JP2011184397A - Method for producing aldehyde, catalyst and method for producing the same - Google Patents
Method for producing aldehyde, catalyst and method for producing the same Download PDFInfo
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- JP2011184397A JP2011184397A JP2010053400A JP2010053400A JP2011184397A JP 2011184397 A JP2011184397 A JP 2011184397A JP 2010053400 A JP2010053400 A JP 2010053400A JP 2010053400 A JP2010053400 A JP 2010053400A JP 2011184397 A JP2011184397 A JP 2011184397A
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- gold
- producing
- platinum
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- crosslinkable functional
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 8
- 229920000642 polymer Polymers 0.000 claims abstract description 64
- 125000000524 functional group Chemical group 0.000 claims abstract description 41
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000006229 carbon black Substances 0.000 claims abstract description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 239000010931 gold Substances 0.000 claims abstract description 17
- 229910052737 gold Inorganic materials 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 150000003138 primary alcohols Chemical class 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 claims description 28
- -1 aluminum hydride compound Chemical class 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 18
- 150000002344 gold compounds Chemical class 0.000 claims description 16
- 150000003058 platinum compounds Chemical class 0.000 claims description 16
- 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
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000002105 nanoparticle Substances 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
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 150000001299 aldehydes Chemical class 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
- 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
- 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
- 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
- ZADXFVHUPXKZBJ-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxymethyl]oxirane Chemical compound C1=CC(C=C)=CC=C1COCC1OC1 ZADXFVHUPXKZBJ-UHFFFAOYSA-N 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- 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
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- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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Abstract
Description
本発明は一級アルコールの酸化によりアルデヒドを製造する方法、並びに当該製造方法に好適に使用される触媒及びその製造方法に関する。 The present invention relates to a method for producing an aldehyde by oxidation of a primary alcohol, a catalyst suitably used for the production method, and a method for producing the catalyst.
金ナノサイズクラスターを触媒として用いる酸素酸化反応は1989年Harutaらによって、低温一酸化炭素酸化反応において非常に高活性であると報告された(非特許文献1)。 Oxygen oxidation using gold nanosize clusters as a catalyst was reported by Haruta et al. In 1989 to be very highly active in low temperature carbon monoxide oxidation (Non-patent Document 1).
一方、酸素を酸化剤として用いた金属触媒によるアルコールのアルデヒド、ケトン、カルボン酸への酸化反応は、ルテニウムやパラジウム触媒等を用いる例が、均一系触媒、固相触媒ともに多数報告されている。また、近年、金クラスターを触媒として用いる例も多数報告されている(非特許文献2)。 On the other hand, as for the oxidation reaction of alcohol to aldehyde, ketone and carboxylic acid by a metal catalyst using oxygen as an oxidizing agent, many examples using ruthenium or palladium catalyst have been reported for both homogeneous and solid phase catalysts. In recent years, many examples using gold clusters as catalysts have been reported (Non-patent Document 2).
本願発明者らは、マイクロカプセル化法を用いてスチレン系高分子に遷移金属ナノサイズクラスターを担持することにより、パラジウムや白金に於いて非常に高活性な触媒の製造ができることを見出してきた(非特許文献3〜4、特許文献1)。また、金触媒についても、酸化反応でカルボニル化合物が生成することが報告されている(特許文献2)。 The inventors of the present application have found that a highly active catalyst in palladium or platinum can be produced by supporting a transition metal nanosize cluster on a styrenic polymer using a microencapsulation method ( Non-Patent Documents 3 to 4, Patent Document 1). Further, it has been reported that a carbonyl compound is produced by an oxidation reaction for a gold catalyst (Patent Document 2).
これまで、金クラスターを触媒として用いる例が多数報告されているが、適用可能な基質が限られていることや、選択性が悪いといった問題点が残っている。 Many examples of using gold clusters as catalysts have been reported so far, but problems remain such as limited applicable substrates and poor selectivity.
本発明は、高い選択性及び高い転化率をもって、一級アルコールの酸化によりアルデヒドを製造する方法、並びに、当該製造方法に好適に使用される触媒及びその製造方法を提供することを目的とする。 An object of the present invention is to provide a method for producing an aldehyde by oxidation of a primary alcohol with high selectivity and a high conversion rate, a catalyst suitably used in the production method, and a production method thereof.
本発明は、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を提供する。 The present invention provides a carrier obtained by crosslinking the crosslinkable functional group of a styrenic polymer having a side chain containing a crosslinkable functional group, a gold-platinum nanosize cluster and carbon black supported on the carrier. There is provided a method for producing an aldehyde, comprising a step of obtaining an aldehyde by oxidation of a primary alcohol in the presence of a catalyst having the same.
本発明のアルデヒドの製造方法においては、上記スチレン系高分子が上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が好ましい。 In the aldehyde production method of the present invention, the styrenic polymer preferably contains an epoxy group and a hydroxyl group as the crosslinkable functional group.
本発明のアルデヒドの製造方法においては、上記工程を塩基の非存在下で行うことができる。 In the method for producing an aldehyde of the present invention, the above step can be performed in the absence of a base.
また、本発明のアルデヒドの製造方法においては、上記工程を塩基の存在下で行うことができる。 Moreover, in the manufacturing method of the aldehyde of this invention, the said process can be performed in presence of a base.
上記スチレン系高分子は、下記式(1)で表される重合性単量体と、下記式(2)で表される重合性単量体と、下記式(3)で表される重合性単量体との重合体であることが好ましい。
本発明は、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触媒を提供する。 The present invention provides a carrier obtained by crosslinking the crosslinkable functional group of a styrenic polymer having a side chain containing a crosslinkable functional group, a gold-platinum nanosize cluster and carbon black supported on the carrier. The present invention provides a catalyst characterized by comprising:
また、本発明は、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、上記溶液に、上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上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、上記第2の工程の後で上記スチレン系高分子の上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触媒の製造方法を提供する。 The present invention also provides a monovalent or trivalent gold compound and a divalent or tetravalent platinum compound by a reducing agent in a solution containing a styrene polymer having a side chain containing a crosslinkable functional group and carbon black. A first step of reducing, and a second solvent for supporting the gold-platinum nano-sized clusters and the carbon black on the styrene polymer by adding a poor solvent for the styrene polymer to the solution to cause phase separation. And a third step of crosslinking the crosslinkable functional group of the styrenic polymer after the second step, the styrenic polymer having a side chain containing a crosslinkable functional group. There is provided a method for producing a catalyst, characterized in that a catalyst comprising a carrier obtained by crosslinking a crosslinkable functional group, a gold-platinum nanosize cluster and carbon black supported on the carrier is obtained.
上記スチレン系高分子の重量平均分子量は1万〜15万であることが好ましい。 The weight average molecular weight of the styrenic polymer is preferably 10,000 to 150,000.
また、上記第3の工程において、上記スチレン系高分子の上記架橋性官能基を加熱により架橋させることが好ましい。 In the third step, the crosslinkable functional group of the styrenic polymer is preferably crosslinked by heating.
また、上記還元剤は、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が好ましい。 The reducing agent is preferably a borohydride compound, an aluminum hydride compound, or a silicon hydride compound.
また、上記金化合物は、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が好ましい。 The gold compound is preferably a gold halide or a triphenylphosphine complex of gold halide.
さらに、上記白金化合物は、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が好ましい。 Furthermore, the platinum compound is preferably platinum halide or a triphenylphosphine complex of platinum halide.
また、上記金化合物はAuCl(PPh3)であることが好ましく、上記白金化合物はNa2PtCl6であることが好ましい。 The gold compound is preferably AuCl (PPh 3 ), and the platinum compound is preferably Na 2 PtCl 6 .
本発明によれば、高い選択性及び高い転化率をもって、一級アルコールの酸化によりアルデヒドを製造する方法、並びに、当該製造方法に好適に使用される触媒及びその製造方法を提供することができる。 According to the present invention, it is possible to provide a method for producing an aldehyde by oxidation of a primary alcohol with high selectivity and a high conversion rate, a catalyst suitably used for the production method, and a method for producing the same.
以下に、本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
本実施形態に係る触媒は、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。 The catalyst according to the present embodiment includes a support obtained by crosslinking the crosslinkable functional group of a styrenic polymer having a side chain containing a crosslinkable functional group, a gold-platinum nanosize cluster supported on the support, and Carbon black.
また、本実施形態に係る触媒の製造方法は、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、上記溶液に、上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上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、上記第2の工程の後で上記スチレン系高分子の上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ものである。 Moreover, the method for producing a catalyst according to this embodiment includes a monovalent or trivalent gold compound and a divalent or tetravalent platinum compound, a styrenic polymer having a side chain containing a crosslinkable functional group, and carbon black. A first step of reducing with a reducing agent in a solution containing the solution, and adding a poor solvent for the styrenic polymer to the solution to cause phase separation by adding a gold-platinum nanosize cluster and the carbon black to a styrenic polymer. A side chain containing a crosslinkable functional group is passed through a second step of supporting the molecule and a third step of crosslinking the crosslinkable functional group of the styrenic polymer after the second step. A catalyst having a support obtained by crosslinking the crosslinkable functional group of the styrene polymer having the polymer, and a gold-platinum nanosize cluster and carbon black supported on the support is obtained.
上記第1及び第2の工程で、金−白金のナノサイズクラスター及びカーボンブラックをスチレン系高分子に担持するには、1価又は3価の金化合物及び2価又は4価の白金化合物と、スチレン系高分子及びカーボンブラックとを、a)適当な極性の良溶媒に溶解し還元剤と混合した後適当な非極性の貧溶媒で凝集させる、又はb)適当な非極性又は低極性の良溶媒に溶解し還元剤と混合した後適当な極性の貧溶媒で凝集させる、ことにより行われる。金−白金クラスターはスチレン系高分子の芳香環との相互作用により担持される。 In order to support the gold-platinum nano-sized clusters and carbon black on the styrenic polymer in the first and second steps, a monovalent or trivalent gold compound and a divalent or tetravalent platinum compound; Styrenic polymer and carbon black are a) dissolved in a suitable polar good solvent and mixed with a reducing agent and then aggregated with a suitable nonpolar poor solvent, or b) a suitable nonpolar or low polarity good It is carried out by dissolving in a solvent, mixing with a reducing agent, and then aggregating with a poor solvent having an appropriate polarity. The gold-platinum cluster is supported by the interaction with the aromatic ring of the styrenic polymer.
尚、極性の良溶媒としてはテトラヒドロフラン(THF)、ジオキサン、アセトン、N,N−ジメチルホルムアミド(DMF)、N−メチル−2−ピロリドン(NMP)などがあり、非極性又は低極性の良溶媒としてはトルエン、ジクロロメタン、クロロホルムなどが使用できる。極性の貧溶媒としてはメタノール、エタノール、ブタノール、アミルアルコールなどがあり、非極性の貧溶媒としてはヘキサン、ヘプタン、オクタンなどが使用できる。 Examples of good polar solvents include tetrahydrofuran (THF), dioxane, acetone, N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and the like. For example, toluene, dichloromethane, chloroform and the like can be used. Examples of the polar poor solvent include methanol, ethanol, butanol, and amyl alcohol, and examples of the nonpolar poor solvent include hexane, heptane, and octane.
金−白金クラスターを架橋性ポリマーに担持する際のポリマーの濃度は、用いる溶媒やポリマーの分子量によっても異なるが、約5.0〜200mg/mL、好ましくは10〜100mg/mlである。1価又は3価の金化合物は、ポリマー1gに対して、0.01〜0.5mmol、好ましくは0.03〜0.2mmol使用する。2価又は4価の白金化合物は、ポリマー1gに対して、0.01〜0.5mmol、好ましくは0.05〜0.2mmol使用する。還元剤は、還元に必要な量の1〜10当量使用するが、例えば1価の金化合物及び4価の白金化合物を、水素化ホウ素ナトリウムで還元する場合の水素化ホウ素ナトリウムは、金化合物及び白金化合物の0.5〜5倍モルが好適である。還元に必要な温度および時間は金化合物、白金化合物及び還元剤の種類によるが、通常は0℃〜50℃の間、好ましくは室温で、1〜24時間で行われる。相分離する際の貧溶媒は、良溶媒に対して1〜10(v/v)倍量、好ましくは2〜5倍量使用し、0.5〜5時間程度で滴下する。 The concentration of the polymer when the gold-platinum cluster is supported on the crosslinkable polymer varies depending on the solvent used and the molecular weight of the polymer, but is about 5.0 to 200 mg / mL, preferably 10 to 100 mg / ml. The monovalent or trivalent gold compound is used in an amount of 0.01 to 0.5 mmol, preferably 0.03 to 0.2 mmol, relative to 1 g of the polymer. The divalent or tetravalent platinum compound is used in an amount of 0.01 to 0.5 mmol, preferably 0.05 to 0.2 mmol, with respect to 1 g of the polymer. The reducing agent is used in an amount of 1 to 10 equivalents necessary for the reduction. For example, when reducing a monovalent gold compound and a tetravalent platinum compound with sodium borohydride, the sodium borohydride is a gold compound and 0.5-5 times mole of the platinum compound is suitable. The temperature and time required for the reduction depend on the type of gold compound, platinum compound and reducing agent, but are usually between 0 ° C. and 50 ° C., preferably at room temperature, for 1 to 24 hours. The poor solvent for phase separation is used in an amount of 1 to 10 (v / v) times, preferably 2 to 5 times the good solvent, and is dropped in about 0.5 to 5 hours.
1価又は3価の金化合物としては、ハロゲン化金や、ハロゲン化金のトリフェニルホスフィン錯体が好ましい。特に、AuCl(PPh3)が好ましい。 As the monovalent or trivalent gold compound, a gold halide or a triphenylphosphine complex of gold halide is preferable. In particular, AuCl (PPh 3 ) is preferable.
2価又は4価の白金化合物としては、ハロゲン化白金や、ハロゲン化白金のトリフェニルホスフィン錯体が好ましい。特に、Na2PtCl6が好ましい。 As the divalent or tetravalent platinum compound, platinum halide or a triphenylphosphine complex of platinum halide is preferable. In particular, Na 2 PtCl 6 is preferable.
カーボンブラックとしては、ケッチェンブラック等が挙げられる。 Examples of carbon black include ketjen black.
還元剤としては、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、好ましくは水素化ホウ素ナトリウム又はボランを用いることができる。 As the reducing agent, a borohydride compound, an aluminum hydride compound or a silicon hydride compound, preferably sodium borohydride or borane can be used.
スチレン系高分子は、架橋性官能基を含む側鎖を有する。上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が好ましい。架橋性官能基を含む側鎖としては、架橋性官能基のみから成るものであっても、二価の基に架橋性官能基が結合したものでもよい。 The styrenic polymer has a side chain containing a crosslinkable functional group. The crosslinkable functional group preferably contains an epoxy group and a hydroxyl group. The side chain containing a crosslinkable functional group may be composed of only a crosslinkable functional group, or may be one in which a crosslinkable functional group is bonded to a divalent group.
上基二価の基としては、比較的短いアルキレン基、例えば、炭素数が1〜6程度のアルキレン基であってもよいが、−R1(OR2)w−、−R1(COOR2)x−、又は−R1(COOR2)y(OR2)z−(式中、R1は共有結合又は炭素数1〜6、好ましくは共有結合又は炭素数1〜2のアルキレン基を表し、R2はそれぞれ独立して炭素数2〜4、好ましくは炭素数2のアルキレン基を表し、w、x及びzは1〜10の整数、yは1又は2を表す。)で表される主鎖をもつものが親水性であるため好ましい。このような好ましい二価の基として、−CH2(OC2H4)4−や−CO(OC2H4)4−等が挙げられる。 The upper divalent group may be a relatively short alkylene group, for example, an alkylene group having about 1 to 6 carbon atoms, but —R 1 (OR 2 ) w —, —R 1 (COOR 2 ) x -, or -R 1 (COOR 2) y ( oR 2) z - ( wherein, R 1 represents a covalent bond or 1 to 6 carbon atoms, preferably an alkylene group of a covalent bond or a C 1-2 , R 2 each independently represents an alkylene group having 2 to 4 carbon atoms, preferably 2 carbon atoms, w, x and z are integers of 1 to 10 and y represents 1 or 2. Those having a main chain are preferred because they are hydrophilic. Examples of such a preferable divalent group include —CH 2 (OC 2 H 4 ) 4 — and —CO (OC 2 H 4 ) 4 —.
このようなスチレン系高分子として、例えば、下記式(4):
(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。
As such a styrenic polymer, for example, the following formula (4):
(Wherein X a represents an alkylene group or an alkylene group containing an ether bond) or the following formula (5):
(In the formula, Xb represents an alkylene group or an alkylene group containing an ether bond.) A monomer having a structure represented by the formula:
(Wherein X c represents an alkylene group or an alkylene group containing an ether bond) or the following formula (7):
(In the formula, Xd represents an alkylene group or an alkylene group containing an ether bond.) Monomers having a structure represented by the formula: In addition, when the total of these is less than 100%, a styrenic polymer obtained by copolymerizing a monomer mixture containing a styrene monomer as the balance may be mentioned.
好ましいスチレン系高分子として下記式(1)で表される重合性単量体と、下記式(2)で表される重合性単量体と、下記式(3)で表される重合性単量体との重合体が挙げられる。
上記スチレン系高分子は、式(2)で表される重合性単量体を、全単量体中に5〜60%含むことが好ましく、10〜50%含むことがより好ましい。また、式(3)で表される重合性単量体を、10〜60%含むことが好ましく、20〜50%含むことがより好ましい。また、式(2)及び(3)で表される重合性単量体の合計が100%未満となるように含み、残部として式(1)で表されるスチレンモノマーを含むことが好ましい。 The styrenic polymer preferably contains 5 to 60%, more preferably 10 to 50%, of the polymerizable monomer represented by the formula (2). Moreover, it is preferable to contain 10-60% of the polymerizable monomer represented by Formula (3), and it is more preferable to contain 20-50%. Moreover, it is preferable to include so that the sum total of the polymerizable monomer represented by Formula (2) and (3) may be less than 100%, and to contain the styrene monomer represented by Formula (1) as a remainder.
スチレン系高分子の重量平均分子量は、1万から15万であることが好ましい。重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定することができる。 The weight average molecular weight of the styrene polymer is preferably 10,000 to 150,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC).
上述したようなスチレン系高分子、カーボンブラック、金化合物及び白金化合物を、上記のような適当な溶媒に還元剤と共に溶解すると、金化合物及び白金化合物がまず還元を受ける。金化合物及び白金化合物に配位子が結合していた場合は、その際に配位子が脱離する。還元された金及び白金はクラスターとして高分子の疎水性部分に取り込まれ、高分子の芳香環から電子供与を受け微小な状態でも安定化される。その後、高分子に対する貧溶媒を加えることにより、金−白金クラスター及びカーボンブラックを担持した、スチレン系高分子を相分離させることができる。 When the styrenic polymer, carbon black, gold compound and platinum compound as described above are dissolved in a suitable solvent as described above together with a reducing agent, the gold compound and platinum compound are first reduced. When a ligand is bonded to the gold compound and the platinum compound, the ligand is detached at that time. Reduced gold and platinum are incorporated as a cluster into the hydrophobic part of the polymer and are stabilized even in a microscopic state by receiving electrons from the aromatic ring of the polymer. Thereafter, by adding a poor solvent for the polymer, the styrenic polymer carrying the gold-platinum cluster and the carbon black can be phase-separated.
カーボンブラックと共にスチレン系高分子に担持されている金−白金クラスター1個の平均径は20nm以下、好ましくは0.3〜20nm、より好ましくは0.3〜10nm、更に好ましくは0.3〜5nm、より更に好ましくは0.3〜2nm、最も好ましいのは0.3〜1nmであり、数多くの金−白金クラスターがミセルの疎水性部分(スチレン系高分子の芳香環)に均一に分散して存在していると考えられる。このように金属が微小なクラスター(微小金属塊)となっているため、高い触媒活性を示すことができる。 The average diameter of one gold-platinum cluster supported on a styrene polymer together with carbon black is 20 nm or less, preferably 0.3 to 20 nm, more preferably 0.3 to 10 nm, still more preferably 0.3 to 5 nm. More preferably, the thickness is 0.3 to 2 nm, and most preferably 0.3 to 1 nm, and many gold-platinum clusters are uniformly dispersed in the hydrophobic portion of the micelle (the aromatic ring of the styrenic polymer). It is considered to exist. Thus, since the metal is a minute cluster (minute metal lump), high catalytic activity can be exhibited.
金−白金クラスターの径及び価数等の周辺環境は、透過型電子顕微鏡(TEM)又は拡張X線吸収微細構造(EXAFS)で測定することができる。 The surrounding environment such as the diameter and valence of the gold-platinum cluster can be measured with a transmission electron microscope (TEM) or an extended X-ray absorption fine structure (EXAFS).
上記第3の工程では、上述のように金−白金クラスター及びカーボンブラックを担持したスチレン系高分子の架橋性官能基を架橋させる。架橋により金−白金クラスターは安定化すると共に種々の溶剤に対して不溶化し、担持した金−白金クラスターの漏れを防止することができる。架橋反応により、金−白金クラスターを担持した高分子鎖同士を結合させることや、架橋基を有する材料など適当な担体に結合させることもできる。架橋反応は、無溶媒条件で、加熱や紫外線照射、好ましくは加熱により架橋性官能基を反応させることにより行う。架橋反応は、これらの方法以外にも、使用する直鎖型有機高分子化合物を架橋するための従来公知の方法である、例えば架橋剤を用いる方法、過酸化物やアゾ化合物等のラジカル重合触媒を用いる方法、酸又は塩基を添加して加熱する方法、例えばカルボジイミド類のような脱水縮合剤と適当な架橋剤を組み合わせて反応させる方法等に準じても行うことができる。 In the third step, the crosslinkable functional group of the styrenic polymer carrying the gold-platinum cluster and carbon black is crosslinked as described above. By the crosslinking, the gold-platinum cluster is stabilized and insolubilized in various solvents, and leakage of the supported gold-platinum cluster can be prevented. By the crosslinking reaction, polymer chains carrying gold-platinum clusters can be bonded to each other, or can be bonded to an appropriate carrier such as a material having a crosslinking group. The crosslinking reaction is carried out by reacting the crosslinkable functional group under heating and ultraviolet irradiation, preferably by heating, in a solvent-free condition. In addition to these methods, the crosslinking reaction is a conventionally known method for crosslinking a linear organic polymer compound to be used. For example, a method using a crosslinking agent, a radical polymerization catalyst such as a peroxide or an azo compound This method can also be carried out according to a method of using an acid, a method of heating by adding an acid or a base, for example, a method of reacting by combining a dehydrating condensing agent such as carbodiimide and an appropriate crosslinking agent.
架橋性官能基を加熱により架橋させる際の温度は、通常50〜200℃、好ましくは70〜180℃、より好ましくは100〜160℃である。加熱架橋反応させる際の反応時間は、通常0.1〜100時間、好ましくは1〜50時間、より好ましくは2〜10時間である。 The temperature at which the crosslinkable functional group is crosslinked by heating is usually 50 to 200 ° C, preferably 70 to 180 ° C, more preferably 100 to 160 ° C. The reaction time for the heat crosslinking reaction is usually 0.1 to 100 hours, preferably 1 to 50 hours, more preferably 2 to 10 hours.
上記の様にして製造した、高分子担持金−白金クラスターは、塊や膜としたり、担体に固定することもできる。ガラス、シリカゲル、樹脂などの担体表面の架橋性官能基(例えば、水酸基やアミノ基など)と金−白金含有ポリマーの架橋性官能基とを架橋反応させると、高分子担持金−白金クラスターは担体表面に強固に固定される。また、適当な樹脂やガラスで出来た反応容器の表面に、ミセルの架橋性官能基を使用して高分子担持金−白金クラスター組成物を固定化してやれば、より再使用が簡便な触媒担持反応容器として使用できる。 The polymer-supported gold-platinum cluster produced as described above can be made into a lump or membrane, or fixed to a carrier. When a crosslinkable functional group (for example, a hydroxyl group or an amino group) on the surface of a carrier such as glass, silica gel, or resin is crosslinked with a crosslinkable functional group of a gold-platinum-containing polymer, the polymer-supported gold-platinum cluster becomes a carrier. It is firmly fixed on the surface. In addition, if the polymer-supported gold-platinum cluster composition is immobilized on the surface of a reaction vessel made of an appropriate resin or glass using a crosslinkable functional group of micelles, the catalyst-supported reaction can be reused more easily. Can be used as a container.
このようにして得られた架橋型金−白金含有ポリマーミセルは多くの空孔を有しており、適当な溶剤で膨潤して表面積を拡大する。また担持された金及び白金は数ナノメートル以下の非常に小さいクラスターを形成する。 The cross-linked gold-platinum-containing polymer micelle thus obtained has many pores, and swells with an appropriate solvent to increase the surface area. The supported gold and platinum form very small clusters of several nanometers or less.
本実施形態に係るアルデヒドの製造方法は、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。上記製造方法を用いると、高い選択性及び高い転化率をもって、一級アルコールの酸化によりアルデヒドを製造することができる。 The method for producing an aldehyde according to the present embodiment comprises a carrier obtained by crosslinking the crosslinkable functional group of a styrene polymer having a side chain containing a crosslinkable functional group, and a gold-platinum nanoparticle carried on the carrier. A step of obtaining an aldehyde by oxidation of a primary alcohol in the presence of a catalyst having size clusters and carbon black. When the above production method is used, an aldehyde can be produced by oxidation of a primary alcohol with high selectivity and high conversion.
本実施形態に係るアルデヒドの製造方法においては、上記工程を塩基の非存在下で行うことができる。上記工程を塩基の非存在下で行うと、生成したアルデヒドからカルボン酸への更なる酸化反応の進行を抑制することができる。 In the method for producing an aldehyde according to this embodiment, the above steps can be performed in the absence of a base. When the above step is performed in the absence of a base, the progress of further oxidation reaction from the generated aldehyde to the carboxylic acid can be suppressed.
また、本実施形態に係るアルデヒドの製造方法においては、上記工程を塩基の存在下で行うことができる。上記工程を塩基の存在下で行うと、一級アルコールの酸化反応が一層促進され、転化率をさらに高めることができる。塩基としては、アルカリ金属炭酸塩、アルカリ金属カルボン酸塩や水酸化物塩が好適であり、具体的には、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸水素ナトリウム、炭酸セシウム、酢酸ナトリウム、酢酸カリウムなどが挙げられる。塩基の量は、基質に対して0.05〜3当量用いることが好ましい。また、塩基は、水溶液として用いることが好ましい。 Moreover, in the manufacturing method of the aldehyde which concerns on this embodiment, the said process can be performed in presence of a base. When the above step is performed in the presence of a base, the oxidation reaction of the primary alcohol is further promoted, and the conversion rate can be further increased. As the base, alkali metal carbonates, alkali metal carboxylates and hydroxide salts are suitable. Specifically, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate , Cesium carbonate, sodium acetate, potassium acetate and the like. The amount of base is preferably 0.05 to 3 equivalents relative to the substrate. The base is preferably used as an aqueous solution.
基質である一級アルコールを、R3CH2OHで表した場合、R3は脂肪族基、脂環式脂肪族基、又は芳香族基を示し、ヘテロ原子が含まれていてもよい。本実施形態に係るアルデヒドの製造方法は、特にR3が炭素数1〜Xのアルキル基を示す場合に効果的である。この場合、R3は直鎖状でも分岐状でも良い。 The primary alcohol is a substrate, when expressed in R 3 CH 2 OH, R 3 represents an aliphatic group, an alicyclic aliphatic group, or an aromatic group, may contain hetero atoms. The aldehyde production method according to this embodiment is particularly effective when R 3 represents an alkyl group having 1 to X carbon atoms. In this case, R 3 may be linear or branched.
本実施形態に係るアルデヒドの製造方法で用いる酸化剤としては、酸素ガス、又は空気を用いることができる。反応溶媒としては、高分子を膨潤させ基質アルコールを溶解するものであれば、単一溶媒でも混合溶媒でも使用できる。水と有機溶媒の混合溶媒が有効な場合もある。有機溶媒としてはベンゾトリフルオリド(BTF)や、メチルエチルケトンなどが挙げられる。混合溶媒を用いる場合、水と有機溶媒の混合比は1:1〜1:10(容積比)であることが好ましい。触媒量は、基質に対して、金として0.1〜10%(mol/mol)、白金として0.1〜10%(mol/mol)であることが好ましい。基質の濃度は、0.01〜1mmol/ml、好ましくは0.05〜0.5mmol/mlである。反応温度は、0〜80℃、好ましくは室温〜60℃であり、反応時間は、1〜50時間である。 As the oxidizing agent used in the method for producing aldehyde according to the present embodiment, oxygen gas or air can be used. The reaction solvent may be a single solvent or a mixed solvent as long as it can swell the polymer and dissolve the substrate alcohol. A mixed solvent of water and an organic solvent may be effective. Examples of the organic solvent include benzotrifluoride (BTF) and methyl ethyl ketone. When a mixed solvent is used, the mixing ratio of water and organic solvent is preferably 1: 1 to 1:10 (volume ratio). The catalyst amount is preferably 0.1 to 10% (mol / mol) as gold and 0.1 to 10% (mol / mol) as platinum with respect to the substrate. The concentration of the substrate is 0.01 to 1 mmol / ml, preferably 0.05 to 0.5 mmol / ml. The reaction temperature is 0 to 80 ° C., preferably room temperature to 60 ° C., and the reaction time is 1 to 50 hours.
以下、実施例にて本発明を例証するが本発明を限定することを意図するものではない。4−ビニルベンジルグリシジルエーテルは特許文献1に記載の方法に従って合成した。他の化合物は市販品を必要に応じて精製して使用した。酸化反応で得られたアルデヒドの収率は内部標準を用いたガスクロマトグラフィーで定量した。ガスクロマトグラフとして、島津製作所(株)製GC−17Aを用いた。 The following examples illustrate the invention but are not intended to limit the invention. 4-vinylbenzyl glycidyl ether was synthesized according to the method described in Patent Document 1. As other compounds, commercially available products were purified as necessary. The yield of aldehyde obtained by the oxidation reaction was quantified by gas chromatography using an internal standard. As a gas chromatograph, GC-17A manufactured by Shimadzu Corporation was used.
[製造例1]
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。
[Production Example 1]
Sodium hydride (60% in mineral oil, 5.2 g) was added to 150 mL of THF, and tetraethylene glycol (25.4 g, 131 mmol) was added to the reaction solution at 0 ° C. After stirring at room temperature for 1 hour, 1-chloromethyl-4-vinylbenzene (13.3 g, 87.1 mmol) was added and stirring was continued for another 12 hours. After cooling to 0 ° C., diethyl ether was added, and saturated aqueous ammonium chloride solution was added to stop the reaction. The aqueous phase was extracted with ether, the combined organic phases were dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 2- (2- (2- (2- (4-vinylbenzyloxy) ethyoxy) ethyoxy) ethanol) (20.6 g, 66.2 mmol, 76). %).
1 H-NMR (CDCl 3 ) δ2.55-2.59 (m, 1H), 3.59-3.73 (m, 16H), 4.55 (s, 2H), 5.25 (d, 1H , J = 6.4 Hz), 5.53 (d, 1H, J = 18 Hz), 6.71 (dd, 1H, J = 11.0, 17.9 Hz), 7.22-7.27 (m, 3H), 7.31-7.39 (m, 2H);
13 C-NMR δ 61.8, 69.5, 70.5, 70.69, 70.74, 72.6, 73.0, 113.8, 126.3, 128.0, 136.0, 137. 1,138.0.
[製造例2]
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。
Styrene (2.6 g, 25 mmol), 4-vinylbenzyl glycidyl ether (synthesized according to the method described in WO2005 / 085307) (4.75 g, 25 mmol), 2- (2- (2- (2- (2- (4-vinylbenzoyloxy) ethyoxy) ethanol) ethanol (7.67 g, 25 mmol) and a polymerization initiator (V-70, 308 mg, 1 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in chloroform (15 ml). After the deaeration operation, the mixture was stirred in argon at room temperature for 72 hours. After cooling the reaction solution to room temperature, the reaction solution to which 100 ml of THF was added was slowly dropped into 1 liter of diethyl ether at room temperature, and the resulting precipitate was collected by filtration and washed thoroughly with diethyl ether. Then, it dried under reduced pressure at room temperature, and obtained the following formula styrene polymer (polymer A) (8.98 g, x: y: z = 29: 35: 36) as a transparent gum-like solid. The ratio of monomer components of the copolymer was determined by 1 H-NMR.
[製造例3]
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。
[Production Example 3]
A catalyst (PI-CB / Au-Pt) was produced as follows.
500.0 mg of Polymer A obtained in Production Example 2 was dissolved in 32 mL of diglyme (made by Wako Pure Chemical Industries, Ltd., special grade), cooled to 0 ° C., and then 500.0 mg of Ketjen Black (Lion Corporation, carbon ECP) was added. added. The mixture was stirred at 0 ° C. for 15 minutes, and then a solution of 87 mg of sodium borohydride dissolved in 8 mL of diglyme was slowly added to the mixture. The mixture was stirred at 0 ° C. for 15 minutes, and dissolved in 20 mL of diglyme of 141.0 mg of AuClPPh 3 (manufactured by Strem, special grade) and 158.0 mg of Na 2 PtCl 6 (manufactured by Alderich, special grade). The solution was added slowly. After the mixture was stirred at 0 ° C. to room temperature for 12 hours, 120 mL of diethyl ether was slowly added at room temperature. An encapsulated black powder (catalyst capsule) enclosing the dispersed metal was produced. The catalyst capsule was washed several times with diethyl ether and dried at room temperature. Next, this catalyst capsule was heated at 120 ° C. for 5 hours under solvent-free conditions, and the resulting black powder was washed with methylene chloride, water and tetrahydrofuran, and dried at room temperature to produce 1.036 g of black powder (hereinafter “ PI-CB / Au-Pt ").
10-20 mg of PI-CB / Au-Pt was heated at 200 ° C. for 3 hours in a 1: 1 mixture of sulfuric acid and nitric acid, returned to room temperature, and aqua regia was added. When the contents of gold and platinum in the catalyst were measured by ICP analysis of this solution, they were Au: 0.1196 mmol / g and Pt: 0.1764 mmol / g.
[実施例1]
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。
1-octanol (manufactured by Tokyo Chemical Industry Co., Ltd., special grade) (32.6 mg, 0.25 mmol), PI-CB / Au—Pt (Au content 0.1196 mmol / g, 1 mol% in terms of Au), water (2.0 mL) Benzotrifluoride (manufactured by Kanto Chemical Co., Ltd., special grade) (2.0 mL) was mixed in a round bottom flask. After stirring for 24 hours at room temperature under an oxygen atmosphere, the catalyst was recovered by filtration and washing with acetone. The yield was determined by gas chromatography using anisole as an internal standard substance. The reaction formula is shown below. The reaction results (aldehyde yield, carboxylic acid yield, alcohol recovery rate) are shown in Table 1.
[実施例2、3]
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。
[Examples 2 and 3]
In Examples 2 and 3, an oxidation reaction was performed in the same manner as in Example except that the substrate shown in Table 1 was used instead of 1-octanol in Example 1. The reaction results (aldehyde yield, carboxylic acid yield, alcohol recovery rate) are shown in Table 1.
[実施例4]
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。
[Example 4]
200 mg of PI-CB / Au-Pt (Au content 0.1196 mmol / g) and 760 mg of Celite (manufactured by Kanto Chemical Co., Inc.) were mixed and packed into a glass column (diameter 5 mm, total length 100 mm). This column was heated to 60 ° C., and benzotrifluoride in which 0.108 mmol / mL of 1-octanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was 0.0070 mL / min, water was 0.0070 mL / min, and oxygen gas was added. It introduce | transduced using the pump and the mass flow controller at 1 mL / min, respectively, and the oxidation reaction in a distribution system was performed. The liquid phase that passed through the column was collected and diluted with acetone. The yield was determined by gas chromatography using anisole as an internal standard substance. A schematic diagram of the flow system used for the reaction is shown in FIG. The reaction results (aldehyde yield, carboxylic acid yield, alcohol recovery rate) are shown in Table 2.
[実施例5]
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。
[Example 5]
The oxidation reaction was carried out in the same manner as in Example 5 except that the substrate shown in Table 2 was used instead of 1-octanol in Example 4. The reaction results (aldehyde yield, carboxylic acid yield, alcohol recovery rate) are shown in Table 2.
[実施例6〜9]
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。
[Examples 6 to 9]
In Examples 6 to 9, instead of 1-octanol in Example 1, the substrates shown in Table 2 were used, and potassium hydroxide (Wako Pure Chemicals / special grade) 0.324 mmol / L was used instead of water. The oxidation reaction was carried out in the same manner as in Example 4 except that dissolved water was used, the flow rate of benzotrifluoride and water was 0.0140 mL / min, and the flow rate of oxygen gas was 7 mL / min. Went. The reaction results (aldehyde yield, carboxylic acid yield, alcohol recovery rate) are shown in Table 2.
Claims (13)
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触媒の製造方法。 A first step of reducing a monovalent or trivalent gold compound and a divalent or tetravalent platinum compound with a reducing agent in a solution containing a styrene polymer having a side chain containing a crosslinkable functional group and carbon black. When,
A second step of supporting the gold-platinum nano-sized clusters and the carbon black on the styrene polymer by adding a poor solvent for the styrene polymer to the solution to cause phase separation;
A third step of crosslinking the crosslinkable functional group of the styrenic polymer after the second step;
And a carrier obtained by crosslinking the crosslinkable functional group of a styrenic polymer having a side chain containing a crosslinkable functional group, and a gold-platinum nanosize cluster and carbon black supported on the carrier. A method for producing a catalyst, comprising obtaining a catalyst.
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