CN102443186A - Preparation method of epoxy chloropropane cross-linked chitosan microspheres - Google Patents
Preparation method of epoxy chloropropane cross-linked chitosan microspheres Download PDFInfo
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- CN102443186A CN102443186A CN2011102966893A CN201110296689A CN102443186A CN 102443186 A CN102443186 A CN 102443186A CN 2011102966893 A CN2011102966893 A CN 2011102966893A CN 201110296689 A CN201110296689 A CN 201110296689A CN 102443186 A CN102443186 A CN 102443186A
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 108
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000004005 microsphere Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000011806 microball Substances 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- 230000006196 deacetylation Effects 0.000 claims description 6
- 238000003381 deacetylation reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 108090000623 proteins and genes Proteins 0.000 abstract description 3
- 102000004169 proteins and genes Human genes 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 229940079593 drug Drugs 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 150000005837 radical ions Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 235000011167 hydrochloric acid Nutrition 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- -1 epoxy chloropropane forms carbonium ion Chemical class 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 241000238421 Arthropoda Species 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 150000004753 Schiff bases Chemical group 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention relates to the technical field of fine and deep processing and utilizing of medicines and aquatic products, and aims at providing a preparation method for preparing cross-linked chitosan microspheres with epoxy chloropropane as a cross-linking agent. The preparation method comprises the steps of: firstly preparing chitosan microspheres by an antiphase suspension method, making partial hydroxy on chitosan molecules to participate in cross-linking reaction with epoxy chloropropane as the cross-linking agent, thus converting linear chitosan molecules into reticular high polymer, and preparing cross-linked chitosan microspheres having a porous reticular structure with calcium carbonate as a pore-forming agent. The cross-linked chitosan microspheres prepared by the preparation method provided by the invention can be biodegraded, have good acid and base resistance, better adsorption effect on acid radical ions and proteins, and strong heavy metal ion loading capacity, and can be applied to foodstuff, medicine chemical industry and other fields.
Description
Technical field
The present invention relates to medicine and the fishery products intensive processing utilizes technical field, particularly a kind of preparation method of epoxy chloropropane crosslinked chitosan microsphere.
Background technology
Chitosan is a chitin through the product of deacetylated reaction, and its formal name used at school is β-(1,4)-2-amino-2-deoxy-D-glucose, in ocean arthropods such as a large amount of existence and shrimp, crab and part lower animal mushroom, insect, the alga cells film.Chitosan is the alkaline polysaccharide of the unique existence of occurring in nature; Its water insoluble and alkaline solution; Dissolve in most of diluted acid example hydrochloric acids, acetic acid, naphthenic acid and phenylformic acid etc.; Contain in its molecule-OH ,-functional group such as NH2, pyranoid ring, oxo bridge, be prone to carry out chemically modified, zwitterion is had exchange interaction, have biocompatibility.The tegument glycan is Powdered, is soluble in acidic medium and runs off, and can fully send out its advantage if chitosan is made micro-sphere structure.
The existing method for preparing crosslinked chitosan resin: as on March 14th, 2007 disclosed publication number be " lysine-chitosan resin and preparation method thereof " patent of CN1927892A; Disclosed method is: after the chitosan system is carried out emulsification 20-30min; Add glutaraldehyde solution, add CaCO then
3As pore-creating agent, behind the reaction 60-80min, use the pH value of diluted sodium hydroxide solution regulation system to be 9-10; Temperature control 60-70 ℃, stir 2.5-3.5h, filter; Abandon the filtrate collection filter residue, filter residue is respectively washed 3-5 time with sherwood oil, ethanol successively, with the CaCO in the diluted hydrochloric acid dissolution filter residue
3, be washed with distilled water to neutrality at last.This method is to utilize amino and aldehyde radical reaction on the chitosan to form schiff base structure and form cross-linked network; The main drawback of this method be in reaction process the amino on the chitosan by mass consumption; And have lone-pair electron amino is the important factor that chitosan has absorption property, utilizes the adsorptivity of cross-linked chitosan of this method preparation relatively poor.
Summary of the invention
The objective of the invention is to solve the above-mentioned deficiency that prior art exists; Providing a kind of is the preparation method of the crosslinked chitosan microsphere of linking agent preparation with the epoxy chloropropane; The chitosan microball absorption property of the present invention's preparation is good, can be used as the carrier of enzyme, pharmaceutical carrier etc., can biological degradation.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of epoxy chloropropane crosslinked chitosan microsphere, and described preparing method's step is following:
(1) the chitosan powder being dissolved in volumetric concentration is in 1 ~ 4% the hydrochloric acid, abundant stirring and dissolving under the room temperature, massfraction is 1 ~ 4% chitosan colloidal sol;
(2) it is in the whiteruss that equates of 1 ~ 4% hydrochloric acid volume that the chitosan colloidal sol that step (1) is made slowly is added to the described volumetric concentration of step (1) under agitation condition; Continue to stir 10 ~ 20 minutes; Chitosan colloidal sol is dispersed in the whiteruss, makes the chitosan microball system;
(3) the chitosan microball system that step (2) is made is warming up to 50 ~ 55 ℃, in the chitosan microball system, drips emulsifying agent under the agitation condition, continues to stir to make the emulsification of chitosan microball system drip the ethanolic soln and the lime carbonate suspension liquid of epoxy chloropropane after 10 ~ 20 minutes successively; Regulating the chitosan microball system pH then is 10 ~ 11; Continue to be warming up to 70 ~ 75 ℃, reacted 240 ~ 360 minutes, filter; Collect the globe filter residue; The globe filter residue, soaked 20 ~ 30 minutes with Hydrogen chloride respectively after the soaking flushing 4 ~ 6 times with sherwood oil and ethanol successively again, at last with deionized water rinsing to neutral; Vacuum lyophilization makes the cross linked porous chitosan microball of epoxy chloropropane.The volume(tric)fraction of Hydrogen chloride is 3 ~ 6%.
The present invention at first inverse suspension method prepares chitosan microball; Be that linking agent makes the part of hydroxyl on the chitosan molecule participate in crosslinking reaction again with the epoxy chloropropane; Make linear chitosan molecule change webbed superpolymer; With lime carbonate is pore-creating agent, makes to have how empty cancellated crosslinked chitosan microsphere.
The present invention is through under alkaline condition; Carbon chlorine bond rupture in the epoxy chloropropane forms carbonium ion and becomes ether, the epoxy addition of the while the other end with hydroxyl in the chitosan molecule; Become ether with the hydroxyl in another chitosan molecule; Realize the crosslinked of chitosan, make crosslinking reaction avoid the use of amino, the excellent adsorption of the crosslinked chitosan microsphere of preparation.
As preferably, the deacetylation of the chitosan powder described in the step (1) is more than 95%.The deacetylation of chitosan powder is high more, and the carrying capacity to metals ion of the crosslinked chitosan microsphere of preparation is strong more.
As preferably, drip the ethanolic soln of epoxy chloropropane in the step (3) and the consumption standard of lime carbonate suspension liquid is: chitosan, epoxy chloropropane, lime carbonate three's mass ratio is 1:0.4 ~ 0.56:1.8 ~ 2.2.The adition process of the ethanolic soln of epoxy chloropropane and lime carbonate suspension liquid is also all carried out under agitation condition; The lime carbonate suspension liquid is formulated as and takes by weighing lime carbonate; Add deionized water, stir into suspension liquid, the present invention adopts the lime carbonate suspension liquid and does not adopt calcium carbonate powders; Lime carbonate is mixed more fully, in lime carbonate being wrapped in after chitosan crosslinked reaction is accomplished with the chitosan sol particle.
As preferably, the stirring velocity of the stirring described in step (2) and the step (3) is 800-1200 rev/min.Such stirring velocity stirs gentle and evenly, mixing effect is good.
As preferably, the emulsifying agent described in the step (3) is span-80 or tween 80.Span-80 Chinese name: Span-80, sorbitol anhydride oleate, S-80 emulsifying agent.Tween 80: Tween 80, Chinese synonym: polysorbate, emulsifying agent T-80.
As preferably, the ethanolic soln of the epoxy chloropropane described in the step (3), the volumetric concentration of epoxy chloropropane is 5 ~ 20%.Epoxy chloropropane is easy to volatilization; Directly use epoxy chloropropane; Therefore be unfavorable for more accurately controlling the add-on of epoxy chloropropane, and epoxy chloropropane is water insoluble, epoxy chloropropane is dissolved in ethanol and adds again and control suitable concentration; Can avoid the epoxy chloropropane volatilization, thereby accurately control the add-on of epoxy chloropropane.
As preferably, the consumption of emulsifying agent is that the volume(tric)fraction that emulsifying agent accounts for the chitosan microball system is 0.1% ~ 0.15% in the step (3).
The invention has the beneficial effects as follows:
1, reaction conditions is gentle, and preparation process is simple;
2, the crosslinked chitosan microsphere prepared of the present invention can biological degradation, and resistance to acids and bases is good, and acid ion, protein are had adsorption effect preferably, and is strong to the carrying capacity of heavy metal ion, can be applicable to fields such as food, medicine, chemical industry.
Embodiment
Through specific embodiment, technical scheme of the present invention is further specified below.
Embodiment 1
(1) with deacetylation be 95% chitosan powder to be dissolved in volumetric concentration be in 1% the hydrochloric acid, abundant stirring and dissolving under the room temperature, massfraction is 1% chitosan colloidal sol;
(2) it is in the whiteruss that equates of 1% hydrochloric acid volume that the chitosan colloidal sol that step (1) is made slowly is added to the described volumetric concentration of step (1) under agitation condition; The control stirring velocity is 800 rev/mins; Continue to stir 10 minutes; Chitosan colloidal sol is dispersed in the whiteruss, makes the chitosan microball system;
(3) the chitosan microball system that step (2) is made is warming up to 50 ℃, in the chitosan microball system, drips span80 under the agitation condition, makes its (span80) volume(tric)fraction in system account for 0.1%; Continue to stir and to make the emulsification of chitosan microball system drip ethanolic soln and the lime carbonate suspension liquid that volumetric concentration is 5% epoxy chloropropane after 10 minutes successively; Chitosan, epoxy chloropropane, lime carbonate three's mass ratio is 1:0.4:1.8, use then mass concentration be about 2% dilute sodium hydroxide to regulate the chitosan microball system pH be 10, continue to be warming up to 70 ℃; Reacted 360 minutes; Filter, collect the globe filter residue, after the globe filter residue is distinguished soaking flushing 4 times with sherwood oil and ethanol successively; Use again volume(tric)fraction be 6% Hydrogen chloride soak made in 20 minutes the cross-linked chitosan parcel dissolution of calcium carbonate; Extremely neutral with deionized water rinsing at last, vacuum lyophilization makes the cross linked porous chitosan microball of epoxy chloropropane.
Embodiment 2
(1) with deacetylation be 96% chitosan powder to be dissolved in volumetric concentration be in 2.5% the hydrochloric acid, abundant stirring and dissolving under the room temperature, massfraction is 2% chitosan colloidal sol;
(2) it is in the whiteruss that equates of 2.5% hydrochloric acid volume that the chitosan colloidal sol that step (1) is made slowly is added to the described volumetric concentration of step (1) under agitation condition; The control stirring velocity is 1000 rev/mins; Continue to stir 15 minutes; Chitosan colloidal sol is dispersed in the whiteruss, makes the chitosan microball system;
(3) the chitosan microball system that step (2) is made is warming up to 53 ℃, in the chitosan microball system, drips span80 under the agitation condition, makes its (span80) volume(tric)fraction in system account for 0.13%; Continue to stir and to make the emulsification of chitosan microball system drip ethanolic soln and the lime carbonate suspension liquid that volumetric concentration is 10% epoxy chloropropane after 15 minutes successively; Chitosan, epoxy chloropropane, lime carbonate three's mass ratio is 1:0.5:2, use then mass concentration be about 2% dilute sodium hydroxide to regulate the chitosan microball system pH be 10, continue to be warming up to 73 ℃; Reacted 300 minutes; Filter, collect the globe filter residue, after the globe filter residue is distinguished soaking flushing 5 times with sherwood oil and ethanol successively; Use again volume(tric)fraction be 5% Hydrogen chloride soak made in 25 minutes the cross-linked chitosan parcel dissolution of calcium carbonate; Extremely neutral with deionized water rinsing at last, vacuum lyophilization makes the cross linked porous chitosan microball of epoxy chloropropane.
Embodiment 3
(1) with deacetylation be 98% chitosan powder to be dissolved in volumetric concentration be in 4% the hydrochloric acid, abundant stirring and dissolving under the room temperature, massfraction is 4% chitosan colloidal sol;
(2) it is in the whiteruss that equates of 4% hydrochloric acid volume that the chitosan colloidal sol that step (1) is made slowly is added to the described volumetric concentration of step (1) under agitation condition; The control stirring velocity is 1200 rev/mins; Continue to stir 10 minutes; Chitosan colloidal sol is dispersed in the whiteruss, makes the chitosan microball system;
(3) the chitosan microball system that step (2) is made is warming up to 55 ℃, in the chitosan microball system, drips tween 80 under the agitation condition, makes its (tween 80) volume(tric)fraction in system account for 0.15%; Continue to stir and to make the emulsification of chitosan microball system drip ethanolic soln and the lime carbonate suspension liquid that volumetric concentration is 20% epoxy chloropropane after 20 minutes successively; Chitosan, epoxy chloropropane, lime carbonate three's mass ratio is 1:0.56:2.2, use then mass concentration be about 2% dilute sodium hydroxide to regulate the chitosan microball system pH be 11, continue to be warming up to 75 ℃; Reacted 240 minutes; Filter, collect the globe filter residue, after the globe filter residue is distinguished soaking flushing 6 times with sherwood oil and ethanol successively; Use again volume(tric)fraction be 3% Hydrogen chloride soak made in 30 minutes the cross-linked chitosan parcel dissolution of calcium carbonate; Extremely neutral with deionized water rinsing at last, vacuum lyophilization makes the cross linked porous chitosan microball of epoxy chloropropane.
Epoxy chloropropane crosslinked chitosan microsphere of the present invention and glutaraldehyde cross-linking chitosan microball get the physical and chemical index contrast and see table 1, and the adsorptive power of epoxy chloropropane crosslinked chitosan microsphere of the present invention is seen table 2.The crosslinked chitosan microsphere of the present invention preparation can biological degradation, and it is good to have a resistance to acids and bases, and acid ion, protein are had adsorption effect preferably, to characteristics such as the carrying capacity of heavy metal ion are strong.
Above-described embodiment is a kind of preferable scheme of the present invention, is not that the present invention is done any pro forma restriction, under the prerequisite that does not exceed the technical scheme that claim puts down in writing, also has other variant and remodeling.
Claims (7)
1. the preparation method of an epoxy chloropropane crosslinked chitosan microsphere, it is characterized in that: described preparing method's step is following:
(1) the chitosan powder being dissolved in volumetric concentration is in 1 ~ 4% the hydrochloric acid, abundant stirring and dissolving under the room temperature, massfraction is 1 ~ 4% chitosan colloidal sol;
(2) it is in the whiteruss that equates of 1 ~ 4% hydrochloric acid volume that the chitosan colloidal sol that step (1) is made slowly is added to the described volumetric concentration of step (1) under agitation condition; Continue to stir 10 ~ 20 minutes; Chitosan colloidal sol is dispersed in the whiteruss, makes the chitosan microball system;
(3) the chitosan microball system that step (2) is made is warming up to 50 ~ 55 ℃, in the chitosan microball system, drips emulsifying agent under the agitation condition, continues to stir to make the emulsification of chitosan microball system drip the ethanolic soln and the lime carbonate suspension liquid of epoxy chloropropane after 10 ~ 20 minutes successively; Regulating the chitosan microball system pH then is 10 ~ 11; Continue to be warming up to 70 ~ 75 ℃, reacted 240 ~ 360 minutes, filter; Collect the globe filter residue; The globe filter residue, soaked 20 ~ 30 minutes with Hydrogen chloride respectively after the soaking flushing 4 ~ 6 times with sherwood oil and ethanol successively again, at last with deionized water rinsing to neutral; Vacuum lyophilization makes the cross linked porous chitosan microball of epoxy chloropropane.
2. the preparation method of epoxy chloropropane crosslinked chitosan microsphere according to claim 1 is characterized in that: the deacetylation of the chitosan powder described in the step (1) is more than 95%.
3. the preparation method of epoxy chloropropane crosslinked chitosan microsphere according to claim 1 and 2 is characterized in that: the ethanolic soln of dropping epoxy chloropropane and the consumption standard of lime carbonate suspension liquid are in the step (3): chitosan, epoxy chloropropane, lime carbonate three's mass ratio is 1:0.4 ~ 0.56:1.8 ~ 2.2.
4. the preparation method of epoxy chloropropane crosslinked chitosan microsphere according to claim 1 and 2 is characterized in that: the stirring velocity of the stirring described in step (2) and the step (3) is 800-1200 rev/min.
5. the preparation method of epoxy chloropropane crosslinked chitosan microsphere according to claim 1 and 2 is characterized in that: the emulsifying agent described in the step (3) is span-80 or tween 80.
6. the preparation method of epoxy chloropropane crosslinked chitosan microsphere according to claim 1 and 2 is characterized in that: the ethanolic soln of the epoxy chloropropane described in the step (3), the volumetric concentration of epoxy chloropropane are 5 ~ 20%.
7. the preparation method of epoxy chloropropane crosslinked chitosan microsphere according to claim 1 and 2 is characterized in that: the consumption of emulsifying agent is that the volume(tric)fraction that emulsifying agent accounts for the chitosan microball system is 0.1% ~ 0.15% in the step (3).
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265720A (en) * | 2013-05-30 | 2013-08-28 | 重庆大学 | Novel method for preparing porous crosslinked chitosan microsphere |
| CN104117344A (en) * | 2014-08-06 | 2014-10-29 | 兰州城市学院 | Preparation method of novel chitosan metal ion adsorbent |
| CN104549172A (en) * | 2015-01-26 | 2015-04-29 | 重庆大学 | Method for preparing sulfydryl-modified chitosan short hole microspheres |
| CN106620710A (en) * | 2016-08-16 | 2017-05-10 | 张豪 | Microcarrier as well as preparation method and application thereof |
| CN107266704A (en) * | 2017-07-12 | 2017-10-20 | 浙江大学 | A kind of preparation method of cross linked porous chitosan oligosaccharide |
| CN108854986A (en) * | 2018-06-29 | 2018-11-23 | 成都纺织高等专科学校 | A kind of epoxychloropropane modified chitosan and preparation method thereof for adsorbing heavy metal ion |
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| CN109867967A (en) * | 2019-01-21 | 2019-06-11 | 华中科技大学鄂州工业技术研究院 | The preparation method of the complete biological base epoxy of dual cross-linking system |
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| CN111203192A (en) * | 2020-01-17 | 2020-05-29 | 南方科技大学 | Preparation method and application of modified chitosan microsphere adsorbent for adsorbing perchlorate |
| CN112842582A (en) * | 2020-12-31 | 2021-05-28 | 深圳新致美精密齿研有限公司 | Surface treatment method for denture implant |
| US20220227893A1 (en) * | 2017-08-22 | 2022-07-21 | China Petroleum & Chemical Corporation | Starch-containing microsphere and preparation method and use thereof |
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