WO2012088698A1 - 一种光伏聚合物材料、其制备方法和应用 - Google Patents

一种光伏聚合物材料、其制备方法和应用 Download PDF

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WO2012088698A1
WO2012088698A1 PCT/CN2010/080532 CN2010080532W WO2012088698A1 WO 2012088698 A1 WO2012088698 A1 WO 2012088698A1 CN 2010080532 W CN2010080532 W CN 2010080532W WO 2012088698 A1 WO2012088698 A1 WO 2012088698A1
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monomer
polymer material
photovoltaic polymer
preparation
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French (fr)
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周明杰
王平
张振华
梁禄生
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海洋王照明科技股份有限公司
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Priority to EP10861508.9A priority Critical patent/EP2660264A4/en
Priority to CN201080069692.5A priority patent/CN103168062B/zh
Priority to PCT/CN2010/080532 priority patent/WO2012088698A1/zh
Priority to JP2013545006A priority patent/JP5688164B2/ja
Priority to US13/992,166 priority patent/US8802812B2/en
Publication of WO2012088698A1 publication Critical patent/WO2012088698A1/zh

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    • C—CHEMISTRY; METALLURGY
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    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
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    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
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    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
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Definitions

  • the invention belongs to the technical field of organic materials, in particular to a photovoltaic polymer material, a preparation method thereof and application thereof.
  • the research on organic solar cells began in 1959.
  • the structure is a single crystal crucible sandwiched between two cells.
  • the open circuit voltage of the device is 200 mV, but the photoelectric conversion efficiency is very low.
  • Dr. Deng Qingyun reported a two-layer solar cell in 1986 (using a phthalocyanine derivative as a p-type semiconductor and a tetracarboxy-anthracene derivative as an n -type semiconductor to form a double-layer heterojunction structure with a photoelectric conversion efficiency of about 1). % ), creating a new era of organic solar cell research.
  • conjugated photovoltaic polymer materials act as electron donors ( Donor, abbreviated D), and C60 as an electron acceptor (Acceptor, abbreviated A) blends in light induction. Rapid charge transfer can occur under the process, and the rate of the process is much greater than its reverse process. The reason is that C60 is a large conjugate system in which electrons are delocalized in a molecular orbital composed of 60 carbon atoms, thus stabilizing foreign electrons.
  • This discovery has made research on photovoltaic polymer materials solar cells a new research hotspot.
  • Heeger AJ and other bulk heterojunction solar cells prepared by using a photovoltaic polymer material MEH-PPV as a donor and a C60 derivative PCBM as a receptor blending system as an active layer, greatly increasing the interface between the receptors
  • the exciton dissociation efficiency is improved, and the photoelectric conversion efficiency of the battery is further improved.
  • the energy conversion efficiency reaches 2.9%.
  • narrow New semiconductor photovoltaic polymer materials with straps and wide absorption are critical.
  • narrow bandgap photovoltaic polymer materials generally exhibit better absorption in the long wavelength range (e.g., near infrared) and very weak absorption in some visible regions.
  • narrow bandgap photovoltaic polymer materials have the disadvantage of relatively low hole mobility and poor solubility.
  • Wong et al. (Org. Lett. 2006, 8, 5033) synthesized a novel coplanar chromophore. Di-benzene-thiophene.
  • TPT Sub-derivatives
  • an object of the present invention is to provide a photovoltaic polymer material having a high hole mobility, a narrow band gap, and a wide absorption range.
  • the embodiment of the present invention further provides a method for preparing a photovoltaic polymer material; Examples further provide the use of the above-described photovoltaic polymer materials in organic photovoltaic materials, organic solar cell devices, organic field effect transistor devices, organic electroluminescent devices, organic optical memory devices, and organic laser devices.
  • the present invention is implemented in this way,
  • D 2 is selected from the following structures
  • n is any natural number from 6 to 20
  • X is any natural number from 1 to 50
  • y is any natural number from 1 to 50
  • the monomer M, the monomer and the monomer D 2 are dissolved in a solvent, and the Stille reaction is carried out at a temperature of 90-110 ° C under a catalyst condition for 20 minutes to 2 hours to obtain a photovoltaic polymer material.
  • the reaction formula is expressed as:
  • D 2 is one of the following structures: , monomer D 2B NN or monomer D:
  • n is any natural number from 6 to 20
  • x is any natural number from 1 to 50
  • y is any natural number from 1 to 50
  • Embodiments of the present invention further provide applications of the above-described photovoltaic polymer materials in organic photovoltaic materials, organic solar cell devices, organic field effect transistor devices, organic electroluminescent devices, organic optical memory devices, and organic laser devices.
  • the photovoltaic polymer material of the embodiment of the invention adopts a thiophene-benzene-thiophene (TPT) derivative as a basic structural unit, through introduction
  • TPT thiophene-benzene-thiophene
  • the D 2 structure improves the TPT to give the photovoltaic polymer material a higher hole mobility, a narrower band gap, and a broader absorption performance.
  • FIG. 1 is a structural view of a photovoltaic polymer material according to an embodiment of the present invention.
  • FIG. 2 is an optical absorption diagram of a photovoltaic polymer material according to an embodiment of the present invention.
  • FIG. 3 is a structural view of a solar cell device including a photovoltaic polymer material of an embodiment of the present invention. detailed description
  • FIG. 1 shows the structural formula of a photovoltaic polymer material according to an embodiment of the present invention:
  • D 2 is selected from the following structures
  • n is any natural number from 6 to 20
  • X is any natural number from 1 to 50
  • y is any natural number from 1 to 50
  • n is any natural number from 6 to 12
  • X is any natural number from 2 to 40
  • y is any natural number from 2 to 40
  • the photovoltaic polymer material of the embodiment of the invention has a number average molecular weight of 29100-40000 and a molecular weight distribution coefficient of 1.9-2.5.
  • the photovoltaic polymer material of the embodiment of the invention adopts a thiophene-benzene-thiophene (TPT) derivative as a basic structural unit, through introduction D 2 structure improves TPT, making photovoltaic polymer materials have higher space Cavity mobility, narrower band gap and wider absorption performance.
  • TPT thiophene-benzene-thiophene
  • Fig. 2 shows the absorption light transmission of the copolymer of the embodiment of the present invention. It can be seen from Fig. 2 that the copolymer of the embodiment of the present invention has a broader optical absorption.
  • the embodiment of the invention further provides a method for preparing a photovoltaic polymer material, comprising the steps of: providing a monomer M, a monomer and a monomer D 2 respectively ;
  • the reaction formula is expressed as:
  • the monomer is one of the following monomers:
  • D 2 is in the following structure -
  • n is any natural number of 6-20
  • x is any natural number from 1 to 100
  • y is any one of 1-100.
  • the solvent is not limited, and a solvent such as chloroform or benzene can be used in the stille reaction.
  • a solvent such as chloroform or benzene can be used in the stille reaction.
  • the monomer is a dibromo monomer or a derivative thereof containing (thiophene-benzene-thiophene), the monomer is a thienylbistinated monomer or a derivative thereof, and the monomer D 2 is a triazolyl dibromomonomer. Or a derivative thereof, the molar ratio of the monomer M, the monomer and the monomer D 2 is 1-2:4-6:1-2, preferably 1:2:1.
  • the catalyst is an organic palladium or a mixture of organopalladium and organophosphorus ligand in a molar ratio of 1: 1-20, for example, Pd 2 (dba) 3 /P(o-Tol) 3 , Pd(PPh 3 )4, Pd (PPh 3 ) 2 Cl 2 , tris(dibenzylideneacetone)dipalladium, tris(o-phenylphenyl)phosphine, bistriphenylphosphinepalladium dichloride, the molar ratio of the catalyst to the monomer M is 1- 80-120.
  • the anaerobic conditions include various anaerobic conditions, such as 100% nitrogen, argon, etc., and the method of obtaining anaerobic conditions may also include various methods, but it is preferred to evacuate by an oil pump. Nitrogen gas was introduced, and this was repeated 3-4 times, and then the nitrogen gas was passed through to allow the reaction system to be under the protection of nitrogen, while maintaining the protection of the nitrogen gas while the reactants were added to the reaction system.
  • the preparation method of the embodiment of the invention further comprises the preparation method of the monomer M, the monomer and the monomer D 2 :
  • the preparation method of the monomer M is described below by taking the preparation of the monomer (dibromo TPT) as an example:
  • Monomers are prepared according to the methods disclosed in Macromolecules 2008, 41, 5519.
  • This intermediate 1 (3.2 g, 8.3 mmol) was dissolved in tetrahydrofuran (20 mL) and then 4-n-hexylphenylmagnesium bromide (by 1-bromo-4-n-hexylbenzene (1.
  • This intermediate product 2 (907 mg, 1 mmol), N-bromosuccinimide (392 mg, 2.2 mmol) was dissolved in 30 mL of chloroform and then reacted for 12 h in the dark. After the reaction was stopped, it was extracted with chloroform, washed with brine and dried over anhydrous magnesium sulfate. The crude product was recrystallized from decyl alcohol to give a bright yellow product (92%).
  • the reaction formula of the preparation method is expressed as:
  • the preparation method of the monomer M 2 is prepared by referring to the preparation method of the monomer Mi, wherein the "4-n-hexylphenyl magnesium bromide" in the step ii) is replaced with "4-n-octylphenyl magnesium bromide”. Yes;
  • the preparation method of the monomer M 3 is prepared by referring to the preparation method of the monomer, wherein the "4-n-hexylphenyl magnesium bromide" in the step ii) is replaced with "4-n-dodecylphenyl magnesium bromide”. "Yes.
  • the preparation method of the monomer M 4 is prepared by referring to the preparation method of the monomer, wherein the "4-n-hexylphenyl magnesium bromide" in the step ii) is replaced with "4-n-cetylarylphenyl magnesium bromide". "Yes.
  • the preparation method of the other TPT derivative is prepared by referring to the preparation method of the monomer, wherein the "4-n-hexylphenyl magnesium bromide" in the step ii) is replaced with the corresponding monomer, which will not be described herein.
  • the preparation method of the monomer is described below by taking the preparation of the monomer D la : 2, 5-bis(trimethyltin)-thiophene as follows: Preparation method of the monomer D la :
  • the preparation method of the monomer D lb 5, 5, - di(trimethyltin) - 2, 2, -dithiophene is referred to the preparation method of the monomer D la , wherein "thiophene" is replaced by "2, 2 , - even dithiophene, that is, the monomer D lb .
  • the yield was 60%.
  • the preparation method of the monomer D lc 2, 5-bis(trimethyltin)-3,4-ethylenedioxythiophene refers to the preparation method of the monomer D la , in which "thiophene” is replaced by "3, 4- Ethylene dioxythiophene, that is, the monomer D lc .
  • the yield was 65%.
  • Monomer D ld-1 2 to prepare, 5-di (tri Yue tin-yl) -3, 3 - bis [(octyl group B) Yue-yl] thiazol-heptadiene dioxin.
  • the method for preparing the monomer D ld is as follows:
  • the yield was 56%.
  • Monomer D ld-2 2 was prepared, 5-di (tri Yue tin-yl) -3, 3 - bis [(ethylhexyloxy) Yue-yl] thiazol-heptadiene dioxin.
  • the method for preparing the monomer D ld is as follows:
  • Monomer D ld-3 To prepare 2,5-bis(trimethyltin)-3,3,-bis[(ethyldodecyloxy)indenyl]dioxoprene. Method for preparing monomer D ld
  • the yield was 71%.
  • Monomer D le-1 to prepare 3,4-di-n-octyl-2,5-di(tridecyltin)thio. The method for preparing the monomer D le is described.
  • the preparation method of 3,4-di-n-octyl-2,5-bis(trimethyltin)thiophene refers to a preparation method of the monomer D la in which "thiophene" is replaced by "3, 4-di-n-octyl group -thiophene". The yield was 58%.
  • Monomer D le-2 to prepare 3,4-di-n-hexyl-2,5-di(tridecyltin)thio. The method for preparing the monomer D le is described.
  • Monomer D le-3 to prepare 3,4-di-n-dodecyl-2,5-bis(trimethyltin) thiophene. The method for preparing the monomer D le is described.
  • Monomer D le-4 to prepare 3,4-di-n-icosyl-2,5-di(tridecyltin)thio. The method for preparing the monomer D le is described.
  • the preparation method of 5-n-octyl-2,8-bis(trimethyltin)thienopyrrole-4,6-dione refers to the preparation method of the monomer D la , in which "thiophene” is replaced by "5- N-octyl-thienopyrrole-4,6-dione".
  • the yield was 54%.
  • Monomer D 1 Preparation of 5-n-hexyl-2,8-bis(trimethyltin)thienopyrrole-4,6-dione The preparation method of the monomer D lf :
  • the preparation method of 5-n-hexyl-2,8-bis(tridecyltin)thienopyrrole-4,6-dione refers to the preparation method of the monomer D la , in which "thiophene” is replaced by "5-positive Base-thienopyrrole-4,6-dione". The yield was 59%.
  • Monomer D 1 Preparation of 5-D-dodecyl-2,8-bis(trimethyltin)thienopyrrole-4,6-dione The preparation method of the monomer D lf :
  • the preparation method of 5-n-dodecyl-2,8-bis(tridecyltin)thienopyrrole-4,6-dione is referred to the preparation method of the monomer D la , in which "thiophene” is replaced with "5-n-dodecyl-thienopyrrole-4,6-dione".
  • the yield was 75%.
  • Monomer D 1M Preparation of 5-n-eicosyl-2,8-bis(trimethyltin)thienopyrrole-4,6-dione The preparation method of monomer D lf :
  • the preparation method of 5-n-icocosyl-2,8-bis(tridecyltin)thienopyrrole-4,6-dione refers to the preparation method of the monomer D la , in which "thiophene” is replaced with "5-n-icosyl-thienopyrrole-4,6-dione".
  • the yield was 59%.
  • the preparation method of the monomer D 2a is exemplified by preparing a monomer: 4, 7-dibromo-2-n-octyl-1,2,3-benzotriazole.
  • Monomer D 2a-1 4, 7-Dibromo-2-n-octyl-1,2,3-benzotriazole Prepared according to the method disclosed in Macromolecules 2006, 39 3546.
  • the preparation method of the monomer D 2a 4, 7-dibromo-2-n-hexylbenzotriazole is referred to the preparation method of the monomer D 2 ⁇ , wherein "2-n-octylbenzotriazole” is replaced with "2" - n-hexylbenzotriazole", that is, the monomer D 2a-2 is obtained.
  • the yield was 72%.
  • the preparation method of the monomer D 2 3 4, 7-dibromo-2-n-dodecylbenzotriazole is referred to the preparation method of the monomer D 2a in which "2-n-octylbenzotriazole" is replaced Into "2-n-dodecylbenzotriazole", the monomer D 2a _ 3 is obtained.
  • the yield was 71%.
  • Monomer D 2c-2 4, 7-dibromo-5,6-di(n-hexyloxy)benzothiadiazole was prepared according to the procedure disclosed in Macromolecules 2008, 41, 5559. The yield was 65%.
  • Monomer D 2c-3 4, 7-dibromo-5,6-di(n-dodecyloxy)benzothiadiazole was prepared according to the method disclosed in Macromolecules 2008, 41, 5559. The yield was 66%.
  • Monomer D 2c- 4 4,7 -dibromo-5,6-di(n-ocamphenyloxy)benzothiadiazole was prepared according to the procedure disclosed in Macromolecules 2008, 41, 5559. The yield was 62%.
  • the raw materials used are all commercially available. Applications in cell devices, organic field effect transistor devices, organic electroluminescent devices, organic optical memory devices, and organic laser devices.
  • the preparation method of the photovoltaic polymer material P (TPT-6-T-BTz-8) according to the embodiment of the invention comprises the following steps: under the nitrogen protection, the monomer monomer D la: 2, 5-bis(trimethyltin)thiophene , monomer D 2a-1 :
  • 4,7-Dibromo-2-n-octyl-1,2,3-benzotriazole in a monomer molar ratio of monomer monomer D la : monomer D 2a-1 is 1:2:1 added to Tris(dibenzylideneacetone)dipalladium (5.5 mg, 0.006 mmol), tris(o-phenylphenyl)phosphine ( 14.6 mg, 0.048 mmol) and chlorobenzene (5 mL) were combined and reacted in a microcapillary At 30 min, a dark solution containing the photovoltaic polymer material P (TPT-6-T-BTz-8) was obtained.
  • the photovoltaic polymer material P(TPT-12-T-BTz-12) of the embodiment of the invention has the following structural formula:
  • the monomer molar ratio is monomer M 3 : monomer D la : monomer D 2a-3 1:6:2, tris(dibenzylideneacetone)dipalladium: tris(o-phenylphenyl)phosphine is 1:3.
  • the photovoltaic polymer material P (TPT-6-DT-BTz-8) of the embodiment of the invention has the following structural formula:
  • the monomer molar ratio is monomer M 1: monomer D lb : monomer D 2a-1 It is 1:6:2, tris(dibenzylideneacetone)dipalladium: tris(o-phenyl)phosphine has a molar ratio of 1:5.
  • the monomer molar ratio is monomer M 1 : monomer D lc : monomer D 2a-1 is 1 : 5: 2, tris(dibenzylideneacetone) dipalladium: The molar ratio of tris(o-phenyl)phosphine is 1:5.
  • the structural formula of the photovoltaic polymer material P (TPT-6-PDOT-8-BTz-8) of the embodiment of the invention is as follows:
  • the monomer molar ratio is monomer M 1 : monomer D ld-1 : monomer D 2a-1 is 1:4:2, tris(dibenzylideneacetone)dipalladium: tris(o-phenylphenyl)phosphine molar ratio is 1:4.
  • Embodiment P of the present invention (TPT-6-DAT-8-BTz-8) has the following structural formula
  • the preparation method of the invention P (TPT-6-DAT-8-BTz-8), refer to the first embodiment, wherein the monomer molar ratio is monomer M 1 : monomer D le-1 : monomer D 2a-1 It is 1:4:2.5, tris(dibenzylideneacetone)dipalladium: tris(o-phenylphenyl)phosphine molar ratio is 1:4.
  • the photovoltaic polymer material P (TPT-6-TPD-8-BTz-8) of the embodiment of the invention has the following structural formula:
  • the monomer molar ratio is monomer M!: monomer D lf-1 : monomer D 2a-1 is 1:4:2, tris(dibenzylideneacetone)dipalladium: tris(o-phenylphenyl)phosphine molar ratio is 1:3.
  • the yield was 52%.
  • the structure of the photovoltaic polymer material P (TPT-6-T-BBT) of the embodiment of the invention is as follows:
  • monomer M 1 monomer D la : monomer D 2b is 1:3:2, tris(dibenzylideneacetone)dipalladium: tris(o-phenyl)phosphine molar ratio is 1 :3.
  • the structure of the photovoltaic polymer material P (TPT-6-DT-BBT) of the embodiment of the present invention is as follows:
  • the photovoltaic polymer material P (TPT-6-EDOT-BBT) of the embodiment of the invention has the following structural formula:
  • a method for preparing a photovoltaic polymer material P (TPT-6-EDOT-BBT) according to an embodiment of the present invention is as follows .
  • the monomer molar ratio is monomer M 1 : monomer D lc : monomer D 2b is 1:2. :1 ,
  • the molar ratio of tris(o-phenyl)phosphine is 1:8.
  • the photovoltaic polymer material P (TPT-20-PDOT20-BBT) of the embodiment of the invention has the following structure:
  • the monomer molar ratio is monomer M 4 : monomer D 1 (W : monomer D 2b is 1 : 2:1 , Tris(dibenzylideneacetone)dipalladium: The molar ratio of tris(o-phenyl)phosphine is 1:8.
  • the photovoltaic polymer material P (TPT-6-DAT-20-BBT) of the present embodiment has the following structure:
  • the preparation method of the photovoltaic polymer material P (TPT-6-DAT-20-BBT) according to the embodiment of the present invention is as follows .
  • the monomer molar ratio is monomer M 1: monomer D le-4 : monomer D 2b It is 1:2:1, tris(dibenzylideneacetone)dipalladium: tris(o-phenylphenyl)phosphine molar ratio is 1:8.
  • the photovoltaic polymer material P (TPT-6-TPD-20-BTz) of the embodiment of the invention has the following structural formula:
  • the monomer molar ratio is monomer M 1: monomer D lf-4 : monomer D 2b It is 1:2:1, tris(dibenzylideneacetone)dipalladium: tris(o-phenylphenyl)phosphine molar ratio is 1:8.
  • the photovoltaic polymer material P (TPT-6-T-DAOBT-8) of the embodiment of the invention has the following structural formula:
  • TPT-6-T-DAOBT-8 For the preparation method of the photovoltaic polymer material P (TPT-6-T-DAOBT-8), refer to the first embodiment, wherein the monomer molar ratio is monomer M 1: monomer D la : monomer D 2c-1 It is 1:2:1, tris(dibenzylideneacetone)dipalladium: tris(o-phenylphenyl)phosphine molar ratio is 1:8.
  • the photovoltaic polymer material P (TPT-6-DT-DAOBT-8) of the embodiment of the invention has the following structural formula:
  • the monomer molar ratio is monomer M 1: monomer D lb : monomer D 2c-1 It is 1:2:1, tris(dibenzylideneacetone)dipalladium: tris(o-phenylphenyl)phosphine molar ratio is 1:8.
  • the photovoltaic polymer material P (TPT-EDOT-DAOBT-8) of the embodiment of the invention has the following structural formula:
  • TPT-EDOT-DAOBT-8 For the preparation method of the photovoltaic polymer material P (TPT-EDOT-DAOBT-8) according to the embodiment of the present invention, refer to the first embodiment, wherein the monomer molar ratio is monomer M 1: monomer D lc : monomer D 2 (1 is 1 : 2:1, tris(dibenzylideneacetone)dipalladium: The molar ratio of tris(o-phenyl)phosphine is 1:8.
  • the photovoltaic polymer material P (TPT-6-PDOT-6-DAOBT-6) of the embodiment of the invention has the following structural formula:
  • TPT-6-PDOT-6-DAOBT-6 For the preparation method of the photovoltaic polymer material P (TPT-6-PDOT-6-DAOBT-6), refer to the first embodiment, wherein the monomer molar ratio is monomer M 1: monomer D ld monomer D 2 ( 2 is 1:2:1, tris(dibenzylideneacetone)dipalladium: The molar ratio of tris(o-phenylphenyl)phosphine is 1:8.
  • the photovoltaic polymer material P (TPT-12-PDOT-12-DAOBT-12) of the embodiment of the invention has the following structural formula:
  • TPT-12-PDOT-12-DAOBT-12 For the preparation method of the photovoltaic polymer material P (TPT-12-PDOT-12-DAOBT-12), refer to the first embodiment, wherein the monomer molar ratio is monomer M 3 : monomer D 1 (W : monomer) D 2 (3 is 1:2:1, tris(dibenzylideneacetone) dipalladium: The molar ratio of tris(o-phenyl)phosphine is 1:8.
  • the photovoltaic polymer material P (TPT-6-DAT-8-DAOBT-8) of the embodiment of the invention has the following structure
  • the monomer molar ratio is monomer M 1: monomer D le-1 : monomer D 2 (1 is 1:2:1, tris(dibenzylideneacetone) dipalladium: The molar ratio of tris(o-phenyl)phosphine is 1:8.
  • the photovoltaic polymer material P (TPT-12-DAT-12-DAOBT-12) of the embodiment of the invention has the following structural formula:
  • TPT-12-DAT-12-DAOBT-12 For the preparation method of the photovoltaic polymer material P (TPT-12-DAT-12-DAOBT-12), refer to the first embodiment, wherein the monomer molar ratio is monomer M 3 : monomer D le-3 : monomer D 2c-3 is 1:2:1, tris(dibenzylideneacetone)dipalladium: tris(o-phenylphenyl)phosphine molar ratio is 1:8.
  • the photovoltaic polymer material P (TPT-6-TPD-8-DAOBT-8) of the embodiment of the invention has the following structural formula:
  • a method for preparing a photovoltaic polymer material P (TPT-6-DAT-8-DAOBT-8) is described in the first embodiment, wherein the monomer molar ratio is monomer M1 : monomer D lf-1 : monomer D 2c-1 is 1:2:1, tris(dibenzylideneacetone)dipalladium: tris(o-phenylphenyl)phosphine molar ratio is 1:8.
  • the photovoltaic polymer material P (TPT-8-TPD-12-DAOBT-12) of the embodiment of the invention has the following structural formula:
  • TPT-6-DAT-8-DAOBT-8 For the preparation method of the photovoltaic polymer material P (TPT-6-DAT-8-DAOBT-8), refer to the first embodiment, wherein the monomer molar ratio is monomer M 2 : monomer D 1 : monomer D 2 (3 is 1:2:1, tris(dibenzylideneacetone)dipalladium: the molar ratio of tris(o-phenyl)phosphine is 1:8.
  • FIG. 3 shows a photovoltaic polymer material solar cell device structure in which a photovoltaic polymer material according to Embodiment 1 of the present invention is an active layer, comprising: a glass base layer 31, a transparent anode 32, a functional layer 33, and a cathode 34.
  • the functional layer includes The intermediate auxiliary layer 331 and the active layer 332.
  • the glass base layer 31 may include various kinds of glass, and there is no limitation on the material, but it does not hinder the transmission of sunlight.
  • the transparent anode 32 may be, but not limited to, indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ , that is, ITO.
  • the intermediate auxiliary layer 331 may be, but not limited to, PEDOT:PSS, PEDOT is poly(3,3-ethylenedioxythiophene), PSS is poly(styrenesulfonic acid), and active layer 332 is a photovoltaic polymerization of an embodiment of the present invention.
  • the glass base layer 31/transparent anode 32 is an integral member, also referred to as ITO glass, which is commercially available.
  • the active layer material comprises the photovoltaic polymer material of the first embodiment of the present invention as an electron donor material, and [6, 6] phenyl-C 61 -butyric acid decanoate (PCBM ) is used as an electron acceptor material to form an organic electricity.
  • a functional layer of a light-emitting device The photovoltaic polymer material in the present invention uses a spin coating technique as an electron donor material and PCBM as an electron acceptor material, and a metal aluminum electrode is prepared by a vacuum evaporation technique to obtain a photovoltaic polymer material solar cell device.

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Description

说 明 书
一种光伏聚合物材料、 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， 尤其涉及一种光伏聚合物材料、 其制备方 法和应用 背景技术
有机太阳能电池的研究始于 1959年， 其结构为单晶蒽夹在两个电池之间， 器件的开路电压为 200 mV, 但光电转换效率很低。 邓青云博士于 1986年报道 的双层结构太阳能电池（以酞菁衍生物为 p型半导体， 以四羧基茈衍生物作为 n型半导体， 形成双层异质结结构， 其光电转换效率约为 1% ), 开创了有机太 阳能电池研究的新纪元。 该研究首次将电子给体（p型） /电子受体（n型）有 机双层异质结的概念引入了太阳能电池， 并解译了电池效率高的原因是由于光 致激子在双层异质结界面的诱导解离效率较高。
1992年， Heeger.A.J和 Yoshino K.等人发现， 共轭光伏聚合物材料作为电 子给体 ( Donor, 简写 D ), C60作为电子受体（Acceptor, 简写 A ) 的共混体 系， 在光诱导下可发生快速电荷转移， 且该过程的速率远远大于其逆向过程。 原因是 C60是一个很大的共轭体系， 电子在由 60个碳原子组成的分子轨道上 处于离域状态， 因此可以稳定外来电子。 这一发现， 使光伏聚合物材料太阳能 电池的研究成为新的研究热点。
Heeger A. J.等以光伏聚合物材料 MEH-PPV做给体、 C60衍生物 PCBM作 为受体的共混材料体系作为活性层制备的本体异质结太阳能电池， 由于大大增 加了给受体之间的界面，激子解离效率提高， 电池的光电转换效率进一步提高， 在 20 mW/cm2, 430 nm的单色光照射下， 能量转换效率达到 2.9%。
为了进一步提高光伏聚合物材料太阳能电池的能量转换效率， 开发一种窄 带系、 宽吸收的新型半导体光伏聚合物材料材料至关重要。 现有技术中， 窄带 隙光伏聚合物材料通常在长波范围内 （比如， 近红外）展现出较好的吸收， 而 在部分可见光区吸收非常弱。 此外， 窄带隙光伏聚合物材料具有空穴迁移率相 对较低， 溶解性能不好的缺点。 近年来， Wong等（ Org. Lett. 2006, 8, 5033 )合 成了一种新型的共面生色团噻。分-苯 -噻。分衍生物 （TPT ) , 并报道含 TPT的光 伏聚合物材料空穴迁移率、 带隙及对太阳光有较高的吸收系数和较宽的吸收范 围等性能比较优越， 但是， TPT光伏聚合物材料的空穴迁移率、 带隙以及吸收 范围还不够优越， 需要进一步改进。 技术问题
有鉴于此， 本发明实施例目的在于提供一种具有高空穴迁移率、 窄带隙及 宽吸收范围的光伏聚合物材料； 本发明实施例目的还在于一种光伏聚合物材料 制备方法； 本发明实施例进一步提供上述光伏聚合物材料在有机光电材料、 有 机太阳能电池器件、 有机场效应晶体管器件、 有机电致发光器件、 有机光存储 器件及有机激光器件中的应用。 技术解决方案
本发明是这样实现的，
一种光伏聚合物材料， 具有如下结构式：
Figure imgf000004_0001
其中， 选自如下结构中的一种:
Figure imgf000005_0001
D2选自如下结构中的
Figure imgf000005_0002
n为 6-20的任一自然数， X为 1-50的任一自然数， y为 1-50的任一自然数, 2≤x+y≤100。
以及， 一种光伏聚合物材料制备方法， 包括如下步骤：
分别提供单体 M、 单体 及单体 D2;
无氧条件下，将该单体 M、单体 及单体 D2溶于溶剂中，在温度为 90- 110 °C 及催化剂条件下进行 Stille反应 20分钟 -2小时， 得到光伏聚合物材料， 反应式 表示为：
Figure imgf000006_0001
D lc
Figure imgf000006_0002
、单体 D Id 、单体 D le 单体
Figure imgf000006_0003
D2为如下结构中的一种： 、 单 体 D2B N N 或 单 体 D:
Figure imgf000007_0001
n为 6-20的任一自然数， x为 1-50的任一自然数， y为 1-50的任一自然数， 2≤x+y≤100。
本发明实施例进一步提供上述光伏聚合物材料在有机光电材料、 有机太阳 能电池器件、 有机场效应晶体管器件、 有机电致发光器件、 有机光存储器件及 有机激光器件中的应用。 有益效果
本发明实施例光伏聚合物材料， 以噻吩-苯 -噻吩（ TPT )衍生物为基本结构 单元， 通过引入
Figure imgf000007_0002
D2结构对 TPT进行改进， 使光伏聚合物材料具有更高空 穴迁移率、 更窄带隙及更宽吸收的性能。 附图说明
图 1是本发明实施例光伏聚合物材料结构图；
图 2是本发明实施例光伏聚合物材料吸收光语图；
图 3是包括本发明实施例光伏聚合物材料的太阳能电池器件结构图。 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 , 图 1显示本发明实施例光伏聚合物材料的结构式:
Figure imgf000008_0001
其中， 选自如下结构中的一种:
Figure imgf000008_0002
D2选自如下结构中的
Figure imgf000008_0003
n为 6-20的任一自然数， X为 1-50的任一自然数， y为 1-50的任一自然数, 2≤x+y≤100。
进一步， n为 6-12的任一自然数， X为 2-40的任一自然数， y为 2-40的 任一自然数， 4≤x+y≤80。
进一步， 本发明实施例光伏聚合物材料的数均分子量为 29100-40000, 分 子量分布系数为 1.9-2.5。
本发明实施例光伏聚合物材料， 以噻吩-苯 -噻吩（ TPT )衍生物为基本结构 单元， 通过引入
Figure imgf000008_0004
D2结构对 TPT进行改进， 使光伏聚合物材料具有更高空 穴迁移率、 更窄带隙及更宽吸收的性能。
请参阅图 2， 图 2显示本发明实施例共聚物吸收光傳， 从图 2中可以得出， 本发明实施例共聚物具有较宽光语吸收。
本发明实施例进一步提供一种光伏聚合物材料制备方法， 包括如下步骤： 分别提供单体 M、 单体 及单体 D2;
无氧条件下，将该单体 M、单体 Di及单体 D2溶于溶剂中，在温度为 90-110°C 及催化剂条件下进行 stille反应 20分钟 -2小时， 得到光伏聚合物材料， 反应式 表示为：
Figure imgf000009_0001
其中， 单体 为如下单体中的一种:
单体 D la
Figure imgf000009_0002
单体 D lb 单体
Figure imgf000010_0001
D2为如下结构中的-
或 单 体 D 2c
Figure imgf000010_0002
n为 6-20的任一自然数， x为 1-100的任一自然数， y为 1-100的任一自然 具体地， 该溶剂没有限制， stille反应中常用溶剂即可， 例如氯仿、 曱苯、 四氢呋喃、 乙二醇二曱醚、 二氧六环、 Ν,Ν-二曱基曱酰胺、 氯苯或苯的一种或 以上。 该单体 Μ为含（噻吩 -苯-噻吩）的双溴单体或其衍生物， 单体 为噻吩 基双锡化单体或其衍生物， 单体 D2为三唑基双溴单体或其衍生物， 该单体 M、 单体 及单体 D2的摩尔比为 1-2:4-6:1-2, 优选 1:2:1。 该催化剂为有机钯或摩 尔比为 1 : 1-20 的有机钯与有机磷配体的混合物， 例如， Pd2(dba)3/P(o-Tol)3、 Pd(PPh3)4、 Pd(PPh3)2Cl2, 三 (二亚苄基丙酮)二钯、 三 (邻曱苯基)膦， 双三苯基膦 二氯化钯， 该催化剂和单体 M的摩尔比为 1-80-120。
该无氧条件包括各种无氧条件， 例如可以为 100%的氮气、 氩气、 等环境， 无氧条件的获得方法也可以包括各种方法， 但是优选的是通过油泵抽真空， 再 通入氮气， 如此反复 3-4次， 再一直通入氮气使反应体系处于氮气的保护下， 同时在向反应体系加入反应物的时候， 保持该氮气的保护。
具体地， 本发明实施例制备方法还包括单体 M、 单体 及单体 D2的制备 方法：
以下以制备单体 (二溴 TPT ) 为例说明单体 M的制备方法：
单体 M, 当 n为 6时， 为单体
Figure imgf000011_0001
单体 参照 Macromolecules 2008, 41, 5519.公开的方法制备：
步骤 i ):
冰浴条件下， 将 2-溴噻吩（ 2.8 mL, 28.8 mmol )、镁屑（ 702 mg, 28.8 mmol ) 加入到 THF ( 30 mL )溶液中， 分步加入氯化锌溶液（ 3.9 g ), 搅拌 30 min后， 得到混合溶液， 移除冰浴， 再将 2, 5-二噻。分基 -1, 4-二苯曱酸乙酯（4.38 g, 11.5mmol )、 四三苯基膦钯 ( 266 mg, 2 mol% )加入该混合溶液中， 回流反应 12 小时。 停止反应， 过滤， 用乙酸乙酯萃取， 旋蒸溶剂， 粗产物采用淋洗液（乙 酸乙酯 /正己烷 =1/9 )经过硅胶层析柱分离得到亮黄色液体 (即中间产物 1 ) (产 率 56% )。 mp 103 - 104 °C , HNMR (CDC13, 400 MHz) 57.81 (s, 2H), 7.39 (dd, J = 4.8, 1.2 Hz, 2H), 7.08 (m, 4H), 4.22 (q, J = 7.2 Hz, 4H), 1.16 (t, J = 7.2 Hz, 6H)。
步骤 ii ):
将该中间产物 1 ( 3.2 g, 8.3 mmol )溶于四氢呋喃 （ 20 mL ), 再滴加 4-正己 基苯基溴化镁（通过 1-溴 -4-正己基苯（ 10.2 mL, 50 mmol )与镁屑 ( 1.2 g, 50 mmol )反应制备）， 回流反应 13小时， 停止反应， 采用乙酸乙酯萃取， 再用无 水硫酸镁干燥， 旋蒸溶剂， 得到中间产物， 然后将该中间产物溶解在醋酸（ 100 mL )和疏酸（ 5 mL )的混合溶液中， 回流反应 4 h后停止反应， 冷却， 乙酸乙 酯萃取再用无水硫酸镁干燥。 旋蒸溶剂得到粗产物， 采用淋洗液正己烷经过硅 胶层析柱得到黄色固体（即中间产物 2 ) (产率 42% )。
H NMR (CDC13, 400 MHz) δ 7.42 (s, 2H), 7.23 (d, J ) 4.8 Hz, 2H), 7.09 (dd, J ) 14.0, 8.0 Hz, 16H), 6.99 (d, J ) 5.2 Hz, 2H), 2.54 (t, J ) 8.0 Hz, 8H), 1.76 (m, 8H), 1.27-1.29 (m, 24H), 0.87 (t, J ) 6.6 Hz, 12H)。
步骤 iii ):
将该中间产物 2 ( 907 mg, 1 mmol )、 N-溴代丁二酰亚胺（ 392 mg, 2.2mmol ) 溶解在 30mL的氯仿中， 然后在避光条件下反应 12h。 停止反应后， 用氯仿萃 取， 再用饱和食盐水洗涤， 最后用无水硫酸镁干燥。 粗产物用曱醇重结晶得到 亮黄色产物即 ( 92% )。
H NMR (CDC13, 400 MHz) δ 7.32 (s, 2H), 7.07-7.09 (m, 16H), 6.99 (s, 2H), 2.56 (t, J ) 8.0 Hz, 8H), 1.57 (m, 8H), 1.29 (m, 24H), 0.87 (t, J ) 6.6 Hz, 12H)。
该制备方法反应式表示为：
Figure imgf000012_0001
单体 M2:
Figure imgf000013_0001
单体 M2的制备方法参照该单体 Mi的制备方法制备， 其中， 将步骤 ii ) 中 的 "4-正己基苯基溴化镁" 替换成 "4-正辛基苯基溴化镁" 即可；
单体 M3:
Figure imgf000013_0002
单体 M3的制备方法参照该单体 的制备方法制备， 其中， 将步骤 ii ) 中 的 "4-正己基苯基溴化镁" 替换成 "4-正十二烷基苯基溴化镁" 即可。
单体 M4的制备方法参照该单体 的制备方法制备， 其中， 将步骤 ii ) 中 的 "4-正己基苯基溴化镁" 替换成 "4-正二十烷基苯基溴化镁" 即可。
其他 TPT衍生物的制备方法参照该单体 的制备方法制备， 其中， 将步 骤 ii ) 中的 "4-正己基苯基溴化镁" 替换成相应的单体即可， 在此不贅述。
以下以制备单体 Dla： 2, 5-二 (三曱基锡) -噻吩为例说明单体 的制备方法： 单体 Dla制备方法：
在氩气保护下将噻吩（8.4 g, 0.10 mol) 与 60 mL THF混合， 加入丁基锂的 己烷溶液 （丁基锂的己烷溶液为将 73 ml, 0.21 mol, 2.88 M的丁基锂溶于已烷 溶液中）， 升温至回流反应 2h , 移开加热装置， 于 15 °C条件下加入三曱基氯化 锡 (41.9 g, 0.21 mol) , 搅拌反应 12 h, 旋转蒸发除去溶剂， 剩余物质进行减压蒸 馏， 在 O. l mmHg, 220 °C下得到无色液体即为 2, 5-二（三曱基锡）噻吩， 产率 为 53%。 GC-Ms: m/z =412。
单体 Dlb: 5, 5， -二（三曱基锡） -2, 2， -连二噻吩的制备方法参照该单体 Dla的制备方法， 其中将 "噻吩" 替换成 "2, 2， -连二噻吩" ， 即得单体 Dlb。 产率为 60 %。
单体 Dlc： 2, 5-二（三曱基锡） -3, 4-乙烯二氧噻吩的制备方法参照该单体 Dla的制备方法， 其中将 "噻吩" 替换成 "3, 4-乙烯二氧噻吩" ， 即得单体 Dlc。 产率为 65 %。
单体 Dld的制备方法：
单体 Dld-1 : 以制备 2, 5-二（三曱基锡） -3， ，3， -二 [ (乙基辛氧基） 曱基] 二氧杂环庚二烯噻。分说明单体 Dld的制备方法：
2, 5-二（三曱基锡） -3， , 3， -二 [ (乙基辛氧基） 曱基]二氧杂环庚二烯噻 吩的制备方法参照该单体 Dla的制备方法， 其中将 "噻吩" 替换成 "3， , 3， - 二[ (乙基辛氧基） 曱基]二氧杂环庚二烯噻吩" 。
产率为 56%。
单体 Dld-2: 以制备 2, 5-二（三曱基锡） -3， ，3， -二 [ (乙基己氧基） 曱基] 二氧杂环庚二烯噻。分说明单体 Dld的制备方法：
2, 5-二（三曱基锡） -3， , 3， -二 [ (乙基己氧基） 曱基]二氧杂环庚二烯噻 吩的制备方法参照该单体 Dla的制备方法， 其中将 "噻吩" 替换成 "3， , 3， - 二[ (乙基己氧基） 曱基]二氧杂环庚二烯噻吩" 。
产率为 54 %。
单体 Dld-3: 以制备 2, 5-二（三曱基锡） -3， ， 3， -二 [ (乙基十二烷氧基） 曱基]二氧杂环庚二烯噻。分说明单体 Dld的制备方法
2, 5-二（三曱基锡） -3， , 3， -二 [ (乙基十二烷氧基） 曱基]二氧杂环庚二 烯噻吩的制备方法参照该单体 Dla的制备方法， 其中将 "噻吩"替换成 "3， ，3， -二 [ (乙基十二烷氧基） 曱基]二氧杂环庚二烯噻吩" 。
产率为 75 %。 单体 Dld-4: 以制备 2, 5-二（三曱基锡） -3， ， 3， -二 [ (乙基二十烷氧基） 曱基]二氧杂环庚二烯噻。分说明单体 Dld的制备方法
2, 5-二（三曱基锡） -3， , 3， -二 [ (乙基二十烷氧基） 曱基]二氧杂环庚二 烯噻吩的制备方法参照该单体 Dla的制备方法， 其中将 "噻吩"替换成 "3， ，3， -二 [ (乙基二十烷氧基） 曱基]二氧杂环庚二烯噻吩" 。
产率为 71%。
单体 Dle的制备方法
单体 Dle-1: 以制备 3, 4-二正辛基 -2, 5-二 （三曱基锡）噻。分说明单体 Dle的 制备方法。
3, 4-二正辛基 -2, 5-二（三曱基锡）噻吩的制备方法参照该单体 Dla的制备 方法， 其中将 "噻吩" 替换成 "3, 4-二正辛基-噻吩" 。 产率为 58 %。
单体 Dle-2: 以制备 3, 4-二正己基 -2, 5-二（三曱基锡）噻。分说明单体 Dle的 制备方法。
3, 4-二正己基 -2, 5-二（三曱基锡）噻吩的制备方法参照该单体 Dla的制备 方法， 其中将 "噻吩" 替换成 "3, 4-二正己基-噻吩" 。 产率为 57 %。
单体 Dle-3: 以制备 3, 4-二正十二烷基 -2, 5-二（三曱基锡）噻。分说明单体 Dle的制备方法。
3, 4-二正十二烷基 -2, 5-二（三曱基锡）噻吩的制备方法参照该单体 Dla的 制备方法， 其中将 "噻吩" 替换成 "3, 4-二正十二烷基-噻吩" 。 产率为 65 %。 G
单体 Dle-4: 以制备 3, 4-二正二十烷基 -2, 5-二（三曱基锡）噻。分说明单体 Dle的制备方法。
3, 4-二正二十烷基 -2, 5-二 （三曱基锡）噻吩的制备方法参照该单体 Dla的 制备方法， 其中将 "噻吩" 替换成 "3, 4-二正二十烷基-噻吩" 。 产率为 71%。
单体 Dlf的制备方法
单体 Dlf-1: 以制备 5-正辛基 -2, 8-二（三曱基锡 )噻吩并吡咯 -4, 6-二酮说明 单体 Dlf的制备方法：
5-正辛基 -2, 8-二（三曱基锡）噻吩并吡咯 -4, 6-二酮的制备方法参照该单体 Dla的制备方法， 其中将 "噻吩" 替换成 "5-正辛基 -噻吩并吡咯 -4, 6-二酮" 。 产率为 54 %。
单体 D1 ： 以制备 5-正己基 -2, 8-二（三曱基锡）噻吩并吡咯 -4, 6-二酮说明 单体 Dlf的制备方法：
5-正己基 -2, 8-二（三曱基锡）噻吩并吡咯 -4, 6-二酮的制备方法参照该单体 Dla的制备方法， 其中将 "噻吩" 替换成 "5-正己基 -噻吩并吡咯 -4, 6-二酮" 。 产率为 59 %。
单体 D1 ： 以制备 5-正十二烷基 -2, 8-二（三曱基锡 )噻吩并吡咯 -4, 6-二酮 说明单体 Dlf的制备方法：
5-正十二烷基 -2, 8-二（三曱基锡）噻吩并吡咯 -4, 6-二酮的制备方法参照该 单体 Dla的制备方法， 其中将 "噻吩" 替换成 "5-正十二烷基 -噻吩并吡咯 -4, 6- 二酮" 。 产率为 75%。
单体 D1M： 以制备 5-正二十烷基 -2, 8-二（三曱基锡 )噻吩并吡咯 -4, 6-二酮 说明单体 Dlf的制备方法：
5-正二十烷基 -2, 8-二（三曱基锡）噻吩并吡咯 -4, 6-二酮的制备方法参照该 单体 Dla的制备方法， 其中将 "噻吩" 替换成 "5-正二十烷基 -噻吩并吡咯 -4, 6- 二酮" 。 产率为 59 %。
以下以制备单体 ： 4, 7-二溴 -2-正辛基 -1, 2, 3-苯并三唑为例说明单体 D2a的制备方法
单体 D2a-1: 4, 7-二溴 -2-正辛基 -1, 2, 3-苯并三唑按照 Macromolecules 2006, 39 3546.公开的方法制备：
将 2-正辛基苯并三唑 (2.9 g, 12.6 mmol)和 HBr溶液 (5.8 mol/L, 14.4 mL)混合， 在 100°C搅拌反应 1 h,緩慢滴加液溴 (5.5g, 34.6 mmol), 升温至 135°C搅拌反应 12 h, 反应完毕后冷却至室温， 加入饱和碳酸氢钠溶液， 三氯曱烷萃取。 然后用无 水硫酸镁干燥后过滤， 蒸除溶剂， 剩余物采用硅胶层析柱分离得到亮黄色油状 液体即 4, 7-二溴 -2-正辛基苯并三唑。 产率为 75%。
HNMR (CDC13, 400 MHz) δ 7.43 (s, 2H), 4.78 (t, 2H), 2.15 (m, 2H), 1.40-1.25 (m, 1 OH), 0.87 (t, 3H)。
单体 D2a 4, 7-二溴 -2-正己基苯并三唑的制备方法参照该单体 D2^的制备 方法， 其中将 "2-正辛基苯并三唑" 替换成 "2-正己基苯并三唑" ， 即得单体 D2a-2。 产率为 72%。
单体 D2 3: 4, 7-二溴 -2-正十二烷基苯并三唑的制备方法参照该单体 D2a 制备方法， 其中将 "2-正辛基苯并三唑" 替换成 "2-正十二烷基苯并三唑" ， 即得单体 D2a_3。 产率为 71%。
单体 D2b: 4, 8-二溴苯并二噻二唑的制备方法参照按照 Org. Lett., 2010, 12, 3340公开的方法制备。
单体 D2c的制备方法：
单体 D2c-1： 4, 7-二溴 -5, 6-二（正辛氧基）苯并噻二唑按照 Macromolecules 2008, 41, 5559公开的方法制备。 产率为 70%„
单体 D2c-2: 4, 7-二溴 -5, 6-二（正己氧基）苯并噻二唑按照 Macromolecules 2008, 41, 5559公开的方法制备。 产率为 65%。
单体 D2c-3: 4, 7-二溴 -5, 6-二（正十二烷氧基）苯并噻二唑按照 Macromolecules 2008, 41, 5559公开的方法制备。 产率为 66%。
单体 D2c-4: 4, 7-二溴 -5, 6-二（正二十烷氧基）苯并噻二唑按照 Macromolecules 2008, 41, 5559公开的方法制备。 产率为 62%。
上述单体^、单体 及单体 D2制备方法中，使用的原料均从市面上购得。 池器件、 有机场效应晶体管器件、 有机电致发光器件、 有机光存储器件及有机 激光器件中的应用。
Figure imgf000018_0001
本发明实施例光伏聚合物材料 P(TPT-6-T-BTz-8)制备方法， 包括如下步骤 氮气保护下， 将单体 单体 Dla: 2, 5-二（三曱基锡）噻吩、 单体 D2a-1 :
4, 7-二溴 -2-正辛基 -1, 2, 3-苯并三唑按单体摩尔比为单体 单体 Dla： 单体 D2a-1为 1 :2:1加入到三 (二亚苄基丙酮)二钯（5.5 mg, 0.006 mmol )、 三 (邻曱苯 基)膦（ 14.6 mg,0.048 mmol )及氯苯（ 5 mL )混合，在微^ ^应器中反应 30 min, 得到含光伏聚合物材料 P(TPT-6-T-BTz-8)的深色溶液。 将深色溶液倒入曱醇中 ( 1L ), 过滤得到黑色沉淀， 粗产物通过索氏提取器分别采用曱醇、 丙酮、 正 己烷抽提 24 h, 再用氯仿收集可溶的部分， 最后用曱醇层析。 离心收集固体， 真空干燥得到提纯后的光伏聚合物材料。 产率 76%。 Molecular weight ( GPC, THF, R. I): Mn = 38600, M Mn = 2.1 )。
实施例二
Figure imgf000018_0002
其中单体摩尔比为单体 M2: 单体 Dla： 单体 D2a-2为 1:3: 1 , 三 (二亚苄基丙酮) 二钯： 三 (邻曱苯基)膦为 1:6。
产率 75%。 Molecular weight ( GPC, THF, R. I): n = 37600, M Ma = 2.3 )。 实施例三
本发明实施例光伏聚合物材料 P(TPT-12-T-BTz-12)具有如下结构式：
Figure imgf000019_0001
本发明实施例光伏聚合物材料 P(TPT-12-T-BTz-12)制备方法参照实施例 一， 其中， 单体摩尔比为单体 M3: 单体 Dla： 单体 D2a-3为 1:6:2, 三 (二亚苄基 丙酮)二钯： 三 (邻曱苯基)膦为 1:3。
产率 85%。 Molecular weight ( GPC, THF, R. I): n = 48500, M Mn =1.1)。 实施例四
本发明实施例光伏聚合物材料 P ( TPT-6-DT-BTz-8 )具有如下结构式：
Figure imgf000019_0002
本发明实施例光伏聚合物材料 P ( TPT-6-DT-BTZ-8 )制备方法参照实施例 一， 其中， 单体摩尔比为单体 M1: 单体 Dlb: 单体 D2a-1为 1:6:2, 三 (二亚苄基 丙酮)二钯： 三 (邻曱苯基)膦摩尔为 1:5。
产率 69%。 Molecular weight ( GPC, THF, R. I): n = 36700, M Ma = 2.2 )。 实施例五 本发明实施例光伏聚合物材料 P ( TPT-6-EDOT-BTz-8 ) 结构式如下：
Figure imgf000020_0001
本发明实施例光伏聚合物材料 P ( TPT-6-EDOT-BTz-8 )制备方法参照实施 例一， 其中单体摩尔比为单体 M1 : 单体 Dlc： 单体 D2a-1为 1 :5:2， 三 (二亚苄基 丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1 :5。
产率 71%。 Molecular weight ( GPC, THF, R. I): Mn = 37900, M Ma = 2.1 )。 实施例六
本发明实施例光伏聚合物材料 P ( TPT-6-PDOT-8-BTz-8 )结构式如下：
Figure imgf000020_0002
本发明实施例光伏聚合物材料 P ( TPT-6-PDOT-8-BTz-8 )制备方法， 参照 实施例一， 其中单体摩尔比为单体 M1 : 单体 Dld-1: 单体 D2a-1为 1 :4:2, 三 (二亚 苄基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:4。
产率 65%。 Molecular weight ( GPC, THF, R. I): Mn = 32400, MJMa =2.4 )。 实施例七
本发明实施例 P ( TPT-6-DAT-8-BTz-8 )具有如下结构式
Figure imgf000021_0001
本发明实施例 P ( TPT-6-DAT-8-BTz-8 )制备方法， 参照实施例一， 其中单 体摩尔比为单体 M1 : 单体 Dle-1: 单体 D2a-1为 1:4:2.5, 三 (二亚苄基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1 :4。
产率 68%。 Molecular weight ( GPC, THF, R. I): Mn = 35600, M Ma =2.3 )。 实施例八
本发明实施例光伏聚合物材料 P ( TPT-6-TPD-8-BTz-8 ) 结构式如下：
Figure imgf000021_0002
本发明实施例光伏聚合物材料 P ( TPT-6-TPD-8-BTZ-8 )制备方法， 参照实 施例一， 其中单体摩尔比为单体 M!: 单体 Dlf-1: 单体 D2a-1为 1:4:2， 三 (二亚苄 基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1 :3。产率 52%。 Molecular weight ( GPC, THF, R. I): Mn = 29100, M Ma =2.1 )。
实施例九
本发明实施例光伏聚合物材料 P ( TPT-6-T-BBT )结构是如下：
Figure imgf000022_0001
其中单体摩尔比为单体 M1: 单体 Dla： 单体 D2b为 1:3:2, 三 (二亚苄基丙酮)二 钯： 三 (邻曱苯基)膦摩尔比为 1:3。
产率 79%。 Molecular weight ( GPC, THF, R. I): Ma =38700, M Ma =2.1 )。 实施例十
本发明实施例光伏聚合物材料 P ( TPT-6-DT-BBT )结构是如下：
Figure imgf000022_0002
一， 其中单体摩尔比为单体 M1: 单体 Dlb: 单体 D2b为 1:2:1, 三 (二亚苄基丙酮) 二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 70%。 Molecular weight ( GPC, THF, R. I): Mn = 36200, M Mn = 2.2 )。 实施例十一
本发明实施例光伏聚合物材料 P ( TPT-6-EDOT-BBT )具有如下结构式：
Figure imgf000023_0001
本发明实施例光伏聚合物材料 P ( TPT-6-EDOT-BBT )制备方法， 参照实施 例一， 其中单体摩尔比为单体 M1 : 单体 Dlc： 单体 D2b为 1:2:1 , 三 (二亚苄基丙 酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 75%。 Molecular weight ( GPC, THF, R. I): Ma = 34600, M Ma = 2.4 )。 实施例十二
本发明实施例光伏聚合物材料 P ( TPT-20-PDOT20-BBT )具有如下结构：
Figure imgf000023_0002
本发明实施例光伏聚合物材料 P ( TPT-20-PDOT20-BBT )制备方法， 参照 实施例一， 其中单体摩尔比为单体 M4: 单体 D1(W: 单体 D2b为 1:2:1 , 三 (二亚 苄基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 62%。 Molecular weight ( GPC, THF, R. I): Ma = 28800, M Ma =2.5 )。 实施例十三
本法实施例光伏聚合物材料 P ( TPT-6-DAT-20- BBT )具有如下结构：
Figure imgf000024_0001
本发明实施例光伏聚合物材料 P ( TPT-6-DAT-20- BBT )制备方法， 参照实 施例一， 其中单体摩尔比为单体 M1: 单体 Dle-4: 单体 D2b为 1:2:1, 三 (二亚苄 基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 64%。 Molecular weight ( GPC, THF, . I): Ma =31600, M Ma =1.9)。 实施例十四
本发明实施例光伏聚合物材料 P ( TPT-6-TPD-20-BTz )具有如下结构式：
Figure imgf000024_0002
本发明实施例光伏聚合物材料 P ( TPT-6-TPD-20-BTZ )制备方法， 参照实 施例一， 其中单体摩尔比为单体 M1: 单体 Dlf-4: 单体 D2b为 1:2:1, 三 (二亚苄 基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 59%。 Molecular weight ( GPC, THF, . I): n = 30000, MJMn =2.2 )。 实施例十五
本发明实施例光伏聚合物材料 P ( TPT-6-T-DAOBT-8 )具有如下结构式：
Figure imgf000025_0001
本发明实施例光伏聚合物材料 P ( TPT-6-T-DAOBT-8 )制备方法， 参照实 施例一， 其中单体摩尔比为单体 M1: 单体 Dla： 单体 D2c-1为 1:2:1, 三 (二亚苄 基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 82%。 Molecular weight ( GPC, THF, . I): Mn =39200, M Ma =1.9)。 实施例十六
本发明实施例光伏聚合物材料 P ( TPT-6-DT-DAOBT-8 )具有如下结构式：
Figure imgf000025_0002
本发明实施例光伏聚合物材料 P ( TPT-6-DT-DAOBT-8 )制备方法， 参照实 施例一， 其中单体摩尔比为单体 M1: 单体 Dlb： 单体 D2c-1为 1:2:1, 三 (二亚苄 基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 57%。 Molecular weight ( GPC, THF, . I): Ma = 34700, M Ma = 2.1 )。 实施例十七
本发明实施例光伏聚合物材料 P ( TPT-EDOT-DAOBT-8 )具有如下结构式：
Figure imgf000026_0001
本发明实施例光伏聚合物材料 P ( TPT-EDOT-DAOBT-8 )制备方法， 参照 实施例一， 其中单体摩尔比为单体 M1: 单体 Dlc： 单体 D2( 1为 1:2:1, 三 (二亚 苄基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 74%。 Molecular weight ( GPC, THF, R. I): Mn = 35600, M Mn = 2.1)。 实施例十八
本发明实施例光伏聚合物材料 P ( TPT-6-PDOT-6-DAOBT-6 )具有如下结构 式：
Figure imgf000026_0002
本发明实施例光伏聚合物材料 P( TPT-6-PDOT-6-DAOBT-6 )制备方法， 参照实施例一， 其中单体摩尔比为单体 M1: 单体 Dld 单体 D2( 2为 1:2:1, 三 (二亚苄基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 77%。 Molecular weight ( GPC, THF, R. I): n = 31800, M Ma =2.0 )。 实施例十九
本发明实施例光伏聚合物材料 P ( TPT- 12-PDOT- 12-DAOBT- 12 )具有如下 结构式：
Figure imgf000027_0001
本发明实施例光伏聚合物材料 P ( TPT- 12-PDOT- 12-DAOBT- 12 )制备 方法，参照实施例一，其中单体摩尔比为单体 M3:单体 D1(W:单体 D2( 3为 1:2:1, 三 (二亚苄基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 77%。 Molecular weight ( GPC, THF, R. I): n = 31800, M Mn =2.0 )。 实施例二十
本发明实施例光伏聚合物材料 P ( TPT-6-DAT-8-DAOBT-8 )具有如下结构
Figure imgf000027_0002
本发明实施例光伏聚合物材料 P (TPT-6-DAT-8-DAOBT-8)制备方法， 参 照实施例一， 其中单体摩尔比为单体 M1: 单体 Dle-1: 单体 D2( 1为 1:2:1, 三 (二 亚苄基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 71%。 Molecular weight ( GPC, THF, R. I): Mn = 30800, M Mn =2.1 )。 实施例二十
本发明实施例光伏聚合物材料 P ( TPT- 12-DAT- 12-DAOBT- 12 )具有如下结 构式：
Figure imgf000028_0001
本发明实施例光伏聚合物材料 P ( TPT-12-DAT-12-DAOBT-12 )制备方法， 参照实施例一， 其中单体摩尔比为单体 M3: 单体 Dle-3: 单体 D2c-3为 1:2:1 , 三 (二亚苄基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1:8。
产率 80%。 Molecular weight ( GPC， THF, R. I): Mn = 35600， Mw/Mn =2.3 )。 实施例二十一
本发明实施例光伏聚合物材料 P ( TPT-6-TPD-8-DAOBT-8 )具有如下结构 式：
Figure imgf000028_0002
本发明实施例光伏聚合物材料 P ( TPT- 6- DAT- 8- DAOBT- 8 )制备方法， 参 照实施例一， 其中单体摩尔比为单体 M1 : 单体 Dlf-1: 单体 D2c-1为 1:2:1 , 三 (二 亚苄基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1 :8。
产率 71%。 Molecular weight ( GPC, THF, R. I): Mn = 30800, M Ma =2.1 )。 实施例二十二
本发明实施例光伏聚合物材料 P ( TPT-8-TPD-12-DAOBT-12 )具有如下结 构式：
Figure imgf000029_0001
本发明实施例光伏聚合物材料 P ( TPT-6-DAT-8-DAOBT-8 )制备方法， 参 照实施例一， 其中单体摩尔比为单体 M2: 单体 D1 ： 单体 D2( 3为 1:2:1 , 三 (二 亚苄基丙酮)二钯： 三 (邻曱苯基)膦摩尔比为 1 :8。
产率 67%。 Molecular weight ( GPC, THF, R. I): Mn = 30100, M Mn =2.3 )。 应用例
图 3显示以本发明实施例一的光伏聚合物材料为活性层的光伏聚合物材料 太阳能电池器件结构， 包括结构为： 玻璃基层 31、 透明阳极 32、 功能层 33、 阴极 34, 该功能层包括中间辅助层 331、 活性层 332。 其中， 玻璃基层 31可以 包括各种玻璃， 对材质没有限制， 但是不能阻碍太阳光的透射。 透明阳极 32 可以为但不限于方块电阻为 10-20Ω/口的氧化铟锡， 即 ITO。 中间辅助层 331 可以为但不限于 PEDOT:PSS, PEDOT为聚（ 3,3-亚乙二氧基噻吩）， PSS为聚 (苯乙烯磺酸）， 活性层 332为本发明实施例的光伏聚合物材料。本发明实施例 的有机太阳能电池器件 3中，玻璃基层 31/透明阳极 32为整体部件，也称为 ITO 玻璃， 可以从市场上买到。 其中， 活性层材料包含本发明实施例一的光伏聚合 物材料作为电子给体材料， [6, 6]苯基 -C61 -丁酸曱酯（简称 PCBM )作为电子受 体材料共同构成有机电致发光器件的功能层。 本发明中的光伏聚合物材料作为 电子给体材料和 PCBM作为电子受体材料采用旋涂技术，金属铝电极通过真空 蒸镀技术制备， 得到光伏聚合物材料太阳能电池器件。
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、 一种光伏聚合物材料， 具有如下结构式:
Figure imgf000030_0001
其中， 选自如下结构中的一种:
Figure imgf000030_0002
D2选自如下结构中的
Figure imgf000030_0003
n为 6-20的任一自然数， X为 1-50的任一自然数， y为 1-50的任一自然数, 2 x+y 100。
2、 如权利要求 1所述的光伏聚合物材料， 其特征在于， 所述 n为 6-12的 任一自然数。
3、 如权利要求 1所述的光伏聚合物材料， 其特征在于， 所述 X为 2-40的 任一自然数， 所述 y为 2-40的任一自然数， 4 x+y 80。
4、 如权利要求 1所述的光伏聚合物材料， 其特征在于， 所述的光伏聚合物 材料的数均分子量为 29100-40000, 分子量分布系数为 1.9-2.5。
5、 一种光伏聚合物材料制备方法， 包括如下步骤：
分别提供单体 M、 单体 及单体 D2;
无氧条件下， 将所述单体 M、 单体 及单体 D2溶于溶剂中， 在温度为 90-110°C及催化剂条件下进行 Stille反应 20分钟 -2小时，得到光伏聚合物材料， 反应式表示为：
Figure imgf000031_0001
其中， 单体 0 为如下单体中的一种:
单体 D la
Figure imgf000031_0002
单体 D lb 单体
Figure imgf000032_0001
D2为如下结构中的
或 单 体 D 2c
Figure imgf000032_0002
n为 6-20的任一自然数， x为 1-50的任一自然数， y为 1-50的任一自然数， 2 x+y 100。
6、 如权利要求 5 所述的光伏聚合物材料制备方法， 其特征在于， 所述 n 为 6-12的任一自然数， X为 2-40的任一自然数， y为 2-40的任一自然数， 4 < x+y < 80„
7、 如权利要求 5所述的光伏聚合物材料制备方法， 其特征在于， 所述单体 M、 单体 及单体 D2的摩尔比为 1-2:2-6: 1-2。
8、 如权利要求 5所述的光伏聚合物材料制备方法， 其特征在于， 所述催化 剂为有机钯或摩尔比为 1 : 3-10的有机钯与有机磷配体的混合物。
9、 如权利要求 5所述的光伏聚合物材料制备方法， 其特征在于， 所述催化 剂和单体 M的摩尔比为 1 : 80-120。
10、 如权利要求 1-4任一所述的光伏聚合物材料在有机光电材料、 有机太 阳能电池器件、 有机场效应晶体管器件、 有机电致发光器件、 有机光存储器件 及有机激光器件中的应用。
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