WO2011116516A1 - 含芴卟啉-苯共聚物、其制备方法和应用 - Google Patents

含芴卟啉-苯共聚物、其制备方法和应用 Download PDF

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WO2011116516A1
WO2011116516A1 PCT/CN2010/071228 CN2010071228W WO2011116516A1 WO 2011116516 A1 WO2011116516 A1 WO 2011116516A1 CN 2010071228 W CN2010071228 W CN 2010071228W WO 2011116516 A1 WO2011116516 A1 WO 2011116516A1
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porphyrin
organic
containing benzene
benzene copolymer
reaction
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PCT/CN2010/071228
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English (en)
French (fr)
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周明杰
黄杰
刘贻锦
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海洋王照明科技股份有限公司
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Priority to PCT/CN2010/071228 priority Critical patent/WO2011116516A1/zh
Priority to EP10848178.9A priority patent/EP2551271B1/en
Priority to US13/582,807 priority patent/US8546512B2/en
Priority to JP2012555280A priority patent/JP5688420B2/ja
Priority to CN201080061237.0A priority patent/CN102712652B/zh
Publication of WO2011116516A1 publication Critical patent/WO2011116516A1/zh

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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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    • H—ELECTRICITY
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    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of organic materials, and in particular to a porphyrin-containing benzene copolymer, a preparation method thereof and an application thereof.
  • Organic solar cells are a new type of solar cells. Compared with inorganic semiconductor materials, which are limited in source, expensive, toxic, complicated in preparation process and high in cost, they have some advantages that inorganic solar cells cannot match, such as a wide range of materials. Structure diversity and controllability, low cost, safety and environmental protection, simple production process, light weight, large area flexible preparation, etc., can be widely used in various fields such as construction, lighting and power generation, with important development and application. prospect. However, to the eyes Until now, the photoelectric conversion efficiency of organic solar cells has been lower than that of inorganic solar cells. Therefore, the development of new organic materials is of great significance for improving the efficiency of organic solar cells and other semiconductor devices or optoelectronic devices. Summary of the invention
  • a porphyrin-benzene-containing copolymer having a wide light-response response and good stability and a preparation method of a porphyrin-benzene-containing copolymer having a simple synthesis route and low cost are provided.
  • the embodiment of the invention further provides the above porphyrin-containing benzene copolymer in an organic photoelectric material, a solar cell device, an organic field effect transistor, an organic electroluminescent device, an organic optical storage device, an organic nonlinear material or an organic laser device. application.
  • a porphyrin-containing benzene copolymer comprising the copolymer represented by the following structural formula (1):
  • R 2 , R 3 and R 4 are the same or different -C 16 alkyl groups; n is an integer from 1 to 100.
  • a method for preparing a porphyrin-containing benzene copolymer comprising the steps of:
  • R 2 , R 3 , R 4 are the same or different C An alkyl group of C 16 ;
  • the compound VIII, B and 1,4--p-dipyrrolyl fluorenylbenzene are subjected to a polycondensation oxidation reaction to obtain a copolymer represented by the following structural formula (1); or
  • the compound, B and dipyrrolidine are subjected to a polycondensation oxidation reaction, and the product is subjected to a bromination substitution reaction to obtain a brominated product and then 1,4-bis (4, 4, 5, The 5-tetradecyl-1,3,2-dioxaborolanylbenzene is subjected to a Suzuki coupling reaction to obtain a copolymer represented by the following structural formula (1):
  • n in the structural formula (1) is an integer of 1-100.
  • the ruthenium or its derivative contained has excellent photothermal stability and film formability, and has an easily modified structure, and the above copolymer also introduces benzene into the polymer.
  • the ring can increase the density of the electron cloud of the polymer skeleton, so that the band gap of the fluorenyl copolymer is narrowed, and the range of the light word response is wider.
  • the porphyrin structure enables the copolymer to have higher quantum efficiency of charge transfer and energy transfer reactions, good electron buffering and photoelectricity, good rigidity, good thermal stability and environmental stability.
  • the photoelectricity thereof can be improved Or semiconductor-related performance, and can reduce the quality of the device, and is easy to Batch preparation.
  • FIG. 1 is a schematic view showing the structural formula of a porphyrin-containing benzene copolymer according to an example of the present invention.
  • FIG. 2 is a flow chart showing a preparation method of a porphyrin-containing benzene copolymer according to an embodiment of the present invention.
  • Fig. 3 is a schematic view showing the structure of a porphyrin-benzene copolymer-containing solar cell device using an embodiment of the present invention.
  • Fig. 4 is a view showing the structure of an organic electroluminescent device containing a porphyrin-benzene copolymer according to an embodiment of the present invention.
  • Fig. 5 is a view showing the structure of an organic field effect transistor containing a porphyrin-benzene copolymer according to an embodiment of the present invention. detailed description
  • a structural formula of a porphyrin-containing benzene copolymer according to an embodiment of the present invention which is a copolymer represented by the following structural formula (1):
  • R 2 , R 3 and R 4 are the same or different alkyl groups of Crds; n is an integer of 1 -.
  • fluorene-containing porphyrin - each cell in the two benzene copolymer containing alkylfluorenyl groups are the same, i.e., for example, R 3 are the same C r C 16 alkyl , R 2, R 4 are the same C r C 16 alkyl group, or in other words, R R4 are the same C r C 16 alkyl group, R 2, R 3 are the same dC 16 alkyl.
  • R 3 are the same C r C 16 alkyl
  • R 2 are the same C r C 16 alkyl group
  • R 4 are the same C r C 16 alkyl group
  • R 2 , R 3 and R 4 are the same ( ⁇ -0 16 alkyl group.
  • n is preferably from 5 to 50, more preferably from 10 to 30.
  • Ri, R 2 , R 3 and R 4 are alkyl groups of 0 6 or more.
  • the porphyrin-containing benzene copolymer includes hydrazine or a derivative thereof, a porphyrin structure, and a benzene ring structure.
  • ruthenium or a derivative thereof has excellent photothermal stability and film formability, and has an easily modified structure.
  • a benzene ring structure is introduced to increase a skeleton electron cloud containing a porphyrin-benzene copolymer.
  • the density of the copolymer narrows the band gap and broadens the spectral absorption range.
  • the porphyrin structure enables the copolymer to have higher quantum efficiency of charge transfer and energy transfer reaction, good electron buffering and photoelectricity, good rigidity, good thermal stability and environmental stability.
  • the porphyrin-containing benzene copolymer has a broad spectral response, the wavelength band is about 300-700 nm, and substantially covers the visible light band, and has better thermal stability and environmental stability, and exhibits better performance. Photoelectric performance.
  • R 2 , R 3 preferably an alkyl chain, for example, an alkyl chain of C 6 or more, is advantageous in that the solubility of the material is improved by introducing an alkyl chain. Film forming processing expands its range of applications.
  • the preparation method of the above porphyrin-benzene-containing copolymer comprises the following steps:
  • R 2 , R 3 , R 4 are the same or different C An alkyl group of C 16 ;
  • n in the structural formula (1) is an integer of 1-100.
  • step S01 the compounds A and B can be directly obtained from the market or prepared by an existing synthesis method.
  • the description is the same as the above description of the porphyrin-containing benzene copolymer, and R 2 , R 3 and R 4 are in the structural form described above, and are not described herein again.
  • R 3 is the same dC 16 alkyl group
  • R 2 and R 4 are the same C ds alkyl group, in which case the compounds VIII and B have the same structure, thereby Providing one less material simplifies the preparation process and reduces the cost, and has a higher yield relative to the use of different compounds A and B.
  • the preparation thereof comprises the following steps:
  • a substitution reaction of 2-bromoindole with a bromine in a catalyst or an organic solvent to obtain 9,9-dialkyl-2-bromoindole is obtained.
  • the catalyst is tetrabutylammonium bromide or benzyltriethylammonium chloride
  • the organic solvent is toluene, disulfoxide or tetrahydrofuran.
  • the brominated alkane is a brominated alkane having an alkyl group of R 2 .
  • the two reaction steps i.e., steps i and ii, are carried out separately using two bromodes (when R 2 are the same), and the reaction route is as follows:
  • reaction of bromination hydroformylation in an alkyllithium, dimercaptoamide and an organic solvent system is as follows:
  • the alkyl lithium is n-butyllithium
  • the organic solvent may be tetrahydrofuran.
  • the condensation reaction is carried out in a system containing furfural, a catalyst and pyrrole to obtain dipyrrolidine, and the reaction equation is as follows:
  • the catalyst of step iv may be trifluoroacetic acid or boron trifluoride complex of boron trifluoride.
  • the substance (BF 3 .(CH 3 ) 2 0) is not limited thereto; the pyrrole is both an organic solvent and a reactant.
  • Detailed procedures for the preparation of dipyrrole can be found in the literature: "Tetrahedron" Tetrahednm, 1994, 39, 1 1427.
  • the condensation reaction is carried out in a system containing terephthalic acid, a catalyst and pyrrole to obtain 1,4-di-p-pyrrolylnonylbenzene, and the reaction equation is as follows:
  • the catalyst of the step iv' may be trifluoroacetic acid or a boron trifluoride dimercaptooxy complex (BF 3 CH 3 ) 2 0), and is not limited thereto; the pyrrole is an organic solvent and a reactant .
  • a boron trifluoride dimercaptooxy complex BF 3 CH 3 ) 2 0
  • step S02 two different reactants based on dipyrrolidine and 1,4--p-dipyrrolylnonylbenzene can be classified into two schemes.
  • the first scheme is: polycondensation and oxidation reaction of compound VIII, B with 1,4-p-dipyrrolyl fluorenylbenzene in a system containing a catalyst, an oxidizing agent and an organic solvent to obtain the above porphyrin-containing benzene copolymer .
  • the second scheme is: in a system containing a catalyst, an oxidant and an organic solvent, the compound, B and dipyrrolidine are subjected to a polycondensation oxidation reaction, and the product is subjected to a bromination substitution reaction to obtain a brominated product and then 1,4. -Suzuki coupling reaction of bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan)benzene to obtain the above porphyrin-containing benzene copolymer.
  • the molar ratio of each reactant may be the following reaction according to the chemical reaction ratio or other reaction ratio, for example, an excess of some reactants, without affecting the progress of the reaction. The following is introduced separately.
  • the first scheme for realizing step S02 is carried out by polycondensation and oxidation of the compounds A, B and 1,4 p-dipyrrolylnonylbenzene.
  • the catalyst for the polycondensation oxidation reaction may be trifluoroacetic acid or the like, and the oxidizing agent may be dichlorodiphenyl benzoquinone (DDQ) or the like, and is not limited thereto.
  • the organic solvent may be dichlorosilane, tetrahydrofuran, or the like. Carbon chloride, chloroform or acetonitrile. Its reaction formula is as follows:
  • the specific implementation process is as follows: Set up the anhydrous oxygen-free device, weigh the compound A, B and 1,4 p-dipyrrolyl nonylbenzene (in a molar ratio of 1/1/1), add to the reaction vessel, and dissolve in an organic solvent. Add appropriate amount of trifluoroacetic acid, stir overnight (for example, 12-14 hours), add two molar equivalents (that is, twice the reaction ratio) of dichlorodiphenyl benzoquinone, continue stirring, add triethylamine Eliminate the reaction.
  • the following purification is carried out: concentration, filtration, washing the solid, collecting the filtrate, distilling off half of the solvent, adding a methanol solution, static precipitation, filtering, collecting the solid, separating it by silica gel column chromatography and drying to obtain the product, that is, the above-mentioned hydrazine Porphyrin-benzene copolymer.
  • the silica gel column chromatography was carried out using petroleum acid/ethyl acetate as the eluent.
  • the second solution of the implementation step S02 specifically includes the following steps:
  • a compound, B and dipyrrolidine are subjected to a polycondensation oxidation reaction to form a mercaptoporphyrin compound.
  • This step 1) is similar to the reaction of the first embodiment, and the principle is basically the same, and is also a polycondensation oxidation reaction, except that the reactant is dipyrrolidine, thereby obtaining a mercaptoporphyrin compound.
  • the catalyst may be trifluoroacetic acid or the like
  • the oxidizing agent may be dichlorodiyl phenylhydrazine or the like, and is not limited thereto.
  • the organic solvent may be dichlorosilane, tetrahydrofuran, carbon tetrachloride or chloroform. Or acetonitrile, etc. Its reaction formula is as follows:
  • the specific implementation process is as follows: set up a waterless and oxygen-free device, weigh the compounds A, B and dipyrrolidine (for example, weighed in 1/1/2 of the molar ratio), dissolve in an organic solvent, pass nitrogen, add three Fluoroacetic acid, stirred, then add two molar equivalents of dichlorodiphenyl benzoquinone, continue to stir, then add triethylamine to quench the reaction, then purify as follows: Concentrate the organic solvent, filter, collect the filtrate and spin dry the organic solvent The mixture was quickly rinsed on a silica gel column with dichloromethane, the organic solvent was evaporated, and the product was recrystallized from acetic acid/nonyl alcohol to give the product, that is, the mercaptoporphyrin compound.
  • the sulfhydryl porphyrin compound produced in the step 1) is subjected to a bromination substitution reaction in a system containing a catalyst and an organic solvent to form a dibromo-substituted fluorenyl porphyrin compound.
  • the catalyst may be, but not limited to, pyridine, a pyridine derivative or triethylamine
  • the organic solvent may be, but not limited to, chloroform, tetrahydrofuran, dimercaptophthalamide (DMF), carbon tetrachloride, dichlorodecane or acetonitrile.
  • N-bromosuccinimide (NBS), Br 2 , HBr or PBr 3 or the like is added as a bromine source, preferably NBS.
  • NBS N-bromosuccinimide
  • the specific implementation process is as follows: a mercaptoporphyrin compound (such as 5,15-bis(9,9-dialkylfluorene) porphyrin) is dissolved in chloroform, a small amount of pyridine is added, and the reactant is lowered to 0 ° C. An appropriate amount of N-bromosuccinimide was added, and after stirring, the mixture was returned to room temperature, and then stirring was continued for several hours. The reaction was quenched by the addition of acetone, the solvent was removed, and the product was recrystallized from acetic acid / methanol.
  • the reaction is as follows:
  • the catalyst in the step 3) may be an organic palladium catalyst in an amount of 1,4-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan)benzene. 0.1-20% of the dosage.
  • the organic palladium catalyst may be, for example but not limited to, Pd 2 (dba) 3 /P(o-Tol) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 .
  • the organic solvent may be, but not limited to, tetrahydrofuran, dichlorodecane, ethylene glycol dioxime ether, benzene or toluene, and the like, and is preferably anthracene.
  • the organic solvent is used in an amount sufficient to dissolve and sufficiently react the respective reactants.
  • the alkaline solution may be an inorganic alkali solution or an organic alkali solution, and the inorganic alkali solution may be an aqueous solution of an alkali metal hydroxide or an alkali metal carbonate, and may be, for example but not limited to, a sodium hydroxide solution, a potassium hydroxide solution, or a sodium carbonate.
  • the solution, the potassium carbonate solution or the like is preferably a sodium carbonate solution
  • the organic alkali solution may be an aqueous solution of an alkyl ammonium hydroxide, such as, but not limited to, tetradecyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl hydroxide.
  • the above alkaline solution may be used in an amount of 5 to 20 times the molar amount of the compound D.
  • 1,4-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan)benzene can be prepared in advance, for example by butyllithium. Prepared by the following substitution reaction under the action of boron ester:
  • the specific implementation process is as follows: Under the protection of N 2 , add p-dibromobenzene to a three-necked bottle, inject a tetrahydrofuran solvent into a syringe, and slowly inject n-butyllithium with a syringe at -78 ° C, and continue to stir the reaction number. Hours, at -78. 2-Isopropoxy-4,4,5,5-tetradecyl-1,3,2-dioxaborolane was injected into a syringe under C conditions, and stirred at room temperature overnight (about 12-14 hours).
  • reaction was quenched by the addition of a saturated aqueous solution of sodium chloride, and extracted with chloroform and dried over anhydrous sodium sulfate, and the filtrate was collected and evaporated. Finally, the crude product was separated by silica gel column chromatography using petroleum acid/ethyl acetate as eluent to give the product.
  • the specific implementation process of the step 3) is as follows: 1,4-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan)benzene, 5 is added to the reaction vessel. 15-Dibromo-10,20-bis(9,9-dialkylfluorene)porphyrin, tetrakis(triphenylphosphine)palladium, wherein the first two reactants can be used in an amount of 1/1, tetrakis (triphenyl) Palladium is used as a catalyst in an amount of about 0.1-20% by mole of the reactant, and a certain amount of an aqueous solution of Na 2 CO 3 and an organic solvent such as toluene are added to dissolve the reactant, and then the reaction vessel is evacuated to remove oxygen.
  • the solution is heated to 50-120 ° C, the reaction for 12-80 hours.
  • the product is then purified: the product of the reaction is poured into methanol, the precipitate is separated by filtration through a Buchner funnel, washed with dilute HC1, and the solid is washed with acetone in a Soxhlet extractor for 12-72 hours to remove The monomer and catalyst residue, the remaining polymer was dissolved in tetrahydrofuran and chloroform, which is the copolymer of this example.
  • the n in the copolymer is preferably from 5 to 50, more preferably from 10 to 30.
  • the choice of organic solvent, reaction temperature, reaction The time, the amount of the reactant added, the type and amount of the catalyst are controlled to obtain the desired degree of polymerization.
  • the compounds A, B and 1,4 p-dipyrrolylnonylbenzene are directly synthesized into a copolymer, and the synthesis route is relatively simple and mature, and is basically a one-step synthesis, thereby reducing the process.
  • the process reduces the manufacturing cost.
  • both the bromination substitution reaction and the Suzuki coupling reaction are mature reactions, so the synthesis route is relatively mature, the manufacturing cost is low, and the yield is high, the conditions are mild, and the control is easy. Both schemes readily increase the solubility and molecular weight of the product by introducing an alkyl group to achieve a spin coatable polymer.
  • the porphyrin-containing benzene copolymer of the present embodiment can be used as an organic photoelectric material in various photoelectric or semiconductor devices, for example, for organic photoelectric materials, solar cell devices, organic field effect transistors, and organic electroluminescent devices. , organic optical storage devices, organic nonlinear materials and organic laser devices.
  • the organic photoelectric material includes the above porphyrin-containing benzene copolymer for use as an electron donor material or a photoelectric conversion material.
  • the solar cell device, the organic field effect transistor, and the organic electroluminescent device will be described below as an example.
  • Others such as organic optical storage devices, organic nonlinear materials and organic laser devices are similar to the following, using the porphyrin-containing benzene copolymer of the present embodiment as its optical storage material, nonlinear material, laser material or semiconductor material. Wait.
  • a solar cell device comprising the porphyrin-benzene copolymer in the above embodiment, comprising a glass substrate 11, a transparent anode 12, an intermediate auxiliary layer 13, an active layer 14, and a cathode 15 which are sequentially laminated.
  • the auxiliary layer 13 is made of polyethylene dioxythiophene: polystyrene-cross-acid composite material (abbreviated as PEDOT:PSS), the active layer 14 includes an electron donor material and an electron acceptor material, and the electron donor material adopts the above-mentioned ruthenium-containing material.
  • the porphyrin-benzene copolymer, the electron acceptor material may be [6,6]phenyl-C 61 -butyric acid decanoate (abbreviated as PCBM).
  • the transparent anode 12 may be indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ /.
  • the cathode 15 may be an aluminum electrode or a bimetal layer electrode such as Ca/Al or Ba/Al or the like. Wherein, the glass base layer 11 can be used as the bottom layer.
  • the ITO glass When the ITO glass is selected, it is ultrasonically cleaned, treated with oxygen-Plasma, and the intermediate auxiliary layer 13 is coated on the ITO glass, and then the porphyrin-benzene copolymer and The electron acceptor material is coated (eg, spin-coated) on the intermediate auxiliary layer 13 by blending to form the active layer 14, and then the cathode 15 is deposited on the active layer 14 by vacuum evaporation to obtain A solar cell device.
  • the thickness of the transparent anode 12, the intermediate auxiliary layer 13, the active layer 14, the bimetal layer Ca, and the A1 layer are 160 nm, 40 nm, 150 nm, 20 nm, and 70 nm, respectively.
  • the porphyrin-containing benzene copolymer can more fully utilize light energy due to its wide optical response range, thereby achieving higher photoelectric conversion efficiency and increasing the power generation capability of the solar cell device.
  • the organic material can also reduce the quality of the solar cell device, and can be produced by a technique such as spin coating by introducing an alkyl group, which is convenient for mass production.
  • an organic electroluminescent device comprising the porphyrin-benzene copolymer in the above embodiment is shown, which comprises a glass base layer 21, a transparent anode 22, a light-emitting layer 23, a buffer layer 24, which are sequentially stacked.
  • the transparent anode 22 may be indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ /.
  • the light-emitting layer 23 contains the porphyrin-containing benzene copolymer in the above examples.
  • the buffer layer 24 may be LiF or the like, but is not limited thereto.
  • the cathode 25 may be, but not limited to, metal A1 or Ba or the like, but is not limited thereto.
  • the organic electroluminescent device structure is represented by: ITO/porphyrin-containing benzene copolymer/LiF/Al.
  • the layers can be formed by existing methods, and the porphyrin-benzene-containing copolymer can be formed on ITO by a spin coating technique.
  • an organic field effect transistor comprising the porphyrin-benzene copolymer in the above embodiment is shown, which comprises a substrate 31, an insulating layer 32, a modifying layer 33, an organic semiconductor layer 34 and a layer which are sequentially stacked.
  • the substrate 31 may be, but not limited to, a highly doped silicon wafer (Si), and the insulating layer 32 may be, but not limited to, a micro-nano (eg, 450 nm) thick Si0 2 .
  • the organic semiconductor layer 34 employs the porphyrin-containing benzene copolymer described above.
  • Source electrode 35 Both the drain electrode 36 and the drain electrode 36 can be used without limitation.
  • the modifying layer 33 can be, but is not limited to, octadecyltrichlorosilane.
  • the substrate 31, the insulating layer 32, the modifying layer 33, and the source electrode 35 and the drain electrode 36 can be formed by a conventional method.
  • the organic semiconductor layer 34 may be a spin coating of the porphyrin-containing benzene copolymer in the above embodiment on the insulating layer 32 modified by the modifying layer 33.
  • Ri, R 2 , R 3 and R 4 are taken as an example, and the structural formula is as follows:
  • the porphyrin-containing benzene copolymer of the first embodiment has a symmetric dimercapto structure, and the porphyrin-containing benzene copolymer has better light absorption by such a uniform symmetrical structure.
  • the preparation method of the porphyrin-containing benzene copolymer of the first embodiment adopts the first scheme, and the compounds A and B are 9, since R 2 , R 3 and R 4 both adopt a hexyl group. 9-Dihexyl-2-aldehyde oxime, thus only one kind of raw material is needed, which simplifies the preparation process and reduces the cost, and the yield is high. If it is not such a symmetrical structure, then the compounds A and B are different in structure, and it is necessary to obtain different raw materials, and the by-products are relatively more.
  • the specific preparation process is as follows: weigh 9,9-dihexyl-2-aldoxime and 1,4-p-dipyrrolylnonylbenzene (in a molar ratio of 2/1), and add to the reaction vessel, using dichloroanthracene.
  • the hexyl group is taken as an example of R 2 , R 3 and R 4 , except that the second scheme is adopted, and the specific operation is as follows:
  • 5,15-bis(9,9-dihexylindole) porphyrin is prepared.
  • the specific process is as follows: Set up an anhydrous oxygen-free device, and weigh compounds A and B according to a molar ratio of 1: 1: 2 Dipyrrole, the compounds A and B are of the same structure, all of which are 9,9-dihexyl-2-aldoxime, which are dissolved in dichloromethane, and nitrogen gas is introduced for 30 minutes, and an appropriate amount of trifluoroacetic acid is added by a syringe.
  • the third step the preparation of the porphyrin-benzene copolymer, the specific process is as follows: Add 1.0 mmol 1,4-bis(4,4,5,5-tetradecyl-1,3,2) to the round bottom flask. - dioxaborolan) hydrazine, 1.0 mmol 5, 15-dibromo-10,20-di(9,9-dialkylfluorene) porphyrin, 0.01 mmol tetrakis(triphenylphosphine)palladium, 3 Mol Na 2 C0 3 aqueous solution (2 11101 / 1 ⁇ and 20 1111 benzene solvent, vacuum deoxidation, and filled with nitrogen, the solution was first refluxed under N 2 atmosphere for 48 hours, the reaction was carried out.
  • the product was subjected to Purification: The reaction product was poured into methanol, and the precipitate was separated by filtration using a Buchner funnel and washed with dilute HC1. The solid was washed with acetone in a Soxhlet extractor for 12-72 hours to remove monomer and catalyst residue. The lower polymer is dissolved in tetrahydrofuran With chloroform, the yield is about 30-51%.
  • the ruthenium or its derivative contained has excellent photothermal stability and film formability, and has an easily modified structure, and the above copolymer also introduces benzene into the polymer.
  • the ring can increase the density of the electron cloud of the polymer skeleton, so that the band gap of the fluorenyl copolymer is narrowed, and the range of the light word response is wider.
  • the porphyrin structure enables the copolymer to have higher quantum efficiency of charge transfer and energy transfer reactions, good electron buffering and photoelectricity, good rigidity, good thermal stability and environmental stability.
  • the photoelectricity thereof can be improved Or semiconductor-related properties, and can reduce the quality of the device, and facilitate the preparation of large quantities.

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Description

含芴卟啉 -苯共聚物、 其制备方法和应用 技术领域 本发明属于有机材料技术领域， 具体涉及一种含芴卟啉 -苯共聚物、 其制备 方法和应用。
说 背景技术
当今世界经济主要是建立在以化石能源， 如煤炭、 石油和天然气等基石出之 上的经济。然而，这些不可再生的化石能源都在书不断的枯竭。进入 21世纪以来， 全球性的能源问题以及随之而来的环境污染和气候变暖等问题日益凸现和逐渐 加剧。 由于太阳能具有分布普遍和广阔， 资源数量多， 无污染， 清洁， 安全以 及获取方便等突出优点， 被认为是最有希望的可再生能源之一。
为充分利用太阳光照射的能量， 人们不断开发出能够吸收太阳光的新型材 料， 其中无机半导体材料获得较为广泛的发展和应用， 例如目前用于地面的硅 晶电池， 然而由于其生产工艺复杂、 成本高， 使其应用受到限制。 为了降低成 本， 拓展应用范围， 长期以来人们一直在寻找新型的替代的半导体材料。
近年来，有机材料逐渐引起人们广泛的兴趣，例如，在 1992年 N. S. Sariciftci 等报道了共轭聚合物与 C6。之间的光诱导电子转移现象后， 人们在共轭聚合物 用作太阳能电池等方面投入了大量研究， 并取得了飞速的发展。 太阳能电池直 接把太阳光能转化成电能， 是利用太阳能切实可行的有效方法。
有机太阳能电池是一种新型的太阳能电池， 相对于无机半导体材料来源有 限、 价格昂贵、 有毒、 制备工艺复杂、 成本太高等而言， 它具有无机太阳能电 池无法比拟的一些优点， 如材料来源广泛、 结构多样性和可调控性、 成本低廉、 安全环保、 制作工艺简单、 产品重量轻、 可大面积柔性制备等等， 可以广泛应 用在建筑、 照明和发电等多种领域， 具有重要的发展和应用前景。 然而， 到目 前为止， 有机太阳能电池的光电转换效率比无机太阳能电池还是要低 ^艮多。 因 此， 开发新型的有机材料对于提高有机太阳能电池及其它半导体器件或光电器 件的效率具有重要意义。 发明内容
有鉴于此， 提供一种光语响应宽、 稳定性好的含芴卟啉 -苯共聚物， 以及一 种合成路线简单、 成本低的含芴卟啉-苯共聚物制备方法。
本发明实施例还提供上述含芴卟啉-苯共聚物在有机光电材料、太阳能电池 器件、 有机场效应晶体管、 有机电致发光器件、 有机光存储器件、 有机非线性 材料或有机激光器件中的应用。
一种含芴卟啉 -苯共聚物， 其包含如下结构式（1 )表示的共聚物：
Figure imgf000004_0001
( 1 )
式中： R2、 R3、 R4为相同或不相同的 -C16的烷基； n为 1-100的整 数。
一种含芴卟啉-苯共聚物制备方法， 其包括如下步骤：
分别提供如下结构式表示的化合物 A和 B, 以及二吡咯曱烷或 1,4 对二吡 咯基曱基苯，
Figure imgf000004_0002
； 其中， R2、 R3、 R4为相同或不同的 C C16的烷基；
在含有催化剂、 氧化剂和有机溶剂的体系中， 将化合物八、 B与 1,4--对二 吡咯基曱基苯进行缩聚氧化反应， 获得如下结构式 (1)表示的共聚物； 或者在含 有催化剂、 氧化剂和有机溶剂的体系中， 将化合物 、 B与二吡咯曱烷进行缩 聚氧化反应， 并将产物进行溴化取代反应， 获得溴化产物再与 1,4-二 (4,4,5,5- 四曱基 -1,3,2-二杂氧戊硼烷)基苯进行 Suzuki耦合反应，获得如下结构式 (1)表示 的共聚物：
Figure imgf000005_0001
(1)，
结构式 (1)中的 n为 1-100的整数。
以及， 上述含芴卟啉-苯共聚物在有机光电材料、 太阳能电池器件、 有机场 效应晶体管、 有机电致发光器件、 有机光存储器件、 有机非线性材料或有机激 光器件中的应用。
在上述含芴卟啉-苯共聚物中，所含的芴或其衍生物具有优异的光热稳定性 和成膜性， 并具有易修饰的结构， 上述共聚物还通过在聚合物中引入苯环， 可 以增大聚合物骨架电子云的密度， 使得芴基共聚物的带隙变窄， 光语响应范围 更宽。 卟啉结构能使共聚物具有较高的电荷转移和能量转移反应的量子效率， 具有良好的电子緩冲性和光电磁性， 良好的刚柔性、 较好热稳定性和环境稳定 性。 上述含芴卟啉 -苯共聚物应用于有机光电材料、 太阳能电池器件、 有机场效 应晶体管、 有机电致发光器件、 有机光存储器件、 有机非线性材料或有机激光 器件中时， 可提高其光电或半导体相关性能， 并能减轻器件的质量， 且便于大 批量的制备。 附图说明
下面将结合附图及实施例对本发明作进一步说明， 附图中：
图 1是本发明实施例的含芴卟啉-苯共聚物的结构式的示意图。
图 2是本发明实施例的含芴卟啉 -苯共聚物制备方法流程图。
图 3 是采用本发明实施例的含芴卟啉-苯共聚物的太阳能电池器件结构示 意图。
图 4是采用本发明实施例的含芴卟啉-苯共聚物的有机电致发光器件的结 构示意图。
图 5 是采用本发明实施例的含芴卟啉-苯共聚物的有机场效应晶体管的结 构示意图。 具体实施方式
为了使本发明的目的、 技术方案及优点更加清楚明白， 以下结合附图及实 施例， 对本发明进行进一步详细说明。 应当理解， 此处所描述的具体实施例仅 仅用以解释本发明， 并不用于限定本发明。
请参阅图 1 , 显示本发明实施例的含芴卟啉-苯共聚物的结构式， 即为如下 结构式（ 1 )表示的共聚物：
Figure imgf000006_0001
式中： R2、 R3、 R4为相同或不相同的 Crds的烷基; n为 1-謂的整 数。
在本发明的一个实施例中，含芴卟啉-苯共聚物的每个单元中的两个含烷基 芴基团是相同的， 也即， 例如 R3为相同的 CrC16烷基， R2、 R4为相同的 CrC16烷基，或者换句话说， R R4为相同的 CrC16烷基， R2、 R3为相同的 d-C16 烷基。 这样可以简化制备工艺， 降低生产成本。 通过在 9位引入烷基有助于提 高共聚物的溶解性能， 有利于成膜加工， 扩大其应用范围。 优选地， 所述 R2、 R3、 R4为相同的（^-0 16的烷基。 n优选为 5-50, 更优选为 10-30的整数。 在本发明的一个具体实施例中， Ri、 R2、 R3、 R4为 06以上的烷基。
在该含芴卟啉-苯共聚物中， 包括芴或其衍生物、 卟啉结构和苯环结构。 其 中， 芴或其衍生物具有优异的光热稳定性和成膜性， 并具有易修饰的结构， 本 实施例即通过引入苯环结构来增大含芴卟啉 -苯共聚物的骨架电子云的密度，使 得共聚物的带隙变窄， 光谱吸收范围加宽。 卟啉结构能使共聚物具有较高的电 荷转移和能量转移反应的量子效率， 具有良好的电子緩冲性和光电磁性， 良好 的刚柔性、 较好热稳定性和环境稳定性。
由此， 上述含芴卟啉 -苯共聚物具有较宽的光谱响应， 波段大约在 300 -700 nm, 基本涵盖可见光波段， 还具有较好的热稳定性和环境稳定性， 表现出较好 的光电性能。 在本实施例的含芴卟啉-苯共聚物中， R2、 R3、 优选为烷基 链， 例如 C6以上的烷基链， 通过引入烷基链以提高材料的溶解性能， 有利于成 膜加工， 扩大其应用范围。
请参阅图 2, 上述含芴卟啉-苯共聚物的制备方法包括如下步骤：
S01 : 分别提供如下结构式表示的化合物 A和 B, 以及二吡咯曱烷或 1,4 对二吡咯基曱基苯，
Figure imgf000007_0001
； 其中： R2、 R3、 R4为相同或不同的 C C16的烷基；
S02: 在含有催化剂、 氧化剂和有机溶剂的体系中， 将化合物 、 B与 1,4 对二吡咯基曱基苯进行缩聚氧化反应， 获得如下结构式 (1)表示的共聚物； 或者 在含有催化剂、 氧化剂和有机溶剂的体系中， 将化合物 、 B与二吡咯曱烷进 行缩聚氧化反应， 并将产物进行溴化取代反应， 获得溴化产物再与 1,4-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基苯进行 Suzuki耦合反应， 获得如下结构 式 (1)表示的共聚物：
Figure imgf000008_0001
(1)，
结构式 (1)中的 n为 1-100的整数。
在步骤 S01中， 化合物 A、 B可直接从市场上购得或者通过现有的合成方 法制备。 其中， 与上述含芴卟啉-苯共聚物的描述基本相同， R2、 R3、 R4 采用上面描述的结构形式， 在此不再贅述。 例如， 如前所述， 在一个优选的实 施例中， R3为相同的 d-C16烷基， R2、 R4为相同的 C ds烷基， 此时化合 物八、 B结构相同， 由此可少提供一种原料， 简化了制备工艺和降低了成本， 且相对于采用不同化合物 A和 B时具有更高的产率。
本实施例中， 化合物 A、 B, 以及二吡咯曱烷、 1,4 对二吡咯基曱基苯分 别制备而得， 具体如下：
1、 化合物 A和 B的制备
以化合物 A为例， 其制备包括以下步骤： 第一步， 由 2-溴芴与溴烷在催化剂、 有机溶剂条件下进行取代反应， 制得 9,9-二烷基 -2-溴芴。 催化剂为四丁基溴化铵或者苄基三乙基氯化铵， 有机溶剂 为曱苯、 二曱亚砜或四氢呋喃等。 对应地， 溴烷分别是烷基为 R2的溴烷。 如下所示， 分两个反应步骤， 即步骤 i和 ii, 用两种溴烷（当 、 R2相同时为 同一种）分别进行取代反应， 其反应路线如下：
Figure imgf000009_0001
9,9-二烷基 -2-溴芴的详细制备过程可参考文献：《高分子〉 X Macromolecules ) 2002, 35, 3474。
第二步， 在含有烷基锂、 二曱基曱酰胺和有机溶剂体系中进行溴基醛化的 反应， 其反应路线如下：
Figure imgf000009_0002
在一个具体的实施例中， 烷基锂为正丁基锂， 有机溶剂可为四氢呋喃， 详 细制备过程可参考文献： 《高分子》 ( Macromolecules ), 2006, 39, 456。
在制备化合物 B 时， 各步骤基本相同， 不同在于两种溴烷的烷基分别为
R3、 R4„
2、 二吡咯曱烷的制备
在含有曱醛、 催化剂和吡咯的体系中进行缩合反应， 制得二吡咯曱烷， 其 反应方程式如下：
Figure imgf000009_0003
其中步骤 iv的催化剂可以为三氟乙酸，也可以为三氟化硼二曱基氧基络合 物 (BF3.(CH3)20) , 并不限于此； 吡咯既是有机溶剂又是反应物。 二吡咯曱烷的 制备详细步骤可参考文献： 《四面体》 Tetrahednm , 1994, 39, 1 1427。
3、 1,4 对二吡咯基曱基苯的制备
在含有对苯二曱醛、 催化剂和吡咯的体系中进行缩合反应， 制得 1 ,4--对二 吡咯基曱基苯， 其反应方程式如下：
Figure imgf000010_0001
其中步骤 iv'的催化剂可以为三氟乙酸， 也可以为三氟化硼二曱基氧基络合 物 (BF3 CH3)20) , 并不限于此； 吡咯既是有机溶剂又是反应物。 1,4 对二吡咯 基曱基苯的制备详细步骤可参考文献：《四面体》（ Tetrahedron ), 1994, 39, 1 1427。
在步骤 S02中， 根据采用二吡咯曱烷、 1,4--对二吡咯基曱基苯这两种不同 反应物可分为两种方案。 第一种方案为： 在含有催化剂、 氧化剂和有机溶剂的 体系中， 将化合物八、 B与 1,4-对二吡咯基曱基苯进行缩聚氧化反应， 获得上 述含芴卟啉 -苯共聚物。 第二种方案为： 在含有催化剂、 氧化剂和有机溶剂的体 系中， 将化合物 、 B与二吡咯曱烷进行缩聚氧化反应， 并将产物进行溴化取 代反应， 获得溴化产物再与 1,4-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基苯进行 Suzuki耦合反应， 获得上述含芴卟啉 -苯共聚物。 各反应物的摩尔比例可以是按 照化学反应计量比或者其它反应比例， 例如某些反应物过量， 都可以进行本实 施例的如下反应， 且不影响反应进行。 以下分别进行介绍。
由上可知， 实现步骤 S02的第一种方案通过将化合物 A、 B与 1,4 对二吡 咯基曱基苯进行缩聚氧化反应。 缩聚氧化反应的催化剂可采用三氟乙酸或其类 似物， 氧化剂可采用二氯二氛基苯醌 (DDQ)或其类似物， 并不限于此， 有机溶 剂可采用二氯曱烷、 四氢呋喃、 四氯化碳、 氯仿或乙腈等。 其反应式如下所示：
Figure imgf000011_0001
具体实施过程如下： 搭好无水无氧装置， 称取化合物 A、 B与 1,4 对二吡 咯基曱基苯 (摩尔比例为 1/1/1), 加入反应容器中， 加入有机溶剂溶解， 加入适 量的三氟乙酸， 搅拌过夜（例如 12-14小时） ， 加入两个摩尔当量（即为反应 计量比的两倍） 的二氯二氛基苯醌， 继续搅拌， 加入三乙胺淬灭反应。 然后进 行如下提纯： 浓缩， 过滤， 洗涤固体， 收集滤液， 蒸去一半溶剂， 加入曱醇溶 液， 静止沉淀后过滤， 收集固体后进行硅胶柱层析分离并干燥处理， 得到产物， 即上述含芴卟啉-苯共聚物。 硅胶柱层析分离采用石油酸 /乙酸乙酯为淋洗液。
实现步骤 S02的第二种方案具体包括如下步骤：
1 )在含有催化剂、 氧化剂和有机溶剂的体系中， 将化合物 、 B与二吡咯 曱烷进行缩聚氧化反应， 生成芴基卟啉化合物。 此步骤 1 )类似于第一种方案 的反应， 原理基本相同， 也是缩聚氧化反应， 不同在于反应物为二吡咯曱烷， 从而获得芴基卟啉化合物。 同样， 催化剂可采用三氟乙酸或其类似物， 氧化剂 可采用二氯二氛基苯醌或其类似物， 并不限于此， 有机溶剂可采用二氯曱烷、 四氢呋喃、 四氯化碳、 氯仿或乙腈等。 其反应式如下所示：
Figure imgf000012_0001
具体实施过程如下：搭好无水无氧装置，称取化合物 A、 B和二吡咯曱烷 (例 如按照摩尔比例 1/1/2称取)， 溶解于有机溶剂中， 通入氮气， 加入三氟乙酸， 搅拌， 然后加入两个摩尔当量的二氯二氛基苯醌， 继续搅拌， 然后加入三乙胺 淬灭反应， 然后进行如下提纯： 浓缩有机溶剂， 过滤， 收集滤液并旋干有机溶 剂， 用二氯曱烷在硅胶柱上快速淋洗， 旋干有机溶剂， 用乙酸 /曱醇重结晶到产 物， 即芴基卟啉化合物。
2 )在含有催化剂和有机溶剂的体系中， 将步骤 1 )生成的芴基卟啉化合物 进行溴化取代反应， 生成二溴取代的芴基卟啉化合物。 具体地， 催化剂可以为 但不限于吡啶、 吡啶衍生物或三乙胺， 有机溶剂可以为但不限于氯仿、 四氢呋 喃、 二曱基曱酰胺（DMF ) 、 四氯化碳、 二氯曱烷或乙腈等， 并加入 N-溴代丁 二酰亚胺（NBS ) 、 Br2、 HBr或 PBr3等作为溴源， 优选为 NBS。 其具体实施 过程如下： 将芴基卟啉化合物 （如 5,15-二 (9,9-二烷基芴）卟啉）溶解于氯仿中， 加入少量吡啶， 将反应物降到 0°C , 加入适量 N-溴代丁二酰亚胺， 搅拌后， 混 合物恢复到室温， 然后继续搅拌数小时， 加入丙酮终止反应， 除去溶剂， 用乙 酸 /曱醇进行重结晶得到产物。 其反应如下式所示：
Figure imgf000013_0001
3) 在催化剂、 有机溶剂和碱性溶液存在的条件下， 将二溴取代的芴基卟啉 化合物与 1,4-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基苯进行 Suzuki耦合反应， 获得上述含芴卟啉-苯共聚物。
步骤 3)中的催化剂可以为有机钯催化剂， 其用量为 1,4-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基苯的摩尔用量的 0.1-20%。 有机钯催化剂例如可以是但 不限于 Pd2(dba)3/P(o-Tol)3、 Pd(PPh3)4或 Pd(PPh3)2Cl2。 有机溶剂可以是但不限 于四氢呋喃、 二氯曱烷、 乙二醇二曱醚、 苯或曱苯等， 优选为曱苯。 有机溶剂 的用量足量， 以使各反应物溶解并充分反应。 碱性溶液可以是无机碱溶液或有 机碱溶液， 无机碱溶液可以是碱金属氢氧化物或碱金属碳酸盐的水溶液， 例如 可以是但不限于氢氧化钠溶液、 氢氧化钾溶液、 碳酸钠溶液、 碳酸钾溶液等， 优选为碳酸钠溶液， 有机碱溶液可以是烷基氢氧化铵水溶液， 例如可以是但不 限于四曱基氢氧化铵、 四乙基氢氧化铵、 四丙基氢氧化铵、 四丁基氢氧化铵等 水溶液。 上述碱性溶液的用量可以为化合物 D的摩尔用量的 5-20倍。
在一个具体实施例中， 1,4-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基苯可预 先制备， 例如通过在丁基锂、 硼酯作用下进行如下取代反应制得：
Figure imgf000013_0002
具体实施过程如下： 在 N2的保护下， 往三口瓶中加入对二溴苯， 用注射器 注入四氢呋喃溶剂，在 -78°C条件下再用注射器慢慢注入正丁基锂，继续搅拌反 应数小时， 在 -78。C条件下用注射器注入 2-异丙氧基 -4,4,5,5-四曱基 -1,3,2-二杂 氧戊硼烷， 室温下搅拌过夜（约 12-14小时）。加入饱和氯化钠水溶液终止反应， 用氯仿萃取， 无水硫酸钠干燥， 抽虑后将滤液收集并旋蒸掉溶剂。 最后将粗产 物用石油酸 /乙酸乙酯为淋洗液进行硅胶柱层析分离， 得到产物。
获得的 1,4-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基苯与二溴取代的芴基 卟啉化合物进行的反应如下式所示：
Figure imgf000014_0001
步骤 3)的具体实施过程如下： 在反应容器中加入 1,4-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基苯、 5,15-二溴 -10,20-二 (9,9-二烷基芴）卟啉、 四 (三苯基 膦)钯， 其中前两者反应物用量可以为 1/1 , 四 (三苯基膦)钯作为催化剂， 其用量 约为反应物摩尔量的 0.1-20%, 并加入一定量的 Na2C03水溶液和曱苯等有机溶 剂， 将反应物溶解， 然后将反应容器抽真空除氧， 并充入氮气， 将溶液加热到 50-120 °C , 反应 12-80 小时。 反应结束后， 然后对产物进行提纯： 将反应的产 物倒进曱醇中， 布氏漏斗过滤分离沉淀物， 并用稀 HC1洗涤， 固体用丙酮在索 氏提取器中洗涤 12-72小时， 以除去单体和催化剂残留物， 剩下的聚合物溶于 四氢呋喃与氯仿， 即为本实施例的共聚物。 共聚物中的 n优选为 5-50, 更优选 为 10-30。 在实际制备过程中， 可通过对有机溶剂的选择、 对反应温度、 反应 时间、反应物的加入量、催化剂种类和用量进行控制， 以获得所想要的聚合度。 在上述方法的第一种方案中， 化合物 A、 B与 1,4 对二吡咯基曱基苯三种 单体直接合成共聚物， 合成路线比较简单且成熟， 基本上是一步合成， 从而减 少工艺流程， 降低制造成本， 在第二种方案中， 溴化取代反应和 Suzuki耦合反 应都是成熟的反应， 因而合成路线比较成熟， 制造成本低， 而且产率高、 条件 温和， 易于控制。 两种方案都易通过引入烷基提高产物的溶解性和分子量， 以 实现可旋涂的聚合物。
本实施例的含芴卟啉 -苯共聚物可作为有机光电材料，应用于各种光电或半 导体器件中， 例如， 可用于有机光电材料、 太阳能电池器件、 有机场效应晶体 管、有机电致发光器件、 有机光存储器件、有机非线性材料和有机激光器件等。 其中， 有机光电材料包括上述含芴卟啉 -苯共聚物， 以用作电子给体材料或光电 转换材料等。 下面以太阳能电池器件、 有机场效应晶体管， 有机电致发光器件 为例进行说明。 其它如有机光存储器件， 有机非线性材料和有机激光器件与下 面类似， 都是以本实施例的含芴卟啉 -苯共聚物作为其的光存储材料、 非线性材 料、 激光材料或半导体材料等。
请参阅图 3 ,显示采用上述实施例中含芴卟啉 -苯共聚物的太阳能电池器件， 其包括依次层叠的玻璃基层 11、 透明阳极 12、 中间辅助层 13、 活性层 14、 阴 极 15, 中间辅助层 13采用聚乙烯二氧基噻吩： 聚苯乙烯-横酸复合材料 (简称 为 PEDOT:PSS ), 活性层 14包括电子给体材料和电子受体材料， 电子给体材料 采用上述含芴卟啉 -苯共聚物， 电子受体材料可以是 [6,6]苯基 -C61 -丁酸曱酯（简 称为 PCBM )。 透明阳极 12可采用氧化铟锡（简称为 ITO ) , 优选为方块电阻 为 10-20 Ω/ 的氧化铟锡。 阴极 15可采用铝电极或者双金属层电极，例如 Ca/Al 或 Ba/Al等。 其中， 玻璃基层 11可作为底层， 制作时， 选取 ITO玻璃， 并经超 声波清洗后， 用氧 -Plasma处理， 在 ITO玻璃上涂覆中间辅助层 13 , 再将含芴 卟啉-苯共聚物和电子受体材料通过共混后涂覆 (如旋涂 )于中间辅助层 13上， 形成活性层 14, 然后再通过真空蒸镀技术在活性层 14上沉积阴极 15, 获得上 述太阳能电池器件。 在一个优选的实施例中， 透明阳极 12、 中间辅助层 13、 活 性层 14、 双金属层 Ca和 A1层的厚度分别为 160 nm、 40 nm, 150 nm, 20 nm, 70 nm。
如图所示， 在光照下， 光透过玻璃基层 11和 ITO电极 12, 活性层 14中的 含芴卟啉-苯共聚物吸收光能， 并产生激子， 这些激子再迁移到电子给体 /受体 材料的界面处， 并将电子转移给电子受体材料， 如 PCBM, 实现电荷的分离， 从而形成自由的载流子， 即自由的电子和空穴。 这些自由的电子沿电子受体材 料向金属阴极传递并被阴极所收集， 自由的空穴沿电子给体材料向 ITO阳极传 递并被阳极所收集， 从而形成光电流和光电压， 实现光电转换， 外接负载 16 时， 可对其进行供电。 在此过程中， 含芴卟啉 -苯共聚物由于其具有很宽的光语 响应范围， 能够更充分地利用光能， 以获得更高的光电转换效率， 增加太阳能 电池器件的产电能力。 而且这种有机材料还能减轻太阳能电池器件的质量， 并 通过引入烷基， 从而利用旋涂等技术即可制作， 便于大批量的制备。
请参阅图 4, 显示采用上述实施例中的含芴卟啉 -苯共聚物的有机电致发光 器件， 其包括依次层叠设置的玻璃基层 21、 透明阳极 22、 发光层 23、 緩冲层 24、 阴极 25。 透明阳极 22可采用氧化铟锡（简称为 ITO ) , 优选为方块电阻 为 10-20 Ω/ 的氧化铟锡。 发光层 23包含上述实施例中的含芴卟啉 -苯共聚物。 緩冲层 24可采用 LiF等， 但不限于此。 阴极 25可以是但不限于金属 A1或 Ba 等， 但不限于此。 因而， 在一个具体实施例中， 有机电致发光器件结构表示为： ITO/含芴卟啉-苯共聚物 /LiF/Al。 各层可采用现有方法形成， 而含芴卟啉 -苯共 聚物可通过旋涂技术形成于 ITO上。
请参阅图 5, 显示采用上述实施例中的含芴卟啉 -苯共聚物的有机场效应晶 体管， 其包括依次层叠设置的衬底 31、 绝缘层 32、 修饰层 33、 有机半导体层 34以及设于有机半导体层 34上的源电极 35和漏电极 36。 其中， 衬底 31可以 是但不限于高掺杂的硅片（ Si ) ,绝缘层 32可以是但不限于微纳米（如 450 nm ) 厚的 Si02。 有机半导体层 34采用上述描述的含芴卟啉 -苯共聚物。 源电极 35 和漏电极 36均可采用但不限于金。 修饰层 33可以是但不限于十八烷基三氯硅 烷。 衬底 31、 绝缘层 32、 修饰层 33以及源电极 35和漏电极 36都可采用现有 的方法形成。 有机半导体层 34可以是将上述实施例中的含芴卟啉 -苯共聚物旋 涂于由修饰层 33修饰的绝缘层 32上。
以下通过具体实施例来举例说明含芴卟啉-苯共聚物制备方法以及其性能 等方面。 下面实施例中的 、 B, 以及二吡咯曱烷、 1,4—对二吡咯基曱基苯、 1,4- 二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基苯分别按照上述方法直接制备而得，当 然， 在其它实施例中也可以直接从市场上购得， 并不限于此。
实施例 1
本实施例 1以 Ri、 R2、 R3、 R4采用己基为例， 其结构式如下所示：
Figure imgf000017_0001
由该结构式可知， 本实施例 1 的含芴卟啉-苯共聚物具有对称的二芴基结 构， 通过此种均匀对称的结构， 使得这种含芴卟啉-苯共聚物具有更好的吸光性 能和光电性能等， 本实施例 1 的含芴卟啉-苯共聚物的制备方法采用第一种方 案， 由于 R2、 R3、 R4均采用己基， 因此化合物 A、 B均为 9,9-二已基 -2- 醛芴， 由此原料只需要一种， 简化了制备工艺并降低了成本， 而且产率较高。 如果不是这种对称的结构， 那么化合物 A和 B结构不同， 则需要获取不同的原 料， 且副产物相对多些。
其具体制备过程为：称取 9,9-二已基 -2-醛芴与 1,4-对二吡咯基曱基苯 (摩尔 比例为 2/1), 加入反应容器中， 用二氯曱烷溶解， 加入适量的三氟乙酸， 搅拌 过夜（约 12-14小时）， 加入二氯二氛基苯醌（两个摩尔当量）， 继续搅拌， 加 入三乙胺淬灭反应， 然后进行提成： 浓缩反应产物， 过滤， 洗涤固体， 收集滤 液， 蒸去一半溶剂， 加入曱醇溶液， 静止沉淀后过滤， 收集固体后石油酸 /乙酸 乙酯为淋洗液进行硅胶柱层析分离并干燥处理， 得到产物， 即如上结构式所示 的共聚物。
实施例 2
本实施例 2同样以 R2、 R3、 R4采用己基为例， 不同之处在于采用第二 种方案来制备， 具体操作如下：
第一步， 制备 5,15-二 (9,9-二已基芴）卟啉， 具体过程如下： 搭好无水无氧 装置， 按照摩尔比例 1 : 1 : 2称取化合物 A、 B与二吡咯曱烷， 化合物 A和 B 结构相同， 均为 9,9-二己基 -2-醛芴， 将它们溶解于二氯曱烷中， 通入氮气 30 分钟， 用注射器加入适量三氟乙酸， 室温下搅拌 3小时， 然后加入两个摩尔当 量的二氯二氛基苯醌， 继续在室温下搅拌 30分钟， 然后加入三乙胺淬灭反应。 进行提成： 浓缩有机溶剂， 过滤， 收集滤液并旋干有机溶剂， 用二氯曱烷在硅 胶柱上快速淋洗， 旋干有机溶剂， 用乙酸 /曱醇重结晶， 得到产物。
第二步， 制备 5,15-二溴 -10,20-二 (9,9-二己基芴）卟啉
将 5,15-二 (9,9-二己基芴）卟啉溶解于氯仿中， 加入少量吡啶， 将反应物降到 0°C , 加入适量 N-溴代丁二酰亚胺， 搅拌 0.5小时后， 混合物恢复到室温， 然后 继续搅拌 4小时， 加入丙酮终止反应， 除去有机溶剂， 用乙酸 /曱醇进行重结晶 得到产物。
第三步， 含芴卟啉 -苯共聚物的制备， 具体过程如下： 在圓底烧瓶中加入 1.0 mmol 1,4-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷）基蒽、 1.0 mmol 5, 15-二溴 -10,20-二 (9,9-二烷基芴）卟啉、 0.01 mmol四 (三苯基膦)钯， 3 ml Na2C03水溶液 (2 11101/1^和20 1111曱苯溶剂， 抽真空除氧， 并充入氮气， 溶液首先在 N2氛围下 回流 48小时， 进行反应。 反应结束后， 对产物进行提纯： 将反应产物倒进曱醇 中， 用布氏漏斗过滤分离沉淀物， 并用稀 HC1洗涤， 固体用丙酮在索氏提取器 中洗涤 12-72小时， 以除去单体和催化剂残留物， 剩下的聚合物溶于四氢呋喃 与氯仿， 产率约 30-51%。
在上述含芴卟啉-苯共聚物中，所含的芴或其衍生物具有优异的光热稳定性 和成膜性， 并具有易修饰的结构， 上述共聚物还通过在聚合物中引入苯环， 可 以增大聚合物骨架电子云的密度， 使得芴基共聚物的带隙变窄， 光语响应范围 更宽。 卟啉结构能使共聚物具有较高的电荷转移和能量转移反应的量子效率， 具有良好的电子緩冲性和光电磁性， 良好的刚柔性、 较好热稳定性和环境稳定 性。 上述含芴卟啉 -苯共聚物应用于有机光电材料、 太阳能电池器件、 有机场效 应晶体管、 有机电致发光器件、 有机光存储器件、 有机非线性材料或有机激光 器件中时， 可提高其光电或半导体相关性能， 并能减轻器件的质量， 且便于大 批量的制备。
以上所述仅为本发明的较佳实施例而已， 并不用以限制本发明， 凡在本发 明的精神和原则之内所作的任何修改、 等同替换和改进等， 均应包含在本发明 的保护范围之内。

Claims

权 利 要 求 书
1、 一种含芴卟啉 -苯共聚物， 其包含如下结构式（1 )表示的共聚物:
Figure imgf000020_0001
式中： R2、 R3、 R4为相同或不相同的 -C16的烷基； n为 1-100的整 数。
2、 如权利要求 1所述的含芴卟啉 -苯共聚物， 其特征在于， 所述 、 R3为 相同的 d-C16烷基， 所述 R2、 R4为相同的 CrC16烷基。
3、 如权利要求 1所述的含芴卟啉 -苯共聚物， 其特征在于， 所述 R2、 R3、 R4为相同的 CrC1(^ 烷基。
4、 如权利要求 1所述的含芴卟啉 -苯共聚物， 其特征在于， 所述 n为 5-50 的整数。
5、 一种含芴卟啉-苯共聚物制备方法， 其包括如下步骤：
分别提供如下结构式表示的化合物 A和 B, 以及二吡咯曱烷或 1,4 对二吡 咯基曱基苯，
Figure imgf000020_0002
； 其中： R2、 R3、 R4为相同或不同的 - C16的烷基；
在含有催化剂、 氧化剂和有机溶剂的体系中， 将化合物八、 B与 1,4--对二 吡咯基曱基苯进行缩聚氧化反应， 获得如下结构式 (1)表示的共聚物； 或者在含 有催化剂、 氧化剂和有机溶剂的体系中， 将化合物 、 B与二吡咯曱烷进行缩 聚氧化反应， 并将产物进行溴化取代反应， 获得溴化产物再与 1,4-二 (4,4,5,5- 四曱基 -1,3,2-二杂氧戊硼烷)基苯进行 Suzuki耦合反应，获得如下结构式 (1)表示 的共聚物：
Figure imgf000021_0001
结构式 (1)中的 n为 1-100的整数。
6、 如权利要求 5所述的含芴卟啉-苯共聚物制备方法， 其特征在于， 所述 缩聚氧化反应过程为： 选取化合物 A、 B以及二吡咯曱烷或 1,4-对二吡咯基曱 基苯， 用有机溶剂溶解， 加入三氟乙酸作催化剂， 搅拌 12-14小时， 加入二氯 二氛基苯醌作氧化剂， 继续搅拌， 加入三乙胺淬灭反应， 然后提纯， 得到产物。
7、 如权利要求 5所述的含芴卟啉-苯共聚物制备方法， 其特征在于， 所述 Suzuki耦合反应过程为： 选取 1,4-二 (4,4,5,5-四曱基 -1,3,2-二杂氧戊硼烷)基苯、 5,15-二溴 -10,20-二 (9,9-二烷基芴）卟啉、 有机钯催化剂， 加入碱性溶液和有机溶 剂， 将反应物溶解， 抽真空除氧， 并充入氮气， 将溶液加热到 50-120°C , 反应 12-80小时， 得到所述含芴卟啉 -苯共聚物。
8、 如权利要求 5所述的含芴卟啉-苯共聚物制备方法， 其特征在于， 所述 溴化取代反应过程为： 将缩聚氧化反应产物溶解于有机溶剂中， 加入吡啶、 吡 啶衍生物或三乙胺作催化剂， 将反应物降到 0°C , 加入 N-溴代丁二酰亚胺， 搅 拌后， 恢复到室温， 然后继续搅拌数小时， 加入丙酮终止反应， 除去溶剂， 用 乙酸 /曱醇进行重结晶， 得到溴化产物。
9、如权利要求 5所述的含芴卟啉 -苯共聚物制备方法，其特征在于，在 Suzuki 耦合反应后进行如下提纯步骤： 将 Suzuki耦合反应产物倒入曱醇中， 过滤分离 沉淀物， 洗涤， 获得的固体用丙酮在索氏提取器中洗涤， 除去单体和催化剂残 留物， 获得所述含芴卟啉 -苯共聚物。
10、 如权利要求 1-4任一项所述的含芴卟啉-苯共聚物在有机光电材料、 太 阳能电池器件、 有机场效应晶体管、 有机电致发光器件、 有机光存储器件、 有 机非线性材料或有机激光器件中的应用。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957579A (zh) * 2022-05-09 2022-08-30 同济大学 一种自支撑晶态二维高分子非线性薄膜材料及其制备方法和应用
CN115260554A (zh) * 2022-08-25 2022-11-01 南京工业大学 一种具有光栅结构的芴基高分子薄膜及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103025737B (zh) 2010-09-13 2015-07-01 海洋王照明科技股份有限公司 硅芴金属卟啉-苯有机半导体材料及其制备方法和应用
CN111925506B (zh) * 2020-07-10 2022-06-28 华南理工大学 三苯胺-芴-苯并咪唑低带隙三元共聚物、电存储器件及其制备
CN115304622A (zh) * 2022-08-08 2022-11-08 南昌航空大学 一种芴类分子锁小分子阴极界面层及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1459127A (zh) * 2000-07-21 2003-11-26 北卡罗莱纳州立大学 光捕获阵列

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3160999B2 (ja) * 1992-03-09 2001-04-25 剛夫 清水 ポルフィリン誘導体およびその製造方法
JP3150948B2 (ja) * 1998-09-21 2001-03-26 科学技術振興事業団 メソ位直結型ポルフィリンポリマーとその製造方法
KR100482276B1 (ko) * 2002-08-12 2005-04-13 한국과학기술연구원 피롤계 화합물, 그 중합체 및 이들을 이용한 ｅｌ 소자
AU2003900404A0 (en) * 2003-01-31 2003-02-13 Massey University Conducting polymers with porphyrin cross-linkers
CN1887033B (zh) * 2003-10-31 2010-12-15 日产化学工业株式会社 含带有1，4-二噻因环的化合物的电荷传输性有机材料
JP4883898B2 (ja) * 2004-11-18 2012-02-22 パナソニック株式会社 電子デバイスおよびそれを用いた電子機器
JP2008068330A (ja) * 2006-09-12 2008-03-27 Kyushu Univ ナノメートルオーダーで配列制御されたカーボンナノチューブ・合成高分子複合材料
WO2008144750A1 (en) * 2007-05-21 2008-11-27 Plextronics, Inc. Porphyrin and conductive polymer compositions for use in solid-state electronic devices
JP5546070B2 (ja) * 2010-01-30 2014-07-09 海洋王照明科技股▲ふん▼有限公司 フルオレニルポルフィリン−アントラセンを含むコポリマー、その製造方法およびその応用

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1459127A (zh) * 2000-07-21 2003-11-26 北卡罗莱纳州立大学 光捕获阵列

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PAUL-ROTH, CHRISTINE ET AL.: "Selective anodic preparation of 1D or 2D electroactive deposits from 5,15-bis-(9H-fluoren-2-yl)-10,20-diphenyl porphyrins", JOURNAL OF ELECTROANALYTICAL CHEMISTRY, vol. 606, no. 2, 2007, pages 103 - 116, XP022162608, DOI: doi:10.1016/j.jelechem.2007.06.003 *
See also references of EP2551271A4
TETRAHEDRON, vol. 39, 1994, pages 11427
YANG, CHANGDUK ET AL.: "Synthesis and Photochromic Properties of Ladderized Poly(p-phenylene-alt-9,l0-anthrylene)s", MACROMOLECULES, vol. 39, no. 17, 2006, pages 5696 - 5704, XP055062256, DOI: doi:10.1021/ma060722w *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114957579A (zh) * 2022-05-09 2022-08-30 同济大学 一种自支撑晶态二维高分子非线性薄膜材料及其制备方法和应用
CN114957579B (zh) * 2022-05-09 2023-06-02 同济大学 一种自支撑晶态二维高分子非线性薄膜材料及其制备方法和应用
CN115260554A (zh) * 2022-08-25 2022-11-01 南京工业大学 一种具有光栅结构的芴基高分子薄膜及其制备方法
CN115260554B (zh) * 2022-08-25 2023-04-14 南京工业大学 一种具有光栅结构的芴基高分子薄膜及其制备方法

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