CN111187433A - Lipoic acid modified ethyl cellulose film and preparation method thereof - Google Patents
Lipoic acid modified ethyl cellulose film and preparation method thereof Download PDFInfo
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- CN111187433A CN111187433A CN202010079744.2A CN202010079744A CN111187433A CN 111187433 A CN111187433 A CN 111187433A CN 202010079744 A CN202010079744 A CN 202010079744A CN 111187433 A CN111187433 A CN 111187433A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
A lipoic acid modified ethyl cellulose film and a preparation method thereof are disclosed, wherein the first step is that ethyl cellulose is weighed and put into a reaction vessel, an organic solvent is added, the temperature is raised and the stirring is continued until the ethyl cellulose is completely dissolved, and then the ethyl cellulose solution is cooled to room temperature, thus obtaining the ethyl cellulose solution; secondly, weighing solid lipoic acid, adding the solid lipoic acid into a reaction container, and adding an organic solvent for dissolving to obtain a lipoic acid solution; thirdly, measuring a proper amount of lipoic acid solution, ethyl cellulose solution and polymerization inhibitor, blending, stirring until the mixed solution is clear, pouring into a mould, and putting into an oven to form a film. Compared with a pure ethyl cellulose film, the film material of the invention has greatly improved mechanical properties, and can widen the application range of the ethyl cellulose film. In addition, the invention takes renewable ethyl cellulose with wide sources as raw material and takes nontoxic and environment-friendly lipoic acid as modifier, and the prepared film has excellent performance and the advantages of water resistance, degradability and the like.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a lipoic acid modified ethyl cellulose film and a preparation method thereof.
Background
Cellulose is the oldest and most abundant natural polymer on earth, is the main component of plant cell walls and accounts for more than 50% of the carbon content in plants. The research on the application of cellulose and its derivatives, which are the most valuable natural renewable resources for human beings, began more than 160 years ago. Because of the water sensitivity, the difficult solubility and the difficult fusibility of the cellulose, the development of the cellulose in various fields is limited; meanwhile, with the rise of petrochemical synthetic products and materials, the research heat of people on cellulose is gradually reduced. However, the increasing significance of the petroleum crisis and the pollution of its products to the environment has led to the search for suitable petroleum substitutes, which once again have been aimed at biodegradable, renewable and biocompatible celluloses.
The ethyl cellulose is nonionic thermoplastic cellulose ether with special performance obtained by further reacting with ethyl chloride after cellulose is alkalized. Ethyl cellulose is tough, has good plasticity and biocompatibility, can maintain mechanical strength and flexibility in an extremely wide temperature range, and most importantly, can be dissolved in an organic solvent, so that researchers can modify the ethyl cellulose and prepare materials with better performance. At present, industrial grade ethyl cellulose is mainly applied to coatings, plastics, adhesives and the like, and food grade ethyl cellulose is mainly applied to cosmetics, medicines, foods and the like. In addition, the ethyl cellulose also has film forming property, and the prepared film can be applied to biological separation, microcapsule materials, crystal orientation and the like.
However, the strong hydrogen bonding between the molecular chains of ethyl cellulose causes the prepared film to be brittle and hard, and the glass transition temperature is high, so that the application of the film in certain fields is limited. At present, the flexibility of the ethyl cellulose film is increased by adding a flexibility modifier, and the glass transition temperature of the ethyl cellulose film is reduced. Along with the development of economy, people pay more and more attention to the problems of body health and environmental pollution, so that the development of a nontoxic and environment-friendly modifier for improving the flexibility of the ethyl cellulose film has important significance.
Disclosure of Invention
The technical problem to be solved is as follows: in order to solve the problems of brittle flexibility and poor flexibility of the pure ethyl cellulose film, the lipoic acid which is widely existed in food and animal mitochondrial cells is selected as a modifier, and the lipoic acid modified ethyl cellulose film and the preparation method thereof are designed by utilizing the characteristic that a sulfur atom and a carboxyl group in the lipoic acid structure can form a hydrogen bond with hydroxyl of ethyl cellulose, so that the flexibility of the ethyl cellulose film can be improved. The method has simple preparation process and easy operation, and the obtained film has good stability.
The technical scheme is as follows: the preparation method of the lipoic acid modified ethyl cellulose film comprises the following steps of weighing ethyl cellulose, adding the ethyl cellulose into a reaction container according to a mass ratio of ethyl cellulose to glacial acetic acid of 7: adding a certain amount of glacial acetic acid into 100, heating the reaction temperature to 70-80 ℃, continuously stirring for 2-3 hours until the ethyl cellulose is completely dissolved in the glacial acetic acid, and cooling to room temperature to obtain an ethyl cellulose solution with the mass fraction of 6.5%; secondly, respectively weighing quantitative lipoic acid and placing the lipoic acid in reaction bottles, adding glacial acetic acid, raising the temperature to 80-90 ℃, and stirring for 0.5-1h until the lipoic acid is completely dissolved in the glacial acetic acid, so as to obtain lipoic acid solutions with different mass fractions; thirdly, adding a lipoic acid solution containing different mass fractions and a polymerization inhibitor accounting for 0.1-0.5 percent of the mass fraction of the lipoic acid into an ethyl cellulose solution accounting for 6.5 percent of the mass fraction, wherein the mass ratio of the lipoic acid to the ethyl cellulose is respectively 1: (1-9), stirring for 0.5h at 80-85 ℃, cooling to room temperature, pouring into a mold, and then putting into an oven at 120 ℃ for 2h to form a film.
Preferably, the ethylcellulose viscosity in the first step is from 40 to 100 MPa-s.
Preferably, the polymerization inhibitor in the third step is hydroquinone.
Preferably, the mass ratio of the liponic acid solution to the ethylcellulose in the third step is 10/90, 20/80, 30/70, 40/60 or 50/50.
The lipoic acid modified ethyl cellulose film prepared by the preparation method.
Has the advantages that: 1. the lipoic acid modified ethyl cellulose film prepared by the method has the advantages that the raw materials are ethyl cellulose with wide sources and can be regenerated, the performance and the value of the traditional products of biomass resources are improved, and the research direction of the biomass resource industrial chain is expanded. 2. Compared with a pure ethyl cellulose film, the flexibility of the lipoic acid modified ethyl cellulose film prepared by the method is greatly improved, and the application field of the ethyl cellulose film is widened. 3. The non-toxic and pollution-free lipoic acid is used as a modifier, so that the health of a human body is guaranteed.
Drawings
Fig. 1 is an infrared spectrum of a lipoic acid modified ethylcellulose film and a pure ethylcellulose film. 1730cm in lipoic acid modified ethyl cellulose film-1The peak is the characteristic peak of ester carbonyl, which shows that the ethyl cellulose and the lipoic acid are mixed uniformly and the composite membrane is uniform.
Detailed Description
Example 1
Step one, weighing ethyl cellulose, adding the ethyl cellulose into a reaction container, and mixing the ethyl cellulose and glacial acetic acid according to a mass ratio of 7: adding a certain amount of glacial acetic acid into 100, heating the reaction temperature to 72 ℃, continuously stirring for 2 hours until the ethyl cellulose is completely dissolved in the glacial acetic acid, and cooling to room temperature to obtain an ethyl cellulose solution with the mass fraction of 6.5%; and secondly, pouring the ethyl cellulose solution with the mass fraction of 6.5% into a mould, and then putting the mould into a 120 ℃ oven for 2 hours to form a film, thus obtaining the pure ethyl cellulose film.
Example 2
Step one, weighing ethyl cellulose, adding the ethyl cellulose into a reaction container, and mixing the ethyl cellulose and glacial acetic acid according to a mass ratio of 7: adding a certain amount of glacial acetic acid into 100, heating the reaction temperature to 72 ℃, continuously stirring for 2 hours until the ethyl cellulose is completely dissolved in the glacial acetic acid, and cooling to room temperature to obtain an ethyl cellulose solution with the mass fraction of 6.5%; secondly, weighing a certain amount of lipoic acid and placing the lipoic acid in a reaction bottle, wherein the mass ratio of the lipoic acid to the ethyl cellulose is 10/90, then adding glacial acetic acid, raising the temperature to 80 ℃, and stirring for 0.5h until the lipoic acid is completely dissolved in the glacial acetic acid to obtain a lipoic acid solution; and thirdly, respectively adding a lipoic acid solution and a polymerization inhibitor accounting for 0.1 percent of the mass fraction of the lipoic acid into an ethyl cellulose solution accounting for 6.5 percent of the mass fraction, stirring for 0.5h at 80 ℃, cooling to room temperature, pouring into a mold, and then putting into a 120-DEG C oven for 2h to form a film, thus obtaining the ethyl cellulose film with the mass ratio of the lipoic acid to the ethyl cellulose being 10/90.
Example 3
Step one, weighing ethyl cellulose, adding the ethyl cellulose into a reaction container, and mixing the ethyl cellulose and glacial acetic acid according to a mass ratio of 7: adding quantitative glacial acetic acid 100, heating the reaction temperature to 73 ℃, continuously stirring for 2.5 hours until the ethyl cellulose is completely dissolved in the glacial acetic acid, and cooling to room temperature to obtain an ethyl cellulose solution with the mass fraction of 6.5%; secondly, weighing a certain amount of lipoic acid and placing the lipoic acid in a reaction bottle, wherein the mass ratio of the lipoic acid to the ethyl cellulose is 20/80, then adding glacial acetic acid, raising the temperature to 83 ℃, stirring for 1h until the lipoic acid is completely dissolved in the glacial acetic acid, and thus obtaining a lipoic acid solution; and thirdly, respectively adding a lipoic acid solution and a polymerization inhibitor accounting for 0.2 percent of the mass fraction of the lipoic acid into an ethyl cellulose solution accounting for 6.5 percent of the mass fraction, stirring at 83 ℃ for 0.5h, cooling to room temperature, pouring into a mold, and then putting into a 120 ℃ oven for 2h to form a film, thus obtaining the ethyl cellulose film with the mass ratio of the lipoic acid to the ethyl cellulose being 20/80.
Example 4
Step one, weighing ethyl cellulose, adding the ethyl cellulose into a reaction container, and mixing the ethyl cellulose and glacial acetic acid according to a mass ratio of 7: adding a certain amount of glacial acetic acid into 100, heating the reaction temperature to 75 ℃, continuously stirring for 3 hours until the ethyl cellulose is completely dissolved in the glacial acetic acid, and cooling to room temperature to obtain an ethyl cellulose solution with the mass fraction of 6.5%; secondly, weighing a certain amount of lipoic acid and placing the lipoic acid in a reaction bottle, wherein the mass ratio of the lipoic acid to the ethyl cellulose is 30/70, then adding glacial acetic acid, raising the temperature to 82 ℃, and stirring for 1h until the lipoic acid is completely dissolved in the glacial acetic acid to obtain a lipoic acid solution; and thirdly, respectively adding a lipoic acid solution and a polymerization inhibitor accounting for 0.5 percent of the mass fraction of the lipoic acid into an ethyl cellulose solution accounting for 6.5 percent of the mass fraction of the lipoic acid, stirring the mixture at 81 ℃ for 0.5 hour, cooling the mixture to room temperature, pouring the cooled mixture into a mold, and then putting the mold into a 120 ℃ oven for 2 hours to form a film, thus obtaining the ethyl cellulose film with the mass ratio of the lipoic acid to the ethyl cellulose being 30/70.
Example 5
Step one, weighing ethyl cellulose, adding the ethyl cellulose into a reaction container, and mixing the ethyl cellulose and glacial acetic acid according to a mass ratio of 7: adding a certain amount of glacial acetic acid into 100, heating the reaction temperature to 77 ℃, continuously stirring for 2 hours until the ethyl cellulose is completely dissolved in the glacial acetic acid, and cooling to room temperature to obtain an ethyl cellulose solution with the mass fraction of 6.5%; secondly, weighing a certain amount of lipoic acid and placing the lipoic acid in a reaction bottle, wherein the mass ratio of the lipoic acid to the ethyl cellulose is 40/60, then adding glacial acetic acid, raising the temperature to 81 ℃, and stirring for 1h until the lipoic acid is completely dissolved in the glacial acetic acid to obtain a lipoic acid solution; and thirdly, respectively adding a lipoic acid solution and a polymerization inhibitor accounting for 0.3 percent of the mass fraction of the lipoic acid into an ethyl cellulose solution accounting for 6.5 percent of the mass fraction, stirring at 84 ℃ for 0.5h, cooling to room temperature, pouring into a mold, and then putting into a 120 ℃ oven for 2h to form a film, thus obtaining the ethyl cellulose film with the mass ratio of the lipoic acid to the ethyl cellulose being 40/60.
Example 6
Step one, weighing ethyl cellulose, adding the ethyl cellulose into a reaction container, and mixing the ethyl cellulose and glacial acetic acid according to a mass ratio of 7: adding quantitative glacial acetic acid 100, heating the reaction temperature to 78 ℃, continuously stirring for 3 hours until the ethyl cellulose is completely dissolved in the glacial acetic acid, and cooling to room temperature to obtain an ethyl cellulose solution with the mass fraction of 6.5%; secondly, weighing a certain amount of lipoic acid and placing the lipoic acid in a reaction bottle, wherein the mass ratio of the lipoic acid to the ethyl cellulose is 50/50, then adding glacial acetic acid, raising the temperature to 85 ℃, and stirring for 1h until the lipoic acid is completely dissolved in the glacial acetic acid to obtain a lipoic acid solution; and thirdly, respectively adding a lipoic acid solution and a polymerization inhibitor accounting for 0.5 percent of the mass fraction of the lipoic acid into an ethyl cellulose solution accounting for 6.5 percent of the mass fraction of the lipoic acid, stirring the mixture at 84 ℃ for 0.5 hour, cooling the mixture to room temperature, pouring the cooled mixture into a mold, and then putting the mold into a 120 ℃ oven for 2 hours to form a film, thus obtaining the ethyl cellulose film with the mass ratio of the lipoic acid to the ethyl cellulose being 50/50.
Comparative example:
experimental group 1: the tensile strength and elongation at break of the pure ethylcellulose film prepared in example 1 were 34.43Mpa and 20.12%, respectively.
Experimental group 2: the tensile strength and elongation at break of the lipoic acid-modified ethylcellulose film prepared in example 2 were 24.88Mpa and 6.78%, respectively.
Experimental group 3: the tensile strength and elongation at break of the lipoic acid-modified ethylcellulose film prepared in example 3 were 20.18Mpa and 20.12%, respectively.
Experimental group 4: the tensile strength and elongation at break of the lipoic acid-modified ethylcellulose film prepared in example 4 were 5.85Mpa and 25.19%, respectively.
Experimental group 5: the tensile strength and elongation at break of the lipoic acid-modified ethylcellulose film prepared in example 5 were 1.56Mpa and 35.27%, respectively.
Experimental group 6: the tensile strength and elongation at break of the lipoic acid-modified ethylcellulose film prepared in example 6 were 0.43Mpa and 45.96%, respectively.
The following table shows the mechanical property comparison of each experimental group:
note: the tensile property of the material is measured by a CMT4000 model microcomputer controlled electronic universal tester (Shenzhen New Sansi) according to a test method of the tensile property of a GB/T13022-91 plastic film, the tensile test speed is 5mm/min, and the test temperature is 25 ℃.
Claims (5)
1. The preparation method of the lipoic acid modified ethyl cellulose film is characterized by comprising the following steps of:
step one, weighing ethyl cellulose, adding the ethyl cellulose into a reaction container, and mixing the ethyl cellulose and glacial acetic acid according to a mass ratio of 7: adding a certain amount of glacial acetic acid into 100, heating the reaction temperature to 70-80 ℃, continuously stirring for 2-3 hours until the ethyl cellulose is completely dissolved in the glacial acetic acid, and cooling to room temperature to obtain an ethyl cellulose solution with the mass fraction of 6.5%;
secondly, respectively weighing quantitative lipoic acid and placing the lipoic acid in reaction bottles, adding glacial acetic acid, raising the temperature to 80-90 ℃, and stirring for 0.5-1h until the lipoic acid is completely dissolved in the glacial acetic acid, so as to obtain lipoic acid solutions with different mass fractions;
thirdly, adding a lipoic acid solution containing different mass fractions and a polymerization inhibitor accounting for 0.1-0.5 percent of the mass fraction of the lipoic acid into an ethyl cellulose solution accounting for 6.5 percent of the mass fraction, wherein the mass ratio of the lipoic acid to the ethyl cellulose is respectively 1: (1-9), stirring for 0.5h at 80-85 ℃, cooling to room temperature, pouring into a mold, and then putting into an oven at 120 ℃ for 2h to form a film.
2. The method for preparing lipoic acid modified ethylcellulose film according to claim 1, characterized in that said ethylcellulose viscosity in the first step is 40-100 MPa-s.
3. The method for preparing lipoic acid modified ethyl cellulose film according to claim 1, characterised in that in said third step said polymerization inhibitor is hydroquinone.
4. The method for preparing lipoic acid modified ethylcellulose thin film according to claim 1, characterized in that the mass ratio of said lipoic acid solution to ethylcellulose in said third step is 10/90, 20/80, 30/70, 40/60 or 50/50.
5. A lipoic acid-modified ethylcellulose thin film prepared by the preparation method of any one of claims 1 to 4.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736410A (en) * | 2022-05-09 | 2022-07-12 | 南京林业大学 | Preparation method and application of turpentine modified polythiooctanoic acid antibacterial film |
| CN115058066A (en) * | 2022-06-10 | 2022-09-16 | 闽江学院 | Lipoic acid supramolecular film with self-repairing function and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401336A (en) * | 2018-10-25 | 2019-03-01 | 华东理工大学 | The preparation method of supermolecule polymer film with humidity response and recoverable |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401336A (en) * | 2018-10-25 | 2019-03-01 | 华东理工大学 | The preparation method of supermolecule polymer film with humidity response and recoverable |
Non-Patent Citations (1)
| Title |
|---|
| TIM LIEBERT等: "Synthesis and Characterization of Cellulose α-Lipoates: A Novel Material for Adsorption onto Gold", 《POLYMER BULLETIN》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736410A (en) * | 2022-05-09 | 2022-07-12 | 南京林业大学 | Preparation method and application of turpentine modified polythiooctanoic acid antibacterial film |
| CN115058066A (en) * | 2022-06-10 | 2022-09-16 | 闽江学院 | Lipoic acid supramolecular film with self-repairing function and preparation method thereof |
| CN115058066B (en) * | 2022-06-10 | 2023-08-18 | 闽江学院 | Lipoic acid supermolecule film with self-repairing function and preparation method thereof |
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