CN109651231A - Derivative and its preparation method and application is supportted to styrene containing carbazole structure and the poly- of cyano - Google Patents
Derivative and its preparation method and application is supportted to styrene containing carbazole structure and the poly- of cyano Download PDFInfo
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- CN109651231A CN109651231A CN201811604614.5A CN201811604614A CN109651231A CN 109651231 A CN109651231 A CN 109651231A CN 201811604614 A CN201811604614 A CN 201811604614A CN 109651231 A CN109651231 A CN 109651231A
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- China
- Prior art keywords
- poly
- cyano
- derivative
- styrene
- carbazole
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 405
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title claims abstract description 189
- 125000004093 cyano group Chemical group *C#N 0.000 title claims abstract description 179
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 238000001514 detection method Methods 0.000 claims abstract description 26
- 239000002360 explosive Substances 0.000 claims abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 120
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 83
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 74
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 70
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 46
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 42
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 32
- 239000003960 organic solvent Substances 0.000 claims description 31
- -1 2- ethyl hexyl oxy Chemical group 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 16
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 13
- XNBVDORAKLGCKG-UHFFFAOYSA-N 1,2-dihexoxybenzene Chemical compound CCCCCCOC1=CC=CC=C1OCCCCCC XNBVDORAKLGCKG-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 11
- 229910002027 silica gel Inorganic materials 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000011895 specific detection Methods 0.000 claims description 3
- LNDJVIYUJOJFSO-UHFFFAOYSA-N cyanoacetylene Chemical group C#CC#N LNDJVIYUJOJFSO-UHFFFAOYSA-N 0.000 claims description 2
- 230000005622 photoelectricity Effects 0.000 claims description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims 6
- 150000001412 amines Chemical class 0.000 claims 2
- 238000005352 clarification Methods 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 claims 2
- 239000011591 potassium Substances 0.000 claims 2
- YKYMGFHOJJOSEB-UHFFFAOYSA-N butan-1-ol;potassium Chemical compound [K].CCCCO YKYMGFHOJJOSEB-UHFFFAOYSA-N 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- DNLBLJSRCNPEGS-UHFFFAOYSA-N 9h-carbazole-1,2-dicarbaldehyde Chemical compound C1=CC=C2NC3=C(C=O)C(C=O)=CC=C3C2=C1 DNLBLJSRCNPEGS-UHFFFAOYSA-N 0.000 abstract 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 30
- 239000010408 film Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 14
- 230000008859 change Effects 0.000 description 13
- 230000004044 response Effects 0.000 description 11
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical group CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 9
- 230000004580 weight loss Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- 241001597008 Nomeidae Species 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 4
- 125000003367 polycyclic group Polymers 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910001451 bismuth ion Inorganic materials 0.000 description 3
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 150000005839 radical cations Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Indole Compounds (AREA)
Abstract
Derivative and its preparation method and application is supportted to styrene containing carbazole structure and the poly- of cyano, the present invention relates to support derivative and its preparation method and application to styrene containing carbazole structure and the poly- of cyano.Derivative and its preparation method and application is supportted to styrene containing carbazole structure and the poly- of cyano the present invention provides a kind of.The present invention synthesizes the carbazole dialdehyde monomer containing carbazole structure, then prepares and supports derivative to styrene containing carbazole structure and the poly- of cyano, which is applied to electrochromic material, hole mobile material, camouflage material, automobile rearview mirror material as photoelectric material；It can also be used in ion detection, explosive detection.The present invention is applied to Photoelectric Detection and display field.
Description
Technical field
The present invention relates to support derivative and its preparation method and application to styrene containing carbazole structure and the poly- of cyano.
Background technique
Poly- is the outstanding high temperature polymeric materials of a kind of comprehensive performance to styrene support (PPV), has good chemistry
Stability, excellent dielectric properties and radiation resistance etc. can be prepared into film, composite material, insulated paint, capacitor equipment
Material, is widely used in the fields such as aerospace, electroluminescent, sensor.Although poly- support excellent combination property to styrene, pass
Uniting, there are some disadvantages by PPV, and such as the problems such as difficulty of processing is high, dissolubility is poor, film strength is poor, flexible difference is easy to break, this is big
The poly- application to styrene timbering material industrially is limited greatly.Therefore, we introduce alkyloxy side chain on PPV to enhance it
Dissolubility, while electrophilic group cyano is introduced on PPV main chain to improve its Electronic Performance, reduce its energy band.In addition, now more
It is required that material has multi-functional and miniaturization, and can be integrated in a small chip, and traditional PPV is as photoelectric material
With detection display material since the limitation of its dissolubility and processing performance is slightly inadequate.Therefore, PPV class material Photoelectric Detection with
The application of display field is all to be improved always.
Summary of the invention
The present invention is to solve the problems, such as that existing PPV class material using less, is provided in Photoelectric Detection and display field
It is poly- to styrene support derivative and its preparation method and application containing carbazole structure and cyano.
The present invention is poly- to benzene containing carbazole structure and cyano to styrene support derivative containing the poly- of carbazole structure and cyano
Vinylene derivative P1 supports derivative P2 to styrene containing carbazole structure and the poly- of cyano；
The poly- structural formula for supportting derivative P1 to styrene wherein containing carbazole structure and cyano is as follows:
,
The integer that n is 3~10 in formula；
It is wherein poly- as follows to styrene support derivative P2 structural formula containing carbazole structure and cyano:
,
The integer that n is 3~10 in formula.
The present invention containing carbazole structure and cyano it is poly- to styrene support derivative P1's the preparation method comprises the following steps:
One, the monomer of N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine containing carbazole structure is synthesized
By (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of N- bis- with except water-toluene mixes, logical nitrogen is vacuumized, then be placed in low temperature
In reaction kettle, -70 degrees Celsius are cooled to, reducing agent diisobutyl aluminium hydride is added, stirs 10min under -70 degrees celsius, closes
Cooling valve is closed, is kept stirring until temperature of reaction system time is warmed to room temperature, taking-up reaction system, which is placed on magnetic stirring apparatus, to be continued
Stirring sequentially adds the ammonia spirit of acetone, ethyl acetate, ammonium chloride, and obvious layering occurs in stirring to system, and upper layer is
There are solid precipitation in supernatant liquid, lower layer, system are filtered, and gained liquid revolving obtains N- bis- (4- benzaldehyde)-N '-carbazole benzene
Diamines；
Two, it prepares and derivative is supportted to styrene containing carbazole structure and the poly- of cyano
By N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, solvent, 2- (2- ethyl hexyl oxy) -5- containing cyano
Methoxyl group-Isosorbide-5-Nitrae-benzene diacetonitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide are added in there-necked flask, are warming up to 50 DEG C of stirrings
Flow back 20min, pours into the methanol with acetic acid after cooling, refilters and wash solid up to methanol is without color with methanol,
Obtained solid is dried in vacuo, obtains supportting derivative P1 to styrene containing carbazole structure and the poly- of cyano；
Wherein the volume ratio of (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of the N- bis- in step 1 and diisobutyl aluminium hydride is
(1.0-1.5)g:(2-3)mL；
Remove water-toluene and the volume mass ratio of N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are 10mL:
(1.0-1.5)g；
The volume mass ratio of acetone and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3) mL:
(1.0-1.5)g；
The volume mass ratio of ethyl acetate and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3)
mL:(1.0-1.5)g；
N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, bis- hexyloxy benzene -1,4- diacetyl of 2,5- in step 2
The mass ratio of nitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide is 0.2g:0.15g:0.12g:5mL；
The volume mass ratio of solvent and N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer in step 2 is 20mL:
0.2g；Solvent is that 1:1 is mixed by volume for the tert-butyl alcohol and tetrahydrofuran.
Containing carbazole structure and cyano it is poly- to styrene support derivative P2's the preparation method comprises the following steps:
One, the monomer of N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine containing carbazole structure is synthesized
By (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of N- bis- with except water-toluene mixes, logical nitrogen is vacuumized, then be placed in low temperature
In reaction kettle, -70 degrees Celsius are cooled to, reducing agent diisobutyl aluminium hydride is added, stirs 10min under -70 degrees celsius, closes
Cooling valve is closed, is kept stirring until temperature of reaction system time is warmed to room temperature, taking-up reaction system, which is placed on magnetic stirring apparatus, to be continued
Stirring sequentially adds the ammonia spirit of acetone, ethyl acetate, ammonium chloride, and obvious layering occurs in stirring to system, and upper layer is
There are solid precipitation in supernatant liquid, lower layer, system are filtered, and gained liquid revolving obtains N- bis- (4- benzaldehyde)-N '-carbazole benzene
Diamines；
Two, it prepares and derivative is supportted to styrene containing carbazole structure and the poly- of cyano
By N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, solvent, the bis- hexyloxy benzene -1,4- diacetyl containing 2,5-
Nitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide are added in there-necked flask, are warming up to 50 DEG C and are stirred at reflux 20min, after cooling
It pours into the methanol with acetic acid, refilter and wash solid up to methanol is without color with methanol, the solid vacuum that will be obtained
It is dry, it obtains supportting derivative P2 to styrene containing carbazole structure and the poly- of cyano；
Wherein the volume ratio of (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of the N- bis- in step 1 and diisobutyl aluminium hydride is
(1.0-1.5)g:(2-3)mL；
Remove water-toluene and the volume mass ratio of N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are 10mL:
(1.0-1.5)g；
The volume mass ratio of acetone and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3) mL:
(1.0-1.5)g；
The volume mass ratio of ethyl acetate and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3)
mL:(1.0-1.5)g；
N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, bis- hexyloxy benzene -1,4- diacetyl of 2,5- in step 2
The mass ratio of nitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide is 0.2g:0.15g:0.12g:5mL；
The volume mass ratio of solvent and N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer in step 2 is 20mL:
0.2g；Solvent is that 1:1 is mixed by volume for the tert-butyl alcohol and tetrahydrofuran.
Poly- application to styrene support derivative as photoelectric material of the present invention containing carbazole structure and cyano.
The present invention applies in metal ion detection styrene support derivative P2 containing carbazole structure and the poly- of cyano.
The present invention answers styrene support derivative as acidic and alkaline gas detection material containing carbazole structure and the poly- of cyano
With.
The present invention applies in explosive detection styrene support derivative P1 containing carbazole structure and the poly- of cyano.
Beneficial effects of the present invention:
The present invention greatly expands the application range of PPV class material, and poly- support to styrene with cyano containing Long carbon chain is gathered
Object material is closed, since its excellent heat resistance and mechanical performance cause the great interest of researcher.There to be destruction
The carbazole group and Long carbon chain of bulk property are introduced into poly- in styrene support structure, being not only able to maintain original poly- support to styrene
High thermal stability, and being capable of increasing its solubility enhances film forming ability, and this is not only advantageous to the thin-film electro of manufacture large area
Mutagens color device additionally provides electric activity center to promote the processing and application of electrochromic device；Poly- pair prepared by the present invention
Styrene supports derivative and, as monomer, polymerization can be effectively reduced using underslung N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine
Strong effect power between object strand increases the dissolubility of polymer, while carbazole is easily formed radical cation, presents
It is different from the color of middle condition carbazole out.Poly- containing carbazole structure and cyano in the present invention has styrene support derivative very high
Performance resistant to high temperature, generally under the atmosphere of nitrogen, decomposition temperature at 350 DEG C or more, be suitble to use in the devices.This is sent out
It is bright that film is made to styrene support derivant material containing carbazole structure and the poly- of cyano, there is no embrittlement on ITO substrate and is crushed
Phenomenon shows good wet ability on ITO substrate.This means that poly- support to styrene containing carbazole structure and cyano derives
Object material has good film Formation and characteristics, can be used to make the film of large area.Polymer during applying voltage
Film is able to maintain circulating ring and has good stability, and is recycled 20 times or more and has good stability.
The poly- electrochromic property to styrene support derivative of the invention has following superiority in practical applications:
(1) there is good electrochemical redox invertibity, be still able to maintain after tens redox cycles reversible；(2)
The response time of color change is fast, after making alive, can change colour rapidly within 0.8 second；(3) variation of color is reversible
's；(4) color change high sensitivity；(5) there is higher cycle life；(6) there is preferable chemical stability in material discoloration front and back,
Under normal temperature and pressure, it may be stabilized in air.(7) derivative P1 is supportted to soda acid to styrene containing carbazole structure and the poly- of cyano
Property gas and explosive TNT, picric acid has response；Derivative P2 is supportted to soda acid to styrene containing carbazole structure and the poly- of cyano
Property gas and metal ion have response.
Detailed description of the invention
It is poly- to the red of styrene support derivative containing carbazole structure and cyano that Fig. 1 is that Fig. 1 is prepared by embodiment one and two
Outer spectrogram；
Fig. 2 is the poly- proton magnetic spectrum that derivative P1 is supportted to styrene containing carbazole structure and cyano prepared by embodiment one
Figure；
Fig. 3 is the poly- proton magnetic spectrum that derivative P2 is supportted to styrene containing carbazole structure and cyano prepared by embodiment two
Figure；
Fig. 4 is the poly- cyclic voltammetric that derivative P1 is supportted to styrene containing carbazole structure and cyano prepared by embodiment one
Figure；
Fig. 5 is the poly- cyclic voltammetric that derivative P2 is supportted to styrene containing carbazole structure and cyano prepared by embodiment two
Figure；
Fig. 6 is the poly- electrochromism that derivative P1 is supportted to styrene containing carbazole structure and cyano prepared by embodiment one
Figure；
Fig. 7 is the poly- electrochromism that derivative P2 is supportted to styrene containing carbazole structure and cyano prepared by embodiment two
Figure；
Fig. 8 is the poly- electroluminescent fluorescent that derivative P1 is supportted to styrene containing carbazole structure and cyano prepared by embodiment one
Figure；
Fig. 9 is the poly- electroluminescent fluorescent that derivative P2 is supportted to styrene containing carbazole structure and cyano prepared by embodiment two
Figure；
Figure 10 is the poly- thermal weight loss that derivative is supportted to styrene containing carbazole structure and cyano prepared by embodiment one and two
Curve graph；
Figure 11 be embodiment one prepare containing carbazole structure and cyano it is poly- to styrene support derivative P1 to acid-base property
Gas response diagram；
Figure 12 be embodiment one prepare containing carbazole structure and cyano it is poly- to styrene support derivative P1 to organic acid
Picric detection figure；
Figure 13 be embodiment two it is standby containing carbazole structure and cyano it is poly- to styrene support derivative P2 to explosive TNT
Detection figure；
Figure 14 is ringing to styrene support derivative P2 to aluminium ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 15 is ringing to styrene support derivative P2 to bismuth ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 16 is ringing to styrene support derivative P2 to cadmium ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 17 is ringing to styrene support derivative P2 to cobalt ions containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 18 is ringing to styrene support derivative P2 to chromium ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 19 is ringing to styrene support derivative P2 to copper ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 20 is ringing to styrene support derivative P2 to iron ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 21 is ringing to styrene support derivative P2 to potassium ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 22 is ringing to styrene support derivative P2 to magnesium ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 23 is ringing to styrene support derivative P2 to nickel ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 24 is ringing to styrene support derivative P2 to lead ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；
Figure 25 is ringing to styrene support derivative P2 to lead ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, further include each specific embodiment it
Between any combination.
Specific embodiment 1: present embodiment is containing carbazole to styrene support derivative containing carbazole structure and the poly- of cyano
Structure and the poly- of cyano support derivative P1 to styrene or support derivative P2 to styrene containing carbazole structure and the poly- of cyano；
The poly- structural formula for supportting derivative P1 to styrene wherein containing carbazole structure and cyano is as follows:
,
The integer that n is 3~10 in formula；
It is wherein poly- as follows to styrene support derivative P2 structural formula containing carbazole structure and cyano:
,
The integer that n is 3~10 in formula.
Present embodiment is poly- 1- (N- carbazole-N '-hexichol to styrene support derivative P1 containing carbazole structure and the poly- of cyano
Base-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl oxy)) phenylethylene；Containing click
Azoles structure and the poly- of cyano are poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- to styrene support derivative P2
(bis- hexyloxy -4- of 2,5- (1- cyanoacrylate base)) phenylethylene.
Present embodiment the utility model has the advantages that
Present embodiment greatly expands the application range of PPV class material, poly- to styrene with cyano containing Long carbon chain
Polymer material is supportted, since its excellent heat resistance and mechanical performance cause the great interest of researcher.To have
The carbazole group and Long carbon chain for destroying bulk property are introduced into poly- original poly- to styrene to being not only able to maintain in styrene support structure
The high thermal stability of support, and being capable of increasing its solubility enhances film forming ability, and this is not only advantageous to the thin of manufacture large area
Film electrochromic device additionally provides electric activity center to promote the processing and application of electrochromic device；Present embodiment system
Standby gathering, can be effectively as monomer using underslung N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine to styrene support derivative
The strong effect power between polymer molecular chain is reduced, increases the dissolubility of polymer, while carbazole is easily formed cation certainly
By base, the color different from middle condition carbazole is showed.It is poly- to styrene containing carbazole structure and cyano in present embodiment
Support derivative has very high performance resistant to high temperature, and generally under the atmosphere of nitrogen, decomposition temperature is suitble at 350 DEG C or more in device
It is used in part.Film is made to styrene support derivant material containing carbazole structure and the poly- of cyano in present embodiment, is served as a contrast in ITO
There is no embrittlement and Fragmentation Phenomena on bottom, good wet ability is shown on ITO substrate.This means that containing carbazole structure and cyano
It is poly- there are good film Formation and characteristics to styrene support derivant material, can be used to make the film of large area.Applying
Thin polymer film is able to maintain circulating ring and has good stability during voltage, is recycled 20 times or more and has good stability.
The poly- electrochromic property to styrene support derivative of present embodiment has following superior in practical applications
Property: (1) there is good electrochemical redox invertibity, is still able to maintain after tens redox cycles reversible；
(2) response time of color change is fast, after making alive, can change colour rapidly within 0.8 second；(3) variation of color is
Reversible；(4) color change high sensitivity；(5) there is higher cycle life；(6) material discoloration front and back has preferable chemistry steady
It is qualitative, under normal temperature and pressure, it may be stabilized in air.(7) derivative P1 is supportted to styrene containing carbazole structure and the poly- of cyano
To acidic and alkaline gas and explosive TNT, picric acid has response；Derivative P2 is supportted to styrene containing carbazole structure and the poly- of cyano
There is response to acidic and alkaline gas and metal ion.
Specific embodiment 2: poly- preparation to styrene support derivative P1 of the present embodiment containing carbazole structure and cyano
Method are as follows:
One, the monomer of N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine containing carbazole structure is synthesized
By (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of N- bis- with except water-toluene mixes, logical nitrogen is vacuumized, then be placed in low temperature
In reaction kettle, -70 degrees Celsius are cooled to, reducing agent diisobutyl aluminium hydride is added, stirs 10min under -70 degrees celsius, closes
Cooling valve is closed, is kept stirring until temperature of reaction system time is warmed to room temperature, taking-up reaction system, which is placed on magnetic stirring apparatus, to be continued
Stirring sequentially adds the ammonia spirit of acetone, ethyl acetate, ammonium chloride, and obvious layering occurs in stirring to system, and upper layer is
There are solid precipitation in supernatant liquid, lower layer, system are filtered, and gained liquid revolving obtains N- bis- (4- benzaldehyde)-N '-carbazole benzene
Diamines；
Two, it prepares and derivative is supportted to styrene containing carbazole structure and the poly- of cyano
By N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, solvent, 2- (2- ethyl hexyl oxy) -5- containing cyano
Methoxyl group-Isosorbide-5-Nitrae-benzene diacetonitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide are added in there-necked flask, are warming up to 50 DEG C of stirrings
Flow back 20min, pours into the methanol with acetic acid after cooling, refilters and wash solid up to methanol is without color with methanol,
Obtained solid is dried in vacuo, obtains supportting derivative P1 to styrene containing carbazole structure and the poly- of cyano；
Wherein the volume ratio of (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of the N- bis- in step 1 and diisobutyl aluminium hydride is
(1.0-1.5)g:(2-3)mL；
Remove water-toluene and the volume mass ratio of N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are 10mL:
(1.0-1.5)g；
The volume mass ratio of acetone and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3) mL:
(1.0-1.5)g；
The volume mass ratio of ethyl acetate and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3)
mL:(1.0-1.5)g；
N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, bis- hexyloxy benzene -1,4- diacetyl of 2,5- in step 2
The mass ratio of nitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide is 0.2g:0.15g:0.12g:5mL；
The volume mass ratio of solvent and N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer in step 2 is 20mL:
0.2g；Solvent is that 1:1 is mixed by volume for the tert-butyl alcohol and tetrahydrofuran.
