WO2005108451A1 - 高分子グラフト微粒子によるコロイド結晶の製造方法 - Google Patents
高分子グラフト微粒子によるコロイド結晶の製造方法 Download PDFInfo
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- WO2005108451A1 WO2005108451A1 PCT/JP2005/008249 JP2005008249W WO2005108451A1 WO 2005108451 A1 WO2005108451 A1 WO 2005108451A1 JP 2005008249 W JP2005008249 W JP 2005008249W WO 2005108451 A1 WO2005108451 A1 WO 2005108451A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Definitions
- the present invention relates to a composite fine particle in which a polymer graft chain is bonded to the surface of a fine particle at a very high density, and a colloid crystal structure in which the composite fine particle force is also formed. More specifically, the present invention relates to a highly ordered colloidal crystal expected to be applied to the optical communication field, color imaging equipment, high-power laser field, and the like in the future. The present invention further relates to a method for producing a composite fine particle and a colloidal crystal structure in which a polymer graft chain is bonded to the surface of the fine particle at a very high density.
- Living radical polymerization is a polymerization method that has recently attracted worldwide attention as a method for easily synthesizing a polymer having a narrow molecular weight distribution and a well-defined structure by radical polymerization. This is because it has advantages not found in other living polymerization systems, such as simple operation and simple operation.
- the present inventors succeeded in grafting a polymer chain having a controlled chain length and chain length distribution at an unprecedentedly high density.
- Patent Document 2 Attempts have been made to construct a structure (see Patent Document 2). Specifically, a disulfide compound having a polymerization initiating group is self-adsorbed on the surface of gold (Au) nanoparticles of 100 nm or less, and even 50 nm or less, in the presence of an initiator compound not fixed on the surface of the particles. Then, living radical 'graft polymerization is performed, and a single particle film, a multilayer particle film, and a cast film are formed from the resulting polymer graft fine particles by the Langmuir-Blodget (LB) method.
- LB Langmuir-Blodget
- Patent Document 1 JP-A-11-263819
- Patent Document 2 Japanese Patent Application Laid-Open No. 2003-327641
- An object of the present invention is to provide a composite fine particle in which a polymer graft chain is bonded to the surface of a fine particle at a very high density.
- the goal is to construct a colloidal crystal structure that is promising as a future nano-optical material by synthesizing particles.
- the present inventors have conducted intensive studies, and as a result, confirmed that the graft chains obtained by living radical polymerization from the polymerization initiation groups on the surface of the fine particles had a high density and a narrow chain length distribution.
- the above problem was solved by confirming that the dispersion exhibited an opal color indicating the formation of colloidal crystals.
- the present invention provides the following.
- the polymer graft chain is obtained by a living radical polymerization of acrylic acid derivative, methacrylic acid derivative, styrene derivative, butyl acetate or acrylonitrile starting from the polymerization initiation group on the surface of the fine particles. Or the composite fine particles according to (2).
- the fine particles are 50 ⁇ ! 2.
- the fine particles have ⁇ ! 2.
- n is an integer of 3 to 10
- R represents CI to C3 alkyl
- R represents C1 to C2 alkyl.
- X represents a halogen atom
- X represents a halogen atom
- X is based on the polymerization initiation group of the fine particles in which the compound represented by the formula (1) is bonded to the surface of the fine particles, based on acrylic acid derivative, methacrylic acid derivative, styrene derivative, butyl acetate or acrylonitrile Composite fine particles obtained by living radical polymerization.
- the monomer having a light or heat sensitive group is oxetane methacrylate, oxetane acrylate, cinnamoethyl acrylate or cinnamoethyl methacrylate. The described method.
- the present invention it is possible to provide a composite microparticle in which a polymer graft chain is bonded to the surface of a microparticle at an ultra-high density, and the composite microparticle power is also expected to be a promising nano-optical material for a colloid crystal structure. It is possible to build.
- FIG. 1 shows a method for synthesizing silica fine particles having a high-density graft film of the present invention.
- FIG. 2 shows a first-order plot of a monomer transfer ratio with respect to a polymerization time.
- FIG. 3 shows M and M / M of a free polymer and a graft polymer with respect to a monomer transfer ratio.
- FIG. 4 shows the relationship between polymerization time and graft density.
- Figure 5 shows a TEM photograph of a water surface monolayer of PMMA-SiP (silica particles have a diameter of 130 nm and M of the graft polymer is (a) 139000, (b) 354000) .
- FIG. 6 shows a toluene dispersion of PMMA-SiP.
- FIG. 7 shows a CSLM photograph of a high-density grafted rhodamine-labeled silica fine particle dispersion.
- FIG. 8 is a conceptual diagram of the construction of a colloidal crystal using composite fine particles in which ultrahigh-density graft chains are bonded to the surface of the fine particles.
- FIG. 9 is a photograph of PMMA-SiP dispersions at various concentrations.
- FIG. 10 is a phase diagram of the PMMA-SiP dispersion from which the results of FIG. 9 were also obtained.
- polymer graft chain means a polymer chain having a chain length of 2 or more formed by elongating the surface force of the fine particles by a polymerization reaction.
- graft density or “density” means the number of graft chains bonded to the surface of a fine particle surface per unit area (nm 2 ). Graft density was determined by elemental analysis to determine the amount of polymer graft chains formed by elongating the surface force of the fine particles (graft amount), and that value, the specific gravity of the fine particles (g / cm 3 ), the surface area (nm 2 ), Furthermore, it is calculated using Mn of the graft polymer.
- the term "ultra-high density” refers to a high graft density that is unprecedented, and is a graph chain in which the graft chains are dense until steric repulsion occurs between the graft chains. In this case, the graft chains take an almost extended shape in a direction perpendicular to the surface. For example, when poly (methyl methacrylate) chains are grafted, an ultra high density of 0.1 or more Znm 2 is achieved.
- fine particles refers to 50 ⁇ ! As long as the particles are monodisperse particles having a particle size of 1 to 1 ⁇ m, they may be inorganic substances or organic substances without particular limitation.
- composite fine particles refers to a polymer graft chain bonded to the surface of the fine particles. It refers to what is formed and is used herein to distinguish it from “fine particles” as defined above.
- bond means a bond formed by a general chemical reaction, and specifically includes a covalent bond and an ionic bond.
- living radical polymerization refers to a polymerization reaction in which a chain transfer reaction and a termination reaction do not occur or are negligibly small, and the polymerization activity is maintained at the end of the produced polymer even after the completion of the polymerization reaction. The polymerization is held so that the polymerization reaction can be started again when the monomer is added.
- the characteristics of living radical polymerization are that a polymer having an arbitrary average molecular weight can be synthesized by adjusting the concentration ratio between the monomer and the polymerization initiator, and the molecular weight distribution of the resulting polymer is extremely narrow. And application to block copolymers.
- living radical polymerization is abbreviated as “LRP”. Examples of the radical polymerizable monomer constituting the graft chain include MMA (methyl methacrylate), styrene, and vinyl acetate.
- living radical polymerization conditions is appropriately selected by those skilled in the art because living radical polymerization starting from a polymerization initiating group provided on the surface of fine particles proceeds reliably and well. It means adopting polymerization conditions.
- the "polymerization initiating group” means a substance added to a monomer in a small amount and playing a role of initiating a polymerization reaction, and is not particularly limited as long as it has such a role.
- colloidal crystal generally refers to a colloidal dispersion liquid in which fine particles of the order of nm are dispersed in a liquid, and the fine particles are regularly arranged in a crystalline form. First, it behaves in the same way as a crystal, regardless of its nucleation and crystal growth mechanism. The fine particles in the colloidal crystal fluctuate in a state where a repulsive force acts between the composite fine particles in which the polymer graft chains are bonded to the surface of the fine particles at an extremely high density. Colloidal crystals exhibit a unique structural color. “Structural color” means the appearance of a color tone that is produced by light falling on a regular structure in the order of the wavelength of light. Structural color is an important indicator to determine whether colloidal crystals are forming.
- “fixing a colloidal crystal” means within the colloidal crystal as defined above. This means that processing is performed so that the relative positional relationship between regularly arranged particles is maintained for at least a certain period of time.
- Such colloidal crystal fixation includes, for example, (1) connecting regularly arranged particles within the colloidal crystal defined above by diagonal bonding; (2) preparing a colloidal crystal and then dispersing the colloidal crystal in a dispersion solvent. (3) coexist with a polyfunctional monomer or oligomer in the dispersion medium of colloidal crystals, and after crystallization, light or heat-treat in the presence or absence of an initiator. This is done by the method described above.
- the present invention provides composite fine particles in which a polymer graft chain is bonded to the surface of the fine particles at a very high density. Considering the ratio of the polymer graft chain to the conventional! /! By grafting the ultrafine particles onto the surface of the fine particles, a strong repulsion force against compression can be obtained between the composite fine particles of the entire system in a good solvent (Fig. 8) This allows the composite microparticles to form colloidal crystals (Figs. 6 and 7). To produce a compression repulsive force between such composite particles, the graft density on the particle surface from 0.1 to 1.
- the polymer graft chain is obtained by living radical polymerization of a monomer starting from the polymerization initiation group on the surface of the fine particles.
- the type of the monomer include an acrylic acid derivative, a methacrylic acid derivative, a styrene derivative, vinyl acetate, acrylonitrile, or a combination thereof, but are not limited thereto, and may be appropriately selected within a range recognized by those skilled in the art. Is done.
- the molecular weight distribution of the polymer graft chain is preferably from 1 to 1.5, and more preferably a value substantially close to 1.
- Fine Particle Surface Force In order to carry out graft polymerization at an ultra-high density, monodisperse fine particles having a particle diameter of 50 nm to 1 ⁇ m are preferred, and more preferably ⁇ ! ⁇ 1 ⁇ m particle size Are monodisperse fine particles. If the particle size is less than 50 nm, the grafting from the surface of the fine particles is affected by the curvature of the particles, so that the density of the graft is reduced and the compression repulsion force is not obtained between the composite fine particles. Colloidal crystals are not formed and are not preferred.
- the obtained colloidal crystals have poor optical properties, and are suitable for application to nano-optical materials in the fields of optical communications, color imaging equipment and high-power lasers. Dispersion of the composite fine particles in a solvent is not easy and is not preferable.
- the fine particles used in the present invention typically, silicon oxides such as silica; noble metals such as Au (gold), Ag (silver), Pt (platinum), Pd (palladium); Ti , Zr, Ta, Sn, Zn, Cu, V, Sb, In, Hf, Y, Ce, Sc, La, Eu, Ni, Co, Fe, etc. transition metals, and their inorganic substances such as oxides or nitrides Or organic substances, but is not limited thereto.
- preferred fine particles are silica, metal oxide or metal sulfide, and a graft density of 0.4 to 1.2 double-stranded Znm 2 is achieved.
- the graft density is at most 0.3 graphene Znm 2 .
- the composite fine particles of the present invention in which the polymer graft chains are bonded to the surface of the fine particles at a very high density are produced through the following steps:
- the following formula is used for bonding a polymerization initiator for living radical polymerization to the surface of the fine particles:
- silane coupling agent containing a polymerization initiator or a silane coupling agent containing a polymerization initiator and a silane coupling agent not containing a polymerization initiator represented by the formula The procedure of binding to the child surface is taken.
- the spacer chain length n is preferably an integer of 3 to 10, more preferably an integer of 4 to 8, and most preferably 6.
- R is preferably C1-C3 alkyl, more preferably C1 or C2 alkyl.
- R is C1 or C2 alkyl.
- X is halo
- alkyl refers to a monovalent group generated by the loss of one hydrogen atom from an aliphatic hydrocarbon (alkane) such as methane, ethane, and propane, and is generally represented by CH— ( Where n is a positive integer).
- Alkyl can be straight or branched.
- the above-mentioned silane coupling agent containing a polymerization initiating group can be synthesized by the synthesis procedure of FIG. 1 based on general organic chemistry.
- a typical polymerization initiator group-containing silane coupling agent includes, for example, (2-promo-2-methyl) propio-loxyhexyltriethoxysilane (BHE) (Fig. 1).
- Typical silane coupling agents not containing a polymerization initiator include, for example, generally used alkyl silane coupling agents.
- the polymer graft chains can be formed at an ultra-high density.
- the composite fine particles bonded to the fine particle surface can be obtained ((step b)).
- the type of the monomer to be brought into contact with the fine particles having a polymerization initiation group on the surface may be a single type or a plurality of types.
- the graft density on the surface of the fine particles can be freely changed by adjusting the ratio of the silane coupling agent containing a polymerization initiator and the silane coupling agent not containing a polymerization initiator.
- the silane coupling agents are silane coupling agents containing a polymerization initiator group (FIG. 1)
- the graft density is at least 0.7-chain Znm 2 .
- the target product is obtained by removing contaminants (unreacted weight loss, by-products, solvent, etc.) from the reaction solution by a method commonly used in the art (for example, extraction, distillation, washing, etc.). (E.g., purification, concentration, precipitation, filtration, drying, etc.) followed by a combination of post-treatment methods commonly used in the art (e.g., adsorption, elution, distillation, precipitation, precipitation, chromatography, etc.). Can be isolated.
- a method commonly used in the art for example, extraction, distillation, washing, etc.
- post-treatment methods e.g., adsorption, elution, distillation, precipitation, precipitation, chromatography, etc.
- the composite fine particles of the present invention in which the polymer graft chains are bonded to the surface of the fine particles at a very high density are composed.
- the formed two-dimensional array structure can be confirmed by transferring the water surface film of the composite fine particles to a grit for a transmission electron microscope (abbreviation: TEM) and performing TEM observation.
- FIG. 5 shows a TEM photograph of a PMMA-SiP monolayer on the water surface (the diameter of the silica particles is 130 nm, and the M of the graft polymer is (a) 139000, (b) 354000). From this, it was confirmed that the composite fine particles of the present invention formed a single particle film without agglomeration in two dimensions.
- the colloidal crystal structure of the present invention is produced through the following steps:
- the concentration of the composite fine particles in the step c) is adjusted to a concentration at which the composite fine particles come into contact with each other.
- concentration at which the composite fine particles come into contact with each other include 1 to 30% by weight.
- concentration of the composite fine particles is less than 1% or more than 30% by weight, a colloidal crystal having a beautiful structural color cannot be obtained.
- the formation of colloidal crystals can also be confirmed by a three-dimensional image with a confocal laser scanning microscope (abbreviation: CSLM), which can also be made by visually confirming whether the dispersion emits structural color. it can.
- CSLM confocal laser scanning microscope
- CSLM CSLM-coaxial low-density lipoprotein
- a pinhole stop is provided at a position that is optically conjugate to the focal plane of the sample.
- a two-dimensional image inside the sample can be obtained without any stray light.
- the same operation is performed by moving the sample along the Z-axis direction.
- a three-dimensional image can be constructed from a large number of two-dimensional plane slice images thus captured.
- the solvent in which the composite fine particles are dispersed in the above step c) is adjusted by combining any appropriate solvents so that the density of the fine particles is substantially the same as that of the fine particles. It is. Thereby, the regularity of the fine particles constituting the colloidal crystal is improved, and the quality of the colloidal crystal is improved.
- colloidal crystals are prepared using the conventional sedimentation method (the particles are heavier than the solvent), there is a drawback that the regular size does not increase and the crystal size does not increase.
- the colloidal crystal can be fixed using the following three methods.
- a monomer in which a functional group having a cross-linking or polymerization function by an external stimulus such as light or heat is introduced into one of the above monomers into a side chain, and after grafting, is subjected to light or heat treatment.
- the colloidal crystals are fixed.
- the above-mentioned functional group having a crosslinking or polymerization function is provided near the end of the graft chain after performing block polymerization of a monomer having a functional group having a crosslinking or polymerization function as described above on a side chain. Is introduced, and light or heat treatment is performed. By this method, it is possible to fix the colloid while maintaining the crystal structure of the colloid.
- Examples of such a monomer having a functional group having a cross-linking or polymerization function introduced into a side chain include oxetane methacrylate, oxetane acrylate, cinnamoinoleethyl acrylate, and cinnamoethyl methacrylate. Forces are not limited to these.
- the light or heat treatment is performed in the presence or absence of an initiator.
- an oxetane-based monomer such as oxetane methacrylate or oxetane acrylate
- a cinnamoyl-based monomer such as cinnamoylethyl acrylate or cinnamoethyl metharylate
- light or heat treatment is performed in the presence or absence of an initiator.
- the temperature is lowered to the melting point of the dispersion solvent or lower to fix the colloidal crystal.
- a polyfunctional monomer or oligomer is allowed to coexist in the dispersion solvent of the colloidal crystal, and after crystallization, the crystal is fixed by light or heat treatment in the presence or absence of an initiator.
- the polyfunctional monomer or oligomer is not particularly limited as long as the monomer or oligomer has a plurality of light- or heat-sensitive functional groups in the molecule.
- the colloidal crystal structure of the present invention is produced through the following steps:
- step d) exposing the dispersion obtained in step c) to light or heat to form a chemical bond between a plurality of polymer graft chains of the composite fine particles adjacent to each other.
- the colloidal crystal structure of the present invention is produced through the following steps: a) a step of binding a polymerization initiation group to the surface of fine particles;
- the polymer graft chains are super-high-density fine particles. Forming composite microparticles bound to the surface;
- step d) exposing the dispersion obtained in step d) to light or heat to form a chemical bond between a plurality of polymer graft chains of the composite fine particles adjacent to each other.
- colloidal crystal structure of the present invention is produced through the following steps:
- step c) dispersing the composite fine particles obtained in @b) in a solvent; d) a step of lowering the temperature of the dispersion obtained in step c) below the melting point of the solvent.
- colloidal crystal structure of the present invention is produced through the following steps:
- step b) dispersing the composite fine particles obtained in step b) and a polyfunctional monomer or oligomer in a solvent;
- step d) exposing the dispersion obtained in step c) to light or heat to form a chemical bond between the polyfunctional monomers or oligomers.
- the distance between the particles in the ordered structure is adjusted to the surface of the fine particles. It can be widely and easily controlled by the graft chain length. This reflects the higher density of the graft chains and the narrower chain length distribution, and it is thought that the compression repulsion peculiar to the ultra-high-density graft membrane acts evenly between the particles in the entire system, and as a result, the particles form an ordered structure. This is experimental evidence that the precise control of the structure of the polymer brush surface is a useful basis for designing and creating new materials.
- the present invention succeeded in constructing the world's first fine particle colloidal crystal having an ultra-high density graft membrane.
- Conventional colloidal particles in the form of fine particles are formed by long-distance electrostatic repulsion due to the surface charge of the particles.
- Colloidal crystals could be constructed using a completely different concept of creation.
- BHE was synthesized by a two-step reaction ( Figure 1).
- a solution of a mixture of 5-hexen-1-ol (43 g), triethylamine (71 mL) and tetrahydrofuran (THF; 1 L) was cooled on ice, and 2-bromoisobutyryl bromide (63 mL) was added into the solution. Was dropped. Thereafter, the reaction solution was stirred at 0 ° C. for 3 hours, and further stirred at room temperature for 10 hours.
- BPH 40 g
- toluene 500 mL
- triethoxysilane 500 mL
- Karsted's catalyst 450 mL
- silica fine particles The introduction of the initiating group on the surface of the silica fine particles was performed in the following procedure (FIG. 1). Ethanol dispersion (7.7 wt%, 30 mL) of silica fine particles (abbreviation: SiP, manufactured by Nippon Shokubai, average particle size 130 nm) is added to a mixture of 28% ammonia aqueous solution (13.9 g) and ethanol (200 mL). Was. After the mixture was stirred at 40 ° C. for 2 hours, an ethanol solution (10 mL) of BHE (2 g) synthesized in Example 1 was added dropwise, and the mixture was stirred at 40 ° C. for 18 hours. After that, the silica fine particles are centrifuged. It was collected by a machine, washed with ethanol and ethanol, and then stored in ethanol.
- SiP silica fine particles
- Purification of silicic acid microparticles (PMMA-SiP) grafted with poly (methyl methacrylate) obtained by the above polymerization was performed by repeating centrifugation and redispersion in THF.
- the silica fine particles (PMMA-SiP) were also cut out of the graft polymer.
- FIG. 2 shows a linear plot of the monomer transfer ratio with respect to the polymerization time. Since a linear relationship is obtained, it can be seen that the radical concentration is kept almost constant during the polymerization.
- FIG. 3 shows the number average molecular weight (M) and the molecular weight distribution index (M / M) of the free polymer (solid circle in the figure) and the graft polymer (open circle in the figure) with respect to the monomer transfer ratio. It can be seen that the molecular weights of both polymers increase with an increase in the monomer transfer ratio which is almost equal.
- M number average molecular weight
- M / M molecular weight distribution index
- the / M value shows a small value in each case.
- Figure 4 shows the graft density versus polymerization time. Graft density is calculated using the amount of PMMA (graft amount) grafted onto the SiP surface by elemental analysis, and using that value, the specific gravity of SiP (1.9 gZcm 3 ), the surface area (53200 nm 2 ), and the Mn of the graft polymer did. It can be seen that the graft density is almost constant (about 0.7-chain Znm 2 ) irrespective of the polymerization time.
- a toluene solution of silica microparticles (PMMA-SiP) grafted with poly (methyl methacrylate) was dropped on the water surface to prepare a PMMA-SiP water surface monolayer.
- the result was transferred to a grid for a transmission electron microscope (TEM) and observed by TEM. It can be seen that the fine particles are arranged in a crystalline form, and that the spacing between the particles increases as the graft chain length increases.
- TEM transmission electron microscope
- silica fine particles containing a fluorescent dye rhodamine
- PMMA polymethyl methacrylate
- a confocal laser scanning microscope Carl Zeiss, model number: LSM 5 PASCAL
- Example 5 Phase transition behavior of silica fine particles having a high-density graft film
- the present invention it is possible to provide a composite microparticle in which a polymer graft chain is bonded to the surface of a microparticle at an ultra high density, and the composite microparticle power is also expected to be a promising nano-optical material for a colloid crystal structure. It is possible to build. Also, the colloidal crystals of the present invention have several advantages over conventional colloidal crystals, as listed below:
- the colloidal crystal of the present invention has high versatility and convenience (productivity).
- Conventional colloidal crystals based on electrostatic repulsion require a high dielectric constant solvent (mainly water) as a medium, and it is essential to expand the electric double layer on the particle surface by sufficient desalination in the system.
- the present invention does not require complicated processing such as desalting, which basically has no solvent restrictions;
- a wide variety of colloidal crystals can be constructed.
- the LRP method is simple and excellent in versatility, the molecular structure in the film thickness direction can be controlled by introducing various copolymers. For example, if the cross-linking function is properly introduced, the colloidal crystal can be fixed, which leads to material design with consideration for applicability.
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