WO2013141444A1 - Composite de nanoparticule inorganique présentant une orientation - Google Patents

Composite de nanoparticule inorganique présentant une orientation Download PDF

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WO2013141444A1
WO2013141444A1 PCT/KR2012/003707 KR2012003707W WO2013141444A1 WO 2013141444 A1 WO2013141444 A1 WO 2013141444A1 KR 2012003707 W KR2012003707 W KR 2012003707W WO 2013141444 A1 WO2013141444 A1 WO 2013141444A1
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group
compound
organic compound
hydrogen
inorganic
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Korean (ko)
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이동진
임형미
김영희
차수진
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한국세라믹기술원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Definitions

  • the present invention relates to an inorganic nanoparticle composite in which inorganic nanoparticles have an orientation using an organic compound. More particularly, the present invention relates to an aromatic nanoparticle composite having an aromatic structure using mutual hydrogen bonds between functional groups formed on the surface of the inorganic nanoparticles and functional groups in the organic compound. Hybrid technology to form a new unit structure with orientation.
  • an aqueous dispersion of inorganic particles may be a slurry for polishing cosmetics, coatings, coatings or semiconductor wafers, and the raw materials thereof may be, for example, inorganic particles synthesized by a gas phase method such as a fume method (high-humidity flame hydrolysis method). High purity raw materials with very few impurities are used. However, since these inorganic particles have severe secondary aggregation, it is necessary to redisperse the aggregate in water when the inorganic particles are dispersed in water.
  • the conventional coating method using many negative metal ions to connect the inorganic particles and the surface modifier is that the organic molecular component connected by the change of pH and external environment or friction between the particles is separated from the particles after coating the organic molecules. There is a problem.
  • An object of the present invention is to orient the inorganic particles using a hybrid method between the inorganic nanoparticles having at least one functional group X, the organic compound A having the functional group Y and the organic compound B having the functional group Z, and the inorganic nanoparticles and the organic compound.
  • the present invention is an inorganic nanoparticle formed with at least one functional group X as a means for solving the above problems;
  • At least one organic compound B having a hydrogen bondable functional group Z in the structure At least one organic compound B having a hydrogen bondable functional group Z in the structure,
  • the inorganic nanoparticles and the organic compound A are each hydrogen bonded through a functional group X and a functional group Y1,
  • the organic compound A and the organic compound B are each hydrogen bonded through a functional group Y2 and a functional group Z to provide a nanoparticle composite having an orientation.
  • the present invention also provides an inorganic nanoparticle having at least one functional group X, an organic compound having a hydrogen bondable functional group Y1 and Y2 in the structure, and an organic compound having a hydrogen bondable functional group Z in the structure. It provides a method for producing a nanoparticle composite comprising reacting B to prepare a composite in which inorganic nanoparticles, organic compound A and organic compound B are sequentially hydrogen bonded.
  • the organic and inorganic compounds can form a new network, thereby forming a new orientation structure having a direction.
  • FIG. 1 is a schematic diagram showing a process for producing a nanoparticle composite having an orientation according to an example of the present invention.
  • Figure 2 shows a polarization micrograph of the nanoparticle composite having an orientation prepared by the present invention.
  • FIG. 3 is a schematic view for explaining the photograph of FIG. 2.
  • FIG. 4 is an incineration XRD graph of the inorganic nanoparticle composition prepared by Example 3.
  • FIG. 4 is an incineration XRD graph of the inorganic nanoparticle composition prepared by Example 3.
  • FIG. 5 is a TEM photograph of titania particles prepared in Example 1.
  • the present invention provides inorganic nanoparticles formed with at least one functional group X;
  • At least one organic compound B having a hydrogen bondable functional group Z in the structure At least one organic compound B having a hydrogen bondable functional group Z in the structure,
  • the inorganic nanoparticles and the organic compound A are each hydrogen bonded through a functional group X and a functional group Y1,
  • the organic compound A and the organic compound B each relates to a nanoparticle composite having an orientation by being hydrogen bonded through a functional group Y2 and a functional group Z, respectively.
  • nanoparticle composite having the orientation according to the present invention will be described in detail.
  • hydrogen bond refers to a chemical bond formed by entering a hydrogen atom between two atoms having strong electronegativity, such as oxygen, nitrogen, sulfur, or halogen atoms (for example, fluorine, chlorine, etc.).
  • strong electronegativity such as oxygen, nitrogen, sulfur, or halogen atoms (for example, fluorine, chlorine, etc.).
  • X-H... Represented by Y (where X and Y are electronegative atoms)
  • the electrons of hydrogen atoms are strongly attracted to the X side by the strong electronegativity of X, and H acts as a proton (donor) Y, which has a negative degree, is a proton acceptor (receptor) that approaches H to form a bond.
  • the functional group X of the inorganic nanoparticles forms a hydrogen bond with the functional group Y1 in the organic compound A
  • the functional group Y2 in the organic compound A forms a hydrogen bond with the functional group Z in the organic compound B.
  • the kind of functional groups X, Y1 and Y2 in the present invention is not particularly limited, for example, when X and Z each independently represent an atom selected from the group consisting of nitrogen, oxygen, sulfur, fluorine and chlorine, Y1 and Y2 Each independently represents a functional group selected from the group consisting of an amino group, a hydroxyl group, a carboxyl group, a thiol group, a hydrogen fluoride group and a hydrogen chloride group.
  • Y1 and Y2 are each independently nitrogen, oxygen, sulfur, fluorine and chlorine. It may be an atom selected from the group consisting of.
  • X and Z may each independently be an amino group, a hydroxyl group or a carboxyl group
  • Y1 and Y2 may each independently be a nitrogen, oxygen or sulfur atom.
  • the type of the inorganic nanoparticles is not particularly limited.
  • ceramics may be used, and specifically, silica (SiO 2 ) and alumina (Al 2 O 3 ).
  • Oxides such as titania (TiO 2 ), zirconia (ZrO 2 ), tin oxide (SnO 2 ) or zinc oxide (ZnO); Carbides such as titanium carbide (TiC) or silicon carbide (SiC); Nitrides such as titanium nitride (TiN) or boron nitride (BN); Hydroxides such as magnesium hydroxide (Mg (OH 2 )) or aluminum hydroxide (Al (OH) 3 ); And inorganic powders such as calcium carbonate (CaCO 3 ) or beryllium carbide (Be 2 C), and the like, and may be used. More specifically, titania may be used.
  • the inorganic nanoparticles may have a particle diameter of 10 nm to 1 ⁇ m. In the particle size range, the inorganic nanoparticles do not aggregate and have excellent orientation.
  • the inorganic nanoparticles on which the functional group X is formed may be those obtained by modifying the inorganic nanoparticles with a silane compound and / or an organic compound.
  • the surface of an inorganic nanoparticle has a hydroxyl group (hydroxy group).
  • the functional group X using the silane compound and / or the organic compound on the surface of the inorganic nanoparticle, it is possible to facilitate the bonding of the inorganic nanoparticle and the organic compound A.
  • inorganic nanoparticles modified with silane compounds are suitable for particle orientation.
  • examples of the silane compound include aminosilanes such as 4-aminobutylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane or N-2-aminoethyl-3-aminopropyldiethylisopropoxysilane; Mercaptosilanes such as (mercaptomethyl) dimethylethoxysilane, di-4-mercaptobutyldimethoxysilane, 3-mercaptopropyltriisopropoxysilane, and the like; Acrylosilanes such as 3-methacryloxypropyldimethylethoxysilane or 3-acryloxypropyltrimethoxysilane; Epoxysilanes such as (3-glycidoxypropyl) methyldimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like; Haloalkylsilanes such as 3-chloropropy
  • one or more selected from the group consisting of 3- (triethoxysilyl) propylsuccinic anhydride, (methacryloxy) propyltrimethoxysilane and aminopropyltriethoxysilane can be used as the silane compound.
  • At least one alcohol, amine, urea, anhydride, acetacetoxy group, aldehyde, carboxylic acid, ester and / or mercaptan may be formed on the surface of the inorganic nanoparticle modified with the silane compound.
  • the inorganic nanoparticles modified with the silane compound may be used by further reacting with the organic compound.
  • the surface of the inorganic nanoparticles modified with the silane compound is an amine (terminal amino group) or carboxylic acid (terminal carboxyl group)
  • it may be used directly for the reaction with the organic compound A, but the organic compound for the stability of the reaction It can be used by further reacting with.
  • the terminal of the inorganic nanoparticles modified with the silane compound is alcohol, amine, urea or anhydride
  • a compound including isocyanate or isothiocyanate may be used as the organic compound
  • the terminal of the inorganic nanoparticle may be acetacene.
  • a compound including an aldehyde group may be used as an organic compound.
  • a compound including an acetacetoxy group may be used as the organic compound.
