CN114539079B - 含有四苯基乙烯-双芳胺结构的二胺单体、制备方法及其在超稳定电致变色材料中的应用 - Google Patents
含有四苯基乙烯-双芳胺结构的二胺单体、制备方法及其在超稳定电致变色材料中的应用 Download PDFInfo
- Publication number
- CN114539079B CN114539079B CN202210052799.3A CN202210052799A CN114539079B CN 114539079 B CN114539079 B CN 114539079B CN 202210052799 A CN202210052799 A CN 202210052799A CN 114539079 B CN114539079 B CN 114539079B
- Authority
- CN
- China
- Prior art keywords
- polyimide
- bis
- diamine monomer
- methoxyphenyl
- tetraphenyl ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 28
- 150000004985 diamines Chemical class 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004642 Polyimide Substances 0.000 claims abstract description 34
- 229920001721 polyimide Polymers 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000010992 reflux Methods 0.000 claims description 23
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 claims description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims 1
- FVIQSVDKVHAYRT-UHFFFAOYSA-N COC(C=C1)=CC=C1N(C(C=C1)=CC=C1C(C(C=C1)=CC=C1N)=C(C(C=C1)=CC=C1N)C(C=C1)=CC=C1N(C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC Chemical compound COC(C=C1)=CC=C1N(C(C=C1)=CC=C1C(C(C=C1)=CC=C1N)=C(C(C=C1)=CC=C1N)C(C=C1)=CC=C1N(C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC)C(C=C1)=CC=C1OC FVIQSVDKVHAYRT-UHFFFAOYSA-N 0.000 abstract description 15
- -1 biaryl amine Chemical class 0.000 abstract description 12
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000007323 disproportionation reaction Methods 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 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 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- VCOONNWIINSFBA-UHFFFAOYSA-N 4-methoxy-n-(4-methoxyphenyl)aniline Chemical compound C1=CC(OC)=CC=C1NC1=CC=C(OC)C=C1 VCOONNWIINSFBA-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 description 1
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/92—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the nitrogen atom of at least one of the amino groups being further bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- C08G73/12—Unsaturated polyimide precursors
- C08G73/123—Unsaturated polyimide precursors the unsaturated precursors comprising halogen-containing substituents
-
- 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
- C08G73/12—Unsaturated polyimide precursors
- C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
-
- 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
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
- C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic containing oxygen in the form of ether bonds in the main chain
-
- 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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- 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
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—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
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
含有四苯基乙烯‑双芳胺结构的二胺单体、制备方法及其在超稳定电致变色材料中的应用，属于有机化合物制备技术领域。本发明所述的一种含有四苯基乙烯‑双芳胺结构的二胺单体，该单体的命名为N‑{4‑[1,2‑双(4‑氨基苯基)‑2‑{4‑[双(4‑甲氧基苯基)氨基]苯基}乙烯基]苯基}‑4‑甲氧基‑N‑(4‑甲氧基苯基)苯胺。本发明采用将扭转的四苯基乙烯结构和螺旋桨型双芳胺结合到一起，以二胺单体的形式引入聚酰亚胺中，四苯基乙烯较高的下吸光系数有效地提供了全黑的电致变色颜色，同时利用歧化作用也可以降低聚酰亚胺的氧化电位，通过此方法可以显著提高黑色电致变色聚合物材料的稳定性。
Description
技术领域
本发明属于有机化合物制备技术领域，具体涉及一种含有四苯基乙烯-双芳胺结构的二胺单体、制备方法及其在制备具有超高稳定性和电致变色功能的聚酰亚胺中的应用。
背景技术
电致变色是指在外加电场的情况下材料能发生颜色的改变，同时在施加反向电场的情况下又能恢复成原本颜色的现象。双芳胺基团在外加电场的作用下，容易形成稳定的阳离子自由基，产生颜色的变化。而在众多电致变色材料中，由透明状态变为黑色的电致变色材料，由于其巨大的应用前景，长久以来一直受到广泛的研究。
相较于无机材料，有机高分子聚合物由于其低廉的价格和易加工等特点，一直受到科研人员的关注。而聚酰亚胺材料更是研究的热门。目前，获得黑色高分子电致变色材料的方法大多是通过混合多种色团，利用不同色团吸收光范围不同，通过叠加光谱的方式获得覆盖全部可见光范围，也就是获得黑色。然而这种方法往往会产生较高的电致变色氧化电位。较高的电致变色氧化电位使得材料的稳定性受到很大的影响，严重限制了黑色电致变色材料的应用。
发明内容
为了解决上述问题，本发明将二苯胺与四苯基乙烯相结合，以二胺单体的形式引入聚酰亚胺中，通过四苯基乙烯连接的双芳香胺具有较高的消光系数，电化学氧化时可以产生纯粹的黑颜色。此外，四苯基乙烯的歧化现象，有助于降低电化学氧化电位，实现较高的循环稳定性。
本发明所述的一种含有四苯基乙烯-双芳胺结构的二胺单体，该单体的命名为N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺，其结构式如式(Ⅰ)所示：
本发明所述的一种含有四苯基乙烯-双芳胺结构的二胺单体的制备方法，其步骤如下：
1)以摩尔比(1～2)：(2～4)：(1～2)的4-溴二苯基酮、锌粉和四氯化钛为原料，四氢呋喃为溶剂，反应体系中固含量为10～20％；先在四氢呋喃中加入4-溴二苯基酮和锌粉，冷却至-85～-78℃后滴加四氯化钛，在搅拌及氮气保护下升温至 80～90℃下反应12～24h，再冷却至室温后加入10wt％碳酸钾水溶液淬灭反应；将反应液过滤后收集有机层，滤液水层用乙酸乙酯萃取3～5次，合并有机相并用硫酸镁干燥过夜，蒸出乙酸乙酯和四氢呋喃后得到固体粗产物，粗产物用甲醇重结晶、过滤干燥后得到白色1,2-二(4-溴)-1,2-二苯乙烯晶体，产率为50～60％；
反应式如下：
