CN109485832A - Conjugated polymer and its preparation method and application based on 4 '-trifluoromethyl substituted quinoxaline structural units - Google Patents

Conjugated polymer and its preparation method and application based on 4 '-trifluoromethyl substituted quinoxaline structural units Download PDF

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CN109485832A
CN109485832A CN201811292386.2A CN201811292386A CN109485832A CN 109485832 A CN109485832 A CN 109485832A CN 201811292386 A CN201811292386 A CN 201811292386A CN 109485832 A CN109485832 A CN 109485832A
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trifluoromethyl
bis
quinoxaline
conjugated polymer
structural unit
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吴忠联
修文华
杨菁菁
庄海玉
朱雯
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Jiangsu University of Technology
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Abstract

The invention belongs to organic polymer field of photoelectric technology, more particularly to a kind of conjugated polymer and its preparation method and application based on 4'- trifluoromethyl substituted quinoxaline structural unit, contain 2 in the main polymer chain, 3- bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoxaline structural unit, the conjugated polymer molecular structure are shown belowN is the degree of polymerization, the integer between 10~300 in formula；Wherein, R is the alkyl of carbon atom number 1-12；D is supplied for electronic conjugated structure unit.The utility model has the advantages that the present invention prepares the trifluoromethyl substituent in quinoxaline polymer with strong electronegativity and high stability, HOMO energy level can be further decreased and improve device open-circuit voltage.Quinoxaline polymer of the invention may be used as the donor material of organic solar batteries, and the active layer as organic solar batteries device uses.

Description

Conjugated polymer based on 4 '-trifluoromethyl substituted quinoxaline structural units and Preparation method and application
Technical field
The invention belongs to organic polymer field of photoelectric technology, and in particular to one kind is replaced based on 4'- trifluoromethyl The conjugated polymer and its preparation method and application of quinoxaline structural unit.
Background technique
Organic solar batteries are low cost, light, Yi Shixian relative to conventional crystal silicon solar cell advantage Flexibility etc., so by academic and industrial circle extensive concern.The basic device structure of organic photovoltaic cell is ontology at present Heterojunction structure, conjugated polymer donor material and fullerene derivate or non-fowler of the optically active layer by solution processable Alkene electron acceptor material is constituted.Conjugated polymer donor material is constructed point relative to acceptor material more easily by chemical means Minor structure realizes its good absorption spectrum and absorption intensity, suitable molecular entergy level and excellent carrier mobility.
The basic structure of current most efficient conjugated polymer donor material is electron donor-electron receptor (D-A) structure, The conjugated polymer for the D-A structure constructed using quinoxaline structural unit as electron acceptor as donor material device most Big incident photon-to-electron conversion efficiency has been more than 10% at present, shows good application prospect (Z.Zheng, et al.Adv.Mater.2017,29(5),1604241；M.Liu,et al.Polym.Chem.2017,8,4613.).Chinese patent CN102827356A, CN102816307A, CN102816304A, CN102816303A and CN102816301A disclose one kind and exist Strong electron-withdrawing group fluorine atom is introduced in short of electricity subelement quinoxaline structure, reduce the HOMO energy level of material and improves light The open-circuit voltage of battery is lied prostrate, for device open-circuit voltage in 0.74~0.86V, HOMO energy level is -5.36~-5.26eV.
Trifluoromethyl (CF3) substituent group is with strong electronegativity and high stability, in the electron acceptor unit quinoline of electron deficient Trifluoromethyl is introduced in quinoline and prepares D-A type polymer donor material, is expected to that HOMO energy level can be further decreased, is improved opening for device Road voltage (Voc)；Simultaneously in trifluoromethyl fluorine atom introducing, it is non-covalent to form FH, FS, F π etc. Key effect, can further improve the effect of polymer molecule interchain, thus be expected to improve carrier mobility, due to these because The effect of element is expected to improve the photovoltaic performance of device.Do not have been reported that design and synthesis 4'- trifluoromethyl replaces quinoline also at present The conjugated polymer of quinoline structural unit is applied in organic solar batteries as donor material.
