CN105542130B - Conjugated polymer based on B ← N bridgings thiophene connection thiazole and preparation method and application - Google Patents
Conjugated polymer based on B ← N bridgings thiophene connection thiazole and preparation method and application Download PDFInfo
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Abstract
Conjugated polymer based on B ← N bridgings thiophene connection thiazole and preparation method and application, belongs to macromolecular solar battery technical field.Solve the problems, such as that macromolecular solar battery energy conversion efficiency is low in the prior art.The conjugated polymer has the structure as shown in formula (I), passes through bridging unit (Ar2) length of different electron donation, the different bonding angles from drawing electronic unit copolymerization and alkyl chain changes, the electronic structure of conjugated polymer can effectively be adjusted, the advantages that making it have narrow band gap, wide absorption spectrum, low LUMO/HOMO energy levels, high electron mobility, after testing, the lumo energy of conjugated polymer arrives -4.0eV in -3.60eV, optical band gap is less than 1.8eV, and film state absorption spectrum is in 300~900nm, and electron mobility is 10‑2~10‑5cm2V‑1s‑1, can be as the acceptor material of high performance solar cells.
Description
Technical field
The invention belongs to macromolecular solar battery technical field, and in particular to one kind is based on B ← N bridgings thiophene connection thiazole
Conjugated polymer and preparation method and application.
Background technology
Solar cell is can effectively to absorb solar energy, and converts it into the semiconductor device of electric energy.With reliable
Property high, long lifespan, the advantages that high conversion efficiency.Solar cell can be divided mainly into according to the difference of material therefor：Silicon solar
Battery (solar cell using silicon as matrix material), compound semiconductor solar cell are (by two or more member
Solar cell made of the compound with characteristic of semiconductor of element composition), organic semiconductor solar cell is (with containing carbon
Battery (molecular crystal, electric charge transfer network made of the semi-conducting material of carbon key and conductive capability between metal and insulator
Compound, macromolecule etc.)).Wherein, macromolecular solar battery, which has, can be achieved outstanding advantages of flexible, cost is low, in light weight,
Had broad application prospects in green energy resource for building, energy source of car etc., be recent academia and industrial circle both at home and abroad
Study hotspot.
If solar cell thinks actual use, it is necessary to have the photoelectric transformation efficiency of higher device.Macromolecular solar
In battery, the donor material and acceptor material of active layer largely determine the device performance of solar cell, therefore design
It is to realize one of core methed that device performance is constantly broken through to synthesize outstanding active layer material.In the prior art, conventional height
Molecular solar cells are usually using conjugated polymer as donor, derive the blend film that (PCBM) is acceptor with fullerene.It is this kind of
Solar cell has certain energy conversion efficiency, still, can not regulate and control because fullerene derivate has energy level, absorption spectrum
It is narrow and prepare high technical problem of cost etc., limit performance boost and the practical application of solar cell.Such as with polyhenylene
Derivative (MEH-PPV) is used as donor, PC61The organic solar batteries that BM is prepared as acceptor, under 430nm monochromatic light exposures
Energy conversion efficiency is up to 2.9%, but PC in device61BM absorption spectrum is in ultraviolet region, and LUMO/HOMO can fraction
It not in -4.0eV/-6.0eV or so, can not regulate and control, limit continuing to lift up for shorted devices electric current and open-circuit voltage.
The content of the invention
Present invention aim to address the relatively low technology of the energy conversion efficiency of macromolecular solar battery in the prior art
Problem, there is provided the conjugated polymer of one kind based on B ← N bridgings thiophene connection thiazole (BNTTZ) and preparation method and application.
The conjugated polymer based on B ← N bridgings thiophene connection thiazole of the present invention, has the structure as shown in formula (I)：
Formula (I)
In formula (I), n is 2~100 integer；
-Ar1For one kind in following structure：
-Ar2- be following structure in one kind：
-Ar2- structure in, R C4~C24Alkyl chain.
The preparation method of the above-mentioned conjugated polymer based on B ← N bridgings thiophene connection thiazole is as follows：
Under inert atmosphere protection, by BNTTZ double tin trimethyl monomers, double bromine Ar2Monomer, three (dibenzalacetones)
Two palladiums and the dissolving of three (adjacent methyl) phenyl phosphorus in organic solvent, obtain mixed solution, mixed solution is in lucifuge and is heated to reflux
Under conditions of occur Stille polymerisations, after Stille polymerisations terminate, add end-capping reagent blocked, purify, obtain
Conjugated polymer；
The structural formula of double tin trimethyl monomers of the BNTTZ is
Double bromine Ar2The structural formula of monomer is Br-Ar2-Br。
Preferably, the organic solvent is toluene.
Preferably, double tin trimethyl monomers of the BNTTZ, double bromine Ar2Monomer, three (dibenzalacetone) two palladium and three
The amount of the material of (adjacent methyl) phenyl phosphorus is than 1:1:0.02:0.16.
Preferably, BNTTZ double tin trimethyl monomers and double bromine Ar in the mixed solution2The concentration of monomer is respectively
0.005~0.1M.
Preferably, the reaction temperature of the Stille polymerisations is 110~120 DEG C, and the reaction time is 24~48h.
The above-mentioned conjugated polymer based on B ← N bridgings thiophene connection thiazole can be as the acceptor of macromolecular solar battery
Materials application.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, the conjugated main chain of the conjugated polymer based on B ← N bridgings thiophene connection thiazole of the invention contains two units, point
Wei not BNTTZ units and bridging unit (Ar2).Wherein, BNTTZ units have strong electron deficient, the big dipole of B ← N coordinate bonds
Property and unit between the feature such as weak interaction, by change bridging unit push-and-pull electronic capability, with BNTTZ units be copolymerized into
The length of key dihedral angle, alkyl side chain, the electronic structure of conjugated polymer is effectively adjusted, so as to obtain with arrowband
The conjugated polymer of the advantages that gap, wide absorption spectrum, low LUMO/HOMO energy levels, high electron mobility.Through experimental tests, this hair
The lumo energy of bright conjugated polymer arrives -4.0eV scopes in -3.60eV, and optical band gap is less than 1.8eV, film state absorption spectrum
In 300~900nm, electron mobility 10-2~10-5cm2V-1s-1, it is suitable as high-performance acceptor material and prepares efficiently too
Positive energy battery.
2nd, the preparation method of the conjugated polymer based on B ← N bridgings thiophene connection thiazole of the invention is simple, and purifying technique is just
Victory, be advantageous to the industrialized production of macromolecular solar battery device.
3rd, conjugated polymer of the invention as solar cell prepared by acceptor material there is higher photoelectric conversion to imitate
Rate.High molecular extension conjugated structure, make macromolecule that there is higher electron mobility, therefore can be obtained as acceptor material
Higher photoelectric transformation efficiency.Through experimental tests, the electricity conversion of solar cell can reach more than 5.0%.
Brief description of the drawings
Fig. 1 is the conjugated polymer P-BNTTZ-IID of embodiment 1 ultraviolet-visible absorption spectroscopy；
Fig. 2 is the conjugated polymer P-BNTTZ-IID of embodiment 1 electro-chemical test curve；
Fig. 3 is the I-V curve of the macromolecular solar battery device of embodiment 21 and embodiment 22；
Fig. 4 is the EQE curves of the macromolecular solar battery device of embodiment 21 and embodiment 22.
Embodiment
In order to further illustrate the present invention, the preferred embodiments of the invention are retouched with reference to embodiment
State, but it is to be understood that these descriptions are simply for further explanation the features and advantages of the present invention rather than to patent of the present invention
It is required that limitation.
The conjugated polymer based on B ← N bridgings thiophene connection thiazole of the present invention, has the structure as shown in formula (I)：
Formula (I)
In formula (I), n is 2~100 integer；
-Ar1For one kind in following structure：
-Ar2- represent the construction unit being copolymerized with BNTTZ, also referred to as bridging unit ,-Ar2- structure here is omitted,
It should be noted that-Ar2- structure in, R represent C4~C24Alkyl chain, can be that straight chain can also contain side chain.This hair
In bright, by changing bridging unit-Ar2- push-and-pull electronic capability, with BNTTZ units copolymerization bonding dihedral angle, alkyl side chain
Length, the electronic structure of conjugated polymer is effectively adjusted, so as to prepare with narrow band gap, wide absorption spectrum, low
The conjugated polymer of the advantages that LUMO/HOMO energy levels, high electron mobility.Through experimental tests, conjugated polymer of the invention
Lumo energy arrives -4.0eV scopes in -3.60eV, and optical band gap is less than 1.8eV, and film state absorption spectrum is in 300~900nm, electronics
Mobility 10-2~10-5cm2V-1s-1, it is suitable as high-performance acceptor material and prepares high performance solar batteries.
The end-capping group of the conjugated polymer of the present invention is different and different according to end-capping reagent, according to those skilled in the art
Conventional selection, it is not particularly limited, as long as because conjugated polymer has the structure as shown in formula (I), can just solves this
The technical problem of invention, and obtain corresponding effect.Phenyl boric acid and bromobenzene are such as used, then macromolecule is blocked by phenyl group, uses thiophene
Boric acid and bromo thiophene, then macromolecule is by thiophene end-blocking etc..
The above-mentioned conjugated polymer based on B ← N bridgings thiophene connection thiazole is reacted by Stille- types to be prepared, as preferred
Scheme, the preparation method can be：
(typically using argon gas) under inert atmosphere protection, by BNTTZ double tin trimethyl monomers, double bromine Ar2Monomer, three
(dibenzalacetone) two palladium and three (adjacent methyl) phenyl phosphorus press the amount of material than 1:1:0.02:0.16 is dissolved in toluene solution
In, BNTTZ double tin trimethyl monomers and double bromine Ar2The concentration of monomer can be 0.005~0.1M respectively, under the conditions of lucifuge,
With 110~120 DEG C of 24~48h of backflow, Stille polymerisations occur, then add blocking agent, end-capping reagent typically uses
Phenyl boric acid and bromobenzene, purify after end-blocking, obtain conjugated polymer；
Reaction equation is as follows：
The double bromine monomers of BNTTZ double tin trimethyl monomers；
It should be noted that the method for purification of conjugated polymer prepared by the above method can be：Reaction product system is cold
But room temperature is arrived, is dissolved in chloroform, is washed, organic phase is dried, and after removing organic solvent, remaining solution is instilled to pure acetonitrile
In solvent, solid is separated out.Then using apparatus,Soxhlet's will separate out solid washed away successively with acetone, n-hexane, tetrahydrofuran it is low
Polymers and catalyst, most of organic solvent then is removed with chloroform, revolving, finally viscous solution sinks in acetonitrile
Drop, obtains conjugated polymer.
The conjugated polymer of the present invention can be as the acceptor material of macromolecular solar battery, and it is in macromolecular solar
The application process of battery is not particularly limited, the application method use according to the standard receptor material of this area.Generally, too
The structure of positive energy battery sequentially consists of conductive layer, hole transmission layer, photosensitive layer, electron transfer layer and metal electrode；Lead
The material of electric layer can be ITO, FTO or AZO, and thickness is 50nm~200nm, and the material of hole transmission layer can be PEDOT:
PSS, thickness can be 20nm~60nm；The material of photosensitive layer is the mixed of existing donor material and the acceptor material of the present invention
Close, hybrid mode can use the amount of material than 1 according to routine operation:1, thickness can be 100nm~150nm；Electronics
The material of transport layer can be Ca, and thickness can be 15nm~20nm；The material of metal electrode can be Al, and thickness can be
100nm~200nm.
The present invention is further illustrated with reference to embodiments.
Embodiment 1
BNTTZ-IID macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
Preparation method is：BNTTZ double tin trimethyl monomers are added into the clean polymerization bottle through overbaking
127.7mg, 0.19mmol), double brominated monomers (168.9mg, 0.19mmol) of bioxindol, three (dibenzylidene indenes acetone) two palladiums
(3.9mg, 0.0038mmol) and three (adjacent methyl) phenyl phosphorus (9.3mg, 0.0304mmol), then vacuumize, lead to argon gas to body
System substitutes that gas is multiple, adds the toluene solvant (10mL) of distillation under lucifuge state, after 115 DEG C of backflow 48h, then first adds benzene boron
Sour (100mg, 0.82mmol) continues the 3h that flows back, and adds bromobenzene (200mg, 1.28mmol) backflow 3h.Reaction system is cooled down
To room temperature, dissolve in 100 milliliters of chloroforms, wash, dry, remove most of solvent, remaining solution is dropped in acetonitrile, polymer
Separate out, precipitate is washed away into small molecule and catalyst with acetone, n-hexane, tetrahydrofuran successively with apparatus,Soxhlet's, finally used
Chloroform extracts polymer.Measuring yield is：86%.
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 77.50；H, 8.15；B, 1.04；N,
4.05；O, 3.08；S, 6.18.Experiment value is C, 78.64；H, 9.02；N, 1.32；S, 5.34.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=18000, PDI=2.5.
Ultraviolet-visible absorption spectroscopy analysis and electro-chemical test are carried out to polymer B NTTZ-IID prepared by embodiment 1, surveyed
Test result difference is as depicted in figs. 1 and 2.Polymer B NTTZ-IID-T solution state and thin-film state is can be seen that from Fig. 1 and Fig. 2
Ultraviolet-visible absorption spectroscopy wide absorption spectrum, Absorption edge to 750nm is all presented；Polymer B NTTZ-IID LUMO/
HOMO energy levels are -3.80/-5.84eV, illustrate the polymer of the present invention and can be used as acceptor material；Polymer B NTTZ-IID's
Film state electron mobility is 2 × 10-4cm2V-1s-1, high-performance may be obtained as acceptor material by illustrating the polymer of the present invention
Device.
Embodiment 2
BNTTZ-DPP macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
Preparation method is：The BNTTZ double pink salts of double tin trimethyl monomers are added in the clean polymerization bottle through overbaking
(126.3mg, 0.19mmol), DPP double brominated monomers (174.4mg, 0.19mmol), three (dibenzylidene indenes acetone) two palladiums
(4.0mg, 0.0038mmol) and three (adjacent methyl) phenyl phosphorus (9.3mg, 0.0304mmol), then vacuumize, lead to argon gas to body
System substitutes that gas is multiple, adds the toluene solvant (10mL) of distillation under lucifuge state, after 115 DEG C of backflow 48h, first adds phenyl boric acid
(100mg, 0.82mmol) backflow 3h, add bromobenzene (200mg, 1.28mmol) backflow 3h.Reaction system is cooled to room temperature,
Dissolve in 100 milliliters of chloroforms, wash, dry, remove most of solvent, remaining solution is dropped in acetonitrile, and polymer separates out, will
Precipitate washes away small molecule and catalyst with acetone, n-hexane, tetrahydrofuran successively with apparatus,Soxhlet's, finally will be poly- with chloroform
Compound extracts.Polymerizate BNTTZ-DPP yield：180mg (yield 88%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 72.53；H, 7.68；B, 1.00；N,
3.90；O, 2.97；S, 11.92.Experiment value is C, 73.42；H, 9.034；N, 1.54；S, 11.445.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=17000, PDI=2.48.
Embodiment 3
BNTTZ-TTF macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
Preparation method is：Double bromo BNTTZ double tin trimethyl monomers are added in the clean polymerization bottle through overbaking
(126.3mg, 0.19mmol), TTF monomers (121.7mg, 0.19mmol) three (dibenzylidene indenes acetone) two palladiums (3.6mg,
0.004mmol) and three (adjacent methyl) phenyl phosphorus (9.7mg, 0.032mmol), it is multiple to system substitute gas, under lucifuge state
Add distillation toluene solvant (9mL), 115 DEG C backflow 48h after, first add phenyl boric acid (100mg, 0.82mmol) backflow 3h, then
Add bromobenzene (200mg, 1.28mmol) backflow 3h.Reaction system is cooled to room temperature, dissolved in 100 milliliters of chloroforms, is washed, is done
It is dry, most of solvent is removed, remaining solution is dropped in acetonitrile, and polymer is separated out, and precipitate is used successively with apparatus,Soxhlet's
Acetone, n-hexane, tetrahydrofuran wash away small molecule and catalyst, are finally extracted polymer with chloroform.Polymerizate
BNTTZ-TTF yield：130mg (yield 85%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 68.04；H, 6.83；B, 1.33；F,
2.34；N, 1.72, O, 3.94.Experiment value is C, 73.55；H, 10.50；N, 8.54.
Gel permeation chromatography is carried out to the polymer of preparation (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C)：Mn=
10000, PDI=2.16.
Embodiment 4
BNTTZ-TPDT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
Preparation method is：BNTTZ double tin trimethyl monomers are added in the clean polymerization bottle through overbaking
(105.1mg, 0.16mmol), double bromo TPDT (120.9mg, 0.16mmol), weigh three (dibenzylidene indenes acetone) two palladiums
(3.4mg, 0.0032mmol) and three (adjacent methyl) phenyl phosphorus (8.4mg, 0.026mmol), it is multiple then to substitute gas to system, keeps away
Add the toluene solvant (9mL) of distillation under light state, after 115 DEG C of backflow 48h, first add phenyl boric acid (100mg, 0.82mmol) and return
3h is flowed, adds bromobenzene (200mg, 1.28mmol) backflow 3h.Reaction system is cooled to room temperature, dissolved in 100 milliliters of chloroforms,
Washing, dry, remove most of solvent, remaining solution is dropped in acetonitrile, and polymer separates out, by precipitate apparatus,Soxhlet's
Small molecule and catalyst are washed away with acetone, n-hexane, tetrahydrofuran successively, is finally extracted polymer with chloroform.Polymerization
Product BNTTZ-TPDT yield：122mg (yield 80%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 68.81；H, 6.21；B, 1.17；N,
3.03；O, 3.46；S, 17.33.Experiment value is C, 72.50；H, 10.21；N, 8.35；S, 15.8.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=11000, PDI=1.63.
Embodiment 5
BNTTZ-NDI macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-NDI polymer is in the same manner as in Example 1.The phenyl on BNTTZ B is simply replaced with p- three
Methyl fluoride, and double brominated monomers of double brominated monomers replacement IID using NDI.Polymerizate BNTTZ-NDI yield：188mg
(80%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 68.18；H, 6.83；B, 0.92；F,
9.66；N, 3.56；O, 5.43；S, 5.42.Experiment value is C, 69.22；H, 10.04；N, 7.22；S, 5.02.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=25000, PDI=2.01.
Embodiment 6
BNTTZ-PDI macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-PDI polymer is in the same manner as in Example 1.The phenyl on BNTTZ B is simply replaced with p- three
Methyl fluoride, and double brominated monomers of double brominated monomers replacement IID using PDI.Polymer B NTTZ-PDI yield：173mg (productions
Rate 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 72.06；H, 7.11；B, 0.76；F,
8.05；N, 2.97；O, 4.53；S, 4.53.Experiment value is C, 70.3；H, 8.52；N, 3.43；S, 4.35.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=46000, PDI=2.21.
Embodiment 7
BNTTZ-CDTZ macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-CDTZ polymer is in the same manner as in Example 1.The phenyl on BNTTZ B is simply replaced with 2,4,
6- trimethylphenyls, and double brominated monomers of double brominated monomers replacement IID using CDTZ.Polymerizate BNTTZ-CDTZ is produced
Amount：173mg (yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 70.47；H, 7.39；B, 1.32；N,
5.14；S, 15.68.Experiment value is C, 69.98；H, 7.65；N, 5.01；S, 15.83.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=32000, PDI=1.8.
Embodiment 8
BNTTZ-TN macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-TN polymer is in the same manner as in Example 1.The phenyl on BNTTZ B is simply replaced with 2,4,6-
Trimethylphenyl, and double brominated monomers of double brominated monomers replacement IID using TN.Polymerizate BNTTZ-TN yield：173mg
(yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 71.09；H, 7.48；B, 1.16；F,
8.77；N, 3.01；O, 3.44；S, 13.80.Experiment value is C, 71.35；H, 7.35；N, 3.21；S, 14.0.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=24000, PDI=1.91.
Embodiment 9
BNTTZ-NDIT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-NDIT polymer is in the same manner as in Example 1.The phenyl on BNTTZ B is simply replaced with 2,4,
6- trimethylphenyls, and double brominated monomers of double brominated monomers replacement IID using NDIT.Polymerizate BNTTZ-NDIT is produced
Amount：173mg (yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 72.61；H, 7.64；B, 0.87；N,
3.39；O, 5.16；S, 10.34.Experiment value is C, 72.35；H, 7.43；N, 3.31；S, 10.15.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=26300, PDI=2.1.
Embodiment 10
BNTTZ-TBT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-TBT polymer is in the same manner as in Example 1.The phenyl on BNTTZ B is simply replaced with 2,4,6-
Trimethylphenyl, and double brominated monomers of double brominated monomers replacement IID using TBT.Polymerizate BNTTZ-TBT yield：
173mg (yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 71.38；H, 8.10；B, 0.90；N,
3.52；O, 2.68；S, 13.42.Experiment value is C, 71.22；H, 8.31；N, 3.42；S, 13.25.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=19800, PDI=1.92.
Embodiment 11
BNTTZ-TT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-TT polymer is in the same manner as in Example 1.The phenyl on BNTTZ B is simply replaced with into 4- methyl
Phenyl, and double brominated monomers of double brominated monomers replacement IID using TT.Polymerizate BNTTZ-TT yield：173mg (yields
87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 68.99；H, 6.84；B, 1.41；N,
1.83；O, 4.81；S, 16.74.Experiment value is C, 68.78；H, 6.73；N, 1.71；S, 16.62.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=37000, PDI=2.30.
Embodiment 12
BNTTZ-DPP macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-DPP polymer is in the same manner as in Example 1.The phenyl on BNTTZ B is simply replaced with into 4- methyl
Phenyl, and double brominated monomers of double brominated monomers replacement IID using DPP.Polymerizate BNTTZ-DPP yield：173mg (productions
Rate 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 75.83；H, 7.53；B, 0.73；N,
2.85；O, 4.34；S, 8.71.Experiment value is C, 75.63；H, 7.35；N, 2.71；S, 8.92.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=23000, PDI=2.60.
Embodiment 13
BNTTZ-PDIT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-PDIT polymer is in the same manner as in Example 1.The phenyl on BNTTZ B is simply replaced with into 4- first
Base phenyl, and double brominated monomers of double brominated monomers replacement IID using PDIT.Polymerizate BNTTZ-PDIT yield：173mg
(yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 75.64；H, 7.39；B, 0.75；N,
2.91；O, 4.43；S, 8.88.Experiment value is C, 75.38；H, 7.28；N, 2.83；S, 8.73.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=29000, PDI=2.35.
Embodiment 14
BNTTZ-NDIT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-NDIT polymer is in the same manner as in Example 1.The phenyl on BNTTZ B is simply replaced with 2,3,
4,5,6- pentafluorophenyl groups, and double brominated monomers of double brominated monomers replacement IID using NDIT.Polymerizate BNTTZ-NDIT is produced
Amount：173mg (yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 66.15；H, 6.92；B, 0.67；F,
11.76；N, 2.60；O, 3.96；S, 7.94.Experiment value is C, 66.01；H, 6.83；N, 2.45；S, 8.01.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=16000, PDI=2.39.
Embodiment 15
BNTTZ-NTT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-NTT polymer is in the same manner as in Example 1.Simply the double of IID are substituted using NTT double brominated monomers
Brominated monomer.Polymerizate BNTTZ-NTT yield：173mg (yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 69.84；H, 7.14；B, 0.91；N,
5.90；S, 16.21.Experiment value is C, 69.58；H, 7.01；N, 5.80；S, 16.01.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=19300, PDI=2.60.
Embodiment 16
BNTTZ-FBTT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-FBTT polymer is in the same manner as in Example 1.Simply IID is substituted using FBTT double brominated monomers
Double brominated monomers.Polymerizate BNTTZ-FBTT yield：173mg (yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 70.30；H, 7.62；B, 0.97；N,
3.78；O, 2.88；S, 14.44.Experiment value is C, 69.99；H, 7.51；N, 3.58；S, 14.58.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=23000, PDI=1.93.
Embodiment 17
BNTTZ-BTTT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-BTTT polymer is in the same manner as in Example 1.Simply IID is substituted using BTTT double brominated monomers
Double brominated monomers.Polymerizate BNTTZ-BTTT yield：173mg (yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 73.63；H, 8.46；B, 0.91；N,
3.53；O, 4.39；S, 13.46.Experiment value is C, 73.58；H, 8.29；N, 3.48；S, 13.28.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=16000, PDI=2.4.
Embodiment 18
BNTTZ-BZTT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-BZTT polymer is in the same manner as in Example 1.Simply IID is substituted using BZTT double brominated monomers
Double brominated monomers.Polymerizate BNTTZ-BZTT yield：173mg (yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 72.56；H, 8.37；B, 0.91；N,
4.70；S, 13.45.Experiment value is C, 72.39；H, 8.31；N, 4.53；S, 13.28.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=16800, PDI=2.5.
Embodiment 19
BNTTZ-FBTTT macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-FBTTT polymer is in the same manner as in Example 1.Simply IID is substituted using FBTTT double brominated monomers
Double brominated monomers.Polymerizate BNTTZ-FBTTT yield：173mg (yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 71.47；H, 8.05；B, 0.88；F,
3.10；N, 3.43；S, 13.07.Experiment value is C, 71.28；H, 8.32；N, 3.21；S, 13.21.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=23000, PDI=2.28.
Embodiment 20
BNTTZ-TIID macromolecules, structural formula are (in structural formula, omitting end-capping group) as follows：
The preparation of BNTTZ-TIID polymer is in the same manner as in Example 1.Simply IID is substituted using TIID double brominated monomers
Double brominated monomers.Polymerizate BNTTZ-TIID yield：173mg (yield 87%).
Elementary analysis is carried out to the polymer of preparation, it is as a result as follows：Calculated value is C, 74.91；H, 7.38；B, 0.90；N,
3.49；O, 2.66；S, 10.67.Experiment value is C, 74.82；H, 7.30；N, 3.58；S, 10.49.
Gel permeation chromatography (GPC, trichloro-benzenes, polystyrene do standard, 150 DEG C) analysis is carried out to the polymer of preparation,
Obtain:Mn=29000, PDI=2.6.
Embodiment 21
The application of the acceptor material of macromolecular solar battery：Using macromolecule PTB7-Th as donor material, with embodiment 1
Polymer P-BNTTZ-IID be used as acceptor material, according to donor material and the mass ratio 1 of acceptor material:1, prepare overall height point
Sub- solar cell device, the structure of solar cell device is ITO (100nm)/PEDOT:PSS(50nm)/PTB7-Th:P-
BNTTZ-IID(100nm)/Ca(20nm)/Al(200nm)。
Performance detection is carried out to the overall height molecular solar cells device of embodiment 21, as a result as shown in Figure 3 and Figure 4.
Embodiment 22
The application of the acceptor material of macromolecular solar battery：Using macromolecule PTB7 as donor material, with the poly- of embodiment 1
Compound P-BNTTZ-IID is as acceptor material, according to donor material and the mass ratio 1 of acceptor material:1, prepare overall height molecule too
Positive energy battery device, the structure of solar cell device is ITO (100nm)/PEDOT:PSS(50nm)/PTB7:P-BNTTZ-
IID(100nm)/Ca(20nm)/Al(200nm)。
Performance detection is carried out to the overall height molecular solar cells device of embodiment 22, as a result as shown in Figure 3 and Figure 4.
Curve is respectively the I-V curve of the macromolecular solar battery device of embodiment 21 and embodiment 22 in Fig. 3, Fig. 4
In curve be respectively embodiment 21 and embodiment 22 macromolecular solar battery device EQE curves, can from Fig. 3 and Fig. 4
To find out, boracic conjugated polymer of the invention can be used as the acceptor material of structure high performance device, and different donor materials
Material mixing is provided with preferable effect, and PTB7-Th is 5.04%, PTB7 as donor as device efficiency prepared by donor material
Device efficiency prepared by material is 3.8%.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (7)
1. the conjugated polymer based on B ← N bridgings thiophene connection thiazole, it is characterised in that there is the structure as shown in formula (I)：
In formula (I), n is 2~100 integer；
-Ar1For one kind in following structure：
-Ar2- be following structure in one kind：
-Ar2- structure in, R C4~C24Alkyl chain.
2. the preparation method of the conjugated polymer based on B ← N bridgings thiophene connection thiazole described in claim 1, it is characterised in that
Under inert atmosphere protection, by BNTTZ double tin trimethyl monomers, double bromine Ar2Monomer, three (dibenzalacetone) two palladium and three
(adjacent methyl) phenyl phosphorus dissolves in organic solvent, obtains mixed solution, mixed solution issues in lucifuge and heated reflux condition
Raw Stille polymerisations, after Stille polymerisations terminate, add end-capping reagent and blocked, purify, obtain conjugated polymer；
The structural formula of double tin trimethyl monomers of the BNTTZ is
Double bromine Ar2The structural formula of monomer is Br-Ar2-Br。
3. the preparation method of the conjugated polymer according to claim 2 based on B ← N bridgings thiophene connection thiazole, its feature
It is, the organic solvent is toluene.
4. the preparation method of the conjugated polymer according to claim 2 based on B ← N bridgings thiophene connection thiazole, its feature
It is, double tin trimethyl monomers, the double bromine Ar of the BNTTZ2Monomer, three (dibenzalacetone) two palladium and three (adjacent methyl) benzene
The amount of the material of base phosphorus is than 1:1:0.02:0.16.
5. the preparation method of the conjugated polymer according to claim 2 based on B ← N bridgings thiophene connection thiazole, its feature
It is, BNTTZ double tin trimethyl monomers and double bromine Ar in the mixed solution2The concentration of monomer is respectively 0.005~0.1M.
6. the preparation method of the conjugated polymer according to claim 2 based on B ← N bridgings thiophene connection thiazole, its feature
It is, the reaction temperature of the Stille polymerisations is 110~120 DEG C, and the reaction time is 24~48h.
7. the conjugated polymer based on B ← N bridgings thiophene connection thiazole described in claim 1 is as macromolecular solar battery
Acceptor material application.
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