  • the ends of the inorganic nanoparticles are alcohols, carboxylic acids, anhydrides, amines, or mercaptans, compounds including epoxide, thiolan, and aziridine may be used as organic compounds, and the terminals of the inorganic nanoparticles may be carboxyl.
  • carboxylic acids, anhydrides, amines, or mercaptans compounds including epoxide, thiolan, and aziridine may be used as organic compounds, and the terminals of the inorganic nanoparticles may be carboxyl.
  • a compound containing carbodiimide may be used as an organic compound.
  • a compound containing haloalkane may be used as an organic compound.
  • a compound including an amine and a thiol group may be used as an organic compound, and when the terminal of the inorganic nanoparticles is an epoxide, aziridine, thioran, amine, ester or carbodiimide
  • the organic compound a compound containing carboxylic acid can be used.
  • the functional group X may be formed on the surface of the nanoparticle by directly reacting with the organic compound without modifying the nanoparticle with the silane compound.
  • the organic compound may interact with the nanoparticles, which are inorganic substances, and have excellent interaction with the organic compound A, thereby forming hydrogen bonds with the nanoparticles.
  • a compound having an -CONH group, a hydroxyl group, a carboxyl group or an alkoxy group or an amine compound can be used as an organic compound, and it is possible to mix and use these compounds.
  • examples of the compound having a -CONH group include acrylamides such as N-alkylacrylamide, N, N-dialkylacrylamide or acrylamide; And methacrylamides such as N-alkyl methacrylamide, N, N-dialkyl methacrylamide, methacrylamide and the like can be used.
  • Amine compounds, specifically, diamine compounds include 4,4-diaminodiphenylmethane, 3,4-diaminodiphenylmethane, 3,3-diaminodiphenylmethane, 3,3-dimethyl-4,4- Diaminodiphenylmethane, 4,4-diaminodiphenylether, 4,4-diaminodiphenylsulfide, 3,4-diaminodiphenylsulfide, 3,3-diaminodiphenylsulfide, 3 , 3-dimethyl-4,4-diaminodiphenylsulfide, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,2-bis [4- (3-aminophenoxy) One or more selected from the group consisting of phenyl] propane, and the like, and may also be used.
  • one or more hydroxymethacrylates selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and the like can be used.
  • At least one alkoxy methacrylate selected from the group consisting of methoxyethyl methacrylate, ethoxyethyl methacrylate and the like can be used.
  • the nitro compound may include a chloride group, specifically, 2,4-nitrobenzoic acid chloride, 2,6-nitrobenzoic acid chloride, 3,4-nitrobenzoic acid chloride, 3,5-nitrobenzoic acid Chloride, 5,5-methylene bis2-nitrobenzoic acid chloride, 4,4-nitrophenylether-3,3-dicarboxylic acid chloride and 4,4-nitrobiphenyl-3,3-dicarboxylic acid chloride
  • One or more selected from the group consisting of and the like can be used, and as the alkylphenyl compound having a hydroxyl group, a compound of the same kind as described above can be used.
  • the organic compound A and the organic compound B each include a functional group Y and Z capable of hydrogen bonding, and in particular, in the case of the organic compound A, a hydrogen bond is formed with the functional group X of the inorganic nanoparticles and the functional group Z of the organic compound B. Therefore, it includes functional groups Y1 and Y2 at both ends.
  • the types of organic compounds A and B are not particularly limited as long as they include functional groups Y (Y1 and Y2) and Z, respectively.
  • the organic compounds A and B each independently represent an amine compound (including an amino group), a hydroxyl compound (including a hydroxyl group), a carboxyl compound (including a carboxyl group), a thiol compound (including a thiol group), and a fluorinated compound. It may be selected from the group consisting of a compound containing a hydrogen group, a compound containing a hydrogen chloride group and a heterocyclic compound containing nitrogen, oxygen or sulfur in the ring.
  • the compounds may generally play a donor role or a receptor role.
  • a donor in the case of an amine compound, -NH in the amine group in the compound may serve as a donor, and the nitrogen atom (N) may serve as a receptor.
  • N nitrogen atom
  • some heterocyclic compounds eg, heteroaryl compounds including pyridine
  • heterocyclic compounds having no hydrogen at the end can be used only in one of the organic compounds A and B.
  • the organic compound A may be an amine compound or a heterocyclic compound containing nitrogen, oxygen or sulfur in the ring
  • the organic compound B may be an amine compound, a hydroxyl compound or a carboxyl compound.
  • the heterocyclic compound containing nitrogen, oxygen or sulfur in the ring may be a heteroaryl compound containing nitrogen, oxygen or sulfur in the ring.