It is repeated in present embodiment step 1 and vacuumizes logical nitrogen three times；Mixing speed be 800r/min~
900r/min。
Specific embodiment 3: poly- preparation to styrene support derivative P2 of the present embodiment containing carbazole structure and cyano
Method are as follows:
One, the monomer of N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine containing carbazole structure is synthesized
By (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of N- bis- with except water-toluene mixes, logical nitrogen is vacuumized, then be placed in low temperature
In reaction kettle, -70 degrees Celsius are cooled to, reducing agent diisobutyl aluminium hydride is added, stirs 10min under -70 degrees celsius, closes
Cooling valve is closed, is kept stirring until temperature of reaction system time is warmed to room temperature, taking-up reaction system, which is placed on magnetic stirring apparatus, to be continued
Stirring sequentially adds the ammonia spirit of acetone, ethyl acetate, ammonium chloride, and obvious layering occurs in stirring to system, and upper layer is
There are solid precipitation in supernatant liquid, lower layer, system are filtered, and gained liquid revolving obtains N- bis- (4- benzaldehyde)-N '-carbazole benzene
Diamines；
Two, it prepares and derivative is supportted to styrene containing carbazole structure and the poly- of cyano
By N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, solvent, the bis- hexyloxy benzene -1,4- diacetyl containing 2,5-
Nitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide are added in there-necked flask, are warming up to 50 DEG C and are stirred at reflux 20min, after cooling
It pours into the methanol with acetic acid, refilter and wash solid up to methanol is without color with methanol, the solid vacuum that will be obtained
It is dry, it obtains supportting derivative P2 to styrene containing carbazole structure and the poly- of cyano；
Wherein the volume ratio of (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of the N- bis- in step 1 and diisobutyl aluminium hydride is
(1.0-1.5)g:(2-3)mL；
Remove water-toluene and the volume mass ratio of N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are 10mL:
(1.0-1.5)g；
The volume mass ratio of acetone and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3) mL:
(1.0-1.5)g；
The volume mass ratio of ethyl acetate and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3)
mL:(1.0-1.5)g；
N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, bis- hexyloxy benzene -1,4- diacetyl of 2,5- in step 2
The mass ratio of nitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide is 0.2g:0.15g:0.12g:5mL；
The volume mass ratio of solvent and N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer in step 2 is 20mL:
0.2g；Solvent is that 1:1 is mixed by volume for the tert-butyl alcohol and tetrahydrofuran.
It is repeated in present embodiment step 1 and vacuumizes logical nitrogen three times；Mixing speed be 800r/min~
900r/min。
Specific embodiment 4: present embodiment supports derivative as photoelectricity to styrene containing carbazole structure and the poly- of cyano
The application of material.
Specific embodiment 5: present embodiment is unlike specific embodiment four: containing carbazole structure and cyano
The poly- application method to styrene support derivative as photoelectric material: poly- support to styrene containing carbazole structure and cyano is derived
Object is dissolved in organic solvent, is obtained supportting derivative solution to styrene containing carbazole structure and the poly- of cyano, then will be contained carbazole knot
Structure and the poly- of cyano carry out film to styrene support derivative on electro-conductive glass, obtain photoelectric material；Wherein organic solvent is
Tetrahydrofuran, chlorobenzene, N, N '-dimethyl acetamide or N, N '-dimethylformamide.Other and four phase of specific embodiment
Together.
Specific embodiment 6: present embodiment is used as gold to styrene support derivative P2 containing carbazole structure and the poly- of cyano
Belong to the application of ion detection material.
Metal ion in present embodiment is aluminium ion and copper ion.
Specific embodiment 7: present embodiment is unlike specific embodiment six: containing carbazole structure and cyano
The poly- application method to styrene support derivative P2 as metal ion detection are as follows: by gathering to benzene second containing carbazole structure and cyano
Alkene support derivative P2 is dissolved in protic organic solvent, is obtained poly- molten to styrene support derivative containing carbazole structure and cyano
Then aqueous solution to be measured is added dropwise and supports in derivative solution in containing carbazole structure and the poly- of cyano to styrene, utilizes solution by liquid
The variation of fluorescence intensity carrys out the metal ion in specific detection solution；Protic organic solvent is THF or DMF.Other with
Specific embodiment six is identical.
Specific embodiment 8: present embodiment supports derivative as soda acid to styrene containing carbazole structure and the poly- of cyano
The application of property gas detection material.
Specific embodiment 9: present embodiment is unlike specific embodiment eight: containing carbazole structure and cyano
The poly- application method to styrene support derivative as acidic and alkaline gas detection material are as follows: by poly- pair containing carbazole structure and cyano
Styrene support derivative is dissolved in organic solvent, obtains supportting derivative solution, drop to styrene containing carbazole structure and the poly- of cyano
One drop supports derivative solution on silica gel plate to styrene containing carbazole structure and the poly- of cyano, and drying removes solvent evaporation, so
It is placed on the bottleneck of under test gas, observes and records fluorescence in the UV lamp, utilizes the variation of polymer fluorescent power on silica gel plate
To detect whether that, there are acidic and alkaline gas, organic solvent is methylene chloride or THF.
Present embodiment will be dissolved in organic solvent styrene support derivative containing carbazole structure and the poly- of cyano, be contained
Carbazole structure and the poly- of cyano support derivative solution to styrene, drip and spread out containing carbazole structure and the poly- of cyano to styrene support
For biology on silica gel plate, solvent is evaporated removing by drying, is observed and recorded fluorescence in the UV lamp, is taken volatile bronsted lowry acids and bases bronsted lowry respectively
It is respectively placed in two weighing bottles, the poly- silica gel plate to styrene support derivative containing carbazole structure and cyano will be loaded with and be placed in title
Measuring bottle mouth certain time, then puts and observes and records fluorescence in the UV lamp.Utilize the change of polymer fluorescent power on silica gel plate
Change to detect whether that there are acidic and alkaline gas.
Specific embodiment 10: present embodiment applies styrene support derivative P1 containing carbazole structure and the poly- of cyano
In explosive detection.
Specific embodiment 11: present embodiment is unlike specific embodiment ten: containing carbazole structure and cyano
The poly- application method to styrene support derivative P1 detection explosive are as follows: styrene will be supportted containing carbazole structure and the poly- of cyano
Derivative P1 is dissolved in organic solvent, obtain containing carbazole structure and cyano it is poly- derivative solution is supportted to styrene, then will be to
It detects solution dropwise addition to support in derivative solution styrene in containing carbazole structure and the poly- of cyano, utilizes the change of solution fluorescence intensity
Change to detect in solution with the presence or absence of explosive；Wherein organic solvent is methylene chloride or THF.Other with specific embodiment
Ten is identical.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: being poly- pair containing carbazole structure and cyano to styrene support derivative containing carbazole structure and the poly- of cyano
The structural formula that styrene supports derivative P1 is as follows:
,
The integer that n is 3~10 in formula；
The present invention containing carbazole structure and cyano it is poly- to styrene support derivative P1's the preparation method comprises the following steps:
One, the monomer of N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine containing carbazole structure is synthesized
By (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of N- bis- with except water-toluene mixes, logical nitrogen is vacuumized, then be placed in low temperature
In reaction kettle, -70 degrees Celsius are cooled to, reducing agent diisobutyl aluminium hydride is added, stirs 10min under -70 degrees celsius, closes
Cooling valve is closed, is kept stirring until temperature of reaction system time is warmed to room temperature, taking-up reaction system, which is placed on magnetic stirring apparatus, to be continued
Stirring sequentially adds the ammonia spirit of acetone, ethyl acetate, ammonium chloride, and obvious layering occurs in stirring to system, and upper layer is
There are solid precipitation in supernatant liquid, lower layer, system are filtered, and gained liquid revolving obtains N- bis- (4- benzaldehyde)-N '-carbazole benzene
Diamines；
Two, it prepares and derivative is supportted to styrene containing carbazole structure and the poly- of cyano
By N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, solvent, 2- (2- ethyl hexyl oxy) -5- containing cyano
Methoxyl group-Isosorbide-5-Nitrae-benzene diacetonitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide are added in there-necked flask, are warming up to 50 DEG C of stirrings
Flow back 20min, pours into the methanol with acetic acid after cooling, refilters and wash solid up to methanol is without color with methanol,
Obtained solid is dried in vacuo, poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- is obtained
(1- cyanoacrylate base) -5- (2- ethyl hexyl oxy)) phenylethylene, i.e., support derivative to styrene containing carbazole structure and the poly- of cyano
Object P1；
Wherein the volume ratio of (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of the N- bis- in step 1 and diisobutyl aluminium hydride is
1.5g:(2-3)mL；
Remove water-toluene and the volume mass ratio of N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are 10mL:
1.5g；
The volume mass ratio of acetone and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3) mL:
1.5g；
The volume mass ratio of ethyl acetate and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3)
mL:1.5g；
N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, bis- hexyloxy benzene -1,4- diacetyl of 2,5- in step 2
The mass ratio of nitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide is 0.2g:0.15g:0.12g:5mL；
The volume mass ratio of solvent and N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer in step 2 is 20mL:
0.2g；Solvent is that 1:1 is mixed by volume for the tert-butyl alcohol and tetrahydrofuran.
It is as the preparation method of electrochromic material to styrene support derivative P1 containing carbazole structure and the poly- of cyano: will
Poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl
Oxygroup)) phenylethylene is dissolved in organic solvent, obtain poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- first
Oxygroup -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl oxy)) phenylethylene solution, then by poly- 1- (N- carbazole-N '-hexichol
Base-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl oxy)) phenylethylene solution
Film is carried out on electro-conductive glass, obtains electrochromic material；Wherein organic solvent is tetrahydrofuran, chlorobenzene, N, N '-diformazan
Yl acetamide or N, N '-dimethylformamide.
It is as the preparation method of electroluminescent fluorescent materials to styrene support derivative P1 containing carbazole structure and the poly- of cyano: will
Poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl
Oxygroup)) phenylethylene is dissolved in organic solvent, obtain poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- first
Oxygroup -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl oxy)) phenylethylene solution, then by poly- 1- (N- carbazole-N '-hexichol
Base-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl oxy)) phenylethylene solution
Film is carried out on electro-conductive glass, obtains electroluminescent fluorescent materials；Wherein organic solvent is tetrahydrofuran, chlorobenzene, N, N '-diformazan
Yl acetamide or N, N '-dimethylformamide.
The poly- method to styrene support derivative P1 detection explosive containing carbazole structure and cyano are as follows: by poly- 1- (N- click
Azoles-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl oxy)) benzene
Base ethylene is dissolved in organic solvent, obtains poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- methoxyl group -4-
(1- cyanoacrylate base) -5- (2- ethyl hexyl oxy)) phenylethylene solution, then solution to be detected is added dropwise in by poly- 1- (N-
Carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl oxy))
In phenylethylene solution, detected using the variation of solution fluorescence intensity in solution with the presence or absence of explosive；Wherein organic solvent
For methylene chloride or THF.
The poly- application side to styrene support derivative P1 as acidic and alkaline gas detection material containing carbazole structure and cyano
Method are as follows: by poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyanoacrylate base) -5-
(2- ethyl hexyl oxy)) phenylethylene is dissolved in organic solvent, obtain poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyanogen
Base -2- (2- methoxyl group -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl oxy)) phenylethylene solution, drips poly- 1- (N- click
Azoles-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyanoacrylate base) -5- (2- ethyl hexyl oxy)) benzene
For base vinyl solution on silica gel plate, solvent is evaporated removing by drying, is observed and recorded fluorescence in the UV lamp, is gathered using on silica gel plate
The variation of object fluorescence power is closed to detect whether that, there are acidic and alkaline gas, organic solvent is methylene chloride or THF.
Test poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyanoacrylate
Base) -5- (2- ethyl hexyl oxy)) phenylethylene dissolubility, the results are shown in Table 1, and solubility is to be dissolved in 1 with 10 milligrams of samples
It is measured in milliliter solution.++, dissolve in room temperature.+, it dissolves by heating.The part of+- during heating is solvable.It is insoluble.By table
1 it is found that the present embodiment poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2- methoxyl group -4- (1- cyano third
Alkenyl) -5- (2- ethyl hexyl oxy)) phenylethylene have good dissolubility.
Table 1
Embodiment two: poly- as follows to styrene support derivative P2 structural formula containing carbazole structure and cyano:
,
The integer that n is 3~10 in formula.
The present embodiment containing carbazole structure and cyano it is poly- to styrene support derivative P2's the preparation method comprises the following steps:
One, the monomer of N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine containing carbazole structure is synthesized
By (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of N- bis- with except water-toluene mixes, logical nitrogen is vacuumized, then be placed in low temperature
In reaction kettle, -70 degrees Celsius are cooled to, reducing agent diisobutyl aluminium hydride is added, stirs 10min under -70 degrees celsius, closes
Cooling valve is closed, is kept stirring until temperature of reaction system time is warmed to room temperature, taking-up reaction system, which is placed on magnetic stirring apparatus, to be continued
Stirring sequentially adds the ammonia spirit of acetone, ethyl acetate, ammonium chloride, and obvious layering occurs in stirring to system, and upper layer is
There are solid precipitation in supernatant liquid, lower layer, system are filtered, and gained liquid revolving obtains N- bis- (4- benzaldehyde)-N '-carbazole benzene
Diamines；
Two, it prepares and derivative is supportted to styrene containing carbazole structure and the poly- of cyano
By N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, solvent, the bis- hexyloxy benzene -1,4- diacetyl containing 2,5-
Nitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide are added in there-necked flask, are warming up to 50 DEG C and are stirred at reflux 20min, after cooling
It pours into the methanol with acetic acid, refilter and wash solid up to methanol is without color with methanol, the solid vacuum that will be obtained
It is dry, obtain poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2,5- bis- hexyloxy -4- (1- cyanoacrylates
Base)) phenylethylene, i.e., support derivative P2 to styrene containing carbazole structure and the poly- of cyano；
Wherein the volume ratio of (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of the N- bis- in step 1 and diisobutyl aluminium hydride is
1.5g:(2-3)mL；
Remove water-toluene and the volume mass ratio of N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are 10mL:
1.5g；
The volume mass ratio of acetone and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3) mL:
1.5g；
The volume mass ratio of ethyl acetate and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3)
mL:1.5g；
N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, bis- hexyloxy benzene -1,4- diacetyl of 2,5- in step 2
The mass ratio of nitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide is 0.2g:0.15g:0.12g:5mL；
The volume mass ratio of solvent and N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer in step 2 is 20mL:
0.2g；Solvent is that 1:1 is mixed by volume for the tert-butyl alcohol and tetrahydrofuran.
It is as the preparation method of electrochromic material to styrene support derivative P2 containing carbazole structure and the poly- of cyano: will
Poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (bis- hexyloxy -4- of 2,5- (1- cyanoacrylate base)) phenyl second
Alkene is dissolved in organic solvent, obtains poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2,5- bis- hexyloxy -4-
(1- cyanoacrylate base)) phenylethylene solution, then by poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2,
Bis- hexyloxy -4- of 5- (1- cyanoacrylate base)) phenylethylene solution carries out film on electro-conductive glass, obtain electrochromism material
Material；Wherein organic solvent is tetrahydrofuran, chlorobenzene, N, N '-dimethyl acetamide or N, N '-dimethylformamide.
It is as the preparation method of electroluminescent fluorescent materials to styrene support derivative P2 containing carbazole structure and the poly- of cyano: will
Poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (bis- hexyloxy -4- of 2,5- (1- cyanoacrylate base)) phenyl second
Alkene is dissolved in organic solvent, obtains poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2,5- bis- hexyloxy -4-
(1- cyanoacrylate base)) phenylethylene solution, then by poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2,
Bis- hexyloxy -4- of 5- (1- cyanoacrylate base)) phenylethylene solution carries out film on electro-conductive glass, obtain electroluminescent fluorescent material
Material；Wherein organic solvent is tetrahydrofuran, chlorobenzene, N, N '-dimethyl acetamide or N, N '-dimethylformamide.
The poly- application side to styrene support derivative P2 as acidic and alkaline gas detection material containing carbazole structure and cyano
Method are as follows: by poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (bis- hexyloxy -4- of 2,5- (1- cyanoacrylate base))
Phenylethylene is dissolved in organic solvent, obtains poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2,5- bis- own oxygen
Base -4- (1- cyanoacrylate base)) phenylethylene solution, drips poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -
For 2- (2,5- bis- hexyloxy -4- (1- cyanoacrylate base)) phenylethylene solution on silica gel plate, solvent is evaporated removing by drying,
Fluorescence is observed and recorded under ultraviolet lamp, detects whether that there are acid-base property gas using the variation of polymer fluorescent power on silica gel plate
Body, organic solvent are methylene chloride or THF.
The poly- application method to styrene support derivative P2 as metal ion detection containing carbazole structure and cyano are as follows: will
Poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (bis- hexyloxy -4- of 2,5- (1- cyanoacrylate base)) phenyl second
Alkene is dissolved in protic organic solvent, obtains poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (2,5- bis- own oxygen
Base -4- (1- cyanoacrylate base)) phenylethylene solution, then aqueous solution to be measured is added dropwise in poly- 1- (N- carbazole-N '-diphenyl -
Phenylenediamine) in -2- cyano -2- (2,5- bis- hexyloxy -4- (1- cyanoacrylate base)) phenylethylene solution, it is strong using solution fluorescence
The variation of degree carrys out the metal ion in specific detection solution；Protic organic solvent is THF or DMF.
Test poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (bis- hexyloxy -4- (1- cyano third of 2,5-
Alkenyl)) dissolubility of phenylethylene, the results are shown in Table 2, and solubility is to be dissolved in 1 milliliter of solution to measure with 10 milligrams of samples
's.++, dissolve in room temperature.+, it dissolves by heating.The part of+- during heating is solvable.It is insoluble.As shown in Table 2, the present embodiment
Poly- 1- (N- carbazole-N '-diphenyl-phenylenediamine) -2- cyano -2- (bis- hexyloxy -4- of 2,5- (1- cyanoacrylate base)) phenyl
Ethylene has good dissolubility.
Table 2
It will form a film containing carbazole structure and the poly- of cyano to styrene support derivative coating, its performance tested:
Fig. 1 is the poly- INFRARED SPECTRUM that derivative is supportted to styrene containing carbazole structure and cyano prepared by embodiment one and two
Figure；From fig. 1, it can be seen that in 2220-2250cm-1The characteristic absorption peak at place, corresponding to the stretching vibration peak of C-N key in cyano,
2915-2918cm-1Neighbouring peak is the stretching vibration peak of methyl, in 1670-1690cm-1The characteristic peak at place is stretching for C=C key
Contracting vibration peak.
Fig. 2 is the poly- proton magnetic spectrum that derivative P1 is supportted to styrene containing carbazole structure and cyano prepared by embodiment one
Figure；Fig. 3 is the poly- hydrogen nuclear magnetic spectrogram that derivative P2 is supportted to styrene containing carbazole structure and cyano prepared by embodiment two；From figure
2 and 3 it is found that δ=7.11-8.18ppm is the chemical shift of H on phenyl ring, specifically as figure indicates.
Fig. 4 is the poly- cyclic voltammetric that derivative P1 is supportted to styrene containing carbazole structure and cyano prepared by embodiment one
Figure；Fig. 5 is the poly- cyclic voltammogram that derivative P2 is supportted to styrene containing carbazole structure and cyano prepared by embodiment two；From figure
4 and Fig. 5 is easily oxidized reduction it is found that it has lower initial potential and reduction potential, there are two oxidation peak and theoretical speculates
As a result it is consistent.
Fig. 6 is the poly- electrochromism that derivative P1 is supportted to styrene containing carbazole structure and cyano prepared by embodiment one
Figure；Fig. 7 is the poly- electrochromism figure that derivative P2 is supportted to styrene containing carbazole structure and cyano prepared by embodiment two；From figure
6 and Fig. 7 has suction to styrene support derivative P1 containing carbazole structure and the poly- of cyano it is found that before not applying voltage at 365nm
Peak is received, when applied voltage is from 0.0V to 1.7V, absorption peak is gradually increasing at 365nm, new absorption peak occurs simultaneously at 565nm
It is gradually increasing；Electrochromic color is from light yellow to navy blue；P2 has absorption peak before no applied voltage at 412nm, when
When applied voltage is from 0.0V to 1.5V, absorption peak is gradually reduced at 412nm, occur at the 1332nm new absorption peak and gradually on
It rises, electrochromic color is from light yellow to navy blue.
Fig. 8 is the poly- electroluminescent fluorescent that derivative P1 is supportted to styrene containing carbazole structure and cyano prepared by embodiment one
Figure；Fig. 9 is the poly- electroluminescent fluorescent figure that derivative P2 is supportted to styrene containing carbazole structure and cyano prepared by embodiment one；Not
Before applying voltage, fluorescence intensity reaches highest level, and as applied voltage increases, the fluorescence intensity of polymer P 1 is gradually reduced,
P2 fluorescence intensity, which is gradually reduced, finally almost levels off to zero.
Figure 10 is the poly- thermal weight loss that derivative is supportted to styrene containing carbazole structure and cyano prepared by embodiment one and two
Curve graph；As can be seen from Figure 10, styrene support derivative P1 is about started greatly at 400 DEG C or so containing carbazole structure and the poly- of cyano
Amount is weightless, and P2 is when temperature is at 350 DEG C, weight loss 5%, when temperature is 392 DEG C, weight loss 10%；When temperature is 437
DEG C when, weight loss 20%, when temperature reaches 800 DEG C, embodiment one is prepared poly- to styrene containing carbazole structure and cyano
Supportting derivative carbon residual volume is 47%；P1 is when temperature is at 340 DEG C, weight loss 5%, and when temperature is 404 DEG C, weight loss is
10%；When temperature is 437 DEG C, weight loss 20% is poly- to benzene second containing carbazole structure and cyano when temperature reaches 800 DEG C
It is 40% that alkene, which supports derivative carbon residual volume, has preferable high temperature resistance.
Figure 11 is that the poly- of the cyano containing carbazole structure prepared by embodiment one supports derivative P1 to volatility soda acid to styrene
The fluorogram of gas response；It obviously dies down when with ten seconds post-consumer polymer fluorescence of sour gas contact number as seen from Figure 11,
Fluorescence intensity on the basis of this with ten seconds polymer of alkaline gas contact number is gradually replied.
Figure 12 is ringing to styrene support derivative P1 to picric acid containing carbazole structure and the poly- of cyano for the preparation of embodiment one
The fluorogram answered；As seen from Figure 12 with the increase of bitter taste acid concentration, the fluorescence intensity of polymer solution gradually weakens.
Figure 13 is responding to styrene support derivative P1 to TNT containing carbazole structure and the poly- of cyano for the preparation of embodiment one
Fluorogram；As seen from Figure 13 with the increase of TNT concentration, the fluorescence intensity of polymer solution gradually weakens.
Figure 14 is ringing to styrene support derivative P2 to aluminium ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.30mL aluminium ion is added；
Figure 15 is ringing to styrene support derivative P2 to bismuth ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.45mL bismuth ion is added；
Figure 16 is ringing to styrene support derivative P2 to cadmium ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.4mL cadmium ion is added；
Figure 17 is ringing to styrene support derivative P2 to cobalt ions containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.4mL cobalt ions is added；
Figure 18 is ringing to styrene support derivative P2 to chromium ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.4mL chromium ion is added；
Figure 19 is ringing to styrene support derivative P2 to copper ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.35mL copper ion is added；
Figure 20 is ringing to styrene support derivative P2 to iron ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.4mL iron ion is added；
Figure 21 is ringing to styrene support derivative P2 to potassium ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.4mL potassium ion is added；
Figure 22 is ringing to styrene support derivative P2 to magnesium ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.4mL magnesium ion is added；
Figure 23 is ringing to styrene support derivative P2 to nickel ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.35mL nickel ion is added；
Figure 24 is ringing to styrene support derivative P2 to lead ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered；Curve is respectively fluorescence intensity curves when 0-0.4mL lead ion is added；
Figure 25 is ringing to styrene support derivative P2 to lead ion containing carbazole structure and the poly- of cyano for the preparation of embodiment two
The fluorogram answered, curve are respectively fluorescence intensity curves when 0-0.35mL lead ion is added.
The present embodiment is altogether tested 12 metal ion species, and wherein metal ion solution is with 10^-5mol/L's
Concentration carries out this test, by Figure 14-25 it can be seen that P2 is for Cu2+And Al3+There is special identification function, with Cu2+Content liter
Height, P2 fluorescence intensity weaken；With Al3+Content increases, and P2 fluorescence intensity first enhances to be weakened afterwards；And for other metal ions with
Content increase, the trend of enhancing is presented in P2 fluorescence intensity.
By above-mentioned test it is found that it is manufactured in the present embodiment it is poly- to styrene support derivative with underslung dialdehyde-based carbazole and
The reacting dicyanobenzenes even containing long alkoxy is made, and the strong effect power between polymer molecular chain can be effectively reduced,
Increase the dissolubility of polymer, while carbazole is easily formed radical cation and shows carbazole different from middle condition.This hair
There is very high performance resistant to high temperature to styrene support derivative containing carbazole structure and the poly- of cyano in bright, generally in the gas of nitrogen
Under atmosphere, decomposition temperature is suitble to use in the devices at 350 DEG C or more.By the present invention containing the poly- to benzene second of carbazole structure and cyano
Film is made in alkene support derivant material, does not have big clustering phenomena and Fragmentation Phenomena on ITO substrate, also shows on ITO substrate
Good wet ability is shown.This means that PPV material has good film Formation and characteristics, can be used to make the thin of large area
Film.After application of a voltage, the transmitance of film still can achieve 40%, and transparency is relatively good, and apply alive process
Middle thin polymer film is able to maintain circulating ring and has good stability, and is recycled 20 times or more and transparency is constant.
The poly- electrochromic property to styrene support derivative of the present embodiment has following superior in practical applications
Property: (1) there is good electrochemical redox invertibity, is still able to maintain after tens redox cycles reversible；
(2) response time of color change is fast, after making alive, can change colour rapidly within 0.8 second；(3) variation of color is
Reversible；(4) color change high sensitivity；(5) there is higher cycle life；(6) material discoloration front and back has preferable chemistry steady
It is qualitative, under normal temperature and pressure, it may be stabilized in air.(7) derivative P1 is supportted to styrene containing carbazole structure and the poly- of cyano
To acidic and alkaline gas and explosive TNT, picric acid has response；Derivative P2 is supportted to styrene containing carbazole structure and the poly- of cyano
There is response to acidic and alkaline gas and metal ion.
Claims (10)
1. poly- containing carbazole structure and cyano supports derivative to styrene, it is characterised in that poly- to benzene containing carbazole structure and cyano
Vinylene derivative is poly- poly- pair to styrene support derivative P1 or containing carbazole structure and cyano containing carbazole structure and cyano
Styrene supports derivative P2；
The poly- structural formula for supportting derivative P1 to styrene wherein containing carbazole structure and cyano is as follows:
,
The integer that n is 3~10 in formula；
It is wherein poly- as follows to styrene support derivative P2 structural formula containing carbazole structure and cyano:
,
The integer that n is 3~10 in formula.
2. preparing the poly- method to styrene support derivative containing carbazole structure and cyano as described in claim 1, feature
Be containing carbazole structure and cyano it is poly- to styrene support derivative P1's the preparation method comprises the following steps:
One, the monomer of N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine containing carbazole structure is synthesized
By (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of N- bis- with except water-toluene mixes, logical nitrogen is vacuumized, then be placed in low-temp reaction
In kettle, -70 degrees Celsius are cooled to, reducing agent diisobutyl aluminium hydride is added, 10min is stirred under -70 degrees celsius, closes drop
Warm valve is kept stirring until temperature of reaction system time is warmed to room temperature, and taking-up reaction system, which is placed in, to be continued to stir on magnetic stirring apparatus,
The ammonia spirit of acetone, ethyl acetate, ammonium chloride is sequentially added, obvious layering occurs in stirring to system, and upper layer is clarification
There are solid precipitation in liquid, lower layer, system are filtered, and gained liquid revolving obtains (4- benzaldehyde)-the N '-carbazole of N- bis- benzene two
Amine；
Two, it prepares and derivative is supportted to styrene containing carbazole structure and the poly- of cyano
By N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, solvent, 2- (2- ethyl hexyl oxy) -5- methoxy containing cyano
Base-Isosorbide-5-Nitrae-benzene diacetonitrile, potassium tert-butoxide and catalyst tetrabutylammonium hydroxide are added in there-necked flask, are warming up to 50 DEG C and are stirred at reflux
20min is poured into the methanol with acetic acid after cooling down, and is refiltered and is washed solid with methanol until methanol is incited somebody to action without color
The solid vacuum drying arrived obtains supportting derivative P1 to styrene containing carbazole structure and the poly- of cyano；
Wherein the volume ratio of (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of the N- bis- in step 1 and diisobutyl aluminium hydride is (1.0-
1.5)g:(2-3)mL；
Remove water-toluene and the volume mass ratio of N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are 10mL:(1.0-
1.5)g；
The volume mass ratio of acetone and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3) mL:(1.0-
1.5)g；
The volume mass ratio of ethyl acetate and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3) mL:
(1.0-1.5)g；
N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, bis- hexyloxy benzene -1,4- diethyl acyl cyanide of 2,5-, uncle in step 2
Butanol potassium and the mass ratio of catalyst tetrabutylammonium hydroxide are 0.2g:0.15g:0.12g:5mL；
The volume mass ratio of solvent and N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer in step 2 is 20mL:0.2g；
Solvent is that 1:1 is mixed by volume for the tert-butyl alcohol and tetrahydrofuran.
3. preparing the poly- method to styrene support derivative containing carbazole structure and cyano as described in claim 1, feature
Be containing carbazole structure and cyano it is poly- to styrene support derivative P2's the preparation method comprises the following steps:
One, the monomer of N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine containing carbazole structure is synthesized
By (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of N- bis- with except water-toluene mixes, logical nitrogen is vacuumized, then be placed in low-temp reaction
In kettle, -70 degrees Celsius are cooled to, reducing agent diisobutyl aluminium hydride is added, 10min is stirred under -70 degrees celsius, closes drop
Warm valve is kept stirring until temperature of reaction system time is warmed to room temperature, and taking-up reaction system, which is placed in, to be continued to stir on magnetic stirring apparatus,
The ammonia spirit of acetone, ethyl acetate, ammonium chloride is sequentially added, obvious layering occurs in stirring to system, and upper layer is clarification
There are solid precipitation in liquid, lower layer, system are filtered, and gained liquid revolving obtains (4- benzaldehyde)-the N '-carbazole of N- bis- benzene two
Amine；
Two, it prepares and derivative is supportted to styrene containing carbazole structure and the poly- of cyano
By N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, solvent, contain bis- hexyloxy benzene -1,4- diethyl acyl cyanide of 2,5-, uncle
Butanol potassium and catalyst tetrabutylammonium hydroxide are added in there-necked flask, are warming up to 50 DEG C and are stirred at reflux 20min, pour into use after cooling
In the methanol of acetic acid, refilters and wash solid with methanol until obtained solid is dried in vacuo, obtains without color by methanol
Derivative P2 is supportted to styrene to containing carbazole structure and the poly- of cyano；
Wherein the volume ratio of (4- benzene first cyanogen)-the N '-carbazole phenylenediamine of the N- bis- in step 1 and diisobutyl aluminium hydride is (1.0-
1.5)g:(2-3)mL；
Remove water-toluene and the volume mass ratio of N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are 10mL:(1.0-
1.5)g；
The volume mass ratio of acetone and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3) mL:(1.0-
1.5)g；
The volume mass ratio of ethyl acetate and N- bis- (4- benzene first cyanogen)-N '-carbazole phenylenediamine in step 1 are as follows: (2-3) mL:
(1.0-1.5)g；
N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer, bis- hexyloxy benzene -1,4- diethyl acyl cyanide of 2,5-, uncle in step 2
Butanol potassium and the mass ratio of catalyst tetrabutylammonium hydroxide are 0.2g:0.15g:0.12g:5mL；
The volume mass ratio of solvent and N- bis- (4- benzaldehyde)-N '-carbazole phenylenediamine monomer in step 2 is 20mL:0.2g；
Solvent is that 1:1 is mixed by volume for the tert-butyl alcohol and tetrahydrofuran.
4. the poly- application to styrene support derivative containing carbazole structure and cyano as described in claim 1, it is characterised in that
The poly- application to styrene support derivative as photoelectric material containing carbazole structure and cyano.
5. the poly- application to styrene support derivative according to claim 4 containing carbazole structure and cyano, feature exist
In the poly- application method to styrene support derivative as photoelectric material containing carbazole structure and cyano: carbazole structure and cyanogen will be contained
The poly- of base is dissolved in organic solvent styrene support derivative, obtains supportting derivative to styrene containing carbazole structure and the poly- of cyano
Then solution will carry out film to styrene support derivative containing carbazole structure and the poly- of cyano on electro-conductive glass, obtain photoelectricity
Material；Wherein organic solvent is tetrahydrofuran, chlorobenzene, N, N '-dimethyl acetamide or N, N '-dimethylformamide.
6. the poly- application to styrene support derivative containing carbazole structure and cyano as described in claim 1, it is characterised in that
The poly- application to styrene support derivative P2 as metal ion detection material containing carbazole structure and cyano.
7. the poly- application to styrene support derivative according to claim 6 containing carbazole structure and cyano, feature exist
In the poly- application method to styrene support derivative P2 as metal ion detection containing carbazole structure and cyano are as follows: carbazole will be contained
Structure and the poly- of cyano are dissolved in protic organic solvent to styrene support derivative P2, obtain poly- pair containing carbazole structure and cyano
Styrene supports derivative solution, and then aqueous solution to be measured is added dropwise and supports in derivative solution in poly- to styrene, glimmering using solution
The variation of luminous intensity carrys out the metal ion in specific detection solution；Protic organic solvent is THF or DMF.
8. the poly- application to styrene support derivative containing carbazole structure and cyano as described in claim 1, it is characterised in that
The poly- application to styrene support derivative as acidic and alkaline gas detection material containing carbazole structure and cyano.
9. the poly- application to styrene support derivative according to claim 8 containing carbazole structure and cyano, feature exist
In the poly- application method to styrene support derivative as acidic and alkaline gas detection material containing carbazole structure and cyano are as follows: will contain
The poly- of carbazole structure and cyano is dissolved in organic solvent to styrene support derivative, obtains poly- to benzene second containing carbazole structure and cyano
Alkene supports derivative solution, drips and supports derivative solution on silica gel plate to styrene containing carbazole structure and the poly- of cyano, dries
Solvent is evaporated and is removed, the bottleneck of under test gas is subsequently placed in, observes and records fluorescence in the UV lamp, using polymerizeing on silica gel plate
The variation of object fluorescence power detects whether that there are acidic and alkaline gas, organic solvent is methylene chloride or THF.
10. the poly- application to styrene support derivative containing carbazole structure and cyano as described in claim 1, it is characterised in that
The poly- application to styrene support derivative P1 in explosive detection containing carbazole structure and cyano.
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