Summary of the invention
Aiming at the shortcomings in the prior art, the HOMO energy level of material is further effectively reduced and improves quinoxaline polymer light The open-circuit voltage for lying prostrate battery, the object of the present invention is to provide one kind to be based on 4'- trifluoromethyl substituted quinoxaline structure Conjugated polymer of unit and its preparation method and application, the polymer is due in the electron acceptor unit quinoxaline of electron deficient It introduces trifluoromethyl and prepares D-A type polymer donor material, be expected to that HOMO energy level can be further decreased, improve the open circuit electricity of device Press (Voc), the donor material of organic solar batteries can be made, the active layer as organic solar batteries device uses.Its skill Art scheme is as follows:
A kind of conjugated polymer based on 4'- trifluoromethyl substituted quinoxaline structural unit, the conjugated polymer Main chain in contain 2,3- bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoxaline structural unit, the conjugated polymer Chemical structural formula following (A) shown in:
In formula, n is the degree of polymerization, 10~300 integer；R is the alkyl of carbon atom number 1~12；
D is with one of following supplied for electronic conjugated structure unit:
Wherein, R1For the alkyl of carbon atom number 1-12；R2For hydrogen or the alkyl of carbon atom number 1-12.
The preparation method of the conjugated polymer based on 4'- trifluoromethyl substituted quinoxaline structural unit, packet Include following steps:
(1) monomer of 2,3- bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoxaline structure will be contained and containing supplied for electronic The monomer of structure D is dissolved in dry toluene, and catalyst, temperature reaction under inert gas shielding is added；
(2) methanol extraction is used, n-hexane, acetone and chloroform Soxhlet extraction are successively used, chloroform soln is concentrated, is sunk Shallow lake agent precipitating, is dried to obtain fibrous polymer.
Preferably, the catalyst is tris(dibenzylideneacetone) dipalladium (Pd2(dba)3) and three (2- tolyl) phosphine (P (o-toyl)3) combination or tetrakis triphenylphosphine palladium (Pd (PPh3)4)。
Preferably, described to contain 2,3- bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoxaline structure monomer, contain The monomer of supplied for electronic conjugated structure D and the molar ratio of catalyst are 1:1:0.01~0.1.
Preferably, the temperature of the reaction be 90~120 DEG C, the reaction time be 10~for 24 hours.
Preferably, described to contain 2,3- bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoxaline structure monomer molecule Structure such as following formula (B) or (C) are shown:
Wherein, R is the alkyl of carbon atom number 1~12.
The system of bromo- 2,3- bis- (4'- the trifluoromethyl) -6,7- dialkoxy quinoxaline monomer of formula (B) 5,8- bis- Preparation Method is as follows:
By bromo- 5, the 6- dialkoxy -2,1 of 4,7- bis-, 3- diazosulfide is added in ethyl alcohol, and sodium borohydride is then added, Product after reaction is added to the water, and filters or extracts, and the product being dried to obtain is not purified to be directly used in the next step；Add Enter 4,4'- bis- (trifluoromethyl) benzil, anhydrous sodium acetate and dehydrated alcohol, carries out back flow reaction, it is cooling, it filters, recrystallization Or column chromatography for separation obtains target product.
Preferably, bromo- 5, the 6- dialkoxy -2,1 of 4, the 7- bis-, 3- diazosulfide, 4,4'- bis- (trifluoromethyl) benzene The molar ratio of even acyl, anhydrous sodium acetate and sodium borohydride is 1:1:2~5:10~20.
Preferably, the time of back flow reaction is 12~20h.
Formula (C) 5,8- bis- (5'- bromothiophene -2'- base) -2,3- two (4'- the trifluoromethyl) -6,7- dialkoxy Quinoxaline monomer the preparation method is as follows:
(1) by bromo- bis- (4'- the trifluoromethyl) -6,7- dialkoxy quinoxaline of 2,3- of 5,8- bis- and 2- tributyl first Tin alkylthrophene is added in dry toluene, inert gas shielding, and catalyst is added, and heating reflux reaction is spin-dried for, silica gel column chromatography Isolated intermediate product；
(2) above-mentioned intermediate product is dissolved in chloroform/glacial acetic acid, is added N- bromo-succinimide (NBS), room temperature Reaction, is poured into water after reaction, methylene chloride extraction, dry, is spin-dried for, with the isolated target product of silica gel column chromatography.
Preferably, the catalyst is tetrakis triphenylphosphine palladium (Pd (PPh3)4)。
Preferably, bromo- 2,3-, bis- (4'- trifluoromethyl) -6, the 7- dialkoxy quinoxaline of 5,8- bis-, 2- tributyl first The molar ratio of tin alkylthrophene, tetrakis triphenylphosphine palladium and N- bromo-succinimide be 1:2.5~5:0.01~0.05:2~ 3。
Preferably, the time of back flow reaction be 12~for 24 hours.
Preferably, the time of room temperature reaction be 8~for 24 hours.
The utility model has the advantages that
(1) present invention is from the Molecular Design of material, (the 4'- trifluoro of 2,3- bis- of design synthesis electrophilic characteristic Aminomethyl phenyl) -6,7- dialkoxy quinoxaline structures alone, and be copolymerized with supplied for electronic structures alone, obtain the conjugation of narrow band gap Polymer can be used as the donor material of organic solar batteries.
(2) 2,3- bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoxaline structures alone of present invention design synthesis In trifluoromethyl (- CF3) substituent group is with strong electronegativity and high stability, in the electron acceptor unit quinoxaline of electron deficient It introduces trifluoromethyl and prepares D-A type polymer donor material, HOMO energy level can be further decreased, improve the open-circuit voltage of device (Voc)。
(3) in trifluoromethyl fluorine atom introducing, form FH, the non-covalent bonds such as FS, F π are made With, it can further improve the effect of polymer molecule interchain, so that it is expected to the mobility of raising carrier, and then raising device Photovoltaic performance.
(4) conjugated polymer material of the 4'- trifluoromethyl substituted quinoxaline structural unit of present invention design synthesis It is blended with suitable acceptor material, the active layer suitable for organic solar batteries device.
Detailed description of the invention
Fig. 1 is (two octyloxy quinoxaline-alt-2,2'- bithiophene of 2,3- bis- (4'- trifluoromethyl) -6,7-) copolymerization Object (PDTCF3Qx) in CHCl3In solution and the uv-visible absorption spectra of solid film；
Fig. 2 is (4,8- bis- (5'- ((2- ethylhexyl) sulphur) thiophene -2- base) benzo [1,2-b:4,5-b'] Dithiophene - Alt-5,8- bis- (thiophene -2- base) -2,3- two (4'- trifluoromethyl) -6,7- two (dodecyloxy) quinoxaline) copolymer (PBDTTCF3Qx) in CHCl3In solution and the uv-visible absorption spectra of solid film.
Fig. 3 is (two octyloxy quinoxaline-alt-2,2'- bithiophene of 2,3- bis- (4'- trifluoromethyl) -6,7-) copolymerization Object (PDTCF3Qx cyclic voltammetry curve).
Fig. 4 is (4,8- bis- (5'- ((2- ethylhexyl) sulphur) thiophene -2- base) benzo [1,2-b:4,5-b'] Dithiophene - Alt-5,8- bis- (thiophene -2- base) -2,3- two (4'- trifluoromethyl) -6,7- two (dodecyloxy) quinoxaline) copolymer (PBDTTCF3Qx cyclic voltammetry curve).
Specific embodiment
Experimental method in following embodiment is conventional method unless otherwise required, related experiment reagent and material Material is conventional biochemical reagent and material unless otherwise required.
Embodiment 1
One, the synthesis of the bromo- two octyloxy quinoxaline of 2,3- bis- (4'- trifluoromethyl) -6,7- of 5,8- bis-:
In 100mL flask be added the bromo- bis- octyloxy -2,1,3- diazosulfide of 5,6- of 4,7- bis- (0.89g, 1.6mmol) with 20mL ethyl alcohol, it is cooled to 0 DEG C, is slowly added into NaBH4(1.2g, 31.7mmol) is then heated to reflux 3h, cold But, distilled water stirring is added, ether extraction is spin-dried for obtaining yellow solid, without being further purified, is directly used in anti-in next step It answers.Above-mentioned product, anhydrous Na OAc (0.37g, 4.5mmol), 4,4'- bis- (trifluoromethyl) benzil are added in 100mL flask (0.55g, 1.6mmol) and 20mL ethyl alcohol, nitrogen protection are heated to reflux, and react 20h.It is cooling, it filters, washing, drying.It is thick to produce Object purifies (200-300 mesh silica gel, eluent: petrol ether/ethyl acetate=8/1, v/v) with silica gel column chromatography, and it is shallow to obtain 0.64g Yellow solid, yield 48%.1H NMR(400MHz,CDCl3, TMS), δ (ppm): 7.77 (d, J=8Hz, 4H), 7.67 (d, J= 8Hz,4H),4.24(t,4H),1.90-1.98(m,4H),1.33-1.40(m,20H),0.90-0.93(m,6H)。
Two, the synthesis of conjugated polymer
(two octyloxy quinoxaline-alt-2,2'- bithiophene of 2,3- bis- (4'- trifluoromethyl) -6,7-) copolymer (PDTCF3Qx synthesis):
(the trimethylstannyl) -2,2'- of 5,5'- bis- bithiophene (98mg, 0.2mmol) is added in 25mL there-necked flask and prepares The bromo- two octyloxy quinoxaline (167mg, 0.2mmol) of 2,3- bis- (4'- trifluoromethyl) -6,7- of 5,8- bis-, nitrogen protection Under, catalyst Pd (PPh is added3)4(8mg) and 8mL dry toluene is warming up to 110 DEG C, and reaction is for 24 hours, cooling, methanol extraction, mistake Filter, using toluene as eluant, eluent, silica gel column chromatography separation is concentrated, methanol extraction, and filtering, vacuum drying obtains fibrous polymer (polymer 1), number-average molecular weight 23000, polydispersity coefficient 2.8.Uv-visible absorption spectra is as shown in Figure 1, available Optical bandwidthFrom Fig. 3 it can be seen that: EHOMO=-5.45eV, ELUMO=-3.03eV.
Three, the preparation of organic solar batteries device:
Device (basic device structure: ITO/PEDOT:PSS/ fibrous polymer (polymer 1): fullerene derivate (PC61BM)/LiF/Al) manufacturing process: ito glass is after ultrasonic cleaning, with oxygen plasma treatment, one layer of conduction of subsequent spin coating Macromolecule-PEDOT:PSS aqueous dispersions, with sol evenning machine high speed spin coating, thickness is determined by solution concentration and revolving speed, is taken turns with surface Wide instrument actual measurement monitoring.After film forming, drive away solvent residues, post bake in vacuum drying oven；Then spin coating is different on PEDOT Then the polymer of ratio and the mixed solution of fullerene derivate, control active layer thickness are deposited one layer in 100nm or so LiF, thickness control is in 0.5nm or so, cathode of the Al of last evaporation metal 100nm thickness as device.
It obtains after tested, device performance: open-circuit voltage Voc=1.02V, short circuit current Jsc=3.72mA/cm2, fill factor FF=29.2%, energy conversion efficiency PCE=1.11%.
Embodiment 2
One, 5,8- bis- (5'- bromothiophene -2'- base) -2,3- two (4'- trifluoromethyl) -6,7- two (dodecyloxy) The synthesis of quinoxaline:
(1) synthesis of bromo- 2,3- bis- (4'- trifluoromethyl) -6,7- two (dodecyloxy) quinoxaline of 5,8- bis-
In 100mL flask be added bromo- bis- (the dodecyloxy) -2,1,3- diazosulfide of 5,6- of 4,7- bis- (0.99g, 1.5mmoL) with 20mL ethyl alcohol, it is cooled to 0 DEG C, is slowly added into NaBH4(1.13g, 30mmoL) is then heated to reflux 3h, cooling, adds Enter distilled water stirring, ether extraction is spin-dried for obtaining yellow solid, without being further purified, is directly used in and reacts in next step.? Above-mentioned product, anhydrous Na OAc (0.37g, 4.5mmoL), 4,4'- bis- (trifluoromethyl) benzil are added in 100mL flask (0.52g, 1.5mmoL) and 20mL ethyl alcohol, nitrogen protection are heated to reflux, and react 12h.It is cooling, it filters, washing, drying.It is thick to produce Object silica gel column chromatography purifies (200-300 mesh silica gel, eluent: petrol ether/ethyl acetate=8/1, v/v), and it is pale yellow to obtain 0.84g Color solid, yield 59%.1H NMR(400MHz,CDCl3, TMS), δ (ppm): 7.75 (d, J=8Hz, 4H), 7.65 (d, J= 8Hz,4H),4.19(t,4H),1.91(m,4H),1.27(m,36H),0.88(m,6H)。
(2) 5,8- bis- (thiophene -2'- base) -2,3- two (4'- trifluoromethyl) -6,7- two (dodecyloxy) quinoline The synthesis of quinoline
In 100mL there-necked flask, bromo- 2,3- bis- (4'- trifluoromethyl) -6, the 7- bis- (dodecyloxy) of 5,8- bis- is added Quinoxaline (0.94g, 1mmol), 2- (tributylstamlyl) thiophene (1.49g, 4mmol) and 20mL dry toluene, nitrogen are protected 56mg Pd (PPh is added in shield3)4, it is heated to reflux for 24 hours, it is cooling, it is spin-dried for.Crude product silica gel column chromatography purifies (200-300 mesh silicon Glue, eluent: petroleum ether/CH2Cl2=8/1, v/v), obtain 0.87g yellow solid, yield 91%.1H NMR(400MHz, CDCl3,TMS),δ(ppm):7.99(dd,J1=4Hz, J2=8Hz, 2H), 7.76 (d, J=8Hz, 4H), 7.62 (d, J=8Hz, 4H),7.59(dd,J1=4Hz, J2=8Hz, 2H), 7.23 (dd, J1=4Hz, J2=8Hz, 2H), 4.04 (t, J=4Hz, 4H), 1.78(m,4H),1.27-1.39(m,36H),0.89(m,6H)。
(3) 5,8- bis- (5'- bromothiophene -2'- base) -2,3- two (4'- trifluoromethyl) -6,7- two (dodecyloxy) The synthesis of quinoxaline
In 100mL there-necked flask, 5,8- bis- (thiophene -2'- base) -2,3- bis- (4'- trifluoromethyl) -6,7- bis- is added (dodecyloxy) quinoxaline (0.95g, 1mmol), 10mLCHCl3With 2mL glacial acetic acid, be protected from light, be slowly added into NBS (0.39g, 2.2mmol).12h is stirred, pours into 50mL water, uses CH2Cl2Extraction, anhydrous Na2SO4It is dry, it is spin-dried for.Crude product silica gel column layer Analysis purification (200-300 mesh silica gel, eluent: petroleum ether/CH2Cl2=8/1, v/v), obtain 0.78g red solid, yield 70%.1H NMR(400MHz,CDCl3, TMS), δ (ppm): 7.91 (d, J=4Hz, 2H), 7.74 (d, J=8Hz, 4H), 7.16 (d, J=4Hz, 2H), 4.08 (t, J=4Hz, 4H), 1.78-1.86 (m, 4H), 1.25-1.43 (m, 36H), 0.87-0.90 (m, 6H)。
Two, the synthesis of conjugated polymer
(4,8- bis- (5'- ((2- ethylhexyl) sulphur) thiophene -2- base) benzo [1,2-b:4,5-b'] Dithiophene-alt-5, 8- bis- (thiophene -2- base) -2,3- two (4'- trifluoromethyl) -6,7- two (dodecyloxy) quinoxaline) copolymer (PDTCF3Qx synthesis):
4,8- bis- (5 '-(2- ethylhexyl sulfenyl) thiophene -2- base) benzo [1,2-b is added in 25mL there-necked flask；4,5- B '] Dithiophene -2,6- two (trimethyl stannane) (193mg, 0.2mmol) and preparation 5,8- bis- (5'- bromothiophene -2'- base) -2, 3- bis- (4'- trifluoromethyl) -6,7- bis- (dodecyloxy) quinoxaline (222mg, 0.2mmol) under nitrogen protection, is added Catalyst tris(dibenzylideneacetone) dipalladium (Pd2(dba)3, 2mg), three (2- tolyl) phosphine (P (o-toyl)3, 4mg) and 8mL Dry toluene is warming up to 110 DEG C, and reaction is for 24 hours, cooling, methanol extraction, and n-hexane, acetone and chloroform rope are successively used in filtering Family name extracts, and chloroform soln, methanol extraction is finally concentrated, and filtering is dried in vacuo and obtains fibrous polymer (polymer 2). Number-average molecular weight is 24500, polydispersity coefficient 2.9.Uv-visible absorption spectra is as shown in Figure 1, can be obtained optical bandwidth Eo g pt=1.55eV.From Fig. 4 it can be seen that: EHOMO=-5.42eV, ELUMO=-3.49eV, than prior art CN102827356A, HOMO disclosed in CN102816307A, CN102816304A, CN102816303A and CN102816301A can it is low 0.06~ 0.19eV。
Three, the preparation of organic solar batteries device:
It will be prepared in 1 alternative costs embodiment of polymer in embodiment 1 in organic solar batteries basic device structure Obtained polymer 2, other structures and manufacturing process are the same as embodiment 1.
It obtains after tested, device performance: open-circuit voltage Voc=0.94V, than prior art CN102827356A, Open-circuit voltage disclosed in CN102816307A, CN102816304A, CN102816303A and CN102816301A is high by 0.08~ 0.28V；Short circuit current Jsc=13.53mA/cm2；Fill factor FF=61%；Energy conversion efficiency PCE=7.76%, than existing Disclosed in technology CN102827356A, CN102816307A, CN102816304A, CN102816303A and CN102816301A Energy conversion efficiency is high by 3.45%.
Other conjugated polymer examples and optical bandwidth based on 4'- trifluoromethyl substituted quinoxaline structural unit, (polymer 1 in embodiment 1 is only substituted for phase emergencing copolymer, other structures by basic device structure for molecular entergy level and device And manufacturing process is with embodiment 1) result summary be shown in Table 1, the synthetic method of these polymer is referring to embodiment 1 or embodiment 2.
Table 1
As seen from Table 1, the conjugation prepared by the present invention based on 4'- trifluoromethyl substituted quinoxaline structural unit is poly- That closes object has lower HOMO energy level and higher device open-circuit voltage, further illustrates the trifluoro in quinoxaline polymer The strong electronegativity and high stability of methyl substituents, further reduced the HOMO energy of polymer, and then improve the open circuit of device Voltage.The structure formula (I) of quinoxaline conjugated polymer disclosed in polymer 6 and CN102827356A in table 1:
Although structure is close, in the polymer architecture that is prepared in the present invention by In the substitution for having trifluoromethyl, open-circuit voltage and HOMO energy level are compared with the excellent benefit of formula (I) effect in documents.
Conjugated polymer prepared by the present invention based on 4'- trifluoromethyl substituted quinoxaline structural unit it is organic too It is positive to show good application prospect in the active layer of battery device.
It will be apparent to those skilled in the art that can make various other according to the above description of the technical scheme and ideas It is corresponding to change, and all these changes all should belong within the scope of protection of the claims of the present invention.

Claims (10)

1. a kind of conjugated polymer based on 4'- trifluoromethyl substituted quinoxaline structural unit, which is characterized in that described total Contain 2,3- bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoxaline structural unit in the main chain of conjugated polymer, it is described total Shown in the chemical structural formula of conjugated polymer following (A):
In formula, n is the degree of polymerization, in 10~300 integer；R is the alkyl of carbon atom number 1~12；
D is with one of following supplied for electronic conjugated structure unit:
Wherein, R1For the alkyl of carbon atom number 1~12；R2For hydrogen or the alkyl of carbon atom number 1~12.
2. a kind of conjugated polymer described in claim 1 based on 4'- trifluoromethyl substituted quinoxaline structural unit Preparation method, which comprises the following steps:
(1) monomer of 2,3- bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoxaline structure will be contained and be conjugated containing supplied for electronic The monomer of structure D is dissolved in dry toluene, and catalyst, temperature reaction under inert gas shielding is added；
(2) methanol extraction is used, n-hexane, acetone and chloroform Soxhlet extraction are successively used, chloroform soln is concentrated, uses again Methanol extraction is dried to obtain fibrous polymer.
3. the conjugated polymer according to claim 2 based on 4'- trifluoromethyl substituted quinoxaline structural unit Preparation method, which is characterized in that catalyst described in step (1) is tris(dibenzylideneacetone) dipalladium and three (2- tolyl) phosphines Combination or tetrakis triphenylphosphine palladium；It is described containing 2,3- bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoxaline structure The molar ratio of monomer, the monomer of the D of conjugated structure containing supplied for electronic and catalyst is 1:1:0.01~0.1；The temperature of the reaction is 90~120 DEG C, the reaction time be 10~for 24 hours.
4. the conjugated polymer according to claim 2 based on 4'- trifluoromethyl substituted quinoxaline structural unit Preparation method, which is characterized in that described to contain 2,3- bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoxaline structure list Body molecular structure such as following formula (B) or (C) are shown:
Wherein, R is the alkyl of carbon atom number 1~12.
5. the conjugated polymer according to claim 4 based on 4'- trifluoromethyl substituted quinoxaline structural unit Preparation method, which is characterized in that bromo- 2,3-, bis- (4'- trifluoromethyl) -6,7- dialkoxy quinoline of 5,8- of the formula (B) bis- Quinoline monomer the preparation method is as follows: by 4, bromo- 5, the 6- dialkoxy -2,1 of 7- bis-, 3- diazosulfide is added in ethyl alcohol, so After sodium borohydride is added, product after reaction is added to the water, filter or extract, the product being dried to obtain it is not purified directly For the next step；4,4'- bis- (trifluoromethyl) benzil, anhydrous sodium acetate and dehydrated alcohol is added, carries out back flow reaction, it is cold But, it filters, recrystallization or column chromatography for separation obtain target product.
6. the conjugated polymer according to claim 5 based on 4'- trifluoromethyl substituted quinoxaline structural unit Preparation method, which is characterized in that bromo- 5, the 6- dialkoxy -2,1 of 4, the 7- bis-, 3- diazosulfide, 4,4'-, bis- (fluoroform Base) molar ratio of benzil, anhydrous sodium acetate and sodium borohydride is 1:1:2~5:10~20, the time of the back flow reaction is 12~20h.
7. the conjugated polymer according to claim 4 based on 4'- trifluoromethyl substituted quinoxaline structural unit Preparation method, which is characterized in that 5,8- of the formula (C) bis- (5'- bromothiophene -2'- base) -2,3- bis- (4'- trifluoromethyl) - 6,7- dialkoxy quinoxaline monomer the preparation method is as follows:
(1) by bromo- bis- (4'- the trifluoromethyl) -6,7- dialkoxy quinoxaline of 2,3- of 5,8- bis- and 2- tributylstannyl Base thiophene is added in dry toluene, inert gas shielding, and catalyst is added, and heating reflux reaction is spin-dried for, silica gel column chromatography separation Obtain intermediate product；
(2) above-mentioned intermediate product is dissolved in chloroform/glacial acetic acid, N- bromo-succinimide is added, reacted at room temperature, reaction After be poured into water, methylene chloride extraction is dry, is spin-dried for, with the isolated target product of silica gel column chromatography.
8. the conjugated polymer according to claim 7 based on 4'- trifluoromethyl substituted quinoxaline structural unit Preparation method, which is characterized in that the catalyst is tetrakis triphenylphosphine palladium；3- bis- (4'- trifluoromethyl) -6,7- dioxane Oxygroup quinoxaline, 2- tributylstamlyl thiophene, catalyst and N- bromo-succinimide molar ratio be 1:2.5~5: 0.01~0.05:2~3, time of back flow reaction described in step (1) is 12~for 24 hours, room temperature reaction described in step (2) Time be 8~for 24 hours.
9. the conjugated polymer described in claim 1 based on 4'- trifluoromethyl substituted quinoxaline structural unit, which is used as, to be had The application of machine solar cell device donor material.
10. application according to claim 9, which is characterized in that in use, the conjugated polymer and acceptor material fowler Ene derivative is codissolved in organic solvent, forms a film to form the photoactive layer material of organic solar cell device by spin coating proceeding Material.
CN201811292386.2A 2018-11-01 2018-11-01 Conjugated polymer and its preparation method and application based on 4 '-trifluoromethyl substituted quinoxaline structural units Pending CN109485832A (en)

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CN114507337A (en) * 2022-02-21 2022-05-17 东华大学 Conjugated polymer containing quinoxaline structure, and synthetic method and application thereof
CN114874418A (en) * 2022-04-24 2022-08-09 广东聚石科技研究有限公司 Conjugated polymer based on trifluoromethyl substituted quinoxaline and preparation method and application thereof
CN114874418B (en) * 2022-04-24 2023-12-19 广东聚石科技研究有限公司 Conjugated polymer based on trifluoromethyl substituted quinoxaline, and preparation method and application thereof

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