CN113801301B - Isoindigo polymer of fused pyrrole ring type perylene imide with pendant gulf-position and preparation method thereof - Google Patents
Isoindigo polymer of fused pyrrole ring type perylene imide with pendant gulf-position and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- MLCPSWPIYHDOKG-BUHFOSPRSA-N (3e)-3-(2-oxo-1h-indol-3-ylidene)-1h-indol-2-one Chemical compound O=C\1NC2=CC=CC=C2C/1=C1/C2=CC=CC=C2NC1=O MLCPSWPIYHDOKG-BUHFOSPRSA-N 0.000 title claims abstract description 61
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- -1 perylene imide Chemical class 0.000 title claims abstract description 27
- 125000000168 pyrrolyl group Chemical group 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 30
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006467 substitution reaction Methods 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- 229940126062 Compound A Drugs 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims 6
- 239000012298 atmosphere Substances 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000012429 reaction media Substances 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- DOIRPCDOGSNNCS-UHFFFAOYSA-N trimethyl-[5-(5-trimethylstannylthiophen-2-yl)thiophen-2-yl]stannane Chemical compound S1C([Sn](C)(C)C)=CC=C1C1=CC=C([Sn](C)(C)C)S1 DOIRPCDOGSNNCS-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- C08G61/124—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 with a five-membered ring containing one nitrogen atom in the ring
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- C08G61/126—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 with a five-membered ring containing one sulfur atom in the ring
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Abstract
The invention discloses an isoindigo polymer of fused pyrrole ring type perylene imide with pendant gulf position and a preparation method thereof. Firstly, a monomer M1 is prepared by linking gulf-position fused pyrrole rings of perylene imide with isoindigo through a substitution reaction, and then the monomer M1 is heated and polymerized with a methyl tin conjugated monomer M2 to prepare the isoindigo polymer of the side-chain-hung gulf-position fused pyrrole ring type perylene imide. A side chain hanging gulf-position fused pyrrole ring type perylene imide structural unit is introduced into an isoindigo blue polymer donor material to form a novel polymer semiconductor material with a side chain hanging perylene imide derived structural unit. The polymer has good solubility, higher molecular weight and good thermal stability.
Description
Technical Field
The invention belongs to the field of organic synthesis, and relates to an isoindigo polymer of side-chain-hung gulf-position fused pyrrole ring type perylene bisimide and a preparation method thereof.
Background
The perylene bisimide compound is an important small molecule receptor in the field of organic semiconductor materials, the isoindigo compound is an important small molecule donor in the field of organic semiconductor materials, and the introduction of the organic small molecule receptor as a side chain unit into a polymer donor material to form a single-component polymer active layer is an important way for preparing polymer solar cells.
However, the current research work mainly focuses on introducing pendant perylene imide into side chains, and the research on introducing side chains into cross-pendant perylene imide is rare.
Based on the method, a side chain hanging gulf-position fused pyrrole ring type perylene bisimide structural unit is introduced into the isoindigo polymer donor material to form a novel polymer with a side chain hanging perylene bisimide derived structural unit.
Disclosure of Invention
Compared with other isoindigo polymers, the isoindigo polymer has the innovation that perylene imide micromolecule receptors are transversely hung in side chains of donor polymers to form a novel polymer with a side chain hanging structure.
The perylene bisimide has a large plane conjugated system and is a typical construction unit for constructing an organic small molecule receptor. The perylene imide structure is usually designed to be vertically suspended on a main chain as a side chain electron-withdrawing building unit, and an unmodified perylene imide conjugated core is relatively purely applied. By modifying the molecular skeleton, the aggregation state and the physicochemical property of the perylene bisimide structural unit are regulated and controlled, and the possibility that the perylene bisimide structural unit is applied to constructing a single polymer active layer as a side chain receptor is expanded. Therefore, it is of positive interest to study the pendant side chains of perylene imides in other forms from polymers.
The polymer is prepared by introducing the cross-hanging perylene bisimide into the side chain of the polymer, and has the advantages of good chemical stability, higher molecular weight, good solubility and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to protect isoindigo polymer of fused pyrrole ring type perylene imide with pendant gulf position, which has the structural formula:
The second purpose of the invention is to protect the isoindigo polymer of the side chain hanging gulf-position condensed pyrrole ring type perylene diimide, which is a preparation method of monomers M1 and M2 and a catalyst tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) And the ligand tris (o-methylphenyl) phosphorus (P)3) Dissolving in an anhydrous organic solvent, heating, refluxing and polymerizing under the protection of inert gas, purifying by Soxhlet extraction, and drying in vacuum to obtain the polymer;
wherein the structural formula of the monomer M1 is:
the organic solvent is toluene.
The preparation method of the monomer M1 is as follows:
(1) isoindigo compound A substituted by 1 equivalent of bromoalkyl chain under anhydrous, oxygen-free and argon atmosphere
And 2.4 equivalent of gulf-position fused pyrrole ring type perylene diimide compound B
Dissolving in organic solvent N, N-dimethylformamide, taking 3 equivalents of potassium carbonate as a catalyst, stirring and reacting at 80 ℃, extracting by ethyl acetate, and purifying by a silica gel chromatography column by taking dichloromethane to petroleum ether with the volume ratio of 7 to 1 as an eluent to obtain the monomer M1.
The polymer preparation method comprises the following steps:
(1) under an anhydrous oxygen-free and argon atmosphere, 1 equivalent of monomer M1
And 1 equivalent of monomer M2
Dissolving in toluene, an organic solvent, and reacting in the presence of 0.2% equivalent of tris (dibenzylideneacetone) dipalladium (Pd) catalyst2(dba)3) 0.8% equivalent of the ligand tris (o-methylphenyl) phosphorus (P)3) Reacting at 65 deg.C for 5 hr, sequentially extracting with methanol, petroleum ether and chloroform, and vacuum drying to obtain the final productA polymer.
Significant advantages of the invention
(1) The raw materials adopted by the invention are relatively cheap, and the synthesis path is not complex;
(2) the polymer synthesized by the method has good solubility in common organic solvents such as chloroform, tetrahydrofuran, chlorobenzene and the like, is easy to form a film by a dripping or spin coating mode, and has a good light absorption range and good chemical stability.
(3) The polymer synthesized by the invention has excellent thermal stability and can be applied to devices such as polymer solar cells and the like.
Description of the drawings:
FIG. 1 shows the synthetic procedure of this example;
FIG. 2 is a NMR spectrum of monomer M1;
FIG. 3 is a NMR hydrogen spectrum of a polymer;
FIG. 4 is a thermogravimetric analysis curve of a polymer;
FIG. 5 is a gel permeation chromatogram of a polymer;
FIG. 6 is a film UV-VIS absorption spectrum of polymer and monomer M1;
FIG. 7 is a cyclic voltammogram of a polymer.
The specific implementation mode is as follows:
in order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
EXAMPLE 1 preparation of bromoalkyl chain-substituted isoindigo Compound A
Bromoalkyl chain-substituted isoindigo compound a is prepared according to the literature "Brynn p. charron, Michael u. ocheje, Mariia serivanova, et al, Electronic properties of isoindigo-based conjugated polymers bearing-binding and linear alkyl peptides, Journal of Materials Chemistry c.2018, 6, 12070" and has the formula:
example 2 bay-position fused pyrrole-ring type perylene imide Compound B
A gulf-fused pyrrole-ring type perylene imide compound B of the formula:
example 3 preparation of monomer M1:
compound B (1.69mmol, 1.20g) obtained in example 2, compound A (0.70mmol, 0.52g) obtained in example 1 and potassium carbonate (2.1mmol, 0.29g) were dissolved in a 100mL pressure-resistant tube containing N, N-dimethylformamide (30mL) under an argon atmosphere, reacted with stirring at 80 ℃ and followed by TLC. After 36 hours the reaction was complete and cold water was added. And extracting with ethyl acetate, washing the obtained organic phase with water, collecting the organic phase, drying with anhydrous magnesium sulfate, and removing the solvent from the obtained filtrate under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel (eluent dichloromethane: petroleum ether in a volume ratio of 7: 1), recrystallized from methanol and dried under vacuum to give a reddish brown solid, monomer M1, in a yield of 1.40g, in a yield of 50%, TLC shift Rf0.48 (developing solvent is dichloromethane: petroleum ether: 7:1, volume ratio).1HNMR(400MHz,CDCl3) δ 8.99(s,8H),8.87(s,2H),8.82(s,4H),6.99(s,2H),6.78(s,2H),5.30(s,4H),4.87(s,4H),3.64(s,4H),2.30(s,8H),2.20(s,4H),1.92(s,8H),1.62(s,4H),1.30(s,58H),0.81(s, 24H). The structure is as follows:
example 4 preparation of monomer M2:
monomer M2 was prepared according to the literature "Joonhyong choice, Ki-Yun Kim, Hojeong Yu, Import of Electron Transport instability in Nathalhalene dioxide-Based Polymer accumulators for High-Performance, Additive-Free, All-Polymer Solar Cells, Chemistry of Materials 201527 (15), 5230-5237" and has the structure:
example 5 preparation of isoindigo polymer of gulf-position fused pyrrole ring type perylene imide with pendant side chains:
monomer M1(0.1mmol, 200.8mg) and monomer M2(0.1mmol, 49.2mg) were added to a 100mL Schleck reaction tube under argon and 7mL of anhydrous toluene was added. After bubbling deoxygenation for 30 minutes, the catalyst tris (dibenzylideneacetone) dipalladium (Pd) was added2(dba)3) (0.002mmol, 1.9mg), ligand tris (o-methylphenyl) phosphorus (P (o-tolyl)3) (0.008mmol, 2.5mg) and the tube sealed and reacted at 65 ℃ for 5 hours. Cooling the reaction to room temperature, precipitating with methanol to obtain crude product, sequentially performing Soxhlet extraction with methanol, petroleum ether and chloroform, and collecting chloroform extract. After removal of the solvent under reduced pressure, a second precipitation with methanol was carried out, and filtration and vacuum drying were carried out to obtain a black solid as a polymer at a yield of 197mg and a yield of 98%.1H NMR (400MHz, CDCl3) Δ 8.86(s,6H),8.61(s,3H),7.52(s,1H),7.00(s,3H),6.90(s,1H),6.62(s,2H),6.30(s,1H),5.23(s,2H),4.84(s, 1H). The structure is as follows:
thermogravimetric analysis, gel permeation chromatography, ultraviolet absorption spectrum and cyclic voltammogram of polymer
FIG. 4 shows the thermogravimetric analysis curve of a polymer at the temperature (T) corresponding to a loss of 5% by weightd) The thermal decomposition temperature of the material is considered. As can be seen from FIG. 4, the thermal decomposition temperature (T) of the polymerd) 375 deg.c, indicating excellent thermal stability. FIG. 5 shows gel permeation of polymersChromatographic GPC curves determined a number average molecular weight of 20866 and a weight average molecular weight of 51234. FIG. 6 shows the UV-visible absorption spectrum of a polymer film and monomer M1, from which FIG. 6 shows the initial absorption (. lamda.) of the polymer filmonset film) At 776nm, the polymer is polymerized from monomer M1, and monomer M1 is a polymer in which two conjugated structural units are bridged by a non-conjugated alkyl chain. The absorption of the polymer is divided into two parts: isoindigo units as comonomer backbone; and the other is perylene diimide side chain unit. When conjugated unit bithiophene is introduced into the conjugated molecular chain, the effective conjugation length of the conjugated molecular chain is obviously improved, the charge transfer effect in the molecular chain is obvious, and the initial absorption wavelength (lambda) of the polymer in a film state is realizedonset film) Compared with the initial absorption wavelength of M1 under the same condition, the absorption wavelength is increased by about 200nm, which expands the absorption range of the polymer to visible light and contributes to the improvement of the utilization rate of the light. FIG. 7 shows a cyclic voltammogram of a polymer, characterizing the electrochemical properties of the polymer, and the cyclic voltammetry test was performed on a PGSTAT302N type electrochemical workstation. Three-electrode system: the working electrode is a platinum electrode, the auxiliary electrode is a platinum wire electrode, and the reference electrode is an Ag/AgCl electrode. The electrolyte is 0.1M tetrabutylammonium hexafluorophosphate solution (the solvent is anhydrous acetonitrile). Under the nitrogen atmosphere, the scanning speed is 100mV/s, ferrocene is used as an external standard before and after a test sample, and during the test, the polymer is dissolved and then is dripped on a platinum disk electrode to form a film, and then the electrochemical test is carried out.
Claims (10)
1. The utility model provides an isoindigo polymer of fused pyrrole ring type perylene imide of gulf position of side chain suspension which characterized in that, its structure is:
2. The preparation method of the isoindigo polymer of the side-chain-suspended gulf-position fused pyrrole ring type perylene diimide of claim 1, characterized in that monomers M1 and M2 and a catalyst are dissolved in an anhydrous organic solvent, heated and refluxed under inert gas for polymerization, and then purified and dried at high temperature in vacuum to obtain the polymer; wherein the structural formula of the monomer M1 is:
the structure of monomer M2 is:
3. the method for preparing the isoindigo polymer of the side-chain-suspended gulf-position fused pyrrole-ring type perylene imide according to claim 2, which is characterized by comprising the following steps:
(1) carrying out substitution reaction on isoindigo compound A substituted by bromoalkyl chain and gulf-position fused pyrrole ring type perylene diimide compound B in an organic solvent to obtain a monomer M1;
(2) the monomer M1 and the methyl tin conjugated monomer M2 are subjected to polymerization reaction in an anhydrous organic solvent under the action of a catalyst and a ligand, and the polymer is obtained through soxhlet extraction.
4. The method for preparing isoindigo polymer of fused pyrrole ring type perylene imide with pendant gulf position according to claim 3, wherein the bromoalkyl chain substituted isoindigo compound A in the step (1) has the structural formula:
5. The method for preparing the side-chain-suspended gulf-position fused pyrrole-ring perylene imide isoindigo polymer according to claim 3, wherein the gulf-position fused pyrrole-ring perylene imide compound B in the step (1) has a structural formula as follows:
6. The preparation method of the side-chain-suspended gulf-position fused pyrrole ring type perylene imide isoindigo polymer according to claim 3, wherein the specific method of the step (1) is as follows: under the atmosphere of anhydrous oxygen-free and argon gas, 1 equivalent of isoindigo compound A substituted by bromoalkyl chain and 2.4 equivalents of gulf-position fused pyrrole ring type perylene diimide compound B react by taking 3 equivalents of potassium carbonate as a catalyst and N, N-dimethylformamide as a reaction medium; extracting, and purifying by a silica gel chromatographic column to obtain the monomer M1.
7. The preparation method of the side-chain-hung gulf-position fused pyrrole-ring type perylene imide isoindigo polymer according to claim 6, wherein the extracting agent is ethyl acetate for extraction; the eluent for purifying the silica gel chromatographic column is the eluent with the volume ratio of dichloromethane to petroleum ether being 7 to 1.
8. The method for preparing the side-chain-suspended gulf-position fused pyrrole ring type perylene imide isoindigo polymer according to claim 6, wherein the specific reaction temperature is 80 ℃ and the reaction time is 36 hours.
9. The preparation method of the side-chain-suspended gulf-position fused pyrrole ring type perylene imide isoindigo polymer according to claim 3, wherein the specific method of the step (2) is as follows: 1 equivalent of monomer M1 and 1 equivalent of 5,5 '-bis (trimethylstannyl) -2,2' -bithiophene monomer M2 were dissolved in anhydrous toluene in an anhydrous oxygen-free and argon atmosphere, and 2% equivalent of catalyst tris (dibenzylideneacetone) dipalladium Pd was dissolved at 65 ℃ in an anhydrous toluene atmosphere2(dba)3And 8% equivalent of ligand III(o-methylphenyl) phosphorus P (o-tolyl)3Reacting under the action of the alcohol, sequentially performing Soxhlet extraction by using methanol, petroleum ether and chloroform, and performing vacuum drying to obtain the polymer.
10. The method for preparing the perylene ring type perylene imide isoindigo polymer with pendant gulf sites according to claim 9, wherein the reaction time is 5 hours.
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