CN103937267A - Core-shell-type optical diffusion hybrid microsphere and preparation method thereof - Google Patents
Core-shell-type optical diffusion hybrid microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a core-shell-type optical diffusion hybrid microsphere and a preparation method thereof. The hybrid microsphere is obtained by carrying out a copolymerization reaction, a hydrolysis reaction and a condensation reaction on a cerium complex, a vinyl unsaturated monomer, a siloxane monomer containing double bonds and a sulfur-containing initiator, wherein an inner core of the hybrid microsphere is formed by a nanometer ceria hybrid copolymer; the nanometer ceria is from 30nm to 40nm in size; and a shell layer of the hybrid microsphere is formed by a polysiloxane condensation polymer. The white hybrid microsphere is from 350nm to 500nm in size and can be used for preparing an optical diffusion film in a liquid crystal display backlight module and ensuring that the good mechanical and abrasion-resistant performance of the optical diffusion film is obtained as well as the heat stability and the transparency of the optical diffusion film are improved. Thus, the hybrid microsphere is especially suitable for preparing an ultra-thin scratch-resistant optical diffusion film with good flexibility.
Description
Technical field
The present invention relates to a kind of hud typed light diffusion microballoon and preparation method thereof, belong to technical field of function materials.
Background technology
Present electronic commerce times, a lot of staff need to handle official business facing to computer, but have often all ignored a problem, are exactly computer radiate.The hazard ratio of Radiation On Human body is larger, and computer radiate pollutes not only can affect the recycle system, immunity, reproduction and the metabolic function of human body, serious also can bring out cancer, and can accelerate the cancer cell multiplication of human body.In addition, the reproductive system that also can affect people shows as man's sperm quality to be reduced, and spontaneous abortion and fetal anomaly etc. occur pregnant woman; The cardiovascular systems that affects people shows as palpitaition, insomnia, and some women disorder of menstrual cycle, bradyrhythmia, heartbeat oligohemia, sinus rate are uneven, oligoleukocythemia, lower immune function etc.; The vision system that affects people shows as visual deterioration, causes cataract etc.More than harm belongs to more serious, also has some slight harm, also can bring to people uncomfortable.Therefore the optically functional film that, research has an electromagnetic radiation in shielding computer or mobile phone has very important significance.
The future developments such as current, liquid-crystal display (LCD) is towards frivolous, and display interface is large, and the stable and electromagnetic radiation of display frame is little, wherein in LCD, in backlight module, the functional design of optical diffusion film seems particularly important.Not yet there is solving at present the optically functional film, particularly easy unheeded computer radiate pollution problem of this series of problems both at home and abroad.Present research both at home and abroad focuses mostly in the preparation of organic-inorganic hybrid material, but rarely have hybrid microspheres to be used as the report of optically functional film, and the research about cerium dioxide with low cost all can not be eliminated itself have light yellow, thereby limit its application on optically functional film.In recent years, producer of a lot of scientific research institutions all in succession develops various types of optical diffusion films and has applied for patent, use organic light diffusion microballoon but all concentrate on, as the patent CN102736146A of Hefei Lucky Science & Technology Industry Co., Ltd.'s application has just used the raw materials of two kinds of organic microballoons as diffusion barrier.And some patents are for making that optical diffusion film is thinner, mist degree and hardness higher, add specially in addition inorganic particulate, as the patent CN102778712A of Kunshan Lucky Jinfu Optoelectronic Technology Co., Ltd.'s application has used the inorganic particulate of a kind of 2～4 μ m as diffusion microballoon and the organic light diffusion of a kind of 10～25 μ m microballoon.At present, organic inorganic hybridization microballoon is had no precedent report in the utilization in optical diffusion film field.
The present invention uses nano ceric oxide at the original position generation of polymerization system and the hydrolysis-condensation reaction of siloxanes, prepare the nano ceric oxide polymer hybrid microballoon with hud typed structure, this white microballoon of preparation not only has good light diffusion effect first, and has anti-short-wave radiation and good heat-proof aging function.This method for preparing microsphere is simple, has larger potential using value, with low cost, and preparation technology's environmental protection.
Summary of the invention
Technical problem: the object of the invention is to provide a kind of hud typed light diffusion microballoon and preparation method thereof, this hybrid microspheres is by cerium complexes, containing unsaturated vinyl monomer, carry out copolymerization, hydrolysis and condensation reaction and obtain containing two key siloxanyl monomers, sulfur-bearing initiator by one kettle way, its kernel is nano ceric oxide hybrid copolymers, and shell is polysiloxane polycondensate.Wherein cerium complexes is to be prepared by cerous salt and hydramine reaction.
Technical scheme: this microballoon of the present invention is by cerium complexes, containing unsaturated vinyl monomer, carries out copolymerization, hydrolysis and condensation reaction and obtain containing two key siloxanyl monomers, sulfur-bearing initiator, its kernel is nano ceric oxide hybrid copolymers, and shell is polysiloxane polycondensate.Its preparation method is: first prepared cerium complexes, the original position that adopts again one kettle way to carry out cerium dioxide nano grain in the aqueous solution generates, contains the hydrolysis of double bond monomer copolymerization and siloxanes, and the condensation reaction that finally regulates pH to carry out siloxanes has obtained a kind of light diffusion microballoon of cerium dioxide/polymer hybrid nucleocapsid structure; Concrete preparation process is:
Cerium salt is added reactor by step a), be that 20:1～50:1 adds dehydrated alcohol by the mass ratio of dehydrated alcohol and cerium salt, obtaining cerium salt ethanolic soln, is then 4:1～9:1 by the mole ratio of hydramine and cerium salt, and hydramine is joined in cerium salt ethanolic soln, room temperature reaction 3～5h, leave standstill, filter, extremely neutral with absolute ethanol washing, 50～70 DEG C of dry 2～4h, obtain cerium complexes;
The cerium complexes quality of step b) to obtain in step a), by cerium complexes, 3～15 times of cerium complexes quality containing unsaturated vinyl monomer, 3～15 times of cerium complexes quality containing two key siloxanyl monomers, the distilled water of 150～350 times of quality cerium complexes, the sulfur-bearing initiator of 0.25～1.5 times of cerium complexes quality adds in reactor, at 75～90 DEG C, react 3～6h, add to and in emulsion, adjust pH to 8～9 with the ammoniacal liquor that concentration is 1wt%～10wt% again, at 50～80 DEG C, continue reaction 2～6h, on cerium dioxide hybrid copolymers, form polysiloxane polycondensate shell, cooling, filter, be washed with distilled water to neutrality, dry 4～10h at 50～80 DEG C, obtain hud typed light diffusion hybrid microspheres.
Cerium salt described in above-mentioned preparation method's step a) is the one in cerous nitrate, cerous compounds, and described hydramine is the one in trolamine, diethanolamine; Described in step b) is one or more the combination in methyl methacrylate, vinylbenzene, isobornyl acrylate, isobornyl methacrylate containing unsaturated vinyl monomer, described is the one in vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane and vinyl three ('beta '-methoxy oxyethyl group) silane containing two key siloxanyl monomers, and described sulfur-bearing initiator is ammonium persulphate or Potassium Persulphate.
Beneficial effect: nucleocapsid structure microballoon has multi-functional character, shows that aspect optics multilayer specific refractory power can play good light diffusion.Combining nano granule in-situ method of formation of the present invention and sol-gel method use the aqueous solution one kettle way of easy environmental protection to synthesize cerium dioxide/polymer hybrid nucleocapsid structure microballoon, first make cerium complexes, thereby then under aqueous solution polymerization system, be hydrolyzed and be oxidized and produce cerium oxide nanoparicles by persulfide initiator, meanwhile containing two key siloxanyl monomers with containing in unsaturated vinyl monomer generation copolymerization and be slowly hydrolyzed.Then by regulating suitable pH value to make the product after hydrolysis carry out polycondensation, thereby form polysiloxane shell.This microballoon of preparing has good light diffusion effect, and also has stronger electromagnetic radiation resisting function, can shield the serious harm that shortwave brings, the absorption of uv-radiation is bordering on completely, and thermostability and ageing-resistant ability strong.This material has huge potential using value in the field such as multifunctional material and optics.
Feature of the present invention is:
(1), this hud typed hybrid microspheres has stronger uv absorption property, and short-wave radiation is had to obvious shielding effect.
(2), the hybrid microspheres prepared has good dispersing property, all there will not be the phenomenon of reunion for the thermofixation moulding of optical diffusion film or UV curing molding.
(3), this hybrid microspheres has good heat aging property.
Embodiment
Embodiment 1:
Get 10g six water cerous nitrates and be dissolved in 250g dehydrated alcohol, then toward wherein adding 26g trolamine, stirring at room temperature reaction 3h, leave standstill, filter, be neutral to filtrate for several times with 20g absolute ethanol washing at every turn, then dry 3h at 60 DEG C, obtains cerous nitrate trolamine title complex.Respectively this cerium complexes of 1g, 200g distilled water, 3g methyl methacrylate, 3g γ-methacryloxypropyl trimethoxy silane (KH570) and 0.3g ammonium persulphate are added in reactor again, 75 DEG C of reaction 4h, then adjusting pH with 10wt% ammoniacal liquor is 8.5,50～60 DEG C of reaction 3h, cooling, filtration, for several times be neutral to filtrate with distilled water wash, dry 5～8h at 70 DEG C, obtains hud typed light diffusion hybrid microspheres.
Embodiment 2:
Get 10g six water cerous nitrates and be dissolved in 250g dehydrated alcohol, then toward wherein adding 25g trolamine, stirring at room temperature reaction 3h, leave standstill, filter, be neutral to filtrate for several times with 20g absolute ethanol washing at every turn, then dry 3h at 60 DEG C, obtains cerous nitrate trolamine title complex.Get again this title complex of 1g, 200g H
2o, 3g isobornyl acrylate, 3g vinyltrimethoxy silane (VTMS) and 0.3g ammonium persulphate react 4h at 80 DEG C, then adjusting pH with 8wt% ammoniacal liquor is 8.5,50～60 DEG C of reaction 3h, cooling, filter, be for several times neutral to filtrate with distilled water wash, dry 5～8h at 70 DEG C, obtains hud typed light diffusion hybrid microspheres.
Embodiment 3:
Get 10g seven water Cerium II Chlorides and be dissolved in 300g dehydrated alcohol, then toward wherein adding 30g trolamine, stirring at room temperature reaction 3h, leave standstill, filter, be neutral to filtrate for several times with 20g absolute ethanol washing at every turn, then dry 3h at 60 DEG C, obtains Cerium II Chloride trolamine title complex.Get again this title complex of 1g, 200g H
2o, 3g vinylbenzene, 3g vinyl three ('beta '-methoxy oxyethyl group) silane (KH172) and 0.3g ammonium persulphate react 4h at 75 DEG C, then adjusting pH with 6wt% ammoniacal liquor is 8.5,50～60 DEG C of reaction 3h, cooling, filter, be for several times neutral to filtrate with distilled water wash, dry 5～8h at 70 DEG C, obtains hud typed light diffusion hybrid microspheres.
Embodiment 4:
Get 10g seven water Cerium II Chlorides and be dissolved in 300g dehydrated alcohol, then toward wherein adding 26g trolamine, stirring at room temperature reaction 3h, leave standstill, filter, be neutral to filtrate for several times with 20g absolute ethanol washing at every turn, then dry 3h at 60 DEG C, obtains Cerium II Chloride trolamine title complex.Get again this title complex of 1g, 200g H
2o, 5g methyl methacrylate, 3g γ-methacryloxypropyl trimethoxy silane (KH570) and 0.4g ammonium persulphate react 4h at 80 DEG C, then adjusting pH with 5wt% ammoniacal liquor is 8.5,50～60 DEG C of reaction 3h, cooling, filter, be for several times neutral to filtrate with distilled water wash, dry 5～8h at 70 DEG C, obtains hud typed light diffusion hybrid microspheres.
Embodiment 5:
Get 10g six water cerous nitrates and be dissolved in 250g dehydrated alcohol, then toward wherein adding 26g trolamine, stirring at room temperature reaction 3h, leave standstill, filter, be neutral to filtrate for several times with 20g absolute ethanol washing at every turn, then dry 3h at 60 DEG C, obtains cerous nitrate trolamine title complex.Get again this title complex of 1g, 200g H
2o, 3g isobornyl methacrylate, 3g γ-methacryloxypropyl trimethoxy silane (KH570) and 0.3g Potassium Persulphate react 4h at 90 DEG C, then adjusting pH with 5wt% ammoniacal liquor is 8.5,50～60 DEG C of reaction 3h, cooling, filter, be for several times neutral to filtrate with distilled water wash, dry 5～8h at 70 DEG C, obtains hud typed light diffusion hybrid microspheres.
Embodiment 6:
10g six water cerous nitrates are dissolved in 200g dehydrated alcohol, then toward wherein adding 23g trolamine, stirring at room temperature reaction 3h, leave standstill, filter, be neutral to filtrate for several times with 20g absolute ethanol washing at every turn, then dry 3h at 60 DEG C, obtains cerous nitrate trolamine title complex.Again respectively by this title complex of 1.5g, 300g H
2o, 4.5g isobornyl acrylate, 5g γ-methacryloxypropyl trimethoxy silane (KH570) and 0.45g ammonium persulphate join in reactor, at 80 DEG C, react 4h, then adjusting pH with 5wt% ammoniacal liquor is 8.5, be cooled to 50～60 DEG C and continue reaction 3h, cooling, filtration, be washed with distilled water to neutrality, dry 5～8h at 70 DEG C, obtains hud typed light diffusion hybrid microspheres.
Claims (4)
1. a hud typed light diffusion hybrid microspheres, it is characterized in that this microballoon is by cerium complexes, containing unsaturated vinyl monomer, carries out copolymerization, hydrolysis and condensation reaction and obtain containing two key siloxanyl monomers, sulfur-bearing initiator, its kernel is nano ceric oxide hybrid copolymers, and shell is polysiloxane polycondensate.
2. a preparation method for a kind of hud typed light diffusion hybrid microspheres as claimed in claim 1, is characterized in that this preparation method is:
Cerium salt is added reactor by step a), be that 20:1～50:1 adds dehydrated alcohol by the mass ratio of dehydrated alcohol and cerium salt, obtaining cerium salt ethanolic soln, is then 4:1～9:1 by hydramine with adding the mole ratio of cerium salt, and hydramine is joined in cerium salt ethanolic soln, room temperature reaction 3～5h, leave standstill, filter, extremely neutral with absolute ethanol washing, 50～70 DEG C of dry 2～4h, obtain cerium complexes;
The cerium complexes quality of step b) to obtain in step a), by cerium complexes, 3～15 times of cerium complexes quality containing unsaturated vinyl monomer, 3～15 times of cerium complexes quality containing two key siloxanyl monomers, the distilled water of 150～350 times of quality cerium complexes, the sulfur-bearing initiator of 0.25～1.5 times of cerium complexes quality adds in reactor, at 75～90 DEG C, react 3～6h, obtain nano ceric oxide hybrid copolymers emulsion, again the ammoniacal liquor of 1wt%～10wt% is added in this emulsion and adjusts pH to 8～9, at 50～80 DEG C, continue reaction 2～6h, on cerium dioxide hybrid copolymers, form polysiloxane polycondensate shell, through cooling, filter, be washed with distilled water to neutrality, dry 4～10h at 50～80 DEG C, obtain hud typed light diffusion hybrid microspheres.
3. the preparation method of a kind of hud typed light diffusion hybrid microspheres according to claim 2, it is characterized in that the cerium salt described in this preparation method's step a) is the one in cerous nitrate, cerous compounds, described hydramine is the one in trolamine, diethanolamine.
4. the preparation method of a kind of hud typed light diffusion hybrid microspheres according to claim 2, it is characterized in that described in this preparation method's step b) being methyl methacrylate containing unsaturated vinyl monomer, vinylbenzene, isobornyl acrylate, the combination of one or more in isobornyl methacrylate, described is vinyltrimethoxy silane containing two key siloxanyl monomers, one in γ-methacryloxypropyl trimethoxy silane and vinyl three ('beta '-methoxy oxyethyl group) silane, described sulfur-bearing initiator is ammonium persulphate or Potassium Persulphate.
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Cited By (6)
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| CN104231830A (en) * | 2014-08-08 | 2014-12-24 | 佛山佛塑科技集团股份有限公司 | Preparation method of diffusion film coating composition, preparation method of diffusion film, and corresponding diffusion film |
| CN104730605A (en) * | 2015-03-04 | 2015-06-24 | 东南大学 | Light diffusion membrane for display and preparation method thereof |
| CN105131197A (en) * | 2015-09-24 | 2015-12-09 | 浙江衢州万能达科技有限公司 | Preparation method of polycarbonate photodiffusion material |
| CN106279549A (en) * | 2016-08-09 | 2017-01-04 | 广州市新稀冶金化工有限公司 | A kind of Multifunction light diffusing agent and preparation method thereof |
| CN107175054A (en) * | 2017-05-31 | 2017-09-19 | 东南大学 | FPD conversion light spreads microballoon and preparation method thereof |
| CN108976338A (en) * | 2018-07-10 | 2018-12-11 | 东南大学 | A kind of novel display optical material and preparation method thereof |
-
2014
- 2014-04-11 CN CN201410147116.8A patent/CN103937267A/en active Pending
Non-Patent Citations (3)
| Title |
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| JINGANG HU， YUMING ZHOU，MAN HE，XIAOMING YANG: "Novel multifunctional microspheres of polysiloxane@CeO2-PMMA: Optical properties and their application in optical diffusers", 《OPTICAL MATERIALS》 * |
| JINGANG HU， YUMING ZHOU，MAN HE，XIAOMING YANG: "Novelpolysiloxane@CeO2-PMMA hybridmaterials", 《MATERIALS LETTERS》 * |
| 陆馨 辛忠: "微米级聚苯乙烯/聚硅氧烷核壳微球的制备、表征及其作为光散射剂的应用", 《化工学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231830A (en) * | 2014-08-08 | 2014-12-24 | 佛山佛塑科技集团股份有限公司 | Preparation method of diffusion film coating composition, preparation method of diffusion film, and corresponding diffusion film |
| CN104730605A (en) * | 2015-03-04 | 2015-06-24 | 东南大学 | Light diffusion membrane for display and preparation method thereof |
| CN105131197A (en) * | 2015-09-24 | 2015-12-09 | 浙江衢州万能达科技有限公司 | Preparation method of polycarbonate photodiffusion material |
| CN105131197B (en) * | 2015-09-24 | 2017-10-17 | 浙江衢州万能达科技有限公司 | A kind of preparation method of makrolon photodiffusion material |
| CN106279549A (en) * | 2016-08-09 | 2017-01-04 | 广州市新稀冶金化工有限公司 | A kind of Multifunction light diffusing agent and preparation method thereof |
| CN107175054A (en) * | 2017-05-31 | 2017-09-19 | 东南大学 | FPD conversion light spreads microballoon and preparation method thereof |
| WO2018219255A1 (en) * | 2017-05-31 | 2018-12-06 | 东南大学 | Up-conversion light diffusion micro-sphere for panel display and preparation method thereof |
| CN107175054B (en) * | 2017-05-31 | 2019-04-30 | 东南大学 | FPD conversion light spreads microballoon and preparation method thereof |
| CN108976338A (en) * | 2018-07-10 | 2018-12-11 | 东南大学 | A kind of novel display optical material and preparation method thereof |
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Application publication date: 20140723 |