CN101235101B - Preparation method for water-soluble low molecular weight chitosan - Google Patents
Preparation method for water-soluble low molecular weight chitosan Download PDFInfo
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- CN101235101B CN101235101B CN2008100345105A CN200810034510A CN101235101B CN 101235101 B CN101235101 B CN 101235101B CN 2008100345105 A CN2008100345105 A CN 2008100345105A CN 200810034510 A CN200810034510 A CN 200810034510A CN 101235101 B CN101235101 B CN 101235101B
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Abstract
The invention relates to a method for preparing soluble low-molecular-weight chitose via catalyzing, oxidizing and degrading chitose, belonging to the technical field of organic chemical synthesis, which comprises using chitose as material, using metal phthalocyanine dissolved in hydrophobic ion liquid as catalyst and using hydrogen dioxide as oxidant to prepare soluble chitose in a reactor. The invention has mild reaction conditions and even chitose can be completely degraded into soluble chitose at room temperature in short time, the invention has low cost, which eliminates adjuvants as dilute hydrochloric acid and caustic soda, and the catalyst system can be separated from reaction system and be repeatedly used.
Description
Technical field
The present invention relates to a kind of method of chitosan of catalyzing oxidizing degrading Preparation of Chitosan water-soluble low molecular weight, exactly, be a kind ofly to prepare the method for the chitosan of water-soluble low molecular weight, belong to organic chemistry synthetic technical field by the catalytic oxidation of hydrogen peroxide degrade chitosan.
Background technology
Chitosan has another name called chitosan, Viartril-S, takes off caproyl chitin, chitosan, is the product of chitin deacetylation after concentrated base is handled, and is that annual production is only second to cellulosic second largest natural polymer, also is the unique natural alkaline polysaccharide of finding so far.But because it has formed orderly macromolecular structure, chitosan can only be dissolved in the minority diluted acid, can not water-soluble and common organic solvents, and this has limited its application to a great extent.Through the low-molecular weight chitoglycan that degraded obtains, particularly relative molecular mass is 1 * 10
4Following chitosan oligomer, not only water-soluble, also have unique physiologically active and physico-chemical property, thereby range of application is widened greatly.Have the spleen of promotion antibody as chitosan oligomer and generate, suppress the physiological function of tumor growth; Can effectively reduce the cholesterol in liver and the serum; Liver function be can strengthen, gout and stomach ulcer prevented.In addition, it also can be used for foodstuff additive, immobilized enzyme, proteinic purification, aspects such as paper industry and water treatment industry.The method for preparing low-molecular water-soluble chitosan by DeR is broadly divided into enzyme liberating method, oxidation degradation method and acid degradation method three major types.Wherein, oxidative degradation is studied more at present, comprises H
2O
2Method, H
2O
2-NaClO
2Method, H
2O
2-HCl methods etc., other oxidation degradation method also has NaBO
3Method, ClO
2Method, Cl
2Oxidation style etc.H wherein
2O
2Method because of low, the easy processing of cost, pollution-free, be easy to advantages such as industrialization, become the maximum a kind of method of present research and production application.Utilizing the hydrogen peroxide oxidation degrade chitosan to prepare water miscible low-molecular weight chitoglycan carries out usually in two ways, a kind of is to carry out the homogeneous oxidizing method with diluted acid dissolving chitosan, this technology will consume a large amount of acid in process of production, to consume a large amount of alkali simultaneously and come neutralizing acid, the production cost height is difficult for realizing industrialization; Another kind is the heterogeneous oxidization method.As disclosing a kind of method of heterogeneous oxidization degrade chitosan in 51～54 pages of (2002) the 18th the 6th phases of volume of Liu's big equal " polymer material science and engineering ", directly be that to have prepared molecular weight be 2～40,000 low-molecular-weight chitosan to oxygenant oxidation degrade chitosan promptly with the hydrogen peroxide not adding under the situation of catalyzer, but the reaction times is long, need reaction 24 hours, production efficiency is lower.For improving oxidation efficiency, usually need in reaction process, add catalyzer, recently people such as Chinese scholar gold phoenix discloses a kind of method of heterocatalysis oxidative degradation chitosan, i.e. hydrogen peroxide degrade chitosan under the catalysis of phospho-wolframic acid in 34～37 pages of " applied chemistry " (2006) the 23rd volume first phases.Although it is about 12000 water-soluble chitosan to the sticking quality of dividing equally that this method can make degradation of chitosan effectively, catalyzer is difficult to realize reclaiming effectively.
Summary of the invention
The object of the present invention is to provide a kind of reaction conditions gentleness, environmental friendliness, the efficient height, catalyst recirculation is used, the preparation method of the water-soluble low molecular weight chitosan that green degree is high.
For realizing purpose of the present invention, by the following technical solutions.With the chitosan is raw material, is catalyzer with hydrophobic ionic liquid dissolved metal phthalocyanine, and hydrogen peroxide is an oxygenant, prepared in reaction water-soluble chitosan in reactor.Concrete steps are as follows:
The first step is 1 with metal phthalocyanine and hydrophobic ionic liquid by mass ratio: (1～50) is put into reactor and is mixed, and adds aqueous hydrogen peroxide solution and chitosan more successively;
It is 20 ℃～90 ℃ water-bath isothermal reactions 10 minutes～120 minutes that second step will place temperature through the reactor that the first step is handled, leave standstill and be cooled to the room temperature hypsokinesis and pour out supernatant liquid, it is revolved add a large amount of dehydrated alcohols again after inspissation contracts and separate out water miscible low-molecular weight chitoglycan.
Metal phthalocyanine and hydrophobic ionic liquid in the first step of the present invention are preferably 1 by mass ratio: (3～30).
Temperature of reaction in second step of the present invention is preferably 50 ℃～90 ℃.
Reaction times in the present invention second step is preferably 20 minutes～and 80 minutes.
The present invention second is used to separate out water-soluble chitosan in the step organic solvent is preferably ethanol.
The present invention and existing technology comparatively speaking have following remarkable advantage:
(1) reaction conditions gentleness, even at room temperature chitosan just can be degraded to water-soluble chitosan in a short period of time fully.
(2) production cost is low, does not use auxiliary agents such as dilute hydrochloric acid, sodium hydroxide.
(3) catalyst system easily separates with reaction system, and catalyzer can recycle.
Embodiment
Embodiment 1:
The first step, with 0.050g iron-phthalocyanine and 2.0g BMImPF
6Ionic liquid is put into reactor and is mixed, and adds aqueous hydrogen peroxide solution and the 0.10g chitosan of 5.0g 6.0% more successively;
Second step, the reactor through the first step processing is placed temperature is 20 ℃ of water-bath isothermal reactions 10 minutes, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, it is revolved add a large amount of dehydrated alcohols again after inspissation contracts and separate out water miscible low-molecular weight chitoglycan.
The 3rd goes on foot, gets catalyst system reuses, and does not find obviously that the catalytic activity of catalyzer decreases.
Embodiment 2:
The first step, with 0.020g cobalt phthalocyanine and 0.020g HMImBF
4Ionic liquid is put into reactor and is mixed, and adds aqueous hydrogen peroxide solution and the 0.10g chitosan of 5.0g 3.0% more successively;
Second step, the reactor through the first step processing is placed temperature is 40 ℃ of water-bath isothermal reactions 50 minutes, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, it is revolved add a large amount of dehydrated alcohols again after inspissation contracts and separate out water miscible low-molecular weight chitoglycan.
The 3rd goes on foot, gets catalyst system reuses, and does not find obviously that the catalytic activity of catalyzer decreases.
Embodiment 3:
The first step, with 0.10g copper phthalocyanine and 0.30g BMImPF
6Ionic liquid is put into reactor and is mixed, and adds aqueous hydrogen peroxide solution and the 0.10g chitosan of 5.0g 6.0% more successively;
Second step, the reactor through the first step processing is placed temperature is 90 ℃ of water-bath isothermal reactions 20 minutes, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, it is revolved add a large amount of dehydrated alcohols again after inspissation contracts and separate out water miscible low-molecular weight chitoglycan.
The 3rd goes on foot, gets catalyst system reuses, and does not find obviously that the catalytic activity of catalyzer decreases.
Embodiment 4:
The first step, with 0.050g vanadyl phthalocyanine and 2.5g[BMIm] [Tf
2N] ionic liquid puts into reactor and mixes, and adds aqueous hydrogen peroxide solution and the 0.10g chitosan of 5.0g 9.0% more successively;
Second step, the reactor through the first step processing is placed temperature is 60 ℃ of water-bath isothermal reactions 60 minutes, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, it is revolved add a large amount of dehydrated alcohols again after inspissation contracts and separate out water miscible low-molecular weight chitoglycan.
The 3rd goes on foot, gets catalyst system reuses, and does not find obviously that the catalytic activity of catalyzer decreases.
Embodiment 5:
The first step, with 0.20g iron-phthalocyanine and 3.0g[HMIm] [Tf
2N] ionic liquid puts into reactor and mixes, and adds aqueous hydrogen peroxide solution and the 0.10g chitosan of 5.0g 8.0% more successively;
Second step, the reactor through the first step processing is placed temperature is 70 ℃ of water-bath isothermal reactions 80 minutes, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, it is revolved add a large amount of dehydrated alcohols again after inspissation contracts and separate out water miscible low-molecular weight chitoglycan.
The 3rd goes on foot, gets catalyst system reuses, and does not find obviously that the catalytic activity of catalyzer decreases.
Embodiment 6:
The first step, with 0.15g copper phthalocyanine and 2.5g 0MImPF
6Ionic liquid is put into reactor and is mixed, and adds aqueous hydrogen peroxide solution and the 0.10g chitosan of 5.0g 10.0% more successively;
Second step, the reactor through the first step processing is placed temperature is 60 ℃ of water-bath isothermal reactions 100 minutes, leaves standstill to be cooled to the room temperature hypsokinesis and to pour out supernatant liquid, it is revolved add a large amount of dehydrated alcohols again after inspissation contracts and separate out water miscible low-molecular weight chitoglycan.
The 3rd goes on foot, gets catalyst system reuses, and does not find obviously that the catalytic activity of catalyzer decreases.
Claims (6)
1. the preparation method of a water-soluble low molecular weight chitosan, with the chitosan is raw material, is catalyzer with hydrophobic ionic liquid dissolved metal phthalocyanine, and hydrogen peroxide is an oxygenant, the chitosan of prepared in reaction water-soluble low molecular weight is characterized in that may further comprise the steps:
The first step: is 1 with metal phthalocyanine and hydrophobic ionic liquid by mass ratio: (1～50) is put into reactor and is mixed, and adds aqueous hydrogen peroxide solution and chitosan more successively;
Second step: will place temperature through the reactor that the first step is handled is 20 ℃～90 ℃ water-bath isothermal reactions 10 minutes～120 minutes, leave standstill and be cooled to the room temperature hypsokinesis and pour out supernatant liquid, it is revolved add a large amount of dehydrated alcohols again after inspissation contracts and separate out water miscible low-molecular weight chitoglycan.
2. the preparation method of water-soluble low molecular weight chitosan as claimed in claim 1 is characterized in that the metal phthalocyanine in the first step and the mass ratio of hydrophobic ionic liquid are 1: (3～30).
3. the preparation method of water-soluble low molecular weight chitosan as claimed in claim 1 is characterized in that the temperature of reaction in second step is 50 ℃～90 ℃.
4. the preparation method of water-soluble low molecular weight chitosan as claimed in claim 1 is characterized in that the reaction times in second step is preferably 20 minutes～80 minutes.
5. the preparation method of water-soluble low molecular weight chitosan as claimed in claim 1 is characterized in that described metal phthalocyanine is iron-phthalocyanine, cobalt phthalocyanine, copper phthalocyanine or vanadyl phthalocyanine.
6. the preparation method of water-soluble low molecular weight chitosan as claimed in claim 1 is characterized in that described hydrophobic ionic liquid is BMImPF
6Ionic liquid, HMImBF
4Ionic liquid, [BMIm] [Tf
2N] ionic liquid, [HMIm] [Tf
2N] ionic liquid, OMImPF
6Ionic liquid.
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| CN2008100345105A CN101235101B (en) | 2008-03-13 | 2008-03-13 | Preparation method for water-soluble low molecular weight chitosan |
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| CN2008100345105A CN101235101B (en) | 2008-03-13 | 2008-03-13 | Preparation method for water-soluble low molecular weight chitosan |
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| CN101235101B true CN101235101B (en) | 2010-06-02 |
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| CN108484790A (en) * | 2018-05-24 | 2018-09-04 | 青岛科技大学 | A kind of preparation method for the water soluble amino polysaccharide that molecular weight is controllable |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3072501B2 (en) * | 1995-11-09 | 2000-07-31 | 原子燃料工業株式会社 | A holding and rotating device for measuring and inspecting the accuracy of welding position of a rectangular water channel in a fuel assembly for a boiling water reactor. |
| CN1460687A (en) * | 2003-04-24 | 2003-12-10 | 中国科学院兰州化学物理研究所 | Method for preparing high-qualtiy chitosan |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3072501B2 (en) * | 1995-11-09 | 2000-07-31 | 原子燃料工業株式会社 | A holding and rotating device for measuring and inspecting the accuracy of welding position of a rectangular water channel in a fuel assembly for a boiling water reactor. |
| CN1460687A (en) * | 2003-04-24 | 2003-12-10 | 中国科学院兰州化学物理研究所 | Method for preparing high-qualtiy chitosan |
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