CN108586741B - Fluorescent polyamic acid polymer, preparation method and application thereof in fluorescent multi-stimulus response - Google Patents
Fluorescent polyamic acid polymer, preparation method and application thereof in fluorescent multi-stimulus response Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 22
- 230000004044 response Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 18
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000012153 distilled water Substances 0.000 abstract description 7
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002244 precipitate Substances 0.000 abstract description 6
- KQIKKETXZQDHGE-FOCLMDBBSA-N 4,4'-diaminoazobenzene Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=C(N)C=C1 KQIKKETXZQDHGE-FOCLMDBBSA-N 0.000 abstract description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- -1 anilino diamine Chemical class 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 238000000967 suction filtration Methods 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 229920001109 fluorescent polymer Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen 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
- 238000004528 spin coating Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IWRVPXDHSLTIOC-UHFFFAOYSA-N 4-phenyldiazenylbenzene-1,3-diamine Chemical compound NC1=CC(N)=CC=C1N=NC1=CC=CC=C1 IWRVPXDHSLTIOC-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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Abstract
A fluorescent polyamide acid polymer with aniline chain segment and azobenzene group as sensitive elements, a preparation method and application of the polymer in the aspect of fluorescent multi-stimulus response belong to the field of functional polymer materials. Adding an anilino diamine monomer, 9-bis (4-aminophenyl) fluorene, p-diaminoazobenzene, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride into a reaction vessel, adding a solvent dimethylacetamide, and magnetically stirring for room-temperature polymerization reaction for 20-30 hours; pouring the mixed solution into distilled water, precipitating a precipitate, performing suction filtration, washing the precipitate with distilled water for 3-5 times, washing with methanol for 3-5 times, and finally drying the product for 20-30 hours under the conditions of vacuum and 30-50 ℃ to obtain the anilinoazobenzene fluorescent polyamic acid polymer. The polymer was spin coated on conductive glass and the films were tested for fluorescent on-off response under external pH, voltage, chemical/redox and uv-vis stimuli.
Description
Technical Field
The invention belongs to the field of functional polymer materials, and particularly relates to a novel fluorescent polyamide acid polymer taking an aniline chain segment and an azobenzene group as sensitive elements, a preparation method and application of the polymer in the aspect of fluorescent multi-stimulus response.
Background
Fluorescent materials are widely used in human life, from displays, sensors, to medical diagnostics and drug delivery, and smart device manufacturing. Compared with other fluorescent materials, the polymer fluorescent material has the advantages of light weight, easy molecular design, excellent processing performance and the like. With the rapid development of material science, people put higher requirements on materials, such as good stability, specific responsiveness and the like. Therefore, researchers have recently studied the action principle and law of the influence of external environment changes (such as light, electricity, pH value, pressure, heat, magnetic field and chemicals) on the fluorescence property of the fluorescent polymer, so as to prepare the multi-stimulus response fluorescent material capable of adapting to the external complex environment and further widen the application range of the material.
An effective method for obtaining the multi-stimulus responsive fluorescent polymer is to introduce a fluorophore and a plurality of sensitive groups into the polymer simultaneously, and realize the fluorescent switch response phenomenon of the polymer through the response change of the sensitive groups to the external environment change and the energy transfer channel between the fluorescent groups. The aniline chain segment is used as a model compound of polyaniline, has good solubility, a designable molecular structure and tunable electro-optic characteristics, and can respond to stimulation such as pH value, redox substances, potential and the like. The azobenzene group can generate unique conversion between cis-trans structures under the irradiation of light waves with proper wavelength, and the azobenzene group are simultaneously introduced into a fluorescent polymer molecular chain segment, and can interact with external stimuli to change the self structural state, so that various molecular conformations are driven to change, and the fluorescent polymer generates reversible fluorescent switch response behavior.
According to the invention, from the angle of molecular design, anilino diamine monomer, p-diaminoazobenzene, 9-bis (4-aminophenyl) fluorene and 1,2,4, 5-cyclohexane tetracarboxylic dianhydride are reacted to prepare fluorescent polyamic acid, aniline chain segments and azobenzene groups are used as sensitive elements, and the fluorescent polyamic acid with multi-stimulus response is synthesized through molecular design so as to obtain the fluorescent response type material more suitable for external environment change.
