CN103304782A - Conjugated polymer with N-acyl-substituted isoindigo radical and preparation method of conjugated polymer - Google Patents
Conjugated polymer with N-acyl-substituted isoindigo radical and preparation method of conjugated polymer Download PDFInfo
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 42
- MLCPSWPIYHDOKG-BUHFOSPRSA-N trans-isoindigo Natural products O=C\1NC2=CC=CC=C2C/1=C1/C2=CC=CC=C2NC1=O MLCPSWPIYHDOKG-BUHFOSPRSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001335 aliphatic alkanes Chemical group 0.000 claims abstract description 5
- -1 alkyl acid chloride Chemical compound 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 238000000944 Soxhlet extraction Methods 0.000 claims 2
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 claims 2
- 238000010828 elution Methods 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 239000003208 petroleum Substances 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000003381 solubilizing effect Effects 0.000 abstract 1
- GSNCQSIZHAMPRE-UHFFFAOYSA-N 1-(2-oxo-3H-indol-1-yl)-3H-indol-2-one Chemical class O=C1CC2=CC=CC=C2N1N1C2=CC=CC=C2CC1=O GSNCQSIZHAMPRE-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000005669 field effect Effects 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000006181 N-acylation Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000005257 alkyl acyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 238000003808 methanol extraction Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000008279 sol Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 0 *C(*(C(C1C(C(*2C(*)=O)=O)c(cc3)c2cc3N)=O)c2c1ccc(*)c2)=O Chemical compound *C(*(C(C1C(C(*2C(*)=O)=O)c(cc3)c2cc3N)=O)c2c1ccc(*)c2)=O 0.000 description 1
- 241000124815 Barbus barbus Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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Abstract
本发明公开了一种N-酰基取代异靛蓝基的共轭聚合物及其制备方法。所述共轭聚合物的结构式如式(I)所示：其中，R为含碳原子数6～20的烷烃链，100＞n＞1，Ar为式(II)、(III)或(IV)所示的结构式：
The invention discloses an N-acyl-substituted isoindigo conjugated polymer and a preparation method thereof. The structural formula of described conjugated polymer is as shown in formula (I): Wherein, R is an alkane chain containing 6 to 20 carbon atoms, 100>n>1, Ar is the structural formula shown in formula (II), (III) or (IV):
Description
Technical field
The present invention relates to a kind of organic semiconductor material of low lumo energy of solution-processible, especially conjugated polymers of a class N-acyl substituted bioxindol base and preparation method thereof.
Background technology
Find that at Barbe in 1970 Phthalocyanine has the field-effect characteristic, but organic field effect tube truly (organic field-effect transistor, OFETs) is to be made with the electrochemical polymerization thiophene by Koezuka in 1987.OFETs is one of important organic semiconductor device.Then go through the development of two more than ten years, OFETs research has become the key areas of the multidisciplinary forward position crossing research such as chemistry, physics, materialogy, electronics and information science.(referring to document: Zaumseil, J.; Sirringhaus, H.Electron and ambipolar transport in organic field-effect transistors.Chem.Rev., 107,1296 (2007); Guo, Y.; Yu, G.; Liu, Y.Functional Organic Field-Effect Transistors.Adv.Mater., 22,4427 (2010))
The OFETs that conjugated polymers forms has some unique advantages and is subject to researchist's very big attention and since in recent years the novel organic semi-conductor material continually develop research, its performance has realized important breakthrough.(referring to document: Huang, H.; Chen, Z.; Ortiz, R.P.; Newman, C.; Usta, H.; Lou, S.; Youn, J.; Noh, Y.-Y.; Baeg, K.-J.; Chen, L.X.; Facchetti, A.; Marks, T.Combining Electron-Neutral Building Blocks with Intramolecular " Conformational Locks " Affords Stable, High-Mobility P-and N-Channel Polymer Semiconductors.J.Am.Chem.Soc.134,10966 (2012)) energy level of conjugated polymers has important impact for stability and the electric transmission of OFETs.The conjugated polymers of low lumo energy is conducive to improve the air stability of device, so that material tends to electronic migration more, but not hole migration.The conjugated polymers of a class N-acyl substituted bioxindol that the present invention relates to; the carbonyl that will have strong electron-withdrawing power is incorporated in the conjugated main chain of polymkeric substance; reduced significantly the lumo energy of polymkeric substance; has large pi-conjugated system in such conjugated polymer backbone simultaneously, so that such material is having potential application prospect aspect bipolar or the N-type organic field effect tube material.
Summary of the invention
The purpose of this invention is to provide conjugated polymers that contains N-acyl substituted bioxindol base of a class solution-processible and preparation method thereof.N-acyl substituted bioxindol in this conjugated polymers is to react generation by alkyl acyl chloride and bioxindol under the effect of pyridine.Have large pi-conjugated system in the conjugated polymer backbone of the present invention, its side chain contains strong electrophilic carbonyl and flexible short molten alkyl chain.The conjugated polymers that the present invention relates to belongs to the low energy gap polymkeric substance of low lumo energy of the solution-processible of main chain conjugation.
The objective of the invention is to realize by following technical scheme:
First aspect the present invention relates to a kind of conjugated polymers of N-acyl substituted bioxindol base, and the structural formula of described conjugated polymers is suc as formula shown in (I):
Wherein, R is the alkane chain of carbon atom quantity 6～20,100＞n＞1, Ar be formula (II), (III) or (IV) shown in structural formula:
Second aspect the present invention relates to a kind of preparation method of conjugated polymers of bioxindol base of above-mentioned N-acyl substituted, comprises the steps:
A, will be not by the bioxindol intermediate A of acyl substituted
Reacting by heating is introduced flexible acyl side-chain in pyridine, obtains the bioxindol monomer M of acyl substituted
Wherein, R is the alkane chain of carbon atom quantity 6～20;
B, the copolymerization in anhydrous organic solvent with described bioxindol monomer M and tin methide conjugative monomer, Soxhlet is extracted, and namely gets the conjugated polymers of the bioxindol base of described N-acyl substituted.
Preferably, among the step a, with described bioxindol intermediate A and alkyl acyl chloride take pyridine as medium, back flow reaction 4～18 hours; Take volume ratio as 1: 1～1: 2 methylene dichloride and sherwood oil as eluent, wash-out obtains described bioxindol monomer M.
Preferably, among the step b, described tin methide conjugative monomer is BDT-T
BDT-O
Or 2T
Preferably, among the step b, the reaction times of described copolymerization is 4～24 hours, and temperature of reaction is 70～110 ℃.
Preferably, among the step b, described anhydrous organic solvent is dry toluene or anhydrous chlorobenzene.
Preferably, among the step b, it is methyl alcohol, normal hexane and chloroform that described Soxhlet is extracted the solvent that adopts successively.
The third aspect, the purposes of the conjugated polymers that the present invention relates to a kind of aforesaid N-acyl substituted bioxindol base in preparation OFETs device, described conjugated polymers is the low energy gap polymkeric substance of low lumo energy of the solution-processible of main chain conjugation.
Preferably, the solution in the described solution-processible is chloroform, toluene or dichlorobenzene.This conjugated polymers has good solubleness in usual vehicle (such as chloroform, toluene or dichlorobenzene).
Compared with prior art, the present invention has following beneficial effect:
1, the synthetic method of the present invention's disclosure is simply effective; Synthetic cost is low, and the target compound productive rate that obtains is high; Have large pi-conjugated system in the conjugated polymer backbone of the present invention, its side chain contains strong electrophilic carbonyl and flexible short molten alkyl chain.
2, the material solution-processible is processed, and the acylations side chain of introducing reduces the lumo energy of material effectively; Such material can be applied to the OFETs device.
Description of drawings
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is embodiment 1 compound M1, M2 and M3 synthetic route chart.
Fig. 2 is embodiment 1 polymer P 1, P2 and P3 synthetic route chart.
Fig. 3 is polymkeric substance ultra-violet absorption spectrum of (b) when (a) and film forming in chloroform.
Fig. 4 is the polymkeric substance cyclic voltammetry curve.
Fig. 5 is polymkeric substance thermogravimetric analysis curve.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.Following examples will help those skilled in the art further to understand the present invention, but not limit in any form the present invention.Should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
The conjugated polymers of the bioxindol base of embodiment 1, preparation N-acylations
The present embodiment provides the conjugated polymers of the N-acylations bioxindol base of 3 kinds of solubilities, its structural formula (wherein, 100＞n＞1) as shown in table 1, and its synthetic route is referring to Fig. 2.
