CN101955613A - Method for preparing polymer-zinc oxide nano composite microspheres - Google Patents
Method for preparing polymer-zinc oxide nano composite microspheres Download PDFInfo
- Publication number
- CN101955613A CN101955613A CN 201010513013 CN201010513013A CN101955613A CN 101955613 A CN101955613 A CN 101955613A CN 201010513013 CN201010513013 CN 201010513013 CN 201010513013 A CN201010513013 A CN 201010513013A CN 101955613 A CN101955613 A CN 101955613A
- Authority
- CN
- China
- Prior art keywords
- microsphere
- zno
- polymkeric substance
- component
- composite nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for preparing polymer-zinc oxide nano composite microspheres and belongs to the technical field of preparation of organic-inorganic nano composite microspheres. The method comprises the following steps of: firstly, copolymerizing a vinyl monomer and organosiloxane to prepare polymer microspheres of which the surfaces are provided with active silicon hydroxyl through miniemulsion polymerization; and secondly, generating nano ZnO on the surfaces of the polymer microspheres by reacting an organic amine alkali source with the active silicon hydroxyl function on the surfaces of the polymer microspheres so as to prepare the polymer/ZnO nano composite microspheres. The prepared polymer/ZnO nano composite microspheres have the advantages of controllable grain size and nano ZnO shape on the surfaces of the polymer microspheres, capacity of overcoming the defects of easy agglomeration and poor dispersibility of nano ZnO grains, and wide application to the fields of UV-resistant coatings, photo-catalytic environment-friendly materials, and the like.
Description
Technical field
The present invention relates to the preparation of organic-inorganic nano composite microsphere, particularly the preparation method of polymkeric substance-ZnO composite nano-microsphere belongs to the composite nano-microsphere preparing technical field.
Background technology
Nano zine oxide (ZnO) has absorption, scatters ultraviolet and photo-catalysis capability etc., and at uvioresistant paint, fields such as photocatalytic environmental-protection material have a wide range of applications.Yet nano-ZnO is easily reunited, and is restricted in application process.In recent years, the nano-ZnO surface is modified and be that template prepares the ZnO nano composite structure and receives publicity with organism or inorganics.Because polystyrene (PS) preparation is simple, the easy functionalization of PS microsphere surface, size is easy to control, and it is that template prepares the shell-nuclear compounded particle of PS/ nano-ZnO with PS that report is arranged." material and chemistry " (Chemistry of Materials, 2007,19,1845-1852) introduction is carried out emulsion copolymerization with 2-acetoacetoxyethyl methacrylate and vinylbenzene (St), PS is carried out the surface-functionalized PS of making microsphere surface have active beta-dicarbonyl, by beta-dicarbonyl and nano-ZnO presoma (zn cpds) effect, generate nano-ZnO at the PS microsphere surface, preparation PS/ZnO composite nano-microsphere.But the PS/ZnO composite nano-microsphere particle diameter that above method makes is big (500nm-600nm), and the 2-acetoacetoxyethyl methacrylate of Shi Yonging is expensive in addition." European polymkeric substance " (European polymer Journal, 44 (2008) 3271 – 3279) introduced a kind of method of the simple PS/ZnO of preparation composite nano-microsphere, with octadecenic acid the nano-ZnO surface is handled, with the St monomer copolymerization, wherein nano-ZnO plays tensio-active agent again.This method for preparing the PS/ZnO composite nano-microsphere is simple to operation, but the nano-ZnO particle of the PS/ZnO composite nano-microsphere PS microsphere surface that makes is inhomogeneous, and is dispersed bad, can not well embody some performances of nano-ZnO in application.The present invention proposes to adopt the method for mini-emulsion polymerization to prepare polymer microballoon on the basis of above research, adopts in-situ method to prepare nano-ZnO on the polymer microballoon surface, finally makes polymkeric substance/ZnO composite nano-microsphere.
Summary of the invention
It is controlled to the purpose of this invention is to provide a kind of particle diameter and form, disperses the preparation method of better polymerization thing/ZnO composite nano-microsphere.
