CN1185048C - Method for covering high polymer gel microsphere by using emulsion method - Google Patents
Method for covering high polymer gel microsphere by using emulsion method Download PDFInfo
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- CN1185048C CN1185048C CNB031372309A CN03137230A CN1185048C CN 1185048 C CN1185048 C CN 1185048C CN B031372309 A CNB031372309 A CN B031372309A CN 03137230 A CN03137230 A CN 03137230A CN 1185048 C CN1185048 C CN 1185048C
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Abstract
The present invention relates to an emulsion method for coating a gelatin microsphere as a high polymer, which belongs to the technical field of preparation of a microcapsule in a nuclear shell type. The present invention discloses the emulsion method for coating the gelatin microsphere as a high polymer so as to solve the problems of poor mechanical property, easy biodegradation and incapability of long-term repeat use of the gelatin microsphere. The method comprises the following steps: a high polymer material A as a wall material and a solvent B are selected to prepare a high polymer solution; a solvent C and a surface active agent D which are immiscible with B are added to the high polymer solution, the mixture is stirred at high speed to prepare emulsion; swollen gelatin microsphere prepared from a natural high polymer is used as a core material E, and the core material E is added to the emulsion; next, the mixture is continuously stirred, and the high polymer material A is solidified on the walls of the core material E; an amount of emulsion G is added to the mixture, and the mixture is continuously stirred at high speed, so that milk drips which are not solidified and are stuck to the surface of the microsphere are completely solidified, and a microencapsulation process is ended; finally, the microsphere is filtered out, and a microencapsulation microsphere coated by A is obtained after the microsphere is washed completely. The method has the advantages of simple operation and low equipment requirement.
Description
Technical field
The present invention relates to the technology of preparing and the microcapsules technology of the new separation material that uses in chemical industry, metallurgy, the medicine and other fields, particularly a kind of preparation method of hud typed microcapsules.
Background technology
Microcapsules technology is a kind of technology that the world today develops rapid, of many uses and comparative maturity.The process of preparation microcapsules is called microencapsulation.It is that solid, liquid or gas are wrapped in the small capsule.The wall shell of sealing usefulness is called the wall material; The capsule-core that is wrapped is called core.In recent years, microcapsules technology had obtained increasingly extensive application in fields such as chemical industry, metallurgy, medicine, food, fertilizer, feeds.Core material and external environment are isolated with making after the microencapsulation of core material, play the protective effect to core.
In recent years, some natural high polymers had obtained using widely as the separation function material.Receive that as the heavy metal ions of gel micro-ball (diameter 500 μ m～3000 μ m) in handling waste water that shitosan and alginate are made people pay attention to widely.Contain amino on the chitosan molecule segment, then also has carboxyl on the alginate molecule segment, under certain conditions, complexing can take place with heavy metal ion such as copper, chromium, manganese, mercury, lead etc. in these two kinds of natural high polymers, form comparatively stable complex compound, thereby reach the purpose of absorption, recycling heavy metal ion.But existing technology is merely able to that these two kinds of natural high polymers are made single spherical gel to be used, and this gel micro-ball has certain disadvantages in actual use, such as biodegradation easily, bad mechanical strength, is unable to undergo long-continued use or the like.
Microencapsulation technology commonly used mainly is divided into chemical method, comprise interfacial polymerization, in-situ polymerization etc., physical method comprises water oil-phase separating method, dry bath method etc., and the method for machinery, comprise air suspension film forming method (fluidized bed process), spray drying process, static combined techniques or the like.These technology all have the field of its each self application, through the analysis to principle, use these methods that shitosan and alginate gel micro-ball are carried out not too big advantage of microencapsulation, what have is not suitable, the then cost that has is too high, and complicated operation requires high to equipment.Therefore developing a kind of new microencapsulation technology has great importance.
Summary of the invention
The bad mechanical property of the gel micro-ball that shitosan and alginate are made self, biodegradation easily, can not reuse for a long time, therefore be subjected to very big restriction in actual applications, the object of the invention just is to overcome above-mentioned gel micro-ball many shortcomings in use.Use the stable synthesized polymer material of a kind of physicochemical properties that the gel micro-ball of shitosan and alginate is coated as core.
The invention discloses the method that a kind of emulsion method coats the high polymer gel micro-ball, it is characterized in that this method comprises the steps:
1) selects suitable wall material high-molecular material A and be used for dissolving the solvent B of wall material high-molecular material A, the preparation high polymeric solution; Described wall material high-molecular material A is polysulfones, polyether sulfone or polyacrylonitrile;
2) add and immiscible solvent C of B and surfactant D in above-mentioned solution, high-speed stirred prepares water-in-oil emulsion;
3) will join in the above-mentioned emulsion as core E with the gel micro-ball of the swelling of natural high polymer preparation, continue to stir, make high polymeric solution drop and core E collision in the emulsion, the effect of the material F that makes core E swelling that contains in core E issues looks and shifts, thereby makes high-molecular material A be solidificated in the wall of core E; Described natural high polymer is shitosan or alginate;
4) in above-mentioned system, add a certain amount of stable emulsion G that makes by C, D, F, continue high-speed stirred, the uncured emulsion droplet of microsphere surface adhesion is all solidified, end the microencapsulation process;
5) microballoon is filtered out, and, obtain the microencapsulation microballoon of the A coating of good dispersion at last through degree of depth rinse.
Solvent B of the present invention is N, dinethylformamide, N, N-dimethylacetylamide, dichloroethanes or carrene.
Solvent C of the present invention is heptane, octane or paraffin oil.
Surfactant D of the present invention is SPAN80 or SPAN85.
Material F of the present invention is water, ethanol or methyl alcohol.
System emulsion process of the present invention is the method for preparing emulsion of the prior art, as dispersed with stirring method, excusing from death dispersion method, film system breast method etc.
Principle of the present invention is: one, in the emulsion that wall material macromolecular material is made during the collision of the gel micro-ball of a large amount of emulsion droplet and core, high polymer solvent in the emulsion droplet is diffused into rapidly in the core gel micro-ball, phase transfer takes place, high polymer in the emulsion droplet is separated out simultaneously, forms small bead and is bonded on the wall of gel micro-ball.The result that a large amount of emulsion droplets solidifies has just formed one deck high polymer layer at microsphere surface.Two, adding a large amount of emulsion G afterwards rapidly all solidifies the uncured emulsion droplet of microsphere surface adhesion.Form the microencapsulation microballoon of good dispersion at last.
Beneficial effect of the present invention is: present technique is applied to the microencapsulation of natural high polymer gel micro-ball, have easy and simple to handle, characteristics such as equipment is simple.Whole process does not relate to chemical reaction, is suitable for control.Wall material high polymer material can reclaim use.By the parameters such as composition, high polymeric solution concentration, coating time of control polymer emulsion, can control the parameters such as structure of microencapsulation speed, clad wall thickness, clad wall easily.Utilize present technique, can overcome not microencapsulation the gel micro-ball bad mechanical property, be unable to undergo shortcoming such as long-term use.
Description of drawings
Fig. 1 coats the principle schematic of high polymer gel micro-ball for emulsion method.
Fig. 2 is the influence figure of coating time to coating thickness.
Fig. 3 is the influence figure of initial polysulfones solution concentration to coating thickness.
The specific embodiment
The method of the invention can utilize simple equipment to realize that implementation step comprises at normal temperatures and pressures:
1) selects suitable wall material high-molecular material A and solvent B thereof, the preparation high polymeric solution;
2) add and immiscible solvent C of B and surfactant D in above-mentioned solution, high-speed stirred prepares water-in-oil emulsion;
3) will join in the above-mentioned emulsion as core E with the gel micro-ball of the swelling of natural high polymer preparation, continue to stir, make high polymeric solution drop and core E collision in the emulsion, the effect of the material F that makes core E swelling that contains in core E issues looks and shifts, thereby makes high-molecular material A be solidificated in the wall of core E;
4) in above-mentioned system, add a certain amount of emulsion G, continue high-speed stirred, the uncured emulsion droplet of microsphere surface adhesion is all solidified, end the microencapsulation process;
5) microballoon is filtered out, and, obtain the microencapsulation microballoon of the A coating of good dispersion at last through degree of depth rinse.
Details are as follows for specific embodiment.
Embodiment 1:
A is a polysulfones, and B is N, and dinethylformamide, C are paraffin oil, and D is Span 80, and core E is that F is a water with the gel micro-ball of the swelling of Chitosan Preparation, and G is made by water, paraffin oil and Span 80.
Take by weighing the 10g polysulfones, be dissolved in the N of 90g, in the dinethylformamide, make the solution 1 that contains polysulfones 10% (W/W); Take by weighing 2g Span 80 in addition, be dissolved in and obtain solution 2 in the 98g paraffin oil.Solution 1 and solution 2 are mixed according to mass ratio at 6: 4, stir and make comparatively stable emulsion.Chitosan microball with swelling joins in the above-mentioned emulsion then, behind the stirring at low speed 10s, add the emulsion G that makes in 70: 28: 2 ratio by water, paraffin oil, Span 80 rapidly, high-speed stirred, filter after 10 minutes, with ether, ethanol, deionized water the microballoon of microencapsulation is carried out degree of depth rinse respectively, finally obtain the chitosan microcapsules that polysulfones coats.
The time (promptly coating the time) of adjusting stirring at low speed in the above-mentioned steps more respectively is 20s, 30s, 40s, 120s; All the other raw materials, step are the same, compare test.To the mapping of coating time, as shown in Figure 2, with the increase of the time of coating, coating thickness increases with the coating thickness of the chitosan microcapsules that obtains under the difference coating time.
Embodiment 2:
A is a polysulfones, and B is N, and dinethylformamide, C are paraffin oil, and D is Span 80, and core E is that F is a water with the gel micro-ball of the swelling of Chitosan Preparation, and G is made by water, paraffin oil and Span 80.
At first make the N that contains polysulfones 7% (W/W), dinethylformamide solution 1; Take by weighing 2g Span 80 in addition, be dissolved in and obtain solution 2 in the 98g paraffin oil.Solution 1 and solution 2 are mixed according to mass ratio at 7: 3, stir and make comparatively stable emulsion.Chitosan microball with swelling joins in this emulsion then, add the emulsion G that makes in 70: 28: 2 ratio by water, paraffin oil, Span 80 behind the stirring at low speed 30s rapidly, high-speed stirred, filter after 10 minutes, with ether, ethanol, deionized water the microballoon of microencapsulation is carried out degree of depth rinse respectively, finally obtain the chitosan microcapsules that polysulfones coats.
Make the N that contains polysulfones 10%, 14% (W/W) more respectively, dinethylformamide solution 1; All the other raw materials, step are the same, compare test.
Different initial polysulfones solution concentrations to the influence of coating thickness as shown in Figure 3, along with the polysulfones solution concentration raises, the microcapsules coating thickness that obtains increases.
Embodiment 3:
A is a polysulfones, and B is N, and dinethylformamide, C are paraffin oil, and D is Span 80, and core E is that F is a water with the gel micro-ball of the swelling of calcium alginate preparation, and G is made by water, paraffin oil and Span 80.
Similar embodiment 1 is made the N that contains polysulfones 7% (W/W), dinethylformamide solution 1; Take by weighing 2g Span 80 in addition, be dissolved in and obtain solution 2 in the 98g paraffin oil.Solution 1 and solution 2 are mixed according to mass ratio at 7: 3, stir and make comparatively stable emulsion.Calcium alginate microsphere (the about 3mm of particle diameter) with swelling adds wherein then, behind the stirring at low speed 30s, add the emulsion G that makes in 70: 28: 2 ratio by water, paraffin, Span 80 rapidly, high-speed stirred, filter after 10 minutes, with ether, ethanol, deionized water the microballoon of microencapsulation is carried out degree of depth rinse respectively, finally obtain the calcium alginate microcapsule of the polysulfones coating of homogeneous, the average thickness of clad is about 200 μ m respectively.
Embodiment 4:
A is a polysulfones, and B is N, and dinethylformamide, C are paraffin oil, and D is Span 80, and core E is that F is a water with the gel micro-ball of the swelling of calcium alginate preparation, and G is made by water, paraffin oil and Span 80.
Similar embodiment 1 is made the N that contains polysulfones 14% (W/W), dinethylformamide solution 1; Take by weighing 2g Span 80 in addition, be dissolved in and obtain solution 2 in the 98g paraffin oil.Solution 1 and solution 2 are mixed according to mass ratio at 7: 3, stir and make comparatively stable emulsion.Calcium alginate microsphere (the about 3mm of particle diameter) with swelling adds wherein then, behind the stirring at low speed 30s, add the emulsion G that makes in 70: 28: 2 ratio by water, paraffin, Span 80 rapidly, high-speed stirred, filter after 10 minutes, with ether, ethanol, deionized water the microballoon of microencapsulation is carried out degree of depth rinse respectively, finally obtain the calcium alginate microcapsule of the polysulfones coating of homogeneous, the average thickness of clad is about 310 μ m respectively.
Claims (5)
1. the method for an emulsion method coating high polymer gel micro-ball is characterized in that this method comprises the steps:
1) selects suitable wall material high-molecular material A and be used for dissolving the solvent B of wall material high-molecular material A, the preparation high polymeric solution; Described wall material high-molecular material A is polysulfones, polyether sulfone or polyacrylonitrile;
2) add and immiscible solvent C of B and surfactant D in above-mentioned solution, high-speed stirred prepares water-in-oil emulsion;
3) will join in the above-mentioned emulsion as core E with the gel micro-ball of the swelling of natural high polymer preparation, continue to stir, make high polymeric solution drop and core E collision in the emulsion, the effect of the material F that makes core E swelling that contains in core E issues looks and shifts, thereby makes high-molecular material A be solidificated in the wall of core E; Described natural high polymer is shitosan or alginate;
4) in above-mentioned system, add a certain amount of stable emulsion G that makes by C, D, F, continue high-speed stirred, the uncured emulsion droplet of microsphere surface adhesion is all solidified, end the microencapsulation process;
5) microballoon is filtered out, and, obtain the microencapsulation microballoon of the A coating of good dispersion at last through degree of depth rinse.
2. emulsion method according to claim 1 coats the method for high polymer gel micro-ball, and it is characterized in that: described solvent B is N, dinethylformamide, N, N-dimethylacetylamide, dichloroethanes or carrene.
3. emulsion method according to claim 1 coats the method for high polymer gel micro-ball, and it is characterized in that: described solvent C is heptane, octane or paraffin oil.
4. emulsion method according to claim 1 coats the method for high polymer gel micro-ball, and it is characterized in that: described surfactant D is SPAN80 or SPAN85.
5. emulsion method according to claim 1 coats the method for high polymer gel micro-ball, and it is characterized in that: described material F is water, ethanol or methyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB031372309A CN1185048C (en) | 2003-06-03 | 2003-06-03 | Method for covering high polymer gel microsphere by using emulsion method |
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| CNB031372309A CN1185048C (en) | 2003-06-03 | 2003-06-03 | Method for covering high polymer gel microsphere by using emulsion method |
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| CN1185048C true CN1185048C (en) | 2005-01-19 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100522246C (en) * | 2005-03-18 | 2009-08-05 | 中国科学院过程工程研究所 | Chitosan pellet/microsac and preparation thereof |
| SG11201404038PA (en) * | 2012-02-06 | 2014-08-28 | Univ Nanyang Tech | Methods of manufacturing core-shell microparticles, and microparticles formed thereof |
| CN109046194A (en) * | 2018-08-21 | 2018-12-21 | 武汉佰玛生物科技有限公司 | A kind of method that limonene emulsification prepares chitosan microball |
| CN109647296A (en) * | 2019-01-18 | 2019-04-19 | 东华大学 | A kind of Porous hollow microballoon and its preparation method and application |
| CN114748675B (en) * | 2022-03-31 | 2023-04-07 | 苏州大学 | Method for preparing gelatin/chitosan embolism microsphere by ionic gel-S/W/O emulsification multi-stage balling method |
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