CN104892833A - Preparation method of polyacrylic acid hollow microgel - Google Patents
Preparation method of polyacrylic acid hollow microgel Download PDFInfo
- Publication number
- CN104892833A CN104892833A CN201510261987.7A CN201510261987A CN104892833A CN 104892833 A CN104892833 A CN 104892833A CN 201510261987 A CN201510261987 A CN 201510261987A CN 104892833 A CN104892833 A CN 104892833A
- Authority
- CN
- China
- Prior art keywords
- polyacrylic acid
- preparation
- acid hollow
- microgel
- hollow microgel
- 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
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of polyacrylic acid hollow microgel. According to the preparation method, an oil phase is added into a water phase, triethylamine and tetraethoxysilane are dropwise added under an alkaline condition to carry out in-situ hydrolysis to generate nano-silica particles as a surfactant, and a stable 'oil-in-water' form Pickering emulsion is generated; polyacrylonitrile is incompatible with isooctane, so that raw monomer droplets are subjected to phase separation, and isooctane is extruded to the centers of the droplets of a mini-emulsion to form liquid cores; after monomers are polymerized, polyacrylonitrile hollow microspheres are obtained and are subjected to basic hydrolysis to generate the polyacrylic acid hollow microgel. The preparation method has the advantages that the process is simple, the operation is feasible, reaction conditions are mild and easy to control, the consumption of the surfactant is reduced, and the preparation method is applicable to industrial production and is environment-friendly. The prepared polyacrylic acid hollow microgel is stable in structure and controllable in hollow size and can be applied to the fields of medicine controlled release, chemical separation, biosensing and the like.
Description
Technical field
the invention belongs to the preparation field of microgel, particularly a kind of preparation method of polyacrylic acid hollow microgel.
Background technology
Polymer nanocomposite hollow microsphere is a kind of functional materials with special construction, owing to there is high specific surface area, compared with features such as low density, larger load space and parcel effector functions, receiving in fields such as biology, chemistry, catalysis, optics and pay close attention to widely.Polymer nanocomposite hollow microsphere, normally by the outer field spherical shell of polymer formation, contains magnetic particle, photoactivatable groups, Thermo-sensitive group or-COOH ,-NH if form in the polymkeric substance of hollow microsphere
2,-CONH
2etc. easy ionogen, then hollow microsphere will have the condition depended characteristics such as very strong magnetic field, optics, temperature, pH or ionic strength.This environmental response characteristic makes polymer nanocomposite hollow microsphere have a good application prospect in biological, chemistry, optics and medicine and other fields.
Microgel be a kind of size between 1 ~ 1000nm, there is the polymer particles of intramolecular crosslinking structure, its structure, between branched chain polymer and macro mesh cross-linked polymer, to swell in certain solvent and high dispersing with colloidal form usually.Wherein environment-responsive microgel controls the Swelling and contraction of microgel volume by the condition such as pH, temperature, ionic strength, magnetic field changed in environment, thus causes the change as the physics such as porosity, rheological or chemical property.In numerous environment-responsive microgel, pH or temperature-responsive microgel because of its preparation comparatively easy, and there is high responsiveness, become one of study hotspot of current people.PH responsiveness microgel is as wherein important one, general many containing-COOH ,-NH in its molecular structure
2or-CONH
2group, changes and ionizes, and then cause the hydrogen bond that in microgel network, macromolecular chain is intersegmental to dissociate with environmental pH, ionic strength, thus cause the swelling of volume or contraction change.
Polyacrylic acid hollow microgel is as one typical pH responsiveness microgel, containing a large amount of-COOH group on its molecular chain, there is good water-soluble and pH responsiveness, and show low density because inside has hollow structure, high-ratio surface sum can hold the features such as guest molecule, therefore have a wide range of applications in fields such as medicine controlled releasing, chemical separation, catalysis.But monomer propylene acid reactivity is high, and polyacrylic acid has good solubility in general polar solvent, easily forms hydrogen bond and produces molecular aggregates and form macroscopical cross-linking products, cause the preparation of polyacrylic acid microgel comparatively difficult; Adopt self-assembly method and template synthesis hollow microgel to require system comparatively tight in addition, need to carry out under extremely low polymer concentration, and operation sequence is loaded down with trivial details, easily makes hollow structure be out of shape, the practical application of restriction microgel.
