CN108144558A - A kind of hollow porous micro sphere of cladding titanium dioxide nano particle and preparation method thereof - Google Patents
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle and preparation method thereof Download PDFInfo
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- CN108144558A CN108144558A CN201810029341.XA CN201810029341A CN108144558A CN 108144558 A CN108144558 A CN 108144558A CN 201810029341 A CN201810029341 A CN 201810029341A CN 108144558 A CN108144558 A CN 108144558A
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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
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
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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
Abstract
The present invention relates to a kind of hollow porous micro spheres of cladding titanium dioxide nano particle and preparation method thereof, by styrene, bifunctionality dimethylacrylate class organic monomer and photoinitiator dissolving obtain EFI solution in a solvent, the double bond containing modifying titanium dioxide in surface is added in EFI solution again and is uniformly dispersed, electrostatic spray is carried out under visible light conditions to be made by titania nanoparticles and be coated on the hollow porous micro sphere of cladding titanium dioxide nano particle that the crosslinking ball on titania nanoparticles surface forms, it is crosslinked ball inner hollow, porous surface and with by the cross-linked structure that is formed of being cross-linked with each other between copolymer molecule chain, by being covalently keyed between titania nanoparticles and crosslinking ball.The method of the present invention simple process, preparation flow is reasonable, and final hollow porous micro sphere extinction effect obtained is good, and centering long wave ultraviolet shield effectiveness is good and melting temperature and heat decomposition temperature are very high, there is fabulous promotional value.
Description
Technical field
The invention belongs to high molecule nano material preparation fields, and in particular in a kind of cladding titanium dioxide nano particle
Empty porous microsphere and preparation method thereof.
Background technology
In recent years, people have found the harm of ultraviolet radiation more and more.The excessive exposure of ultraviolet light can lead to skin
Skin cancer.Ultraviolet light can not only make the macromolecular chain in plastics, synthetic resin and rubber degrade, and lead to the aging of material, moreover it is possible to make
The weatherability of paint is deteriorated, and leads to the easy dusting of paint, easy to crack or even come off, in addition, the flavescence of paper, becoming fragile
Deng related with ultraviolet light.Therefore ultraviolet light screener is more and more added into high molecular material, for compound ultraviolet
The research of the high molecular material of light absorbers also increasingly causes the concern of people.
High-voltage electrostatic spraying method is that polymer solution or melt are prepared into high score by a kind of utilization electrohydrodynamics technology
The method of sub- particle.The method such as precipitation method, inverse suspension crosslinking method, the spray drying process of high molecular particle are prepared relative to other
It prepares that micro-sphere material is simple for process, controllability is strong, environmentally protective and without using a large amount of emulsifiers Deng, electrostatic spraying processes, uses
The particle that electrostatic spraying processes are easily made monodispersity particle and finally obtain can have different morphologies, such as hollow porous, example
Such as have document (war is that universe method of electrostatic spinning prepares polystyrene functional material [D] Jilin University, 2010.) report, polyphenyl
Vinyl solution can prepare Porous hollow microballoon by electrostatic spray molding, and polystyrene (PS) hollow microsphere obtained is in room temperature
Lower chemical property is stablized, and has preferable machinability, but since the glass transition temperature of polystyrene (PS) only has 100
DEG C, three-dimensional structure can be destroyed under the high temperature conditions, thus can not be applied to melt-processed.This largely affects PS
The application of hollow microsphere.
Tinting strength, tinting power, covering power and the extinction capability of titanium dioxide protrude, and are a kind of current best white of performance in the world
Pigment can be widely applied to the industrial circles such as coating, plastics, ink and papermaking, and demand is larger, and pass through the members such as Al or Si
Element, which carries out inorganic coating, can effectively solve the disadvantage that its bad dispersibility in polymer matrix, there is fabulous application prospect.
However the compatibility of titanium dioxide and polymer is poor, when causing the titanium dioxide to prepare delustering fibre as additive, is adding
Measure it is smaller in the case of, the extinction effect of delustering fibre is poor, at the same in fiber add titanium dioxide can also deposit delustering fibre
It is being difficult to the shortcomings that thinner.In addition, when preparing ultraviolet shielded material using titanium dioxide, because absorbing wavelength is by the chemical combination
The band gap of object determines, therefore its shield effectiveness to the ultraviolet light that long wave ultraviolet (UV-A) i.e. wavelength is 320-400nm is poor,
The protective capacities of centering long wave ultraviolet is also limited.
Therefore, study a kind of extinction effect it is good, dispersion compatibility it is good, centering long wave ultraviolet shield effectiveness is good, melting temperature
The hollow porous micro sphere of degree and the high cladding titanium dioxide nano particle of heat decomposition temperature has a very important significance.
Invention content
The purpose of the invention is to titanium dioxide in the prior art is overcome to prepare macromolecule as additive to answer
Extinction effect is poor during condensation material, dispersion poor compatibility, centering long wave ultraviolet shield effectiveness is poor, melting is low with heat decomposition temperature
Shortcoming, provide a kind of extinction effect it is good, dispersion compatibility it is good, centering long wave ultraviolet shield effectiveness is good, melting temperature and heat point
Solve the hollow porous micro sphere of the high cladding titanium dioxide nano particle of temperature.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle mainly by titania nanoparticles and is coated on
The crosslinking ball composition on titania nanoparticles surface；
The crosslinking ball inner hollow, porous surface and with cross-linked structure, the cross-linked structure is by containing styrene and double
It is cross-linked with each other to be formed between the copolymer molecule chain of degree of functionality dimethylacrylate class monomeric building blocks；
By being covalently keyed between the titania nanoparticles and crosslinking ball.
As preferred technical solution：
The hollow porous micro sphere of cladding titanium dioxide nano particle as described above, the cladding titanium dioxide nano particle
Hollow porous micro sphere melting temperature>530 DEG C, heat decomposition temperature>380℃.Generally processed with the compound base material of titanium dioxide
Temperature is both less than 280 DEG C, thus during machining composite material, the hollow porous micro sphere of cladding titanium dioxide nano particle can be kept
Preferable three-dimensional structure is not damaged, and is conducive to give full play to its effect.
The hollow porous micro sphere of cladding titanium dioxide nano particle as described above, the crosslinking ball a diameter of 500~
1500nm, the wall thickness of the crosslinking ball is 50~100nm；A diameter of 300~400nm of the titania nanoparticles；Institute
The quantity for stating crosslinking ball inner silica titanium nano particle is 1~4.
The hollow porous micro sphere of cladding titanium dioxide nano particle as described above, when crosslinking ball inner silica titanium nanometer
During the quantity of particle≤2, the distribution density of the surface aperture of the crosslinking ball is 1~60/1000nm2, the aperture of aperture is
10~30nm；
When the quantity of crosslinking ball inner silica titanium nano particle>When 2, the distribution density of the surface aperture of the crosslinking ball
For 1~20/1000nm2, the aperture of aperture is 10~80nm.