  • heteroaryl compounds containing nitrogen in the ring may contain at least one functional group selected from the group consisting of pyrrole, pyridine and azepine (containing at least two when used as organic compound A) in the compound.
  • heteroaryl compounds containing oxygen in the ring may contain at least one functional group selected from the group consisting of furan, pyran and azepine (containing at least two when used as organic compound A) in the compound.
  • the hetero aryl compound (sulfur-containing aryl compound) containing sulfur in the ring may contain at least one functional group selected from the group consisting of thiophene, thiopyran, and thiene (when used as organic compound A) )can do.
  • the amine compound may include one or more amino groups in the compound, and may be prepared by reacting a nitro compound with an alkylphenyl compound in the presence of an alkaline catalyst.
  • nitro compound for example, 6-chloro-2,4-nitroaniline, 2,4-nitroaniline, 2,6-nitroaniline, 5,5-methylene bis (1-nitroaniline), 3 , 3-diamino-4,4-nitrodiphenylether, 3,3-diamino-4,4-nitrobiphenyl, 2-trifluoromethylaniline, 3-trifluoromethylaniline, 4-trifluoromethylaniline , 2-trifluoromethoxyaniline, 3-trifluoromethoxyaniline, 4-trifluoromethoxyaniline, 4-pentafluoroethylaniline, 4-heptafluoropropylaniline, 4-pentafluoroethoxyaniline, 4- Heptafluoroepoxyaniline, 2,4-trifluoromethylaniline, 2,5-trifluoromethylaniline, 3,4-trifluoromethylaniline, 3,5-trifluoromethylaniline, 2,4-trifluoromethoxyaniline ,
  • the alkylphenyl compound may comprise chloride in the compound, for example 2-trifluoromethylbenzoic acid chloride, 3-trifluoromethylbenzoic acid chloride, 4-trifluoromethylbenzoic acid chloride, 2-trifluoromethoxy Benzoic acid chloride, 3-trifluoromethoxybenzoic acid chloride, 4-trifluoromethoxybenzoic acid chloride, 4-pentafluoroethylbenzoic acid chloride, 4-heptafluoropropylbenzoic acid chloride, 4-pentafluoroethoxybenzoic acid Chloride, 4-heptafluoropropoxybenzoic acid chloride, 2,4-trifluoromethylbenzoic acid chloride, 2,5-trifluoromethylbenzoic acid chloride, 3,4-trifluoromethylbenzoic acid chloride, 3,5-tri Fluoromethylbenzoic acid chloride, 2,4-trifluoromethoxybenzoic acid chloride, 2,5-trifluoromethoxybenz
  • the carboxyl compound includes one or more carboxyl groups in the compound, and when used as the organic compound A, may include two or more carboxyl groups.
  • the carboxyl compound include tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane Acid anhydrides such as tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride or 2-dicarboxylic dianhydride, and the like; And 2-2-hydroxy-4-pyrrolidinebenzoylbenzoic acid, 2-nitro-4-trifluoromethylbenzoic acid, 4-ethylthiolbenzoic acid, 4-2-aminoethylbenzoic acid hydrochloride, 5-bro Mono-2-nitrobenzoic acid, 3-acetoxybenzo
  • one or more selected from the group consisting of 4-hexylbenzoic acid and alkoxy benzoic acid may be used as the carboxyl compound.
  • the present invention also relates to inorganic nanoparticles by reacting an inorganic nanoparticle having at least one functional group X, an organic compound A having a hydrogen bondable functional group Y1 and Y2 in the structure, and an organic compound B having a hydrogen bondable functional group Z in the structure,
  • the present invention relates to a method for preparing a nanoparticle composite having an orientation including preparing a composite in which organic compound A and organic compound B are hydrogen-bonded sequentially.
  • the type of the inorganic nanoparticles is not particularly limited, and the above-described type may be used, and specifically, titania may be used.
  • the inorganic nanoparticles may be commercially available products or may be synthesized in a laboratory or the like.
  • the formation of the functional group X in the inorganic nanoparticles may be performed using the silane compound and / or the organic compound described above.
  • a compound containing a carbonyl group may be specifically used as the silane compound, and more specifically, 3- (triethoxysilyl) propyl succinic acid may be used.
  • the functional group X is formed at the end of the inorganic nanoparticle, and the type of the functional group is not particularly limited as long as it can form a hydrogen bond, and the aforementioned kind can be used.
