CN103396533A - Methoxytriphenylamine-fluorene-containing copolymer, and preparation method and application thereof - Google Patents
Methoxytriphenylamine-fluorene-containing copolymer, and preparation method and application thereof Download PDFInfo
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- CN103396533A CN103396533A CN2013103536957A CN201310353695A CN103396533A CN 103396533 A CN103396533 A CN 103396533A CN 2013103536957 A CN2013103536957 A CN 2013103536957A CN 201310353695 A CN201310353695 A CN 201310353695A CN 103396533 A CN103396533 A CN 103396533A
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Abstract
The invention provides a methoxytriphenylamine-fluorene-containing copolymer, and a preparation method and application thereof, relates to an organic electroluminescent material, a preparation method and application thereof, and aims to solve the problems that the existing polyfluorene electroluminescent polymer is low in light and heat stability, blue light emitted by the material is insufficient in saturation chroma and the solubility in organic solvent is poor. The methoxytriphenylamine-fluorene-containing copolymer provided by the invention is poly[2,7-(9,9-dioctylfluorene)-alternated-N-phenyl-N-(4-methoxyphenyl)aniline]. The preparation method comprises the following steps: 1, synthesizing a monomer from 4-methoxyaniline and 1-bromo-4-iodobenzene; and 2, synthesizing the methoxytriphenylamine-fluorene-containing copolymer from 9,9-dioctylfluorene-2,7-diboronic acid cis(1,3-propanediol)ester and the monomer. The polyfluorene luminescent material has favorable light and heat stability; the solubility in organic solvent can be up to 15-35%; and the material is applied to an electrogenerated blue light device, the emitted light approximates saturated deep blue.
Description
Technical field
The present invention relates to a kind of electroluminescent organic material, preparation method and application, electroluminescent organic material is specifically related to a kind of methoxyl group triphenylamine-fluorene copolymer that contains.
Background technology
In various electroluminescent organic materials, poly-fluorenes has higher light and thermally stable, and the fluorescence quantum efficiency of fluorenes is up to 60%～80% when solid-state, and band-gap energy is greater than 2.90eV, thereby becomes a kind of common blue-light emitting material.Fluorenes can obtain a series of derivative by introduce different groups on 9,2 and 7 carbon, thereby has again certain modifiability on the structure of fluorenes, and therefore poly-fluorenes also becomes a kind of important luminescent material.But the rigid plane biphenyl unit that poly-fluorenes has makes again material easily form excimer and the long wave emission when luminous, the serious stability that affects the radiative saturated colour purity of device and glow color.
At present the modification of poly-fluorenes is mainly concentrated on 9 carbon of high reaction activity of fluorenes.The side group of introducing is generally fatty carbon chain, aromatic nucleus or other groups.The introducing of side group has improved the solvability of poly-fluorenes in organic solvent on the one hand, has improved the film properties that is processed into of product material; Can regulate the aggregated structure of material by steric hindrance on the other hand, keep the crystalline stability of poly-fluorenes in certain temperature range, prevent that exciton from transmitting cancellation between high polymer main chain, improve the luminous efficiency of material.In polyfluorene compound, electronic injection is occupied an leading position, in the process of preparation PLED, because the HOMO and the LUMO that gather fluorenes do not mate with the work function of LEDs anode and negative electrode, the imbalance that causes electronics and hole to inject, therefore luminous efficiency reduces, the ion electric potential of poly-fluorenes is 5.8eV, this means that there is huge energy barrier in hole by the ITOIY injection, occur in order to overcome this situation, can introduce hole injection and transmittability that cavity transmission group (triphenylamine, carbazole, thiophene etc.) improves material in its structure, effectively composite electron, suppress to assemble simultaneously.
Summary of the invention
The objective of the invention is to solve the light and thermally stable that has poly-fluorene analogue electroluminescent polymkeric substance now on the low side, the saturated colourity of material emission blue light be not enough to and in organic solvent the poor problem of solubleness, contain methoxyl group triphenylamine-fluorene copolymer, preparation method and application thereof and provide.
