CN102600778A - Nanometer composite epoxy resin self-repairing microcapsule and preparation method thereof - Google Patents
Nanometer composite epoxy resin self-repairing microcapsule and preparation method thereof Download PDFInfo
- Publication number
- CN102600778A CN102600778A CN2012100495289A CN201210049528A CN102600778A CN 102600778 A CN102600778 A CN 102600778A CN 2012100495289 A CN2012100495289 A CN 2012100495289A CN 201210049528 A CN201210049528 A CN 201210049528A CN 102600778 A CN102600778 A CN 102600778A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- preparation
- microcapsule
- water
- repairing microcapsule
- 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
Abstract
The invention discloses a nanometer composite epoxy resin self-repairing microcapsule and a preparation method of the microcapsule. The preparation method comprises the following steps: dispersing silicon dioxide nanometer particles in water, dissolving oil-soluble cross-linking agent into ethyl phenylacetate, mixing oil with water, and shaking by hand to vibrate and emulsify into Pickering latex; dripping the Pickering latex into melamine formaldehyde pre-polymer solution, and finally obtaining a target product by carrying out in-situ cross-linking polymerization of the pre-polymer at the surface of the latex drops under an acidic condition. Due to use of the stable Pickering latex drops as the template of the prepared microcapsule, the prepared microcapsule is regularly spherical, the size distribution is featured with polydispersity; the silicon dioxide particles doped in the capsule wall effectively enhance the mechanical strength and the thermal stability of the microcapsule, and synchronously increase the brittleness of the microcapsule; in this way, better releasing effect is obtained when the capsule of core material ethyl phenylacetate is broken.
Description
Technical field
The present invention relates to the intelligent macromolecule material field, be specifically related to be enclosed with microcapsules of epoxy resin renovation agent and preparation method thereof a kind of the preparation with pik woods emulsion droplet template.
Background technology
The thermosetting resin that with epoxy resin is matrix is applied to various fields, auto industry for example, space flight and aviation, electronics industry etc.Yet the composite of epoxy resin-base, is easy at the inner micro-crack that produces of matrix when receiving lasting load action owing to the attribute of himself seems very crisp.The growth of these crackles if leave, the destruction that finally inevitably causes whole material recurring structure property.Therefore, a kind of crackle of can repairing automatically of preparation keeps the intelligent response composite in the service life that the complete sum of structure prolongs extremely urgent.According to bibliographical information (Nature, 2001, the preparation that 409:794-797) White is successful a kind ofly be used for the microcapsules that the epoxy resin selfreparing is used.This microcapsules have wrapped up liquid renovation agent---and endo-dicyclopentadiene (endo-DCPD), microcapsules and the heeling-in in advance of Gubbs ' catalyst are in epoxy resin-base.When crackle was grown in matrix, microcapsules rupture also discharged DPCD in crackle.Subsequently, ring-opening polymerisation generation dicyclopentadiene film takes place after touching Grubbs ' catalyst in DCPD, fills whole crackle, and has stoped the extension of crackle, has played the effect of repairing.Bibliographical information (Macromolecules
,2007,40:8830-8832) Caruso prepares neat solvent type epoxy resin self-repairing microcapsule.This microcapsules are nuclear material with the organic good solvent of epoxy resin, ethyl phenylacetate for example, chlorobenzene, phenylacetic acid etc.After the capsules break; Organic solvent goes owing to capillarity is siphoned in the crackle; These solvents can be at cracks swelling epoxy resin-base, makes that remaining amine curing agent continues cross-linking reaction with the epoxy monomer that remains in the matrix in the matrix, has played the excellent repairing effect.Follow-up a lot of bibliographical informations (J. Mater. Chem., 2011,21:9060-9065; Macromolecules 2010; 43:1855 – 1859, Macromol. Rapid Commun. 2011,32:82 – 87) the epoxy resin selfreparing of having prepared of all successes uses microcapsules.These work have proved that all microcapsules heeling-in method is a kind of effective method for preparing the selfreparing epoxy resin composite material.
Microcapsules major parts of these parcel renovation agents all are to be that template prepares with the stable emulsion of emulsifying agent (for example ethene-copolymer-maleic anhydride).Yet the stable emulsion droplet of this emulsifying agent all is unsettled on thermodynamics and kinetics, and it can not provide enough structural stabilities to prevent that emulsion droplet from melting mutually, causes whole parcel efficient not high, and the microcapsules that prepare also irregular shape can occur.Therefore the stability of emulsion has faced great challenge in the preparation process of capsule.Recent years bibliographical information pickering emulsion, be a kind ofly to come stable emulsion by solid nano particle with suitable hydrophilic and hydrophobic, attracted the interest in each a lot of field.The emulsion stable with respect to emulsifying agent, pickering emulsion is because nano particle irreversible suction-operated on oil-water interfaces has better stability, and the pickering emulsion for preparing can keep enough stability at some months even in the several years.Therefore prepare the epoxy resin selfreparing can at utmost keep renovation agent with microcapsules parcel efficient with pik woods emulsion droplet template; The existence of its solid nano particle guarantee that microcapsules have regular sphere, and the stable emulsion of emulsifying agent is the microcapsules of template preparation relatively, owing to can give microcapsules more different character; Different rough surface is for example arranged; Better release efficiency, finer and close cyst wall, thus be more suitable in the selfreparing system.
Therefore, we have prepared the microcapsules of the selfreparing system that is used for epoxy resin that is enclosed with ethyl phenylacetate with pik woods emulsion droplet template.On the basis of the various superperformances of the self-repairing microcapsule that this neat solvent type self-repairing microcapsule prepares when keeping the stable emulsion of emulsifying agent for template; Because pik woods emulsion droplet template inherent attribute; Improve the release efficiency of the parcel efficient renovation agent of nuclear material, and given microcapsules different surface topography.
Summary of the invention
The object of the invention and content are that being directed against existing is defective and the deficiency that template prepares the epoxy resin self-repairing microcapsule with the stable emulsion of emulsifying agent, provides a kind of nanometer composite epoxy resin self-repairing microcapsule and preparation method thereof.The emulsifying agent that this method is traditional is relatively stablized the emulsion droplet template; Existing good stable property; And, make the mechanical strength of microcapsules and heat endurance be greatly improved owing to increased solid nano particle in the cyst wall, also increased the fragility of cyst wall; Make microcapsules under the stress effect, have more completely and break, improved the release efficiency of nuclear material.
The epoxy resin self-repairing microcapsule that the present invention is prepared; Be that pickering emulsion with the stable water bag ethyl phenylacetate of the random Nano particles of silicon dioxide of gas phase hydrophily is a template; Form fine and close cyst wall in the in-situ cross-linked polymerisation of aqueous phase through the melamino-formaldehyde performed polymer then and be prepared from, concrete technical scheme is following.
A kind of preparation method of nanometer composite epoxy resin self-repairing microcapsule; Ultrasonic being scattered in of the aerosil nano particle that its relative water mass fraction is 0.5%-5% gets solution 1 in the water; Be relative oil phase mass fraction that polyoxypropyleneglycol and the biphenyl methane diisocyanate prepolymer of 0.1%-2% be dissolved in the ethyl phenylacetate must solution 1, solution 1 is become the oil-in-water pickering emulsion with solution 2 mixing and emulsifyings; Be added drop-wise to the oil-in-water pickering emulsion in the melamino-formaldehyde prepolymer solution, be adjusted to pH to 3-5, under 40-60 ℃, in-situ cross-linked polymerization takes place on the emulsion droplet surface and obtains said epoxy resin self-repairing microcapsule in performed polymer.
Among the above-mentioned preparation method, preparation process acid-base condition will be controlled proper, and pH is 3-5, not so more side reaction can take place, even can not form the melamine resin cyst wall in the experiment imagination.
Among the above-mentioned preparation method, the aerosil nano particle adopts ultrasonic dispersing mode to be dispersed in the water, makes the reunion that reduces Nano particles of silicon dioxide to guarantee that the particle diameter of pik woods stable particle is evenly distributed.
Among the above-mentioned preparation method, under said 40-60 ℃, mechanical agitation 200-600rpm, reaction 3-5h gets epoxy resin self-repairing microcapsule suspension.Repeatedly wash the epoxy resin self-repairing microcapsule suspension of gained, filter, drying at room temperature obtains the epoxy resin self-repairing microcapsule.
Among the above-mentioned preparation method, the epoxy resin self-repairing microcapsule suspension for preparing is at last washed repeatedly, filters, and drying goes out the melamine resin particulate that generates in the dereaction, influences the repairing effect of self-repairing microcapsule.
Among the above-mentioned preparation method, adopt acetate to transfer said pH.Said hydromining is used deionized water.
Among the above-mentioned preparation method; Join the microcapsules of relative substrate quality mark 5%-20% in the E51 liquid epoxies; Add the diethylenetriamine curing agent, degasification 2-5min in a vacuum then, cold curing 20-30h; And then 30-40 ℃ of curing 20-30h, obtain the epoxy resin composite material that heeling-in has self-repairing microcapsule.After freezing under the liquid nitrogen, make crackle to the composite that obtains, then observing to the releasing effect of microcapsules wall thickness and nuclear material with razors slice.
The present invention and current material and compared with techniques have following advantage:
1, preparation method of the present invention is simple, does not need special installation, and normal temperature and pressure is operation down, the reaction simple controllable, and cost is low, is suitable for applying;
2, the present invention prepares the epoxy resin self-repairing microcapsule through pik woods emulsion droplet template, and pik woods emulsion droplet template has improved the stability of emulsion droplet, makes the microcapsules that prepare that regular sphere arranged; The particle diameter polydispersity of pickering emulsion, the particle diameter of the feasible microcapsules that prepare distributes also bigger, therefore can produce response to crackle not of uniform size, the raising remediation efficiency.
3, the present invention is a template with pik woods emulsion droplet; On cyst wall, introduced the solid nano-silicon dioxide particle of one deck; The mechanical strength and the heat endurance of cyst wall have been improved; And the fragility of raising microcapsules, make microcapsules under the stress effect, have more completely and break, improved the release efficiency of nuclear material.
4, the size of the epoxy resin self-repairing microcapsule of the present invention's preparation and wall thickness can be regulated optimization through regulating nanometer stable particle content, water-oil factor and feeding intake of melamino-formaldehyde performed polymer, to satisfy the demand under the different operating positions.
Description of drawings
Fig. 1 is the flying-spot microscope photo of microcapsules.
Fig. 2 is that the microcapsules ethyl phenylacetate discharges the petrographic microscope photo in the epoxy resin.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail.To the epoxy resin self-repairing microcapsule that obtains among the embodiment; Adopt ChemPhysChem 2007 such as Wang; The open method of 8:1157-1160 document is measured size and its distribution of pickering emulsion, adopts Colloid Polym Sci. such as Wang, 2009; The open method of 287:1089-1097 document is carried out the nuclear material content measuring of microcapsules; Adopt Polymer 2009,50 such as Blaiszik: the open method of 990-997 document carries out the surface of microcapsule pattern and the wall thickness pattern detects, and under petrographic microscope, observes the releasing effect of nuclear material ethyl phenylacetate.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.
Embodiment 1
Be scattered in the 5 ml deionized waters 50 mg aerosil nano particles are ultrasonic, shake up 50 mg PPG-TDI and be dissolved in the 5 ml ethyl phenylacetates.Profit mixes mutually, and shaken by hand emulsification obtains the stable oil-in-water pickering emulsion of Nano particles of silicon dioxide.Add 37 wt % formalins, 2 ml triethanolamines, 10 ml water and the 1.75 g melamines of 3.35ml in two mouthfuls of flasks of 50ml successively, 60 ℃ of lower magnetic forces stir 30 min, obtain the melamino-formaldehyde performed polymer aqueous solution.Be added drop-wise to the above-mentioned oil-in-water pickering emulsion that obtains in the melamino-formaldehyde performed polymer aqueous solution, and transfer pH=4 with acetate, be heated to 50 ℃ with the heating rate of 5 ℃/min, the mechanical agitation of 400 rpm is reacted 4 h.Speed with 2 ℃/min cools to room temperature.The suspension of gained washing 3 times, filter, drying at room temperature 24 h obtain the epoxy resin self-repairing microcapsule.Join 0.75 g microcapsules in the 5 gE51 liquid epoxies; Add 0.6 g diethylenetriamine curing agent, degasification 3min in a vacuum then, cold curing 24h; And then 35 ℃ of curing 24h, obtain the epoxy resin composite material that heeling-in has self-repairing microcapsule.With the composite that liquid nitrogen frozen obtains, make crackle with razors slice, then observing to the releasing effect of microcapsules wall thickness and nuclear material.The average grain diameter of these microcapsules is at 21 ± 5 μ m; The TG test obtains nuclear material content at 67wt %; The flying-spot microscope (see figure 1) is observed microcapsules has regular sphere, and size distribution has polydispersity, has smooth inner surface and coarse outer surface; Wall thickness is 500-700nm, observes the nuclear material ethyl phenylacetate under the petrographic microscope and has good release efficiency (see figure 2).
Embodiment 2
Be scattered in the 5 ml deionized waters 37.5 mg aerosil nano particles are ultrasonic, shake up 5 mg PPG-TDI and be dissolved in the 5 ml ethyl phenylacetates.Profit mixes mutually, and shaken by hand emulsification obtains the stable oil-in-water pickering emulsion of Nano particles of silicon dioxide.Add 37 wt % formalins, 2 ml triethanolamines, 10 ml water and the 1.75 g melamines of 3.35ml in two mouthfuls of flasks of 50ml successively, 60 ℃ of lower magnetic forces stir 30 min, obtain the melamino-formaldehyde performed polymer aqueous solution.Be added drop-wise to the above-mentioned oil-in-water pickering emulsion that obtains in the melamino-formaldehyde performed polymer aqueous solution, and transfer pH=3 with acetate, be heated to 60 ℃ with the heating rate of 5 ℃/min, the mechanical agitation of 200 rpm is reacted 3 h.Speed with 2 ℃/min cools to room temperature.The suspension of gained washing 3 times, filter, drying at room temperature 24 h obtain the epoxy resin self-repairing microcapsule.Join 0.25 g microcapsules in the 5 gE51 liquid epoxies; Add 0.6 g diethylenetriamine curing agent, degasification 3min in a vacuum then, cold curing 20h; And then 35 ℃ of curing 30h, obtain the epoxy resin composite material that heeling-in has self-repairing microcapsule.With the composite that liquid nitrogen frozen obtains, make crackle with razors slice, then observing to the releasing effect of microcapsules wall thickness and nuclear material.The average grain diameter of these microcapsules is at 21 ± 5 μ m; The TG test obtains nuclear material content at 67wt %; The flying-spot microscope (see figure 1) is observed microcapsules has regular sphere, and size distribution has polydispersity, has smooth inner surface and coarse outer surface; Wall thickness is 500-700nm, observes the nuclear material ethyl phenylacetate under the petrographic microscope (see figure 2) and has good release efficiency.
Embodiment 3
Be scattered in the 5 ml deionized waters 25 mg aerosil nano particles are ultrasonic, shake up 100 mg PPG-TDI and be dissolved in the 5 ml ethyl phenylacetates.Profit mixes mutually, and shaken by hand emulsification obtains the stable oil-in-water pickering emulsion of Nano particles of silicon dioxide.Add 37 wt % formalins, 2 ml triethanolamines, 10 ml water and the 1.75 g melamines of 3.35ml in two mouthfuls of flasks of 50ml successively, 60 ℃ of lower magnetic forces stir 30 min, obtain the melamino-formaldehyde performed polymer aqueous solution.Be added drop-wise to the above-mentioned oil-in-water pickering emulsion that obtains in the melamino-formaldehyde performed polymer aqueous solution, and transfer PH=5, be heated to 40 ℃, the mechanical agitation of 600 rpm, reaction 5zz h with the heating rate of 5 ℃/min with acetate.Speed with 2 ℃/min cools to room temperature.The suspension of gained washing 3 times, filter, drying at room temperature 24 h obtain the epoxy resin self-repairing microcapsule.Join 1 g microcapsules in the 5 gE51 liquid epoxies, add 0.6 g diethylenetriamine curing agent, degasification 5min in a vacuum then, cold curing 30h, and then 35 ℃ solidify 204h, obtains the epoxy resin composite material that heeling-in has self-repairing microcapsule.With the composite that liquid nitrogen frozen obtains, make crackle with razors slice, then observing to the releasing effect of microcapsules wall thickness and nuclear material.The average grain diameter of these microcapsules is at 21 ± 3 μ m; The TG test obtains nuclear material content at 67wt %; Flying-spot microscope is observed microcapsules has regular spherical (see figure 1), and size distribution has polydispersity, has smooth inner surface and coarse outer surface; Wall thickness is 500-700nm, observes the nuclear material ethyl phenylacetate under the petrographic microscope and has good release efficiency (see figure 2).
Embodiment 4
Present embodiment except that following characteristics with embodiment 1: be scattered in the 8 ml deionized waters 80 mg aerosil nano particles are ultrasonic, shake up 20 mgPPG-TDI and be dissolved in the 2 ml ethyl phenylacetates.The average grain diameter of these microcapsules is at 17 ± 5 μ m; The TG test obtains nuclear material content at 67wt %; Flying-spot microscope is observed microcapsules has regular spherical (see figure 1), and size distribution has polydispersity, has smooth inner surface and coarse outer surface; Wall thickness is 500-700nm, observes the nuclear material ethyl phenylacetate under the petrographic microscope and has good release efficiency (see figure 2).
Embodiment 5
Present embodiment except that following characteristics with embodiment 1: be scattered in the 7.5 ml deionized waters 75 mg aerosil nano particles are ultrasonic, shake up 25 mg PPG-TDI and be dissolved in the 2.5 ml ethyl phenylacetates.The average grain diameter of these microcapsules is at 22 ± 7 μ m; The TG test obtains nuclear material content at 67wt %; Flying-spot microscope is observed microcapsules has regular spherical (see figure 1), and size distribution has polydispersity, has smooth inner surface and coarse outer surface; Wall thickness is 500-700nm, observes the nuclear material ethyl phenylacetate under the petrographic microscope and has good release efficiency (see figure 2).
Embodiment 6
Present embodiment except that following characteristics with embodiment 1: be scattered in the 6.6 ml deionized waters 66 mg aerosil nano particles are ultrasonic, shake up 33 mg PPG-TDI and be dissolved in the 3.3 ml ethyl phenylacetates.The average grain diameter of these microcapsules is at 21 ± 5 μ m; The TG test obtains nuclear material content at 67wt %; Flying-spot microscope is observed microcapsules has regular spherical (see figure 1), and size distribution has polydispersity, has smooth inner surface and coarse outer surface; Wall thickness is 500-700nm, observes the nuclear material ethyl phenylacetate under the petrographic microscope and has good release efficiency (see figure 2).
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. the preparation method of a nanometer composite epoxy resin self-repairing microcapsule; It is characterized in that ultrasonic being scattered in of an aerosil nano particle that relative water mass fraction is 0.5%-5% gets solution 1 in the water; Be relative oil phase mass fraction that polyoxypropyleneglycol and the biphenyl methane diisocyanate prepolymer of 0.1%-2% be dissolved in the ethyl phenylacetate must solution 1, solution 1 is become the oil-in-water pickering emulsion with solution 2 mixing and emulsifyings; Be added drop-wise to the oil-in-water pickering emulsion in the melamino-formaldehyde performed polymer aqueous solution, be adjusted to pH to 3-5, under 40-60 ℃, in-situ cross-linked polymerization takes place on the emulsion droplet surface and obtains said epoxy resin self-repairing microcapsule in performed polymer.
2. preparation method according to claim 1 is characterized in that the aerosil nano particle adopts ultrasonic dispersing mode to be dispersed in the water.
3. preparation method according to claim 1 is characterized in that adopting acetate to transfer said pH.
4. preparation method according to claim 3 is characterized in that under said 40-60 ℃, mechanical agitation 200-600rpm, and reaction 3-5h gets epoxy resin self-repairing microcapsule suspension.
5. preparation method according to claim 4 is characterized in that repeatedly washing at the epoxy resin self-repairing microcapsule suspension gained, filters, and drying at room temperature obtains the epoxy resin self-repairing microcapsule.
6. preparation method according to claim 1; It is characterized in that the said melamino-formaldehyde performed polymer aqueous solution prepares through following method: add 37 wt % formalins, 2 ml triethanolamines, 10 ml water and the 1.75 g melamines of 3.35ml in two mouthfuls of flasks of 50ml successively, 60 ℃ of lower magnetic forces stir 30 min.
7. be used in the epoxy resin self-repairing microcapsule by what each said preparation method of claim 1 ~ 4 made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210049528.9A CN102600778B (en) | 2012-02-29 | 2012-02-29 | Nanometer composite epoxy resin self-repairing microcapsule and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210049528.9A CN102600778B (en) | 2012-02-29 | 2012-02-29 | Nanometer composite epoxy resin self-repairing microcapsule and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102600778A true CN102600778A (en) | 2012-07-25 |
| CN102600778B CN102600778B (en) | 2014-12-03 |
Family
ID=46518769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210049528.9A Expired - Fee Related CN102600778B (en) | 2012-02-29 | 2012-02-29 | Nanometer composite epoxy resin self-repairing microcapsule and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102600778B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265793A (en) * | 2013-06-17 | 2013-08-28 | 泰山体育产业集团有限公司 | Internal recoverable carbon fiber reinforced epoxy resin matrix composite and preparation method thereof |
| CN105833811A (en) * | 2016-03-27 | 2016-08-10 | 华南理工大学 | Double-capsule self-repairing epoxy coating and preparation method thereof |
| CN107159070A (en) * | 2017-06-16 | 2017-09-15 | 中国人民解放军装甲兵工程学院 | Self-repairing microcapsule and preparation method thereof, coating, coating and epoxy resin composite material |
| CN107312140A (en) * | 2017-06-27 | 2017-11-03 | 沈阳化工研究院有限公司 | It is a kind of for self-repairing microcapsule of metal anti-corrosive paint and preparation method thereof |
| CN107429089A (en) * | 2015-02-26 | 2017-12-01 | 波林复合材料美国股份有限公司 | filler |
| CN108579629A (en) * | 2018-04-28 | 2018-09-28 | 北京航空航天大学 | A kind of organic-inorganic hybrid nanometer capsule and preparation method thereof |
| CN109679114A (en) * | 2018-12-12 | 2019-04-26 | 青岛古高生物科技有限公司 | The preparation method and applications of the stable Pickering lotion of protein nano cage |
| CN111298733A (en) * | 2020-04-03 | 2020-06-19 | 兰州交通大学 | Concrete structure self-immune self-repairing microcapsule and preparation method thereof |
| CN111450771A (en) * | 2020-04-01 | 2020-07-28 | 中国石油天然气股份有限公司 | Multifunctional integrated Pickering particle emulsifier and preparation method thereof |
| WO2020200300A1 (en) * | 2019-04-03 | 2020-10-08 | 苏州丝美特生物技术有限公司 | Method for stabilizing and enhancing silk fibroin microcapsule shell structure using nanoparticles |
| CN114097777A (en) * | 2021-12-08 | 2022-03-01 | 四川大学 | Double-layer drug-loaded sustained-release microcapsule and preparation method and application thereof |
| CN114616052A (en) * | 2019-11-05 | 2022-06-10 | 株式会社Lg生活健康 | Naturally degradable microcapsule and preparation method thereof |
| CN115322982A (en) * | 2022-08-15 | 2022-11-11 | 北京工商大学 | Preparation method and application of cell-loaded microcapsule |
| CN115414877A (en) * | 2022-08-01 | 2022-12-02 | 浙江理工大学 | Method for preparing phase change energy storage microcapsule based on poly-p-phenylenediamine stabilized Pickering emulsion |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0987003A2 (en) * | 1998-09-18 | 2000-03-22 | Beiersdorf Aktiengesellschaft | Emulsifier-free finely dispersed systems of the oil-in-water or water-in-oil type |
| WO2009063257A2 (en) * | 2008-03-13 | 2009-05-22 | Syngenta Limited, | Microencapsulation |
| CN101495223A (en) * | 2006-07-14 | 2009-07-29 | 纳米运动技术有限公司 | Preparation of composite nano/microcapsules comprising nanoparticles |
| CN101775158A (en) * | 2010-03-12 | 2010-07-14 | 北京橡胶工业研究设计院 | Microencapsulated rubber accessory ingredient |
-
2012
- 2012-02-29 CN CN201210049528.9A patent/CN102600778B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0987003A2 (en) * | 1998-09-18 | 2000-03-22 | Beiersdorf Aktiengesellschaft | Emulsifier-free finely dispersed systems of the oil-in-water or water-in-oil type |
| CN101495223A (en) * | 2006-07-14 | 2009-07-29 | 纳米运动技术有限公司 | Preparation of composite nano/microcapsules comprising nanoparticles |
| WO2009063257A2 (en) * | 2008-03-13 | 2009-05-22 | Syngenta Limited, | Microencapsulation |
| CN101775158A (en) * | 2010-03-12 | 2010-07-14 | 北京橡胶工业研究设计院 | Microencapsulated rubber accessory ingredient |
Non-Patent Citations (3)
| Title |
|---|
| 《Journal of Materials Chemistry》 20110518 Li Yao，et al Self-healing of thermoplastics via reversible addition-fragmentation chain transfer polymerization 第21卷, * |
| LI YAO，ET AL: "Self-healing of thermoplastics via reversible addition–fragmentation chain transfer polymerization", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 21, 18 May 2011 (2011-05-18) * |
| QUANXING GAO，ET AL: "Suspension polymerization based on inverse Pickering emulsion droplets for thermo-sensitive hybrid microcapsules with tunable supracolloidal structures", 《POLYMER》, vol. 50, 12 April 2009 (2009-04-12) * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265793B (en) * | 2013-06-17 | 2016-01-20 | 泰山体育产业集团有限公司 | Can the carbon fiber reinforced epoxy resin-based composite of internal repair and preparation method |
| CN103265793A (en) * | 2013-06-17 | 2013-08-28 | 泰山体育产业集团有限公司 | Internal recoverable carbon fiber reinforced epoxy resin matrix composite and preparation method thereof |
| CN107429089A (en) * | 2015-02-26 | 2017-12-01 | 波林复合材料美国股份有限公司 | filler |
| CN105833811A (en) * | 2016-03-27 | 2016-08-10 | 华南理工大学 | Double-capsule self-repairing epoxy coating and preparation method thereof |
| CN105833811B (en) * | 2016-03-27 | 2018-06-22 | 华南理工大学 | A kind of double-capsule selfreparing epoxy coating and preparation method thereof |
| CN107159070A (en) * | 2017-06-16 | 2017-09-15 | 中国人民解放军装甲兵工程学院 | Self-repairing microcapsule and preparation method thereof, coating, coating and epoxy resin composite material |
| CN107312140A (en) * | 2017-06-27 | 2017-11-03 | 沈阳化工研究院有限公司 | It is a kind of for self-repairing microcapsule of metal anti-corrosive paint and preparation method thereof |
| CN107312140B (en) * | 2017-06-27 | 2020-03-31 | 沈阳化工研究院有限公司 | Self-repairing microcapsule for metal anticorrosive coating and preparation method thereof |
| CN108579629A (en) * | 2018-04-28 | 2018-09-28 | 北京航空航天大学 | A kind of organic-inorganic hybrid nanometer capsule and preparation method thereof |
| CN108579629B (en) * | 2018-04-28 | 2021-01-26 | 北京航空航天大学 | Organic-inorganic hybrid nanocapsule and preparation method thereof |
| CN109679114A (en) * | 2018-12-12 | 2019-04-26 | 青岛古高生物科技有限公司 | The preparation method and applications of the stable Pickering lotion of protein nano cage |
| CN109679114B (en) * | 2018-12-12 | 2021-06-04 | 青岛古高生物科技有限公司 | Preparation method and application of Pickering emulsion with stable protein nanocages |
| WO2020200300A1 (en) * | 2019-04-03 | 2020-10-08 | 苏州丝美特生物技术有限公司 | Method for stabilizing and enhancing silk fibroin microcapsule shell structure using nanoparticles |
| CN114616052A (en) * | 2019-11-05 | 2022-06-10 | 株式会社Lg生活健康 | Naturally degradable microcapsule and preparation method thereof |
| CN111450771A (en) * | 2020-04-01 | 2020-07-28 | 中国石油天然气股份有限公司 | Multifunctional integrated Pickering particle emulsifier and preparation method thereof |
| CN111298733A (en) * | 2020-04-03 | 2020-06-19 | 兰州交通大学 | Concrete structure self-immune self-repairing microcapsule and preparation method thereof |
| CN114097777A (en) * | 2021-12-08 | 2022-03-01 | 四川大学 | Double-layer drug-loaded sustained-release microcapsule and preparation method and application thereof |
| CN115414877A (en) * | 2022-08-01 | 2022-12-02 | 浙江理工大学 | Method for preparing phase change energy storage microcapsule based on poly-p-phenylenediamine stabilized Pickering emulsion |
| CN115414877B (en) * | 2022-08-01 | 2024-01-05 | 浙江理工大学 | Method for preparing phase-change energy-storage microcapsule based on p-phenylenediamine stable Pickering emulsion |
| CN115322982A (en) * | 2022-08-15 | 2022-11-11 | 北京工商大学 | Preparation method and application of cell-loaded microcapsule |
| CN115322982B (en) * | 2022-08-15 | 2023-08-15 | 北京工商大学 | Preparation method and application of cell-loaded microcapsule |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102600778B (en) | 2014-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102600778B (en) | Nanometer composite epoxy resin self-repairing microcapsule and preparation method thereof | |
| Fan et al. | Effect of emulsifier on poly (urea–formaldehyde) microencapsulation of tetrachloroethylene | |
| CN103464203B (en) | Preparation method of thermosensitive microgel asymmetric supported nano silver catalyst | |
| Xue et al. | Architectural Design of Self‐Assembled Hollow Superstructures | |
| CN102580639A (en) | Method for preparing cellulose microspheres from microfluidic chip | |
| CN103387691B (en) | A kind of hollow polystyrene plastic pellet and its preparation method and application | |
| CN106986989B (en) | Preparation method of polyamide hollow nano-microspheres | |
| CN103374141B (en) | Method for preparing faveolate polymer microsphere on basis of micro-fluidic chip | |
| Zhang et al. | Porous microcapsules with tunable pore sizes provide easily controllable release and bioactivity | |
| CN104762289B (en) | The method that microporous membrane permeation emulsification prepares the gelatine microsphere of fixed alcohol dehydrogenase | |
| CN102164988B (en) | Method for producing single-hole hollow polymer microparticles | |
| Cao et al. | Facile fabrication of hollow polymer microspheres through the phase-inversion method | |
| CN106890607A (en) | The preparation method and liquid crystal microcapsule of a kind of liquid crystal microcapsule | |
| Rong et al. | Microcapsules with compact membrane structure from gelatin and styrene–maleic anhydride copolymer by complex coacervation | |
| JP2008161817A (en) | Method for manufacturing hollow microcapsule | |
| Pang et al. | Preparation and application performance of lignin-polyurea composite microcapsule with controlled release of avermectin | |
| CN103275268B (en) | Preparation method of pH responsive cation nanogel | |
| Liu et al. | Sacrificial functional polystyrene template to prepare chitosan nanocapsules and in vitro drug release properties | |
| Naseem et al. | Core‐shell microgel stabilized silver nanoparticles for catalytic reduction of aryl nitro compounds | |
| Hong et al. | Preparation of polyurea microcapsules containing ovalbumin | |
| Cao et al. | Synthesis of oily core‐hybrid shell nanocapsules through interfacial free radical copolymerization in miniemulsion: Droplet formation and nucleation | |
| CN109265690A (en) | A kind of hollow polymer nanosphere and preparation method thereof | |
| CN108355591A (en) | Dimethyl silicone polymer causes ethyl cellulose phase separation and prepares microcapsule method | |
| Zhai et al. | Synthesis of polydopamine capsules via SPG membrane emulsion templating: tuning of capsule size | |
| Fu et al. | Pore decoration on microcapsule surface using nonionic surfactant micelles as template: Temperature effect and encapsulation mechanism investigation |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141203 Termination date: 20210228 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |