CN103694457A - Preparation methods for fluorine-containing thienopyrrolodione monomer and copolymer thereof - Google Patents
Preparation methods for fluorine-containing thienopyrrolodione monomer and copolymer thereof Download PDFInfo
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Abstract
The invention relates to preparation methods for a fluorine-containing thienopyrrolodione monomer and a copolymer thereof. According to the invention, thiophene-3,4-dicarboxylic acid is mixed with thionyl chloride, and then an organic solvent and a methylbenzene solution containing pentafluoroaniline are added so as to obtain a white crystal pentafluorophenyl-4H-thieno[3,4-c]pyrrolo-4,6-(5H)dione; then mixed liquor of N-bromo-succinimide, trifluoroacetic acid and concentrated H2SO4 is added so as to obtain a fluorine-containing thienopyrrolodione-benzodithiophene-pentafluorophenyl-4H-thieno[3,4-c]pyrrolo-4,6-(5H)dione bromide monomer; a benzodithiophene derivative monomer and the fluorine-containing thienopyrrolodione monomer are mixed, and a catalyst and an organic solvent are added so as to obtain the fluorine-containing thienopyrrolodione-benzodithiophene copolymer. Compared with the prior art, the invention has the following advantages: the utilization rate of sunlight, carrier mobility and thermal stability of the copolymer can be effectively improved, and the life of a device can be prolonged.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to fluorine-containing Thienopyrroles two one monomers and multipolymer preparation method thereof.
Technical background
Polymer solar battery (Polymer Solar Cells, PSCs) overcome the shortcomings such as expensive, the difficult flexible processing of silicon and inorganic semiconductor solar cell, toxicity are large, also there is portable, environmental friendliness, technique is simple and the unique advantage such as big area process for processing simultaneously.Therefore polymer solar battery technology is expected to solve largely day by day serious energy dilemma and ecocrisis, is a kind of novel organic solar batteries.Realize polymer solar battery commercialization, its energy conversion efficiency value should reach and more than 10% require high work-ing life simultaneously.Therefore the polymer solar battery of developing high-performance and high stability becomes the focus of organic solar batteries research.
The character of photosensitive activity layer has material impact to the performance of polymer solar battery.At present, few as the kind of acceptor material, be mainly the soluble derivative of PCBM.Yet because solar irradiation is mapped to the most of sunlight of device surface by Give body absorbed; structure and the performance of Give body material have considerable influence to the performance of solar cell, in order to obtain the efficiency of conversion of higher organic polymer solar cell, increasing D-A type narrowband gap conjugated polymer is applied in polymer solar battery, and has obtained larger development.D-A type narrowband gap conjugated polymer comprises that electron rich heterocycle is to body unit and electron deficiency heterocyclic receptor unit, and they form π key conjugation track jointly, make polymkeric substance chromophoric group generation red shift, makes polymkeric substance to the absorption grow of visible ray and wide.Because the pyrroledione on Thienopyrroles diketone molecule (TPD) has very strong electrophilic characteristic, therefore can be used as and be subject to body unit; And benzo two thiophene derivants (BDT) have good symmetry and planarity, intermolecular have tight and orderly accumulation and make it have higher charge mobility, therefore can be used as well to body unit, the solar device that the TPD based on N atomchain spreading alkyl and the multipolymer of BDT derivative are made as photosensitive activity layer donor material has obtained higher photoelectric transformation efficiency.But because the N atomchain spreading alkyl on TPD unit causes thermostability poor, visible-range absorption region is wide not enough, causes the photoelectric transformation efficiency of this analog copolymer and work-ing life not ideal enough.
Summary of the invention
One of object of the present invention is poor for the thermostability of the D-A narrow band gap multipolymer based on TPD and BDT in prior art, the defect that visible absorption scope is wide not enough, a kind of Heat stability is good is provided, Thienopyrroles two one monomers of the fluoro-containing group that the wide and absorbancy of absorption region is strong, have good charge transport properties and with the multipolymer of benzo two thiophene derivants.This multipolymer, because the N atom on TPD is introduced aromatic nucleus and the strong electrophilic fluorin radical with conjugative effect, improves the stability of multipolymer and the absorption region of visible ray effectively.
Two of object of the present invention is the application that utilize fluorine-containing Thienopyrroles two one monomers and benzo two thiophene derivants to manufacture at polymer solar device after being copolymerized into multipolymer.
Fluorine-containing Thienopyrroles two one monomers of the present invention have following structural formula:
After fluorine-containing Thienopyrroles two one monomers of the present invention and benzo two thiophene derivant polymerizations, obtain fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers, there is following general structure:
Wherein, the integer that n is 10 ~ 100, R
1, R
2be selected from hydrogen, C
1~ C
20alkyl or phenyl.
Fluorine-containing Thienopyrroles two one monomers of the present invention and the concrete preparation scheme of multipolymer thereof are:
(1) fluorine-containing Thienopyrroles two one monomers
1, the preparation of thiophene dimethyl chloride crude product
Be full of under the oxygen-free environment of rare gas element 3,4-thiophene dioctyl phthalate and thionyl chloride are mixed after in 10～100 ℃ of reactions 1～14 hour, be cooled to room temperature, underpressure distillation obtains crude product 3,4-thiophene dimethyl chloride.
2, pentafluorophenyl group-4
h-thiophene [3,4-c] pyrroles 4,6-(5
h) preparation of diketone
Be full of under the oxygen-free environment of rare gas element crude product 3,4-thiophene dimethyl chloride and organic solvent heating for dissolving, slowly splash into the toluene solution that contains penta fluoro benzene amine, 10～120 ℃ of reaction 1-14 hour, are cooled to room temperature, revolve steaming, extraction, washing, obtains pentafluorophenyl group-4 after column chromatography is refining
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone white crystal.
3, pentafluorophenyl group-4
h-thiophene [3,4-c] pyrroles 4,6-(5
h) preparation of diketone bromo-derivative monomer
In pentafluorophenyl group-4
h-thiophene [3,4-c] pyrroles 4,6-(5
h) add N-bromo-succinimide, trifluoroacetic acid and dense H in diketone
2sO
4mixed solution, under lucifuge condition, 0～70 ℃ of reaction 1～24 h, after reaction finishes, revolves steaming, extraction, washing, obtains pentafluorophenyl group-4H-thiophene [3,4-c] pyrroles 4,6-(5H) diketone bromo-derivative monomer after column chromatography is refining.
In the preparation of described thiophene dimethyl chloride crude product, the mol ratio of 3,4-thiophene Er Jia Suan ︰ penta fluoro benzene amine is 1:(1.1～3).
Described trifluoroacetic acid and dense H
2sO
4mixed solution in the volume ratio of trifluoroacetic acid and the vitriol oil be 1:(0.1～1).
In the described toluene solution that contains penta fluoro benzene amine, the massfraction of penta fluoro benzene amine is than being 1:(3～30).
Described pentafluorophenyl group-4
h-thiophene [3,4-c] pyrroles 4,6-(5
h) in the preparation of diketone bromo-derivative monomer, pentafluorophenyl group-4
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone: N mono-bromo-succinimide: the mol ratio of trifluoroacetic acid is 1:(2～5): (10～100).
(2) preparation of fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers
Under oxygen-free environment, by benzo two thiophene derivant monomers and pentafluorophenyl group-4H-thiophene [3,4-c] pyrroles 4,6-(5H) diketone bromo-derivative monomer mixed, and successively adds organic palladium catalyzer and organic solvent, in 40～110 ℃ of reactions 12～72 hours; After being cooled to room temperature, be added dropwise in anhydrous methanol, after filtration, obtain multipolymer crude product.After crude product is dry, use respectively again methyl alcohol, after normal hexane and chloroform extracting, obtain being the fluorine-containing Thienopyrroles diketone-benzo of atropurpureus two thiophene copolymers solidss.
Described benzo two thiophene derivant monomers refer to 2,6-bis-(tin trimethyl)-4,8-bis-(2-octyl group undecyl oxygen base)-benzo two thiophene monomers, 2,6-bis-(tin trimethyl)-4,8-diheptyl-benzo two thiophene monomers or 2,6-bis-(tin trimethyl)-4,8-bis-(2-hexyl nonyl oxygen base)-benzo two thiophene monomers.
Benzo two thiophene derivant Dan Ti ︰ pentafluorophenyl group-4H-thiophene [3,4-c] pyrroles 4,6-(5H) diketone bromo-derivative monomers: the mol ratio of organic palladium catalyzer is 1 ︰ 1 ︰ (0.01～0.1).
Described organic palladium catalyzer is Pd
2(dba)
3or Pd(PPh
3)
4.
Described organic solvent is tetrahydrofuran (THF), benzene, toluene, chlorobenzene or dioxane.
(3) fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers are applied in multipolymer solar cell
Active layer material comprises fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers of the present invention as electron donor material, and [6,6] phenyl-C61-methyl-butyrate (is called for short PC
61bM) as electron acceptor material, be that device architecture is glass/ITO/PEDOT:PSS/ active coating/Al, wherein ito glass is after ultrasonic cleaning, with oxygen-Plasma, process, on ITO, coat PEDOT:PSS, then fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers in the present invention and PCBM are covered above with spin coating after orthodichlorobenzene dissolving blend, then evaporation negative electrode aluminum metal, polymer solar device obtained.
Above-mentioned fabricate devices technique is carried out being full of under the oxygen-free environment of rare gas element.
The present invention compared with prior art possesses following advantage:
1, in multipolymer, on the N atom in TPD unit, introduced aromatic nucleus and the strong electrophilic fluorin radical with conjugative effect, chain alkyl compared to existing technology, the main chain of multipolymer and side chain all have regular and structure conjugation, the introducing of strong electrophilic fluorin radical simultaneously all can effectively extend the conjugation performance of polymkeric substance of the present invention, reduce the energy gap of this polymkeric substance, improved the utilization ratio of sunlight and increased carrier mobility efficiency.
2, in molecule, introduce fluorin radical, can effectively improve the thermostability of polymkeric substance of the present invention, when being applied in solar cell, can effectively improve the life-span of device.
Accompanying drawing explanation
Fig. 1 is fluorine-containing Thienopyrroles two one monomers of the present invention and multipolymer technology of preparing route map thereof.
Fig. 2 is fluorine-containing Thienopyrroles diketone monomer structure formula of the present invention.
Fig. 3 is fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers general structures of the present invention.
Fig. 4 is fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P1 structural formulas of the present invention.
Fig. 5 is fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P2 structural formulas of the present invention.
Fig. 6 is fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P3 structural formulas of the present invention.
Fig. 7 is the uv-vis spectra comparison diagram of copolymer p 1 of the present invention and prior art PBDTCTPD.
Fig. 8 is that the copolymer p 1 of usining in the present invention is as the configuration diagram of the polymer solar cell device of active coating.
Embodiment
For better understanding technical scheme of the present invention, the mode below in conjunction with accompanying drawing with embodiment is described further.
In Fig. 3, the integer that n is 10 ~ 100, R
1, R
2be selected from hydrogen, C
1~ C
20alkyl or phenyl.
In Fig. 4, atropurpureus solid P1, n=10 in formula.
In Fig. 5, fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P2, n=10 in formula.
In Fig. 6, prepare fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P3, n=16 in formula.
In Fig. 7, solid line represents the UV, visible light light absorption line of copolymer p 1, and dotted line represents the copolymer p BDTCTPD of TPD unit N atomchain spreading alkyl in prior art.
In Fig. 8, wherein polymer active layer is copolymer p 1 of the present invention, and PEDOT:PSS is poly-3,4-ethylene dioxythiophene: polystyrolsulfon acid.
