CN110713556A - Method for preparing carboxymethyl chitosan by using Antarctic krill shells - Google Patents
Method for preparing carboxymethyl chitosan by using Antarctic krill shells Download PDFInfo
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
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- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The invention relates to the field of preparation of chitosan derivatives, and provides a method for preparing carboxymethyl chitosan by utilizing Antarctic krill shells, aiming at the problems of multiple steps and dangerous reagents in the existing preparation of carboxymethyl chitosan, which comprises the following steps: 1) pretreatment: cleaning, drying, crushing and sieving antarctic krill shells, sequentially decalcifying, deproteinizing and decoloring; 2) adding the product obtained in the step 1) into a sodium hydroxide solution for reaction at the temperature of 120-140 ℃ for 4-7h, adjusting to be neutral after the reaction is finished, filtering and drying to obtain chitosan; 3) dissolving chitosan in acetic acid solution, adding methanol for dilution and stirring to obtain chitosan solution, dissolving succinic anhydride in acetone, adding into the chitosan solution, reacting to obtain viscous solution, adjusting pH to 9-11, washing with acetone solution, and freeze drying to obtain carboxymethyl chitosan. The method has the advantages of saving alkalization treatment, avoiding using isopropanol and chloroacetic acid, having higher substitution degree, improving operation environment and simplifying flow.
Description
Technical Field
The invention relates to the field of preparation of chitosan derivatives, in particular to a method for preparing carboxymethyl chitosan by using antarctic krill shells.
Background
A large amount of waste such as shrimp heads, shrimp shells and the like can be generated in the treatment process of the antarctic krill, most of the waste is discharged into the sea, so that not only is the resource seriously wasted, but also the marine ecological environment is polluted. The krill shells contain a large amount of chitin, and the krill is small and thin, so that the chitin can be easily extracted from the krill shells. Chitosan can be obtained by deacetylating chitin, but the chitosan has large molecular weight, poor water solubility and low utilization rate of human body, and the application of the chitosan is limited, so that the chitosan can be chemically modified to become a functional biological material. The carboxymethyl chitosan as a chitosan derivative has various characteristics such as good biodegradability, biocompatibility, adhesiveness and the like, and can be widely applied to the fields of biotechnology, medicine, adsorbing materials and the like. More importantly, in a drug delivery system, because the carboxymethyl chitosan contains amino and carboxyl, when the carboxymethyl chitosan meets a weak acid environment of lysosome, a reversible protonation-deprotonation reaction can occur, and a pH response effect is exerted; the application of the adsorbent to the adsorption of pollutants (such as heavy metals and dyes) can enhance the interaction between the pollutants and the adsorbent.
At present, chitosan powder is used as a raw material in a preparation method of carboxymethyl chitosan for industrial production, and chloroacetic acid is dripped into an isopropanol reaction solvent for grafting reaction after alkalization treatment, so that the production process has many problems: 1. the alkalization process needs sodium hydroxide concentrated alkali liquor and high-temperature treatment, and the alkali consumption in the preparation process and the water consumption in the process of after-treatment to neutrality are large; 2. chloroacetic acid and sodium hydroxide are neutralized in the early stage of the reaction for preparing carboxymethyl chitosan from chitosan, heat is released violently, chloroacetic acid is hydrolyzed in a large amount, byproducts such as diglycolic acid are more, the carboxylation degree is easily influenced by temperature fluctuation, the reaction speed is slow, the reaction time is longer by more than 20 hours, the working procedures are complex during post-treatment purification, and the cost is higher; 3. hazard of chloroacetic acid: the chloroacetic acid solution used in industrial production is prepared by adding ethanol into solid chloroacetic acid, so that the volatility of the chloroacetic acid is accelerated, the chloroacetic acid solution can be rapidly absorbed in a large amount after high-concentration product steam is inhaled or the skin contacts the solution, acute poisoning is caused, the product acid mist with low concentration is frequently contacted, headache and dizziness can occur, toxic corrosive smoke is generated by high-temperature decomposition, and the chloroacetic acid has risks in each link of transportation, storage, use and the like, so that the industrial production is seriously influenced.
Disclosure of Invention
The invention provides a method for preparing carboxymethyl chitosan by utilizing Antarctic krill shells, aiming at overcoming the problems of multiple steps and dangerous reagents in the existing preparation of carboxymethyl chitosan, and the method has higher substitution degree under the conditions of omitting alkalization treatment and avoiding the use of isopropanol and chloroacetic acid, greatly improves the production operation environment and simplifies the production flow.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing carboxymethyl chitosan by using Antarctic krill shells comprises the following steps:
1) pretreatment: cleaning, drying and crushing euphausia superba shells, sieving the euphausia superba shells through a 60-80-mesh sieve, and sequentially decalcifying, deproteinizing and decoloring;
2) deacetylation: adding the product obtained in the step 1) into a sodium hydroxide solution for reaction at the temperature of 120-140 ℃ for 4-7h, adjusting the pH value to be neutral after the reaction is finished, filtering and drying to obtain chitosan;
3) carboxymethylation: dissolving chitosan in an acetic acid solution, adding methanol for dilution and stirring to obtain a chitosan solution, dissolving succinic anhydride in acetone, adding the chitosan solution, reacting for 10-20 h to obtain a viscous solution, adjusting the pH value to 9-11 with a NaOH solution, washing with an acetone solution, and freeze-drying to obtain carboxymethyl chitosan.
In the conventional reaction, isopropanol is used as a solvent, and chitosan is subjected to alkalization treatment and then is dropwise added with chloroacetic acid to perform grafting reaction. Because the chitosan is a higher crystalline region polymer and has different crystalline states, if the alkalization reaction is not carried out, the chloroacetic acid is directly added for carboxymethylation reaction, reaction reagents are not easy to enter a crystallization region, so that the reaction time is longer, most chloroacetic acid does not permeate into the particles, the side reaction is serious, and the utilization rate of the chloroacetic acid is low. The chitosan is dissolved in an acid solution, the succinic anhydride is insoluble in water and soluble in acetone, and the water and the acetone are soluble in each other, so that the method adopts the acetic acid-acetone as a reaction medium to carry out the reaction in a homogeneous system. The ammonium salt formed by the action of the amino group of the chitosan and the proton in the acetic acid can destroy the hydrogen bond between the molecules of the solid chitosan, so that the chitosan exists in the acetic acid-acetone reaction medium in the form of electrolyte, which is beneficial to the reaction, and the alkalization treatment is not needed any more to improve the reaction activity, thereby saving the alkali and reducing the reaction steps. Chloroacetic acid is dropwise added into the isopropanol solution, the pungent smell of the working environment is large, the reaction system is neutralized with sodium hydroxide in the early stage to release heat violently, the temperature of the reaction system is difficult to control, a large number of byproducts are generated, and the requirements on early-stage reaction cooling and later-stage reaction heating of reaction equipment are high. The succinic anhydride is adopted to replace chloroacetic acid for production, the operation is simple and convenient, the reaction condition is mild, the grafting rate is high, the reaction process is environment-friendly, and the solid succinic anhydride is more convenient to transport and store than irritant chloroacetic acid.
Preferably, the drying temperature in the step 1) is 40-50 ℃, the decalcifying reagent is a mixed acid solution formed by mixing hydrochloric acid and phosphoric acid in a volume ratio of (4-7):1, and 3-6 mL of the mixed acid solution is added into each 1 g of the shell of the antarctic krill and stirred for 5-10 min. The decalcification efficiency is improved by using a mixed acid solution of hydrochloric acid and phosphoric acid.
Preferably, the mass concentration of the sodium hydroxide solution in the step 2) is 40-50%, and 10-30 mL of the sodium hydroxide solution is added to 1 g of the product in the step 1).
Preferably, the deacetylation degree of chitosan in the step 2) is 40-60%.
Preferably, the mass ratio of the chitosan to the succinic anhydride in the step 3) is 1 (1-3).
Preferably, the concentration of the acetic acid solution in the step 3) is more than 1%, and the reaction temperature is 10-50 ℃.
Preferably, the freeze-drying in step 3) is: freezing at-50 deg.C to-10 deg.C for 4-10 hr to obtain solid, and drying under vacuum of atmospheric pressure below 15Pa for 6-8 hr.
Therefore, the invention has the following beneficial effects: (1) the invention adopts acetic acid-acetone as a reaction medium, so that the reaction is carried out in a homogeneous system, and the ammonium salt formed by the action of the amino group of the chitosan and the proton in the acetic acid can destroy the hydrogen bond between molecules of the solid chitosan, so that the chitosan exists in the acetic acid-acetone reaction medium in the form of electrolyte, which is beneficial to the reaction, and the alkalization treatment is not needed any more to improve the reaction activity, thereby saving alkali and reducing the reaction steps; (2) chloroacetic acid is dropwise added into the isopropanol solution, the pungent smell of the working environment is large, the reaction is violently released by neutralization with sodium hydroxide in the early stage of the reaction, the temperature of the reaction system is difficult to control, and the requirements on the early-stage reaction temperature reduction and the later-stage reaction temperature rise of reaction equipment are high. The succinic anhydride is adopted to replace chloroacetic acid for production, the operation is simple and convenient, the reaction condition is mild, the reaction process is environment-friendly, and the solid succinic anhydride is more convenient to transport and store than irritant chloroacetic acid; (3) the reaction is mild, the side reaction is less, the grafting rate is high, and the utilization rate of the reaction reagent is improved.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
1) Cleaning antarctic krill shells, drying at 40 ℃ for 14 h, crushing, and sieving with a 60-mesh sieve; firstly, decalcification: weighing 50 g of shrimp shell powder, adding 150 mL of mixed acid (hydrochloric acid and phosphoric acid are mixed according to a volume ratio of 7: 1) at 25 ℃, electromagnetically stirring for 5 min, washing to be neutral, performing suction filtration, washing for 10min by using hydrochloric acid solution with the concentration of 3%, repeating for 2 times, filtering to remove acid solution, and washing to be neutral by using water; and (3) deproteinization: adding into 50 mL of 8% sodium hydroxide solution, stirring in boiling water bath for 6 h, centrifuging at 4800 r/min for 22 min, filtering, and washing with distilled water at room temperature to neutrality; then, decoloring: adding 50 mL of hydrogen peroxide with the mass concentration of 6%, stirring at room temperature for 5 hours, washing with distilled water to be neutral, and performing suction filtration;
2) adding 10 mL of sodium hydroxide solution into 1) of the product, adding 40% of sodium hydroxide solution, reacting for 7h in an oil bath at 120 ℃, filtering, washing with 65 ℃ distilled water to be neutral, filtering, freezing for 4 h at-50 ℃ to be solid, and drying for 8 h in vacuum at atmospheric pressure of 15Pa to obtain Antarctic krill chitosan with deacetylation degree of 60%;
3) dissolving the chitosan in 6% (v/v) acetic acid solution, diluting the solution with 300 mL of methanol and stirring for 1 h, dissolving succinic anhydride with the mass 3 times that of the chitosan in 100 mL of acetone, adding the solution into the chitosan solution, reacting at 10 ℃ for 20h, diluting the obtained viscous solution with 400 mL of distilled water, adjusting the pH to 9 with NaOH solution, washing with 50% (v/v) acetone solution for 3 times, freezing at-50 ℃ for 4 h to be solid, and drying in vacuum at the atmospheric pressure of 15Pa for 6 h to obtain the carboxymethyl chitosan.
The carboxymethyl chitosan was detected according to the method in YY0953-2015 medical carboxymethyl chitosan, with a degree of substitution of 95.9%, a degree of deacetylation of 83.4% and a purity of 85.3%.
Example 2
1) Cleaning antarctic krill shells, drying at 45 ℃ for 12 h, crushing, and sieving with a 80-mesh sieve; firstly, decalcification: weighing 50 g of shrimp shell powder, adding 300 mL of mixed acid (hydrochloric acid and phosphoric acid are mixed according to a volume ratio of 4: 1) at 25 ℃, electromagnetically stirring for 8 min, washing to be neutral, performing suction filtration, washing for 10min by using hydrochloric acid solution with the concentration of 3%, repeating for 2 times, filtering to remove acid solution, and washing to be neutral by using water; and (3) deproteinization: adding into 50 mL of 9% sodium hydroxide solution, stirring in boiling water bath for 4 h, centrifuging at 5000 r/min for 20 min, filtering, and washing with distilled water at room temperature to neutrality; then, decoloring: adding 50 mL of hydrogen peroxide with the mass concentration of 8%, stirring at room temperature for 3 h, washing with distilled water to be neutral, and performing suction filtration;
2) adding 30 mL of sodium hydroxide solution into 1) of the product, adding 50% of sodium hydroxide solution, reacting for 4 h at 140 ℃ in an oil bath, filtering, washing with 75 ℃ distilled water to be neutral, filtering, freezing for 10h at-10 ℃ to be solid, and drying for 6 h in vacuum at 5Pa under atmospheric pressure to obtain the euphausia superba chitosan with the deacetylation degree of 40%;
3) dissolving the chitosan in 2% (v/v) acetic acid solution, diluting the solution with 300 mL of methanol and stirring for 1 h, dissolving succinic anhydride with the same mass as chitosan in 100 mL of acetone, adding the solution into the chitosan solution, reacting at 50 ℃ for 10h, diluting the obtained viscous solution with 400 mL of distilled water, adjusting the pH to 11 with NaOH solution, washing with 50% (v/v) acetone solution for 3 times, freezing at-10 ℃ for 10h to be solid, and drying in vacuum of the atmospheric pressure of 1 Pa for 7h to obtain carboxymethyl chitosan.
The carboxymethyl chitosan was detected according to the method in YY0953-2015 medical carboxymethyl chitosan, with a degree of substitution of 91.5%, a degree of deacetylation of 79.8% and a purity of 89.0%.
Example 3
1) Cleaning Antarctic phosphorus shrimp shell, drying at 50 deg.C for 10h, pulverizing, and sieving with 80 mesh sieve; firstly, decalcification: weighing 50 g of shrimp shell powder, adding 200 mL of mixed acid (hydrochloric acid and phosphoric acid are mixed according to a volume ratio of 6: 1) at 25 ℃, electromagnetically stirring for 10min, washing to be neutral, performing suction filtration, washing for 10min by using hydrochloric acid solution with the concentration of 3%, repeating for 2 times, filtering to remove acid solution, and washing to be neutral by using water; and (3) deproteinization: adding into 50 mL of 10% sodium hydroxide solution, stirring in boiling water bath for 3 h, centrifuging at 5200 r/min for 18 min, vacuum filtering, and washing with distilled water at room temperature to neutrality; then, decoloring: adding 50 mL of hydrogen peroxide with the mass concentration of 7%, stirring at room temperature for 4 hours, washing with distilled water to be neutral, and performing suction filtration;
2) adding 20 mL of sodium hydroxide solution into 1) of the product, adding 40% of sodium hydroxide solution into the product, reacting for 6 h in an oil bath at 130 ℃, filtering, washing with 65 ℃ distilled water to be neutral, filtering, freezing for 6 h at-30 ℃ to be solid, and drying for 7h in vacuum at the atmospheric pressure of 1 Pa to obtain euphausia superba chitosan with deacetylation degree of 52%;
3) dissolving the chitosan in 1% (v/v) acetic acid solution, diluting the solution with 300 mL of methanol and stirring for 1 h, dissolving succinic anhydride 2 times the mass of the chitosan in 100 mL of acetone, adding the solution into the chitosan solution, reacting for 15h at 30 ℃, diluting the obtained viscous solution with 400 mL of distilled water, adjusting the pH to 10 with NaOH solution, washing with 50% (v/v) acetone solution for 3 times, freezing for 6 h at-20 ℃ to be solid, and drying for 8 h in vacuum of 5Pa at atmospheric pressure to obtain the carboxymethyl chitosan.
The carboxymethyl chitosan was detected according to the method in YY0953-2015 medical carboxymethyl chitosan, with a degree of substitution of 98.2%, a degree of deacetylation of 85.3% and a purity of 92.7%.
The experimental results show that the invention still has higher degree of substitution under the conditions of omitting alkalization treatment and avoiding the use of isopropanol and chloroacetic acid. The basically N-substituted carboxymethyl chitosan prepared by the invention has high selectivity because: the reactive sequence for the reaction of amino groups with anhydrides is superior to that for the reaction of hydroxyl groups with anhydrides, and the substitution of anhydrides on oxygen to form esters is a reversible reaction, with the reverse reaction in an acid medium releasing the anhydride, which forms a relatively stable amic acid with the amino group.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A method for preparing carboxymethyl chitosan by using Antarctic krill shells is characterized by comprising the following steps:
1) pretreatment: cleaning, drying and crushing euphausia superba shells, sieving the euphausia superba shells through a 60-80-mesh sieve, and sequentially decalcifying, deproteinizing and decoloring;
2) deacetylation: adding the product obtained in the step 1) into a sodium hydroxide solution for reaction at the temperature of 120-140 ℃ for 4-7h, adjusting the pH value to be neutral after the reaction is finished, filtering and drying to obtain chitosan;
3) carboxymethylation: dissolving chitosan in an acetic acid solution, adding methanol for dilution and stirring to obtain a chitosan solution, dissolving succinic anhydride in acetone, adding the chitosan solution, reacting for 10-20 h to obtain a viscous solution, adjusting the pH value to 9-11 with a NaOH solution, washing with an acetone solution, and freeze-drying to obtain carboxymethyl chitosan.
2. The method for preparing carboxymethyl chitosan from Antarctic krill shells according to claim 1, wherein the drying temperature in step 1) is 40-50 ℃, the decalcifying agent is a mixed acid solution of hydrochloric acid and phosphoric acid in a volume ratio of (4-7):1, and 3-6 mL of the mixed acid solution is added to each 1 g of Antarctic krill shells and stirred for 5-10 min.
3. The method for preparing carboxymethyl chitosan from Antarctic krill shells according to claim 1, wherein the mass concentration of the sodium hydroxide solution in step 2) is 40-50%, and 10-30 mL of the sodium hydroxide solution is added to 1 g of the product in step 1).
4. The method for preparing carboxymethyl chitosan according to claim 1, wherein the deacetylation degree of chitosan in step 2) is 40-60%.
5. The method for preparing carboxymethyl chitosan according to claim 4, wherein the mass ratio of chitosan to succinic anhydride in the step 3) is 1 (1-3).
6. The method for preparing carboxymethyl chitosan according to claim 1, wherein the concentration of the acetic acid solution in the step 3) is more than 1%, and the reaction temperature is 10-50 ℃.
7. The method for preparing carboxymethyl chitosan from Antarctic krill shells according to claim 1, 2 or 3, wherein the freeze-drying in step 3) is: freezing at-50 deg.C to-10 deg.C for 4-10 hr to obtain solid, and drying under vacuum of atmospheric pressure below 15Pa for 6-8 hr.
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