CN110229315A - A kind of broad-band gap copolymer acceptor material and preparation method thereof based on imidodicarbonic diamide - Google Patents
A kind of broad-band gap copolymer acceptor material and preparation method thereof based on imidodicarbonic diamide Download PDFInfo
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Abstract
The invention belongs to solar cell material technical fields, disclose a kind of broad-band gap copolymer acceptor material and preparation method thereof based on imidodicarbonic diamide, it is the random copolymer organic solar batteries acceptor material with D-A structure, general structure such as formula I based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar batteries acceptor material；Random copolymer organic solar batteries receptor structure with D-A structure further can be formula II and formula III.Broad-band gap copolymer acceptor material molecular structure provided by the invention in imidodicarbonic diamide is simple, and preparation step is less and simple, and synthesis material is cheap and easily-available, has good visible absorption range and absorption intensity；Imidodicarbonic diamide analog copolymer molecule of the invention can solwution method processing and have preferable sunlight capture ability and thermal stability, be the ideal material of all-polymer organic solar batteries.
Description
Technical field
The invention belongs to organic photovoltaic fields, and in particular to a kind of broad-band gap copolymer receptor material based on imidodicarbonic diamide
Material and preparation method thereof.
Background technique
The problem of energy problem is the final and decisive juncture that the current whole mankind is faced, solar energy are that a kind of reserves are sufficient, are distributed
Most wide, free of contamination clean energy resource, is utilized by plant already between 1 years, is one of the energy for most having application prospect.Too
Positive energy battery is the device that solar energy is directly changed into electric energy, is always the emphasis of scientist's research, however at high cost at present
High, complex process, the disadvantages of volume is larger, aesthetics is poor, so that people, which shift to sight, develops cheap and easy to get, stability
High, the novel solar battery material with outstanding photovoltaic effect.
Organic solar batteries as third generation solar cell, have it is inexpensive, flexible, translucent, roll-to-roll can print
, there is wide prospect in the features such as brush.Wherein, compared to small molecule, all-polymer solar battery has more outstanding light
Capture ability and good charge transport ability, become the emphasis studied at this stage.
Currently, the problem that all-polymer battery is lower there are still energy conversion efficiency, therefore develop efficient polymerization
Object donor material and polymeric acceptor material become the research focus in the field.It is existing in the research of polymer battery
It is more that efficient polymer donor material can be achieved, therefore develop matching high-efficiency polymer acceptor material and compel in eyebrow
Eyelash.
In conclusion problem of the existing technology is:
In the prior art, organic solar batteries to prepare material dissolubility poor, it is complementary not have good absorption spectrum
Performance.
And the light for preparing material and not having higher molar extinction coefficient and widening of existing organic solar batteries
Spectrum, can not achieve higher short circuit current function.And existing imidodicarbonic diamide polymeric acceptor light absorption range is relatively narrow, is unfavorable for
Photoelectric current generates.
Summary of the invention
In view of the problems of the existing technology, a kind of broad-band gap copolymer acceptor material and its system based on imidodicarbonic diamide
Preparation Method.Such polymeric acceptor and narrow band gap polymer donor material can form that good absorption spectrum is complementary, level-density parameter,
To meet the needs of all-polymer photovoltaic cell acceptor material.
It is another object of the present invention to by fluoro- 2,2 ' the bithiophene random copolymerization of obtained imidodicarbonic diamide-porphyrin -3,3 '-two
Object is used to prepare all-polymer photovoltaic cell, using the electron and extinction characteristic of porphyrin, so that absorption spectrum Einstein shift, Jin Erti
Rise the short circuit current of all-polymer photovoltaic cell.
In order to achieve the above object, the present invention takes following technical solution: one kind based on imidodicarbonic diamide, porphyrin and
Thiophene terpolymer organic solar batteries acceptor material, it is described to be based on imidodicarbonic diamide, porphyrin and thiophene terpolymer
Organic solar batteries acceptor material is the random copolymer organic solar batteries acceptor material with D-A structure, and structure is logical
Formula is as shown in formula I:
Wherein, 0 < x < 1, n are number of repeat unit.
Further, D is electron unit, and structural formula is selected from such as flowering structure:
Further, described to be based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar batteries acceptor material
Structure is as shown in formula II:
Another object of the present invention is to provide a kind of structure such as formulas II based on imidodicarbonic diamide, porphyrin and thiophene
The preparation method of terpolymer organic solar batteries acceptor material, the preparation method include:
Further, the synthesis of compound 2 includes: to be dissolved compound 1 with 10mL methylene chloride, and Br is added2, stir 3 days；
Solution is slowly imported in excessive saturated sodium thiosulfate solution under ice bath, stirs a hour, then uses deionization
Water repeatedly washs mixture, makes to be extracted with dichloromethane, and anhydrous sodium sulfate dries, filters, and is spin-dried for solvent, with petroleum ether: dichloro
Methane=4:1 is solvent, and column separation obtains red crystals 2；
The synthesis of compound 3: the methylene chloride of the pure and mild 120mL of 2- octyldodecyl is added, adds PCC, at room temperature instead
It answers 4 hours.Direct methylene chloride extraction, saturated common salt water washing is repeated multiple times, is spin-dried for, is purified using silica gel column chromatography, elutes
Agent is methylene chloride, obtains transparency liquid product 3；
The synthesis of compound 4: being added new steaming pyrroles and formaldehyde, and argon gas protects lower slowly injection trifluoroacetic acid, at room temperature instead
The NaOH aqueous solution of 70mL 0.1mol/L is added after answering 15 minutes, the reaction was continued half an hour.Vacuum distillation removes remaining pyrroles,
Crude product is obtained, purify using silica gel column chromatography, eluant, eluent is methylene chloride: petroleum ether=1:3 is spin-dried for, and is dried in vacuo white
Solid product；
The synthesis of compound 5: under argon gas protection, compound 1 and compound 2 is added, adds 1L methylene chloride, is protected from light down
Trifluoroacetic acid slowly is squeezed into, reaction solution can become light red from colourless in injection process, gradually deepen；After room temperature reaction 2 hours, add
5mL triethylamine is added after entering DDQ the reaction was continued 1 hour and terminates reaction, is spin-dried for, is petroleum ether with eluant, eluent: methylene chloride=4:1
Column is crossed, purple solid product is obtained；
The synthesis of compound 6: under argon gas protection, 50mL methylene chloride and compound 3 is added, is added dropwise and is dissolved under ice bath
The bromo-succinimide of 30mL methylene chloride reacts 6 hours, and acetone is quenched, and is spin-dried for, methylene chloride extraction, saturated salt solution
Washing, it is repeated multiple times, it is spin-dried for, silica gel column chromatography purifying, eluent petroleum ether: methylene chloride=6:1 is spin-dried for, and it is solid to obtain aubergine
Body product；
The synthesis of compound 7: compound 4 and 60mL methylene chloride, 30mL methanol is added, adds Zn (OAc)2·
2H2O is stirred at room temperature 4 hours；It is spin-dried for, methylene chloride extraction, saturated common salt water washing is repeated multiple times, is spin-dried for, using silicagel column
Chromatographic purifying, eluent petroleum ether: methylene chloride=1:1 is spin-dried for, obtains purple solid product；
The synthesis of copolymer p 1: under protection of argon gas, the addition compound 2 into 10mL reaction flask, compound 7, (3,3 '-
Two fluoro- [2,2 '-bithiophenes] -5,5 '-diyls) double tin trimethyls, tetrakis triphenylphosphine palladium, 0.3 mL DMF and 1.2mL first
Benzene stirs 24 hours at 110 DEG C；Product is precipitated in bottom of bottle, stops reaction, reaction solution is cooled to room temperature, and is added dropwise to
Methanol solution filters, vacuum drying；By Soxhlet extractor, successively respectively extract removing small molecule and other with acetone, petroleum ether
Then by-product goes out subject polymer with the chloroform of chromatographically pure.
Further, described to be based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar batteries acceptor material
Structure such as formula III:
Another object of the present invention is to provide a kind of structure such as formulas III based on imidodicarbonic diamide, porphyrin and thiophene
The preparation method of terpolymer organic solar batteries acceptor material, the preparation method include:
Further, the synthesis of copolymer p 2: under protection of argon gas, the addition compound 2 into 10mL reaction flask, compound 7,
(3,3 '-two fluoro- [2,2 '-bithiophenes] -5,5 '-diyls) double tin trimethyls (82.3 mg, 0.16mmol), four (triphenylphosphines)
Palladium (9mg, 0.0078mmol), 0.3mL DMF and 1.2mL toluene stir 24 hours at 110 DEG C；Product is precipitated in bottom of bottle,
Stop reaction, reaction solution is cooled to room temperature, and is added dropwise to methanol solution, is filtered, vacuum drying；By Soxhlet extractor,
Small molecule and other by-products are successively respectively extracted and removed with acetone, petroleum ether, then go out target with the chloroform of chromatographically pure
Polymer；It is spin-dried for obtaining product.
It is total based on imidodicarbonic diamide, porphyrin and thiophene ternary using described that another object of the present invention is to provide a kind of
The all-polymer solar battery of polymers organic solar batteries acceptor material preparation.
This is in conclusion advantages of the present invention and good effect are as follows:
The broad-band gap random copolymer receptor based on imidodicarbonic diamide of synthesis has good dissolubility, can be dissolved in big
Part organic solvent, such as methylene chloride, chloroform, tetrahydrofuran, dichloro-benzenes.
The broad-band gap random copolymer acceptor material based on imidodicarbonic diamide of synthesis, can be with narrow band gap polymeric donor material
Material has good absorption spectrum complementary.
The broad-band gap random copolymer acceptor material molar extinction coefficient with higher based on imidodicarbonic diamide of synthesis
With the spectrum widened, higher short circuit current may be implemented.
Detailed description of the invention
Fig. 1 is the UV-Vis figure of polymer provided in an embodiment of the present invention.
Fig. 2 is the C-V figure of polymer provided in an embodiment of the present invention.
Fig. 3 is cyclic voltammetry test chart of the polymer provided in an embodiment of the present invention in film.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Experimental method described in embodiment is unless otherwise specified conventional method；The reagent and material, such as without spy
Different explanation, commercially obtains.
In the prior art, organic solar batteries to prepare material dissolubility poor, it is complementary not have good absorption spectrum
Performance.And the spectrum for preparing material and not having higher molar extinction coefficient and widening of existing organic solar batteries,
It can not achieve higher short circuit current function.
In view of the problems of the existing technology, the present invention provides a kind of broad-band gap copolymer based on imidodicarbonic diamide by
Body material and preparation method thereof is explained in detail the present invention below with reference to concrete scheme.
It is provided in an embodiment of the present invention based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar batteries by
Body material, imidodicarbonic diamide, porphyrin and the thiophene terpolymer organic solar batteries acceptor material of being based on is with D-A
The random copolymer organic solar batteries acceptor material of structure, general structure is as shown in formula I:
Wherein, 0 < x < 1, n are number of repeat unit.
D is electron unit, and structural formula is selected from such as flowering structure:
The invention will be further described combined with specific embodiments below.
Embodiment 1
Fluoro- 2,2 ' the connection thiophene of imidodicarbonic diamide-porphyrin -3,3 '-two that porphyrin content provided in an embodiment of the present invention is 10%
Pheno random copolymer receptor, synthetic route are as follows:
The synthesis of compound 2: compound 1 (3.002g, 3.98mmol) is dissolved in 250mL twoport with 10mL methylene chloride
In flask, Br is added2(10ml, 195.17mmol), stirring at normal temperature 3 days.Solution is slowly imported to excessive saturation under ice bath
In hypo solution, a hour is stirred, then mixture is repeatedly washed using deionized water, is extracted using methylene chloride
It takes, anhydrous sodium sulfate dries, filters, and is spin-dried for solvent, and with petroleum ether: methylene chloride (v:v=4:1) is solvent, column separation
Obtain red crystals 2 (762mg, 21%).1H NMR (400MHz, Chloroform-d) δ 9.49 (d, J=8.2Hz, 2H),
9.04–8.85(m,2H),8.78–8.52(m,2H),5.30–5.03(m,2H),2.23(m,4H),1.84 (m,4H),1.49–
1.06(m,32H),0.92–0.72(m,12H)。
The synthesis of compound 3: 2- octyldodecanol (12 g, 40.19mmol) are added in two mouthfuls of round-bottomed flasks of 250mL
With the methylene chloride of 120mL, PCC (16.8g, 60.276mmol) is added, is reacted 4 hours at room temperature.Direct methylene chloride extraction
It takes, saturated common salt water washing is repeated multiple times, is spin-dried for, is purified using silica gel column chromatography, and eluant, eluent is methylene chloride, obtains transparent
Product liquid 3 (11.2g, 94%).1H NMR (400MHz, CDCl3) δ 9.57 (d, J=3.2Hz, 1H), 2.25 (m, 1H),
1.71-1.53 (m, 5H), 1.5-1.35 (m, 3H), 1.28 (s, 21H), 0.90 (t, J=6.7Hz, 10H).
The synthesis of compound 4: new steaming pyrroles (39.89g, 595.35mmol) and formaldehyde are added in 250mL twoport flask
(5.5g, 18.337mmol), lower slowly injection trifluoroacetic acid (295.9mg, 2.6mmol) of argon gas protection, reacts 15 points at room temperature
The NaOH aqueous solution of 70mL 0.1mol/L is added after clock, the reaction was continued half an hour.Vacuum distillation removes remaining pyrroles, obtains and slightly produces
Object is purified using silica gel column chromatography, and eluant, eluent is methylene chloride: petroleum ether (1:3) is spin-dried for, and is dried in vacuo to obtain white solid production
Object 7.5g.1HNMR(400MHz,CDCl3): δ7.86(s,2H),6.65(s,2H),6.14(s,2H),6.03(s,2H),3.98
(s,2H)。
The synthesis of compound 5: argon gas protection under, into two mouthfuls of round-bottomed flasks of 3L addition compound 1 (4.4g,
14.9mmol) and compound 2 (2.1g, 14.385mmol), 1L methylene chloride is added, is protected from light and lower slowly squeezes into trifluoroacetic acid
(0.63mL, 14.4mmol), reaction solution can become light red from colourless in injection process, gradually deepen.After room temperature reaction 2 hours,
The termination reaction of 5mL triethylamine is added after the reaction was continued 1 hour in addition DDQ (4.86g, 21.577mmol), is spin-dried for, uses eluant, eluent
For petroleum ether: methylene chloride (4:1) crosses column, obtains purple solid product 1.97g, yield 32.5%.1H NMR(400MHz,
CDCl3) δ 10.22 (s, 2H), 9.70 (d, J=32.2Hz, 4H), 9.42 (d, J=3.2Hz, 4H), 5.18 (s, 2H),
3.02-2.84(m,4H),2.84-2.62(m,4H),1.55(s,10H),1.26(s,60H),-2.45(s,2H).13C NMR
(100MHz,CDCl3)δ149.56,149.41,147.11,146.98,144.62,144.36,142.40, 142.16,
132.11,132.01,129.01,128.79,128.37,128.13,122.93,104.80,104.40, 104.00,46.33,
42.35,31.94,31.87,30.06,29.71,29.62,29.54,29.33,22.74,22.67, 14.21,
14.16.MALDI-TOF-MS 843.77(M+)。
The synthesis of compound 6: under argon gas protection, 50mL methylene chloride and chemical combination are added into 250mL twoport round-bottomed flask
The bromo-succinimide (NBS) for being dissolved in 30mL methylene chloride is added dropwise under ice bath in object 3 (945mg, 1.113mmol)
(439mg, 2.457mmol) reacts 6 hours, and acetone is quenched, and is spin-dried for, methylene chloride extraction, and saturated common salt water washing is repeatedly more
It is secondary, it is spin-dried for, silica gel column chromatography purifying, eluent petroleum ether: methylene chloride (6:1) is spin-dried for, and obtains aubergine solid product 924mg,
Yield 83%.1H NMR (400 MHz, CDCl3) δ 9.72-9.51 (m, 8H), 5.03 (s, 2H), 2.85 (t, J=13.7,4H),
2.72-2.64 (m,4H),1.51(m,8H),1.51-1.04(m,48H),0.88(m,12H),-2.45(s,2H).13C NMR
(100MHz,CDCl3)δ150.29,152.24,149.72,149.45,147.72,147.46,133.28,132.92,
131.86,131.65,131.02,130.80,130.13,129.60,126.35,125.15,105.04,104.50,
103.95,47.22,42.63,32.00,31.82,29.97,29.84,29.77,22.76,22.62,14.18,14.07.
MALDI-TOF-MS 1000.53(M+)。
The synthesis of compound 7: in 250mL single port bottle, compound 4 (735mg, 0.734mmol) and 60mL dichloro is added
Methane, 30mL methanol add Zn (OAc)22H2O (1.73g, 7.34mmol) is stirred at room temperature 4 hours.It is spin-dried for, dichloromethane
Alkane extraction, saturated common salt water washing is repeated multiple times, is spin-dried for, is purified using silica gel column chromatography, eluent petroleum ether: methylene chloride
(1:1), is spin-dried for, and obtains purple solid product 656mg, yield 84%.1H NMR(400MHz,CDCl3)δ9.86-9.45(m,8H),
5.18(s,2H), 2.91(m,4H),2.74(m,4H),1.49(s,8H),1.38-0.96(m,48H),0.78(m12H).13C
NMR (100MHz,CDCl3)δ152.58,152.52,150.30,149.71,149.43,147.70,147.43, 133.28,
132.91,131.87,131.66,131.05,130.82,126.36,104.46,47.26,42.66,31.84, 31.78,
30.01,29.88,29.55,29.51,29.24,22.65,22.58,14.11,14.05.MALDI-TOF MS
(C58H86Br2N4Zn)MALDI-TOF-MS 1064.32(M+)。
The synthesis of copolymer p 1: under protection of argon gas, into 10mL reaction flask be added compound 2 (128.1 mg,
0.14mmol), compound 7 (16.6mg, 0.016mmol), (3,3 '-two fluoro- [2,2 '-bithiophenes] -5,5 '-diyls) double three
Methyl tin (82.3mg, 0.16mmol), tetrakis triphenylphosphine palladium (9mg, 0.0078mmol), 0.3mL DMF and 1.2mL first
Benzene stirs 24 hours at 110 DEG C.Product is precipitated in bottom of bottle, stops reaction, and reaction solution is cooled to room temperature, is drawn using dropper
And be added dropwise in methanol solution, it is precipitated, filters along with solid crude product at this time, vacuum drying.Pass through Soxhlet extraction
Device successively respectively extracts one day removing small molecule and other by-products with acetone, petroleum ether, is then gone out with the chloroform of chromatographically pure
Subject polymer.It is spin-dried for obtaining product 121.1mg, yield 79.9%.Number-average molecular weight 16100, molecular weight dispersion index 2.13.
Embodiment 2
Fluoro- 2,2 ' the bithiophene of imidodicarbonic diamide-porphyrin -3,3 '-two that porphyrin content provided in an embodiment of the present invention is 5%
Random copolymer receptor, synthetic route are as follows:
The synthesis of copolymer p 2: under protection of argon gas, into 10mL reaction flask be added compound 2 (135.2mg,
0.15mmol), compound 7 (8.3mg, 0.0078mmol), (3,3 '-two fluoro- [2,2 '-bithiophenes] -5,5 '-diyls) double three
Methyl tin (82.3mg, 0.16mmol), tetrakis triphenylphosphine palladium (9mg, 0.0078mmol), 0.3mL DMF and 1.2mL first
Benzene stirs 24 hours at 110 DEG C.Product is precipitated in bottom of bottle, stops reaction, and reaction solution is cooled to room temperature, is drawn using dropper
And be added dropwise in methanol solution, it is precipitated, filters along with solid crude product at this time, vacuum drying.Pass through Soxhlet extraction
Device successively respectively extracts one day removing small molecule and other by-products with acetone, petroleum ether, is then gone out with the chloroform of chromatographically pure
Subject polymer.It is spin-dried for obtaining product 108.7mg, yield 72.3%.Number-average molecular weight 6300, molecular weight dispersion index 1.65.
Embodiment 3
Fluoro- 2,2 ' the bithiophene random copolymer receptor of imidodicarbonic diamide-porphyrin -3,3 '-two provided in an embodiment of the present invention
The absorption spectrum test of P1 and P2 is as follows.
Fig. 1 and Fig. 2 be respectively fluoro- 2,2 ' the bithiophene random copolymer receptor P1 of imidodicarbonic diamide-porphyrin -3,3 '-two and
Uv-visible absorption spectra of the P2 on chloroformic solution and quartz plate.
The maximum value of the film absorption of P1 and P2 is respectively in 346,439,566nm and 352,439,590nm as shown in Figure 2
Peak value is played respectively in 719nm and 722nm or so in left and right, and optical band gap is that (optical band gap can be according to formula Eg=by 1.72eV
1240/ λ onset is calculated, and wherein Eg is optical band gap, is the absorption maximum sideband value of λ onset film absorption), data are listed in table
In 1.
Embodiment 4
Fluoro- 2,2 ' the bithiophene random copolymer receptor of imidodicarbonic diamide-porphyrin -3,3 '-two provided in an embodiment of the present invention
The electro-chemical test of P1 and P2 is as follows.
Fig. 3 is fluoro- 2,2 ' the bithiophene random copolymer receptor P1 and P2 of imidodicarbonic diamide-porphyrin -3,3 '-two in film
Cyclic voltammetry test, electrolyte is the anhydrous acetonitrile of tetra-n-butyl ammonium hexafluorophosphate (0.1M), then by blasting
Argon gas deoxygenation.Use glass-carbon electrode as working electrode, platinum line is used as to electrode, and Ag/Ag+ electrode is used as reference electrode.It will give
Body or receptor are wrapped on glassy carbon electrode, and correct all current potentials using Fc/ Fc+.
The initial oxidation potential of P1 and P2 is respectively 1.50V and 1.52V as shown in Figure 3, and initial reduction current potential is respectively-
0.41V and -0.42V.Pass throughWith LUMO energyFormula can be calculated P1 and P2 HOMO energy level be respectively -5.80eV
With -5.82eV, lumo energy is respectively -3.89eV and -3.88eV, and data are listed in Table 1 below.
The optics and chemical property of table 1 P1 and P2
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
1. one kind is existed based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar batteries acceptor material, feature
In imidodicarbonic diamide, porphyrin and the thiophene terpolymer organic solar batteries acceptor material of being based on is with D-A structure
Random copolymer organic solar batteries acceptor material, general structure is as shown in formula I:
Wherein, 0 < x < 1, n are number of repeat unit.
2. being based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar batteries receptor as described in claim 1
Material, which is characterized in that D is electron unit, and structural formula is with a kind of in flowering structure；
3. being based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar batteries receptor as described in claim 1
Material, which is characterized in that described to be based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar batteries acceptor material
Structure is as shown in formula II:
Formula II:
4. a kind of structure as claimed in claim 3 such as formula II is organic based on imidodicarbonic diamide, porphyrin and thiophene terpolymer
The preparation method of solar battery acceptor material, which is characterized in that the preparation method includes:
5. preparation method as claimed in claim 4, which is characterized in that the synthesis of compound 2 includes: will with 10mL methylene chloride
Compound 1 dissolves, and Br is added2, stir 3 days；Solution is slowly imported in excessive saturated sodium thiosulfate solution under ice bath,
A hour is stirred, then mixture is repeatedly washed using deionized water, makes to be extracted with dichloromethane, anhydrous sodium sulfate is dry,
Filtering, is spin-dried for solvent, using petroleum ether: for methylene chloride=4:1 as solvent, column separation obtains red crystals 2；
The synthesis of compound 3: being added the methylene chloride of the pure and mild 120mL of 2- octyldodecyl, add PCC, and it is small to react 4 at room temperature
When；Direct methylene chloride extraction, saturated common salt water washing is repeated multiple times, is spin-dried for, is purified using silica gel column chromatography, and eluant, eluent is
Methylene chloride obtains transparency liquid product 3；
The synthesis of compound 4: being added new steaming pyrroles and formaldehyde, and the lower slowly injection trifluoroacetic acid of argon gas protection reacts 15 at room temperature
The NaOH aqueous solution of 70mL 0.1mol/L is added after minute, the reaction was continued half an hour；Vacuum distillation removes remaining pyrroles, obtains slightly
Product is purified using silica gel column chromatography, and eluant, eluent is methylene chloride: petroleum ether=1:3 is spin-dried for, and is dried in vacuo to obtain white solid
Product；
The synthesis of compound 5: under argon gas protection, being added compound 1 and compound 2, add 1L methylene chloride, is protected from light lower slow
Trifluoroacetic acid is squeezed into, reaction solution can become light red from colourless in injection process, gradually deepen；After room temperature reaction 2 hours, it is added
The termination reaction of 5mL triethylamine is added after the reaction was continued 1 hour in DDQ, is spin-dried for, is petroleum ether with eluant, eluent: methylene chloride=4:1 mistake
Column obtains purple solid product；
The synthesis of compound 6: under argon gas protection, 50mL methylene chloride and compound 3 is added, is added dropwise under ice bath and is dissolved in 30mL
The bromo-succinimide of methylene chloride reacts 6 hours, and acetone is quenched, and is spin-dried for, methylene chloride extraction, saturated common salt water washing,
It is repeated multiple times, it is spin-dried for, silica gel column chromatography purifying, eluent petroleum ether: methylene chloride=6:1 is spin-dried for, and obtains the production of aubergine solid
Object；
The synthesis of compound 7: compound 4 and 60mL methylene chloride, 30mL methanol is added, adds Zn (OAc) 22H2O, room
Temperature stirring 4 hours；It is spin-dried for, methylene chloride extraction, saturated common salt water washing is repeated multiple times, is spin-dried for, pure using silica gel column chromatography
Change, eluent petroleum ether: methylene chloride=1:1 is spin-dried for, obtains purple solid product；
The synthesis of copolymer p 1: under protection of argon gas, compound 2 is added into 10mL reaction flask, compound 7, (3,3 '-two is fluoro-
[2,2 '-bithiophene] -5,5 '-diyls) double tin trimethyls, tetrakis triphenylphosphine palladium, 0.3mL DMF and 1.2mL toluene,
It is stirred 24 hours at 110 DEG C；Product is precipitated in bottom of bottle, stops reaction, reaction solution is cooled to room temperature, and it is molten to be added dropwise to methanol
Liquid filters, vacuum drying；By Soxhlet extractor, is successively respectively extracted with acetone, petroleum ether and remove small molecule and other by-products
Then object goes out subject polymer with the chloroform of chromatographically pure.
6. being based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar batteries receptor as described in claim 1
Material, which is characterized in that described to be based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar batteries acceptor material
Structure such as formula III:
7. a kind of structure as claimed in claim 6 such as formula III is organic based on imidodicarbonic diamide, porphyrin and thiophene terpolymer
The preparation method of solar battery acceptor material, which is characterized in that the preparation method includes:
8. preparation method as claimed in claim 7, which is characterized in that the synthesis of copolymer p 2: under protection of argon gas, toward 10mL
Compound 2, compound 7, (3,3 '-two fluoro- [2,2 '-bithiophenes] -5,5 '-diyls) double tin trimethyls are added in reaction flask
(82.3mg, 0.16mmol), tetrakis triphenylphosphine palladium (9mg, 0.0078mmol), 0.3mL DMF and 1.2mL toluene, 110
It is stirred 24 hours at DEG C；Product is precipitated in bottom of bottle, stops reaction, and reaction solution is cooled to room temperature, and is added dropwise to methanol solution,
Filtering, vacuum drying；By Soxhlet extractor, small molecule and other by-products are successively respectively extracted and removed with acetone, petroleum ether,
Then go out subject polymer with the chloroform of chromatographically pure；It is spin-dried for obtaining product.
9. a kind of electric based on imidodicarbonic diamide, porphyrin and thiophene terpolymer organic solar using described in claim 1
The all-polymer solar battery of pond acceptor material preparation.
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| CN111471060A (en) * | 2020-05-12 | 2020-07-31 | 山东师范大学 | Oxygen-fused perylene diimide dimer small molecule receptor material and preparation method and application thereof |
| CN111944127A (en) * | 2020-08-06 | 2020-11-17 | 中山大学 | D-A polymer based on perylene bisimide conjugated plane expansion and preparation method thereof |
| CN113045590A (en) * | 2021-04-01 | 2021-06-29 | 四川大学 | Perylene diimide non-fullerene acceptor material and application thereof |
| CN113666949A (en) * | 2021-08-30 | 2021-11-19 | 陕西师范大学 | Gold (III) complex-perylene diimide derivative and fluorescent sensing tube and tubular fluorescent sensor prepared from same |
| CN114316220A (en) * | 2021-12-20 | 2022-04-12 | 晋能控股煤业集团有限公司 | Polymer donor material and method for preparing same |
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| CN111471060A (en) * | 2020-05-12 | 2020-07-31 | 山东师范大学 | Oxygen-fused perylene diimide dimer small molecule receptor material and preparation method and application thereof |
| CN111471060B (en) * | 2020-05-12 | 2021-10-15 | 山东师范大学 | Oxygen-fused perylene diimide dimer small molecule receptor material and preparation method and application thereof |
| CN111944127A (en) * | 2020-08-06 | 2020-11-17 | 中山大学 | D-A polymer based on perylene bisimide conjugated plane expansion and preparation method thereof |
| CN111944127B (en) * | 2020-08-06 | 2021-10-26 | 中山大学 | D-A polymer based on perylene bisimide conjugated plane expansion and preparation method thereof |
| CN113045590A (en) * | 2021-04-01 | 2021-06-29 | 四川大学 | Perylene diimide non-fullerene acceptor material and application thereof |
| CN113666949A (en) * | 2021-08-30 | 2021-11-19 | 陕西师范大学 | Gold (III) complex-perylene diimide derivative and fluorescent sensing tube and tubular fluorescent sensor prepared from same |
| CN113666949B (en) * | 2021-08-30 | 2022-07-12 | 陕西师范大学 | Gold (III) complex-perylene diimide derivative and fluorescent sensing tube and tubular fluorescent sensor prepared from same |
| CN114316220A (en) * | 2021-12-20 | 2022-04-12 | 晋能控股煤业集团有限公司 | Polymer donor material and method for preparing same |
| CN114316220B (en) * | 2021-12-20 | 2023-05-30 | 晋能控股煤业集团有限公司 | Polymeric donor material and method of making same |
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