CN102391130A - Preparation method of 9, 9- diamino-(4-aminophenyl) fluorene - Google Patents
Preparation method of 9, 9- diamino-(4-aminophenyl) fluorene Download PDFInfo
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- CN102391130A CN102391130A CN2011102870867A CN201110287086A CN102391130A CN 102391130 A CN102391130 A CN 102391130A CN 2011102870867 A CN2011102870867 A CN 2011102870867A CN 201110287086 A CN201110287086 A CN 201110287086A CN 102391130 A CN102391130 A CN 102391130A
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Abstract
The invention discloses a preparation method of 9, 9-diamino (4-aminophenyl) fluorene. Both 9, 9- dichloro fluorine and aniline are added into a three-opening bottle provided with a temperature meter, a stirrer, an oil-water separator and a reflux condensing tube, the weight ratio of the 9, 9- dichloro fluorine and aniline is 1 to 4-6, N2 is introduced for protection, heating is carried out, then thermal insulation reaction is performed for 7 to 10 hours, after the reaction is finished, underpressure distillation is performed, after distillationm, NaOH solution is dripped, and the pH value is adjusted to be within the range of 10 to 13; and underpressure distillation, recrystallization, carbon decolourizing, vacuum drying and the like are performed, the product of white solid 9, 9-diamino (4-aminophenyl) fluorene with high purity is obtained, and the MP (melting point) ranges from 234 DEG C to 235 DEG C. The product has higher purity, and can be used as raw materials for synthesizing polyfluorene, derivative electronic luminescent material thereof, and high-quality polyimide, and also can be used as raw materials of optical fiber, gas separation membranes, fuel cell ptoton transportion membranes, liquid crystal displays, electroluminescence devices, heat-resisting resin and engineering plastics.
Description
Technical field
The present invention relates to a kind of 9; The preparation method of 9-two (4-aminophenyl) fluorenes; Relate in particular to a kind of raw-material 9 as optical lens, fiber optics, gas separation membrane, fuel cell proton transmission film, liquid-crystal display, electroluminescence device, heat stable resin and engineering plastics etc., the preparation method of 9-two (4-aminophenyl) fluorenes.
Background technology
9,9-two (4-aminophenyl) fluorenes is to be used for the important monomer raw material of synthesis of polyimides.U.S. Pat 4794159, US4845185 are with 9; 9-two (4-aminophenyl) fluorenes respectively with four benzoyl oxides, two phthalic anhydride ketones, biphenyl acid anhydride and other anhydride reaction; Synthesized and had the polyimide of solubility property preferably; It is dissolved in organic solvents such as N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, m-cresols, ortho chloro phenol and methylene dichloride; Can process have excellent mechanical property, the Kapton of electrical property, chemicalstability and very high radiation resistance, high temperature resistant and resistance to low temperature (269 ℃ to+500 ℃), can be used as optical lens, fiber optics, gas separation membrane, fuel cell proton transmission film, liquid-crystal display, electroluminescence device, heat stable resin and engineering plastics.Donghui Yu etc. are with 9; 9-two (4-aminophenyl) fluorenes is a raw material; Through diazotization, bromo is under the effect of n-Butyl Lithium; With diphenyl phosphine chloride reaction, processed the intermediary material (CHEMISTRY A EUROPEANJOURNAL DOI:10.1002/chem.201003434) of phosphorescence Organic Light Emitting Diode that is expected to be used for high energy-conservation large-area flat-plate indicating meter or solid-state illumination of better performances.
Research in recent years proves; The polymkeric substance of fluorenes and verivate thereof is one type and has light, electroactive important organic polymer; Through adjustment, be expected to prepare Heat stability is good, red bluish-green three primary colors luminescent material that luminous efficiency is high to the structure of the substituting group of fluorenes or multipolymer.9,9-two (4-aminophenyl) fluorenes also is the important intermediate raw material that is used for synthesizing these luminescent materials, yet the report of its preparation method is actually rare.Someone reports and uses the 9-Fluorenone to be raw material and aniline reaction, has synthesized 9,9-two (4-aminophenyl) fluorenes.In building-up process, in reaction system, add benzene or toluene, utilize the azeotropic principle to remove the water of generation.After reaction finishes, with sodium hydroxide or potassium hydroxide aqueous solution neutralization reaction liquid, distillation, the dry finished product that gets.Use Fluorenone and the Acetanilide that also have are raw material, methanesulfonic acid catalyzed, and under 150 ℃ the heating condition, nitrogen protection, back flow reaction 2 days also need stir 24 hours in the treating process, had synthesized 9 through the process of a complicacy, 9-two (4-aminophenyl) fluorenes.This shows; Use Fluorenone to synthesize 9 as raw material, the time of 9-two (4-aminophenyl) fluorenes is longer, and the product that obtains also has darker color; Handling the effect that does not all reach with recrystallization or activated carbon decolorizing, is not the desirable feedstock of synthetic polymer electronic luminescent material.
Summary of the invention
The object of the invention aims to provide a kind of ideal easily 9, and the preparation method of 9-two (4-aminophenyl) fluorenes gathers fluorenes and verivate electronic luminescent material and high-quality polyimide thereof proper raw material is provided for synthetic.
The present invention realizes like this; A kind of 9, the preparation method of 9-two (4-aminophenyl) fluorenes is characterized in: in the 500ml there-necked flask of TM, whisking appliance, water-and-oil separator, reflux condensing tube is housed, add raw material 9; 9-dichloro fluorenes and aniline; 9, the weight ratio of 9-dichloro fluorenes and aniline is 1: 4～6, feeds N
2Protection, heating, the control heat-up rate is warming up to 60 ℃ (when beginning to heat up in 30min; Have comparatively violent exothermic phenomenon in the system), be heated to 130 ℃ then, the insulation reaction time is 7～10 hours; Reaction is carried out underpressure distillation after finishing, and distills out unnecessary aniline; Distillation finishes, and begins to drip NaOH solution, regulates pH=10～13; Dropwise, add toluene, reflux; Black in color soup compound in the system, cooling crystallization, suction filtration; Obtain gray solid, gray solid is with cold toluene and normal hexane washing, vacuum-drying; Obtain 9, the thick product of 9-two (4-aminophenyl) fluorenes, thick product carries out recrystallization with ETHYLE ACETATE and toluene mixed solvent; The weight ratio of toluene and ETHYLE ACETATE is 5～8: 7～10 in the mixed solvent, activated carbon decolorizing, and reflux, filtered while hot, vacuum-drying obtains white solid 9,9-two (4-aminophenyl) fluorenes product, MP234 ℃～235 ℃.
Among the present invention, employed raw material 9, the weight ratio of 9-dichloro fluorenes and aniline is preferably 1: 5.
Among the present invention, 9,9-dichloro fluorenes and aniline are under nitrogen protection, and heat-up rate is controlled in heating, in 30min, is warming up to 60 ℃, is heated to 130 ℃ then, and the insulation reaction time is preferably 10 hours.
Among the present invention, reaction is carried out underpressure distillation after finishing, and distills out unnecessary aniline, and distillation finishes, and begins to drip NaOH solution, regulates pH=13.
Among the present invention, with cold toluene and normal hexane washing gray solid, the weight ratio of toluene and normal hexane is 1～10: 10～1.
Among the present invention, to 9, toluene and ETHYLE ACETATE weight ratio that the thick product of 9-two (4-aminophenyl) fluorenes carries out in the mixed solvent of recrystallization are preferably 7: 9.