The present invention contains the number-average molecular weight M of methoxyl group triphenylamine-fluorene copolymer
n=23000～56000, its structural formula is as follows:
The present invention contains methoxyl group triphenylamine-fluorene copolymer and is poly-[2,7-(9,9-dioctyl fluorene)-alternately-N-phenyl-N-(4-p-methoxy-phenyl) aniline].
The preparation method that the present invention contains methoxyl group triphenylamine-fluorene copolymer follows these steps to realize:
One, be in molar ratio 1:(2～2.5) 4-anisidine and 1-bromo-4-iodobenzene are joined in organic solvent a, then add palladium catalyst Pd
2(dba)
3, 1, two (diphenylphosphine) ferrocene (DPPF) of 1'-and sodium tert-butoxide (t-BuONa), temperature of reaction is controlled at 90～105 ℃, reaction 5～10h, then remove organic solvent a by revolving to steam, revolve reaction product after steaming and cross the thin layer chromatography post separate after extraction, distillation, obtain N, two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers (M) of N-;
Two, be 1:(1～1.3 according to mol ratio) with 9,9-dioctyl fluorene-2, the 7-hypoboric acid is along (1,3-PD) ester and N, two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers (M) of N-join in organic solvent b, then add palladium catalyst Pd (PPh
3)
4With the sodium carbonate solution with the isopyknic 2～3mol/L of organic solvent b; under argon gas or nitrogen protection, reflux 48～60h, then with the ice methyl alcohol polymkeric substance that settles out; extract 36～60h by Soxhlet again after suction filtration and drying, oven dry obtains containing methoxyl group triphenylamine-fluorene copolymer.
Methoxyl group triphenylamine-the fluorene copolymer that contains of the present invention is applied in the blue light electroluminescence device as electroluminescent material.
It is on the low side that the copolymer analog electroluminescent material of existing fluorenes exists light and thermally stable, and the saturated colourity of material emission blue light is not enough, and the solubleness in organic solvent is poor and be processed into the not good problem of film properties.The triphenylamine that the present invention will contain methoxyl group is incorporated on the side group of poly-fluorenes, can effectively stop on the one hand buildup effect between macromolecular chain and the generation of excimer, keeps good purity of color; N atom on triphenylamine demonstrates electropositivity when forming radical cation (hole) on the other hand, and the oxygen on ehter bond has to electronics, therefore can improve the stability of N radical cation, and then improve electroluminescent stability, the aniline fragment not only has good cavity transmission ability, is also good blue light chromophoric group, can effectively regulate the maximum emission wavelength of material, improve the transmittability of current carrier, be conducive to improve the light and thermally stable of device.
To sum up the present invention's electrochromic property of containing methoxyl group triphenylamine-fluorene copolymer has the following advantages:
1, have good light and thermally stable, under the atmosphere of nitrogen, decomposition temperature, more than 400 ℃, is adapted at using in device;
2, be applied in the trigger voltage 3.5～4.8V of device in the blue light electroluminescence device, brightness 450～1180cd/m
2, chromaticity coordinates is (0.16,0.05), near saturated mazarine, the device luminous efficiency is high.
3, contain the solubleness of methoxyl group triphenylamine-fluorene copolymer in organic solvent and can reach 15～35%, organic solvent is toluene, tetrahydrofuran (THF) or this area organic solvent commonly used.
Description of drawings
Fig. 1 is the N that in embodiment one, step 1 obtains, the infrared spectrogram of two (4-bromophenyl)-4-(4-methoxyl group) aniline of N-;
Fig. 2 is the N that in embodiment one, step 1 obtains, the hydrogen nuclear magnetic resonance spectrogram of two (4-bromophenyl)-4-(4-methoxyl group) aniline of N-;
Fig. 3 is the N that in embodiment one, step 1 obtains, the carbon-13 nmr spectra figure of two (4-bromophenyl)-4-(4-methoxyl group) aniline of N-;
Fig. 4 is the synthetic infrared spectrogram that contains methoxyl group triphenylamine-fluorene copolymer of embodiment one;
Fig. 5 is the synthetic proton nmr spectra that contains methoxyl group triphenylamine-fluorene copolymer of embodiment one;
Fig. 6 is the synthetic carbon-13 nmr spectra that contains methoxyl group triphenylamine-fluorene copolymer of embodiment one;
Fig. 7 is the synthetic ultra-violet absorption spectrum that contains methoxyl group triphenylamine-fluorene copolymer of embodiment one;
Fig. 8 is the synthetic fluorescence excitation spectrum that contains methoxyl group triphenylamine-fluorene copolymer of embodiment one;
Fig. 9 is the synthetic fluorescence emission spectrum that contains methoxyl group triphenylamine-fluorene copolymer of embodiment one;
Figure 10 is the synthetic thermogravimetric curve that contains methoxyl group triphenylamine-fluorene copolymer of embodiment one;
Figure 11 is the structural representation of the blue light electroluminescence device of Application Example preparation, 1-glass matrix, 2-ito glass, 3-hole transmission layer, 4-polymer layer, 5-Ca negative electrode, 6-Al protective layer.
