CN107954470B - A kind of preparation method and applications of water-soluble titanium dioxide nano particle - Google Patents

A kind of preparation method and applications of water-soluble titanium dioxide nano particle Download PDF

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CN107954470B
CN107954470B CN201711194452.8A CN201711194452A CN107954470B CN 107954470 B CN107954470 B CN 107954470B CN 201711194452 A CN201711194452 A CN 201711194452A CN 107954470 B CN107954470 B CN 107954470B
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ptba
nano particle
titanium dioxide
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CN107954470A (en
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裴东杰
吴斌
刘刚
于航
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Henan Kedou New Materials Research Institute Co., Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/802—Photocatalytic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The invention discloses a kind of preparation method and applications of water-soluble titanium dioxide nano particle, use beta-cyclodextrin for initial reaction raw material, through modifying synthetic macromolecule initiator, using ATRP technology, and the technology that ATRP and " link " chemical (Click Chemistry) are combined, multi-arm star block copolymer is made, based on solution phase synthesis, using the multi-arm star block copolymer as unimolecular micelle template, the water-soluble titanium dioxide nano particle of size uniformity and favorable dispersibility is made.TiO produced by the present invention2Nanoparticle mass is stablized, and particle size is uniform, and can stablize in nanoscale, can effectively ensure that TiO2The performance of nano particle performance.The present invention is to TiO2The surface of nano particle is modified, it can be made to be uniformly dispersed in water, avoids that reuniting effect occurs.

Description

A kind of preparation method and applications of water-soluble titanium dioxide nano particle
Technical field
The present invention relates to a kind of preparation method and applications of water-soluble titanium dioxide nano particle, belong to inorganic nano material Expect synthesis technical field.
Background technique
There is one-dimensional dimensions above in 1-100nm or be generally referred to as the substance that basic unit is constituted by them be nano material, This is about as much as the scale that 10-100 atom is arranged closely together.Nano material is due to skin effect, micro-dimension The unique effect such as effect and quantum tunneling effect, thus show unique electricity, optics, magnetics and catalytic performance.
Titanium dioxide has greater band gap, good biocompatibility, resists various chemistry rotten as a kind of typical N-type semiconductor The characteristics of candle, human body nonhazardous, while there is good optical power, photocatalysis performance, photoelectric conversion rate, antimicrobial efficiency, Be widely used in cosmetics, coating, water body purification, air cleaning, solar battery, dye-sensitized cell, biological medicine and The multiple fields such as antibiotic and sterilizing.
Photocatalysis oxidation technique has outstanding advantages of efficient, energy conservation, nontoxic cleaning, and being one has wide application prospect Novel air pollution and water pollution processing technique.Optically catalytic TiO 2 research origin in Fujishima in 1979 and Honda decomposes the experiment of water with luminous energy using titanium deoxid film as electrode.Since then, optically catalytic TiO 2 technology just causes The extensive concern of scientist.Titanium dioxide can generate a large amount of electron hole and extremely strong oxygen under sunlight and radiation of visible light The oxidation operation of absorption on the titanium dioxide can be the nonhazardous substances such as water and carbon dioxide by the active oxygen of change effect, It not will cause secondary pollution, thus be a kind of very with the environment-friendly materials of application prospect.Further, good light will urges The nano-titanium dioxide for changing performance is added in coating, forms photo-catalytic coating.The photo-catalytic coating new clothes that can effectively degrade are repaired the house Between the TVOCs such as formaldehyde, toluene, purify the air of a room.Photo-catalytic coating can also effectively kill the various bacteria in air, It is able to suppress various bacteria growth simultaneously, brings glad tidings for newly-decorated family.
There are many kinds of the synthetic methods of titania nanoparticles, can be generally divided into liquid phase method and vapor phase method.Vapor phase method Mainly gas phase TiCl4Oxidizing process.Liquid phase method mainly includes sol-gal process, chemical precipitation method and hydrothermal synthesis method etc..Tradition The titania nanoparticles of method synthesis usually have the shortcomings that size and are distributed uncontrollable, and the property of titanium dioxide and answer With the size and dispersibility depended greatly in particle, therefore find that a kind of particle size is uniform and favorable dispersibility The simple and convenient process for preparing of titania nanoparticles be very crucial.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation method of water-soluble titanium dioxide nano particle and It is applied, the titania nanoparticles size uniformity of this method preparation, favorable dispersibility.
To achieve the goals above, the technical scheme adopted by the invention is that:
A kind of preparation method of water-soluble titanium dioxide nano particle, comprising the following steps:
(1) beta-cyclodextrin is dissolved in N-Methyl pyrrolidone, 2- bromine isobutyl acylbromide, room temperature is added under the conditions of being placed in 0 DEG C Reaction, is made starlike macromole evocating agent 21Br- β-CD；
(2) starlike macromole evocating agent 21Br- β-CD initiation tert-butyl acrylate monomer is reacted by ATRP polymerization to gather It closes, multi-arm star β-CD-g-PtBA is made；
(3) multi-arm star β-CD-g-PtBA is subjected to Azide processing, then with end group modification for the mono methoxy with alkynyl Polyethylene glycol is the presoma of most outer segment block, is prepared radial block polymer β-CD-g- [PtBA-b-PEG]；
(4) in methylene chloride by radial block polymer β-CD-g- [PtBA-b-PEG] dissolution, trifluoroacetic acid is added, Normal temperature condition is lauched solution and obtains multi-arm star block copolymer β-CD-g- [PAA-b-PEG]；
(5) it regard multi-arm star block copolymer β-CD-g- [PAA-b-PEG] as unimolecular micelle template, then with solvable Property containing titanium oxide compounds be presoma, be made water-soluble titanium dioxide nano particle.
The molar ratio of the beta-cyclodextrin and 2- bromine isobutyl acylbromide is 1:42.
Step (2) method particularly includes: in ampoule bottle be added 0.0707g CuBr, 0.1707g PMDETA, 0.1g21Br- β-CD, 20mL tert-butyl acrylate monomer, 20mL butanone are placed in liquid nitrogen by freezing-vacuumizing degassing- Defrosting is de-gassed, and circulation three times, is put into ampoule bottle in 60 DEG C of oil baths, magnetic agitation 12-24h after closed；Ampoule bottle is taken out, It is put into mixture of ice and water, terminates reaction；Acetone dilution is added, is splined on neutral alumina column, collects efflux ,- It being precipitated in 20 DEG C of methanol and the mixed liquor of 4 DEG C of water, the volume ratio of methanol and water is 1:1, after repeating dissolution/precipitation operation twice, Gained white powder product be dried in vacuo at 50 DEG C 12h to get.
Step (3) method particularly includes:
(a) synthesis of star end group Azide PtBA
Above-mentioned gained β-CD-g-PtBA 3.60g is taken, is dissolved in 15mL DMF, sodium azide, sodium azide and β-is added The molar ratio of Br atom is 10:1 in CD-g-PtBA, and sealing is stirred for 24 hours at room temperature；Acetone dilution is added, is splined on Neutral alumina column is collected efflux, is precipitated in mixed liquor of -20 DEG C of methanol with 4 DEG C of water, and the volume ratio of methanol and water is 1: 1, after repeating dissolution/precipitation operation twice, gained white powder product is placed at 50 DEG C and is dried in vacuo 12h to obtain the final product, name For β-CD-g-PtBA-N3；
(b) synthesis of benzhydryl sodium DPMNa
100mL tetrahydrofuran and 7.7g naphthalene are added in 250mL three-necked flask, stirring is opened, after waiting naphthalenes to be completely dissolved, 1.38g metallic sodium is added under the protection of inert gas argon gas, reacts 4h under the conditions of 40 DEG C, 11.1g hexichol first is then added Alkane flows back for 24 hours under the conditions of 80 DEG C, obtains the THF solution of the wine-colored sodium containing benzhydryl；
(c) synthesis of the mPEG of alkynyl sealing end
In dry three-necked flask, 10g mPEG and 150mL tetrahydrofuran is added, the sodium containing benzhydryl is then added THF solution, benzhydryl sodium molal quantity are 5 times of mPEG, and solution colour becomes brownish red；It is then placed in ice-water bath, is added dropwise Propargyl bromide, propargyl bromide molal quantity are 5 times of mPEG, are reacted at room temperature for 24 hours；Methylene chloride dilution is added, is splined on Neutral alumina column collects efflux, is concentrated, is precipitated in -20 DEG C of ether, sediment is in vacuum drying oven with Rotary Evaporators 50 DEG C of dry 5h to obtain the final product, are named as mPEG-propargyl；
(d) synthesis of multi-arm star block copolymer β-CD-g- [PtBA-b-PEG]
CuBr, PMDETA, β-CD-g-PtBA-N are added in ampoule bottle3, mPEG-propargyl, their molar ratio For CuBr:PMDETA: β-CD-g-PtBA-N3: mPEG-propargyl=10:10:1:1.2, and DMF is added as solvent, make β-CD-g-PtBA-N3Concentration be 1g/10mL；It is subsequently placed in liquid nitrogen and is taken off by freezing-vacuumizing degassing-defrosting Gas, circulation three times, are put into ampoule bottle in 90 DEG C of oil baths, magnetic agitation is for 24 hours after closed；It is cooled to room temperature, adds dichloromethane Alkane dilution, is splined on neutral alumina column, collects efflux, precipitates in -20 DEG C of methanol, repeats dissolution/precipitation operation twice Afterwards, gained white powder product be placed at 60 DEG C be dried in vacuo 12h to get.
Step (4) method particularly includes: 0.3g β-CD-g- [PtBA-b-PEG] is dissolved in 30mL methylene chloride, 0 It DEG C is added with stirring trifluoroacetic acid, trifluoroacetic acid additional amount is that tert-butyl acrylate monomer rubs in β-CD-g- [PtBA-b-PEG] 5 times of that amount continue at 0 DEG C after keeping 3h, continue to be stirred to react 21h at room temperature, generate white depositions, filtering, with two Chloromethanes washing precipitate, and vacuum freeze drying to get.
Step (5) method particularly includes: β-CD-g- [PAA-b-PEG] is dissolved in DMF, unimolecular micelle mould is made Plate solution；Presoma isopropyl titanate is added, water-soluble titanium dioxide nano particle is made in back flow reaction.
The molar ratio of the presoma isopropyl titanate and acrylic acid repetitive unit in β-CD-g- [PAA-b-PEG] is not small In 5:1.
The back flow reaction temperature is 150-200 DEG C, time 2-4h.
The sodium dioxide nano particle of method preparation described in a kind of is in the photocatalytic degradation and conjunction for preparing organic pollutant At the application in photo-catalytic coating.
The utility model has the advantages that
1, the present invention uses beta-cyclodextrin for initial reaction raw material, through modifying synthetic macromolecule initiator, using ATRP skill The technology that art and ATRP and " link " chemical (Click Chemistry) are combined, is made multi-arm star block copolymer, Based on solution phase synthesis, using the multi-arm star block copolymer as unimolecular micelle template, size uniformity is made and divides Dissipate the good water-soluble titanium dioxide nano particle of property.
2、TiO2For nano particle since its surface is the unordered noncrystalline layer of short distance, inside is complete crystallization, period row The atom of cloth, therefore it is special with small-size effect, skin effect, quantum size effect, macro quanta tunnel effect etc. Property:
(1)TiO2Nano particle has photocatalysis, and the electronics in valence band is excited, and transits to conduction band, generates high living Property light induced electron (e-), while corresponding photohole (h+) can be generated in valence band.Light induced electron and photohole can be with absorption - OH, O in nano grain surface2And H2O reaction, generates activity hydroxy (- OH), hydroperoxyl (- OOH), superoxide ion (- O2) With hydrogen peroxide (H2O2)。TiO2This performance of nano particle has extremely strong lethality to microorganism, has in emulsion paint Important function.
