CN104722251A - Preparation method of porous chitosan-based microspheres - Google Patents
Preparation method of porous chitosan-based microspheres Download PDFInfo
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- CN104722251A CN104722251A CN201510105427.2A CN201510105427A CN104722251A CN 104722251 A CN104722251 A CN 104722251A CN 201510105427 A CN201510105427 A CN 201510105427A CN 104722251 A CN104722251 A CN 104722251A
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000007711 solidification Methods 0.000 claims abstract description 17
- 230000008023 solidification Effects 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000005453 pelletization Methods 0.000 claims abstract description 10
- 230000008929 regeneration Effects 0.000 claims abstract description 7
- 238000011069 regeneration method Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 229920000159 gelatin Polymers 0.000 claims description 10
- 235000019322 gelatine Nutrition 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 108010010803 Gelatin Proteins 0.000 claims description 9
- 239000008273 gelatin Substances 0.000 claims description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000052 vinegar Substances 0.000 claims description 4
- 235000021419 vinegar Nutrition 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000023597 hemostasis Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 238000002145 thermally induced phase separation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003937 drug carrier Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000011806 microball Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 229910017489 Cu I Inorganic materials 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000002439 hemostatic effect Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The invention relates to the field of high-molecular porous materials and particularly relates to a preparation method of porous chitosan-based microspheres for medicine carriers, adsorption and separation, hemostasis and wound dressing. The preparation method comprises the following steps: (a) respectively preparing solidification liquid, an emsulsifying-agent solution and a diluted-acid solution of pelletizing materials and precooling the solidification solution to minus 20 DEG C; (b) dripping the chitosan diluted-acid solution into the emsulsifying-agent solution, homogenizing and stirring to form emulsion; and (c) carrying out thermally-induced phase separation on the emulsion under the temperature ranging from minus 60 DEG C to minus 10 DEG C, adding precooled solidification liquid, carrying out reverse-phase regeneration and thus obtaining the chitosan-based porous microspheres. The preparation method has the beneficial effect that the surfaces and the inner parts of the porous microspheres have porous structures with communicated heights.
Description
Technical field
The present invention relates to high-molecular porous Material Field, be specifically related to a kind of preparation method of porous chitosan base microballoon that can be used for pharmaceutical carrier, adsorbing separation, hemostasis, wound dressing.
Background technology
Porous polymer bead has abundant pore space structure and the feature of high-specific surface area, makes it to be widely used in the field such as pharmaceutical carrier and Co ntrolled release, tissue engineering bracket, catalyst carrier, metal ion and gas adsorbing separation, hemostasis.The such as micropore of farina base gathers polysaccharide microsphere hemostatic material by C.R. Bard company trade (trade name: ARISTATM AH); Chitosan porous microsphere loaded Cu I catalyst (Chinese patent, CN102407162B); Hydrophilic porous dextran-based microsphere is used for medicine embedding release (Chinese patent, CN102258787B); Metal ion blotting chitosan porous microsphere is used for metal biosorption and is separated (Chinese patent, CN102827380B).The technology of preparing of these natural porous polymer beads all have employed glutaraldehyde, the crosslinking agents such as epoxychloropropane, or polyethylene glycol (PEO) pore-foaming agent.On the one hand, there is the shortcoming of bio-toxicity in crosslinking agent, on the other hand, and adding of crosslinking agent and pore-foaming agent, crosslinking agent and high molecular reaction, and subsequent wash is removed, and all needs consumption of raw material, solvent and the energy, thus cause complex process, cost increases, and environmental pressure increases the weight of.
Summary of the invention
The present invention adopts emulsification balling-up successively, and a kind of chitosan-based porous microsphere has been prepared in Thermal inactive and anti-phase regeneration.This microballoon is made up of the top layer of porous and internal layer.By controlling solution composition, be separated, anti-phase regeneration and the drying condition regulation and control structure of ball, pattern and size.
To achieve these goals, technical scheme of the present invention is as follows:
A preparation method for chitosan-based porous microsphere, it comprises the steps:
A, prepare the shitosan dilute acid soln of solidification liquid, emulsifier solution and pelletizing material respectively, and described solidification liquid is precooled to-20 DEG C;
B, be added dropwise in emulsifier solution by described shitosan dilute acid soln, homogeneous stirs and forms emulsion;
C, emulsion is carried out freezing quenching Thermal inactive at-60 ~-10 DEG C, the time of separation is 4 ~ 12h, add again afterwards pre-cooled after solidification liquid, carry out anti-phase regeneration, washing is also dry, obtains shitosan
baseporous microsphere.
Wherein:
The volume ratio of the use amount of the shitosan dilute acid soln of emulsifier solution and pelletizing material is 10:1 ~ 3.
Described solidification liquid take inorganic base as solute, the solution being solvent with the mixture of water and alcohol, and wherein said inorganic base is at least one in NaOH, sodium carbonate, sodium acid carbonate, and in solidification liquid, the mass fraction of inorganic base is 1 ~ 3%; Described alcohol is ethanol or ethylene glycol, and the volume ratio of water and alcohol is 1 ~ 3:1.
Described pelletizing material is shitosan, or the polyvinyl alcohol of the shitosan of 1 ~ 2 weight portion and 0 ~ 1 weight portion, gelatin, cellulose, the mixture of at least one in starch.
Described shitosan dilute acid soln is the solution obtained after shitosan is dissolved in watery hydrochloric acid or spirit of vinegar; In described shitosan dilute acid soln, the mass fraction of pelletizing material is 1 ~ 2%; The mass fraction of described watery hydrochloric acid or spirit of vinegar is 1 ~ 2%; The number-average molecular weight of described shitosan is 50 ~ 1,000,000, and deacetylation is not less than 80%.
Described emulsifier solution is the solution obtained after w/o type Span 80 or Span 85 emulsifying agent are dissolved in organic solvent.
Described organic solvent is benzinum, mineral oil or hexane.
The invention provides " green " preparation method of a kind of chitosan porous microsphere.The method comprises emulsification balling-up successively, Thermal inactive and anti-phase regeneration, without the need to crosslinking agent and pore-foaming agent, has saved raw material, has reduced cost; The microspherulite diameter produced is even, and microsphere surface and inner void enrich, and interconnect.Production technology is simple, can produce in batches.The abundance of natural polymer chitosan, be that a class is nontoxic and under natural environment, be easy to the environment-friendly material of degrading, it has the characteristics such as good biocompatibility, antibiotic property, hemostasis, anti-inflammatory.Thus this microballoon is applicable to the fields such as pharmaceutical carrier is separated with Co ntrolled release, adsorption of metal ions, hemostasis.
The mechanism of the formation of chitosan-based porous microsphere of the present invention is after chitosan solution is emulsified into liquid pearl in oil phase; Liquid pearl has been frozen into ice pearl at-60 ~-10 DEG C, and wherein solvent becomes ice, and shitosan etc. are made material polymer generation Thermal inactive and are scattered among ice phase; Then with the ethanol water of alkali for the anti-phase regeneration of solidification liquid, by solvent remove, regenerate the polymer microballoons such as shitosan.After washing drying, leaving away of solvent result in the generation of hole, obtains porous microsphere.
The advantage of chitosan-based porous microsphere of the present invention and preparation method:
1. porous microsphere surface and the inner loose structure having height UNICOM.
2. the formation of chitosan porous microsphere does not need to add crosslinking agent, avoids the bio-toxicity that crosslinking agent may bring; Also without the need to pore-foaming agent, technique is simple.
3. the loose structure of microballoon enhances the mass exchange efficiency inside and outside ball, enhances the adsorption capacity of microballoon.Microballoon can be used as wound auxiliary material, sorbing material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of chitosan porous microsphere different amplification;
Fig. 2 is the scanning electron microscope (SEM) photograph of chitosan porous microsphere tangent plane;
Fig. 3 is the scanning electron microscope (SEM) photograph of shitosan/PVA porous microsphere different amplification;
Fig. 4 is the scanning electron microscope (SEM) photograph of shitosan/Porous Gelatin Microspheres By Using different amplification.
Detailed description of the invention
Below by embodiment, the present invention will be further described by reference to the accompanying drawings.
In Fig. 1 (1-a) to be chitosan porous microsphere multiplication factor be 50 scanning electron microscope (SEM) photograph;
In Fig. 1 (1-b) to be chitosan porous microsphere multiplication factor be 100 scanning electron microscope (SEM) photograph;
In Fig. 1 (1-c) to be chitosan porous microsphere multiplication factor be 1000 scanning electron microscope (SEM) photograph;
In Fig. 1 (1-d) to be chitosan porous microsphere multiplication factor be 3000 scanning electron microscope (SEM) photograph.
In Fig. 3, (3-a) is shitosan/PVA porous microsphere multiplication factor is the scanning electron microscope (SEM) photograph of 50;
In Fig. 3, (3-b) is shitosan/PVA porous microsphere multiplication factor is the scanning electron microscope (SEM) photograph of 100;
In Fig. 3, (3-c) is shitosan/PVA porous microsphere multiplication factor is the scanning electron microscope (SEM) photograph of 1000;
In Fig. 3, (3-d) is shitosan/PVA porous microsphere multiplication factor is the scanning electron microscope (SEM) photograph of 3000.
In Fig. 4, (4-a) is shitosan/Porous Gelatin Microspheres By Using multiplication factor is the scanning electron microscope (SEM) photograph of 50;
In Fig. 4, (4-b) is shitosan/Porous Gelatin Microspheres By Using multiplication factor is the scanning electron microscope (SEM) photograph of 100;
In Fig. 4, (4-c) is shitosan/Porous Gelatin Microspheres By Using multiplication factor is the scanning electron microscope (SEM) photograph of 1000;
In Fig. 4, (4-d) is shitosan/Porous Gelatin Microspheres By Using multiplication factor is the scanning electron microscope (SEM) photograph of 3000.
the preparation method of embodiment 1 chitosan porous microsphere comprises the steps:
1,1 g shitosan is dissolved in the aqueous acetic acid of the 1wt% of 100mL, de-bubble.
2,5gSpan 80 is dissolved in 100mL petroleum ether solution.
3, the chitosan solution 10mL getting step 1 gained slowly adds in the continuous phase solution of step 2 gained as decentralized photo, and high-speed stirred obtains emulsion.
4, emulsion is placed in the freezing quenching of deep freezer 4 hours of-20 DEG C.
5, the mixing solidification liquid of the NaOH ethanol water of-20 DEG C of 1wt% is poured in the emulsion after quenching, soak 3 hours.
6, centrifugally obtain chitosan microball, ethanol and water wash drying for several times respectively and obtain product.
Chitosan microball prepared by the present embodiment, as shown in Figure 1, Microsphere Size is 600 ~ 1000 μm for its size and surface topography, and surface has abundant hole, and aperture is 5 ~ 30 μm, and specific area is 10.01 m
2/ g.Fig. 2 is the sectional drawing of microballoon.Microballoon inside is the intercommunicating pore of tens microns containing a large amount of size.Pore wall thickness is tens nanometers.
the preparation method of embodiment 2 shitosans/PVA porous microsphere comprises the steps:
1,0.5g shitosan and 0.5gPVA are dissolved in the aqueous acetic acid of 1wt% of 100mL, de-bubble.
2,5gSpan 80 is dissolved in 100mL petroleum ether solution.
3, the mixed solution 10mL getting step 1 gained slowly adds in the continuous phase solution of step 2 gained as decentralized photo, and high-speed stirred obtains emulsion.
4, emulsion is placed in the freezing quenching of deep freezer 4 hours of-20 DEG C.
5, the mixing solidification liquid of the NaOH ethanol water of-20 DEG C of 1wt% is poured in the emulsion after quenching, soak 3 hours.
6, centrifugally obtain shitosan/PVA complex microsphere, wash drying for several times respectively with ethanol and water and obtain product.
Shitosan/PVA complex microsphere prepared by the present embodiment, as shown in Figure 3, Microsphere Size is 50 ~ 300 μm to its pattern, and surface is containing a large amount of hole, and hole size is 1 ~ 3 μm.The specific area of microballoon is 15.45 m
2/ g.
the preparation method of embodiment 3 shitosans/Porous Gelatin Microspheres By Using comprises the steps:
1, by 0.5 g shitosan and 0.5g Gelatin in the aqueous acetic acid of the 1wt% of 100mL, de-bubble.
2,5gSpan 80 is dissolved in 100mL toluene solution.
3, the mixed solution 10mL getting step 1 gained slowly adds in the continuous phase solution of step 2 gained as decentralized photo, and high speed homogenization stirring obtains emulsion.
4, emulsion is placed in the freezing quenching of deep freezer 4 hours of-20 DEG C.
5, the mixing solidification liquid of the NaOH ethanol water of-20 DEG C of 1wt% is poured in the emulsion after quenching, soak 3 hours.
6, centrifugally obtain shitosan/gelatin-compounded microballoon, ethanol and water wash final vacuum drying for several times respectively and obtain product.
Shitosan/gelatine composite porous microballoon prepared by the present embodiment, as shown in Figure 4, Microsphere Size is 200 ~ 600 μm to its pattern, and specific area is 14.45 m
2/ g, microsphere surface possesses abundant pore space structure, and hole size is 4 ~ 10 μm.
In sum, be only preferred embodiment of the present invention, not be used for limiting scope of the invention process, all equalizations of doing according to shape, structure, feature and the spirit described in the claims in the present invention scope change and modify, and all should be included in right of the present invention.
Claims (7)
1. a preparation method for chitosan-based porous microsphere, is characterized in that, comprises the steps:
A, prepare the shitosan dilute acid soln of solidification liquid, emulsifier solution and pelletizing material respectively, and described solidification liquid is precooled to-20 DEG C;
B, be added dropwise in emulsifier solution by the shitosan dilute acid soln of described pelletizing material, homogeneous stirs and forms emulsion;
C, described emulsion is carried out freezing quenching Thermal inactive at-60 ~-10 DEG C, the time of separation is 4 ~ 12h, add again afterwards pre-cooled after solidification liquid, carry out anti-phase regeneration, washing is also dry, obtains chitosan-based porous microsphere.
2. the preparation method of a kind of chitosan-based porous microsphere as claimed in claim 1, is characterized in that, the volume ratio of the use amount of the shitosan dilute acid soln of described emulsifier solution and pelletizing material is 10:1 ~ 3.
3. the preparation method of a kind of chitosan-based porous microsphere as claimed in claim 1, it is characterized in that described solidification liquid is take inorganic base as solute, with the solution that the mixture of water and alcohol is solvent, wherein said inorganic base is at least one in NaOH, sodium carbonate, sodium acid carbonate, and in solidification liquid, the mass fraction of inorganic base is 1 ~ 3%; Described alcohol is ethanol or ethylene glycol, and the volume ratio of water and alcohol is 1 ~ 3:1.
4. the preparation method of a kind of chitosan-based porous microsphere as claimed in claim 1, it is characterized in that described pelletizing material is shitosan, or the polyvinyl alcohol of the shitosan of 1 ~ 2 weight portion and 0 ~ 1 weight portion, gelatin, cellulose, the mixture of at least one in starch.
5. the preparation method of a kind of chitosan-based porous microsphere as claimed in claim 1, is characterized in that described shitosan dilute acid soln is the solution obtained after shitosan is dissolved in watery hydrochloric acid or spirit of vinegar; In described shitosan dilute acid soln, the mass fraction of pelletizing material is 1 ~ 2%; The mass fraction of described watery hydrochloric acid or spirit of vinegar is 1 ~ 2%; The number-average molecular weight of described shitosan is 50 ~ 1,000,000, and deacetylation is not less than 80%.
6. the preparation method of a kind of chitosan-based porous microsphere as claimed in claim 1, is characterized in that described emulsifier solution is the solution obtained after w/o type Span 80 or Span 85 emulsifying agent are dissolved in organic solvent.
7. the preparation method of a kind of chitosan-based porous microsphere as claimed in claim 1, is characterized in that described organic solvent is benzinum, mineral oil or hexane.
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