CN103221369A - 金刚烷多元醇的制造方法 - Google Patents
金刚烷多元醇的制造方法 Download PDFInfo
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- CN103221369A CN103221369A CN2011800559922A CN201180055992A CN103221369A CN 103221369 A CN103221369 A CN 103221369A CN 2011800559922 A CN2011800559922 A CN 2011800559922A CN 201180055992 A CN201180055992 A CN 201180055992A CN 103221369 A CN103221369 A CN 103221369A
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- China
- Prior art keywords
- reaction
- manufacture method
- sorbent material
- inorganic
- ruthenium
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 title abstract description 14
- -1 adamantane polyol Chemical class 0.000 title abstract description 9
- 229920005862 polyol Polymers 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 150000003304 ruthenium compounds Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 claims description 21
- 239000002594 sorbent Substances 0.000 claims description 21
- 239000001506 calcium phosphate Substances 0.000 claims description 16
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 10
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 9
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 9
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 7
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical group [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 7
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- 235000011010 calcium phosphates Nutrition 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 abstract 3
- 230000002051 biphasic effect Effects 0.000 abstract 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 22
- 229910052707 ruthenium Inorganic materials 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052587 fluorapatite Inorganic materials 0.000 description 2
- 229940077441 fluorapatite Drugs 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- VJVWNPYNKXNTJV-UHFFFAOYSA-K [Ru+3].I(=O)(=O)[O-].I(=O)(=O)[O-].I(=O)(=O)[O-] Chemical compound [Ru+3].I(=O)(=O)[O-].I(=O)(=O)[O-].I(=O)(=O)[O-] VJVWNPYNKXNTJV-UHFFFAOYSA-K 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052589 chlorapatite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PROQIPRRNZUXQM-ZXXIGWHRSA-N estriol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)C4)O)[C@@H]4[C@@H]3CCC2=C1 PROQIPRRNZUXQM-ZXXIGWHRSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 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
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229940099204 ritalin Drugs 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Abstract
根据本发明可提供一种金刚烷多元醇的制造方法，该方法为使金刚烷类在水/有机溶剂的2相体系中与钌化合物及次氯酸盐反应制造金刚烷多元醇的方法，其具有：在反应体系中添加无机系吸附剂的工序；以及在反应混合液中添加碱，将上述钌化合物连同上述无机系吸附剂一起分离，将分离出的该钌化合物及该无机系吸附剂再次用于下次反应的工序。
Description
技术领域
本发明涉及作为高功能性聚合物、合成润滑油、增塑剂等的中间原料或医药农药等有机药品的中间体有用的金刚烷多元醇的制造方法。
背景技术
作为金刚烷多元醇(金刚烷二醇、金刚烷三醇等)的制法，有在水/有机溶剂的2相体系中使金刚烷类与钌化合物及次氯酸盐反应的方法(参照专利文献1～3)。但是，由于钌化合物昂贵，因此需要回收并再次使用。其中，由于钌可以取各种价数，因此存在难以以单一化合物的形式回收、其回收率低的问题。
为了解决该问题点，有如下方法：在反应后的溶液中添加氧化剂使钌成为高氧化状态之后，转移到有机相中进行回收(参照专利文献4)；将含钌原料与碱氢氧化物混合，使其与氧化剂反应提取钌，进而通过用低级醇还原而回收(参照专利文献5)；用碱熔融含钌原料之后，加入氧化剂使其浸出，湿式还原、酸洗涤后进行回收(参照专利文献6)。
然而，即使采用上述任意的方法，为了将钌化合物再次用作氧化反应的催化剂，均需要繁杂的工序，且由于需要使用还原剂等，因此成本方面也存在问题。
现有技术文献
专利文献
专利文献1:日本特开2000-219646号公报
专利文献2:日本特开2001-335519号公报
专利文献3:日本特开2004-339105号公报
专利文献4:日本特开2001-031603号公报
专利文献5:日本特开2003-201526号公报
专利文献6:日本特开2009-057611号公报
发明内容
发明要解决的问题
本发明以提供下述制法为课题，该制法为：在制造金刚烷多元醇的方法中，可高收率且容易地分离回收催化剂即钌化合物并供给下次反应的制法。
用于解决问题的方案
本发明人等进行了深入的研究，结果发现，在使金刚烷类在水/有机溶剂的2相体系中与钌化合物及次氯酸盐反应的方法中，通过将无机系吸附剂添加到反应体系中，可容易地回收钌化合物并可再次供给氧化反应，从而完成本发明。
即本发明涉及一种金刚烷多元醇的制造方法，其特征在于，其为使通式(1)表示的金刚烷在水/有机溶剂的2相体系中与钌化合物及次氯酸盐反应制造金刚烷多元醇的方法，该方法具有：在反应体系中添加无机系吸附剂的工序；以及在反应混合液中添加碱，将所述钌化合物连同所述无机系吸附剂一起分离，将分离出的该钌化合物及该无机系吸附剂再次用于下次反应的工序。
（式中，取代基Rn各自独立地表示烷基、芳基、环烷基、羟基、烷氧基、芳氧基、酰氧基或卤素基团，n为0～13的整数。）
发明的效果
根据本发明，可以简单高收率地回收作为氧化反应的催化剂的昂贵的钌化合物，进而可容易地进行它的再活化。
具体实施方式
本发明中使用上述通式(1)表示的金刚烷。通式(1)中，取代基Rn各自独立地表示甲基、乙基、丙基、丁基、己基等碳原子数1～10的烷基；苯基、萘基等芳基；环己基、环辛基等环烷基；羟基；甲氧基、乙氧基、丙氧基、丁氧基、己氧基等碳原子数1～10的烷氧基；苯氧基等芳氧基；乙酰氧基、丙酰氧基、丁酰氧基等碳原子数2～6的酰氧基；或氟基、氯基、溴基、碘基等卤素基团。其中，取代基Rn优选为碳原子数1～6的烷基，进一步优选为碳原子数1～4的烷基。
本发明中所使用的钌化合物可单独或以混合物的方式使用钌金属、二氧化钌、四氧化钌、氢氧化钌、氯化钌、溴化钌、碘化钌、硫酸钌或它们的水合物等。从抑制昂贵的钌的使用量的观点出发，钌化合物优选相对于1摩尔原料金刚烷类为0.005～2.0摩尔，尤其从抑制副反应的观点出发，更优选为0.01～0.4摩尔的比例。
作为本发明中使用的次氯酸盐类，优选为次氯酸钠。次氯酸盐类以6～35重量%的水溶液的方式使用。次氯酸盐类的浓度低于该范围时，水相的量增多，从水相中提取产物的效率降低，还加重废液处理的负担。另一方面，次氯酸盐类的浓度高于该范围时，容易引起副反应，金刚烷多元醇的收率降低。为了高效率并且高收率地得到金刚烷多元醇，次氯酸盐类的添加量相对于1摩尔金刚烷类优选设为0.5～5.0摩尔、更优选设为1.0～3.0摩尔的范围。
本发明中使用的有机溶剂优选使用对高氧化状态的钌溶解性高并且耐氧化性优异的非活性溶剂。对高氧化状态的钌溶解性低时，反应速度降低，反应时间延长。另外，耐氧化性差的溶剂的情况下，由于溶剂自身的分解或副产物生成，因此不优选。作为优选的有机溶剂的例子，例如可列举出二氯甲烷、1,2-二氯乙烷、氯仿、四氯化碳、1,1,2-三氯乙烷、1,4-二氯丁烷、1,6-二氯己烷等卤代烷类；醋酸甲酯、醋酸乙酯、醋酸异丙酯等酯类；六氯苯、1,1,1-三氟甲苯等卤代芳烃类；己烷、庚烷、辛烷等脂肪族烃类等溶剂。这些溶剂可单独使用，也可使用混合2种以上的溶剂的体系。溶剂优选相对于1质量份用作原料的金刚烷类以0.1～50质量份的比例、更优选以1～30质量份的比例来使用。
本发明中使用的无机系吸附剂若为具有吸附能力或离子交换能力且为了在反应体系中共存而不被钌化合物氧化的无机系吸附剂，则没有特别地限制，优选选自由磷酸钙类、滑块石(talcite)类及非晶性铝硅酸盐类组成的组中的1种以上。
作为磷酸钙，可列举出羟基磷灰石、氟磷灰石、氯磷灰石、碳酸羟基磷灰石、碳氟磷灰石（carbonate fluorapatite）、磷酸氢钙、磷酸二氢钙、磷酸三钙等。并且，作为滑块石可列举出水滑石，作为非晶性铝硅酸盐可例示伊毛缟石、水铝英石等，可将它们混合使用。
对于磷酸钙，在例示的物质中从钌化合物的吸附能力、获得的难易的观点出发，特别优选为磷酸三钙、羟基磷灰石。对于滑块石也从与上述同样的观点出发，优选使用Mg-Al型或Li-Al型的水滑石。
水铝英石、伊毛缟石那样的非晶性铝硅酸盐为硅酸盐中的一部分被铝取代的物质，一部分也可被其它的金属取代。
无机系吸附剂的添加量可优选相对于1质量份钌化合物以0.1质量份～100质量份的范围来添加，更优选以0.5质量份～20质量份的范围来使用。无机系吸附剂的添加量适当时，可容易地回收钌化合物而不对反应产生影响，但添加量过少时，不能抑制钌化合物的损失，相反过量添加时，带来反应速度的降低、副反应等影响，经济上也出现问题。并且，对添加无机系吸附剂的时机没有特别地限制，任何时候均可，可预先添加到反应器中，也可在反应即将结束前添加。
作为本发明中的氧化反应的一个方式，将反应溶剂及原料投入到反应器中，进而加入钌催化剂及无机系吸附剂。最后边使温度升高边添加氧化剂即次氯酸盐与pH调整用酸开始反应。反应方式从操作、原料处理、反应温度控制等观点出发优选间歇式，也可以预先制备将基质溶解于反应溶剂的反应液和含有催化剂及无机系吸附剂的次氯酸盐水溶液，例如采用流过静态混合器那样的静止型混合器(管道混合器)的流通方式来实施。氧化反应的条件为常压下、反应温度为10～100℃，优选为了防止次氯酸盐自身分解以40～70℃的范围来实施。另外，反应时间优选为100～1500分钟。使用的反应器可没有特别地限制利用公知的带搅拌机的反应器来进行。另外，反应器的材质优选为耐钌化合物腐蚀性的材质，可例示出玻璃内衬制、聚四氟乙烯内衬制。
本发明的氧化反应的水相的pH调整很重要，可在3～10的范围任意选择。特别是为了在反应结束后效率良好地回收钌，优选在pH为6以下的弱酸侧进行反应。另外，为了调整反应中的pH可添加酸。作为添加的酸，可任意为水溶性的酸即甲酸、醋酸、丙酸等有机酸；盐酸、硫酸、硝酸、磷酸等无机酸，但从产物的纯化考虑时优选为无机酸，更优选为对反应产生影响的可能性低的盐酸及硫酸。使用的酸的浓度没有特别地限制。
反应结束后，通过在反应混合液中添加碱，使反应水相的pH成为7以上从而还原钌化合物，使钌化合物连同无机系吸附剂一起以黑色晶体的形式沉淀，通过过滤等固液分离而进行回收。该固液分离的方法可使用公知的方法，可选择过滤、沉淀分离、离心分离等。并且，也可用水、溶剂洗涤分离后的催化剂及无机系吸附剂。这样操作而分离出的钌化合物和无机系吸附剂可直接再次用于下次反应。
为了还原钌化合物而添加的碱可列举出氢氧化钠、氢氧化钾、氢氧化锂、或氢氧化钡等金属氢氧化物；碳酸钠、碳酸钾、碳酸锂、碳酸氢钠等金属碳酸盐；或者四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵或四丁基氢氧化铵等四烷基氢氧化铵。其中，优选氢氧化钠、氢氧化钾。添加的碱的浓度没有特别地限制，可以固体状态添加，也可预先制备碱水溶液、将水溶液连续地或间歇地添加。添加量以反应水相的pH变为7以上的方式来添加。
催化剂分离后的反应混合液中的金刚烷多元醇可用萃取、洗涤、过滤、浓缩、蒸馏、析晶、重结晶等公知方法来分离、纯化。
实施例
以下，通过实施例进一步具体地说明本发明，但本发明不受这些实施例的限定。对于水相中包含的金刚烷多元醇的生成量，利用具有FID检测器的气相色谱仪进行分析。另外，对于水相中包含的钌化合物的定量，通过用盐酸溶解试样从而制成均一溶液之后，用ICP发射光谱分析进行。另外，对于钌回收效率，固液分离后，测定废水中流出的钌的量，求出其浓度。
(实施例1)
在具备电磁感应式搅拌装置、温度计、迪姆罗特冷凝器、pH电极的容量2L的带夹套的玻璃制可拆式烧瓶中，投入54g金刚烷、3.6g作为无机系吸附剂的磷酸三钙(和光纯药工业制造的化学用，以下简称为“TCP”)、2.7g n水合氯化钌(N.E.CHEMCAT CORPORATION制造，Ru含量为43%、即约1.2gRu)、415ml醋酸乙酯、400ml水，滴加1200g12重量%次氯酸钠水溶液。此时，同时滴加10重量%硫酸使反应液的pH变为3.5。次氯酸钠的滴加需要的时间约为12小时。并且，在次氯酸钠滴加过程中以温度为55℃±5℃的方式进行调整。反应结束后，滴加25%氢氧化钠溶液至反应液的pH变为7为止。接着静置反应液，蒸馏除去以醋酸乙酯作为主成分的有机相，得到包含钌化合物(催化剂)及金刚烷多元醇类的水相。用气相色谱仪分析该水相，结果1,3,5-金刚烷三醇的收率为64%。进而，通过将得到的水相抽滤从而将钌催化剂连同无机系吸附剂一起分离，作为母液得到1800g包含金刚烷三醇类的水相。用ICP发射光谱分析定量该水相中的钌浓度，结果为5.0ppm。
(实施例2)
直接使用实施例1中过滤后的吸附有钌催化剂的磷酸三钙代替重新添加磷酸三钙和n水合氯化钌，除此以外，实施与实施例1同样的操作。与实施例1同样地用气相色谱仪分析水相，结果1,3,5-金刚烷三醇的收率为66%。用ICP发射光谱分析定量所得到的水相中的钌浓度，结果为3.7ppm。将结果记载于表1中。
(实施例3)
添加3.6g羟基磷灰石(和光纯药制造的生物材料研究用，以下简称为“HAP”)代替实施例1中使用的磷酸三钙，除此以外，实施与实施例1同样的操作。与实施例1同样地用气相色谱仪分析水相，结果1,3,5-金刚烷三醇的收率为66%。用ICP发射光谱分析定量所得到的水相中的钌浓度，结果为2.6ppm。将结果记载于表1中。
(实施例4)
直接使用实施例3中过滤后的吸附有钌催化剂的羟基磷灰石代替重新添加羟基磷灰石和n水合氯化钌，除此以外，实施与实施例3同样的操作。与实施例3同样地用气相色谱仪分析水相，结果1,3,5-金刚烷三醇的收率为66%。用ICP发射光谱分析定量所得到的水相中的钌浓度，结果为4.2ppm。将结果记载于表1中。
(实施例5)
添加1.8g水滑石(和光纯药制造，以下简称为“HT”)代替实施例1中使用的磷酸三钙，除此以外，实施与实施例1同样的操作。与实施例1同样地用气相色谱仪分析水相，结果1,3,5-金刚烷三醇的收率为66%。用ICP发射光谱分析定量所得到的水相中的钌浓度，结果为9.5ppm。
(比较例1)
除不使用实施例1中的磷酸三钙以外，实施与实施例1同样的操作。与实施例1同样地用气相色谱仪分析水相，结果1,3,5-金刚烷三醇的收率为64%，用ICP发射光谱分析定量所得到的水相中的钌浓度，结果为100ppm。
[表1]
产业上的可利用性
根据本发明，在制造金刚烷多元醇时，可高回收率地分离回收昂贵的钌化合物，可廉价地制造高功能性聚合物的中间原料、医药农药等有机药品的中间体。
Claims (7)
1.一种金刚烷多元醇的制造方法，其特征在于，其为使通式(1)表示的金刚烷在水/有机溶剂的2相体系中与钌化合物及次氯酸盐反应制造金刚烷多元醇的方法，该方法具有：
在反应体系中添加无机系吸附剂的工序；以及
在反应混合液中添加碱，将所述钌化合物连同所述无机系吸附剂一起分离，将分离出的该钌化合物及该无机系吸附剂再次用于下次反应的工序，
式(1)中，取代基Rn各自独立地表示烷基、芳基、环烷基、羟基、烷氧基、芳氧基、酰氧基或卤素基团，n为0～13的整数。
2.根据权利要求1所述的制造方法，其中，将所述无机系吸附剂预先添加到反应器中，或在反应即将结束前添加。
3.根据权利要求1或2所述的制造方法，其中，添加所述碱使反应水相的pH为7以上。
4.根据权利要求1～3中任一项所述的制造方法，其中，所述无机系吸附剂为选自由磷酸钙类、滑块石类及非晶性铝硅酸盐类组成的组中的1种以上。
5.根据权利要求4所述的制造方法，其中，所述磷酸钙类为磷酸三钙。
6.根据权利要求4所述的制造方法，其中，所述滑块石类为水滑石。
7.根据权利要求4所述的制造方法，其中，所述磷酸钙为羟基磷灰石。
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| US6342462B1 (en) * | 1999-03-22 | 2002-01-29 | Uop Llc | Process for regenerating an adsorbent |
| JP4395926B2 (ja) | 1999-07-16 | 2010-01-13 | 三菱瓦斯化学株式会社 | アダマンタノール類の製造方法 |
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| JP2000178301A (ja) * | 1998-12-14 | 2000-06-27 | Mitsubishi Gas Chem Co Inc | カルボキシ多糖類の製造方法 |
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