The present invention also provides a kind of hollow porous micro spheres for preparing cladding titanium dioxide nano particle as described above
The dissolving of styrene, bifunctionality dimethylacrylate class organic monomer and photoinitiator is obtained EFI by method in a solvent
Solution, then the double bond containing modifying titanium dioxide in surface is added in EFI solution and is uniformly dispersed, it is carried out under visible light conditions
Electrostatic spray is made the hollow porous micro sphere of cladding titanium dioxide nano particle, the double bond containing modified titanium dioxide in surface in the present invention
Titanium can uniformly disperse since surface is with organo-functional group, be conducive to prepare uniform electrostatic spray system in a solvent.
As preferred technical solution：
Method as described above, the rotating speed mechanical agitation 1h referred to 200~500rpm that is uniformly dispersed；The modification
The preparation process of titanium dioxide is as follows：
(1) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid；The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4~6 in the mixed dispersion liquid:150~250:1；
(2) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4~5h of reaction at 60~70 DEG C, room temperature ageing 10~
12h obtains ageing liquid；The mass ratio of ethyl alcohol and water is 2~5 in the ethyl alcohol water mixed liquid:1, the ethyl alcohol water mixed liquid adds
Enter 20~30% that amount is mixed dispersion liquid volume；
(3) silane coupling agent is instilled in ethanol water, 2~3h of hydrolysis is stirred at room temperature, is added to ultrasonic disperse
In the ageing liquid of 30~60min, 4~5h of back flow reaction at 60~70 DEG C；The quality of ethyl alcohol and water in the ethanol water
Than being 2~5:1, the mass ratio of the silane coupling agent and ethanol water is 1:8~12, the addition of the silane coupling agent
It is 5~10% of titanium dioxide quality in ageing liquid, the silane coupling agent is γ-methacryloxypropyl trimethoxy
Silane；
(4) 12~16h is dried in vacuo at 70~80 DEG C after evaporation drying is rotated at 50~70 DEG C, obtains surface containing double
The modifying titanium dioxide of key.
Method as described above, the bifunctionality dimethylacrylate class organic monomer for Bis-GMA, EBPADMA,
One or more of UDMA, TEGDMA and D3MA；The concrete structure of the bifunctionality dimethylacrylate class organic monomer
Formula is as follows：
The photoinitiator for DMPOH (N, N- dimethylanunuphenylelhvl alcohol) and/or CQ (1,7,7- trimethyl bicyclics (2,2,
1) -2,3 heptadione)；
The wavelength of the visible ray is 400~500nm；
The solvent is one or more of DMF, chloroform, dichloromethane and tetrahydrofuran.
Method as described above, bifunctionality dimethylacrylate class organic monomer accounts for styrene in the EFI solution
With 5~25wt% of bifunctionality dimethylacrylate class organic monomer total amount, solvent accounts for styrene and bifunctionality diformazan
50~80wt% of base esters of acrylic acid organic monomer total amount, photoinitiator account for styrene and bifunctionality dimethylacrylate
0.5~1.2wt% of class organic monomer total amount；The addition of the modifying titanium dioxide for EFI solution quality 15~
40%.Bifunctionality dimethylacrylate class organic monomer accounts for styrene and bifunctionality dimethacrylate in EFI solution
The ratio of esters organic monomer total amount is directly proportional to the degree of cross linking of microsphere surface cross-linked structure, and the degree of cross linking is higher, and crosslinking mesh is got over
Greatly, exchange velocity is faster, but can reduce the intensity of cross-linked structure to a certain extent, conversely, the degree of cross linking is lower, is crosslinked mesh
Smaller, cross-link intensity is higher, but poor to the swellability of water；The organic list of bifunctionality dimethylacrylate class in EFI solution
It is low that the concentration of body crosses low crosslinking degree, can not be applied to melt-processed, and the excessively high viscosity for influencing compound system can not form microballoon；
The too low efficiency of initiation of the concentration of photoinitiator is too low in EFI solution can not cause monomer polymerization.
Method as described above, the parameter of electrostatic spray are：10~15kV of output voltage of high voltage power supply, atomizing nozzle is with coagulating
Gu 7~13cm of distance of bathing pool, 25~50 DEG C of temperature, promote 1~4mL/h of fltting speed of pump, and the diameter 5 of propeller~
15mm, 3~10mL of volume of propeller.
Method as described above is washed in cladding titanium dioxide nano particle with methanol or ethyl alcohol after electrostatic spray
Empty porous microsphere and drying.It washs and to dry styrene-bifunctionality dimethylacrylate class monomer copolymer hollow porous
The effect of microballoon is to remove the impurity of microsphere surface during electrostatic spray, such as extra polymerized monomer and photoinitiator etc..
Invention mechanism：
The prior art prepares hollow microsphere commonly used in fields such as medicament slow releases using electrostatic spray, generally by that will polymerize
Electrostatic spray obtains microballoon in a solvent for object dissolving, after this method obtains microballoon, polymer can still keep its original thermal property and
It is melted in melt-processed and its microballoon pattern cannot be kept, be not used to melt-processed.The present invention devises electrostatic spray-light
Cause the method that polymerization crosslinking prepares the hollow porous micro sphere of cladding titanium dioxide nano particle, first the benzene second of single functionality
EFI solution is made in alkene monomer, bifunctionality dimethylacrylate class organic monomer and photoinitiator dissolving in a solvent, so
The double bond containing modifying titanium dioxide in surface is added in afterwards to be uniformly mixed, and electrostatic spray is then carried out under high-voltage field and forms drop, profit
Cause styrene monomer, the bifunctionality dimethyl allene in drop with visible ray (according to initiation wavelength law of photoinitiator)
The double bond of esters of gallic acid monomer and modifying titanium dioxide surface carries out free radical polymerization, formed containing styrene in titanium dioxide surface and
The copolymer of bifunctionality dimethylacrylate class monomeric building blocks, simultaneously because bifunctionality dimethylacrylate class
The bifunctionality of monomer, the strand of the copolymer containing styrene and bifunctionality dimethylacrylate class monomeric building blocks
Between can be cross-linked with each other to form three-dimensional-structure, because of the volatilization of polymerization shrinkage and solvent and in coagulating bath in forming process
The hollow porous micro sphere of cladding titanium dioxide nano particle is spread and is formed, so as to which melting temperature be made>530 DEG C, thermal decomposition temperature
Degree>The hollow porous micro sphere of 380 DEG C of cladding titanium dioxide nano particle, containing styrene and bifunctionality dimethylacrylate
The three-dimensional-structure being cross-linked to form between the strand of the copolymer of class monomeric building blocks so that its melting temperature is high, follow-up
Three-dimensional structure can be kept during melt-processed, its function is given full play to, has expanded hollow microsphere structure in actual use
Application range.
Titanium dioxide possesses the ultraviolet shielded effect (scattering of good extinction effect (scattering) and good middle long wave in itself
+ absorb), the strong anti-uv-ray of nano-titanium dioxide is since it is with high refractivity and high photolytic activity, uvioresistant
Ability and its mechanism are related with its grain size：When grain size is larger, the barrier to ultraviolet light is and the centering based on reflecting, scatter
Wave area and long-wavelength region ultraviolet light are effective.Porous structure can effectively scatter incident light, improve the utilization rate to incident light.This
By coated by titanium dioxide inside porous microsphere, light is incident on titanium dioxide surface by titanium dioxide across porous structure for invention
After the scattering of titanium, it can be repeated as many times and scatter between titanium dioxide and microballoon inner wall, finally only a small amount of light can penetrate micro-
Ball overflows, thus improves extinction effect and ultraviolet shielded effect.Simultaneously because the polystyrene type organic material of cladding and height
It is more compatible between copolymer matrix,
Advantageous effect：
(1) hollow porous micro sphere of a kind of cladding titanium dioxide nano particle of the invention, extinction effect is good, dispersion is compatible
It is good, centering long wave ultraviolet shield effectiveness is good, melting temperature and thermal degradation temperature are high, meets the requirement of general fiber process, should
It is wide with range.
(2) preparation method of the hollow porous micro sphere of a kind of cladding titanium dioxide nano particle of the invention, simple process,
Preparation flow is reasonable, there is fabulous promotional value.
Description of the drawings
Fig. 1 is the nucleocapsid schematic diagram of the hollow porous micro sphere of the present invention.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle, preparation method are as follows：
(1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 in liquid, wherein mixed dispersion liquid:150:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 70 DEG C, room temperature ageing 11h is aged
Liquid, the mass ratio of ethyl alcohol and water is 2 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
20%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
Solve 2h, be added in the ageing liquid of ultrasonic disperse 30min, the back flow reaction 4h at 60 DEG C, wherein in ethanol water ethyl alcohol with
The mass ratio of water is 2:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:12,
The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 5%；
D) 13h is dried in vacuo at 70 DEG C after rotating evaporation drying at 60 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
(2) styrene, Bis-GMA and DMPOH are dissolved in DMF and obtain EFI solution, Bis-GMA is accounted in EFI solution
The 10wt% of styrene and Bis-GMA total amounts, DMF account for styrene and the 50wt% of Bis-GMA total amounts, DMPOH account for styrene and
The 0.5wt% of Bis-GMA total amounts；
(3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation 1h of 200rpm
Modifying titanium dioxide is made to be uniformly dispersed in EFI solution, electrostatic spray system is carried out in the case where wavelength is the visible light conditions of 400nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is obtained, the wherein addition of modifying titanium dioxide is EFI solution quality
15%, the parameter of electrostatic spray is：The output voltage 10kV of high voltage power supply, the distance 13cm of atomizing nozzle and solidification bathing pool, temperature
25 DEG C, promote the fltting speed 4mL/h of pump, the diameter 15mm of propeller, the volume 3mL of propeller；
(4) hollow porous micro sphere and the drying of cladding titanium dioxide nano particle are washed after electrostatic spray with methanol.
The hollow porous micro sphere of cladding titanium dioxide nano particle as made from the above method, structure diagram such as Fig. 1 institutes
Show, mainly by titania nanoparticles and be coated on the crosslinking ball on titania nanoparticles surface and form, wherein being crosslinked ball
Inner hollow, porous surface and with cross-linked structure, cross-linked structure is by the copolymer containing styrene and Bis-GMA structural units point
It is cross-linked with each other to be formed between subchain, by being covalently keyed between titania nanoparticles and crosslinking ball, is crosslinked the diameter of ball
For 500nm, the wall thickness for being crosslinked ball is 50nm, a diameter of 310nm of titania nanoparticles, and crosslinking ball inner silica titanium is received
The quantity of rice grain is 1, and the distribution density for being crosslinked the surface aperture of ball is 1~10/1000nm2, the aperture of aperture is 25
~30nm.The melting temperature of the hollow porous micro sphere of cladding titanium dioxide nano particle is 561 DEG C, and heat decomposition temperature is 410 DEG C,
There is good dispersion effect to visible ray, pure PET fiber fracture strength and elongation at break are 2.45cN/dtex and 58.0%,
Fracture strength and elongation at break are 1.59cN/dtex and 0% after radiation 240h under the ultraviolet light that wavelength is 365nm, work as fibre
When the additive amount of titanium dioxide is 2.2wt% in dimension, you can reach full-dull, the fiber number of fiber is up to 121dtex, made fiber
Fracture strength 3.02cN/dtex, elongation at break 60.2%, centering long wave ultraviolet has preferable shield effectiveness, institute
It is 2.96cN/ that PET fiber obtained radiates fracture strength and elongation at break after 240h under the ultraviolet light that wavelength is 365nm
Dtex and 15.3%.
Embodiment 2
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle, preparation method are as follows：
(1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 5 in liquid, wherein mixed dispersion liquid:200:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 60 DEG C, room temperature ageing 10h is aged
Liquid, in ethyl alcohol water mixed liquid ethyl alcohol with addition is mixed dispersion liquid volume 30%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
3h is solved, is added in the ageing liquid of ultrasonic disperse 40min, the back flow reaction 4.5h at 65 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 3:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:
The addition of 11, γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 6%；
D) 14h is dried in vacuo at 80 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
(2) styrene, EBPADMA and CQ are dissolved in chloroform and obtain EFI solution, EBPADMA in EFI solution
Styrene and the 15wt% of EBPADMA total amounts are accounted for, chloroform accounts for styrene and the 60wt% of EBPADMA total amounts, and CQ accounts for benzene second
The 0.6wt% of alkene EBPADMA total amounts；
(3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation 1h of 300rpm
Modifying titanium dioxide is made to be uniformly dispersed in EFI solution, electrostatic spray system is carried out in the case where wavelength is the visible light conditions of 420nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is obtained, the wherein addition of modifying titanium dioxide is EFI solution quality
20%, the parameter of electrostatic spray is：The output voltage 11kV of high voltage power supply, the distance 12cm of atomizing nozzle and solidification bathing pool, temperature
30 DEG C, promote the fltting speed 3mL/h of pump, the diameter 13mm of propeller, the volume 4mL of propeller；
(4) hollow porous micro sphere and the drying of cladding titanium dioxide nano particle are washed after electrostatic spray with ethyl alcohol.
The hollow porous micro sphere of cladding titanium dioxide nano particle as made from the above method, mainly by nano titania
Particle and the crosslinking ball composition for being coated on titania nanoparticles surface, wherein crosslinking ball inner hollow, porous surface and tool
Crosslinking structure, cross-linked structure by being formed containing being cross-linked with each other between styrene and the copolymer molecule chain of Bis-GMA structural units,
By being covalently keyed between titania nanoparticles and crosslinking ball, a diameter of 700nm of ball is crosslinked, the wall thickness for being crosslinked ball is
60nm, a diameter of 330nm of titania nanoparticles, the quantity of crosslinking ball inner silica titanium nano particle is 1, crosslinking
The distribution density of the surface aperture of ball is 15~25/1000nm2, the aperture of aperture is 10~18nm.Cladding titanium dioxide is received
The melting temperature of the hollow porous micro sphere of rice grain is 532 DEG C, and heat decomposition temperature is 415 DEG C, there is good scattering to visible ray
Effect, when the additive amount of titanium dioxide in fiber is 2.2wt%, you can reach full-dull, the fiber number of fiber is reachable
112dtex, centering long wave ultraviolet have preferable shield effectiveness, and made fibrous fracture intensity and elongation at break are
3.01cN/dtex and 58.4%, fiber fracture strength and elongation at break after 240h is radiated under wavelength is the ultraviolet light of 365nm
For 2.95cN/dtex and 14.2%.
Embodiment 3
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle, preparation method are as follows：
(1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 in liquid, wherein mixed dispersion liquid:250:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4.5h is reacted at 65 DEG C, room temperature ageing 11h is aged
Liquid, the mass ratio of ethyl alcohol and water is 3 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
25%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
2.5h is solved, is added in the ageing liquid of ultrasonic disperse 50min, the back flow reaction 5h at 70 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 4:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:
The addition of 10, γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 7%；
D) 12h is dried in vacuo at 75 DEG C after rotating evaporation drying at 70 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
(2) by the mixture of styrene, UDMA and DMPOH and CQ (mass ratio 1:1) dissolving obtains in methylene chloride
To EFI solution, UDMA accounts for styrene and the 5wt% of UDMA total amounts in EFI solution, and dichloromethane accounts for styrene and UDMA total amounts
The mixture of 70wt%, DMPOH and CQ account for styrene and the 0.7wt% of UDMA total amounts；
(3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation 1h of 400rpm
Modifying titanium dioxide is made to be uniformly dispersed in EFI solution, electrostatic spray system is carried out in the case where wavelength is the visible light conditions of 440nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is obtained, wherein the addition of the modifying titanium dioxide is EFI solution matter
The 25% of amount, the parameter of electrostatic spray are：The output voltage 12kV of high voltage power supply, the distance 11cm of atomizing nozzle and solidification bathing pool,
35 DEG C of temperature promotes the fltting speed 2mL/h of pump, the diameter 11mm of propeller, the volume 5mL of propeller；
(4) hollow porous micro sphere and the drying of cladding titanium dioxide nano particle are washed after electrostatic spray with methanol.
The hollow porous micro sphere of cladding titanium dioxide nano particle as made from the above method, mainly by nano titania
Particle and the crosslinking ball composition for being coated on titania nanoparticles surface, wherein crosslinking ball inner hollow, porous surface and tool
Crosslinking structure, cross-linked structure containing being cross-linked with each other between styrene and the copolymer molecule chain of UDMA structural units by forming, and two
By being covalently keyed between Titanium dioxide nanoparticle and crosslinking ball, a diameter of 900nm of ball is crosslinked, the wall thickness for being crosslinked ball is
70nm, a diameter of 350nm of titania nanoparticles, the quantity of crosslinking ball inner silica titanium nano particle is 1, crosslinking
The distribution density of the surface aperture of ball is 52~60/1000nm2, the aperture of aperture is 20~24nm.Cladding titanium dioxide is received
The melting temperature of the hollow porous micro sphere of rice grain is 535 DEG C, and heat decomposition temperature is 390 DEG C, there is good scattering to visible ray
Effect, when the additive amount of titanium dioxide in fiber is 2.0wt%, you can reach full-dull, the fiber number of fiber is reachable
121dtex, centering long wave ultraviolet have preferable shield effectiveness, and made fibrous fracture intensity and elongation at break are
3.01cN/dtex and 58.4%, fiber fracture strength and elongation at break after 240h is radiated under wavelength is the ultraviolet light of 365nm
For 2.95cN/dtex and 14.2%.
Embodiment 4
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle, preparation method are as follows：
(1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 in liquid, wherein mixed dispersion liquid:180:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 63 DEG C, room temperature ageing 12h is aged
Liquid, the mass ratio of ethyl alcohol and water is 4 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
22%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
Solve 3h, be added in the ageing liquid of ultrasonic disperse 60min, the back flow reaction 5h at 60 DEG C, wherein in ethanol water ethyl alcohol with
The mass ratio of water is 5:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:9,
The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 8%；
D) 15h is dried in vacuo at 70 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
(2) styrene, TEGDMA and CQ are dissolved in tetrahydrofuran and obtain EFI solution, TEGDMA is accounted in EFI solution
The 20wt% of styrene and TEGDMA total amounts, tetrahydrofuran account for styrene and the 80wt% of TEGDMA total amounts, CQ account for styrene and
The 0.8wt% of TEGDMA total amounts；
(3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation 1h of 500rpm
Modifying titanium dioxide is made to be uniformly dispersed in EFI solution, electrostatic spray system is carried out in the case where wavelength is the visible light conditions of 450nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is obtained, wherein the addition of the modifying titanium dioxide is EFI solution matter
The 30% of amount, the parameter of electrostatic spray are：The output voltage 13kV of high voltage power supply, the distance 10cm of atomizing nozzle and solidification bathing pool,
40 DEG C of temperature promotes the fltting speed 1mL/h of pump, the diameter 10mm of propeller, the volume 6mL of propeller；
(4) hollow porous micro sphere and the drying of cladding titanium dioxide nano particle are washed after electrostatic spray with ethyl alcohol.
The hollow porous micro sphere of cladding titanium dioxide nano particle as made from the above method, mainly by nano titania
Particle and the crosslinking ball composition for being coated on titania nanoparticles surface, wherein crosslinking ball inner hollow, porous surface and tool
Crosslinking structure, cross-linked structure by being formed containing being cross-linked with each other between styrene and the copolymer molecule chain of TEGDMA structural units,
By being covalently keyed between titania nanoparticles and crosslinking ball, a diameter of 1000nm of ball is crosslinked, is crosslinked the wall thickness of ball
For 80nm, a diameter of 300nm of titania nanoparticles, the quantity of crosslinking ball inner silica titanium nano particle is 2, is handed over
The distribution density for joining the surface aperture of ball is 30~55/1000nm2, the aperture of aperture is 20~30nm.Cladding titanium dioxide
The melting temperature of the hollow porous micro sphere of nano particle is 540 DEG C, and heat decomposition temperature is 385 DEG C, there is good dissipate to visible ray
Effect is penetrated, when the additive amount of titanium dioxide in fiber is 2.0wt%, you can reach full-dull, the fiber number of fiber is reachable
120dtex, centering long wave ultraviolet have preferable shield effectiveness, and made fibrous fracture intensity and elongation at break are
2.84cN/dtex and 56.3%, fiber fracture strength and elongation at break after 240h is radiated under wavelength is the ultraviolet light of 365nm
For 2.78cN/dtex and 16.4%.
Embodiment 5
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle, preparation method are as follows：
(1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 5 in liquid, wherein mixed dispersion liquid:240:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 5h is reacted at 60 DEG C, room temperature ageing 12h is aged
Liquid, the mass ratio of ethyl alcohol and water is 2 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
28%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
2.5h is solved, is added in the ageing liquid of ultrasonic disperse 35min, the back flow reaction 4h at 65 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 2:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:8,
The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 9%；
D) 12h is dried in vacuo at 80 DEG C after rotating evaporation drying at 65 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
(2) by styrene, D3MA and DMPOH is dissolved in the mixture (mass ratio 1 of DMF and chloroform:2) it is obtained in
EFI solution, D in EFI solution3MA accounts for styrene and D3The mixture of the 25wt% of MA total amounts, DMF and chloroform accounts for benzene second
Alkene and D3The 55wt% of MA total amounts, DMPOH account for styrene and D3The 0.9wt% of MA total amounts；
(3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation 1h of 250rpm
Modifying titanium dioxide is made to be uniformly dispersed in EFI solution, electrostatic spray system is carried out in the case where wavelength is the visible light conditions of 460nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is obtained, wherein the addition of the modifying titanium dioxide is EFI solution matter
The 35% of amount, the parameter of electrostatic spray are：The output voltage 14kV of high voltage power supply, the distance 9cm of atomizing nozzle and solidification bathing pool, temperature
45 DEG C of degree promotes the fltting speed 2mL/h, the diameter 8mm of propeller, the volume 6mL of propeller of pump；
(4) hollow porous micro sphere and the drying of cladding titanium dioxide nano particle are washed after electrostatic spray with methanol.
The hollow porous micro sphere of cladding titanium dioxide nano particle as made from the above method, mainly by nano titania
Particle and the crosslinking ball composition for being coated on titania nanoparticles surface, wherein crosslinking ball inner hollow, porous surface and tool
Crosslinking structure, cross-linked structure is by containing styrene and D3It is cross-linked with each other to be formed between the copolymer molecule chain of MA structural units, two
By being covalently keyed between Titanium dioxide nanoparticle and crosslinking ball, a diameter of 1250nm of ball is crosslinked, the wall thickness for being crosslinked ball is
90nm, a diameter of 330nm of titania nanoparticles, the quantity of crosslinking ball inner silica titanium nano particle is 3, crosslinking
The distribution density of the surface aperture of ball is 1~8/1000nm2, the aperture of aperture is 10~20nm.Cladding titanium dioxide nano
The melting temperature of the hollow porous micro sphere of particle is 538 DEG C, and heat decomposition temperature is 400 DEG C, there is good scattering effect to visible ray
Fruit, when the additive amount of titanium dioxide in fiber is 2.2wt%, you can reach full-dull, the fiber number of fiber up to 117dtex,
Centering long wave ultraviolet has a preferable shield effectiveness, made fibrous fracture intensity and elongation at break for 3.02cN/dtex and
59.6%, it is 2.96cN/dtex that fiber radiates fracture strength and elongation at break after 240h under the ultraviolet light that wavelength is 365nm
With 15.6%.
Embodiment 6
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle, preparation method are as follows：
(1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 in liquid, wherein mixed dispersion liquid:170:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 62 DEG C, room temperature ageing 11h is aged
Liquid, the mass ratio of ethyl alcohol and water is 4 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
24%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
2h is solved, is added in the ageing liquid of ultrasonic disperse 45min, the back flow reaction 4.5h at 70 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 3:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:
The addition of 12, γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 10%；
D) 16h is dried in vacuo at 75 DEG C after rotating evaporation drying at 55 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
(2) by the mixture (mass ratio 2 of Bis-GMA and EBPADMA:1), the mixing of styrene and DMPOH and CQ
Object (mass ratio 1:1) it is dissolved in mixture (the mass ratio 1 of dichloromethane and tetrahydrofuran:2) EFI solution is obtained in, electricity
The mixture of Bis-GMA and EBPADMA accounts for the amount of the mixture of styrene and Bis-GMA and EBPADMA in spray solution
The mixture of 20wt%, dichloromethane and tetrahydrofuran accounts for the amount of the mixture of styrene and Bis-GMA and EBPADMA
The mixture of 65wt%, DMPOH and CQ account for the 1.0wt% of the amount of the mixture of styrene and Bis-GMA and EBPADMA；
(3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation 1h of 350rpm
Modifying titanium dioxide is made to be uniformly dispersed in EFI solution, electrostatic spray system is carried out in the case where wavelength is the visible light conditions of 480nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is obtained, wherein the addition of the modifying titanium dioxide is EFI solution matter
The 40% of amount, the parameter of electrostatic spray are：The output voltage 15kV of high voltage power supply, the distance 8cm of atomizing nozzle and solidification bathing pool, temperature
50 DEG C of degree promotes the fltting speed 3mL/h, the diameter 7mm of propeller, the volume 7mL of propeller of pump；
(4) hollow porous micro sphere and the drying of cladding titanium dioxide nano particle are washed after electrostatic spray with ethyl alcohol.
The hollow porous micro sphere of cladding titanium dioxide nano particle as made from the above method, mainly by nano titania
Particle and the crosslinking ball composition for being coated on titania nanoparticles surface, wherein crosslinking ball inner hollow, porous surface and tool
Crosslinking structure, cross-linked structure is by the copolymer containing styrene and bifunctionality dimethylacrylate class monomeric building blocks point
It is cross-linked with each other to be formed between subchain, by being covalently keyed between titania nanoparticles and crosslinking ball, is crosslinked the diameter of ball
For 1300nm, the wall thickness for being crosslinked ball is 100nm, a diameter of 360nm of titania nanoparticles, is crosslinked ball inner silica titanium
The quantity of nano particle is 3, and the distribution density for being crosslinked the surface aperture of ball is 10~15/1000nm2, the aperture of aperture is
30~40nm.The melting temperature of the hollow porous micro sphere of cladding titanium dioxide nano particle is 545 DEG C, heat decomposition temperature 410
DEG C, there is good dispersion effect to visible ray, when the additive amount of titanium dioxide in fiber is 2.0wt%, you can reach and totally disappeared
Light, for the fiber number of fiber up to 121dtex, centering long wave ultraviolet has a preferable shield effectiveness, made fibrous fracture intensity and
Elongation at break is 2.83cN/dtex and 55.9%, and fiber radiates fracture strength after 240h under ultraviolet light of the wavelength for 365nm
It is with elongation at break：2.78cN/dtex with 14.8%.
Embodiment 7
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle, preparation method are as follows：
(1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 in liquid, wherein mixed dispersion liquid:230:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4.5h is reacted at 65 DEG C, room temperature ageing 10h is aged
Liquid, the mass ratio of ethyl alcohol and water is 2 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
30%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
3h is solved, is added in the ageing liquid of ultrasonic disperse 55min, the back flow reaction 4.5h at 60 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 4:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:
The addition of 10, γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 9%；
D) 16h is dried in vacuo at 80 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
(2) by UDMA and D3Mixture (the mass ratio 1 of MA:2), styrene and DMPOH are dissolved in DMF, three chloromethanes
The mixture of alkane and dichloromethane (mass ratio 1:1:2) EFI solution is obtained in, UDMA and D in EFI solution3The mixing of MA
Object accounts for styrene and UDMA and D3The 5wt% of the amount of the mixture of MA, the mixture of DMF, chloroform and dichloromethane account for benzene
Ethylene and UDMA and D3The 75wt% of the amount of the mixture of MA, DMPOH account for styrene and UDMA and D3The amount of the mixture of MA
1.1wt%；
(3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation 1h of 450rpm
Modifying titanium dioxide is made to be uniformly dispersed in EFI solution, electrostatic spray system is carried out in the case where wavelength is the visible light conditions of 500nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is obtained, wherein the addition of the modifying titanium dioxide is EFI solution matter
The 18% of amount, the parameter of electrostatic spray are：The output voltage 10kV of high voltage power supply, the distance 7cm of atomizing nozzle and solidification bathing pool, temperature
25 DEG C of degree promotes the fltting speed 1mL/h, the diameter 6mm of propeller, the volume 8mL of propeller of pump；
(4) hollow porous micro sphere and the drying of cladding titanium dioxide nano particle are washed after electrostatic spray with methanol.
The hollow porous micro sphere of cladding titanium dioxide nano particle as made from the above method, mainly by nano titania
Particle and the crosslinking ball composition for being coated on titania nanoparticles surface, wherein crosslinking ball inner hollow, porous surface and tool
Crosslinking structure, cross-linked structure is by the copolymer containing styrene and bifunctionality dimethylacrylate class monomeric building blocks point
It is cross-linked with each other to be formed between subchain, by being covalently keyed between titania nanoparticles and crosslinking ball, is crosslinked the diameter of ball
For 1500nm, the wall thickness for being crosslinked ball is 50nm, a diameter of 300nm of titania nanoparticles, is crosslinked ball inner silica titanium
The quantity of nano particle is 3, and the distribution density for being crosslinked the surface aperture of ball is 14~20/1000nm2, the aperture of aperture is
60~65nm.The melting temperature of the hollow porous micro sphere of cladding titanium dioxide nano particle is 545 DEG C, heat decomposition temperature 392
DEG C, there is good dispersion effect to visible ray, when the additive amount of titanium dioxide in fiber is 1.9wt%, you can reach and totally disappeared
Light, for the fiber number of fiber up to 126dtex, centering long wave ultraviolet has a preferable shield effectiveness, made fibrous fracture intensity and
Elongation at break is 2.69cN/dtex and 54.6%, and fiber radiates fracture strength after 240h under ultraviolet light of the wavelength for 365nm
It is 2.63cN/dtex and 15.9% with elongation at break.
Embodiment 8
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle, preparation method are as follows：
(1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 in liquid, wherein mixed dispersion liquid:150:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 67 DEG C, room temperature ageing 12h is aged
Liquid, the mass ratio of ethyl alcohol and water is 5 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
26%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
2.5h is solved, is added in the ageing liquid of ultrasonic disperse 30min, the back flow reaction 4.5h at 65 DEG C, wherein second in ethanol water
The mass ratio of alcohol and water is 5:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:
The addition of 12, γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 7%；
D) 14h is dried in vacuo at 70 DEG C after rotating evaporation drying at 70 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
(2) by the mixture (mass ratio 1 of Bis-GMA, EBPADMA and UDMA:1:1), styrene and CQ are dissolved in
Obtain EFI solution in DMF, in EFI solution the mixture of Bis-GMA, EBPADMA and UDMA account for styrene and Bis-GMA,
The 10wt% of the amount of the mixture of EBPADMA and UDMA, DMF account for styrene and the mixture of Bis-GMA, EBPADMA and UDMA
The 80wt% of total amount, CQ account for the 1.2wt% of styrene and the amount of the mixture of Bis-GMA, EBPADMA and UDMA；
(3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation 1h of 500rpm
Modifying titanium dioxide is made to be uniformly dispersed in EFI solution, electrostatic spray system is carried out in the case where wavelength is the visible light conditions of 400nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is obtained, wherein the addition of the modifying titanium dioxide is EFI solution matter
The 27% of amount, the parameter of electrostatic spray are：The output voltage 12kV of high voltage power supply, the distance 13cm of atomizing nozzle and solidification bathing pool,
35 DEG C of temperature promotes the fltting speed 2mL/h of pump, the diameter 5mm of propeller, the volume 9mL of propeller；
(4) hollow porous micro sphere and the drying of cladding titanium dioxide nano particle are washed after electrostatic spray with methanol.
The hollow porous micro sphere of cladding titanium dioxide nano particle as made from the above method, mainly by nano titania
Particle and the crosslinking ball composition for being coated on titania nanoparticles surface, wherein crosslinking ball inner hollow, porous surface and tool
Crosslinking structure, cross-linked structure is by the copolymer containing styrene and bifunctionality dimethylacrylate class monomeric building blocks point
It is cross-linked with each other to be formed between subchain, by being covalently keyed between titania nanoparticles and crosslinking ball, is crosslinked the diameter of ball
For 1500nm, the wall thickness for being crosslinked ball is 50nm, a diameter of 310nm of titania nanoparticles, is crosslinked ball inner silica titanium
The quantity of nano particle is 4, and the distribution density for being crosslinked the surface aperture of ball is 1~5/1000nm2, the aperture of aperture is 70
~80nm.The melting temperature of the hollow porous micro sphere of cladding titanium dioxide nano particle is 550 DEG C, and heat decomposition temperature is 418 DEG C,
There is good dispersion effect to visible ray, when the additive amount of titanium dioxide in fiber is 2.0wt%, you can reach full-dull,
For the fiber number of fiber up to 122dtex, centering long wave ultraviolet has preferable shield effectiveness, made fibrous fracture intensity and fracture
Elongation is 2.85cN/dtex and 55.9%, fiber fracture strength and disconnected after radiation 240h in the case where wavelength is the ultraviolet light of 365nm
Elongation is split for 2.76cN/dtex and 16.4%.
Embodiment 9
A kind of hollow porous micro sphere of cladding titanium dioxide nano particle, preparation method are as follows：
(1) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 in liquid, wherein mixed dispersion liquid:220:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 70 DEG C, room temperature ageing 10h is aged
Liquid, the mass ratio of ethyl alcohol and water is 3 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
20%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
2h is solved, is added in the ageing liquid of ultrasonic disperse 60min, the back flow reaction 4.5h at 70 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 5:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:9,
The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 5%；
D) 15h is dried in vacuo at 80 DEG C after rotating evaporation drying at 60 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
(2) by UDMA, TEGDMA and D3Mixture (the mass ratio 1 of MA:2:2), styrene and DMPOH's and CQ is mixed
Close object (mass ratio 2:1) it is dissolved in chloroform and obtains EFI solution, UDMA, TEGDMA and D in EFI solution3MA's is mixed
It closes object and accounts for styrene and UDMA, TEGDMA and D3The 25wt% of the amount of the mixture of MA, chloroform account for styrene and UDMA,
TEGDMA and D3The mixture of 50wt%, DMPOH and the CQ of the amount of the mixture of MA account for styrene and UDMA, TEGDMA and D3MA
Amount of the mixture 0.5wt%；
(3) the double bond containing modifying titanium dioxide in surface is added in EFI solution with the rotating speed mechanical agitation 1h of 200rpm
Modifying titanium dioxide is made to be uniformly dispersed in EFI solution, electrostatic spray system is carried out in the case where wavelength is the visible light conditions of 430nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is obtained, wherein the addition of the modifying titanium dioxide is EFI solution matter
The 39% of amount, the parameter of electrostatic spray are：The output voltage 14kV of high voltage power supply, the distance 10cm of atomizing nozzle and solidification bathing pool,
Temperature 45 C promotes the fltting speed 3mL/h of pump, the diameter 15mm of propeller, the volume 10mL of propeller；
(4) hollow porous micro sphere and the drying of cladding titanium dioxide nano particle are washed after electrostatic spray with ethyl alcohol.
The hollow porous micro sphere of cladding titanium dioxide nano particle as made from the above method, mainly by nano titania
Particle and the crosslinking ball composition for being coated on titania nanoparticles surface, wherein crosslinking ball inner hollow, porous surface and tool
Crosslinking structure, cross-linked structure is by the copolymer containing styrene and bifunctionality dimethylacrylate class monomeric building blocks point
It is cross-linked with each other to be formed between subchain, by being covalently keyed between titania nanoparticles and crosslinking ball, is crosslinked the diameter of ball
For 600nm, the wall thickness for being crosslinked ball is 100nm, a diameter of 340nm of titania nanoparticles, is crosslinked ball inner silica titanium
The quantity of nano particle is 1, and the distribution density for being crosslinked the surface aperture of ball is 30~37/1000nm2, the aperture of aperture is
10~13nm.The melting temperature of the hollow porous micro sphere of cladding titanium dioxide nano particle is 546 DEG C, heat decomposition temperature 398
DEG C, there is good dispersion effect to visible ray, when the additive amount of titanium dioxide in fiber is 2.2wt%, you can reach and totally disappeared
Light, for the fiber number of fiber up to 114dtex, centering long wave ultraviolet has a preferable shield effectiveness, made fibrous fracture intensity and
Elongation at break is 3.03cN/dtex and 60.7%, and fiber radiates fracture strength after 240h under ultraviolet light of the wavelength for 365nm
It is 2.97cN/dtex and 17.2% with elongation at break.
Claims (10)
1. a kind of hollow porous micro sphere of cladding titanium dioxide nano particle, it is characterized in that：Mainly by titania nanoparticles
And it is coated on the crosslinking ball composition on titania nanoparticles surface；
The crosslinking ball inner hollow, porous surface and with cross-linked structure, the cross-linked structure is by containing styrene and difunctionality
It is cross-linked with each other to be formed between the copolymer molecule chain of degree dimethylacrylate class monomeric building blocks；
By being covalently keyed between the titania nanoparticles and crosslinking ball.
2. the hollow porous micro sphere of cladding titanium dioxide nano particle according to claim 1, it is characterised in that：The packet
Cover the melting temperature of the hollow porous micro sphere of titania nanoparticles>530 DEG C, heat decomposition temperature>380℃.
3. the hollow porous micro sphere of cladding titanium dioxide nano particle according to claim 1, which is characterized in that the friendship
Join a diameter of 500~1500nm of ball, the wall thickness of the crosslinking ball is 50~100nm；The titania nanoparticles it is straight
Diameter is 300~400nm；The quantity of the crosslinking ball inner silica titanium nano particle is 1~4.
4. the hollow porous micro sphere of cladding titanium dioxide nano particle according to claim 3, which is characterized in that work as crosslinking
During the quantity of ball inner silica titanium nano particle≤2, the distribution density of the surface aperture of the crosslinking ball for 1~60/
1000nm2, the aperture of aperture is 10~30nm；
When the quantity of crosslinking ball inner silica titanium nano particle>When 2, the distribution density of the surface aperture of the crosslinking ball is 1
~20/1000nm2, the aperture of aperture is 10~80nm.
5. a kind of prepare such as the hollow porous micro sphere of Claims 1 to 4 any one of them cladding titanium dioxide nano particle
Method, it is characterized in that：By the dissolving of styrene, bifunctionality dimethylacrylate class organic monomer and photoinitiator in a solvent
EFI solution is obtained, then the double bond containing modifying titanium dioxide in surface is added in EFI solution and is uniformly dispersed, in visible striation
The hollow porous micro sphere that cladding titanium dioxide nano particle is made in electrostatic spray is carried out under part.
6. the according to the method described in claim 5, it is characterized in that, rotating speed referred to 200~500rpm that is uniformly dispersed
Mechanical agitation 1h；The preparation process of the modifying titanium dioxide is as follows：
(1) titanium dioxide is dispersed in after being stirred by ultrasonic in absolute ethyl alcohol and tetrabutyl titanate is added dropwise obtains mixed dispersion liquid；
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4~6 in the mixed dispersion liquid:150~250:1；
(2) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4~5h is reacted at 60~70 DEG C, room temperature is aged 10~12h and obtains
To ageing liquid；The mass ratio of ethyl alcohol and water is 2~5 in the ethyl alcohol water mixed liquid:1, the addition of the ethyl alcohol water mixed liquid
20~30% for mixed dispersion liquid volume；
(3) by silane coupling agent instill ethanol water in, 2~3h of hydrolysis is stirred at room temperature, be added to ultrasonic disperse 30~
In the ageing liquid of 60min, 4~5h of back flow reaction at 60~70 DEG C；The mass ratio of ethyl alcohol and water is 2 in the ethanol water
~5:1, the mass ratio of the silane coupling agent and ethanol water is 1:8~12, the addition of the silane coupling agent is old
Change 5~10% of titanium dioxide quality in liquid, the silane coupling agent is γ-methacryloxypropyl trimethoxy silicon
Alkane；
(4) 12~16h is dried in vacuo at 70~80 DEG C after evaporation drying is rotated at 50~70 DEG C, it is double bond containing to obtain surface
Modifying titanium dioxide.
7. the according to the method described in claim 5, it is characterized in that, bifunctionality dimethylacrylate class organic monomer
For Bis-GMA, EBPADMA, UDMA, TEGDMA and D3One or more of MA；
The photoinitiator is DMPOH and/or CQ；
The wavelength of the visible ray is 400~500nm；
The solvent is one or more of DMF, chloroform, dichloromethane and tetrahydrofuran.
8. according to the method described in claim 5, it is characterized in that, bifunctionality dimethylacrylate in the EFI solution
Class organic monomer accounts for styrene and 5~25wt% of bifunctionality dimethylacrylate class organic monomer total amount, and solvent accounts for benzene
50~80wt% of ethylene and bifunctionality dimethylacrylate class organic monomer total amount, photoinitiator account for styrene and double officials
0.5~1.2wt% of energy degree dimethylacrylate class organic monomer total amount；The addition of the modifying titanium dioxide is EFI
The 15~40% of solution quality.
9. according to the method described in claim 5, it is characterized in that, the parameter of electrostatic spray is：The output voltage of high voltage power supply
10~15kV, atomizing nozzle and the 7~13cm of distance for solidifying bathing pool, 25~50 DEG C of temperature promote 1~4mL/h of fltting speed of pump,
5~15mm of diameter of propeller, 3~10mL of volume of propeller.
10. according to the method described in claim 5, it is characterized in that, cladding is washed with methanol or ethyl alcohol after electrostatic spray
The hollow porous micro sphere of titania nanoparticles and drying.
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| CN108726485A (en) * | 2018-06-29 | 2018-11-02 | 华中科技大学 | A kind of Porous hollow oxidate nano microballoon and the preparation method and application thereof |
| CN109876147A (en) * | 2019-02-28 | 2019-06-14 | 李琳 | A kind of preparation method and applications of fibroin albumen microsphere drug slow-released carrier |
| CN114523105A (en) * | 2021-12-31 | 2022-05-24 | 新辉（中国）新材料有限公司 | High-crosslinking-degree organic silicon polymer/metal composite microsphere and preparation method thereof |
| CN115919664A (en) * | 2022-12-27 | 2023-04-07 | 广东普本纳米科技有限公司 | Ultrafine titanium dioxide and preparation method thereof |
| CN114988466B (en) * | 2022-05-20 | 2024-04-09 | 佛山(华南)新材料研究院 | Mesoporous TiO with high tap density 2 Microsphere and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067432A (en) * | 1991-03-22 | 1992-12-30 | 罗姆和哈斯公司 | The preparation method of the crosslinked copolymer beads of porous surface |
| CN101205259A (en) * | 2007-12-07 | 2008-06-25 | 北京化工大学 | Method for preparing high-crosslinking-degree hollow polymeric microspheres |
| CN103387717A (en) * | 2012-05-07 | 2013-11-13 | 中国石油化工股份有限公司 | Organic/inorganic composite hollow microspheres, and preparation method and application thereof |
| CN104250350A (en) * | 2014-09-30 | 2014-12-31 | 复旦大学 | Method for preparing porous polymer material with through-pore structure |
| WO2015054493A1 (en) * | 2013-10-09 | 2015-04-16 | Nanocomposix, Inc. | Encapsulated particles |
| CN107540775A (en) * | 2016-06-29 | 2018-01-05 | 中国石油天然气股份有限公司 | A kind of preparation method of organic/inorganic complex carrier |
-
2018
- 2018-01-12 CN CN201810029341.XA patent/CN108144558B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067432A (en) * | 1991-03-22 | 1992-12-30 | 罗姆和哈斯公司 | The preparation method of the crosslinked copolymer beads of porous surface |
| CN101205259A (en) * | 2007-12-07 | 2008-06-25 | 北京化工大学 | Method for preparing high-crosslinking-degree hollow polymeric microspheres |
| CN103387717A (en) * | 2012-05-07 | 2013-11-13 | 中国石油化工股份有限公司 | Organic/inorganic composite hollow microspheres, and preparation method and application thereof |
| WO2015054493A1 (en) * | 2013-10-09 | 2015-04-16 | Nanocomposix, Inc. | Encapsulated particles |
| CN104250350A (en) * | 2014-09-30 | 2014-12-31 | 复旦大学 | Method for preparing porous polymer material with through-pore structure |
| CN107540775A (en) * | 2016-06-29 | 2018-01-05 | 中国石油天然气股份有限公司 | A kind of preparation method of organic/inorganic complex carrier |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108726485A (en) * | 2018-06-29 | 2018-11-02 | 华中科技大学 | A kind of Porous hollow oxidate nano microballoon and the preparation method and application thereof |
| CN108726485B (en) * | 2018-06-29 | 2020-07-10 | 华中科技大学 | Porous hollow oxide nano-microsphere and preparation method and application thereof |
| CN109876147A (en) * | 2019-02-28 | 2019-06-14 | 李琳 | A kind of preparation method and applications of fibroin albumen microsphere drug slow-released carrier |
| CN114523105A (en) * | 2021-12-31 | 2022-05-24 | 新辉（中国）新材料有限公司 | High-crosslinking-degree organic silicon polymer/metal composite microsphere and preparation method thereof |
| CN114523105B (en) * | 2021-12-31 | 2024-03-22 | 新辉（中国）新材料有限公司 | High-crosslinking-degree organosilicon polymer/metal composite microsphere and preparation method thereof |
| CN114988466B (en) * | 2022-05-20 | 2024-04-09 | 佛山(华南)新材料研究院 | Mesoporous TiO with high tap density 2 Microsphere and preparation method thereof |
| CN115919664A (en) * | 2022-12-27 | 2023-04-07 | 广东普本纳米科技有限公司 | Ultrafine titanium dioxide and preparation method thereof |
| CN115919664B (en) * | 2022-12-27 | 2023-11-28 | 广东普本纳米科技有限公司 | Ultrafine titanium dioxide and preparation method thereof |
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