CN108586741A - Fluorescence polyamic acid polymer, preparation method and its application in terms of fluorescence thorniness swashs response - Google Patents
Fluorescence polyamic acid polymer, preparation method and its application in terms of fluorescence thorniness swashs response Download PDFInfo
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- CN108586741A CN108586741A CN201810329086.0A CN201810329086A CN108586741A CN 108586741 A CN108586741 A CN 108586741A CN 201810329086 A CN201810329086 A CN 201810329086A CN 108586741 A CN108586741 A CN 108586741A
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- fluorescence
- polymer
- oligoanilines
- polyamic acid
- anilino
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- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 17
- 230000004044 response Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004952 Polyamide Substances 0.000 claims abstract description 10
- 229920002647 polyamide Polymers 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 claims abstract description 8
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- VYRSENJTOJNBJV-UHFFFAOYSA-N cyclohexa-3,5-diene-1,1,2-triamine Chemical compound NC1C=CC=CC1(N)N VYRSENJTOJNBJV-UHFFFAOYSA-N 0.000 claims abstract description 6
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000013019 agitation Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- -1 dimethylacetamide Amine Chemical class 0.000 claims description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000002220 fluorenes Chemical class 0.000 claims 2
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 claims 1
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical class C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 6
- 229920001109 fluorescent polymer Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 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
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 0 *c(cc1)ccc1N Chemical compound *c(cc1)ccc1N 0.000 description 2
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- NWAKEUPRSCUPMP-UHFFFAOYSA-N O=C(C(CC1C(S2)=O)C3C=C1C2=O)OC3=O Chemical compound O=C(C(CC1C(S2)=O)C3C=C1C2=O)OC3=O NWAKEUPRSCUPMP-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity 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
- 238000004528 spin coating Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying 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
- 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
-
- 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
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
A kind of application using Oligoanilines and azobenzene group as fluorescence polyamic acid polymer, preparation method and the polymer of sensitive primitive in terms of fluorescence thorniness swashs response belongs to functional polymer material field.It is by anilino- diamine monomer, 9,9 bis- (4 aminophenyl) fluorenes, p-diaminoazobenzene, 1,2,4,5 cyclohexanetetracarboxylic acid dianhydrides are added in reaction vessel, add solvent dimethylacetylamide, then magnetic agitation polymerized at room temperature reacts 20~30 hours；Mixed liquor is poured into distilled water, precipitation is precipitated, is filtered, precipitation is washed with distilled water 3~5 times again, methanol washs 3~5 times, finally that product is 20~30 hours dry under the conditions of vacuum, 30~50 DEG C, to obtain anilino- azobenzene fluorescent polyamide acid polymer.Polymer is spin-coated on electro-conductive glass, fluorescent switch responsive status of its film under external pH value, voltage, chemistry/reductant-oxidant and UV, visible light light stimulus is tested.
Description
Technical field
The invention belongs to functional polymer material fields, and in particular to a kind of novel with Oligoanilines and azobenzene group
As the fluorescence polyamic acid polymer of sensitive primitive, preparation method and the polymer answering in terms of fluorescence thorniness swashs response
With.
Background technology
It is manufactured from display, sensor to medical diagnosis and drug delivery and smart machine, fluorescent material is answered extensively
In people’s lives.Compared to other fluorescent materials, polymerization species fluorescent material have it is light, be easy to MOLECULE DESIGN,
The advantages that processing performance is excellent.With the fast development of material science, more stringent requirements are proposed to material by people, such as good
Stability, special response etc..Therefore, researchers begin one's study recently external environment variation (such as light, electricity, pH value, pressure
Power, heat, magnetic field and chemicals) action principle and rule that the photoluminescent property of fluorescent polymer is had an impact, to prepare
The more stimuli responsive fluorescent materials for going out can adapt to extraneous complex environment, further widen the application range of material.
A kind of effective method for obtaining more stimulating responsive fluorescent polymers is that fluorogen and a variety of sensitive groups is same
When be introduced into polymer, pass through sensitive group to extraneous environmental change response change and fluorophor between energy transfer
Channel responds phenomenon to realize that fluorescent switch occurs for polymer.Model compound of the Oligoanilines as polyaniline has good
Good dissolubility, programmable molecular structure, tunable electro-optical characteristic, while to pH value, redox materials and current potential
Equal stimulations can respond.Azobenzene group will produce turn between unique Cis-trans structures under the light-wave irradiation of appropriate wavelength
It changes, they is introduced into fluorescent polymer molecule segment simultaneously, it can interact with environmental stimuli changes self structure shape
State makes fluorescent polymer that reversible fluorescent switch respondent behavior occur to drive the change of various molecular conformations.
The present invention is from the angle of MOLECULE DESIGN, and by anilino- diamine monomer, p-diaminoazobenzene and 9,9- is bis-
(4- aminophenyls) fluorenes and 1, fluorescent polyamide acid is made in 2,4,5- cyclohexanetetracarboxylic acid, two anhydride reactant, by Oligoanilines and azo
Phenyl group synthesizes the fluorescent polyamide acid of more stimuli responsives by MOLECULE DESIGN as sensitive primitive, outer to obtain more adaptation
The fluorescence response proximate matter material of boundary's environmental change.
Fluorescent polymer prepared by the present invention is using Oligoanilines and azobenzene group as sensitivity primitive, high-luminous-efficiency
Fluorophor as fluorescent emission primitive, utilize the electronics between sensitive primitive and fluorescent emission primitive/energy transfer to realize
The switch of polymer fluorescent property changes, and synthesizes high-performance fluorescence response polymer by MOLECULE DESIGN.
Invention content
The object of the present invention is to provide a kind of novel using Oligoanilines and azobenzene group as the fluorescence of sensitive primitive
Property polyamic acid polymer, preparation method and the polymer fluorescence thorniness swash response in terms of application.
The present invention is that (contents such as synthesis, characterization of the monomer refer to Chinese special using anilino- diamine monomer (M) first
Profit：201410010359.7, side chain type electroactive polyurea polymer, preparation method and its application in terms of anti-corrosion) and 1,2,
Bis- (4- aminophenyls) fluorenes (N) of 4,5- cyclohexanetetracarboxylic acids dianhydride, 9,9- and p-diaminoazobenzene (Q) (are conventional original
Material, can be commercially available) combined polymerization obtains anilino- azobenzene fluorescent polyamide acid polymer.
Anilino- diamine monomer (M) structural formula is as follows：
9,9- bis- (4- aminophenyls) fluorenes (N) structural formula is as follows：
P-diaminoazobenzene (Q) structural formula is as follows：
1,2,4,5- cyclohexanetetracarboxylic acids dianhydride (R) structural formula is as follows：
The preparation method of anilino- azobenzene fluorescent polyamide acid polymer of the present invention, the following institute of reaction process
Show：
The preparation method of anilino- azobenzene fluorescent polyamide acid polymer of the present invention, it is characterised in that：It will be anti-
After answering monomer to grind, be placed under vacuum 30~50 DEG C it is 20-30 hours dry；After being completely dried by molar ratio be 1：2：1：4 benzene
Bis- (4- aminophenyls) fluorenes (N) of amido diamine monomer (M), 9,9-, p-diaminoazobenzene (Q), 1,2,4,5- hexamethylene tetramethyls
Acid dianhydride (R) is added in reaction vessel, adds solvent dimethylacetylamide, dimethylacetylamide dosage is to ensure reactant
Solid content is 15~20g/100mL in system；Monomer is set fully to dissolve under nitrogen protection, after monomer is completely dissolved, then magnetic force
Stir room temperature polymerisation 20~30 hours；After the completion of polymerisation, mixed liquor is poured into distilled water, precipitation is precipitated, is filtered,
Precipitation is washed with distilled water 3~5 times again, methanol washs 3~5 times, finally that product is dry under the conditions of vacuum, 30~50 DEG C
20~30 hours, to obtain anilino- azobenzene fluorescent polyamide acid polymer P1 of the present invention, yield is 85~
90%.
Working electrode used is tested in the present invention using tin indium oxide (ITO) glass as substrate, and ITO substrate is cut into
It, is cleaned by ultrasonic 2~4 times by the size of 1.2cm × 5.5cm respectively in dichloromethane, acetone, absolute ethyl alcohol, distilled water, most
It uses absolute ethyl alcohol ultrasound again afterwards 1~2 time, is put into baking oven to dry tack free cleaning；It is again that the anilino- prepared by the present invention is even
Pyridine fluorescent polyamide acid polymer P1 is dissolved in N, N '-dimethyl acetamide, with fluorophor (9,9- bis- (4- aminophenyls)
Fluorenes) a concentration of standard, be configured to solution (0.01~0.05g/mL), be then spin coated onto in above-mentioned processed ITO substrate, revolve
Selected rotating speed is followed successively by 1200r/s 15s, 900r/s 60s when painting；Polymer after spin coating/ITO substrate is dried, from
And polyamic acid/ITO samples are obtained, polymer is always solid film state in test process.
