CN115260455A - 一种基于联苯结构的低温长余辉聚合物及其制备方法 - Google Patents
一种基于联苯结构的低温长余辉聚合物及其制备方法 Download PDFInfo
- Publication number
- CN115260455A CN115260455A CN202211010424.7A CN202211010424A CN115260455A CN 115260455 A CN115260455 A CN 115260455A CN 202211010424 A CN202211010424 A CN 202211010424A CN 115260455 A CN115260455 A CN 115260455A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- polymer
- group
- reaction
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 15
- 239000004305 biphenyl Substances 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 107
- 238000006243 chemical reaction Methods 0.000 claims description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000007112 amidation reaction Methods 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 7
- 239000012312 sodium hydride Substances 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 6
- 230000009435 amidation Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 6
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 claims description 5
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 230000002688 persistence Effects 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 150000003456 sulfonamides Chemical class 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 claims description 2
- 230000002862 amidating effect Effects 0.000 claims 1
- 238000003384 imaging method Methods 0.000 claims 1
- 238000005580 one pot reaction Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001212 derivatisation Methods 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000004458 analytical method Methods 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000012984 biological imaging Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- MKPDAJWEBQRQCO-UHFFFAOYSA-N (4-aminophenyl)boronic acid Chemical compound NC1=CC=C(B(O)O)C=C1 MKPDAJWEBQRQCO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000001906 matrix-assisted laser desorption--ionisation mass spectrometry Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/143—Side-chains containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/411—Suzuki reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/52—Luminescence
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/59—Stability
- C08G2261/592—Stability against heat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/59—Stability
- C08G2261/598—Chemical stability
-
- 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
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明公开了一种基于联苯结构的长余辉聚合物及其制备方法。本发明提供的长余辉聚合物的结构式如式TM中所示。本发明提供的长余辉聚合物表现出优异的低温长余辉性质并具备良好的热稳定性、电化学稳定性和成膜性,能够进一步应用于有机发光材料等领域。本发明提供的长余辉聚合物的制备方法,原料廉价易得,合成方法简单易操作,产物产率高易纯化。本发明长余辉聚合物具有易衍生化和高稳定性的特点,在极端环境的有机发光材料领域具有很好的应用前景。
Description
技术领域
本发明涉及一种基于联苯结构的低温长余辉聚合物及其制备方法,属于有机发光材料领域。
背景技术
低温长余辉材料是一类特殊的发光材料。这类材料在极低温度环境(液氮)下,光致激发会发出极强且寿命极长的磷光。关闭激发光源后,会持续发光20~60秒。从光物理过程上分析,这类材料表现为极快的系间窜越速率和极慢的磷光辐射跃迁速率(图1)。这类材料的系间窜越速率越快,磷光辐射跃迁速率越慢,则在低温下表现出来的余辉现象越长。基于这一特殊性质,这类材料在极低温环境中有很多潜在应用,如光学加密、生物成像。迄今为止低温长余辉的纯有机小分子也只有一例报道,相关的纯有机聚合物更是尚无文献报道。
发明内容
本发明的目的是提供一种基于联苯结构的低温长余辉聚合物,所述聚合物都表现出优异的低温长余辉性质并具备良好的热稳定性、电化学稳定性和成膜性,能够进一步应用于有机发光材料等领域。
本发明提供的基于联苯结构的低温长余辉聚合物,其结构式如式TM所示;
式TM中,基团d为富电子给体基团,基团x为所述低温长余辉聚合物的共聚单体;
所述基团d选自咔唑和3,6-二叔丁基咔唑;
所述基团x选自以下结构a1~a12中的任一种,均为已知化合物,简单易得;
本发明提供的基于联苯结构的长余辉聚合物优选为下述结构中任一种:
本发明进一步提供了所述基于联苯结构的低温长余辉聚合物的制备方法,包括如下步骤:
1)式A所示化合物与磺酰胺进行酰胺化并脱水反应得到式B所示化合物;
这种方法能够在苯环上溴原子和氟原子不被破坏的情况下将羧基高效转变为氰基;
2)在氢化钠存在的条件下,式B所示化合物与基团d所对应的化合物进行亲核取代反应分别得到式C1所示化合物和式C2所示化合物;
控制好投料比,该步骤中给电子基团d所对应化合物会优先与苯环上的强拉电子氟原子高效反应而难以与苯环上的溴原子反应;
基团d为富电子给体基团,选自咔唑和3,6-二叔丁基咔唑;
3)式C1所示化合物或式C2所示化合物与基团x所对应的化合物经Suzuki偶联聚合反应、Buchwald–Hartwig偶联聚合反应或酰胺化聚合反应得到式TM所示聚合物;
基团x所对应的化合物为式TM所示聚合物的共聚单体,来自式a1~a12所示结构中的任一种;
上述的制备方法中,步骤1)中,所述酰胺化反应和所述脱水反应在二甲砜溶剂中进行;
式A所示化合物与所述磺酰胺的摩尔比为1:2~4;
所述反应的过程如下:在160℃下反应3~4小时;
式A所示化合物可以根据现有文献(Chin.J.Org.Chem.2013,33,2349.DIO:10.6023/cjoc201306029)中记载的方法制备;
反应无需要惰性气体保护。
上述的制备方法中,步骤2)中,所述亲核取代反应的步骤如下:
将式B所示化合物与所述氢化钠在干燥的N,N-二甲基甲酰胺中于室温下搅拌0.5~1小时,然后加入所述基团d所对应的化合物,在60~80℃下反应10~12h;
式B所示化合物、所述氢化钠与所述基团d所对应的化合物给的摩尔比为1:1.1~1.2:1.9~2;
反应需要惰性气体保护。
上述的制备方法中,步骤3)中,所述Suzuki偶联聚合反应的条件如下:
在四(三苯基膦)钯和碳酸钾存在的条件下进行;
式C1所示化合物或式C2所示化合物、所述基团x所对应的化合物、所述、四(三苯基膦)钯与所述碳酸钾的摩尔比为1:1~1.05:0.05~0.1:5~8;
溶剂为甲苯与水的混合液,体积比为1:0.3~0.5;
反应需要惰性气体保护;
反应温度为105~110℃;
反应时间为20~24h。
上述的制备方法中,步骤3)中,所述Buchwald-Hartwig偶联聚合反应的条件如下:
在三(二亚苄基丙酮)二钯和叔丁醇钠存在的条件下进行;
式C1所示化合物或式C2所示化合物、所述基团x所对应的化合物、所述三(二亚苄基丙酮)二钯与所述叔丁醇钠的摩尔比为1:1~1.05:0.05~0.1:5~8;
溶剂为干燥的甲苯;
反应需要惰性气体保护;
反应温度为105~110℃;
反应时间为20~24h。
上述的制备方法中,步骤3)中,所述酰胺化聚合反应的条件如下:
式C1所示化合物或式C2所示化合物与所述基团x所对应的化合物的摩尔比为1:1~1.05;
溶剂为四氢呋喃、N,N-二甲基甲酰胺和N,N-二甲基乙酰胺中的任一种。
反应需要惰性气体保护;
反应温度为室温;
反应时间为20~24h。
本发明提供的式TM所示基于联苯结构的长余辉聚合物是一系列纯有机发光材料,其中每一种聚合物都具有极快的系间窜越速率和极慢的磷光辐射跃迁速率,宏观表现为低温下20~60秒的长余辉现象。
本发明提供的制备具有低温长余辉性质的发光聚合物的方法,原料廉价易得,合成步骤简单高效,反应产率高且产率分离纯化容易。
本发明提供的基于联苯结构的长余辉聚合物中的每一种都具有良好的热稳定性、电化学稳定性和成膜性,在极端环境中的发光材料领域具有广泛的应用前景。
附图说明
图1为低温长余辉光物理过程示意图。
图2为本发明中式D所示聚合物在液氮中的a)磷光寿命衰减曲线和b)长余辉图片演示。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径或已报道文献中查询得到。
本发明提供的合成式TM所示低温长余辉聚合物的反应路线如下所示:
中间产物C1和C2是本发明的关键中间产物,在各个实例中都需要经过这两个中间化合物。
中间产物C1和C2的具体合成步骤如下:
本发明方法中具体步骤I:在室温下向100mL两口圆底烧瓶中加入化合物A(4.36g,10mmol,1.0equiv)、30mL二氯亚砜溶剂和催化量的4-二甲氨基吡啶(48.9mg,0.4mmol,0.04equiv),然后将混合物加入至回流搅拌5小时。反应结束后减压蒸馏除去过量的二氯亚砜,然后向圆底烧瓶中加入磺酰胺(2.88g,30mmol,3equiv)和二甲砜(10mL)并升温至160摄氏度继续搅拌3小时。反应结束后冷却至室温,加入80毫升1摩尔每升氢氧化钠水溶液并搅拌几分钟。静置沉淀并过滤,将滤渣用柱层析法进行纯化(流动相为石油醚:二氯甲烷=5:4),得到1.27g白色固体粉末B,产率为32%。
本发明方法中具体步骤II:向100mL两口圆底烧瓶中加入咔唑(1.67g,10mmol,2.5equiv)、氢化钠(440mg,11mmol,2.75equiv,60%分散在矿物油)和N,N-二甲基甲酰胺(40mL)并在氮气保护下室温搅拌2小时。缓慢加入式B所示化合物(1.59g,4mmol,1.0equiv),然后将混合物在70摄氏度下加热搅拌12小时。反应结束后将反应液倒入40mL水中,静置沉淀并过滤,将滤渣用柱层析法进行纯化(流动相为石油醚:二氯甲烷=2:1),得到1.97g白色固体粉末C1,产率为71%。
本发明中具体步骤III:向100mL单口圆底烧瓶中加入3,6-二叔丁基咔唑(0.7g,2.5mmol,2equiv)、氢化钠(105mg,2.64mmol,2.1equiv,60%分散在矿物油)和N,N-二甲基甲酰胺(20mL)并在氮气保护下室温搅拌2小时。缓慢加入式B所示化合物(0.5g,1.25mmol,1.0equiv),然后将混合物在65摄氏度下加热搅拌12小时。反应结束后将反应液倒入40mL水中,静置沉淀并过滤,将滤渣用柱层析法进行纯化(流动相为石油醚:二氯甲烷=2:1),得到1.04g白色固体粉末C2,产率为90%。
各中间产物的核磁氢谱、碳谱和质谱分析结果如下:
中间产物B:mp 172-173℃;1H NMR(400MHz,CDCl3):δ7.81(S,2H),7.70(d,J=8.0Hz,2H);13C NMR(101MHz,CDCl3):δ159.3(d,J=258.6Hz),132.25(t,J=2.0Hz),125.4(d,J=10.1Hz),125.3(d,J=2.0Hz),124.9(d,J=25.3Hz),124.8(d,J=16.2Hz),121.33(d,J=20.2Hz),116.4(t,J=2.0Hz),114.50(t,J=2.0Hz);HR-MS(APCI):m/zcalcd forC14H3N2Br2F2 -[M-H]-394.86365,found 394.86325.
中间产物C1:mp 253-257℃;1H NMR(400MHz,d6-DMSO):δ8.77(d,J=4Hz,2H),8.09(d,J=8Hz,2H),7.82(d,J=4Hz,2H),7.78(d,J=8Hz,2H),7.31(t,J=8Hz,2H),7.24(t,J=8Hz,2H),6.98(d,J=8Hz,2H),6.87(t,J=8Hz,2H),6.53(t,J=8Hz,2H),5.39(d,J=8Hz,2H);13C NMR(101MHz,d6-DMSO):δ141.1,139.8,139.0,138.3,137.0,135.0,126.6,126.0,125.2,124.2,123.9,121.4,121.3,121.1,120.1,118.4,117.2,108.9,108.8;HR-MS(ESI):m/z calcd for C38H20N4Br2Na+[M-Na]+712.99469,found712.994692.
中间产物C2:mp 300-301℃;1H NMR(400MHz,CDCl3):δ8.08(d,J=2Hz,2H),7.87(d,J=4Hz,2H),7.63(d,J=4Hz,2H),7.38(d,J=2Hz,2H),7.31(dd,J=8Hz,J=2Hz,2H),6.89(d,J=8Hz,2H),6.64(dd,J=8Hz,J=2Hz,2H),5.53(6,J=8Hz,2H),1.43(s,9H),1.32(s,9H);13C NMR(101MHz,CDCl3):δ144.2,143.6,141.5,140.4,139.4,137.5,135.6,134.9,124.9,124.8,124.4,123.6,123.3,118.4,116.8,116.7,115.5,109.9,109.0,34.7,34.5,32.0,31.9;MALDI-MS:m/z calcd for C54H52N4Br2 914.256,found 914.092.
