CN106675554B - Can be used environmentally friendly solvent processing using alkyl phenanthrene unit as bipolarity small molecule emitter material of core and the preparation method and application thereof - Google Patents

Can be used environmentally friendly solvent processing using alkyl phenanthrene unit as bipolarity small molecule emitter material of core and the preparation method and application thereof Download PDF

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CN106675554B
CN106675554B CN201710005317.8A CN201710005317A CN106675554B CN 106675554 B CN106675554 B CN 106675554B CN 201710005317 A CN201710005317 A CN 201710005317A CN 106675554 B CN106675554 B CN 106675554B
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郭婷
赵森
应磊
杨伟
彭俊彪
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses can be used environmentally friendly solvent processing using alkyl phenanthrene unit as bipolarity small molecule emitter material of core and the preparation method and application thereof.What environmentally friendly solvent processing can be used in the present invention is the bipolarity small molecule emitter material of core using alkyl phenanthrene unit as core using alkyl phenanthrene unit, by Suzuki coupling reaction, electrophilic unit and electron unit is connected to alkyl phenanthrene unit two sides and are prepared.Of the invention has good dissolubility, film forming and film morphology stability by the bipolarity small molecule emitter material of core of alkyl phenanthrene unit in environmentally friendly solvent, there is good electrons and holes transmission performance simultaneously, it can be with the injection and transmission of equilbrium carrier, so that more excitons are effectively compound, luminescent layer based on the material can be to avoid the mixing phenomena between hole/electron-transport bed boundary, to improve the luminous efficiency of device, and do not have to annealing when preparing electroluminescent device, so that preparation process is simple.

Description

Can be used environmentally friendly solvent processing using alkyl phenanthrene unit as small point of the bipolarity of core Sub- luminescent material and the preparation method and application thereof
Technical field
The invention belongs to organic photoelectric technical fields, and in particular to it is a kind of can be used environmentally friendly solvent processing with alkyl Luxuriant and rich with fragrance unit is the bipolarity small molecule emitter material and the preparation method and application thereof of core.
Background technique
Organic Light Emitting Diode (OLED) is easy to large area preparation and obtains people because having many advantages, such as efficient, low voltage drive Extensive concern.The research of OLED starts from the 1950s, until doctor Deng Qingyun of Kodak in 1987 adopts Having developed OLED device light emission luminance under 10V direct voltage drive with sandwich device architecture can reach 1000cd/m2, make OLED obtains epoch-making development.OLED device is made of cathode, anode and the organic layer of centre, and organic layer generally comprises electricity Sub- transport layer, luminescent layer and hole transmission layer, first electrons and holes are injected from yin-yang the two poles of the earth respectively, and respectively in functional layer It is migrated, then electrons and holes form exciton in place, and exciton is migrated in a certain range, last exciton It shines.
In order to realize the commercialization of organic/polymer electroluminescent device early, full color can be realized in addition to that should meet It has been shown that, monochromatic purity is high, thermo-chemical stability be good and the requirements such as long service life outside, it is also desirable to device is with high luminous effect Rate.At present influence OLED device efficiency principal element first is that material itself electrons and holes transmission injection imbalance. Therefore, in order to obtain efficient OLED device, it is necessary to rationally adjust the balance of the electrons transmission and injection of material.In recent years Come, bipolar materials have attracted people extensive because having the hole of balance and electronic carrier stream in field of organic electroluminescence Concern, and the material make device structure simplify.This novel technology is not only in theoretical research field by scientist Favored, and the production that gradually moves towards the industrialization, thus develops bipolar materials there is practical value.
Summary of the invention
The purpose of the present invention is to provide it is a kind of can be used environmentally friendly solvent processing using alkyl phenanthrene unit as the double of core Polar micromolecules luminescent material.The material have good electrons and holes transmission performance, can with the injection of equilbrium carrier with Transmission, so that more excitons are effectively compound, to improve the luminous efficiency of device.
The object of the invention is also to provide it is described can be used environmentally friendly solvent processing using alkyl phenanthrene unit as core The preparation method of bipolarity small molecule emitter material.
