CN113337131A - High-strength and anti-ultraviolet soybean protein film and preparation method and application thereof - Google Patents
High-strength and anti-ultraviolet soybean protein film and preparation method and application thereof Download PDFInfo
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- CN113337131A CN113337131A CN202110567127.1A CN202110567127A CN113337131A CN 113337131 A CN113337131 A CN 113337131A CN 202110567127 A CN202110567127 A CN 202110567127A CN 113337131 A CN113337131 A CN 113337131A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention relates to the technical field of high polymer materials, and particularly discloses a high-strength and anti-ultraviolet soybean protein film as well as a preparation method and application thereof. The method for preparing the soybean protein film takes the soybean protein isolate powder as a base material, and is prepared by matching a toughening agent and a dispersion medium; the toughening agent is aminated dialdehyde starch which is prepared by grafting dialdehyde starch on long-chain polyamide. The soybean protein film prepared by the method has high toughness and strength and excellent ultraviolet resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-strength and anti-ultraviolet soybean protein film and a preparation method and application thereof.
Background
Biomass materials (mainly proteins, polysaccharides and lignin) provide the most effective solution to the huge environmental problems due to their sustainability and richness, and can also bring a revolution of excessive dependence on petroleum resources.
The soybean protein has the characteristics of low price, no toxicity and environmental friendliness, and is widely applied to the aspects of adhesives, films, hydrogels and the like. In practical applications, the inherent hydrophilicity and strong molecular interactions of natural soy protein isolates result in their limited mechanical strength and toughness. Although modification of small molecule plasticizers such as glycerol may have great potential for increasing protein chain mobility, there are still a number of strength-reducing problems that remain to be overcome. The use of chemical crosslinkers can improve the mechanical properties to a large extent, but has no positive effect on the plasticizing effect of the protein films.
For the reasons, the development of an environment-friendly high-performance soybean protein film with high strength and high ductility is of great significance.
Disclosure of Invention
In view of the problems of the prior art, the invention aims to provide a soybean protein film which has both toughness and strength and excellent ultraviolet resistance and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing soybean protein film, it is to isolate the protein powder to be the base material with soybean, cooperate flexibilizer and disperse medium to prepare to get final product; the toughening agent is aminated dialdehyde starch which is prepared by grafting dialdehyde starch on long-chain polyamide.
According to the invention, through a large number of researches, the aminated dialdehyde starch with a specific comb-like structure (synthesized by dialdehyde starch and long-chain polyamide with a specific structure through Schiff base reaction) is prepared, the tail end of the aminated dialdehyde starch has a large number of hydroxyl and amino, the aminated dialdehyde starch and the long-chain polyamide with a specific structure can form a specific multiple hydrogen bond effect with soybean protein, and energy can be effectively dissipated in the stretching process of a soybean protein film; and the soybean protein film has excellent dispersibility in water, and can provide effective space and strong sites for the formation of strong hydrogen bonds, thereby enhancing the toughness of the soybean protein film. The finally prepared soybean protein film has both toughness and strength, and has excellent ultraviolet resistance.
In the invention, the raw materials for preparing the long-chain polyamide are diethylenetriamine and adipic acid, and the molar ratio of the diethylenetriamine to the adipic acid is (1-1.1): 1.
preferably, the molar ratio of the diethylenetriamine to the adipic acid is 1.05: 1.
according to the research of the invention, the film obtained by using the molar ratio of diethylenetriamine to adipic acid in the limit of the invention has good effect, the molar ratio is too low, the molecular chain of the synthetic polyamide is too long, and the long molecular chain can cause the reduction of the reaction activity. Too high a molar ratio is also not effective. When the ratio of the molecular chain length to the molecular weight is 1.05:1, the molecular chain length is appropriate, the relative molecular weight of the synthesized long-chain polyamide is higher, a specific cohesive force is formed among molecules, the cohesive strength is improved, the energy dissipation is increased, and the strength and the toughness of the soybean protein film are finally improved.
In the present invention, the molecular weight of the long-chain polyamide is 635-1711 g/mol.
In the invention, when the aminated dialdehyde starch is prepared, the mass ratio of the long-chain polyamide to the dialdehyde starch is (1.4-1.6): 1.
Preferably, the mass ratio of the long-chain polyamide to the dialdehyde starch is 1.5: 1.
According to the invention, the research discovers that the brush-shaped polymer is generated by the reaction of the long-chain polyamide and the dialdehyde starch through Schiff base, has a proper space density under the condition that the mass ratio is (1.4-1.6):1, preferably 1.5:1, can provide an effective reaction site for a system, and realizes effective energy dissipation through hydrogen bond combination with the soybean protein, so that the strength and the toughness of the soybean protein film are improved. When the mass ratio is 1:1, the binding site of the amino group is insufficient, so that the prepared soybean protein film has low strength; when the mass ratio is 2:1, more flexible chains of the aminated starch dominate the system, resulting in a lower rigidity of the soy protein film and therefore lower strength.
According to the invention, the content of the soybean protein isolate powder is 4 parts, the content of the aminated dialdehyde starch is 2-6 parts, and the content of the dispersion medium is 96 parts by weight.
In the invention, the protein content of the soybean protein isolate powder is more than 90%, and the particle size of the soybean protein isolate powder is more than 200 meshes, preferably more than 200 meshes and 250 meshes.
In the present invention, the dispersion medium is water.
In the present invention, the dispersion medium may be selected from common tap water or distilled water.
The method specifically comprises the following steps:
(1) preparation of an aqueous solution of the long-chain polyamide:
1) mixing diethylenetriamine and adipic acid at 75-85 ℃, adding p-benzenesulfonic acid monohydrate, and carrying out closed-loop reaction at 155-165 ℃ for 115-125 minutes;
2) without additional temperature control, the opening is cooled to 115-125 ℃ after continuously reacting for 175-185 minutes, then water with the temperature of 80-100 ℃ is sequentially added for reacting for 3-10 minutes, and water with the temperature of 60-80 ℃ is added for reacting for 25-35 minutes at the temperature of 65-75 ℃;
3) cooling to 25-35 deg.C;
(2) preparing the aminated dialdehyde starch:
mixing the aqueous solution of the long-chain polyamide, dialdehyde starch and water, and carrying out Schiff base reaction at 55-65 ℃;
(3) preparing a soybean protein film:
1) dispersing the aminated dialdehyde starch and the soybean protein isolate powder in the dispersion medium, and adjusting the pH value to 8.0-10.0;
2) heating in water bath at 80-90 deg.C for 25-35 min, and ultrasonic emulsifying for 25-35 min to obtain film forming liquid;
3) and (3) casting the film-forming solution into a film, drying the film for 20 to 28 hours at 40 to 50 ℃, taking out the film, and balancing the film for 20 to 28 hours.
When the aqueous solution of the long-chain polyamide is prepared, the method of heating water firstly and then adding cold water is adopted, so that the temperature of reactants is uniformly reduced to the subsequent reaction temperature, the stability of a reaction system is facilitated, and the uniformity of the molecular weight of the system is ensured.
The invention also provides a soybean protein film which is prepared according to the method.
The invention provides a simple method for manufacturing a tough, high-ductility and soybean protein-based composite film, which has wide application prospect, such as being used in the fields of packaging engineering, ultraviolet shielding and the like.
The invention has the beneficial effects that:
the invention realizes the effect of toughening and reinforcing the soybean protein film by using the specific aminated dialdehyde starch. The tail end of the protein film is provided with a large number of hydroxyl and amino, which is beneficial to the formation of hydrogen bond interaction between the aminated dialdehyde starch and the protein and improves the strength of the protein film; in addition, the aminated dialdehyde starch provides effective hydrogen bond sites, and energy can be effectively dissipated through formation, breakage and recombination of a large number of hydrogen bonds in the stretching process, so that the toughness of the protein film is increased.
The tensile strength of the protein film manufactured by the product can reach more than 25MPa, the enhancement effect is obvious, and the film forming property is good; in addition, the product of the invention has excellent ultraviolet resistance.
Drawings
FIG. 1 is a graph showing the results of performance tests of protein films prepared in examples 1 to 3 and comparative examples 1 to 4 of Experimental example 1 of the present invention.
In the figure, a curve a is the experimental result of example 1, a curve b is the experimental result of example 2, a curve c is the experimental result of example 3, a curve d is the experimental result of comparative example 1, a curve e is the experimental result of comparative example 2, a curve f is the experimental result of comparative example 3, a curve g is the experimental result of comparative example 4 with a mass ratio of long-chain polyamide to dialdehyde starch of 1:1, and a curve h is the experimental result of comparative example 4 with a mass ratio of long-chain polyamide to dialdehyde starch of 2: 1.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The soybean protein isolate powder used in the embodiment of the invention has a protein content of 95% and a particle size of 200 meshes.
Dialdehyde starch is a commercial product and has a number average molecular weight of 2043 g/mol.
Example 1
The embodiment provides a soybean protein film and a preparation method thereof, and the preparation method comprises the following steps:
(1) diethylenetriamine (76g) was added to a 500mL three-necked flask equipped with a mechanical stirrer, a condenser and a 200 ℃ thermometer, adipic acid (103g) was mixed into the reactor with continuous stirring while the temperature was raised to 80 ℃, then to the mixture was added terephthalic acid monohydrate (2.68g), and the resulting solution was heated to 160 ℃ and kept closed for 2 hours; after that, the condenser and the thermometer were removed, the reaction was allowed to proceed for 3 hours by opening, then cooled to 120 ℃, and 80g of hot water of 90 ℃ was slowly added to the flask; after 5 minutes, 80g of warm water at 70 ℃ was added to the flask; the mixture was stirred at 70 ℃ for half an hour and then cooled to 30 ℃ to obtain an aqueous solution of long-chain polyamide (mass fraction 50%, number average molecular weight of long-chain polyamide 1071 g/mol);
(2) dialdehyde starch and distilled water are added into the prepared long-chain polyamide aqueous solution, so that the mass ratio of the long-chain polyamide to the dialdehyde starch to the water in the reaction system is 1.5:1:9.5, and the amination dialdehyde starch is prepared by heating at 60 ℃ for 3 hours to carry out Schiff base reaction.
(3) Weighing the components according to the mass ratio, and dispersing 2g of aminated dialdehyde starch in 96g of distilled water;
(4) uniformly dispersing 4g of soybean protein isolate powder in the amination dialdehyde starch dispersion liquid obtained in the step (3), and stirring for 10 minutes;
(5) adjusting the pH value of the dispersion liquid prepared in the step (4) to 9.0 by using 0.1mol/L NaOH solution;
(6) heating the solution prepared in the step (5) in water bath at 85 ℃ for 30 minutes, and then performing ultrasonic emulsification for 30 minutes (the ultrasonic power is 200W) to obtain a film-forming solution;
(7) and (3) uniformly pouring 60g of the film forming solution in the step (6) on a circular polytetrafluoroethylene die with the diameter of 15cm, casting to form a film, putting the film into a 45 ℃ oven, taking out the film after 24 hours, uncovering the film, and placing the film in a constant temperature and humidity dryer for balancing for 24 hours.
Example 2
This example provides a soy protein film of the invention and a method of making the same, as in example 1, except that: the addition amount of the aminated dialdehyde starch is 4 g.
Example 3
This example provides a soy protein film of the invention and a method of making the same, as in example 1, except that: the addition amount of the aminated dialdehyde starch is 6 g.
Comparative example 1
The comparative example provides a soy protein film and a method for preparing the same, specifically as follows:
(1) weighing the components according to the mass ratio, and dispersing 2g of glycerol in 96g of distilled water;
(2) uniformly dispersing 4g of soybean protein isolate powder in the glycerol dispersion liquid obtained in the step (1), stirring for 10 minutes,
(3) adjusting the pH value of the dispersion liquid prepared in the step (2) to 9.0 by using 0.1mol/L NaOH solution;
(4) heating the solution prepared in the step (3) in water bath at 85 ℃ for 30 minutes, and then performing ultrasonic emulsification for 30 minutes (the ultrasonic power is 200W) to obtain a film-forming solution;
(5) and (4) uniformly pouring 60g of the film forming liquid in the step (4) on a circular polytetrafluoroethylene die with the diameter of 15cm, casting to form a film, putting the film into a 45 ℃ oven, taking out the film after 24 hours, uncovering the film, and placing the film in a constant temperature and humidity dryer to balance for 24 hours.
Comparative example 2
This comparative example provides a soy protein film and a method of making the same as example 1, except that: when the polyamide aqueous solution in the step (1) is prepared, the using amount of the diethylenetriamine is 115.34g, and the using amount of the adipic acid is 103 g. The mass fraction of the obtained polyamide aqueous solution was 50%.
Comparative example 3
This comparative example provides a soy protein film and a method of making the same as example 1, except that: when the polyamide aqueous solution in the step (1) is prepared, 211.11g of phthalic anhydride is used for replacing adipic acid, and the molar ratio of diethylenetriamine to phthalic anhydride is 1.05: 1. The obtained long-chain polyamide aqueous solution has a mass fraction of 50% and a number average molecular weight of 1717 g/mol. See example 1 for the remaining steps.
Comparative example 4
This comparative example provides a soy protein film and a method of making the same as example 1, except that: the mass ratio of the long-chain polyamide to the dialdehyde starch in the reaction system in the step (2) is 1:1 and 2:1 respectively, and the rest is the same as that in the example 1. Namely, the mass ratio of the long-chain polyamide, the dialdehyde starch and the water in the step (2) is 1:1:9.5 and 2:1:9.5 respectively.
Experimental example 1
The performance of the soybean protein films prepared in examples 1 to 3 of the present invention and comparative examples 1 to 4 was tested as follows:
mechanical properties of the protein film: measured according to ASTM D882-12 at a loading rate of 20 mm/min. The film samples were tested at 100 x 10 x 0.2mm gauge length and 6 samples were tested per type (examples, comparative products). The test results are shown in FIG. 1 and Table 1.
The performance and quality indexes of the protein film obtained in example 1 are shown in curve a in FIG. 1.
The performance and quality indexes of the protein membrane obtained in example 2 are shown in curve b of FIG. 1.
The performance and quality indexes of the protein membrane obtained in example 3 are shown in curve c in FIG. 1.
The performance and quality index of the protein membrane obtained in comparative example 1 is shown in the curve d in FIG. 1.
The performance and quality indexes of the protein membrane obtained in comparative example 2 are shown in curve e in FIG. 1.
The performance and quality indexes of the protein film obtained in comparative example 3 are shown in curve f in FIG. 1.
Comparative example 4 the performance and quality index of the protein film obtained when the mass ratio of the long-chain polyamide to the dialdehyde starch is 1:1 is shown in the curve g in fig. 1; the performance and quality index of the obtained protein film when the mass ratio of the long-chain polyamide to the dialdehyde starch is 2:1 is shown in a curve h in figure 1.
TABLE 1
The experimental result shows that the tensile strength of the protein film prepared by the invention can reach 25MPa, which is improved by about 968.4% compared with that of comparative example 1(2.34MPa), and the enhancement effect is obvious.
Experimental example 2
This experimental example was conducted to test the ultraviolet resistance (ultraviolet blocking ability) of the soybean protein films prepared in examples 1 to 3 of the present invention and comparative examples 1 to 4. See table 2 for specific results.
Ultraviolet-visible (UV-vis) absorption spectra were collected in an UV-visible spectrophotometer with a scan range of 200 and 800nm, scan rate: 1 nm/s.
TABLE 2
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for preparing soybean protein film, characterized by, it is to regard isolated protein powder of soybean as the base material, mix flexibilizer and disperse medium to prepare to get final product; the toughening agent is aminated dialdehyde starch which is prepared by grafting dialdehyde starch on long-chain polyamide.
2. The method according to claim 1, wherein the raw materials for preparing the long-chain polyamide are diethylenetriamine and adipic acid, and the molar ratio of the diethylenetriamine to the adipic acid is (1-1.1): 1.
3. the method according to claim 2, wherein the molar ratio of diethylenetriamine to adipic acid is 1.05: 1.
4. the method according to any one of claims 1 to 3, characterized in that the mass ratio of the long-chain polyamide to the dialdehyde starch in the preparation of the aminated dialdehyde starch is (1.4-1.6): 1.
5. The method according to claim 4, wherein the mass ratio of the long-chain polyamide to the dialdehyde starch is 1.5: 1.
6. The method as claimed in claim 4 or 5, wherein the soybean protein isolate powder is used in an amount of 4 parts, the aminated dialdehyde starch is used in an amount of 2-6 parts, and the dispersion medium is used in an amount of 96 parts by weight.
7. The method as claimed in claim 6, wherein the protein content of the isolated soy protein powder is above 90%, the particle size of the isolated soy protein powder is above 200 mesh, preferably 200-250 mesh; and/or the dispersion medium is water.
8. The method according to any one of claims 1 to 7, comprising in particular:
(1) preparation of an aqueous solution of the long-chain polyamide:
1) mixing diethylenetriamine and adipic acid at 75-85 ℃, adding p-benzenesulfonic acid monohydrate, and carrying out closed-loop reaction at 155-165 ℃ for 115-125 minutes;
2) without additional temperature control, the opening is cooled to 115-125 ℃ after continuously reacting for 175-185 minutes, then water with the temperature of 80-100 ℃ is sequentially added for reacting for 3-10 minutes, and water with the temperature of 60-80 ℃ is added for reacting for 25-35 minutes at the temperature of 65-75 ℃;
3) cooling to 25-35 deg.C;
(2) preparing the aminated dialdehyde starch:
mixing the aqueous solution of the long-chain polyamide, dialdehyde starch and water, and carrying out Schiff base reaction at 55-65 ℃;
(3) preparing a soybean protein film:
1) dispersing the aminated dialdehyde starch and the soybean protein isolate powder in the dispersion medium, and adjusting the pH value to 8-10;
2) heating in water bath at 80-90 deg.C for 25-35 min, and ultrasonic emulsifying for 25-35 min to obtain film forming liquid;
3) and (3) casting the film-forming solution into a film, drying the film for 20 to 28 hours at 40 to 50 ℃, taking out the film, and balancing the film for 20 to 28 hours.
9. A soy protein film, prepared according to the method of any one of claims 1-8.
10. Use of the soy protein film of claim 9 in packaging engineering or in the field of uv shielding.
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Citations (4)
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| US5639518A (en) * | 1994-07-11 | 1997-06-17 | Nissei Kabushiki Kaisha | Method for manufacturing biodegradable molded articles |
| JP2011084709A (en) * | 2010-02-15 | 2011-04-28 | Nuclear Engineering Ltd | Biodegradable molded article |
| JP2019065145A (en) * | 2017-09-29 | 2019-04-25 | 大日本印刷株式会社 | Ultraviolet-blocking packaging film and package |
| CN113603920A (en) * | 2021-09-08 | 2021-11-05 | 仲恺农业工程学院 | Method for secondary crosslinking of water vapor-assisted protein-based composite membrane material |
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2021
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Patent Citations (4)
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| US5639518A (en) * | 1994-07-11 | 1997-06-17 | Nissei Kabushiki Kaisha | Method for manufacturing biodegradable molded articles |
| JP2011084709A (en) * | 2010-02-15 | 2011-04-28 | Nuclear Engineering Ltd | Biodegradable molded article |
| JP2019065145A (en) * | 2017-09-29 | 2019-04-25 | 大日本印刷株式会社 | Ultraviolet-blocking packaging film and package |
| CN113603920A (en) * | 2021-09-08 | 2021-11-05 | 仲恺农业工程学院 | Method for secondary crosslinking of water vapor-assisted protein-based composite membrane material |
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| EMILIANO M. CIANNAMEA等: ""Soybean protein films. Characterization and potential as novel delivery device of Duddingtonia flagrans chlamydospores"", 《BIOLOGICAL CONTROL》 * |
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