WO2008056431A1 - Fines particules supportant de l'or ayant une activite catalytique, leur procédé de fabrication et procédé d'oxydation avec celles-ci - Google Patents

Fines particules supportant de l'or ayant une activite catalytique, leur procédé de fabrication et procédé d'oxydation avec celles-ci Download PDF

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Publication number
WO2008056431A1
WO2008056431A1 PCT/JP2007/000503 JP2007000503W WO2008056431A1 WO 2008056431 A1 WO2008056431 A1 WO 2008056431A1 JP 2007000503 W JP2007000503 W JP 2007000503W WO 2008056431 A1 WO2008056431 A1 WO 2008056431A1
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Prior art keywords
gold
polymer
star
fine particles
ether
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PCT/JP2007/000503
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English (en)
Japanese (ja)
Inventor
Sadahito Aoshima
Shokyoku Kanaoka
Naoto Yagi
Yukiko Fukuyama
Hidehiro Sakurai
Tatsuya Tsukuda
Hironori Tsunoyama
Original Assignee
Osaka University
Inter-University Research Institute Corporation National Institutes Of Natural Sciences
Maruzen Petrochemical Co., Ltd.
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Application filed by Osaka University, Inter-University Research Institute Corporation National Institutes Of Natural Sciences, Maruzen Petrochemical Co., Ltd. filed Critical Osaka University
Priority to JP2008542983A priority Critical patent/JP5408648B2/ja
Publication of WO2008056431A1 publication Critical patent/WO2008056431A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/18—Gold