Technical scheme of the present invention: the preparation method of a kind of polymkeric substance-ZnO composite nano-microsphere, adopt the method for mini-emulsion polymerization that vinyl monomer and organo-siloxane are carried out the polymer microballoon that the copolymerization surface has the activated silica hydroxyl; Activated silica hydroxyl by organic amine alkali source and described polymer microballoon surface acts on polymer microballoon surface in situ generation nano-ZnO again, makes polymkeric substance-ZnO composite nano-microsphere; Step is:
1) prepare the polymer microballoon of surface silanol groupization with the method for mini-emulsion polymerization, consist of: vinyl monomer, organo-siloxane, emulsifying agent, co-stabilizer, initiator and pH regulator agent and deionized water, the quality consumption is as follows:
Vinyl monomer 85-95,
Organo-siloxane 5-15,
The percentage consumption that other component accounts for vinyl monomer and organo-siloxane quality sum is:
Emulsifying agent 0.5-1.5,
Co-stabilizer 2-7,
Initiator 0.5-1.5,
PH regulator agent 0.5-1.5,
Deionized water 500-900.
Operation steps is: by proportioning emulsifying agent, pH regulator agent, deionized water are mixed, be the A component; By proportioning vinyl monomer, organo-siloxane, co-stabilizer and initiator are mixed, be the B component; At ambient temperature the B component slowly is added drop-wise in the A component, stirs while dripping; Drip back continuation stirring 0.5h and carry out emulsification; Again with the thin emulsification 10min of ultrasonic wave; After the thin emulsification under 60-70 ℃ of condition polyase 13 h, make the polymer microballoon of surface silanol groupization.
Described emulsifying agent is selected sodium laurylsulfonate (SLS), sodium lauryl sulphate (SDS) or Trimethyllaurylammonium bromide (DTAB) etc. for use.
Described co-stabilizer is selected hexadecanol (CA), lauryl mercaptan, Stearyl mercaptan or hexadecane (HD) etc. for use.
Described initiator is a water soluble starter: select a kind of of Potassium Persulphate (KPS), ammonium persulphate (APS) for use; Or oil-soluble initiator: select a kind of of Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), dibenzoyl peroxide (BPO), lauroyl peroxide (LPO) for use.
One or both of sodium hydroxide, sodium bicarbonate, yellow soda ash, sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium hydrogen phosphate are selected in described pH regulator agent for use.
2) in-situ method prepares polymkeric substance-ZnO composite nano-microsphere, in a certain amount of above-mentioned polymer microballoon emulsion, add organic amine, the alcoholic solution that adds zn cpds again, activated silica hydroxyl effect by organic amine alkali source and polymer microballoon surface prepares polymkeric substance-ZnO composite nano-microsphere, and the quality consumption is as follows:
Polymer microballoon emulsion 3-10
Deionized water 30-50
Organic amine 5-17
Zn cpds 0.1-0.5
Alcohol 25-45
Operation steps is: take out the above-mentioned polymer microballoon emulsion of part, be raised to 45-60 ℃ with the deionized water dilution and with temperature, slowly drip organic amine, stir while dripping, add the back and continue to stir 0.5h, be the C component; Zn cpds is dissolved in the alcohol, is the D component; The D component slowly is added dropwise in the C component, stirs, add the back and continue reaction 0.5h, make polymkeric substance-ZnO composite nano-microsphere while dripping.
Described vinyl monomer is selected vinylbenzene, methyl methacrylate, vinyl-acetic ester, vinyl cyanide or vinylchlorid etc. for use.
Described organo-siloxane is selected 3-methacryloxypropyl trimethoxy silane, methacryloxypropyl triethoxyl silane or vinyltriethoxysilane etc. for use.
Described organic amine is selected trolamine or tri-isopropanolamine etc. for use.
Described zn cpds is selected Zinc diacetate dihydrate, zinc acetate, zinc nitrate, zinc sulfate or zinc chloride etc. for use.
Described alcohol is selected methyl alcohol, dehydrated alcohol, propyl alcohol, butanols or Virahol etc. for use.
Beneficial effect of the present invention: the polymkeric substance/ZnO composite nano-microsphere of the present invention's preparation has the following advantages: the nano-ZnO form on the particle diameter of complex microsphere and polymer microballoon surface is controlled; Has dispersion stabilization preferably.Be widely used in fields such as uvioresistant paint and photocatalytic environmental-protection materials.
Description of drawings
Fig. 1 AIBN causes the TEM photo of the PS sample that makes.
Fig. 2 AIBN causes the TEM photo of the polymkeric substance ZnO composite nano-microsphere sample that makes.
Fig. 3 KPS causes the TEM photo of the polymkeric substance ZnO composite nano-microsphere sample that makes.
Embodiment
The present invention will be described below in conjunction with example.
Embodiment 1
Take by weighing 0.1g SDS, the 0.1g sodium bicarbonate, the 0.1g SODIUM PHOSPHATE, MONOBASIC, with the dilution of 90g deionized water, immigration has whipping appts, in the 250mL four-hole bottle of thermometer and reflux condensate device (A component); Take by weighing 8.5g vinylbenzene (St) monomer, 1.5g 3-methacryloxypropyl trimethoxy silane (MEMO), 0.5g HD, 0.1g AIBN(B component), the back that stirs moves in the dropping funnel.Under the room temperature condition B component slowly is added drop-wise in the A component, adds back continuation stirring 0.5h and carry out emulsification.Take out above-mentioned mixed composition, the thin emulsification 10min of ultrasonic wave.Continue to transfer to whipping appts is housed, in the 250mL four-hole bottle of thermometer and reflux condensate device, temperature is slowly risen to 70 ℃, polyase 13 h makes the PS microballoon of surface silanol groupization.
The above-mentioned PS emulsion of taking-up 5g is diluted with the 40g deionized water, transfers to have whipping appts, in the 250mL four-hole bottle of thermometer and reflux condensate device, temperature slowly is raised to 55 ℃; In four-hole bottle, slowly drip the 8g trolamine, stir, add the back and continue to stir the 0.5h(C component) while dripping; Take by weighing the 0.1g Zinc diacetate dihydrate, use the 30g anhydrous alcohol solution, transfer to (D component) in the dropping funnel after the dissolving fully; The D component slowly is added drop-wise in the C component, stirs, add the back and continue reaction 0.5h, make polymkeric substance/ZnO composite nano-microsphere while dripping.By transmission electron microscope (TEM) image of Fig. 2 as can be known the PS microsphere surface wrapped one deck nano-ZnO particle uniformly.
Embodiment 2
Take by weighing 0.1g SDS, 0.1g sodium bicarbonate (NaHCO
3), 0.1g SODIUM PHOSPHATE, MONOBASIC (NaH
2PO
4), with the dilution of 90g deionized water, immigration has whipping appts, in the 250mL four-hole bottle of thermometer and reflux condensate device (A component); Take by weighing 8.5g vinylbenzene (St) monomer, 1.5g 3-methacryloxypropyl trimethoxy silane (MEMO), 0.5g HD, 0.1g KPS(B component), the back that stirs moves in the dropping funnel.Under the room temperature condition B component slowly is added drop-wise in the A component, adds back continuation stirring 0.5h and carry out emulsification.Take out above-mentioned mixed composition, the thin emulsification 10min of ultrasonic wave.Continue to transfer to whipping appts is housed, in the 250mL four-hole bottle of thermometer and reflux condensate device, temperature is slowly risen to 70 ℃, polyase 13 h makes the PS microballoon of surface silanol groupization.
The above-mentioned PS emulsion of taking-up 5g is diluted with the 40g deionized water, transfers to have whipping appts, in the 250mL four-hole bottle of thermometer and reflux condensate device, temperature slowly is raised to 55 ℃; In four-hole bottle, slowly drip the 8g trolamine, stir, add the back and continue to stir the 0.5h(C component) while dripping; Take by weighing the 0.1g Zinc diacetate dihydrate, use the 30g anhydrous alcohol solution, transfer to (D component) in the dropping funnel after the dissolving fully; The D component slowly is added drop-wise in the C component, stirs, add the back and continue reaction 0.5h, make polymkeric substance/ZnO composite nano-microsphere while dripping.Transmission electron microscope (TEM) image by Fig. 3 has been wrapped one deck nano-ZnO particle in the PS surface as can be known uniformly.