Embodiment
Embodiment one: present embodiment contains the number-average molecular weight M of methoxyl group triphenylamine-fluorene copolymer
n=23000～56000, its structural formula is as follows:
Present embodiment contains methoxyl group triphenylamine-fluorene copolymer and is poly-[2,7-(9,9-dioctyl fluorene)-alternately-N-phenyl-N-(4-p-methoxy-phenyl) aniline].
Embodiment two: the preparation method that present embodiment contains methoxyl group triphenylamine-fluorene copolymer follows these steps to realize:
One, be in molar ratio 1:(2～2.5) 4-anisidine and 1-bromo-4-iodobenzene are joined in organic solvent a, then add palladium catalyst Pd
2(dba)
3, 1, two (diphenylphosphine) ferrocene (DPPF) of 1'-and sodium tert-butoxide (t-BuONa), temperature of reaction is controlled at 90～105 ℃, reaction 5～10h, then remove organic solvent a by revolving to steam, revolve reaction product after steaming and cross the thin layer chromatography post separate after extraction, distillation, obtain N, two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers (M) of N-;
Two, be 1:(1～1.3 according to mol ratio) with 9,9-dioctyl fluorene-2, the 7-hypoboric acid is along (1,3-PD) ester and N, two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers (M) of N-join in organic solvent b, then add palladium catalyst Pd (PPh
3)
4With the sodium carbonate solution with the isopyknic 2～3mol/L of organic solvent b; under argon gas or nitrogen protection, reflux 48～60h, then with the ice methyl alcohol polymkeric substance that settles out; extract 36～60h by Soxhlet again after suction filtration and drying, oven dry obtains containing methoxyl group triphenylamine-fluorene copolymer.
The described reflux temperature of present embodiment step 2 is 95～110 ℃.
At first present embodiment synthesizes N by step 1, two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers of N-, the final acquisition of the further polymerization of monomer that obtains of purifying again gathers [2,7-(9, the 9-dioctyl fluorene)-alternately-N-phenyl-N-(4-p-methoxy-phenyl) aniline], then the aniline polymer that will obtain is dissolved in solvent.
The synthetic N of step 1 wherein, the structural formula of two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers of N-is as follows:
Embodiment three: present embodiment is different from embodiment two is that organic solvent a in step 1 is toluene, dimethylbenzene, THF, dioxane, DMF or DMSO.Other step and parameter are identical with embodiment two.
Embodiment four: what present embodiment was different from embodiment two or three is that every mmol4-anisidine is dissolved in 1～1.5mL organic solvent a.Other step and parameter are identical with embodiment two or three.
Embodiment five: that present embodiment is different from one of embodiment two to four is the described palladium catalyst Pd of step 1
2(dba)
3With the mol ratio of 4-anisidine be 1:(70～110).Other step and parameter are identical with one of embodiment two to four.
Embodiment six: present embodiment is different from one of embodiment two to five is that step 1 is described 1, and two (diphenylphosphine) ferrocene (DPPF) of 1'-are 1:(20～30 with the mol ratio of 4-anisidine).Other step and parameter are identical with one of embodiment two to five.
Embodiment seven: what present embodiment was different from one of embodiment two to six is that the described sodium tert-butoxide of step 1 (t-BuONa) is (2～4) with the mol ratio of 4-anisidine: 1.Other steps and parameter are identical with one of embodiment two to six.
Embodiment eight: present embodiment is different from one of embodiment two to seven is that organic solvent b in step 2 is toluene, DMF or DMSO.Other step and parameter are identical with one of embodiment two to seven.
The every 1mmol N of present embodiment, two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers (M) of N-join in the organic solvent b of 8～30mL.
Embodiment nine: that present embodiment is different from one of embodiment two to eight is the described palladium catalyst Pd of step 2 (PPh
3)
4With 9,9-dioctyl fluorene-2, the 7-hypoboric acid is 1:(25～35 along the mol ratio of (1,3-PD) ester).Other step and parameter are identical with one of embodiment two to eight.
Embodiment ten: the methoxyl group triphenylamine-fluorene copolymer that contains of present embodiment application embodiment one is applied in the blue light electroluminescence device as electroluminescent material.
Embodiment one: the preparation method that the present embodiment contains methoxyl group triphenylamine-fluorene copolymer follows these steps to realize:
One, the 1-bromo-4-iodobenzene of the 4-anisidine of 13.6mmol and 29.92mmol is joined in 18mL toluene, then add 0.136mmol palladium catalyst Pd
2(dba)
3, 0.544mmol 1, the sodium tert-butoxide (t-BuONa) of two (diphenylphosphine) ferrocene (DPPF) of 1'-and 40.79mmol, temperature of reaction is controlled at 105 ℃, reaction 6h, then remove toluene by revolving to steam, revolve reaction product after steaming and cross the thin layer chromatography post separate after extraction, distillation, obtain N, two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers (M) of N-;
Two, with 9 of 0.8954mmol, 9-dioctyl fluorene-2, the 7-hypoboric acid is along the N of (1,3-PD) ester and 0.8954mmol, two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers (M) of N-join in 14mL toluene, then add 2.686 * 10
-2Mmol palladium catalyst Pd (PPh
3)
4With the sodium carbonate solution with the isopyknic 2.5mol/L of toluene, under argon shield, reflux 60h, then, with the ice methyl alcohol polymkeric substance that settles out, extract 48h by Soxhlet again after suction filtration and drying, and oven dry obtains containing methoxyl group triphenylamine-fluorene copolymer.
The N that the present embodiment step 1 obtains, the structural formula of two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers (M) of N-is:
Monomer N, the infrared spectrogram of two (4-bromophenyl)-4-(4-methoxyl group) aniline of N-as shown in Figure 1, at wave number 1881.38cm
-1And 821.82cm
-1The phenyl ring contraposition two of place's expression triphenylamine replaces; At wave number 1285.69cm
-1And 1309.10cm
-1There is the C-N stretching vibration of triphenylamine in place; At wave number 1240.34cm
-1There is the stretching vibration of the Ar-O of triphenylamine; At wave number 1030.96cm
-1There is the C-O stretching vibration of triphenylamine; At wave number 584.21cm
-1, 536.79cm
-1And 507.14cm
-1There is the C-Br stretching vibration of triphenylamine.
Monomer N, the proton nmr spectra of two (4-bromophenyl)-4-(4-methoxyl group) aniline of N-
1As shown in Figure 2, its proton nmr spectra data are H-NMR:
1H-NMR (400MHz, CDCl
3) δ (ppm): 3.796 (3H, H
a), 6.829～6.900 (6H, H
c, H
d), 7.001～7.032 (2H, H
b), 7.276～7.314 (4H, H
e).
Monomer N, the carbon-13 nmr spectra of two (4-bromophenyl)-4-(4-methoxyl group) aniline of N-
13As shown in Figure 3, its carbon-13 nmr spectra data are C-NMR:
13C-NMR (100MHz, CDCl
3), δ
C(ppm): 55.434 (C
1), 114.495 (C
3), 114.989 (C
9), 124.205 (C
4), 127.345 (C
7), 132.109 (C
8), 139.642 (C
5), 146.742 (C
6), 156.680 (C
2).
The final synthetic methoxyl group triphenylamine-fluorene copolymer that contains is poly-[2,7-(9,9-dioctyl fluorene)-alternately-N-phenyl-N-(4-p-methoxy-phenyl) aniline], and its structural formula is as follows:
Contain the solubleness of methoxyl group triphenylamine-fluorene copolymer in organic solvent and can reach 15～35%.
Contain the infrared spectrogram of methoxyl group triphenylamine-fluorene copolymer as shown in Figure 4, scheme thus FT-IR spectrum (KBr pellet, v/cm as can be known
-1): at wave number 2925.95cm
-1There is the C-H stretching vibration that contains methoxyl group triphenylamine-fluorene copolymer in place; At wave number 1506.73cm
-1And 1464.73cm
-1There is the C=C skeletal vibration that contains methoxyl group triphenylamine-fluorene copolymer in place; At wave number 1241.84cm
-1There is the Ar-O stretching vibration that contains methoxyl group triphenylamine-fluorene copolymer in place.
The proton nmr spectra that contains methoxyl group triphenylamine-fluorene copolymer
1H-NMR as shown in Figure 5; Wherein, solvent: deuterochloroform (CDCl
3), in figure:
1H-NMR (400MHz, CDCl
3) δ
H(ppm): 0.736～0.814 (t, 6H, H
p), 1.067～1.257 (m, 24H, H
j, H
k, H
l, H
m, H
n, H
o), 2.014～2.353 (4H, H
i), 3.837 (s, 3H, H
a), 6.984～6.916 (d, 2H, H
c), 7.186～7.206 (d, 6H, H
b, H
b), 7.555～7.584 (m, 8H, H
e, H
g, H
h), 7.731～7.750 (d, 2H, H
f).
The carbon-13 nmr spectra that contains methoxyl group triphenylamine-fluorene copolymer
13C-NMR as shown in Figure 6; In figure:
13C-NMR (100MHz, CDCl
3), δ
C(ppm): 155.407 (C
2), 150.599 (C
10), 146.145 (C
6), 139.423 (C
15), 138.672 (C
12), 138.349 (C
5), 134.086 (C
11), 126.693 (C
8), 126.420 (C
14), 124.436 (C
13), 122.039 (C
4), 119.840 (C
9), 118.875 (C
7), 113.870 (C
3), 54.471 (C
1), 39.462 (C
16), 30.753 (C
17), 29.850 (C
22), 29.030 (C
19), 28.200 (C
20), 28.185 (C
21), 22.814 (C
18), 21.564 (C
23), 13.040 (C
24).
Contain the ultra-violet absorption spectrum of methoxyl group triphenylamine-fluorene copolymer as shown in Figure 7, contain as shown in Figure 7 methoxyl group triphenylamine-fluorene copolymer the strongest in the uv-absorbing at wavelength 391.6nm place.
Contain the fluorescence excitation spectrum of methoxyl group triphenylamine-fluorene copolymer as shown in Figure 8, contain as shown in Figure 8 the fluorescence intensity of methoxyl group triphenylamine-fluorene copolymer in wavelength 464nm place fluorescence emission spectrum the strongest.
Contain the fluorescence emission spectrum of methoxyl group triphenylamine-fluorene copolymer as shown in Figure 9, contain as shown in Figure 9 the fluorescence intensity of methoxyl group triphenylamine-fluorene copolymer in wavelength 442nm place fluorescence emission spectrum the strongest.
Contain the thermogravimetric curve of methoxyl group triphenylamine-fluorene copolymer as shown in figure 10, contain as shown in Figure 10 methoxyl group triphenylamine-fluorene copolymer and have good thermostability, its heat decomposition temperature is at 423 ℃.Proved also that thus the introducing of triphenylamine can increase the thermostability of material.
Application Example: will contain methoxyl group triphenylamine-fluorene copolymer and be applied in the blue light electroluminescence device, the preparation process of blue light electroluminescence device is as follows:
Tin indium oxide (ITO) glass is placed in successively acetone, stain remover, deionized water and aqueous isopropanol and carries out ultrasonic cleaning, use oxygen plasma treatment 5min, place on glass matrix handle well ito glass, then spin coating a layer thickness is poly--(3 of 40nm, the 4-Ethylenedioxy Thiophene): gather (p styrene sulfonic acid) (PEDOT:PSS), then at 80 ℃ of vacuum-drying 3h; The polymers soln that to prepare in nitrogen environment is spin-coated on the PEDOT:PSS(hole transmission layer) on, forming thickness is the polymer layer of 65nm, then in vacuum pressure lower than 2 * 10
-4During Pa, as the electronic injection negative electrode, the aluminium by mask heat deposition 100nm, as protective layer, obtains the blue light electroluminescence device by calcium that on the vacuum evaporation heat deposition, 10nm is thick;
Wherein polymers soln is to be dissolved in toluene containing methoxyl group triphenylamine-fluorene copolymer.The structural representation of blue light electroluminescence device as shown in figure 11.
Wherein the test of the spin coating process of luminescent layer and device performance is all completed in the nitrogen atmosphere in glove box.The blue light electroluminescence device trigger voltage that final test the present embodiment obtains is 4.2V, brightness 750cd/m
2, chromaticity coordinates is (0.16,0.05), near saturated mazarine.
Claims (9)
1. contain methoxyl group triphenylamine-fluorene copolymer, it is characterized in that containing the number-average molecular weight M of methoxyl group triphenylamine-fluorene copolymer
n=23000～56000, its structural formula is as follows:
2. prepare the method that contains methoxyl group triphenylamine-fluorene copolymer as claimed in claim 1, it is characterized in that the preparation method who contains methoxyl group triphenylamine-fluorene copolymer follows these steps to realize:
One, be in molar ratio 1:(2～2.5) 4-anisidine and 1-bromo-4-iodobenzene are joined in organic solvent a, then add palladium catalyst Pd
2(dba)
3, 1, two (diphenylphosphine) ferrocene of 1'-and sodium tert-butoxide, temperature of reaction is controlled at 90～105 ℃, reaction 5～10h, then remove organic solvent a by revolving to steam, revolve reaction product after steaming and cross the thin layer chromatography post separate after extraction, distillation, obtain N, two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers of N-;
Two, be 1:(1～1.3 according to mol ratio) with 9,9-dioctyl fluorene-2, the 7-hypoboric acid is along (1,3-PD) ester and N, two (4-bromophenyl)-4-(4-methoxyl group) aniline monomers of N-join in organic solvent b, then add palladium catalyst Pd (PPh
3)
4With the sodium carbonate solution with the isopyknic 2～3mol/L of organic solvent b; under argon gas or nitrogen protection, reflux 48～60h, then with the ice methyl alcohol polymkeric substance that settles out; extract 36～60h by Soxhlet again after suction filtration and drying, oven dry obtains containing methoxyl group triphenylamine-fluorene copolymer.
3. the preparation method who contains methoxyl group triphenylamine-fluorene copolymer according to claim 2, is characterized in that the organic solvent a in step 1 is toluene, dimethylbenzene, THF, dioxane, DMF or DMSO.
4. the preparation method who contains methoxyl group triphenylamine-fluorene copolymer according to claim 2, is characterized in that the described palladium catalyst Pd of step 1
2(dba)
3With the mol ratio of 4-anisidine be 1:(70～110).
5. the preparation method who contains methoxyl group triphenylamine-fluorene copolymer according to claim 2, is characterized in that step 1 is described 1, and the mol ratio of two (diphenylphosphine) ferrocene of 1'-and 4-anisidine is 1:(20～30).
6. the preparation method who contains methoxyl group triphenylamine-fluorene copolymer according to claim 2, is characterized in that the mol ratio of the described sodium tert-butoxide of step 1 and 4-anisidine is (2～4): 1.
7. the preparation method who contains methoxyl group triphenylamine-fluorene copolymer according to claim 2, is characterized in that the organic solvent b in step 2 is toluene, DMF or DMSO.
8. the preparation method who contains methoxyl group triphenylamine-fluorene copolymer according to claim 2, is characterized in that the described palladium catalyst Pd of step 2 (PPh
3)
4With 9,9-dioctyl fluorene-2, the 7-hypoboric acid is 1:(25～35 along the mol ratio of (1,3-PD) ester).
9. the application that contains methoxyl group triphenylamine-fluorene copolymer as claimed in claim 1, is characterized in that containing methoxyl group triphenylamine-fluorene copolymer and be applied in the blue light electroluminescence device as electroluminescent material.
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| CN111925506B (en) * | 2020-07-10 | 2022-06-28 | 华南理工大学 | Triphenylamine-fluorene-benzimidazole low-band-gap terpolymer, electric storage device and preparation of electric storage device |
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