JP4656292B2 - Method for producing metal alkanolamine compounds - Google Patents
Method for producing metal alkanolamine compounds Download PDFInfo
- Publication number
- JP4656292B2 JP4656292B2 JP2004263686A JP2004263686A JP4656292B2 JP 4656292 B2 JP4656292 B2 JP 4656292B2 JP 2004263686 A JP2004263686 A JP 2004263686A JP 2004263686 A JP2004263686 A JP 2004263686A JP 4656292 B2 JP4656292 B2 JP 4656292B2
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- Prior art keywords
- metal
- alkanolamine
- reaction
- tea
- 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.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 title claims description 26
- 229910052751 metal Inorganic materials 0.000 title description 33
- 239000002184 metal Substances 0.000 title description 32
- 238000004519 manufacturing process Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- 241001122767 Theaceae Species 0.000 description 23
- 229910044991 metal oxide Inorganic materials 0.000 description 17
- 150000004706 metal oxides Chemical class 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000011133 lead Substances 0.000 description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 metal complex compounds Chemical class 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 9
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 150000004703 alkoxides Chemical class 0.000 description 7
- 239000012702 metal oxide precursor Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 description 5
- 150000004692 metal hydroxides Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052689 Holmium Inorganic materials 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- JDIBGQFKXXXXPN-UHFFFAOYSA-N bismuth(3+) Chemical compound [Bi+3] JDIBGQFKXXXXPN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- MSBGPEACXKBQSX-UHFFFAOYSA-N (4-fluorophenyl) carbonochloridate Chemical compound FC1=CC=C(OC(Cl)=O)C=C1 MSBGPEACXKBQSX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HBTIIPFPZQBHRE-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;bismuth Chemical class [Bi].OCCN(CCO)CCO HBTIIPFPZQBHRE-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- XBRVPWBNRAPVCC-UHFFFAOYSA-N 4,6,11-trioxa-1-aza-5$l^{3}-silabicyclo[3.3.3]undecane Chemical compound C1CO[Si]2OCCN1CCO2 XBRVPWBNRAPVCC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- MBMKFKOVXPKXCV-UHFFFAOYSA-N CCO[Ti]OCC Chemical compound CCO[Ti]OCC MBMKFKOVXPKXCV-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920005588 metal-containing polymer Polymers 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 1
- 235000008160 pyridoxine Nutrition 0.000 description 1
- 239000011677 pyridoxine Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、簡便かつ均質な金属のアルカノールアミン化合物の製造法に関するものである。 The present invention relates to a method for producing a simple and homogeneous metal alkanolamine compound.
金属酸化物は、種々の光学デバイス、種々の誘電体、超伝導、電池などの電気デバイスや様々なデバイスとして応用されている。金属酸化物の形成方法には、スパッタ法、CVD法、MOCVD法、及び真空蒸着法などの気相法、ゾルゲル法、MOD法などの液相法や様々な方法があるが、複雑で高価な装置を必要とせず、均質に形成物ができやすいなどの利点を有する液相法は、特に注目される方法である。 Metal oxides are applied as various optical devices, various dielectrics, superconductors, electric devices such as batteries, and various devices. There are various metal oxide formation methods such as sputtering, CVD, MOCVD, and vapor phase methods such as vacuum deposition, liquid phase methods such as sol-gel method and MOD, and various methods. The liquid phase method which has the advantage of easily forming a uniform product without requiring an apparatus is a method particularly noted.
金属酸化物前駆体には、製造上使用される際には安定性の向上などの必要性から、金属の錯体化合物が用いられる場面が多く、Mg,Ca,Sr,Ba,Sc,Y,La,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Zr,Hf,V,Nb,Ta,Cr,Mo,W,Mn,Fe,Ru,Co,Ni,Cu,Ag,Zn,Cd,Hg,Al,Ga,In,Tl,Ge,Sn,Pb,SbまたはBiには、それぞれMg(tea)H,Mg(tea)2Cl2,Ca(tea)H,Ca(tea)2Cl2,Sr(tea)2Cl2,Ba(tea)2Cl2,Sc(tea)2Cl3,Y(tea)2(ClO4)3.3C5H5N,H3La[(OC2H4)3N]2,RE(PN)3(tea)(NO3)2Cl(PN=pyridoxol,RE=La,Ce,Pr,Nd,Sm,Tb,Dy,Ho,Er,Y),M(acac)3(M=Y,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb and Lu; acac=acetylacetonate ligand),(iso−PrO)2Zr「OC2H4N(C2H4OH)2」2,VO[N(CH2CH2O)3],Bu2Sn(tea){M(OPri)n}[M=Al(n=2); Ti,Zr(n=3),Nb(n=4)],Ta(OC2H5)4(etac)(etac=Ethyl Acetoacetate),「Cr(N3)tea(H2O)2」(NO3)2,[Ni(N3)2tea2]・10H2O,[CuN3tea](NO3)[Cr(N3)dea(H2O)4](NO3)2,[AOH2]2[MoO2(Sb2OCl6)Cl2](H2O)2,[MoO2(AOH)2(H2O)2][Sb2OCl6],[Mo2O4(Sb2OCl(OH)3)Cl2(H2O)2(AO)2],H2[(MoO3)2Sb2O2Cl2(OH)2(H2O)2](AOH=neutral triethanolamine),meaH2[WO3(mea)],[Mn2(tea)Mo(CN)7]・H2O,[Mn2(tea)Mo(CN)7],Fe(tea)2Cl3,[Co2(μ−tea)2(NCS)2],Ni(tea)2Cl2,[Cu(N3)dea(H2O)2](NO3),Zn(tea)2Br2,Zn(tea)2(NO3)2,Cd(tea)2Cl2,Cd(tea)2(NO3)2,[(C4H9)2AlteaAl(Cl)]2,Pb(tea)2(OAc)2,Bi(tea)2Cl3(Hmea=mono−ethanolamine,H2dea=diethanolamine,H3tea=triethanolamine)などのβ−ジケトン類、β−ケトエステル類、カルボン酸類、アルカノールアミン類、ジオール類、エステル類などの金属の錯体化合物があり、それらの錯体化合物は金属酸化物前駆体の原料として、非常に有用である。 In metal oxide precursors, metal complex compounds are often used because of the need for improved stability when used in production, and Mg, Ca, Sr, Ba, Sc, Y, La are often used. , Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru , Co, Ni, Cu, Ag, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, or Bi are Mg (tea) H, Mg (tea) 2 Cl 2 , respectively. Ca (tea) H, Ca (tea) 2 Cl 2 , Sr (tea) 2 Cl 2 , Ba (tea) 2 Cl 2 , Sc (tea) 2 Cl 3 , Y (tea) 2 (ClO 4 ) 3.3 C 5 H 5 N, H 3 La [(OC 2 H 4) 3 N 2, RE (PN) 3 ( tea) (NO 3) 2 Cl (PN = pyridoxol, RE = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Y), M (acac) 3 ( M = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; acac = acetylacetonate ligand), (iso-PrO) 2 Zr “OC 2 H 4 n (C 2 H 4 OH) 2 "2, VO [n (CH 2 CH 2 O) 3], Bu 2 Sn (tea) {M (OPri) n} [M = Al (n = 2); Ti, Zr (n = 3), Nb (n = 4)], Ta (OC 2 H 5 ) 4 (etac) (etac = Ethyl Acetoacetate), “Cr (N 3 ) tea (H 2 O) 2 ” (NO 3 2 , [Ni (N 3 ) 2 tea 2 ] · 10H 2 O, [CuN 3 tea] (NO 3 ) [Cr (N 3 ) dea (H 2 O) 4 ] (NO 3 ) 2 , [AOH 2 ] 2 [MoO 2 (Sb 2 OCl 6 ) Cl 2 ] (H 2 O) 2 , [MoO 2 (AOH) 2 (H 2 O) 2 ] [Sb 2 OCl 6 ], [Mo 2 O 4 (Sb 2 OCl ( OH) 3 ) Cl 2 (H 2 O) 2 (AO) 2 ], H 2 [(MoO 3 ) 2 Sb 2 O 2 Cl 2 (OH) 2 (H 2 O) 2 ] (AOH = neutral triethanolamine), meH 2 [WO 3 (mea)], [Mn 2 (tea) Mo (CN) 7 ] · H 2 O, [Mn 2 (tea) Mo (CN) 7 ], Fe (tea) 2 Cl 3 , [Co 2 ( μ-tea) 2 (NCS) 2 ], Ni (tea) 2 Cl 2 , [Cu (N 3 ) dea (H 2 O) 2 ] (NO 3 ), Zn (tea) 2 Br 2 , Zn (tea) 2 (NO 3 ) 2 , Cd (Tea) 2 Cl 2 , Cd (tea) 2 (NO 3 ) 2 , [(C 4 H 9 ) 2 AlteaAl (Cl)] 2 , Pb (tea) 2 (OAc) 2 , Bi (tea) 2 Cl 3 (Hmea = mono-ethanolamine, H 2 dea = diethanolamine, H 3 tea = triethanolamine) β- diketones such as, beta-ketoesters, carboxylic acids, alkanolamines, diols, complex compounds of metals such as esters These complex compounds are very useful as raw materials for metal oxide precursors.
金属のアルカノールアミン化合物はこれまでに金属アルコキシドや金属水酸化物とジエタノールやトリエタノールアミンなどのアルカノールアミンの反応により合成されている。金属アルコキシドを用いる反応では、式(1)に示したテトラエトキシシランとトリエタノールアミンのアルコール交換反応によりエトキシ基を有するシラトランが合成されている(非特許文献1参照)。この反応は、対応する金属アルコキシドを用いることにより、目的とする金属のアルカノールアミン化合物が得られるが、一般に加水分解性が高く、合成や取扱いが困難である金属アルコキシドを用いる点に欠点がある。 Metal alkanolamine compounds have been synthesized so far by reaction of metal alkoxides or metal hydroxides with alkanolamines such as diethanol and triethanolamine. In the reaction using a metal alkoxide, silatrane having an ethoxy group is synthesized by an alcohol exchange reaction of tetraethoxysilane and triethanolamine shown in Formula (1) (see Non-Patent Document 1). In this reaction, an alkanolamine compound of a target metal can be obtained by using the corresponding metal alkoxide, but there is a drawback in that a metal alkoxide which is generally highly hydrolyzable and difficult to synthesize and handle.
一方、金属水酸化物を用いる反応では、式(2)に示した硼酸とトリエタノールアミンの反応によりボラトランが合成されている(非特許文献2参照)。この反応に用い得る金属水酸化物の中でも、特に14〜16属の金属元素では一般に化学的に不安定な化合物が多く、吸湿性が高いので、式(2)の方法を適用することができない。 On the other hand, in the reaction using a metal hydroxide, boratolane is synthesized by the reaction of boric acid and triethanolamine shown in Formula (2) (see Non-Patent Document 2). Among the metal hydroxides that can be used in this reaction, particularly the metal elements of groups 14 to 16 are generally chemically unstable and have high hygroscopicity, so the method of formula (2) cannot be applied. .
また、第3級アミノ基及び第一および/または第二水酸基を有する窒素含有バインダーと水にわずかに溶けるかまたは不溶性のコバルト、銅、鉛、ニッケルまたはマンガン化合物の反応(特許文献1参照)や、酸化鉛(II)とβ−ヒドロキシアミノ構造を有する化合物が以下の反応式により反応し水を分離することにより、金属のアルカノールアミン化合物が得られる(特許文献2参照)ことが開示されているが、溶液中で錯体形成をするに留まり、それらの金属のアルカノールアミン化合物を単離するには至っていない。 Further, a reaction of a nitrogen-containing binder having a tertiary amino group and a primary and / or secondary hydroxyl group with a slightly soluble or insoluble cobalt, copper, lead, nickel or manganese compound in water (see Patent Document 1) It is disclosed that lead (II) oxide and a compound having a β-hydroxyamino structure react by the following reaction formula to separate water to obtain a metal alkanolamine compound (see Patent Document 2). However, they have only been complexed in solution and have not been able to isolate alkanolamine compounds of these metals.
従って、本発明の目的は、複雑な工程及び特別な装置を必要とせずに、比較的安価で安定な金属酸化物から金属のアルカノールアミン化合物を製造する方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing a metal alkanolamine compound from a relatively inexpensive and stable metal oxide without requiring complicated steps and special equipment.
本発明者らは、鋭意研究を重ねた結果、金属酸化物とアルカノールアミンとの反応により金属のアルカノールアミン化合物を効率的に生成し、生成物である金属のアルカノールアミン化合物を生成物に可溶な溶媒で抽出し、再結晶などにより単離できる方法を見出した。即ち、本発明は、 As a result of extensive research, the present inventors have efficiently produced a metal alkanolamine compound by a reaction between a metal oxide and an alkanolamine, and the product metal alkanolamine compound is soluble in the product. The present inventors have found a method that can be extracted with a suitable solvent and isolated by recrystallization or the like. That is, the present invention
Bi 2O3からなる酸化ビスマスとNRnR’3−n(Rは炭素の数が1から4で水酸基を1つ以上有する炭化水素基、R’は水素または炭素数が1から4の炭化水素基、nは1〜3の整数)からなるアルカノールアミンを反応させることを特徴とするビスマス(III)のアルカノールアミン化合物の製造法。
に関する。
Bismuth oxide composed of B i 2 O 3 and NR n R ′ 3-n (R is a hydrocarbon group having 1 to 4 carbon atoms and having one or more hydroxyl groups, R ′ is hydrogen or having 1 to 4 carbon atoms. A process for producing an alkanolamine compound of bismuth (III), wherein an alkanolamine comprising a hydrocarbon group, n is an integer of 1 to 3) is reacted.
About.
酢酸塩、クエン酸塩、硝酸塩、シュウ酸塩、カルボン酸塩、金属アルコキシドなどの有機または無機金属化合物は、アルコール類(メタノール、エタノール、1−プロパノール、2−プロパノール、1−ブタノール、2−ブタノール、ヘキサノノールなど)、テトラヒドロフラン、ジオキサンなどのエーテル類、セロソルブ類(メチルセロソルブ、エチルセロソルブ、プロピルセロソルブ、ブチルセロソルブなど)、グリコール類(エチレングリコール、プロピレングリコール、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、2,3−ブタンジオール、ヘキシレングリコールなど)、アセトン、クロロホルム、四塩化炭素、ベンゼン、トルエンなどの有機溶媒に溶けにくいことが多く、溶媒中に有機または無機金属化合物を溶解し、その後エタノールアミンを加えて反応させることにより溶液中でエタノールアミン錯体を形成するよりも、単離した溶解性の高いエタノールアミン錯体を溶媒に溶解させる方が、より高濃度のエタノールアミン錯体を用いた金属酸化物の前駆体を製造することができる。 Organic or inorganic metal compounds such as acetate, citrate, nitrate, oxalate, carboxylate, metal alkoxide are alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol ), Ethers such as tetrahydrofuran and dioxane, cellosolves (methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, etc.), glycols (ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butane) Diol, 1,4-butanediol, 2,3-butanediol, hexylene glycol, etc.), acetone, chloroform, carbon tetrachloride, benzene, toluene, etc. It is better to dissolve the isolated highly soluble ethanolamine complex in the solvent than to dissolve the metal compound and then react with ethanolamine to form an ethanolamine complex in solution. A metal oxide precursor using an ethanolamine complex can be produced.
従来の金属のアルカノールアミン化合物の製造方法では金属アルコキシドや金属水酸化物が有効であると報告されているが、本発明の製造方法によれば、加水分解性の高い金属アルコキシドや潮解性の高い金属水酸化物を用いることなく、金属のアルカノールアミンが製造できるという特徴を持つ。
本発明によって製造しうる金属のアルカノールアミン化合物はMxOy(Mはz価の金属元素、zは1から5の整数、xは1から3の整数、yは(z)×(x)/2で表される整数)の組成からなる金属酸化物とNRnR’3−n(Rは炭素の数が1〜4であり1つ以上の水酸基で置換された炭化水素基、R’は水素または炭素数が1から4の炭化水素基、nは1〜3の整数)からなる化合物である。
例えば、酸化鉛(II)(PbO,z=2,x=1,Y=1)とトリエタノールアミン(N(CH2CH2OH)3,R=CH2CH2OH,n=3)の反応によりPb(OCH2CH2)2N(CH2CH2OH)の組成からなる鉛(II)のトリエタノールアミン化合物が得られる。
さらに、酸化ビスマス(III)(Bi2O3,z=3,x=2,Y=3)とトリエタノールアミン(N(CH2CH2OH)3,R=CH2CH2OH,n=3)の反応によりBi(OCH2CH2)3Nの組成からなるビスマス(III)のトリエタノールアミン化合物が得られる。
本発明の方法は、[1]金属酸化物とアルカノールアミンとの反応→[2]共沸蒸留による反応系内からの水分除去→[3]溶媒の除去→[4]生成物の溶解・抽出→[5]濃縮→[6]再結晶からなる。以上の方法により、金属アルカノールアミン化合物を単離する。以下に詳細を示す。
Although it has been reported that metal alkoxides and metal hydroxides are effective in the conventional methods for producing metal alkanolamine compounds, according to the production method of the present invention, highly hydrolyzable metal alkoxides and high deliquescence are high. It has a feature that a metal alkanolamine can be produced without using a metal hydroxide.
The metal alkanolamine compound that can be produced according to the present invention is M x O y (M is a metal element having a z value, z is an integer of 1 to 5, x is an integer of 1 to 3, and y is (z) × (x) NR n R ′ 3-n (R is a hydrocarbon group having 1 to 4 carbon atoms and substituted with one or more hydroxyl groups, R ′, an integer represented by / 2) Is a compound consisting of hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and n is an integer of 1 to 3.
For example, lead (II) oxide (PbO, z = 2, x = 1, Y = 1) and triethanolamine (N (CH 2 CH 2 OH) 3 , R = CH 2 CH 2 OH, n = 3) By the reaction, a triethanolamine compound of lead (II) having a composition of Pb (OCH 2 CH 2 ) 2 N (CH 2 CH 2 OH) is obtained.
Furthermore, bismuth oxide (III) (Bi 2 O 3 , z = 3, x = 2, Y = 3) and triethanolamine (N (CH 2 CH 2 OH) 3 , R = CH 2 CH 2 OH, n = The triethanolamine compound of bismuth (III) having the composition of Bi (OCH 2 CH 2 ) 3 N is obtained by the reaction of 3).
The method of the present invention comprises: [1] Reaction of metal oxide with alkanolamine → [2] Removal of water from the reaction system by azeotropic distillation → [3] Removal of solvent → [4] Dissolution / extraction of product → [5] Concentration → [6] Recrystallization. The metal alkanolamine compound is isolated by the above method. Details are shown below.
[1]金属酸化物とアルカノールアミンとの反応
金属酸化物とアルカノールアミンとの反応は、有機溶媒中に溶解または分散した金属酸化物とアルカノールアミンを反応させることにより得られる。その際、有機溶媒中の金属酸化物含量は1〜10wt%が好ましい。金属酸化物含量が1wt%以下の場合、濃縮するために多量の溶媒を留去しなければならず経済的でない。一方、10wt%を超えると金属酸化物の溶解や分散が困難になり、且つ均一な反応を行わせることが困難になる。
アルカノールアミンは、金属酸化物に対して1.0〜5.0の物質量比の範囲で使用される。上記物質量比が1.0より小さいと金属酸化物とアルカノールアミンの反応が十分に進行せず、生成物の収率が著しく低下する。一方、5.0より大きくても、金属酸化物に対してアルカノールアミンが過剰となり、その後の濃縮・再結晶の操作にも時間がかかり経済的でない。アルカノールアミンは、金属酸化物に対して1.0〜4.0の物質量比の範囲で使用されることがのぞましい。反応温度は通常60〜180℃であるが、反応温度が用いる有機溶媒の還流温度であると温度制御がより簡便である。また、反応時間は反応温度によって異なり、即ち低温では長時間を要し、高温では短時間で済むが、通常1.0〜5.0時間行われる。
金属酸化物とアルカノールアミンとの反応に用いる有機溶媒としては、ベンゼン、トルエン、o−キシレン、m−キシレン、p−キシレン、メシチレンなどの芳香族炭化水素やオクタンやデカンなどの飽和炭化水素など、水と共沸し得る有機溶媒ならば、どんな溶媒でも使用することができる。
[1] Reaction of metal oxide and alkanolamine The reaction of metal oxide and alkanolamine is obtained by reacting a metal oxide dissolved or dispersed in an organic solvent with an alkanolamine. At that time, the metal oxide content in the organic solvent is preferably 1 to 10 wt%. When the metal oxide content is 1 wt% or less, a large amount of solvent must be distilled off for concentration, which is not economical. On the other hand, if it exceeds 10 wt%, it becomes difficult to dissolve and disperse the metal oxide, and it is difficult to perform a uniform reaction.
Alkanolamine is used in the range of a substance amount ratio of 1.0 to 5.0 with respect to the metal oxide. When the above-mentioned substance amount ratio is less than 1.0, the reaction between the metal oxide and the alkanolamine does not proceed sufficiently, and the yield of the product is remarkably reduced. On the other hand, even if it is larger than 5.0, the alkanolamine is excessive with respect to the metal oxide, and the subsequent concentration and recrystallization operations take time and are not economical. The alkanolamine is preferably used in a mass ratio range of 1.0 to 4.0 with respect to the metal oxide. The reaction temperature is usually 60 to 180 ° C., but temperature control is easier when the reaction temperature is the reflux temperature of the organic solvent used. The reaction time varies depending on the reaction temperature, that is, it takes a long time at low temperatures and a short time at high temperatures, but it is usually carried out for 1.0 to 5.0 hours.
Examples of the organic solvent used in the reaction between the metal oxide and the alkanolamine include aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene, and saturated hydrocarbons such as octane and decane. Any organic solvent that can azeotrope with water can be used.
[2]反応系内からの水分除去
反応系内からの水分除去は、有機溶媒中に無水硫酸ナトリウムや塩化カルシウム、モレキュラーシーブスなどの脱水剤を共存させることでもできるが、Dean−Stark水分定量器を用いて有機溶媒と水を共沸させることにより除去するのが望ましい。反応により生成する水を随時除去することにより反応時間を短縮し、且つ合成物の生成を促進することができる。
[3]溶媒の除去
溶媒の除去は、反応終了後に、温度40〜80℃、圧力1〜25mmHgの減圧下で行い、重量減少が無くなるまで反応に用いた有機溶媒を留去することで行われる。
[4]生成物の溶解・抽出
生成物の溶解・抽出には、アルカノールアミン化合物を溶解する有機溶媒が用いられる。一例を挙げるならば、メタノール、エタノールなどのアルコール類、テトラヒドロフラン、ジオキサンなどのエーテル類、セロソルブ類、グリコール類、アセトン、クロロホルム、四塩化炭素、ベンゼン、トルエンなどであり、これらが一種以上用いられる。
金属酸化物とアルカノールアミンの反応に用いた溶媒の除去後、金属アルカノールアミン化合物を溶解する最低限以上の有機溶媒を加え、適宜加熱して生成物の溶解・抽出を行う。加熱の際、有機溶媒が環流してもかまわない。
[2] Water removal from the reaction system Water removal from the reaction system can be carried out by allowing a dehydrating agent such as anhydrous sodium sulfate, calcium chloride, and molecular sieves to coexist in an organic solvent. It is desirable to remove the organic solvent and water by azeotroping with the use of. By removing water generated by the reaction as needed, the reaction time can be shortened and the production of the synthesized product can be promoted.
[3] Removal of solvent Removal of the solvent is carried out by removing the organic solvent used in the reaction until the weight loss is eliminated after the reaction is completed under reduced pressure at a temperature of 40 to 80 ° C. and a pressure of 1 to 25 mmHg. .
[4] Product dissolution / extraction An organic solvent that dissolves the alkanolamine compound is used for product dissolution / extraction. For example, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, cellosolves, glycols, acetone, chloroform, carbon tetrachloride, benzene, toluene, and the like are used.
After removing the solvent used for the reaction between the metal oxide and the alkanolamine, a minimum or more organic solvent that dissolves the metal alkanolamine compound is added, and the product is dissolved and extracted by heating as appropriate. During heating, the organic solvent may be refluxed.
[5]濃縮
生成物を溶解・抽出した後、不溶物をろ別し、ろ液の濃縮を行う。濃縮は、減圧度25mmHg以下において60〜80℃で溶媒を留去することにより行われる。濃縮は金属アルカノールアミン化合物のその温度における飽和溶解度に達するまで行われる。濃縮時に金属アルカノールアミン化合物が析出した場合は、加熱または溶媒を加えて飽和溶液とする。
[6]再結晶
上記操作により得られた飽和溶液をその溶媒の融点以上、通常は0〜10℃に冷却し、結晶を析出させる。その後、ろ過により固体をろ別し、再結晶に用いた溶媒、もしくはメタノール、エタノールなどの溶媒で洗浄する。
さらに、洗浄後の生成物を温度40〜80℃、圧力1〜25mmHgの減圧下で乾燥させる。
[5] Concentration After dissolving and extracting the product, insoluble matters are filtered off, and the filtrate is concentrated. Concentration is performed by distilling off the solvent at 60 to 80 ° C. at a reduced pressure of 25 mmHg or less. Concentration is performed until the saturation solubility of the metal alkanolamine compound at that temperature is reached. When a metal alkanolamine compound precipitates during concentration, heating or a solvent is added to form a saturated solution.
[6] Recrystallization The saturated solution obtained by the above operation is cooled to a temperature equal to or higher than the melting point of the solvent, usually 0 to 10 ° C. to precipitate crystals. Thereafter, the solid is separated by filtration and washed with a solvent used for recrystallization or a solvent such as methanol or ethanol.
Further, the washed product is dried under reduced pressure at a temperature of 40 to 80 ° C. and a pressure of 1 to 25 mmHg.
本発明で得られたアルカノールアミン化合物の一部は、クロロホルム、テトラヒドロフラン、ジオキサン、アセトン、プロパノール、エタノール、メタノールなどの極性溶媒に対して溶解性を示し、ベンゼン、四塩化炭素などの非極性溶媒には溶解性を示さない。しかし、アルカノールアミン化合物の溶解性を損ない程度であれば他の非極性溶媒を一部加えることができる。例えば、鉛のトリエタノールアミン化合物は、エタノール、メタノールなどのアルコールに溶解し、ビスマスのトリエタノールカミン化合物はプロピレングリコールなどに溶解する。また、鉛のトリエタノールアミン化合物及びビスマスのトリエタノールアミン化合物は共に水で分解を起こす。
本発明で得られたアルカノールアミン化合物の一部は、他の金属錯体と反応させることで、アルカノールアミンを介して高分子量化が進み、均質で有機溶媒可溶な金属含有高分子量体となる。生成された金属含有高分子量体は、金属酸化物前駆物質として利用することができ、さらに、金属酸化物前駆物質を用いて調製した金属酸化物前駆体及び金属酸化物前駆物質は適当な条件で焼成することで均質性に優れたセラミックスとなる。
以下に実施例を挙げ、本発明を更に具体的に説明するが、本発明はこれらに限定されるものではない。
Some of the alkanolamine compounds obtained in the present invention are soluble in polar solvents such as chloroform, tetrahydrofuran, dioxane, acetone, propanol, ethanol and methanol, and in nonpolar solvents such as benzene and carbon tetrachloride. Does not show solubility. However, other nonpolar solvents can be partially added as long as the solubility of the alkanolamine compound is impaired. For example, a lead triethanolamine compound is dissolved in an alcohol such as ethanol or methanol, and a bismuth triethanolcamine compound is dissolved in propylene glycol or the like. Both lead triethanolamine compounds and bismuth triethanolamine compounds decompose in water.
A part of the alkanolamine compound obtained in the present invention is reacted with another metal complex to increase the molecular weight through the alkanolamine, thereby obtaining a metal-containing high molecular weight material that is homogeneous and soluble in an organic solvent. The produced metal-containing polymer can be used as a metal oxide precursor, and the metal oxide precursor and metal oxide precursor prepared using the metal oxide precursor can be used under appropriate conditions. By firing, it becomes a ceramic with excellent homogeneity.
Examples Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
実施例で用いた分析法は以下の通りである。
[1] 誘導結合プラズマ金属分析(ICP)
ICPS−7500型(島津製作所製)にて測定した。試料の前処理は次のようにして行った。試料0.01gを秤量し、2mlの濃硝酸を加えて溶解してから、2次蒸留水で100mlに定容とした。また、濃度が既知である市販の標準試料を希釈することにより0ppm、50ppm、100ppmの含金属水溶液を用いて検量線を作成し、検量線法により試料の金属重量含有率を算出した。
[2]単結晶X線構造解析
日本ブルカー・エイエックスエス(株)製SMART APEXにより測定した。0.5 x 0.4 x 0.3 mmの無色板状結晶をガラスキャピラリーの先端に乗せ、CCD検出器を備えたBruker SMART APEX, Mo Ka線(λ=0.71073Å)により、−53±2℃で測定した。構造はSHELLXL−97により解析した。
[3] 赤外吸収(IR)スペクトル分析
日本電子(株)製JIR−5300型により、KBr錠剤法を用いて、4cm−1の分解能4000−400cm−1の範囲で測定した。
The analytical methods used in the examples are as follows.
[1] Inductively coupled plasma metal analysis (ICP)
It was measured with ICPS-7500 type (manufactured by Shimadzu Corporation). The sample was pretreated as follows. A sample of 0.01 g was weighed and dissolved by adding 2 ml of concentrated nitric acid, and the volume was adjusted to 100 ml with secondary distilled water. Moreover, a calibration curve was created using a metal-containing aqueous solution of 0 ppm, 50 ppm, and 100 ppm by diluting a commercially available standard sample having a known concentration, and the metal weight content of the sample was calculated by the calibration curve method.
[2] Single crystal X-ray structural analysis It was measured by SMART APEX manufactured by Nippon Bruker AXS Co., Ltd. A colorless plate-like crystal of 0.5 × 0.4 × 0.3 mm was placed on the tip of a glass capillary, and −53 ± by a Bruker SMART APEX, Mo Ka line (λ = 0.7073Å) equipped with a CCD detector. Measured at 2 ° C. The structure was analyzed by SHELLXL-97.
[3] The infrared absorption (IR) spectrum analysis JEOL Ltd. JIR-5300 type, with a KBr tablet method, was measured in the range of resolution 4000-400 -1 of 4 cm -1.
[4]溶解性の評価方法
試料0.01gを計り取り、ヘキサン、ベンゼン、トルエン、四塩化炭素、クロロホルム、テトラヒドロフラン(THF)、メタノール(MeOH)、エタノール(EtOH)及び水を1mL,5mL,10mL加えて沸点まで加熱し,溶液に残存する粉末の有無を目視によって確認した。サンプルが溶解したときの溶媒の量が1ml以下で++:Easily soluble、1〜5mlで+:soluble、5〜10mlで−:slightly soluble、10ml以上で−−:insolubleとし、分解したものはD:decompositionとした。加えた溶媒にすべての試料が溶解したと目視できるときに溶解とし、溶媒を加えても試料が溶解せずに残存していることを目視したときに不溶解とした。また、化学変化により試料が変質した場合を分解とした。
[5]融点、沸点、分解点の測定
密閉したガラス細管に試料を充填し、ヤナコ製Micro Meltingpoint Apparatus MP−S3型融点測定器を用いて測定した。同一試料について試料が液化した温度前後で数回測定を繰り返し、毎回同一温度で液化した場合を融点とし、試料に形状や色の変化が見られ、その温度前後で数回測定を繰り返し、毎回その温度が変化する場合を分解点とした。
[6] 熱重量示差熱分析(TG−DTA)
TG−DTA装置:TG−DTA2020S((株)マック・サイエンス製)で測定した。測定条件:空気気流中、昇温速度:10℃/min。
[7] 結晶構造解析(X線回折分析)
X線回折結晶構造解析装置:X’Pert−MPD(日本フィリップス製(株))(45KV,40mA,Cu−Kα radiation,X線波長1.5418nm)で測定した。測定範囲は2θ=10〜70deg.。
[4] Method for evaluating solubility 0.01 g of a sample is weighed and 1 mL, 5 mL, or 10 mL of hexane, benzene, toluene, carbon tetrachloride, chloroform, tetrahydrofuran (THF), methanol (MeOH), ethanol (EtOH), and water. In addition, the mixture was heated to the boiling point, and the presence or absence of powder remaining in the solution was visually confirmed. When the amount of the solvent when the sample was dissolved was 1 ml or less, ++: Easyly soluble, 1 to 5 ml +: soluble, 5 to 10 ml-: lightly soluble, 10 ml or more-: insoluble; It was set as decomposition. When it was visually observed that all the samples were dissolved in the added solvent, the sample was dissolved. When it was visually observed that the sample remained undissolved even when the solvent was added, the sample was insoluble. The case where the sample was altered due to a chemical change was regarded as decomposition.
[5] Measurement of Melting Point, Boiling Point, and Decomposition Point A sealed glass capillary was filled with a sample, and measured using a Micro Meltingpoint Apparatus MP-S3 melting point measuring device manufactured by Yanaco. Repeat the measurement several times before and after the temperature at which the sample was liquefied for the same sample, and the melting point is when the sample is liquefied at the same temperature each time.Changes in the shape and color are observed in the sample. The case where the temperature changed was taken as the decomposition point.
[6] Thermogravimetric differential thermal analysis (TG-DTA)
TG-DTA apparatus: Measured with TG-DTA2020S (manufactured by Mac Science Co., Ltd.). Measurement conditions: In air stream, temperature rising rate: 10 ° C./min.
[7] Crystal structure analysis (X-ray diffraction analysis)
X-ray diffraction crystal structure analyzer: X'Pert-MPD (Nippon Philips Co., Ltd.) (45 KV, 40 mA, Cu-Kα radiation, X-ray wavelength 1.5418 nm). The measurement range is 2θ = 10 to 70 deg. .
〔実施例1〕 鉛(II)のトリエタノールアミン化合物の合成
Dean−Stark水分定量器を取付けた200mLフラスコに、酸化鉛(II)10.4g、トリエタノールアミン14.9g、メシチレン100mLを入れた。その際の物質量の比率は酸化鉛(II):トリエタノールアミン=1:2である。150℃で2時間加熱した後、メシチレンを留去し、EtOH 10mlを加えて還流することにより生成物を抽出した。ろ液を粉末が析出するまで濃縮し,粉末が析出したところで濃縮を止めた。その後,溶媒の還流温度付近で粉末が溶解するまで溶媒を添加して熱飽和溶液を調製し、5℃/hで室温まで放冷した後、冷凍庫(−10℃)で冷却して再結晶することで14.8gの生成物を得た。析出した結晶をろ過により分離し、温度40℃、圧力5mmHgで2時間乾燥して生成物を単離した。生成物の収率は83.72%であった。生成物はエタノール、メタノールなどのアルコールに溶解し、分解点は249.2〜250.5℃であった。ICP分析による分子中のPb金属含有比率は58.43%(Pb(OCH2CH2)2N(CH2CH2OH)としての計算値58.46%)であった。
得たれた生成物の単結晶X線構造解析の結果、最終段階で4125個の反射点(1>2σ(1))と201個の可変変数を用いて全域に最小二乗法による精密化を行うことにより、R1=0.0529,wR2=0.1343で収束した。よって、得たられた鉛(II)のトリエタノールアミン化合物の結晶構造は図1に示した。
Example 1 Synthesis of Lead (II) Triethanolamine Compound A 200 mL flask equipped with a Dean-Stark moisture meter was charged with 10.4 g of lead (II) oxide, 14.9 g of triethanolamine, and 100 mL of mesitylene. . The ratio of the amount of substances at that time is lead (II) oxide: triethanolamine = 1: 2. After heating at 150 ° C. for 2 hours, mesitylene was distilled off, and 10 ml of EtOH was added and refluxed to extract the product. The filtrate was concentrated until the powder precipitated, and the concentration was stopped when the powder precipitated. Then, a solvent is added until the powder dissolves near the reflux temperature of the solvent to prepare a heat saturated solution, which is allowed to cool to room temperature at 5 ° C./h, then cooled in a freezer (−10 ° C.) and recrystallized. This gave 14.8 g of product. The precipitated crystals were separated by filtration and dried at a temperature of 40 ° C. and a pressure of 5 mmHg for 2 hours to isolate the product. The product yield was 83.72%. The product was dissolved in alcohol such as ethanol and methanol, and the decomposition point was 249.2 to 250.5 ° C. The Pb metal content ratio in the molecule by ICP analysis was 58.43% (calculated value as Pb (OCH 2 CH 2 ) 2 N (CH 2 CH 2 OH) 58.46%).
As a result of single-crystal X-ray structural analysis of the obtained product, refinement by the least-squares method is performed over the entire area using 4125 reflection points (1> 2σ (1)) and 201 variable variables in the final stage. Thus, convergence was achieved with R1 = 0.0529 and wR2 = 0.1343. Therefore, the crystal structure of the lead (II) triethanolamine compound obtained is shown in FIG.
〔実施例2〕 ビスマス(III)のトリエタノールアミン化合物の合成
Dean−Stark水分定量器を取付けた100mLフラスコに、酸化ビスマス(III)8.33g、トリエタノールアミン11.0g、メシチレン100mLを入れた。その際の物質量の比率は酸化ビスマス(III):トリエタノールアミン=1:4である。150℃で2時間加熱した後、プロピレングリコール200mLを加え,90℃で加熱して生成物を抽出した。その後、エタノールを20mL加えて5℃/hで室温まで放冷した後、冷凍庫(−10℃)で冷却して、再結晶することで6.60gの生成物を得た。析出した結晶をろ過により分離し、温度40℃、圧力5mmHgで2時間乾燥して生成物を単離した。生成物の収率は50.3%であった。生成物はプロピレングリコールなどの有機溶媒に溶解し、分解点は250.6〜251.5℃であった。ICP分析による分子中のPb金属含有比率は58.4%(Bi(OCH2CH2)3Nとしての計算値58.8%)であった。
得たれた生成物のIRスペクトル解析の結果、Bi(OCH2CH2)3Nの構造に特徴的な2900cm−1(νC−H)、1130cm−1(νC−O)、1300〜1360cm−1(νN−C)のピークが見られた。
[Example 2] Synthesis of triethanolamine compound of bismuth (III) A 100 mL flask equipped with a Dean-Stark moisture meter was charged with 8.33 g of bismuth (III) oxide, 11.0 g of triethanolamine, and 100 mL of mesitylene. . The ratio of the amount of substances at that time is bismuth oxide (III): triethanolamine = 1: 4. After heating at 150 ° C. for 2 hours, 200 mL of propylene glycol was added, and the product was extracted by heating at 90 ° C. Then, 20 mL of ethanol was added and allowed to cool to room temperature at 5 ° C./h, then cooled in a freezer (−10 ° C.) and recrystallized to obtain 6.60 g of product. The precipitated crystals were separated by filtration and dried at a temperature of 40 ° C. and a pressure of 5 mmHg for 2 hours to isolate the product. The yield of product was 50.3%. The product was dissolved in an organic solvent such as propylene glycol, and the decomposition point was 250.6 to 251.5 ° C. The Pb metal content ratio in the molecule by ICP analysis was 58.4% (calculated value as Bi (OCH 2 CH 2 ) 3 N 58.8%).
As a result of IR spectrum analysis of the obtained product, 2900 cm −1 (ν C—H ), 1130 cm −1 (ν C—O ), 1300 to 1360 cm characteristic of the structure of Bi (OCH 2 CH 2 ) 3 N −1 (ν N—C ) peak was observed.
〔実施例3〕
鉛のトリエタノールアミン錯体0.71g、ビスアセト酢酸エチルチタンジエトキシド0.40g、ビスアセト酢酸エチルジルコニウムジエトキシド0.44gを100mLのエタノールに溶解し、モル比がPb:Zr:Ti=2:1:1の溶液を調製した。この溶液を60℃で1時間加熱し、40℃、2mmHgで2時間濃縮することで1.50gの金属の高分子量体である前駆物質を得た。得られた前駆物質は、濃縮段階で析出が全く見られず、均質なものであった。この前駆物質は褐色の粉末であり、TG−DTA測定の結果(図2参照)から、800℃でのセラミック収率は53.77%であり、得られた前駆物質は450℃程度で完全にセラミック化したことが示された。
Example 3
0.71 g of lead triethanolamine complex, 0.40 g of ethyl bisacetoacetate titanium diethoxide and 0.44 g of ethyl zirconium bisacetoacetate diethoxide were dissolved in 100 mL of ethanol, and the molar ratio was Pb: Zr: Ti = 2: A 1: 1 solution was prepared. This solution was heated at 60 ° C. for 1 hour and concentrated at 40 ° C. and 2 mmHg for 2 hours to obtain 1.50 g of a precursor that is a high molecular weight metal. The obtained precursor was homogeneous with no precipitation observed at the concentration stage. This precursor is a brown powder. From the result of TG-DTA measurement (see FIG. 2), the ceramic yield at 800 ° C. is 53.77%, and the obtained precursor is completely at about 450 ° C. It was shown to be ceramicized.
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Free format text: JAPANESE INTERMEDIATE CODE: R350 |