CN103480030A - Method for preparing high-strength chitosan hydrogel through thermal gelation-nearly neutral water bath - Google Patents
Method for preparing high-strength chitosan hydrogel through thermal gelation-nearly neutral water bath Download PDFInfo
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- CN103480030A CN103480030A CN201310405057.5A CN201310405057A CN103480030A CN 103480030 A CN103480030 A CN 103480030A CN 201310405057 A CN201310405057 A CN 201310405057A CN 103480030 A CN103480030 A CN 103480030A
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Abstract
The invention discloses a method for preparing high-strength chitosan hydrogel through thermal gelation-nearly neutral water bath. The method comprises the following steps: preparing 0.5-8.0wt% of chitosan, 4.0-6.0wt% of lithium hydroxide, 4.0-8.0wt% of potassium hydroxide and water, mixing and dissolving the components, freezing, thawing, filtering, centrifuging and defoaming the mixture, injecting the mixture into a gel preparation mould to carry out thermal gelation, and then, demolding and soaking in water, removing the alkaline hydroxide in nearly neutral water bath by utilizing phenolphthalein or bromothymol blue as an indicator, and removing the neutral salt and the indicator by using deionized water, thus obtaining the high-strength chitosan hydrogel.
Description
Technical field
The present invention relates to a kind of preparation method of aquagel, especially with Thermogelling-nearly neutral water-bath, prepare the method for high strength aquagel.
Background technology
Chitosan is second largest class natural organic high-molecular material except cellulose, is also unique natural alkaline polysaccharide.Chitosan has multiple advantageous property: biocompatibility, antibiotic property, reduced immunogenicity, hypotoxicity, biological degradability etc.Many advantageous properties make chitosan all enjoy favor in fields such as food industry, textile industry, environmental conservation, medicines and health protections.And its source and abundant reserves make the development and application of chitosan material have concurrently and improve human lives's quality and the double meaning made full use of the natural resources.
The polysaccharide cellular construction of chitosan, determine in its molecule and a large amount of hydrogen bonds of intermolecular existence, thereby can form the network structure hydrogel.Aquagel has good hydrophilic and biocompatibility, in fields such as hygienic article, medicine carrying, burn dressing, applications well is arranged.Yet, the aquagel intensity space that still is much improved.Along with innovation and the improvement of its mechanical performance, not only in application at present, the intensity relevant issues can be resolved, and may open up new application.At present, cross-linking modified method commonly used improves aquagel intensity, comprising: use the chemical cross-linking agents such as glutaraldehyde, or strengthen physical crosslinking with change Hyarogen-bondings such as polyvinylpyrrolidones.But all there is its drawback in two kinds of methods: the biocompatibility of many cross-linking agent is indefinite, or has certain bio-toxicity, and the blend meeting weakens chitosan intrinsic advantage characteristic.Therefore, developing a kind of high strength pure chitosan hydrogel is significant and challenges.
Due to chitosan macromole characteristic, be difficult to carry out the processing methods such as melting, therefore, at first the preparation of chitosan material needs to make solution, thereby gives the chitosan processability.Chitosan is dissolvable in water in multiple mineral acid and some organic acid, as dilute hydrochloric acid, acetic acid etc., with the polycation form, exists in solution.Acid catalyzed hydrolysis, in put procedure, occurs in the acid solution of chitosan, and its main chain constantly ruptures because of hydrolysis, causes molecular weight to reduce and the Polydispersity increase, and then has a strong impact on every qualities such as mechanical performance of goods.
Summary of the invention
The purpose of this invention is to provide a kind of Thermogelling-nearly neutral water-bath and prepare the method for high strength aquagel, to improve the aquagel mechanical performance, widen the chitosan hydrogel material application.
Thermogelling of the present invention-nearly neutral water-bath prepares the method for high strength aquagel, comprises the steps:
1) by weight percentage containing measuring each component: chitosan 0.5 ~ 8.0%, Lithium hydrate 4.0 ~ 6.0 %, potassium hydroxide 4.0 ~ 8.0%, all the other are water, swelling 1 ~ 3h after said components is mixed, by swelling solution at-60 ℃ ~-20 ℃ freezing 1 ~ 4h, then at room temperature thaw, and be aided with stirring, obtain chitosan alkaline aqueous solution system;
2) chitosan alkaline aqueous solution system step 1) made is filtered, centrifugal, deaeration, obtains still chitosan alkaline aqueous solution;
3) by step 2) the still chitosan alkaline aqueous solution that makes injects gel and prepares mould, puts into baking oven Thermogelling 30 ~ 120min at 40 ~ 80 ℃ of temperature, by the gel demoulding;
4) the chitosan base gel after the demoulding is immersed in the water, take phenolphthalein or bromthymol blue as indicator, with the inner alkaline hydrated oxide diffusion of gel, in water-bath, add the H that mass concentration is 1.0 ~ 2.0%
2sO
4, keep the nearly neutral state of water-bath, dipping bath to indicator shows that solution no longer is alkalescence, the aquagel of the alkaline hydrated oxide that is removed, then by its dipping bath in deionized water, remove residual neutral salt and indicator.
The invention has the advantages that:
The present invention is dissolved chitosan with the basic solvent system, has avoided the adverse effect that in acid chitosan solution, acid-catalyzed hydrolysis brings.
Use the Thermogelling method, make chitosan solution change the alkaline water gel into, after the demoulding, the goods all surface all contacts water-bath, starts diffusion process simultaneously, and it is fast that speed is removed in inner alkaline hydrated oxide diffusion, and goods all directions character homogeneous.
Use dilution heat of sulfuric acid to adjust water-bath, make it remain nearly neutral state, avoid using large water gaging to clean the higher concentration alkaline hydrated oxide; Simultaneously, gel is inner exists larger alkaline hydrated oxide concentration difference all the time with water-bath, can keep higher diffusion velocity, improves the hydrogel preparation efficiency.
Coagulating bath remains nearly neutral state, avoids hydrogel swelling deliquescing in the sulphuric acid coagulating bath, stops the adverse effects such as hydrogel articles decortication, deliquescing, obtains evenly and the high strength aquagel.
The specific embodiment
Embodiment 1:
1) get chitosan 0.5g, Lithium hydrate 4.0g, potassium hydroxide 4.0g, water 91.5g.Swelling 3h after said components is mixed, at-60 ℃ of freezing 1h, then at room temperature thaw swelling solution, and be aided with stirring, obtains chitosan alkaline aqueous solution system.
2) chitosan alkaline aqueous solution system step 1) made is filtered, centrifugal, deaeration, obtains transparent still chitosan alkaline aqueous solution.
3) by step 2) the still chitosan alkaline aqueous solution that makes injects gel and prepares mould, put into baking oven and carry out Thermogelling.Oven temperature is 40 ℃, and the Thermogelling time is 120min, by the gel demoulding.
4) the chitosan base gel after the demoulding is immersed in the water, to remove alkaline hydrated oxide.Take phenolphthalein as indicator, with the inner alkaline hydrated oxide diffusion of gel, in water-bath, add the H that mass concentration is 1.0%
2sO
4, keep the nearly neutral state of water-bath.Dipping bath to indicator shows that solution no longer is alkalescence, the aquagel of the alkaline hydrated oxide that is removed, then by its dipping bath in deionized water, remove residual neutral salt and indicator, obtain the high strength aquagel.When the compression height ratio is 50%, its compressive strength is: 0.31MPa.
Embodiment 2:
1) get chitosan 1.0g, Lithium hydrate 6.0g, potassium hydroxide 4.0g, water 89g.Swelling 1h after said components is mixed, at-20 ℃ of freezing 1h, then at room temperature thaw swelling solution, and be aided with stirring, obtains chitosan alkaline aqueous solution system.
2) chitosan alkaline aqueous solution system step 1) made is filtered, centrifugal, deaeration, obtains transparent still chitosan alkaline aqueous solution.
3) by step 2) the still chitosan alkaline aqueous solution that makes injects gel and prepares mould, put into baking oven and carry out Thermogelling.Oven temperature is 40 ℃, and the Thermogelling time is 30min, by the gel demoulding.
4) the chitosan base gel after the demoulding is immersed in the water, to remove alkaline hydrated oxide.Take bromthymol blue as indicator, with the inner alkaline hydrated oxide diffusion of gel, in water-bath, add the H that mass concentration is 2.0%
2sO
4, keep the nearly neutral state of water-bath.Dipping bath to indicator shows that solution no longer is alkalescence, the aquagel of the alkaline hydrated oxide that is removed, then by its dipping bath in deionized water, remove residual neutral salt and indicator, obtain the high strength aquagel.When the compression height ratio is 50%, its compressive strength is: 0.74MPa.
Embodiment 3:
1) get chitosan 8.0g, Lithium hydrate 6.0g, potassium hydroxide 8.0g, water 78g.Swelling 2h after said components is mixed, at-20 ℃ of freezing 4h, then at room temperature thaw swelling solution, and be aided with stirring, obtains chitosan alkaline aqueous solution system.
2) chitosan alkaline aqueous solution system step 1) made is filtered, centrifugal, deaeration, obtains transparent still chitosan alkaline aqueous solution.
3) by step 2) the still chitosan alkaline aqueous solution that makes injects gel and prepares mould, put into baking oven and carry out Thermogelling.Oven temperature is 80 ℃, and the Thermogelling time is 30min, by the gel demoulding.
4) the chitosan base gel after the demoulding is immersed in the water, to remove alkaline hydrated oxide.Take phenolphthalein as indicator, with the inner alkaline hydrated oxide diffusion of gel, in water-bath, add the H that mass concentration is 1.5%
2sO
4, keep the nearly neutral state of water-bath.Dipping bath to indicator shows that solution no longer is alkalescence, the aquagel of the alkaline hydrated oxide that is removed, then by its dipping bath in deionized water, remove residual neutral salt and indicator, obtain the high strength aquagel.When the compression height ratio is 50%, its compressive strength is: 1.84MPa.
Embodiment 4:
1) get chitosan 6.0g, Lithium hydrate 5.0g, potassium hydroxide 7.0g, water 82g.Swelling 2h after said components is mixed, at-40 ℃ of freezing 4h, then at room temperature thaw swelling solution, and be aided with stirring, obtains chitosan alkaline aqueous solution system.
2) chitosan alkaline aqueous solution system step 1) made is filtered, centrifugal, deaeration, obtains transparent still chitosan alkaline aqueous solution.
3) by step 2) the still chitosan alkaline aqueous solution that makes injects gel and prepares mould, put into baking oven and carry out Thermogelling.Oven temperature is 50 ℃, and the Thermogelling time is 120min, by the gel demoulding.
4) the chitosan base gel after the demoulding is immersed in the water, to remove alkaline hydrated oxide.Take bromthymol blue as indicator, with the inner alkaline hydrated oxide diffusion of gel, in water-bath, add the H that mass concentration is 2.0%
2sO
4, keep the nearly neutral state of water-bath.Dipping bath to indicator shows that solution no longer is alkalescence, the aquagel of the alkaline hydrated oxide that is removed, then by its dipping bath in deionized water, remove residual neutral salt and indicator, obtain the high strength aquagel.When the compression height ratio is 50%, its compressive strength is: 1.41MPa.
Claims (1)
1. Thermogelling-nearly neutral water-bath prepares the method for high strength aquagel, it is characterized in that comprising the steps:
1) by weight percentage containing measuring each component: chitosan 0.5 ~ 8.0%, Lithium hydrate 4.0 ~ 6.0 %, potassium hydroxide 4.0 ~ 8.0%, all the other are water, swelling 1 ~ 3h after said components is mixed, by swelling solution at-60 ℃ ~-20 ℃ freezing 1 ~ 4h, then at room temperature thaw, and be aided with stirring, obtain chitosan alkaline aqueous solution system;
2) chitosan alkaline aqueous solution system step 1) made is filtered, centrifugal, deaeration, obtains still chitosan alkaline aqueous solution;
3) by step 2) the still chitosan alkaline aqueous solution that makes injects gel and prepares mould, puts into baking oven Thermogelling 30 ~ 120min at 40 ~ 80 ℃ of temperature, by the gel demoulding;
4) the chitosan base gel after the demoulding is immersed in the water, take phenolphthalein or bromthymol blue as indicator, with the inner alkaline hydrated oxide diffusion of gel, in water-bath, add the H that mass concentration is 1.0 ~ 2.0%
2sO
4, keep the nearly neutral state of water-bath, dipping bath to indicator shows that solution no longer is alkalescence, the aquagel of the alkaline hydrated oxide that is removed, then by its dipping bath in deionized water, remove residual neutral salt and indicator.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111821953A (en) * | 2020-07-20 | 2020-10-27 | 南昌师范学院 | Preparation method and application of amidoximated polyacrylonitrile grafted magnetic chitosan |
| CN112023110A (en) * | 2020-08-06 | 2020-12-04 | 西安交通大学 | Active antibacterial dressing based on bamboo fungus egg extract |
| CN112029158A (en) * | 2020-07-31 | 2020-12-04 | 华南理工大学 | Chitosan-based composite response membrane with carbon dioxide response behavior and preparation method and application thereof |
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| JP2005008795A (en) * | 2003-06-20 | 2005-01-13 | Se Chemical Kk | Manufacturing process of alkaline chitosan hydrogel and chitosan and chitin fiber |
| WO2006067987A1 (en) * | 2004-12-21 | 2006-06-29 | A School Corporation Kansai University | Neutral chitosan hydrogel and method for producing same |
| CN101215341A (en) * | 2008-01-14 | 2008-07-09 | 浙江大学 | Basic solvent for dissolving chitosan and using method thereof |
| CN101636181A (en) * | 2006-12-11 | 2010-01-27 | 莫尔研究应用有限公司 | Novel injectable chitosan mixtures forming hydrogels |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005008795A (en) * | 2003-06-20 | 2005-01-13 | Se Chemical Kk | Manufacturing process of alkaline chitosan hydrogel and chitosan and chitin fiber |
| WO2006067987A1 (en) * | 2004-12-21 | 2006-06-29 | A School Corporation Kansai University | Neutral chitosan hydrogel and method for producing same |
| CN101636181A (en) * | 2006-12-11 | 2010-01-27 | 莫尔研究应用有限公司 | Novel injectable chitosan mixtures forming hydrogels |
| CN101215341A (en) * | 2008-01-14 | 2008-07-09 | 浙江大学 | Basic solvent for dissolving chitosan and using method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111821953A (en) * | 2020-07-20 | 2020-10-27 | 南昌师范学院 | Preparation method and application of amidoximated polyacrylonitrile grafted magnetic chitosan |
| CN112029158A (en) * | 2020-07-31 | 2020-12-04 | 华南理工大学 | Chitosan-based composite response membrane with carbon dioxide response behavior and preparation method and application thereof |
| CN112029158B (en) * | 2020-07-31 | 2021-06-08 | 华南理工大学 | Chitosan-based composite response membrane with carbon dioxide response behavior and preparation method and application thereof |
| CN112023110A (en) * | 2020-08-06 | 2020-12-04 | 西安交通大学 | Active antibacterial dressing based on bamboo fungus egg extract |
| CN112023110B (en) * | 2020-08-06 | 2021-11-19 | 西安交通大学 | Active antibacterial dressing based on bamboo fungus egg extract |
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