CN101935461A - 一种双吩噻嗪基染料及其制法和应用 - Google Patents
一种双吩噻嗪基染料及其制法和应用 Download PDFInfo
- Publication number
- CN101935461A CN101935461A CN201010242218XA CN201010242218A CN101935461A CN 101935461 A CN101935461 A CN 101935461A CN 201010242218X A CN201010242218X A CN 201010242218XA CN 201010242218 A CN201010242218 A CN 201010242218A CN 101935461 A CN101935461 A CN 101935461A
- Authority
- CN
- China
- Prior art keywords
- branched
- straight chained
- hydrogen
- chain alkyl
- alkyl
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229950000688 phenothiazine Drugs 0.000 title abstract 6
- 239000000975 dye Substances 0.000 claims abstract description 69
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical class OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 206010070834 Sensitisation Diseases 0.000 claims description 23
- 230000008313 sensitization Effects 0.000 claims description 23
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- -1 4Be hydrogen Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Chemical group 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 150000003053 piperidines Chemical class 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 150000002990 phenothiazines Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000370 acceptor Substances 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000011521 glass Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 0 *c(cc1*)c(*)c2c1Sc(c(*)c(*)c(*)c1*)c1N2 Chemical compound *c(cc1*)c(*)c2c1Sc(c(*)c(*)c(*)c1*)c1N2 0.000 description 7
- 239000003086 colorant Substances 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920001651 Cyanoacrylate Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 229920003944 DuPont™ Surlyn® 1702 Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
- 239000013504 Triton X-100 Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- SZPAKLWKGFHLKV-UHFFFAOYSA-N C(C)(=O)O.CC=1C(=O)CC(CC1C)(C)C.N#CC#N.N#CC#N Chemical compound C(C)(=O)O.CC=1C(=O)CC(CC1C)(C)C.N#CC#N.N#CC#N SZPAKLWKGFHLKV-UHFFFAOYSA-N 0.000 description 1
- VZPDSWAVERHAPI-UHFFFAOYSA-N CS(C(N1c(ccc(C=O)c2)c2Sc2c1cccc2)N1c2ccc(C=O)cc2Sc2c1cccc2)=C Chemical compound CS(C(N1c(ccc(C=O)c2)c2Sc2c1cccc2)N1c2ccc(C=O)cc2Sc2c1cccc2)=C VZPDSWAVERHAPI-UHFFFAOYSA-N 0.000 description 1
- MTKIUELLNRWLRW-DFEHQXHXSA-N N#C/C(/C(O)=O)=C\c(cc1)cc2c1N(CCN1c3ccc(/C=C(/C(O)=O)\C#N)cc3Sc3c1cccc3)c(cccc1)c1S2 Chemical compound N#C/C(/C(O)=O)=C\c(cc1)cc2c1N(CCN1c3ccc(/C=C(/C(O)=O)\C#N)cc3Sc3c1cccc3)c(cccc1)c1S2 MTKIUELLNRWLRW-DFEHQXHXSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B21/00—Thiazine dyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
- C07D279/24—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom
- C07D279/26—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom without other substituents attached to the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
- C07D279/24—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom
- C07D279/28—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with hydrocarbon radicals, substituted by amino radicals, attached to the ring nitrogen atom with other substituents attached to 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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
- C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
- C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
- C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
- H10K85/652—Cyanine dyes
-
- 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
-
- 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
- Y02E10/542—Dye sensitized solar cells
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
Abstract
本发明公开了一种双吩噻嗪基染料及其制法和应用，属于精细化工中的光电转化材料应用领域。本发明将双吩噻嗪及其衍生物单元通过烷基连接形成双电子给体，在此基础上分别用双键延伸共轭π桥，末端接上氰基乙酸作为电子受体，应用该方法合成了一系列染料。由于双吩噻嗪基染料具有与TiO2更强的结合能力，并且有效地防止染料在TiO2表面的聚集，使得其在相同条件下具有比单吩噻嗪基染料更优越的性能。而且双吩噻嗪基染料的合成方法简单，原料易得，可代替价格昂贵、制备提纯较难的贵金属光敏染料，有效地降低染料敏化太阳能电池成本。
Description
技术领域
本发明公开了一类双吩噻嗪基染料的制法及其在染料敏化太阳能电池上的应用，属于精细化工中的光电转化材料应用领域，具体涉及一类双吩噻嗪基染料及其衍生物的设计、合成，以及所述染料在染料敏化太阳能电池方面的应用。
技术背景
染料敏化太阳能电池(DSSCs)是1991年瑞士科学家M.
首次提出并设计的一种新型的将太阳能转化为电能的装置。其构成一般由以下几方面组成：以镀Pt的导电玻璃为基板的光阴极，吸附了光敏染料的纳米多孔氧化物薄膜和透明导电基板组成的光阳极，填充在两电极之间的电解质以及密封材料。这类电池与传统的硅基太阳能电池相比具有结构简单、制作成本低等优点，而且其光电转化效率目前已达11％以上，是一类具有广泛应用前景的光电转换装置。光敏染料是染料敏化太阳能电池中非常重要的组成部分，染料的结构设计对于这类电池至关重要。目前，光电转化效率最高的依然是钌多吡啶配合物。然而钌属于稀有贵金属，相应的钌多吡啶配合物的分离提纯也有相当的难度，这限制了DSSCs成本的降低和未来的大规模实用化。为此，不含金属的有机光敏染料近年来在DSSCs中得到广泛的应用。同钉多吡啶配合物染料(如N3，N719等)相比，有机光敏染料具有结构多样、制备提纯相对容易、摩尔消光系数高等诸多优点。近年来品种多样的有机光敏染料发展迅速，为了进一步降低染料敏化太阳能电池成本，本发明设计合成了一类新型的吩噻嗪类有机光敏染料。
发明内容
本发明的目的在于克服现有技术的缺点，提供一种双吩噻嗪基染料及其制法及其应用。本发明染料不含金属纯有机光敏染料，这类染料是以双吩噻嗪及其衍生物为共轭体系，通过烷基链将双吩噻嗪单元连接起来，在此基础上分别延伸共轭π桥，在末端接上氰基乙酸，用来吸附在TiO2上，组成一类双链电子推拉型染料。这类染料在染料敏化太阳能电池上具有很好的应用性能。
本发明提供了一类新型的吩噻嗪光敏染料，具有以下结构通式：
其中：R1～R6为氢、C1～C20的直链烷基、C1～C20的支链烷基、C1～C20的酰胺基、C1～C20烷氧基或卤素；m为16的自然数；X为氢、C1～C20的直链烷基、C1～C20的支链烷基、C1～C20的酰胺基、C1～C20烷氧基、卤素或
其中，X1～X5为氢，C1～C20的直链烷基，C1～C20的支链烷基，C1～C20的酰胺基，C1～C20烷氧基或卤素；X6，X7为氢，C1～C20的直链烷基，C1～C20的支链烷基或C1～C20烷氧基；X8，X9为氢，C1～C20的直链烷基或C1～C20的支链烷基；Y为C4～C20的直链烷基，C4～C20的支链烷基或
其中，Y1～Y4为氢，C1～C20的直链烷基，C1～C20的支链烷基，C1～C20的酰胺基，C1～C20烷氧基或卤素；W为氮，氧或硫。
一种双吩噻嗪基染料的制备方法，包括以下步骤：
反应均在惰性气氛中进行；
(1)将碱和A按照摩尔比为1～5∶1混合，在0～40℃下搅拌1～60min；然后滴加B，B与A的摩尔比为1∶2，反应1～48h；加入到冰水混合物中搅拌10～30min，过滤，将固体溶于二氯甲烷中，水洗，分液，干燥有机相，重结晶后得到化合物M1；
(2)向冰浴中的N，N-二甲基甲酰胺中缓慢滴加POCl3，N，N-二甲基甲酰胺与POCl3的摩尔比为1～5∶1，恢复室温，搅拌1～2h；然后滴加溶于溶剂的M1，M1与POCl3的摩尔比为1∶8～1∶1，在50～120℃下搅拌1～24h；调节pH为6～7，搅拌1～10h，加入二氯甲烷萃取，有机相水洗，干燥，浓缩，得到化合物M2；
(3)将M2与氰基乙酸按摩尔比为1∶20～1∶2加入到溶剂中，滴加4～10滴有机碱，在50～120℃下搅拌1～24h；调节pH为1～5，搅拌1～60min，过滤，固体干燥后进行柱层析分离得到化合物M3；
所述化合物A为：
所述化合物B为Br-Y-Br；
所述化合物M1为：
所述化合物M2为：
所述化合物M3为：
其中：R1～R6为氢、C1～C20的直链烷基、C1～C20的支链烷基、C1～C20的酰胺基、C1～C20烷氧基或卤素；m为1～6的自然数；X为氢、C1～C20的直链烷基、C1～C20的支链烷基、C1～C20的酰胺基、C1～C20烷氧基、卤素或
X1～X5为氢，C1～C20的直链烷基，C1～C20的支链烷基，C1～C20的酰胺基，C1～C20烷氧基或卤素；X6，X7为氢，C1～C20的直链烷基，C1～C20的支链烷基或C1～C20烷氧基；X8，X9为氢，C1～C20的直链烷基或C1～C20的支链烷基；
其中，
Y为C4～C20的直链烷基，C4～C20的支链烷基或
Y1～Y4为氢，C1～C20的直链烷基，C1～C20的支链烷基，C1～C20的酰胺基，C1～C20烷氧基或卤素；W为氮、氧或硫。
所述碱为氢氧化钠或氢氧化钾。
所述有机碱为吡啶、哌啶或三乙胺。
步骤(1)所述溶剂为二甲基亚砜或N，N-二甲基甲酰胺。
步骤(2)所述溶剂为氯仿、二氯甲烷或1，2-二氯乙烷。
步骤(3)所述溶剂为氯仿、乙腈或醋酸。
一种双吩噻嗪基染料在染料敏化太阳能电池中的应用。
本发明吩噻嗪染料的合成方法简单，原料价廉易得，其合成按如下反应式进行：
当m＝1时的反应式：
本发明合成的吩噻嗪染料在染料料敏化太阳能电池中的应用，包括染料敏化太阳能电池的组成和构造、制备步骤和电池性能测试为：
(1)染料敏化太阳能电池的组成和构造：染料敏化太阳能电池主要由光阳极、光阴极及它们的基板(导电玻璃)和电解质组成；光阳极基板工作区域一侧导电玻璃中间设有纳米多孔TiO2薄膜，并浸染有吩噻嗪染料；光阴极基板工作区域一侧电玻璃中间设有催化剂(Pt)层；光阳极和光阴极相对间隔设置，中间纳米多孔TiO2薄膜周边用密封材料密封形成密闭的腔体，腔体内填充有电解质；
(2)所述染料敏化太阳能电池的制备步骤如下：
(a)导电玻璃的预处理：将导电玻璃依次在去油剂、无水乙醇和去离子水中用超声波清洗，然后烘干备用；
(b)TiO2浆料的制备：将2g P25型二氧化钛纳米颗粒分散在4ml去离子水与0.1ml乙酰丙酮的混合溶剂中，加入两滴Triton X-100；
(c)染料溶液的配制：将权利要求1所述的吩噻嗪染料溶于四氢呋喃中，配制成5×10-4mol·L-1溶液；
(d)电解质溶液的配制：用绝对干燥的乙腈配制含有0.6M四丁基碘化铵，0.1M LiI，0.05M I2和0.5M对叔丁基吡啶的溶液；
(e)光阳极的制备：在步骤(1)处理好的导电玻璃上，通过丝网印刷制备底面积为0.237cm2，厚度为15～20μm的圆柱形纳米多孔TiO2薄膜材料，并在450℃下保持30分钟后缓慢降至室温，再将其浸于40mM TiCl4水溶液中，在70℃保持半小时，取出后用去离子水冲洗干净，在500℃烘焙半小时；
(f)光阳极的敏化：将步骤(5)制备的光阳极纳米多孔TiO2薄膜层浸染在权利要求1所述的吩噻嗪染料按步骤(3)配制后的溶液中，染浴12～24h；
(g)光阴极的制备：在经过预处理的光阴极基板上，通过热分解法镀上Pt做催化剂层，然后钻针头大小孔备用；
(h)电池的封装：在光阳极TiO2薄膜的周边位置，放上经用磨具分割成内圆回字形的Surlyn1702热熔膜，盖上光阴极，然后在100℃加热2分钟密封；
(i)将上述电解质通过真空或者手工方法从光阴极的小孔注入，待两个电极之间没有气泡后，将其密封，制得染料敏化太阳能电池；
(3)电池性能测试：从电池的光阳极和光阴极分别引出导线，接到电池性能测试装置上，电池的工作面积为0.237cm2，用太阳光模拟器模拟太阳光，将光强度调节至100mW/cm2测得的光电转化效率为1.23～4.18％，短路电流为2.87-8.24mA/cm2，开路电压为0..512～0.747V，填充因子为0.60-0.73。
本发明相对于现有技术所具有的优点及有益效果如下：
吩噻嗪是一种富电子的含氮杂环化合物，由于其不共平面的蝴蝶状结构使得基于其为电子给体的染料具有防止分子堆积和激基缔合的作用；
本发明设计并合成一类基于双吩噻嗪及其衍生物为电子给体、双氰基乙酸为受体的新型染料。该染料具有结构简单，合成容易，防止染料分子间堆积，光电转化性能高等优点。
附图说明
图1为染料敏化太阳能电池封装俯视图，
图2为染料敏化太阳能电池封装侧视图；其中：
101导电玻璃
102镀铂的导电玻璃
103吸附了光敏染料的纳米TiO2膜
104热固性密封圈
105电解液注入小孔
图3为实施例1及实施例2中所合成的染料在四氢呋喃溶剂中(浓度2×10-5M)紫外/可见吸收谱图。横坐标表示的是吸收波长，单位为纳米，纵坐标表示的是吸光强度，单位为1。
图4为实施例1及实施例2中所合成的染料在四氢呋喃溶剂中(浓度2×10-5M)的荧光发射谱图。横坐标表示的是发射波长，单位为纳米，纵坐标表示的是发射强度，单位为1。
图5和图6为染料敏化太阳能电池的放电曲线图。
横坐标表示的是电压，单位为伏；纵坐标表示的是电流密度，单位为毫安每平方厘米。其中：图5为用Solaronix公司提供的N719光敏染料，并按照实施例4所述方法组装的电池测得的放电曲线图，图6为利用实施例1及实施例2中合成的光敏染料，并按照实施例4所述方法组装的电池测得的电池放电曲线图。
具体实施方式
下面结合实施例对本发明做进一步地详细说明，但是本发明要求保护的范围并不局限于实施例表示的范围。
实施例1
1，6-双-(3-氰基丙烯酸基吩噻嗪基)-正己烷的合成
反应均在氮气保护下的干燥环境中进行
(1)1，6-双吩噻嗪基正己烷的合成
将1.99g(10mmol)的吩噻嗪溶于15ml DMSO中，加入2.24g(40mmol)KOH，在室温下剧烈搅拌20min。然后滴加1.22g(5mmol)的1，6-二溴己烷，继续反应48h。反应结束后倒入冰水混合物中剧烈搅拌30min，过滤，固体溶解于二氯甲烷中，水洗3次，干燥有机相，粗产物进行重结晶得到2.01g(4.18mmol)产物，收率为83.6％。熔点：163-165℃。
(2)1，6-双-(3-甲酰基吩噻嗪基)-正己烷的合成
向冰浴中的1～20份731mg(10mmol)DMF中加入1.23g(8mmol)POCl3入，然后撤去冰浴，恢复至室温，搅拌反应1h。然后缓慢滴加481mg(1mmol)溶于15ml 1，2-二氯乙烷中的1，6-双吩噻嗪基正己烷，在85℃下回流反应24h。反应结束后冷却，滴加2M的NaOH溶液调节pH≈6，搅拌2h，分液，再用二氯甲烷萃取3次，合并有机层，有机相水洗3次，干燥，浓缩，粗产物通过柱层析分离提纯，得到420mg(0.78mmol)产物，收率为78.0％。熔点：141-142℃。
(3)1，6-双(3-氰基丙烯酸基吩噻嗪基)-正己烷的合成
将268mg(0.5mmol)1，6-双-(3-甲酰基吩噻嗪基)-正己烷加入到三口瓶中，以15ml氯仿作为溶剂，加入425mg(5mmol)氰基乙酸，滴加8滴哌啶，在75℃下搅拌反应8h。反应结束后冷却，滴加0.1M的盐酸，调节pH≈3，搅拌30min，过滤，固体干燥后进行柱层析分离得到282mg(0.42mmol)产物，收率为84.1％。核磁1H-NMR(400MHz，DMSO-d6)(δ/ppm)：1.40(4H，m)，1.65(4H，m)，3.90(4H，t)，6.99(2H，t)，7.04(2H，d，J＝8Hz)，7.12(2H，d，J＝8.8Hz)，7.14(2H，d，J＝1.2Hz)7.19(2H，t)，7.77(2H，d，J＝2Hz)，7.88(2H，dd，J1＝2Hz，J2＝2Hz)，8.14(s，2H).质谱ESI-MS：Found m/z 669.2([M-H]-).ELEM.ANAL.Calc.For C38H30N4O4S2：C，68.04；H，4.51；N，8.35；S，9.56.Found：C，68.01；H，4.50；N，8.32；S，9.55.
实施例2
N-乙基-3-氰基丙烯酸基-吩噻嗪的合成
反应均在氮气保护下的干燥环境中进行
(1)N-乙基吩噻嗪的合成
将1.99g(10mmol)的吩噻嗪溶于15ml DMSO中，加入2.24g(40mmol)KOH，在室温下搅拌20min。然后滴加1.64g(15mmol)的溴乙烷，继续反应48h。倒入冰水混合物中搅拌10min，过滤，固体溶解于二氯甲烷中，水洗3次，干燥有机相，粗产物进行重结晶得到1.70g(7.48mmol)产物，收率为75％。熔点：104-105℃。
(2)N-乙基-3-甲酰基-吩噻嗪的合成
在冰裕中1～20份的731mg(10mmol)DMF中加入1.23g(8mmol)POCl3，然后撤去冰浴，恢复至室温，搅拌反应1h。然后缓慢滴加455mg(2mmol)溶于15ml 1，2-二氯乙烷中的N-乙基吩噻嗪，在85℃下回流反应24h。反应结束后冷却，倒入适量冷水，滴加2M的NaOH溶液调节pH≈6，搅拌2h，分液，再用二氯甲烷萃取3次，合并有机层，有机相水洗3次，干燥，浓缩，粗产物通过柱层析分离提纯，得到408mg(1.6mmol)产物，收率为80％。熔点：88-89℃。
(3)N-乙基-3-氰基丙烯酸基-吩噻嗪的合成
将255mg(1mmol)N-乙基3-甲酰基-吩噻嗪加入到三口瓶中，以15ml氯仿作为溶剂，加入425mg(5mmol)氰基乙酸，滴加8滴哌啶，在75℃下搅拌反应8h。反应结束后冷却，滴加0.1M的盐酸，调节pH≈3，搅拌30min，过滤，固体干燥后进行柱层析分离得到274mg(0.85mmol)产物，收率为85％。核磁1H-NMR(400MHz，DMSO-d6)(δ/ppm)：1.29(3H，t)，3.96(2H，t)，6.97(1H，t)，7.06(1H，d，J＝8Hz)，7.12(1H，d，J＝8.8Hz)，7.18(1H，d，J＝1.2Hz)7.21(1H，t)，7.77(1H，d，J＝2Hz)，7.88(1H，dd，J1＝2Hz，J2＝2Hz)，8.13(s，1H)，13.72(s，0.8H).质谱ESI-MS：Found m/z 321.6([M-H]-).ELEM.ANALCalc.For C38H30N4O4S2：C，67.06；H，4.38；N，8.69；S，9.95.Found：C，67.05；H，4.39；N，8.67；S，9.94.
实施例3
对实施例1及实施例2染料的紫外-可见吸收光谱/荧光光谱测试，紫外-可见吸收光谱和荧光发射谱图分别为图3、图4所示。
溶剂：四氢呋喃
浓度：2×10-5M
温度：室温
仪器：Shimadzu UV-2450紫外可见风光光度计，Hitachi F-4500荧光光谱仪
表1实施例1和2中染料的最大紫外/可见吸收波长和最大荧光发射波长(nm)数据比较，将所得的数据汇总于表1中
表1
| 染料 | 最大紫外/可见光吸收波长(nm) | 最大荧光发射波长(nm) |
| 实施例1 | 436 | 585 |
| 实施例2 | 438 | 585 |
实施例4
本发明中染料敏化太阳能电池如图1和2的制作如下：
(1)导电玻璃(FTO)的预处理：将导电玻璃依次在去油剂、无水乙醇和去离子水中用超声波充分清洗，然后烘干备用；
(2)TiO2浆料的制备：将2g P25二氧化钛纳米颗粒分散在4ml去离子水和0.1ml的乙酰丙酮混合溶剂中，分散结束后加入两滴Triton X-100；
(3)染料溶液的配制：将实施例1制的的吩噻嗪染料溶于四氢呋喃中，配制成2×10-4mol·L-1溶液；
(4)电解质溶液的配制：用绝对干燥的乙腈配制含有0.6M四丁基碘化铵，0.1M LiI，0.05M I2和0.5M对叔丁基吡啶的溶液；
(5)光阳极的制备：在步骤(1)处理好的导电玻璃上，通过丝网印刷制备底面积为0.237cm2，厚度为15～20μm的圆柱形纳米多孔TiO2薄膜材料，并在450℃下保持30分钟后缓慢降至室温，再将其浸于40mM TiCl4水溶液中，在70℃保持半小时，取出后用去离子水冲洗干净，在500℃烘焙半小时；
(6)光阳极的敏化：将步骤(5)制备的光阳极纳米多孔TiO2薄膜层浸染在实施例1的吩噻嗪染料按步骤(3)配制后的溶液中，染浴12～24h；
(7)光阴极的制备：在经过预处理的光阴极基板上，通过热分解法镀上Pt做催化剂层，然后钻针头大小孔备用；
(8)电池的封装：在光阳极纳米多孔TiO2薄膜的周边位置，放上经用磨具分割成内圆回字形的Surlyn1702热熔膜，上面盖上光阴极，然后通过100℃加热2分钟进行密封；
(9)将上述电解质通过真空或者手工方法从光阴极的小孔注入，待两个电极之间没有气泡后，将小孔密封，制得染料敏化太阳能电池供测试使用；
实施例5
染料敏化太阳能电池性能测试：
将按照实施例4中的电池制备步骤，以N719为敏化染料组装成电池，分别从光阳极和光阴极引出导线，接到电池性能测试装置上，电池的有效工作面积为0.237cm2时，用太阳光模拟器模拟太阳光，将光强度调节至100mW/cm2测得的光电转化效率为5.82％，短路电流为12.61mA/cm2，开路电压为0.734V，填充因子为0.624；测得的电池放电曲线如图5所示。
将按照实施例4中的电池制备步骤，分别以实施例1和实施例2合成的染料组装成电池，分别从光阳极和光阴极引出导线，接到电池性能测试装置上，电池的工作面积为0.237cm2时，用太阳光模拟器模拟太阳光，将光强度调节至100mW/cm2分别测其光电转化效率。图6为利用实施例1及实施例2中合成的光敏染料，并按照实施例4所述方法组装的电池测得的电池放电曲线图。N719、实施例1和实施例2染料用于染料敏化太阳能电池性能数据对比，将所测数据汇总于表2。
表2
Claims (8)
1.一种双吩噻嗪基染料，其特征在于，具有以下结构通式：
其中：R1～R6为氢、C1～C20的直链烷基、C1～C20的支链烷基、C1～C20的酰胺基、C1～C20烷氧基或卤素；m为1～6的自然数；X为氢、C1～C20的直链烷基、C1～C20的支链烷基、C1～C20的酰胺基、C1～C20烷氧基、卤素或
其中，X1～X5为氢，C1～C20的直链烷基，C1～C20的支链烷基，C1～C20的酰胺基，C1～C20烷氧基或卤素；X6，X7为氢，C1～C20的直链烷基，C1～C20的支链烷基或C1～C20烷氧基；X8，X9为氢，C1～C20的直链烷基或C1～C20的支链烷基；Y为C4～C20的直链烷基，C4～C20的支链烷基或
其中，Y1～Y4为氢，C1～C20的直链烷基，C1～C20的支链烷基，C1～C20的酰胺基，C1～C20烷氧基或卤素；W为氮，氧或硫。
2.权利要求1所述的一种双吩噻嗪基染料的制备方法，其特征在于，包括以下步骤：
反应均在惰性气氛中进行；
(1)将碱和A按照摩尔比为1～5∶1混合，在0～40℃下搅拌1～60min；然后滴加B，B与A的摩尔比为1∶2，反应1～48h；加入到冰水混合物中搅拌10～30min，过滤，将固体溶于二氯甲烷中，水洗，分液，干燥有机相，重结晶后得到化合物M1；
(2)向冰浴中的N，N-二甲基甲酰胺中缓慢滴加POCl3，N，N-二甲基甲酰胺与POCl3的摩尔比为1～5∶1，恢复室温，搅拌1～2h；然后滴加溶于溶剂的M1，M1与POCl3的摩尔比为1∶8～1∶1，在50～120℃下搅拌1～24h；调节pH为6～7，搅拌1～10h，加入二氯甲烷萃取，有机相水洗，干燥，浓缩，得到化合物M2；
(3)将M2与氰基乙酸按摩尔比为1∶20～1∶2加入到溶剂中，滴加4～10滴有机碱，在50～120℃下搅拌1～24h；调节pH为1～5，搅拌1～60min，过滤，固体干燥后进行柱层析分离得到化合物M3；
所述化合物A为：
所述化合物B为Br-Y-Br；
所述化合物M1为：
所述化合物M2为：
所述化合物M3为：
其中：R1～R6为氢、C1～C20的直链烷基、C1～C20的支链烷基、C1～C20的酰胺基、C1～C20烷氧基或卤素；m为1～6的自然数；X为氢、C1～C20的直链烷基、C1～C20的支链烷基、C1～C20的酰胺基、C1～C20烷氧基、卤素或
X1～X5为氢，C1～C20的直链烷基，C1～C20的支链烷基，C1～C20的酰胺基，C1～C20烷氧基或卤素；X6，X7为氢，C1～C20的直链烷基，C1～C20的支链烷基或C1～C20烷氧基；X8，X9为氢，C1～C20的直链烷基或C1～C20的支链烷基；
其中，
Y为C4～C20的直链烷基，C4～C20的支链烷基或
Y1～Y4为氢，C1～C20的直链烷基，C1～C20的支链烷基，C1～C20的酰胺基，C1～C20烷氧基或卤素；W为氮、氧或硫。
3.根据权利要求2所述的制备方法，其特征在于，所述碱为氢氧化钠或氢氧化钾。
4.根据权利要求2所述的制备方法，其特征在于，所述有机碱为吡啶、哌啶或三乙胺。
5.根据权利要求2-4之一所述的制备方法，其特征在于，步骤(1)所述溶剂为二甲基亚砜或N，N-二甲基甲酰胺。
6.根据权利要求2-4之一所述的制备方法，其特征在于，步骤(2)所述溶剂为氯仿、二氯甲烷或1，2-二氯乙烷。
7.根据权利要求2-4之一所述的制备方法，其特征在于，步骤(3)所述溶剂为氯仿、乙腈或醋酸。
8.权利要求1所述的一种双吩噻嗪基染料在染料敏化太阳能电池中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010242218XA CN101935461B (zh) | 2010-07-30 | 2010-07-30 | 一种双吩噻嗪基染料及其制法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010242218XA CN101935461B (zh) | 2010-07-30 | 2010-07-30 | 一种双吩噻嗪基染料及其制法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101935461A true CN101935461A (zh) | 2011-01-05 |
| CN101935461B CN101935461B (zh) | 2013-08-28 |
Family
ID=43389043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010242218XA Expired - Fee Related CN101935461B (zh) | 2010-07-30 | 2010-07-30 | 一种双吩噻嗪基染料及其制法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101935461B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145644A (zh) * | 2013-03-01 | 2013-06-12 | 陕西科技大学 | 一种制备3-甲酰基-10-烷基吩噻嗪的方法 |
| CN103497532A (zh) * | 2013-07-02 | 2014-01-08 | 华南理工大学 | 一类三向延长共轭链吩噻嗪染料及其在染料敏化太阳电池中的应用 |
| CN103788679A (zh) * | 2014-01-24 | 2014-05-14 | 华南理工大学 | 在π桥中引入苯并三氮唑的双链吩噻嗪染料及其在制备染料敏化太阳电池中的应用 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125960A (zh) * | 2007-06-11 | 2008-02-20 | 大连理工大学 | 一类用于染料敏化太阳能电池的吩噻嗪染料 |
-
2010
- 2010-07-30 CN CN201010242218XA patent/CN101935461B/zh not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125960A (zh) * | 2007-06-11 | 2008-02-20 | 大连理工大学 | 一类用于染料敏化太阳能电池的吩噻嗪染料 |
Non-Patent Citations (2)
| Title |
|---|
| J.SIMOKAITIENE ET AL.: "Phenotiazinyl-based hydrazones as new hole-transporting materials for electrophotographic photoreceptors", 《SYNTHETIC METALS》 * |
| TZI-YI WU ET AL.: "Synthesis and Characterization of Organic Dyes Containing Various Donors and Acceptors", 《INT. J. MOL. SCI.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145644A (zh) * | 2013-03-01 | 2013-06-12 | 陕西科技大学 | 一种制备3-甲酰基-10-烷基吩噻嗪的方法 |
| CN103145644B (zh) * | 2013-03-01 | 2016-01-20 | 陕西科技大学 | 一种制备3-甲酰基-10-烷基吩噻嗪的方法 |
| CN103497532A (zh) * | 2013-07-02 | 2014-01-08 | 华南理工大学 | 一类三向延长共轭链吩噻嗪染料及其在染料敏化太阳电池中的应用 |
| CN103497532B (zh) * | 2013-07-02 | 2017-03-01 | 华南理工大学 | 一类三向延长共轭链吩噻嗪染料及其在染料敏化太阳电池中的应用 |
| CN103788679A (zh) * | 2014-01-24 | 2014-05-14 | 华南理工大学 | 在π桥中引入苯并三氮唑的双链吩噻嗪染料及其在制备染料敏化太阳电池中的应用 |
| CN103788679B (zh) * | 2014-01-24 | 2015-09-16 | 华南理工大学 | 在π桥中引入苯并三氮唑的双链吩噻嗪染料及其在制备染料敏化太阳电池中的应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101935461B (zh) | 2013-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lee et al. | Organic dyes incorporating low-band-gap chromophores based on π-extended benzothiadiazole for dye-sensitized solar cells | |
| Hara et al. | Dye-sensitized nanocrystalline TiO2 solar cells based on novel coumarin dyes | |
| Hagberg et al. | Symmetric and unsymmetric donor functionalization. comparing structural and spectral benefits of chromophores for dye-sensitized solar cells | |
| Kim et al. | Novel conjugated organic dyes containing bis-dimethylfluorenyl amino phenyl thiophene for efficient solar cell | |
| Wan et al. | Phenothiazine–triphenylamine based organic dyes containing various conjugated linkers for efficient dye-sensitized solar cells | |
| Warnan et al. | A compact diketopyrrolopyrrole dye as efficient sensitizer in titanium dioxide dye-sensitized solar cells | |
| Srinivas et al. | D-π-A organic dyes with carbazole as donor for dye-sensitized solar cells | |
| Zafer et al. | New perylene derivative dyes for dye-sensitized solar cells | |
| Onozawa-Komatsuzaki et al. | Near-IR dye-sensitized solar cells using a new type of ruthenium complexes having 2, 6-bis (quinolin-2-yl) pyridine derivatives | |
| Wang et al. | Porphyrins bearing long alkoxyl chains and carbazole for dye-sensitized solar cells: tuning cell performance through an ethynylene bridge | |
| Kandavelu et al. | Novel iminocoumarin dyes as photosensitizers for dye-sensitized solar cell | |
| Pasunooti et al. | Synthesis, characterization and application of trans-D–B–A-porphyrin based dyes in dye-sensitized solar cells | |
| Chen et al. | Novel cyanine dyes with different methine chains as sensitizers for nanocrystalline solar cell | |
| Huang et al. | Novel dyes based on naphthalimide moiety as electron acceptor for efficient dye-sensitized solar cells | |
| Wan et al. | Influence of different arylamine electron donors in organic sensitizers for dye-sensitized solar cells | |
| Babu et al. | From Molecular Design to Co-sensitization; High performance indole based photosensitizers for dye-sensitized solar cells | |
| Iqbal et al. | Influence of spatial arrangements of π-spacer and acceptor of phenothiazine based dyes on the performance of dye-sensitized solar cells | |
| Zhou et al. | Triphenylamine-based organic dyes containing benzimidazole derivatives for dye-sensitized solar cells | |
| Qian et al. | Triazatruxene-based organic dyes containing a rhodanine-3-acetic acid acceptor for dye-sensitized solar cells | |
| EP1885015A1 (en) | Dye-sensitized photoelectric conversion device | |
| Baik et al. | Synthesis and photovoltaic properties of novel organic sensitizers containing indolo [1, 2-f] phenanthridine for solar cell | |
| CN102250484B (zh) | 用于染料敏化太阳能电池的咔唑基有机染料的制备方法 | |
| Iqbal et al. | Impact of hydroxy and octyloxy substituents of phenothiazine based dyes on the photovoltaic performance | |
| Zhang et al. | Anti-recombination organic dyes containing dendritic triphenylamine moieties for high open-circuit voltage of DSSCs | |
| Horiuchi et al. | Highly efficient metal-free organic dyes for dye-sensitized solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130828 Termination date: 20200730 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |