CN111944127A - D-A polymer based on perylene bisimide conjugated plane expansion and preparation method thereof - Google Patents
D-A polymer based on perylene bisimide conjugated plane expansion and preparation method thereof Download PDFInfo
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- CN111944127A CN111944127A CN202010783916.4A CN202010783916A CN111944127A CN 111944127 A CN111944127 A CN 111944127A CN 202010783916 A CN202010783916 A CN 202010783916A CN 111944127 A CN111944127 A CN 111944127A
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- polymer
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- perylene imide
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- 229920000642 polymer Polymers 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 35
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 perylene imide Chemical class 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 34
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- 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 14
- 239000000376 reactant Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 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 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000007363 ring formation reaction Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 claims description 3
- FZGMWHGBNKDYIX-UHFFFAOYSA-N thiophene;trimethyltin Chemical group C[Sn](C)C.C=1C=CSC=1 FZGMWHGBNKDYIX-UHFFFAOYSA-N 0.000 claims description 3
- HVPQMLZLINVIHW-UHFFFAOYSA-N 6-bromo-1h-indole-2,3-dione Chemical compound BrC1=CC=C2C(=O)C(=O)NC2=C1 HVPQMLZLINVIHW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 229960002799 stannous fluoride Drugs 0.000 claims description 2
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 238000010438 heat treatment Methods 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000000835 fiber Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 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 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000003480 eluent Substances 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 238000007664 blowing Methods 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 229920000547 conjugated polymer Polymers 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MCFWJICUYRUOFF-UHFFFAOYSA-N 6-bromo-1-(2-decyltetradecyl)-3H-indol-2-one Chemical compound BrC1=CC=C2CC(N(C2=C1)CC(CCCCCCCCCCCC)CCCCCCCCCC)=O MCFWJICUYRUOFF-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 description 3
- NJHWUYSMTWJVAF-UHFFFAOYSA-N 1,7-dibromoperylene Chemical group C1=CC(C=2C(Br)=CC=C3C=2C2=CC=C3)=C3C2=C(Br)C=CC3=C1 NJHWUYSMTWJVAF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- CPJFUPIDKKCBKE-UHFFFAOYSA-N 1,2-dibromoperylene Chemical class C1=CC(C2=C(C(Br)=CC=3C2=C2C=CC=3)Br)=C3C2=CC=CC3=C1 CPJFUPIDKKCBKE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 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 description 1
- CCRMAATUKBYMPA-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C.C[Sn](C)C CCRMAATUKBYMPA-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- 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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- C08G61/12—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
- C08G61/126—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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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- C08G2261/1412—Saturated aliphatic units
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- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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Abstract
The invention discloses a novel, stable and good-solubility D-A polymer based on perylene bisimide conjugated plane expansion and a preparation method thereof, and the polymer effectively improves the device performance of an organic semiconductor. The general structural formula of the D-A polymer based on perylene imide conjugated plane expansion is shown as the following formulas (I) and (II):wherein R and R' are branched or straight chains of C5-C18, and n is a positive integer of 1-100.
Description
Technical Field
The invention relates to the technical field of material synthesis and organic semiconductors, in particular to a D-A polymer based on perylene bisimide conjugated plane expansion and a preparation method thereof.
Background
In recent years, research on conjugated polymers is underway, and a research field integrating multiple subjects such as chemistry, physics, materials science, information science and the like, including design and synthesis of conjugated polymers, structure-activity relationship of photoelectric functional materials of conjugated polymers and physical research of corresponding devices is gradually formed. Compared with the traditional inorganic semiconductor material, the conjugated polymer has more effective performance adjustability, and the solubility, optical performance, electrochemical performance, crystallization, assembly performance and the like of the polymer can be conveniently adjusted by changing the main chain and the side chain substituent of the polymer. In addition, the conjugated polymer material has excellent film forming processing performance, and can be made into large-area, light and flexible devices in modes of spin coating, screen printing, ink-jet printing and the like, thereby showing unique charm.
Perylene-3, 4:9, 10-tetracarboxylic diimide compounds, namely perylene bisimide (PDI), have high electron mobility and electron affinity, strong light absorption capability in a visible light region, easily adjustable energy level and low synthesis cost, and are widely applied to the technical field of organic semiconductors. The isoindigo molecule not only has the function of electron deficiency and becomes a core framework of a D-A type molecule, but also can adjust the molecular energy level (the highest occupied molecular orbital-HOMO and the lowest unoccupied molecular orbital-LUMO) of isoindigo through a series of modifications on the structure, so that the isoindigo molecule becomes an ideal electron-withdrawing framework group. However, in the conventional findings, the system has not been studied by fusing these two kinds of building units.
Therefore, a novel perylene bisimide fused isoindigo monomer is synthesized by a simple and green method, and the synthesis method has important significance for the development of D-A polymer.
Disclosure of Invention
The invention aims to provide a novel stable D-A polymer with good solubility and based on perylene imide conjugated plane expansion, which effectively improves the device performance of an organic semiconductor.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a D-A polymer based on perylene imide conjugated plane extension is disclosed, and the structural general formula of the polymer is shown as the following formula (I):
in the formula, R and R' are branched chains or straight chains of C5-C18, and n is a positive integer of 1-100; in the perylene imide conjugated plane expansion-based D-A polymer, R or R' is one of the following groups (n, m is a positive integer):
ar is one of the following groups:
ar' is one of the following groups:
the molecular structure of the polymer is shown as any one of the following:
the invention also provides another D-A polymer based on perylene bisimide conjugated plane expansion, and the structural general formula of the polymer is shown as the formula (II):
in the formula, R and R' are branched chains or straight chains of C5-C18, and n is a positive integer of 1-100; r or R' of the D-A polymer based on perylene imide conjugated plane expansion is one of the following groups:
the molecular structure of the polymer is as follows:
the invention also aims to provide a preparation method of the D-A polymer (I) based on perylene imide conjugated plane expansion, which comprises the following steps:
step S1: under the protection of inert gas, adding 1, 7-dibromo perylene imide and 6-boron ester isatin into tetrahydrofuran containing a catalyst, carrying out Suzuki coupling reaction at 80 ℃, carrying out photocatalytic ring-closing reaction, and purifying to obtain a compound a 1;
step S2: under the protection of inert gas, adding a compound a1 and 6-bromoindole diketone into a reaction vessel, reacting in acetic acid, and purifying to obtain a compound b 1;
step S3: under the protection of inert gas, adding a compound b1 and an Ar-containing tin reagent into a reaction vessel, performing Still polymerization reaction in a solvent containing a catalyst at 110-120 ℃ for 12-36 hours, and purifying to obtain the polymer (I).
Further, the molar ratio of the 1, 7-dibromo perylene bisimide and the 6-boron ester isatin in the step S1 is 1: 2-1: 2.5; the illumination is blue light of 450 nm; the catalyst is prepared from the following components in a molar ratio of 1: 3-1: 4 of a mixture of bis (triphenylphosphine) palladium dichloride and tris (o-methylphenyl) phosphine or tris (dibenzylideneacetone) dipalladium and tri-tert-butylphosphine tetrafluoroborate, wherein the molar ratio of the catalyst is 10-12% of that of the reactant A;
further, the molar ratio of the compound a1 to the 6-bromoindole diketone in the step S2 is 1: 1-1: 3; the reaction temperature is 110-120 ℃, and the reaction time is 12-24 hours;
further, the molar ratio of the compound b1 to the Ar-containing tin reagent in the step S3 is 1: 1-1: 1.2; the Ar-containing tin reagent is trimethyl tin thiophene, trimethyl tin bithiophene and trimethyl tin difluoride bithiophene; the catalyst is a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine in a molar ratio of 1: 3-1: 4; the solvent is at least one of tetrahydrofuran, dioxane, N-dimethyl diamide and toluene; the reaction temperature is 110-120 ℃, and the reaction time is 12-36 hours.
A process for the preparation of a polymer of formula (II) based on the extension of the conjugated plane of perylene bisimide as described above, comprising the following steps:
step S4: under the protection of inert gas, adding a perylene bisimide dibromide product and a 2, 7-trimethyltin symmetric indacenodithiophene derivative into a reaction vessel, carrying out Still polymerization reaction for 12-36 hours at 110-120 ℃ in a solvent containing a catalyst, carrying out ring closing reaction, and purifying to obtain a (II) polymer;
further, in step S4, the solvent is at least one of tetrahydrofuran, dioxane, N-dimethyl diamide, and toluene; the molar ratio of the perylene bisimide dibromide product to the 2, 7-trimethyltin symmetric indacenodithiophene derivative is 1: 1-1: 1.2; the catalyst is a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine in a molar ratio of 1: 3-1: 4; the molar ratio of the catalyst is 10-12% of the reactant A; the reaction temperature is 110-120 ℃, and the reaction time is 12-36 hours.
Specifically, the step S1 is: weighing 1, 7-dibromo perylene bisimide and 6-boron ester isatin, adding into a reaction sealed bottle, degassing, and exchanging high-purity nitrogen for three times continuously; adding a catalyst in an air blowing state, wherein the using amount of the catalyst is 10-12% of that of the reactant A, adding a toluene solvent, stirring to ensure that the molar concentration of the reactant A is 0.3-0.6mol.L, heating to 80 ℃ for reaction for 12 hours, recovering the room temperature after the reaction is finished, extracting, and purifying by a chromatographic column; weighing the obtained crude product, adding the crude product into a cylindrical reaction bottle, adding an iodine simple substance as a catalyst, then adding a toluene solvent to enable the molar concentration of a reactant to be 0.001-0.003mol.L, heating at 80-90 ℃, continuously irradiating for 12-24 hours by using LED blue light in the atmosphere of air, recovering the room temperature after the reaction is finished, carrying out reduced pressure distillation on the reaction solution, and then carrying out chromatographic column separation and purification to obtain a product a 1;
specifically, the step S2 is: adding a product a1, 6-bromoindole dione prepared in S1 into a two-mouth reaction bottle according to a molar ratio of 1: 2-1: 3, degassing to exchange high-purity nitrogen, repeating the operation for three times, injecting hydrochloric acid and a solvent acetic acid into an injector in a nitrogen environment to ensure that the molar concentration of a reactant is 0.1-0.3mol.L, heating to 110-120 ℃, heating and stirring, reacting for 12-24 hours, recovering to room temperature after the reaction is finished, extracting, rotationally evaporating the solvent, and finally separating and purifying by a chromatographic column to obtain a product b 1;
specifically, the step S3 is: weighing a polymerized monomer b1 and trimethyltin thiophene, trimethyltin bithiophene and trimethyltin difluoride bithiophene in a polymerization reaction bottle according to a molar ratio of 1:1, degassing to exchange high-purity nitrogen, repeating the operation for three times, sequentially adding a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine with a molar ratio of 1: 3-1: 4 as a catalyst under an air blowing state, wherein the molar ratio of the catalyst is 10-12% of a reactant A, adding an anhydrous toluene solvent to ensure that the molar concentration of the reactant is 0.01-0.02mol.L, pumping and exchanging air for 15-20 times to ensure a completely anhydrous and oxygen-free reaction environment, heating and stirring at 110-120 ℃, and reacting for 12-36 hours; after the reaction, recovering to room temperature, adding a toluene solvent, heating and stirring until the toluene solvent is dissolved, recovering to room temperature, dropwise adding the toluene solvent into a methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain pure polymers 1, 2 and 3;
specifically, the step S4 is: weighing a perylene bisimide dibromide product and a 2, 7-trimethyltin symmetric indacenodithiophene derivative in a polymerization reaction bottle according to a molar ratio of 1:1, degassing to exchange high-purity nitrogen, repeating the operation for three times, sequentially adding a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine with a molar ratio of 1: 3-1: 4 as a catalyst under an air blowing state, wherein the molar ratio of the catalyst is 10-12% of a reactant A, adding an anhydrous toluene solvent to ensure that the molar concentration of the reactant is 0.01-0.02mol.L, pumping and exchanging air for 15-20 times to ensure a completely anhydrous and oxygen-free reaction environment, heating and stirring at 110-120 ℃, and reacting for 12-36 hours; after the reaction, recovering to room temperature, adding a toluene solvent, heating and stirring until the toluene solvent is dissolved, recovering to room temperature, dropwise adding the toluene solvent into a methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain a pure polymer 4 unclosed ring precursor; adding the polymer into a round-bottom flask, adding a toluene solvent to enable the concentration of a reactant to be 0.001-0.003mol/L, slowly dropwise adding a mixed solution of anhydrous ferric trichloride and nitromethane, wherein the molar ratio of a catalyst is 1: 5-1: 10 of the reactant, heating and stirring at 60-80 ℃, reacting for 12-24 hours, recovering to room temperature after reaction, extracting, performing Soxhlet extraction, settling, and drying to obtain a polymer 4;
compared with the prior art, the invention has the following advantages:
(1) the novel perylene bisimide fused isoindigo monomer is synthesized by a simple and green method, the structure contains imide and amido bonds, and the perylene bisimide fused isoindigo monomer has lower lowest unoccupied molecular orbit and higher electron affinity and is a good electron acceptor unit.
(2) The polymerized monomer is polymerized with thiophene monomers rich in electron groups to obtain a series of D-A polymers. The polymer has good solubility, high yield and high thermal stability, and is beneficial to the preparation of large-area devices.
(3) Compared with the conventional polymer, the polymer has a larger conjugated structure, is more favorable for electron transmission, has a maximum absorption wavelength in the visible light field and a narrow optical band gap, and has potential application prospects in the fields of Organic Field Effect Transistors (OFETs) and organic solar cells (OPVs).
Drawings
FIG. 1 is a chemical reaction equation for the preparation of perylene imide conjugated flat expanded D-A polymers;
FIG. 2 is a 1H NMR spectrum of compound b1 in example 1;
FIG. 3 is a 1H NMR spectrum of polymer 1 in example 1;
FIG. 4 is a cyclic voltammogram of polymer 1 from example 1;
FIG. 5 is a UV absorption curve of Polymer 2 of example 1;
FIG. 6 is a cyclic voltammogram of polymer 2 from example 1;
FIG. 7 is a UV absorption curve of polymer 3 of example 1;
FIG. 8 is a cyclic voltammogram of polymer 3 from example 1;
FIG. 9 is a UV absorption curve of polymer 4 from example 1.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The invention adopts AVANCE III 400M type liquid nuclear magnetic resonance spectrometer produced by Bruker company of Switzerland to detect the product to obtain 1H NMR and spectrogram, and the solvent is deuterated chloroform (CDCl)3) Tetramethylsilane (TMS) was used as an internal standard. In the experiment, an ultraviolet absorption spectrum of a product is measured by adopting a UV-3600 type ultraviolet-visible spectrophotometer of Shimadzu company, a quartz cuvette with the size of 1 multiplied by 1cm is used as a sample cell, and a CHI620E electrochemical analyzer of Shanghai Chenghua apparatus Limited is adopted. A high-temperature light parallel reaction instrument WP-TEC-1020HSL of the Huataikesi (WATTCAS) company Limited is adopted for carrying out the photocatalytic ring closing reaction.
The chemical reaction equation in the preparation process of the perylene bisimide conjugated plane extended D-A polymer in the following embodiment of the invention is shown in FIG. 1.
Example 1
(1) 0.76g of 2-decyltetradecan-1-amine-substituted 1, 7-dibromoperylene imide (DT-PDI) and 0.84g of 1-bromo-2-decyltetradecan-substituted 6-boroester isatin were added to a vial and degassed and ventilated for three consecutive times; then adding 20ML tetrahydrofuran solvent and 1.5ML (2mol.L) tripotassium phosphate aqueous solution, stirring, adding 17.2mg of tris (dibenzylideneacetone) dipalladium catalyst and 21.8mg of tri-tert-butylphosphine tetrafluoroborate in an air blowing state, pumping and ventilating for three times, then heating to 80 ℃ for reaction for 12 hours, recovering the room temperature after the reaction is finished, extracting, and then purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 3: 5; weighing 50mg of the obtained crude product, adding the crude product into a cylindrical reaction bottle, adding one iodine simple substance as a catalyst, adding 20ML of toluene solvent, heating at 90 ℃, continuously irradiating LED blue light for 12 hours in the atmosphere of air, recovering the room temperature after the reaction is finished, carrying out reduced pressure distillation on the reaction solution, separating and purifying by using a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 1:1, and obtaining a product a 1;
(2) 350mg of a1 and 309mg of 6-bromo-1- (2-decyltetradecyl) indol-2-one are put into a two-neck round-bottom reaction flask, the operation is repeated three times by evacuating and aerating, under a nitrogen atmosphere, 16.5mg of p-toluenesulfonic acid monohydrate and 17.2mg of phosphorus pentoxide are added, 10ML of anhydrous toluene solvent is injected, and the reaction is heated and stirred at 115 ℃ for 48 hours; returning to room temperature, extracting, distilling the solution under reduced pressure, separating and purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 2:3, and obtaining a product b 1;
(3) adding 54mg of b1 and 7.17mg of 2, 5-trimethyltin thiophene into a polymerization bottle, pumping and ventilating the polymerization bottle, repeating the operation for three times, adding 1.5ML of anhydrous oxygen-free toluene solvent into the blowing gas, then adding 1.81mg of tris (dibenzylideneacetone) dipalladium catalyst and 2.41mg of tris (o-methylphenyl) phosphine ligand, pumping and ventilating the polymerization bottle for 15-20 times, and heating and stirring the polymerization bottle at 110 ℃ for 36 hours; after the reaction is finished, recovering the room temperature, adding 2ML toluene solvent, heating to 120 ℃ for dissolution, then recovering the room temperature, dropwise adding the solution into the methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain pure polymer 1;
example 2
(1) 0.76g of 2-decyltetradecan-1-amine-substituted 1, 7-dibromoperylene imide (DT-PDI) and 0.84g of 1-bromo-2-decyltetradecan-substituted 6-boroester isatin were added to a vial and degassed and ventilated for three consecutive times; then adding 20ML tetrahydrofuran solvent and 1.5ML (2mol.L) tripotassium phosphate aqueous solution, stirring, adding 17.2mg of tris (dibenzylideneacetone) dipalladium catalyst and 21.8mg of tri-tert-butylphosphine tetrafluoroborate in an air blowing state, pumping and ventilating for three times, then heating to 80 ℃ for reaction for 12 hours, recovering the room temperature after the reaction is finished, extracting, and then purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 3: 5; weighing 50mg of the obtained crude product, adding the crude product into a cylindrical reaction bottle, adding one iodine simple substance as a catalyst, adding 20ML of toluene solvent, heating at 90 ℃, continuously irradiating LED blue light for 12 hours in the atmosphere of air, recovering the room temperature after the reaction is finished, carrying out reduced pressure distillation on the reaction solution, separating and purifying by using a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 1:1, and obtaining a product a 1;
(2) 350mg of a1 and 309mg of 6-bromo-1- (2-decyltetradecyl) indol-2-one are put into a two-neck round-bottom reaction flask, the operation is repeated three times by evacuating and aerating, under a nitrogen atmosphere, 16.5mg of p-toluenesulfonic acid monohydrate and 17.2mg of phosphorus pentoxide are added, 10ML of anhydrous toluene solvent is injected, and the reaction is heated and stirred at 115 ℃ for 48 hours; returning to room temperature, extracting, distilling the solution under reduced pressure, separating and purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 2:3, and obtaining a product b 1;
(3) 63.16mg of b1 and 10.07mg of 5,5 '-bis (trimethylstannyl) -2,2' -bithiophene were added to a polymerization flask, the gas was evacuated and the operation was repeated three times, 1.5ML of an anhydrous oxygen-free toluene solvent was added to the gas, followed by 1.55mg of tris (dibenzylideneacetone) dipalladium catalyst and 2.06mg of tris (o-methylphenyl) phosphine ligand, the gas was evacuated and heated and stirred at 110 ℃ for 36 hours; after the reaction is finished, recovering the room temperature, adding 2ML toluene solvent, heating to 120 ℃ for dissolution, then recovering the room temperature, dropwise adding the solution into the methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain pure polymer 2;
example 3
(1) 0.76g of 2-decyltetradecan-1-amine-substituted 1, 7-dibromoperylene imide (DT-PDI) and 0.84g of 1-bromo-2-decyltetradecan-substituted 6-boroester isatin were added to a vial and degassed and ventilated for three consecutive times; then adding 20ML tetrahydrofuran solvent and 1.5ML (2mol.L) tripotassium phosphate aqueous solution, stirring, adding 17.2mg of tris (dibenzylideneacetone) dipalladium catalyst and 21.8mg of tri-tert-butylphosphine tetrafluoroborate in an air blowing state, pumping and ventilating for three times, then heating to 80 ℃ for reaction for 12 hours, recovering the room temperature after the reaction is finished, extracting, and then purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 3: 5; weighing 50mg of the obtained crude product, adding the crude product into a cylindrical reaction bottle, adding one iodine simple substance as a catalyst, adding 20ML of toluene solvent, heating at 90 ℃, continuously irradiating LED blue light for 12 hours in the atmosphere of air, recovering the room temperature after the reaction is finished, carrying out reduced pressure distillation on the reaction solution, separating and purifying by using a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 1:1, and obtaining a product a 1;
(2) 350mg of a1 and 309mg of 6-bromo-1- (2-decyltetradecyl) indol-2-one are put into a two-neck round-bottom reaction flask, the operation is repeated three times by evacuating and aerating, under a nitrogen atmosphere, 16.5mg of p-toluenesulfonic acid monohydrate and 17.2mg of phosphorus pentoxide are added, 10ML of anhydrous toluene solvent is injected, and the reaction is heated and stirred at 115 ℃ for 48 hours; returning to room temperature, extracting, distilling the solution under reduced pressure, separating and purifying by a chromatographic column, wherein the ratio of an eluent to dichloromethane to petroleum ether is 2:3, and obtaining a product b 1;
(3) 43.24mg of b1 and 7.4mg of (3,3' -difluoro- [2,2' -dithiophene ] -5,5' -diyl) bis (trimethyltin) were charged into a polymerization flask, the gas was evacuated, the operation was repeated three times, 1.0ML of an anhydrous oxygen-free toluene solvent was added to the gas blown, subsequently 2.47mg of tris (dibenzylideneacetone) dipalladium catalyst and 3.28mg of tris (o-methylphenyl) phosphine ligand were added, the gas was evacuated 15 to 20 times, and heated and stirred at 110 ℃ for 36 hours; after the reaction is finished, recovering the room temperature, adding 2ML toluene solvent, heating to 120 ℃ for dissolution, then recovering the room temperature, dropwise adding the solution into the methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain pure polymer 3;
example 4
(1) 80.66mg of undecaexamine-substituted dibromoperylene bisimide (isomers of 1, 7-substituted and 1, 6-substituted dibromides in a ratio of about 4:1) and 116.08mg of 2, 7-trimethyltin sym-indacenodithiophene derivative were added to a polymerization flask, the reaction was evacuated and purged, the operation was repeated three times, 2.0ML of anhydrous oxygen-free toluene solvent was added to the air, 2.59mg of tris (dibenzylideneacetone) dipalladium catalyst and 3.44mg of tris (o-methylphenyl) phosphine ligand were then added, the evacuation and purging were carried out 15 to 20 times, and the mixture was heated and stirred at 110 ℃ for 36 hours; after the reaction is finished, recovering the room temperature, adding 2ML toluene solvent, heating to 120 ℃ for dissolution, then recovering the room temperature, dropwise adding the solution into the methanol solution, stirring and settling for at least 30 minutes, pouring the mixed solution into a fiber filter cylinder, and filtering; placing the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting methanol, acetone, normal hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain a precursor of the pure polymer 4;
(2) adding 60mg of a precursor of the polymer 4 into a single-opening round-bottom reaction bottle, adding 80ML of anhydrous toluene solvent, dropwise adding a mixed solution of 2ML of nitromethane and 50mg of anhydrous ferric trichloride, continuously blowing nitrogen into a reaction system, and heating and stirring at 65 ℃ for reacting for 48 hours; returning to room temperature, extracting, rotationally evaporating the solvent, dissolving and settling, putting the filtered fiber filter cartridge into a Soxhlet extractor, and sequentially extracting with methanol, acetone, n-hexane, dichloromethane and chloroform; settling methanol, filtering, heating and drying in a vacuum drying oven to obtain pure polymer 4;
Claims (12)
7. the preparation method of the perylene imide conjugated plane expansion based D-A polymer according to claim 1, wherein the preparation method comprises the following steps:
step S1: under the protection of inert gas, adding 1, 7-dibromo perylene imide and 6-boron ester isatin into tetrahydrofuran containing a catalyst, carrying out Suzuki coupling reaction at 80 ℃, carrying out photocatalytic ring-closing reaction, and purifying to obtain a compound a 1;
step S2: under the protection of inert gas, adding a compound a1 and 6-bromoindole diketone into a reaction vessel, reacting in acetic acid, and purifying to obtain a compound b 1;
step S3: under the protection of inert gas, adding a compound b1 and an Ar-containing tin reagent into a reaction vessel, performing Still polymerization reaction in a solvent containing a catalyst at 110-120 ℃ for 12-36 hours, and purifying to obtain the polymer (I).
8. The preparation method of the D-A polymer based on perylene imide conjugated plane expansion according to claim 5, wherein the molar ratio of the 1, 7-dibromo perylene imide and the 6-boron ester isatin in the step S1 is 1:2 to 1: 2.5; the illumination is blue light of 450 nm; the catalyst is a mixture of bis (triphenylphosphine) palladium dichloride and tri (o-methylphenyl) phosphine or tri (dibenzylideneacetone) dipalladium and tri-tert-butylphosphine tetrafluoroborate with a molar ratio of 1: 3-1: 4, and the molar ratio of the catalyst is 10% -12% of that of the reactant A.
9. The preparation method of a perylene imide conjugated plane expansion based D-A polymer according to claim 5, wherein the molar ratio of the compound a1 to the 6-bromoindole dione in the step S2 is 1:1 to 1: 3; the reaction temperature is 110-120 ℃, and the reaction time is 12-24 hours.
10. The preparation method of D-A polymer based on perylene imide conjugated plane expansion according to claim 5, wherein the molar ratio of the compound b1 to the Ar-containing tin reagent in the step S3 is 1:1 to 1: 1.2; the Ar-containing tin reagent is trimethyl tin thiophene, trimethyl tin bithiophene and trimethyl tin difluoride bithiophene; the catalyst is a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine in a molar ratio of 1: 3-1: 4; the solvent is at least one of tetrahydrofuran, dioxane, N-dimethyl diamide and toluene; the reaction temperature is 110-120 ℃, and the reaction time is 12-36 hours.
11. The preparation method of the perylene imide conjugated plane expansion based D-A polymer according to claim 3, wherein the preparation method comprises the following steps:
step S4: under the protection of inert gas, adding a perylene bisimide dibromide product and a 2, 7-trimethyltin symmetric indacenodithiophene derivative into a reaction vessel, carrying out Still polymerization reaction for 12-36 hours at 110-120 ℃ in a solvent containing a catalyst, carrying out ring closing reaction, and purifying to obtain the (II) polymer.
12. The method for preparing a perylene imide conjugated planar extended D-a polymer according to claim 8, wherein in step S4 said solvent is at least one of tetrahydrofuran, dioxane, N-dimethyldiamide, and toluene; the molar ratio of the perylene bisimide dibromide product to the 2, 7-trimethyltin symmetric indacenodithiophene derivative is 1: 1-1: 1.2; the catalyst is a mixture of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphine in a molar ratio of 1: 3-1: 4; the molar ratio of the catalyst is 10-12% of the reactant A; the reaction temperature is 110-120 ℃, and the reaction time is 12-36 hours.
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XIAOFEN WANG ET AL.: ""High-Performance All-Polymer Photoresponse Devices Based on Acceptor–Acceptor Conjugated Polymers"", 《ADVANCED FUNCTIONAL MATERIALS》 * |
YU YAPING ET AL.: ""Effect of conjugation length on the properties of fused perylene diimides with variable isoindigos"", 《JOURNAL OF MATERIALS CHEMISTRY C: MATERIALS FOR OPTICAL AND ELECTRONIC DEVICES》 * |
Cited By (2)
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CN113801301A (en) * | 2021-10-13 | 2021-12-17 | 福州大学 | Isoindigo polymer of fused pyrrole ring type perylene imide with pendant gulf-position and preparation method thereof |
CN113801301B (en) * | 2021-10-13 | 2022-05-13 | 福州大学 | Isoindigo polymer of fused pyrrole ring type perylene imide with pendant gulf-position and preparation method thereof |
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