  • the type of the organic compound A and the organic compound B is not particularly limited, and the above-described types may be used without limitation.
  • the organic compound may be a commercially available product or may be synthesized in a laboratory or the like.
  • the step may be performed by mixing the inorganic nanoparticles in which the functional group X is formed in the organic mixture including the organic compound A and the organic compound B.
  • the inorganic nanoparticles on which the functional group X is formed may include 4 to 100 parts by weight based on 100 parts by weight of the organic mixture. Prepared within the above range is excellent in the orientation of the composite.
  • the molar ratio of the organic compound A and the organic compound B may be 1: 0.1 to 1: 10.
  • the orientation of the composite produced in the above range is excellent.
  • the functional group X and the functional group Y1 of the organic compound A formed on the inorganic nanoparticles form a hydrogen bond by the above step, and the functional group Y2 of the organic compound A and the functional group Z of the organic compound B form a hydrogen bond to form a nanoparticle composite. It can be manufactured.
  • the composite prepared by the above step is superior in flexibility and mechanical strength as compared to conventional inorganic nanoparticles.
  • the organic compound A and the organic compound B when the inorganic nanoparticles having the functional group X are formed, the organic compound A and the organic compound B, the inorganic nanoparticles having the functional group X and the inorganic nanoparticles of different kinds can be reacted together.
  • the above-described kind may be used as the kind of the inorganic nanoparticles.
  • Nanoparticle composite having an orientation according to the present invention is applicable to high-strength lightweight composite parts, and can be used as interior and exterior materials for automobiles, ships, aircraft and energy-efficient buildings.
  • FIG. 1 shows a method for producing a nanoparticle composite having an orientation according to an example of the present invention.
  • organic compounds A and B (heterocyclic compound and carboxyl compound) It can be prepared by hydrogen bonding with.
  • Form control method using precursor method after mixing TTIP (Titanium tetraisopropoxide) and Triethanolamine (TEOA) to hydrolyze TTIP, add 1,12-Dodecanediamine (DDA) as a surfactant (acid) or base pH was adjusted. Thereafter, TiO 2 was synthesized by hydrothermal reaction. At this time, the charge state of DDA is changed according to the change of pH, and therefore, the adsorption potential of DDA is changed on TiO 2 surface, resulting in various shapes (sphere type, rode). shape is controlled by 3 types: type, flower like type).
  • TTIP Tin tetraisopropoxide
  • TEOA Triethanolamine
  • Anatase particles were added to a 10 M NaOH solution and stirred while sonicating for 30 minutes. Thereafter, the hydrothermal reactor was filled with 70 to 80% content and hydrothermally treated at 150 ° C. for 24 hours to terminate the reaction. After washing with distilled water and 0.1 M hydrochloric acid (HCl) at least three times to remove Na, filtered to a pH of 7 (paper filter), and dried at 100 °C for 12 hours to nanotube titanium dioxide particles (Diameter: 5-10 nm, length: 100-300 nm) was manufactured. The prepared particles were heat-treated at 500 ° C. to produce titania (diameter: 5-15 nm, length: 20-50 nm) particles on a rod.
  • HCl hydrochloric acid
  • the organic silane (3- (triethoxysilyl) propyl diluted in alcohol after adjusting the pH of the colloidal nanoparticle inorganic material prepared in (1) or (2) Succinic anhydride) or r-MPS (r [-(methacryloxy) propyl] trimethoxysilane) was added to react the nanoparticle inorganic surface.
  • 3- (triethoxysilyl) propyl succinic anhydride serves to introduce the COOH group on the inorganic surface.
  • r-MPS condenses three methoxy groups with the OH group of the hydrophobized colloidal inorganic interface and exposes a vinyl group
  • the hydrophobized colloidal inorganic particles may form vinyl groups or other reactive groups.
  • the modified (reactor formed) inorganic nanoparticles were redissolved in dichloromethane and then washed with acid.
  • the washed particles were dried using anhydrous magnesium sulfate, and then recrystallized twice in ethanol to prepare a final inorganic particle compound.
  • Carboxylic compound 4-hexylbenzoic acid (C13H18O2, Aldrich, 99%) and heterocyclic compound 4-ethylpyridine (C 7 H 9 N, Aldrich) or 1,2-Di (4-pyridyl) ethylene (C 12 H 10 N 2 , Aldrich) was used.
  • the carboxyl compound 4-hexylbenzoic acid (C 13 H 18 O 2 , Aldrich, 99%) and the heterocyclic compound 1,2-Di (4-pyridyl) ethylene (C 12 H 10 N 2 , Aldrich)
  • the dispersion was prepared by dispersing in acetone in a molar ratio of 1: 1, 1: 1, 1: 2 or 1: 4 and stirring for 24 hours to separate solids using an evaporator to prepare an organic mixture.
  • alkoxy benzoic acid 4-alkoxy benzoic acid (carbon number of alkyl chains: 1-8, 10), 4-alkyl benzoic acid (carbon number of alkyl chains: 4, 5, 8) or trans-4-alkylcyclo Hexane carboxylic acid was used.
  • the prepared organic compound and 1,2-Di (4-pyridyl) ethylene (C 12 H 10 N 2 , Aldrich) difunctional material were acetone (acetone) at a molar ratio of 1: 1, 1: 2, 1: 4. ), And the dispersion was prepared by stirring for 24 hours to separate the solids by an evaporator to prepare an organic mixture.
  • Example 3 An organic mixture was prepared in the same manner as in (1), except that 4-ethylpyridine (C 7 H 9 N, Aldrich) was used as a heterocyclic compound, and 4-hexylbenzoic acid (C 13 H 18 O 2 was used as a carboxyl compound. , Aldrich, 99%) was used.
  • Example 2 The organic mixture prepared in (1) and the titania (inorganic nanoparticles) prepared in Example 1 were mixed and then stirred again for 24 hours. Thereafter, the stirred dispersion was separated by using an evaporator to prepare an inorganic nanoparticle composite using a hybrid method.
  • Example 3 An inorganic nanoparticle composite was prepared in the same manner as in (1), but the organic mixture prepared in Example 2. (2) was used.
  • Example 3 An inorganic nanoparticle composite was prepared in the same manner as in (1), but the organic mixture prepared in Example 2. (3) was used.
  • Anhydrous ethanol (anhydrous ethyl alcohol) was used as a solvent for the sand mill.
  • 1 kg of ⁇ 0.1 zirconia beads, 10 g of titania particles, and 180 g of anhydrous ethanol were put into a 1 L glass beaker, and the disk was mounted on a machine and sand milled.
  • Zirconia beads are heavy, which facilitates particle separation in the beads mill after milling.
  • the dispersion solution was taken at 10 minute intervals to check particle size and dispersibility.
  • Figure 2 is a polarization micrograph of the inorganic nanoparticle composite prepared in Example 3. (1).
  • the inorganic nanoparticle composite shows a uniformly oriented state.
  • FIG. 3 is a schematic diagram for explaining the photograph of FIG. 2, and it can be seen that the nanoparticle composite shows a state in which the nanoparticle composite is uniformly oriented in one direction as compared with the related art.
  • FIG. 4 is an incineration XRD graph of the inorganic nanoparticle composition prepared by Example 3.
  • FIG. The XRD was measured using a High / Low Temperature X-ray Diffractometer and a scan speed of 1 deg./min.
  • Figure 5 is a TEM picture of the titania particles prepared in Example 1, it can be seen that the inorganic nanoparticles have an orientation compared to the TEM picture (Fig. 6) of the nanoparticle composition prepared in Comparative Example 1.
  • the organic and inorganic compounds can form a new network, thereby forming a new orientation structure having a direction.
  • Nanoparticle composite having an orientation according to the present invention is applicable to high-strength lightweight composite parts, and can be used as interior and exterior materials for automobiles, ships, aircraft and energy-efficient buildings.

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Abstract

La présente invention concerne un composite de nanoparticule qui présente une orientation et qui comprend : des nanoparticules inorganiques présentant un ou plusieurs groupes fonctionnels X ; un ou plusieurs composés organiques A ayant des groupes fonctionnels Y1 et Y2 capables de se lier à l'hydrogène dans la structure de celui-ci ; et un ou plusieurs composés organiques B ayant un groupe fonctionnel Z capable de se lier à l'hydrogène dans la structure de celui-ci, les nanoparticules inorganiques et le composé organique A étant liés à l'hydrogène par les groupes fonctionnels X et Y1, respectivement. Le composé organique A et le composé organique B sont liés à l'hydrogène par un groupe fonctionnel Y2 et un groupe fonctionnel Z, respectivement. Selon la présente invention, le composite peut être utilisé comme matériau composite hybride pour améliorer de façon remarquable la flexibilité et la force mécanique.
PCT/KR2012/003707 2012-03-22 2012-05-11 Composite de nanoparticule inorganique présentant une orientation WO2013141444A1 (fr)

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