2)以摩尔比(1～3)：(1～3)：(1～2)的1,2-二(4-溴)-1,2-二苯乙烯、硝酸和醋酸为原料，与醋酸体积比为20：1～5的二氯甲烷为溶剂，反应体系中固含量为10～20％；在搅拌及氮气保护，先将1,2-二(4-溴)-1,2-二苯乙烯和醋酸溶解到二氯甲烷中，然后缓慢向体系滴加硝酸，-10～0℃下反应6～12h；反应液出料于冰水中，乙酸乙酯萃取 3～5次，合并有机相，真空蒸出溶剂后干燥，甲醇重结晶后得到黄色1,2-双(4-溴苯基)-1,2-双(4-硝基苯基)乙烷晶体，产率为50～85％；
反应式如下：
3)以摩尔比(1～2)：(3～4)：(3～5)：(0.1～0.5)：(0.3～0.6)的4-甲氧基-N-(4-甲氧基苯基)苯胺、1,2-双(4-溴苯基)-1,2-双(4-硝基苯基)乙烷、叔丁醇钾、醋酸钯和三丁基膦为原料，甲苯为溶剂，反应体系固含量为5～20％；搅拌及氮气保护下，加热至回流后反应24～48h；反应液出料于石油醚中，产物水洗多次后烘干，甲醇重结晶、过滤干燥后得到橘黄色N-{4-[-2-{4-[双(4-甲氧基苯基)氨基]苯基}-1,2-双(4-硝基苯基)乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺晶体，产率为50～85％；
反应式如下：
4)将N-{4-[-2-{4-[双(4-甲氧基苯基)氨基]苯基}-1,2-双(4-硝基苯基)乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)和钯碳催化剂(Pd/C)按质量比5～10：1的比例加入到1,4-二氧六环中，反应体系固含量为5～10％；氮气保护下搅拌均匀得到悬浊液，加热至回流，然后向悬浊液中缓慢滴加入质量分数80wt％的水合肼溶液，水合肼与 N-{4-[-2-{4-[双(4-甲氧基苯基)氨基]苯基}-1,2-双(4-硝基苯基)乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)的摩尔比为1～3：1，继续回流搅拌12～48h；反应完毕后趁热过滤反应液去除Pd/C后出料到冰水中，烘干后用体积比1：1～3的乙酸乙酯和石油醚进行柱层析，得到产物N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺，即本发明所述的含有四苯基乙烯 -三苯胺结构的二胺单体，经过质谱、核磁测试，证明了所得化合物的结构，产率为 70～90％。
反应式如下：
本发明所述的含有四苯基乙烯-双芳胺结构的二胺单体可以与不同的酸酐单体反应制备得到电致变色聚酰亚胺，制备方法如下：
以摩尔比为1～3：1的含有四苯基乙烯-双芳胺胺结构的二胺单体和酸酐单体为原料，以N,N-二甲基乙酰胺为溶剂，反应体系固含量为15～35％，室温下反应12～24h 后向体系中加入二胺单体摩尔数30～50倍的醋酸酐和20～30倍的吡啶，升温至 100～120℃反应3～5h，冷却至室温后出料到乙醇后用水和乙醇回流洗涤数遍，真空干燥后得到聚酰亚胺产物。
其中，酸酐单体包括但不限于均苯四甲酸二酐、3,3',4,4'-二苯酮四酸二酐、4,4'- 联苯醚二酐、六氟二酐、1,2,4,5-环己烷四甲酸二酐。
聚酰亚胺合成反应式如下：
其中n为10～80之间的整数，得到的聚酰亚胺聚合物的数均分子量Mn为 40000～100000，重均分子量为40000～100000；
R为中的一种。本发明的有益效果：
本发明采用将扭转的四苯基乙烯结构和螺旋桨型双芳胺结合到一起，以二胺单体的形式引入聚酰亚胺中，四苯基乙烯较高的下吸光系数有效地提供了全黑的电致变色颜色，同时利用歧化作用也可以降低聚酰亚胺的氧化电位，通过此方法可以显著提高黑色电致变色聚合物材料的稳定性。
附图说明
图1：实施例1制备的N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺的核磁谱图。
图2：实施例1制备的N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺的质谱图。
图3：实施例6制备的1,2,4,5-环己烷四甲酸二酐型聚酰亚胺的红外图。
图4：实施例6制备的1,2,4,5-环己烷四甲酸二酐型聚酰亚胺的TGA曲线图。
图5：实施例6制备的1,2,4,5-环己烷四甲酸二酐型聚酰亚胺的循环伏安曲线图。
图6：实施例6制备的1,2,4,5-环己烷四甲酸二酐型聚酰亚胺的电致变色谱图。
图7：实施例6制备的1,2,4,5-环己烷四甲酸二酐型聚酰亚胺的电致变色稳定性谱图。
具体实施方式
实施例1：N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺的制备
第一步反应：在装有机械搅拌的1000mL的三颈烧瓶中加入24g的4-溴二苯甲酮、15.7g锌粉，500mL四氢呋喃后冷却至-78℃，搅拌及氮气保护下，缓慢滴加23g 的四氯化钛，恢复至室温后加热至85℃反应24h。混合物再冷却至室温后，用500mL、 10wt％碳酸钾水溶液淬灭反应，过滤后收集有机层，滤液水层用乙酸乙酯萃取三次，合并有机相并用硫酸镁干燥过夜后，蒸出乙酸乙酯和四氢呋喃后得到固体粗产物，粗产物用甲醇重结晶，过滤干燥后得到白色晶体1,2-二(4-溴)-1,2-二苯乙烯12.4g，产率51.6％。
第二步反应：在500mL的三口瓶中，加入1,2-二(4-溴)-1,2-二苯乙烯5g，醋酸20mL，300mL的二氯甲烷，搅拌及氮气保护下冷却至0℃，然后逐渐滴加25mL硝酸，反应12h后，反应液出料到冰水中，水层用乙酸乙酯萃取4次，合并有机相，真空蒸出溶剂后，置于真空烘箱充分干燥。干燥产物用甲醇重结晶后得到黄色1,2- 双(4-溴苯基)-1,2-双(4-硝基苯基)乙烷4.8g，产率73％。
第三步反应：在100mL的三口瓶中，加入1,2-双(4-溴苯基)-1,2-双(4-硝基苯基)乙烷3.56g，4-甲氧基-N-(4-甲氧基苯基)苯胺4g，醋酸钯0.133g，三叔丁基膦0.375g， 25mL的甲苯，在搅拌及氮气保护下加热至回流反应48h，反应液出料到石油醚中，产物水洗多次后烘干，用甲醇重结晶，过滤干燥得橘黄色晶体的N-{4-[-2-{4-[双(4- 甲氧基苯基)氨基]苯基}-1,2-双(4-硝基苯基)乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺4.72g，产率87.4％。
第四步反应：在100mL三口瓶中，加入N-{4-[-2-{4-[双(4-甲氧基苯基)氨基]苯基}-1,2-双(4-硝基苯基)乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺4g，钯碳催化剂0.7g，以50mL 1,4-二氧六环为溶剂，在搅拌及氮气保护下加热至回流，然后缓慢滴加10mL、80wt％水合肼溶液，继续回流反应12h；反应完毕后趁热过滤反应液去除Pd/C后出料到冰水中，烘干后用体积比1：2的乙酸乙酯和石油醚柱层析，得到淡棕色晶体N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基] 苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺3.2g，即本发明所述的含有四苯基乙烯-双芳胺结构的二胺单体，产率86.5％。
如图1所示的核磁谱图可以看出H原子的化学位移归属明确，且一一对应，证明了所得二胺单体的结构，且如图2所示的质谱图，其质量分布也与二胺单体符合。需要说明的是，本发明中N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺为顺反两种异构体的混合物。
实施例2：N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺制备均苯四甲酸二酐型聚酰亚胺。
向装有磁子、氮气进出口、温度计的三颈烧瓶中，加入实施例1制得的0.290g N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺和0.078g的均苯四甲酸二酐，加入4mL的N,N-二甲基乙酰胺(固含量27％)，室温反应24h后得到粘稠的聚酰胺酸，然后投入1.4mL醋酸酐和0.7mL吡啶，升温至110℃反应3h，反应完毕后，冷却至室温，出料至乙醇中得白色纤维状产物，乙醇回流洗涤30min，水回流洗涤一遍，乙醇回流洗涤30min，真空烘箱90℃烘干，得到均苯四甲酸二酐聚酰亚胺0.284g，产率81％。所得聚合物数均分子量Mn 59756，重均分子量Mw 54785，结构式如下：
实施例3：N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)对3,3',4,4'-二苯酮四酸二酐聚合制备聚酰亚胺
向装有磁子、氮气进出口、温度计的三颈烧瓶中，加入实施例1制得的0.29g N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基 -N-(4-甲氧基苯基)苯胺和0.112g的3,3',4,4'-二苯酮四酸二酐，加入4mL的N,N-二甲基乙酰胺，室温反应24h后得到粘稠的聚酰胺酸，然后投入1.4mL醋酸酐和0.7mL 吡啶，升温至110℃反应3h，反应完毕后，冷却至室温，出料至乙醇中得黄白色纤维状产物，乙醇回流洗涤30min，水回流洗涤一遍，乙醇回流洗涤30min，真空烘箱 90℃烘干，得到3,3',4,4'-二苯酮四酸二酐聚酰亚胺0.335g，产率88％。所得聚合物数均分子量Mn 58651，重均分子量Mw60059，结构式如下：
实施例4：N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺对,4，4'-联苯醚二酐聚合制备聚酰亚胺
向装有磁子、氮气进出口、温度计的三颈烧瓶中，加入实施例1制得的0.29g N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基 -N-(4-甲氧基苯基)苯胺和0.108g的,4，4'-联苯醚二酐，加入,4mL的N,N-二甲基乙酰胺，室温反应24h后得到粘稠的聚酰胺酸，然后投入1.4mL醋酸酐和0.7mL吡啶，升温至110℃反应3h，反应完毕后，冷却至室温，出料至乙醇中得白色纤维状产物，乙醇回流洗涤30min，水回流洗涤一遍，乙醇回流洗涤30min，真空烘箱90℃烘干，得到4，4'-联苯醚二酐聚酰亚胺0.354g，产率93％。所得聚合物数均分子量 Mn 52764，重均分子量Mw 53775，结构式如下：
实施例5：N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺对六氟二酐聚合制备聚酰亚胺。
向装有磁子、氮气进出口、温度计的三颈烧瓶中，加入实施例1制得的0.29g N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基 -N-(4-甲氧基苯基)苯胺和0.155g的六氟二酐，加入4mL的N,N-二甲基乙酰胺，室温反应24h后得到粘稠的聚酰胺酸，然后投入1.4mL醋酸酐和0.7mL吡啶，升温至 110℃反应3h，反应完毕后，冷却至室温，出料至乙醇中得黄色纤维状产物，乙醇回流洗涤30min，水回流洗涤一遍，乙醇回流洗涤30min，真空烘箱90℃烘干，得到对六氟二酐聚酰亚胺0.361g，产率85％。所得聚合物数均分子量Mn 67593，重均分子量Mw 66284，结构式如下：
实施例6：N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基-N-(4-甲氧基苯基)苯胺对1,2,4,5-环己烷四甲酸二酐聚合制备聚酰亚胺。
向装有磁子、氮气进出口、温度计的三颈烧瓶中，加入实施例1制得的0.29g N-{4-[1,2-双(4-氨基苯基)-2-{4-[双(4-甲氧基苯基)氨基]苯基}乙烯基]苯基}-4-甲氧基 -N-(4-甲氧基苯基)苯胺和0.078g的1,2,4,5-环己烷四甲酸二酐，加入4mL的N,N-二甲基乙酰胺，室温反24h后得到粘稠的聚酰胺酸，然后投入1.4mL醋酸酐和0.7mL 吡啶，升温至110℃反应3h，反应完毕后，冷却至室温，出料至乙醇中得白色纤维状产物，乙醇回流洗涤30min，水回流洗涤一遍，乙醇回流洗涤30min，真空烘箱 90℃烘干，得到1,2,4,5-环己烷四甲酸二酐聚酰亚胺0.294g，产率87％。所得聚合物数均分子量Mn 79562，重均分子量Mw 87415，结构式如下：
如图3中的红外谱图所示，图中1720cm-1和1590cm-1处为酰胺键特征吸收峰，如图4所示，说明其10％失重温度为474℃，具有很好的耐热稳定性。
性能表征和测试：
制备的聚酰亚胺的电致变色性能的测试采用如下方法：将聚酰亚胺聚合物溶于N,N-二甲基乙酰胺中配制成浓度为50mg/mL的溶液，滴涂于ITO玻璃板上，烘干后(膜厚度为100μm)作为工作电极，铂丝作为对电极，Ag/AgNO3作为参比电极，以含有0.1M四丁基高氯酸铵(TBAP)的乙腈溶液作为电解质溶液。化学工作站施加递增的电压，观察其颜色变化，在此过程中，用紫外可见光谱仪监测其吸收光谱的变化。如图5所示，用电化学工作站实施循环伏安，说明其有良好的氧化还原可逆性。如图6所示，当外加电压从0V升至0.6V，318nm处吸收峰逐渐降低，382nm、 768nm处出现新的吸收峰，并且随着外加电压的增大而逐渐增高，同时薄膜的颜色由无色变为蓝色。如图7所示，薄膜在自然状态下几乎无可见光吸收，达到无色透明，且随着外加电压的增加，透过率逐渐减弱。如图7所示，在768nm吸收光谱检测下，对其施加0～0.6V方波电压，对其进行稳定性检测，循环2500圈仍有很好的稳定性，表现出较高的透过对比度。
Claims (4)
1.一种具有超高稳定性和电致变色功能的聚酰亚胺，其特征在于：聚酰亚胺的结构式如下所示，
其中n为10～80之间的整数，得到的聚酰亚胺聚合物的数均分子量Mn为40000～100000，重均分子量为40000～100000；
R为中的一种。
2.权利要求1所述的一种具有超高稳定性和电致变色功能的聚酰亚胺的制备方法，其特征在于：是以摩尔比为1～3：1的含有四苯基乙烯-双芳胺胺结构的二胺单体和酸酐单体为原料，以N,N-二甲基乙酰胺为溶剂，反应体系固含量为15～35％，室温下反应12～24h后向体系中加入二胺单体摩尔数30～50倍的醋酸酐和20～30倍的吡啶，升温至100～120℃反应3～5h，冷却至室温后出料到乙醇后用水和乙醇回流洗涤数遍，真空干燥后得到电致变色功能的聚酰亚胺产物。
3.如权利要求2所述的一种具有超高稳定性和电致变色功能的聚酰亚胺的制备方法，其特征在于：酸酐单体为均苯四甲酸二酐、3,3',4,4'-二苯酮四酸二酐、4,4'-联苯醚二酐、六氟二酐或1,2,4,5-环己烷四甲酸二酐。
4.如权利要求2所述的一种具有超高稳定性和电致变色功能的聚酰亚胺的制备方法，其特征在于：含有四苯基乙烯-双芳胺结构的二胺单体的结构式如式(Ⅰ)所示：
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210052799.3A CN114539079B (zh) | 2022-01-18 | 2022-01-18 | 含有四苯基乙烯-双芳胺结构的二胺单体、制备方法及其在超稳定电致变色材料中的应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210052799.3A CN114539079B (zh) | 2022-01-18 | 2022-01-18 | 含有四苯基乙烯-双芳胺结构的二胺单体、制备方法及其在超稳定电致变色材料中的应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114539079A CN114539079A (zh) | 2022-05-27 |
| CN114539079B true CN114539079B (zh) | 2024-04-09 |
Family
ID=81671668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210052799.3A Active CN114539079B (zh) | 2022-01-18 | 2022-01-18 | 含有四苯基乙烯-双芳胺结构的二胺单体、制备方法及其在超稳定电致变色材料中的应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114539079B (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013154238A1 (ko) * | 2012-04-09 | 2013-10-17 | 건국대학교 산학협력단 | 신규한 황산화 컨쥬게이션 테트라페닐에틸렌 폴리이미드 및 이를 이용한 연료전지용 양성자 교환막 |
| CN105503775A (zh) * | 2015-12-14 | 2016-04-20 | 吉林大学 | 含有对位取代环状胺的三苯胺结构的二胺单体、制备方法及其应用 |
| CN110606810A (zh) * | 2019-10-08 | 2019-12-24 | 吉林大学 | 含四苯基乙烯-双芳胺结构的二胺单体、制备方法及其在聚酰胺合成中的应用 |
| CN112745236A (zh) * | 2021-01-05 | 2021-05-04 | 吉林大学 | 含有四苯基乙烯-三苯胺结构的二胺单体、制备方法及其在制备无色聚酰亚胺中的应用 |
-
2022
- 2022-01-18 CN CN202210052799.3A patent/CN114539079B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013154238A1 (ko) * | 2012-04-09 | 2013-10-17 | 건국대학교 산학협력단 | 신규한 황산화 컨쥬게이션 테트라페닐에틸렌 폴리이미드 및 이를 이용한 연료전지용 양성자 교환막 |
| CN105503775A (zh) * | 2015-12-14 | 2016-04-20 | 吉林大学 | 含有对位取代环状胺的三苯胺结构的二胺单体、制备方法及其应用 |
| CN110606810A (zh) * | 2019-10-08 | 2019-12-24 | 吉林大学 | 含四苯基乙烯-双芳胺结构的二胺单体、制备方法及其在聚酰胺合成中的应用 |
| CN112745236A (zh) * | 2021-01-05 | 2021-05-04 | 吉林大学 | 含有四苯基乙烯-三苯胺结构的二胺单体、制备方法及其在制备无色聚酰亚胺中的应用 |
Non-Patent Citations (1)
| Title |
|---|
| "Novel Functional TPE Polymers: Aggregated Induced Emission, pH Response and Solvatochromic Behavior";Wei Huang;《Macromol. Rapid Commun》;补充信息 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114539079A (zh) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110606810B (zh) | 含四苯基乙烯-双芳胺结构的二胺单体、制备方法及其在聚酰胺合成中的应用 | |
| Nakano | Synthesis, structure and function of π-stacked polymers | |
| Chang et al. | Novel anodic polyelectrochromic aromatic polyamides containing pendent dimethyltriphenylamine moieties | |
| TWI426065B (zh) | 用於垂直配向模式的液晶顯示裝置之配向材料及其製備方法（ⅱ） | |
| CN101560302A (zh) | 具有双向形状记忆效应的液晶弹性体或纤维及其制备方法 | |
| Liu et al. | New triphenylamine-based poly (amine-imide) s with carbazole-substituents for electrochromic applications | |
| Wang et al. | High coloration efficiency and fast switching speed of poly (amic acid-imide) s containing triphenylamine in acidic electrolyte | |
| CN109880084A (zh) | 含三苯胺结构及四苯乙烯单元的共轭聚合物及其制备方法和在电致变色中的应用 | |
| Sun et al. | High-contrast electrochromic and electrofluorescent dual-switching materials based on 2-diphenylamine-(9, 9-diphenylfluorene)-functionalized semi-aromatic polymers | |
| Lam et al. | Helical conjugated polymers: Synthesis, stability, and chiroptical properties of poly (alkyl phenylpropiolate) s bearing stereogenic pendants | |
| CN114539079B (zh) | 含有四苯基乙烯-双芳胺结构的二胺单体、制备方法及其在超稳定电致变色材料中的应用 | |
| CN104277458A (zh) | 一种高粘附性低线膨胀系数聚酰亚胺膜材料及其制备方法 | |
| Patil et al. | Synthesis, characterization, and electrical and thermal stability of semiconducting π-conjugated polyazomethines containing a tetraphenylthiophene-oxazole unit | |
| CN112745236B (zh) | 含有四苯基乙烯-三苯胺结构的二胺单体、制备方法及其在制备无色聚酰亚胺中的应用 | |
| Stenger‐Smith et al. | Poly [(4‐N‐ethylene‐N‐ethylamino)‐α‐cyanocinnamate]: A nonlinear optical polymer with a chromophoric mainchain. I. Synthesis and spectral characterization | |
| Tao et al. | Synthesis and photoluminescent property of star polymers with carbzole pendent and a zinc porphyrin core by ATRP | |
| CN100441567C (zh) | 丙烯酸酯及甲基丙烯酸酯类侧链型发光聚合物及其合成 | |
| Zhou et al. | Synthesis and properties of polyacetylenes containing terphenyl pendent group with different spacers | |
| CN110343079B (zh) | 一种可Diels-Alder加成反应偶氮苯单体的制备方法及应用 | |
| Wang et al. | Multicolor electrochromic poly (amide-imide) s with N, N-diphenyl-N′, N′-di-4-tert-butylphenyl-1, 4-phenylenediamine moieties | |
| Peng et al. | Luminescent mesogen jacketed poly (1‐alkyne) bearing lateral terphenyl with hexyloxy tail | |
| CN113024380A (zh) | 一种基于原儿茶酸的丙烯酸树脂的合成和应用 | |
| Bag et al. | Synthesis and characterization of photoactive chiral copolymers of (S)‐N‐(1‐phenyl ethyl) methacrylamide and disperse red 1 methacrylate | |
| CN1884429A (zh) | 一种新型偶氮苯侧基型聚脲光致变色材料 | |
| Kim et al. | Electro-optic effect of a soluble nonlinear optical polyimide containing two different chromophores with different sizes in the side chain |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |