CN102658072A - Preparation method for monodispersed chitosan hollow microspheres - Google Patents
Preparation method for monodispersed chitosan hollow microspheres Download PDFInfo
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- CN102658072A CN102658072A CN2012101592657A CN201210159265A CN102658072A CN 102658072 A CN102658072 A CN 102658072A CN 2012101592657 A CN2012101592657 A CN 2012101592657A CN 201210159265 A CN201210159265 A CN 201210159265A CN 102658072 A CN102658072 A CN 102658072A
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Abstract
The invention discloses a preparation method for monodispersed chitosan hollow microspheres. Adding a polystyrene microsphere dispersion while mixing to a chitosan organic acid aqueous solution, and adding a cross-linking agent to obtain polystyrene/chitosan composite particles; and adding the polystyrene/chitosan composite particles to a specific organic solvent to remove polystyrene template microspheres, and finally to obtain chitosan hollow microspheres. A particle size of the chitosan hollow microsphere and a thickness of a shell have certain controllabilities.
Description
Technical field
The invention belongs to hollow microsphere material technology field, be specifically related to a kind of preparation method of shitosan hollow microsphere.
Background technology
Density is low because of having for hollow microsphere, specific area big, the shell penetrating power is controlled and cavity can store characteristics such as guest species; And receiving the concern more than the People more and more, prospect has a very wide range of applications at aspects such as catalyst carrier, medicament slow release, sensor, light filler, cosmetics.
At present the most of right and wrong of the hollow microsphere of preparation are biocompatible and abiotic degradable, therefore, use have a biocompatibility be the material preparation hollow microsphere with biodegradable shitosan, can make its application become more extensive.The preparation method of shitosan hollow microsphere mainly is a template, and wherein the most frequently used template is a polystyrene microsphere, and this is because the preparation method of polystyrene microsphere is simple, cost is low, monodispersity good and controllable size.People such as Z.Qian and W.Liu carries out copolymerization with acrylic acid and styrene in advance; Obtain the polystyrene microsphere that the surface is rich in carboxyl; Utilize electrostatic interaction to realize the absorption of shitosan subsequently, at last through the glutaraldehyde cross-linking shitosan and remove the polystyrene moulding microballoon and obtain shitosan hollow microsphere (list of references 1:Journal of Polymer Science Part A:Polymer Chemistry, 2008 on the polystyrene microsphere surface; 46,228-237; List of references 2:Journal of Materials Science, 2011,46,6758-6765).People such as H.Li at first carry out sulfonation with concentrated sulfuric acid p-poly-phenyl ethene microballoon; Then utilize electrostatic interaction and realize the enrichment of shitosan on polystyrene microsphere surface, at last equally through glutaraldehyde cross-linking with remove polystyrene microsphere template and obtain the shitosan hollow microsphere.(list of references 3:Colloid and Polymer Science, 2008,286,819-825).People such as C.Lu are template with the sulfonated polystyrene microballoon equally; Utilization is based on the self-assembly method layer by layer of electrostatic interaction; Surface with the shitosan and the electronegative CMC of positively charged is adsorbed onto template microsphere makes shitosan hollow microsphere (list of references 4:Colloids and Surfaces B:Biointerfaces, 2011 through removing template microsphere at last; 83,254-259).
Obviously, surface design, modification and functionalization have targetedly all been passed through in above-mentioned polystyrene microsphere surface, thereby have increased more preparation process, make the preparation process become more loaded down with trivial details.
Summary of the invention
The objective of the invention is to propose the single new method of disperseing the shitosan hollow microsphere of a kind of preparation simply, fast and efficiently.Need not p-poly-phenyl ethene template microsphere and carry out any design in advance and surface modification and modification, the purpose that reach the simplification process, reduces cost.
Core technology thought of the present invention is: disobey the static or the chemical interaction of being disinclined between the xenogenesis component; But utilize the colloid-stabilised special effects that produces; Impel and realize effective, controllable compound between polystyrene microsphere and the shitosan; Simultaneously, the cross-linking reaction of control shitosan and the template microsphere of selecting different sizes realize the effective regulation and control to shitosan hollow microsphere size and shell thickness.
The process of method proposed by the invention is: adopt polystyrene microsphere; Do not carry out any surface design, modification and functionalization, stir down and it is joined in the shitosan aqueous solutions of organic acids back adding crosslinking agent; Like glutaraldehyde; The polystyrene microsphere surface has formed crosslinked shitosan shell in the system, utilizes solvent that template microsphere is removed subsequently, finally obtains the shitosan hollow microsphere.
The synthetic method concrete steps of shitosan hollow microsphere proposed by the invention are following: 1. the preparation of polystyrene microsphere can be adopted conventional polymerizations such as dispersin polymerization; As comprise monomer, pure medium or alcohol-water blending agent, the polymerization system of nonionic amphiphilic macromolecular stabilizing agent and oil-soluble initiator; Also can directly adopt commercially available polystyrene microsphere.Polystyrene microsphere is scattered in the water after washing, is mixed with the polystyrene microsphere dispersion liquid.2. the polystyrene microsphere dispersion liquid is joined in the shitosan aqueous solutions of organic acids, stir the adding crosslinking agent under the uniform temperature, reaction is more than 2 hours.Through centrifugal, washing and dry, promptly get polystyrene/shitosan compound particle powder.3. polystyrene/shitosan compound particle powder is joined in the specific organic solvent, hold over night through centrifugal, washing and dry, finally obtains the shitosan hollow microsphere.
Among the present invention, the number average bead diameter of polystyrene microsphere is not less than 500 nanometers.
Among the present invention, organic acid is the mixture of any one or several kinds in acetic acid, formic acid, benzoic acid, acrylic acid, lactic acid, monoxone, TGA, butyric acid, isobutyric acid, neopentanoic acid, isovaleric acid, caproic acid, maleic acid, sorbic acid, tartaric acid, citric acid, malic acid or the butanedioic acid.
Among the present invention, crosslinking agent is one or several the mixture in aldehydes, anhydrides, isocyanide sulfuric acid ester, expoxy propane class, acyl chloride or the polyethylene glycols crosslinking agent.
Above-mentioned aldehydes crosslinking agent is the mixture of any one or several kinds in glutaraldehyde, formaldehyde, glyoxal or the acetic anhydride.
Among the present invention, the solvent of polystyrene microsphere is oxolane, toluene, xylenes, chloroform, dimethyl formamide, dimethyl sulfoxide (DMSO), limonene, butanone, cyclohexanone, butyl acetate, carbon disulfide etc.
Among the present invention, the preparation method's who is proposed characteristics are: 1. need not the polystyrene microsphere as template microsphere is carried out specific design, modification and functionalization; 2. the controllability that has form can be through regulating the shitosan hollow microsphere that multiple factor obtains to have different-grain diameter and shell thickness.
The specific embodiment:
Embodiment 1:
In four-necked bottle, 3.5 gram PVPs are dissolved in 160 milliliters of isopropyl alcohols, be warming up to 70 ℃.Again 0.3 gram azo diisobutyl nitrile is dissolved in the 20 gram styrene, under nitrogen protection, joins in the above-mentioned solution.Mechanical agitation, isothermal reaction was cooled to room temperature after 24 hours.The gained dispersion liquid washs respectively 6 times with ethanol and water through centrifugation successively, and water is mixed with the polystyrene microsphere dispersion liquid that solid content is 10wt%.The number average bead diameter of polystyrene microsphere is 1300 nanometers.
In 50 milliliters of polystyrene microsphere dispersion liquids acetic acid aqueous solution (1wt%) that to join 40 milliliters of chitosan mass marks be 10wt%, stirred 2 hours under the room temperature, add 4 milliliters of the glutaraldehydes of 25wt%, continue reaction 8 hours down at 40 ℃.Through centrifugal, washing and dry, obtain polystyrene/shitosan compound particle powder then.
5 gram polystyrene/shitosan compound particles join in 50 milliliters of toluene, leave standstill 5 hours, through centrifugal, washing and dry, obtain the shitosan hollow microsphere then, and its shell thickness is about 10 nanometers.
Embodiment 2:
Adopt the polystyrene microsphere particle among the embodiment 1.
In 50 milliliters of polystyrene microsphere dispersion liquids acetic acid aqueous solution (2wt%) that to join 40 milliliters of chitosan mass marks be 10wt%, stirred 6 hours under the room temperature, add 4 milliliters of the glutaraldehydes of 25wt%, continue reaction 16 hours down at 40 ℃.Through centrifugal, washing and dry, obtain polystyrene/shitosan compound particle powder then.
5 gram polystyrene/shitosan compound particles join in 50 milliliters of toluene, leave standstill 5 hours, through centrifugal, washing and dry, obtain the shitosan hollow microsphere then, and its shell thickness is about 28 nanometers.
Embodiment 3:
Adopt the polystyrene microsphere particle among the embodiment 1.
In 50 milliliters of polystyrene microsphere dispersion liquids acetic acid aqueous solution (3wt%) that to join 40 milliliters of chitosan mass marks be 10wt%, stirred 12 hours under the room temperature, add 4 milliliters of the glutaraldehydes of 25wt%, continue reaction 24 hours down at 40 ℃.Through centrifugal, washing and dry, obtain polystyrene/shitosan compound particle powder then.
5 gram polystyrene/shitosan compound particles join in 50 milliliters of toluene, leave standstill 5 hours, through centrifugal, washing and dry, obtain the shitosan hollow microsphere then, and its shell thickness is about 42 nanometers.
Embodiment 4:
In four-necked bottle, 3.0 gram PVPs are dissolved in 160 milliliters of ethanol, be warming up to 70 ℃.Again 0.2 gram azo diisobutyl nitrile is dissolved in the 20 gram styrene, under nitrogen protection, joins in the above-mentioned solution.Mechanical agitation, isothermal reaction was cooled to room temperature after 24 hours.The gained dispersion liquid washs respectively 6 times with ethanol and water through centrifugation successively, and water is mixed with the polystyrene microsphere dispersion liquid that solid content is 10wt%.The number average bead diameter of polystyrene microsphere is 1600 nanometers.
In 50 milliliters of polystyrene microsphere dispersion liquids acetic acid aqueous solution (4wt%) that to join 40 milliliters of chitosan mass marks be 10wt%; Stirred 12 hours under the room temperature; 4 milliliters of the glutaraldehydes of adding 25wt%; Continue reaction 24 hours down at 40 ℃, through centrifugal, washing and dry, obtain polystyrene/shitosan compound particle powder then.
5 gram polystyrene/shitosan compound particles join in 50 milliliters of toluene, leave standstill 5 hours, through centrifugal, washing and dry, obtain the shitosan hollow microsphere then, and its shell thickness is about 23 nanometers.
Embodiment 5:
Adopting commercially available particle diameter is 3 microns polystyrene microsphere dispersion liquid, and solid content is 10wt%.
In 50 milliliters of polystyrene microsphere dispersion liquids acetic acid aqueous solution (3wt%) that to join 40 milliliters of chitosan mass marks be 10wt%, stirred 12 hours under the room temperature, add 4 milliliters of the glutaraldehydes of 25wt%, continue reaction 24 hours down at 40 ℃.Through centrifugal, washing and dry, obtain polystyrene/shitosan compound particle powder then.
5 gram polystyrene/shitosan compound particles join in 50 milliliters of toluene, leave standstill 5 hours, through centrifugal, washing and dry, obtain the shitosan hollow microsphere then, and its shell thickness is about 53 nanometers.
Claims (6)
1. the preparation method of shitosan hollow microsphere: it is characterized in that adopting the polystyrene microsphere that does not carry out any surface design, modification and functionalization as template; After cleaning, be scattered in the water; Be mixed with the polystyrene microsphere dispersion liquid, join in the shitosan aqueous solutions of organic acids under stirring, and then add crosslinking agent; Reaction is more than 2 hours, through centrifugal, washing back acquisition polystyrene/shitosan compound particle under the uniform temperature; Polystyrene/shitosan compound particle is joined in the specific organic solvent, and hold over night through centrifugal, washing and dry, obtains the shitosan hollow microsphere.
2. the preparation method of shitosan hollow microsphere according to claim 1 is characterized in that the particle diameter of polystyrene microsphere template is not less than 500 nanometers.
3. the preparation method of shitosan hollow microsphere according to claim 1 is characterized in that shitosan is more than 50% of polystyrene microsphere weight.
4. the preparation method of shitosan hollow microsphere according to claim 1 is characterized in that organic acid is the mixture of any one or several kinds in acetic acid, formic acid, benzoic acid, acrylic acid, lactic acid, monoxone, the TGA.Acid concentration is: 1～5%.
5. the preparation method of shitosan hollow microsphere according to claim 1 is characterized in that crosslinking agent is one or several the mixture in aldehydes, anhydrides, isocyanide sulfuric acid ester, expoxy propane class, acyl chloride or the polyethylene glycols crosslinking agent.Wherein crosslinking agent weight is 15～100% of shitosan weight.
6. the preparation method of shitosan hollow microsphere according to claim 1; The solvent that it is characterized in that the dissolved polystyrene microballoon is oxolane, toluene, xylenes, chloroform, dimethyl formamide, dimethyl sulfoxide (DMSO), limonene, butanone, cyclohexanone; Butyl acetate, carbon disulfide etc.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143399A (en) * | 2012-10-10 | 2013-06-12 | 倪忠 | Preparation method of modified resin supported transition metal catalyst carrier |
| CN104923135A (en) * | 2015-06-19 | 2015-09-23 | 东华大学 | Method for preparing morphology-controllable chitosan micro-spheres at one step |
| CN107081138A (en) * | 2017-05-19 | 2017-08-22 | 上海工程技术大学 | Magnetic polystyrene base enclosure glycan composite adsorbent and preparation method and application |
| CN107828037A (en) * | 2017-11-06 | 2018-03-23 | 东莞市雄林新材料科技股份有限公司 | A kind of TPU materials available for drinking-water pipe and preparation method 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 |
| CN109134758A (en) * | 2018-07-24 | 2019-01-04 | 青岛大学 | A kind of chitosan sodium carboxymethylcellulose grafting hollow ball and preparation method thereof |
| CN109180967A (en) * | 2018-07-24 | 2019-01-11 | 青岛大学 | A kind of chitosan sodium carboxymethylcellulose composite hollow ball and preparation method thereof |
| CN110508260A (en) * | 2019-09-03 | 2019-11-29 | 晋江瑞碧科技有限公司 | A kind of preparation method of lead ion trace composite hollow microballoon |
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| CN1290524A (en) * | 1999-09-30 | 2001-04-11 | 浙江大学 | Ion crosslinking process of preparing medicinal slow-releasing chitosan microball |
| CN1607033A (en) * | 2003-10-15 | 2005-04-20 | 中国科学院过程工程研究所 | Chitose microsphere and microcapsule with uniform size and its preparation method |
| WO2009075652A1 (en) * | 2007-12-11 | 2009-06-18 | Nanyang Technological University | Hollow multi-layered microspheres for delivery of hydrophilic active compounds |
| US20110123456A1 (en) * | 2008-03-20 | 2011-05-26 | National University Of Ireland, Galway | Hollow biodegradable nanospheres and nanoshells for delivery of therapeutic and/or imaging molecules |
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Patent Citations (4)
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| CN1290524A (en) * | 1999-09-30 | 2001-04-11 | 浙江大学 | Ion crosslinking process of preparing medicinal slow-releasing chitosan microball |
| CN1607033A (en) * | 2003-10-15 | 2005-04-20 | 中国科学院过程工程研究所 | Chitose microsphere and microcapsule with uniform size and its preparation method |
| WO2009075652A1 (en) * | 2007-12-11 | 2009-06-18 | Nanyang Technological University | Hollow multi-layered microspheres for delivery of hydrophilic active compounds |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143399A (en) * | 2012-10-10 | 2013-06-12 | 倪忠 | Preparation method of modified resin supported transition metal catalyst carrier |
| CN104923135A (en) * | 2015-06-19 | 2015-09-23 | 东华大学 | Method for preparing morphology-controllable chitosan micro-spheres at one step |
| CN104923135B (en) * | 2015-06-19 | 2016-10-19 | 东华大学 | A kind of method that a step prepares morphology controllable chitosan microball |
| CN107081138A (en) * | 2017-05-19 | 2017-08-22 | 上海工程技术大学 | Magnetic polystyrene base enclosure glycan composite adsorbent and preparation method and application |
| CN107828037A (en) * | 2017-11-06 | 2018-03-23 | 东莞市雄林新材料科技股份有限公司 | A kind of TPU materials available for drinking-water pipe and preparation method thereof |
| CN109134758A (en) * | 2018-07-24 | 2019-01-04 | 青岛大学 | A kind of chitosan sodium carboxymethylcellulose grafting hollow ball and preparation method thereof |
| CN109180967A (en) * | 2018-07-24 | 2019-01-11 | 青岛大学 | A kind of chitosan sodium carboxymethylcellulose composite hollow ball and preparation method thereof |
| CN109180967B (en) * | 2018-07-24 | 2021-03-30 | 青岛大学 | Chitosan and sodium carboxymethylcellulose composite hollow sphere and preparation method thereof |
| CN109134758B (en) * | 2018-07-24 | 2021-03-30 | 青岛大学 | Chitosan sodium carboxymethylcellulose grafted hollow sphere and preparation method 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 |
| CN110508260A (en) * | 2019-09-03 | 2019-11-29 | 晋江瑞碧科技有限公司 | A kind of preparation method of lead ion trace composite hollow microballoon |
| CN110508260B (en) * | 2019-09-03 | 2022-02-15 | 晋江瑞碧科技有限公司 | Preparation method of lead ion imprinted composite hollow microspheres |
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