Claims (6)
1. the preparation method of polymkeric substance-ZnO composite nano-microsphere is characterized in that: adopt the method for mini-emulsion polymerization that vinyl monomer and organo-siloxane are carried out the polymer microballoon that the copolymerization surface has the activated silica hydroxyl; Activated silica hydroxyl by organic amine alkali source and described polymer microballoon surface acts on polymer microballoon surface in situ generation nano-ZnO again, makes polymkeric substance-ZnO composite nano-microsphere; Step is:
(1) prepare the polymer microballoon of surface silanol groupization with the method for mini-emulsion polymerization, consist of: vinyl monomer, organo-siloxane, emulsifying agent, co-stabilizer, initiator, pH regulator agent and deionized water, the quality consumption is as follows:
Vinyl monomer 85-95,
Organo-siloxane 5-15,
The percentage consumption that other component accounts for vinyl monomer and organo-siloxane quality sum is:
Emulsifying agent 0.5-1.5,
Co-stabilizer 2-7,
Initiator 0.5-1.5,
PH regulator agent 0.5-2.5,
Deionized water 500-900,
Operation steps is: by proportioning emulsifying agent, pH regulator agent, deionized water are mixed, be the A component; By proportioning vinyl monomer, organo-siloxane, co-stabilizer and initiator are mixed, be the B component; At ambient temperature the B component slowly is added drop-wise in the A component, stirs while dripping; Drip back continuation stirring 0.5h and carry out emulsification; Again with the thin emulsification 10min of ultrasonic wave; After the thin emulsification under 60-70 ℃ of condition polyase 13 h, make the polymer microballoon of surface silanol groupization;
Described emulsifying agent is selected sodium laurylsulfonate, sodium lauryl sulphate or Trimethyllaurylammonium bromide for use;
Described co-stabilizer is selected hexadecanol, lauryl mercaptan, Stearyl mercaptan or hexadecane for use;
Described initiator is a water soluble starter: select a kind of of Potassium Persulphate, ammonium persulphate for use; Or oil-soluble initiator: select a kind of of Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, lauroyl peroxide for use;
One or both of sodium hydroxide, sodium bicarbonate, yellow soda ash, sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium hydrogen phosphate are selected in described pH regulator agent for use;
(2) in-situ method prepares polymkeric substance-ZnO composite nano-microsphere, in a certain amount of above-mentioned polymer microballoon emulsion, add organic amine, the alcoholic solution that adds zn cpds again, activated silica hydroxyl effect by organic amine alkali source and polymer microballoon surface prepares polymkeric substance-ZnO composite nano-microsphere, and the quality consumption is as follows:
Polymer microballoon emulsion 3-10
Deionized water 30-50
Organic amine 5-17
Zn cpds 0.1-0.5
Alcohol 25-45
Operation steps is: take out the above-mentioned polymer microballoon emulsion of part, be raised to 45-60 ℃ with the deionized water dilution and with temperature, slowly drip organic amine, stir while dripping, add the back and continue to stir 0.5h, be the C component; Zn cpds is dissolved in the alcohol, is the D component; The D component slowly is added dropwise in the C component, stirs, add the back and continue reaction 0.5h, make polymkeric substance-ZnO composite nano-microsphere while dripping.
2. the preparation method of polymkeric substance according to claim 1-ZnO composite nano-microsphere is characterized in that described vinyl monomer selects vinylbenzene, methyl methacrylate, vinyl-acetic ester, vinyl cyanide or vinylchlorid for use.
3. the preparation method of polymkeric substance according to claim 1-ZnO composite nano-microsphere is characterized in that described organo-siloxane selects 3-methacryloxypropyl trimethoxy silane, methacryloxypropyl triethoxyl silane or vinyltriethoxysilane for use.
4. the preparation method of polymkeric substance according to claim 1-ZnO composite nano-microsphere is characterized in that described organic amine selects trolamine or tri-isopropanolamine for use.
5. the preparation method of polymkeric substance according to claim 1-ZnO composite nano-microsphere is characterized in that described zn cpds selects Zinc diacetate dihydrate, zinc acetate, zinc nitrate, zinc sulfate or zinc chloride for use.
6. the preparation method of polymkeric substance according to claim 1-ZnO composite nano-microsphere is characterized in that described alcohol selects methyl alcohol, dehydrated alcohol, propyl alcohol, butanols or Virahol for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105130130A CN101955613B (en) | 2010-10-20 | 2010-10-20 | Method for preparing polymer-zinc oxide nano composite microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105130130A CN101955613B (en) | 2010-10-20 | 2010-10-20 | Method for preparing polymer-zinc oxide nano composite microspheres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101955613A true CN101955613A (en) | 2011-01-26 |
| CN101955613B CN101955613B (en) | 2011-11-16 |
Family
ID=43483221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105130130A Expired - Fee Related CN101955613B (en) | 2010-10-20 | 2010-10-20 | Method for preparing polymer-zinc oxide nano composite microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101955613B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344697A (en) * | 2011-06-23 | 2012-02-08 | 江南大学 | Preparation method for photosensitive and amphiphilic polyurethane-stabilized nano-zinc oxide |
| CN104610686A (en) * | 2015-03-05 | 2015-05-13 | 河北工业大学 | Preparation method of strawberry type organic-inorganic composite particles |
| CN104774397A (en) * | 2014-12-29 | 2015-07-15 | 江南大学 | Amphiphilic polymer/ Ag nano composite microsphere preparation method |
| CN105622891A (en) * | 2015-12-21 | 2016-06-01 | 江南大学 | Preparation method for polysiloxane emulsion modified waterborne polyurethane emulsion |
| CN105837840A (en) * | 2016-05-11 | 2016-08-10 | 江南大学 | Preparation method of polymer/ZnO/SiO2 nano-composite microspheres |
| CN109276474A (en) * | 2018-09-30 | 2019-01-29 | 江南大学 | A kind of preparation method of nano zine oxide/cationic polysaccharide hybrid nanomaterial |
| CN110105686A (en) * | 2019-05-24 | 2019-08-09 | 广州大学 | A kind of anti-biotic material and its preparation method and application |
| CN111574881A (en) * | 2018-07-10 | 2020-08-25 | 成都虹润制漆有限公司 | Filling material for terrace paint and preparation method thereof |
| CN114517423A (en) * | 2021-12-16 | 2022-05-20 | 杭州锦添装饰纸有限公司 | Decorative paper suitable for digital printing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372527A (en) * | 2008-10-21 | 2009-02-25 | 河北科技大学 | Nano-zinc oxide/acrylic ester grafting composite emulsion and preparation thereof |
| CN101845124A (en) * | 2010-03-23 | 2010-09-29 | 武汉力诺化学集团有限公司 | Water-based hydrophobic nano-resin, glass thermal insulating coating and preparation method |
| US20100249335A1 (en) * | 2004-05-19 | 2010-09-30 | Texas A&M University System | Methods of producing zinc oxide polymer nanocomposites |
-
2010
- 2010-10-20 CN CN2010105130130A patent/CN101955613B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100249335A1 (en) * | 2004-05-19 | 2010-09-30 | Texas A&M University System | Methods of producing zinc oxide polymer nanocomposites |
| CN101372527A (en) * | 2008-10-21 | 2009-02-25 | 河北科技大学 | Nano-zinc oxide/acrylic ester grafting composite emulsion and preparation thereof |
| CN101845124A (en) * | 2010-03-23 | 2010-09-29 | 武汉力诺化学集团有限公司 | Water-based hydrophobic nano-resin, glass thermal insulating coating and preparation method |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344697B (en) * | 2011-06-23 | 2013-06-12 | 江南大学 | Preparation method for photosensitive and amphiphilic polyurethane-stabilized nano-zinc oxide |
| CN102344697A (en) * | 2011-06-23 | 2012-02-08 | 江南大学 | Preparation method for photosensitive and amphiphilic polyurethane-stabilized nano-zinc oxide |
| CN104774397A (en) * | 2014-12-29 | 2015-07-15 | 江南大学 | Amphiphilic polymer/ Ag nano composite microsphere preparation method |
| CN104774397B (en) * | 2014-12-29 | 2017-09-01 | 江南大学 | A kind of preparation method of amphiphilic polymers/Ag composite nano-microspheres |
| CN104610686B (en) * | 2015-03-05 | 2016-08-24 | 河北工业大学 | A kind of preparation method of strawberry type organo-mineral complexing particle |
| CN104610686A (en) * | 2015-03-05 | 2015-05-13 | 河北工业大学 | Preparation method of strawberry type organic-inorganic composite particles |
| CN105622891B (en) * | 2015-12-21 | 2018-04-17 | 江南大学 | A kind of preparation method of polysiloxane emulsion modified aqueous polyurethane emulsion |
| CN105622891A (en) * | 2015-12-21 | 2016-06-01 | 江南大学 | Preparation method for polysiloxane emulsion modified waterborne polyurethane emulsion |
| CN105837840A (en) * | 2016-05-11 | 2016-08-10 | 江南大学 | Preparation method of polymer/ZnO/SiO2 nano-composite microspheres |
| CN105837840B (en) * | 2016-05-11 | 2018-07-10 | 江南大学 | A kind of polymer/ZnO/SiO2The preparation method of composite nano-microsphere |
| CN111574881A (en) * | 2018-07-10 | 2020-08-25 | 成都虹润制漆有限公司 | Filling material for terrace paint and preparation method thereof |
| CN111574881B (en) * | 2018-07-10 | 2022-05-20 | 成都虹润制漆有限公司 | Filler for terrace paint and preparation method thereof |
| CN109276474A (en) * | 2018-09-30 | 2019-01-29 | 江南大学 | A kind of preparation method of nano zine oxide/cationic polysaccharide hybrid nanomaterial |
| CN109276474B (en) * | 2018-09-30 | 2020-11-03 | 江南大学 | Preparation method of nano zinc oxide/cationic polysaccharide hybrid nano particles |
| CN110105686A (en) * | 2019-05-24 | 2019-08-09 | 广州大学 | A kind of anti-biotic material and its preparation method and application |
| CN114517423A (en) * | 2021-12-16 | 2022-05-20 | 杭州锦添装饰纸有限公司 | Decorative paper suitable for digital printing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101955613B (en) | 2011-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101955613B (en) | Method for preparing polymer-zinc oxide nano composite microspheres | |
| CN102604006B (en) | Preparation method for acidic silica sol in-situ modified acrylate emulsion | |
| US8552110B2 (en) | Polymerization process for preparing monodispersal organic/inorganic composite nano-microsphere | |
| CN108948246B (en) | Method for modifying and phase-inverting solid particles and stabilizing Pickering inverse miniemulsion | |
| CN103464203B (en) | Preparation method of thermosensitive microgel asymmetric supported nano silver catalyst | |
| CN102492428B (en) | Uniform fluorescent microball and preparation method | |
| CN104558393A (en) | N-tetradecanol phase change microcapsule and preparation method thereof | |
| CN101720335A (en) | Composite material granular and preparation method thereof | |
| CN108213456A (en) | A kind of preparation method of cube copper nanoparticle | |
| CN108641024B (en) | Method for synthesizing magadiite/PMMA (polymethyl methacrylate) nano composite microspheres in Pickering emulsion by utilizing pH value regulation | |
| JP2006036982A (en) | Method for producing carboxy group-containing water-soluble polymer | |
| CN104028182B (en) | A kind of preparation method of zinc oxide tri compound nano material of yolk-eggshell structure | |
| CN104262531A (en) | Unmodified silica sol/polyacrylate core-shell emulsion and preparation method thereof | |
| CN102344697B (en) | Preparation method for photosensitive and amphiphilic polyurethane-stabilized nano-zinc oxide | |
| CN103360529B (en) | A kind of controllable synthesis method of micron-grade monodisperse polystyrene microspheres | |
| EP1230855A1 (en) | Sustained-release preparation of aqueous dispersion type and process for producing the same | |
| CN105777978A (en) | Preparation method of monodisperse polymer/SiO2 nano composite particles | |
| CN105732905A (en) | Raspberry-shaped organic/organic compound emulsion particles and preparation method thereof | |
| CN107955092A (en) | A kind of gas hydrate nanometer accelerating agent of size tunable and preparation method thereof | |
| CN106986972B (en) | A kind of more performance hydrogels and its synthetic method | |
| CN104774397B (en) | A kind of preparation method of amphiphilic polymers/Ag composite nano-microspheres | |
| CN110407212A (en) | A kind of nano-carbonate gelinite of polymolecularity and its preparation method and application | |
| JP2008138161A (en) | Polystyrene-maleic anhydride/magnesium hydroxide composite particles and methods for preparing the same | |
| CN105001576B (en) | A kind of preparation method of hud typed cationic microgel nano-noble metal composite | |
| Gao et al. | Growth from spherical to rod-like SiO2: Impact on microstructure and performance of nanocomposite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20110126 Assignee: Yangzhou Kaier Chemical Co., Ltd. Assignor: Jiangnan University Contract record no.: 2012320000936 Denomination of invention: Method for preparing polymer-zinc oxide nano composite microspheres Granted publication date: 20111116 License type: Exclusive License Record date: 20120817 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111116 Termination date: 20171020 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |