CN113185734A - Carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane and preparation method thereof - Google Patents
Carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane and a preparation method thereof, wherein carboxymethyl cellulose is dissolved in water to obtain carboxymethyl cellulose solution, the carboxymethyl cellulose solution is uniformly mixed with sodium periodate aqueous solution to carry out light-resistant reaction, then ethylene glycol is added to terminate the reaction, and the obtained reaction solution is dialyzed, purified, concentrated and dried in vacuum to obtain hydroformylation carboxymethyl cellulose; dissolving carboxymethyl chitosan in water to obtain a carboxymethyl chitosan solution, then adding the hydroformylation carboxymethyl cellulose and a plasticizer, and uniformly stirring and mixing to obtain a coating liquid; and uniformly coating the coating liquid on a substrate, and drying to form a film after bubbles are eliminated, thus obtaining the coating liquid. The carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane has good mechanical property; the water vapor transmission rate is high, the ultraviolet light absorption is good, the ultraviolet light damage can be effectively blocked, and the aspergillus niger and penicillium are well inhibited.
Description
Technical Field
The invention belongs to the technical field of food fresh-keeping antibacterial materials, and particularly relates to a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite film and a preparation method thereof.
Background
The fruits and vegetables are the main sources of essential vitamins and inorganic salts for human intake, and are important foods for ensuring human health. With the improvement of the life quality of people, the demand of fruits and vegetables is increasing day by day, but the fruits and vegetables have shorter shelf life and are easy to rot and deteriorate, and are also limited by seasons and regions. In 2019, the planting area of vegetables and fruits in China is 3.314 ten thousand square kilometers, the annual output of the fruits reaches 2.74 hundred million tons, and the loss rate reaches 30 percent due to improper storage and transportation, imperfect preservation technology and the like after picking. The aim of fruit and vegetable fresh-keeping is to keep the quality, nutrient content and appearance of the fruits and vegetables in the link from picking to point of sale circulation, so as to keep the freshness and reduce the loss of the nutrient content to improve the commodity value.
The Film-coating preservation technology is that a layer of high molecular liquid Film is coated on the surface of fruit, and after drying, a uniform Film can be formed to play a role in isolating air, so that the respiration of the fruit is reduced, the consumption of nutrient substances is reduced, the hardness and freshness of the fruit can be maintained, and the rot caused by the pollution of pathogenic bacteria is reduced. In recent years, the selection of the coating preservative is also changed to the direction of safety, no toxicity and edible use.
Carboxymethyl chitosan (CMCS) is a water-soluble chitosan derivative, which retains the advantages of chitosan and has been improved in antibacterial properties, and thus has received much attention. The bacteriostatic action of carboxymethyl chitosan may have the following mechanisms: firstly, through adsorbing and forming one deck macromolecular membrane on the cell surface, prevent the transportation of nutrient substance to the cell, perhaps changed the permselectivity of cell membrane, cause the cytoplasm to run off, the cell plasmolysis wall separation to play antibacterial effect of disinfecting. Secondly, the cell body permeates into the cell body, adsorbs cytoplasm with charges in the cell body, generates flocculation, disturbs normal physiological activities of the cell, or blocks the transcription of DNA in the bacterial body so as to inhibit the propagation of the bacteria.
Carboxymethyl cellulose (CMC) is a cellulose ether obtained by chemically modifying natural cellulose. Is white fibrous or granular powder, has hygroscopicity, and is easily soluble in water. CMC has many special properties, such as thickening, binding, film forming, water holding and emulsification, and has the characteristics of no toxicity, no smell, difficult fermentation, good thermal stability and the like, so that the CMC is widely applied to the industries of food, medicine, petroleum, textile and the like.
The carboxymethyl chitosan and the carboxymethyl cellulose do not have covalent interaction, and the performance of the prepared composite membrane is still insufficient, so that the composite material is modified by using a chemical cross-linking agent, but the performance of the composite material is influenced by adding an exogenous cross-linking agent, and a composite system capable of realizing self-crosslinking is ideal.
For food fresh-keeping antibacterial materials, the invention patent CN109320787A discloses a preparation method of a carboxymethyl chitosan film, which comprises the steps of dissolving carboxymethyl chitosan in water to form a solution, adding a proper amount of plasticizer and surfactant, strongly stirring to obtain a casting solution, pouring the casting solution into a film forming container, defoaming under vacuum, and drying in an oven to form a film; adding excessive coagulating liquid into a film forming container containing a dry film to carry out coagulating bath for a certain time to obtain a carboxymethyl chitosan wet film; the solidification liquid is ethanol, methanol or acetone; and drying the obtained wet film to obtain the carboxymethyl chitosan film. However, the above-disclosed carboxymethyl chitosan composite film has disadvantages that the solidification solution used for film preparation is ethanol, methanol or acetone, the residue of organic solvent in the food preservative film has toxic and side effects on human body, and the antibacterial effect of the composite film is not studied. The invention patent CN108030776A discloses a matrine chitosan carboxymethyl chitosan membrane and a preparation method thereof, which is prepared by taking chitosan and carboxymethyl chitosan as matrix materials, matrine as a medicament and glycerol as a plasticizer through a solution casting method. However, the natural traditional Chinese medicine matrine has certain toxicity to human bodies, and has certain risk to human bodies when being applied to the aspect of food preservation.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art, and provides a preparation method of a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite film, which realizes the self-crosslinking of two high polymers and prepares a preservative film which is nontoxic, safe, biodegradable, good in water solubility and antifungal.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane comprises the following steps:
(1) dissolving carboxymethyl cellulose in water to obtain carboxymethyl cellulose solution, uniformly mixing the carboxymethyl cellulose solution with sodium periodate aqueous solution for light-resistant reaction, then adding ethylene glycol to terminate the reaction, and dialyzing, purifying, concentrating and vacuum-drying the obtained reaction solution to obtain hydroformylation carboxymethyl cellulose;
(2) dissolving carboxymethyl chitosan in water to obtain a carboxymethyl chitosan solution, then adding the hydroformylation carboxymethyl cellulose obtained in the step (1) and a plasticizer, and uniformly stirring and mixing to obtain a coating solution;
(3) and (3) uniformly coating the coating liquid obtained in the step (2) on a substrate, and drying to form a film after bubbles are eliminated, thus obtaining the coating liquid.
Preferably, in the step (1), the mass concentration of the carboxymethyl cellulose solution is 0.5-1%; the molar ratio of the sodium periodate to the carboxymethyl cellulose in the sodium periodate aqueous solution is 1.5-2.5: 1.
Preferably, in the step (1), the temperature of the reaction protected from light is controlled to be 20-30 ℃, and the reaction time is 2-3 h.
Preferably, the dialysis purification is to fill the reaction solution into a 3500Da dialysis bag and then dialyze the reaction solution in deionized water for 72 hours, and the water is changed every 12 hours.
Preferably, in step (1), the obtained hydroformylation carboxymethylcellulose has a spongy hydroformylation degree of 13 to 15%.
Preferably, in the step (2), the mass concentration of the carboxymethyl chitosan solution is 1-3%.
Preferably, in the step (2), the hydroformylation carboxymethyl cellulose is added to the carboxymethyl chitosan solution in a mass fraction of 0.1 to 1%.
Preferably, in the step (2), the plasticizer is glycerol, and is added into the carboxymethyl chitosan solution according to the mass fraction of 0.1-1%.
Preferably, in the step (3), 10-20ml of coating liquid is measured according to a substrate with the diameter of 90mm for coating, the coating liquid is kept stand for 10min to eliminate bubbles, and then the coating liquid is dried at 50 ℃ to form a film.
Furthermore, the invention also claims the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane prepared by the preparation method.
Has the advantages that:
1. the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane uses carboxymethyl chitosan, and the hydroformylation carboxymethyl cellulose is natural macromolecules and derivatives thereof, and is nontoxic and degradable as a food antibacterial material for a human body. Schiff base reaction is carried out between two macromolecules of carboxymethyl chitosan and hydroformylation carboxymethyl cellulose, and the cross-linking effect of the Schiff base reaction enables the texture of the composite membrane to be more compact and uniform; can effectively solve the problems that fruits and vegetables are easy to be damaged and rotten and go bad due to the infection of microorganisms and are not storage-resistant in the storage and transportation process.
2. The carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane has good mechanical property; the water vapor transmission rate is high, the ultraviolet light absorption is good, the ultraviolet light damage can be effectively blocked, and the aspergillus niger and penicillium are well inhibited. The used raw materials of carboxymethyl chitosan and hydroformylation carboxymethyl cellulose are both natural macromolecules and derivatives thereof, and are nontoxic and biodegradable to human bodies as food antibacterial materials.
3. Compared with a pure carboxymethyl chitosan film, the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite film has obviously enhanced antibacterial property; the antibacterial film has good mechanical property, water vapor permeability and optical property, can be biodegraded, cannot pollute the environment, can prevent food from being polluted by microorganisms, thereby achieving the effect of prolonging the shelf life and being used in the field of food packaging.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is an infrared image of carboxymethyl cellulose, a hydroformylated carboxymethyl cellulose.
FIG. 2 is a graph of the effect of mass fraction of the hydroformylation carboxymethylcellulose on film light transmission.
FIG. 3 is a scanning electron microscope image of a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite film.
Fig. 4 shows the bacteriostatic effect of three coating films on aspergillus niger.
FIG. 5 shows the bacteriostatic effect of three coating films on Penicillium.
Detailed Description
The invention will be better understood from the following examples.
Example 1
(1) Dissolving carboxymethyl cellulose in water, stirring at 30 ℃ to form a carboxymethyl cellulose solution with the mass fraction of 0.5%, and placing the carboxymethyl cellulose solution in a round-bottom flask. Dissolving 1.5 times mol of sodium periodate in deionized water, shaking to dissolve, and adding into a round-bottom flask. The flask was wrapped with tinfoil and protected from light. After 2.5h of reaction, 8mL of ethylene glycol was added to stop the reaction for 1 h. And filling the reaction solution into a 3500Da dialysis bag, dialyzing in deionized water for 72 hours for purification, changing water once every 12 hours, performing rotary evaporation and concentration after three days, pre-freezing the liquid at-80 ℃, and putting the liquid into a vacuum freeze dryer for drying for 48 hours to obtain the spongy hydroformylation carboxymethyl cellulose with the hydroformylation degree of 13%.
(2) Respectively dissolving carboxymethyl chitosan (CMCS) in water to form carboxymethyl chitosan solutions with the mass fractions of 1.5%, 2.0% and 2.5%, then adding a proper amount of hydroformylation carboxymethyl cellulose to enable the mass fraction of the hydroformylation carboxymethyl cellulose in the coating liquid to be 0.5%, adding glycerol as a plasticizer to enable the mass fraction of the glycerol in the coating liquid to be 0.5%, and uniformly mixing to obtain the coating liquid.
(3) Weighing 10-20ml of the film-forming solution, uniformly coating the film-forming solution on a culture dish with the diameter of 90mm, standing for 10min, eliminating bubbles, placing the culture dish in a 50 ℃ oven, and drying for 8h to form a film.
(4) The thickness of the film was measured using a digital micrometer caliper. The effect of the mass fraction of carboxymethyl chitosan on the thickness of the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite film is shown in table 1.
(5) According to the national standard GB/T1040.3-2006 of the people's republic of China, part 3 of the determination of tensile properties of plastics: film and sheet test conditions "method of measuring the mechanical properties of the film. The influence of the mass fraction of carboxymethyl chitosan on the mechanical properties of the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane is shown in table 1.
(6) The water permeability of the film is determined according to the method of the national standard GB/T1037-1988 of the people's republic of China, the test method of the water vapor permeability of the plastic film and the sheet material-the cup method. The influence of the mass fraction of carboxymethyl chitosan on the water permeability of the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane is shown in table 1.
TABLE 1
The influence of the mass fraction of carboxymethyl chitosan on the thickness and mechanical properties of the film is shown in Table 1. The stress at break and elongation at break may reflect the mechanical strength and elongation toughness of the film. With the increase of the concentration of the carboxymethyl chitosan, the breaking stress of the film is increased and then reduced, and the breaking elongation rate is continuously reduced. This is probably because as the concentration of carboxymethyl group increases, intermolecular force increases, and the breaking stress of the film increases. When the concentration continues to increase, the viscosity of the membrane solution gradually increases, resulting in a decrease in membrane uniformity and a decrease in fracture stress. As the concentration of carboxymethyl chitosan increases, the hardness of the prepared film gradually increases, the flexibility of the film becomes poor, and the elongation at break decreases. When the mass fraction of the carboxymethyl chitosan is 1.5-2.5%, the elongation at break of the film is 20-35%, and the stress at break is 15-40 Mpa. The addition of carboxymethyl chitosan reduces the moisture permeability of the film. The moisture permeability of the membrane gradually decreases with the increase of the mass fraction of carboxymethyl chitosan, probably because the addition of carboxymethyl chitosan increases the compactness of the membrane, which increases the water vapor barrier property of the membrane.
Example 2
(1) Dissolving carboxymethyl cellulose in water, stirring at 30 ℃ to form a carboxymethyl cellulose solution with the mass fraction of 0.8%, and placing the carboxymethyl cellulose solution in a round-bottom flask. Dissolving 2 times mol of sodium periodate in deionized water, shaking to dissolve the sodium periodate, and adding the solution into a round-bottom flask. The flask was wrapped with tinfoil and protected from light. After 2.5h of reaction, 10mL of ethylene glycol was added to stop the reaction for 1 h. And filling the reaction solution into a 3500Da dialysis bag, dialyzing in deionized water for 72 hours for purification, changing water once every 12 hours, performing rotary evaporation and concentration after three days, pre-freezing the liquid at-80 ℃, and putting the liquid into a vacuum freeze dryer for drying for 48 hours to obtain the spongy hydroformylation carboxymethyl cellulose with the hydroformylation degree of 15%.
(2) Dissolving carboxymethyl chitosan in water to form a carboxymethyl chitosan solution with the mass fraction of 2.0%, then respectively adding a proper amount of hydroformylation carboxymethyl cellulose (CMC-CHO) to ensure that the mass fractions of the hydroformylation carboxymethyl cellulose in the coating solution are respectively 0.3%, 0.5% and 0.8%, adding glycerol as a plasticizer to ensure that the mass fraction of the glycerol in the coating solution is 0.5%, and uniformly mixing to obtain the coating solution.
(3) Weighing 10-20ml of the film-forming solution, uniformly coating the film-forming solution on a culture dish with the diameter of 90mm, standing for 10min, eliminating bubbles, placing the culture dish in a 50 ℃ oven, and drying for 8h to form a film.
The mass fraction of the hydroformylation carboxymethylcellulose to the thickness, mechanical properties and water permeability of the carboxymethyl chitosan/hydroformylation carboxymethylcellulose composite film are shown in Table 2. (the test method is the same as in example 1)
TABLE 2
As can be seen from table 2, as the concentration of the hydroformylation carboxymethylcellulose increases, the breaking stress of the film increases and the elongation at break increases. The main reason may be that carboxymethyl chitosan and hydroformylation carboxymethyl cellulose have polymerization reaction, and the cross-linked network of the film has a denser structure and higher mechanical property, so that the toughness of the film is increased. When the mass fraction of the hydroformylation carboxymethyl cellulose is 0.3 to 0.8 percent, the breaking stress of the film is 20 to 40Mpa, and the breaking elongation is 5 to 10 percent.
The addition of the hydroformylation carboxymethyl cellulose increases the moisture permeability of the film. The moisture permeability of the film gradually increases with the increase of the mass fraction of the hydroformylation carboxymethyl cellulose, probably because the addition of the hydroformylation carboxymethyl cellulose increases the compactness of the film and increases the water vapor barrier property of the film, and the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose schiff base is a hydrophilic substance and increases the water vapor permeability.
Example 3
(1) Dissolving carboxymethyl cellulose in water, stirring at 30 ℃ to form a carboxymethyl cellulose solution with the mass fraction of 1%, and placing the carboxymethyl cellulose solution in a round-bottom flask. 2.5 times mol of sodium periodate is dissolved in deionized water, and added into a round-bottom flask after shaking and dissolving. The flask was wrapped with tinfoil and protected from light. After 2.5h of reaction, 12mL of ethylene glycol was added to stop the reaction for 1 h. And filling the reaction solution into a 3500Da dialysis bag, dialyzing in deionized water for 72 hours for purification, changing water once every 12 hours, performing rotary evaporation and concentration after three days, pre-freezing the liquid at-80 ℃, and putting the liquid into a vacuum freeze dryer for drying for 48 hours to obtain the spongy hydroformylation carboxymethyl cellulose with the hydroformylation degree of 15%.
(2) Dissolving carboxymethyl chitosan in water to form a carboxymethyl chitosan solution with the mass fraction of 2.0%, then adding a proper amount of hydroformylation carboxymethyl cellulose to enable the mass fraction of the hydroformylation carboxymethyl cellulose in the coating solution to be 0.5%, respectively adding glycerol as a plasticizer to enable the mass fraction of the glycerol in the coating solution to be 0.5%, 0.8% and 1.0%, and uniformly mixing to obtain the coating solution.
(3) Weighing 10-20ml of the film-forming solution, uniformly coating the film-forming solution on a culture dish with the diameter of 90mm, standing for 10min, eliminating bubbles, placing the culture dish in a 50 ℃ oven, and drying for 8h to form a film.
The mass fraction of glycerol versus the thickness, mechanical properties and water permeability of the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite film are shown in Table 3. (the test method is the same as in example 1)
TABLE 3
As can be seen from table 3, the breaking stress and breaking elongation of the film both increased and then decreased with the increase in the concentration of glycerin. This is probably due to the fact that glycerol, as a plasticizer, can disperse between macromolecules to weaken intermolecular forces, reducing the degree of crosslinking of the film-forming molecules, resulting in a decrease in film strength and an increase in toughness. When the mass fraction is 0.5-0.1%, the stress at break and the elongation at break can both be maximized.
The glycerin addition increases the moisture permeability of the membrane, and the possible reason is that the glycerin addition increases the content of hydrophilic groups in the membrane, affects the compactness of the structure of the polymer, makes water molecules diffuse more easily, and the moisture permeability of the membrane is higher, but the continuous increase of the addition amount increases the overall density of the membrane, reduces pores, inhibits the diffusion of the water molecules, and reduces the moisture permeability of the membrane.
Example 4
The carboxymethyl cellulose and the hydroformylation carboxymethyl cellulose in example 2 were subjected to infrared characterization, and the results are shown in fig. 1. As can be seen, the infrared spectrum of the hydroformylation carboxymethyl cellulose is similar to that of the carboxymethyl cellulose at 1560cm-1An asymmetric stretching vibration peak of-C ═ O with carboxyl groups nearby, but at 1723cm-1A new characteristic peak appears, corresponding to the stretching vibration of-C ═ O in the aldehyde group, indicating that a part of-OH in CMC is indeed oxidized to — CHO.
TABLE 4
Table 4 shows the effect of mass fraction of the hydroformylated carboxymethylcellulose on the near uv transmission of the film. FIG. 2 is a graph showing the effect of mass fraction of the hydroformylated carboxymethylcellulose in example 2 on film light transmission. As is clear from Table 4 and FIG. 2, the transparency of the film is not greatly affected by the hydroformylation of carboxymethyl cellulose in the visible light range (wavelength 390-700nm), and the transmittance of each film is 80% or more. In the near ultraviolet range (200-.
FIG. 3 is a scanning electron microscope image of the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite film prepared in example 2. As can be seen from the figure, the cross-linking reaction makes the composite membrane compact and uniform, and the small-molecule glycerol is dispersed in the polymer structure, so that the membrane is more uniform, compact and smooth.
Example 5
(1) Directly coating 10-20ml of carboxymethyl chitosan solution (CMCS, mass fraction of 2%) on a culture dish with the diameter of 90mm, standing for 10min, eliminating bubbles, placing in a 50 ℃ oven, and drying for 8h to form a film.
(2) Dissolving carboxymethyl chitosan (CMCS) in water to form a carboxymethyl chitosan solution with the mass fraction of 2%, then adding hydroformylation carboxymethyl cellulose (CMC-CHO) to ensure that the mass fraction of the hydroformylation carboxymethyl cellulose in the coating solution is 0.5%, uniformly mixing to obtain the coating solution, finally measuring 10-20ml of film forming solution, uniformly coating the film forming solution on a culture dish with the diameter of 90mm, standing for 10min, eliminating bubbles, placing the culture dish in a 50 ℃ oven, and drying for 8h to form the film.
(3) Taking the coating solution of 2.0 mass percent of carboxymethyl chitosan (CMCS), 0.5 mass percent of hydroformylation carboxymethyl cellulose (CMC-CHO) and 0.5 mass percent of glycerol in example 2, measuring 10-20ml of the coating solution, uniformly coating the coating solution on a culture dish with the diameter of 90mm, standing for 10min, eliminating bubbles, placing the culture dish in an oven at 50 ℃, and drying for 8h to form the membrane.
The three films obtained by the preparation are processed into three parallel films by an agar hole method, and sterile water is used for blank control. And finally, culturing for 40-50h in an incubator at 28 ℃, checking the bacteriostasis result, and measuring the diameter of the bacteriostasis zone by using a vernier caliper. The inhibition of both Aspergillus niger and Penicillium expansum moulds by different coatings was obtained and the results are shown in Table 5 and in FIG. 4 and FIG. 5.
TABLE 5
FIG. 4 shows the bacteriostatic effect of three coating films on Aspergillus niger. FIG. 5 shows the bacteriostatic effect of three coating films on Penicillium. As can be seen from fig. 4, fig. 5 and table 5, all three coating films have certain bacteriostatic effect on aspergillus niger, carboxymethyl chitosan has bacteriostatic activity, and after the cross-linking agent is added to hydroformylate carboxymethyl cellulose, the generated schiff base compound also has bacteriostatic and bactericidal effects and exerts bacteriostatic effect together with residual carboxymethyl chitosan, while the addition of glycerol reduces the concentration of other substances, so that the bacteriostatic effect is reduced. This also corresponds to the result of the zone diameter.
The present invention provides a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane and a method and a thinking for implementing the same, and a method for preparing the same, and a method and a way for implementing the technical scheme are many, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and modifications can be made without departing from the principle of the present invention, and the improvements and modifications should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A preparation method of a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane is characterized by comprising the following steps:
(1) dissolving carboxymethyl cellulose in water to obtain carboxymethyl cellulose solution, uniformly mixing the carboxymethyl cellulose solution with sodium periodate aqueous solution for light-resistant reaction, then adding ethylene glycol to terminate the reaction, and dialyzing, purifying, concentrating and vacuum-drying the obtained reaction solution to obtain hydroformylation carboxymethyl cellulose;
(2) dissolving carboxymethyl chitosan in water to obtain a carboxymethyl chitosan solution, then adding the hydroformylation carboxymethyl cellulose obtained in the step (1) and a plasticizer, and uniformly stirring and mixing to obtain a coating solution;
(3) and (3) uniformly coating the coating liquid obtained in the step (2) on a substrate, and drying to form a film after bubbles are eliminated, thus obtaining the coating liquid.
2. The method for preparing the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane according to claim 1, wherein in the step (1), the mass concentration of the carboxymethyl cellulose solution is 0.5-1%; the molar ratio of the sodium periodate to the carboxymethyl cellulose in the sodium periodate aqueous solution is 1.5-2.5: 1.
3. The method for preparing the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane according to claim 1, wherein in the step (1), the temperature for the light-shielding reaction is controlled to be 20-30 ℃ and the reaction time is 2-3 h.
4. The method for preparing the carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane according to claim 1, wherein in the step (1), the reaction solution is purified by being filled in a 3500Da dialysis bag and then dialyzed in deionized water for 72 hours, and water is changed every 12 hours.
5. The method for preparing a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane according to claim 1, wherein the spongy hydroformylation degree of the obtained hydroformylation carboxymethyl cellulose in the step (1) is 13 to 15%.
6. The method for preparing a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane according to claim 1, wherein in the step (2), the mass concentration of the carboxymethyl chitosan solution is 1 to 3%.
7. The method for preparing a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane according to claim 1, wherein, in the step (2), the hydroformylation carboxymethyl cellulose is added to the carboxymethyl chitosan solution in a mass fraction of 0.1 to 1%.
8. The method for preparing a carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane according to claim 1, wherein in the step (2), the plasticizer is glycerol, and is added into the carboxymethyl chitosan solution according to a mass fraction of 0.1 to 1%.
9. The method for preparing carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane according to claim 1, wherein in the step (3), 10 to 20ml of coating liquid is measured according to a substrate with the diameter of 90mm, the coating liquid is coated, the coating liquid is kept stand for 10min to eliminate bubbles, and then the coating liquid is dried at 50 ℃ to form the membrane.
10. The carboxymethyl chitosan/hydroformylation carboxymethyl cellulose composite membrane prepared by the preparation method of any one of claims 1 to 9.
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| CN113749976A (en) * | 2021-08-27 | 2021-12-07 | 华南理工大学 | Portable nano antibacterial hand washing gel bead and preparation method, use method and application thereof |
| CN115382000A (en) * | 2022-07-11 | 2022-11-25 | 上海健康医学院 | Dressing with antibacterial coating and preparation method thereof |
| CN116355258A (en) * | 2021-12-20 | 2023-06-30 | 北京健康广济生物技术有限公司 | Preparation method of chitosan film and sodium carboxymethyl cellulose hydrogel burn dressing based on double-layer structure |
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| CN103709267A (en) * | 2013-11-28 | 2014-04-09 | 江南大学 | Preparation method of dialdehyde carboxymethyl chitosan |
| CN106674612A (en) * | 2016-12-30 | 2017-05-17 | 齐鲁工业大学 | Preparation method of antibacterial and hydrophobic biodegradable membrane |
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| CN103709267A (en) * | 2013-11-28 | 2014-04-09 | 江南大学 | Preparation method of dialdehyde carboxymethyl chitosan |
| CN106674612A (en) * | 2016-12-30 | 2017-05-17 | 齐鲁工业大学 | Preparation method of antibacterial and hydrophobic biodegradable membrane |
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| CN113749976A (en) * | 2021-08-27 | 2021-12-07 | 华南理工大学 | Portable nano antibacterial hand washing gel bead and preparation method, use method and application thereof |
| CN113749976B (en) * | 2021-08-27 | 2022-10-25 | 华南理工大学 | Portable nano antibacterial hand washing gel bead as well as preparation method, use method and application thereof |
| CN116355258A (en) * | 2021-12-20 | 2023-06-30 | 北京健康广济生物技术有限公司 | Preparation method of chitosan film and sodium carboxymethyl cellulose hydrogel burn dressing based on double-layer structure |
| CN115382000A (en) * | 2022-07-11 | 2022-11-25 | 上海健康医学院 | Dressing with antibacterial coating and preparation method thereof |
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