CN108543505A - A kind of compound particle and preparation method thereof with multiple nucleocapsid - Google Patents
A kind of compound particle and preparation method thereof with multiple nucleocapsid Download PDFInfo
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- CN108543505A CN108543505A CN201810371585.6A CN201810371585A CN108543505A CN 108543505 A CN108543505 A CN 108543505A CN 201810371585 A CN201810371585 A CN 201810371585A CN 108543505 A CN108543505 A CN 108543505A
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- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of compound particles with multiple nucleocapsid, using inorganic silicon dioxide nano particle as kernel, using organic crylic acid esters polymer as middle layer, using carbon nanotube adsorption layer as shell.The invention also discloses the preparation processes of the compound particle, first pass throughMethod synthesizes nano silicon dioxide, it is based on dispersion copolymerization method again, acrylic polymer layer cladding is carried out to its surface, and the initiator ionized using hydrolyzable, one step realizes that synthesis nano-silica surface polymer overmold and chargeization are modified, and then directly further adsorbs carbon nanotube by electrostatic self-assembled.The present invention provides a kind of compound particle and preparation method thereof with multiple nucleocapsid, preparation process green high-efficient is not necessarily to complicated functional modification, the compound particle excellent combination property being prepared.
Description
Technical field
The present invention relates to multifunctional nano compound particle technical fields, and in particular to a kind of answering with multiple nucleocapsid
Close particle and preparation method thereof.
Background technology
With the continuous development of science and technology, nano material plays increasingly important role in new material development process.
Due to low-density (40~200kg/m3), high-specific surface area (400~1500m2/ g) and lower thermal conductivity (0.02W/m/K) etc. it is excellent
Physical and chemical performance, nano-silicon dioxide particle is all the time in high efficiency insulation heat-insulating material, high-strength material and gas-adsorbing material
It is widely used in the fields such as material.Likewise, since Japanese Scientists Iijima in 1991 has found, carbon nanotube is as one
Kind new one-dimensional functional material also receives the concern of researchers.Carbon nanotube has high draw ratio and hollow structure, excellent
Electric conductivity, high mechanical strength and it is good it is flexible can be used as a kind of super fiber, enhancing is played to composite material
Effect.
But since the specific structural features of nano material make it nevertheless suffer from larger challenge in commercial application:One side
Face nano-material surface can be high, and is usually present stronger Van der Waals force and π-πconjugation each other, and easily itself is rolled into a ball
It is poly-;Another aspect nano material is commonly present that compatibility is bad in filling-modified basis material, and showing in disordered state is easily precipitated
As composite material combination property deterioration.
In order to solve the problems, such as nano material in the application it is existing these, improve point of nano material in a polymer matrix
Property and compatibility are dissipated, many researchs synthesize the compound grain of inorganic/organic nano compound particle, especially nucleocapsid by design
Son.It refers to graphene uniform being coated on silica if in the Chinese patent literature of 106517215 A of Publication No. CN
Surface synthesis core shell structure material, effectively prevents the reunion of silica and graphene, is prepared for compound with regular structure, hole
Rate height and low density excellent properties material.But often nucleocapsid is acted in molding process by compared with Strong shear power
It is more easily damaged, nano-particle is exposed to reunite again, greatly affected performance boost and the long-time stability of composite material.Greatly
Quantity research shows that above-mentioned problem can be well solved to nanoparticle surface cladding using polymer.Such as Publication No. CN
A kind of nano modified chlorinated polyether resin with nucleocapsid and its preparation side are disclosed in the Chinese patent literature of 102199259 A
Method carries out nano modification to chlorinated polyether resin using the method for polymerization cladding, farthest solves the agglomeration traits of nano-particle,
Realize nano-particle good dispersion in the polymer.
Liquid phase method is to prepare the most common method of nucleocapsid polymer overmold nano composition, but the current party
Method often because of solvent contamination, the problems such as process is cumbersome and post-processing is complicated limits the development of nucleocapsid compound particle and answers
With.Increase in demand with people to high performance material simultaneously, compared to the Core-shell structure material of simple function, multiple nucleocapsid is more
The preparation of functional material becomes very urgent.In the design synthesis of nuclear-shell structured nano-composite material, shell material is not merely
" barrier " for preventing nuclear particle from reuniting is served as, even more there is oneself unique performance.In order to realize multi-functional multiple nucleocapsid
Preparation, need to generally carry out more modification process.As Wu Chao et al. is advanced to polymeric body surface and graphene surface difference
Row function dough, then carry out multiple nucleocapsid and construct.But it tends to bring impurity into this way and destroys decorative layer graphene-structured, increase
The interface resistance for adding conductive material influences final performance, and combined coefficient is low.
Therefore, the orderly Inorganic/Organic Composite Particles of Multifunctional height how are constructed, and can simple Yi works with green high-efficient
The mode of industry is realized, is still a problem urgently to be resolved hurrily.
Invention content
The present invention is in order to solve the above technical problems, provide a kind of compound particle with multiple nucleocapsid and its preparation
Method, preparation process green high-efficient, without complicated functional modification, the compound particle excellent combination property being prepared.
Specific technical solution is as follows:
A kind of compound particle with multiple nucleocapsid, using inorganic silicon dioxide nano particle as kernel, with organic third
Olefin(e) acid esters polymer is middle layer, using carbon nanotube adsorption layer as shell.
It is inorganic silicon dioxide nano particle that NEW TYPE OF COMPOSITE particle disclosed by the invention, which has three-decker, kernel, is had
Excellent mechanical performance and dimensional stability;Middle layer is organic crylic acid esters polymer, can not only be effectively reduced two
Reunion between silicon oxide particle, and the toughness of matrix polymer can be improved;The carbon nanotube adsorption layer of shell can provide good
Good electric conductivity and mechanical performance.
Preferably, the grain size of the kernel is 70~300nm, and the thickness of middle layer is 5~300nm, and the thickness of shell is
0.1~5nm.
Preferably, by mass percentage, the compound particle with multiple nucleocapsid includes:
60~85wt% of inorganic silicon dioxide nano particle;
5~37wt% of organic crylic acid esters polymer;
3~10wt% of carbon nanotube.
The organic crylic acid esters polymer is selected from polymethyl acrylate, polyethyl acrylate, butyl polyacrylate, gathers
At least one of methyl methacrylate, polyethyl methacrylate, polybutyl methacrylate.
The invention also discloses the preparation methods of the compound particle with multiple nucleocapsid, and steps are as follows:
(1) it usesMethod synthesizes nano silicon dioxide, then carries out surface modification through silane coupling agent, and it is pre- to obtain surface
Modified SiO 2 powder;
(2) SiO 2 powder by the pre- modification in surface prepared by step (1) is mixed with ethanol-water solution, is added and is stablized
It is uniformly mixed after agent, adds initiator and acrylic ester monomer carries out polymerisation, obtain polymer surfaces coating modification
Silica suspension;
The initiator is in azodiisobutyronitrile, azobisisoheptonitrile, 2,2'- azo diisobutyl amidine dihydrochlorides
At least one;
(3) acidified modified to carbon nanotube progress to obtain acidification carbon nano-tube aqueous solutions, polymer prepared by step (2)
The silica suspension of surface coating modification is mixed with the acidification carbon nano-tube aqueous solutions, is stood after stirring, certainly through electrostatic
Assembling obtains the compound particle with multiple nucleocapsid.
Preparation process disclosed by the invention, first passes throughMethod synthesizes nano silicon dioxide, then is based on dispersion copolymerization method
Acrylic polymer layer cladding, and the initiator ionized using hydrolyzable are carried out to its surface, a step realizes synthesis nanometer
Silica surface polymer overmold and chargeization are modified, and then directly further adsorb carbon nanotube by electrostatic self-assembled.
Initiator of the present invention can generate cation after hydrolytic dissociation, be carried with acidified processing rear surface
The carbon nanotube of the anion such as carboxyl, hydroxyl is mutually adsorbed, and is further coated in polymer overmold layer surface through electrostatic self-assembled
Carbon nanotube adsorption layer.
The preparation process will not both destroy polymer covering layer without making further modification to polymer covering layer
Mechanical property will not be further introduced into impurity.
Preferably, in step (1):
The useMethod synthesizes nano silicon dioxide, specially:
Absolute ethyl alcohol, ammonium hydroxide and ethyl orthosilicate are mixed, stirred at 20 DEG C~50 DEG C with 300~700 revs/min of rotating speeds
It mixes 15~30 hours, then is purified to after pH is 7~8 with deionized water centrifugation and obtain nanometer titanium dioxide silicon suspension;
The volume ratio of the ammonium hydroxide and absolute ethyl alcohol is 1:7~15, the volume ratio of ethyl orthosilicate and absolute ethyl alcohol is 1:
10~30;
The nano silicon dioxide suspension concentration being prepared is 5~10g/L.
Preferably, in step (1), the silane coupling agent is selected from gamma-aminopropyl-triethoxy-silane, γ-glycidol
At least one of ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane;
The surface is modified, specially:
The nanometer titanium dioxide silicon suspension is mixed with silane coupling agent, at room temperature with 200~500 revs/min of stirrings 2
After~5 hours, continuation is stirred 2~3 hours at 70~100 DEG C, then carries out ethyl alcohol centrifugal purification, and rotating speed is 3500~4500
Rev/min, the single treatment time is 15~25 minutes, and number is 2~5 times, and purified product is dried in vacuo at 25 DEG C~40 DEG C
15~30 hours to get to the SiO 2 powder of the pre- modification in surface;
The mass ratio of solid content and silane coupling agent is 10~50 in the nanometer titanium dioxide silicon suspension:1.
Preferably, in step (2):
The nano silicon dioxide of the pre- modification in surface and the mass ratio of ethanol-water solution are 1:20~50;
In the ethanol-water solution, the volume ratio of water and ethyl alcohol is 4:1~18;
The stabilizer is selected from polyvinylpyrrolidone or polyvinyl alcohol, and addition is the 5 of acrylic ester monomer quality
~15%;
The initiator addition is the 0.3~0.8% of acrylic ester monomer quality;
The acrylic ester monomer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate
At least one of ester, ethyl methacrylate, butyl methacrylate;
The polymerisation carries out in a nitrogen atmosphere, and reaction temperature is 60~90 DEG C, and it is small to be stirred to react carry out 15~20
When, speed of agitator is 100~200 revs/min;
A concentration of 5~15g/L of the silica suspension of polymer surfaces coating modification is prepared.
Preferably, in step (3):
It is described acidified modified to carbon nanotube progress, specially:
Multi-walled carbon nanotube is mixed, ultrasonic disperse 1~2 hour with the concentrated sulfuric acid and concentrated nitric acid, then is warming up to 40~70 DEG C,
Mechanical agitation 2~4 hours;It is slowly added to deionized water, it is straight as solvent centrifugal purification using deionized water after settling 10~15 hours
It is in neutrality to pH value of solution, obtains acidification carbon nano-tube aqueous solutions;
A diameter of 5~30nm of the multi-walled carbon nanotube, length are 10~35 μm;
The mass ratio 1 of the multi-walled carbon nanotube and the concentrated sulfuric acid:60~90, the mass ratio of multi-walled carbon nanotube and concentrated nitric acid
1:5~30;
A concentration of 1~10g/L of acidification carbon nano-tube aqueous solutions is prepared.
Preferably, in step (3), solid content changes with polymer surfaces cladding in the acidification carbon nano-tube aqueous solutions
Property silica suspension in solid content mass ratio be 1:10~20.
Preferably, in step (3), the rotating speed of the stirring is 100~150 revs/min, and the time is 3~5 hours;Then
Stand the progress for promoting electrostatic self-assembled in 1~2 hour;
Mixture after electrostatic self-assembled centrifuges 20~30 minutes removal upper liquids with 4000~7000 revs/min of rotating speeds
Body, it is no longer muddy to supernatant liquid by solvent centrifugal purification of water, it can be obtained after freeze-drying described with multiple nucleocapsid knot
The compound particle of structure.
Compared with prior art, the invention has the advantages that:
In the preparation process of the present invention, first pass throughMethod synthesizes nano silicon dioxide, then is based on dispersion copolymerization method pair
Its surface carries out acrylic polymer layer cladding, and surface difference polymerization is prepared only by the ratio for changing second alcohol and water
The compound particle of object coating efficiency is avoided using exhibiting high surface activating agent;And ionize out cation group using hydrolyzable
Specific initiator, a step realizes that synthesis nano-silica surface polymer overmold and chargeization are modified, then directly by quiet
Carbon nanotube is further adsorbed in electric self assembly, avoids complicated grafting modification, and can be by changing initiator content tune
Control the thickness of carbon nanotube adsorption layer.Preparation process is simple, controllable, green, efficient.
The compound particle that the present invention is prepared has multiple nucleocapsid, and meets thermal stability and dimensionally stable simultaneously
Property it is high, matrix compatibility is good, comprehensive performance with certain flexibility and with superior electrical conductivity.
Description of the drawings
Fig. 1 is the scanning electron microscope shape appearance figure of nano silicon dioxide prepared by embodiment 1;
Fig. 2 is the saturating of the nuclear shell structure nano silica dioxide granule of polymethyl methacrylate cladding prepared by embodiment 1
Radio mirror shape appearance figure;
Fig. 3 is nano silicon dioxide/polymethyl methacrylate/carbon with multiple nucleocapsid prepared by embodiment 1
The transmission electron microscope shape appearance figure of nanotube compound particle.
Specific implementation mode
The material and preparation method thereof of the present invention is specifically described by the following examples, but embodiment is served only for pair
The present invention further illustrates, is not intended to limit protection scope of the present invention.
Embodiment 1
(1) nano silicon dioxide synthesizes:
140mL absolute ethyl alcohols, 20mL ammonium hydroxide and 14mL ethyl orthosilicates are poured into three-necked flask, turned with 500 revs/min
Speed stirs 20 hours at 30 DEG C.Again with deionized water centrifugation purify to pH be 7 after, be added appropriate amount of deionized water obtain it is a concentration of
The nanometer titanium dioxide silicon suspension of 10g/L, the nano silicon dioxide grain size are~250nm, and the nano silicon dioxide of gained is swept
It is as shown in Figure 1 to retouch Electronic Speculum pattern.
(2) nano-silica surface is pre-processed:
0.05g γ-(methacryloxypropyl) third is added in 100mL nanometer titanium dioxides silicon suspension (a concentration of 10g/L)
Base trimethoxy silane, after being stirred 4 hours with 200 revs/min at room temperature, continuation is stirred 2 hours at 90 DEG C.Modified receives
Rice silica carries out ethyl alcohol centrifugal purification (rotating speed is 4000 revs/min, and single time is 15 minutes, and number is 3 times), obtains
Product is dried in vacuo 25 hours to get to the SiO 2 powder of the pre- modification in surface at 30 DEG C.
(3) nano-silica surface polymer overmold:
The above-mentioned silane coupler modified nano silicon dioxides of 20g and 0.1g polyvinylpyrrolidones are added to 400mL
In ethanol/water solution, the volume ratio of ethyl alcohol and water is 1:1.It after leading to 2~4 hours nitrogen, is added and contains 5mg 2,2'- azos two are different
The 1mL methyl methacrylate monomers of butyl amidine dihydrochloride initiator are immediately warmed to reflux, and controlling reaction temperature is 60~70
DEG C, it reacts 20~30 hours, speed of agitator 150rpm.It is carried out repeatedly washing centrifugation with deionized water after reaction, be added
Appropriate amount of deionized water obtains nuclear shell structure nano silica suspension (a concentration of 10g/ of polymethyl methacrylate cladding
L), the nuclear shell structure nano silica dioxide granule Electronic Speculum pattern of the polymethyl methacrylate cladding of gained is as shown in Fig. 2, poly- first
The thickness of base methyl acrylate clad is about 200nm.
(4) multi-walled carbon nanotube is acidified:2.5g multi-walled carbon nanotubes, 62.5mL concentrated nitric acids are sequentially added into single-necked flask
With the 187.5mL concentrated sulfuric acids, and be ultrasonically treated 1~2 hour;Mixture oil bath after ultrasound is warming up to 40~70 DEG C, machinery stirs
It mixes 2~4 hours;It is slowly added to deionized water, using deionized water is solvent centrifugal purification up to solution after sedimentation 10~15 hours
PH is in neutrality, and appropriate amount of deionized water is added and obtains acidification carbon nano-tube aqueous solutions (a concentration of 2g/L).
(5) prepared by the nano silicon dioxide/polymethyl methacrylate of multiple nucleocapsid/carbon nanotube compound particle:
By the silica suspension (a concentration of 10g/L) of 500mL polymethyl methacrylate surface coating modifications with
150mL acidification carbon nano-tube aqueous solutions (a concentration of 2g/L) mix in beaker, are stirred 3~5 hours, speed of agitator is
100~150 revs/min.It then stands 1~2 hour and promotes the two absorption.By said mixture with 4000~7000 revs/min
Rotating speed centrifuges 20~30 minutes removal supernatant liquids, freeze-drying no longer muddy to supernatant liquid by solvent centrifugal purification of water
It can be obtained nano silicon dioxide/polymethyl methacrylate/carbon nanotube compound particle of multiple nucleocapsid, particle shape afterwards
Looks transmission plot is as shown in Figure 3.
Claims (10)
1. a kind of compound particle with multiple nucleocapsid, which is characterized in that using inorganic silicon dioxide nano particle as kernel,
Using organic crylic acid esters polymer as middle layer, using carbon nanotube adsorption layer as shell.
2. the compound particle according to claim 1 with multiple nucleocapsid, which is characterized in that the grain size of the kernel
Thickness for 70~300nm, middle layer is 5~300nm, and the thickness of shell is 0.1~5nm.
3. the compound particle according to claim 1 with multiple nucleocapsid, which is characterized in that by mass percentage
Meter, including:
60~85wt% of inorganic silicon dioxide nano particle;
5~37wt% of organic crylic acid esters polymer;
3~10wt% of carbon nanotube;
The organic crylic acid esters polymer is selected from polymethyl acrylate, polyethyl acrylate, butyl polyacrylate, poly- methyl
At least one of methyl acrylate, polyethyl methacrylate, polybutyl methacrylate.
4. a kind of preparation method according to any compound particle with multiple nucleocapsid of claims 1 to 3, special
Sign is that steps are as follows:
(1) it usesMethod synthesizes nano silicon dioxide, then carries out surface modification through silane coupling agent, obtains the pre- modification in surface
SiO 2 powder;
(2) SiO 2 powder by the pre- modification in surface prepared by step (1) is mixed with ethanol-water solution, after stabilizer is added
It is uniformly mixed, adds initiator and acrylic ester monomer carries out polymerisation, obtain the two of polymer surfaces coating modification
Aoxidize silicon suspension;
The initiator in azodiisobutyronitrile, azobisisoheptonitrile, 2,2'- azo diisobutyl amidine dihydrochlorides extremely
Few one kind;
(3) acidified modified to carbon nanotube progress to obtain acidification carbon nano-tube aqueous solutions, polymer surfaces prepared by step (2)
The silica suspension of coating modification is mixed with the acidification carbon nano-tube aqueous solutions, is stood after stirring, through electrostatic self-assembled
Obtain the compound particle with multiple nucleocapsid.
5. the preparation method of the compound particle according to claim 4 with multiple nucleocapsid, which is characterized in that step
(1) in:
The useMethod synthesizes nano silicon dioxide, specially:
Absolute ethyl alcohol, ammonium hydroxide and ethyl orthosilicate are mixed, 15 are stirred at 20 DEG C~50 DEG C with 300~700 revs/min of rotating speeds
~30 hours, then purified to after pH is 7~8 with deionized water centrifugation and obtain nanometer titanium dioxide silicon suspension;
The volume ratio of the ammonium hydroxide and absolute ethyl alcohol is 1:7~15, the volume ratio of ethyl orthosilicate and absolute ethyl alcohol is 1:10~
30;
The nano silicon dioxide suspension concentration being prepared is 5~10g/L.
6. the preparation method of the compound particle according to claim 4 with multiple nucleocapsid, which is characterized in that step
(1) in, the silane coupling agent is selected from gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicon
At least one of alkane, γ-(methacryloxypropyl) propyl trimethoxy silicane;
The surface is modified, specially:
The nanometer titanium dioxide silicon suspension is mixed with silane coupling agent, at room temperature with 200~500 revs/min of stirrings 2~5
After hour, continuation is stirred 2~3 hours at 70~100 DEG C, then carries out ethyl alcohol centrifugal purification, and rotating speed is 3500~4500 revs/min
Clock, single treatment time are 15~25 minutes, and number is 2~5 times, and purified product is dried in vacuo 15~30 at 25 DEG C~40 DEG C
Hour to get to the SiO 2 powder of the pre- modification in surface;
The mass ratio of solid content and silane coupling agent is 10~50 in the nanometer titanium dioxide silicon suspension:1.
7. the preparation method of the compound particle according to claim 4 with multiple nucleocapsid, which is characterized in that step
(2) in:
The nano silicon dioxide of the pre- modification in surface and the mass ratio of ethanol-water solution are 1:20~50;
In the ethanol-water solution, the volume ratio of water and ethyl alcohol is 4:1~18;
The stabilizer be selected from polyvinylpyrrolidone or polyvinyl alcohol, addition be acrylic ester monomer quality 5~
15%;
The initiator addition is the 0.3~0.8% of acrylic ester monomer quality;
The acrylic ester monomer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, first
At least one of base ethyl acrylate, butyl methacrylate;
The polymerisation carries out in a nitrogen atmosphere, and reaction temperature is 60~90 DEG C, is stirred to react carry out 15~20 hours, stirs
Mix rotating speed is 100~200 revs/min;
A concentration of 5~15g/L of the silica suspension of polymer surfaces coating modification is prepared.
8. the preparation method of the compound particle according to claim 4 with multiple nucleocapsid, which is characterized in that step
(3) in:
It is described acidified modified to carbon nanotube progress, specially:
Multi-walled carbon nanotube is mixed, ultrasonic disperse 1~2 hour with the concentrated sulfuric acid and concentrated nitric acid, then is warming up to 40~70 DEG C, machinery
Stirring 2~4 hours;It is slowly added to deionized water, using deionized water is solvent centrifugal purification up to molten after sedimentation 10~15 hours
Liquid pH is in neutrality, and obtains acidification carbon nano-tube aqueous solutions;
A diameter of 5~30nm of the multi-walled carbon nanotube, length are 10~35 μm;
The mass ratio 1 of the multi-walled carbon nanotube and the concentrated sulfuric acid:60~90, the mass ratio 1 of multi-walled carbon nanotube and concentrated nitric acid:5
~30;
A concentration of 1~10g/L of acidification carbon nano-tube aqueous solutions is prepared.
9. the preparation method of the compound particle according to claim 4 with multiple nucleocapsid, which is characterized in that step
(3) in, the silica suspension of solid content and the polymer surfaces coating modification in the acidification carbon nano-tube aqueous solutions
The mass ratio of middle solid content is 1:10~20.
10. the preparation method of the compound particle according to claim 4 with multiple nucleocapsid, which is characterized in that step
Suddenly in (3), the rotating speed of the stirring is 100~150 revs/min, and the time is 3~5 hours;It is quiet then to stand promotion in 1~2 hour
The progress of electric self assembly;
Mixture after electrostatic self-assembled centrifuges 20~30 minutes removal supernatant liquids with 4000~7000 revs/min of rotating speeds,
It is no longer muddy to supernatant liquid by solvent centrifugal purification of water, it can be obtained after freeze-drying described with multiple nucleocapsid
Compound particle.
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