CN109231255A - A kind of preparation method of poly metal oxide nano particle - Google Patents
A kind of preparation method of poly metal oxide nano particle Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of poly metal oxide nano particle, cyclodextrin block polymer molecules brush is prepared using Transfer Radical Polymerization, it is that template adsorbs multi-element metal oxide presoma using block polymer on the inside of cyclodextrin, outside block polymer is interleaving agent, prepares that monodisperse, regular appearance, size are controllable and the adjustable poly metal oxide nano particle of component through calcine technology.Poly metal oxide nano particle produced by the present invention has the characteristics that size tunable, of uniform size, component is adjustable, can be applied to catalysis, fine ceramics, energy storage device, magnetic material, fluorescent material, sensor, absorbing material, biological medicine, adsorbs and the fields such as separate.
Description
Technical field
The present invention relates to a kind of preparation methods of poly metal oxide nano particle, belong to technical field of nano material.
Background technique
Metal oxide nano-material be widely used in catalysis, fine ceramics, energy storage device, magnetic material, fluorescent material,
Sensor, biological medicine, adsorbs and the fields such as separates absorbing material.
There are many methods for preparing nano-metal-oxide at present, such as sol-gel method, alkoxide hydrolysis, forced hydrolysis
Method, the gas-phase decomposition method of solution, wet chemical methods, microemulsion method etc..Related nano metal oxide materials development in recent years
More rapidly, the report of the preparation method of metal oxide nano-material is increasing, and laser technology, surpasses microwave irradiation technology
The methods of audio technology, AC electrodeposition technology, supercritical fluid drying technology, nonaqueous solvents hydrothermal technique introduce metal oxidation
In the traditional preparation methods of object nano material, preparation method has obtained biggish perfect and development.The above method, Ke Yifen
For solid phase method, liquid phase method and vapor phase method.Conventional solid phase method preparation method is anti-after mixing metal salt and metal hydroxides
Predecessor should be generated, is fully ground and is calcined, nanoparticle is obtained after grinding.This method simple process, yield is high, at low cost,
It is low in the pollution of the environment, but Granularity Distribution is uneven, it is easy to reunite.Liquid phase method is easier control nucleation, to be easy to control particle
Chemical composition, form and dimension, have stronger technology competition advantage.But, which easily introduces impurity and causes gained powder
Body purity is inadequate.Vapor phase method is directly to utilize gas or substance is become gas by various means, is allowed to occur in the gaseous state
Physical change or chemical change finally agglomerate the method to form nanoparticle of growing up in condensation process.The characteristics of vapor phase method is
Powder purity is high, particle size is small, reunite less, component is easily-controllable, lacks liquid, thus can reach a high temperature and be well suited to oxide and receive
The synthesis at rice flour end.With making rapid progress for nano material preparation technology development, people have used many different physical methods
It prepares that particle is small, brilliant degree is high, is uniformly dispersed and metal oxide nano-material that yield is high with chemical method, and it is showed
The characteristic different from ontology conducts extensive research out.But metal oxide nanoparticles carry out size and cut and pattern control
And how research is modified to nano-metal-oxide, it is still desirable to further controlledly synthesis further investigation.Especially
In order to assign metal oxide nano-material more excellent property, the controllable conjunction of poly metal oxide nano particle is explored
At being the direction that scientific worker needs to keep punching such as ternary, quaternary even five yuan of composite nanoparticle.
But which kind of preparation method no matter is taken, in order to give full play to and imitate using the surface of metal oxide nanoparticles
Answer, small-size effect and macro quanta tunnel effect, require the regular shape of the particle of preparation, particle diameter distribution uniformly, granularity
Controllably, not easy to reunite, while also to have and be easy to the characteristics of collecting.
[1] Gao Shuyan, model person of outstanding talent are notified to based on the pseudocapacitors chemistry of metal oxide, 2013,76 (03): 202-209.
[2] preparing for Tang Bo, Ge Jiechao, Wang Chunxian, Zhang Guoying, Wu Changju, Shu Chun English metal oxide nano-material is new
Be in progress chemical industry progress, 2002 (10): 707-712+717.
[3] Zhu Yajie, Wu Pingxiao, Yang Lin, old ideal, yellow column heavily fortified point .ZnO-ZnCr2O4The preparation of mixed-metal oxides and
Photocatalytic degradation bisphenol-A ACTA Scientiae Circumstantiae, 2016,36 (07): 2428-2435.
[4] Liu Xiangjun, Tan Xiangqian, stone Metal Oxide Gas Sensors Guangzhou University's journal (natural science edition) of washing,
2007(05):42-46.
[5]Chen,P.C.,Liu,X.,Hedrick,J.L.,Xie,Z.,Wang,S.,Lin,Q.Y.,Hersam
M.C.Dravid V.P.,Mirkin,C.A.(2016).Polyelemental nanoparticle
libraries.Science,352(6293),1565-1569.
Summary of the invention
In view of this, the present invention provides a kind of preparation methods of poly metal oxide nano particle.Present invention preparation
The poly metal oxide nano particle morphology of acquisition is uniform, size is controllable, component is adjustable, and good dispersion, soilless sticking, can
It is applied in the fields such as catalysis, energy storage device.
The preparation method of poly metal oxide nano particle of the present invention, using Transfer Radical Polymerization (ATRP)
Cyclodextrin block polymer molecules brush is prepared, is before template adsorbs multi-element metal oxide using block polymer on the inside of cyclodextrin
Body is driven, outside block polymer is interleaving agent, prepares that monodisperse, regular appearance, size are controllable and component is adjustable through calcine technology
Poly metal oxide nano particle, it is uneven to avoid the nano-particles size that other preparation methods generate in calcination process
One, defect easy to reunite.
The preparation method of poly metal oxide nano particle of the present invention, includes the following steps:
Step 1: cyclodextrin is formed to uniform cyclodextrin solution in organic solvent, it is then molten to gained cyclodextrin
Halide reagent is added in liquid, temperature reaction, precipitation purification, obtains halogenation cyclodextrin after reaction；
Step 2: by step 1 obtain by halogenation cyclodextrin in polar organic solvent, sequentially add acrylic acid
Tert-butyl ester monomer, copper halide and organic ligand are uniformly mixed；Nitrogen deoxygenation is then passed to, it is with liquid nitrogen that Schlenk reaction flask is cold
Freeze, cuprous halide is then added, heating carries out first stage ATRP reaction after sealing；It is subsequently added into second comonomer, carries out second
The reaction of stage ATRP, obtains cyclodextrin block polymer molecules brush；
Step 3: obtaining cyclodextrin-g- polyacrylic acid-after the cyclodextrin block polymer molecules brush that step 2 obtains is hydrolyzed
Then b- polymer is added the presoma of multi-element metal oxide and carries out high-temperature calcination sufficiently after absorption, obtain multi-element metal
Oxide nano-particles.
In step 1, the organic solvent can satisfy dissolution cyclodextrin, form the condition of uniform solution；Preferably
Methyl phenyl ethers anisole, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, toluene, dimethylbenzene, tetrahydrofuran, acetone, butanone or
Cyclohexanone.The cyclodextrin is one of alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin.
In step 1, the halide reagent is the bromo- 2- methyl propionyl bromide of 2-, 2- bromine isobutyl acylbromide, 4- chlorobutanoylchloride, 2- bromo-
2- methyl propionyl chloride or 4- brombutyl chloric acid；The molar ratio of hydroxyl is 1:0.5-5 in halide reagent and cyclodextrin.
In step 1, the reaction temperature of temperature reaction is 30-70 DEG C, and the reaction time is 6-24 hours.
In step 2, the polar organic solvent is selected from dimethylformamide, dimethyl sulfoxide, sulfolane or nitric acid Asia second
Base ester.
In step 2, the copper halide is copper chloride or copper bromide；The organic ligand is selected from 4,4'- dinonyl -2,2'-
Bipyridyl, 2,2'- bipyridyl, three (2- pyridylmethyl) amine, three (2- dimethylaminoethyl) amine or pentamethyl-diethylenetriamine；
The cuprous halide is stannous chloride or cuprous bromide；The second comonomer is styrene, butyl acrylate, methyl methacrylate
The double bond containing polymerized monomer such as ester, acrylonitrile or methyl acrylate.
In step 2, halogenation cyclodextrin, tert-butyl acrylate, copper halide, cuprous halide and organic ligand molar ratio be 1:
100-1000:0.1-1.0:0.9-10:2-20 preferably 1:200-600:0.1-1.0:0.9-10:2-20 is 1:200-600:
0.1-1.0:0.9-10:2-20；The molar ratio of second comonomer and tert-butyl acrylate is 1:1-20.
In step 2, the reaction temperature of first stage ATRP reaction is 40-90 DEG C, and the reaction time is 3-24 hours；Second-order
The reaction temperature of section ATRP reaction is 40-90 DEG C, and the reaction time is 2-24 hours.
In step 3, the presoma of the multi-element metal oxide is multiple metal ion salting liquid, preferably Au, Ag,
Two or more any combination in Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Eu, Mn, Ca, Zn and Fe etc.
Soluble perchlorate, chloride, nitrate or sulfate liquor.
In step 3, the hydrolysis is the trifluoroacetic acid that the cyclodextrin block polymer molecules brush is added to 3-7mol/L
In solution, hydrolyze 8-24h at room temperature, the dosage of the trifluoroacetic acid solution account for tert-butyl acrylate monomer weight 1000%~
1500%.
In step 3, the dosage of the presoma of multi-element metal oxide is different according to the partial size of final polynary nanometer particle,
It is preferred that its dosage is the 10-1000% of cyclodextrin block polymer molecules brush weight, adsorption time is 8-36 hours.
In step 3, the temperature of high-temperature calcination is 200-800 DEG C, and calcination time is 1-5 hours.
The diameter of poly metal oxide nano particle prepared by the present invention is 2-100nm.The polynary gold that the present invention obtains
Belonging to oxide nano-particles has the characteristics that compound with regular structure, size uniformity, size tunable, component are adjustable, specific surface is big, can apply
In fields such as catalysis, supercapacitor, Separation of Proteins, organic pollutants removals.
Poly metal oxide nano particle of the present invention is using cyclodextrin block polymer molecules brush as template, preparation method letter
Single, the reaction time is short, advantage of lower cost.Interior block polymer is used for adsorbing metal oxide precursor, outside block polymerization
Object plays the role of interleaving agent, prevents fusion and reunion between the high-temperature heat treatment stage, oxide nano-particles, helps to obtain
Obtain the poly metal oxide nano particle of size uniformity, size tunable, soilless sticking.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the poly metal oxide nano particle of the embodiment of the present invention 1.
Fig. 2 is the grading curve figure of the poly metal oxide nano particle of the embodiment of the present invention 1.
Fig. 3 is the capacitor of the poly metal oxide nano particle of the embodiment of the present invention 1 with the change curve of current density.
Fig. 4 is the grading curve figure of the poly metal oxide nano particle of the embodiment of the present invention 2.
Specific embodiment
Embodiment 1: the block polymer degree of polymerization is the partial size of 30 or so, Ni-Co-Mn poly metal oxide nano particle
About 5nm.
First the beta-cyclodextrin of 0.5g is dissolved in the methyl phenyl ethers anisole of 10.0g and forms uniform solution；A certain amount of 2- is added
Temperature reaction is carried out after bromine isobutyl acylbromide, reaction solution repeated precipitation is purified, and obtains bromination cyclodextrin；10mg brominated is pasted again
Smart polymer is dissolved in n,N-Dimethylformamide, and 20ml tert-butyl acrylate, 10mg copper bromide and 10mg 2 is then added,
2'- bipyridyl, liquid nitrogen frozen after nitrogen deoxygenation are added cuprous bromide, are warming up to 60 DEG C of polymerizations 2-6 hours, tert-butyl acrylate
After monomer conversion reaches 95%, styrene is added and continues polymerization reaction, obtains cyclodextrin block polymer molecules brush.Polymerization is anti-
It during answering, is sampled every half an hour, monomer conversion is measured by nuclear magnetic resonance (NMR), it is each when before reaction with reaction terminating
It is a NMR, the amount and starting peak area ratio of displacement peak area reduction of the C=C double bond on NMR, are exactly the conversion of monomer
Rate.By multi-element metal oxide precursor mixture (0.3g Ni (CH3COO)2·4H2O、0.3gCo(CH3COO)2·4H2O and
0.15gMn(CH3COO)2·4H2O it) is added in cyclodextrin block polymer molecules brush solution, sufficiently after absorption, is placed on vacuum
It dries within 4 hours at 50 DEG C of baking oven, is placed in porcelain boat and calcines 2h at 650 DEG C to get poly metal oxide nano particle is arrived.It should
Poly metal oxide nano particle can be used as high catalytic activity and recyclable new catalyst and supercapacitor
Electrode material.
Fig. 1 is the infrared spectrogram of poly metal oxide nano particle manufactured in the present embodiment, golden as seen from Figure 1
The characteristic peak for belonging to oxide nano-particles, has prepared multivariant oxide nanoparticle.Fig. 2 is the multi-element metal oxygen of the present embodiment
The grading curve of compound nanoparticle, the as seen from Figure 2 size uniformity of metal oxide nanoparticles, average grain diameter
About 5nm.Fig. 3 is the capacitor of the poly metal oxide nano particle of the present embodiment with the change curve of current density.By Fig. 3
It can be seen that specific capacitance when current density is 1A/g, reaches 623F/g, efficiency (specific capacitance: has much higher than other carbon-based materials
Sequence mesoporous carbon 200F/g, carbon fiber 80F/g, ordered mesopore carbon/carbon fiber 190F/g).
Embodiment 2: the block polymer degree of polymerization is the grain of 500 or so, Ti-Fe-Mn poly metal oxide nano particle
Diameter is about 85nm.
First the beta-cyclodextrin of 0.5g is dissolved in the methyl phenyl ethers anisole of 10.0g and forms uniform solution；A certain amount of 2- is added
Temperature reaction is carried out after bromine isobutyl acylbromide, reaction solution repeated precipitation is purified, and obtains bromination cyclodextrin；10mg brominated is pasted again
Smart polymer is dissolved in n,N-Dimethylformamide, and 20ml tert-butyl acrylate, 10mg copper bromide and 15mg 4 is then added,
4'- dinonyl -2,2'- bipyridyl, liquid nitrogen frozen after nitrogen deoxygenation are added cuprous bromide, are warming up to 60 DEG C of polymerizations 2-6 hours,
After tert-butyl acrylate monomer conversion reaches 95%, styrene is added and continues polymerization reaction, obtains cyclodextrin block polymer
Molecular brush.In polymerization process, every half an hour sample, by nuclear magnetic resonance (NMR) measure monomer conversion, reaction before with
A NMR, the amount that is displaced peak area reduction of the C=C double bond on NMR and starting peak area ratio are respectively done when reaction terminating, just
It is the conversion ratio of monomer.By multi-element metal oxide precursor mixture (0.144g TiOSO4、0.149g Mn(NO3)3With
0.582g Fe(NO3)3) be added in cyclodextrin block polymer molecules brush solution, sufficiently after absorption, it is placed on 50 DEG C of vacuum drying oven
It dries within lower 4 hours, is placed in porcelain boat and calcines 2h at 650 DEG C to get poly metal oxide nano particle is arrived.The multi-element metal
Oxide nano-particles can be used as the electrode material and catalyst carrier of supercapacitor.Fig. 4 is the polynary gold of the present embodiment
Belong to the grading curve figure of oxide nano-particles, as seen from Figure 4 the size uniformity of metal oxide nanoparticles, puts down
Equal partial size about 85nm.Ti-Fe-Mn poly metal oxide nano particle prepared by the embodiment is used for catalyst carrier,
After having preferable catalytic performance, catalysis to react 1h chemical industrial park waste water, COD (COD) removal rate of waste water reaches
68.5%.
Embodiment 3: the block polymer degree of polymerization is the straight of 200 or so, Sn-In-Ti poly metal oxide nano particle
Diameter is about 25nm.
First the beta-cyclodextrin of 0.5g is dissolved in the methyl phenyl ethers anisole of 10.0g and forms uniform solution；A certain amount of 2- is added
Temperature reaction is carried out after bromine isobutyl acylbromide, reaction solution repeated precipitation is purified, and obtains bromination cyclodextrin；10mg brominated is pasted again
Smart polymer is dissolved in n,N-Dimethylformamide, and 20ml tert-butyl acrylate, tri- (2- of 10mg copper bromide and 12mg is then added
Pyridylmethyl) amine, liquid nitrogen frozen after nitrogen deoxygenation, be added cuprous bromide, be warming up to 60 DEG C of polymerizations 2-6 hours, acrylic acid uncle
After butyl ester monomer conversion reaches 95%, styrene is added and continues polymerization reaction, obtains cyclodextrin block polymer molecules brush.It is poly-
It closes in reaction process, is sampled every half an hour, monomer conversion is measured by nuclear magnetic resonance (NMR), react preceding and reaction terminating
When be respectively a NMR, the amount and starting peak area ratio of displacement peak area reduction of the C=C double bond on NMR, exactly monomer
Conversion ratio.By multi-element metal oxide precursor mixture (0.6g SnCl4·5H2O、0.4g In(Cl)3·4H2O and 0.20g
TiCl4) be added in cyclodextrin block polymer molecules brush solution, sufficiently after absorption, dry within 4 hours at 50 DEG C of vacuum drying oven,
It is placed in porcelain boat and calcines 2h at 650 DEG C to get poly metal oxide nano particle is arrived.The poly metal oxide nano grain
Son can be used as gas sensitive for improve to CO and NO2Sensitivity and selectivity.Sn-In-Ti prepared by the embodiment
Poly metal oxide nano particle is to 1000 μ g/g CO and 450 μ g/g NO2Maximum sensitivity be respectively 19.4 and 9.5,
Show excellent sensitivity and selectivity.
Embodiment 4: the block polymer degree of polymerization is 400 or so, Zn-Ni-Al-Co poly metal oxide nano particle
Diameter is about 50nm.
First the beta-cyclodextrin of 0.5g is dissolved in the methyl phenyl ethers anisole of 10.0g and forms uniform solution；A certain amount of 2- is added
Temperature reaction is carried out after bromine isobutyl acylbromide, reaction solution repeated precipitation is purified, and obtains bromination cyclodextrin；10mg brominated is pasted again
Smart polymer is dissolved in n,N-Dimethylformamide, and 20ml tert-butyl acrylate, five first of 10mg copper bromide and 10mg is then added
Base diethylenetriamine, liquid nitrogen frozen after nitrogen deoxygenation are added cuprous bromide, are warming up to 60 DEG C of polymerizations 2-6 hours, the tertiary fourth of acrylic acid
After ester monomer conversion ratio reaches 95%, styrene is added and continues polymerization reaction, obtains cyclodextrin block polymer molecules brush.Polymerization
It in reaction process, is sampled every half an hour, monomer conversion is measured by nuclear magnetic resonance (NMR), when before reaction with reaction terminating
It is respectively a NMR, the amount and starting peak area ratio of displacement peak area reduction of the C=C double bond on NMR, are exactly turning for monomer
Rate.By multi-element metal oxide precursor mixture (0.12g Zn (NO3)2·6H2O、0.35g Ni(NO3)2·6H2O、
0.15gAl(NO3)3·9H2O and 1.0g Co (NO3)2·6H2O it) is added in cyclodextrin block polymer molecules brush solution, fills
It after dividing absorption, is placed on 4 hours at 50 DEG C of vacuum drying oven and dries, be placed in porcelain boat and calcine 2h at 600 DEG C to get multi-element metal is arrived
Oxide nano-particles.The poly metal oxide nano particle can be used as the electrode material of supercapacitor.By the implementation
The Zn-Ni-Al-Co poly metal oxide nano particle of example preparation is used for supercapacitor, and test result, which is shown, to be had preferably
Fake capacitance characteristic, current density be 0.5A/g when, the specific capacity of electrode reaches 548.2F/g, when current density increases to
When 8A/g, specific capacity 356.4F/g, the conservation rate of specific capacity is 65%, and shows excellent impedance behavior.
Embodiment 5: the block polymer degree of polymerization is the straight of 1000 or so, Ni-Mo-Co poly metal oxide nano particle
Diameter is about 100nm.
First the beta-cyclodextrin of 0.5g is dissolved in the methyl phenyl ethers anisole of 10.0g and forms uniform solution；A certain amount of 2- is added
Temperature reaction is carried out after bromine isobutyl acylbromide, reaction solution repeated precipitation is purified, and obtains bromination cyclodextrin；10mg brominated is pasted again
Smart polymer is dissolved in n,N-Dimethylformamide, and 20ml tert-butyl acrylate, tri- (2- of 10mg copper bromide and 10mg is then added
Dimethylaminoethyl) amine, liquid nitrogen frozen after nitrogen deoxygenation, be added cuprous bromide, be warming up to 60 DEG C of polymerizations 2-6 hours, acrylic acid
After tert-butyl ester monomer conversion reaches 95%, styrene is added and continues polymerization reaction, obtains cyclodextrin block polymer molecules brush.
In polymerization process, sampled every half an hour, monomer conversion measured by nuclear magnetic resonance (NMR), before reaction with react whole
A NMR is respectively when only, the amount and starting peak area ratio of displacement peak area reduction of the C=C double bond on NMR, are exactly monomer
Conversion ratio.By multi-element metal oxide precursor mixture (0.50g NiSO4·7H2O,0.35g(NH4)6Mo7O24·4H2O
With 0.3g Co (CH3COO)2·4H2O it) is added in cyclodextrin block polymer molecules brush solution, sufficiently after absorption, is placed on true
It dries within 4 hours at 50 DEG C of empty baking oven, is placed in porcelain boat and calcines 2h at 700 DEG C to get poly metal oxide nano particle is arrived.
The poly metal oxide nano particle can be used for catalytic hydrogen evolution reaction.
Implementation method of the present invention is easy to operate, process control, the removal of template and the generation of metal oxide simultaneously into
Row does not need the lengthy process for additionally increasing template agent removing, improves the efficiency of preparation, poly metal oxide nano obtained
Particle has the characteristics that of uniform size, controlled diameter, pore-size distribution are narrow.
Claims (10)
1. a kind of preparation method of poly metal oxide nano particle, it is characterised in that:
Cyclodextrin block polymer molecules brush is prepared using Transfer Radical Polymerization, utilizes block polymerization on the inside of cyclodextrin
Object be template adsorb multi-element metal oxide presoma, outside block polymer be interleaving agent, through calcine technology prepare monodisperse,
Regular appearance, size be controllable and the adjustable poly metal oxide nano particle of component.
2. preparation method according to claim 1, it is characterised in that include the following steps:
Step 1: cyclodextrin being formed to uniform cyclodextrin solution in organic solvent, then into gained cyclodextrin solution
Halide reagent is added, temperature reaction, precipitation purification, obtains halogenation cyclodextrin after reaction；
Step 2: by step 1 obtain by halogenation cyclodextrin in polar organic solvent, sequentially add the tertiary fourth of acrylic acid
Ester monomer, copper halide and organic ligand are uniformly mixed；Nitrogen deoxygenation is then passed to, is freezed Schlenk reaction flask with liquid nitrogen,
Cuprous halide is then added, heating carries out first stage ATRP reaction after sealing；It is subsequently added into second comonomer, carries out second stage
ATRP reaction, obtains cyclodextrin block polymer molecules brush；
Step 3: obtaining cyclodextrin-g- polyacrylic acid-b- after the cyclodextrin block polymer molecules brush that step 2 obtains is hydrolyzed and gather
Object is closed, the presoma of multi-element metal oxide is then added and carries out high-temperature calcination sufficiently after absorption, obtains multi-element metal oxidation
Object nanoparticle.
3. preparation method according to claim 2, it is characterised in that:
In step 1, the halide reagent is the bromo- 2- methyl propionyl bromide of 2-, 2- bromine isobutyl acylbromide, 4- chlorobutanoylchloride, the bromo- 2- first of 2-
Base propionyl chloride or 4- brombutyl chloric acid；The molar ratio of hydroxyl is 1:0.5-5 in halide reagent and cyclodextrin.
4. preparation method according to claim 2, it is characterised in that:
In step 1, the reaction temperature of temperature reaction is 30-70 DEG C, and the reaction time is 6-24 hours.
5. preparation method according to claim 2, it is characterised in that:
In step 2, the copper halide is copper chloride or copper bromide；The organic ligand is selected from 4,4'- dinonyl -2,2'- and joins pyrrole
Pyridine, 2,2'- bipyridyl, three (2- pyridylmethyl) amine, three (2- dimethylaminoethyl) amine or pentamethyl-diethylenetriamine；It is described
Cuprous halide is stannous chloride or cuprous bromide；The second comonomer be styrene, butyl acrylate, methyl methacrylate,
The double bond containing polymerized monomer such as acrylonitrile or methyl acrylate.
6. preparation method according to claim 2, it is characterised in that:
In step 2, halogenation cyclodextrin, tert-butyl acrylate, copper halide, cuprous halide and organic ligand molar ratio be 1:100-
1000:0.1-1.0:0.9-10:2-20；The molar ratio of second comonomer and tert-butyl acrylate is 1:1-20.
7. preparation method according to claim 2, it is characterised in that:
In step 2, the reaction temperature of first stage ATRP reaction is 40-90 DEG C, and the reaction time is 3-24 hours；Second stage
The reaction temperature of ATRP reaction is 40-90 DEG C, and the reaction time is 2-24 hours.
8. preparation method according to claim 2, it is characterised in that:
In step 3, the presoma of the multi-element metal oxide is Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni,
The soluble perchlorate of two or more any combination in Co, Cu, Pd, Eu, Mn, Ca, Zn, Fe etc., chloride, nitrate or
Sulfate liquor.
9. preparation method according to claim 2, it is characterised in that:
In step 3, the hydrolysis is that the cyclodextrin block polymer molecules brush is added to the trifluoroacetic acid solution of 3-7mol/L
In, hydrolyze 8-24h at room temperature, the dosage of the trifluoroacetic acid solution account for tert-butyl acrylate monomer weight 1000%~
1500%.
10. preparation method according to claim 2, it is characterised in that:
In step 3, the temperature of high-temperature calcination is 200-800 DEG C, and calcination time is 1-5 hours.
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| CN107954470A (en) * | 2017-11-24 | 2018-04-24 | 洛阳量子纳米科技有限公司 | A kind of preparation method and applications of water-soluble titanium dioxide nano particle |
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