Table 1
The described preparation method who contains the polymkeric substance (P1, P2 and P3) of bioxindol base comprises the steps:
(a) midbody compound A's is synthetic
The structural formula of midbody compound A is
(b) compound M1, M2's is synthetic
The structural formula of compound M1, M2 is
M1 preparation method: as shown in Figure 1; under nitrogen protection; with intermediate A (1.50g; 3.57mmol), pyridine (40mL) joins in the two-mouth bottle; at room temperature; drip 2-ethyl hexanoyl chloro (5.81g, 35.70mmol), temperature rising reflux reaction certain hour (can be the arbitrary value in 6～18 hours).With the reaction solution cool to room temperature, add dilute hydrochloric acid, separatory, water dichloromethane extraction, merge organic phase, massive laundering, saturated nacl aqueous solution is washed, dried over mgso, steaming desolventizes, be that with sherwood oil and methylene dichloride mixed solvent (can be 1: 1～in 1: 2 arbitrary value) eluent, silica gel are that sorbent material crosses that post separates, air drying obtains red-brown solid M1,1.87g (productive rate: 78.1%).
M2 preparation method: as shown in Figure 1; under nitrogen protection; with intermediate A (1.00g; 2.38mmol), pyridine (30mL) joins in the two-mouth bottle; under the ice bath cooling, drip 2-heptyl pelargonyl chloride (4.33g, 14.28mmol);, rise to temperature reaction certain hour (can be the arbitrary value in 6～18 hours).With the reaction solution cool to room temperature, add dilute hydrochloric acid, separatory, water dichloromethane extraction, merge organic phase, massive laundering, saturated nacl aqueous solution is washed, dried over mgso, steaming desolventizes, be that with sherwood oil and methylene dichloride mixed solvent (can be 1: 1～in 1: 2 arbitrary value) eluent, silica gel are that sorbent material crosses that post separates, air drying obtains red-brown solid M2,1.71g (productive rate: 64.2%).
(c) the tin methide conjugative monomer is synthetic
The structural formula of tin methide conjugative monomer is
Its preparation method is referring to document " Cao, K.; Li, S.; Sun, B.; Zhang, Q.A Low Bandgap Polymer Based on Isoindigo and Bis (dialkylthienyl) benzodithiophene for Organic Photovoltaic Applications.J.Polym.Sci.Part A:Polym.Chem.2013,51,94.; Zhang, G.B.; Fu, Y.Y.; Xie, Z.Y.; Zhang, Q.Synthesis of low bandgap polymer based on3,6-dithien-2-yl-2,5-dialkylpyrrolo[3,4-c] pyrrole-1,4-dione for photovoltaic applications.Sol.Energy Mater.Sol.Cells2011,95,1168-1173.; Hu, X.; Shi, M.; Chen, J.; Zuo, L.; Fu, L.; Liu, Y.; Chen, H.Synthesis and photovoltaic properties of ester group functionalized polythiophene derivatives.Macromol.Rapid Commun.2011,32,506. ".
(d) polymer P 1, P2 and P3's is synthetic
As shown in Figure 2, under nitrogen protection, with tin methide conjugative monomer (0.3mmol) and two bromine monomeric compound M1 or M2 (all being 0.3mmol) catalyst P d
2(dba)
3(0.0055g, 0.0060mmol), part P (o-toly)
3(0.0073g, 0.0240mmol), dry toluene (10mL) (also can be anhydrous chlorobenzene or tetrahydrofuran (THF)) adds in the reaction flask, in certain temperature (can be the arbitrary value in 70 ℃～110 ℃) reaction certain hour (can be the arbitrary value in 4～24 hours), with the reaction solution cool to room temperature, add the 50mL methanol extraction, filter out solid, extract with methyl alcohol, normal hexane and chloroform Soxhlet successively, collect chloroformic solution, obtain again the polymkeric substance of metalluster after being spin-dried for methanol extraction.P1 is 0.26g, and productive rate is 72.3%, and number-average molecular weight is 92.2kDa, and molecular weight distribution is 2.2, n=76.7; P2 is 0.27g, and productive rate is 69.2%, and number-average molecular weight is 78.7kDa, and molecular weight distribution is 2.1, n=60.8; P3 is 0.20g, and productive rate is 70.2%, and number-average molecular weight is 43.5kDa, and molecular weight distribution is 2.7, n=45.4.
Ultra-violet absorption spectrum and the electrochemical properties of embodiment 2, polymer P 1, P2 and P3
Fig. 3 has provided polymer P 1, P2 and the P3 ultra-violet absorption spectrum of (b) when chloroform (a) and the film, the maximum absorption peak position of conjugated polymers in chloroformic solution is at 765nm (P1), 760nm (P2), about and759nm (P3), the maximum absorption peak position of film is at 780nm (P1), 780nm (P2), and788nm (P3), optical band gap is 1.30eV (P1), 1.29eV (P1), and1.29eV (P3).Fig. 4 has provided the cyclic voltammetry curve of polymer P 1, P2 and P3.The cyclic voltammetry test is carried out at computer-controlled CHI610D telephone wire analyser, adopt three traditional electrode test systems, platinum electrode is working electrode, silver/silver ion electrode is reference electrode, ionogen is the acetonitrile solution (0.1M) of tetra-n-butyl ammonium hexafluorophosphate, sweep velocity is 50mv/s, take ferrocene as reference.The oxidizing potential that ferrocene records under this system is 0.09eV, because the energy level of ferrocene under the vacuum condition is 4.8eV, the energy level of material can be calculated by the formula of following energy level: E (LUMO)=-(Ered, onset-0.09+4.8) eV=-(Ered, onset+4.71) eV, E (HOMO)=-(Eox, onset-0.09+4.8) eV=-(Eox, onset+4.71) eV.The initial reduction potential that electro-chemical test shows it-0.61eV (P1) ,-0.83eV (P2) ,-0.80eV (P3), the lumo energy that calculates thus is-4.10eV (P1) ,-3.88eV (P2) ,-3.91eV (P3); Initial reduction-oxidation current potential is at 0.76eV (P1), 0.69eV (P2), 0.99eV (P3), and the HOMO energy level that calculates thus is-5.47eV (P1) ,-5.40eV (P2) ,-5.70eV (P3).Fig. 5 shows that conjugated polymers has good thermostability.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367757A (en) * | 2015-11-19 | 2016-03-02 | 上海交通大学 | Isoindigo derivative polymer with butadiene as space isolation group, preparation and use thereof |
| CN105914298A (en) * | 2016-05-15 | 2016-08-31 | 吉林大学 | Polymer photovoltaic cell taking isoindigo derivative as cathode interface modification layer |
| CN110878136A (en) * | 2019-10-17 | 2020-03-13 | 华南师范大学 | A kind of conjugated polymer containing N-acyl substitution and its application |
| CN111004372A (en) * | 2019-12-03 | 2020-04-14 | 西安近代化学研究所 | Conjugated polymer based on fluoroisoindigo |
| CN112574397A (en) * | 2021-01-12 | 2021-03-30 | 长春工业大学 | Preparation and application of electrochromic conjugated polymer capable of being processed by green solvent |
| CN116135902A (en) * | 2021-11-16 | 2023-05-19 | 电子科技大学中山学院 | Isoindigo-based double-cable conjugated polymer and application thereof in electrochromic field |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105367757A (en) * | 2015-11-19 | 2016-03-02 | 上海交通大学 | Isoindigo derivative polymer with butadiene as space isolation group, preparation and use thereof |
| CN105914298A (en) * | 2016-05-15 | 2016-08-31 | 吉林大学 | Polymer photovoltaic cell taking isoindigo derivative as cathode interface modification layer |
| CN105914298B (en) * | 2016-05-15 | 2018-12-25 | 吉林大学 | Using bioxindol derivative as the polymer photovoltaic cell of embellishing cathode interface layer |
| CN110878136A (en) * | 2019-10-17 | 2020-03-13 | 华南师范大学 | A kind of conjugated polymer containing N-acyl substitution and its application |
| CN111004372A (en) * | 2019-12-03 | 2020-04-14 | 西安近代化学研究所 | Conjugated polymer based on fluoroisoindigo |
| CN111004372B (en) * | 2019-12-03 | 2022-03-29 | 西安近代化学研究所 | Conjugated polymer based on fluoroisoindigo |
| CN112574397A (en) * | 2021-01-12 | 2021-03-30 | 长春工业大学 | Preparation and application of electrochromic conjugated polymer capable of being processed by green solvent |
| CN116135902A (en) * | 2021-11-16 | 2023-05-19 | 电子科技大学中山学院 | Isoindigo-based double-cable conjugated polymer and application thereof in electrochromic field |
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