Preparation in accordance with the present invention, the product 9 that obtains, 9-two (4-aminophenyl) fluorenes is a white solid, purity is higher, can be used as the synthetic raw material that gathers fluorenes and verivate electronic luminescent material and high-quality polyimide.Through the comparison of experimental result, the consumption of the raw material that increases the principal reaction thing or the time of proper extension reaction are described, can obtain 9 of better yield, 9-two (4-aminophenyl) fluorenes product, and 9,9-two (4-aminophenyl) fluorenes product gas purity also has raising.
Embodiment
Below with embodiment the present invention is further described, but embodiment is not a limitation of the present invention.
Embodiment 1
In the 500ml there-necked flask of TM, whisking appliance, water-and-oil separator, reflux condensing tube is housed, add 60.02g (0.26mol)) 9,9-dichloro fluorenes and 300.01g (3.22mol) aniline.Feed N
2Protection, heating, the control heat-up rate is warming up to 60 ℃ (when beginning to heat up, having comparatively violent exothermic phenomenon in the system) in 30min.After being warming up to 60 ℃, direct heating to 130 ℃, insulation reaction 7h.Reaction is carried out underpressure distillation after finishing, and distills out unnecessary aniline.Distillation finishes, and begins to drip 450g5%NaOH solution, regulates pH=13.Dropwise, add 100mL toluene, reflux 30min.Black in color pulpous state phenomenon in the system.Cooling crystallization, suction filtration obtains gray solid, and with cold toluene and normal hexane washing, vacuum-drying obtains gray solid.Carry out recrystallization with 900mL ETHYLE ACETATE and 700mL toluene mixed solvent, and use activated carbon decolorizing, be heated to backflow; Filtered while hot, vacuum-drying obtains 9 of 37.5g white solid; 9-two (4-aminophenyl) fluorenes; Yield 65%, detecting its purity with gc (GC) is 99.6%, MP234 ℃～235 ℃.
1HNMR(D-DMSO)：δ4.86(S，-NH
2，2H)，δ6.4(d，Ar-H，4H)，δ6.7(d，Ar-H，4H)，δ7.2～7.3(m，fluorene，6H)，δ7.8(m，fluorine，2H)。
Embodiment 2
Add 60.02g (0.26mol) in the reaction unit identical with embodiment 1) 9,9-dichloro fluorenes and 310.01g (3.32mol) aniline.Feed N
2Protection, heating, the control heat-up rate is warming up to 60 ℃ (when beginning to heat up, having comparatively violent exothermic phenomenon in the system) in 30min.After being warming up to 60 ℃, direct heating to 130 ℃, insulation reaction 7h.Reaction is carried out underpressure distillation after finishing, and distills out unnecessary aniline.Distillation finishes, and beginning Dropwise 5 00g5%NaOH solution is regulated PH=13.Dropwise, add 100mL toluene, reflux 30min.Black in color pulpous state phenomenon in the system.Cooling crystallization, suction filtration obtains gray solid, and with cold toluene and normal hexane washing, vacuum-drying obtains gray solid.Carry out recrystallization with 900mL ETHYLE ACETATE and 700mL toluene mixed solvent, and use activated carbon decolorizing, be heated to backflow; Filtered while hot, vacuum-drying obtains 9 of 40.5g white solid; 9-two (4-aminophenyl) fluorenes; Yield 67.5%, detecting its purity with gc (GC) is 99.8%, MP233.7 ℃～234.5 ℃.
1HNMR(D-DMSO)：δ4.86(S，-NH
2，2H)，δ6.4(d，Ar-H，4H)，δ6.7(d，Ar-H，4H)，δ7.1～7.3(m，fluorene，6H)，δ7.7～7.8(m，fluorine，2H)。
Embodiment 3
Add 58.8g (0.25mol) in the reaction unit identical with embodiment 1) 9,9-dichloro fluorenes and 300.01g (3.22mol) aniline.Feed N
2Protection, heating, the control heat-up rate is warming up to 60 ℃ (when beginning to heat up, having comparatively violent exothermic phenomenon in the system) in 30min.After being warming up to 60 ℃, direct heating to 130 ℃, insulation reaction 7h.Reaction is carried out underpressure distillation after finishing, and distills out unnecessary aniline.Distillation finishes, and begins to drip 450g5%NaOH solution, regulates PH=13.Dropwise, add 100mL toluene, reflux 30min.Black in color pulpous state phenomenon in the system.Cooling crystallization, suction filtration obtains gray solid, and with cold toluene and normal hexane washing, vacuum-drying obtains gray solid.Carry out recrystallization with 900mL ETHYLE ACETATE and 700mL toluene mixed solvent, and use activated carbon decolorizing, be heated to backflow; Filtered while hot, vacuum-drying obtains 9 of 41.2g white solid; 9-two (4-aminophenyl) fluorenes; Yield 70%, detecting its purity with gc (GC) is 99.7%, MP234 ℃～235 ℃.
1HNMR(D-DMSO)：δ4.84(S，-NH
2，2H)，δ6.5(d，Ar-H，4H)，δ6.8(d，Ar-H，4H)，δ7.1～7.3(m，fluorene，6H)，δ7.7(m，fluorine，2H)。
Embodiment 4
Add 60.02g (0.26mol) in the reaction unit identical with embodiment 1) 9,9-dichloro fluorenes and 300.01g (3.22mol) aniline.Feed N
2Protection, heating, the control heat-up rate is warming up to 60 ℃ (when beginning to heat up, having comparatively violent exothermic phenomenon in the system) in 30min.After being warming up to 60 ℃, direct heating to 130 ℃, insulation reaction 10h (comparing embodiment 1 prolongs reaction 3h).Reaction is carried out underpressure distillation after finishing, and distills out unnecessary aniline.Distillation finishes, and begins to drip 450g5% NaOH solution, regulates pH=13.Dropwise, add 100mL toluene, reflux 45min (comparing embodiment 1 prolongs 15min).Black in color pulpous state phenomenon in the system.Cooling crystallization, suction filtration obtains gray solid, and with cold toluene and normal hexane washing, vacuum-drying obtains gray solid.Carry out recrystallization with 900mL ETHYLE ACETATE and 700mL toluene mixed solvent, and use activated carbon decolorizing, be heated to backflow; Filtered while hot, vacuum-drying obtains 9 of 45.5g white solid; 9-two (4-aminophenyl) fluorenes; Yield 75%, detecting its purity with gc (GC) is 99.8%, MP234 ℃～234.8 ℃.
1HNMR(D-DMSO)：δ4.76(S，-NH
2，2H)，δ6.4(d，Ar-H，4H)，δ6.6(d，Ar-H，4H)，δ7.2～7.4(m，fluorene，6H)，δ7.6(m，fluorine，2H)。
Preparation in accordance with the present invention, the product 9 that obtains, 9-two (4-aminophenyl) fluorenes is a white solid, purity is higher, can be used as the synthetic raw material that gathers fluorenes and verivate electronic luminescent material and high-quality polyimide.Through the comparison of 4 embodiment, the consumption of the raw material that increases the principal reaction thing or the time of proper extension reaction are described, can obtain the product of better yield, and product gas purity also there is raising.
Claims (6)
1. one kind 9, the preparation method of 9-two (4-aminophenyl) fluorenes is characterized in that: in the 500ml there-necked flask of TM, whisking appliance, water-and-oil separator, reflux condensing tube is housed, add raw material 9; 9-dichloro fluorenes and aniline; 9, the weight ratio of 9-dichloro fluorenes and aniline is 1: 4～6, feeds N
2Protection, heating, the control heat-up rate is warming up to 60 ℃ in 30min, be heated to 130 ℃ then, insulation reaction 7～10 hours, reaction is carried out underpressure distillation after finishing, and distills out unnecessary aniline; Distillation finishes, and begins to drip NaOH solution, regulates pH=10～13; Dropwise, add toluene, reflux; Black in color soup compound in the system, cooling crystallization, suction filtration; Obtain gray solid, gray solid is with cold toluene and normal hexane washing, vacuum-drying; Obtain 9, the thick product of 9-two (4-aminophenyl) fluorenes, thick product carries out recrystallization with ETHYLE ACETATE and toluene mixed solvent; The weight ratio of toluene and ETHYLE ACETATE is 5～8: 7～10 in the mixed solvent, activated carbon decolorizing, and reflux, filtered while hot, vacuum-drying obtains white solid 9,9-two (4-aminophenyl) fluorenes product, MP234 ℃～235 ℃.
2. preparation method according to claim 1 is characterized in that: employed raw material 9, the weight ratio of 9-dichloro fluorenes and aniline is preferably 1: 5.
3. preparation method according to claim 1 is characterized in that: 9, and 9-dichloro fluorenes and aniline are under nitrogen protection, and heat-up rate is controlled in heating, in 30min, is warming up to 60 ℃, is heated to 130 ℃ then, insulation reaction 10 hours.
4. preparation method according to claim 1 is characterized in that: reaction is carried out underpressure distillation after finishing, and distills out unnecessary aniline, and distillation finishes, and begins to drip NaOH solution, regulates pH=13.
5. preparation method according to claim 1 is characterized in that: with cold toluene and normal hexane washing gray solid, the weight ratio of toluene and normal hexane is 1～10: 10～1.
6. preparation method according to claim 1 is characterized in that: to 9, toluene and the weight ratio of ETHYLE ACETATE that the thick product of 9-two (4-aminophenyl) fluorenes carries out in the mixed solvent of recrystallization are preferably 7: 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586741A (en) * | 2018-04-13 | 2018-09-28 | 吉林大学 | Fluorescence polyamic acid polymer, preparation method and its application in terms of fluorescence thorniness swashs response |
| CN108676159A (en) * | 2018-06-12 | 2018-10-19 | 江西师范大学 | A kind of Nomex of the structure containing xanthene and preparation method thereof |
| CN109509678A (en) * | 2018-11-22 | 2019-03-22 | 漳州雅宝电子有限公司 | A kind of high temperature resistant thermo-sensitive material that fusing point is 236 ± 2 DEG C |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1728228A1 (en) * | 1989-12-26 | 1992-04-23 | Рубежанский филиал Днепропетровского химико-технологического института им.Ф.Э.Дзержинского | Method of 9,9-bis-(4-aminophenyl)-fluorene synthesis |
| US5387725A (en) * | 1991-11-07 | 1995-02-07 | The Dow Chemical Company | Chlorination process, alkylation of products of said process and some products thereof |
-
2011
- 2011-09-23 CN CN2011102870867A patent/CN102391130A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1728228A1 (en) * | 1989-12-26 | 1992-04-23 | Рубежанский филиал Днепропетровского химико-технологического института им.Ф.Э.Дзержинского | Method of 9,9-bis-(4-aminophenyl)-fluorene synthesis |
| US5387725A (en) * | 1991-11-07 | 1995-02-07 | The Dow Chemical Company | Chlorination process, alkylation of products of said process and some products thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586741A (en) * | 2018-04-13 | 2018-09-28 | 吉林大学 | Fluorescence polyamic acid polymer, preparation method and its application in terms of fluorescence thorniness swashs response |
| CN108586741B (en) * | 2018-04-13 | 2020-09-22 | 吉林大学 | Fluorescent polyamic acid polymer, preparation method and application thereof in fluorescent multi-stimulus response |
| CN108676159A (en) * | 2018-06-12 | 2018-10-19 | 江西师范大学 | A kind of Nomex of the structure containing xanthene and preparation method thereof |
| CN109509678A (en) * | 2018-11-22 | 2019-03-22 | 漳州雅宝电子有限公司 | A kind of high temperature resistant thermo-sensitive material that fusing point is 236 ± 2 DEG C |
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Application publication date: 20120328 |