CN116082780B - Nanoscale biodegradable composite material and preparation method and application thereof - Google Patents
Nanoscale biodegradable composite material and preparation method and application thereof Download PDFInfo
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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Abstract
The invention belongs to the technical field of degradable materials, and particularly relates to a nanoscale biodegradable composite material, and a preparation method and application thereof. The preparation method of the material comprises the following steps: mixing polyvinyl chloride with polyvinylpyrrolidone monomer, adding organic alcohol solution and catalyst, stirring uniformly, and stirring the obtained mixture to react to obtain a product I; mixing silicon carbide whiskers with organic acid, then placing the mixture in a high-pressure reaction kettle for reaction, grinding the obtained product into powder, mixing the powder with deionized water, adding the product I for ultrasonic dispersion, placing the mixture in a water bath for stirring and heating, and dropwise adding sodium bicarbonate solution in the stirring process to obtain a product II; mixing the product II with plant fiber, freeze drying, and adding plasticizer, antioxidant and filler for mixing; pulverizing the product, superfine processing to obtain nanometer grade with a particle size of above 1000 meshes, and granulating by extrusion. The material of the invention is environment-friendly and degradable, has little environmental pollution, high biological decomposition rate and high strength.
Description
Technical Field
The invention belongs to the technical field of degradable materials, and particularly relates to a nanoscale biodegradable composite material, and a preparation method and application thereof.
Background
The wide use of the polymer materials, especially plastic films, sheets and plates brings great convenience to the life of people. Most of the current polymer materials, such as polyethylene, polypropylene, polyvinyl chloride, polystyrene and the like, can be used as food packaging, stationery products, tableware products, craft electromechanical packaging and other products related to living aspects. However, these polymers are generally chemically stable and difficult to degrade, and their use, especially in large quantities in agriculture and packaging where disposable consumer products are often used, can cause serious white pollution. In fact, many plastic articles do not require too long a service life in the agricultural, packaging and medical industries. Accordingly, various studies on polymers degradable under natural conditions have been conducted. Among them, biodegradable polymers, which are polymer materials that can be degraded by microorganisms (such as fungi, bacteria, algae, etc.) or their secretions under a certain period of time and under appropriate natural conditions under enzymatic or chemical decomposition, have become a hot spot of research today as an important classification in degradable polymers.
The currently used biodegradable materials mainly comprise poly (adipic acid)/butylene terephthalate (PBAT), poly (butylene succinate-co-butylene adipate) (PBSA), polylactic acid (PLA), polyhydroxyfatty acids (PHAs), poly (butylene succinate) (PBS), polycaprolactone (PCL), and the like. The aromatic-aliphatic copolymer has excellent heat stability and film forming property due to the chain structure, has good prospect in the fields of packaging and films, but has excessively high price which is 2-3 times of that of common plastics, can not be applied on a large scale in the market, and if the cost is reduced and thinning processing is carried out, the mechanical property of the aromatic-aliphatic copolymer can not reach the acceptance of the market.
For example, chinese patent application No. CN111019304a discloses a biodegradable nanocomposite, which is prepared by mixing a polymer resin, a first nanofiller, a compound stabilizer, and an interfacial compatibilizer in a screw extruder to obtain a resin melt, and melt-blending the resin melt with a second nanofiller. For another example, the chinese patent application No. CN110029383a discloses a degradable zinc-copper foam biomaterial, which is prepared by the following steps: (1) Adopting a foam metal material Cu as a template to perform degreasing treatment; (2) Etching the degreased foam metal material Cu; (3) Preparing a zinc coating on the etched foam metal material Cu through electroplating treatment to obtain Zn-Cu foam metal; (4) vacuum sealing the Zn-Cu foam metal in a quartz tube; (5) Heating to 250-350 deg.c and maintaining at the temperature for 1-3 hr; (6) Heating to 450-550 deg.c and maintaining at the temperature for 0.5-2 hr; (7) Heating to 650-750 ℃ and preserving heat for 0.5-1 h, then cooling to room temperature in a furnace, and taking out the sample to obtain the degradable zinc-copper foam biological material.
At present, the existing degradable materials are basically prepared by taking degradable materials as raw materials, and no better decomposition method is available for some refractory high molecular compounds.
Disclosure of Invention
The invention aims to solve the problem of overcoming the defects of the prior art and provides a nanoscale biodegradable composite material and a preparation method and application thereof. The composite material is environment-friendly and degradable, reduces pollution to the environment, and has high biological decomposition rate, high strength and low cost.
The aim and the technical problems of the invention are realized by adopting the following technical proposal.
The invention provides a preparation method of a nanoscale biodegradable composite material, which comprises the following steps:
mixing polyvinyl chloride and polyvinylpyrrolidone monomer according to the mass ratio of 1:2-4, then adding an organic alcohol solution with the concentration of 10-20mol/L and a catalyst, uniformly stirring, and placing the obtained mixture at 40-60 ℃ for stirring reaction for 36-48h to obtain a product I;
mixing silicon carbide whiskers with organic acid according to the mass ratio of 1:0.3-0.9, placing the mixture in a high-pressure reaction kettle for reaction for 4-6 hours at 80-100 ℃, cooling to room temperature after the reaction is finished, grinding the obtained product into powder, mixing the obtained powder with deionized water according to the mass ratio of 1:5-10, adding the product I for ultrasonic dispersion, placing the mixture in a water bath at 60-80 ℃ for stirring and heating for 2-4 hours after the mixture is uniformly dispersed, and dripping sodium bicarbonate solution in the stirring process to obtain a product II;
mixing the product II with plant fibers according to a physical ratio of 2-4:1, and freeze-drying at-40 to-20 ℃ for 6-8 hours to obtain a dried material, putting the dried material into a high-speed mixer, sequentially putting a plasticizer, an antioxidant and a filler, and mixing the raw materials in the high-speed mixer for 20-30 minutes; crushing the obtained mixture and performing superfine treatment with the granularity of more than 1000 meshes to make the mixture be nano-sized, and finally adding the nano-sized mixture into a double-screw extruder, and performing extrusion granulation to obtain the nano-sized biodegradable composite material.
Preferably, the organic alcohol is selected from one of ethanol, methanol, hexanediol, and glycerol.
Preferably, the catalyst is selected from any one of stannous bromide, tin bromide, dibutyl tin oxide, stannous chloride and stannic chloride.
Preferably, the organic acid is selected from one of citric acid, oxalic acid and acetic acid.
Preferably, the mass ratio of the added amount of the product I to the powder is 1:2-3.
Preferably, the ultrasound conditions are: the frequency is 80-100KHz, and the time is 60-90min.
Preferably, the plant fiber is at least one selected from cotton fiber, coconut fiber, jute fiber, sisal fiber, ramie fiber, bamboo fiber and kapok fiber.
Preferably, the plasticizer is one or more of glycerol, monoglyceride, sorbitol, stearic acid; the filler is one or more of calcium carbonate, talcum powder and titanium dioxide; the antioxidant is dilauryl thiodipropionate and pentaerythritol tetra [ beta- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionate ].
Preferably, the mass ratio of the plasticizer, the antioxidant and the filler is 2:1:1.
Preferably, the first-zone extrusion temperature of the twin-screw extruder is 90-100 ℃, the second-zone extrusion temperature is 110-120 ℃, and the third-zone extrusion temperature is 120-130 ℃.
By means of the technical scheme, the invention has at least the following advantages: the invention takes the polyvinyl chloride which is a polymer material and is difficult to degrade as a raw material, and the polyvinyl chloride/polyvinylpyrrolidone monomer graft copolymer is obtained by graft polymerization reaction with polyvinylpyrrolidone monomer in an alkaline environment containing a catalyst. The organic alcohol provides an alkaline environment for the whole reaction, so that the activity of the catalyst can be improved, the reaction is accelerated, and the reaction efficiency is improved. The presence of the organic alcohol solution provides a rich OH-microenvironment, such that the surface charge of product I increases, and thus the covalent binding capacity of product I increases. The silicon carbide whisker has excellent properties of high strength, high modulus, high elongation and the like, can increase the strength and activity of the silicon carbide whisker through high-temperature reaction with organic acid, then carries out water bath heating reaction with the product I in water environment, and the silicon carbide whisker is more easily combined with the product I through covalent bonds and Van der Waals force, namely, the modification effect of the silicon carbide whisker on the product I is realized, so that the finally obtained product II becomes a biodegradable material. The dropping of sodium bicarbonate solution can ensure the stability of the pH of the whole system. Finally, as the product II is in a liquid form, the product II is mixed with the plant fiber and freeze-dried to form a solid mixture, and the plant fiber enables the product II to be attached to a plant fiber net, so that the dispersibility of the monomers of the product II is improved, and the decomposition rate and strength of the product are increased. Finally, mixing and crushing the mixture with auxiliary materials to obtain nanoscale materials, and carrying out conventional treatment to obtain nanoscale composite material particles. The nano-scale biodegradable composite material obtained by the method is environment-friendly and degradable, reduces the pollution to the environment, and has high biological decomposition rate, high strength and low cost. The invention makes full use of polyvinyl chloride, and makes the final product become a degradable material through grafting, modification and other treatment processes, so that the raw material sources are rich, and the production cost is reduced. The preparation process has mild conditions and is beneficial to implementation.
The foregoing description is only an overview of the present invention, and is intended to provide a more thorough understanding of the present invention, and is to be accorded the full scope of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement of the purposes and the effects of the present invention easy to understand, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of the nanoscale biodegradable composite material comprises the following steps:
mixing polyvinyl chloride and polyvinylpyrrolidone monomer according to the mass ratio of 1:3, then adding ethanol solution with the concentration of 15mol/L and tin chloride, uniformly stirring, and stirring the obtained mixture at 50 ℃ for reacting for 42h to obtain a product I;
mixing silicon carbide whiskers with citric acid according to the mass ratio of 1:0.6, placing the mixture into a high-pressure reaction kettle to react for 5 hours at 90 ℃, cooling the mixture to room temperature after the reaction is finished, grinding the obtained product into powder, mixing the obtained powder with deionized water according to the mass ratio of 1:8, adding a product I (the mass ratio of the product I to the powder is 1:2) to carry out ultrasonic (frequency of 90KHz, time of 75 min) dispersion, placing the mixture into a 70 ℃ water bath to be stirred and heated for 3 hours after the uniform dispersion, and dripping a small amount of sodium bicarbonate solution in the stirring process to obtain a product II;
mixing the product II with cotton fiber according to a physical ratio of 3:1 and freeze-drying the mixture at the temperature of minus 30 ℃ for 7 hours to obtain a dried material, putting the dried material into a high-speed mixer, and sequentially putting sorbitol, tetra [ beta- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionic acid ] pentaerythritol ester and talcum powder according to a mass ratio of 2:1:1, and mixing the raw materials in the high-speed mixer for 20-30 minutes; and (3) crushing the obtained mixture and performing superfine treatment of more than 1000 meshes to obtain a mixture with a nanoscale, and finally adding the nanoscale mixture into a double-screw extruder (the extrusion temperature of a first area is 90 ℃, the extrusion temperature of a second area is 110 ℃, and the extrusion temperature of a third area is 120 ℃), and extruding and granulating to obtain the nanoscale biodegradable composite material.
Example 2
A preparation method of the nanoscale biodegradable composite material comprises the following steps:
mixing polyvinyl chloride and polyvinylpyrrolidone monomer according to the mass ratio of 1:2, then adding a methanol solution with the concentration of 15mol/L and stannous chloride, uniformly stirring, and stirring the obtained mixture at 50 ℃ for reacting for 42 hours to obtain a product I;
mixing silicon carbide whiskers with oxalic acid according to the mass ratio of 1:0.9, placing the mixture in a high-pressure reaction kettle to react for 5 hours at 90 ℃, cooling the mixture to room temperature after the reaction is finished, grinding the obtained product into powder, mixing the obtained powder with deionized water according to the mass ratio of 1:6, adding the product I (the mass ratio of the product I to the powder is 1:2) to carry out ultrasonic (frequency of 90KHz, time of 75 min) dispersion, placing the mixture in a 70 ℃ water bath to stir and heat for 3 hours after the uniform dispersion, and dripping a small amount of sodium bicarbonate solution in the stirring process to obtain a product II;
mixing the product II with coconut fibers according to a physical ratio of 4:1 and freeze-drying the mixture at-30 ℃ for 7 hours to obtain a dried material, putting the dried material into a high-speed mixer, and sequentially putting glycerol, tetra [ beta- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionic acid ] pentaerythritol ester and calcium carbonate according to a mass ratio of 2:1:1, and mixing the raw materials in the high-speed mixer for 20-30 minutes; and (3) crushing the obtained mixture and performing superfine treatment of more than 1000 meshes to obtain a mixture with a nanoscale, and finally adding the nanoscale mixture into a double-screw extruder (the extrusion temperature of a first area is 90 ℃, the extrusion temperature of a second area is 110 ℃, and the extrusion temperature of a third area is 120 ℃), and extruding and granulating to obtain the nanoscale biodegradable composite material.
Example 3
A preparation method of the nanoscale biodegradable composite material comprises the following steps:
mixing polyvinyl chloride and polyvinylpyrrolidone monomer according to the mass ratio of 1:4, then adding hexanediol solution with the concentration of 15mol/L and dibutyl tin oxide, uniformly stirring, and stirring the obtained mixture at 50 ℃ for reacting for 42 hours to obtain a product I;
mixing silicon carbide whiskers with acetic acid according to the mass ratio of 1:0.3, placing the mixture into a high-pressure reaction kettle to react for 5 hours at 90 ℃, cooling the mixture to room temperature after the reaction is finished, grinding the obtained product into powder, mixing the obtained powder with deionized water according to the mass ratio of 1:10, adding the product I (the mass ratio of the product I to the powder is 1:3) to carry out ultrasonic (frequency of 90KHz, time of 75 min) dispersion, placing the mixture into a 70 ℃ water bath to stir and heat for 3 hours after the uniform dispersion, and dripping a small amount of sodium bicarbonate solution in the stirring process to obtain a product II;
mixing the product II with jute fiber according to the physical ratio of 2:1 and freeze-drying the mixture at the temperature of minus 30 ℃ for 7 hours to obtain a dried material, putting the dried material into a high-speed mixer, and mixing the raw materials in the high-speed mixer according to the mass ratio of 2:1 and sequentially adding sorbitol, dilauryl thiodipropionate and talcum powder for 20-30 minutes; and (3) crushing the obtained mixture and performing superfine treatment of more than 1000 meshes to obtain a mixture with a nanoscale, and finally adding the nanoscale mixture into a double-screw extruder (the extrusion temperature of a first area is 90 ℃, the extrusion temperature of a second area is 110 ℃, and the extrusion temperature of a third area is 120 ℃), and extruding and granulating to obtain the nanoscale biodegradable composite material.
Example 4
A preparation method of the nanoscale biodegradable composite material comprises the following steps:
mixing polyvinyl chloride and polyvinylpyrrolidone monomer according to the mass ratio of 1:3, then adding glycerol solution with the concentration of 20mol/L and tin bromide, uniformly stirring, and stirring the obtained mixture at 60 ℃ for reaction for 36h to obtain a product I;
mixing silicon carbide whiskers with citric acid according to the mass ratio of 1:0.3, placing the mixture into a high-pressure reaction kettle to react for 4 hours at the temperature of 100 ℃, cooling the mixture to room temperature after the reaction is finished, grinding the obtained product into powder, mixing the obtained powder with deionized water according to the mass ratio of 1:5, adding the product I (the mass ratio of the product I to the powder is 1:3) to carry out ultrasonic (frequency of 100KHz, time of 60 minutes) dispersion, placing the mixture into a water bath at the temperature of 60 ℃ to stir and heat for 4 hours after the uniform dispersion, and dripping a small amount of sodium bicarbonate solution in the stirring process to obtain a product II;
mixing the product II and sisal fibers according to a physical ratio of 3:1 and freeze-drying the mixture at-40 ℃ for 6 hours to obtain a dried material, putting the dried material into a high-speed mixer, and sequentially putting sorbitol, dilauryl thiodipropionate and calcium carbonate according to a mass ratio of 2:1, mixing the raw materials in the high-speed mixer for 20-30 minutes; and (3) crushing the obtained mixture and performing superfine treatment of more than 1000 meshes to obtain a mixture with a nanoscale, and finally adding the nanoscale mixture into a double-screw extruder (the extrusion temperature of a first area is 100 ℃, the extrusion temperature of a second area is 120 ℃, and the extrusion temperature of a third area is 130 ℃), and extruding and granulating to obtain the nanoscale biodegradable composite material.
Example 5
A preparation method of the nanoscale biodegradable composite material comprises the following steps:
mixing polyvinyl chloride and polyvinylpyrrolidone monomer according to the mass ratio of 1:4, then adding ethanol solution with the concentration of 10mol/L and tin bromide, uniformly stirring, and placing the obtained mixture at 40 ℃ for stirring reaction for 48 hours to obtain a product I;
mixing silicon carbide whiskers with oxalic acid according to the mass ratio of 1:0.4, placing the mixture in a high-pressure reaction kettle to react for 6 hours at 80 ℃, cooling the mixture to room temperature after the reaction is finished, grinding the obtained product into powder, mixing the obtained powder with deionized water according to the mass ratio of 1:9, adding the product I (the mass ratio of the product I to the powder is 1:2) to carry out ultrasonic (frequency 80KHz, time 90 min) dispersion, placing the mixture in a water bath at 80 ℃ to stir and heat for 2 hours after the uniform dispersion, and dripping a small amount of sodium bicarbonate solution in the stirring process to obtain a product II;
mixing the product II with ramie fibers according to the physical ratio of 3:1, freeze-drying for 8 hours at the temperature of minus 20 ℃ to obtain a dried material, putting the dried material into a high-speed mixer, and sequentially putting glycerin, dilauryl thiodipropionate and talcum powder according to the mass ratio of 2:1:1, and mixing the raw materials in the high-speed mixer for 20-30 minutes; and (3) crushing the obtained mixture and performing superfine treatment of more than 1000 meshes to obtain a mixture with a nanoscale, and finally adding the nanoscale mixture into a double-screw extruder (the extrusion temperature of a first area is 100 ℃, the extrusion temperature of a second area is 120 ℃, and the extrusion temperature of a third area is 130 ℃), and extruding and granulating to obtain the nanoscale biodegradable composite material.
Example 6
A preparation method of the nanoscale biodegradable composite material comprises the following steps:
mixing polyvinyl chloride and polyvinylpyrrolidone monomer according to the mass ratio of 1:2, then adding glycerol solution with the concentration of 15mol/L and stannous bromide, uniformly stirring, and stirring the obtained mixture at 60 ℃ for reacting for 48 hours to obtain a product I;
mixing silicon carbide whiskers with acetic acid according to the mass ratio of 1:0.8, placing the mixture into a high-pressure reaction kettle to react for 4 hours at 90 ℃, cooling the mixture to room temperature after the reaction is finished, grinding the obtained product into powder, mixing the obtained powder with deionized water according to the mass ratio of 1:7, adding the product I (the mass ratio of the product I to the powder is 1:3) to carry out ultrasonic (frequency 80KHz, time 90 min) dispersion, placing the mixture into a water bath at 80 ℃ to stir and heat for 3 hours after the uniform dispersion, and dripping a small amount of sodium bicarbonate solution in the stirring process to obtain a product II;
mixing the product II with bamboo fibers according to a physical ratio of 4:1 and freeze-drying the mixture at-30 ℃ for 8 hours to obtain a dried material, putting the dried material into a high-speed mixer, and sequentially putting glycerin, dilauryl thiodipropionate and calcium carbonate according to a mass ratio of 2:1:1, and mixing the raw materials in the high-speed mixer for 20-30 minutes; and (3) crushing the obtained mixture and performing superfine treatment of more than 1000 meshes to obtain a mixture with a nanoscale, and finally adding the nanoscale mixture into a double-screw extruder (the extrusion temperature of a first area is 100 ℃, the extrusion temperature of a second area is 120 ℃, and the extrusion temperature of a third area is 130 ℃), and extruding and granulating to obtain the nanoscale biodegradable composite material.
Comparative example 1
A preparation method of the nanoscale biodegradable composite material comprises the following steps:
mixing polyvinyl chloride and polyvinylpyrrolidone monomer according to the mass ratio of 1:3, then adding ethanol solution with the concentration of 15mol/L and tin chloride, uniformly stirring, and stirring the obtained mixture at 50 ℃ for reacting for 42h to obtain a product I;
mixing the product I with cotton fiber according to a physical ratio of 3:1 and freeze-drying the mixture at-30 ℃ for 7 hours to obtain a dried material, putting the dried material into a high-speed mixer, and sequentially putting sorbitol, tetra [ beta- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionic acid ] pentaerythritol ester and talcum powder according to a mass ratio of 2:1:1, and mixing the raw materials in the high-speed mixer for 20-30 minutes; and (3) crushing the obtained mixture and performing superfine treatment of more than 1000 meshes to obtain a mixture with a nanoscale, and finally adding the nanoscale mixture into a double-screw extruder (the extrusion temperature of a first area is 90 ℃, the extrusion temperature of a second area is 110 ℃, and the extrusion temperature of a third area is 120 ℃), and extruding and granulating to obtain the nanoscale biodegradable composite material.
Comparative example 2
A preparation method of the nanoscale biodegradable composite material comprises the following steps:
mixing polyvinyl chloride and polyvinylpyrrolidone monomer according to the mass ratio of 1:3, then adding ethanol solution with the concentration of 15mol/L and tin chloride, uniformly stirring, and stirring the obtained mixture at 50 ℃ for reacting for 42h to obtain a product I;
mixing silicon carbide whiskers with citric acid according to the mass ratio of 1:0.6, placing the mixture into a high-pressure reaction kettle to react for 5 hours at 90 ℃, cooling the mixture to room temperature after the reaction is finished, grinding the obtained product into powder, mixing the obtained powder with deionized water according to the mass ratio of 1:8, adding a product I (the mass ratio of the product I to the powder is 1:2) to carry out ultrasonic (frequency of 90KHz, time of 75 min) dispersion, placing the mixture into a 70 ℃ water bath to be stirred and heated for 3 hours after the uniform dispersion, and dripping a small amount of sodium bicarbonate solution in the stirring process to obtain a product II;
freeze-drying the product II at the temperature of minus 30 ℃ for 7 hours to obtain a dried material, putting the dried material into a high-speed mixer, and sequentially putting sorbitol, tetra [ beta- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionic acid ] pentaerythritol ester and talcum powder into the mixer according to the mass ratio of 2:1:1, and mixing the raw materials in the high-speed mixer for 20-30 minutes; and (3) crushing the obtained mixture and performing superfine treatment of more than 1000 meshes to obtain a mixture with a nanoscale, and finally adding the nanoscale mixture into a double-screw extruder (the extrusion temperature of a first area is 90 ℃, the extrusion temperature of a second area is 110 ℃, and the extrusion temperature of a third area is 120 ℃), and extruding and granulating to obtain the nanoscale biodegradable composite material.
Test example Material Performance detection
The experimental object: examples 1-6 and comparative examples 1-2
The experimental method comprises the following steps: the plastic product is obtained by blow molding the material at 200 ℃, and the tensile strength and the biodegradation rate of the plastic product are counted.
1. Tensile Strength
The test was carried out according to GB/T1040.1-2018& GB/T1040.3-2006, and the results are shown in Table 1.
Table 1 tensile strength results for each material
As can be seen from the results of Table 1, the nano-sized biodegradable composite material obtained according to the method of the present invention has good tensile properties as compared with comparative examples 1-2.
2. Biological decomposition Rate
The biological decomposition process in the natural water-containing environment was simulated using GB/T19276.1-2003 standard, and the test results are shown in Table 2.
TABLE 2 biological decomposition Rate
As can be seen from the results of Table 2, the decomposition rate of the nano-sized biodegradable composite material obtained by the method according to the present invention is significantly improved as compared with comparative examples 1-2.
While the invention has been described with respect to preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and that any such changes and modifications as described in the above embodiments are intended to be within the scope of the invention.
Claims (10)
1. A method for preparing a nanoscale biodegradable composite material, the method comprising the steps of:
mixing polyvinyl chloride and polyvinylpyrrolidone monomer according to the mass ratio of 1:2-4, then adding an organic alcohol solution with the concentration of 10-20mol/L and a catalyst, uniformly stirring, and placing the obtained mixture at 40-60 ℃ for stirring reaction for 36-48h to obtain a product I;
mixing silicon carbide whiskers with organic acid according to the mass ratio of 1:0.3-0.9, placing the mixture in a high-pressure reaction kettle for reaction for 4-6 hours at 80-100 ℃, cooling to room temperature after the reaction is finished, grinding the obtained product into powder, mixing the obtained powder with deionized water according to the mass ratio of 1:5-10, adding the product I for ultrasonic dispersion, placing the mixture in a water bath at 60-80 ℃ for stirring and heating for 2-4 hours after the mixture is uniformly dispersed, and dripping sodium bicarbonate solution in the stirring process to obtain a product II;
mixing the product II with plant fibers according to a physical ratio of 2-4:1, and freeze-drying at-40 to-20 ℃ for 6-8 hours to obtain a dried material, putting the dried material into a high-speed mixer, sequentially putting a plasticizer, an antioxidant and a filler, and mixing the raw materials in the high-speed mixer for 20-30 minutes; crushing the obtained mixture and performing superfine treatment with the granularity of more than 1000 meshes to make the mixture be nano-sized, and finally adding the nano-sized mixture into a double-screw extruder, and performing extrusion granulation to obtain the nano-sized biodegradable composite material.
2. The method of preparing a nano-scale biodegradable composite according to claim 1, wherein the organic alcohol is one selected from the group consisting of ethanol, methanol, hexanediol, and glycerol.
3. The method for preparing the nano-scale biodegradable composite material according to claim 1, wherein the catalyst is selected from any one of stannous bromide, tin bromide, dibutyl tin oxide, stannous chloride and stannic chloride.
4. The method for preparing a nano-scale biodegradable composite material according to claim 1, wherein the organic acid is one selected from the group consisting of citric acid, oxalic acid, and acetic acid.
5. The method for preparing the nanoscale biodegradable composite material according to claim 1, wherein the mass ratio of the added amount of the product I to the powder is 1:2-3.
6. The method of preparing a nanoscale biodegradable composite material according to claim 1, wherein the ultrasound conditions are: the frequency is 80-100KHz, and the time is 60-90min.
7. The method of preparing a nano-scale biodegradable composite material according to claim 1, wherein the plant fiber is at least one selected from cotton fiber, coconut fiber, jute fiber, sisal fiber, ramie fiber, bamboo fiber, kapok fiber.
8. The method for preparing the nano-scale biodegradable composite material according to claim 1, wherein the plasticizer is one or more of glycerin, monoglyceride, sorbitol, and stearic acid; the filler is one or more of calcium carbonate, talcum powder and titanium dioxide; the antioxidant is dilauryl thiodipropionate and pentaerythritol tetra [ beta- (3 ',5' -di-tert-butyl-4 ' -hydroxyphenyl) propionate ].
9. The method of preparing a nanoscale biodegradable composite material according to claim 1, wherein the mass ratio of plasticizer, antioxidant and filler is 2:1:1.
10. The method for preparing a nano-scale biodegradable composite material according to claim 1, wherein the twin-screw extruder has a first-zone extrusion temperature of 90-100 ℃, a second-zone extrusion temperature of 110-120 ℃, and a third-zone extrusion temperature of 120-130 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417248A (en) * | 2002-12-06 | 2003-05-14 | 暨南大学 | Chitosan grafted polyvinylpyrrolidone and its prepn process and application in preparing biodegradable material |
| CN101654499A (en) * | 2009-09-02 | 2010-02-24 | 陈煜� | Composite of natural macromolecule or amphiphilic grafting copolymer of water-soluble derivant and nanometer iodine and preparation method thereof |
| CN111019304A (en) * | 2019-12-23 | 2020-04-17 | 浙江大学 | Biodegradable nano composite material |
| CA3150607A1 (en) * | 2019-09-09 | 2021-03-18 | Jianyong Cai | Inorganic degradable plastic masterbatch material and preparation method therefor |
| CN113683874A (en) * | 2021-09-24 | 2021-11-23 | 南京五瑞生物降解新材料研究院有限公司 | Full-biomass full-degradable material and preparation method and application thereof |
-
2022
- 2022-12-07 CN CN202211564775.2A patent/CN116082780B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417248A (en) * | 2002-12-06 | 2003-05-14 | 暨南大学 | Chitosan grafted polyvinylpyrrolidone and its prepn process and application in preparing biodegradable material |
| CN101654499A (en) * | 2009-09-02 | 2010-02-24 | 陈煜� | Composite of natural macromolecule or amphiphilic grafting copolymer of water-soluble derivant and nanometer iodine and preparation method thereof |
| CA3150607A1 (en) * | 2019-09-09 | 2021-03-18 | Jianyong Cai | Inorganic degradable plastic masterbatch material and preparation method therefor |
| CN111019304A (en) * | 2019-12-23 | 2020-04-17 | 浙江大学 | Biodegradable nano composite material |
| CN113683874A (en) * | 2021-09-24 | 2021-11-23 | 南京五瑞生物降解新材料研究院有限公司 | Full-biomass full-degradable material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 一种新型可光降解的PVC-OA-TiO_2纳米复合膜;法文君;龚楚清;杨昌军;彭天右;昝菱;;武汉大学学报(理学版)(第05期);摘要 * |
| 聚偏氟乙烯/聚氯乙烯/聚甲基丙烯酸甲酯共混多孔中空纤维膜的制备与性能测试;戎静;奚旦立;李运清;;工业用水与废水(第05期);2 结果与讨论 * |
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