CN103265720A - Novel method for preparing porous crosslinked chitosan microsphere - Google Patents
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Abstract
一种制备多孔交联壳聚糖微球的新方法，具体涉及一种以1，2-环己二醇二缩水甘油醚为交联剂制备交联壳聚糖微球的方法。本发明以以市售壳聚糖、1，2-环己二醇二缩水甘油醚和氯化石蜡为原料，经溶解、分散成球、制孔、交联及干燥，制得多孔交联壳聚糖微球。该方法具有反应条件温和、制备步骤简单、资源综合利用率高、无有害物质产生等特点。采用本方法制备出的交联壳聚糖微球具有可生物降解、耐酸碱性好，对酸根离子、蛋白质的吸附效果较好，对重金属离子的负载能力较强等特点，可应用于食品、医药、化工等领域。The invention discloses a new method for preparing porous cross-linked chitosan microspheres, in particular to a method for preparing cross-linked chitosan microspheres by using 1,2-cyclohexanediol diglycidyl ether as a cross-linking agent. The present invention uses commercially available chitosan, 1,2-cyclohexanediol diglycidyl ether and chlorinated paraffin as raw materials to prepare a porous cross-linked shell through dissolution, dispersion into balls, pore making, cross-linking and drying. Glycan microspheres. The method has the characteristics of mild reaction conditions, simple preparation steps, high comprehensive utilization rate of resources, and no generation of harmful substances. The cross-linked chitosan microspheres prepared by this method have the characteristics of biodegradability, good acid and alkali resistance, good adsorption effect on acid radical ions and proteins, strong loading capacity on heavy metal ions, etc., and can be used in food , medicine, chemical industry and other fields.
Description
One, technical field
The invention belongs to biological medicine and wastewater treatment and prepare the chitosan microball technical field, being specifically related to a kind of is the method that linking agent prepares crosslinked chitosan microsphere with 1,2-cylohexanediol diglycidyl ether.
Two, background technology
Chitosan is the chitin deacetylase based products, is the alkaline polysaccharide of the unique existence of occurring in nature, and water insoluble and alkaline solution dissolves in most of diluted acid example hydrochloric acids, acetic acid, naphthenic acid and phenylformic acid etc., is widely used in food, medicine, chemical industry and environmental area.The tegument glycan is powder, because a large amount of hydrogen bonds of intermolecular formation, causes the main active function groups amino of polymkeric substance to be closed, and is difficult to exchange, absorption, chelating and chemical reaction etc., also causes the resistance to mass transfer of said process big.This has greatly limited the expansion of chitosan range of application, therefore is necessary it is modified, to improve character such as its mass transfer, reaction.
The existing method for preparing crosslinked chitosan resin: as on March 11st, 2007 disclosed publication number be: " lysine-chitosan resin and preparation method thereof " patent of CN1927892A, disclosed method is: at first use glutaraldehyde cross-linking, add CaCO then
3As pore-creating agent, hierarchy of control pH value is 9～10, and 60～70 ℃ of temperature stir 2.5～3.0h, filters and the collection filter residue, then uses diluted hydrochloric acid dissolution CaCO
3Drilling is washed with distilled water to neutrality at last.This method forms the chitosan microball that the Schiff key connects with the glutaraldehyde cross-linking amino of chitosan, and its main drawback is that the main functional group amino of chitosan is consumed, and therefore the chitosan microball functional property of preparing is poor.And for example, publication number is the patent " method of synthesizing heavy metal adsorbent from silica gel and chitosan " of CN1359750A, and disclosed method is: at first just chitosan joins in the acetic acid, agitation and filtration, add the silica gel pore, add the sulfur-bearing organic solvent again, ultra-sonic dispersion added epoxy chloropropane crosslinked 12 hours at last, elimination filtrate, the oven dry solid, water and ethanol cleaning, drying obtain finished product.This method is used propylene oxide base substituted-amino hydrogen earlier under acidic conditions, re-adjustment pH attacks hydroxyl with epoxide group, generates etherate.Its main drawback is: the energy consumption height all need be at high temperature carried out in two reactions; The chitosan microball of preparation still consumes part amino, influences the functional property of product.
Three, summary of the invention
Main purpose of the present invention is that providing a kind of is the method for the cross linked porous chitosan microball of preparation of linking agent with 1,2-cylohexanediol diglycidyl ether at the weak point of existing preparation crosslinked chitosan microsphere method.This method has characteristics such as reaction conditions gentleness, preparation process are simple, operation facility, comprehensive utilization of resources rate height, unharmful substance generation.That the crosslinked chitosan microsphere that employing a process for preparing has is biodegradable, resistance to acids and bases good, better to acid ion, absorption of proteins effect, to characteristics such as the carrying capacity of heavy metal ion is stronger, can be applicable to fields such as food, medicine, chemical industry.
Principle of the present invention is: free amine group is the important indicator of weighing the crosslinked chitosan microsphere functional property, and therefore, the preparation crosslinked chitosan microsphere should be avoided consuming amino as far as possible.Solution is dispersed into the microspheroidal particle under centrifugal action, in basic solution, because the gelation point of chitosan is near pH6.4, therefore, under alkaline condition, chitosan is frozen into microballoon with chitosan-solid chloroparaffin powder mixed solution high speed dispersion; Clorafin is dissolved in ethanol, and the clorafin with in the dissolve with ethanol chitosan microball namely forms the porous chitosan microballoon; Under alkaline condition, hydroxyl can react with epoxide group, form ehter bond, and there are a plurality of free hydroxyl groups in the essentially consist unit of chitosan molecule glucosamine, therefore, available 1, the 2-cylohexanediol diglycidyl ether carries out crosslinked, form etherate, so just prepare cross linked porous chitosan microball.
The object of the present invention is achieved like this: a kind of novel method for preparing cross linked porous chitosan microball, with commercially available chitosan, 1,2-cylohexanediol diglycidyl ether and clorafin are raw material, through dissolving, dispersion balling-up, drilling, crosslinked and dry, make cross linked porous chitosan microball.Its concrete method steps is as follows:
1. prepare chitosan colloidal sol
The ratio that according to chitosan mass (g) and massfraction is 0.5～3.0% dilute hydrochloric acid volume (mL) is 1: 20～200 ratio, under agitation be that 40,000～120,000 Da, deacetylation are that 85%～95% chitosan powder is dissolved in the dilute hydrochloric acid with molecular weight, prepare the chitosan mass mark and be 5.0～0.5% colloidal sol, be used for step preparation chitosan microball down;
2. preparation chitosan microball
Add particle diameter in the chitosan sol solutions that makes to step 1 and be 20～60 microns solid chloroparaffin powder, pump into after stirring in the spraying whizzer, the control centrifuge speed is 4000～8000r/min dispersions of spraying, and the chitosan microball liquid of ejection is with the aqueous sodium carbonate reception of pH8～10.Particle diameter is that 20～60 microns solid chloroparaffin powder quality (g) and chitosan mass mark is that the ratio of 5.0～0.5% sol volume (mL) is 1: 2～5.After spraying is finished, slowly stirred 10-30 minute with electric blender, filter then, collect filter residue and filtered liquid, the filter residue of collection is chitosan microball, is used for step drilling down; For the filtrate of collecting, can be used for accepting chitosan microball liquid again;
3. prepare the porous chitosan microballoon
The 2nd the step finish after, be that the ratio of 75～95% volumes of aqueous ethanol (mL) is 1: 4～8 ratio according to chitosan microball quality (g) and volume fraction, it is in 75～95% the ethanolic soln that the 2nd chitosan microball prepared of step is scattered in volume fraction, under the speed of 30～90r/min, carry out the dissolved chlorine fossil waxes powder first time, behind stir process 30～60min, filter, collect filtrate and the filter residue that filters for the first time respectively.To the filter residue of the collecting first time, condition according to the dissolved chlorine fossil waxes powder first time, adding volume fraction is that 75～95% ethanolic solns carry out the dissolved chlorine fossil waxes powder second time, and the adding volume fraction is that volume and the treatment condition of 75～95% ethanolic solns all are same as dissolved chlorine fossil waxes powder for the first time.After dissolved chlorine fossil waxes powder is finished for the second time, filter, collect filtered solution and filter residue for the second time respectively.The filter residue second time to collecting is the porous chitosan microballoon, is used for step preparation crosslinked chitosan microsphere down; For the filtered solution of the collecting second time, merge with the filtered solution of the collecting first time, be used for reclaiming ethanol and the clorafin of regenerating;
4. prepare the wet microballoon of cross-linked chitosan
The 3rd the step finish after, the porous chitosan microballoon of the 3rd step preparation is scattered in the aqueous solution, under agitation is warming up to 60～90 ℃ earlier, regulating pH with dilute sodium hydroxide again is 8.5～10.5, add 1,2-cylohexanediol diglycidyl ether then and carried out crosslinking reaction 60～90 minutes.1,2-cylohexanediol diglycidyl ether quality (g) is 1: 50～20 with the ratio of porous chitosan microsphere volume (mL).After-filtration is finished in reaction, collects filtrate and filter residue respectively, to the filtrate of collecting, is used for disperseing again the porous chitosan microballoon; To the filter residue of collecting, use the pure water repetitive scrubbing, when being neutrality, washings pH value ends.After washing is finished, filter, collect filter residue and wash filtrate respectively, the wash filtrate to collecting carries out biochemical treatment, back up to standard discharging; The filter residue of collecting is the wet microballoon of cross linked porous chitosan, is used for going on foot down carrying out drying treatment;
5. prepare cross linked porous chitosan microball
The 4th step was sent into the wet microballoon of cross linked porous chitosan of the 4th step preparation in the vacuum drying oven after finishing, and was that 0.05～0.09Mpa, temperature are 60～80 ℃ of following vacuum-dryings 5～10 hours in vacuum tightness, namely prepared cross linked porous chitosan microball.After testing, the mean pore size of chitosan microball is 50～100 μ m, and specific area reaches 720.8～810.2m
2G
-1
After the present invention adopts technique scheme, mainly contain following effect:
(1) the cross linked porous chitosan microball prepared of the present invention, mean diameter 600～900 μ m, mean pore size is 50～100 μ m, specific surface area is up to 720.8～810.2m
2G
-1, productive rate reaches 93.7～98.5% in chitosan mass.The reaction conditions gentleness, preparation process is simple.
(2) to prepare cross linked porous chitosan microball raw materials used nontoxic in the present invention, safe preparation process, and the treated back up to standard discharging of the scrub raffinate of generation meets the demand for development of Green Chemistry.
(3) the cross linked porous chitosan microball prepared of the present invention is biodegradable, has kept whole amino, can be applicable to fields such as food, medicine, chemical industry, environmental protection, absorbing carbon dioxide, exchange negatively charged ion, chelating heavy metal ion, isolated protein etc.
Embodiment
Below in conjunction with concrete mode, further specify the present invention.
Embodiment 1
1. be 120,000 Da with molecular weight, taking off second phthalein degree and be 95% 5g chitosan powder, to be dissolved in volumetric concentration be in 3% the 1000mL hydrochloric acid, and abundant stirring and dissolving under the room temperature gets massfraction and be 0.5% chitosan colloidal sol;
2. add particle diameter in the chitosan sol solutions that makes to step 1 and be 60 microns solid chloroparaffin powder, pump into after stirring in the spraying whizzer, the control centrifuge speed is 8000r/min dispersions of spraying, and the chitosan microball liquid of ejection is with the aqueous sodium carbonate reception of pH10.Particle diameter is that 60 microns solid chloroparaffin powder quality (g) and chitosan mass mark is that the ratio of 0.5% sol volume (mL) is 1: 5.After spraying is finished, slowly stirred 30 minutes with electric blender, filter then, collect filter residue and filtered liquid, the filter residue of collection is chitosan microball, is used for step drilling down; For the filtrate of collecting, can be used for accepting chitosan microball liquid again;
3. the 2nd chitosan microball prepared of step is scattered in volume fraction and is among 95% the ethanolic soln 100mL, under the speed of 90r/min, carry out the dissolved chlorine fossil waxes powder first time, behind the stir process 60min, filter, collect filtrate and the filter residue that filters for the first time respectively.To the filter residue of the collecting first time, condition according to the dissolved chlorine fossil waxes powder first time, adding volume fraction is that 95% ethanolic soln carries out the dissolved chlorine fossil waxes powder second time, and the volume fraction of adding is that volume and the treatment condition of 95% ethanolic soln all are same as dissolved chlorine fossil waxes powder for the first time.After dissolved chlorine fossil waxes powder is finished for the second time, filter, collect filtered solution and filter residue for the second time respectively.The filter residue second time to collecting is the porous chitosan microballoon, is used for step preparation crosslinked chitosan microsphere down; For the filtered solution of the collecting second time, merge with the filtered solution of the collecting first time, be used for reclaiming ethanol and the clorafin of regenerating;
4. after the 3rd step finished, the porous chitosan microballoon of the 3rd step preparation is scattered in the aqueous solution, under agitation is warming up to 90 ℃ earlier, regulating pH with dilute sodium hydroxide again is 10.5, adds 1,2-cylohexanediol diglycidyl ether then and carries out crosslinking reaction 90 minutes.1,2-cylohexanediol diglycidyl ether quality (g) is 1: 20 with the ratio of porous chitosan microsphere volume (mL).After-filtration is finished in reaction, collects filtrate and filter residue respectively, to the filtrate of collecting, is used for disperseing again the porous chitosan microballoon; To the filter residue of collecting, use the pure water repetitive scrubbing, when being neutrality, washings pH value ends.After washing is finished, filter, collect filter residue and wash filtrate respectively, the wash filtrate to collecting carries out biochemical treatment, back up to standard discharging; The filter residue of collecting is the wet microballoon of cross-linked chitosan, is used for going on foot down carrying out drying treatment;
5. after the 4th step finished, the wet microballoon of cross-linked chitosan of the 4th step preparation being sent in the vacuum drying oven, is that 0.09Mpa, temperature are 80 ℃ of following vacuum-dryings 10 hours in vacuum tightness, namely prepares crosslinked chitosan microsphere.
Embodiment 2
1. be 80,000 Da with molecular weight, taking off second phthalein degree and be 90% 5g chitosan powder, to be dissolved in massfraction be abundant stirring and dissolving under the room temperature in 2% the 250mL hydrochloric acid, gets massfraction and be 2% chitosan colloidal sol;
2. add particle diameter in the chitosan sol solutions that makes to step 1 and be 40 microns solid chloroparaffin powder, pump into after stirring in the spraying whizzer, the control centrifuge speed is 6000r/min dispersions of spraying, and the chitosan microball liquid of ejection is with the aqueous sodium carbonate reception of pH9.Particle diameter is that 40 microns solid chloroparaffin powder quality (g) and chitosan mass mark is that the ratio of 2% sol volume (mL) is 1: 3.After spraying is finished, slowly stirred 20 minutes with electric blender, filter then, collect filter residue and filtered liquid, the filter residue of collection is chitosan microball, is used for step drilling down; For the filtrate of collecting, can be used for accepting chitosan microball liquid again;
3. the 2nd chitosan microball prepared of step is scattered in volume fraction and is in 85% the 150mL ethanolic soln, under the speed of 60r/min, carry out the dissolved chlorine fossil waxes powder first time, behind the stir process 45min, filter, collect filtrate and the filter residue that filters for the first time respectively.To the filter residue of the collecting first time, condition according to the dissolved chlorine fossil waxes powder first time, adding volume fraction is that 85% ethanolic soln carries out the dissolved chlorine fossil waxes powder second time, and the volume fraction of adding is that volume and the treatment condition of 85% ethanolic soln all are same as dissolved chlorine fossil waxes powder for the first time.After dissolved chlorine fossil waxes powder is finished for the second time, filter, collect filtered solution and filter residue for the second time respectively.The filter residue second time to collecting is the porous chitosan microballoon, is used for step preparation crosslinked chitosan microsphere down; For the filtered solution of the collecting second time, merge with the filtered solution of the collecting first time, be used for reclaiming ethanol and the clorafin of regenerating;
4. after the 3rd step finished, the porous chitosan microballoon of the 3rd step preparation is scattered in the aqueous solution, under agitation is warming up to 75 ℃ earlier, regulating pH with dilute sodium hydroxide again is 9.5, adds 1,2-cylohexanediol diglycidyl ether then and carries out crosslinking reaction 75 minutes.1,2-cylohexanediol diglycidyl ether quality g) ratio with porous chitosan microsphere volume (mL) is 1: 35.After-filtration is finished in reaction, collects filtrate and filter residue respectively, to the filtrate of collecting, is used for disperseing again the porous chitosan microballoon; To the filter residue of collecting, use the pure water repetitive scrubbing, when being neutrality, washings pH value ends.After washing is finished, filter, collect filter residue and wash filtrate respectively, the wash filtrate to collecting carries out biochemical treatment, back up to standard discharging; The filter residue of collecting is the wet microballoon of cross-linked chitosan, is used for going on foot down carrying out drying treatment;
5. after the 4th step finished, the wet microballoon of cross-linked chitosan of the 4th step preparation being sent in the vacuum drying oven, is that 0.075Mpa, temperature are 70 ℃ of following vacuum-dryings 7.5 hours in vacuum tightness, namely prepares crosslinked chitosan microsphere.
Embodiment 3
1. be 40,000 Da with molecular weight, taking off second phthalein degree and be 85% 5g chitosan powder, to be dissolved in volumetric concentration be in 1% the 100mL hydrochloric acid, and abundant stirring and dissolving under the room temperature gets massfraction and be 5% chitosan colloidal sol;
2. add particle diameter in the chitosan sol solutions that makes to step 1 and be 20 microns solid chloroparaffin powder, pump into after stirring in the spraying whizzer, the control centrifuge speed is 4000r/min dispersions of spraying, and the chitosan microball liquid of ejection is with the aqueous sodium carbonate reception of pH8.Particle diameter is that 20 microns solid chloroparaffin powder quality (g) and chitosan mass mark is that the ratio of 5% sol volume (mL) is 1: 2.After spraying is finished, slowly stirred 10 minutes with electric blender, filter then, collect filter residue and filtered liquid, the filter residue of collection is chitosan microball, is used for step drilling down; For the filtrate of collecting, can be used for accepting chitosan microball liquid again;
3. the 2nd chitosan microball prepared of step is scattered in volume fraction and is in 75% the 200mL ethanolic soln, under the speed of 30r/min, carry out the dissolved chlorine fossil waxes powder first time, behind the stir process 30min, filter, collect filtrate and the filter residue that filters for the first time respectively.To the filter residue of the collecting first time, condition according to the dissolved chlorine fossil waxes powder first time, adding volume fraction is that 75% ethanolic soln carries out the dissolved chlorine fossil waxes powder second time, and the volume fraction of adding is that volume and the treatment condition of 75% ethanolic soln all are same as dissolved chlorine fossil waxes powder for the first time.After dissolved chlorine fossil waxes powder is finished for the second time, filter, collect filtered solution and filter residue for the second time respectively.The filter residue second time to collecting is the porous chitosan microballoon, is used for step preparation crosslinked chitosan microsphere down; For the filtered solution of the collecting second time, merge with the filtered solution of the collecting first time, be used for reclaiming ethanol and the clorafin of regenerating;
4. after the 3rd step finished, the porous chitosan microballoon of the 3rd step preparation is scattered in the aqueous solution, under agitation is warming up to 60 ℃ earlier, regulating pH with dilute sodium hydroxide again is 8.5, adds 1,2-cylohexanediol diglycidyl ether then and carries out crosslinking reaction 60 minutes.1,2-cylohexanediol diglycidyl ether quality (g) is 1: 50 with the ratio of porous chitosan microsphere volume (mL).After-filtration is finished in reaction, collects filtrate and filter residue respectively, to the filtrate of collecting, is used for disperseing again the porous chitosan microballoon; To the filter residue of collecting, use the pure water repetitive scrubbing, when being neutrality, washings pH value ends.After washing is finished, filter, collect filter residue and wash filtrate respectively, the wash filtrate to collecting carries out biochemical treatment, back up to standard discharging; The filter residue of collecting is the wet microballoon of cross-linked chitosan, is used for going on foot down carrying out drying treatment;
5. after the 4th step finished, the wet microballoon of cross-linked chitosan of the 4th step preparation being sent in the vacuum drying oven, is that 0.05Mpa, temperature are 60 ℃ of following vacuum-dryings 5 hours in vacuum tightness, namely prepares crosslinked chitosan microsphere.
Claims (1)
1. novel method for preparing cross linked porous chitosan microball is characterized in that concrete steps are as follows:
(1) preparation chitosan colloidal sol
Under agitation be that 40,000～120,000 Da, deacetylation are that 85%～95% chitosan powder is dissolved in the dilute hydrochloric acid with molecular weight, prepare the chitosan mass mark and be 5.0～0.5% colloidal sol;
(2) preparation chitosan microball
Add particle diameter in the chitosan sol solutions that makes to step (1) and be 20～60 microns solid chloroparaffin powder, solid chloroparaffin powder quality and chitosan mass mark are that the ratio of 5.0～0.5% sol volume is 1g: 2～5mL, pump into after stirring in the spraying whizzer, the control centrifuge speed is 4000～8000r/min dispersion of spraying, the chitosan microball liquid of ejection receives with the aqueous sodium carbonate of pH8～10, after spraying is finished, slowly stirred 10～30 minutes with electric blender, filter then, the filter residue of collection is chitosan microball;
(3) preparation porous chitosan microballoon
(2) step finish after, be that 75～95% volumes of aqueous ethanol are than being the ratio of 1g: 4～8mL according to chitosan microball quality and volume fraction, it is in 75～95% the ethanolic soln that the chitosan microball that (2) step was collected is scattered in volume fraction, under the speed of 30～90r/min, carry out the dissolved chlorine fossil waxes powder first time, behind stir process 30～60min, filter and collect filter residue, adding volume fraction in filter residue is that 75～95% ethanolic solns carry out the dissolved chlorine fossil waxes powder second time, the volumes of aqueous ethanol that adds and treatment condition all are same as dissolved chlorine fossil waxes powder for the first time, filter after dissolved chlorine fossil waxes powder treatment is finished for the second time, collect filter residue and be the porous chitosan microballoon;
(4) the wet microballoon of preparation cross-linked chitosan
(3) step finish after, the porous chitosan microballoon of (3) step preparation is scattered in the aqueous solution, under agitation be warming up to 60～90 ℃ earlier, regulating pH with dilute sodium hydroxide again is 8.5～10.5, according to 1,2-cylohexanediol diglycidyl ether quality is 1g: 50～20mL with porous chitosan microsphere volume ratio, add 1, the 2-cylohexanediol diglycidyl ether carried out crosslinking reaction 60～90 minutes, and after-filtration is finished in reaction, use pure water repetitive scrubbing filter residue again, when washings pH value is neutrality, end, filter then, collect filter residue and be the wet microballoon of cross-linked chitosan;
(5) prepare cross linked porous chitosan microball
(4) step was sent the wet microballoon of cross linked porous chitosan of (4) step preparation into drying in the vacuum drying oven after finishing, and namely prepared cross linked porous chitosan microball.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549172A (en) * | 2015-01-26 | 2015-04-29 | 重庆大学 | Method for preparing sulfydryl-modified chitosan short hole microspheres |
| CN104815348A (en) * | 2014-11-28 | 2015-08-05 | 杨子中 | Preparation method for composite micro-sphere for stopping bleeding in clinical operation |
| WO2022165877A1 (en) * | 2021-02-05 | 2022-08-11 | 青岛科技大学 | Malic acid-chitosan nanopore hydrogel microsphere, and preparation method therefor and application thereof |
| CN116803482A (en) * | 2023-05-12 | 2023-09-26 | 安徽建筑大学 | Preparation and application method of acid-resistant composite material based on chitosan and graphite-phase carbon nitride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030094719A1 (en) * | 2001-05-02 | 2003-05-22 | Jean-Dean Yang | Method for producing water-insoluble polysaccharides |
| CN102443186A (en) * | 2011-09-30 | 2012-05-09 | 浙江省海洋开发研究院 | Preparation method of epichlorohydrin crosslinked chitosan microspheres |
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2013
- 2013-05-30 CN CN201310223533.1A patent/CN103265720B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030094719A1 (en) * | 2001-05-02 | 2003-05-22 | Jean-Dean Yang | Method for producing water-insoluble polysaccharides |
| CN102443186A (en) * | 2011-09-30 | 2012-05-09 | 浙江省海洋开发研究院 | Preparation method of epichlorohydrin crosslinked chitosan microspheres |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815348A (en) * | 2014-11-28 | 2015-08-05 | 杨子中 | Preparation method for composite micro-sphere for stopping bleeding in clinical operation |
| CN104549172A (en) * | 2015-01-26 | 2015-04-29 | 重庆大学 | Method for preparing sulfydryl-modified chitosan short hole microspheres |
| CN104549172B (en) * | 2015-01-26 | 2017-02-22 | 重庆大学 | Method for preparing sulfydryl-modified chitosan short hole microspheres |
| WO2022165877A1 (en) * | 2021-02-05 | 2022-08-11 | 青岛科技大学 | Malic acid-chitosan nanopore hydrogel microsphere, and preparation method therefor and application thereof |
| CN116803482A (en) * | 2023-05-12 | 2023-09-26 | 安徽建筑大学 | Preparation and application method of acid-resistant composite material based on chitosan and graphite-phase carbon nitride |
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