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WO2004069740A1 - Hydrolysat d'alcoxyde de metal - Google Patents

Hydrolysat d'alcoxyde de metal Download PDF

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Publication number
WO2004069740A1
WO2004069740A1 PCT/JP2004/001186 JP2004001186W WO2004069740A1 WO 2004069740 A1 WO2004069740 A1 WO 2004069740A1 JP 2004001186 W JP2004001186 W JP 2004001186W WO 2004069740 A1 WO2004069740 A1 WO 2004069740A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal alkoxide
hydrolysis
product
chemical shift
atom
Prior art date
Application number
PCT/JP2004/001186
Other languages
English (en)
Japanese (ja)
Inventor
Toshimi Fukui
Junko Nakamoto
Kenji Yamada
Mitsuhisa WADA
Yoshitaka Fujita
Nobuo Kimura
Original Assignee
Nippon Soda Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Soda Co., Ltd. filed Critical Nippon Soda Co., Ltd.
Priority to JP2005504878A priority Critical patent/JP4780764B2/ja
Publication of WO2004069740A1 publication Critical patent/WO2004069740A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data

Definitions

  • the present invention relates to a metal alkoxide hydrolysis product having a property of dispersing stably without aggregation in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer.
  • a method for producing a transparent and homogeneous metal oxide sol for example, a method for producing a metal oxide precursor sol by hydrolyzing and polymerizing one or more metal alkoxides, There is known a method for producing a metal oxide precursor sol, characterized in that the addition of water is carried out at a temperature of not more than 120 ° C. (Refer to Japanese Patent Application Laid-Open No. 10-29-87697)
  • organic solvent-soluble high molecular weight ladder-like polytitanoxane is obtained by hydrolyzing tetraalkoxytitanium at a temperature of 20 to 90 ° C using water of 1.0 to 1.7 times mol. Is known.
  • the low molecular weight ladder-like polytinoxane is said to dissolve in the organic solvent even in the case of a high molecular weight that gels and becomes insoluble in the organic solvent with the conventional chain polytitanoxane, and provides a dense thin film.
  • an alcohol solution containing 0.1 to 2.0 moles of water is added to 1 mole of the metal salt partially hydrolyzed by adding water, and the mixture is heated to hydrolyze the metal salt.
  • a method for producing a metal oxide precursor solution by forming a metal hydroxide, condensing it after dehydration condensation, and then concentrating it. It is stated that the metal oxide precursor solution forms a complex to provide a homogeneous metal thin film having excellent storage stability and no cracks.
  • the metal thin film using the metal oxide sol obtained by any of the above methods has a problem that the film is insufficient to satisfy the denseness and smoothness of the film.
  • the present invention is used to obtain a film that can sufficiently satisfy denseness and smoothness. It is an object of the present invention to provide a metal oxide sol comprising a metal alkoxide hydrolysis product whose structure has been clarified spectrally.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, by devising a mixing temperature, a mixing amount, and a mixing method of water with respect to a metal alkoxide, an acid, a base, and the like can be contained in an organic solvent.
  • a metal oxide sol that can stably disperse even without the presence of a dispersion stabilizer and a dispersion stabilizer was found, and various spectra of the particles were measured. Led to.
  • M represents a metal atom
  • R represents a C1- (10 alkyl group
  • n represents 2004/001186
  • the present invention relates to the metal alkoxide hydrolysis product according to any one of (1) to (6), which is a compound represented by the formula:
  • M represents a metal atom
  • R represents a C1-C10 alkyl group
  • n represents a valence
  • the tetramethylsilane in the nuclear magnetic resonance spectrum is 0 p.
  • the standard chemical shift value of pm is a carbon atom which is the chemical shift value shifted to a lower magnetic field than the chemical shift value of the position of the oxygen atom in R in the metal alkoxide represented by the formula (I).
  • the chemical shift value of the carbon atom at the / 3 position of the oxygen atom in the functional group is greater than the chemical shift value of the position of the oxygen atom in R in the metal alkoxide represented by the formula (I). Having a carbon atom having the chemical shift value shifted to a high magnetic field. It relates the metal alkoxide hydrolysis product, wherein Rukoto,
  • the relaxation time ( ⁇ ⁇ ) of the carbon atom which is the chemical shift value shifted to the low magnetic field, is the chemical shift value of the chemical shift region on the high magnetic field side higher than the chemical shift value shifted to the low magnetic field. Shorter than the relaxation time ( ⁇ ⁇ ) of a carbon atom 2004 / 00H86
  • the relaxation time (T,) of the carbon atom which is the chemical shift value shifted to the high magnetic field, is the chemical shift value of the chemical shift region on the lower magnetic field side than the chemical shift value shifted to the high magnetic field.
  • the metal alkoxide hydrolysis product has a property of being stably dispersed without aggregation in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer.
  • the metal alkoxide hydrolysis product having a spectral structural characteristic of the present invention can be stably dispersed without aggregation in an organic solvent in the absence of an acid, a base, and / or a dispersion stabilizer. Has properties.
  • the state in which the metal alkoxide hydrolysis product is stably dispersed without agglomeration is a state in which the metal alkoxide hydrolysis product is not coagulated and is not separated inhomogeneously, preferably a transparent and homogeneous state.
  • transparent refers to a state in which the transmittance of visible light is high. Specifically, the concentration of the dispersoid is 0.5% by weight in terms of oxide, and the optical path length of the quartz cell is 1 cm. It refers to a state in which the target sample is an organic solvent, and preferably exhibits a transmittance of 80 to 100% as represented by a spectral transmittance measured under the condition of a light wavelength of 550 nm.
  • the average particle size of the metal alkoxide is preferably in the range of 1 to 50 nm, more preferably in the range of 1 to 20 nm, and more preferably monodisperse in the particle size distribution of 0 to 50 nm.
  • the organic solvent is not particularly limited as long as the organic solvent is an organic substance capable of dispersing the dispersoid.
  • alcohol solvents such as methanol, ethanol, and isopropyl alcohol; methylene chloride; Chlorinated solvents such as chloroform, hexane, cyclohexane, benzene, toluene, xylene, benzene, etc.
  • Hydrocarbon solvents such as tetrahydrofuran, getyl ether and dioxane; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc.
  • Aprotic polar solvents, and silicones such as methylpolysiloxane and ethylphenylpolysiloxane used as a dispersion medium of a titanium dioxide dispersion described in JP-A-9-120838.
  • a solvent having high water solubility and not coagulating at a low temperature is preferable.
  • a lower alcohol solvent is used.
  • ether-based solvents are used alone or in combination of two or more.
  • the acid or base in this case is used as a deflocculant to re-disperse the precipitate formed by coagulation, or as a catalyst for producing dispersoids such as colloid particles by hydrolyzing and dehydrating and condensing metal alkoxides and the like.
  • the acid is not particularly limited as long as it functions as a dispersant for the generated dispersoid, and specific examples of the acid include mineral acids such as hydrochloric acid, nitric acid, boric acid, and boric hydrofluoric acid, acetic acid, formic acid, and the like.
  • Examples thereof include organic acids such as oxalic acid, carbonic acid, trifluoroacetic acid, P-toluenesulfonic acid, and methanesulfonic acid.
  • a photoacid generator that generates an acid by light irradiation, specifically, Examples thereof include diphenyldoniumhexafluorophosphate, triphenylphosphoniumhexafluorophosphate and the like.
  • Examples of the base include triethanolamine, triethylamine, 1,8-diazapicyclo [5,4,0] -7-decene, ammonia, dimethylformamide, and phosphine.
  • the dispersion stabilizer refers to a component added to disperse the dispersoid in the dispersion medium as stably as possible, and includes an anticoagulant such as a deflocculant, a protective colloid, and a surfactant.
  • an anticoagulant such as a deflocculant, a protective colloid, and a surfactant.
  • Specific examples of the compound having such an action include chelating compounds.
  • the compound has at least one carboxyl group in the molecular skeleton and has a strong chelating effect on metals.
  • such compounds include glycolic acid, dalconic acid, lactic acid, tartaric acid, citric acid, Examples thereof include polycarboxylic acids such as malic acid and succinic acid, and hydroxycarboxylic acids, and further include pyrophosphoric acid and tripolyphosphoric acid.
  • polydentate ligand compounds having strong chelating ability for metal atoms include acetylacetone, methyl acetoacetate, ethyl acetate, ethyl acetate-n-propyl, and acetate acetate-i-one.
  • Examples thereof include 2,4-nonanedione and 5-methyl-hexanedione.
  • Sulpers 3000, 9000, 17000, 20000, 24 000 all manufactured by Zeneca
  • Examples thereof include dimethylpolysiloxane methyl (poly) described in JP-A-9-208438, JP-A-2000-53421, and the like.
  • Examples thereof include silicone compounds such as (siloxyalkylene) siloxane copolymer, trimethylsiloxycyanic acid, carboxy-modified silicone oil, and amine-modified silicone.
  • a solution containing a metal alkoxide is added to a metal alkoxide by adding 1 to 2 moles or more to 2 moles or more of a metal alkoxide.
  • a production method in which less than twice the amount of water is added can be exemplified.
  • a compound represented by the formula (I) can be preferably exemplified.
  • M represents a metal atom.
  • the metal atom used in the present invention is an alkali metal element or an alkaline earth metal element from the second period to the sixth period of the periodic table.
  • One or a combination of two or more metals can be exemplified, such as titanium, zirconium, and aluminum. Particularly preferred is one selected from the group consisting of silicon, germanium, germanium, indium, tin, tantalum, zinc, tungsten and lead.
  • R represents a C1-C10 alkyl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group Group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n_decanyl group and the like.
  • metal alkoxide used in the present invention include: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, tetramethoxysilane, tetramethoxysilane.
  • Silanes and the like can be exemplified, and particularly preferred are tetramethoxysilane, tetraethoxysilane, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetraisopropoxide, zirconium tetrabutoxide and the like.
  • metal alkoxides can be used alone or in combination of two or more.
  • the temperature of at least one of the steps of mixing water is equal to or lower than the hydrolysis start temperature of the metal alkoxide
  • the temperature is raised to a temperature not lower than the hydrolysis start temperature of the metal alkoxide
  • the method of mixing the solution containing the metal alkoxide with water is not particularly limited, and water may be added to the metal alkoxide solution, or the metal alkoxide may be added to the solution containing water. It is preferred to add it later.
  • water to be mixed general tap water, distilled water, ion-exchanged water and the like can be used. Among them, distilled water or ion-exchanged water is preferable, and ion-exchanged water having an electric conductivity of 2 as Zcm or less is particularly preferable.
  • the water is preferably used after being diluted with an organic solvent.
  • an organic solvent those having a freezing point below the temperature at which the metal alkoxide does not react with water and hydrolyze, that is, those having a freezing point of 0 ° C or less, particularly 110 ° C or less are preferred.
  • those having no reactivity with the metal alkoxide are preferable, and specifically, alcohols, aliphatic hydrocarbons, and aromatic hydrocarbons 2004/001186
  • Halogenated hydrocarbons ketones, esters, ethers, ketone ethers, ketone esters, ester ethers, and the like. More specific examples of these organic solvents include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, benzyl alcohol, methylcyclohexanol, ethanediol.
  • Ethanol, hexanol, trimethylhexanol, ethyl acetate, propyl acetate, butyl acetate, pentane, hexane, xylene and the like are preferred.
  • the organic solvents can be used alone or in combination of two or more. When water and the organic solvent are uniformly dissolved and mixed, they can be used as they are. When water and the organic solvent are not mixed uniformly, they can be uniformly dispersed and used by a method such as stirring treatment or ultrasonic treatment.
  • the amount of the organic solvent to be diluted is preferably in the range of 2 to 100 parts by weight with respect to 1 part by weight of water.
  • the amount of water used is preferably in the range of 12 moles or more and less than 2 moles relative to the number of moles of the metal compound. If the molar ratio is less than 1/2 times, hydrolysis and depolymerization do not proceed uniformly, and the metal compound represented by the formula (I) or the like may remain unreacted, and a homogeneous and dense film cannot be formed. .
  • the molar ratio is more than 2 times, gelation or aggregation of particles occurs during the hydrolysis and polycondensation processes, so that a homogeneous and dense film cannot be formed.
  • the hydrolysis start temperature is the lowest temperature at which hydrolysis proceeds when the metal alkoxide comes into contact with water.
  • the hydrolysis initiation temperature described in Japanese Patent Application Laid-Open No. Hei 1-23407 can be exemplified.
  • the temperature below the hydrolysis initiation temperature is not particularly limited as long as the solution does not solidify, but is preferably a temperature in the range of ⁇ 50 to ⁇ 100 ° C. After mixing with water at a temperature equal to or lower than the hydrolysis start temperature, it is preferable to carry out the reaction by raising the temperature to a temperature equal to or higher than the hydrolysis start temperature.
  • the hydrolysis and polycondensation process of the metal alkoxide under the above conditions is preferably performed in an organic solvent.
  • organic solvent include those similar to the organic solvents used by mixing with water.
  • Preferred examples are hydrocarbon solvents such as benzene and toluene, and ether solvents such as tetrahydrofuran and getyl ether.
  • the amount of the organic solvent to be used is 100 to 100,000 parts by weight, preferably 100 to 3,000 parts by weight, and preferably less than 100 parts by weight, based on 100 parts by weight of the metal alkoxide.
  • the generated fine particles grow in a bonded state, making it difficult to control the particle size.
  • the content exceeds 10,000,000 parts by weight, the solution is too dilute to produce fine particles. There is.
  • the metal alkoxide hydrolyzate obtained by the above method is dissolved or uniformly dispersed in the used organic solvent without aggregation without using an acid, a base, or a dispersion stabilizer. And forms a clear solution.
  • this solution can be used as it is, or can be used after diluting with an appropriate solvent, distilling off the solvent and re-dissolving in another solvent.
  • this dispersion when this dispersion is used, gel films, gel fibers, bulk gels, and the like having a low content of organic substances are obtained.
  • the organic substances are desorbed from these gels by heat treatment, etc., The destruction of the microstructure and the amount of residual pores can be reduced.
  • the various spectra of the metal alkoxide hydrolysis product obtained as described above were measured, it was found that the metal alkoxide had features not found in the past. The details will be described in Examples.
  • FIG. 1 shows the results of the titanium alkoxide hydrolysis product prepared in Example 1.
  • FIG. 2 shows a 13 C NMR spectrum diagram of the hydrolysis product of titanium alkoxide prepared in Example 1.
  • FIG. 3 shows a spectrum diagram of 13 C NMR in which the relaxation time of the titanium alkoxide hydrolysis product prepared in Example 1 was changed.
  • FIG. 4 shows a 17 O NMR spectrum diagram of the titanium alkoxide hydrolysis product prepared in Example 2.
  • Titanium tetraisopropoxide (A-1 manufactured by Nippon Soda Co., Ltd .: purity 99.9%, acid
  • 30 g (1.86 mol 1) of toluene was dissolved in 190 g of toluene, and after displacing with nitrogen gas, a methanol bath containing dry ice was added (approximately 11%).
  • a mixed solution of 30 ⁇ 4 g of ion-exchanged water (H 20 / T i 0.9 mo I / mo I) diluted with 274 g of isopropanol, which was separately prepared, was added dropwise over 90 minutes while stirring.
  • the liquid temperature of the flask during the dropwise addition was kept at ⁇ 15 to 110 ° C. After completion of the dropwise addition, the temperature was maintained at 110 ° C. for 30 minutes, the temperature was further raised to room temperature, and stirring was continued for 1 hour to obtain a colorless transparent liquid.
  • having a hydrogen atom shifted to a low magnetic field means that all the hydrogen atoms are shifted to a low magnetic field as compared with the raw material, and Including cases.
  • Example 1 The solution obtained in Example 1 was applied to a polyethylene terephthalate (PET) substrate whose surface was treated with ozone using No. 3 barco overnight, dried at 100 ° C. for 10 minutes, and dried. A transparent metal oxide film was formed thereon.
  • P PET polyethylene terephthalate
  • SPM Seiko Instruments, SPA-400 (SII)
  • the average roughness of the surface was 5 nm or less.
  • the surface of the material film was found to be smooth.
  • the hydrolysis product obtained by hydrolyzing the metal alkoxide of the present invention is a monodisperse fine particle having a small average particle size, and is a uniform and transparent solution even in an organic solvent.
  • the film has a high industrial value because it can form a transparent and smooth metal oxide thin film and can be widely used as an optical material.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

L'invention concerne un sol d'oxyde métallique constitué d'un hydrolysat d'alcoxyde de métal dont la structure a été spectralement élucidée, que l'on utilise pour obtenir un film faisant preuve d'une densité et d'une planéité très satisfaisantes. L'hydrolysat d'alcoxyde métallique est un produit obtenu par hydrolyse d'un alcoxyde métallique caractérisé en ce que 70 % atomique ou plus des atomes d'oxygène apportés dans le produit dans l'eau utilisée pour l'hydrolyse sont des atomes d'oxygène ν3.
PCT/JP2004/001186 2003-02-05 2004-02-05 Hydrolysat d'alcoxyde de metal WO2004069740A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005504878A JP4780764B2 (ja) 2003-02-05 2004-02-05 金属アルコキシド加水分解生成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-28916 2003-02-05
JP2003028916 2003-02-05

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WO2004069740A1 true WO2004069740A1 (fr) 2004-08-19

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006069876A (ja) * 2004-09-06 2006-03-16 Nippon Soda Co Ltd 新規骨格を有する金属化合物、その製造方法、分散液及び分散体
WO2009057675A1 (fr) * 2007-11-02 2009-05-07 Toyota Jidosha Kabushiki Kaisha Poudre pour noyau magnétique, noyau magnétique pulvérulent et procédés de production de ceux-ci
US8598380B2 (en) 2010-02-23 2013-12-03 Asahi Kasei Chemicals Corporation Method for producing aryloxytitanium composition and aryloxytitanium composition
US9079170B2 (en) 2010-02-23 2015-07-14 Asahi Kasei Chemicals Corporation Method for producing diaryl carbonate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01230407A (ja) * 1987-11-17 1989-09-13 Japan Synthetic Rubber Co Ltd 微粒子状金属化合物の製造方法
JPH0959022A (ja) * 1995-08-23 1997-03-04 Nippon Steel Corp Ｍｎ系ペロフスカイト酸化物薄膜の製造方法
JPH10298769A (ja) * 1997-04-18 1998-11-10 Kansai Shin Gijutsu Kenkyusho:Kk 金属酸化物前駆体ゾルの製造方法および金属酸化物成形体の製造方法
JP2001026421A (ja) * 1999-07-14 2001-01-30 Fukuoka Prefecture ゾル・ゲル法による結晶性薄膜の形成方法
JP2001342018A (ja) * 2000-05-31 2001-12-11 Japan Carlit Co Ltd:The 金属酸化物前駆体溶液及び金属酸化物薄膜
WO2003014022A1 (fr) * 2001-08-03 2003-02-20 Nippon Soda Co., Ltd. Substance dispersee contenant des liaisons metal-oxygene

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JPH05805A (ja) * 1991-06-20 1993-01-08 Sumitomo Electric Ind Ltd ゾルゲル法による薄膜の作製方法
JPH07171397A (ja) * 1993-12-21 1995-07-11 Nippon Oil Co Ltd 固体酸触媒およびその製造方法
JP2002275390A (ja) * 2001-03-15 2002-09-25 Fukuoka Prefecture 結晶性ゲル分散コーティング溶液及び結晶性ゲル分散コーティング溶液を用いた薄膜形成方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01230407A (ja) * 1987-11-17 1989-09-13 Japan Synthetic Rubber Co Ltd 微粒子状金属化合物の製造方法
JPH0959022A (ja) * 1995-08-23 1997-03-04 Nippon Steel Corp Ｍｎ系ペロフスカイト酸化物薄膜の製造方法
JPH10298769A (ja) * 1997-04-18 1998-11-10 Kansai Shin Gijutsu Kenkyusho:Kk 金属酸化物前駆体ゾルの製造方法および金属酸化物成形体の製造方法
JP2001026421A (ja) * 1999-07-14 2001-01-30 Fukuoka Prefecture ゾル・ゲル法による結晶性薄膜の形成方法
JP2001342018A (ja) * 2000-05-31 2001-12-11 Japan Carlit Co Ltd:The 金属酸化物前駆体溶液及び金属酸化物薄膜
WO2003014022A1 (fr) * 2001-08-03 2003-02-20 Nippon Soda Co., Ltd. Substance dispersee contenant des liaisons metal-oxygene

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006069876A (ja) * 2004-09-06 2006-03-16 Nippon Soda Co Ltd 新規骨格を有する金属化合物、その製造方法、分散液及び分散体
JP4585256B2 (ja) * 2004-09-06 2010-11-24 日本曹達株式会社 チタン化合物の微粒子を含む分散体の製造方法
WO2009057675A1 (fr) * 2007-11-02 2009-05-07 Toyota Jidosha Kabushiki Kaisha Poudre pour noyau magnétique, noyau magnétique pulvérulent et procédés de production de ceux-ci
US8598380B2 (en) 2010-02-23 2013-12-03 Asahi Kasei Chemicals Corporation Method for producing aryloxytitanium composition and aryloxytitanium composition
US9079170B2 (en) 2010-02-23 2015-07-14 Asahi Kasei Chemicals Corporation Method for producing diaryl carbonate

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JPWO2004069740A1 (ja) 2006-05-25

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