The object of the invention is also to provide it is described can be used environmentally friendly solvent processing using alkyl phenanthrene unit as core Application of the bipolarity small molecule emitter material in the luminescent layer for preparing light emitting diode.
The specific technical solution of the present invention is as follows.
Can be used environmentally friendly solvent processing using alkyl phenanthrene unit as the bipolarity small molecule emitter material of core, have such as Lower chemical structural formula:
In formula, Ar1For electrophilic unit, Ar2For electron unit；
In formula, R is-(CH2)k-O-(CH2)t- X, wherein k=1-10, t=1-10, X are as any one in flowering structure Kind:
Further, electrophilic unit Ar1For any one in such as flowering structure:
Wherein, n=1-3, R1For the straight chain or branched alkyl of carbon atom number 1-20 or the alcoxyl of carbon atom number 1-20 Base.
Further, electron unit Ar2For any one in such as flowering structure:
It is described can be used environmentally friendly solvent processing using alkyl phenanthrene unit as the bipolarity small molecule emitter material of core Preparation method, include the following steps:
Using alkyl phenanthrene unit as core, by Suzuki coupling reaction, electrophilic unit and electron unit are connected to alkane Base phenanthrene unit two sides obtain described sending out by the bipolarity small molecule of core of alkyl phenanthrene unit for environmentally friendly solvent processing can be used Luminescent material.
Further, the temperature of the Suzuki coupling reaction is 110~160 DEG C, and the time is 18~24 hours.
It is described can be used environmentally friendly solvent processing using alkyl phenanthrene unit as the bipolarity small molecule emitter material of core Applied to the luminescent layer for preparing light emitting diode, by can be used environmentally friendly solvent processing using alkyl phenanthrene unit as the bipolar of core Property small molecule emitter material be dissolved in environmentally friendly solvent, by spin coating, inkjet printing or printing form a film, obtain light emitting diode Luminescent layer；Light emitting diode based on the luminescent layer can be used for preparing flat-panel monitor.
Further, the environmentally friendly solvent includes ethyl alcohol, isopropanol, ethyl acetate or tetrahydrofuran.
Compared with prior art, the invention has the following advantages that
(1) it centered on the alkyl phenanthrene unit of the invention for using polar functionalities for the first time, has synthesized bipolarity small molecule and has shone Material, and synthetic method is simple, is easily purified, and is conducive to industrial applications；
(2) of the invention to have in environmentally friendly solvent by the bipolarity small molecule emitter material of core of alkyl phenanthrene unit Good dissolubility, film forming and film morphology stability, and do not have to annealing when preparing electroluminescent device, so that system Standby simple process；
(3) of the invention that there are good electrons and holes by the bipolarity small molecule emitter material of core of alkyl phenanthrene unit Transmission performance, can be with the injection and transmission of equilbrium carrier, so that more exciton is effectively compound, shining based on the material Layer can be to avoid the mixing phenomena between hole/electron-transport bed boundary, to improve the luminous efficiency of device.
Detailed description of the invention
Fig. 1 is using alkyl phenanthrene unit as the Thermal Chart of the bipolarity small molecule emitter material D1 of core；
Fig. 2 is the ultraviolet-visible using alkyl phenanthrene unit as the bipolarity small molecule emitter material D2 of core under filminess Absorb spectrogram；
Fig. 3 is using alkyl phenanthrene unit as the electroluminescent spectrogram of the bipolarity small molecule emitter material D3 of core；
Fig. 4 is using alkyl phenanthrene unit as luminous efficiency-current density spectrogram of the bipolarity small molecule emitter material D4 of core.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, but embodiments of the present invention be not limited to Lower embodiment.
Embodiment 1
The preparation of compound M2
Under argon atmosphere, by the bromo- 3- oxapentane (M1) (10g, 51mmol) of 1- amino -5- and magnesium chips (6.2g, It 254.99mmol) is added in dry two-mouth bottle, adds 0.5g elemental iodine, be added anhydrous tetrahydro furan (THF), be heated to 110 DEG C are flowed back 16 hours, then the anhydrous THF of 100mL are added dropwise, and are finally reacted two hours at reflux, are changed Close object M2.
