CN101362069B - Hollow porous micro-capsule and preparation method thereof - Google Patents
Hollow porous micro-capsule and preparation method thereof Download PDFInfo
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- CN101362069B CN101362069B CN2008102235862A CN200810223586A CN101362069B CN 101362069 B CN101362069 B CN 101362069B CN 2008102235862 A CN2008102235862 A CN 2008102235862A CN 200810223586 A CN200810223586 A CN 200810223586A CN 101362069 B CN101362069 B CN 101362069B
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Abstract
The invention provides a polymer microcapsule characterized by being simultaneously provided with both a hollow lumen and a porous shell, and also provides a preparation method for emulsifying the polymer microcapsule. The preparation method includes the steps of multiple emulsification loading, the morphology control of emulsion dripping and macromolecule suspension polymerization, and the scale of the preparation can be enlarged easily. The microcapsule is suitable for loading wide core materials which include biological activity materials and materials with catalytic function. With the microencapsulation method provided by the invention, the problem of the hard recovery of a nanometer catalyst can be solved, the pollution to the environment by nanometer powder can be avoided, and the collocation and loading of multiple catalysts can also be realized to construct a composite catalyst.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the processing and forming of polymer microsphere and microencapsulated material and as the application of composite.
Technical background
Micro-capsule is a ubiquitous material aggregation form in the biological phenomena, and synthetic micro-capsule also is a kind of successful commercial form, has widely to use.A kind of shell material wraps up another kind of functional material, be the main make of capsule, and micro-capsule typically refers to the compact capsule from the sub-micron to the mm-scale.No matter with which kind of form exist, functional material and shell material are the two class basic elements that constitute micro-capsule; The former has determined the function of micro-capsule, and the latter is mainly used in the realization of auxiliary the former function.The preparation of micro-capsule refers to by certain method functional material is wrapped up or is dispersed in the support material, thus the process of preparation granular composite material.Can reach many purposes by material is carried out the microencapsulation embedding, as chemistry or the physical stability that can improve core materials, smell, color and the toxicity of shielding capsule-core can also realize that the control release of capsule-core material or target discharge.Microencapsulation is the important method that makes up composite, also is the important means that improves the core materials handling; Along with the continuous progress of material technology, increasing functional material has been realized the micro-capsule embedding, and the application of functional material is constantly expanded.
The present invention is devoted to development of new capsule system, realizes the microencapsulation to emerging nanoscale functional material.In many new function materials, nano-functional material is a most noticeable recent class.This class material has excellent performance in application; As nanocatalyst, compare unit mass with traditional large scale catalyst and have bigger contact surface, more help catalytic reaction and carry out.But small scale has also caused the difficulty of unit operations, is that high speed centrifugation or ultrafiltration all can expend lot of energy and man-hour; Nano-powder is diffused in the environment in addition, can be remaining for a long time, health is worked the mischief.Realize the microencapsulation of nano particle, can improve the size of functional unit on the one hand so that unit operations can prevent effectively that on the other hand the nano-powder loss from entering environment.Nano material is carried out micro-embeddedly being seen in report, but the nano particle after the embedding tends to lose original dispersiveness and motility, the advantage of nano material has very big loss.In order both to realize the micro-embedded of nano material, keep the advantage of nano material again, the present invention has invented a kind of micro-capsule of new structure.It is characterized by: capsule possesses tens of microns cavity, and nano particle can keep original dispersiveness and free-moving characteristics in the space that limits; Secondly micro-capsule possesses the shell of porous, and the shell duct is a nano-pore, can stop nano material to external diffusion, can realize the transmission of micro-capsule inner chamber with extraneous molecule again.The micro-capsule of this specific form has proposed very high requirement to the preparation method; In addition, the capsule with this morphological feature also will be used for the embedding of the nanocatalyst of biologically active, and preparation process must guarantee the biologically active of core materials, and this also has higher requirement to the micro-capsule preparation of this specific form.
The present invention proposes brand-new microcapsule preparation method, this method is based upon double emulsion, and (the W/O/W type is W/0/W) on the basis of embedding and suspension polymerisation.Wherein the interior water of emulsion drop can produce the single inner chamber of tens of microns of diameters by the control of prescription and technology; And suspension polymerisation can generate the firm shell that possesses the nanometer through hole by the use of composite pore-forming; Two kinds of technology are followed distinct Regulation Mechanism, can satisfy the form requirement of two different scales.Because the inner chamber of micro-capsule is made up of water in the preparation process, can be used for the hydrophilic nano material of embedding, and be suitable for the nano material of embedding biologically active, the protection biologically active is not damaged.The micro-capsule of multi-emulsion method preparation is generally multi-cavity structure, the present invention has proposed the preparation method of a kind of single chamber emulsion micro-capsule first, compare with traditional multi-cavity structure, single chamber has clear superiority: at first be the internal cavity that can provide spacious, help improving useful load, also help freely disperseing of nano particle; Single in addition chamber capsule has only one deck shell, helps material Transfer, and after nanocatalyst incapsulated, substrate can diffuse into rapidly, and product also can remove rapidly.The present invention has considered the needs that amplify on stream, and emulsification and suspension polymerisation all are the conventional modes of production, are fit to large-scale production; And considered the versatility of institute's development to make novel micro-capsule be applicable to core materials widely, by embedding, can prepare the micro-capsule product of multiple different functions to different materials.
Summary of the invention
The invention provides a kind of new type of polymer capsule and preparation method thereof, such capsule has the shell of hollow cavity and porous, and preparation process combines the advantage of emulsionization and suspension polymerisation.This capsule bio-compatibility is good, and cavity volume is big, the mechanical strength height, and also preparative-scale amplifies easily.The present invention has proposed a kind of method that the emulsion drop develops of controlling first, obtains the emulsion drop of single interior water cavity, thereby prepares the capsule fortreating AIDS of single inner chamber.The particle diameter of preparation capsule is controlled at 10-100 μ m; Intracavity diameter is controlled at several microns in tens of micrometer ranges; Shell effective aperture scope is 2-200nm.The present invention has verified the application of this capsule system, comprising: load immobilized enzyme particle, load living cell body, load magnetic Nano material and nano-photocatalyst.The present invention has also further verified the possibility of multiple particle combination embedding, proves that this capsule system is applicable to the integrated of complex reaction process.
Capsule preparation method thereof is as follows:
1. configuration oil phase (O) wherein comprises vinyl monomer, divinyl crosslinking agent, radical initiator, oil phase emulsifier and perforating agent; Wherein can also comprise trivinyl crosslinking agent, proportion mediator agent, viscosity mediator agent and hydrophobic mediator agent.
2. aqueous phase solution (W in disposing
1) and outer aqueous phase solution (W
2), comprise macromolecule stabilizer, water soluble surfactant active, inorganic salts and radical polymerization polymerization inhibitor respectively; Use nonionic surface active agent among the W1, W
2The middle ionic surfactant that uses; W before the emulsification
1And W
2 Logical nitrogen 1 hour is got rid of the oxygen that dissolves in the water; Be loaded particle and be dispersed in W
1In the solution;
3. will be by emulsionization by occluded water phase component W
1Be embedded in the emulsion drop, as shown in Figure 1; At first W1 is distributed among the O by ultrasonication, forms colostric fluid (W
1/ O), W
1With the O volume ratio be 1:10; Again colostric fluid is distributed to W
2In, form W
1/ O/W
2Double emulsion, colostric fluid and W
2Volume ratio is 1:20;
4. regulation and control emulsion droplet morphology develops, and prepares single chamber emulsion drop; The double emulsion of preparation is encapsulated in the closed container inflated with nitrogen protection, gentle agitation or vibration; W
2Middle stabilizer concentration will be higher than W
1, and salinity is lower than W
1, interior water drop can oil droplet inside be fused to gradually single in water cavity; Can pass through at W
2The middle dispersant solution that adds high concentration further improves W
2Dispersant concentration reduces salinity simultaneously; Through differentiation after a while, most emulsion drops will only contain an interior water cavity, and evolution process as shown in Figure 2;
5. suspension polymerisation is solidified oil phase; Can select thermal-initiated polymerization, also can select the ultraviolet initiated polymerization, select corresponding initator respectively; When interior water embedding biological active component, should select wavelength is the ultraviolet initiated polymerization of 360-380nm;
6. removing assistant formation reagent, mainly is to remove oil phase perforating agent, oil phase surfactant and water dispersant; Can use the washing of alcoholic solution and deionized water to solidify capsule respectively; Behind the embedding biological active component, should use nonionic surface active agent solution and buffer salt solution washing capsule system.
The stability of emulsion is the difficult problem of double emulsion preparation, and traditional emulsion loading process generally adopts the emulsion form of multi-cavity chamber, and water is stable in being beneficial to.The multi-cavity cell structure is unfavorable for improving the volume of inner chamber, and what also be unfavorable for material strides the film transmission.The present invention has proposed a kind of method of controlling emulsion drop external morphology first according to the rule that the emulsion droplet morphology develops, and preparation has the emulsion drop of single interior water cavity.Control emulsion drop external morphology, water is stable at first will guaranteeing, and aqueous phase solution merges with outer water in avoiding as far as possible, will promote the fusion between the emulsion inner water droplets afterwards.This just requires outer water and oil phase interface (O and W
2The interface) stability is high, and interior water of hope simultaneously and oil phase interface stability are relatively poor.The present invention also proposes to control the method that interior water merges by the water salinity.As interior water (W
1) salinity surpasses outer water (W
2), outer aqueous phase hydrone can see through oil reservoir and enter interior water, and water constantly expands in making, and has quickened the fusion between interior water drop.By regulating inside and outside water inorganic salt concentration, water merges speed in can effectively controlling; Interior water salinity is high more, and imbibition is just obvious more, and fusion speed is also just fast more.
Stable colostric fluid is the prerequisite that realizes that emulsion evenly loads, and in first emulsification stage, improve emulsion strength as far as possible, with the diameter of water drop in reducing, and the difference of specific gravity between water and oil phase in reducing as far as possible.Interior water drop is more little, disperses evenly more, just helps emulsion more and loads.The emulsion drop comprises a lot of fine liquid particles when just having formed, along with interior water (W
1) between fusion, the number of interior water drop can reduce gradually.Merge when requiring when reaching, cause the oil phase monomer polymerization, shell solidifies the rear interior cavity form and just forever remains.
Method of the present invention is applicable to loads the solid granulates component.Solid granulates can be suspended in interior aqueous phase before loading, particle just is trapped within the capsule cavity inside after the polymerization.Being loaded particle does not have strict spatial constraints in the capsule cavity, can freely-movable; The solid granulates of nanoscale has kept the characteristics of Brownian movement in the water environment of capsule.For the catalyst or catalyst carrier of some nanoscale, nanoscale is the prerequisite of catalytic activity, by stowage of the present invention, hundreds of nano-carrier can be packaged in the capsule, and the dispersiveness in restriceted envelope is not destroyed, and its catalysis characteristics can well keep.
Method of the present invention not only can be loaded inorganic material, can also load bioactive materials and cell body.When loading biological active component, select suitable first emulsification intensity, should satisfy the emulsification requirement, can not destroy the biologically active that is loaded component again; Want simultaneously the polymerization methods that ultraviolet causes or other physics rays cause.This method can realize the loading of nanometer enzyme-support particle, and the freely-movable in cavity of nanometer enzyme-support particle has kept higher enzyme to live; The hole of capsule shell can allow little molecule substrate and product to free in and out, and guarantees that simultaneously nano particle do not lose.This method can realize the loading of active somatic cell.Cell also has certain growing space after by embedding, can further produce to be full of the capsule inner chamber.Cell can property performance period growth in capsule: when growth cycle finished, the parts of fine dysuria with lower abdominal colic was gone into dormancy, or generated brood body; After treating that new nutritional labeling is replenished again, rest cell reenters growth period, and brood body germinates into cell.
Method provided by the invention can be loaded different types of functional molecular or functional particulate, can realize multiple integration of function and parallelization with different molecules or the mutual assembly packaging of particle in a collection of capsule.
Capsule of the present invention is the rigid resin structure, can be filled in the fixed bed, can bear the 1.5Mpa compression shock; Also be applicable to the reactor that suspends and stir, can resist conventional mechanical shearing.
Description of drawings:
Fig. 1 emulsion operational flowchart schematic diagram;
The emulsion form photo of different differentiation times of Fig. 2, A:1min, B:15min, C:30min, D:90min;
Fig. 3 embodiment 1 described hollow capsules microphotograph;
Fig. 4 embodiment 1 described capsule electron micrograph;
Fig. 5 embodiment 2 described photocatalytic degradation methylene blue experimental results were shone 40 minutes;
The microphotograph of Fig. 6 embodiment 3 described loading of capsules supperparamagnetic particles;
The laser co-focusing photo of Fig. 7 embodiment 4 described loading of capsules immobilised enzymes nano particles;
The repeat performance of the repeat performance of Fig. 8 embodiment 4 described nanometer enzyme-support particles and loading of capsules nanometer enzyme-support particle;
The laser co-focusing photo of two kinds of fluorescent nanospheres of Fig. 9 embodiment 5 described loading of capsules;
The microphotograph of Figure 10 embodiment 6 described loading of capsules yeast cells.
Concrete embodiment
Embodiment 1: the preparation of single chamber capsule
The prescription of table 1 preparation hollow emulsion capsule
Dispose oil phase O, interior water W respectively according to table 1 prescription
1With outer water W
2At first with W
1Mix with O, ultrasonication emulsification is 20 seconds in ice-water bath, ultrasound intensity 200V, every ultrasonic 1 second 5 seconds at interval.Obtain Water-In-Oil (W after the ultrasonic emulsification
1/ O) colostric fluid mixes colostric fluid again with outer water, the use mechanical agitation prepares double emulsion (W
1/ O/W
2), mixing speed 400rpm, emulsification times are 2min.The reactor of packing into after the double emulsion preparation, normal pressure leads to nitrogen protection, and the adjustment speed of agitator is 100rpm, stirs 2hr under the room temperature; In this process, the emulsion drop will develop into single chamber form gradually.After the double emulsion form reaches requirement, to reactor water-bath heating, keep speed of agitator, be warming up to 70 ℃, sustained response 6 hours.After reacting end, filter and collect the preparation capsule, use ethanol and deionized water drip washing capsule repeatedly, remove perforating agent, surfactant and stabilizing agent.The preparation capsule overwhelming majority be single chamber form, optical microscope photograph as shown in Figure 3, the capsule in the photo through and screening, particle diameter is at 50-60 μ m.The microsphere surface form as shown in Figure 4, from electron scanning micrograph as can be seen, the capsule shell is a loose structure.
Embodiment 2: loading of capsules TiO2 nanocatalyst
The prescription of table 2 preparation embedding TiO2 nanometer powder capsule
Dispose oil phase O, interior water W respectively according to table 2 prescription
1With outer water W
2With the Degussa nano-TiO
2Powder P250 at first is distributed to target powder in the interior aqueous phase solution by ultrasonication W for loading target
1Solids content is controlled at 3%.With W
1Mix ice-water bath ultrasonic emulsification 60 seconds, ultrasonic power 200V with O.Again colostric fluid is mixed with outer water, use mechanical agitation to prepare double emulsion (W
1/ O/W
2).The reactor of packing into after the double emulsion preparation, normal pressure leads to nitrogen protection, and the control speed of agitator is 100rpm, stirs 2hr under the room temperature; The emulsion drop will develop into single chamber form gradually.After the double emulsion form reaches requirement, keep speed of agitator, be warming up to 70 ℃, sustained response 6 hours.After reacting end, filter and collect the preparation capsule, use ethanol and deionized water drip washing capsule repeatedly, remove perforating agent, surfactant and stabilizing agent.The preparation capsule is with capsule shown in Figure 3, and shell has good light transmittance.With the methylene blue is substrate, investigates embedding TiO
2The catalytic capability of powder.Configuration 20mg/L methylene blue solution, same respectively TiO
2The catalyst system of nano-powder and loading of capsules mixes mutually, and reaction system is packed in the quartzy bottle, uses high voltage mercury lamp radiation, and the hunting speed of reaction system is 100rpm.Fig. 5 has shown that 30 minutes catalytic result: A is the blank system that does not have catalyst; B is loading of capsules TiO
2System, 30 minutes afterreaction systems become clarification; C is for using nano-TiO
2System, post catalyst reaction are not easy to separate.The loading of capsules nano-TiO
2The catalytic capability that can keep nano-powder, loading of capsules help the separation and the recycling of catalyst.
Embodiment 3: the loading of capsules supperparamagnetic particles
The prescription of table 3 preparation embedded magnetic particle capsule
With the particle with superparamagnetism is the embedding target, and the target particles surface is SiO
2Material, in comprise super-paramagnetism nano nuclear, particle is on average directly at 1-2 μ m.Dispose oil phase O, interior water W respectively according to table 3 prescription
1With outer water W
2With W
1Mix with O, ultrasonic emulsification is 60 seconds in ice-water bath, ultrasonic power 200V.Obtain Water-In-Oil (W after the ultrasonic emulsification
1/ O) colostric fluid mixes colostric fluid again with outer water, the use mechanical agitation prepares double emulsion (W
1/ O/W
2), mixing speed 400rpm, emulsification times are 2min.The reactor of packing into after the double emulsion preparation, normal pressure leads to nitrogen protection, and the adjustment speed of agitator is 100rpm, stirs 2hr under the room temperature; In this process, the emulsion drop will develop into single chamber form gradually.After the double emulsion form reaches requirement, reactor is heated by water-bath, keep speed of agitator, be warming up to 70 ℃, sustained response 6 hours.After reacting end, filter and collect the preparation capsule, use ethanol and deionized water drip washing capsule repeatedly, remove perforating agent, surfactant and stabilizing agent.The preparation capsule overwhelming majority is single chamber form, and optical microscope photograph as shown in Figure 6.The magnetic-particle of loading of capsules is free dispersity, and the embedding process can not cause magnetic loss, can not lose superparamagnetism because of particle agglomeration.
Embodiment 4: loading of capsules immobilised enzymes nano particle
The prescription of table 4 preparation embedded nano enzyme-support particle capsule
Selecting the polymer nanocomposite ball of 400nm is fixed enzyme vector, for ease of detecting the nanosphere rhodamine B mark that uses.The method of alpha-chymotrypsin by covalent cross-linking is fixed on the nanosphere surface.The embedding prescription that provides according to table 2 will carry the enzyme nanoparticles embedded in the emulsion drop again.Embedding method is with embodiment 1, at first with W
1Mix ultrasonic emulsification, ultrasound intensity 100V with O.After the ultrasonic emulsification colostric fluid is mixed with outer water, use mechanical agitation to prepare double emulsion (W
1/ O/W
2), mixing speed 400rpm, emulsification 2min.The quartz reaction bottle of packing into after the double emulsion preparation, the above gas nitrogen replacement of emulsion bottle places quartz on the vertical blender, and 90min slowly vibrates; In this process, the emulsion drop will develop into single chamber form gradually, and the immobilised enzymes powder by embedding wherein.After the double emulsion form reaches requirement, the quartz bottle is placed under the ultraviolet black light lamp, illumination wavelength is 365nm, irradiation power is 50V/100ml.Under ultraviolet irradiation, oil phase begins to solidify, and polymerisation continues 8 hours.After reaction finishes, filter and collect the preparation capsule, use the 1%Tween20 solution washing to prepare capsule, remove the dispersant of capsule shell perforating agent and inside and outside aqueous phase; Replace the water environment of capsule again with the Tris-HCl buffer salt of PH7.8, and as the final buffer system of preserving.The preparation capsule overwhelming majority is single chamber form, and the nanometer enzyme-support particle that is loaded has kept good dispersity in the capsule cavity.Observe the capsule system by laser confocal microscope, as shown in Figure 7; Microscopically can be observed the Brownian movement of nanosphere in the capsule.The nanometer enzyme-support particle has kept most catalytic activitys through after the embedding; The catalytic activity of capsule system reaches the 2U/g capsule.Repeat performance is significantly improved after the loading of capsules, and as shown in Figure 8, the nanometer enzyme-support particle uses activity after 20 times to be reduced to half of original activity, uses 100 activity still not descend after the loading of capsules.
5: two kinds of nano particle mixing of embodiment embedding
The prescription of the capsule of two kinds of fluorescent grains is loaded in table 5 preparation
The embedding target is the nanosphere of two kinds of unlike materials, and for observing convenient, two kinds of nanospheres are used different fluorochrome labels respectively: rhodamine B has red fluorescence excitation, and tetrabromofluorescein has the yellow green fluorescence excitation.Dispose oil phase O, interior water W respectively according to table 5 prescription
1With outer water W
2Two kinds of nanospheres of equal proportion are distributed to W
1In, the control solids content is 4%.With W
1Mix with O, ultrasonication emulsification is 60 seconds in ice-water bath, ultrasound intensity 200V.Obtain Water-In-Oil (W after the ultrasonic emulsification
1/ O) colostric fluid mixes colostric fluid again with outer water, the use mechanical agitation prepares double emulsion (W
1/ O/W
2), mixing speed 400rpm, emulsification times are 2min.The reactor of packing into after the double emulsion preparation, normal pressure leads to nitrogen protection, and the adjustment speed of agitator is 100rpm, stirs 2hr under the room temperature; In this process, the emulsion drop will develop into single chamber form gradually.After the double emulsion form reaches requirement, to reactor water-bath heating, keep speed of agitator, be warming up to 70 ℃, sustained response 6 hours.After reaction finishes, filter and collect the preparation capsule, prepare capsule, remove perforating agent, surfactant and stabilizing agent with the 1%Tween20 solution washing.Observe embedding system altogether by laser confocal microscope, as shown in Figure 9.Two kinds of nano-powders are through having kept good dispersity and uniform admixture after the loading of capsules.
Embodiment 6: the loading of capsules cell
The prescription of the capsule of cell is loaded in table 6 preparation
The loading target is a yeast cells, at first with yeast-inoculated in fluid nutrient medium, cultivate 24 hours certain cell concentrations of accumulation.Dispose oil phase O, interior water W respectively according to table 6 prescription
1With outer water W
2At first the target cell body is replaced into W
1, the control solids content is about 1%; Again with W
1Mix with O, ultrasonication emulsification is 20 seconds in ice-water bath, ultrasound intensity 100V, every ultrasonic 1 second 5 seconds at interval.Obtain Water-In-Oil (W after the ultrasonic emulsification
1/ O) colostric fluid mixes colostric fluid again with outer water, the use mechanical agitation prepares double emulsion (W
1/ O/W
2), mixing speed 400rpm, emulsification times are 2min.The quartz reaction bottle of packing into after the double emulsion preparation, the above gas nitrogen replacement of emulsion bottle places quartz on the vertical blender, and 90min slowly vibrates; In this process, the emulsion drop will develop into single chamber form gradually, and the immobilised enzymes powder by embedding wherein.After the double emulsion form reaches requirement, the quartz bottle is placed under the ultraviolet black light lamp, illumination wavelength is 365nm, irradiation power is 50V/100ml.Under ultraviolet irradiation, oil phase begins to solidify, and polymerisation continues 8 hours.After reacting end, filter and collect the preparation capsule, use ethanol and deionized water drip washing capsule repeatedly, remove perforating agent, surfactant and stabilizing agent.The preparation capsule overwhelming majority is single chamber form, and optical microscope photograph as shown in figure 10.After the embedding, the cellular morphology that yeast cells is kept perfectly; Use fluid nutrient medium to cultivate embedding cell, cultivate, find the yeast cells growth that begins to sprout through 12hr.
Claims (4)
1. polymer microcapsule, it is characterized by: possess the shell of single hollow cavity and porous simultaneously, capsule is the rigid resin material, and the shell duct is inside and outside through hole; Capsule diameter is in the 1-1000 mu m range, and intracavity diameter is in the 0.1-999 mu m range, and the shell aperture is in the 2-200nm scope; Its preparation process comprises 6 steps:
1) uses vinyl monomer, vinyl crosslinking agent, initator, diluent, oil soluble surfactant, proportion mediator agent and viscosity mediator agent preparation oil phase;
2) use water and outer water in macromolecule stabilizer, water soluble surfactant active and the inorganic salts configuration respectively, will be loaded component and mix mutually with interior water, outer aqueous phase stabilizer concentration is higher than interior water, and interior aqueous phase inorganic salt concentration is higher than outer water;
3) by the emulsion method interior water component is loaded in the W/O/W type emulsion drop;
4) regulation and control emulsion droplet morphology, the water drop merges mutually in emulsion oil droplet inside in the control, and preparation has the emulsion drop of single interior water cavity;
5) realize that by suspension polymerisation oil phase solidifies, and form the polymer shell of porous;
6) remove oil phase diluent, surfactant and stabilizing agent, obtain the shell duct of running through.
2. polymer microcapsule as claimed in claim 1 is characterized by shell and has light transmission.
3. polymer microcapsule as claimed in claim 1 is characterized by: preparation process 5) use ultraviolet irradiation to cause suspension polymerisation, embedding bioactive materials.
4. polymer microcapsule as claimed in claim 1 is used for the granular material of stowing dimensions at 10nm-100 μ m, and particle keeps free dispersity in blister cavities.
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| CN102443088A (en) * | 2011-09-22 | 2012-05-09 | 中国科学院过程工程研究所 | Uniform-size small-particle-size super-macroporous polymer microspheres and preparation method thereof |
| CN102489230B (en) * | 2011-12-06 | 2015-08-19 | 中国科学院过程工程研究所 | A kind of preparation method of biodegradable polymer microcapsules |
| CN103374143B (en) * | 2012-04-28 | 2015-08-19 | 中国科学院过程工程研究所 | A kind of super large pore polymer microsphere and preparation method thereof |
| CN102698664B (en) * | 2012-05-26 | 2014-03-12 | 云南恩典科技产业发展有限公司 | Method for preparing water microcapsule |
| PT108665B (en) * | 2015-07-05 | 2020-11-02 | Universidade Do Minho | MICRO OR NANOCAPSULES WITH PHOTOCATALYTIC PROPERTIES FOR CONTROLLED RELEASE OF DIFFUSING AGENTS AND THEIR METHOD OF OBTAINING |
| EP3144058A1 (en) | 2015-09-16 | 2017-03-22 | Calyxia | Method for preparing microcapsules by double emulsion |
| CN108130742B (en) * | 2016-12-01 | 2020-07-10 | 广州蓝月亮实业有限公司 | Nursing composition, nursing agent, and preparation method and application thereof |
| CN108130225B (en) * | 2016-12-01 | 2020-09-15 | 广州蓝月亮实业有限公司 | Cleaning composition, cleaning agent, and preparation method and application thereof |
| FR3059666B1 (en) * | 2016-12-01 | 2019-05-17 | Calyxia | PROCESS FOR PREPARING MICROCAPSULES OF CONTROLLED SIZE COMPRISING A PHOTOPOLYMERIZATION STEP |
| CN108160013B (en) * | 2017-12-15 | 2020-08-18 | 华南理工大学 | Water-soluble carbon quantum dot sustained-release microcapsule and preparation method and application thereof |
| CN111841656A (en) * | 2019-09-02 | 2020-10-30 | 汪永强 | Preparation method of high-dispersion composite photocatalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002041987A2 (en) * | 2000-10-25 | 2002-05-30 | Tufts University | Polymeric microspheres |
| JP2007075698A (en) * | 2005-09-13 | 2007-03-29 | Sanyo Chem Ind Ltd | Hollow resin particle |
| WO2007102929A2 (en) * | 2005-12-30 | 2007-09-13 | Applera Corporation | Synthesis and use of cross-linked hydrophilic hollow spheres for encapsulating hydrophilic cargo |
| CN101121112A (en) * | 2007-05-17 | 2008-02-13 | 浙江大学 | Method for preparing hollow microsphere with hydrogel microsphere as stencil |
-
2008
- 2008-10-08 CN CN2008102235862A patent/CN101362069B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002041987A2 (en) * | 2000-10-25 | 2002-05-30 | Tufts University | Polymeric microspheres |
| JP2007075698A (en) * | 2005-09-13 | 2007-03-29 | Sanyo Chem Ind Ltd | Hollow resin particle |
| WO2007102929A2 (en) * | 2005-12-30 | 2007-09-13 | Applera Corporation | Synthesis and use of cross-linked hydrophilic hollow spheres for encapsulating hydrophilic cargo |
| CN101121112A (en) * | 2007-05-17 | 2008-02-13 | 浙江大学 | Method for preparing hollow microsphere with hydrogel microsphere as stencil |
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