JP2008006350A - Method for carrying metal catalyst on fibrous protein - Google Patents
Method for carrying metal catalyst on fibrous protein Download PDFInfo
- Publication number
- JP2008006350A JP2008006350A JP2006177371A JP2006177371A JP2008006350A JP 2008006350 A JP2008006350 A JP 2008006350A JP 2006177371 A JP2006177371 A JP 2006177371A JP 2006177371 A JP2006177371 A JP 2006177371A JP 2008006350 A JP2008006350 A JP 2008006350A
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- metal catalyst
- fibrous protein
- osmium
- catalyst compound
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 66
- 239000002184 metal Substances 0.000 title claims abstract description 66
- 108091005899 fibrous proteins Proteins 0.000 title claims abstract description 32
- 102000034240 fibrous proteins Human genes 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 230000001603 reducing effect Effects 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 62
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 229910052763 palladium Inorganic materials 0.000 claims description 32
- 108010022355 Fibroins Proteins 0.000 claims description 17
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052762 osmium Inorganic materials 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- XSXHWVKGUXMUQE-UHFFFAOYSA-N dioxoosmium Chemical compound O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 claims description 8
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000489 osmium tetroxide Inorganic materials 0.000 claims description 8
- 239000012285 osmium tetroxide Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- TWKVUTXHANJYGH-UHFFFAOYSA-L allyl palladium chloride Chemical compound Cl[Pd]CC=C.Cl[Pd]CC=C TWKVUTXHANJYGH-UHFFFAOYSA-L 0.000 claims description 3
- JMVOCSLPMGHXPG-UHFFFAOYSA-N dipotassium;dioxido(dioxo)osmium Chemical compound [K+].[K+].[O-][Os]([O-])(=O)=O JMVOCSLPMGHXPG-UHFFFAOYSA-N 0.000 claims description 3
- VGKQJCSDERXWRV-UHFFFAOYSA-H dipotassium;hexachloroosmium(2-) Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[K+].[K+].[Os+4] VGKQJCSDERXWRV-UHFFFAOYSA-H 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- IHUHXSNGMLUYES-UHFFFAOYSA-J osmium(iv) chloride Chemical compound Cl[Os](Cl)(Cl)Cl IHUHXSNGMLUYES-UHFFFAOYSA-J 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims 1
- 108090000623 proteins and genes Proteins 0.000 claims 1
- 102000004169 proteins and genes Human genes 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 2
- -1 palladium halides Chemical class 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000007810 chemical reaction solvent Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 241000255789 Bombyx mori Species 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229940035429 isobutyl alcohol Drugs 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 2
- 150000002908 osmium compounds Chemical class 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical class [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- VNNMRVBJAGPLQV-UHFFFAOYSA-N 1,2-dichlorocycloocta-1,5-diene;ruthenium Chemical compound [Ru].ClC1=C(Cl)CCC=CCC1 VNNMRVBJAGPLQV-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- GPOFSFLJOIAMSA-UHFFFAOYSA-N 1-chloro-4-ethylbenzene Chemical compound CCC1=CC=C(Cl)C=C1 GPOFSFLJOIAMSA-UHFFFAOYSA-N 0.000 description 1
- ZXFDJWMFCAEGED-UHFFFAOYSA-N 1-chlorocycloocta-1,5-diene;iridium Chemical compound [Ir].ClC1=CCCC=CCC1 ZXFDJWMFCAEGED-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MNWOUQVWYUQQPI-UHFFFAOYSA-N C1(=CC=CCCCC1)[Ru]C1=CC=CCCCC1 Chemical compound C1(=CC=CCCCC1)[Ru]C1=CC=CCCCC1 MNWOUQVWYUQQPI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- 229910021603 Ruthenium iodide Inorganic materials 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
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- VVAOPCKKNIUEEU-PHFPKPIQSA-L dichloro(cycloocta-1,5-diene)platinum(ii) Chemical compound Cl[Pt]Cl.C\1C\C=C/CC\C=C/1 VVAOPCKKNIUEEU-PHFPKPIQSA-L 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- JFROQFOCFOKDKU-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;dihydrate Chemical compound O.O.[K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O JFROQFOCFOKDKU-UHFFFAOYSA-L 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 1
- VWQMDHRZIPQGJQ-UHFFFAOYSA-N n-ethylethanamine;formic acid Chemical compound [O-]C=O.CC[NH2+]CC VWQMDHRZIPQGJQ-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 description 1
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- HDKCVDHYIIKWFM-UHFFFAOYSA-K octanoate;rhodium(3+) Chemical compound [Rh+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HDKCVDHYIIKWFM-UHFFFAOYSA-K 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- INXLGDBFWGBBOC-UHFFFAOYSA-N platinum(2+);dicyanide Chemical compound [Pt+2].N#[C-].N#[C-] INXLGDBFWGBBOC-UHFFFAOYSA-N 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- AFGAERUSIXWDRP-UHFFFAOYSA-N potassium osmium(6+) Chemical compound [K+].[Os+6] AFGAERUSIXWDRP-UHFFFAOYSA-N 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- 229940032753 sodium iodate Drugs 0.000 description 1
- 235000015281 sodium iodate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Abstract
Description
本発明は、繊維状タンパク質への金属触媒の担持方法に関する。 The present invention relates to a method for supporting a metal catalyst on a fibrous protein.
従来より、パラジウム−炭素触媒に代表されるような、酸化又は還元反応に使用される不均一系の金属触媒が数多く知られている。従来の不均一系触媒は、容易に発火し易い、触媒の回収又は再利用等が煩雑になる等の問題点があった。このような問題点を解決するため、近年、不均一系の金属触媒を担体に担持させたものが開発されており、中でも不均一系の金属触媒を繊維状タンパク質に担持させたもの（例えば絹フィブロイン担持パラジウム［Ｐｄ／Ｆｉｂ］触媒等）が、従来の金属触媒と官能基選択性等の触媒活性が異なる点から注目を集めている（例えば非特許文献１、非特許文献２、非特許文献３）。 Conventionally, many heterogeneous metal catalysts used for oxidation or reduction reactions, such as palladium-carbon catalysts, are known. Conventional heterogeneous catalysts have problems such as being easy to ignite, and complicated recovery or reuse of the catalyst. In order to solve such problems, in recent years, a material in which a heterogeneous metal catalyst is supported on a carrier has been developed. Among them, a material in which a heterogeneous metal catalyst is supported on a fibrous protein (for example, silk Fibroin-supported palladium [Pd / Fib] catalysts, etc.) are attracting attention because they differ from conventional metal catalysts in catalytic activity such as functional group selectivity (for example, Non-Patent Document 1, Non-Patent Document 2, Non-Patent Documents). 3).
これら不均一系の金属触媒を繊維状タンパク質に担持させたものの製造方法としては、例えば〈１〉パラジウムを絹に吸着させた触媒を高温、高圧、強酸性条件下で調製する方法（例えば非特許文献１）、〈２〉絹フィブロインを酢酸パラジウムのメタノール溶液に室温下４日間静置する方法（例えば非特許文献２、非特許文献３）等が知られている。しかしながら、〈１〉の方法では、得られた触媒の一部を切り取って反応に使用した場合、切り取る箇所によって触媒活性に差が出てしまい反応の再現性に悪影響を及ぼしてしまう等の問題点があり、〈２〉の方法は、調製に４日間もの時間を要することから、工業的生産には有利なものではなかった。 For example, <1> a method of preparing a catalyst in which palladium is adsorbed on silk under high temperature, high pressure, and strong acidic conditions (for example, non-patented) Literature 1), <2> A method in which silk fibroin is allowed to stand in a methanol solution of palladium acetate for 4 days at room temperature (for example, Non-Patent Literature 2 and Non-Patent Literature 3) is known. However, in the method <1>, when a part of the obtained catalyst is cut out and used for the reaction, there is a problem in that the catalytic activity varies depending on the portion to be cut out and adversely affects the reproducibility of the reaction. The method <2> is not advantageous for industrial production because it takes 4 days to prepare.
そのため、繊維状タンパク質に担持させた金属触媒（以下、繊維状タンパク質担持金属触媒と略記する場合がある。）のどの部分を切り取って使用してもほぼ同等の触媒活性を有し、また、短時間で調製が可能で工業的生産に適した、繊維状タンパク質への金属触媒の担持方法の開発が望まれていた。 Therefore, any portion of a metal catalyst supported on a fibrous protein (hereinafter sometimes abbreviated as “fibrous protein-supported metal catalyst”) has almost the same catalytic activity even if it is cut out and used. It has been desired to develop a method for supporting a metal catalyst on a fibrous protein that can be prepared in time and is suitable for industrial production.
本発明は、工業的生産に適した繊維状タンパク質への金属触媒の担持方法を提供することにある。さらに詳しくは、得られる繊維状タンパク質担持金属触媒のどの部分を切り取って使用しても、その触媒活性がほぼ同等で、なおかつ、短時間で調製が可能な、繊維状タンパク質への金属触媒の担持方法を提供することにある。 It is an object of the present invention to provide a method for supporting a metal catalyst on a fibrous protein suitable for industrial production. More specifically, no matter what part of the resulting fibrous protein-supported metal catalyst is cut out, the catalytic activity is almost the same, and the metal catalyst can be supported on the fibrous protein that can be prepared in a short time. It is to provide a method.
本発明は、金属触媒化合物と繊維状タンパク質とを、水、金属触媒化合物を還元し得る有機溶媒、これらの混合液又は還元剤を含む溶媒中で、超音波照射下に接触させることを特徴とする、繊維状タンパク質への金属触媒の担持方法である。 The present invention is characterized in that the metal catalyst compound and the fibrous protein are brought into contact with each other under ultrasonic irradiation in water, an organic solvent capable of reducing the metal catalyst compound, a mixture thereof, or a solvent containing a reducing agent. This is a method for supporting a metal catalyst on a fibrous protein.
本発明の担持方法によれば、従来の担持方法で得られたものと同程度の活性を有する繊維状タンパク質担持金属触媒を、短時間で調製することが可能となる。 According to the supporting method of the present invention, it is possible to prepare a fibrous protein-supported metal catalyst having an activity comparable to that obtained by the conventional supporting method in a short time.
本発明に於ける繊維状タンパク質としては、具体的には、例えば絹糸、絹フィブロイン、羊毛等が挙げられ、中でも絹糸、絹フィブロインが好ましく、その中でも絹フィブロインがより好ましい。 Specific examples of the fibrous protein in the present invention include silk thread, silk fibroin and wool, among which silk thread and silk fibroin are preferable, and silk fibroin is more preferable.
尚、絹フィブロインとは、カイコ（Bombyx mori）に代表される絹糸虫から合成される繭の主要な繊維状タンパク質を意味する。当該絹フィブロインは、繊維業者から購入することも可能であるが、例えばカイコから得られた繭を炭酸ナトリウム、亜ジチオン酸ナトリウム及びエチレンジアミン四酢酸二カリウム塩（EDTA dipotassium salt dihydrate）を含む水溶液中で煮沸し、次いで水洗、乾燥することにより調製することができる。 Silk fibroin means the main fibrous protein of cocoons synthesized from silkworms represented by silkworm (Bombyx mori). The silk fibroin can be purchased from a textile company. For example, silkworms obtained from silkworms in an aqueous solution containing sodium carbonate, sodium dithionite and dipotassium salt of ethylenediaminetetraacetate (EDTA dipotassium salt dihydrate). It can be prepared by boiling, then washing with water and drying.
本発明に於ける金属触媒は、主として０価の金属触媒を意味するが、１価や２価等の低原子価の金属触媒を完全に排除するものではない。尚、以下これらを０価の金属触媒と称する。また、上記金属触媒としては、具体的には、例えばパラジウム、オスミウム、白金、ルテニウム、ロジウム、イリジウム、ニッケル等が挙げられ、中でもパラジウム、オスミウムが好ましく、その中でもパラジウムがより好ましい。 The metal catalyst in the present invention mainly means a zero-valent metal catalyst, but does not completely exclude a low-valence metal catalyst such as monovalent or divalent. Hereinafter, these are referred to as zero-valent metal catalysts. Specific examples of the metal catalyst include palladium, osmium, platinum, ruthenium, rhodium, iridium, nickel, etc. Among them, palladium and osmium are preferable, and palladium is more preferable.
本発明に於ける金属触媒化合物としては、本発明で用いられる、水、金属触媒化合物を還元し得る水溶性有機溶媒、これらの混合液又は還元剤を含む溶媒（以下、本発明に係る反応溶媒と略記する場合がある。）中で還元され、０価の金属触媒となるものであれば特に限定されないが、具体的には、上記した如き反応溶媒中で還元され、０価のパラジウム、０価のオスミウム、０価の白金、０価のルテニウム、０価のロジウム、０価のイリジウム又は０価のニッケルとなる、例えば塩化パラジウム、臭化パラジウム、ヨウ化パラジウム等のハロゲン化パラジウム、硝酸パラジウム等のパラジウムの無機酸塩、酢酸パラジウム、トリフルオロ酢酸パラジウム、塩化アリルパラジウム、塩化（１，５−シクロオクタジエン）パラジウム、パラジウムアセチルアセトナート、シアン化パラジウム等のパラジウムの有機酸塩、塩化オスミウム等のハロゲン化オスミウム、二酸化オスミウム、四酸化オスミウム、オスミウム酸（VI）カリウム、ヘキサクロロオスミウム酸カリウム等のオスミウムの無機酸塩、塩化白金、臭化白金、ヨウ化白金等のハロゲン化白金、酸化白金、クロロ白金酸、テトラクロロ白金酸アンモニウム、ヘキサクロロ白金酸カリウム等の白金の無機酸塩、白金アセチルアセトナート、白金ヘキサフルオロアセチルアセトナート、ジクロロ（１，５−シクロオクタジエン）白金、シアン化白金等の白金の有機酸塩、塩化ルテニウム、臭化ルテニウム、ヨウ化ルテニウム等のハロゲン化ルテニウム、酸化ルテニウム、ルテニウム酸カリウム、ペンタクロロルテニウム酸カリウム等のルテニウムの無機酸塩、ビス（シクロオクタジエニル）ルテニウム、クロロ（シクロペンタジエニル）ビス（トリフェニルホスフィン）ルテニウム、ジクロロ（１，５−シクロオクタジエン）ルテニウム、ルテニウムアセチルアセトナート等のルテニウムの有機酸塩、塩化ロジウム、臭化ロジウム、ヨウ化ロジウム等のハロゲン化ロジウム、硝酸ロジウム、酸化ロジウム、ヘキサクロロロジウム酸アンモニウム、ヘキサクロロロジウム酸ナトリウム等のロジウムの無機酸塩、酢酸ロジウム、トリフルオロ酢酸ロジウム、ロジウムアセチルアセトナート、オクタン酸ロジウム等のロジウムの有機酸塩、塩化イリジウム、臭化イリジウム等のハロゲン化イリジウム、酸化イリジウム、ヘキサクロロイリジウム酸アンモニウム、ヘキサクロロイリジウム酸ナトリウム等のイリジウムの無機酸塩、クロロ−１，５−シクロオクタジエンイリジウム、イリジウムアセチルアセトナート等のイリジウムの有機酸塩、塩化ニッケル、臭化ニッケル、ヨウ化ニッケル等のハロゲン化ニッケル、酸化ニッケル、過塩素酸ニッケル等のニッケルの無機酸塩、酢酸ニッケル、シュウ酸ニッケル、ステアリン酸ニッケル、ニッケルアセチルアセトナート、臭化ビストリフェニルホスフィンニッケル等のニッケルの有機酸塩等が好ましく挙げられ、中でも塩化パラジウム、臭化パラジウム、ヨウ化パラジウム等のハロゲン化パラジウム、硝酸パラジウム等のパラジウムの無機酸塩、酢酸パラジウム、トリフルオロ酢酸パラジウム、塩化アリルパラジウム、塩化（１，５−シクロオクタジエン）パラジウム、パラジウムアセチルアセトナート、シアン化パラジウム等のパラジウムの有機酸塩、塩化オスミウム等のハロゲン化オスミウム、二酸化オスミウム、四酸化オスミウム、オスミウム酸（VI）カリウム、ヘキサクロロオスミウム酸カリウム等のオスミウムの無機酸塩がより好ましく、その中でも塩化パラジウム、臭化パラジウム、ヨウ化パラジウム等のハロゲン化パラジウム、酢酸パラジウム、トリフルオロ酢酸パラジウム等のパラジウムの有機酸塩、二酸化オスミウム、四酸化オスミウム、オスミウム（VI）カリウム等のオスミウムの無機酸塩がさらに好ましく、さらにその中でも酢酸パラジウム、トリフルオロ酢酸パラジウム等のパラジウムの有機酸塩、四酸化オスミウムが特に好ましく、酢酸パラジウムが最も好ましい。尚、これらの金属触媒化合物は市販品として容易に入手することができる。 Examples of the metal catalyst compound in the present invention include water, a water-soluble organic solvent capable of reducing the metal catalyst compound, a mixed solution thereof or a solvent containing a reducing agent (hereinafter referred to as a reaction solvent according to the present invention). Although it is not particularly limited as long as it can be reduced to a zero-valent metal catalyst, specifically, it is reduced in a reaction solvent as described above to give zero-valent palladium, 0 Valent osmium, zero-valent platinum, zero-valent ruthenium, zero-valent rhodium, zero-valent iridium or zero-valent nickel, for example, palladium halides such as palladium chloride, palladium bromide, palladium iodide, palladium nitrate Inorganic acid salts of palladium such as palladium acetate, palladium trifluoroacetate, allyl palladium chloride, (1,5-cyclooctadiene) palladium chloride, paradiu Organic acid salts of palladium such as acetylacetonate and palladium cyanide, osmium halides such as osmium chloride, osmium dioxide, osmium tetroxide, potassium osmate (VI), potassium hexachloroosmate, etc. Platinum halides such as platinum, platinum bromide and platinum iodide, platinum oxide, chloroplatinic acid, ammonium tetrachloroplatinate, potassium hexachloroplatinate and other inorganic acid salts of platinum, platinum acetylacetonate, platinum hexafluoroacetylacetate Organic acid salts of platinum such as nato, dichloro (1,5-cyclooctadiene) platinum, platinum cyanide, ruthenium halides such as ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium oxide, potassium ruthenate, pentachloro Potassium ruthenate Ruthenium inorganic acid salts such as bis (cyclooctadienyl) ruthenium, chloro (cyclopentadienyl) bis (triphenylphosphine) ruthenium, dichloro (1,5-cyclooctadiene) ruthenium, ruthenium acetylacetonate, etc. Ruthenium organic acid salts, rhodium halides such as rhodium chloride, rhodium bromide, rhodium iodide, rhodium nitrate, rhodium oxide, ammonium hexachlororhodate, sodium hexachlororhodate, etc. inorganic acid salts of rhodium, rhodium acetate, trifluoro Rhodium organic acid salts such as rhodium acetate, rhodium acetylacetonate, rhodium octanoate, iridium halides such as iridium chloride and iridium bromide, iridium oxide, ammonium hexachloroiridate, hexachloroi Inorganic acid salts of iridium such as sodium iodate, organic acid salts of iridium such as chloro-1,5-cyclooctadiene iridium, iridium acetylacetonate, nickel halides such as nickel chloride, nickel bromide, nickel iodide, Preferred examples include nickel oxides, nickel inorganic acid salts such as nickel perchlorate, nickel acetates, nickel oxalate, nickel stearate, nickel acetylacetonate, nickel organic acid salts such as bistriphenylphosphine nickel bromide, and the like. Among them, palladium halides such as palladium chloride, palladium bromide and palladium iodide, inorganic acid salts of palladium such as palladium nitrate, palladium acetate, palladium trifluoroacetate, allyl palladium chloride, (1,5-cyclooctadiene) palladium chloride , Organic salts of palladium such as radium acetylacetonate and palladium cyanide, osmium halides such as osmium chloride, osmium dioxide, osmium tetroxide, potassium osmate (VI), potassium hexachloroosmate, etc. More preferably, among them, palladium halides such as palladium chloride, palladium bromide and palladium iodide, organic acid salts of palladium such as palladium acetate and palladium trifluoroacetate, osmium dioxide, osmium tetroxide, osmium (VI) potassium and the like Inorganic acid salts of osmium are more preferable, and among them, organic acid salts of palladium such as palladium acetate and palladium trifluoroacetate, osmium tetroxide are particularly preferable, and palladium acetate is most preferable. In addition, these metal catalyst compounds can be easily obtained as commercial products.
繊維状タンパク質への金属触媒の担持量は、担持される金属の種類、使用される繊維状タンパク質に担持され得る量及び繊維状タンパク質担持金属触媒の用途等を勘案して適宜設定すれば良いが、繊維状タンパク質１ｇに対して、０．５ｍｇ〜０．５ｇ、好ましくは１ｍｇ〜０．２ｇとなるように設定される。このため、金属触媒化合物の使用量としては、金属触媒化合物の重量のうちの金属触媒の重量が、繊維状タンパク質１ｇに対して、上記した如き数値範囲となるように設定される。具体的には、例えば繊維状タンパク質１ｇに酢酸パラジウムを接触させる場合、パラジウムの使用量として、通常０．５ｍｇ〜０．５ｇ、好ましくは１ｍｇ〜０．２ｇとなるように酢酸パラジウムの使用量が設定されるので、酢酸パラジウムの使用量は、使用した酢酸パラジウム中のパラジウムが全て担持されると仮定して、繊維状タンパク質１ｇに対して、通常１．０５ｍｇ〜１．０５ｇ、好ましくは２．１ｍｇ〜０．４２ｇとなる。 The amount of the metal catalyst supported on the fibrous protein may be appropriately set in consideration of the type of metal to be supported, the amount that can be supported on the fibrous protein used, the use of the fibrous protein-supported metal catalyst, and the like. The amount is set to 0.5 mg to 0.5 g, preferably 1 mg to 0.2 g, with respect to 1 g of fibrous protein. For this reason, the amount of the metal catalyst compound used is set so that the weight of the metal catalyst in the weight of the metal catalyst compound falls within the numerical range as described above with respect to 1 g of the fibrous protein. Specifically, for example, when 1 g of fibrous protein is contacted with palladium acetate, the amount of palladium used is usually 0.5 mg to 0.5 g, preferably 1 mg to 0.2 g. Since it is set, the amount of palladium acetate used is generally 1.05 mg to 1.05 g, preferably 2., per 1 g of fibrous protein, assuming that all of the palladium in the palladium acetate used is supported. 1 mg to 0.42 g.
本発明に於ける金属触媒化合物を還元し得る有機溶媒は、このような還元作用を有する有機溶媒であれば特に限定されないが、具体的には、例えばメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブチルアルコール、ｎ−アミルアルコール、ベンジルアルコール等のモノアルコール類、エチレングリコール、プロピレングリコール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，２−ペンタンジオール、１，５−ペンタンジオール等のジオール類、グリセリン等のトリオール類、ホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド等のアルデヒド類等が好ましく挙げられ、中でもメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブチルアルコール、ｎ−アミルアルコール、ベンジルアルコール等のモノアルコール類がより好ましく、その中でもメタノールがさらに好ましい。また、金属触媒化合物を還元し得る有機溶媒は、一種類のものを単独で用いても良いし、複数種のものを適宜組み合わせて用いても良い。 The organic solvent capable of reducing the metal catalyst compound in the present invention is not particularly limited as long as it has such a reducing action. Specifically, for example, methanol, ethanol, n-propanol, isopropanol, n -Monoalcohols such as butanol, isobutyl alcohol, n-amyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4- Preferable examples include diols such as butanediol, 1,2-pentanediol, 1,5-pentanediol, triols such as glycerin, aldehydes such as formaldehyde, acetaldehyde, and propylaldehyde. Among them, methanol, ethanol, n- Propanol, Isopropanol, n- butanol, isobutyl alcohol, n- amyl alcohol, monoalcohols are more preferred such as benzyl alcohol, methanol among them is more preferable. Moreover, the organic solvent which can reduce | restore a metal catalyst compound may be used individually by 1 type, and may be used in combination of multiple types suitably.
本発明に係る反応溶媒のうち、還元剤を含む溶媒は、例えば水素化ホウ素ナトリウム、水素化ホウ素カリウム等の水素化ホウ素塩、水素化アルミニウムリチウム等の水素化アルミニウム塩、チオ硫酸ナトリウム等のチオ硫酸塩、亜硫酸水素ナトリウム等の亜硫酸水素塩、蟻酸アンモニウム、蟻酸ジエチルアンモニウム等の蟻酸アンモニウム塩、次亜リン酸ナトリウム、次亜リン酸カリウム等の次亜リン酸塩、水素、エチレン、一酸化炭素等の還元性のガス、ヒドラジン等の還元剤を含有する、例えばメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブチルアルコール、ｔ−ブタノール等のアルコール系溶媒、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、ｎ−ヘキサン、ベンゼン、トルエン等の炭化水素系溶媒、水等の溶媒であって、上記還元剤と溶媒とが互いに反応し難い組み合わせのものを意味する。また、これら還元剤と溶媒は、一種類のものを単独で用いても良いし、複数種のものを適宜組み合わせて用いても良い。上記還元剤の使用量は、用いられるオスミウム化合物を還元し得る量であれば、特に限定されないが、具体的には、例えばオスミウム化合物１ｍｏｌに対して、１〜５００ｍｏｌが好ましく挙げられ、中でも１〜５０ｍｏｌがより好ましい。 Among the reaction solvents according to the present invention, the solvent containing a reducing agent is, for example, a borohydride salt such as sodium borohydride or potassium borohydride, an aluminum hydride salt such as lithium aluminum hydride, or a thiol such as sodium thiosulfate. Bisulfite such as sulfate, sodium hydrogen sulfite, ammonium formate, ammonium formate such as diethyl ammonium formate, hypophosphite such as sodium hypophosphite and potassium hypophosphite, hydrogen, ethylene, carbon monoxide Containing a reducing agent such as hydrazine, for example, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, t-butanol, diethyl ether, tetrahydrofuran, dioxane, etc. Ether solvent, n-hexane, Zen, hydrocarbon solvents such as toluene, a solvent such as water, means a combination of hard the reducing agent and a solvent are reacted with each other. Moreover, these reducing agents and solvents may be used alone or in combination of a plurality of kinds as appropriate. Although the usage-amount of the said reducing agent will not be specifically limited if it is the quantity which can reduce | restore the osmium compound to be used, Specifically, 1-500 mol is mentioned preferably with respect to 1 mol of osmium compounds, for example. 50 mol is more preferable.
本発明に係る反応溶媒のうち、金属触媒化合物を還元し得る有機溶媒がより好ましく、中でも一種類の金属触媒化合物を還元し得る有機溶媒を単独で用いることがさらに好ましい。尚、本発明に係る反応溶媒のうち、水と金属触媒化合物を還元し得る有機溶媒との混合液に於ける金属触媒化合物を還元し得る有機溶媒は、水と混和し得る金属触媒化合物を還元し得る有機溶媒を意味する。また、これら反応溶媒の使用量は、特に限定されないが、例えば繊維状タンパク質１ｇに対して、通常０．５ｍＬ〜２００ｍＬ、好ましくは１ｍＬ〜５０ｍＬである。 Of the reaction solvents according to the present invention, an organic solvent capable of reducing a metal catalyst compound is more preferable, and among them, an organic solvent capable of reducing one kind of metal catalyst compound is more preferably used alone. Of the reaction solvents according to the present invention, the organic solvent capable of reducing the metal catalyst compound in the mixed solution of water and the organic solvent capable of reducing the metal catalyst compound is a reduction of the metal catalyst compound miscible with water. An organic solvent that can be used. Moreover, the usage-amount of these reaction solvents is although it does not specifically limit, For example with respect to 1g of fibrous proteins, they are 0.5mL-200mL normally, Preferably they are 1mL-50mL.
本発明で使用される超音波としては、通常１０ｋＨｚ以上の振動数である音波を意味し、通常この分野で用いられる超音波発生装置から照射される音波であれば特に限定されないが、具体的には、例えば２０〜１００ｋＨｚの振動数の音波が好ましく挙げられ、中でも３０〜６０ｋＨｚの振動数の音波がより好ましい。 The ultrasonic wave used in the present invention means a sound wave having a frequency of usually 10 kHz or more, and is not particularly limited as long as it is a sound wave irradiated from an ultrasonic generator normally used in this field. For example, a sound wave having a frequency of 20 to 100 kHz is preferably exemplified, and a sound wave having a frequency of 30 to 60 kHz is more preferable.
本発明の担持方法に於ける反応温度は、本発明の担持方法によって調製される繊維状タンパク質担持金属触媒に影響を与えない温度であれば特に限定されないが、通常０〜７０℃、好ましくは２０〜５０℃が挙げられる。 The reaction temperature in the loading method of the present invention is not particularly limited as long as it does not affect the fibrous protein-supported metal catalyst prepared by the loading method of the present invention, but usually 0 to 70 ° C., preferably 20 Up to 50 ° C.
本発明の担持方法に於ける反応時間は、通常１０分〜９５時間、好ましくは１時間〜４８時間、より好ましくは３時間〜３６時間である。 The reaction time in the loading method of the present invention is usually 10 minutes to 95 hours, preferably 1 hour to 48 hours, more preferably 3 hours to 36 hours.
本発明の担持方法を具体的に説明すると、以下の如くである。例えば金属触媒化合物を還元し得る有機溶媒に金属触媒化合物を上記した如き割合となるよう溶解させた溶液に、繊維状タンパク質を上記した如き割合となるように浸し、超音波照射下、上記した如き条件で放置する。すると、反応溶液は無色に変化し、繊維状タンパク質は金属触媒に由来する色（金属色）に変化する。次いで、金属色に変化した繊維状タンパク質を濾取し、濾取した繊維状タンパク質を適当な洗浄溶媒、例えばメタノール等で洗浄し、適宜乾燥させることにより、目的の繊維状タンパク質担持金属触媒を調製することができる。 The carrying method of the present invention will be specifically described as follows. For example, the fibrous protein is immersed in the above-described ratio in an organic solvent capable of reducing the metal-catalyst compound so that the ratio is as described above, and is irradiated with ultrasonic waves as described above. Leave under conditions. Then, the reaction solution changes to colorless, and the fibrous protein changes to a color derived from the metal catalyst (metal color). Next, the fibrous protein that has changed to a metallic color is filtered, and the filtered fibrous protein is washed with an appropriate washing solvent such as methanol, and dried appropriately to prepare the desired fibrous protein-supported metal catalyst. can do.
本発明の担持方法により調製された繊維状タンパク質担持金属触媒を洗浄する際に用いられる洗浄溶媒としては、通常この分野で用いられる洗浄溶媒であれば特に限定されないが、中でも金属触媒化合物を還元し得る有機溶媒が好ましく、その中でもメタノールがより好ましい。 The washing solvent used for washing the fibrous protein-carrying metal catalyst prepared by the carrying method of the present invention is not particularly limited as long as it is a washing solvent usually used in this field, but among them, the metal catalyst compound is reduced. An organic solvent to be obtained is preferable, and methanol is more preferable among them.
本発明の担持方法に於ける乾燥は、通常この分野で行われる乾燥方法であれば特に限定されないが、減圧下で通常１０〜１００℃、中でも２０〜５０℃で乾燥することが好ましい。 The drying in the carrying method of the present invention is not particularly limited as long as it is a drying method usually carried out in this field, but it is usually preferable to dry at 10 to 100 ° C., particularly 20 to 50 ° C. under reduced pressure.
本発明の担持方法によれば、金属触媒化合物と繊維状タンパク質との接触を、上記の如き反応溶媒中、超音波照射下に行うので、従来の静置、攪拌での接触と比較して、金属触媒化合物が速やかに０価に還元され、還元された０価の金属触媒を繊維状タンパク質に均一に担持させることができ、また、攪拌での接触時に問題となる攪拌子や攪拌棒への繊維状タンパク質の絡みつきも解消できる。 According to the loading method of the present invention, the contact between the metal catalyst compound and the fibrous protein is performed in the reaction solvent as described above under ultrasonic irradiation, so compared with the conventional stationary and stirring contact, The metal catalyst compound is rapidly reduced to zero valence, and the reduced zero valent metal catalyst can be uniformly supported on the fibrous protein, and can be applied to a stir bar or a stirrer that becomes a problem when contacting with stirring. The entanglement of fibrous protein can also be eliminated.
以下、実施例及び比較例に基づいて本発明を具体的に説明するが、本発明はこれらの例によって何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited at all by these examples.
実施例１ 超音波照射下による絹フィブロイン担持パラジウム触媒の調製
５ｍｍ程度に刻んだ絹フィブロイン１．０ｇを、酢酸パラジウム５２．７ｍｇ（０．２３５ｍｍｏｌ）を含有するメタノール溶液（２０ｍＬ）に浸し、超音波照射下（４７ｋＨｚ）、３０℃で２４時間放置した。その後、黒色に変化した絹フィブロインを濾取し、メタノールで洗浄後、減圧下４０℃で２４時間乾燥させて２．５ｗｔ％の絹フィブロイン担持パラジウム触媒１．０２５ｇを得た。尚、ここで言うｗｔ％は、絹フィブロインＹｇに担持された金属触媒の量をＺｇとすると、下記の式で求められるものである（以下、同じ）。
ｗｔ％＝Ｚ／（Ｙ＋Ｚ）×１００
Example 1 Preparation of Silk Fibroin-Supported Palladium Catalyst Under Ultrasonic Irradiation 1.0 g of silk fibroin chopped to about 5 mm was immersed in a methanol solution (20 mL) containing 52.7 mg (0.235 mmol) of palladium acetate, and ultrasonic waves were applied. It was left under irradiation (47 kHz) at 30 ° C. for 24 hours. Thereafter, the silk fibroin turned black was collected by filtration, washed with methanol, and dried under reduced pressure at 40 ° C. for 24 hours to obtain 1.025 g of a 2.5 wt% silk fibroin-supported palladium catalyst. In addition, wt% said here is calculated | required by the following formula, when the quantity of the metal catalyst carry | supported by silk fibroin Yg is set to Zg (hereinafter, the same).
wt% = Z / (Y + Z) × 100
実施例２ 超音波照射下による絹フィブロイン担持オスミウム触媒の調製
絹フィブロイン５ｇを、四酸化オスミウム０．５ｇ（１．９７ｍｍｏｌ）を含有するメタノール溶液（２００ｍＬ）に浸し、超音波照射下（４７ｋＨｚ）、３０℃で３０時間放置した。その後、黒色に変化した絹フィブロインを濾取し、メタノールで洗浄後、減圧下４０℃で２４時間乾燥させて５ｗｔ％の絹フィブロイン担持オスミウム触媒５．２６ｇを得た。
Example 2 Preparation of silk fibroin-supported osmium catalyst under ultrasonic irradiation 5 g of silk fibroin was immersed in a methanol solution (200 mL) containing 0.5 g (1.97 mmol) of osmium tetroxide, and under ultrasonic irradiation (47 kHz). It was left at 30 ° C. for 30 hours. Thereafter, the silk fibroin turned black was collected by filtration, washed with methanol, and dried under reduced pressure at 40 ° C. for 24 hours to obtain 5.26 g of a 5 wt% silk fibroin-supported osmium catalyst.
比較例１ 静置による絹フィブロイン担持パラジウム触媒の調製
絹フィブロイン２０．０ｇを、酢酸パラジウム１．０６ｇ（４．７２ｍｍｏｌ）を含有するメタノール溶液（２００ｍＬ）に浸し、３０℃で４日間静置した。その後、黒色に変化した絹フィブロインを濾取し、メタノールで洗浄後、減圧下４０℃で２４時間乾燥させて２．５％の絹フィブロイン担持パラジウム触媒２０．５ｇを得た。
Comparative Example 1 Preparation of Silk Fibroin-Supported Palladium Catalyst by Standing 20.0 g of silk fibroin was immersed in a methanol solution (200 mL) containing 1.06 g (4.72 mmol) of palladium acetate and allowed to stand at 30 ° C. for 4 days. Thereafter, the silk fibroin turned black was collected by filtration, washed with methanol, and dried under reduced pressure at 40 ° C. for 24 hours to obtain 20.5 g of a 2.5% silk fibroin-supported palladium catalyst.
実施例１で得られた絹フィブロイン担持パラジウム触媒を、例えばｐ−クロロスチレンのような芳香族ハロゲンを有するオレフィン化合物の還元反応に用いた場合、比較例１で得られたものを用いた場合と同様に、脱ハロゲン化は全く進行せず、二重結合が選択的に還元されたｐ−クロロエチルベンゼンが定量的に得られた。このことから、比較例１で得られた従来のものと、同等の触媒活性を有することが判った。また、実施例１で得られた触媒の一部を切り取って還元反応に使用した場合、どの部分を切り取ったものであっても、ほぼ同等の触媒活性を有することから、金属触媒が絹フィブロインに均一に担持していると推測され、再現性に優れる触媒であることが判った。 When the silk fibroin-supported palladium catalyst obtained in Example 1 is used for the reduction reaction of an olefin compound having an aromatic halogen such as p-chlorostyrene, the case obtained by using the one obtained in Comparative Example 1 and Similarly, dehalogenation did not proceed at all, and p-chloroethylbenzene in which the double bond was selectively reduced was quantitatively obtained. From this, it was found that the catalyst had the same catalytic activity as the conventional one obtained in Comparative Example 1. In addition, when a part of the catalyst obtained in Example 1 was cut out and used for the reduction reaction, any part cut out had almost the same catalytic activity, so that the metal catalyst was converted into silk fibroin. It was assumed that the catalyst was uniformly supported, and it was found that the catalyst was excellent in reproducibility.
以上のことから、本発明の担持方法によれば、従来の方法と比較して、短時間で繊維状タンパク質担持金属触媒を調製することができ、しかもこのようにして得られた触媒は従来のものと同等の触媒活性を有し、再現性に優れるものである。 From the above, according to the supporting method of the present invention, it is possible to prepare a fibrous protein-supported metal catalyst in a short time compared to the conventional method, and the catalyst thus obtained is a conventional catalyst. It has the same catalytic activity as that of the product and has excellent reproducibility.
本発明の担持方法は、例えば官能基選択性に優れる等の特徴を有し、有機合成上の有用性が期待されている繊維状タンパク質担持金属触媒を、短時間且つ均一に調製できるため、当該触媒の工業的生産を可能にするものである。
The support method of the present invention has a feature such as excellent functionality group selectivity, and can produce a fibrous protein-supported metal catalyst that is expected to be useful in organic synthesis in a short time and uniformly. It enables industrial production of the catalyst.
Claims (10)
The supporting method according to claim 1, wherein the metal catalyst compound is osmium tetroxide, the fibrous protein is silk fibroin, and these are contacted in methanol.
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| WO2019066037A1 (en) * | 2017-09-29 | 2019-04-04 | Ｓｐｉｂｅｒ株式会社 | Dope liquid and product using same, and structural protein fiber and method for producing same |
| CN111672530A (en) * | 2020-05-19 | 2020-09-18 | 江苏大学 | Preparation method of CuCo-N/C nano catalyst and application of CuCo-N/C nano catalyst in preparing lactic acid by catalytic oxidation of 1, 2-propylene glycol |
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