Definitions

  • Gold-supporting fine particles having catalytic action, production method thereof and oxidation method using the same
  • the present invention relates to a gold-supporting fine particle having a catalytic action, a method for producing the same, and an oxidation method using the same. More specifically, the present invention relates to gold-supported fine particles having a controlled particle size, a production method thereof, and an application thereof as an oxidation catalyst.
  • Nanoparticles have attracted much attention because they can be applied in a wide range of fields.
  • metal-containing nanoparticles are being studied for various uses as, for example, conductive materials, or actively applied to various reactions as supported catalysts.
  • Non-patent document 1 reported the CO oxidation reaction by gold-supported nanoclusters, and this led to the investigation of the oxidation reaction by the gold catalyst.
  • Non-Patent Document 2 reports that gold-supported fine particles prepared in the presence of polyvinylpyrrolidone exhibit catalytic activity in the oxidation reaction of alcohol.
  • the catalyst activity varies depending on the particle size of the fine particles, and it is shown that gold-supported fine particles having a particle size of about 1 nm show catalytic activity. Since the gold-supported fine particles all act as a solid catalyst system, the reaction product and the catalyst can be separated by a simple operation such as filtration.
  • Non-Patent Document 3 shows that a vinyl ether polymer having an oxsitylene chain in the side chain interacts efficiently with metal ions in water.
  • a method for producing a star-shaped vinyl ether polymer using a vinyl ether polymer having an oxchethylene chain in the side chain, and the resulting star-shaped vinyl ether polymer Patent Documents 1 and 2 show the metal scavenging ability of mer.
  • Patent Document 1 JP 2005-1 54497
  • Patent Document 2 JP 2006-070094
  • Non-Patent Document 1 JOURN A L OF CATALYS I S, 1 1 volume 5, 30 1-309 (1 989)
  • Non-Patent Document 2 JOURNAL OF AMER I CAN CHEM I CAL
  • Non-patent document 3 Polymer r Preprits, Jpn., 54, No. 1, 1 885 (2005)
  • An object of the present invention is to provide a gold-supported fine particle catalyst system that can separate a reaction product and a catalyst by a simple operation such as filtration and that can be stably reused by suppressing aggregation between the catalysts. It is another object of the present invention to provide a method for producing gold-supporting fine particles having such catalytic activity.
  • the present inventors produced gold-supported fine particles having a controlled particle size by adsorbing gold ions to a star alkenyl ether polymer and reducing it. I found out that I can do it. Further, the inventors have found that the gold-supported fine particles exhibit a catalytic action in the alcohol oxidation reaction and exist stably without agglomeration after the catalytic reaction, thereby completing the present invention.
  • the present invention provides gold-supported fine particles obtained by supporting gold on a star-shaped alkenyl ether polymer.
  • the present invention also provides an oxidation reaction catalyst containing the gold-supported fine particles. Is.
  • the present invention also includes the following steps (1) to (5);
  • the present invention provides a method for producing gold-supported fine particles containing.
  • the present invention provides a method for oxidizing alcohols using the gold-supported fine particles as a catalyst and molecular oxygen as an oxidizing agent.
  • the present invention it is possible to provide gold-supported fine particles having a controlled particle size that exhibits a catalytic action in the oxidation reaction of alcohols.
  • the gold-supported fine particles can be easily separated from the reaction product and the catalyst by a catalyst separation method utilizing temperature-stimulated responsiveness, and are excellent in stability. It becomes an oxidation catalyst.
  • the alkenyl ether used in the present invention is not particularly limited as long as it has a polymerizable vinyl group.
  • a vinyl group, a propenyl group, a 2_butenyl group, a 3-butenyl group examples thereof include ethers having a linear or branched alkenyl group having 2 to 8 carbon atoms such as a 1-methylaryl group, a 2_pentenyl group, and a 2-hexenyl group.
  • the alkenyl ethers may be one kind or two or more kinds of compounds.
  • vinyl ethers are preferred, and in particular, from the viewpoint of efficiently utilizing the temperature stimulus responsiveness of the fine particles in the separation step after the catalytic reaction of the finally prepared gold-supported fine particles, the following formula (1) Will be shown in An oxyethylene chain-containing vinyl ether having such a stimulus responsiveness is more preferable.
  • R 1 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom, and n represents an integer of 1 to 10]
  • the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • Examples of the aliphatic hydrocarbon group include a chain hydrocarbon group and an alicyclic hydrocarbon group.
  • the chain hydrocarbon group for example, ( ⁇ - ⁇ Al force down, C 2 -C 20 algenic, also can be mentioned C 2 -C 20 alkyne. These a linear, minute
  • examples of the alicyclic hydrocarbon group include C 3 to C 2, cycloalkane, C 3 to C 2, cycloargen, and the like.
  • the hydrocarbon group includes a group in which a chain hydrocarbon group of ( ⁇ to ⁇ ) and an alicyclic hydrocarbon group of C 3 to C 8 are bonded.
  • the aromatic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic aromatic hydrocarbon group include a furan group.
