CN115368600A - Preparation method and application of chitosan proton type ionic liquid water-soluble film - Google Patents
Preparation method and application of chitosan proton type ionic liquid water-soluble film Download PDFInfo
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- CN115368600A CN115368600A CN202210944694.9A CN202210944694A CN115368600A CN 115368600 A CN115368600 A CN 115368600A CN 202210944694 A CN202210944694 A CN 202210944694A CN 115368600 A CN115368600 A CN 115368600A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- 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
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Abstract
The invention discloses a preparation method and application of a chitosan proton type ionic liquid water-soluble film, which is prepared by taking chitosan and carboxyl functionalized ionic liquid as raw materials. The invention takes chitosan as raw material, so that the raw material has wide sources, is green and environment-friendly, the preparation process is relatively simple, the cost is relatively low, the obtained film has degradability and water solubility, and has better antibacterial performance, the antibacterial property is not limited by the pH value of the environment, and the antibacterial property has wider application range.
Description
Technical Field
The invention relates to a preparation method and application of a water-soluble film, in particular to a preparation method and application of a chitosan proton type ionic liquid water-soluble film.
Background
The water-soluble film is generally a film made of a water-soluble polymer material that can be rapidly dissolved in water, and is widely used for packaging products used in water. Such as: in the field of daily chemical articles, the cleaning agent can be used for the external packaging of clothes detergents and closestool cleaning agents, and the products are prevented from being in direct contact with human bodies in the using process; in the field of agricultural material packaging, the packaging film is mainly used for packaging pesticides, fertilizers and seeds, and compared with the traditional plastic or glass packaging, the water-soluble packaging film has better protection on the environment and human bodies; in addition, the water-soluble packaging film has wide application in the fields of embroidery, building and the like.
Polyvinyl alcohol is a water-soluble synthetic polymer, has a large number of hydroxyl groups among molecules, and has good water absorption and excellent gas barrier property. Therefore, the traditional water-soluble packaging film is mostly prepared by using polyvinyl alcohol as a raw material. However, the polyvinyl alcohol has a fatal defect that it is difficult to degrade in the environment, and a large amount of the Water-soluble film of polyvinyl alcohol is discharged into wastewater after use, which greatly increases the chemical oxygen demand and viscosity of the wastewater, and even accelerates the movement of heavy metal ions in a Water body, thereby causing serious environmental problems (Water Research,2017,124,381-387, polymer Degradation and stability,2014,103, 75-82. In addition, the polyvinyl alcohol has no antibacterial property, and an antibacterial agent is required to be added to realize the antibacterial property when the antibacterial water-soluble film is prepared, so that the preparation cost is increased, and the antibacterial water-soluble packaging film has great application potential in special fields such as daily chemical products.
Chitosan is a product of natural polysaccharide chitin with partial acetyl removed, has multiple physiological functions of biodegradability, biocompatibility, nontoxicity, bacteriostasis, anticancer, lipid-lowering property, immunity enhancement and the like, and is widely applied to various fields of food additives, textile, agriculture, environmental protection, beauty and health care, cosmetics, antibacterial agents, medical fibers, medical dressings, artificial tissue materials, drug slow-release materials, gene transduction carriers, biomedical fields, medical absorbable materials, tissue engineering carrier materials, medical treatment, drug development and the like and other daily chemical industries. Recent research reports show that chitosan prepared into a film has good biodegradability and antibacterial property, and the raw material sources are green, environment-friendly, wide and renewable, so that the chitosan film also has the advantages of being green, environment-friendly and wide in raw material sources. However, since chitosan is insoluble in water, it needs to be dissolved by acid when preparing a chitosan film, the preparation cost is high, the process is relatively complicated, and the prepared chitosan film does not have water solubility, so the application of chitosan in the field of water-soluble films is limited, and the antibacterial property of chitosan itself needs to be developed under an acidic environment, so the application range of the antibacterial function is also greatly reduced.
Disclosure of Invention
The invention aims to solve the problems and provide a preparation method and application of a chitosan proton type ionic liquid water-soluble film. The invention takes chitosan as raw material, so that the raw material has wide sources, is green and environment-friendly, the preparation process is relatively simple, the cost is relatively low, the obtained film has degradability and water solubility, and has better antibacterial performance, the antibacterial property is not limited by the pH value of the environment, and the antibacterial property has wider application range.
The technical scheme of the invention is as follows: a preparation method of a chitosan proton type ionic liquid water-soluble film is characterized in that chitosan and carboxyl functionalized ionic liquid are used as raw materials for preparation.
According to the scheme, the film is prepared by taking chitosan and carboxyl functionalized ionic liquid as raw materials, and the chitosan can be obtained by extracting natural biomass, so that the chitosan is wide in source and environment-friendly; the chitosan can be directly mixed with the carboxyl functionalized ionic liquid and then dissolved in water for reaction, so that the step of dissolving the chitosan acid is omitted, the process is simpler, and the cost is relatively lower; in addition, the film prepared by the invention has better biodegradability because the raw material is chitosan, and a brand-new compound is formed after the chitosan reacts with the carboxyl functionalized ionic liquid, so that the water solubility of the chitosan is changed, and the chitosan-based film which can be dissolved in water is obtained, and the application of the chitosan in the field of water-soluble films is promoted; finally, the chitosan of the invention is reacted with the carboxyl functionalized ionic liquid to polymerize the shellThe amino group on the sugar forms NH with antibacterial function 4 + The antibacterial property of the whole water-soluble film is greatly improved by combining the antibacterial property of the carboxyl functionalized ionic liquid, and in addition, the water-soluble film can show the antibacterial property under any pH value condition.
In a further embodiment, the preparation method of the chitosan proton-forming ionic liquid water-soluble film comprises the following steps:
(1) Chitosan and carboxyl functionalized ionic liquid are used as raw materials;
(2) Adding chitosan and carboxyl functionalized ionic liquid into water, and stirring to form a homogeneous solution;
(3) And coating the homogeneous solution on a glass plate in a tape casting manner, soaking in ethanol for regeneration, drying to form a film, and then uncovering the film to obtain the chitosan proton type ionic liquid water-soluble film.
In a further scheme, in the preparation method of the chitosan proton-polymerized ionic liquid water-soluble film, the chitosan is one or any combination of several chitosan extracted from crab shells, shrimp shells, insects and microorganisms, and the extraction method is carried out according to a conventional extraction mode.
In a further scheme, in the preparation method of the chitosan proton type ionic liquid water-soluble film, the deacetylation degree of chitosan is 50-100%.
In a further embodiment, in the preparation method of the chitosan proton type ionic liquid water-soluble film, the structural general formula of the chitosan is as follows:
wherein 50 were n-woven 1000.
In a further embodiment, in the preparation method of the water-soluble film of chitosan deprotonated ionic liquid, the carboxyl functionalized ionic liquid is composed of any one of the following a-type cations and any one of the following B-type anions:
in a further scheme, in the preparation method of the chitosan proton type ionic liquid water-soluble film, the mass concentration of chitosan in the homogeneous solution is 0.1-30%, and the mass concentration of the carboxyl functionalized ionic liquid is 0.1-30%.
In a further scheme, in the preparation method of the chitosan proton type ionic liquid water-soluble film, after the chitosan and the carboxyl functionalized ionic liquid are added into water, the temperature of a solution system is controlled to be 10-80 ℃, and the stirring time is 1-24h.
In a further scheme, in the preparation method of the chitosan proton type ionic liquid water-soluble film, the drying temperature in the step (3) is 20-80 ℃, and the drying time is 1-48h.
The application of the water-soluble film prepared by the method as a packaging film.
The invention has the advantages of
1. The film is prepared by taking chitosan and carboxyl functionalized ionic liquid as raw materials, and the chitosan can be obtained by extracting natural biomass, so that the chitosan is wide in source and environment-friendly.
2. The chitosan of the invention can be directly mixed with the carboxyl functionalized ionic liquid and then dissolved in water for reaction, so that the chitosan is more environment-friendly by taking water as a reaction solvent.
2. The film prepared by the invention has better biodegradability because the raw material is chitosan, and the chitosan reacts with the carboxyl functionalized ionic liquid to form brand new chitosan polyprotic ionic liquid, so that the water solubility of the chitosan is changed, the chitosan-based film capable of being dissolved in water is obtained, and the application of the chitosan in the field of water-soluble films is promoted.
4. After the chitosan reacts with the carboxyl functionalized ionic liquid, the amino on the chitosan forms NH with antibacterial function 3 + Incorporating carboxyl functionalised ionic liquidsThe antibacterial property of the whole water-soluble film is greatly improved, and in addition, the water-soluble film can show the antibacterial property under any pH value condition.
Drawings
FIG. 1 is a water solubility test of a packaging film of example 1 of the present invention;
FIG. 2 is a graph showing the light transmittance of the water-soluble packaging film of example 1 of the present invention;
fig. 3 is an antibacterial property test (neutral environment test, test method is a conventional method) of the water-soluble packaging film of example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Examples of the invention
Example 1:
weighing 2.0 g of shrimp chitosan, dispersing in 100mL of deionized water, gradually adding 2.0 g of betaine hydrochloride, mechanically stirring for 1h at the temperature of 25 ℃ to obtain a homogeneous solution, coating the homogeneous solution on a glass plate in a tape casting manner, regenerating with ethanol, drying for 12h at the temperature of 25 ℃, and uncovering the film after film forming to obtain the water-soluble film.
Example 2:
weighing 3.0 g of crab chitosan, dispersing the crab chitosan in 100mL of deionized water, gradually adding 3.0 g of 1-carboxymethyl-3-methylimidazolium tetrafluoroborate, mechanically stirring the mixture at the temperature of 25 ℃ for 2 hours to obtain a homogeneous solution, coating the homogeneous solution on a glass plate in a tape casting manner, regenerating the solution with ethanol, drying the solution at the temperature of 40 ℃ for 18 hours, and removing the film after film forming to obtain the water-soluble film.
Example 3:
weighing 2.5 g of shrimp chitosan, dispersing the shrimp chitosan in 100mL of deionized water, gradually adding 3.0 g of 1-carboxymethyl-3-ethylimidazole hexafluoroborate, mechanically stirring the mixture at the temperature of 30 ℃ for 4 hours to obtain a homogeneous solution, coating the homogeneous solution on a glass plate in a tape casting manner, regenerating ethanol, drying the solution at the temperature of 45 ℃ for 20 hours, and removing the film after film forming to obtain the water-soluble film.
Example 4:
weighing 2.5 g of shrimp chitosan, dispersing in 100mL of deionized water, gradually adding 3.0 g of 1-carboxymethyl-3-ethylimidazole hexafluoroborate, mechanically stirring at 40 ℃ for 8h to obtain a homogeneous solution, coating the homogeneous solution on a glass plate in a tape casting manner, regenerating with ethanol, drying at 50 ℃ for 24h, and removing the film after film formation to obtain the water-soluble film.
Example 5:
weighing 3.0 g of shrimp chitosan, dispersing in 100mL of deionized water, gradually adding 3.5 g of 1-carboxymethyl-3-ethylimidazole iodized salt, mechanically stirring at 40 ℃ for 12h to obtain a homogeneous solution, coating the homogeneous solution on a glass plate in a tape casting manner, regenerating ethanol, drying at 50 ℃ for 24h, and removing the film after film formation to obtain the water-soluble film.
Example 6
Weighing 4.0 g of chitosan extracted from oyster mushroom mycelia, dispersing in 100mL of deionized water, gradually adding 4.5 g of N-carboxyethyl pyridine bromide, mechanically stirring at 50 ℃ for 18h to obtain a homogeneous solution, coating the homogeneous solution on a glass plate in a tape casting manner, regenerating with ethanol, drying at 60 ℃ for 30h, and removing the film after film formation to obtain the water-soluble film.
Example 7
According to the steps of example 1, 5.0 g of chitosan extracted from silkworm pupae is weighed and dispersed in 100mL of deionized water, 7.0 g of triphenylphosphine bis (trifluoromethanesulfonyl) imide salt is gradually added, mechanical stirring is carried out for 24h at the temperature of 80 ℃ to obtain a homogeneous solution, the homogeneous solution is coated on a glass plate in a tape casting mode, ethanol is regenerated, drying is carried out for 48h at the temperature of 80 ℃, and after film forming, the water-soluble film is obtained by uncovering the film.
The above description is only for the purpose of illustrating the present invention and the appended claims, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (10)
1. A preparation method of a chitosan proton type ionic liquid water-soluble film is characterized by comprising the following steps: the chitosan and carboxyl functionalized ionic liquid are used as raw materials for preparation.
2. The method for preparing the chitosan deprotonated ionic liquid water-soluble film according to claim 1, wherein the method comprises the following steps:
(1) Taking chitosan and carboxyl functionalized ionic liquid as raw materials;
(2) Adding chitosan and carboxyl functionalized ionic liquid into water, and stirring to form a homogeneous solution;
(3) And coating the homogeneous solution on a glass plate in a tape casting manner, soaking and regenerating by using ethanol, drying to form a film, and then uncovering the film to obtain the chitosan proton type ionic liquid water-soluble film.
3. The method for preparing the chitosan deprotonated ionic liquid water-soluble film according to claim 1 or 2, characterized in that: the chitosan is one or more of chitosan extracted from crab shell, shrimp shell, insects and microorganism.
4. The method for producing a chitosan deprotonated ionic liquid water-soluble film according to claim 1 or 2, characterized in that: the deacetylation degree of the chitosan is 50% -100%.
5. The method for preparing the chitosan deprotonated ionic liquid water-soluble film according to claim 1 or 2, wherein the structural general formula of the chitosan is as follows:
wherein 50 n are constructed over 1000.
6. The method for preparing the chitosan deprotonated ionic liquid water-soluble film according to claim 1 or 2, wherein the carboxyl functional ionic liquid consists of any one of the following A-type cations and any one of the following B-type anions:
A：
B：Cl - Br - I - 
7. the method for preparing the chitosan proton-forming ionic liquid water-soluble film according to claim 2, wherein the method comprises the following steps: the mass concentration of the chitosan in the homogeneous solution is 0.1-30%, and the mass concentration of the carboxyl functionalized ionic liquid is 0.1-30%.
8. The method for preparing the chitosan proton-forming ionic liquid water-soluble film according to claim 2, wherein the method comprises the following steps: after the chitosan and the carboxyl functionalized ionic liquid are added into water, the temperature of a solution system is controlled to be 10-80 ℃, and the stirring time is 1-24 hours.
9. The method for preparing the chitosan proton-forming ionic liquid water-soluble film according to claim 2, wherein the method comprises the following steps: the drying temperature in the step (3) is 20-80 ℃, and the drying time is 1-48h.
10. Use of a water-soluble film produced according to the process of any one of claims 1 to 9 as a packaging film.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040137041A1 (en) * | 2003-01-09 | 2004-07-15 | Jakwang Co., Ltd. | Water-soluble natural film and its preparing method |
| CN102168323A (en) * | 2011-02-24 | 2011-08-31 | 天津工业大学 | Method for preparing chitosan and chitin functional materials by taking ionic liquid as solvent |
| CN104927070A (en) * | 2015-03-12 | 2015-09-23 | 青岛科技大学 | Preparation method of chitosan membrane |
| CN106380620A (en) * | 2016-09-21 | 2017-02-08 | 福州大学 | Preparation method of chitosan/ionic liquid composite membrane |
| CN108821259A (en) * | 2018-07-18 | 2018-11-16 | 贵州大学 | It is the method and application of precursor preparation nitrogen-doped porous carbon material using chitosan proton type poly ion liquid |
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- 2022-08-08 CN CN202210944694.9A patent/CN115368600A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040137041A1 (en) * | 2003-01-09 | 2004-07-15 | Jakwang Co., Ltd. | Water-soluble natural film and its preparing method |
| CN102168323A (en) * | 2011-02-24 | 2011-08-31 | 天津工业大学 | Method for preparing chitosan and chitin functional materials by taking ionic liquid as solvent |
| CN104927070A (en) * | 2015-03-12 | 2015-09-23 | 青岛科技大学 | Preparation method of chitosan membrane |
| CN106380620A (en) * | 2016-09-21 | 2017-02-08 | 福州大学 | Preparation method of chitosan/ionic liquid composite membrane |
| CN108821259A (en) * | 2018-07-18 | 2018-11-16 | 贵州大学 | It is the method and application of precursor preparation nitrogen-doped porous carbon material using chitosan proton type poly ion liquid |
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