performed using a mixture of polystyrene (PS) and poly (methyl methacrylate) (PMMA) as polymer chains. It was.
2 wt% solution of PS / PMMA (volume ratio of 50:50) in dichloromethane, the crosslinked core shell structure of the gold nanoparticles prepared in Examples 1 to 4 according to the present invention and block air The composite was mixed with a weight ratio of 5.0 wt% and 10.0 wt%. The molecular weight and polydispersity index (PDI) of PS were 56,500 g / mol and 1.07, and PMMA was 57,000 g / mol and 1.15, respectively. The solution was then placed in NaCl substrate and heated at 180 ° C. for 48 hours. The film was floated on a NaCl substrate for TEM examination and transferred to an epoxy support and microtome, and the PS domain was colored with RuO 4 .
5 is a cross-linked TEM image of a PS / PMMA mixture comprising (a) 5.0 wt% and (b) 10.0 wt% crosslinked gold nanoparticle block copolymer composite particles according to the present invention and not crosslinked according to a comparative example. A cross TEM image of a PS / PMMA mixture comprising (a) 5.0 wt% and (b) 10.0 wt% of the gold nanoparticle polystyrene polymer is shown.
In the comparative example, since the PS and PMMA are not easily mixed, it can be seen that the polymer mixture is clearly separated into two regions. According to the present invention, when 5.0 and 10.0 wt% of the crosslinked gold nanoparticles are mixed with the PS / PMMA mixture as shown in FIGS. 5 (a) and 5 (b), the gold nanoparticles are distinctly localized at the interface between the polymers. localization was observed. Regardless of the nanoparticle weight ratio, crosslinked nanoparticles are clearly observed at the PS / PMMA interface, and as the weight ratio of gold nanoparticles increases, the boundary width of the PS / PMMA mixture represented by the width of the gold nanoparticle layer increases. It was.
The effect of the crosslinked gold nanoparticles of the present invention as a compatibilizer in the PS / PMMA mixture was examined to determine the size of the droplets.
Figure 6 shows a TEM of PS / PMMA (volume ratio of 50:50) mixed with (a) 0.0 wt% (b) 5.0 wt% (c) 10 wt% of the photocrosslinked gold nanoparticle block copolymer according to the present invention. Represents an image and a drop size distribution graph.
Since the volume ratio of PS and PMMA is the same, PS and PMMA droplets were observed in all samples.
In the comparative example without the cross-linked gold nanoparticles, the droplet size averaged 0.92 ± 0.33 μm, ranging from sub-μm to several μm. In contrast, when the cross-linked gold nanoparticle block copolymer of the present invention is added to the PS / PMMA mixture, the droplet size is 5.0 and 10.0 wt%, respectively, 0.46 ± 0.14 μm and 0.32 ± 0.09 μm, respectively. I could see.
5 and 6, the photocrosslinked core shell structured gold nanoparticle block copolymer composite of the present invention is located at the interface of the PS / PMMA mixture and effectively delays the drop merging, thereby greatly improving dispersibility. Could confirm.
Claims (16)
ii) synthesizing the block copolymer by polymerizing a monomer B and an initiator represented by the following Formula (1) to the polymer obtained in step i);
(In the formula (1), Y represents an alkyl group having 1 to 10 carbon atoms with or without a hydroxy group or a carboxy group, and Z represents a halogen atom).
iii) stopping the polymerization reaction by adding a polymerization terminator to the block copolymer produced in step ii);
iv) replacing the halogen atom of the block copolymer with a photocrosslinking group; And
v) dissolving the block copolymer in which the photocrosslinking group is introduced into an ultraviolet light-permeable solvent;
vi) preparing a nanoparticle aqueous solution and adding the aqueous nanoparticle solution to a UV-permeable solvent in which the block copolymer into which the photocrosslinking group is introduced is prepared to prepare a nanoparticle block copolymer composite; And
vii) irradiating ultraviolet light to the aqueous nanoparticle block copolymer composite solution prepared in step vi) to photocrosslink the photocrosslinking group.
Vinyl monomer A in step i) is styrene; Divinylbenzene; Ethyl vinyl benzene; Paramethylstyrene; Fluorostyrenes; Vinylpyridine; Vinyl chloride; Acrylonitrile; Methacrylonitrile; Butyl acrylate; 2-ethylhexylethyl acrylate; Glycidyl acrylate; N, N'-dimethylaminoethyl acrylate; Butyl methacrylate; 2-ethylhexylethyl methacrylate; Methyl methacrylate; 2-hydroxyethyl methacrylate; Glycidyl methacrylate; Polyethylene glycol diacrylate; 1,3-butylene glycol diacrylate; 1,6-hexanediacrylate; Ethylene glycol dimethacrylate; Diethylene glycol dimethacrylate; Triethylene glycol dimethacrylate; Polyethylene glycol dimethacrylate; And 1,3-butylene glycol dimethacrylate; and a method for producing a nanoparticle block copolymer composite having a superior thermal stability core shell structure.
The vinyl-based monomer A in step i) is styrene is a method of producing a nanoshell block copolymer composite having a core shell structure excellent thermal stability.
Monomer B in the step ii) is p-chloromethyl styrene is a method of producing a nanoshell block copolymer composite having a good thermal stability core shell structure.
In step ii), the monomer A and the monomer B are prepared in a nanoshell block copolymer composite having excellent thermal stability, wherein the monomer B is polymerized at a ratio of 30 to 50 parts by weight per 100 parts by weight of the monomer A. Way.
The chain transfer agent in step i) is a method for producing a nanoshell block copolymer composite having excellent thermal stability excellent core shell structure, characterized in that the dithio ester-based represented by the following formula (2).
(In the formula (2), R is
The chain transfer agent in step i) is a method of producing a nanoshell having excellent thermal stability core shell structure, characterized in that the methyl ester benzyldithiol.
The initiator in step i) and ii) is one or two or more selected from oxygen, hydroperoxide, perester, percarbonate, peroxide, persulfate and azo initiator. Excellent core shell structure nanoparticle manufacturing method.
The photocrosslinking group in step iv) is an amine group, an azido group, a hydroxyl group, a carboxyl group, a sulfhydryl group, a carbohydrate, A method for producing nanoparticles having a superior thermal stability core shell structure, characterized in that selected from the group consisting of derivatives thereof.
Ultraviolet permeable solvent in the step v) is a method of producing a nanoshell block copolymer composite having excellent thermal stability core shell structure, characterized in that the dioxane or chloroform.
In the step vii) of the nanoshell block copolymer composite having excellent thermal stability, characterized in that the irradiation of light with a wavelength of 200nm-350nm for 1 minute-60 minutes.
The nanoparticles in step vi) are Zn, Cd, Hg, Pb, Sn, Ge, Ga, In, Tl, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb A method for producing a nanoparticle block copolymer composite having excellent thermal stability core shell structure, characterized in that any one selected from the group consisting of, Mo, Tc, Pd, Ag, Au and Pt.
The block copolymer into which the photo-crosslinking group is introduced has a total molecular weight of 1000 g / mol-3000 g / mol.
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| KR1020100022083A KR101238827B1 (en) | 2010-03-12 | 2010-03-12 | Method of preparing thermally-stable core-shell block copolymer-nanocomposite and thermally-stable core-shell block copolymer-nanocomposite made by the same |
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| KR20230069030A (en) | 2021-11-11 | 2023-05-18 | 주식회사 엘지화학 | Compound, method for preparing the same, and monomolecule and polymer derived from the compound |
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| CN108641051B (en) * | 2018-03-19 | 2020-10-02 | 淮海工学院 | Preparation method of oil-soluble hyper-dispersant based on block copolymer |
| KR102293506B1 (en) | 2019-09-25 | 2021-08-24 | 고려대학교 산학협력단 | Thermally and chemically stable colloidal quantum dot encapsulated by functional polymeric ligands, manufacturing method of the same and thermally stable quantum dot based optical film using the same |
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