  • examples of the polycyclic aromatic hydrocarbon group include a biphenyl group, a triphenyl group, a naphthyl group, an indanyl group, an indenyl group, an anthracenyl group, a phenanthryl group, and the like.
  • hetero atom examples include boron, nitrogen, silicon, phosphorus, etc. These may be one or two or more.
  • the alkenyl ethers used in the present invention may have a hydroxyl group.
  • R 1 is a hydrogen atom
  • the alkenyl ether has a hydroxy group
  • the OH group is a trialkylsilyl group
  • a protecting group such as an alkylsiloxy group, a acetoxy group, or a benzoxy group.
  • the protective group is eliminated with an acid or an alkali to obtain a structural unit having an OH group.
  • a method for producing a star-shaped alkenyl ether polymer has already been reported, and a living cationic polymerization method that has been conventionally developed can be suitably used.
  • a living polymer is obtained by living polymerizing an alkenyl ether, and a bifunctional alkenyl ether is added to the resulting living polymer to obtain a polymer having an alkenyl group in the side chain.
  • the star-shaped alkenyl ether polymer can be obtained by intermolecular crosslinking of the polymer.
  • the star-shaped alkenyl ether polymer can undergo phase transition in the microparticles in response to high sensitivity by temperature stimulation. Control of molecular weight distribution by polymerization is essential.
  • the bifunctional alkenyl ether used in the present invention is not particularly limited as long as it has a polymerizable vinyl group, and is a straight chain or branched chain having 2 to 8 carbon atoms as described above.
  • Bifunctional alkenyl ethers having an alkenyl group are listed, but divinyl ethers are preferable, and divinyl ethers having a structure represented by the following formula (2) are particularly preferable.
  • R 2 represents a divalent organic group which may have a hetero atom.
  • Examples of the divalent organic group represented by R 2 include an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an oxyalkylene group having 1 to 20 carbon atoms, and an alicyclic ring. And divalent organic groups having a skeleton. These may be linear or branched.
  • an alkylene group a methylene group, an ethylene group, etc .
  • an alkenylene group a vinylene group, a probeylene group, etc .
  • an oxyalkylene group an oxymethylene group, an oxyethylene group, etc .
  • the valence of the organic group include a divalent organic radical derived from C 3 -C 2 0 cycloalkane, C 3 -C 2 0 Shikuroarugen like.
  • hetero atom examples include boron, nitrogen, silicon, phosphorus, and the like, as described above, and these may be one or two or more.
  • alicyclic vinyl ethers such as norpolnan vinyl ether and polycyclodecane vinyl ether may be copolymerized as long as the performance required for the star alkenyl ether polymer is not impaired.
  • the weight average molecular weight (M w) obtained from a standard polystyrene calibration curve by the gel permeation chromatography (GPC) method of star-shaped alkenyl ether polymers is usually 5 0 0 to 2, 0 0 0, 0 0 0, particularly preferably 1 0, 0 0 The range is 0 to 1, 0 0 0, 0 0 0.
  • the ratio of the weight average molecular weight (M w) to the number average molecular weight (M n) (M wZM n) determined from the standard polystyrene calibration curve by gel permeation chromatography (GPC) method. ) Is usually in the range of 1.0 to 3.0, more preferably in the range of 1.0 to 2.0, and still more preferably in the range of 1.0 to 1.5.
  • a star alkenyl ether polymer is a polymer in which a alkenyl ether polymer is a branch, a dialkenyl ether cross-linked polymer is a nucleus, and a plurality of branches are bonded to the nucleus.
  • Design and introduction are easy and the molecular structure can be adjusted arbitrarily.
  • the structure can be arbitrarily adjusted by the structure of the bifunctional alkenyl ethers to be introduced, and since the metal coordination ability is sufficient, the particle size is controlled. It is a suitable supported polymer for producing supported fine particles.
  • alkenyl ether polymer having an oxyethylene chain and a copolymer thereof are useful polymers for preparing gold-supported fine particles because of their metal coordination ability, but their functions cannot be expressed in homopolymers and random copolymers. It is necessary to produce and use block copolymers.
  • gold-supported fine particles using a star-type alkenyl ether polymer containing an oxyethylene chain are more preferable because they are more excellent in catalytic activity and reusability.
  • the gold-supported fine particles of the present invention can be obtained by supporting gold on a star-shaped alkenyl ether polymer.
  • the gold loading method is not particularly limited, but when a method in which a gold alkenyl ether polymer is brought into contact with a solution containing gold ions to adsorb the gold ions and then the adsorbed gold ions are reduced is used, the gold loading amount is reduced. This is preferable because it can be easily controlled.
  • a star-shaped alkenyl ether polymer having an oxyethylene chain has a high metal collecting ability, such a method can be more suitably used.
  • the star alkenyl ether polymer is based on the alkenyl ether monomer standard.
  • a reducing agent such as that used in ordinary organic synthesis and react in water.
  • the reducing agent for example DI BA L (water hydride diisobutylaluminum), L i AIH 4, N a BH 4, L i BH 4 and the like, especially N a BH 4 preferred.
  • the reducing agent is usually used in an amount of usually 0 to 100 equivalents, preferably 1 to 50 equivalents, based on a water-soluble compound of gold such as chloroauric acid.
  • the reduction reaction is preferably carried out in the range of _50 to 100 ° C. for 0.1 to 100 hours, preferably in the range of 1 to 90 ° C. for 0.1 to 24 hours.
  • the particle size of the obtained gold-supported fine particles is about 1 to 10 nm, and the particle size distribution can be arbitrarily controlled by the structure of the star-shaped alkenyl ether polymer.
  • any compound capable of proceeding with an oxidation reaction by air can be suitably used.
  • methanol, ethanol, n-propanol, 2_propanol, Alcohols such as n-butanol, sec-butanol, t-butanol, propylene glycol, allylic alcohol, cyclohexanol, benzyl alcohol, p_methylbenzyl alcohol, especially benzyl alcohol are suitable for evaluation of catalyst performance Is done.
  • Benzoic acid is efficiently produced by proceeding the oxidation reaction of benzyl alcohol in water at room temperature.
  • the gold-supported fine particles composed of the star-shaped alkenyl ether polymer undergo phase separation in response to the temperature stimulus. Therefore, it is possible to easily separate the reaction solution and the solid catalyst layer by filtration or the like using the temperature-stimulated responsiveness of the star alkenyl ether polymer. Noh.
  • the gold-supported fine particles exist stably without agglomeration after the reaction, and can be reused as a catalyst.
  • the weight average molecular weight, the number average molecular weight, and the ratio of the weight average molecular weight to the number average molecular weight (MwZMn) are determined by gel filtration chromatography in terms of polystyrene gel.
  • the molecular weight of the star polymer was measured using GPC-MALLS (manufactured by WyattTechnoGoY), which is a gel filtration chromatography (GPC) connected to a light scattering detector.
  • GPC gel filtration chromatography
  • MAL LS The weight average molecular weight measured by MAL LS is larger than the weight average molecular weight measured by GPC, which means that the polymer has a compact structure with many branches [multi-angle light scattering detector, Column (Showa Denko Co., Ltd. Shode X column GPCK—80 6 LX 3), eluent is black mouth form].
  • the number of branches f was calculated according to the following equation.
  • f (number of branches) (weight fraction of alkenyl ether monomer) X [Mw (star)] Z [Mw (branch)]
  • a glass reaction vessel fitted with a three-way stopcock was heated under a nitrogen gas stream to fully dry the inside of the vessel.
  • 2_ (2-ethoxyethoxy) ethyl vinyl ether (2. OM) 2-ethoxyethoxy) ethyl vinyl ether
  • ethyl acetate (1. OM) 1_isobutyoxy cetyl acetate (10 mM) and toluene into the container.
  • 0.5 mL (2 OmM) of a 20 OmM toluene solution of Et 5 AICI 5 was added to initiate polymerization. 1.
  • the weight average molecular weight (Mw) of the polymer produced from 2_ (2-ethoxyethoxy) ethyl vinyl ether having a polymerization degree of 200 is 3.0 X 10 4
  • the number average molecular weight (Mn) is 2.3 X 1 0 4
  • molecular weight distribution (MwZMn) was filed at 1.31.
  • the weight average molecular weight (Mw) of the polymer obtained by continuing the reaction for 18 hours was 8.1 X 10 4
  • number average molecular weight (Mn) was 6.0 X 10 4
  • the molecular weight distribution (MwZMn) was 1.36, which quantitatively suggested that a star polymer with a narrow molecular weight distribution was obtained.
  • the aqueous solution of star polymer synthesized in Example 1 (1.7 wt%) was added with an aqueous solution of chloroauric acid (1.2 wt%) and allowed to stand at 0 ° C. for 1 hour to form a complex. It was. Thereafter, an aqueous solution of Na BH 4 (10 equivalents with respect to chloroauric acid) was added at 0 ° C. with stirring to perform a reduction reaction, and the polymer containing gold-supported nanoparticles obtained after 1 hour was obtained. The color of the aqueous solution was light brownish. Absorption spectrum measurement As a result, absorption of plasmon resonance was observed in the vicinity of 500 nm, and no absorption was observed at 80 nm or more. In addition, examination by transmission electron microscope (TEM) revealed that gold-supported nanoparticles with a particle size of about 3 nm and a uniform size were created.
  • TEM transmission electron microscope
  • the gold-supported nanoparticle (1.7 wt%) supported on the obtained star polymer was used for the oxidation reaction of benzyl alcohol.
  • oxidation reaction was performed using oxygen in the air as an oxygen source under mild conditions of 27 ° C and potassium carbonate (0.7 wt%) in water, about 80% in 4 hours, 8 hours It was confirmed that about 90% of benzyl alcohol was subjected to the reaction.
  • the reaction rate and compound selectivity were calculated by gas chromatography.
  • the main component of the resulting product was benzoic acid, and the other product contained 18% benzoic acid phenyl ester.
  • the catalyst when the temperature of the system was raised to 50 ° C. after the reaction was completed, the catalyst was precipitated within 1 minute and could be easily separated by filtration. Moreover, when the catalyst separated by filtration was put into an aqueous solution and cooled to 27 ° C, it returned to the original color of the catalyst and could be reused.
  • Example 3 Using the gold-supported nanoparticles supported on the recovered star-shaped polymer used in Example 3, the oxidation reaction was performed under the conditions described in Example 3. As a result, about 90% of benzyl alcohol was obtained in 8 hours. It was confirmed that the oxidation reaction proceeded at almost the same rate. It was clear that the selectivity was the same and the particles were catalytically reusable.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

L'invention porte sur de fines particules supportant de l'or ayant une activité catalytique ; sur un procédé de fabrication des particules ; et sur un procédé d'oxydation avec les particules. Les fines particules supportant de l'or comprennent un polymère d'alcényl éther en étoile et de l'or déposé sur celui-ci. L'invention concerne également un catalyseur pour des réactions d'oxydation qui comprennent les fines particules supportant de l'or.
PCT/JP2007/000503 2006-11-10 2007-05-10 Fines particules supportant de l'or ayant une activite catalytique, leur procédé de fabrication et procédé d'oxydation avec celles-ci WO2008056431A1 (fr)

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JP2008542983A JP5408648B2 (ja) 2006-11-10 2007-05-10 触媒作用を有する金担持微粒子、その製造方法及びそれを用いた酸化方法

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
JP2010017696A (ja) * 2008-07-14 2010-01-28 National Institute Of Advanced Industrial & Technology 金属ナノ粒子触媒及び酸素酸化方法
JP2011052079A (ja) * 2009-08-31 2011-03-17 Daikin Industries Ltd 星形ポリマー
JP2011236273A (ja) * 2010-05-06 2011-11-24 Nippon Carbide Ind Co Inc ビニルエーテル誘導体星形ポリマー及びその製造方法
WO2012102286A1 (fr) 2011-01-26 2012-08-02 丸善石油化学株式会社 Composite de nanoparticule métallique et son procédé de production
JP2018193429A (ja) * 2017-05-12 2018-12-06 旭化成株式会社 金属粒子環状構造体、組成物、積層体、及び金属粒子環状構造体の製造方法
WO2023277184A1 (fr) * 2021-07-02 2023-01-05 ダイキン工業株式会社 Polymère en étoile

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010017696A (ja) * 2008-07-14 2010-01-28 National Institute Of Advanced Industrial & Technology 金属ナノ粒子触媒及び酸素酸化方法
JP2011052079A (ja) * 2009-08-31 2011-03-17 Daikin Industries Ltd 星形ポリマー
JP2011236273A (ja) * 2010-05-06 2011-11-24 Nippon Carbide Ind Co Inc ビニルエーテル誘導体星形ポリマー及びその製造方法
WO2012102286A1 (fr) 2011-01-26 2012-08-02 丸善石油化学株式会社 Composite de nanoparticule métallique et son procédé de production
CN103347628A (zh) * 2011-01-26 2013-10-09 丸善石油化学株式会社 金属纳米粒子复合体及其制造方法
JP5827960B2 (ja) * 2011-01-26 2015-12-02 丸善石油化学株式会社 金属ナノ粒子複合体及びその製造方法
US9598553B2 (en) 2011-01-26 2017-03-21 Maruzen Petrochemical Co., Ltd. Metal nanoparticle composite and method for producing the same
EP2669029A4 (fr) * 2011-01-26 2017-08-23 Maruzen Petrochemical Co., Ltd. Composite de nanoparticule métallique et son procédé de production
KR101850173B1 (ko) * 2011-01-26 2018-05-30 마루젠 세끼유가가꾸 가부시키가이샤 금속 나노 입자 복합체 및 그 제조 방법
JP2018193429A (ja) * 2017-05-12 2018-12-06 旭化成株式会社 金属粒子環状構造体、組成物、積層体、及び金属粒子環状構造体の製造方法
WO2023277184A1 (fr) * 2021-07-02 2023-01-05 ダイキン工業株式会社 Polymère en étoile

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