CN104945858A - Preparation method for carboxylic acid type polyfluorene/titanium dioxide nano-hybrid materials - Google Patents
Preparation method for carboxylic acid type polyfluorene/titanium dioxide nano-hybrid materials Download PDFInfo
- Publication number
- CN104945858A CN104945858A CN201510391619.4A CN201510391619A CN104945858A CN 104945858 A CN104945858 A CN 104945858A CN 201510391619 A CN201510391619 A CN 201510391619A CN 104945858 A CN104945858 A CN 104945858A
- Authority
- CN
- China
- Prior art keywords
- carboxylic acid
- acid type
- type polyfluorene
- preparation
- polyfluorene
- 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
- 229920002098 polyfluorene Polymers 0.000 title claims abstract description 60
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 15
- LCKDOHRDONNZTG-UHFFFAOYSA-N 1,2-dibromo-9h-fluorene Chemical compound C1=CC=C2CC3=C(Br)C(Br)=CC=C3C2=C1 LCKDOHRDONNZTG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 47
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000002585 base Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002148 esters Chemical group 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
- 235000021050 feed intake Nutrition 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- -1 tricyclohexyl phosphine fluoroborate Chemical compound 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 238000010791 quenching Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 230000005622 photoelectricity Effects 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 9
- 150000002220 fluorenes Chemical class 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- 229920000547 conjugated polymer Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- OOLQAKXRETTYOD-UHFFFAOYSA-N CCC(OC1(C2=CC(Br)=CC=C2C(C=C2)=C1C=C2Br)OC(CC)=O)=O Chemical class CCC(OC1(C2=CC(Br)=CC=C2C(C=C2)=C1C=C2Br)OC(CC)=O)=O OOLQAKXRETTYOD-UHFFFAOYSA-N 0.000 description 4
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 4
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000587 hyperbranched polymer Polymers 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 0 C*(C)c(cc1)ccc1-c(cc1)cc2c1-c1ccc(*(C)C)cc1C2(CCC(O)=O)CCC(O)=O Chemical compound C*(C)c(cc1)ccc1-c(cc1)cc2c1-c1ccc(*(C)C)cc1C2(CCC(O)=O)CCC(O)=O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method for carboxylic acid type polyfluorene/titanium dioxide nano-hybrid materials. The preparation method comprises the steps that a dibromo fluorene monomer which contains carboxyl is compounded, carboxylic acid type polyfluorene is compounded, and a sol-gel method is adopted to prepare the carboxylic acid type polyfluorene/TiO2 nano-hybrid materials. The preparation method has the advantages that the anionic type polyfluorene is compounded, the sol-gel method is adopted to prepare the carboxylic acid type polyfluorene/titanium dioxide nano-hybrid materials, the method is simple, the reaction condition is gentle, two-phase mixing is conducted to approach the molecular level, and the hybrid materials are facilitated to form a homogeneous system; according to the prepared carboxylic acid type polyfluorene/titanium dioxide nano-hybrid materials, an obvious fluorescence quenching phenomenon can be observed, separating and transmitting process of electric charges are generated on the interfaces of the polyfluorene and titanium dioxide particles, the film-forming property is good, and therefore the hybrid materials have potential application in the field of photoelectricity.
Description
Technical field
The invention belongs to field of material preparation, relate to the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material.
Background technology
Conjugated polymers refers to a class linear polymeric polymer materials with π-π * conjugated electrons structure, they are as the very important photoconductive organic semiconductor material of a class, obtain research and apply very widely in fields such as photodiode, luminescent electrochemical cell, solar cells, polyfluorene just belongs to wherein a kind of.Conjugated polymers/inorganic semiconductor nano-hybrid material is a class new function matrix material.It combines the superiority of conjugated polymers, inorganic semiconductor nanometer material, the characteristic of semi-conductor can be embodied, the small-size effect of nano material, surface effects can also be shown, also may because synergy, complementary action make hybrid material have the special character such as optical, electrical after coupling.So, once showing up prominently at material science, just cause the extensive concern of researcher, and obtain increasingly deep research, to become in Materials science an important research frontier at present.
The preparation method that conjugated polymers/inorganic semiconductor nano-hybrid material is conventional mainly contains physical blending process, ligand exchange method, situ aggregation method, hyperbranched polymer stabilization method etc.Petrella etc. (The Journal of Physical Chemistry B, 2005,109 (4): 1554-1562.) adopt oleic acid and phosphoric acid as the coated TiO of tensio-active agent
2nanoparticle, more blended with MEH-PPV, obtain MEH-PPV/TiO
2nano-hybrid material, and observed quenching of fluorescence, show MEH-PPV and TiO
2separation and the transmitting procedure of electric charge is there is between the interface of nanoparticle.Liu etc. (Journal of the Chemical Society, 2004,126 (21): 6550-6551.) have synthesized the Polythiophene (P3HT-NH of end with ligand function group
2), and replace with the TOPO of this polymkeric substance by CdSe nanocrystal surface, thus as the part of nanocrystalline photoelectric functional, CdSe is stablized.(the Journal of the Chemical Society such as Emrick, 2004,126:11322-11325) synthesize the PPV monomer of band phosphine oxide group, with this monomer as nanocrystalline surfactivity part, CdSe has been synthesized nanocrystalline under high temperature, finally polymerisablely nanocrystallinely to be polymerized this under certain condition, at nanocrystalline surperficial direct growth PPV, to obtain surface nanocrystalline by the CdSe of PPV grafting.Chinese Academy of Sciences's chemistry (the Langmuir such as Yang Junlin, 2001,17 (19): 5978-5983) hyperbranched poly-phenylene vinylene (ppv) (HPV) has been synthesized, and CdS is dispersed in HPV, carry out observation by atomic force microscope (AFM) to the topological framework of complexes membrane to find, CdS particle is in the pore space structure being dispersed in the molecule of HPV that can be good.
In the preparation method of common conjugated polymers/inorganic semiconductor nano-hybrid material; physical blending process can add surfactants stabilize usually in order to the reunion overcoming inorganic semiconductor nanoparticle, but the membership that adds of tensio-active agent hinders charge separation between inorganic semiconductor nanometer material and conjugated polymers and transmitting procedure.Although ligand exchange method, situ aggregation method, hyperbranched polymer stabilization method can overcome this defect, also there is the complicacy in design and chemosynthesis and limitation.
Summary of the invention
The technical problem to be solved in the present invention is: based on the problems referred to above, the invention provides the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material.
The present invention solves the technical scheme that its technical problem adopts: a kind of preparation method of carboxylic acid type polyfluorene/nano titania hybrid material, comprises the following steps:
(1) synthesis of carboxylic dibromo fluorenes monomer
2 are added in reaction vessel, 7-dibromo fluorenes, phase-transfer catalyst and solvent, inject strong base solution under nitrogen atmosphere, at 30 ~ 40 DEG C, react 0.5 ~ 1h, add α, β containing carboxyl or ester group-unsaturated conjugated compound subsequently, continue reaction 5 ~ 12h; After reaction terminates, reaction solution is poured in appropriate amount of deionized water, extract until water layer is colourless with methylene dichloride or ethylene dichloride, separatory, retain water layer; The pH of water layer is adjusted to acidity, and product is separated out, and filters, dries, obtain carboxylic dibromo fluorenes monomer;
(2) synthesis of carboxylic acid type polyfluorene
Carboxylic dibromo fluorenes monomer, diborate, catalyzer, part, weak base and solvent is added in reaction vessel, under nitrogen atmosphere, be heated to 90 ~ 95 DEG C of reaction 6 ~ 12h, add phenylo boric acid reaction 2 ~ 3h subsequently, finally add bromobenzene reaction 2 ~ 3h again; After reaction terminates, precipitate with the deionized water after acidified, filter, dry, the product of gained is purified through column chromatography again, obtains carboxylic acid type polyfluorene;
(3) carboxylic acid type polyfluorene/TiO
2the preparation of nano-hybrid material
Prepared by employing sol-gel method: in reaction vessel, add solvent and carboxylic acid type polyfluorene successively, after carboxylic acid type polyfluorene is dissolved completely, under the condition stirred, slowly adds TiO
2precursor solution, stirs and obtains solution A; In another reaction vessel, add acid and deionized water, stir and obtain solution B; Under agitation, solution B is slowly dropped in solution A and react 6 ~ 12h under normal temperature, finally obtain the carboxylic acid type polyfluorene/TiO 2 sol of clear; By obtained carboxylic acid type polyfluorene/TiO 2 sol sealing, ageing 2 ~ 4d at 60 ~ 70 DEG C, finally dries and obtains carboxylic acid type polyfluorene/TiO
2nano-hybrid material.
Further, in step (1), phase-transfer catalyst is one or more in Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate or tri-n-octyl methyl ammonium chloride, solvent is one or more in DMSO, DMF or DMAC, highly basic is one or more in sodium hydroxide, potassium hydroxide or potassium tert.-butoxide, and the structure of α, β containing carboxyl or ester group-unsaturated conjugated compound is as follows:
Wherein: R
1for H or-CH
3; R
2for H ,-CH
2cH
2n (CH
3)
2, C
1~ C
12saturated alkane or unsaturated hydrocarbons.
Further, in step (1) 2, the molar ratio of 7-dibromo fluorenes, phase-transfer catalyst, highly basic, α, β containing carboxyl or ester group-unsaturated conjugated compound is 1:(0.06 ~ 0.1): (10 ~ 15): (2.1 ~ 2.5), the consumption of solvent is make to feed intake the volumetric molar concentration of total amount at 6 ~ 8mol/L.
Further, in step (2), carboxylic dibromo fluorenes monomer is dibromo fluorenes monomer synthesized in step (1), and structure is as follows:
Wherein: R is H or-CH
3.
Further, in step (2), diborate is 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-9,9-dialkyl fluorene (I), Isosorbide-5-Nitrae-bis-(4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-benzene (II) or 1,1 '-bis-(4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-4,4 '-biphenyl (III), structure is as follows:
Wherein: R is H, C
1~ C
12saturated alkane or unsaturated hydrocarbons.
Further, in step (2), catalyzer is Pd (OA
c)
2, PdCl
2or Pd (PPh (dppf)
3)
4in one or more, part is one or more in tricyclohexyl phosphine fluoroborate, tricyclohexyl phosphine, tri-butyl phosphine, triphenylphosphine or triethylene diamine, weak base is one or more in tetramethylammonium hydroxide aqueous solution, the tetraethyl ammonium hydroxide aqueous solution, the TPAOH aqueous solution, the TBAH aqueous solution, Potassium ethanoate or salt of wormwood, and solvent is one or more in DMSO, DMF, DMAC or toluene.
Further, in step (2), the molar ratio of carboxylic dibromo fluorenes monomer, diborate, catalyzer, part, weak base, phenylo boric acid, bromobenzene is 1:1:(0.025 ~ 0.04): (0.05 ~ 0.2): (20 ~ 25): 1:1, the consumption of solvent is make to feed intake the volumetric molar concentration of total amount at 1 ~ 3mol/L.
Further, in step (2), the structure of the carboxylic acid type polyfluorene of preparation is as follows:
Wherein: n is the polymerization degree, n is 2 ~ 50, R is H or-CH
3, Ar is:
In Ar: R is H, C
1~ C
12saturated alkane or unsaturated hydrocarbons.
Further, in step (3), solvent is anhydrous methanol or tetrahydrofuran (THF), and carboxylic acid type polyfluorene is carboxylic acid type polyfluorene synthesized in step (2), TiO
2precursor solution is tetrabutyl titanate, isopropyl titanate, metatitanic acid n-propyl or TiCl
4in one, acid is one or more in hydrochloric acid, nitric acid or Glacial acetic acid.
Further, in step (3), in solution A, the concentration of carboxylic acid type polyfluorene is 2 ~ 8mg/mL, TiO
2the add-on of precursor solution is for making TiO
2be 1 ~ 7:1 with the mass ratio of carboxylic acid type polyfluorene, in solution B, the content of acid is 10 ~ 20wt%, and the volume ratio of solution A and B solution is 1:0.05 ~ 0.1.
The invention has the beneficial effects as follows: the present invention has synthesized the conjugated polymers-anionic polyfluorene of a kind of water/alcohol dissolubility, and the carboxylic acid type polyfluorene/nano titania hybrid material that adopted sol-gel method to prepare; This method is simple, reaction conditions is gentle, and two-phase mixtures is close to molecular level, is conducive to hybrid material and forms homogeneous system; Prepared carboxylic acid type polyfluorene/nano titania hybrid material can be observed obvious Fluorescence-quenching, illustrate that polyfluorene exists being separated of electric charge and transmitting procedure with TiO 2 particles interface, and film-forming properties is better, therefore this hybrid material has potential application at photoelectric field.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1 is PF8COOH/TiO
2, PFDPCOOH/TiO
2and PFPCOOH/TiO
2the XRD spectra of nano-hybrid material;
Fig. 2 is PF8COOH solution and PF8COOH/TiO
2the fluorescence emission spectrum of colloidal sol;
Fig. 3 is PF8COOH film and PF8COOH/TiO
2the fluorescence emission spectrum of film;
Fig. 4 is PFDPCOOH solution and PFDPCOOH/TiO
2the fluorescence emission spectrum of colloidal sol;
Fig. 5 is PFDPCOOH film and PFDPCOOH/TiO
2the fluorescence emission spectrum of film;
Fig. 6 is PFPCOOH solution and PFPCOOH/TiO
2the fluorescence emission spectrum of colloidal sol;
Fig. 7 is PFPCOOH film and PFPCOOH/TiO
2the fluorescence emission spectrum of film.
Embodiment
The invention will be further described in conjunction with specific embodiments now, and following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
The carboxylic acid type polyfluorene that the present embodiment is selected is poly-[9,9-dioctyl fluorene-9,9-bis-(propionyloxy) fluorenes] (PF8FCOOH), and its structure is as follows:
Wherein, n=15.
The synthesis of (1) 2,7-bis-bromo-9,9-bis-(propionyloxy) fluorenes
Thermometer is being housed, 3.24g 2 is added successively in the 100mL there-necked flask of magnetic stirring, 7-dibromo fluorenes, 0.25g Tetrabutyl amonium bromide, 25mL DMSO, inject the potassium hydroxide aqueous solution of 5mL massfraction 50% under nitrogen atmosphere, 0.5h is reacted at 30 DEG C, add 1.584g vinylformic acid subsequently, continue reaction 6h.After reaction terminates, reaction solution is poured in the beaker that 200mL deionized water is housed, with ethylene dichloride extraction until water layer is colourless, separatory, retain water layer, the pH of water layer is adjusted to acidity, product is separated out, and filters, dry in the convection oven of 60 DEG C, obtain white powder, productive rate 90%.
(2) synthesis of poly-[9,9-dioctyl fluorene-9,9-bis-(propionyloxy) fluorenes] (PF8FCOOH)
Thermometer is being housed, 0.2808g 2 is added successively in the 100mL there-necked flask of magnetic stirring, 7-bis-bromo-9,9-bis-(propionyloxy) fluorenes, 0.3684g 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-9,9-dioctyl fluorene, 0.004g Pd (OAc)
2, 0.0134g triethylene diamine, 8mL massfraction be 25% the tetraethyl ammonium hydroxide aqueous solution, 5mL DMSO and 5mL toluene, stir, under nitrogen atmosphere, be heated to 90 DEG C of reaction 12h.Add 0.0732g phenylo boric acid reaction 3h afterwards, then add 0.0942g bromobenzene reaction 3h.After reaction terminates, poured into by reaction solution in the deionized water after 200mL acidifying and precipitate, filter, dry, the product of gained is purified through column chromatography again, finally obtains yellow solid powder, productive rate 40%.
(3) PF8FCOOH/TiO
2the preparation of nano-hybrid material
In the 10mL reaction flask that magnetic stirring is housed, add 4mL tetrahydrofuran (THF), 10mg PF8FCOOH successively, after thing to be polymerized dissolves completely, under the condition stirred, slowly add 0.13mL tetrabutyl titanate, stir and obtain solution A.In another 2mL reaction flask, add 0.15mL concentrated hydrochloric acid (38wt%) and 0.15mL deionized water, stir and obtain solution B.Under agitation, solution B to be slowly added drop-wise in solution A stirring reaction 12h under normal temperature, finally to obtain the PF8COOH/TiO of clear
2colloidal sol.By obtained PF8COOH/TiO
2colloidal sol seals, ageing 3d at 60 DEG C, finally dries and obtains PF8COOH/TiO
2the PF8COOH/TiO of=1:3 (mass ratio)
2nano-hybrid material.
Embodiment 2
The carboxylic acid type polyfluorene that the present embodiment is selected is poly-[1,1 '-xenyl-9,9-bis-(propionyloxy) fluorenes] (PFDPCOOH), and its structure is as follows:
Wherein, n=12.
The synthesis of (1) 2,7-bis-bromo-9,9-bis-(propionyloxy) fluorenes
Thermometer is being housed, 3.24g 2 is added successively in the 100mL there-necked flask of magnetic stirring, 7-dibromo fluorenes, 0.25g Tetrabutyl amonium bromide, 25mL DMSO, inject the potassium hydroxide aqueous solution of 5mL massfraction 50% under nitrogen atmosphere, 0.5h is reacted at 30 DEG C, add 1.892g methyl acrylate subsequently, continue reaction 6h.After reaction terminates, reaction solution is poured in the beaker that 200mL deionized water is housed, with ethylene dichloride extraction until water layer is colourless, separatory, retain water layer, the pH of water layer is adjusted to acidity, product is separated out, and filters, dry in the convection oven of 60 DEG C, obtain white powder, productive rate 88%.
(2) synthesis of poly-[1,1 '-xenyl-9,9-bis-(propionyloxy) fluorenes] (PFDPCOOH)
Thermometer is being housed, 0.2808g 2 is added successively in the 100mL there-necked flask of magnetic stirring, 7-bis-bromo-9,9-bis-(propionyloxy) fluorenes, 0.2436g 1,1 '-bis-(4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-4,4 '-biphenyl, 0.004g Pd (OAc)
2, 0.0134g triethylene diamine, 8mL massfraction be 25% the tetraethyl ammonium hydroxide aqueous solution, 5mL DMSO and 5mL toluene, stir, under nitrogen atmosphere, be heated to 90 DEG C of reaction 12h.Add 0.0732g phenylo boric acid reaction 3h afterwards, then add 0.0942g bromobenzene reaction 3h.After reaction terminates, poured into by reaction solution in the deionized water after 200mL acidifying and precipitate, filter, dry, the product of gained is purified through column chromatography again, finally obtains white solid powder, productive rate 42%.
(3) PFDPCOOH/TiO
2the preparation of nano-hybrid material
In the 10mL reaction flask that magnetic stirring is housed, add 4mL tetrahydrofuran (THF), 10mg PFDPCOOH successively, after thing to be polymerized dissolves completely, under the condition stirred, slowly add 0.21mL tetrabutyl titanate, stir and obtain solution A.In another 2mL reaction flask, add 0.15mL concentrated hydrochloric acid (38wt%) and 0.15mL deionized water, stir and obtain solution B.Under agitation, solution B to be slowly added drop-wise in solution A stirring reaction 12h under normal temperature, finally to obtain the PFDPCOOH/TiO of clear
2colloidal sol.By obtained PFDPCOOH/TiO
2colloidal sol seals, ageing 3d at 60 DEG C, finally dries and obtains PFDPCOOH/TiO
2the PFDPCOOH/TiO of=1:5 (mass ratio)
2nano-hybrid material.
Embodiment 3
The carboxylic acid type polyfluorene that the present embodiment is selected is poly-[Isosorbide-5-Nitrae-phenyl-9,9-bis-(propionyloxy) fluorenes] (PFPCOOH), and its structure is as follows:
Wherein, n=14.
The synthesis of (1) 2,7-bis-bromo-9,9-bis-(propionyloxy) fluorenes
Thermometer is being housed, 3.24g 2 is added successively in the 100mL there-necked flask of magnetic stirring, 7-dibromo fluorenes, 0.25g Tetrabutyl amonium bromide, 25mL DMSO, inject the potassium hydroxide aqueous solution of 5mL massfraction 50% under nitrogen atmosphere, 0.5h is reacted at 30 DEG C, add 3.146g dimethylaminoethyl acrylate subsequently, continue reaction 6h.After reaction terminates, reaction solution is poured in the beaker that 200mL deionized water is housed, with ethylene dichloride extraction until water layer is colourless, separatory, retain water layer, the pH of water layer is adjusted to acidity, product is separated out, and filters, dry in the convection oven of 60 DEG C, obtain white powder, productive rate 92%.
(2) synthesis of poly-[Isosorbide-5-Nitrae-phenyl-9,9-bis-(propionyloxy) fluorenes] (PFPCOOH)
Thermometer is being housed, in the 100mL there-necked flask of magnetic stirring, is adding 0.2808g 2,7-bis-bromo-9,9-bis-(propionyloxy) fluorenes, 0.198g 1 successively, 4-two (4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-benzene, 0.004g Pd (OAc)
2, 0.0134g triethylene diamine, 8mL massfraction be 25% the tetraethyl ammonium hydroxide aqueous solution, 5mL DMSO and 5mL toluene, stir, under nitrogen atmosphere, be heated to 90 DEG C of reaction 12h.Add 0.0732g phenylo boric acid reaction 3h afterwards, then add 0.0942g bromobenzene reaction 3h.After reaction terminates, poured into by reaction solution in the deionized water after 200mL acidifying and precipitate, filter, dry, the product of gained is purified through column chromatography again, finally obtains white solid powder, productive rate 45%.
(3) PFPCOOH/TiO
2the preparation of nano-hybrid material
In the 10mL reaction flask that magnetic stirring is housed, add 4mL tetrahydrofuran (THF), 10mg PFPCOOH successively, after thing to be polymerized dissolves completely, under the condition stirred, slowly add 0.30mL tetrabutyl titanate, stir and obtain solution A.In another 2mL reaction flask, add 0.15mL concentrated hydrochloric acid (38wt%) and 0.15mL deionized water, stir and obtain solution B.Under agitation, solution B to be slowly added drop-wise in solution A stirring reaction 12h under normal temperature, finally to obtain the PFPCOOH/TiO of clear
2colloidal sol.By obtained PFPCOOH/TiO
2colloidal sol seals, ageing 3d at 60 DEG C, finally dries and obtains PFPCOOH/TiO
2the PFPCOOH/TiO of=1:7 (mass ratio)
2nano-hybrid material.
PF8COOH/TiO
2, PFDPCOOH/TiO
2and PFPCOOH/TiO
2xRD spectra such as Fig. 1 of nano-hybrid material shows, can find out, adopts carboxylic acid type polyfluorene/TiO prepared by sol-gel method
2tiO in nano-hybrid material
2in rutile-type.
The obtained carboxylic acid type polyfluorene/TiO of embodiment 1 ~ 3
2the fluorescence emission spectrum of colloidal sol and film is shown in Fig. 2 ~ 7, can find out, prepared carboxylic acid type polyfluorene/TiO
2colloidal sol and film can observe obvious Fluorescence-quenching, and TiO
2when content increases, Quenching is more obvious, and carboxylic acid type polyfluorene and TiO are described
2separation and the transmitting procedure of electric charge is there is between interface.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to right.
Claims (10)
1. a preparation method for carboxylic acid type polyfluorene/nano titania hybrid material, is characterized in that: comprise the following steps:
(1) synthesis of carboxylic dibromo fluorenes monomer
2 are added in reaction vessel, 7-dibromo fluorenes, phase-transfer catalyst and solvent, inject strong base solution under nitrogen atmosphere, at 30 ~ 40 DEG C, react 0.5 ~ 1h, add α, β containing carboxyl or ester group-unsaturated conjugated compound subsequently, continue reaction 5 ~ 12h; After reaction terminates, reaction solution is poured in appropriate amount of deionized water, extract until water layer is colourless with methylene dichloride or ethylene dichloride, separatory, retain water layer; The pH of water layer is adjusted to acidity, and product is separated out, and filters, dries, obtain carboxylic dibromo fluorenes monomer;
(2) synthesis of carboxylic acid type polyfluorene
Carboxylic dibromo fluorenes monomer, diborate, catalyzer, part, weak base and solvent is added in reaction vessel, under nitrogen atmosphere, be heated to 90 ~ 95 DEG C of reaction 6 ~ 12h, add phenylo boric acid reaction 2 ~ 3h subsequently, finally add bromobenzene reaction 2 ~ 3h again; After reaction terminates, precipitate with the deionized water after acidified, filter, dry, the product of gained is purified through column chromatography again, obtains carboxylic acid type polyfluorene;
(3) carboxylic acid type polyfluorene/TiO
2the preparation of nano-hybrid material
Prepared by employing sol-gel method: in reaction vessel, add solvent and carboxylic acid type polyfluorene successively, after carboxylic acid type polyfluorene is dissolved completely, under the condition stirred, slowly adds TiO
2precursor solution, stirs and obtains solution A; In another reaction vessel, add acid and deionized water, stir and obtain solution B; Under agitation, solution B is slowly dropped in solution A and react 6 ~ 12h under normal temperature, finally obtain the carboxylic acid type polyfluorene/TiO 2 sol of clear; By obtained carboxylic acid type polyfluorene/TiO 2 sol sealing, ageing 2 ~ 4d at 60 ~ 70 DEG C, finally dries and obtains carboxylic acid type polyfluorene/TiO
2nano-hybrid material.
2. the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material according to claim 1, it is characterized in that: in described step (1), phase-transfer catalyst is one or more in Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate or tri-n-octyl methyl ammonium chloride, solvent is one or more in DMSO, DMF or DMAC, highly basic is one or more in sodium hydroxide, potassium hydroxide or potassium tert.-butoxide, and the structure of α, β containing carboxyl or ester group-unsaturated conjugated compound is as follows:
Wherein: R
1for H or-CH
3; R
2for H ,-CH
2cH
2n (CH
3)
2, C
1~ C
12saturated alkane or unsaturated hydrocarbons.
3. the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material according to claim 1, it is characterized in that: in described step (1) 2, the molar ratio of 7-dibromo fluorenes, phase-transfer catalyst, highly basic, α, β containing carboxyl or ester group-unsaturated conjugated compound is 1:(0.06 ~ 0.1): (10 ~ 15): (2.1 ~ 2.5), the consumption of solvent is make to feed intake the volumetric molar concentration of total amount at 6 ~ 8mol/L.
4. the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material according to claim 1, it is characterized in that: in described step (2), carboxylic dibromo fluorenes monomer is dibromo fluorenes monomer synthesized in step (1), and structure is as follows:
Wherein: R is H or-CH
3.
5. the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material according to claim 1, is characterized in that: in described step (2), diborate is 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-9,9-dialkyl fluorene (I), 1,4-two (4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-benzene (II) or 1,1 '-bis-(4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-4,4 '-biphenyl (III), structure is as follows:
Wherein: R is H, C
1~ C
12saturated alkane or unsaturated hydrocarbons.
6. the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material according to claim 1, is characterized in that: in described step (2), catalyzer is Pd (OA
c)
2, PdCl
2or Pd (PPh (dppf)
3)
4in one or more, part is one or more in tricyclohexyl phosphine fluoroborate, tricyclohexyl phosphine, tri-butyl phosphine, triphenylphosphine or triethylene diamine, weak base is one or more in tetramethylammonium hydroxide aqueous solution, the tetraethyl ammonium hydroxide aqueous solution, the TPAOH aqueous solution, the TBAH aqueous solution, Potassium ethanoate or salt of wormwood, and solvent is one or more in DMSO, DMF, DMAC or toluene.
7. the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material according to claim 1, it is characterized in that: in described step (2), the molar ratio of carboxylic dibromo fluorenes monomer, diborate, catalyzer, part, weak base, phenylo boric acid, bromobenzene is 1:1:(0.025 ~ 0.04): (0.05 ~ 0.2): (20 ~ 25): 1:1, the consumption of solvent is make to feed intake the volumetric molar concentration of total amount at 1 ~ 3mol/L.
8. the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material according to claim 1, is characterized in that: in described step (2), the structure of the carboxylic acid type polyfluorene of preparation is as follows:
Wherein: n is the polymerization degree, n is 2 ~ 50, R is H or-CH
3, Ar is:
In Ar: R is H, C
1~ C
12saturated alkane or unsaturated hydrocarbons.
9. the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material according to claim 1, it is characterized in that: in described step (3), solvent is anhydrous methanol or tetrahydrofuran (THF), carboxylic acid type polyfluorene is carboxylic acid type polyfluorene synthesized in step (2), TiO
2precursor solution is tetrabutyl titanate, isopropyl titanate, metatitanic acid n-propyl or TiCl
4in one, acid is one or more in hydrochloric acid, nitric acid or Glacial acetic acid.
10. the preparation method of a kind of carboxylic acid type polyfluorene/nano titania hybrid material according to claim 1, is characterized in that: in described step (3), in solution A, the concentration of carboxylic acid type polyfluorene is 2 ~ 8mg/mL, TiO
2the add-on of precursor solution is for making TiO
2be 1 ~ 7:1 with the mass ratio of carboxylic acid type polyfluorene, in solution B, the content of acid is 10 ~ 20wt%, and the volume ratio of solution A and B solution is 1:0.05 ~ 0.1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510391619.4A CN104945858B (en) | 2015-07-06 | 2015-07-06 | A kind of preparation method of carboxylic acid type polyfluorene/nano titania hybrid material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510391619.4A CN104945858B (en) | 2015-07-06 | 2015-07-06 | A kind of preparation method of carboxylic acid type polyfluorene/nano titania hybrid material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104945858A true CN104945858A (en) | 2015-09-30 |
CN104945858B CN104945858B (en) | 2017-07-14 |
Family
ID=54160955
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510391619.4A Expired - Fee Related CN104945858B (en) | 2015-07-06 | 2015-07-06 | A kind of preparation method of carboxylic acid type polyfluorene/nano titania hybrid material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104945858B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108461633A (en) * | 2018-03-13 | 2018-08-28 | 常州大学 | A kind of hybrid and preparation method thereof for perovskite solar cell electron transfer layer |
CN108461637A (en) * | 2018-03-13 | 2018-08-28 | 常州大学 | A kind of hybrid and preparation method thereof for polymer solar battery electron transfer layer |
CN111589472A (en) * | 2020-04-22 | 2020-08-28 | 齐齐哈尔大学 | Carboxyl-containing conjugated microporous polymer/TiO2Method for preparing composite material |
WO2020213470A1 (en) * | 2019-04-17 | 2020-10-22 | 大阪ガスケミカル株式会社 | Dicarboxylic acids, and production method and use thereof |
JP7568617B2 (ja) | 2019-04-17 | 2024-10-16 | 大阪ガスケミカル株式会社 | ジカルボン酸類ならびにその製造方法および用途 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007073043A2 (en) * | 2005-12-20 | 2007-06-28 | Lg Chem, Ltd. | Titania sol, method of preparing the same, and coating composition comprising the same |
-
2015
- 2015-07-06 CN CN201510391619.4A patent/CN104945858B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007073043A2 (en) * | 2005-12-20 | 2007-06-28 | Lg Chem, Ltd. | Titania sol, method of preparing the same, and coating composition comprising the same |
Non-Patent Citations (2)
Title |
---|
王萍萍: "共轭聚合物(聚芴)/无机粒子纳米复合体系的光致发光研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技I辑》 * |
高山等: "磺酸型聚芴的合成及性能", 《高分子材料科学与工程》 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108461633A (en) * | 2018-03-13 | 2018-08-28 | 常州大学 | A kind of hybrid and preparation method thereof for perovskite solar cell electron transfer layer |
CN108461637A (en) * | 2018-03-13 | 2018-08-28 | 常州大学 | A kind of hybrid and preparation method thereof for polymer solar battery electron transfer layer |
CN108461633B (en) * | 2018-03-13 | 2021-11-30 | 常州大学 | Hybrid for electronic transmission layer of perovskite solar cell and preparation method thereof |
CN108461637B (en) * | 2018-03-13 | 2021-11-30 | 常州大学 | Hybrid for polymer solar cell electron transport layer and preparation method thereof |
WO2020213470A1 (en) * | 2019-04-17 | 2020-10-22 | 大阪ガスケミカル株式会社 | Dicarboxylic acids, and production method and use thereof |
CN113727961A (en) * | 2019-04-17 | 2021-11-30 | 大阪燃气化学有限公司 | Dicarboxylic acids, process for producing the same, and use thereof |
CN113727961B (en) * | 2019-04-17 | 2024-09-03 | 大阪燃气化学有限公司 | Dicarboxylic acids, process for producing the same, and use thereof |
JP7568617B2 (ja) | 2019-04-17 | 2024-10-16 | 大阪ガスケミカル株式会社 | ジカルボン酸類ならびにその製造方法および用途 |
CN111589472A (en) * | 2020-04-22 | 2020-08-28 | 齐齐哈尔大学 | Carboxyl-containing conjugated microporous polymer/TiO2Method for preparing composite material |
CN111589472B (en) * | 2020-04-22 | 2022-11-29 | 齐齐哈尔大学 | Carboxyl-containing conjugated microporous polymer/TiO 2 Method for preparing composite material |
Also Published As
Publication number | Publication date |
---|---|
CN104945858B (en) | 2017-07-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Pradhan | Tips and twists in making high photoluminescence quantum yield perovskite nanocrystals | |
CN104945858A (en) | Preparation method for carboxylic acid type polyfluorene/titanium dioxide nano-hybrid materials | |
Xiao et al. | A tunable artificial light-harvesting system based on host-guest interaction exhibiting ultrahigh antenna effect and narrowed emission band | |
CN107148686A (en) | Organic illuminating element ink composite and use its organic illuminating element | |
CN110156071A (en) | A kind of preparation method of the full-inorganic perovskite nanocluster assembly of high-sequential | |
CN102876319B (en) | Spirofluorene pyridine fluorescent material and preparation method thereof | |
Xu et al. | In situ-fabricated perovskite nanocrystals for deep-blue light-emitting diodes | |
Maya Pai et al. | Synthesis and catalytic activity of heterogenous hybrid nanocatalyst of copper/palladium MOF, RIT 62-Cu/Pd for stille polycondensation of thieno [2, 3-b] pyrrol-5-one derivatives | |
CN103570070A (en) | Preparation method of self-assembly W18049 nanostructure | |
CN103254373B (en) | Preparation method of stable segmented copolymer PAPMA (Polymethyl Acrylate P-acetamide Phenyl Ester)-b-PNIPAM (Polyisopropyl Acrylamide) based Au nanometer particle | |
CN101575505A (en) | Blue light luminescent material with organic-inorganic hybrid structure, preparation method and application thereof | |
CN107900376B (en) | Preparation method of water-soluble silver nanoparticles | |
CN107759774A (en) | Main chain contains S, the D A type polymer of S dioxydibenze bithiophenes and preparation method and application | |
CN101597489B (en) | Organic, inorganic hybrid green-light material having a network structure, preparation and use thereof | |
WO2024113800A1 (en) | Organic light-emitting diode material, device and apparatus | |
CN110408007B (en) | Preparation method of POSS hybrid conjugated polymer | |
CN101431148A (en) | Method for improving illumination intensity of CdTe nano compound film | |
JP2015171965A (en) | Core-shell type carbon nanotube composite material and production method thereof | |
González-Iñiguez et al. | Synthesis of polypyrrole nanoparticles by batch and semicontinuous heterophase polymerizations | |
CN102477142A (en) | Conjugated block polymer, and its preparation method and application | |
CN101948131A (en) | Chemical preparation method for cadmium sulfide semiconductor nano particles | |
CN108439456A (en) | The preparation method of ZnLiMgO nano particles and product prepared therefrom | |
CN101775122A (en) | Red light conjugated polymer of side-chain quinoline ligand-containing iridium compound and light-emitting device | |
CN101328303B (en) | Photoelectric nano composite material having push-and-pull electronic structure and preparation thereof | |
CN110128632B (en) | Organic electroluminescent polymer material containing tetraphenylethylene, preparation and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170714 |
|
CF01 | Termination of patent right due to non-payment of annual fee |