CN104478900A - Lactam receptor unit as well as preparation method and use thereof - Google Patents

Lactam receptor unit as well as preparation method and use thereof Download PDF

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CN104478900A
CN104478900A CN201410720454.6A CN201410720454A CN104478900A CN 104478900 A CN104478900 A CN 104478900A CN 201410720454 A CN201410720454 A CN 201410720454A CN 104478900 A CN104478900 A CN 104478900A
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CN104478900B (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
    • 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
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/18—Definition of the polymer structure conjugated
    • 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
    • C08G2261/3243—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

The invention relates to a monomer for preparing a donor material used in a polymer solar cell. The monomer is a compound containing two lactam six-membered rings and the lactam structure is connected by a single bond or a conjugated bridge. The lactam compound provided by the invention is used for preparing the donor material used in the polymer solar cell, and the effective conjugation length can be increased; the copolymer donor material obtained by polymerization has a large conjugation plane, strong inter-chain Pi-Pi effect and ordered molecular packing, and thus the carrier mobility and the energy conversion efficiency of the polymer are significantly improved; and the energy conversion efficiency (PCE) of the prepared polymer solar cell can reach up to 7.48%.

Description

A kind of lactams is by body unit and its production and use
Technical field
The invention belongs to solar cell field, be specifically related to the polymerization single polymerization monomer of the donor material for the preparation of polymer solar cells, relate to a kind of lactams monomer and preparation method thereof further, and the donor material for polymer solar cells that described monomer polymerization obtains.
Background technology
Along with global industry and rapid economic development, the demand of the mankind to the energy increases rapidly.Fossil energy is the main energy sources that the current mankind consume, but along with continuous exploitation, the exhaustion of fossil energy is inevitable.The environmental pollution that a large amount of use fossil energy causes is more and more serious.Solar cell directly converts solar energy into electrical energy, and is to solve a kind of effective way of energy dilemma.
Polymer solar cells generally adopts bulk heterojunction structure (G.Yu et al, Polymer PhotovoltaicCells:Enhanced Efficiencies via a Network of Internal Donor-acceptorHeterojunctions.Science, 1995,270,1789-1791), mainly comprise transparency electrode (ITO), hole transmission layer (as PEDOT:PSS), active coating containing donor material and acceptor material, metal electrode (as Al, Ag, Ca).The advantage of bulk heterojunction battery is: to body and the blended formation inierpeneirating network structure of acceptor material, increase to body/acceptor interface, for electronics and hole transport provide rapid passage, improves cell power conversion efficiency.
In polymer donor material, research is D-A type narrow band gap polymkeric substance the most widely, its main chain has electron donor(ED) unit (D) and electron acceptor(EA) unit (A) alternating structure, molecular memory shifts at strong charge, can carry out telomerized polymer band gap by optimizing monomer structure.The D-A type conjugated polymer of the successful synthesis of narrow band gap of scientist, wide absorption spectrum, excellent solubility, high mobility and higher-energy efficiency of conversion.Single battery highest energy efficiency of conversion based on D-A narrow band gap multipolymer donor material has exceeded 9% (J.Hou et al, Highly Efficient 2D-Conjugated Benzodithiophene-Based PhotovoltaicPolymer with Linear Alkylthio Side Chain.Chem.Mater., 2014,26,3603-3605).
In design high-performance D-A polymer donor material, imide or lactams cause people to pay close attention to by body unit, such material comprises pyrrolo-pyrrole-dione (DPP), Thienopyrroles diketone (TPD), bioxindol (iI) and di-thiophene imide (BTI) etc.This receptoroid unit has the following advantages: (1) imide or lactam structure have stronger electron-withdrawing power, can the effectively energy level of telomerized polymer and band gap; (2) brominated monomers can be obtained easily, be obtained the polymkeric substance of high molecular by linked reaction; (3) interchain interaction is conducive to pi-pi accumulation and promotes intermolecular charge transition; (4) atom N can introduce alkyl chain, make polymkeric substance have good solvability, be conducive to battery preparation (X.Guo, Imide-andAmide-Functionalized Polymer Semiconductors.Chem.Rev., 2014,114,8943-9021).Therefore, by the D-A multipolymer that body unit is constructed, there is comparatively low band gaps and higher carrier mobility by imide or lactams.Based on pyrrolo-pyrrole-dione, Thienopyrroles diketone, the effciency of energy transfer of bioxindol and the imido D-A multipolymer of di-thiophene is all more than 8%.
In order to obtain higher effciency of energy transfer, this area needs to develop that a kind of conjugate length is longer, interchain π-π acts on stronger by body unit.
Summary of the invention
For prior art Problems existing, an object of the present invention is to provide a kind of polymerization single polymerization monomer for the preparation of polymer solar cells donor material and preparation method thereof, the donor material for polymer solar cells obtained by described monomer polymerization, and the polymer solar cells containing described donor material.Monomer for the preparation of polymer solar cells donor material of the present invention has longer conjugate length and stronger interchain π-π acts on.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
First aspect present invention provides a kind of lactams polymerization single polymerization monomer for the preparation of polymer solar cells donor material, and described unit is the fused ring compound containing two lactan six-rings, and described lactan is connected by singly-bound or conjugated bridge.
As preferably, described polymerization single polymerization monomer is represented by any one in the structure shown in general formula (I) and general formula (II):
Wherein, R is alkyl or acyl group;
Ar in general formula (I), general formula (II) 1-X is selected from any one in following structure:
Ar 2be selected from any one in following structure:
Ar 3be selected from any one in following structure:
Different loci in a, b, c, d, e, f representative structure formula;
Ar 1in the structure of-X, R 1be selected from any one in hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, alkyl, aryl, alkoxyl group, alkynyl, heterocycle or Hete rocyclic derivatives; R 2for alkyl; X is selected from any one in hydrogen atom, fluorine atom, chlorine atom, bromine atoms or atomic iodine;
Ar 2structure in, R 3be selected from any one in hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, alkyl, aryl, alkoxyl group, alkynyl, heterocycle or Hete rocyclic derivatives; R 4for alkyl;
Ar 3structure in, R 5, R 6and R 7independently selected from any one in hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, alkyl, aryl, alkoxyl group, alkynyl, heterocycle or Hete rocyclic derivatives; R 8for alkyl.
" site " of the present invention refers to certain position in described chemical structural formula, in such as in general formula (I) and general formula (II), a position, b position, d position, c position be in general formula within the position of carbon atom at ortho position of amide nitrogen atom side be starting point, the position of the four carbon atom that lactam nucleus is rotated counterclockwise.At Ar 1, Ar 2, Ar 3structure in, the different loci in the same representative structure formula of a, b, c, d, e, f, works as Ar 1, Ar 2, Ar 3structure in site label and general formula (I), general formula (II), site label identical time, both expressions are connected by this position, such as, for general formula (I), work as Ar 1select ar 2select ar 3select when n selects 2, the described polymerization single polymerization monomer for polymer solar battery donor material has general structure.
As preferably, described R is substituted or unsubstituted C 1~ C 60alkyl or substituted or unsubstituted C 2~ C 60alkyloyl; Be preferably any one in 2-ethylhexyl, 2-butyl octyl, 2-hexyl decyl or 2-octyldodecyl.
As preferably, described R 1, R 3, R 5, R 6, R 7independently selected from hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, substituted or unsubstituted C 1~ C 60alkyl, substituted or unsubstituted C 6~ C 60aryl, substituted or unsubstituted C 1~ C 60alkoxyl group, substituted or unsubstituted C 3~ C 60alkynyl, substituted or unsubstituted C 3~ C 60any one in heterocyclic radical.
Preferably, described substituted or unsubstituted C 3~ C 60heterocyclic radical is C 1~ C 60thiophene, C that alkyl replaces 1~ C 60furans, C that alkyl replaces 1~ C 60the pyrroles that alkyl replaces, C 1~ C 60the thienothiophene that alkyl replaces.
Preferably, described R 2, R 4, R 8independently selected from substituted or unsubstituted C 1~ C 60alkyl, substituted or unsubstituted C 1~ C 60any one in cycloalkyl.
As preferably, described R 1, R 3, R 5, R 6, R 7independently selected from hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptane base, octyl, nonyl, decyl, dodecyl, pentadecyl, triacontyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzene alkyl, substituted or unsubstituted naphthalane base, substituted or unsubstituted perhydroanthracene base, substituted or unsubstituted thiophene alkyl, substituted or unsubstituted pyridine alkyl, substituted or unsubstituted thiazolidyl, substituted or unsubstituted pyrrolidyl, substituted or unsubstituted pentacene alkyl, substituted or unsubstituted alkynyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted benzodiazepine base, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyrazolyl, any one in substituted or unsubstituted pyrimidyl,
Preferably, described R 2, R 4, R 8independently selected from substituted or unsubstituted C 1~ C 30any one in alkyl, preferably from butyl, hexyl, octyl group, decyl, dodecyl, tetradecyl, any one in hexadecyl.
Second aspect present invention provides a kind of preparation method of polymerization single polymerization monomer of the present invention, and when described polymer monomer is for structure shown in general formula (I), described preparation method comprises the steps:
(1) with Ar 2d position replaced by halogen atom, c position is raw material by the compd A of carboxyl substituted, carries out chloride, obtain compd B to carboxyl;
(2) with Ar 1the Compound C that replaced by alkylamino or acyl amino of a position and compd B be raw material, being connected with the nitrogen-atoms of Compound C by the carbonyl of compd B obtains having the Compound D of amido linkage;
(3) be that raw material carries out ring-closure reaction with Compound D, d position be connected with b position, obtain the compound shown in general formula (I) that X is hydrogen atom;
Alternatively, step (4) is carried out after step (3): the compound obtained with step (3) obtains the compound shown in general formula (I) that X is halogen atom for raw material carries out halogenation;
When described polymer monomer is for structure shown in general formula (II), described preparation method comprises the steps:
(1) with Ar 1b position replaced by halogen atom, a position is raw material by the compd E of carboxyl substituted, carries out chloride, obtain compound F 17-hydroxy-corticosterone to carboxyl;
(2) with Ar 2the compound G that replaced by alkylamino or acyl amino of c position and compound F 17-hydroxy-corticosterone be raw material, being connected with the nitrogen-atoms of compound G by the carbonyl of compound F 17-hydroxy-corticosterone obtains having the compound H of amido linkage;
(3) be that raw material carries out ring-closure reaction with compound H, b position be connected with d position, obtain the compound shown in general formula (II) that X is hydrogen atom;
Alternatively, step (4) is carried out after step (3): the compound obtained with step (3) obtains the compound shown in general formula (II) that X is halogen atom for raw material carries out halogenation.
Third aspect present invention provides a kind of donor material for polymer solar battery, and described donor material is polymerized by polymerization single polymerization monomer of the present invention.
Preferably, described donor material is formed by polymerization single polymerization monomer copolymerization of the present invention.
As preferably, described donor material is formed by polymerization single polymerization monomer of the present invention and any one in two tin reagent, two boric acid ester or two acid reagent or at least two copolymerization.
Preferably, the described pair of tin reagent is selected from any one in two tin trimethyl based compounds or two tributyl tin based compound, such as, be: deng,
Wherein, Y 1, Y 2independently be selected from any a kind in substituted or unsubstituted alkyl, substituted or unsubstituted alkoxyl group, the thienyl of alkyl replacement or the furyl of alkyl replacement, preferably from hydrogen atom, substituted or unsubstituted C 1~ C 20alkyl, substituted or unsubstituted C 1~ C 20alkoxyl group etc., any a kind in further preferable methyl, ethyl, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, pentadecyl, octadecyl, 2-ethylhexyl, 2-butyl octyl, 2-hexyl decyl, 2-octyldodecyl, 2-ethyl hexyl oxy, n-Hexadecane oxygen base, 3-butyl oxygen in last of the ten Heavenly stems base, methoxyl group, pentyloxy or heptadecane oxygen base;
Y 3be selected from substituted or unsubstituted C 1~ C 60alkyl in any one, any one in preferable methyl, ethyl, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, pentadecyl, octadecyl, 2-ethylhexyl, 2-butyl octyl, 2-hexyl decyl or 2-octyldodecyl, any one further preferably in hexyl, octyl group, decyl, dodecyl, 2-ethylhexyl, 2-butyl octyl, 2-hexyl decyl or 2-octyldodecyl.
Preferably, described pair of tin reagent is 2, two (trimethyl-tin-radical) thiophene of 5-, 2, two (trimethyl-tin-radical)-4 of 6-, the different octyloxy benzo [1 of 8-bis-, 2-b:3, 4-b'] two thiophene, 2, two (trimethyl-tin-radical)-4 of 6-, 4-diisooctyl thiophene coughs up also [3, 2-b:2 ', 3 '-d] two thiophene, 2, two (trimethyl-tin-radical) thieno-[3 of 5-, 2-b] thiophene, 5, 5 '-bis-(trimethyl-tin-radical)-2, 2 '-di-thiophene, 2, two (trimethyl-tin-radical) selenophen of 5-, 2, two (trimethyl-tin-radical)-4 of 6-, 4-diisooctyl-4H-cyclopenta [2, 1-b:5, 4-b '] two thiophene, 2, two (trimethyl-tin-radical)-4-iso-octyl two thieno-[3 of 6-, 2-b:2 ', 3 '-d] any one in pyrroles.
Preferably, described pair of boric acid ester or two acid reagent are selected from any one in two boric acid esters or two boronic acid compounds, such as, be: deng,
Wherein, Y 4be selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxyl group, alkyl replace thiophene or furans in any one, preferably from hydrogen atom, substituted or unsubstituted C 1~ C 20alkyl, substituted or unsubstituted C 1~ C 20alkoxyl group, any one in further preferable methyl, ethyl, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, pentadecyl, octadecyl, 2-ethylhexyl, 2-butyl octyl, 2-hexyl decyl, 2-octyldodecyl, 2-ethyl hexyl oxy, n-Hexadecane oxygen base, 3-butyl oxygen in last of the ten Heavenly stems base, methoxyl group, pentyloxy or heptadecane oxygen base;
Y 5be selected from substituted or unsubstituted alkyl, any one in preferable methyl, ethyl, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, pentadecyl, octadecyl, 2-ethylhexyl, 2-butyl octyl, 2-hexyl decyl or 2-octyldodecyl, any one further preferably in hexyl, octyl group, decyl, dodecyl, 2-ethylhexyl, 2-butyl octyl, 2-hexyl decyl or 2-octyldodecyl.
Preferably, described pair of boric acid ester or two acid reagent are 2, 7-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate)-9, 9-dioctyl fluorene, 2, 7-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate)-9, 9-dioctyl silicon fluorenes, 2, 7-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate)-9-(1-octyl group nonyl) carbazole, the pyrrolo-pyrrole-dione that two boric acid ester is modified, 4, 7-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate) benzo [c] [1, 2, 5] thiadiazoles, 1, 4-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate) benzene or 2, 6-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate) any one in naphthalene.
Fourth aspect present invention provides a kind of polymer solar battery, and the donor material of described polymer solar battery is donor material of the present invention.
Compared with prior art, the present invention has following beneficial effect:
(1) monomer for the preparation of polymer solar cells donor material provided by the invention is lactam compound, increases effective conjugate length;
(2) the donor material conjugate length for the preparation of polymer solar cells provided by the invention is longer, and interchain π-π acts on strong, and packing of molecules order is high, significantly improves the carrier mobility of polymkeric substance;
(3) donor material provided by the invention is for the preparation of polymer solar battery, and highest energy efficiency of conversion (PCE) reaches 7.48%.
Accompanying drawing explanation
Fig. 1 is PThBDP obtained in embodiment 5-7, the uv-visible absorption spectra of the chloroformic solution of PSeBDP and PBDTBDP;
Fig. 2 is PThBDP obtained in embodiment 5-7, the uv-visible absorption spectra of PSeBDP and PBDTBDP film;
Fig. 3 is PThBDP obtained in embodiment 5-7, the cyclic voltammetry curve of PSeBDP and PBDTBDP;
Fig. 4 is based on the obtained PThBDP/PC of embodiment 5 71the polymer solar cells current-voltage curve of BM;
Fig. 5 is based on the obtained PSeBDP/PC of embodiment 6 71the polymer solar cells current-voltage curve of BM;
Fig. 6 is based on the obtained PBDTBDP/PC of embodiment 7 71the polymer solar cells current-voltage curve of BM;
Fig. 7 is based on PThBDP obtained in embodiment 5-7, the polymer solar cells external quantum efficiency curve of PSeBDP and PBDTBDP.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
The polymerization single polymerization monomer for the preparation of polymer solar cells donor material described in embodiment of the present invention can be any one in following general formula by the compound shown in general formula (I), but is not limited thereto:
Wherein, X is selected from any one in hydrogen atom, fluorine atom, chlorine atom, bromine atoms or atomic iodine; R is alkyl or acyl group;
R 1, R 3and R 5independently selected from any one in hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, alkyl, aryl, alkoxyl group, alkynyl, heterocycle and derivative; R 2and R 8for alkyl;
Can be any one in following general formula by the compound shown in general formula (II), but be not limited thereto:
Wherein, X is selected from any one in hydrogen atom, fluorine atom, chlorine atom, bromine atoms or atomic iodine; R is alkyl or acyl group;
R 1, R 3, R 5, R 6and R 7independently selected from any one in hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, alkyl, aryl, alkoxyl group, alkynyl, heterocycle and derivative; R 2, R 4and R 8for alkyl;
With any one in the compound shown in general formula (I), general formula (II) for polymerization single polymerization monomer, carry out copolymerization with any one in two tin reagent, two boric acid ester or two acid reagent or at least two, obtain the donor material for polymer solar battery.Described two tin reagents, two boric acid ester or two acid reagent are known two tin, any one in two boric acid ester or two boronic acid compounds, such as 2,5-two (trimethyl-tin-radical) thiophene, 2, two (trimethyl-tin-radical)-4 of 6-, 8-bis-different octyloxy benzo [1,2-b:3,4-b '] two thiophene etc., the expertise that those skilled in the art can grasp according to oneself is to described two tin reagents, and two boric acid ester or two acid reagent are selected.
With any one in the compound shown in general formula (I), general formula (II) for polymerization single polymerization monomer, the polymkeric substance that copolymerization obtains can be used 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 should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
Synthesis example 1: by following reaction signal formula synthetic compound 4:
Starting raw material 5,5' bis-bromo-2,2'-di-thiophene-4, the preparation of 4'-dicarboxylic acid ethyl ester (1) 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).
The synthesis of bromo-2,2'-di-thiophene-4, the 4'-dioctyl phthalate (2) of (1) 5,5' bis-
Bromo-2, the 2'-di-thiophene-4 of 1.5g 5,5' bis-are added successively in 250mL single port bottle, 4'-dicarboxylic acid ethyl ester (1) (3.6mmol), 50mL ethanol, 50mL tetrahydrofuran (THF), 10mL water and 0.6g sodium hydroxide (14.4mmol), return stirring spends the night.Revolve after cooling except half solvent, add 50mL water, being adjusted to pH value with dilute hydrochloric acid is 1, and suction filtration washing obtains 1.2g white solid (productive rate 90%).
1H NMR(d6-DMSO,400MHz,δ/ppm)：7.35(s,2H),4.04(br,2H)。
The bromo-N of (2) 5,5' bis- 4, N 4'-bis-(2-octyldodecyl)-N 4, N 4'-two (thiophene-3)-2,2'-synthesis of di-thiophene-4,4'-diamide (3)
1.9g compound 2 (4.6mmol) is added successively, 40mL methylene dichloride, 4mL oxalyl chloride (45.6mmol) and 2 DMFs, isolated moisture room temperature for overnight in 100mL single port bottle.Revolve except methylene dichloride and unnecessary oxalyl chloride, the white solid obtained is directly used in next step reaction.
This white solid is dissolved in 40mL methylene dichloride, drip under ice-water bath containing 4.3g (11.5mmol) N-(2-octyldodecyl)-3-aminothiophene that (preparation method can reference: A New ThiopheneSubstituted Isoindigo Based Copolymer for High Performance Ambipolar Transistors.R.S.Ashraf, et al, Chem.Commun., 2012,48,3939-3941) and the dichloromethane solution (20mL) of 2mL triethylamine.Reaction solution is poured into water, chloroform extraction, anhydrous sodium sulfate drying after spending the night by stirred at ambient temperature reaction.Revolve and desolventize, thick product column chromatography is purified, and methylene dichloride, as eluent, obtains 4.35g faint yellow solid (productive rate 83%).
1H NMR(CDCl 3,400MHz,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(CDCl 3,100MHz,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'-two (2-octyldodecyl)-[7,7'-two (two thieno-s [3,2-b:2', 3'-d] pyridine)]-5,5'(4H, 4'H) synthesis of-diketone (4)
2.78g compound 3 (2.45mmol) and 150mL N is added in 250mL reaction flask; N-N,N-DIMETHYLACETAMIDE; 660mg (1.8mmol) tricyclohexyl phosphine a tetrafluoro borate is added under argon shield; 4.0g (12.3mmol) cesium carbonate and 300mg (1.3mmol) palladium, 120 DEG C of reactions are spent the night.Be cooled to room temperature, be poured into water, chloroform extraction, anhydrous sodium sulfate drying, revolve and desolventize, thick product column chromatography is purified, and sherwood oil/methylene dichloride (1:4), as eluent, obtains 1.32g yellow solid (productive rate 56%).
1H NMR(CDCl 3,400MHz,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(CDCl 3,100MHz,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 carries out bromination for raw material, obtains compd B DP, reaction signal formula is as follows:
2,2'-bis-bromo-4,4'-two (2-octyldodecyl)-[7,7'-two (two thieno-s [3,2-b:2', 3'-d] pyridine)]-5,5'(4H, 4'H) synthesis of-diketone (BDP)
Add 874mg compound 4 (0.90mmol) in 100mL two-mouth bottle, 40mL chloroform and 20mLN, dinethylformamide, under argon shield, add 352mg N-bromo-succinimide (1.98mmol).Pour in 150mL methyl alcohol after stirred at ambient temperature 24h, suction filtration, thick product column chromatography is purified, and sherwood oil/methylene dichloride (1:4), as eluent, obtains 632mg yellow solid (productive rate 62%).
1H NMR(CDCl 3,400MHz,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(CDCl 3,100MHz,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: by following reaction signal formula synthetic compound 8:
The synthesis of intermediate 6 can reference (A New Thiophene Substituted Isoindigo BasedCopolymer for High Performance Ambipolar Transistors.R.S.Ashraf, et al, Chem.Commun.2012,48,3939-3941)
(1) synthesis of intermediate 7
The bromo-thenoic acid of 1.50g 2-(7mmol) is added successively, 40mL methylene dichloride, 2mL oxalyl chloride (23mmol) and 2 DMFs, isolated moisture room temperature for overnight in 100mL single port bottle.Revolve except methylene dichloride and unnecessary oxalyl chloride, the white solid obtained is directly used in next step reaction.
Acid chloride intermediate is dissolved in 30mL methylene dichloride, under ice-water bath, drips the dichloromethane solution (30mL) containing 2.6g (3mmol) intermediate 6 and 2mL triethylamine.Reaction solution is poured into water, chloroform extraction, anhydrous sodium sulfate drying after spending the night by stirred at ambient temperature reaction.Revolve and desolventize, thick product column chromatography is purified, and methylene dichloride, as eluent, obtains 2.69g yellow solid (productive rate 72%).
(3) synthesis of intermediate 8
Intermediate 7 (1.5g is added in 100mL reaction flask; 1.2mmol) with 40mL N; N-N,N-DIMETHYLACETAMIDE; 220mg (0.6mmol) tricyclohexyl phosphine fluoroborate is added under argon shield; 1.05g (3.25mmol) cesium carbonate and 100mg (0.43mmol) palladium, 120 DEG C of reactions are spent the night.Cool to room temperature, is poured into water, chloroform extraction, anhydrous sodium sulfate drying.Revolve and desolventize, thick product column chromatography is purified, and sherwood oil/methylene dichloride (1:4), as eluent, obtains 0.63g yellow solid (productive rate 48%).
Embodiment 4
Synthesis example 4: the compound 8 obtained with embodiment 3 carries out bromination for raw material, obtains compound 9, reaction signal formula is as follows:
The synthesis of product 9
Add 8 (310mg, 0.29mmol) in 100mL two-mouth bottle, 15mL chloroform and 5mL DMF, under argon shield, add 107mg N-bromo-succinimide; Pour in 150mL methyl alcohol after stirred at ambient temperature 24h, suction filtration, thick product column chromatography is purified, and sherwood oil/methylene dichloride (1:3), as eluent, obtains 306mg yellow solid (productive rate 86%).
Embodiment 5
Copolymerization example 1: two (trimethyl-tin-radical) thiophene of the BDP provided with embodiment 2 and 2,5-is monomer, carries out copolymerization and obtains copolymer p ThBDP, and reaction signal formula is as follows:
Operation steps is:
Add 116mg BDP (0.10mmol) in 100mL reaction flask successively, two (trimethyl-tin-radical) thiophene (0.10mmol) of 42mg 2,5-and 30mL newly steam toluene, after the emptying 15min of argon gas, add 8mgPd (PPh 3) 4, continue the emptying 20min of argon gas, back flow reaction 24h under argon shield.After being cooled to room temperature, reaction solution is added drop-wise to precipitating in 150mL methyl alcohol.Suction filtration obtains crude product, uses methyl alcohol, normal hexane and trichloromethane extracting 24h respectively.Again be added drop-wise to precipitating in 150mL methyl alcohol after trichloromethane extract is concentrated, suction filtration obtains red solid 90mg, productive rate 83%.
The nuclear-magnetism result of polymer P ThBDP: 1h NMR (CDCl 3, 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 weight: 89778g/mol, weight-average molecular weight: 264306g/mol, molecular weight distribution: 2.94.
Polymer P ThBDP heat decomposition temperature (5% weight loss) is 439 DEG C.
The absorption peak of polymer P ThBDP solution and film is respectively at 604nm and 620nm, and optical energy gap is 1.86eV.
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, and lowest unoccupied molecular orbital (LUMO) is-2.74eV, and electrochemistry energy gap is 2.78eV.
Fig. 4 is based on the obtained polymer P ThBDP/PC of the present embodiment 71the current-voltage curve of the polymer solar battery of BM.
With method preparation described in embodiment 8 based on PThBDP/PC 71the effciency of energy transfer (PCE) of the solar cell of BM is 7.48%, open circuit voltage (V oc) be 0.94V, short-circuit current (J sc) be 11.58mA/cm 2, packing factor (FF) is 68.74%.
Embodiment 6
Copolymerization example 2: two (trimethyl-tin-radical) selenophen of the BDP provided with embodiment 2 and 2,5-is monomer, carries out copolymerization and obtains copolymer p SeBDP, and reaction signal formula is as follows:
Operation steps is:
Add 81mg BDP (0.07mmol) in 100mL reaction flask successively, two (trimethyl-tin-radical) selenophen (0.07mmol) of 33mg 2,5-and 30mL newly steam toluene, after the emptying 15min of argon gas, add 8mgPd (PPh 3) 4, continue the emptying 20min of argon gas, back flow reaction 24h under argon shield.After being cooled to room temperature, reaction solution is added drop-wise to precipitating in 150mL methyl alcohol.Suction filtration obtains crude product, uses methyl alcohol, normal hexane and trichloromethane extracting 24h respectively.Again be added drop-wise to precipitating in 150mL methyl alcohol after trichloromethane extract is concentrated, suction filtration obtains violet solid 72mg, productive rate 91%.
The nuclear-magnetism result of polymer P SeBDP: 1h NMR (CDCl 3, 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 weight: 62055g/mol, weight-average molecular weight: 183926g/mol, molecular weight distribution: 2.96.
Polymer P SeBDP heat decomposition temperature (5% weight loss) is 431 DEG C.
The absorption peak of polymer P SeBDP solution and film is respectively at 614nm and 641nm, and optical energy gap is 1.80eV.
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, and lowest unoccupied molecular orbital (LUMO) is-2.80eV, and electrochemistry energy gap is 2.71eV.
Fig. 5 is based on the obtained polymer P SeBDP/PC of the present embodiment 71the current-voltage curve of the polymer solar battery of BM.
With method preparation described in embodiment 8 based on PSeBDP/PC 71the effciency of energy transfer (PCE) of the solar cell of BM is 5.08%, open circuit voltage (V oc) be 0.89V, short-circuit current (J sc) be 8.60mA/cm 2, packing factor (FF) is 66.42%.
Embodiment 7
Copolymerization example 3: different octyloxy benzo [1,2-b:3,4-b '] two thiophene of the BDP provided with embodiment 2 and 2,6-two (trimethyl-tin-radical)-4,8-bis-is monomer, carries out copolymerization and obtains copolymer p BDTBDP, and reaction signal formula is as follows:
Operation steps is:
81mg BDP (0.07mmol) is added successively in 100mL single port bottle, 54mg 2, two (trimethyl-tin-radical)-4 of 6-, the different octyloxy benzo [1 of 8-bis-, 2-b:3,4-b '] two thiophene (0.07mmol) and 30mL newly steam toluene, after the emptying 15min of argon gas, adds 8mg Pd (PPh 3) 4, continue the emptying 20min of argon gas, back flow reaction 24h under argon shield.After being cooled to room temperature, reaction solution is added drop-wise to precipitating in 150mL methyl alcohol.Suction filtration obtains crude product, uses methyl alcohol, normal hexane and trichloromethane extracting 24h respectively.Again be added drop-wise to precipitating in 150mL methyl alcohol after trichloromethane extract is concentrated, suction filtration obtains red solid 93mg, productive rate 92%.
The nuclear-magnetism result of polymer P BDTBDP: 1h NMR (CDCl 3, 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 weight: 48951g/mol, weight-average molecular weight: 156392g/mol, molecular weight distribution: 3.20.
Polymer P BDTBDP heat decomposition temperature (5% weight loss) is 331 DEG C.
The absorption peak of polymer P BDTBDP solution and film is respectively at 578nm and 591nm, and optical energy gap is 1.98eV.
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, and lowest unoccupied molecular orbital (LUMO) is-2.68eV, and electrochemistry energy gap is 2.85eV.
Fig. 6 is based on the obtained PBDTBDP/PC of the present embodiment 71the current-voltage curve of the solar cell of BM.
With method described in embodiment 8 prepare based on PBDTBDP/PC 71the effciency of energy transfer (PCE) of the solar cell of BM is 3.14%, open circuit voltage (V oc) be 0.87V, short-circuit current (J sc) be 8.80mA/cm 2, packing factor (FF) is 41.07%.
The uv-visible absorption spectra of polymer P BDTBDP, PThBDP and PSeBDP chloroformic solution is separately shown in Fig. 1; The uv-visible absorption spectra of polymer P BDTBDP, PThBDP and PSeBDP film is shown in Fig. 2; The cyclic voltammetry curve of polymer P BDTBDP, PThBDP and PSeBDP is shown in Fig. 3; Based on the polymer P ThBDP/PC that embodiment 5 is obtained 71bM, the polymer P SeBDP/PC obtained based on embodiment 6 71bM, the polymer P BDTBDP/PC obtained based on embodiment 7 71the external quantum efficiency curve of the solar cell of BM is shown in Fig. 7.
Embodiment 8
The preparation example of solar cell
Solar battery structure is ITO/PEDOT:PSS/Polymer:PC 71bM/Ca/Al, preparation process is:
Ito glass uses clean-out system successively, ultrapure water, acetone and Virahol ultrasonic cleaning 20min, then ozonize 15min.Spin coating PEDOT:PSS (Clevios on ito glass tMp VP Al 4083,30nm), toast 10min at 150 DEG C.The polymkeric substance (Polymer) that embodiment 5 ~ 7 is obtained and PC 71bM is dissolved in orthodichlorobenzene, adds appropriate diiodo-octane (1% ~ 5%), and is spin-coated on PEDOT layer, under high vacuum (10 -4pa) successively evaporation Ca (10nm) and Al (100nm) as negative electrode.Solar cell useful area is 4mm 2.
Utilize solar simulator (Newport, 150W, AM 1.5G, 100mW/cm 2) and Keithley2420 source table performance test is carried out to battery.
Wherein, ITO (Indium Tin Oxide), tin indium oxide, as the anode of polymer solar cells in embodiment;
PEDOT:PSS is a kind of suspension, and be made up of PEDOT and PSS two kinds of materials, PEDOT is poly-(3,4-ethylene dioxythiophene), and PSS is poly styrene sulfonate;
PC 71bM is fullerene derivate electron acceptor(EA);
Polymer is the polymkeric substance that embodiment 5 ~ 7 obtains.
Comparative example
Replace the polymkeric substance (Polymer) in embodiment 8 with the P3HT bought (poly-3-hexyl thiophene), prepare bulk heterojunction polymer solar cells.
Based on P3HT/PC 71the effciency of energy transfer (PCE) of the polymer solar cells of BM is 4.41%, open circuit voltage (V oc) be 0.65V, short-circuit current (J sc) be 9.7mA/cm 2, packing factor (FF) is 70.0%.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (10)

1. for the preparation of a lactams polymerization single polymerization monomer for polymer solar cells donor material, it is characterized in that, described unit is the fused ring compound containing two lactan six-rings, and described lactan is connected by singly-bound or conjugated bridge.
2. polymerization single polymerization monomer according to claim 1, is characterized in that, described polymerization single polymerization monomer is represented by any one in the structure shown in general formula (I) and general formula (II):
Wherein, R is alkyl or acyl group;
Ar in general formula (I), general formula (II) 1-X is selected from any one in following structure:
Ar 2be selected from any one in following structure:
Ar 3be selected from any one in following structure:
Different loci in a, b, c, d, e, f representative structure formula;
Ar 1in the structure of-X, R 1be selected from any one in hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, alkyl, aryl, alkoxyl group, alkynyl, heterocycle or Hete rocyclic derivatives; R 2for alkyl; X is selected from any one in hydrogen atom, fluorine atom, chlorine atom, bromine atoms or atomic iodine;
Ar 2structure in, R 3be selected from any one in hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, alkyl, aryl, alkoxyl group, alkynyl, heterocycle or Hete rocyclic derivatives; R 4for alkyl;
Ar 3structure in, R 5, R 6and R 7independently selected from any one in hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, alkyl, aryl, alkoxyl group, alkynyl, heterocycle or Hete rocyclic derivatives; R 8for alkyl.
3. polymerization single polymerization monomer according to claim 2, is characterized in that, described R is substituted or unsubstituted C 1~ C 60alkyl or substituted or unsubstituted C 2~ C 60alkyloyl; Be preferably any one in 2-ethylhexyl, 2-butyl octyl, 2-hexyl decyl or 2-octyldodecyl;
Preferably, described R 1, R 3, R 5, R 6, R 7independently selected from hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, substituted or unsubstituted C 1~ C 60alkyl, substituted or unsubstituted C 6~ C 60aryl, substituted or unsubstituted C 1~ C 60alkoxyl group, substituted or unsubstituted C 3~ C 60alkynyl, substituted or unsubstituted C 3~ C 60any one in heterocyclic radical;
Preferably, described substituted or unsubstituted C 3~ C 60heterocyclic radical is C 1~ C 60thiophene, C that alkyl replaces 1~ C 60furans, C that alkyl replaces 1~ C 60the pyrroles that alkyl replaces, C 1~ C 60the thienothiophene that alkyl replaces;
Preferably, described R 2, R 4, R 8independently selected from substituted or unsubstituted C 1~ C 60alkyl, substituted or unsubstituted C 1~ C 60any one in cycloalkyl.
4. the polymerization single polymerization monomer according to Claims 2 or 3, is characterized in that, described R 1, R 3, R 5, R 6, R 7independently selected from hydrogen atom, fluorine atom, cyano group, nitro, ester group, acyl group, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptane base, octyl, nonyl, decyl, dodecyl, pentadecyl, triacontyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzene alkyl, substituted or unsubstituted naphthalane base, substituted or unsubstituted perhydroanthracene base, substituted or unsubstituted thiophene alkyl, substituted or unsubstituted pyridine alkyl, substituted or unsubstituted thiazolidyl, substituted or unsubstituted pyrrolidyl, substituted or unsubstituted pentacene alkyl, substituted or unsubstituted alkynyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted benzodiazepine base, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyrazolyl, any one in substituted or unsubstituted pyrimidyl,
Preferably, described R 2, R 4, R 8independently selected from substituted or unsubstituted C 1~ C 30any one in alkyl, preferably from butyl, hexyl, octyl group, decyl, dodecyl, tetradecyl, any one in hexadecyl.
5. a preparation method for the polymerization single polymerization monomer general formula (I) described in any one of claim 1-4, comprises the steps:
(1) with Ar 2d position replaced by halogen atom, c position is raw material by the compd A of carboxyl substituted, carries out chloride, obtain compd B to carboxyl;
(2) with Ar 1the Compound C that replaced by alkylamino or acyl amino of a position and compd B be raw material, being connected with the nitrogen-atoms of Compound C by the carbonyl of compd B obtains having the Compound D of amido linkage;
(3) be that raw material carries out ring-closure reaction with Compound D, d position be connected with b position, obtain the compound shown in general formula (I) that X is hydrogen atom;
Alternatively, step (4) is carried out after step (3): the compound obtained with step (3) obtains the compound shown in general formula (I) that X is halogen atom for raw material carries out halogenation.
6. a preparation method for the polymerization single polymerization monomer general formula (II) described in any one of claim 1-4, comprises the steps:
(1) with Ar 1b position replaced by halogen atom, a position is raw material by the compd E of carboxyl substituted, carries out chloride, obtain compound F 17-hydroxy-corticosterone to carboxyl;
(2) with Ar 2the compound G that replaced by alkylamino or acyl amino of c position and compound F 17-hydroxy-corticosterone be raw material, being connected with the nitrogen-atoms of compound G by the carbonyl of compound F 17-hydroxy-corticosterone obtains having the compound H of amido linkage;
(3) be that raw material carries out ring-closure reaction with compound H, b position be connected with d position, obtain the compound shown in general formula (II) that X is hydrogen atom;
Alternatively, step (4) is carried out after step (3): the compound obtained with step (3) obtains the compound shown in general formula (II) that X is halogen atom for raw material carries out halogenation.
7. a donor material, is characterized in that, described donor material is polymerized by the polymerization single polymerization monomer described in any one of claim 1-4.
8. donor material according to claim 7, is characterized in that, described donor material is formed by described polymerization single polymerization monomer copolymerization;
Preferably, described donor material is formed by described polymerization single polymerization monomer and any one in two tin reagent, two boric acid ester or two acid reagent or at least two copolymerization.
9. donor material according to claim 8, is characterized in that, the described pair of tin reagent is selected from any one in two tin trimethyl based compounds or two tributyl tin based compound;
Preferably, described pair of tin reagent is 2, two (trimethyl-tin-radical) thiophene of 5-, 2, two (trimethyl-tin-radical)-4 of 6-, the different octyloxy benzo [1 of 8-bis-, 2-b:3, 4-b'] two thiophene, 2, two (trimethyl-tin-radical)-4 of 6-, 4-diisooctyl thiophene coughs up also [3, 2-b:2 ', 3 '-d] two thiophene, 2, two (trimethyl-tin-radical) thieno-[3 of 5-, 2-b] thiophene, 5, 5 '-bis-(trimethyl-tin-radical)-2, 2 '-di-thiophene, 2, two (trimethyl-tin-radical) selenophen of 5-, 2, two (trimethyl-tin-radical)-4 of 6-, 4-diisooctyl-4H-cyclopenta [2, 1-b:5, 4-b '] two thiophene, 2, two (trimethyl-tin-radical)-4-iso-octyl two thieno-[3 of 6-, 2-b:2 ', 3 '-d] any one in pyrroles,
Preferably, described pair of boric acid ester or two acid reagent are selected from any one in two boric acid esters or two boronic acid compounds,
Preferably, described pair of boric acid ester or two acid reagent are 2, 7-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate)-9, 9-dioctyl fluorene, 2, 7-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate)-9, 9-dioctyl silicon fluorenes, 2, 7-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate)-9-(1-octyl group nonyl) carbazole, the pyrrolo-pyrrole-dione that two boric acid ester is modified, 4, 7-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate) benzo [c] [1, 2, 5] thiadiazoles, 1, 4-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate) benzene or 2, 6-two (4, 4, 5, 5-tetramethyl--1, 3, 2-dioxaborinate) any one in naphthalene.
10. a polymer solar battery, is characterized in that, the donor material of described polymer solar battery is the donor material described in any one of claim 7-9.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2593492A (en) * 2020-03-24 2021-09-29 Sumitomo Chemical Co Polymer
US11760764B2 (en) 2020-05-22 2023-09-19 Aligos Therapeutics, Inc. Methods and compositions for targeting PD-L1

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013064206A1 (en) * 2011-11-01 2013-05-10 Merck Patent Gmbh Organic electroluminescent device
CN103517936A (en) * 2011-04-27 2014-01-15 巴斯夫欧洲公司 Semiconductor materials based on dithienopyridone copolymers
CN104211926A (en) * 2013-05-31 2014-12-17 国家纳米科学中心 Donor material used for polymer solar battery, and polymerization monomer thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103517936A (en) * 2011-04-27 2014-01-15 巴斯夫欧洲公司 Semiconductor materials based on dithienopyridone copolymers
WO2013064206A1 (en) * 2011-11-01 2013-05-10 Merck Patent Gmbh Organic electroluminescent device
CN104211926A (en) * 2013-05-31 2014-12-17 国家纳米科学中心 Donor material used for polymer solar battery, and polymerization monomer thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
D. H. HEY, G. H. JONES，等: ""Internuclear cyclization. XXXII. Dienol-benzene and related rearrangements of spirocyclohexadiene lactams", 《JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1: ORGANIC AND BIO-ORGANIC CHEMISTRY》 *
D. H. HEY, G. H. JONES，等: "Internuclear cyclization. XXIX. Oxidation of N-methyl-2-biphenylcarboxamides with persulfate", 《JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1: ORGANIC AND BIO-ORGANIC CHEMISTRY》 *
D. H. HEY, G. H. JONES，等: "Internuclear cyclization. XXVIII. Free radical reactions of spirocyclohexadiene lactams", 《JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1: ORGANIC AND BIO-ORGANIC CHEMISTRY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2593492A (en) * 2020-03-24 2021-09-29 Sumitomo Chemical Co Polymer
WO2021191228A1 (en) 2020-03-24 2021-09-30 Cambridge Display Technology Limited Polymer
US11760764B2 (en) 2020-05-22 2023-09-19 Aligos Therapeutics, Inc. Methods and compositions for targeting PD-L1

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