Pickering mini-emulsion polymerization refers to using ultrafine particle as tensio-active agent, and in monomer droplet, nucleation carries out monomer polymerization, utilizes the phase separation principle between lower boiling easy volatile liquid and polymerization single polymerization monomer to prepare the microballoon of hollow structure.Each drop of Pickering miniemulsion, as the reactor of a polyreaction, greatly can improve the stability of particle, and decrease the use of emulsifying agent.Polyacrylic acid is obtained because polyacrylonitrile can be hydrolyzed in the basic conditions, and monomers acrylonitrile is lipophilicity monomer, therefore Pickering mini-emulsion polymerization can be adopted first to prepare polyacrylonitrile hollow microsphere, then obtain polyacrylic acid hollow microgel through alkaline hydrolysis.Up to now, patent or document is not also had to adopt Pickering miniemulsion method to be that monomer is to prepare polyacrylic acid hollow microgel with vinyl cyanide.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyacrylic acid hollow microgel, the method technique is simple, operates easy, and reaction conditions gentleness is easy to control, with low cost, is easy to industrialization, and decreases the use of tensio-active agent, environmentally friendly.
The present invention is by the following technical solutions for achieving the above object:
A preparation method for polyacrylic acid hollow microgel, comprises the following steps:
(1) monomers acrylonitrile, cross-linker divinylbenzene, co-stabilizer n-Hexadecane, octane-iso, tetraethoxy, silane coupling agent and oil-soluble initiator are fully dissolved mixing, as oil phase;
(2) aqueous phase stopper is dissolved in deionized water, as aqueous phase;
(3) oil phase that step (1) obtains under agitation slowly is added dropwise in the aqueous phase that step (2) obtains, and slowly drips triethylamine, stir and make fully to mix, form mixing solutions;
(4) mixing solutions step (3) obtained, under high-speed shearing equipment effect, carries out homogenizing emulsifying with the shearing rate of 16000 ~ 21000rpm, forms miniemulsion;
(5) miniemulsion step (4) obtained is at N
2under atmosphere, polyreaction is carried out in heating, obtains polymer microballoon emulsion;
(6) join in sodium hydroxide solution by the polymer microballoon emulsion that step (5) obtains, heating is hydrolyzed and is obtained by reacting product, product is carried out dialysis treatment, obtains polyacrylic acid hollow microgel.
In the preparation method of polyacrylic acid hollow microgel described above, silane coupling agent described in step (1) is preferably γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane and γ-(2, 3-epoxy third oxygen) one in propyl trimethoxy silicane, described oil-soluble initiator is 2,2'-Azobis(2,4-dimethylvaleronitrile), the one of Diisopropyl azodicarboxylate and hydrogen phosphide cumene/tetraethylene pentamine, wherein, in hydrogen phosphide cumene/tetraethylene pentamine system, the mass ratio of hydrogen phosphide cumene and tetraethylene pentamine is 1:1.
As preferably, in the preparation method of polyacrylic acid hollow microgel described above, the weight ratio of the monomers acrylonitrile described in step (1) and cross-linker divinylbenzene is 10:1 ~ 1.2; Co-stabilizer n-Hexadecane accounts for 6 ~ 8% of monomers acrylonitrile weight; Octane-iso accounts for 10% ~ 20% of monomers acrylonitrile weight; Tetraethoxy accounts for 70% ~ 90% of monomers acrylonitrile weight; Silane coupling agent accounts for 6 ~ 25% of monomers acrylonitrile weight; Oil-soluble initiator accounts for 1 ~ 2% of monomers acrylonitrile weight.
As preferably, in the preparation method of polyacrylic acid hollow microgel described above, the aqueous phase stopper described in step (2) is Sodium Nitrite, and consumption accounts for 0.1 ~ 0.4% of monomers acrylonitrile weight.
As preferably, in the preparation method of polyacrylic acid hollow microgel described above, the triethylamine described in step (3) accounts for 7 ~ 9% of monomers acrylonitrile weight.
As preferably, in the preparation method of polyacrylic acid hollow microgel described above, the homogenizing emulsifying time described in step (4) is 4 ~ 6min is good.
As preferably, in the preparation method of polyacrylic acid hollow microgel described above, the miniemulsion described in step (5) is heated to 40 ~ 70 DEG C; Polymerization reaction time is 7 ~ 10h.
As preferably, in the preparation method of polyacrylic acid hollow microgel described above, the sodium hydroxide solution volumetric molar concentration described in step (6) is 3 ~ 7mol/L, and consumption accounts for 1000 ~ 1500% of monomers acrylonitrile weight; Heating temperature is 70 ~ 90 DEG C; Hydrolysis time is 4 ~ 8h.
As preferably, in the preparation method of polyacrylic acid hollow microgel described above, the dialysis tubing molecular weight cut-off described in step (6) is 3000 ~ 5000, and dialysis time is 2 ~ 5 days.
As preferably, in the preparation method of polyacrylic acid hollow microgel described above, the polyacrylic acid hollow microgel described in step (6) has hollow structure, and size is 100 ~ 500nm.
The present invention take vinyl cyanide as monomer, the silicon dioxide granule utilizing tetraethoxy to be hydrolyzed generation under the effect of triethylamine replaces traditional Small molecular surfactant to be adsorbed on water-oil interface, form stable " oil-in-water " type Pickering emulsion, the droplet nucleation mechanism of mini-emulsion polymerization is adopted to synthesize stable polyacrylonitrile hollow microsphere, be hydrolyzed in basic solution again, prepare polyacrylic acid hollow microgel, because the octane-iso added in system is separated after monomer polymerization, form the core of drop, cause the formation of hollow structure, therefore, the microgel prepared has hollow structure.
Wherein, form polyacrylonitrile after acrylonitrile monemer polymerization, because polyacrylonitrile is incompatible with octane-iso, homogeneous monomer droplet originally there occurs and is separated, and the octane-iso miniemulsion drop centered that is squeezed defines liquid core; After monomer polymerization completes, obtain polyacrylonitrile hollow microsphere, after hydrolyzed under basic conditions, purification processes is carried out to hydrolysate and namely obtains polyacrylic acid hollow microgel.
Beneficial effect of the present invention is:
(1) adopt Pickering original position fine emulsion polymerization to prepare polyacrylic acid hollow microgel, have technique simple, the features such as reaction conditions gentleness is easy to control and cost is low, are suitable for suitability for industrialized production;
(2) adopt Pickering original position fine emulsion polymerization to prepare polyacrylic acid hollow microgel, have particle diameter narrowly distributing, monodispersity is better, the features such as size tunable;
(3) using inorganic particulate silicon-dioxide as tensio-active agent, good emulsion stabilizing effect can not only be played, but also there is environment amenable feature, and wetting ability size can by adjustment uniform recipe design;
(4) the polyacrylic acid hollow microgel that this legal system is standby, hollow structure size can be controlled by the add-on changing octane-iso, simple and convenient, easy to implement;
(5) preparation of polyacrylic acid hollow microgel, can apply in drug controlled release, chemical separation, support of the catalyst etc.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of gained polyacrylic acid hollow microgel of the present invention.
Fig. 2 is the transmission electron microscope picture of gained polyacrylic acid hollow microgel of the present invention.
Embodiment
Following embodiment further illustrates using as the explaination to the technology of the present invention content for content of the present invention; but flesh and blood of the present invention is not limited in described in following embodiment, those of ordinary skill in the art can and should know any simple change based on connotation of the present invention or replace all should belong to protection domain of the presently claimed invention.
embodiment 1
By 12g vinyl cyanide, 1.2g Vinylstyrene, 0.8g n-Hexadecane, 2.4g octane-iso, 10g tetraethoxy, 1.0g γ-(methacryloxypropyl) propyl trimethoxy silicane and 0.2g 2,2'-Azobis(2,4-dimethylvaleronitrile) magnetic agitation 30min, it is made fully to dissolve as oil phase;
Take 0.02g Sodium Nitrite and be dissolved in magnetic agitation 10min in deionized water, make it fully dissolve, as aqueous phase; Oil phase is slowly added in aqueous phase, then adds 1g triethylamine, room temperature magnetic agitation 30min, form mixing solutions; Then under ice-water bath, utilize high-speed shearing equipment homogenizing emulsifying 5min under the shearing rate of 16000rpm, form miniemulsion;
Transferred to by miniemulsion in the there-necked flask that agitator, thermometer and reflux condensing tube are housed, under whipped state, logical nitrogen 30min is to get rid of system air, isothermal reaction 8h under 55 DEG C of water-baths; Add the sodium hydroxide solution that 120g volumetric molar concentration is 5mol/L again, under 80 DEG C of water-baths, obtain product after isothermal reaction 5h; Its acidifying being placed on impouring molecular weight cut-off is again in the dialysis tubing of 3500, and deionized water dialysis purification 3 days, obtain product, Fig. 1 is the infrared spectrogram of product, 1720 ~ 1660cm
-1place is the C=O absorption peak in carboxyl, 3500 ~ 2500cm
-1the broad peak at place and 1450cm
-1absorption peak be O-H vibration absorption peak, show that product component is polyacrylic acid thus.Fig. 2 is the transmission electron microscope picture of gained polyacrylic acid hollow microgel, and microgel is hollow structure, and mean sizes is 350nm.Result shows, embodiment has successfully prepared polyacrylic acid hollow microgel.
embodiment 2
By 12g vinyl cyanide, 1.2g Vinylstyrene, 0.8g n-Hexadecane, 1.2g octane-iso, 10g tetraethoxy, 1.0g γ-(methacryloxypropyl) propyl trimethoxy silicane and 0.2g 2,2'-Azobis(2,4-dimethylvaleronitrile) magnetic agitation 30min, it is made fully to dissolve as oil phase;
Take 0.02g Sodium Nitrite and be dissolved in magnetic agitation 10min in deionized water, make it fully dissolve, as aqueous phase;
Oil phase is slowly added in aqueous phase, then adds 1g triethylamine, room temperature magnetic agitation 30min, form mixing solutions; Then under ice-water bath, utilize high-speed shearing equipment homogenizing emulsifying 5min under the shearing rate of 16000rpm, form miniemulsion;
Transferred to by miniemulsion in the there-necked flask that agitator, thermometer and reflux condensing tube are housed, under whipped state, logical nitrogen 30min is to get rid of system air, isothermal reaction 8h under 55 DEG C of water-baths; Add the sodium hydroxide solution that 120g volumetric molar concentration is 5mol/L again, under 80 DEG C of water-baths, obtain product after isothermal reaction 5h; Its acidifying being placed on impouring molecular weight cut-off is again in the dialysis tubing of 3500, and deionized water dialysis purification 3 days, can obtain polyacrylic acid hollow microgel.Mean sizes is 280nm.Compared with embodiment 1, because octane-iso consumption reduces, final gained hollow microgel mean sizes is reduced relatively.
embodiment 3
By 12g vinyl cyanide, 1.2g Vinylstyrene, 0.8g n-Hexadecane, 2.4g octane-iso, 10g tetraethoxy, 2.0g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane and 0.2g 2,2'-Azobis(2,4-dimethylvaleronitrile) magnetic agitation 30min, make it fully dissolve as oil phase;
Take 0.02g Sodium Nitrite and be dissolved in magnetic agitation 10min in deionized water, make it fully dissolve, as aqueous phase; Oil phase is slowly added in aqueous phase, then adds 1g triethylamine, room temperature magnetic agitation 30min, form mixing solutions; Then under ice-water bath, utilize high-speed shearing equipment homogenizing emulsifying 5min under the shearing rate of 16000rpm, form miniemulsion;
Transferred to by miniemulsion in the there-necked flask that agitator, thermometer and reflux condensing tube are housed, under whipped state, logical nitrogen 30min is to get rid of system air, isothermal reaction 8h under 55 DEG C of water-baths; Add the sodium hydroxide solution that 120g volumetric molar concentration is 5mol/L again, under 80 DEG C of water-baths, obtain product after isothermal reaction 5h; Its acidifying being placed on impouring molecular weight cut-off is again in the dialysis tubing of 3500, and deionized water dialysis purification 3 days, can obtain polyacrylic acid hollow microgel.Mean sizes is 350nm.
embodiment 4
By 12g vinyl cyanide, 1.2g Vinylstyrene, 0.8g n-Hexadecane, 2.4g octane-iso, 10g tetraethoxy, 1.0g γ-aminopropyltrimethoxysilane and 0.2g Diisopropyl azodicarboxylate magnetic agitation 30min, it is made fully to dissolve as oil phase;
Take 0.02g Sodium Nitrite and be dissolved in magnetic agitation 10min in deionized water, make it fully dissolve, as aqueous phase; Oil phase is slowly added in aqueous phase, then adds 1g triethylamine, room temperature magnetic agitation 30min, form mixing solutions; Then under ice-water bath, utilize high-speed shearing equipment homogenizing emulsifying 5min under the shearing rate of 16000rpm, form miniemulsion;
Transferred to by miniemulsion in the there-necked flask that agitator, thermometer and reflux condensing tube are housed, under whipped state, logical nitrogen 30min is to get rid of system air, isothermal reaction 8h under 65 DEG C of water-baths; Add the sodium hydroxide solution that 120g volumetric molar concentration is 5mol/L again, under 80 DEG C of water-baths, obtain product after isothermal reaction 5h; Its acidifying being placed on impouring molecular weight cut-off is again in the dialysis tubing of 3500, and deionized water dialysis purification 3 days, can obtain polyacrylic acid hollow microgel.Mean sizes is 410nm.
embodiment 5
By 12g vinyl cyanide, 1.2g Vinylstyrene, 0.8g n-Hexadecane, 2.4g octane-iso, 10g tetraethoxy, 1.0g γ-(methacryloxypropyl) propyl trimethoxy silicane and 0.2g hydrogen phosphide cumene magnetic agitation 30min, it is made fully to dissolve as oil phase;
Take 0.02g Sodium Nitrite and be dissolved in magnetic agitation 10min in deionized water, make it fully dissolve, as aqueous phase; Oil phase is slowly added in aqueous phase, then adds 1g triethylamine, room temperature magnetic agitation 30min, form mixing solutions; Then under ice-water bath, utilize high-speed shearing equipment homogenizing emulsifying 5min under the shearing rate of 16000rpm, form miniemulsion;
Transferred to by miniemulsion in the there-necked flask that agitator, thermometer and reflux condensing tube are housed, under whipped state, logical nitrogen 30min is to get rid of system air, in system, add 0.20g tetraethylene pentamine and under 40 DEG C of water-baths isothermal reaction 8h; Add the sodium hydroxide solution that 120g volumetric molar concentration is 5mol/L again, under 80 DEG C of water-baths, obtain product after isothermal reaction 5h; Its acidifying being placed on impouring molecular weight cut-off is again in the dialysis tubing of 3500, and deionized water dialysis purification 3 days, can obtain polyacrylic acid hollow microgel.Mean sizes is 500nm.
Claims (10)
1. a preparation method for polyacrylic acid hollow microgel, comprises the following steps:
(1) monomers acrylonitrile, cross-linker divinylbenzene, co-stabilizer n-Hexadecane, octane-iso, tetraethoxy, silane coupling agent and oil-soluble initiator are fully dissolved mixing, as oil phase;
(2) aqueous phase stopper is dissolved in deionized water, as aqueous phase;
(3) oil phase that step (1) obtains under agitation slowly is added dropwise in the aqueous phase that step (2) obtains, and slowly drips triethylamine, stir and make fully to mix, form mixing solutions;
(4) mixing solutions step (3) obtained, under high-speed shearing equipment effect, carries out homogenizing emulsifying with the shearing rate of 16000 ~ 21000rpm, forms miniemulsion;
(5) miniemulsion step (4) obtained is at N
2under atmosphere, polyreaction is carried out in heating, obtains polymer microballoon emulsion;
(6) join in sodium hydroxide solution by the polymer microballoon emulsion that step (5) obtains, heating is hydrolyzed and is obtained by reacting product, product is carried out dialysis treatment, obtains polyacrylic acid hollow microgel.
2. the preparation method of polyacrylic acid hollow microgel according to claim 1, it is characterized in that, silane coupling agent described in step (1) is γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane and γ-(2, 3-epoxy third oxygen) one in propyl trimethoxy silicane, described oil-soluble initiator is 2,2'-Azobis(2,4-dimethylvaleronitrile), the one of Diisopropyl azodicarboxylate and hydrogen phosphide cumene/tetraethylene pentamine, wherein, in hydrogen phosphide cumene/tetraethylene pentamine system, the mass ratio of hydrogen phosphide cumene and tetraethylene pentamine is 1:1.
3. the preparation method of polyacrylic acid hollow microgel according to claim 1, is characterized in that, the weight ratio of the monomers acrylonitrile described in step (1) and cross-linker divinylbenzene is 10:1 ~ 1.2; Co-stabilizer n-Hexadecane accounts for 6 ~ 8% of monomers acrylonitrile weight; Octane-iso accounts for 10 ~ 20% of monomers acrylonitrile weight; Tetraethoxy accounts for 70 ~ 90% of monomers acrylonitrile weight; Silane coupling agent accounts for 6 ~ 25% of monomers acrylonitrile weight; Oil-soluble initiator accounts for 1 ~ 2% of monomers acrylonitrile weight.
4. the preparation method of polyacrylic acid hollow microgel according to claim 1, is characterized in that, the aqueous phase stopper described in step (2) is Sodium Nitrite, and consumption accounts for 0.1 ~ 0.4% of monomers acrylonitrile weight.
5. the preparation method of polyacrylic acid hollow microgel according to claim 1, is characterized in that, the triethylamine described in step (3) accounts for 7 ~ 9% of monomers acrylonitrile weight.
6. the preparation method of polyacrylic acid hollow microgel according to claim 1, is characterized in that, the homogenizing emulsifying time described in step (4) is 4 ~ 6min.
7. the preparation method of polyacrylic acid hollow microgel according to claim 1, is characterized in that, the miniemulsion described in step (5) is heated to 40 ~ 70 DEG C; Polymerization reaction time is 7 ~ 10h.
8. the preparation method of polyacrylic acid hollow microgel according to claim 1, is characterized in that, the sodium hydroxide solution volumetric molar concentration described in step (6) is 3 ~ 7mol/L, and consumption accounts for 1000 ~ 1500% of monomers acrylonitrile weight; Heating temperature is 70 ~ 90 DEG C; Hydrolysis time is 4 ~ 8h.
9. the preparation method of polyacrylic acid hollow microgel according to claim 1, is characterized in that, the dialysis tubing molecular weight cut-off described in step (6) is 3000 ~ 5000, and dialysis time is 2 ~ 5 days.
10. the preparation method of polyacrylic acid hollow microgel according to claim 1, is characterized in that, the polyacrylic acid hollow microgel described in step (6) has hollow structure, and size is 100 ~ 500nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510261987.7A CN104892833B (en) | 2015-05-21 | 2015-05-21 | A kind of preparation method of the hollow microgel of polyacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510261987.7A CN104892833B (en) | 2015-05-21 | 2015-05-21 | A kind of preparation method of the hollow microgel of polyacrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104892833A true CN104892833A (en) | 2015-09-09 |
| CN104892833B CN104892833B (en) | 2017-03-29 |
Family
ID=54025835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510261987.7A Active CN104892833B (en) | 2015-05-21 | 2015-05-21 | A kind of preparation method of the hollow microgel of polyacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104892833B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251418A (en) * | 2015-11-06 | 2016-01-20 | 哈尔滨工业大学 | Method for preparing Pickering microemulsion gel from poly-o-phenylenediamine |
| CN105693924A (en) * | 2016-03-27 | 2016-06-22 | 华南理工大学 | Emulsion-based soft-gel thermally-driven micro motor and preparation method thereof |
| CN108314756A (en) * | 2018-03-09 | 2018-07-24 | 安徽大学 | A kind of microspheres and preparation method thereof prepared based on the original positions Pickering miniemulsion |
| CN108532018A (en) * | 2018-04-27 | 2018-09-14 | 芜湖天科生物科技有限公司 | A kind of gel conductive fiber and preparation method thereof |
| CN108676164A (en) * | 2018-05-29 | 2018-10-19 | 安徽大学 | A kind of preparation method of click chemistry interfacial reaction polymer hybrid hollow microsphere |
| CN110408313A (en) * | 2019-06-21 | 2019-11-05 | 安徽大学 | A kind of aqueous polyurethane matting resin and preparation method that polyacrylonitrile hollow microsphere is modified |
| CN113493573A (en) * | 2021-08-10 | 2021-10-12 | 郑锦芳 | High-thermal-conductivity polyimide film and preparation method thereof |
| CN113755070A (en) * | 2021-10-18 | 2021-12-07 | 天津科瑞达涂料化工有限公司 | Water-based heat-insulating coating for inner wall of passenger car and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569323A (en) * | 2004-04-29 | 2005-01-26 | 西安科技大学 | Preparation of composite hollow nano-structure |
| JP2006257021A (en) * | 2005-03-17 | 2006-09-28 | Shiseido Co Ltd | Skin cosmetic |
| US20060281834A1 (en) * | 2003-07-03 | 2006-12-14 | Kyung-Woo Lee | Method for preparing microcapsule by miniemulsion polymerization |
| CN101113183A (en) * | 2007-04-03 | 2008-01-30 | 南开大学 | Mono-dispersed nano/micron polymer hollow microsphere resin and method for synthesizing the same |
| CN101652395A (en) * | 2007-03-30 | 2010-02-17 | 综研化学株式会社 | Acrylic hollow particles, process for production of the particles, and cosmetics containing the particles |
| CN101836970A (en) * | 2010-04-13 | 2010-09-22 | 南京大学 | Polyacrylic acid nano-gel microspheres, preparation method and application thereof |
| CN102504326A (en) * | 2011-09-28 | 2012-06-20 | 浙江大学 | Method for preparing super thermal isolation polymer materials from polymer nanometer hollow capsules |
| CN102816274A (en) * | 2012-07-06 | 2012-12-12 | 安徽大学 | Silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method |
| CN103788300A (en) * | 2014-01-02 | 2014-05-14 | 安徽大学 | Amphiphilic asymmetric polystyrene-acrylamide microspheres |
| CN104017143A (en) * | 2014-04-29 | 2014-09-03 | 安徽大学 | Silicon dioxide/poly(styrene-methyl methacrylate) nonspherical composite microspheres and preparation method thereof |
| CN104151471A (en) * | 2014-07-03 | 2014-11-19 | 安徽大学 | Nano-silver/polystyrene hollow composite microspheres and preparation method thereof |
-
2015
- 2015-05-21 CN CN201510261987.7A patent/CN104892833B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060281834A1 (en) * | 2003-07-03 | 2006-12-14 | Kyung-Woo Lee | Method for preparing microcapsule by miniemulsion polymerization |
| CN1569323A (en) * | 2004-04-29 | 2005-01-26 | 西安科技大学 | Preparation of composite hollow nano-structure |
| JP2006257021A (en) * | 2005-03-17 | 2006-09-28 | Shiseido Co Ltd | Skin cosmetic |
| CN101652395A (en) * | 2007-03-30 | 2010-02-17 | 综研化学株式会社 | Acrylic hollow particles, process for production of the particles, and cosmetics containing the particles |
| CN101113183A (en) * | 2007-04-03 | 2008-01-30 | 南开大学 | Mono-dispersed nano/micron polymer hollow microsphere resin and method for synthesizing the same |
| CN101836970A (en) * | 2010-04-13 | 2010-09-22 | 南京大学 | Polyacrylic acid nano-gel microspheres, preparation method and application thereof |
| CN102504326A (en) * | 2011-09-28 | 2012-06-20 | 浙江大学 | Method for preparing super thermal isolation polymer materials from polymer nanometer hollow capsules |
| CN102816274A (en) * | 2012-07-06 | 2012-12-12 | 安徽大学 | Silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method |
| CN103788300A (en) * | 2014-01-02 | 2014-05-14 | 安徽大学 | Amphiphilic asymmetric polystyrene-acrylamide microspheres |
| CN104017143A (en) * | 2014-04-29 | 2014-09-03 | 安徽大学 | Silicon dioxide/poly(styrene-methyl methacrylate) nonspherical composite microspheres and preparation method thereof |
| CN104151471A (en) * | 2014-07-03 | 2014-11-19 | 安徽大学 | Nano-silver/polystyrene hollow composite microspheres and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| JIANAN ZHANG ET AL: ""Facile fabrication of poly(acrylic acid) hollow nanogels via in situ Pickering miniemulsion polymerization"", 《POLYM. CHEM.》 * |
| WEN-HSUAN CHIANG ET AL: ""Dual Stimuli-Responsive Polymeric Hollow Nanogels Designed as Carriers for Intracellular Triggered Drug Release"", 《LANGMUIR》 * |
| XIAONA LI ET AL: ""Fabrication of macroporous foam and microspheres of polystyrene by Pickering emulsion polymerization"", 《COLLOID AND POLYMER SCIENCE》 * |
| YING CHEN ET AL: ""Hollow Core-Porous Shell Structure Poly(acrylic acid) Nanogels with a Superhigh Capacity of Drug Loading"", 《ACS APPL. MATER. INTERFACES》 * |
| 陆正全: ""细乳液聚合法制备杂化聚丙烯酸微凝胶及其形貌、性能研究"", 《中国优秀硕士学位论文全文数据库·工程科技I辑》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251418A (en) * | 2015-11-06 | 2016-01-20 | 哈尔滨工业大学 | Method for preparing Pickering microemulsion gel from poly-o-phenylenediamine |
| CN105251418B (en) * | 2015-11-06 | 2017-04-12 | 哈尔滨工业大学 | Method for preparing Pickering microemulsion gel from poly-o-phenylenediamine |
| CN105693924A (en) * | 2016-03-27 | 2016-06-22 | 华南理工大学 | Emulsion-based soft-gel thermally-driven micro motor and preparation method thereof |
| CN105693924B (en) * | 2016-03-27 | 2017-10-20 | 华南理工大学 | A kind of soft gel heat driven minisize motor of emulsion base and preparation method thereof |
| CN108314756A (en) * | 2018-03-09 | 2018-07-24 | 安徽大学 | A kind of microspheres and preparation method thereof prepared based on the original positions Pickering miniemulsion |
| CN108532018A (en) * | 2018-04-27 | 2018-09-14 | 芜湖天科生物科技有限公司 | A kind of gel conductive fiber and preparation method thereof |
| CN108676164A (en) * | 2018-05-29 | 2018-10-19 | 安徽大学 | A kind of preparation method of click chemistry interfacial reaction polymer hybrid hollow microsphere |
| CN108676164B (en) * | 2018-05-29 | 2020-12-15 | 安徽大学 | Preparation method of polymer hybrid hollow microspheres through click chemical interface reaction |
| CN110408313A (en) * | 2019-06-21 | 2019-11-05 | 安徽大学 | A kind of aqueous polyurethane matting resin and preparation method that polyacrylonitrile hollow microsphere is modified |
| CN113493573A (en) * | 2021-08-10 | 2021-10-12 | 郑锦芳 | High-thermal-conductivity polyimide film and preparation method thereof |
| CN113755070A (en) * | 2021-10-18 | 2021-12-07 | 天津科瑞达涂料化工有限公司 | Water-based heat-insulating coating for inner wall of passenger car and preparation method and application thereof |
| CN113755070B (en) * | 2021-10-18 | 2022-09-27 | 天津科瑞达涂料化工有限公司 | Water-based heat-insulating coating for inner wall of passenger car and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104892833B (en) | 2017-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104892833A (en) | Preparation method of polyacrylic acid hollow microgel | |
| CN103342991B (en) | Composite nanocapsule phase-change material and preparation method thereof | |
| CN104449590B (en) | A kind of Nano capsule of phase-changing energy storage material and preparation method thereof | |
| CN102921013B (en) | Preparation method and application of chitosan nanoparticles with pore structures | |
| CN104559935A (en) | Composite-wall phase-change energy storing microcapsule and preparation method thereof | |
| CN105924569A (en) | Preparing method for multi-core wrapped type compound microspheres | |
| CN101050354A (en) | Phase change energy stored microcapsule, preparation method and apparatus | |
| CN113881404B (en) | Organic phase-change microcapsule with high coating rate, high thermal conductivity and high thermal cycling stability and preparation method thereof | |
| CN105622852A (en) | Preparing method for synthesizing shape-controlled anisotropic particles through emulsion polymerization based on asymmetry monomer-swelling non-crosslinking seed particles | |
| CN102229711A (en) | Preparation and application of silicane functionalized high-water-solubility silicon dioxide nano particles | |
| CN103359743B (en) | The preparation method of a kind of size and the controlled single dispersing hollow silica nanometer ball of shell thickness | |
| CN106589464A (en) | Preparation method for vinyl polymer coated nano-silica microsphere and modified epoxy resin | |
| CN103359746B (en) | Double-layer hollow silica nanosphere and preparation method thereof | |
| CN104945558A (en) | Preparing method for multi-responsiveness polymer hollow microgel | |
| CN104193991A (en) | Graphene quantum dot polyaniline composite material and preparation method thereof | |
| CN104072656A (en) | Method for preparing ferroferric oxide-macromolecule magnetic composite microspheres | |
| CN102432744A (en) | Method for preparing monodispersed functional polymer microspheres | |
| CN103788300A (en) | Amphiphilic asymmetric polystyrene-acrylamide microspheres | |
| CN103012985A (en) | Hydrophilic and oleophilic sulfonated polystyrene/polystyrene abnormal composite microsphere and process | |
| CN114790265A (en) | Temperature response type Janus nano-particle and application thereof | |
| CN103194181A (en) | Method for preparing spherical controlled beta-cyclodextrin/melamine resin-TiO2 nano phase-change energy storage material | |
| CN108003272B (en) | Preparation method of nano-cellulose/fluorine-containing polyacrylate soap-free emulsion | |
| CN103421136A (en) | Concave polyacrylonitrile nanoparticles and preparation method thereof | |
| CN103483477B (en) | The preparation method of single dispersing surface chain transfer activity functionalized polymer microsphere | |
| CN115232234B (en) | Preparation method of spherical pore-forming agent for fluorescent ceramics and spherical pore-forming agent obtained by preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |