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
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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.
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| 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 |
| 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 |
| 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 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
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