(2)TiO2The partial size of nano particle is small, large specific surface area generates very between meeting and basis material in the composite Therefore strong binding force can improve the intensity and toughness of material simultaneously, this is that nano material is most aobvious to high molecular polymer modification One of effect of work.
(3)TiO2The size of nano particle drops to nanoscale, and surface area can significantly increase, and causes surface that can increase rapidly Add, easily combined with other atoms and settle out, therefore there is very high chemical activity, it is easy to absorb small point of ambient gas etc. Son, these small molecules are equivalent to one layer of stable gas membrane, make You Heshui can not be in the unfolded surface of material, therefore nanometer material Expect that double thin property are presented in surface, referred to as super parents' interfacial characteristics.
(4) it is also easy to produce reunion in nano material preparation process, so that the actual particle size of material is greater than nanoscale, under various performances Drop does not have the effect of nano material even.Therefore it must be uniformly dispersed, avoid reuniting, this is exactly innovative point of the invention One of.The present invention is to TiO2The surface of nano particle is modified, it can be made to be uniformly dispersed in water, avoids reuniting Effect.
(5)TiO2Nanoparticle has good visible light catalytic performance.
3, TiO produced by the present invention2Nanoparticle mass is stablized, and particle size is uniform, and can stablize in nanometer Grade, can effectively ensure that TiO2The performance of nano particle performance.
Detailed description of the invention
Below in conjunction with attached drawing, specific embodiments of the present invention will be described in further detail.
Fig. 1 is the TEM image of titania nanoparticles.
Fig. 2 is the dissolubility result of titania nanoparticles.
Fig. 3 is the formaldehyde removal effect figure of the photo-catalytic coating of titania nanoparticles preparation.
Fig. 4 is titania nanoparticles photo-catalytic degradation of methyl-orange effect picture.
Specific embodiment
Specific embodiments of the present invention will be described in further detail with reference to embodiments.
Embodiment 1
A kind of preparation method of water-soluble titanium dioxide nano particle, comprising the following steps:
(1) synthesis of starlike macromole evocating agent 21Br- β-CD:
6.82g beta-cyclodextrin is taken, under vacuum conditions in 80 DEG C of dry 12h, is then dissolved in 60mL under normal temperature conditions N-Methyl pyrrolidone, then be placed in ice-water bath, be cooled to 0 DEG C, under this condition, 58g 2- bromine isobutyryl is added dropwise in 2h Bromine is warming up to room temperature after completion of dropwise addition, and the reaction was continued for 24 hours, obtains brown solution, and 100mL dichloromethane is added in vacuum distillation concentration Alkane dilution, is respectively washed three times with 100mL saturated sodium bicarbonate aqueous solution and 100mL deionized water, obtained organic phase respectively It is dry with anhydrous magnesium sulfate, it is then concentrated with Rotary Evaporators, is finally precipitated in -20 DEG C of n-hexanes below, obtain white Sediment, in vacuum drying oven 50 DEG C of dry 12h to get；
(2) synthesis of multi-arm star β-CD-g-PtBA
0.0707g CuBr, 0.1707g PMDETA (pentamethyl-diethylenetriamine), 0.1g are added in ampoule bottle 21Br- β-CD, 20mL tert-butyl acrylate monomer, 20mL butanone are placed in liquid nitrogen by freezing-vacuumizing degassing-defrosting It is de-gassed, circulation three times, is put into ampoule bottle in 60 DEG C of oil baths, magnetic agitation is for 24 hours after closed；Ampoule bottle is taken out, is thrown Enter in mixture of ice and water, terminates reaction；Acetone (50mL) dilution is added, is splined on neutral alumina column, collects efflux ,- It being precipitated in 20 DEG C of methanol and the mixed liquor of 4 DEG C of water, the volume ratio of methanol and water is 1:1, after repeating dissolution/precipitation operation twice, Gained white powder product be dried in vacuo at 50 DEG C 12h to get；
(3) synthesis of star end group Azide PtBA
Above-mentioned gained β-CD-g-PtBA 3.60g is taken, is dissolved in 15mL DMF, sodium azide, sodium azide and β-is added The molar ratio of Br atom is 10:1 in CD-g-PtBA, and sealing is stirred for 24 hours at room temperature；The dilution of 50mL acetone is added, on Sample is collected efflux, is precipitated in mixed liquor of -20 DEG C of methanol with 4 DEG C of water, the volume ratio of methanol and water in neutral alumina column For 1:1, after repeating dissolution/precipitation operation twice, gained white powder product is placed at 50 DEG C and is dried in vacuo 12h to obtain the final product, It is named as β-CD-g-PtBA-N3；
(4) synthesis of benzhydryl sodium DPMNa
100mL tetrahydrofuran and 7.7g naphthalene are added in 250mL three-necked flask, stirring is opened, after waiting naphthalenes to be completely dissolved, 1.38g metallic sodium is added under the protection of inert gas argon gas, reacts 4h under the conditions of 40 DEG C, 11.1g hexichol first is then added Alkane flows back for 24 hours under the conditions of 80 DEG C, obtains the THF solution of the wine-colored sodium containing benzhydryl；Gained benzhydryl sodium solution is used The calibration of 0.1M hydrochloric acid solution, concentration is about 0.56M.
(5) synthesis of the mPEG of alkynyl sealing end
In dry three-necked flask, 10g mono methoxy polyethylene glycol (mPEG) and 150mL tetrahydrofuran is added, then The THF solution of the sodium containing benzhydryl is added, benzhydryl sodium molal quantity is 5 times of mPEG, and solution colour becomes brownish red；Then It is put into ice-water bath, propargyl bromide is added dropwise, propargyl bromide molal quantity is 5 times of mPEG, is reacted at room temperature for 24 hours；It adds The dilution of 100mL methylene chloride, is splined on neutral alumina column, collects efflux, is concentrated with Rotary Evaporators, in -20 DEG C of ether Middle precipitating, sediment 50 DEG C of dry 5h in vacuum drying oven to obtain the final product, are named as mPEG-propargyl；
(6) synthesis of multi-arm star block copolymer β-CD-g- [PtBA-b-PEG]
CuBr, PMDETA, β-CD-g-PtBA-N are added in ampoule bottle3, mPEG-propargyl, their molar ratio For CuBr:PMDETA: β-CD-g-PtBA-N3: mPEG-propargyl=10:10:1:1.2, and DMF is added as solvent, make β-CD-g-PtBA-N3Concentration be 1g/10mL；It is subsequently placed in liquid nitrogen and is taken off by freezing-vacuumizing degassing-defrosting Gas, circulation three times, are put into ampoule bottle in 90 DEG C of oil baths, magnetic agitation is for 24 hours after closed；It is cooled to room temperature, adds dichloromethane Alkane (50-100mL) dilution, is splined on neutral alumina column, collects trickle, precipitates in -20 DEG C of methanol, and repetition dissolution/ Precipitation operation twice after, gained white powder product be placed at 60 DEG C be dried in vacuo 12h to get；
(7) synthesis of multi-arm star block copolymer β-CD-g- [PAA-b-PEG]
0.3g β-CD-g- [PtBA-b-PEG] is dissolved in 30mL methylene chloride, is added with stirring trifluoro second at 0 DEG C Acid, trifluoroacetic acid additional amount are 5 times of tert-butyl acrylate monomer molar amount in β-CD-g- [PtBA-b-PEG], are continued at 0 DEG C After keeping 3h, continue to be stirred to react 21h at room temperature, generates white depositions, filtering, with methylene chloride washing precipitate, and Vacuum freeze drying (- 10 DEG C, 30min) to get；
(8) synthesis of titania nanoparticles
20mg multi-arm star block copolymer β-CD-g- [PAA-b-PEG] is dissolved in 30mL DMF, unimolecule is made Micellar Gel solution；Presoma isopropyl titanate 0.1758g is added, back flow reaction 3h under the conditions of 170 DEG C, finally with centrifugation (revolving speed 1000rpm, be centrifuged 5min) remove by-product to get.
TiO2The TEM of nano particle schemes as shown in Figure 1, nanoparticle size prepared by the present invention is uniform, and average grain diameter is about For 10nm.
To TiO2The solubility of nano particle in water is detected, as a result as shown in Figure 2, it is known that prepared by the present invention TiO2Nano particle has good dissolubility.
Application examples performance evaluation
1, the formaldehyde removal effect test of photo-catalytic coating
It is that 10nm titania nanoparticles are added to (titania nanoparticles quality in commercially available common coating by partial size Score is 3%) to prepare photo-catalytic coating, is then squeegeed onto onto the test plate (panel) of 300 × 500mm.In 1m3Sealing experiment cabin Formaldehyde removal effect under middle test LED light irradiation, formaldehyde test use national standard phenol reagent process.Parallel laboratory test result table three times It is bright, for 24 hours after, the removal rate of formaldehyde reaches 90% or so (as shown in Figure 3).
2, methyl orange measure of merit in titania nanoparticles degradation of dye
It is catalyst of the 10nm titania nanoparticles as methyl orange degradation using partial size, with the methyl orange of 20mg/L Organic solution is target contaminant, and (the nano titania into the organic solution of methyl orange is added in titania nanoparticles Granular mass score is 3%), to test the methyl orange degradation efficiency under sunlight conditions.Three times parallel laboratory test the result shows that, 4h Afterwards, the degradation rate of methyl orange reaches 90% or so (as shown in Figure 4).
The foregoing is merely the optimal embodiments of the present invention, and for those skilled in the art, the present invention can have Various modifications and variations.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on, should all It is included within protection scope of the present invention.

Claims (7)

1. a kind of preparation method of water-soluble titanium dioxide nano particle, which comprises the following steps:
(1) beta-cyclodextrin is dissolved in N-Methyl pyrrolidone, addition 2- bromine isobutyl acylbromide under the conditions of being placed in 0 DEG C, normal-temperature reaction, Starlike macromole evocating agent 21Br- β-CD is made；
(2) starlike macromole evocating agent 21Br- β-CD is reacted by ATRP polymerization and causes tert-butyl acrylate monomer polymerization, system Obtain multi-arm star β-CD-g-PtBA；
(3) multi-arm star β-CD-g-PtBA is subjected to Azide processing, then with end group modification for the poly- second of the mono methoxy with alkynyl Glycol is the presoma of most outer segment block, is prepared radial block polymer β-CD-g- [PtBA-b-PEG]；
(4) in methylene chloride by radial block polymer β-CD-g- [PtBA-b-PEG] dissolution, trifluoroacetic acid, room temperature is added Under the conditions of hydrolysis obtain multi-arm star block copolymer β-CD-g- [PAA-b-PEG]；
(5) it regard multi-arm star block copolymer β-CD-g- [PAA-b-PEG] as unimolecular micelle template, then is contained with solubility Titanium oxide compounds are presoma, and water-soluble titanium dioxide nano particle is made；
Step (5) method particularly includes: β-CD-g- [PAA-b-PEG] is dissolved in DMF, it is molten that unimolecular micelle template is made Liquid；Presoma isopropyl titanate is added, water-soluble titanium dioxide nano particle is made in back flow reaction.
2. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, which is characterized in that the β- The molar ratio of cyclodextrin and 2- bromine isobutyl acylbromide is 1:42.
3. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, which is characterized in that step (2) Method particularly includes: 0.0707g CuBr, 0.1707 g PMDETA, 0.1g 21Br- β-CD, 20mL third are added in ampoule bottle Enoic acid ter-butyl ester monomer, 20mL butanone are placed in liquid nitrogen and are de-gassed by freezing-vacuumizing degassing-defrosting, circulation three It is secondary, ampoule bottle is put into 60 DEG C of oil baths after closed, magnetic agitation 12-24h；Ampoule bottle is taken out, mixture of ice and water is put into In, terminate reaction；Acetone dilution is added, is splined on neutral alumina column, collects efflux, in mixing for -20 DEG C of methanol and 4 DEG C of water Close and precipitated in liquid, the volume ratio of methanol and water is 1:1, gained white powder product be dried in vacuo at 50 DEG C 12h to get.
4. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, which is characterized in that step (3) Method particularly includes:
(a) star end group Azide PtThe synthesis of BA
Above-mentioned gained β-CD-g-PtBA 3.60g is taken, is dissolved in 15mL DMF, sodium azide, sodium azide and β-CD-g- is added The molar ratio of Br atom is 10:1 in PtBA, and sealing is stirred for 24 hours at room temperature；Acetone dilution is added, neutrality is splined on Alumina column is collected efflux, is precipitated in mixed liquor of -20 DEG C of methanol with 4 DEG C of water, and the volume ratio of methanol and water is 1:1, institute White powder product be placed at 50 DEG C be dried in vacuo 12h to obtain the final product, be named as β-CD-g-PtBA-N3；
(b) synthesis of benzhydryl sodium DPMNa
100mL tetrahydrofuran and 7.7g naphthalene are added in 250mL three-necked flask, stirring is opened, after waiting naphthalenes to be completely dissolved, 1.38g metallic sodium is added under the protection of inert gas argon gas, reacts 4h under the conditions of 40 DEG C, 11.1g diphenyl-methane is then added, It flows back for 24 hours under the conditions of 80 DEG C, obtains the THF solution of the wine-colored sodium containing benzhydryl；
(c) synthesis of the mPEG of alkynyl sealing end
In dry three-necked flask, 10g mPEG and 150mL tetrahydrofuran is added, the THF of the sodium containing benzhydryl is then added Solution, benzhydryl sodium molal quantity are 5 times of mPEG, and solution colour becomes brownish red；It is then placed in ice-water bath, bromine third is added dropwise Alkynes, propargyl bromide molal quantity are 5 times of mPEG, are reacted at room temperature for 24 hours；Methylene chloride dilution is added, neutrality is splined on Alumina column collects efflux, is concentrated with Rotary Evaporators, is precipitated in -20 DEG C of ether, sediment is 50 DEG C in vacuum drying oven Dry 5h to obtain the final product, is named as mPEG-propargyl；
(d) synthesis of multi-arm star block copolymer β-CD-g- [PtBA-b-PEG]
CuBr, PMDETA, β-CD-g-PtBA-N are added in ampoule bottle3, mPEG-propargyl, their molar ratio is CuBr:PMDETA: β-CD-g-PtBA-N3: mPEG-propargyl=10:10:1:1.2, and DMF is added as solvent, make β- CD-g-PtBA-N3Concentration be 1g/10mL；It is subsequently placed in liquid nitrogen and is de-gassed by freezing-vacuumizing degassing-defrosting, Circulation three times, is put into ampoule bottle in 90 DEG C of oil baths, magnetic agitation is for 24 hours after closed；It is cooled to room temperature, it is dilute to add methylene chloride It releases, is splined on neutral alumina column, collect efflux, precipitated in -20 DEG C of methanol, gained white powder product is placed at 60 At DEG C be dried in vacuo 12h to get.
5. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, which is characterized in that step (4) Method particularly includes: 0.3g β-CD-g- [PtBA-b-PEG] is dissolved in 30mL methylene chloride, is added with stirring three at 0 DEG C Fluoroacetic acid, trifluoroacetic acid additional amount is 5 times of tert-butyl acrylate monomer molar amount in β-CD-g- [PtBA-b-PEG], at 0 DEG C Continue after keeping 3h, continue to be stirred to react 21h at room temperature, generate white depositions, filtering washs precipitating with methylene chloride Object, and vacuum freeze drying to get.
6. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, which is characterized in that before described The molar ratio for driving acrylic acid repetitive unit in body isopropyl titanate and β-CD-g- [PAA-b-PEG] is not less than 5:1.
7. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, which is characterized in that described returns Flowing reaction temperature is 150-200 DEG C, time 2-4h.
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