JP5590299B2 - アルデヒドの製造方法、触媒及びその製造方法 - Google Patents
アルデヒドの製造方法、触媒及びその製造方法 Download PDFInfo
- Publication number
- JP5590299B2 JP5590299B2 JP2010053400A JP2010053400A JP5590299B2 JP 5590299 B2 JP5590299 B2 JP 5590299B2 JP 2010053400 A JP2010053400 A JP 2010053400A JP 2010053400 A JP2010053400 A JP 2010053400A JP 5590299 B2 JP5590299 B2 JP 5590299B2
- Authority
- JP
- Japan
- Prior art keywords
- gold
- platinum
- producing
- functional group
- crosslinkable functional
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 39
- 239000003054 catalyst Substances 0.000 title claims description 38
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims 8
- 229920000642 polymer Polymers 0.000 claims description 63
- 125000000524 functional group Chemical group 0.000 claims description 39
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 claims description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 23
- -1 aluminum hydride compound Chemical class 0.000 claims description 22
- 239000006229 carbon black Substances 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 238000004132 cross linking Methods 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 17
- 150000002344 gold compounds Chemical class 0.000 claims description 16
- 150000003058 platinum compounds Chemical class 0.000 claims description 16
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 150000003138 primary alcohols Chemical class 0.000 claims description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000005191 phase separation Methods 0.000 claims description 4
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052990 silicon hydride Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 125000002947 alkylene group Chemical group 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- ZADXFVHUPXKZBJ-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxymethyl]oxirane Chemical compound C1=CC(C=C)=CC=C1COCC1OC1 ZADXFVHUPXKZBJ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000007874 V-70 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
- B01J35/45—Nanoparticles
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0211—Impregnation using a colloidal suspension
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(式中、Xaはアルキレン基又はエーテル結合を含むアルキレン基を表す。)又は下記式(5):
(式中、Xbはアルキレン基又はエーテル結合を含むアルキレン基を表す。)で表される構造を有するモノマーを全モノマー中に5〜60%含み、下記式(6):
(式中、Xcはアルキレン基又はエーテル結合を含むアルキレン基を表す。)又は下記式(7):
(式中、Xdはアルキレン基又はエーテル結合を含むアルキレン基を表す。)で表される構造を有するモノマーを全モノマー中に10〜60%含み、かつこれらの合計が100%以下となるように含み、更にこれらの合計が100%未満の場合には残部としてスチレンモノマーを含むモノマー混合物を共重合して得られたスチレン系高分子が挙げられる。
150mLのTHFにソジウムハイドライド(60% in mineral oil,5.2g)を加え、0℃にてその反応液にテトラエチレングリコール(25.4g,131mmol)を加えた。室温で1時間撹拌した後、1−クロロメチル−4−ビニルベンゼン(13.3g,87.1mmol)を加え、さらに12時間撹拌を続けた。0℃に冷却しジエチルエーテルを加え、飽和塩化アンモニウム水溶液を加え、反応を停止した。水相をエーテルで抽出した後、併せた有機相を無水硫酸ナトリウムで乾燥した後、溶媒を減圧下留去した。得られた残さをシリカゲルカラムクロマトグラフィーにて精製し、2−(2−(2−(2−(4−vinylbenzyloxy)ethoxy)ethoxy)ethoxy)ethanolを得た(20.6g,66.2mmol,76%)。
1H−NMR(CDCl3) δ2.55−2.59(m,1H),3.59−3.73(m,16H),4.55(s,2H),5.25(d,1H,J=6.4Hz),5.53(d,1H,J=18Hz),6.71(dd,1H,J=11.0,17.9Hz),7.22−7.27(m,3H),7.31−7.39(m,2H);
13C−NMR δ61.8,69.5,70.5,70.69,70.74,72.6,73.0,113.8,126.3,128.0,136.0,137.1,138.0。
スチレン(2.6g、25mmol)、4−ビニルベンジルグリシジルエーテル(WO2005/085307に記載の方法に従って合成したもの)(4.75g、25mmol)、製造例1で得た2−(2−(2−(2−(4−vinylbenzyloxy)ethoxy)ethoxy)ethoxy)ethanol(7.67g、25mmol)、及び重合開始剤(和光純薬工業社製V−70、308mg、1mmol)をクロロホルム(15ml)に溶解させ、脱気操作後アルゴン中で室温、72時間攪拌した。反応液を室温まで冷却した後、THF100mlを加えた反応液をジエチルエーテル1l中に室温にてゆっくりと滴下し、得られた沈殿物を濾過分取した後、ジエチルエーテルにて十分に洗浄した。その後、室温にて減圧乾燥させ透明ガム状固体として下式のスチレン系高分子(高分子A)(8.98g、x:y:z=29:35:36)を得た。コポリマーのモノマー成分の比は1H−NMRにより決定した。
以下のようにして、触媒(PI−CB/Au−Pt)を製造した。
製造例2で得た高分子A500.0mgをジグライム(和光純薬工業社製、特級)32mLに溶解させ、0℃まで冷却した後、ケッチェンブラック(ライオン社製、カーボンECP)500.0mgを加えた。この混合液を0℃で15分間攪拌した後に、この混合液へ水素化ホウ素ナトリウム87mgのジグライム8mLに溶解させた溶液をゆっくり加えた。この混合液を0℃で15分間攪拌した後に、この混合液へAuClPPh3(Strem社製、特級)141.0mg及びNa2PtCl6(Alderich社製、特級)158.0mgのジグライム20mLに溶解させた溶液をゆっくり加えた。この混合液を0℃から室温で12時間攪拌した後に、ジエチルエーテル120mLを室温でゆっくり加えた。分散した金属を包み込んだ内包した黒色の粉末(触媒カプセル)が生じた。この触媒カプセルをジエチルエーテルで数回洗浄し、室温で乾燥した。次にこの触媒カプセルを無溶媒条件で120℃で5時間加熱し、生成した黒色粉末を塩化メチレンと水とテトラヒドロフランで洗浄し、室温で乾燥することで黒色粉末1.036gが生成した(以下「PI−CB/Au−Pt」という。)。
PI−CB/Au−Pt 10−20mgを硫酸及び硝酸の重量比1:1の混合液中で200℃で3時間加熱し、室温に戻した後に王水を加えた。この溶液のICP分析により触媒中の金と白金の含量を測定したところ、Au:0.1196mmol/g,Pt:0.1764mmol/gであった。
1−オクタノール(東京化成社製、特級)(32.6mg,0.25mmol)、PI−CB/Au−Pt(Au含量0.1196mmol/g,Au換算で1mol%)、水(2.0mL)、ベンゾトリフルオリド(関東化学社製、特級)(2.0mL)を丸底フラスコ内で混合した。酸素雰囲気下、室温で24時間撹拌した後、触媒を濾過してアセトンで洗浄することによって回収した。収率は、アニソールを内部標準物質としてガスクロマトグラフィーで決定した。反応式を下式に示す。また、反応結果(アルデヒド収率、カルボン酸収率、アルコール回収率)を表1に示す。
実施例2、3においては、実施例1における1−オクタノールに代えて、それぞれ表1に示す基質を用いたこと以外は、実施例と同様にして、酸化反応を行った。反応結果(アルデヒド収率、カルボン酸収率、アルコール回収率)を表1に示す。
PI−CB/Au−Pt(Au含量0.1196mmol/g)200mg、セライト(関東化学社製)760mgを混合し、ガラス製カラム(直径5mm、全長100mm)に充填した。このカラムを60℃へ加熱し、1−オクタノール(東京化成社製、特級)を0.108mmol/mL溶解させたベンゾトリフルオリドを0.0070mL/min、水を0.0070mL/min、酸素ガスを1mL/minで、それぞれポンプおよびマスフローコントローラーを用いて導入し、流通系での酸化反応を行った。カラムを通過した液相を回収し、アセトンで希釈した。収率は、アニソールを内部標準物質としてガスクロマトグラフィーで決定した。反応に用いた流通系装置の概略図を図1に示す。また、反応結果(アルデヒド収率、カルボン酸収率、アルコール回収率)を表2に示す。
実施例4における1−オクタノールに代えて、表2に示す基質を用いたこと以外は実施例4と同様にして、実施例5と同様に酸化反応を行った。反応結果(アルデヒド収率、カルボン酸収率、アルコール回収率)を表2に示す。
実施例6〜9においては、実施例1における1−オクタノールに代えて、それぞれ表2に示す基質を用いたこと、水の代わりに水酸化カリウム(和光純薬・特級)0.324mmol/Lを溶解させた水を用いたこと、ベンゾトリフルオリドおよび水の流量を0.0140mL/minとしたこと、酸素ガスの流量を7mL/minとしたこと以外は、実施例4と同様にして、酸化反応を行った。反応結果(アルデヒド収率、カルボン酸収率、アルコール回収率)を表2に示す。
Claims (13)
- 架橋性官能基を含む側鎖を有するスチレン系高分子の該架橋性官能基を架橋させてなる担体と、該担体に担持された金−白金のナノサイズクラスター及びカーボンブラックとを有する触媒の存在下、一級アルコールの酸化によりアルデヒドを得る工程を備えることを特徴とするアルデヒドの製造方法。
- 前記スチレン系高分子が前記架橋性官能基としてエポキシ基及び水酸基を含むことを特徴とする、請求項1に記載のアルデヒドの製造方法。
- 前記工程は塩基の非存在下で行われることを特徴とする、請求項1又は2に記載のアルデヒドの製造方法。
- 前記工程は塩基の存在下で行われることを特徴とする、請求項1又は2に記載のアルデヒドの製造方法。
- 架橋性官能基を含む側鎖を有するスチレン系高分子の該架橋性官能基を架橋させてなる担体と、該担体に担持された金−白金のナノサイズクラスター及びカーボンブラックとを有することを特徴とする一級アルコールからのアルデヒド合成用触媒。
- 1価又は3価の金化合物及び2価又は4価の白金化合物を、架橋性官能基を含む側鎖を有するスチレン系高分子及びカーボンブラックを含む溶液中で還元剤により還元する第1の工程と、
前記溶液に、前記スチレン系高分子に対する貧溶媒を加えて相分離させることにより金−白金のナノサイズクラスター及び前記カーボンブラックをスチレン系高分子に担持する第2の工程と、
前記第2の工程の後で前記スチレン系高分子の前記架橋性官能基を架橋させる第3の工程と、
を経て、架橋性官能基を含む側鎖を有するスチレン系高分子の該架橋性官能基を架橋させてなる担体と、該担体に担持された金−白金のナノサイズクラスター及びカーボンブラックとを有する触媒を得ることを特徴とする一級アルコールからのアルデヒド合成用触媒の製造方法。 - 前記スチレン系高分子の重量平均分子量が1万〜15万であることを特徴とする、請求項7に記載の触媒の製造方法。
- 前記第3の工程において、前記スチレン系高分子の前記架橋性官能基を加熱により架橋させることを特徴とする、請求項7又は8に記載の触媒の製造方法。
- 前記還元剤が水素化ホウ素化合物、水素化アルミニウム化合物又は水素化ケイ素化合物であることを特徴とする、請求項7〜9のいずれか一項に記載の触媒の製造方法。
- 前記金化合物が、ハロゲン化金又はハロゲン化金のトリフェニルホスフィン錯体であることを特徴とする、請求項7〜10のいずれか一項に記載の触媒の製造方法。
- 前記白金化合物が、ハロゲン化白金又はハロゲン化白金のトリフェニルホスフィン錯体であることを特徴とする、請求項7〜11のいずれか一項に記載の触媒の製造方法。
- 前記金化合物がAuCl(PPh3)であり、前記白金化合物がNa2PtCl6であることを特徴とする請求項7〜12のいずれか一項に記載の触媒の製造方法。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010053400A JP5590299B2 (ja) | 2010-03-10 | 2010-03-10 | アルデヒドの製造方法、触媒及びその製造方法 |
PCT/JP2011/055285 WO2011111671A1 (ja) | 2010-03-10 | 2011-03-07 | アルデヒドの製造方法、触媒及びその製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010053400A JP5590299B2 (ja) | 2010-03-10 | 2010-03-10 | アルデヒドの製造方法、触媒及びその製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2011184397A JP2011184397A (ja) | 2011-09-22 |
JP5590299B2 true JP5590299B2 (ja) | 2014-09-17 |
Family
ID=44563472
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2010053400A Expired - Fee Related JP5590299B2 (ja) | 2010-03-10 | 2010-03-10 | アルデヒドの製造方法、触媒及びその製造方法 |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP5590299B2 (ja) |
WO (1) | WO2011111671A1 (ja) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1739104B1 (en) * | 2004-03-08 | 2014-07-09 | Japan Science and Technology Agency | Polymer-supported metal cluster compositions |
JP4792559B2 (ja) * | 2006-03-10 | 2011-10-12 | 独立行政法人科学技術振興機構 | 酸化反応用高分子担持金クラスター触媒 |
JP5322422B2 (ja) * | 2007-10-09 | 2013-10-23 | 独立行政法人科学技術振興機構 | 高分子担持二元金属クラスター触媒 |
JP4689691B2 (ja) * | 2008-03-10 | 2011-05-25 | 独立行政法人科学技術振興機構 | 酸化反応用高分子担持金クラスター触媒、それを用いたカルボニル化合物の製法 |
JP5299992B2 (ja) * | 2008-07-14 | 2013-09-25 | 独立行政法人産業技術総合研究所 | 金属ナノ粒子触媒及び酸素酸化方法 |
-
2010
- 2010-03-10 JP JP2010053400A patent/JP5590299B2/ja not_active Expired - Fee Related
-
2011
- 2011-03-07 WO PCT/JP2011/055285 patent/WO2011111671A1/ja active Application Filing
Also Published As
Publication number | Publication date |
---|---|
WO2011111671A1 (ja) | 2011-09-15 |
JP2011184397A (ja) | 2011-09-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4792559B2 (ja) | 酸化反応用高分子担持金クラスター触媒 | |
Dong et al. | Nanosilver as a new generation of silver catalysts in organic transformations for efficient synthesis of fine chemicals | |
Biondi et al. | Synthesis of gold nanoparticle catalysts based on a new water-soluble ionic polymer | |
CN109603819B (zh) | 一种石墨烯负载PdRu双金属催化剂及其制备方法和应用 | |
CN103657643B (zh) | 一种制备纳米钯金属催化剂的方法 | |
JP4689691B2 (ja) | 酸化反応用高分子担持金クラスター触媒、それを用いたカルボニル化合物の製法 | |
JP5776066B2 (ja) | カルボン酸エステルの製造方法、触媒及びその製造方法 | |
JP5322422B2 (ja) | 高分子担持二元金属クラスター触媒 | |
CN109453814A (zh) | 含磺酸基和膦配体多级孔聚合物固载铑催化剂及制备和应用 | |
Sha et al. | Selective oxidation of fatty alcohol ethoxylates with H2O2 over Au catalysts for the synthesis of alkyl ether carboxylic acids in alkaline solution | |
CN106622224A (zh) | 纳米金基催化剂在甲酸或甲酸盐合成中的应用 | |
CN103864549B (zh) | 一种制备二苯甲酮类化合物的方法 | |
CN105879862A (zh) | 一种蛋壳型贵金属催化剂的制备方法及其用于氧芴加氢开环制备邻苯基苯酚的方法 | |
JP5590299B2 (ja) | アルデヒドの製造方法、触媒及びその製造方法 | |
JP5299992B2 (ja) | 金属ナノ粒子触媒及び酸素酸化方法 | |
CN109134201A (zh) | 高效降解氟代苯酚类化合物的多相催化加氢脱氟处理方法 | |
JP2008222584A (ja) | イミン化合物の製法 | |
JP5534132B2 (ja) | カルボニル化合物の製造方法、触媒及びその製造方法 | |
JP5580613B2 (ja) | 高分子担持金クラスター触媒を用いた非対称エステルの製法 | |
JP5692704B2 (ja) | アミド化合物の製造方法とその触媒 | |
CN114276221A (zh) | 一种烷基取代的二醚型给电子体的制备方法 | |
WO2020022364A1 (ja) | 1,3-ビスアシルオキシ-2-メチレンプロパンの製造方法 | |
CN106967019B (zh) | 一种制备2,5-二甲酰基呋喃的方法 | |
Fan et al. | Highly efficient hydrogenation of methyl propionate to propanol over hydrous zirconia supported ruthenium | |
CN114685252A (zh) | 肉桂醛的合成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130129 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20130129 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140401 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140602 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140624 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140715 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5590299 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |