CN104478900B - A kind of lactams receptor unit and its production and use - Google Patents

A kind of lactams receptor unit and its production and use Download PDF

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CN104478900B
CN104478900B CN201410720454.6A CN201410720454A CN104478900B CN 104478900 B CN104478900 B CN 104478900B CN 201410720454 A CN201410720454 A CN 201410720454A CN 104478900 B CN104478900 B CN 104478900B
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tin
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trimethyl
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CN104478900A (en
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丁黎明
曹佳民
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National Center for Nanosccience and Technology China
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/18—Definition of the polymer structure conjugated
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G2261/32—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G2261/32—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
    • C08G2261/3244—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing only one kind of heteroatoms other than N, O, S
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E10/549—Organic PV cells

Abstract

A kind of monomer for preparing polymer solar cells donor material, the monomer is that, containing two compounds of lactams hexatomic ring, the lactam structure is connected by singly-bound or conjugated bridge.The lactam compound that the present invention is provided is used to prepare polymer solar cells donor material, it is possible to increase effective conjugate length；The copolymer donor material that polymerization is obtained has larger conjugate planes, and stronger interchain π π effects, more orderly packing of molecules significantly improves the carrier mobility and energy conversion efficiency of polymer；The energy conversion efficiency (PCE) of obtained polymer solar cells can be made to be up to 7.48%.

Description

A kind of lactams receptor unit and its production and use
Technical field
The invention belongs to solar cell field, and in particular to the polymerization for preparing the donor material of polymer solar cells Monomer, further to a kind of lactams monomer and preparation method thereof, and monomer polymerization obtain for polymer The donor material of solar cell.
Background technology
With global industry and rapid economic development, the mankind increase rapidly the demand of the energy.Fossil energy is current people The main energy sources of class consumption, but with constantly exploitation, the exhaustion of fossil energy is inevitable.Largely caused using fossil energy Environmental pollution is increasingly severe.Solar cell is directly converted solar energy into electrical energy, and is to solve a kind of effective way of energy crisis.
Polymer solar cells typically use bulk heterojunction structure (G.Yu et al, Polymer Photovoltaic Cells:Enhanced Efficiencies via a Network of Internal Donor-acceptor Heterojunctions.Science, 1995,270,1789-1791), mainly including transparency electrode (ITO), hole transmission layer (such as PEDOT:PSS), the active layer containing donor material and acceptor material, metal electrode (such as Al, Ag, Ca).Bulk heterojunction electricity The advantage in pond is：Donor and acceptor material are blended to form inierpeneirating network structure, increase donor/acceptor interface, are electronics and hole Transmission provides express passway, improves cell power conversion efficiency.
In polymer donor material, it is D-A type narrow band gap polymer to study most commonly used, its main chain have electronics to There is strong charge transfer in body unit (D) and electron acceptor unit (A) alternating structure, intramolecular, can be by optimizing monomer knot Structure adjusts polymer band gap.Scientist successfully synthesis narrow band gap, wide absorption spectrum, excellent solubility, high mobility and compared with The D-A type conjugated polymer of high-energy conversion efficiency.Single battery highest energy based on D-A narrow band gap copolymer donor materials Conversion efficiency has exceeded 9% (J.Hou et al, Highly Efficient 2D-Conjugated Benzodithiophene-Based Photovoltaic Polymer with Linear Alkylthio Side Chain.Chem.Mater.,2014,26,3603-3605)。
In high-performance D-A polymer donor materials are designed, acid imide or lactams receptor unit cause people to pay close attention to, Such material includes pyrrolo-pyrrole-dione (DPP), and Thienopyrroles diketone (TPD), bioxindol (iI) and di- thiophene acyl are sub- Amine (BTI) etc..This kind of receptor unit has advantages below：(1) acid imide or lactam structure have stronger electron-withdrawing power, The energy level and band gap of polymer can effectively be adjusted；(2) brominated monomers can be readily obtained, HMW is obtained by coupling reaction Polymer；(3) interchain interaction is conducive to pi-pi accumulation and promotes intermolecular charge transition；(4) can be introduced on N atoms Alkyl chain, makes polymer have preferable dissolubility, is conducive to battery to prepare (X.Guo, Imide-and Amide- Functionalized Polymer Semiconductors.Chem.Rev.,2014,114,8943-9021).Therefore, by acyl The D-A copolymers that imines or lactams receptor unit are constructed have compared with low band gaps and higher carrier mobility.Based on pyrroles And pyrroledione, Thienopyrroles diketone, the energy conversion efficiency of bioxindol and the imido D-A copolymers of di- thiophene is More than 8%.
In order to obtain energy conversion efficiency higher, this area needs to develop that a kind of conjugate length is longer, interchain π-π are acted on Stronger receptor unit.
The content of the invention
For the problem that prior art is present, an object of the present invention is to provide a kind of for preparing the polymer sun Polymerized monomer of battery donor material and preparation method thereof, by the monomer polymerization obtain for polymer solar cells to Body material, and the polymer solar cells containing the donor material.It is of the invention for prepare polymer solar cells to The monomer of body material has conjugate length more long and stronger interchain π-π effects.
It is that, up to above-mentioned purpose, the present invention is adopted the following technical scheme that：
It is single that first aspect present invention provides a kind of lactams polymerization for preparing polymer solar cells donor material Body, the unit is that, containing two fused ring compounds of lactams hexatomic ring, the lactams is connected by singly-bound or conjugated bridge.
Preferably, any one expression in structure of the polymerized monomer as shown in logical formula (I) and logical formula (II)：
Ar in logical formula (I), logical formula (II)1- X is selected from any one in following structure：
Ar2Selected from any one in following structure：
Ar3Selected from any one in following structure：
Different loci in a, b, c, d, e, f representative structure formula；
Wherein, R is alkyl or acyl group；
Ar1In the structure of-X, R1Selected from hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, C1~C60Alkyl, C6~ C60Aryl, C1~C60Alkoxy, C3~C60Alkynyl, C3~C60Any one in heterocycle；R2It is C1~C60Alkyl；X is selected from Any one in hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom；
Ar2Structure in, R3Selected from hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, C1~C60Alkyl, C6~C60 Aryl, C1~C60Alkoxy, C3~C60Alkynyl, C3~C60Any one in heterocycle；R4It is C1~C60Alkyl；
Ar3Structure in, R5- and R6Independently selected from hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, C1~C60 Alkyl, C6~C60Aryl, C1~C60Alkoxy, C3~C60Alkynyl, C3~C60Any one in heterocycle；R7It is C1~C60Alkane Base.
" site " of the present invention refers to certain position in the chemical structural formula, such as in logical formula (I) and logical In in formula (II), a, b, d, c be in formula within the position of carbon atom at ortho position of amide nitrogen atom side be Point, the position of the four carbon atom of rotate counterclockwise on lactam nucleus.In Ar1、Ar2、Ar3Structure in, a, b, c, d, e, f are same Different loci in sample representative structure formula, works as Ar1、Ar2、Ar3Structure in site label and logical formula (I), logical formula (II), When site label is identical, represent that both are connected by this position, such as, for leading to formula (I), work as Ar1SelectionAr2Choosing SelectAr3SelectionIt is described for the poly- of polymer solar battery donor material during n selections 2 Closing monomer hasGeneral structure.
Preferably, the R is C1~C60Alkyl or C2~C60Alkanoyl；Preferably 2- ethylhexyls, 2- butyl octyls, 2- Any one in hexyl decyl or 2- octyldodecyls.
Preferably, the R1, R3, R5, R6Independently selected from hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, first Base, ethyl, propyl group, butyl, amyl group, hexyl, heptane base, octyl, nonyl, decyl, dodecyl, pentadecyl, 2- Ethylhexyl, 2- butyl octyls, 2- hexyls decyl, 2- octyldodecyls..
Preferably, the R2, R4, R7Independently selected from C1~C30Any one in alkyl, preferably is selected from butyl, and hexyl is pungent Base, decyl, dodecyl, myristyl, any one in cetyl.
Second aspect present invention provides a kind of preparation method of lactams polymerized monomer as described in relation to the first aspect.
When the polymer monomer is the structure shown in logical formula (I), the preparation method comprises the following steps：
(1) with Ar2D replaced by halogen atom, c by carboxyl replace compound A be raw material, acyl chlorides is carried out to carboxyl Change, obtain compound B；
(2) with Ar1The a compound C replaced by alkyl amino or acyl amino and compound B be raw material, by chemical combination The carbonyl of thing B is connected the compound D obtained with amido link with the nitrogen-atoms of compound C；
(3) ring-closure reaction is carried out by raw material of compound D, d is connected with b, obtain the logical formula (I) that X is hydrogen atom Shown compound；
(4) compound for being obtained with step (3) carries out the change that halogenation obtains shown in logical formula (I)s of the X as halogen atom as raw material Compound；
When the polymer monomer is the structure shown in logical formula (II), the preparation method comprises the following steps：
(1) with Ar1B replaced by halogen atom, a by carboxyl replace compound E be raw material, acyl chlorides is carried out to carboxyl Change, obtain compound F；
(2) with Ar2The c compound G replaced by alkyl amino or acyl amino and compound F be raw material, by chemical combination The carbonyl of thing F is connected the compound H obtained with amido link with the nitrogen-atoms of compound G；
(3) ring-closure reaction is carried out by raw material of compound H, b is connected with d, obtain the logical formula (II) that X is hydrogen atom Shown compound；
(4) compound for being obtained with step (3) carries out the change that halogenation obtains shown in logical formula (II)s of the X as halogen atom as raw material Compound.
Third aspect present invention provides a kind of lactams donor material for polymer solar battery, the donor Material is polymerized by polymerized monomer of the present invention.
Preferably, polymerized monomer of the donor material as described in first aspect present invention and double tin reagents, double borates Or any one or at least two copolymerization in double acid reagents are formed.
Preferably, the described pair of tin reagent can be double tin trimethyl based compounds that those skilled in the art can be known or Double tributyl tin based compounds, for example,： Deng,
Wherein, Y1、Y2It is independent selected from substituted or unsubstituted alkyl, it is substituted or unsubstituted alkoxy, alkyl-substituted Any one in thienyl or alkyl-substituted furyl, preferably is selected from hydrogen atom, substituted or unsubstituted C1~C20Alkyl, Substituted or unsubstituted C1~C20Alkoxy etc., further preferred methyl, ethyl, butyl, amyl group, hexyl, heptyl, octyl group, Nonyl, decyl, dodecyl, pentadecyl, octadecyl, 2- ethylhexyls, 2- butyl octyls, 2- hexyls decyl, 2- octyl groups Appointing in dodecyl, 2- ethyl hexyl oxies, hexadecane epoxide, 3- butyl decyloxy, methoxyl group, amoxy or heptadecane epoxide Meaning is a kind of；
Y3Selected from substituted or unsubstituted C1~C60Alkyl in any one, preferably methyl, ethyl, butyl, amyl group, Hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, pentadecyl, octadecyl, 2- ethylhexyls, 2- butyl octyls, 2- Any one in hexyl decyl or 2- octyldodecyls, further preferred hexyl, octyl group, decyl, dodecyl, 2- second Any one in base hexyl, 2- butyl octyls, 2- hexyls decyl or 2- octyldodecyls.
Preferably, described pair of tin reagent is double (trimethyl-tin-radical) thiophene of 2,5-, double (trimethyl-tin-radical) -4, the 8- bis- of 2,6- Different octyloxy benzo [1,2-b:3,4-b'] Dithiophene, double (the trimethyl-tin-radical) -4,4- diisooctyl thiophenes of 2,6- cough up simultaneously [3,2-b: 2 ', 3 '-d] Dithiophene, double (trimethyl-tin-radical) thieno [3,2-b] thiophene of 2,5-, 5,5 '-bis- (trimethyl-tin-radicals) -2,2 ' - Double (trimethyl-tin-radical) selenophens of di- thiophene, 2,5-, double (the trimethyl-tin-radical) -4,4- diisooctyl -4H- cyclopentas of 2,6- [2,1-b:5,4-b '] Dithiophene, double (the trimethyl-tin-radical) -4- iso-octyl dithienos [3,2-b of 2,6-:2 ', 3 '-d] in pyrroles Any one.
During described pair of borate or double acid reagents can be various known double borates or double boronic acid compounds, for example For： Deng,
Wherein, Y4Selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, alkyl-substituted thiophene or furan Any one in muttering, preferably is selected from hydrogen atom, substituted or unsubstituted C1~C20Alkyl, substituted or unsubstituted C1~C20's Alkoxy, further preferred methyl, ethyl, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, pentadecane Base, octadecyl, 2- ethylhexyls, 2- butyl octyls, 2- hexyls decyl, 2- octyldodecyls, 2- ethyl hexyl oxies, 16 Any one in alkoxy, 3- butyl decyloxy, methoxyl group, amoxy or heptadecane epoxide；
Y5Selected from substituted or unsubstituted alkyl, preferably methyl, ethyl, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, Decyl, dodecyl, pentadecyl, octadecyl, 2- ethylhexyls, 2- butyl octyls, 2- hexyls decyl or 2- octyl groups 12 Any one in alkyl, further preferred hexyl, octyl group, decyl, dodecyl, 2- ethylhexyls, 2- butyl octyls, 2- oneself Any one in base decyl or 2- octyldodecyls.
Preferably, described pair of borate or double acid reagents are 2,7- double (4,4,5,5- tetramethyl -1,3,2- dioxa boron Alkane) -9,9- dioctyl fluorenes, 2,7- double (4,4,5,5- tetramethyl -1,3,2- dioxaborinates) -9,9- dioctyls silicon fluorene, 2,7- Double (4,4,5,5- tetramethyl -1,3,2- dioxaborinates) -9- (1- octyl groups nonyl) carbazole, the pyrrolo- pyrrole of double borates modification Cough up double (4,4,5,5- tetramethyl -1,3,2- dioxaborinates) benzo [c] [1,2,5] thiadiazoles of diketone, 4,7-, 1,4- it is double (4, 4,5,5- tetramethyl -1,3,2- dioxaborinates) in double (4,4,5,5- tetramethyl -1,3,2- dioxaborinates) naphthalenes of benzene or 2,6- Any one.
Fourth aspect present invention provides a kind of polymer solar battery, the donor material of the polymer solar battery The lactams donor material for polymer solar battery described in the third aspect.
Compared with prior art, the present invention has the advantages that：
(1) it is lactam compound provided by the present invention for preparing the monomer of polymer solar cells donor material, increases Big effective conjugate length；
(2) more long provided by the present invention for preparing the donor material conjugate length of polymer solar cells, interchain π-π make With strong, packing of molecules order is high, significantly improves the carrier mobility of polymer；
(3) donor material that the present invention is provided is used to prepare polymer solar battery, highest energy conversion efficiency (PCE) Up to 7.48%.
Brief description of the drawings
Fig. 1 is obtained PThBDP, the ultraviolet-ray visible absorbing of the chloroformic solution of PSeBDP and PBDTBDP in embodiment 5-7 Spectrum；
Fig. 2 is obtained PThBDP, the uv-visible absorption spectra of PSeBDP and PBDTBDP films in embodiment 5-7；
Fig. 3 is obtained PThBDP, the cyclic voltammetry curve of PSeBDP and PBDTBDP in embodiment 5-7；
Fig. 4 is based on PThBDP/PC obtained in embodiment 571The polymer solar cells current -voltage curve of BM；
Fig. 5 is based on PSeBDP/PC obtained in embodiment 671The polymer solar cells current -voltage curve of BM；
Fig. 6 is based on PBDTBDP/PC obtained in embodiment 771The polymer solar cells current -voltage curve of BM；
Fig. 7 is, based on obtained PThBDP in embodiment 5-7, to be measured outside the polymer solar cells of PSeBDP and PBDTBDP Sub- efficiency curve.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation Example is used only for help and understands the present invention, is not construed as to concrete restriction of the invention.
The polymerized monomer for preparing polymer solar cells donor material described in specific embodiment of the present invention Can be any one in below general formula, but not limited to this as leading to the compound shown in formula (I)：
Wherein, X is selected from any one in hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom；R is alkyl or acyl Base；
R1, R3And R5Independently selected from hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, alkyl, aryl, alcoxyl Any one in base, alkynyl, heterocycle and derivative；R2And R7It is alkyl；
Can be any one in below general formula, but not limited to this as leading to the compound shown in formula (II)：
Wherein, X is selected from any one in hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom；R is alkyl or acyl Base；
R1, R3, R5And R6Independently selected from hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, alkyl, aryl, alkane Any one in epoxide, alkynyl, heterocycle and derivative；R2, R4And R7It is alkyl；
It is polymerized monomer with any one in the compound shown in logical formula (I), logical formula (II), with double tin reagents, double boron In acid esters or double acid reagents any one or at least two carry out copolymerization, obtain the donor for polymer solar battery Material.Described double tin reagents, double borates or double acid reagents are known double tin, in double borates or double boronic acid compounds Any one, double (trimethyl-tin-radical) thiophene of such as 2,5-, 2, the 6- different octyloxy benzos of double (trimethyl-tin-radical) -4,8- bis- [1,2-b:3,4-b '] Dithiophene etc., those skilled in the art can be tried described double tin according to the professional knowledge oneself grasped Agent, double borates or double acid reagents are selected.
It is polymerized monomer, the polymer that copolymerization is obtained with any one in the compound shown in logical formula (I), logical formula (II) Can act as the donor material of polymer solar cells.
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation Example is only to aid in understanding the present invention, is not construed as to concrete restriction of the invention.
Embodiment 1
Synthesis example 1：Compound 4 is synthesized by following reaction signal formula：
The preparation of the bromo- 2,2'- di-s thiophene -4,4'- dicarboxylic acid ethyl esters (1) of initiation material 5,5' bis- can refer to document synthesis (Selective Photoinduced Energy Transfer from a Thiophene Rotaxane to Acceptor.A.Harada,et al,Org.Lett.,2011,13,672-675)。
(1) synthesis of the bromo- 2,2'- di-s thiophene -4,4'- dioctyl phthalate (2) of 5,5' bis-
The bromo- 2,2'- di-s thiophene -4,4'- dicarboxylic acid ethyl esters (1) of 1.5g 5,5' bis- are sequentially added in 250mL single port bottles (3.6mmol), 50mL ethanol, 50mL tetrahydrofurans, 10mL water and 0.6g NaOH (14.4mmol), are refluxed overnight. Rotation removes half solvent after cooling, adds 50mL water, and it is 1 to be adjusted to pH value with watery hydrochloric acid, and suction filtration washing obtains 1.2g white solids (yield 90%).
1H NMR(d6-DMSO,400MHz,δ/ppm)：7.35(s,2H),4.04(br,2H).
(2) the bromo- N of 5,5' bis-4,N4'-bis- (2- octyldodecyls)-N4,N4'-two (thiophene -3) -2,2'- di-s thiophene - The synthesis of 4,4'- diamides (3)
1.9g compounds 2 (4.6mmol), 40mL dichloromethane, 4mL oxalyl chlorides are sequentially added in 100mL single port bottles (45.6mmol) and 2 drop DMFs, isolation moisture is stirred overnight at room temperature.Rotation removes dichloromethane and unnecessary grass Acyl chlorides, the white solid for obtaining is directly used in next step reaction.
This white solid is dissolved in 40mL dichloromethane, is added dropwise under ice-water bath and is contained 4.3g (11.5mmol) N- (2- octyl groups Dodecyl) (preparation method refers to document to -3- aminothiophenes：A New Thiophene Substituted Isoindigo Based Copolymer for High Performance Ambipolar Transistors.R.S.Ashraf,et al, Chem.Commun., 2012,48,3939-3941) and 2mL triethylamines dichloromethane solution (20mL).Stirring reaction at room temperature After overnight, reaction solution is poured into water, chloroform extraction, anhydrous sodium sulfate drying.Rotation removes solvent, and crude product is purified with column chromatography, Dichloromethane obtains 4.35g faint yellow solids (yield 83%) as eluant, eluent.
1H NMR(CDCl3,400MHz,δ/ppm)：7.16(s,2H),6.87(s,2H),6.78(br,2H),6.41(s, 2H), 3.78 (d, J=6.6Hz, 4H), 1.61 (br, 2H), 1.30-1.24 (m, 64H), 0.90-0.86 (t, 12H)；
13C NMR(CDCl3,100MHz,δ/ppm):164.33,140.33,138.83,135.76,125.53,125.38, 123.69,120.00,111.41,52.57,36.20,31.92,31.91,31.22,30.02,29.66,29.65,29.61, 29.57,29.35,29.32,26.31,22.68,14.12。
(3) 4,4'- double (2- octyldodecyls)-[double (dithieno [3,2-b of 7,7'-:2', 3'-d] pyridine)] -5, 5'(4H, 4'H)-diketone (4) synthesis
2.78g compounds 3 (2.45mmol) and 150mL DMAs, argon gas are added in 250mL reaction bulbs Protection is lower to add 660mg (1.8mmol) tricyclohexyl phosphine tetrafluoroborate, 4.0g (12.3mmol) cesium carbonates and 300mg (1.3mmol) palladium, 120 DEG C of reactions are overnight.Room temperature is cooled to, is poured into water, chloroform extraction, anhydrous sodium sulfate drying, rotation Except solvent, crude product is purified with column chromatography, petroleum ether/dichloromethane (1:4) as eluant, eluent, 1.32g yellow solids are obtained and (is produced Rate 56%).
1H NMR(CDCl3,400MHz,δ/ppm):7.78 (s, 2H), 7.47 (d, J=5.4Hz, 2H), 7.08 (d, J= 5.4Hz, 2H), 4.22 (d, J=4.5Hz, 4H), 2.00 (br, 2H), 1.37-1.23 (m, 64H), 0.88-0.85 (t, 12H).
13C NMR(CDCl3,100MHz,δ/ppm):157.41,140.21,139.89,132.42,128.34,125.15, 122.18,116.51,112.81,48.32,36.21,30.84,30.80,30.61,28.88,28.54,28.48,28.43, 28.24,28.18,25.61,21.59,21.56,12.97。
Embodiment 2
Synthesis example 2：The compound 4 obtained with embodiment 1 obtains compound BDP for raw material carries out bromination, reacts signal formula It is as follows：
The bromo- 4,4'- of 2,2'- bis- double (2- octyldodecyls)-[double (dithieno [3,2-b of 7,7'-:2', 3'-d] pyrrole Pyridine)] -5,5'(4H, 4'H)-diketone (BDP) synthesis
874mg compounds 4 (0.90mmol), 40mL chloroforms and 20mL N, N- dimethyl formyls are added in 100mL two-mouth bottles Amine, argon gas protection is lower to add 352mg N- bromo-succinimides (1.98mmol).At room temperature 150mL first is poured into after stirring 24h In alcohol, suction filtration, crude product is purified with column chromatography, petroleum ether/dichloromethane (1:4) as eluant, eluent, 632mg yellow solids are obtained (yield 62%).
1H NMR(CDCl3,400MHz,δ/ppm):7.75(s,2H),7.06(s,2H),4.14(br,4H),1.95(br, 2H),1.35-1.24(m,64H),0.88-0.85(t,12H)；
13C NMR(CDCl3,100MHz,δ/ppm):157.98,140.27,139.76,133.57,129.40,123.14, 120.55,115.37,114.77,49.31,37.17,31.92,31.89,31.46,29.97,29.64,29.59,29.54, 29.35,29.29,26.56,22.69,22.67,14.11。
Embodiment 3
Synthesis example 3：Compound 8 is synthesized by following reaction signal formula：
The synthesis of intermediate 6 refers to document (A New Thiophene Substituted Isoindigo Based Copolymer for High Performance Ambipolar Transistors.R.S.Ashraf,et al, Chem.Commun.2012,48,3939-3941)
(1) synthesis of intermediate 7
The bromo- thenoic acids of 1.50g 2- (7mmol), 40mL dichloromethane, 2mL grass are sequentially added in 100mL single port bottles Acyl chlorides (23mmol) and 2 drop DMFs, isolation moisture are stirred overnight at room temperature.Rotation is except dichloromethane and unnecessary Oxalyl chloride, the white solid for obtaining is directly used in next step reaction.
Acid chloride intermediate is dissolved in 30mL dichloromethane, is added dropwise under ice-water bath and is contained 2.6g (3mmol) intermediate 6 and 2mL The dichloromethane solution (30mL) of triethylamine.At room temperature stirring reaction overnight after, reaction solution is poured into water, chloroform extraction, nothing Aqueous sodium persulfate is dried.Rotation removes solvent, and crude product is purified with column chromatography, and dichloromethane obtains 2.69g yellow solids as eluant, eluent (yield 72%).
(3) synthesis of intermediate 8
Intermediate 7 (1.5g, 1.2mmol) and 40mL DMAs, argon gas is added to protect in 100mL reaction bulbs Shield is lower to add 220mg (0.6mmol) tricyclohexyl phosphine borofluoride, 1.05g (3.25mmol) cesium carbonates and 100mg (0.43mmol) palladium, 120 DEG C of reactions are overnight.Room temperature is cooled to, is poured into water, chloroform extraction, anhydrous sodium sulfate drying.Rotation Except solvent, crude product is purified with column chromatography, petroleum ether/dichloromethane (1:4) as eluant, eluent, 0.63g yellow solids are obtained and (is produced Rate 48%).
Embodiment 4
Synthesis example 4：The compound 8 obtained with embodiment 3 obtains compound 9 for raw material carries out bromination, and reaction signal formula is such as Under：
The synthesis of product 9
8 (310mg, 0.29mmol), 15mL chloroforms and 5mL DMFs, argon are added in 100mL two-mouth bottles 107mg N- bromo-succinimides are added under gas shielded；Poured into 150mL methyl alcohol after stirring 24h at room temperature, suction filtration, crude product Purified with column chromatography, petroleum ether/dichloromethane (1:3) as eluant, eluent, 306mg yellow solids (yield 86%) are obtained.
Embodiment 5
Combined polymerization example 1：The BDP provided with embodiment 2 and double (trimethyl-tin-radical) thiophene of 2,5- are monomer, carry out copolymerization and obtain Copolymer p ThBDP is obtained, reaction signal formula is as follows：
Operating procedure is：
116mg BDP (0.10mmol), double (trimethyl-tin-radical) thiophene of 42mg 2,5- are sequentially added in 100mL reaction bulbs (0.10mmol) and 30mL newly steam toluene, after argon gas emptying 15min, add 8mg Pd (PPh3)4, continue argon gas emptying 20min, The lower back flow reaction 24h of argon gas protection.After being cooled to room temperature, reaction solution is added drop-wise to precipitating in 150mL methyl alcohol.Suction filtration is slightly produced Thing, extracts 24h with methyl alcohol, n-hexane and chloroform respectively.150mL first is added drop-wise to again after chloroform extract is concentrated Precipitating in alcohol, suction filtration obtains red solid 90mg, yield 83%.
The nuclear-magnetism result of polymer P ThBDP：1H NMR(CDCl3,400MHz,δ/ppm):7.76-6.66(br,6H), 4.21(br,4H),1.58-0.85(br,78H)。
Polymer P ThBDP number-average molecular weights：89778g/mol, weight average molecular weight：264306g/mol, molecular weight distribution： 2.94。
Polymer P ThBDP heat decomposition temperatures (5% weight loss) are 439 DEG C.
Respectively in 604nm and 620nm, optical energy gap is 1.86eV to the absworption peak of polymer P ThBDP solution and film.
The oxidation of polymer P ThBDP and reduction potential are respectively 0.72V and -2.06V.
The highest occupied molecular orbital (HOMO) of polymer P ThBDP is -5.52eV, lowest unoccupied molecular orbital (LUMO) It is -2.74eV, electrochemistry energy gap is 2.78eV.
Fig. 4 is based on polymer P ThBDP/PC obtained in the present embodiment71Electric current-the electricity of the polymer solar battery of BM Buckle line.
Prepared with the methods described of embodiment 8 and be based on PThBDP/PC71The energy conversion efficiency (PCE) of the solar cell of BM is 7.48%, open-circuit voltage (Voc) it is 0.94V, short circuit current (Jsc) it is 11.58mA/cm2, fill factor, curve factor (FF) is 68.74%.
Embodiment 6
Combined polymerization example 2：The BDP provided with embodiment 2 and double (trimethyl-tin-radical) selenophens of 2,5- are monomer, carry out copolymerization and obtain Copolymer p SeBDP is obtained, reaction signal formula is as follows：
Operating procedure is：
81mg BDP (0.07mmol), double (trimethyl-tin-radical) selenophens of 33mg 2,5- are sequentially added in 100mL reaction bulbs (0.07mmol) and 30mL newly steam toluene, after argon gas emptying 15min, add 8mg Pd (PPh3)4, continue argon gas emptying 20min, The lower back flow reaction 24h of argon gas protection.After being cooled to room temperature, reaction solution is added drop-wise to precipitating in 150mL methyl alcohol.Suction filtration is slightly produced Thing, extracts 24h with methyl alcohol, n-hexane and chloroform respectively.150mL first is added drop-wise to again after chloroform extract is concentrated Precipitating in alcohol, suction filtration obtains violet solid 72mg, yield 91%.
The nuclear-magnetism result of polymer P SeBDP：1H NMR(CDCl3,400MHz,δ/ppm):7.66-6.76(br,6H), 4.16(br,4H),1.63-0.84(br,78H)。
Polymer P SeBDP number-average molecular weights：62055g/mol, weight average molecular weight：183926g/mol, molecular weight distribution： 2.96。
Polymer P SeBDP heat decomposition temperatures (5% weight loss) are 431 DEG C.
Respectively in 614nm and 641nm, optical energy gap is 1.80eV to the absworption peak of polymer P SeBDP solution and film.
The oxidation of polymer P SeBDP and reduction potential are respectively 0.71V and -2.00V.
The highest occupied molecular orbital (HOMO) of polymer P SeBDP is -5.51eV, lowest unoccupied molecular orbital (LUMO) It is -2.80eV, electrochemistry energy gap is 2.71eV.
Fig. 5 is based on polymer P SeBDP/PC obtained in the present embodiment71Electric current-the electricity of the polymer solar battery of BM Buckle line.
Prepared with the methods described of embodiment 8 and be based on PSeBDP/PC71The energy conversion efficiency (PCE) of the solar cell of BM is 5.08%, open-circuit voltage (Voc) it is 0.89V, short circuit current (Jsc) it is 8.60mA/cm2, fill factor, curve factor (FF) is 66.42%.
Embodiment 7
Combined polymerization example 3：BDP and the 2,6- different octyloxy benzos of double (trimethyl-tin-radical) -4,8- two provided with embodiment 2 [1,2-b:3,4-b '] Dithiophene be monomer, carry out copolymerization obtain copolymer p BDTBDP, reaction signal formula it is as follows：
Operating procedure is：
81mg BDP (0.07mmol), double (trimethyl-tin-radical) -4,8- of 54mg 2,6- are sequentially added in 100mL single port bottles Two different octyloxy benzo [1,2-b:3,4-b '] Dithiophene (0.07mmol) and 30mL newly steam toluene, after argon gas emptying 15min, plus Enter 8mg Pd (PPh3)4, continue argon gas emptying 20min, the lower back flow reaction 24h of argon gas protection.After being cooled to room temperature, by reaction solution It is added drop-wise to precipitating in 150mL methyl alcohol.Suction filtration obtains crude product, extracts 24h with methyl alcohol, n-hexane and chloroform respectively.By three Precipitating in 150mL methyl alcohol is added drop-wise to again after the concentration of chloromethanes extract, and suction filtration obtains red solid 93mg, yield 92%.
The nuclear-magnetism result of polymer P BDTBDP：1H NMR(CDCl3,400MHz,δ/ppm):7.64-6.21(br,6H), 4.40-3.75(br,8H),1.57-0.84(br,118H)。
Polymer P BDTBDP number-average molecular weights：48951g/mol, weight average molecular weight：156392g/mol, molecular weight distribution： 3.20。
Polymer P BDTBDP heat decomposition temperatures (5% weight loss) are 331 DEG C.
Respectively in 578nm and 591nm, optical energy gap is 1.98eV to the absworption peak of polymer P BDTBDP solution and film.
The oxidation of polymer P BDTBDP and reduction potential are respectively 0.73V and -2.12V.
The highest occupied molecular orbital (HOMO) of polymer P BDTBDP is -5.53eV, lowest unoccupied molecular orbital (LUMO) It is -2.68eV, electrochemistry energy gap is 2.85eV.
Fig. 6 is based on PBDTBDP/PC obtained in the present embodiment71The current -voltage curve of the solar cell of BM.
With the preparation of the methods described of embodiment 8 based on PBDTBDP/PC71The energy conversion efficiency (PCE) of the solar cell of BM It is 3.14%, open-circuit voltage (Voc) it is 0.87V, short circuit current (Jsc) it is 8.80mA/cm2, fill factor, curve factor (FF) is 41.07%.
The uv-visible absorption spectra of the respective chloroformic solution of polymer P BDTBDP, PThBDP and PSeBDP is shown in Fig. 1；It is poly- The uv-visible absorption spectra of compound PBDTBDP, PThBDP and PSeBDP film is shown in Fig. 2；Polymer P BDTBDP, PThBDP and The cyclic voltammetry curve of PSeBDP is shown in Fig. 3；Based on polymer P ThBDP/PC obtained in embodiment 571BM, based on embodiment 6 be obtained Polymer P SeBDP/PC71BM, based on polymer P BDTBDP/PC obtained in embodiment 771The outer quantum of the solar cell of BM Efficiency curve is shown in Fig. 7.
Embodiment 8
The preparation example of solar cell
Solar battery structure is ITO/PEDOT:PSS/Polymer:PC71BM/Ca/Al, preparation process is：
Ito glass uses cleaning agent, ultra-pure water, acetone and isopropanol to be cleaned by ultrasonic 20min successively, then ozone treatment 15min.The spin coating PEDOT on ito glass:PSS(CleviosTMP VP Al 4083,30nm), toast 10min at 150 DEG C. The polymer (Polymer) and PC that embodiment 5~7 is obtained71BM is dissolved in o-dichlorohenzene, the appropriate diiodo-octane of addition (1%~ 5%), and it is spin-coated on PEDOT layers, (10 under high vacuum-4Pa Ca (10nm) and Al (100nm)) are deposited with successively as negative electrode.Too Positive cell active area is 4mm2。
Using solar simulator (Newport, 150W, AM 1.5G, 100mW/cm2) and the source tables pair of Keithley 2420 Battery carries out performance test.
Wherein, ITO (Indium Tin Oxide), tin indium oxide, as the anode of polymer solar cells in embodiment；
PEDOT:PSS is a kind of suspension, is made up of two kinds of materials of PEDOT and PSS, and PEDOT is poly- (3,4- enedioxies Thiophene), PSS is poly styrene sulfonate；
PC71BM is fullerene derivate electron acceptor；
Polymer is the polymer that embodiment 5~7 is obtained.
Comparative example
Replace the polymer (Polymer) in embodiment 8 with the P3HT (poly- 3- hexyl thiophenes) of purchase, prepare bulk heterojunction Polymer solar cells.
Based on P3HT/PC71The energy conversion efficiency (PCE) of the polymer solar cells of BM is 4.41%, open-circuit voltage (Voc) it is 0.65V, short circuit current (Jsc) it is 9.7mA/cm2, fill factor, curve factor (FF) is 70.0%.
Applicant states that the present invention illustrates detailed process equipment of the invention and technological process by above-described embodiment, But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, Addition, the selection of concrete mode to the equivalence replacement and auxiliary element of each raw material of product of the present invention etc., all fall within of the invention Within the scope of protection domain and disclosure.

Claims (9)

1. a kind of lactams polymerized monomer for preparing polymer solar cells donor material, it is characterised in that the list Any one expression in structure of the body as shown in logical formula (I) and logical formula (II)：
Wherein, R is C1~C60Alkyl or C2~C60Alkanoyl；
Ar in logical formula (I), logical formula (II)1- X is selected from any one in following structure：
Ar2Selected from any one in following structure：
Ar3Selected from any one in following structure：
Wherein, the different loci in a, b, c, d, e, f representative structure formula；
Ar1In the structure of-X, R1Selected from hydrogen atom, fluorine atom, cyano group, nitro, C1~C60Alkyl, C6~C60Aryl, C1~C60 Alkoxy, C3~C60Alkynyl, C3~C60Heterocycle, C1~C60Alkyl-substituted thiophene, C1~C60Alkyl-substituted furans, C1~C60 Alkyl-substituted pyrroles, C1~C60Any one in alkyl-substituted thienothiophene；R2It is C1~C60Alkyl；X is selected from chlorine Any one in atom, bromine atoms or iodine atom；
Ar2Structure in, R3Selected from hydrogen atom, fluorine atom, cyano group, nitro, C1~C60Alkyl, C6~C60Aryl, C1~C60Alkane Epoxide, C3~C60Alkynyl, C3~C60Heterocycle, C1~C60Alkyl-substituted thiophene, C1~C60Alkyl-substituted furans, C1~C60Alkane Pyrroles, the C of base substitution1~C60Any one in alkyl-substituted thienothiophene；R4It is C1~C60Alkyl；
Ar3Structure in, R5And R6Independently selected from hydrogen atom, fluorine atom, cyano group, nitro, C1~C60Alkyl, C6~C60Aromatic hydrocarbons Base, C1~C60Alkoxy, C3~C60Alkynyl, C3~C60Heterocycle, C1~C60Alkyl-substituted thiophene, C1~C60Alkyl-substituted furan Mutter, C1~C60Alkyl-substituted pyrroles, C1~C60Any one in alkyl-substituted thienothiophene；R7It is C1~C60Alkane Base；R8It is C1~C60Alkyl.
2. polymerized monomer according to claim 1, it is characterised in that the R is 2- ethylhexyls, 2- butyl octyls, 2- Any one in hexyl decyl or 2- octyldodecyls.
3. polymerized monomer according to claim 1 and 2, it is characterised in that the R1, R3, R5, R6It is former independently selected from hydrogen Son, fluorine atom, cyano group, nitro, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptane base, octyl, nonyl, decane Base, dodecyl, pentadecyl, melissyl, phenyl, pyridine radicals, quinolyl, phenothiazinyl, benzodiazepine base, thiophene Any one in base, furyl, pyrazolyl, pyrimidine radicals.
4. polymerized monomer according to claim 1 and 2, it is characterised in that the R7Selected from methyl, ethyl, propyl group, butyl, Amyl group, hexyl, heptane base, octyl, nonyl, decyl, dodecyl, any one in pentadecyl, melissyl.
5. polymerized monomer according to claim 1 and 2, it is characterised in that the R2, R4, R7, R8Independently selected from butyl, Hexyl, octyl group, decyl, dodecyl, myristyl, any one in cetyl.
6. a kind of preparation method of the compound BDP of following formula, comprises the following steps：
874mg compounds 4,40mL chloroforms and 20mL DMFs are added in 100mL two-mouth bottles, under argon gas protection 352mg N- bromo-succinimides are added, is poured into 150mL methyl alcohol after stirring 24h at room temperature, suction filtration, crude product column chromatography Purification, 1:4 petroleum ether/dichloromethane obtains product BDP as eluant, eluent；
7. a kind of preparation method of the compound 9 of following formula, comprises the following steps：
310mg, the compound 8 of 0.29mmol, 15mL chloroforms and 5mLN, dinethylformamide, argon are added in 100mL two-mouth bottles 107mg N- bromo-succinimides are added under gas shielded；Poured into 150mL methyl alcohol after stirring 24h at room temperature, suction filtration, crude product Purified with column chromatography, 1:3 petroleum ether/dichloromethane obtains product Compound 9 as eluant, eluent；
8. a kind of donor material, it is characterised in that polymerized monomer of the donor material as described in claim any one of 1-5 with Any one or at least two copolymerization in double tin reagents, double borates or double acid reagents are formed；
Described pair of tin reagent is double (trimethyl-tin-radical) thiophene of 2,5-, the 2,6- different octyloxy benzene of double (trimethyl-tin-radical) -4,8- two And [1,2-b:3,4-b'] Dithiophene, double (the trimethyl-tin-radical) -4,4- diisooctyl thiophenes of 2,6- cough up simultaneously [3,2-b:2 ', 3 '-d] two Thiophene, 2,5- double (trimethyl-tin-radical) thieno [3,2-b] thiophene, 5,5 '-bis- (trimethyl-tin-radicals) -2,2 '-di- thiophene, 2, Double (trimethyl-tin-radical) selenophens of 5-, double (the trimethyl-tin-radical) -4,4- diisooctyl -4H- cyclopentas [2,1-b of 2,6-:5,4- B '] Dithiophene, double (the trimethyl-tin-radical) -4- iso-octyl dithienos [3,2-b of 2,6-:2 ', 3 '-d] any one in pyrroles；
Described pair of borate or double acid reagents are double (4,4,5,5- tetramethyl -1,3,2- the dioxaborinates) -9,9- two of 2,7- Double (4,4,5,5- tetramethyl -1,3,2- the dioxaborinates) -9,9- dioctyls silicon fluorenes of octyl group fluorenes, 2,7-, the double (4,4,5,5- of 2,7- Tetramethyl -1,3,2- dioxaborinates) -9- (1- octyl groups nonyl) carbazole, double borates modification pyrrolo-pyrrole-dione, 4,7- Double (the 4,4,5,5- tetramethyls of double (4,4,5,5- tetramethyl -1,3,2- dioxaborinates) benzo [c] [1,2,5] thiadiazoles, 1,4- Base -1,3,2- dioxaborinates) it is any one in double (4,4,5,5- tetramethyl -1,3,2- dioxaborinates) naphthalenes of benzene or 2,6- It is individual.
9. a kind of polymer solar battery, it is characterised in that the donor material of the polymer solar battery will for right Seek the donor material described in 8.
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