CN118027362A - Benzofluorenone polymer and preparation method and application thereof - Google Patents
Benzofluorenone polymer and preparation method and application thereof Download PDFInfo
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- CN118027362A CN118027362A CN202410123763.9A CN202410123763A CN118027362A CN 118027362 A CN118027362 A CN 118027362A CN 202410123763 A CN202410123763 A CN 202410123763A CN 118027362 A CN118027362 A CN 118027362A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 78
- WVXMLBXFHITUIT-UHFFFAOYSA-N benzo[a]fluoren-1-one Chemical compound C1=CC=CC2=CC3=C4C(=O)C=CC=C4C=CC3=C21 WVXMLBXFHITUIT-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000008151 electrolyte solution Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- -1 tetrabutylammonium hexafluorophosphate Chemical compound 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000006880 cross-coupling reaction Methods 0.000 claims description 9
- 239000003115 supporting electrolyte Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 1
- 239000012713 reactive precursor Substances 0.000 claims 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 20
- 239000002861 polymer material Substances 0.000 abstract description 19
- 230000003287 optical effect Effects 0.000 abstract description 17
- 230000004044 response Effects 0.000 abstract description 12
- 125000000468 ketone group Chemical group 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 15
- 230000008859 change Effects 0.000 description 14
- 238000004040 coloring Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229920006254 polymer film Polymers 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- MKVFJLDTIHCXBF-UHFFFAOYSA-N 5,9-dibromobenzo[c]fluoren-7-one Chemical compound BrC1=CC=2C(C=3C=C(C=CC=3C=2C2=C1C=CC=C2)Br)=O MKVFJLDTIHCXBF-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- 238000013375 chromatographic separation Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- USYWCEDYVLPNHH-UHFFFAOYSA-N benzo[c]fluoren-7-one Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C12 USYWCEDYVLPNHH-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011097 chromatography purification Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000004984 smart glass Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HTAZKFRPZRZPKE-UHFFFAOYSA-N 2-butyl-3-methylthiophene Chemical compound CCCCC=1SC=CC=1C HTAZKFRPZRZPKE-UHFFFAOYSA-N 0.000 description 1
- MNDZHERKKXUTOE-UHFFFAOYSA-N 2-butylthiophene Chemical compound CCCCC1=CC=CS1 MNDZHERKKXUTOE-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- 229910000080 stannane Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
-
- 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
- C08G61/126—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/54—Physical properties electrochromatic
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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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/59—Stability
- C08G2261/594—Stability against light, i.e. electromagnetic radiation
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a benzofluorenone polymer and a preparation method and application thereof, and belongs to the technical field of polymer materials. The structural formula of the benzofluorenone polymer provided by the invention is shown in any one of formulas (I) to (III): the polymer has a D-A-D type structure based on 7H-benzo [ c ] fluorene-7-ketone as an acceptor, and has a lower bandwidth and a wider light absorption range due to the strong electron accepting capability of the ketone group in the acceptor unit, so that the polymer has a wider application range. The benzofluorenone polymer has the characteristics of good electrochromic performance, such as quick response time, good optical transmittance, good stability and the like, and has wide application in preparing electrochromic devices.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to a benzofluorenone polymer and a preparation method and application thereof.
Background
Electrochromic refers to the reversible change in optical properties of a particular material under the application of an external voltage, which appears as a reversible change in color and transparency in appearance. Electrochromic materials may be applied to light-weight and portable display devices such as displays, and devices using light transmittance such as smart windows, rear view mirrors, and the like.
Electrochromic materials are often transition metal oxides, which tend to be expensive to manufacture due to the scarce resources. Conductive polymers have many unique advantages as electrochromic materials compared to metal oxide materials: better flexibility; the energy band and the color can be easily changed by changing the structure; low cost and the like. However, with the continuous and intensive research, the conductive polymer electrochromic material has own limitations, such as poor stability of part of the polymer, easy oxidation and the like, and greatly limits the development of the conductive polymer electrochromic material.
The construction of the D-A structure is a technical means for effectively regulating molecular energy bands, can reduce the oxidation potential of the polymer, and has good stability. In recent years, the polymer with the D-A-D structure further developed on the basis of the polymer has the special properties of rich color, easy bandwidth adjustment and the like, so that the polymer becomes an important electrochromic material.
Therefore, the search and development of polymers of D-A-D type structure with good electrochromic properties is a problem that needs to be solved nowadays.
Disclosure of Invention
In order to overcome the problems in the prior art, one of the purposes of the invention is to provide a benzofluorenone polymer which has the characteristics of low bandwidth, rich color, quick response time, high coloring efficiency and the like.
The second object of the present invention is to provide a method for preparing the benzofluorenone polymer.
The invention also provides an application of the benzofluorenone polymer in preparing electrochromic materials, which adopts the following technical scheme:
The first aspect of the invention provides a benzofluorenone polymer, which has a structural formula shown in any one of formulas (I) to (III):
In the formulas (I) to (III), X 1～X3 is O, S, se or N-R' independently; y 1～Y4 are each independently O or S; r 1～R4 and R' are each independently H or C 1～C12 alkyl; n 1～n3 is each independently 3 to 200.
Preferably, in formulas (I) to (III), each X 1～X3 is independently S.
Preferably, in formulas (I) to (III), Y 1～Y4 is each independently O.
Preferably, in formulas (I) to (III), R 1～R4 and R' are each independently H or C 1～C5 alkyl; further preferably, R 1～R4 and R' are each independently H, methyl or ethyl.
Preferably, the structural formula of the polymer is shown in any one of formulas (1) to (4):
In the formulae (1) to (4), n 4～n7 is 3 to 200 independently of each other.
In a second aspect, the present invention provides a method for preparing the benzofluorenone polymer according to the first aspect of the present invention, comprising the steps of: carrying out electrochemical polymerization on active precursors (I ') to (III') of the benzofluorenone polymer to respectively obtain the benzofluorenone polymers (I) to (III); the structural formula of the active precursor is shown as follows:
in the formulae (I ') to (III '), X 1～X3、Y1～Y4、R1～R3 and R ' are as defined in the first aspect of the invention.
Preferably, in the preparation method of the benzofluorenone polymer, the active precursor is prepared by a method comprising the following steps: performing cross-coupling reaction on the acceptor compound and the donor compounds (I ') to (III') in a catalyst and a solvent to obtain active precursors (I ') to (III'), respectively;
The receptor compounds are:
The donor compound is:
the catalyst comprises tetrakis triphenylphosphine palladium (Pd (PPh 3)4), bis triphenylphosphine palladium dichloride (Pd (PPh 3)2Cl2), or a combination thereof;
The solvent includes at least one of benzene, toluene, or N, N-Dimethylformamide (DMF).
Preferably, in the preparation method of the active precursor, the solvent includes toluene and N, N-dimethylformamide; further preferably, in the method for preparing an active precursor, the volume ratio of toluene and N, N-dimethylformamide in the solvent is (3 to 5): 1.
Preferably, in the preparation method of the active precursor, the molar ratio of the acceptor compound to the donor compound is 1: (2-3).
Preferably, in the preparation method of the active precursor, the molar ratio of the acceptor compound to the catalyst is 1: (0.01-0.1); further preferably 1: (0.03-0.05).
Preferably, in the preparation method of the active precursor, the dosage ratio of the acceptor compound to the solvent is 1mmol: (50-200) mL.
Preferably, in the preparation method of the active precursor, the temperature of the cross-coupling reaction is 100-140 ℃; further preferably 110 to 130 ℃.
Preferably, in the preparation method of the active precursor, the time of the cross-coupling reaction is 24-72 h; further preferably for 36 to 60 hours.
Preferably, in the preparation method of the active precursor, the cross-coupling reaction further comprises a purification step; further preferably, the purification means is chromatographic separation purification.
Preferably, the chromatographic column used for the chromatographic separation and purification is selected from silica gel columns.
Preferably, the eluent used for the chromatographic separation and purification comprises Dichloromethane (DCM) and Petroleum Ether (PE); further preferably, the volume ratio of dichloromethane to petroleum ether is 1: (1-3).
In the preparation method of the active precursor, the cross-coupling reaction is Stille/Suzuki palladium catalysis cross-coupling reaction, and the active precursor of D-A-D type containing 7H-benzo [ c ] fluorene-7-ketone, namely the active precursors shown in the formulas (I ')to (III'), can be prepared through the cross-coupling reaction.
Preferably, in the preparation method of the active precursor, the cross-coupling reaction is performed in an inert gas atmosphere. In a specific embodiment of the present invention, the inert gas is selected from nitrogen.
Preferably, in the preparation method of the benzofluorenone polymer, the electrochemical polymerization reaction specifically comprises: and (3) taking the solution containing the active precursor as electrolyte solution, and performing electrodeposition in a three-electrode system consisting of a reference electrode, a counter electrode and a working electrode to obtain the polymer on the working electrode.
Preferably, in the electrochemical polymerization reaction, the concentration of the active precursor in the electrolyte solution is 0.001 to 0.01mmol·l -1.
Preferably, in the electrochemical polymerization reaction, the solvent of the electrolyte solution includes at least one of dichloromethane (CH 2Cl2), chloroform (CHCl 3) or acetonitrile (MeCN).
Preferably, in the electrochemical polymerization reaction, the electrolyte solution further contains a supporting electrolyte.
Preferably, in the electrolyte solution, the supporting electrolyte includes at least one of tetrabutylammonium hexafluorophosphate (PF 6), tetrabutylammonium tetrafluoroborate (BF 4), or lithium perchlorate.
Preferably, the concentration of the supporting electrolyte in the electrolyte solution is 0.01 to 0.2 mmol.L -1.
Preferably, in the electrochemical polymerization, the reference electrode is selected from Ag/AgCl electrodes; the counter electrode is selected from a platinum wire electrode; the working electrode is selected from Pt/ITO conductive glass electrode.
Preferably, in the electrochemical polymerization, the electrodeposition mode is potentiostatic; further preferably, the potentiostatic method is a galvanostatic method or cyclic voltammetry.
Preferably, the electrochemical polymerization is carried out under a protective gas atmosphere. In a specific embodiment of the present invention, the shielding gas is selected from argon.
A third aspect of the invention provides the use of a benzofluorenone polymer of the first aspect of the invention in the manufacture of an electrochromic device.
Preferably, the electrochromic device comprises one or both of a display device or a light transmitting device; further preferably, the electrochromic device comprises at least one of a display, electrochromic glazing, smart window or rear view mirror.
The beneficial effects of the invention are as follows:
the polymer has a D-A-D type structure based on 7H-benzo [ c ] fluorene-7-ketone as an acceptor, and has a lower bandwidth and a wider light absorption range due to the strong electron accepting capability of the ketone group in the acceptor unit, so that the polymer has a wider application range. The benzofluorenone polymer has the characteristics of good electrochromic performance, such as quick response time, good optical transmittance, good stability and the like, and has wide application in preparing electrochromic devices.
Specifically, compared with the prior art, the invention has the following advantages:
1. The polymer of the present invention has 7H-benzo [ c ] fluoren-7-one as an electron acceptor (A) unit and furyl, thienyl, selenophenyl, pyrrolyl derivatives, thienyl derivatives, etc. as a terminal donor (D) unit. By changing the structure of the donor unit, the absorption spectrum of the polymer can be adjusted, and the color of the polymer is changed; the acceptor unit has strong electron withdrawing capability as the acceptor unit due to the existence of the ketone group; meanwhile, due to the addition of benzene rings, fusion ring structures exist in the molecules in a rigid and coplanar mode, and the charge mobility is enhanced, so that the polymer has the characteristics of lower band gap, wider redox peak, good optical contrast, quick response time, high coloring efficiency, good stability and the like when being used as an electrochromic material.
2. The benzofluorenone polymer provided by the invention can observe the stable and reversible color change from gray blue to gray green or from brown yellow to yellow green in appearance under the action of an external voltage, and has good electrochromic properties, including the properties of quick response time, high coloring efficiency, good optical transmittance and the like.
Drawings
FIG. 1 is a nuclear magnetic 1 H NMR spectrum of BZFO-EDOT of example 1.
FIG. 2 is a spectroelectrochemical diagram of polymer P (BZFO-EDOT) of example 1 in a MeCN-Bu 4NPF6(0.1mol·L-1 system.
FIG. 3 is a graph of the transmittance versus time at 433nm and 1100nm of polymer P (BZFO-EDOT) of example 1.
FIG. 4 is a spectroelectrochemical diagram of polymer P (BZFO-Th) of example 2 in a MeCN-Bu 4NPF6(0.1mol·L-1 system.
FIG. 5 is a graph showing the transmittance versus time at 417nm, 750nm and 1100nm of polymer P (BZFO-Th) of example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, since various modifications and adaptations may be made by those skilled in the art in light of the teachings herein. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a selection within the suitable ranges by the description herein and are not intended to be limited to the specific data described below. The starting materials, reagents or apparatus used in the following examples and comparative examples were obtained from conventional commercial sources or by known methods unless otherwise specified.
In the embodiments of the present invention, the coloring efficiency refers to a ratio of a change in absorbance of an electrochromic material at a given wavelength to a change in absorbance resulting in injection or extraction of all electrons.
For an electrochromic material, coloring efficiency is an important parameter for evaluating the material properties. Coloring efficiency study the coloring efficiency of a conductive polymer is combined with the electrochemical and spectral change process of an electrochromic film, wherein Q d refers to the amount of charge transferred in/out per unit area, and the calculation formula is as follows:
CE＝ΔOD/Qd；
Wherein the change in optical contrast (Δod) refers to the corresponding transmittance value (ratio of transmittance T ox in the doped state of the polymer film to transmittance T red in the neutral state) of the electrochemical oxidation and reduction polymer film at a specific wavelength λ max, calculated by the following formula:
ΔOD＝log(Tox/Tred)。
Example 1
Electrochemical synthesis of Polymer P (BZFO-EDOT):
(1) BZFO-EDOT active precursor synthesis:
5, 9-dibromo-7H-benzo [ c ] fluoren-7-one (1.288 mmol,0.5 g), tributyl (2, 3-dihydro [3,4-b ] [1,4] dioxin-5-yl) stannane (3.22 mmol, 1.3991 g) and catalyst Pd (PPh 3)2Cl2 (0.051 mmol,0.036 g) were placed in a 250mL single neck flask under nitrogen atmosphere, DMF (20 mL) and dry toluene (80 mL) were added and stirred uniformly, heated to 120℃for 48 hours of condensation reflux reaction, after the system was cooled, the product was poured into saturated brine, extracted 4 to 5 times with dichloromethane, the organic layer was washed with a small amount of water, then the solvent was removed by rotary evaporation through reduced pressure distillation, separation was performed with a silica gel column chromatography with eluent (DCM: PE=1:2), the product was obtained in the form of light purple powder, and nuclear magnetism 1 H with a yield of 79.14% was purified as shown in FIG. 1, the specific nuclear magnetism data was shown in FIG. 1 ：1H NMR(400MHz,CDCl3)δ8.52-8.35(m,1H),8.09(dd,J＝16.9,9.0Hz,2H),8.04-7.95(m,1H),7.93-7.84(m,1H),7.84-7.72(m,2H),7.61(dd,J＝18.4,7.3Hz,3H),6.51(s,1H),6.35(s,1H),4.41-4.10(m,8H).
(2) Synthesis of Polymer P (BZFO-EDOT):
Under the protection of argon atmosphere, electrochemical polymerization is carried out in a three-electrode system, a silver/silver chloride electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and glassy carbon is used as a working electrode; 10mL of methylene chloride is taken as electrolyte, BZFO-EDOT (0.0051 g,0.0001 mmol) is taken as a polymerization monomer, and a mixed solution of 10mL of acetonitrile and tetrabutylammonium hexafluorophosphate (0.3874 g,0.001 mmol) is taken as a supporting electrolyte; and (3) carrying out polymerization by adopting a cyclic voltammetry, wherein the polymerization potential is 1.15V, the scanning speed is 100mV/s, the polymerization circle number is set to 10, and the polymer film obtained by electrodeposition is soaked and washed by acetonitrile to remove electrolyte solution and precursor in the polymer, so as to obtain the polymer P (BZFO-EDOT).
Electrochromic performance study:
(1) The spectroelectrochemical diagram of the polymer P (BZFO-EDOT) in the MeCN-Bu 4NPF6(0.1mol·L-1 system is shown in FIG. 2, and in combination with visual observation of the color change of the polymer material, it can be seen that as the potential increases, the color of the polymer material changes from gray blue to gray green (gray blue in the fully undoped state) due to the absorption peak of the neutral state polymer material in each of the violet and red regions, the neutral state polymer material appears as gray green; after the polymer material is oxidized, the absorption peak of the purple light area is gradually weakened, the absorption peak of the red light area is gradually weakened, and finally the absorption peak of the red light area completely disappears; thus, the polymer material in the fully undoped state appears gray blue and the polymer material in the doped state appears gray green.
(2) The polymer P (BZFO-EDOT) was tested for transmittance versus time curves at 433nm and 1100 nm. The response time and the coloring efficiency calculated from the time-transmittance curve are shown in table 1, respectively, wherein T red is the transmittance of the polymer film in the neutral state, T ox is the transmittance of the polymer film in the doped state, and Δt=t red-Tox. As is clear from Table 1, the polymer P (BZFO-EDOT) has a fast response time and a high coloring efficiency.
Electrochromic parameters of Table 1P (BZFO-EDOT)
The optical transmittance of P (BZFO-EDOT) was investigated by the time-lapse absorption method at 433nm and 1100nm, and the time interval of the potential step change during the experiment was 5s, as shown in FIG. 3. At both wavelengths, the polymeric material exhibits a certain optical contrast and good optical stability; furthermore, the optical transmittance has a great influence on the color change of the polymer material, which is capable of being converted from gray blue in the fully undoped state to gray green in the doped state.
Example 2
Electrochemical synthesis of Polymer P (BZFO-Th):
(1) BZFO-synthesis of Th active precursor:
5, 9-dibromo-7H-benzo [ c ] fluoren-7-one (1.284 mmol,0.5 g), 2-tin butylthiophene (3.22 mmol,1.201 g), and catalyst Pd (PPh 3)2Cl2 (0.051 mmol,0.036 g) were placed in a 250mL single-neck flask under nitrogen atmosphere, DMF (20 mL) and dry toluene (80 mL) were added and stirred uniformly, heated to 120℃for 48 hours under reflux by condensation, after cooling the system, the product was poured into saturated brine, extracted 4-5 times with dichloromethane, the organic layer was washed with a small amount of water, then the solvent was removed by rotary evaporation, separation was performed with a silica gel column chromatography, eluent (DCM: PE=1:2), purification gave an orange-red solid with a yield of 58.70%.
(2) Synthesis of Polymer P (BZFO-Th):
electrochemical polymerization is carried out in a three-electrode system under the argon atmosphere, a silver/silver chloride electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and glassy carbon is used as a working electrode; 10mL of methylene chloride was used as an electrolyte, BZFO-Th (0.0039 g,0.0001 mmol) was used as a polymerization monomer, and a mixed solution of 10mL of acetonitrile and tetrabutylammonium hexafluorophosphate (0.3874 g,0.001 mmol) was used as a supporting electrolyte; polymerization is carried out by adopting a potentiostatic method, the polymerization potential is 1.35V, the scanning speed is 100mV/s, the polymerization circle number is set to 10, and the polymer film obtained by electrodeposition is soaked and washed by acetonitrile to remove electrolyte solution and precursor in the polymer, so that the polymer P (BZFO-Th) is obtained.
Electrochromic performance study:
(1) The spectroelectrochemical diagram of the polymer P (BZFO-Th) in the MeCN-Bu 4NPF6(0.1mol·L-1 system is shown in FIG. 4, and in combination with visual observation of the color change of the polymer material, it can be seen that as the potential increases, the color of the polymer material changes from brown to yellow-green (brown in the fully undoped state) due to the fact that the neutral state of the polymer material has an absorption peak in each of the violet and red regions, the neutral state of the polymer material appears yellow-green in color; after the polymer material is oxidized, the absorption peak of the purple light area is gradually weakened, the absorption peak of the red light area is gradually weakened, and finally the absorption peak of the red light area completely disappears; thus, the polymer material in the fully undoped state appears brown-yellow and the polymer material in the doped state appears yellowish green.
(2) The polymer P (BZFO-Th) was tested for transmittance versus time curves at 417nm, 750nm and 1100 nm. The response times and the coloring efficiencies calculated from the time-transmittance curves are shown in Table 2, respectively. As is clear from Table 2, the polymer P (BZFO-Th) has a fast response time and a high coloring efficiency.
TABLE 2 electrochromic parameters of Polymer P (BZFO-Th)
The optical transmittance of P (BZFO-Th) was investigated by the time-lapse absorption method at 417nm, 750nm and 1100nm wavelengths, during which the time interval for the step change in potential was 5s, as shown in FIG. 5. At three wavelengths, the polymer material shows certain optical contrast and good optical stability; furthermore, the optical transmission has a great influence on the color change of the polymer material, which is capable of being converted from a brown-yellow in the fully undoped state to a yellow-green in the doped state.
Example 3
Electrochemical synthesis of Polymer P (BZFO-MeTh):
(1) BZFO-synthesis of MeTh active precursor:
5, 9-dibromo-7H-benzo [ c ] fluoren-7-one (1.288 mmol,0.50 g), 2-stannyl-3-methylthiophene (3.22 mmol,1.249 g) and catalyst Pd (PPh 3)2Cl2 (0.051 mmol,0.036 g) were placed in a 250mL single neck flask under nitrogen atmosphere, DMF (20 mL) and dry toluene (80 mL) were added and stirred well, heated to 120℃and condensed and refluxed for 48 hours.
(2) Synthesis of Polymer P (BZFO-MeTh):
Electrochemical polymerization is carried out in a three-electrode system under the argon atmosphere, a silver/silver chloride electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and glassy carbon is used as a working electrode; 10mL of methylene chloride was used as an electrolyte, BZFO-MeTh (0.0042 g,0.0001 mmol) was used as a polymerization monomer, and a mixed solution of 10mL of acetonitrile and tetrabutylammonium hexafluorophosphate (0.3874 g,0.001 mmol) was used as a supporting electrolyte; polymerization is carried out by adopting a potentiostatic method, the polymerization potential is 1.2V, the scanning speed is 100mV/s, the polymerization circle number is set to 10, and the polymer film obtained by electrodeposition is soaked and washed by acetonitrile to remove electrolyte solution and precursor in the polymer, so that the polymer P (BZFO-MeTh) is obtained.
Example 4
Electrochemical synthesis of Polymer P (BZFO-ProEDOT):
(1) BZFO-ProEDOT synthesis of active precursor:
5, 9-dibromo-7H-benzo [ c ] fluoren-7-one (1.288 mmol,0.50 g), 2-tin butyl-3, 3-diethyl-3, 4-propenedioxythiophene 2-tin butyl-3-methylthiophene (3.22 mmol,1.630 g), and catalyst Pd (PPh 3)2Cl2 (0.051 mmol,0.036 g) were placed in a 250mL single neck flask under nitrogen atmosphere, DMF (20 mL) and dry toluene (80 mL) were added and stirred uniformly, heated to 120℃for condensation reflux reaction for 48 hours after cooling the system, the product was poured into saturated brine, extracted 4 to 5 times with dichloromethane, the organic layer was washed with a small amount of water, then the solvent was removed by rotary evaporation under reduced pressure, separation was performed with a silica gel column as eluent (DCM: PE=1:2), and purification gave a red solid in 45.0% yield.
(2) Synthesis of Polymer P (BZFO-ProEDOT):
Electrochemical polymerization is carried out in a three-electrode system under the argon atmosphere, a silver/silver chloride electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and glassy carbon is used as a working electrode; 10mL of methylene chloride is taken as electrolyte, BZFO-ProEDOT (0.0065 g,0.0001 mmol) is taken as a polymerization monomer, and a mixed solution of 10mL of acetonitrile and tetrabutylammonium hexafluorophosphate (0.3874 g,0.001 mmol) is taken as a supporting electrolyte; polymerization is carried out by adopting a potentiostatic method, the polymerization potential is 1.05V, the scanning speed is 100mV/s, the polymerization circle number is set to 10, and the polymer film obtained by electrodeposition is soaked and washed by acetonitrile to remove electrolyte solution and precursor in the polymer, thus obtaining polymer P (BZFO-ProEDOT).
From the above examples, it is understood that the polymer of the present invention has 7H-benzo [ c ] fluoren-7-one as an electron acceptor (A) unit, and furyl, thienyl, selenophenyl, pyrrolyl derivatives, thienyl derivatives, etc. as a terminal donor (D) unit. By changing the structure of the donor unit, the absorption spectrum of the polymer can be adjusted, and the color of the polymer is changed; the acceptor unit has strong electron withdrawing capability as the acceptor unit due to the existence of the ketone group; meanwhile, due to the addition of benzene rings, fusion ring structures exist in the molecules in a rigid and coplanar mode, and the charge mobility is enhanced, so that the polymer has the characteristics of lower band gap, wider redox peak, good optical contrast, quick response time, high coloring efficiency, good stability and the like when being used as an electrochromic material.
The benzofluorenone polymer provided by the invention can observe the stable and reversible color change from gray blue to gray green or from brown yellow to yellow green in appearance under the action of an external voltage, and has good electrochromic properties, including the properties of quick response time, high coloring efficiency, good optical transmittance and the like.
In conclusion, the polymer has a D-A-D type structure based on 7H-benzo [ c ] fluorene-7-ketone as an acceptor, and has a relatively low bandwidth and a relatively wide light absorption range due to the strong electron accepting capability of the ketone group in the acceptor unit. The benzofluorenone polymer has the characteristics of good electrochromic performance, such as quick response time, good optical transmittance, good stability and the like, and has wide application in preparing electrochromic devices.
Claims (10)
1. A benzofluorenone polymer characterized in that the structural formula of the polymer is shown in any one of formulas (I) to (III):
in the formulas (I) to (III), X 1～X3 is O, S, se or N-R' independently; y 1～Y4 are each independently O or S;
R 1～R4 and R' are each independently H or C 1～C12 alkyl; n 1～n3 is each independently 3 to 200.
2. The benzofluorenone polymer according to claim 1, wherein in the formulae (I) to (III), X 1～X3 is each independently S;
and/or, Y 1～Y4 are each independently O;
And/or R 1～R4 and R' are each independently H or C 1～C5 alkyl.
3. The benzofluorenone polymer according to claim 1, wherein the structural formula of the polymer is represented by any one of formulas (1) to (4):
In the formulae (1) to (4), n 4～n7 is 3 to 200 independently of each other.
4. A process for the preparation of a benzofluorenone polymer according to any one of claims 1 to 3, comprising the steps of: carrying out electrochemical polymerization reaction on active precursors (I ') to (III') of the benzofluorenone polymer to obtain the benzofluorenone polymers (I) to (III) respectively; the structural formula of the active precursor is shown as follows:
in the formulae (I ') to (III '), X 1～X3、Y1～Y4、R1～R3 and R ' are as defined in any of claims 1 to 3.
5. The method of claim 4, wherein the reactive precursor is prepared by a process comprising the steps of: performing cross-coupling reaction on the acceptor compound and the donor compounds (I ') to (III') in a catalyst and a solvent to obtain active precursors (I ') to (III'), respectively;
The receptor compounds are:
The donor compound is:
The catalyst comprises tetraphenylphosphine palladium, ditolylphosphine palladium dichloride or a combination thereof;
the solvent comprises at least one of benzene, toluene or N, N-dimethylformamide.
6. The method according to claim 4, wherein the electrochemical polymerization reaction is specifically: and (3) taking the solution containing the active precursor as electrolyte solution, and performing electrodeposition in a three-electrode system consisting of a reference electrode, a counter electrode and a working electrode to obtain the polymer on the working electrode.
7. The method according to claim 6, wherein the concentration of the active precursor in the electrolyte solution is 0.001 to 0.01 mmol.L -1.
8. The method according to claim 6, wherein the solvent of the electrolyte solution comprises at least one of dichloromethane, chloroform or acetonitrile;
And/or the electrolyte solution also contains a supporting electrolyte; preferably, the supporting electrolyte includes at least one of tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate, or lithium perchlorate.
9. The method of preparing according to claim 6, wherein the reference electrode is selected from Ag/AgCl electrodes; the counter electrode is selected from a platinum wire electrode; the working electrode is selected from Pt/ITO conductive glass electrode.
10. Use of a benzofluorenone polymer as claimed in any one of claims 1 to 3 in the preparation of an electrochromic device.
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