CN102321194B - Method for preparing water-soluble chitosan with low molecular weight - Google Patents
Method for preparing water-soluble chitosan with low molecular weight Download PDFInfo
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Abstract
The invention provides a method for preparing water-soluble chitosan with a low molecular weight and relates to chitosan. The invention provides a method for preparing water-soluble chitosan with low molecular weight which has the advantages of low cost, safety, economy, environmental protection and industrialization possibility. The method comprises the following steps: preparing an organic acidity aqueous solution, then adding chitosan solid to stir until the system is formed as a suspended state, performing a first ultrasound; adding hydrogen peroxide, carrying out a second ultrasound after uniformly stirring; adding hydrogen peroxide, uniformly stirring and performing a third ultrasound; decompressing and filtering the obtained solution, spray drying to obtain the powdery water-soluble chitosan with the low molecular weight.
Description
Technical field
The present invention relates to a kind of chitosan, especially relate to a kind of preparation method of water-soluble low molecular weight chitosan.
Background technology
Chitosan is the deacetylated product of chitin; reserves at occurring in nature are very abundant; extensively be present in the cell walls of the shell of shrimp, crab and insect and algae, mushroom; being that annual production is only second to cellulosic second largest natural polymer, also is the unique natural alkaline polysaccharide of finding up to now.Chitosan is that molecular weight does not wait to millions of at hundreds of thousands of usually, because its intramolecularly has stronger hydrogen bond action, can only be dissolved in the dilute acid soln, and can not be directly soluble in water, cause use range to be subjected to bigger restriction.Through degraded back relative molecular weight less than 3000 low-molecular weight chitoglycan, good characteristic when not only having kept polymer also because solvability is strong, is absorbed and used easily, further show physiologically active and the functional property of many uniquenesses, i.e. activation and proliferation bifidus bacillus in human intestinal; Improve the macrophage phagocytic ability; Promote the growth of spleen antibody, suppress growth of tumour cell; Bring high blood pressure down, blood sugar, blood fat, the absorption cholesterol; In microenvironment, have strong bacteriostatic action and the wettability power etc. of significantly preserving moisture; Along with the research of each molecular weight fragment of low-molecular weight chitoglycan deepens continuously, the function of low-molecular weight chitoglycan will be clearer and more definite, and its range of application also can be more extensive.
At present, countries in the world are very many to the preparation method's of low-molecular weight chitoglycan research, and main preparation methods has acid degradation method, oxidation degradation method, enzyme liberating method, synthesis method and mechanical degradation method.The acid degradation method is one of preparation monose and a series of corresponding low-molecular weight chitoglycan main paties, but the bad control of acid degradation method, poor selectivity, separation and purification be difficulty relatively, productive rate is lower, the monose that when the preparation low-molecular weight chitoglycan, mainly obtains, next is disaccharide, is difficult to obtain the low-molecular weight chitoglycan of required activity; Oxidation degradation method is to study more method, wherein H at present
2O
2Oxidation style more has the lot of documents report, but the greatest problem that oxidative degradation exists is that reaction process is wayward, and brown stain takes place easily, has introduced various reaction reagents in degradation process, has increased the difficulty of control degradation side reaction and degraded product separation and purification; The enzyme liberating method be with specificity or non-specificity enzyme to chitosan biodegrade method, can access the lower oligose of averagemolecular wt amount and monose.In whole degradation process, do not have other reaction reagent and add, be unlikely to take place other side reaction, the degradation condition gentleness, degradation process and product molecular mass distribute more easy to control, and shortcoming is that employed enzyme is comparatively special, the cost height, the production cycle is long.The research of synthesis method has obtained bigger progress, process such as sloughs but building-up process relates to radical protection and group, and step is comparatively complicated; at present main research and utilization enzyme process is synthetic; obtain certain achievement, but also rested on laboratory stage, can't realize industrialization.The mechanical degradation method mainly is to utilize physics modes such as microwave, ultrasonic wave, gamma-rays to handle also degradable chitosan, but the mechanical degradation method also exists certain limitation (as: crosslinking reaction to take place easily in the microwave degradation process; Ultrasonic degradation efficient is lower, and degradation speed is slow excessively; Gamma-ray contamination and irradiation source are difficult to the assurance problem), also be not easy to realize industrialization at present.
Chinese patent CN101235101 discloses a kind of method of chitosan of catalyzing oxidizing degrading Preparation of Chitosan water-soluble low molecular weight, be raw material with the chitosan, metal phthalocyanine with the hydrophobic ionic liquid dissolving is catalyzer, hydrogen peroxide is oxygenant, prepared in reaction water-soluble chitosan in reactor.
Summary of the invention
The object of the present invention is to provide that a kind of cost is low, the preparation method of safety economy, environmental protection, water-soluble low molecular weight chitosan capable of being industrialized.
The present invention includes following steps:
1) the preparation aqueous solutions of organic acids adds the chitosan solid again and is stirred to system and is suspension, and the 1st time ultrasonic;
2) add hydrogen peroxide, the back the 2nd time of stirring is ultrasonic;
3) add hydrogen peroxide, the back the 3rd time of stirring is ultrasonic;
4) solution decompression with the step 3) gained filters, and spraying drying gets the powdery, water-soluble low-molecular weight chitoglycan.
In step 1), described organic acid can be selected from a kind of in acetic acid, citric acid, oxalic acid, succsinic acid, oxysuccinic acid, the tartrate etc.; The pH of described aqueous solutions of organic acids can be 3～5; The mass percentage concentration of described chitosan can be 20～25%; Described the 1st ultrasonic frequency can be 28Hz, and the 1st ultrasonic time can be 0.5～1h, can feed water of condensation when ultrasonic, and the control water temperature can be less than 50 ℃.
In step 2) in, the add-on of described hydrogen peroxide can be 10%～20% of chitosan by mass percentage, and described the 2nd ultrasonic frequency can be 28Hz, and the 2nd ultrasonic time can be 1～1.5h, can feed water of condensation when ultrasonic, the control water temperature can be less than 50 ℃.
In step 3), the add-on of described hydrogen peroxide can be 30%～50% of chitosan by mass percentage, and described the 3rd ultrasonic frequency can be 28Hz, and the 3rd ultrasonic time can be 1.5～2h, can feed water of condensation when ultrasonic, the control water temperature can be less than 50 ℃.
The present invention utilizes ultrasonic wave assistant chemical DeR process, and the preparation low-molecular weight chitoglycan compares with traditional technology, has the following advantages:
1) product colour of preparing is shallow, illustrate and do not have tangible brown stain, production cost is lower, and the low-molecular weight chitoglycan range of molecular weight distributions for preparing is narrower, can obtain the low-molecular weight chitoglycan product of molecular weight below 3000, overcome and utilized the low-molecular weight chitoglycan product oxidizing brown stain of chemical method preparation more serious merely, color is darker, the shortcoming that range of molecular weight distributions is wideer.
2) utilize ultrasonic wave to assist the hydrogen peroxide degradation chitosan, overcome the shortcoming of utilizing ultrasonic degradation efficient lower merely, the problem that it is aftertreatment and the easy brown stain of product that the while also overcomes simple use hydrogen peroxide degradation.
3) utilize ultrasonic wave to assist the hydrogen peroxide degradation chitosan, degradation time shortens greatly, overcomes the enzymic degradation chitosan overlong time of generally using at present, the shortcoming that efficient is very low.
4) at present because technical limitation, the low-molecular weight chitoglycan molecular weight product of market sale is bigger, and the product that the present invention produces is on the basis that keeps better quality, and molecular weight is less, activity is higher, and easy to operate, safety economy, yield height, to not influence of environment, speed of response is fast, can overcome brown stain in the reaction process, easy realization of industrialization more effectively.
5) the low-molecular weight chitoglycan percentage composition of the aqueous solution after the degraded is higher, does not need reconcentration, and directly spraying drying obtains pulverulent solids, reduces production link, has saved a large amount of costs.
Description of drawings
Fig. 1 is the infrared spectrum of embodiment 1.In Fig. 1, X-coordinate is wave number Wavenumber (cm
-1), ordinate zou is transmittance Transmittance (%).
Fig. 2 is the infrared spectrum of embodiment 2.In Fig. 2, X-coordinate is wave number Wavenumber (cm
-1), ordinate zou is transmittance Transmittance (%).
Embodiment
Following examples will the present invention is further illustrated by reference to the accompanying drawings.
Embodiment 1
The acetic acid solution of preparation about pH=3 slowly adds mass concentration and is 20% chitosan solid, stirs, and feeds water of condensation, and the control water temperature is no more than 50 ℃, ultrasonic 0.5h; Add hydrogen peroxide to 10% of chitosan mass, the ultrasonic 1.5h in back stirs.And then adding hydrogen peroxide to 30% of chitosan mass, the ultrasonic 2h in back that stirs filters gained solution, directly carries out spraying drying and makes pulverulent solids.Molecular weight product is referring to table 1.
Table 1
| Sample | Molecular weight |
| Embodiment 1 | 2240 |
| Embodiment 2 | 2215 |
Annotate: above data are provided by analytic centre of Beijing University of Chemical Technology.
Embodiment 2
The acetic acid solution of preparation about pH=4 slowly adds mass concentration and is 25% chitosan solid, stirs, and feeds water of condensation, and the control water temperature is no more than 50 ℃, ultrasonic 1h; Add hydrogen peroxide to 20% of chitosan mass, the ultrasonic 1h in back stirs.And then adding hydrogen peroxide to 40% of chitosan mass, the ultrasonic 1.8h in back that stirs filters gained solution, directly carries out spraying drying and makes pulverulent solids.Molecular weight product is referring to table 1.
By Fig. 1 and 2 as seen, degraded back gained low-molecular weight chitoglycan is at 3450cm
-1(υ O-H, υ NH
2), 1650cm
-1(υ C=O), 1550cm
-1(υ N-H), 1375cm
-1(υ-CH
3), 1255cm
-1(υ C-H), 1080cm
-1(υ C-O-C), 897cm
-1(υ ring) has absorption peak.
Embodiment 3
The acetic acid solution of preparation about pH=5 slowly adds mass concentration and is 22% chitosan solid, stirs, and feeds water of condensation, and the control water temperature is no more than 50 ℃, ultrasonic 0.8h; Add hydrogen peroxide to 18% of chitosan mass, the ultrasonic 1.2h in back stirs.And then adding hydrogen peroxide to 50% of chitosan mass, the ultrasonic 1.5h in back that stirs filters gained solution, directly carries out spraying drying and makes pulverulent solids.
Change the acetic acid in above-described embodiment into other organic acid, be respectively citric acid, oxalic acid, succsinic acid, oxysuccinic acid, tartrate, when pH was transferred to numerical value among the embodiment, other steps were identical.
Claims (5)
1. the preparation method of water-soluble low molecular weight chitosan is characterized in that may further comprise the steps:
1) the preparation aqueous solutions of organic acids adds the chitosan solid again and is stirred to system and is suspension, and the 1st time ultrasonic, and the pH of described aqueous solutions of organic acids is 3～5; The mass percentage concentration of described chitosan is 20%～25%;
2) add hydrogen peroxide, the back the 2nd time of stirring is ultrasonic, and the add-on of described hydrogen peroxide is 10%～20% of chitosan by mass percentage;
3) add hydrogen peroxide, the back the 3rd time of stirring is ultrasonic, and the add-on of described hydrogen peroxide is 30%～50% of chitosan by mass percentage;
4) solution decompression with the step 3) gained filters, and spraying drying gets the powdery, water-soluble low-molecular weight chitoglycan.
2. the preparation method of water-soluble low molecular weight chitosan as claimed in claim 1 is characterized in that in step 1), and described organic acid is selected from a kind of in acetic acid, citric acid, oxalic acid, succsinic acid, oxysuccinic acid, the tartrate.
3. the preparation method of water-soluble low molecular weight chitosan as claimed in claim 1 is characterized in that in step 1), and described the 1st ultrasonic frequency is 28kHz, and the 1st ultrasonic time is 0.5～1h, feeds water of condensation when ultrasonic, and the control water temperature is less than 50 ℃.
4. the preparation method of water-soluble low molecular weight chitosan as claimed in claim 1 is characterized in that in step 2) in, described the 2nd ultrasonic frequency is 28kHz, and the 2nd ultrasonic time is 1～1.5h, feeds water of condensation when ultrasonic, and the control water temperature is less than 50 ℃.
5. the preparation method of water-soluble low molecular weight chitosan as claimed in claim 1 is characterized in that in step 3), and described the 3rd ultrasonic frequency is 28kHz, and the 3rd ultrasonic time is 1.5～2h, feeds water of condensation when ultrasonic, and the control water temperature is less than 50 ℃.
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| CN103360514B (en) * | 2013-06-24 | 2015-08-26 | 广西民族大学 | A kind of fast degradation prepares the method for water soluble oligo-chitosan |
| CN104031177A (en) * | 2014-06-30 | 2014-09-10 | 赖禄波 | Method for degrading chitosan |
| CN104488955A (en) * | 2014-12-04 | 2015-04-08 | 苏州市新巷农艺科技园 | Preparation method of environment-friendly flower growth promoter |
| CN105949350A (en) * | 2016-06-14 | 2016-09-21 | 王斐芬 | Chitosan oligosaccharide preparation method |
| US9862780B1 (en) | 2017-01-24 | 2018-01-09 | Jordan University Of Science And Technology | Process of producing and method of using soluble high molecular-weight chitosan |
| CN113234774A (en) * | 2021-05-27 | 2021-08-10 | 厦门海洋职业技术学院 | Preparation method of chitosan oligosaccharide with high amino content |
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| CN1235915C (en) * | 2003-10-23 | 2006-01-11 | 上海交通大学 | Fast degradation method of preparing molecular weight controllable chitosan |
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