Embodiment 2
The preparation of compound M3
Under -20 DEG C of argon atmosphere, 2,7- dibromos phenanthrene -9,10- quinone (8.3g, 22.69mmol) is suspended in the nothing of 600mL In water THF, compound M2 (10g, 45.37mmol) is added dropwise, and temperature is kept to be no more than 0 DEG C；Mixture is then in room temperature Lower stirring 24 hours；Reaction product is cooled with ice, and the glacial acetic acid of 50mL is added, is diluted with ethyl acetate, then with saturation chlorination It is dry with sodium sulphate after sodium solution washes twice, solvent is removed, is obtained product (45g), it is spare.
Embodiment 3
The preparation of compound M4
Under argon atmosphere, compound M3 (20g, 33.31mmol) is suspended in the acetic acid of 420mL and the trifluoro of 210mL In acetic acid solvent, 110 DEG C stirred at reflux 3 hours；It is cooled to room temperature, stirs 24 hours at room temperature, it is remaining with suction filtration Object is washed with water and methanol, is dissolved in toluene, by silica gel filtering solution, is removed solvent, is obtained product (17g), spare.
Embodiment 4
The preparation of compound M5
Under argon atmosphere, 1.3g lithium aluminium hydride reduction is added in dry flask, adds the anhydrous THF of 100mL and carry out Dissolution；The compound M4 (20g, 34.34mmol) being dissolved in the anhydrous THF solution of 150mL is added dropwise, subsequent mixture It is heated to reflux at 110 DEG C 16 hours；It is cooled to room temperature, is placed 24 hours, the water of 2mL is then added, after stirring 15 minutes, The NaOH aqueous solution of 2mL 15wt% is added and is dropwisely added the water of 6mL after stirring 15 minutes, is further continued for stirring 15 minutes, obtains The solid suction filtration arrived, is washed with THF, solvent is removed from filtrate, obtained product (15g), spare.
Embodiment 5
The preparation of compound M6
Under argon atmosphere, compound M5 (30g, 51.34mmol) is suspended in the acetic acid of 610mL, and addition is dissolved in second The iodine of the HBr and 650mg of 3.5mL in acid, heating suspension to 110 DEG C flow back 24 hours；Placement is cooled to room temperature, stirring 16 Hour；Residue is removed with suction filtration, is washed, is obtained product (20g) with water and methanol, it is spare.
Embodiment 6
The preparation of compound M7
Under argon atmosphere, compound M6 (5g, 8.80mmol) and benzimidazole boric acid (2.76g, 8.80mmol) are added Enter into two-mouth bottle, add 100ml toluene and be completely dissolved, adds sodium carbonate (4.66g, 43.98mmol), the tetrabutyl Ammonium bromide (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (175.94mg, 203.31umol), react at 110 DEG C 18h；Reaction mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, adds anhydrous magnesium sulfate It is dry；After solution concentration, with silica gel column chromatography purification (eluant, eluent selects petroleum ether/methylene chloride=6/1, v/v), finally obtain White solid, yield 80%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
Embodiment 7
Using alkyl phenanthrene unit as the preparation of the bipolarity small molecule emitter material D1 of core
Under argon atmosphere, compound M7 (5g, 6.60mmol) and triphenylamine borate (2.45g, 6.60mmol) are added Enter into two-mouth bottle, add 100mL toluene and be completely dissolved, adds sodium carbonate (3.5g, 32.99mmol), the tetrabutyl Ammonium bromide (152.49mg, 967.86umol) and four triphenyl phosphorus palladiums (152.49mg, 131.96umol), react at 110 DEG C 18h；Reaction mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, adds anhydrous magnesium sulfate It is dry；After solution concentration, with silica gel column chromatography purification (eluant, eluent selects petroleum ether/methylene chloride=6/1, v/v), finally obtain White solid, yield 80%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
The thermal multigraph of obtained bipolarity small molecule material D1 is as shown in Figure 1, it can be seen from the figure that the luminous material of small molecule Expect the decomposition temperature T of D1dIt is 212 DEG C, illustrates that small molecule emitter material D1 has good thermal stability.