Description of the drawings
Fig. 1：The nuclear magnetic spectrogram for the polyamic acid polymer that the present invention synthesizes；
Fig. 2：The infrared spectrum for the polyamic acid polymer that the present invention synthesizes；
Fig. 3：The cyclic voltammetry curve spectrogram for the polyamic acid polymer that the present invention synthesizes；
Fig. 4：Oligoanilines state change map in the polyamic acid polymer structure that the present invention synthesizes；
Fig. 5：The fluorescence electroresponse curve spectrogram for the polyamic acid polymer that the present invention synthesizes；
Fig. 6：The polyamic acid polymer fluorescent pH response curve spectrogram that the present invention synthesizes；
Fig. 7：The polyamic acid polymer fluorescence chemical hydrogen reduction response curve spectrogram that the present invention synthesizes；
Fig. 8：The fluorescence photoresponse curve spectrogram for the polyamic acid polymer that the present invention synthesizes；
Fig. 1,2 are synthesized polymer nuclear-magnetism and infrared spectrum, characterization1H NMR(d6- DMSO) ownership：δ=10.29,
10.00 (s ,-CO-NH-), δ=8.11 (d ,-NH-), δ=7.75-6.63 (m, Ar-H).In 3420cm-1Place, which is that N-H is flexible, to shake
Dynamic peak；2985cm-1Place is C-H vibration absorption peaks；1660cm-1Place is the vibration absorption peak of C=O bond；1513cm-1With
1453cm-1Place is the vibration absorption peak of carbon-carbon bond on phenyl ring；1453cm-1Itrogen-to-nitrogen bonds vibration absorption peak, 1314cm-1Carbonnitrogen bond shakes
Dynamic absorption peak, 1229cm-1C-O-C stretching vibration peaks, 868cm-1、753cm-1、596cm-1For the deformation vibration of fingerprint region on phenyl ring
Absorption peak.
Fig. 3 is polymer circulation volt-ampere curve, dissolves a polymer in dimethylacetamide solution, is configured to 0.05g/mL
Solution, be spin-coated in the ITO substrate that cleaned, size is 1.2cm × 5.5cm and be used as working electrode, then be with platinum filament
To electrode, Ag/AgCl is reference electrode, and formation three-electrode system does electrolyte with 1.0M HCl solutions and tested.It is working
Electrode applies in 0.0V~1.0V voltage courses, shows two pairs of reversible redox peaks.Respectively 0.40V/0.36V and
0.53V/0.49V.Wherein, first pair of redox peaks corresponds to electrochemistry mistake of the Oligoanilines from reduction-state to intermediate oxidation state
Journey, second pair of redox peaks correspond to electrochemical process of the Oligoanilines from intermediate oxidation state to highest oxidation state.Oligoanilines
It is different in different state of oxidation lower structures.Meanwhile Oligoanilines also show under same state of oxidation difference acid or alkali environment
Go out different structure changes.
Fig. 4 is the schematic diagram that Oligoanilines change in the different states of oxidation and acid or alkali environment lower structure.Oligoanilines pass through
The increase of degree of oxidation is gradated by the LEB states originated and eventually becomes PNB states for EB states.With oxidation after acid doping
The increase of degree is gradated by the LES states originated and eventually becomes PNS states for ES states.
Fig. 5 is polymer fluorescent electroresponse curve spectrogram, still uses three-electrode system, working electrode is applied respectively
The constant voltage of 0.0V, 0.2V, 0.4V to 1.0V, each application time are 300s, and fluorescence light is carried out to polymer after applying voltage
Spectrum test.Using 315nm as the fluorescence emission spectrum of excitation wavelength polymer, transmitting position is at 485nm, the fluorescence of polymer when 0.0V
Maximum intensity, at this time the Oligoanilines in polymer be in reducing condition, continue to increase Oligoanilines constantly quilt with voltage
Oxidation, fluorescence intensity also decline therewith, and Oligoanilines are to be oxidized to highest oxidation state, polymer after application voltage reaches 1.0V
Fluorescence is reduced to the 20% of initial fluorescence intensity, and voltage reduces fluorescence intensity and is consequently increased the reversible automatically controlled fluorescence phenomenon of appearance
Fig. 6 is polymer fluorescent pH response curve spectrograms, applies the permanent electricity of 300s in 1.0M HCl solutions to P1/ITO films
Pressure, the voltage of application is respectively 0.0V, 0.45V and 1.0V.According to cyclic voltammetry curve it is found that polymer is respectively at reduction
State, intermediate oxidation state and highest oxidation state, and measure the fluorescence spectrum of P1/ITO.Polymer film fluorescence is strong under 0.45V voltages
Degree is reduced to 57% of fluorescence intensity under starting 0.0V voltages, and it is the 20% of starting to apply fluorescence intensity after voltage becomes 1.0V.
Fig. 7 is polymer chemistry hydrogen reduction response curve spectrogram, and P1 films are placed in 1.0M HCl solutions, P1/ITO displayings
Go out the higher launching curve of fluorescence intensity.Ammonium persulfate is added, ammonium persulfate concentrations is made in solution to be 4.0M, aniline in polymer
Segment is gradually aoxidized is changed into PNS by LES, and fluorescence intensity is also gradually reduced.It is dipped in 1.0M NH again4In OH solution, benzene
Amine segment is changed into PNB states by PNS, and fluorescence intensity declines again.Backward alkaline solution in hydrazine hydrate is added, make its solubility
For 4.0M.After reducing agent is added, Oligoanilines are reduced, and are changed into LEB by PNB, fluorescence intensity is also risen.Finally by this
P1/ITO is put into 1.0M HCl solutions, and Oligoanilines revert to LES states originally, and fluorescence intensity level also restores as before.
Fig. 8 is polymer fluorescent photoresponse curve spectrogram, similar to method mentioned above, to P1/ITO films in 1.0M
Apply 300s constant voltages in HCl solution, the voltage of application is respectively 0.0V (Oligoanilines are in LES states), 0.45V (aniline
Segment is in ES states) and 1.0V (Oligoanilines are in PNS states).Under the conditions of Oligoanilines state is fixed, only change
Uv and visible light observes the change in fluorescence of polymer to the irradiation time of film.It is (under LES states) to apply 0.0V voltages
Example, solid film fluorescence intensity under ultraviolet irradiation are gradually reduced, and irradiation falls to the 84% of starting after 30 minutes.Then will
Solid film placement is irradiated under visible light, and fluorescence intensity substantially returns to original state after 200min.
Specific implementation mode
Embodiment 1
First all monomers are ground, are placed under the conditions of 40 DEG C of vacuum 24 hours dry.By 0.1369g (0.2mmol) aniline
Base diamine monomer (M), 0.0425g (0.2mmol) p-diaminoazobenzene (Q), bis- (the 4- amino of 0.1394g (0.4mmol) 9,9-
Phenyl) fluorenes (N), 1,2,4,5- cyclohexanetetracarboxylic acid dianhydrides (R) of 0.1793g (0.8mmol) are added in 50mL three-neck flasks.Again
5mL dimethylacetylamides are added, are allowed to fully dissolve under nitrogen protection, after being completely dissolved, magnetic agitation room temperature reaction 24 is small
When.After the completion of polymerisation, mixed liquor is poured into distilled water, precipitation is precipitated, is filtered.Precipitation is washed with distilled water 3 times again,
Methanol washs 3 times, and product is put into the drying 24 hours of 40 DEG C of vacuum drying oven, obtains the polymerization of anilino- azobenzene fluorescent polyamide acid
Object P1, yield 86%.
Claims (3)
1. a kind of using Oligoanilines and azobenzene group as the fluorescence polyamic acid polymer of sensitive primitive, structural formula is such as
Shown in lower:
2. a kind of fluorescence polyamic acid using Oligoanilines and azobenzene group as sensitive primitive described in claim 1 is poly-
Close the preparation method of object, it is characterised in that：After reaction monomers are ground, be placed under vacuum 30~50 DEG C it is 20-30 hours dry；It is complete
After white drying by molar ratio be 1：2：1：4 anilino- diamine monomer, bis- (4- aminophenyls) fluorenes of 9,9-, p-diaminoazobenzene
With 1,2,4,5- cyclohexanetetracarboxylic acid dianhydrides are added in reaction vessel, add solvent dimethylacetylamide, dimethylacetamide
Amine dosage is to ensure that solid content is 15~20% in reaction system；So that monomer is fully dissolved under nitrogen protection, waits for that monomer is complete
After dissolving, then magnetic agitation polymerized at room temperature reacts 20~30 hours；After the completion of polymerisation, mixed liquor is poured into distilled water,
Precipitation is precipitated, filters, then precipitation is washed with distilled water 3~5 times, methanol washs 3~5 times, finally by product vacuum, 30~
It is 20~30 hours dry under the conditions of 50 DEG C, to obtain anilino- azobenzene fluorescent polyamide acid polymer P1；
Wherein, the structural formula of anilino- diamine monomer is as follows,
The structural formula of 9,9- bis- (4- aminophenyls) fluorenes is as follows,
The structural formula of p-diaminoazobenzene is as follows,
The structural formula of 1,2,4,5- cyclohexanetetracarboxylic acid dianhydride is as follows,
3. a kind of fluorescence polyamic acid using Oligoanilines and azobenzene group as sensitive primitive described in claim 1 is poly-
Close application of the object in terms of fluorescence thorniness swashs response.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437096A (en) * | 2019-07-29 | 2019-11-12 | 安阳工学院 | The preparation method of 2,6- bis- (amino-benzene oxygen)-N- (2- aminofluorene) benzamide monomer |
| CN110437095A (en) * | 2019-07-29 | 2019-11-12 | 安阳工学院 | 2- (3- amino-benzene oxygen) -6- (4- amino-benzene oxygen)-N- (2- aminofluorene) benzamide monomer |
| CN110483328A (en) * | 2019-07-29 | 2019-11-22 | 安阳工学院 | 2,6- bis- (amino-benzene oxygen)-N- [4- (phenylazo) phenyl] benzamide monomer and preparation method |
| WO2020232777A1 (en) * | 2019-05-21 | 2020-11-26 | 武汉华星光电半导体显示技术有限公司 | Electrochromic polyamic acid material, preparation method therefor, and display device |
| WO2020238029A1 (en) * | 2019-05-27 | 2020-12-03 | 武汉华星光电半导体显示技术有限公司 | Modified polyamide acid and preparation method therefor, and preparation method for composite film layer |
| CN113004519A (en) * | 2021-03-08 | 2021-06-22 | 吉林大学 | Aggregation-induced luminescence electro-active polyamic acid polymer, nanofiber detection test strip and application thereof |
| CN114516860A (en) * | 2022-02-24 | 2022-05-20 | 南京大学 | Amide-containing polysubstituted aromatic diamine monomer and preparation method thereof |
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 |
-
2018
- 2018-04-13 CN CN201810329086.0A patent/CN108586741B/en not_active Expired - Fee Related
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 |
|---|
| CHAO D M等: "Synthesis and properties of multifunctional poly(amic acid) with oligoaniline and fluorene groups", 《COLLOID POLYM SCI》 * |
| 张超慧等: "非液晶偶氮苯聚酰胺酸的合成与光响应", 《高等学校化学学报》 * |
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| US11537020B2 (en) | 2019-05-21 | 2022-12-27 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Electrochromic polyamic acid material, preparation method thereof, and display device |
| WO2020238029A1 (en) * | 2019-05-27 | 2020-12-03 | 武汉华星光电半导体显示技术有限公司 | Modified polyamide acid and preparation method therefor, and preparation method for composite film layer |
| US11773288B2 (en) | 2019-05-27 | 2023-10-03 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Modified polyamic acid, preparation method thereof, and preparation method of composite film |
| CN110437096A (en) * | 2019-07-29 | 2019-11-12 | 安阳工学院 | The preparation method of 2,6- bis- (amino-benzene oxygen)-N- (2- aminofluorene) benzamide monomer |
| CN110437095A (en) * | 2019-07-29 | 2019-11-12 | 安阳工学院 | 2- (3- amino-benzene oxygen) -6- (4- amino-benzene oxygen)-N- (2- aminofluorene) benzamide monomer |
| CN110483328A (en) * | 2019-07-29 | 2019-11-22 | 安阳工学院 | 2,6- bis- (amino-benzene oxygen)-N- [4- (phenylazo) phenyl] benzamide monomer and preparation method |
| CN110437096B (en) * | 2019-07-29 | 2022-05-06 | 安阳工学院 | Preparation method of 2, 6-di (aminophenoxy) -N- (2-aminofluorene) benzamide monomer |
| 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 |
| CN113004519A (en) * | 2021-03-08 | 2021-06-22 | 吉林大学 | Aggregation-induced luminescence electro-active polyamic acid polymer, nanofiber detection test strip and application thereof |
| CN114516860A (en) * | 2022-02-24 | 2022-05-20 | 南京大学 | Amide-containing polysubstituted aromatic diamine monomer and preparation method thereof |
| CN114516860B (en) * | 2022-02-24 | 2023-10-13 | 南京大学 | Multi-substituted aromatic diamine monomer containing amide and preparation method thereof |
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