CN114989326B - Oxidized derivative of maleylation chitosan and preparation method and application thereof - Google Patents

Oxidized derivative of maleylation chitosan and preparation method and application thereof Download PDF

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CN114989326B
CN114989326B CN202210858016.0A CN202210858016A CN114989326B CN 114989326 B CN114989326 B CN 114989326B CN 202210858016 A CN202210858016 A CN 202210858016A CN 114989326 B CN114989326 B CN 114989326B
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chitosan
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oxidized
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CN114989326A (en
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沙力争
左金华
伊财富
邱旭峰
赵会芳
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Zhejiang Lover Health Science and Technology Development Co Ltd
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    • C—CHEMISTRY; METALLURGY
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    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • 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
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D21H21/20—Wet strength agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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Abstract

The invention provides a maleylation chitosan oxidation derivative and a preparation method and application thereof. The preparation method comprises the following steps: adding chitosan into water, stirring, adding sodium carbonate, stirring, adding maleic anhydride, stirring again, adding 2, 6-tetramethyl piperidine-1-oxygen free radical, and reacting; centrifuging the reaction product, and collecting supernatant; regulating the pH value of the supernatant to 3-4, centrifuging and drying. According to the preparation method, the toxic acetone is replaced by the water to serve as a solvent, the substitution degree of the prepared maleylation chitosan oxidized derivative is high, and the maleylation chitosan oxidized derivative has good water solubility under neutral and alkaline conditions; the maleylation chitosan oxidation derivative can be used for preparing the dialyzing paper, replaces a wet strength agent PAE which has potential harm to human bodies and the environment, and the prepared dialyzing paper has good physical strength and has air permeability and antibacterial property.

Description

Oxidized derivative of maleylation chitosan and preparation method and application thereof
Technical Field
The invention relates to the technical field of papermaking, in particular to a maleylation chitosan oxidation derivative and a preparation method and application thereof.
Background
As a completely plastic-free biodegradable medical packaging material, namely dialyzing paper, the dialyzing paper is required to have certain physical strength performance, wherein the wet strength is higher than that of other paper, and meanwhile, the dialyzing paper is required to have air permeability, antibacterial property and the like so as to meet the requirements of packaging and sterilizing medical instruments. At present, the dialysis paper produced in China has certain difference with imported medical packaging paper in the aspects of wet tensile strength, tearing strength, air permeability and the like. Therefore, the development of the paper making aid which can simultaneously improve the wet strength and the air permeability of the paper and has antibacterial performance is a problem which needs to be solved urgently by replacing imported high-performance medical dialyzing paper with domestic medical dialyzing paper.
At present, polyamide polyamine epichlorohydrin resin (PAE) is a papermaking wet strengthening agent which is more suitable for medium-alkaline papermaking conditions and is most widely applied. Although PAE can endow necessary wet strength to the dialysis functional paper, the PAE contains chlorine elements, and when the PAE is applied to the production of medical instrument packaging materials, partial residues on the packaging materials cannot be avoided, so that the PAE has hidden danger to human health. The discovery, discovery and adoption of new wet strength agent materials is a necessary trend in the paper industry, particularly in medical sterilization packaging materials.
Numerous studies have shown that hydroxyl and amino groups on Chitosan (CS) can bind to hydroxyl, carboxyl, etc. groups on cellulose, thereby improving the physical strength properties of paper. However, the chitosan molecular structure is due to the presence of C2-NH 2 The three active groups of C3-OH and C6-OH are easy to form intramolecular and intermolecular hydrogen bonds, and molecular chains are closely arranged to form a crystallization area, so that the chitosan is almost insoluble in water and alkaline solution and only can be dissolved in various dilute acids, thereby limiting the application of the chitosan in the paper industry.
Based on the problems of the current application of chitosan in the paper industry, the modification treatment of chitosan is necessary.
Disclosure of Invention
In view of the above, the present invention provides an oxidized derivative of maleylated chitosan, and a preparation method and applications thereof, so as to solve or at least partially solve the technical problems in the prior art.
In a first aspect, the present invention provides a method for preparing an oxidized derivative of maleylated chitosan, comprising the steps of:
adding chitosan into water, stirring, adding sodium carbonate, stirring, adding maleic anhydride, stirring again, adding 2, 6-tetramethyl piperidine-1-oxygen free radical, and reacting;
adjusting the pH value of the reaction product to 10-12, performing centrifugal separation, and collecting supernatant;
regulating the pH value of the supernatant to 3-4, centrifuging to obtain a precipitate, and drying to obtain the maleylation chitosan oxidation derivative.
Preferably, in the preparation method of the maleylation chitosan oxidation derivative, the mass volume ratio of the chitosan, the sodium carbonate, the maleic anhydride and the water is (0.5-1.5), (0.2-0.6), (0.5-2.0) and (80-120) mL;
the addition amount of the 2, 6-tetramethyl piperidine-1-oxygen free radical is 4-10% of the mass of the chitosan.
Preferably, the preparation method of the maleylation chitosan oxidation derivative comprises the steps of adding chitosan into water, stirring for 8-15 min, adding sodium carbonate, continuing to stir for 20-40 min, then adding maleic anhydride, stirring for 3-5 h again, adding 2, 6-tetramethyl piperidine-1-oxygen free radical, reacting for 3-5 h, and stopping reaction.
Preferably, the preparation method of the maleylated chitosan oxidized derivative uses 0.5 to 1.5 mol.L -1 Adjusting the pH value of the reaction product to 10-12 by NaOH, performing centrifugal separation, and collecting supernatant.
Preferably, the preparation method of the maleylation chitosan oxidation derivative comprises the steps of adjusting the pH of a supernatant to 3-4 by using acetic acid, centrifuging to obtain a precipitate, and drying to obtain the maleylation chitosan oxidation derivative.
Preferably, the preparation method of the maleylation chitosan oxidation derivative comprises the steps of adjusting the pH of the supernatant to 3-4, centrifuging to obtain a precipitate, and drying in a freeze dryer for 4-10 hours to obtain the maleylation chitosan oxidation derivative.
Preferably, in the preparation method of the maleylation chitosan oxidized derivative, the molecular weight of the chitosan is 95-105 KDa.
In a second aspect, the invention also provides a maleylation chitosan oxidation derivative prepared by the preparation method.
In a third aspect, the invention also provides a maleylation chitosan oxidation derivative prepared by the preparation method or an application of the maleylation chitosan oxidation derivative in preparation of dialysis paper.
Compared with the prior art, the maleylation chitosan oxidation derivative and the preparation method and the application thereof have the following technical effects:
1. the preparation method of the maleylation chitosan oxidized derivative comprises the steps of adding chitosan into water, stirring and carrying out swelling treatment, wherein sodium carbonate is used as a catalyst to accelerate the swelling of chitosan; then adding maleic anhydride, wherein the maleic anhydride is used as a modifier to perform acetylation reaction with chitosan to generate maleylation chitosan, and the acetylation degree of the maleylation chitosan is controlled by controlling the maleic anhydride and the chitosan with different proportions; then adding 2, 6-tetramethyl piperidine-1-oxygen free radical and 2, 6-tetramethyl piperidine-1-oxygen free radical as oxidant to selectively oxidize the maleylation chitosan; introducing carboxyl into chitosan molecules by using maleic anhydride modified chitosan through acylation reaction, and introducing carboxyl to 2, 6-tetramethyl piperidine-1-oxygen free radical on chitosan molecules C-6 through oxidation reaction to obtain a maleylation chitosan C-6 selective oxidation derivative with better water solubility under neutral and alkaline conditions; according to the preparation method, the toxic acetone is replaced by the used water as the solvent, the preparation reaction time is shortened, the substitution degree of the prepared maleylation chitosan C-6 selective oxidation derivative is higher, and the maleylation chitosan C-6 selective oxidation derivative has better water solubility under neutral and alkaline conditions;
2. the maleylation chitosan C-6 selective oxidation derivative can be used for preparing dialysis paper, replaces a wet strength agent PAE which has potential harm to human bodies and the environment, avoids adding a toxic organic antibacterial agent due to the antibacterial action of the maleylation chitosan C-6 selective oxidation derivative, and prepares medical packaging dialysis paper with good physical strength such as dry and wet tensile strength, tearing strength and the like, and meanwhile, has air permeability and antibacterial property.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic flow diagram of a process for the preparation of oxidized derivatives of maleylated chitosan of the present invention;
FIG. 2 is an infrared spectrum of an oxidized derivative of maleylated chitosan prepared in example 1 of the present invention and chitosan;
FIG. 3 is a graph showing the paper tensile strengths of dialyzing papers prepared in example 9 of the present invention using different qualities of oxidized derivatives of maleylated chitosan.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments.
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides a preparation method of a maleylation chitosan oxidized derivative, as shown in figure 1, comprising the following steps:
s1, adding chitosan into water, stirring, adding sodium carbonate, continuously stirring, then adding maleic anhydride, stirring again, and then adding 2, 6-tetramethyl piperidine-1-oxygen free radical for reaction;
s2, adjusting the pH value of the reaction product to 10-12, performing centrifugal separation, and collecting supernatant;
and S3, adjusting the pH value of the supernatant to 3-4, centrifuging to obtain a precipitate, and drying to obtain the maleylation chitosan oxidation derivative.
In the preparation method of the maleylated chitosan oxidized derivative, chitosan is added into water and stirred for swelling treatment, and sodium carbonate is used as a catalyst to accelerate the swelling of the chitosan; then adding maleic anhydride, wherein the maleic anhydride is used as a modifier to perform acetylation reaction with chitosan to generate maleylation chitosan, and controlling the acetylation degree of the maleylation chitosan by controlling the maleic anhydride and the chitosan with different proportions; adding 2, 6-tetramethylpiperidine-1-oxyl (also called tetramethylpiperidine oxide, molecular formula is C) 9 H 18 NO, abbreviated as TEMPO), 2, 6-tetramethylpiperidin-1-oxyl as an oxidizing agent to selectively oxidize maleylated chitosan; the method comprises the steps of modifying chitosan with maleic anhydride through acylation reaction, introducing carboxyl into chitosan molecules, and introducing 2, 6-tetramethyl piperidine-1-oxygen free radical into carboxyl on chitosan molecules C-6 through oxidation reaction to obtain the selective oxidation derivative of the maleylated chitosan C-6 (namely the maleylated chitosan oxidation derivative) with better water solubility under neutral and alkaline conditions. Specifically, in step S2, the pH of the reaction product is adjusted to 10 to 12, the pH is adjusted to be alkaline and centrifuged to remove unreacted chitosan, and the supernatant is collected; in step S3, the pH of the supernatant is adjusted to 3-4, i.e., the supernatant is adjusted to be acidic to precipitate the maleylated chitosan C-6 selective oxidation derivative. According to the preparation method, the toxic acetone is replaced by the used water to serve as the solvent, the preparation method shortens the reaction time of preparation, the substitution degree of the prepared maleylation chitosan C-6 selective oxidation derivative is high, and the maleylation chitosan C-6 selective oxidation derivative has good water solubility under neutral and alkaline conditions.
In some embodiments, the mass volume ratio of the chitosan, the sodium carbonate, the maleic anhydride and the water is (0.5-1.5) g, (0.2-0.6) g, (0.5-2.0) g, (80-120) mL;
the addition amount of 2, 6-tetramethyl piperidine-1-oxygen free radical is 4-10% of the weight of the chitosan.
In some embodiments, after adding chitosan into water and stirring for 8-15 min, adding sodium carbonate, continuing to stir for 20-40 min, then adding maleic anhydride and stirring again for 3-5 h, then adding 2, 6-tetramethylpiperidine-1-oxygen free radical to react for 3-5 h, and stopping the reaction.
In some embodiments, 0.5 to 1.5 mol.L is used -1 Adjusting the pH value of the reaction product to 10-12 by NaOH, performing centrifugal separation, and collecting supernatant.
In some embodiments, the pH of the supernatant is adjusted to 3-4 using acetic acid, centrifuged to obtain a precipitate, and dried to obtain the maleylated chitosan oxidized derivative.
In some embodiments, the pH of the supernatant is adjusted to 3-4, the supernatant is centrifuged to obtain a precipitate, and the precipitate is dried in a freeze dryer for 4-10 hours to obtain the maleylated chitosan oxidized derivative.
In some embodiments, the chitosan has a molecular weight of 95 to 105kDa.
At present, most of chitosan used as a raw material for preparing the maleylation chitosan is low molecular weight chitosan, the chemical activity of the low molecular weight chitosan is low, the enhancement and antibacterial effects are poor, the water solubility of the maleylation chitosan prepared from a high molecular weight chitosan raw material is poor, and the problems of low reaction speed, use of toxic reagents such as acetone and the like in the preparation process exist. The solvent is safe and nontoxic deionized water, the chitosan is subjected to acylation modification by using maleic anhydride, the C-2 amino group is protected, and simultaneously, 2, 6-tetramethylpiperidine-1-oxygen free radical is added to perform oxidation reaction, so that the reaction rate is increased, the water solubility of the high molecular weight chitosan (with the molecular weight of 95-105 KDa) is obviously improved, and the problems of slow reaction rate and poor water solubility in the chitosan are solved.
Based on the same inventive concept, the embodiment of the application also provides a maleylation chitosan oxidation derivative which is prepared by adopting the preparation method.
Based on the same inventive concept, the embodiment of the application also provides an application of the maleylation chitosan oxidized derivative in the preparation of dialysis paper.
Specifically, the prepared maleylation chitosan C-6 selective oxidation derivative is added into the preparation of the medical packaging dialysis paper to replace a wet strength agent PAE which has potential harm to human bodies and the environment, and due to the antibacterial action of the maleylation chitosan C-6 selective oxidation derivative, the addition of a toxic organic antibacterial agent is avoided, and the medical packaging dialysis paper with better physical strength such as dry and wet tensile strength, tearing strength and the like, air permeability and antibacterial property is prepared.
The preparation of the dialyzing paper by using the oxidized derivative of the maleylation chitosan comprises the following steps:
mixing and disintegrating softwood pulp and hardwood pulp according to the mass ratio of 6;
defibering the pulped pulp, adding cationic etherified starch, maleylation chitosan oxide derivative and AKD sizing agent, mixing uniformly, and making with a sheet making machine to obtain the quantitative 60 g.m -2 The dialysis paper of (1).
The preparation and use of the oxidized derivatives of maleylated chitosan of the present application are further illustrated by the following specific examples. This section further illustrates the present disclosure in connection with specific examples, which should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless otherwise specified. Reagents, methods and apparatus employed in the present invention are conventional in the art unless otherwise indicated.
Example 1
The embodiment of the application provides a preparation method of a maleylation chitosan oxidized derivative, which comprises the following steps:
s1, adding 1g of chitosan (molecular weight is 100 KDa) into 100ml of deionized water, adding 0.4g of sodium carbonate after magnetically stirring for 10min, adding 0.5g of maleic anhydride after magnetically stirring for 30min again, adding 2, 6-tetramethylpiperidine-1-oxygen free radical after magnetically stirring for 4h, and stopping reaction after reacting for 4h to obtain a reaction product; wherein the adding amount of the 2, 6-tetramethyl piperidine-1-oxygen free radical is 8 percent of the mass of the chitosan,
s2, 1 mol. L -1 Adjusting the pH of the reaction product obtained in the step S1 to 11 by using the NaOH solution, then performing centrifugal separation by using a centrifugal machine, removing precipitates, and collecting supernatant;
and S3, adjusting the pH value of the supernatant in the step S2 to 3 by using glacial acetic acid to obtain white flocculent precipitate, centrifuging again to obtain white precipitate, and drying in a freeze dryer for 6 hours to obtain the maleylation chitosan oxidation derivative.
Example 2
The preparation method of the oxidized derivative of maleylated chitosan provided in the embodiment of the present application is the same as that of embodiment 1, except that 1.0g of maleic anhydride is added in step S1, and the rest of the process parameters are the same as those of embodiment 1.
Example 3
The preparation method of the oxidized derivative of maleylated chitosan provided in the embodiment of the present application is the same as that of embodiment 1, except that 1.5g of maleic anhydride is added in step S1, and the rest of the process parameters are the same as those of embodiment 1.
Example 4
The preparation method of the oxidized derivative of maleylated chitosan provided in the embodiment of the present application is the same as that of embodiment 1, except that 2.0g of maleic anhydride is added in step S1, and the rest of the process parameters are the same as those of embodiment 1.
Example 5
The embodiment of the application provides a preparation method of a maleylation chitosan oxidized derivative, which comprises the following steps:
s1, adding 1g of chitosan (molecular weight is 100 KDa) into 100ml of deionized water, adding 0.4g of sodium carbonate after magnetically stirring for 10min, adding 1g of maleic anhydride after magnetically stirring for 30min again, adding 2, 6-tetramethylpiperidine-1-oxygen free radical after magnetically stirring for 4h, and stopping reaction after reacting for 4h to obtain a reaction product; wherein, the adding amount of 2, 6-tetramethyl piperidine-1-oxygen free radical is 4 percent of the chitosan;
s2, 1 mol. L -1 Adjusting the pH value of the reaction product in the step S1 to 11 by using the NaOH solution, then performing centrifugal separation by using a centrifugal machine, removing precipitates, and collecting supernatant;
and S3, regulating the pH value of the supernatant in the step S2 to be 3 by using glacial acetic acid to obtain white flocculent precipitate, centrifuging again to obtain white precipitate, and drying in a freeze dryer for 6 hours to obtain the maleylation chitosan oxidation derivative.
Example 6
The preparation method of the oxidized derivative of maleylated chitosan provided in the present application example is the same as example 5, except that the amount of 2,2,6,6-tetramethylpiperidine-1-oxyl added in step S1 is 6% of that of chitosan, and the rest of the process parameters are the same as example 5.
Example 7
The preparation method of the oxidized derivative of maleylated chitosan provided in the present application example is the same as example 5, except that the amount of 2,2,6,6-tetramethylpiperidine-1-oxyl added in step S1 is 8% of that of chitosan, and the rest of the process parameters are the same as example 5.
Example 8
The preparation method of the oxidized derivative of maleylated chitosan provided in the examples of the present application is the same as example 5, except that the amount of 2,2,6,6-tetramethylpiperidine-1-oxyl added in step S1 is 10% of that of chitosan, and the rest of the process parameters are the same as example 5.
Example 9
The embodiment of the application provides a preparation method of dialysis paper, which comprises the following steps:
s1, mixing and disintegrating softwood pulp and hardwood pulp according to the mass ratio of 6;
s2, taking 2g of the slurry obtained in the step S1, fluffing for 5min, sequentially adding 1mL of cationic etherified starch (purchased from Kull chemical technology, beijing) Co., ltd.) with the mass concentration of 1.0%, the maleylated chitosan oxidized derivative prepared in the example 1, and 1mL of AKD sizing agent (provided by Hengda New materials Co., ltd.) with the mass concentration of 3.0%, uniformly mixing, and then using a laboratory standard sheet making machine to make the mixture to obtain the product with the quantitative of 60g m -2 The dialysis paper of (1); the prepared dialyzing paper is treated for 24 hours at constant temperature and humidity according to TAPPIT402 standard and then is used for testing the physical performance;
wherein the addition amount of the oxidized derivative of the maleylated chitosan is 0.0 percent (namely, the oxidized derivative of the maleylated chitosan is not added), 1.0 percent, 1.5 percent, 2.0 percent, 2.5 percent and 3.0 percent of the mass of the slurry respectively.
Performance testing
FIG. 2 is an infrared spectrum of the oxidized derivative of maleylated chitosan (MACC in FIG. 2) and chitosan (CS in FIG. 2) prepared in example 1. As can be seen from FIG. 2, the oxidized derivative of maleylated chitosan was found at 1573cm -1 Has strong peak vibration, belongs to COO-group, and is 1599cm away from chitosan -1 The N-H bonds overlap, which means that acylation of chitosan occurs. Furthermore, at 865cm -1 And 806cm -1 New absorption peaks appear, which are oscillations of the C-H out-of-plane bending in the-C = C-group. The appearance of the new peaks proves that acylation reaction and oxidation reaction occur on the molecular chain of the chitosan, and the maleylation chitosan oxidation derivative is successfully prepared.
The content (mass%) of elements, the mass ratio of elements, the degree of substitution and the yield of the oxidized derivatives of maleylated chitosan prepared in examples 1 to 4 were measured, and the results are shown in table 1 below.
Wherein, the calculation formulas of the acetylation degree DD of the chitosan and the substitution degree DS of the maleylation chitosan oxidation derivative are respectively as follows:
Figure BDA0003756269440000101
Figure BDA0003756269440000102
(1) And (2) wherein X 1 Is the content ratio (mass percent) of C/N in the chitosan, X 2 Is the content ratio (mass percent) of C/N in the oxidized derivative of the maleylated chitosan, R 1 ，R 2 ，R 3 The mass ratios of the C element, the glucosamine moiety, the acetyl group moiety and the anhydride group moiety, which are oxidation derivatives of the maleylated chitosan, to the N element in the whole chitosan molecule, respectively, in this experiment,
Figure BDA0003756269440000103
wherein M is C And M N Respectively the molar masses of C and N, and R 1 、R 2 、R 3 When the formulae (1) and (2) are substituted, DD = (0.583. X) 1 -3)·100％，DS＝0.292·X 2 -0.5. DD-1.5, X by elemental analysis 1 And X 2 Then, the DD and DS values can be calculated.
Yield (%) = final product mass (g)/reaction mass (g) × 100
TABLE 1 element content, element mass ratio, degree of substitution and yield in oxidized derivatives of maleylated chitosan
Figure BDA0003756269440000111
The content (mass%) of elements, the mass ratio of elements, the degree of substitution and the yield of the oxidized derivatives of maleylated chitosan prepared in examples 5 to 8 were measured, and the results are shown in table 2 below.
TABLE 2 element content, element mass ratio, degree of substitution and yield in the oxidized derivatives of maleylated chitosan
Figure BDA0003756269440000112
From the data in Table 1, the MAAC substitution degree and yield were the lowest when the amount of maleic anhydride used was 0.5 g. The substitution degree of the resulting oxidized derivative of maleylated chitosan gradually increases with the increase of the amount of maleic anhydride, since the amino group on chitosan has more chance to react with the increase of maleic anhydride, thereby obtaining a higher substitution degree. When the mass ratio of chitosan to maleic anhydride is 1.
As can be seen from the data in Table 2, the substitution degree of the oxidized derivative of the maleylated chitosan slowly increased and then slowly decreased with the increase of the amount of TEMPO, while the yield of the product was continuously decreased. The reason is that under the action of TEMPO oxidant, the hydroxyl at C6 position is gradually oxidized into aldehyde group or carboxyl, when TEMPO consumption is less, the reaction is insufficient, and the oxidation degree of the product is low; the oxidation degree increases with the amount, but when the amount is too high, the degradation of the chitosan backbone is caused. Therefore, the optimum amount of TEMPO is 8% of the chitosan mass.
Test example 9 the paper tensile strength of the dialyzing papers prepared using different qualities of the oxidized derivative of maleylated chitosan (MACC) was measured, and the results are shown in fig. 3.
The dialyzing papers prepared from the different qualities of the oxidized derivative of maleylated chitosan (MACC) of example 9 were tested for paper tear index and air permeability, and the results are shown in Table 3.
TABLE 3 paper tear index, air permeability of dialyzing paper
Figure BDA0003756269440000121
As can be seen from fig. 3 and table 3, the dialysis paper prepared by adding the maleylation chitosan oxidized derivative in example 9 has improved dry tensile strength, wet tensile strength and tear strength, has a larger wet tensile strength improvement range, and has reduced air permeability, but can meet the requirements of medical packaging paper on wet strength and air permeability, and meanwhile, the paper has antibacterial property, so that the addition of toxic antibacterial agents is avoided, and the dialysis paper is an environment-friendly antibacterial medical packaging material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims (7)

1. A method for preparing oxidized derivatives of maleylated chitosan is characterized by comprising the following steps:
adding chitosan into water, stirring for 8-15min, adding sodium carbonate, continuing to stir for 20-40min, then adding maleic anhydride, stirring again for 3-5h, then adding 2, 6-tetramethylpiperidine-1-oxygen radical, reacting for 3-5h, and stopping the reaction; adjusting the pH value of a reaction product to 10 to 12, performing centrifugal separation, and collecting a supernatant;
regulating the pH value of the supernatant to 3 to 4, centrifuging to obtain a precipitate, and drying to obtain a maleylation chitosan oxidation derivative;
the mass volume ratio of the chitosan to the sodium carbonate to the maleic anhydride to the water is (0.5-1.5) g, (0.2-0.6) g, (0.5-2.0) g, (80-120) mL;
the addition amount of the 2, 6-tetramethylpiperidine-1-oxygen radical is 4 to 10 percent of the mass of the chitosan.
2. The process for producing an oxidized derivative of maleylated chitosan according to claim 1, wherein the amount of the oxidized derivative of maleylated chitosan is 0.5 to 1.5mol -1 Adjusting the pH of a reaction product to 10 to 12 by NaOH, performing centrifugal separation, and collecting a supernatant.
3. The method for preparing oxidized derivatives of maleylated chitosan according to claim 1, wherein the pH of the supernatant is adjusted to 3 to 4 with acetic acid, and the supernatant is centrifuged to obtain a precipitate, which is dried to obtain the oxidized derivatives of maleylated chitosan.
4. The method for preparing an oxidized derivative of maleylated chitosan according to claim 1, wherein the pH of the supernatant is adjusted to 3 to 4, the supernatant is centrifuged to obtain a precipitate, and the precipitate is dried in a freeze dryer for 4 to 10 hours to obtain the oxidized derivative of maleylated chitosan.
5. The method for preparing an oxidized derivative of maleylated chitosan according to claim 1, wherein the molecular weight of the chitosan is 95 to 105KDa.
6. An oxidized derivative of maleylated chitosan, which is prepared by the preparation method as claimed in any one of claims 1 to 5.
7. Use of the oxidized derivative of maleylated chitosan prepared by the preparation method of any one of claims 1 to 5 or the oxidized derivative of maleylated chitosan of claim 6 in the preparation of dialysis paper.
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CN102083862A (en) * 2008-04-01 2011-06-01 康奈尔大学 Organo-soluble chitosan salts and chitosan-derived biomaterials prepared thereof
CN102731792A (en) * 2012-07-19 2012-10-17 浙江大学 Preparation method of chitosan grafted polymer with thermosensitivity
CN109734824A (en) * 2019-01-03 2019-05-10 昆山京昆油田化学科技有限公司 A kind of N- succinyl group chitosan C-6 selective oxidation derivative and its preparation method and application
CN111635481A (en) * 2020-06-30 2020-09-08 重庆工商大学 Method for preparing chitosan-based flocculant by using titanium dioxide as initiator
CN114622436A (en) * 2022-04-25 2022-06-14 浙江科技学院 Method for enhancing mechanical properties of nano dialysis paper for high-resistance bacteria medical protection in environment-friendly manner

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102083862A (en) * 2008-04-01 2011-06-01 康奈尔大学 Organo-soluble chitosan salts and chitosan-derived biomaterials prepared thereof
CN102731792A (en) * 2012-07-19 2012-10-17 浙江大学 Preparation method of chitosan grafted polymer with thermosensitivity
CN109734824A (en) * 2019-01-03 2019-05-10 昆山京昆油田化学科技有限公司 A kind of N- succinyl group chitosan C-6 selective oxidation derivative and its preparation method and application
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CN114622436A (en) * 2022-04-25 2022-06-14 浙江科技学院 Method for enhancing mechanical properties of nano dialysis paper for high-resistance bacteria medical protection in environment-friendly manner

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