Embodiment 8
Using alkyl phenanthrene unit as the preparation of the bipolarity small molecule emitter material D2 of core
Under argon atmosphere, M7 (5g, 6.60mmol) and carbazole (1.1g, 6.60mmol) are added to 100mL two-mouth bottle In, toluene is added and is completely dissolved, add palladium acetate (29.63mg, 131.96umol) and tri-tert phosphorus (53.4mg, 263.92umol), 18h is reacted at 110 DEG C；Reaction mixture is poured into water, is extracted with ethyl acetate, organic layer salt After water washs completely, add anhydrous magnesium sulfate dry；After solution concentration, with silica gel column chromatography purification, (eluant, eluent selects petroleum ether/bis- Chloromethanes=4/1, v/v), finally obtain white solid, yield 80%.1H NMR、13CNMR, MS and elemental analysis the result shows that Obtained compound is target product.
Embodiment 9
2,7- diborate -9,9- dioctyl fluorene
(1) by 2,7- dibromo fluorenes (10g, 30.86mmol), KOH (8.66g, 154.32mmol) is added to two mouthfuls of 250mL In bottle, adds 100mL n,N-Dimethylformamide and be completely dissolved, after being stirred at room temperature 1 hour, is added at one time Bromooctane (17.88g, 92.59mmol) is stirred at room temperature 24 hours；It is extracted with ethyl acetate, organic layer saline solution is complete After washing, add anhydrous magnesium sulfate dry；After solution concentration, (eluant, eluent selection petroleum ether) is purified with silica gel column chromatography, is obtained Product is recrystallized with acetone, finally obtains white solid.Yield 75%.1H NMR、13CNMR, MS and elemental analysis result Show that obtained compound is target product, preparation process chemical equation is as follows:
(2) under an argon atmosphere, bromo- 9, the 9- dioctyl fluorene (5g, 10.65mmol) of 2,7- bis- is dissolved in 180mL purification THF in, 1.6mol L is gradually added dropwise at -78 DEG C-1N-BuLi 28mL, react 2 hours, then be added 2- isopropyl oxygen Base -4,4,5,5- tetramethyls -1,3,2- dioxaborinate 25mL, the reaction was continued at -78 DEG C 1 hour, is warming up to room temperature reaction 24 hours；Reaction mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, adds anhydrous sulphur Sour magnesium is dry；After solution concentration, thick pale yellow shape crude product is obtained, (eluant, eluent selects petroleum ether/second with silica gel column chromatography purification Acetoacetic ester=20/1, v/v), product is placed in refrigerator, and white solid, yield 70% are obtained.1H NMR、13CNMR, MS and element The result shows that obtained compound is target product, preparation process chemical equation is as follows for analysis:
Embodiment 10
The preparation of compound M8
Under an argon atmosphere, by the bromo- S of 2-, S- dioxydibenze bithiophene (5g, 16.94mmol), 2- borate -9,9- bis- Octyl fluorenes (21.77g, 33.88mmol), Na2CO3(8.98g, 84.70mmol) and tetrabutylammonium bromide 1g, is added to 250mL In two-mouth bottle, after completely dissolution, Pd (PPh is added3)4(391.51mg, 338.81umol) reacts 16h at 110 DEG C；Use acetic acid Ethyl ester extraction after organic layer is washed completely with saline solution, adds anhydrous magnesium sulfate dry；After solution concentration, mentioned with silica gel column chromatography Pure (eluant, eluent selects petroleum ether/methylene chloride=4/1, v/v), product is placed in refrigerator, and white solid, yield 70% are obtained.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
Embodiment 11
The preparation of compound M9
Under argon atmosphere, compound M5 (5g, 8.83mmol) and M8 (6.45g, 8.83mmol) are added to two-mouth bottle In, it adds 100ml toluene and is completely dissolved, add sodium carbonate (4.68g, 44.14mmol), tetrabutylammonium bromide (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (204.03mg, 176.56umol), react 18h at 110 DEG C；It will Reaction mixture is poured into water, and is extracted with ethyl acetate, and after organic layer is washed completely with saline solution, adds anhydrous magnesium sulfate dry； After solution concentration, with silica gel column chromatography purification (eluant, eluent selects petroleum ether/methylene chloride=6/1, v/v), white is finally obtained Solid, yield 80%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
Embodiment 12
It is prepared by the bipolarity small molecule emitter material D3 of core of alkyl phenanthrene unit
Under argon atmosphere, compound M9 (5g, 4.59mmol) and triphenylamine borate (1.70g, 4.59mmol) are added Enter into two-mouth bottle, add 100ml toluene and be completely dissolved, adds sodium carbonate (2.43g, 22.93mmol), the tetrabutyl Ammonium bromide (312.01mg, 967.86umol) and four triphenyl phosphorus palladiums (105.98mg, 91.71umol), react at 110 DEG C 18h；Reaction mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, adds anhydrous magnesium sulfate It is dry；After solution concentration, with silica gel column chromatography purification (eluant, eluent selects petroleum ether/methylene chloride=7/1, v/v), finally obtain White solid, yield 80%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product.
Embodiment 13
Using alkyl phenanthrene unit as the preparation of the bipolarity small molecule emitter material D4 of core
Under argon atmosphere, compound M9 (5g, 4.59mmol) and carbazole (776.76mg, 4.59mmol) are added to two In mouth bottle, adds 100mL toluene and be completely dissolved, add palladium acetate (20.59mg, 91.71umol) and tri-tert Phosphine (37.11mg, 183.43umol), reacts 18h at 110 DEG C；Reaction mixture is poured into water, is extracted with ethyl acetate, After organic layer is washed completely with saline solution, add anhydrous magnesium sulfate dry；After solution concentration, (eluant, eluent is purified with silica gel column chromatography Select petroleum ether/methylene chloride=5/1, v/v), finally obtain white solid, yield 80%.1H NMR、13CNMR, MS and element Analysis is the result shows that obtained compound is target product.
Embodiment 14
The preparation of electroluminescent device based on small molecule
It is on 20 Ω/ tin indium oxide (ITO) glass, first successively with acetone, washing in the square resistance of well in advance Agent, deionized water and isopropanol ultrasonic cleaning, then plasma treatment 10 minutes；Spin coating, which is mixed, on ITO polystyrolsulfon acid Polyethoxy thiophene (PEDOT:PSS) film, with a thickness of 150nm.Drying 8 is small at 80 DEG C in vacuum drying oven for PEDOT:PSS film When；It will then be revolved by the ethanol solution (1wt%) of bipolarity small molecule emitter material D1, D2, D3, D4 of core of alkyl phenanthrene unit It is coated in the surface of PEDOT:PSS film, with a thickness of 80nm；Finally on the light-emitting layer successively be deposited a thin layer CsF (1.5nm) and The metal Al layer of 120nm thickness.
Based on using alkyl phenanthrene unit as the photoelectricity of the electroluminescent device of bipolarity small molecule emitter material D1~D4 of core The performance test results are as shown in table 1.
The photoelectric properties of electroluminescent device of the table 1 based on bipolarity small molecule emitter material D1~D4
As shown in Table 1, using alkyl phenanthrene unit as bipolarity small molecule emitter material D1, D2, D3, the D4 of core, it is based on device Structure: the maximum lumen efficiency of ITO/PEDOT/EML/CsF/Al is 2.1cd/A, 2.4cd/A, 2.2cd/A, 1.68cd/A.
Ultraviolet-ray visible absorbing light using alkyl phenanthrene unit as the bipolarity small molecule emitter material D2 of core under filminess Spectrogram is as shown in Fig. 2, it can be seen from the figure that the absorption peak of small molecule emitter material D2 is located at 327nm and 393nm.
It is the electroluminescent spectrogram of the bipolarity small molecule emitter material D3 of core as shown in figure 3, from figure using alkyl phenanthrene unit In as can be seen that the electroluminescent spectrum of bipolarity small molecule emitter material is located at 421nm.
Device architecture: ITO/PEDOT/EML/ is based on by the bipolarity small molecule emitter material D4 of core of alkyl phenanthrene unit Luminous efficiency-current density plot of CsF/Al is as shown in figure 4, it will be seen that bipolarity small molecule material P4 from Fig. 4 Maximum lumen efficiency be 1.4cd/A.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention should all For equivalent substitute mode, it is included within the scope of the present invention.

Claims (6)

1. can be used environmentally friendly solvent processing using alkyl phenanthrene unit as the bipolarity small molecule emitter material of core, feature exists In with following chemical structural formula:
In formula, Ar1For electrophilic unit, Ar2For electron unit；
In formula, R is-(CH2)k-O-(CH2)t- X, wherein k=1-10, t=1-10, X are such as any one in flowering structure:
2. it is according to claim 1 can be used environmentally friendly solvent processing using alkyl phenanthrene unit as small point of the bipolarity of core Sub- luminescent material, which is characterized in that
Electrophilic unit Ar1For any one in such as flowering structure:
Wherein, n=1-3, R1For the straight chain or branched alkyl of carbon atom number 1-20 or the alkoxy of carbon atom number 1-20；
Electron unit Ar2For any one in such as flowering structure:
3. it is of any of claims 1 or 2 can be used environmentally friendly solvent processing using alkyl phenanthrene unit as small point of the bipolarity of core The preparation method of sub- luminescent material, which comprises the steps of:
Using alkyl phenanthrene unit as core, by Suzuki coupling reaction, electrophilic unit and electron unit are connected to alkyl phenanthrene Unit two sides obtain described shining material using alkyl phenanthrene unit as the bipolarity small molecule of core for environmentally friendly solvent processing can be used Material.
4. it is according to claim 3 can be used environmentally friendly solvent processing using alkyl phenanthrene unit as small point of the bipolarity of core The preparation method of sub- luminescent material, which is characterized in that the temperature of the Suzuki coupling reaction is 110~160 DEG C, the time 18 ~24 hours.
5. it is of any of claims 1 or 2 can be used environmentally friendly solvent processing using alkyl phenanthrene unit as small point of the bipolarity of core Sub- luminescent material is applied to prepare the luminescent layer of light emitting diode, which is characterized in that environmentally friendly solvent processing will can be used Be dissolved in environmentally friendly solvent by the bipolarity small molecule emitter material of core of alkyl phenanthrene unit, by spin coating, inkjet printing or Printing film forming, obtains the luminescent layer of light emitting diode.
6. application according to claim 5, which is characterized in that the environmentally friendly solvent includes ethyl alcohol, isopropanol, acetic acid Ethyl ester or tetrahydrofuran.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
EP1211301A1 (en) * 1996-10-08 2002-06-05 Idemitsu Kosan Co., Ltd. Organic electroluminescent device
CN101068905A (en) * 2004-10-11 2007-11-07 默克专利有限公司 Phenanthrene derivative
CN103224486A (en) * 2013-04-03 2013-07-31 华南理工大学 S,S-dioxo-dibenzothiophene monomer containing polar substituent groups, water/alcohol soluble polymers thereof, and application thereof
CN106187908A (en) * 2016-06-27 2016-12-07 华南理工大学 One class can use small molecule emitter material containing naphtho-indenes fluorenes unit that environmentally friendly solvent processes and preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1211301A1 (en) * 1996-10-08 2002-06-05 Idemitsu Kosan Co., Ltd. Organic electroluminescent device
CN101068905A (en) * 2004-10-11 2007-11-07 默克专利有限公司 Phenanthrene derivative
CN103224486A (en) * 2013-04-03 2013-07-31 华南理工大学 S,S-dioxo-dibenzothiophene monomer containing polar substituent groups, water/alcohol soluble polymers thereof, and application thereof
CN106187908A (en) * 2016-06-27 2016-12-07 华南理工大学 One class can use small molecule emitter material containing naphtho-indenes fluorenes unit that environmentally friendly solvent processes and preparation method and application

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