CN104923135B - A kind of method that a step prepares morphology controllable chitosan microball - Google Patents
A kind of method that a step prepares morphology controllable chitosan microball Download PDFInfo
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- CN104923135B CN104923135B CN201510349557.0A CN201510349557A CN104923135B CN 104923135 B CN104923135 B CN 104923135B CN 201510349557 A CN201510349557 A CN 201510349557A CN 104923135 B CN104923135 B CN 104923135B
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Abstract
The present invention relates to a kind of method that a step prepares morphology controllable chitosan microball, including: under agitation, add chitosan in dilute sulfuric acid aqueous solution, under normal-pressure open system, microwave heating 1～1.5h at 70～90 DEG C, filtered while hot, cooling, centrifugal, washing, lyophilization, obtain chitosan microball.The chitosan microball particle diameter of the present invention is little, is evenly distributed；In preparation in addition to mineral acid, it is not necessary to add other any reagent, the application of chitosan microball and environment will not be produced any impact；Without other special installations in preparation.The chitosan microball morphology controllable of the present invention is strong, and particle diameter is evenly distributed, and productivity is high, and production cost is low, and technique is simple, and reaction temperature is low, and the response time is short, it is easy to accomplish industrialized production；There is the features such as biodegradable, resistance to acids and bases good, preferable to the adsorption effect of acid ion, protein, and the load capacity of heavy metal ion is stronger, can be applicable to the fields such as food, medicine, chemical industry.
Description
Technical field
The invention belongs to the preparation field of chitosan microball, a kind of method preparing morphology controllable chitosan microball particularly to a step.
Background technology
The biodegradability of chitosan, low toxicity, good biocompatibility make it be widely used in biological medicine and preparation, and chitosan has antiacid, antiulcer, promotes the character such as wound healing；As the adjuvant of various dosage forms, chitosan i.e. can be used as tablet disintegrant, adhesive, it is possible to makes granule, ocular inserts etc..Chitosan is the natural mucoadhesive agent of function admirable, is usually used in the mucosal drug delivery of polypeptide drug.The nano-carrier made with chitosan can extend medicine and absorb the retention time of position, reaches controlled release purpose.
The most popular to the research of chitosan microball, particularly Porous Chitosan Microspheres has bigger specific surface area so that it is have important application potential in various fields.Under ion crosslinking agent effect, the amino of chitosan protonates in acid condition, the cation that its macromolecular chain is formed by protonated amino is reacted with the multivalent anions generation Electrostatic Absorption in solution, it is tied by chemical bond and cross-links, forming the netted or macromolecular material of body structure, this character can be applicable to the preparation of chitosan microball.The advantage of ionic cross-linking is that preparation method is the simplest, and preparation process does not use organic solvent, it can be avoided that major part chemical cross-linking agent, as defended the dialdehyde crosslinking agent harm to human body, the activity of medicine can be kept when being applied to medicine, can be used for mucosal drug delivery, be in this way widely used.Conventional ion crosslinking agent is the tripolyphosphate of relatively low molecular weight, four Quadrafos, pyrophosphate, molybdate etc..
But, the most also find no the method preparing chitosan microball for cross-linking agent with sulfate radical closed under microwave-assisted.Microwave method is prepared the particle diameter that chitosan microball advantage compared with additive method is the chitosan microball obtained and is much smaller than conventional heating methods, and particle diameter is evenly distributed；Meanwhile, the time needed for preparation is short, and productivity is high, simple to operate, and without organic solvent in preparation process, separating-purifying is simple.
Summary of the invention
The technical problem to be solved is to provide a kind of method that a step prepares morphology controllable chitosan microball, and the method technique is simple, and the response time is short, and productivity is high, it is not necessary to special installation, the chitosan microball prepared is evenly distributed.Chitosan microball prepared by the method can be used to the carrier as medicine, environment-protecting asepsis.
The method that a kind of step of the present invention prepares morphology controllable chitosan microball, including:
Under agitation, add chitosan in dilute sulfuric acid aqueous solution, under normal-pressure open system, 70-90 DEG C of microwave heating 30～150min, filter, be cooled to room temperature, centrifugal, washing, lyophilization, obtain chitosan microball；Wherein, chitosan is 1g:100mL with the ratio of aqueous sulfuric acid.
The mass percent concentration of described dilute sulfuric acid aqueous solution is 5wt%～18wt%.
Described washing is for washing with water.
The present invention is by microwave heating condition, next step prepares the chitosan microball of morphology controllable.By changing ratio and the microwave heating time of reaction raw materials, the chitosan microball with different-grain diameter and pattern can be obtained.
Beneficial effect
(1) particle diameter of the chitosan microball that employing the inventive method prepares is much smaller than conventional heating methods, and particle diameter is evenly distributed；
(2) in the preparation process of the present invention, in addition to mineral acid, it is not necessary to add other any reagent；Meanwhile, the concentration adding sulphuric acid in preparation process is extremely low, the application of chitosan microball and environment will not be produced any impact；
(3) use the chitosan microball that a process for preparing have biodegradable, resistance to acids and bases good, preferable to the adsorption effect of acid ion, protein, the feature such as the load capacity of heavy metal ion is stronger, can be applicable to the fields such as food, medicine, chemical industry；
(4) present invention has structural controllability by force, and particle diameter is evenly distributed, and productivity is high, and production cost is low, and technique is simple, and reaction temperature is low, and the response time is short, without other special installations in preparation process, it is easy to accomplish features such as industrialized production.
Accompanying drawing explanation
Fig. 1 is the FTIR figure of the chitosan microball prepared in embodiment 1, and wherein a is untreated chitosan, and b is the chitosan microball of embodiment 1 preparation；
Fig. 2 is the XRD figure of the chitosan microball prepared in embodiment 1, and wherein a is untreated chitosan, and b is the chitosan microball of embodiment 1 preparation；
Fig. 3 is the SEM figure of the chitosan microball prepared in embodiment 1；
Fig. 4 is the SEM figure of the chitosan microball prepared in embodiment 2；
Fig. 5 is the SEM figure of the chitosan microball prepared in embodiment 3；
Fig. 6 is the SEM figure of the chitosan microball prepared in embodiment 4；
Fig. 7 is the SEM figure of the chitosan microball prepared in comparative example.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
Under mechanical stirring, 1g chitosan is added in the dilute sulfuric acid aqueous solution of 9.8wt%, in 90 DEG C of microwave heating 1h, after reaction terminates, filtrate filtered while hot obtained is cooled to room temperature, the precipitation that centrifugation generates, and washes postlyophilization and obtain oblate spheroid chitosan microball.
FTIR, XRD and SEM figure of product is shown in Fig. 1-3 respectively.Wherein, Fig. 1 a is the FTIR figure of untreated chitosan；Fig. 1 b is the FTIR figure of the chitosan microball of embodiment 1 preparation；Fig. 2 a is the XRD figure of untreated chitosan；Fig. 2 b is the XRD figure of the chitosan microball of embodiment 1 preparation.
From figure 1 it appears that chitosan microball～3400cm-1The stretching vibration that broad peak is O-H and N-H at place ,～2900cm-1The peak at place is to be produced by the stretching vibration of C-H ,～1524cm-1The peak at place is NH3 +,～1070cm-1There is a stronger absworption peak in place, and this peak is that the stretching vibration of chitosan residue C-O-C causes.
From the XRD figure of Fig. 2 it can be seen that use H2SO4The crystalline element of the chitosan after process is destroyed, and chitosan microball is impalpable structure, and this is consistent with the open structure in its SEM figure.
Scheming it can be seen that the mean diameter of chitosan microball is 3 μm from the SEM of Fig. 3, particle diameter is evenly distributed.
Embodiment 2
Under mechanical stirring, 1g chitosan is added in the dilute sulfuric acid aqueous solution of 11.8wt%, in 90 DEG C of microwave heating 1h, after reaction terminates, filtrate filtered while hot obtained is cooled to room temperature, the precipitation that centrifugation generates, and washes postlyophilization and obtain the compressed globular chitosan microball of center indent.From SEM figure (Fig. 4) it can be seen that mean diameter is 3.5 μm, average thickness 1.5 μm.
Embodiment 3
Under mechanical stirring, 1g chitosan is added in the dilute sulfuric acid aqueous solution of 13.8wt%, in 90 DEG C of microwave heating 1h, after reaction terminates, filtrate filtered while hot obtained is cooled to room temperature, the precipitation that centrifugation generates, and washes postlyophilization and obtain the chitosan microball of pie.From SEM figure (Fig. 5) it can be seen that mean diameter is 2 μm, average thickness 0.7 μm.
Embodiment 4
Under mechanical stirring, 1g chitosan is added in the dilute sulfuric acid aqueous solution of 13.8wt%, in 90 DEG C of microwave heating 1.5h, after reaction terminates, filtrate filtered while hot obtained is cooled to room temperature, the precipitation that centrifugation generates, and washes postlyophilization and obtain the chitosan microball of center indent pie.From SEM figure (Fig. 6) it can be seen that mean diameter is 2 μm, average thickness 1.5 μm.
Comparative example
Under mechanical stirring, 1g chitosan is added in the dilute sulfuric acid aqueous solution of 11.8wt%, heat 1h in 90 DEG C of oil baths, after reaction terminates, filtrate filtered while hot obtained is cooled to room temperature, the precipitation that centrifugation generates, and washes postlyophilization and obtain the chitosan microball of center indent pie.From SEM figure (Fig. 7) it can be seen that mean diameter is 7 μm, average thickness 3 μm.
Claims (2)
1. the method that a step prepares morphology controllable chitosan microball, including:
Under agitation, add chitosan in dilute sulfuric acid aqueous solution, under normal-pressure open system, 70-90 DEG C of microwave heating 30～150
Min, filters, is cooled to room temperature, centrifugal, washing, and lyophilization obtains chitosan microball；Wherein, chitosan and sulphuric acid water
The ratio of solution is 1g:100mL；The mass percent concentration of described dilute sulfuric acid aqueous solution is 5wt%～18wt%.
The method that an a kind of step the most according to claim 1 prepares morphology controllable chitosan microball, it is characterised in that described washing
For washing with water.
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| US20100143259A1 (en) * | 2006-09-18 | 2010-06-10 | Institute Of Process Engineering, Chinese Academy Of Sciences | Fluorescent microspheres, the preparation method and uses thereof |
| CN102258967A (en) * | 2011-04-28 | 2011-11-30 | 华南理工大学 | Chitosan hollow microcapsule and preparation method thereof |
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| CN1485362A (en) * | 2002-09-29 | 2004-03-31 | 中国科学院过程工程研究所 | Ion cross-linked chitosan microballoon, its preparing process and use |
| US20100143259A1 (en) * | 2006-09-18 | 2010-06-10 | Institute Of Process Engineering, Chinese Academy Of Sciences | Fluorescent microspheres, the preparation method and uses thereof |
| CN101601872A (en) * | 2009-07-16 | 2009-12-16 | 浙江大学 | The method of preparing high-strength three-dimensional chitosan rod material by microwave radiation |
| CN102258967A (en) * | 2011-04-28 | 2011-11-30 | 华南理工大学 | Chitosan hollow microcapsule and preparation method thereof |
| CN102558581A (en) * | 2012-01-04 | 2012-07-11 | 上海理工大学 | Method for preparing high-strength solid chitosan microcarriers |
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