WO2010118661A1 - 8-羟基喹啉或其衍生物的金属化合物的制备方法 - Google Patents
8-羟基喹啉或其衍生物的金属化合物的制备方法 Download PDFInfo
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- WO2010118661A1 WO2010118661A1 PCT/CN2010/071409 CN2010071409W WO2010118661A1 WO 2010118661 A1 WO2010118661 A1 WO 2010118661A1 CN 2010071409 W CN2010071409 W CN 2010071409W WO 2010118661 A1 WO2010118661 A1 WO 2010118661A1
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- Prior art keywords
- solvent
- hydroxyquinoline
- aluminum
- water
- preparation
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000005725 8-Hydroxyquinoline Substances 0.000 title claims abstract description 24
- 229960003540 oxyquinoline Drugs 0.000 title claims abstract description 24
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 12
- 150000002736 metal compounds Chemical class 0.000 title abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- -1 Alkoxy aluminum Chemical compound 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical group [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 4
- 239000003021 water soluble solvent Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 150000004325 8-hydroxyquinolines Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000002209 hydrophobic effect Effects 0.000 abstract 4
- 150000004703 alkoxides Chemical class 0.000 abstract 1
- 239000012452 mother liquor Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 4
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 4
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- SXXNJJQVBPWGTP-UHFFFAOYSA-K tris[(4-methylquinolin-8-yl)oxy]alumane Chemical compound [Al+3].C1=CC=C2C(C)=CC=NC2=C1[O-].C1=CC=C2C(C)=CC=NC2=C1[O-].C1=CC=C2C(C)=CC=NC2=C1[O-] SXXNJJQVBPWGTP-UHFFFAOYSA-K 0.000 description 2
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical compound C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- LFHXPRTYXDXTDD-UHFFFAOYSA-H bis(2,2-dioxo-1,3,2,4-dioxathialumetan-4-yl) sulfate octahydrate Chemical compound O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LFHXPRTYXDXTDD-UHFFFAOYSA-H 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- COLNWNFTWHPORY-UHFFFAOYSA-M lithium;8-hydroxyquinoline-2-carboxylate Chemical compound [Li+].C1=C(C([O-])=O)N=C2C(O)=CC=CC2=C1 COLNWNFTWHPORY-UHFFFAOYSA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
- C07D215/30—Metal salts; Chelates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/186—Metal complexes of the light metals other than alkali metals and alkaline earth metals, i.e. Be, Al or Mg
Definitions
- the present invention relates to a method for synthesizing an organic electroluminescent material, and more particularly to a method for preparing a high purity 8-hydroxyquinoline metal (Al, Li) compound.
- 8-hydroxyquinoline aluminum, 8-hydroxyquinoline lithium, bis(2-methyl-8-hydroxyquinoline) phenoxy aluminum is currently the most widely used three 8-hydroxyquinoline metal compounds. It has become a promising electron transport material in organic light-emitting materials and is widely used in various types of electroluminescent devices, and the performance of the device is improved (Liuown, et al. Synthetic Metals, 2002, 128, 221.). However, in the preparation process of the organic light-emitting device, a trace amount of impurities easily cause pinholes, short circuits, and black spots, thereby affecting the life of the device, and thus preparation of a high-purity material is critical.
- the problem to be solved by the present invention is that the yield of 8-hydroxyquinoline is low, the side reaction is large, and the production cycle is long.
- the present invention optimizes the reaction conditions and can control the progress of the reaction.
- a metal compound of a different ligand can be obtained.
- the reaction does not use a protic solvent, easily causes a coordination solvent, avoids the generation of side reactions, improves the yield and purity, and can be directly utilized after the reaction mother liquid is recovered, thereby reducing the cost.
- the reaction temperature is from 25 ° C to 120 ° C.
- the water-soluble solvent I, I I, I I I is one of toluene, xylene, petroleum ether, and halogenated hydrocarbon.
- the water solvents I, II, and III are toluene and xylene; and when the M is lithium, the water solvents I, II, and III are dichloromethane and chloroform.
- the Zengshui Solvent I, the Zengshui Solvent I I, and the Zengshui Solvent I I I are the same solvent.
- the aluminum alkoxide is aluminum isopropoxide.
- the inorganic lithium is hydrated lithium hydroxide or lithium hydroxide.
- the method further comprises a separation step of Mq n q m ', filtering the reaction solution, washing the filtrate, and drying.
- the drying is vacuum drying at a temperature of from 50 ° C to 250 ° C.
- the q' is a phenol and a derivative thereof, a biphenol, and an 8-hydroxyquinoline derivative different from q.
- the raw materials involved in the reaction are respectively dissolved in a water-soluble solvent (an organic solvent which is not miscible with water), and reacted under conditions of nitrogen gas filling and dropping of the raw materials.
- a water-soluble solvent an organic solvent which is not miscible with water
- the solvent and raw materials used are used directly, and no special treatment is required, but the environment for synthesis laboratory, drying and storage should be kept free of acid.
- the aluminum compound is made of organoaluminum and the lithium compound is inorganic aluminum, the aluminum compound is dissolved in the water solvent I, and the lithium compound is not dissolved. In order to facilitate the recycling of the solvent, it is preferred to use the same solvent as the raw material solvent.
- the amount of the solvent is not confirmed according to the solubility of the 8-hydroxyquinoline compound; if a large crystal is desired, the amount of the solvent can be increased; if it is a compound of a misaligned ligand, the compounds of different ligands are separately dissolved.
- the above reaction temperature is controlled at 25 ° C - 120 ° C, and the product is quickly precipitated. After all the stirring is completed until the product is no longer precipitated, the target product can be separated by suction filtration, the solvent is washed, and the purity of the product is 99. Above %, the yield is greatly improved compared with the method of the comparative literature.
- the metal compound obtained by the above process solves the problems of low yield and many side reactions existing at present, and has the following advantages:
- the synthesis process uses a water solvent, which does not require a protic solvent, and easily causes a coordination solvent, thereby avoiding the problem of complexing of solvent molecules.
- the obtained product has no coordinating solvent molecules, and no pinholes are generated during the preparation of the device, and the brightness, efficiency and life of the device are not affected.
- the solvent and raw materials are made of industrial raw materials, and no special treatment is required, which simplifies the reaction step, and the obtained product can be directly used in the light-emitting device.
- the by-product obtained is neutral, avoiding the generation of acidic substances in the prior process, causing side reactions caused by the generation of acidic substances, and not obtaining by-products during product sublimation and use.
- the synthesized 8-hydroxyquinoline metal complex also contains no ionic impurities. Further, in the preparation process of the present invention, the sewage from the washing is not generated, and environmental pollution can be prevented.
- the 8-hydroxyquinoline lithium product has high yield, and the compound is stable, and there is no decomposition in the heating and sublimation processes.
- Comparative Example 1 Synthesis of 8-hydroxyquinoline aluminum by using aluminum stearate as a raw material (refer to World Patent WO0125211)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Description
8-羟基喹啉或其衍生物的金属化合物的制备方法
技术领域
本发明涉及有机电致发光材料的合成方法，特别是涉及一种高纯度 8-羟基喹 啉类金属 （ Al、 Li) 化合物的制备方法。 技术背景
1987年， 美国 Kodak公司的邓青云等人以 Alq3为发光层、 芳香二胺为孔穴 传输层成功制备了夹心型双层有机电致发光器件 （Tang C. W.,et al. Applied Physics Letters,1987,51,913)。 1990年英国剑桥大学 Burroughes J. H.， et al.研制了 有机聚合物发光二极管（Burroughes J. H.， et al.Nartue,1990,347,5395 )，这些重大 突破极大推动了有机电致发光技术领域的发展。 自此之后， 各个国家科学家投入 了很大精力进行研发，越来越多有机电致发光材料被开发和应用， 在各种有机发 光材料中， 8-羟基喹啉类金属配合物具有成膜性好、 发光效率高、 发光亮度高、 电子传输速度高、 玻璃化温度高、 合成工艺简单等特点， 得到广泛应用。
8-羟基喹啉铝、 8-羟基喹啉锂、 二 （2-甲基 -8-羟基喹啉） 联苯氧基铝是目前 使用最广泛的三种 8-羟基喹啉类金属化合物，已经成为有机发光材料中很有前途 的电子传输材料，被广泛应用在各种类型的电致发光器件中， 器件的性能得到提 高 （Liu zugang,et al. Synthetic Metals,2002,128,221.)。 但是在有机发光器件制备 过程中， 微量的杂质容易引起针孔、 短路、 黑点现象， 进而影响器件的寿命， 因 此制备高纯度材料是关键的。 目前存在的合成方法中， 有的制备技术落后， 得到 产品带溶剂分子， 严重影响器件的亮度、 效率 （Kim T.-S.,et al, Science and Technology of Advanced Materials,04,5,331 )； 有的方法合成的化合物带有发光猝 灭的杂质， 严重影响了器件寿命 （Papadimitrakopoulos F., Zhang X. M., Synthetic Metals,1997,85,1221. ) , 而且生产时间长； 有些合成方法涉及原料不容易得到如 三乙基铝，或者反应太剧烈，产生不容易除去的杂质（Wang guang, et al, Synthetic Metals,2002,131,l-5. ), 这给材料的广泛应用、工业化生产造成很大的困难。 因此 寻找一条能够高效合成 8-羟基喹啉类金属化合物，并且能够避免目前合成路线的 缺点是紧迫的。
发明内容
针对目前合成存在的问题，本发明要解决问题是 8-羟基喹啉类产率低、副反 应多、 生产周期长的问题。 本发明优化了反应条件， 可以控制反应进行， 除了得 到单配体金属配合物，还可以得到不同配体的金属化合物。反应不用质子性溶剂、 容易引起配位溶剂， 避免了副反应的产生， 提高了产率和纯度， 反应母液回收之 后可以直接利用， 减低成本。
化合物 Mqnqm '的制备方法， 其中 M为 Al、 Li , n为 1_3， m为 0_2, q为 8_羟 基喹啉及其衍生物， q'为与 q不同的配体， 包括如下步骤：
( 1 ) 配制原料液： 烷氧基铝或锂化合物加入曾水溶剂 I中得 A; q溶在曾水溶 剂 I I中得 B， 将与 q不同的 q'配体溶于曾水溶剂 I I I中得 C， 其中烷氧 基铝的烷氧基的碳原子数为 3-6个，
( 2 ) 反应： 在氮气保护下， 将8、 C依次滴加入 A中反应， 反应温度为 25°C - 140°C。
所述反应温度为 25°C-120°C。
所述曾水溶剂 I、 I I、 I I I为甲苯、 二甲苯、 石油醚、 卤代烃中的一种。 优选所述 M为铝时， 曾水溶剂 I、 II、 III为甲苯、 二甲苯； 所述 M为锂时， 曾水溶剂 I、 II、 III为二氯甲烷、 三氯甲烷。
所述曾水溶剂 I、 曾水溶剂 I I、 曾水溶剂 I I I为同一种溶剂。
所述烷氧基铝为异丙醇铝。
所述无机锂为水合氢氧化锂或氢氧化锂。
所述方法还包括 Mqnqm '的分离步骤， 将反应液过滤、 洗涤滤物， 干燥即可。 所述干燥为真空烘干， 温度 50°C-250°C。
所述 q'为苯酚及其衍生物、 联苯酚、 与 q不同的 8-羟基喹啉衍生物。
本发明把参与反应的原料分别用曾水溶剂（与水不发生混溶的有机溶剂）溶 解， 在充氮气、 原料滴加的条件下发生反应。 所用溶剂、 原料直接使用， 不需要 特别处理， 但合成实验室、 烘干、 保存的环境要保持无酸气。 由于铝化合物是采 用有机铝， 锂化合物是无机铝， 因此在曾水溶剂 I中铝化合物溶解， 锂化合物不 溶解。 为方便溶剂的回收利用， 原料溶剂最好用同种溶剂。 8-羟基喹啉类化合物
溶解在溶剂中，溶剂的用量要根据 8-羟基喹啉类化合物的溶解度不确认；如果想 得到大的晶体， 溶剂量可以增加； 如果是错位配体的化合物， 不同配体的化合物 分别溶解。 上述反应温度控制在 25°C-120°C反应， 很快有产品析出， 全部加完 搅拌直到不再有产品析出时通过抽滤就可以分离出目标产品，溶剂洗涤， 干燥得 产物纯度在 99%以上， 产率与对比文献的方法相比， 收率有了大幅提高。
上面工艺得到的金属化合物， 解决了目前存在的产率低、 副反应多的问题， 具有以下优点：
( 1 ) 合成过程采用曾水溶剂， 不用质子性溶剂、 容易引起配位溶剂， 避免 了溶剂分子络合的问题。得到产品没有配位溶剂分子， 在制备器件过程不会产生 针孔， 也不会影响器件亮度、 效率、 寿命。
(2) 合成过程中， 溶剂、 原料采用工业原料， 不需要特别处理， 简化了反 应步骤， 得到产品可以直接用在发光器件。
(3)合成过程中， 得到的副产物是中性， 避免了以前工艺中产生酸性物质， 产生酸性物质引起副反应， 并且得到产品升华和使用过程也不产生副产物。
(4) 在生产和后处理过程中没有使用水， 避免了水带入最为有害的卤素等 离子性不纯物，合成后的 8-羟基喹啉金属络合物也不含离子性不纯物。而且在本 发明的制备工序中， 并不产生水洗带来的污水， 可以防止环境污染。
( 5 ) 8-羟基喹啉锂得到产品不仅产率高， 而且化合物稳定， 加热、 升华过 程没有分解现象。
(6) 本方法不仅适合目前涉及的化合物， 对于其它金属的 8-羟基喹啉类化 合物以及其它配体的化合物同样适用。 附图说明
图 1、 实施例 1核磁图， 没有溶剂峰。
图 2、 对比例 2核磁图， 核磁有溶剂峰。
图 3、 实施例 3核磁图。
图 4、 对比例 3核磁图。 具体实施方法
实施例 1 : 异丙醇铝作原料合成 8-羟基喹啉铝
120mL甲苯加入 500mL四口瓶， 异丙醇铝加入四口瓶中， 充氮气搅拌， 全溶、 无色透明。 8-羟基喹啉溶于 120mL甲苯中， 通过恒压滴液漏斗加入反应， 滴加 8- 羟基喹啉溶液， 立即有黄绿色产生， 很快产生黄色沉淀， 8-羟基喹啉溶液全部加 完产生大量沉淀。 温度维持在 60°C， 反应 30min停止加热， 冷至室温， 过滤， 得 到大量纤维状固体。用 150x2mL甲苯洗涤 2次； 150x2mL石油醚洗涤 2次， 70°C真空 干燥 6小时， 得到 17. 5克亮黄色产品， 产率 95%。 对比例 1 : 硬脂酸铝作原料合成 8-羟基喹啉铝 （参考世界专利 WO0125211 )
硬脂酸铝 10g、 甲苯 50ML加入 500ml四口瓶， 搅拌呈浑浊。 6. 0g8-羟基喹啉溶 于 150ml甲苯， 充氮气， 室温滴加， 立即有黄绿色产生， 随着 8-羟基喹啉加入， 产生大量黄绿色固体。 升温回流 24小时， 冷却过滤， 得到片状黄绿色固体， 甲苯 洗涤 2次； 70度真空烘干， 得到 5g黄绿色固体， 产率 79%。 对比例 2: 硫酸铝作原料合成 8-羟基喹啉铝 （发光学报， 2003， 24， 44-46 )
取 20.22g十八水硫酸铝溶于 11四口瓶，加入 200ml水，充氮气，升温 65°C。26.4 g 8-羟基喹啉溶在 400ml乙醇中， 滴加， 立即有黄色浑浊， 此时 PH=5-6。 随着 8- 羟基喹啉的加入， 浑浊增多， 1小时全部加完。 乙酸铵缓冲溶液调节 PH6.0-6.5 , 维持温度 65 °C反应 30分钟， 得到产品是浅绿色的固体， 恢复到室温过滤。 100ml 乙醇洗涤 2次， 100ml水洗涤 2次， 100ml乙醇洗涤 2次， 100ml乙醚洗涤 2次， 得到 产品仍然带有浅绿色， 70度干燥过夜， 27.22g， 产率 97.6%， 但核磁中有溶剂峰。 实施例 2: 二 （2-甲基 -8-羟基喹啉） -4- (苯基苯氧基） 铝合成
4-苯基苯酚、 200ml甲苯加入 1L四口瓶， 充氮气搅拌全溶。 异丙醇铝溶于 120ml甲苯， 滴加， 立即有白色混浊， 1. 5小时全部加完， 搅拌 1小时。 滴加 2 一甲基一 8—羟基喹啉， 立即有黄绿色混浊产生， 全部加完需要 1小时， 加完回 流 16小时。 冷却析出略带黄色固体， 过滤， 得到固体白色。 甲苯纯化， 干燥， 产率 80%。
实施例 3: 8—羟基喹啉锂合成
120ml二氯甲烷加入 250ml四口瓶，先加入水合氢氧化锂，搅拌呈白色浑浊。 8-羟基喹啉分批加入， 在不到半分钟有乳黄色产生； 很快乳黄色增多， 25 °C反 应过夜， 得到大量浅黄色固体。 过滤得到大量乳黄色固体， 用二氯甲烷 100ml 分 2次洗涤， 200度 24小时， 产率 90%。 对比例 3: 8—羟基喹啉锂合成 （参考中国专利 CN1513940)
我们重复了中国专利 CN1513940,产率 40%，但加热干燥过程中有大量分解现 象。 实施例 4: 三 （4-甲基 -8-羟基喹啉） 铝
按照实施例 1提供的方法合成三 （4-甲基 -8-羟基喹啉） 铝， 得到黄色固体， 产 率 70%。
Claims
1、 化合物 Mqnqm' 的制备方法， 其中 M为 Al、 Li, n为 1-3， m为 0-2,q 为 8-羟基喹啉及其衍生物， q ' 为与 q不同的配体， 包括如下步骤：
( 1 ) 配制原料液： 烷氧基铝或锂化合物加入曾水溶剂 I中得 A; q溶在曾 水溶剂 II中得 B， 将与 q不同的 q ' 配体溶于曾水溶剂 III中得 C， 其中烷氧基 铝的烷氧基的碳原子数为 3-6个， （2) 反应： 在氮气保护下， 将8、 C依次滴加 入 A中反应， 反应温度为 25°C-140°C。
2、 根据权利要求 1所述的制备方法， 所述反应温度为 25°C-120°C。
3、 根据权利要求 2所述的制备方法， 所述曾水溶剂 I、 II、 III为甲苯、 二甲 苯、 石油醚、 卤代烃溶剂中的一种。
4、 根据权利要求 3所述的制备方法， 所述 M为铝时， 曾水溶剂 I、 II、 III 为甲苯、 二甲苯； 所述 M为锂时， 曾水溶剂 I、 II、 III为二氯甲烷、 三氯甲烷。
5、 根据权利要求 4所述的制备方法， 所述曾水溶剂 I、 曾水溶剂 II、 曾水溶 剂 III为同一种溶剂。
6、 根据权利要求 1所述的制备方法， 所述烷氧基铝为异丙醇铝。
7、 根据权利要求 1所述的制备方法， 所述无机锂为水合氢氧化锂或氢氧化 锂。
8、根据权利要求 1所述的制备方法，所述方法还包括 Mqnqm' 的分离步骤， 将反应液过滤、 洗涤滤物， 干燥即可。
9、 根据权利要求 7所述的制备方法， 所述干燥为真空烘干， 温度 5CTC-250
°C。
10、 根据权利要求 1-9任一所述的制备方法， 所述 q ' 为苯酚及其衍生物、 联苯酚、 与 q不同的 8-羟基喹啉衍生物。
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| CN101768435B (zh) * | 2009-12-31 | 2012-08-22 | 北京化工大学 | 三（8-羟基喹啉-5-磺酸根）合铝配阴离子插层水滑石复合发光材料及其制备方法 |
| CN104151238B (zh) * | 2014-07-30 | 2016-01-20 | 南昌航空大学 | 一种直接制备纯8-羟基喹啉铝的方法 |
| CN105439950B (zh) * | 2015-12-26 | 2020-05-22 | 南昌航空大学 | 一种制备发光材料8-羟基喹啉钙的方法 |
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| JPH07196620A (ja) * | 1994-01-10 | 1995-08-01 | Nippon Steel Chem Co Ltd | ８−オキシキノリン−アルミニウム塩の製造方法 |
| CN101514188A (zh) * | 2009-04-13 | 2009-08-26 | 北京阿格蕾雅科技发展有限公司 | 8-羟基喹啉类金属化合物的制备方法 |
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| JPH07196620A (ja) * | 1994-01-10 | 1995-08-01 | Nippon Steel Chem Co Ltd | ８−オキシキノリン−アルミニウム塩の製造方法 |
| CN101514188A (zh) * | 2009-04-13 | 2009-08-26 | 北京阿格蕾雅科技发展有限公司 | 8-羟基喹啉类金属化合物的制备方法 |
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| CN114621753A (zh) * | 2022-03-03 | 2022-06-14 | 青岛大学 | 一种利用铝络合物制备的青色荧光材料及方法 |
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