The fluorescent polymer prepared by the invention takes the aniline chain segment and the azobenzene group as sensitive elements, takes the fluorescent group with high luminous efficiency as a fluorescence emission element, realizes the on-off conversion of the fluorescence property of the polymer by utilizing the electron/energy transfer between the sensitive elements and the fluorescence emission element, and synthesizes the high-performance fluorescent response polymer through molecular design.
Disclosure of Invention
The invention aims to provide a novel fluorescent polyamic acid polymer taking an aniline chain segment and an azobenzene group as sensitive elements, a preparation method and application of the polymer in the aspect of fluorescent multi-stimulus response.
According to the invention, anilino diamine monomer (M) (the contents of synthesis, characterization and the like of the monomer are shown in Chinese patent: 201410010359.7, and the contents of the side chain type electroactive polyurea polymer, the preparation method and the application of the side chain type electroactive polyurea polymer in corrosion prevention) and 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, 9-bis (4-aminophenyl) fluorene (N) and diaminoazobenzene (Q) (which are conventional raw materials and can be purchased) are copolymerized to obtain the anilino azobenzene fluorescent polyamic acid polymer.
The structural formula of the anilinodiamine monomer (M) is shown as follows:
the structural formula of the 9, 9-bis (4-aminophenyl) fluorene (N) is shown as follows:
the structural formula of the p-diaminoazobenzene (Q) is shown as follows:
the structural formula of the 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (R) is shown as follows:
the preparation method of the anilino azobenzene fluorescent polyamic acid polymer has the following reaction process:
the invention relates to a preparation method of an anilino azobenzene fluorescent polyamic acid polymer, which is characterized by comprising the following steps: grinding the reaction monomer, and drying at 30-50 ℃ for 20-30 hours under vacuum; after complete drying, the molar ratio is 1: 2: 1: 4, adding an anilinodiamine monomer (M), 9-bis (4-aminophenyl) fluorene (N), p-diaminoazobenzene (Q) and 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (R) into a reaction vessel, and adding a solvent, namely dimethylacetamide, wherein the dosage of the dimethylacetamide is used for ensuring that the solid content in the reaction system is 15-20 g/100 mL; fully dissolving the monomers under the protection of nitrogen, and magnetically stirring the mixture for room-temperature polymerization reaction for 20 to 30 hours after the monomers are fully dissolved; and after the polymerization reaction is finished, pouring the mixed solution into distilled water, precipitating a precipitate, performing suction filtration, washing the precipitate for 3-5 times with distilled water, washing the precipitate for 3-5 times with methanol, and finally drying the product for 20-30 hours under the conditions of vacuum and 30-50 ℃ to obtain the anilinoazobenzene fluorescent polyamic acid polymer P1, wherein the yield is 85-90%.
According to the invention, Indium Tin Oxide (ITO) glass is used as a substrate of a working electrode for testing, the ITO substrate is cut into the size of 1.2cm multiplied by 5.5cm, the ITO substrate is respectively subjected to ultrasonic cleaning for 2-4 times in dichloromethane, acetone, absolute ethyl alcohol and distilled water, finally, the absolute ethyl alcohol is used for ultrasonic cleaning for 1-2 times, and the ITO substrate is placed in an oven until the surface is dried and cleaned; dissolving the prepared anilino-azobenzene fluorescent polyamic acid polymer P1 in N, N' -dimethylacetamide, preparing a solution (0.01-0.05 g/mL) by taking the concentration of a fluorescent group (9, 9-bis (4-aminophenyl) fluorene) as a standard, and then spin-coating on the treated ITO substrate at the rotation speed of 1200r/s 15s and 900r/s 60s in sequence; and drying the spin-coated polymer/ITO substrate to obtain a polyamic acid/ITO sample, wherein the polymer is always in a solid film state in the test process.
Drawings
FIG. 1: nuclear magnetic spectrum of the synthesized polyamic acid polymer;
FIG. 2: the infrared spectrum of the polyamic acid polymer synthesized by the invention;
FIG. 3: the cyclic voltammetry curve spectrogram of the synthesized polyamic acid polymer;
FIG. 4: the state change diagram of the aniline chain segment in the structure of the synthesized polyamic acid polymer is shown;
FIG. 5: the fluorescence electric response curve spectrogram of the synthesized polyamic acid polymer;
FIG. 6: the fluorescence pH response curve spectrogram of the polyamic acid polymer synthesized by the invention;
FIG. 7: the fluorescence chemical oxygen reduction response curve spectrogram of the synthesized polyamic acid polymer;
FIG. 8: the fluorescence light response curve spectrogram of the synthesized polyamic acid polymer;
FIGS. 1 and 2 are nuclear magnetic and infrared spectra of the synthesized polymer, and the characteristics1H NMR(d6-DMSO) assignment: 10.29, 10.00(s, -CO-NH-), (8.11 (d, -NH-), (7.75-6.63 (m, Ar-H)). At 3420cm-1Is an N-H stretching vibration peak; 2985cm-1Is a C-H vibration absorption peak; 1660cm-1The position is a vibration absorption peak of a carbon-oxygen double bond; 1513cm-1And 1453cm-1The position is a vibration absorption peak of a carbon-carbon bond on a benzene ring; 1453cm-1Nitrogen-nitrogen bond vibration absorption peak, 1314cm-1Carbon-nitrogen bond shock absorption peak, 1229cm-1C-O-C stretching vibration peak, 868cm-1、753cm-1、596cm-1Is the deformation vibration absorption peak of the fingerprint area on the benzene ring.
FIG. 3 is a cyclic voltammetry curve of a polymer, which is prepared by dissolving the polymer in a dimethylacetamide solution to form a 0.05g/mL solution, spin-coating the solution on a cleaned ITO substrate with the size of 1.2cm × 5.5cm as a working electrode, and then using a platinum wire as a counter electrode and Ag/AgCl as a reference electrode to form a three-electrode system and using a 1.0M HCl solution as an electrolyte for testing. Two pairs of reversible redox peaks appear when a voltage of 0.0V to 1.0V is applied to the working electrode. 0.40V/0.36V and 0.53V/0.49V, respectively. Wherein the first pair of redox peaks corresponds to an electrochemical process of the aniline chain segment from a reduced state to an intermediate oxidation state, and the second pair of redox peaks corresponds to an electrochemical process of the aniline chain segment from the intermediate oxidation state to a highest oxidation state. The aniline segments differ in structure under different oxidation states. Meanwhile, the aniline chain segments show different structural changes under the same oxidation state and different acid-base environments.
FIG. 4 is a schematic diagram of structural changes of an aniline segment under different oxidation states and acid-base environments. The aniline segment is gradually converted from the initial LEB state to the EB state and finally to the PNB state by an increase in the degree of oxidation. The initial LES state is gradually converted into ES state and finally into PNS state with the increase of oxidation degree after acid doping.
FIG. 5 is a fluorescence electric response curve spectrogram of a polymer, still adopting a three-electrode system, applying constant voltages of 0.0V, 0.2V, 0.4V to 1.0V to the working electrode respectively, wherein the application time is 300s each time, and performing fluorescence spectrum test on the polymer after applying the voltage. The fluorescence emission spectrum of the polymer with the excitation wavelength of 315nm is positioned at 485nm, the fluorescence intensity of the polymer is maximum when the voltage is 0.0V, the aniline chain segment in the polymer is in a reduction state, the aniline chain segment is continuously oxidized with the continuous increase of the voltage, the fluorescence intensity is reduced, the aniline chain segment is oxidized to be in the maximum oxidation state after the voltage is applied to reach 1.0V, the fluorescence of the polymer is reduced to 20% of the initial fluorescence intensity, and the reversible electric control fluorescence phenomenon appears when the fluorescence intensity is reduced with the reduction of the voltage and the increase of the fluorescence intensity
FIG. 6 is a graph of the fluorescence pH response curve of a polymer, wherein a constant voltage of 300s is applied to a P1/ITO film in a 1.0M HCl solution, and the applied voltages are 0.0V, 0.45V and 1.0V respectively. According to the cyclic voltammetry curve, the polymer is respectively in a reduction state, an intermediate oxidation state and a highest oxidation state, and the fluorescence spectrum of P1/ITO is measured. The fluorescence intensity of the polymer film at 0.45V dropped to 57% of the fluorescence intensity at the initial 0.0V voltage, and the fluorescence intensity after the applied voltage was 1.0V was 20% of the initial.
FIG. 7 is a graph of the chemical oxygen reduction response curve of a polymer, and the P1 film is placed in a 1.0M HCl solution, and P1/ITO shows an emission curve with higher fluorescence intensity. Ammonium persulfate is added to ensure that the concentration of the ammonium persulfate in the solution is 4.0M, the aniline chain segment in the polymer is gradually oxidized and converted from LES to PNS, and the fluorescence intensity is also gradually reduced. Then immersing it in 1.0M NH4In the OH solution, the aniline chain segment is converted from PNS to PNB state, and the fluorescence intensity is reduced again. Then, hydrazine hydrate was added to the alkaline solution to make the solubility thereof 4.0M. After addition of the reducing agent, aniline chainThe fragment is reduced and converted from PNB to LEB, and the fluorescence intensity is also increased. Finally, the P1/ITO was put into 1.0M HCl solution, the aniline chain segment recovered to the original LES state, and the fluorescence intensity recovered as before.
FIG. 8 is a graph of the fluorescence photoresponse curve of a polymer, similar to the above-mentioned method, obtained by applying a constant voltage of 300s to a P1/ITO film in a 1.0MHCl solution at 0.0V (aniline segments in LES state), 0.45V (aniline segments in ES state) and 1.0V (aniline segments in PNS state), respectively. Under the condition that the state of the aniline chain segment is fixed, the irradiation time of the film is changed only by ultraviolet light and visible light, and the fluorescence change of the polymer is observed. Taking the application of 0.0V voltage (in LES state) as an example, the fluorescence intensity of the solid film gradually decreased under the irradiation of ultraviolet rays, and decreased to 84% of the initial value after 30 minutes of irradiation. The solid film was then exposed to visible light and the fluorescence intensity returned to substantially the original state after 200 min.
Detailed Description
Example 1
All monomers were ground and dried under vacuum at 40 ℃ for 24 hours. 0.1369g (0.2mmol) of anilinodiamine monomer (M), 0.0425g (0.2mmol) of p-diaminoazobenzene (Q), 0.1394g (0.4mmol) of 9, 9-bis (4-aminophenyl) fluorene (N), 0.1793g (0.8mmol) of 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (R) were charged into a 50mL three-necked flask. Then, 5mL of dimethylacetamide was added and dissolved sufficiently under nitrogen protection, and after complete dissolution, the mixture was reacted at room temperature for 24 hours with magnetic stirring. And after the polymerization reaction is finished, pouring the mixed solution into distilled water, precipitating, and performing suction filtration. The precipitate was washed with distilled water 3 times, methanol 3 times, and the product was dried in a vacuum oven at 40 ℃ for 24 hours to obtain anilinoazobenzene fluorescent polyamic acid polymer P1 with a yield of 86%.
Claims (1)
1. The application of the fluorescent polyamic acid polymer taking the aniline chain segment and the azobenzene group as sensitive elements in the aspect of fluorescent multi-stimulus response is shown in the structural formula,
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| CN110093034A (en) * | 2019-05-27 | 2019-08-06 | 武汉华星光电半导体显示技术有限公司 | The preparation method of modified polyamic acid and preparation method thereof, composite film |
| CN110483328B (en) * | 2019-07-29 | 2022-06-17 | 安阳工学院 | 2, 6-di (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide monomer and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391130A (en) * | 2011-09-23 | 2012-03-28 | 上海固创化工新材料有限公司 | Preparation method of 9, 9- diamino-(4-aminophenyl) fluorene |
| CN105669972A (en) * | 2016-01-27 | 2016-06-15 | 吉林大学 | Side chain type electroactive polyamide, preparation method and application of side chain type electroactive polyamide in corrosion prevention |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391130A (en) * | 2011-09-23 | 2012-03-28 | 上海固创化工新材料有限公司 | Preparation method of 9, 9- diamino-(4-aminophenyl) fluorene |
| CN105669972A (en) * | 2016-01-27 | 2016-06-15 | 吉林大学 | Side chain type electroactive polyamide, preparation method and application of side chain type electroactive polyamide in corrosion prevention |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and properties of multifunctional poly(amic acid) with oligoaniline and fluorene groups;Chao d m等;《Colloid Polym Sci》;20130628;第291卷;2631-2637页 * |
| 非液晶偶氮苯聚酰胺酸的合成与光响应;张超慧等;《高等学校化学学报》;20100510;第31卷(第3期);432-434页 * |
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