Embodiment 1
The preparation of fluorine-containing Thienopyrroles two one monomers
Be full of under the oxygen-free environment of rare gas element by (1 g, 5.8 mmol) 3,4-thiophene dioctyl phthalate and 10 ml thionyl chlorides react 1 hour after mixing under 100 ℃ of conditions, are cooled to room temperature, underpressure distillation obtains crude product 3,4-thiophene dimethyl chloride.
Be full of under the oxygen-free environment of rare gas element the crude product obtaining 3,4-thiophene dimethyl chloride and dry toluene heating for dissolving, slowly splash into (1.17 g, 3.5 ml toluene solutions of penta fluoro benzene amine 6.38 mmol) react 1 hour under 120 ℃ of conditions, are cooled to room temperature, revolve steaming, extraction, washing, obtains white crystal pentafluorophenyl group-4 after column chromatography is refining
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone 0.86g.
Get pentafluorophenyl group-4 of (0.408 g, 1.27 mmol)
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone joins containing in the 1.4 mL trifluoroacetic acids of (0.452 g, 2.54 mmol) NBS, then add the dense H of 1.4 mL
2sO
4, under lucifuge condition, in 0 ℃ of reaction 24 h, after reaction finishes, revolve steaming, extraction, washing, white crystal pentafluorophenyl group-4 after column chromatography is refining
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone bromo-derivative monomer 0.4 g.Structural formula as shown in Figure 2.
Embodiment 2
The preparation of fluorine-containing Thienopyrroles two one monomers
Be full of under the oxygen-free environment of rare gas element by (2 g, 11.6 mmol) 3,4-thiophene dioctyl phthalate and 30ml thionyl chloride react 7 h after mixing under 10 ℃ of conditions, are cooled to room temperature, underpressure distillation obtains crude product 3,4-thiophene dimethyl chloride.
Be full of under the oxygen-free environment of rare gas element the crude product obtaining 3,4-thiophene dimethyl chloride and dry toluene heating for dissolving, slowly splash into (6.35 g, 180 mL toluene solutions of penta fluoro benzene amine 34.8mmol) react 14 hours under 10 ℃ of conditions, are cooled to room temperature, revolve steaming, extraction, washing, obtains white crystal pentafluorophenyl group-4 after column chromatography is refining
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone 1.96 g.
Get pentafluorophenyl group-4 of (1.2 g, 3.76 mmol)
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone joins containing in the 40 mL trifluoroacetic acids of (3.34 g, 18.8 mmol) NBS, then add the dense H of 4 mL
2sO
4, under lucifuge condition, in 75 ℃ of reaction 7 h, after reaction finishes, revolve steaming, extraction, washing, white crystal pentafluorophenyl group-4 after column chromatography is refining
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone bromo-derivative monomer 1.3 g.
Embodiment 3
The preparation of fluorine-containing Thienopyrroles two one monomers
Be full of under the oxygen-free environment of rare gas element by (1.2g, 7.0 mmol) 3,4-thiophene dioctyl phthalate and 10ml thionyl chloride react 14 hours after mixing under 50 ℃ of conditions, are cooled to room temperature, underpressure distillation obtains crude product 3,4-thiophene dimethyl chloride.
Be full of under the oxygen-free environment of rare gas element the crude product obtaining 3,4-thiophene dimethyl chloride and dry toluene heating for dissolving, slowly splash into (1.8 g, 10 mmol) penta fluoro benzene carbaryl solution reacts 7 hours under 75 ℃ of conditions, is cooled to room temperature, revolve steaming, extraction, washing, obtains white crystal pentafluorophenyl group-4 after column chromatography is refining
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone 1.12 g.
Get pentafluorophenyl group-4 of (1.0 g, 3.13 mmol)
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone joins containing in the 16 mL trifluoroacetic acids of (1.79 g, 10 mmol) NBS, then add the dense H of 8 mL
2sO
4, under lucifuge condition, in 50 ℃ of reaction 1 h, after reaction finishes, revolve steaming, extraction, washing, white crystal pentafluorophenyl group-4 after column chromatography is refining
h-thiophene [3,4-c] pyrroles 4,6-(5
h) diketone bromo-derivative monomer 0.6 g.
Embodiment 4
The preparation of fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P1
Under oxygen-free environment, by (0.205 g, 0.184 mmol) monomer 2,6-bis-(tin trimethyl)-4, the monomer (0.088g, 0.184 mmol) that 8-bis-(2-octyl group undecyl oxygen base)-benzene 1,4-Dithiapentalene and embodiment 1 obtain adds (2.1 mg, 0.184 * 10 after mixing
-2mmol) Pd (PPh
3)
4after catalyzer, add toluene, under 110 ℃ of conditions, react 12 hours; After being cooled to room temperature, be added dropwise in anhydrous methanol, after filtration, obtain copolymer p 1 crude product; After crude product is dry, use respectively methyl alcohol again, obtain fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P1 after normal hexane and chloroform extracting, its structural formula as shown in Figure 4.
Copolymer p 1 and PBDTCTPD are dissolved in toluene, and concentration is 1 * 10
-5/ L, carry out the test of UV, visible light light absorption line, as shown in Figure 7, in way, dotted line represents the UV, visible light light absorption line of the copolymer p BDTCTPD of TPD unit N atomchain spreading alkyl in prior art to result, and solid line represents the UV, visible light light absorption line of copolymer p 1.
Embodiment 5
The preparation of fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P1
Under oxygen-free environment, by (0.25g, 0.225mmol) monomer 2,6-bis-(tin trimethyl)-4, the monomer (0.107 g, 0.225 mmol) that 8-bis-(2-octyl group undecyl oxygen base)-benzene 1,4-Dithiapentalene and embodiment 2 obtain adds (20.5 mg, 0.225 * 10 after mixing
-1mmol) Pd
2(dba)
3after catalyzer, add anhydrous chlorobenzene, under 40 ℃ of conditions, react 72 hours; After being cooled to room temperature, be added dropwise in anhydrous methanol, after filtration, obtain copolymer p 1 crude product; After crude product is dry, use respectively again methyl alcohol, after normal hexane and chloroform extracting, obtain fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P1.
Embodiment 6
Prepare fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P2
Under oxygen-free environment, by (0.2 g, 0.206 mmol) monomer 2,6-bis-(tin trimethyl)-4,8-diheptyl-benzene 1,4-Dithiapentalene and (0.0982 g, 0.206 mmol pentafluorophenyl group-4
h-thiophene [3,4-c] pyrroles 4,6-(5
h) rear (1.88 mg, 0.206 * 10 of successively adding of diketone bromo-derivative monomer mixing
-2mmol) Pd
2(dba)
3catalyzer and tetrahydrofuran (THF) organic solvent react 36 hours under 75 ℃ of conditions; After being cooled to room temperature, be added dropwise in anhydrous methanol, after filtration, obtain copolymer p 2 crude products.After crude product is dry, use respectively methyl alcohol again, obtain 0.158 g atropurpureus solid P2 after normal hexane and chloroform extracting, its structural formula as shown in Figure 5.
Embodiment 7
Prepare fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P2
Under oxygen-free environment, by (0.25 g, 0.257 mmol) monomer 2,6-bis-(tin trimethyl)-4,8-diheptyl-benzene 1,4-Dithiapentalene and (0.123 g, 0.257 mmol) pentafluorophenyl group-4
h-thiophene [3,4-c] pyrroles 4,6-(5
h) rear (29.6 mg, 0.257 * 10 of successively adding of diketone bromo-derivative monomer mixing
-1mmol) Pd(PPh
3)
4catalyzer and dioxane organic solvent react 12 hours at 110 ℃; After being cooled to room temperature, be added dropwise in anhydrous methanol, after filtration, obtain copolymer p 2 crude products.After crude product is dry, use respectively again methyl alcohol, after normal hexane and chloroform extracting, obtain atropurpureus solid P2.
Embodiment 8
Prepare fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P3
Under oxygen-free environment, by (0.200 g, 0.200 mmol) monomer 2,6-bis-(tin trimethyl)-4,8-bis-(2-hexyl nonyl oxygen base)-benzene 1,4-Dithiapentalene and (0.956 g, 0.200 mmo) l pentafluorophenyl group-4
h-thiophene [3,4-c] pyrroles 4,6-(5
h) rear (5mg, 0.500 * 10 of successively adding of diketone bromo-derivative monomer mixing
-2mmol) Pd (PPh
3)
4catalyzer and toluene react 72 hours at 90 ℃.After being cooled to room temperature, be added dropwise in anhydrous methanol, after filtration, obtain copolymer p 3 crude products.After being dried, use respectively methyl alcohol again, obtain 0.132 g atropurpureus solid P3 after normal hexane and chloroform extracting, its structural formula as shown in Figure 6.
Embodiment 9
Prepare fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P3
Under oxygen-free environment, by (0.25g, 0.251mmol) monomer 2,6-bis-(tin trimethyl)-4,8-bis-(2-hexyl nonyl oxygen base)-benzene 1,4-Dithiapentalene and (0.1196g, 0.251mmol) pentafluorophenyl group-4
h-thiophene [3,4-c] pyrroles 4,6-(5
h) rear (11mg, 1.000 * 10 of successively adding of diketone bromo-derivative monomer mixing
-2mmol) Pd(PPh
3)
4catalyzer and chlorobenzene organic solvent react 12 hours at 110 ℃.After being cooled to room temperature, be added dropwise in anhydrous methanol, after filtration, obtain copolymer p 3 crude products.After being dried, use respectively again methyl alcohol, after normal hexane and chloroform extracting, obtain atropurpureus solid P3.
Embodiment 10
The preparation of the solar cell device that fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P1 of take are active coating.
Active layer material comprises fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P1 of the present invention as electron donor material, [6, 6] phenyl-C61-methyl-butyrate (being called for short PCBM) is as electron acceptor material, be that device architecture is glass/ITO/PEDOT:PSS/ active coating/Al, wherein ito glass is after ultrasonic cleaning, with oxygen-Plasma, process, on ITO, coat PEDOT:PSS, then the fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P1 in the present invention and PCBM are covered with spin coating after orthodichlorobenzene dissolving blend, evaporation negative electrode aluminum metal again, obtain polymer solar device, its structure is as Fig. 8.
Wherein to be fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P1 and PCBM dissolve with orthodichlorobenzene the film that spin coating covers after blend to the polymer active layer in Fig. 8.
Embodiment 11
The preparation of the solar cell device that fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P2 of take are active coating.
Active layer material comprises fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P2 of the present invention as electron donor material, and [6,6] phenyl-C71-methyl-butyrate (is called for short PC
71bM) as electron acceptor material, be that device architecture is glass/ITO/PEDOT:PSS/ active coating/Al, wherein ito glass is after ultrasonic cleaning, with oxygen-Plasma, process, on ITO, coat PEDOT:PSS, then by fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P2 and the PC in the present invention
71after BM dissolves blend with orthodichlorobenzene, spin coating covers above, then evaporation negative electrode aluminum metal, obtains polymer solar device.
Embodiment 12
The preparation of the solar cell device that fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P3 of take are active coating.
Active layer material comprises fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P3 of the present invention as electron donor material, and [6,6] phenyl-C61-methyl-butyrate (is called for short PC
61bM) as electron acceptor material, be that device architecture is glass/ITO/PEDOT:PSS/ active coating/Al, wherein ito glass is after ultrasonic cleaning, with oxygen-Plasma, process, on ITO, coat PEDOT:PSS, then by fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers P3 and the PC in the present invention
61after BM dissolves blend with chlorobenzene, spin coating covers above, then evaporation negative electrode aluminum metal, obtains polymer solar device.
Claims (11)
1. fluorine-containing Thienopyrroles two one monomers, have following structure:
2. fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers, have following structure:
Wherein, the integer that n is 10～100; R
1, R
2be selected from hydrogen; C
1～C
20alkyl or phenyl.
3. fluorine-containing Thienopyrroles two one monomers and a multipolymer preparation method thereof, is characterized in that:
Be full of under the oxygen-free environment of rare gas element 3,4-thiophene dioctyl phthalate and thionyl chloride are mixed after in 10～100 ℃ of reactions 1～14 hour, be cooled to room temperature, underpressure distillation obtains crude product 3,4-thiophene dimethyl chloride;
Be full of under the oxygen-free environment of rare gas element crude product 3,4-thiophene dimethyl chloride and organic solvent heating for dissolving, slowly splash into the toluene solution that contains penta fluoro benzene amine, 10～120 ℃ of reaction 1-14 hour, are cooled to room temperature, revolve steaming, extraction, washing, obtains pentafluorophenyl group-4H-thiophene [3 after column chromatography is refining, 4-c] and pyrroles 4,6-(5H) diketone white crystal;
Pentafluorophenyl group-4H-thiophene [3,4-c] pyrroles 4,6-(5H) in diketone, add N-bromo-succinimide, trifluoroacetic acid and dense H
2sO
4mixed solution, under lucifuge condition, 0～70 ℃ of reaction 1～24h, after reaction finishes, revolves steaming, extraction, washing, obtains pentafluorophenyl group-4H-thiophene [3,4-c] pyrroles 4,6-(5H) diketone bromo-derivative after column chromatography is refining) monomer;
Under oxygen-free environment, by benzo two thiophene derivant monomers and pentafluorophenyl group-4H-thiophene [3,4-c] pyrroles 4,6-(5H) diketone bromo-derivative monomer mixed, and successively adds organic palladium catalyzer and organic solvent, in 40～110 ℃ of reactions 12～72 hours; After being cooled to room temperature, be added dropwise in anhydrous methanol, after filtration, obtain multipolymer crude product; After crude product is dry, use respectively again methyl alcohol, after normal hexane and chloroform extracting, obtain the fluorine-containing Thienopyrroles diketone-benzo of atropurpureus two thiophene copolymers solids.
4. a kind of fluorine-containing Thienopyrroles two one monomers according to claim 3 and multipolymer preparation method thereof, is characterized in that in the preparation of described thiophene dimethyl chloride crude product, and the mol ratio of 3,4-thiophene, two first acid ︰ penta fluoro benzene amine is 1:(1.1～3).
5. a kind of fluorine-containing Thienopyrroles two one monomers according to claim 3 and multipolymer preparation method thereof, is characterized in that in described mixed solution, the volume ratio of trifluoroacetic acid and the vitriol oil is 1:(0.1～1).
6. a kind of fluorine-containing Thienopyrroles two one monomers according to claim 3 and multipolymer preparation method thereof, is characterized in that in the described toluene solution that contains penta fluoro benzene amine, and the massfraction of penta fluoro benzene amine is than being 1:(3～30).
7. a kind of fluorine-containing Thienopyrroles two one monomers according to claim 3 and multipolymer preparation method thereof, it is characterized in that described pentafluorophenyl group-4H-thiophene [3,4-c] and pyrroles 4,6-(5H) in the preparation of diketone bromo-derivative monomer, pentafluorophenyl group-4H-thiophene [3,4-c] and pyrroles 4,6-(5H) diketone: N mono-bromo-succinimide: the mol ratio of trifluoroacetic acid is 1:(2～5): (10～100).
8. a kind of fluorine-containing Thienopyrroles two one monomers according to claim 3 and multipolymer preparation method thereof, it is characterized in that described benzo two thiophene derivant monomers refer to 2,6-bis-(tin trimethyl)-4,8-bis-(2-octyl group undecyl oxygen base)-benzo two thiophene monomers, 2,6-bis-(tin trimethyl)-4,8-diheptyl-benzo two thiophene monomers or 2,6-bis-(tin trimethyl)-4,8-bis-(2-hexyl nonyl oxygen base)-benzo two thiophene monomers.
9. a kind of fluorine-containing Thienopyrroles two one monomers according to claim 3 and multipolymer preparation method thereof, is characterized in that described fluorine-containing Thienopyrroles two one monomers of benzo two thiophene derivant list body ︰: the mol ratio of organic palladium catalyzer is 1 ︰ 1 ︰ (0.01～0.1).
10. a kind of fluorine-containing Thienopyrroles two one monomers according to claim 3 and multipolymer preparation method thereof, is characterized in that described described organic palladium catalyzer is Pd
2(dba)
3or Pd(PPh
3)
4; Described organic solvent is tetrahydrofuran (THF), benzene, toluene, chlorobenzene or dioxane.
11. 1 kinds of fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers are applied in polymer solar battery, it is characterized in that: be full of under the oxygen-free environment of rare gas element, fluorine-containing Thienopyrroles diketone-benzo two thiophene copolymers in the present invention and PCBM are covered with spin coating after orthodichlorobenzene dissolving blend, evaporation negative electrode aluminum metal, obtains polymer solar device again.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119354A (en) * | 2014-05-14 | 2014-10-29 | 杭州师范大学 | Cross benzodithiophene compound and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011063534A1 (en) * | 2009-11-30 | 2011-06-03 | UNIVERSITé LAVAL | Novel photoactive polymers |
| JP2011168747A (en) * | 2010-02-22 | 2011-09-01 | Kyoto Univ | Conjugated polymer, and organic thin film solar cell using the same |
| CN102812016A (en) * | 2009-09-04 | 2012-12-05 | 普莱克斯托尼克斯公司 | Organic Electronic Devices And Polymers, Including Photovoltaic Cells And Diketone-based Polymers |
| JP2012241017A (en) * | 2011-05-13 | 2012-12-10 | Mitsubishi Chemicals Corp | Polymer, organic semiconductor material, and organic electronic device, photoelectric transducer, and solar cell module using the organic semiconductor material |
| WO2013047858A1 (en) * | 2011-09-29 | 2013-04-04 | 住友化学株式会社 | High-molecular-weight compound and organic photoelectric conversion element |
| JP2013065722A (en) * | 2011-09-16 | 2013-04-11 | Mitsubishi Chemicals Corp | Photoelectric conversion element and solar cell module |
| CN103380506A (en) * | 2011-01-28 | 2013-10-30 | 三菱化学株式会社 | Photoelectric conversion element, solar cell, and solar cell module |
-
2013
- 2013-11-25 CN CN201310603651.5A patent/CN103694457A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102812016A (en) * | 2009-09-04 | 2012-12-05 | 普莱克斯托尼克斯公司 | Organic Electronic Devices And Polymers, Including Photovoltaic Cells And Diketone-based Polymers |
| WO2011063534A1 (en) * | 2009-11-30 | 2011-06-03 | UNIVERSITé LAVAL | Novel photoactive polymers |
| JP2011168747A (en) * | 2010-02-22 | 2011-09-01 | Kyoto Univ | Conjugated polymer, and organic thin film solar cell using the same |
| CN103380506A (en) * | 2011-01-28 | 2013-10-30 | 三菱化学株式会社 | Photoelectric conversion element, solar cell, and solar cell module |
| JP2012241017A (en) * | 2011-05-13 | 2012-12-10 | Mitsubishi Chemicals Corp | Polymer, organic semiconductor material, and organic electronic device, photoelectric transducer, and solar cell module using the organic semiconductor material |
| JP2013065722A (en) * | 2011-09-16 | 2013-04-11 | Mitsubishi Chemicals Corp | Photoelectric conversion element and solar cell module |
| WO2013047858A1 (en) * | 2011-09-29 | 2013-04-04 | 住友化学株式会社 | High-molecular-weight compound and organic photoelectric conversion element |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119354A (en) * | 2014-05-14 | 2014-10-29 | 杭州师范大学 | Cross benzodithiophene compound and preparation method thereof |
| CN104119354B (en) * | 2014-05-14 | 2016-08-24 | 杭州师范大学 | A kind of cross benzo two thiophene compound and preparation method thereof |
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