实施例1、式D所示聚合物的制备
具体反应步骤IV-1如下:
向10mL schlenk管中加入式C1所示化合物(138.5mg,0.2mmol,1.0equiv)、式a1所示化合物(133.3mg,0.2mmol,1.0equiv)、四(三苯基膦)钯(11.5mg,0.01mmol,0.05equiv)、碳酸钾(138.2mg,1.0mmol,5.0equiv)。抽换氮气3次,再用注射器注入2mL脱气甲苯和0.5mL脱气水。在110℃下加热搅拌36小时。反应结束后,将混合物滴入100mL甲醇,过滤出不溶固体,用滤纸包好放入索氏提取器中依次用丙酮和氯仿各索提24小时。收集氯仿索提液,减压旋干至几毫升的体积,滴入100mL甲醇中沉淀,过滤出白色固体。将白色固体在100摄氏度干燥箱中烘干12小时,得到式D所示聚合物,产率52%。
GPC分析结果:Mn,29.4kDa;Mw,54.9kDa;Mw/Mn,1.87.
实施例2、式E所示聚合物的制备
具体反应步骤IV-2如下:
本实施例与聚合物D合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a2所示化合物(139.7mg,0.2mmol,1.0equiv),得到式E所示聚合物,产率57%。
GPC分析结果:Mn,18.4kDa;Mw,29.3kDa;Mw/Mn,1.59.
实施例3、式F所示聚合物的制备
具体反应步骤IV-3如下:
本实施例与聚合物D合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a3所示化合物(84.0mg,0.2mmol,1.0equiv),得到式F所示聚合物,产率78%。
GPC分析结果:Mn,10.7kDa;Mw,19.5kDa;Mw/Mn,1.82.
实施例4、式G所示聚合物的制备
具体反应步骤IV-4如下:
本实施例与聚合物D合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a4所示化合物(86.8mg,0.2mmol,1.0equiv),得到式G所示聚合物,产率67%。
GPC分析结果:Mn,12.3kDa;Mw,22.8kDa;Mw/Mn,1.85.
实施例5、式H所示聚合物的制备
具体反应步骤IV-5如下:
本实施例与聚合物D合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a5所示化合物(92.4mg,0.2mmol,1.0equiv),得到式H所示聚合物,产率87%。
GPC分析结果:Mn,17.7kDa;Mw,26.3kDa;Mw/Mn,1.49.
实施例6、式I所示聚合物的制备
具体反应步骤IV-6如下:
式C1所示化合物由步骤I、II可以得到。
本实施例与聚合物D合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a6所示化合物(98.1mg,0.2mmol,1.0equiv),得到式I所示聚合物,产率83%。
GPC分析结果:Mn,19.8kDa;Mw,29.5kDa;Mw/Mn,1.49.
实施例7、式J所示聚合物的制备
具体反应步骤IV-7如下:
本实施例与聚合物D合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a7所示化合物(103.7mg,0.2mmol,1.0equiv),得到式J所示聚合物,产率57%。
GPC分析结果:Mn,9.5kDa;Mw,16.7kDa;Mw/Mn,1.76.
实施例8、式K所示聚合物的制备
具体反应步骤IV-8下:
式C1所示化合物由步骤I、II可以得到。
本实施例与聚合物D合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a8所示化合物(94.0mg,0.2mmol,1.0equiv),得到式K所示聚合物,产率46%。
GPC分析结果:Mn,8.6kDa;Mw,18.3kDa;Mw/Mn,2.13.
实施例9、式L所示聚合物的制备
具体反应步骤IV-9如下:
向50mL中schlenk管中加入式C1所示化合物(692.4mg,1mmol,1.0equiv)、对氨基苯硼酸(876.4mg,4mmol,4.0equiv)、四(三苯基膦)钯(57.8mg,0.05mmol,0.05equiv)、碳酸钾(691.0mg,5.0mmol,5.0equiv)。抽换氮气3次,再用注射器注入30mL脱气甲苯和10mL脱气水。在100℃下加热搅拌24小时。反应结束后,乙酸乙酯萃取,旋干,柱层析法纯化,得到浅黄色目标产物。向10mL schlenk管中加入式浅黄色目标产物(143.4mg,0.2mmol,1.0equiv)和式a9所示化合物(43.6mg,0.2mmol,1.0equiv)。抽换氮气3次,再用注射器注入2mL脱气四氢呋喃。在室温下搅拌24小时,结束后再注入0.5mL乙酸酐和0.5mL吡啶,再搅拌24小时。反应结束后,加入甲醇,过滤出式L所示黄色固体聚合物,产率94%。
GPC分析结果:Mn,12.8kDa;Mw,28.3kDa;Mw/Mn,2.21.
实施例10、式M所示聚合物的制备
具体反应步骤IV-10如下:
本实施例与聚合物L合成基本相同,其不同之处在于将例1中式a9所示化合物改为式a10所示化合物(44.8mg,0.2mmol,1.0equiv),得到式M所示聚合物,产率96%。
GPC分析结果:Mn,16.3kDa;Mw,31.7kDa;Mw/Mn,1.94.
实施例11、式N所示聚合物的制备
具体反应步骤IV-11如下:
向10mL schlenk管中加入式C1所示化合物(138.5mg,0.2mmol,1.0equiv)、式a11所示化合物(69.3mg,0.2mmol,1.0equiv)、三(二亚苄基丙酮)二钯(9.1mg,0.01mmol,0.05equiv)、叔丁醇钠(138.2mg,1.0mmol,5.0equiv)。抽换氮气3次,再用注射器注入2mL干燥甲苯。在110℃下加热搅拌24小时。反应结束后,将混合物滴入100mL甲醇,过滤出不溶固体,用滤纸包好放入索氏提取器中依次用丙酮和氯仿各索提24小时。收集氯仿索提液,减压旋干至几毫升的体积,滴入100mL甲醇中沉淀,过滤出黄色固体。将黄色固体在100摄氏度干燥箱中烘干12小时,得到式N所示聚合物,产率51%。
GPC分析结果:Mn,29.3kDa;Mw,44.8kDa;Mw/Mn,1.53.
实施例12、式O所示聚合物的制备
具体反应步骤IV-12如下:
本实施例与聚合物N合成基本相同,其不同之处在于将例1中式a11所示化合物改为式a12所示化合物(92.9mg,0.2mmol,1.0equiv),得到式O所示聚合物,产率63%。
GPC分析结果:Mn,27.1kDa;Mw,45.7kDa;Mw/Mn,1.69.
本发明中具体步骤V:
实施例13、式P所示聚合物的制备
具体反应步骤IV-1如下:
向10mL schlenk管中加入式C2所示化合物(183.4mg,0.2mmol,1.0equiv)、式a1所示化合物(133.3mg,0.2mmol,1.0equiv)、四(三苯基膦)钯(11.5mg,0.01mmol,0.05equiv)、碳酸钾(138.2mg,1.0mmol,5.0equiv)。抽换氮气3次,再用注射器注入2mL脱气甲苯和0.5mL脱气水。在110℃下加热搅拌36小时。反应结束后,将混合物滴入100mL甲醇,过滤出不溶固体,用滤纸包好放入索氏提取器中依次用丙酮和氯仿各索提24小时。收集氯仿索提液,减压旋干至几毫升的体积,滴入100mL甲醇中,过滤出白色固体。将白色固体在100摄氏度干燥箱中烘干12小时,得到式P所示聚合物,产率52%。
实施例P的GPC分析结果:Mn,28.5kDa;Mw,54.0kDa;Mw/Mn,1.89.
实施例14、式Q所示聚合物的制备
具体反应步骤V-2如下:
本实施例与聚合物P合成基本相同,其不同之处在于将原例中式a1所示化合物改为式a2所示化合物(139.7mg,0.2mmol,1.0equiv),得到式Q所示聚合物,产率68%。
GPC分析结果:Mn,17.4kDa;Mw,35.3kDa;Mw/Mn,2.03.
实施例15、式R所示聚合物的制备
具体反应步骤V-3如下:
本实施例与聚合物P合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a3所示化合物(84.0mg,0.2mmol,1.0equiv),得到式F所示聚合物,产率53%。
GPC分析结果:Mn,11.6kDa;Mw,18.7kDa;Mw/Mn,1.61.
实施例16、式S所示聚合物的制备
具体反应步骤V-4如下:
本实施例与聚合物P合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a4所示化合物(86.8mg,0.2mmol,1.0equiv),得到式S所示聚合物,产率62%。
GPC分析结果:Mn,10.7kDa;Mw,22.9kDa;Mw/Mn,2.14.
实施例17、式T所示聚合物的制备
具体反应步骤V-5如下:
式C2所示化合物由步骤I、III可以得到。
本实施例与聚合物P合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a5所示化合物(92.4mg,0.2mmol,1.0equiv),得到式T所示聚合物,产率75%。
GPC分析结果:Mn,15.9kDa;Mw,28.8kDa;Mw/Mn,1.81.
实施例18、式U所示聚合物的制备
具体反应步骤V-6如下:
本实施例与聚合物P合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a6所示化合物(98.1mg,0.2mmol,1.0equiv),得到式U所示聚合物,产率69%。
GPC分析结果:Mn,15.7kDa;Mw,24.8kDa;Mw/Mn,1.58.
实施例19、式V所示聚合物的制备
具体反应步骤V-7如下:
本实施例与聚合物P合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a7所示化合物(103.7mg,0.2mmol,1.0equiv),得到式V所示聚合物,产率54%。
GPC分析结果:Mn,11.7kDa;Mw,23.0kDa;Mw/Mn,1.97.
实施例20、式W所示聚合物的制备
具体反应步骤V-8下:
本实施例与聚合物P合成基本相同,其不同之处在于将例1中式a1所示化合物改为式a8所示化合物(94.0mg,0.2mmol,1.0equiv),得到式W所示聚合物,产率69%。
GPC分析结果:Mn,10.1kDa;Mw,26.2kDa;Mw/Mn,2.59.
实施例21、式X所示聚合物的制备
具体反应步骤V-9如下:
向50mL中schlenk管中加入式C2所示化合物(692.4mg,1mmol,1.0equiv)、对氨基苯硼酸(876.4mg,4mmol,4.0equiv)、四(三苯基膦)钯(57.8mg,0.05mmol,0.05equiv)、碳酸钾(691.0mg,5.0mmol,5.0equiv)。抽换氮气3次,再用注射器注入30mL脱气甲苯和10mL脱气水。在100℃下加热搅拌24小时。反应结束后,乙酸乙酯萃取,旋干,柱层析法纯化,得到浅黄色目标产物。向10mL schlenk管中加入式浅黄色目标产物(143.4mg,0.2mmol,1.0equiv)和式a9所示化合物(43.6mg,0.2mmol,1.0equiv)。抽换氮气3次,再用注射器注入2mL脱气四氢呋喃。在室温下搅拌24小时,结束后再注入0.5mL乙酸酐和0.5mL吡啶,再搅拌24小时。反应结束后,加入甲醇,过滤出式X所示黄色固体聚合物,产率91%。
GPC分析结果:Mn,19.1kDa;Mw,59.4kDa;Mw/Mn,3.11.
实施例22、式Y所示聚合物的制备
具体反应步骤V-10如下:
本实施例与聚合物X合成基本相同,其不同之处在于将例1中式a9所示化合物改为式a10所示化合物(44.8mg,0.2mmol,1.0equiv),得到式Y所示聚合物,产率87%。
GPC分析结果:Mn,19.1kDa;Mw,56.7kDa;Mw/Mn,2.97.
实施例23、式Z所示聚合物的制备
具体反应步骤V-11如下:
向10mL schlenk管中加入式C2所示化合物(138.5mg,0.2mmol,1.0equiv)、式a11所示化合物(69.3mg,0.2mmol,1.0equiv)、三(二亚苄基丙酮)二钯(9.1mg,0.01mmol,0.05equiv)、叔丁醇钠(138.2mg,1.0mmol,5.0equiv)。抽换氮气3次,再用注射器注入2mL干燥甲苯。在110℃下加热搅拌24小时。反应结束后,将混合物滴入100mL甲醇,过滤出不溶固体,用滤纸包好放入索氏提取器中依次用丙酮和氯仿各索提24小时。收集氯仿索提液,减压旋干至几毫升的体积,滴入100mL甲醇中,过滤出黄色固体。将黄色固体在100干燥箱中烘干12小时,得到式Z所示聚合物,产率55%。
GPC分析结果:Mn,26.7kDa;Mw,47.9kDa;Mw/Mn,1.79.
实施例24、式ZZ所示聚合物的制备
具体反应步骤V-12如下:
本实施例与聚合物Z合成基本相同,其不同之处在于将例1中式a11所示化合物改为式a12所示化合物(92.9mg,0.2mmol,1.0equiv),得到式ZZ所示聚合物,产率68%。
GPC分析结果:Mn,25.3kDa;Mw,44.8kDa;Mw/Mn,1.77.
本发明制备的实施例1-14制备的聚合物溶于色谱纯甲苯中配成浓度为10-5mol/L的稀溶液,并测试各稀溶液的光物理性质。最大吸收波长、最大发射波长、磷光寿命和液氮中长余辉时长如表1所示。液氮中的磷光寿命衰减曲线和长余辉图片演示如图2所示。由表1和图2的结果可以看出,这一系列基于联苯结构的聚合物在低温下都表现出长的磷光寿命(1.44~3.23s)和长的余晖时间(18~40s)。
表1化合物D-ZZ的光物理性质
本发明通过在C-C偶联、C-N偶联和酰胺化聚合得到一系列具有低温长余辉性质的共聚物。这类特殊的发光材料在极低温度环境(液氮)下,光致激发会发出极强且寿命极长的磷光。关闭激发光源后,会持续发光20~60s。从光物理过程上分析,这类材料表现出快的系间窜越速率和慢的磷光辐射跃迁速率,系间窜越速率越快,磷光辐射跃迁速率越慢,低温下表现出来的余辉现象越长。基于这一特殊性质,这类材料在极低温环境下有很多潜在应用如,光学加密、生物成像等。
Claims (10)
4.根据权利要求3所述的制备方法,其特征在于:步骤1)中,所述酰胺化反应和所述脱水反应在二甲砜溶剂中进行;
式A所示化合物与所述磺酰胺的摩尔比为1:2~4;
所述反应的过程如下:在160℃下反应3~4小时。
5.根据权利要求3或4所述的制备方法,其特征在于:步骤2)中,所述亲核取代反应的步骤如下:
将式B所示化合物与所述氢化钠在干燥的N,N-二甲基甲酰胺中于室温下搅拌0.5~1小时,然后加入所述基团d所对应的化合物,在60~80℃下反应10~12h;
式B所示化合物、所述氢化钠与所述基团d所对应的化合物给的摩尔比为1:1.1~1.2:1.9~2。
6.根据权利要求3-5中任一项所述的制备方法,其特征在于:步骤3)中,所述Suzuki偶联聚合反应的条件如下:
在四(三苯基膦)钯和碳酸钾存在的条件下进行;
式C1所示化合物或式C2所示化合物、所述基团x所对应的化合物、所述四(三苯基膦)钯与所述碳酸钾的摩尔比为1:1~1.05:0.05~0.1:5~8;
溶剂为甲苯与水的混合液,体积比为1:0.3~0.5;
反应温度为105~110℃;
反应时间为20~24h。
7.根据权利要求3-5中任一项所述的制备方法,其特征在于:步骤3)中,所述Buchwald-Hartwig偶联聚合反应的条件如下:
在三(二亚苄基丙酮)二钯和叔丁醇钠存在的条件下进行;
式C1所示化合物或式C2所示化合物、所述基团x所对应的化合物、所述三(二亚苄基丙酮)二钯与所述叔丁醇钠的摩尔比为1:1~1.05:0.05~0.1:5~8;
溶剂为干燥的甲苯;
反应温度为105~110℃;
反应时间为20~24h。
8.根据权利要求3-5中任一项所述的制备方法,其特征在于:步骤3)中,所述酰胺化聚合反应的条件如下:
式C1所示化合物或式C2所示化合物与所述基团x所对应的化合物的摩尔比为1:1~1.05;
溶剂为四氢呋喃、N,N-二甲基甲酰胺和N,N-二甲基乙酰胺中的任一种;
反应温度为室温;
反应时间为20~24h。
9.权利要求1或2所述基于联苯结构的低温长余辉聚合物在作为或制备有机发光材料中的应用。
10.权利要求1或2所述基于联苯结构的低温长余辉聚合物在光学加密、生物成像中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211010424.7A CN115260455B (zh) | 2022-08-23 | 2022-08-23 | 一种基于联苯结构的低温长余辉聚合物及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211010424.7A CN115260455B (zh) | 2022-08-23 | 2022-08-23 | 一种基于联苯结构的低温长余辉聚合物及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115260455A true CN115260455A (zh) | 2022-11-01 |
CN115260455B CN115260455B (zh) | 2023-12-22 |
Family
ID=83752488
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211010424.7A Active CN115260455B (zh) | 2022-08-23 | 2022-08-23 | 一种基于联苯结构的低温长余辉聚合物及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115260455B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115504926A (zh) * | 2022-09-30 | 2022-12-23 | 中国科学院化学研究所 | 一种新型低温超长余辉分子材料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109535420A (zh) * | 2018-11-14 | 2019-03-29 | 武汉华星光电半导体显示技术有限公司 | 一种热活化延迟荧光深红光高分子材料及其制备方法 |
CN110423244A (zh) * | 2019-08-06 | 2019-11-08 | 南京邮电大学 | 一种具有超长余辉发光性能的有机硼磷光材料的制备及其应用 |
CN113387956A (zh) * | 2021-06-11 | 2021-09-14 | 华南师范大学 | 一种聚合物长余辉材料及其制备方法和应用 |
-
2022
- 2022-08-23 CN CN202211010424.7A patent/CN115260455B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109535420A (zh) * | 2018-11-14 | 2019-03-29 | 武汉华星光电半导体显示技术有限公司 | 一种热活化延迟荧光深红光高分子材料及其制备方法 |
CN110423244A (zh) * | 2019-08-06 | 2019-11-08 | 南京邮电大学 | 一种具有超长余辉发光性能的有机硼磷光材料的制备及其应用 |
CN113387956A (zh) * | 2021-06-11 | 2021-09-14 | 华南师范大学 | 一种聚合物长余辉材料及其制备方法和应用 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115504926A (zh) * | 2022-09-30 | 2022-12-23 | 中国科学院化学研究所 | 一种新型低温超长余辉分子材料及其制备方法 |
CN115504926B (zh) * | 2022-09-30 | 2024-04-19 | 中国科学院化学研究所 | 一种新型低温超长余辉分子材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN115260455B (zh) | 2023-12-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN115260455B (zh) | 一种基于联苯结构的低温长余辉聚合物及其制备方法 | |
JP2008127387A (ja) | イリジウム錯体、カルバゾール誘導体、およびそれらを有する共重合体 | |
Lee et al. | Facile synthesis of Frechet type dendritic benzyl azides and dendrimer via cycloaddition reaction with tripodal core | |
CN107501242B (zh) | D-π-A型二吡咯荧光染料及其合成方法 | |
CN108997299B (zh) | 一种高效长寿命的有机室温磷光材料及其制备方法 | |
Li et al. | Metal-free polycycloaddition of aldehyde-activated internal diynes and diazides toward post-functionalizable poly (formyl-1, 2, 3-triazole) s | |
CN115819281B (zh) | 一种氰基取代的对苯撑乙烯衍生物、制备方法及应用 | |
CN115260205B (zh) | 双芘基掺杂的扩展卟啉、其双钯金属络合物、其制备方法及其应用 | |
CN107880265B (zh) | 一种聚喹啉高分子材料及其制备方法 | |
CN114573749B (zh) | 一种室温磷光共聚物及其制备方法和应用 | |
CN113896675A (zh) | 基于咔唑-三苯胺衍生物的有机发光材料及其制备方法 | |
CN107151324A (zh) | 热响应荧光型聚芳亚胺醚砜及其制备方法 | |
CN114163617A (zh) | 一种热致变色聚合物材料及其应用 | |
WO2021064416A1 (en) | Process of forming a conjugated polymer | |
Tomita et al. | Rearrangements versus ligand exchange reactions of organocobalt polymer having cobaltacyclopentadiene moieties in the main chain | |
CN108530387B (zh) | 一种苯基桥联和羧基封端的A1-π-A-D-A-π-A1型BT衍生物及其制备方法 | |
CN110746462A (zh) | 一种树枝状环三磷腈化合物的高效合成方法 | |
CN115504926B (zh) | 一种新型低温超长余辉分子材料及其制备方法 | |
KR20190083236A (ko) | 화합물, 상기 화합물을 포함하는 조성물 및 구조체, 및 포스젠 검출방법 | |
Chen et al. | Synthesis and properties of polyacetylenes containing bis (4-alkylphenyl) terephthalate as pendant and methyleneoxy as spacer | |
CN110437095B (zh) | 2-(3-氨基苯氧基)-6-(4-氨基苯氧基)-n-(2-氨基芴)苯甲酰胺单体 | |
RU2321601C1 (ru) | Разветвленные полифенилены и способ их получения | |
CN113214250B (zh) | 一种稠合六氢-1,6-萘啶类化合物的合成方法 | |
CN114933595B (zh) | 一种2-苯基苯并噁唑多刺激响应荧光材料及其制备方法 | |
CN115304749B (zh) | 一种含邻苯二酚侧基的荧光共轭高分子及其制备方法 |
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 |