CN112442262A - Titanium dioxide modified biodegradable composite material and preparation method and application thereof - Google Patents
Titanium dioxide modified biodegradable composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a titanium dioxide modified biodegradable composite material and a preparation method and application thereof, wherein the composite material is prepared by mixing the following raw materials in proportion, wherein the proportion is as follows: 20-70% of poly (butylene adipate/terephthalate), 5-30% of polylactic acid, 5-20% of a compatilizer, 5-15% of a plasticizer, 3-15% of a tackifier, 10-50% of nano plant fiber powder and 0.2-1.5% of nano titanium dioxide. The invention adopts the synergistic effect of the degradable plastic, the nano plant fiber powder and the nano titanium dioxide to carry out functional modification on the biodegradable composite material, improves the application range of the modified degradable plastic, not only effectively reduces the production cost of the biodegradable composite material, but also has quick degradation performance after being used, can ensure the environmental protection property of the biodegradable composite material returning to nature after being used, simultaneously endows the biodegradable composite material with the antibacterial and bactericidal performance, and provides an excellent substitute product for food fresh-keeping materials and medical appliance packaging materials.
Description
Technical Field
The invention relates to the technical field of biodegradation, and particularly relates to a titanium dioxide modified biodegradable composite material, and a preparation method and application thereof.
Background
The application of plastics in real life is ubiquitous at present, and the harm to the environment caused by the difficulty of degradation of the plastics is obvious. With the increasing public awareness of environmental protection, degradable plastics are beginning to be used to protect the human living environment. In the field of food packaging, most of the packaging materials for medical disposable instruments are common plastic films, and a large amount of fresh-keeping materials are required to be used after packaging, so that great material waste (a large amount of disposable packaging materials are used) and environmental pollution are caused.
But the biodegradable plastic has high technical content, so the required cost is also high, the price of the biodegradable plastic product in the current market is more than one time higher than that of the common plastic product, and the price of the biodegradable plastic product is even 2-8 times higher than that of the common plastic product, so the application of the biodegradable material is limited. The plastic packaging material, especially the food packaging material, can be polluted by the environment in the use process, so that bacteria, mold, even viruses and the like are bred on the surface of the material, and the shelf life and the storage life of the food are influenced. Therefore, the antibacterial function of the material is more and more emphasized.
Disclosure of Invention
In view of the above, there is a need to provide a low-cost titanium dioxide modified biodegradable composite material, and a preparation method and applications thereof.
In order to solve the technical problems, the invention provides a titanium dioxide modified biodegradable composite material and a preparation method and application thereof, and adopts the following technical scheme:
the titanium dioxide modified biodegradable composite material is prepared by mixing the following raw materials in percentage by weight:
as an improvement of the titanium dioxide modified biodegradable composite material provided by the invention, the nano titanium dioxide is nano anatase titanium dioxide.
As an improvement of the titanium dioxide modified biodegradable composite material provided by the invention, the compatilizer is one or a mixture of more than one of glycidyl methacrylate, oligomeric epoxy chain extender, ethanolamine and tetrabutyl titanate.
As an improvement of the titanium dioxide modified biodegradable composite material provided by the invention, the plasticizer is one or a mixture of more than one of epoxidized soybean oil, white oil, glycerol, polyethylene glycol, citric acid, dimethyl phthalate and acetylated triethyl citrate.
As an improvement of the titanium dioxide modified biodegradable composite material provided by the invention, the tackifier is maleic anhydride.
As an improvement of the titanium dioxide modified biodegradable composite material provided by the invention, the plant fiber of the nano plant fiber powder is at least one of wood chips, bamboo chips, fruit shells, rice hulls, wheat hulls, peanut shells, soybean shells, bagasse, rice straws, wheat straws, sorghum stalks, cotton stalks, hemp stalks, corn cob powder, bean curd residues and coffee grounds.
A preparation method of a titanium dioxide modified biodegradable composite material comprises the following steps:
(1) grinding the dried plant fiber powder into nanometer plant fiber powder with nanometer fineness in a high-grade grinder;
(2) adding 20-70 wt% of polybutylene adipate/terephthalate, 5-30 wt% of polylactic acid, 5-20 wt% of compatilizer, 5-15 wt% of plasticizer, 3-15 wt% of tackifier, 10-50 wt% of nano plant fiber powder and 0.2-1.5 wt% of nano titanium dioxide into a mixer for uniform mixing to obtain a mixture;
(3) and adding the uniformly mixed mixture into a double-screw extruder, and extruding the mixture at a preset extrusion temperature to obtain the titanium dioxide modified biodegradable composite material.
As an improvement of the preparation method of the titanium dioxide modified biodegradable composite material provided by the invention, the preset extrusion temperature is 170-220 ℃.
A food preservative film is prepared from the titanium dioxide modified biodegradable composite material.
A medical or food packaging bag is made of the titanium dioxide modified biodegradable composite material.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the synergistic effect of the degradable plastic, the nano plant fiber powder and the nano titanium dioxide to carry out functional modification on the biodegradable composite material, improves the application range of the modified degradable plastic, not only effectively reduces the production cost of the biodegradable composite material, but also has quick degradation performance after being used, can ensure the environmental protection property of the biodegradable composite material returning to nature after being used, simultaneously endows the biodegradable composite material with the antibacterial and bactericidal performance, and provides an excellent substitute product for food fresh-keeping materials and medical appliance packaging materials.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to solve the technical problems of the background art, the invention provides a titanium dioxide modified biodegradable composite material and a preparation method thereof, and particularly,
a biodegradable composite material is prepared by mixing the following raw materials in percentage by weight:
the preparation method of the titanium dioxide modified biodegradable composite material comprises the following steps:
(1) grinding the dried plant fiber powder into nanometer plant fiber powder with nanometer fineness in a high-grade grinder;
(2) adding 20-70 wt% of polybutylene adipate/terephthalate, 5-30 wt% of polylactic acid, 5-20 wt% of compatilizer, 5-15 wt% of plasticizer, 3-15 wt% of tackifier, 10-50 wt% of nano plant fiber powder and 0.2-1.5 wt% of nano titanium dioxide into a mixer for uniform mixing to obtain a mixture;
(3) and adding the uniformly mixed mixture into a double-screw extruder, and extruding the mixture at a preset extrusion temperature to obtain the titanium dioxide modified biodegradable composite material.
Poly (butylene adipate terephthalate) (PBAT) is a natural biodegradable plastic that biodegrades in the presence of natural enzymes for several weeks. The PBAT has high mechanical property, good toughness and good processability. Blending with polylactic acid (PLA) to improve the brittleness of PLA;
polylactic acid (PLA) is a natural biodegradable plastic, and is now industrially produced. Polylactic acid has excellent optical properties and a very high modulus, but has low elongation at break, tear strength and breaking strength.
The nano titanium dioxide can absorb ultraviolet rays, reflect and scatter the ultraviolet rays, can transmit visible light, has superior performance and has a promising physical shielding type ultraviolet protective agent. The nano titanium dioxide has long-term sterilization effect under the action of ultraviolet rays in light. At 0.1mg/cm3The anatase type nano titanium dioxide with the concentration can thoroughly kill malignant Hela cells, and has good effect on killing malignant Hela cellsThe killing rate of bacillus subtilis black variant spore, pseudomonas aeruginosa, escherichia coli, staphylococcus aureus, salmonella and aspergillus can reach more than 98%.
The nano plant fiber powder is prepared by selecting natural plant fiber materials, such as at least one of wood chips, bamboo scraps, fruit shells, rice hulls, wheat hulls, peanut shells, soybean shells, bagasse, rice straws, wheat straws, sorghum straws, cotton stalks, hemp stalks, corncob powder, bean curd residues, coffee grounds and the like, and then grinding the materials in a high-grade grinder to a nanometer-grade fineness. The plant fiber is an agricultural byproduct, is a natural organic substance, contains cellulose, hemicellulose, lignin and the like, is converted into an organic fertilizer under natural conditions, and has wide sources.
The compatilizer is one or a mixture of more than one of Glycidyl Methacrylate (GMA), oligomeric epoxy chain extender, ethanolamine and tetrabutyl titanate. The addition of the compatilizer improves the compatibility of the mixed materials and is beneficial to mixing and processing.
The plasticizer is one or more of epoxidized soybean oil, white oil, glycerol, polyethylene glycol, citric acid, dimethyl phthalate and acetylated triethyl citrate (ATBC).
The tackifier is Maleic Anhydride (MAH), and the tackifier has a tackifying effect in the mixing process.
In order to make the technical solutions of the present application better understood by those skilled in the art, the technical solutions in the embodiments of the present application are clearly and completely described below.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
Example 1
The titanium dioxide modified biodegradable composite material is prepared by mixing the following raw materials in percentage by weight: 20% of polybutylene adipate/terephthalate, 30% of polylactic acid, 5% of glycidyl methacrylate, 9.2% of polyethylene glycol, 10% of maleic anhydride, 25% of nano plant fiber powder and 0.8% of nano anatase titanium dioxide;
the preparation method of the titanium dioxide modified biodegradable composite material comprises the following steps:
(1) mixing the dried fruit shells, rice hulls and wheat hulls in a high-grade grinder and grinding the mixture into nano plant fiber powder with nano-grade fineness;
(2) adding 20 percent of poly (butylene adipate/terephthalate), 30 percent of polylactic acid, 5 percent of glycidyl methacrylate, 9.2 percent of polyethylene glycol, 10 percent of maleic anhydride, 25 percent of nano plant fiber powder and 0.8 percent of nano anatase titanium dioxide into a mixer by weight percent for uniform mixing to obtain a mixture;
(3) adding the uniformly mixed mixture into a double-screw extruder, and extruding the mixture at a certain extrusion temperature (170 ℃ C. and 220 ℃ C.), thereby obtaining the titanium dioxide modified biodegradable composite material.
When in specific application, the titanium dioxide modified biodegradable composite material is processed by film blowing according to different purposes to be made into various disposable packaging materials (such as food fresh-keeping bags and medical article packaging bags) or food fresh-keeping films and the like.
Example 2
The titanium dioxide modified biodegradable composite material is prepared by mixing the following raw materials in percentage by weight: 25% of polybutylene adipate/terephthalate, 20% of polylactic acid, 5% of oligomeric epoxy chain extender, 14.8% of acetylated triethyl citrate, 3% of maleic anhydride, 32% of nano plant fiber powder and 0.2% of nano anatase titanium dioxide;
the preparation method of the titanium dioxide modified biodegradable composite material comprises the following steps:
(1) mixing and grinding the dried rice straws, sorghum straws, cotton stalks and hemp straws into nano plant fiber powder with nano-grade fineness in a high-grade grinder;
(2) adding 25% of polybutylene adipate/terephthalate, 20% of polylactic acid, 5% of oligomeric epoxy chain extender, 14.8% of acetylated triethyl citrate, 3% of maleic anhydride, 32% of nano plant fiber powder and 0.2% of nano anatase titanium dioxide into a mixer by weight percent, and uniformly mixing to obtain a mixture;
(3) adding the uniformly mixed mixture into a double-screw extruder, and extruding the mixture at a certain extrusion temperature (170 ℃ C. and 220 ℃ C.), thereby obtaining the titanium dioxide modified biodegradable composite material.
When in specific application, the titanium dioxide modified biodegradable composite material is processed by film blowing according to different purposes to be made into various disposable packaging materials (such as food fresh-keeping bags and medical article packaging bags) or food fresh-keeping films and the like.
Example 3
The titanium dioxide modified biodegradable composite material is prepared by mixing the following raw materials in percentage by weight: 30% of polybutylene adipate/terephthalate, 10% of polylactic acid, 10% of glycidyl methacrylate, 10% of oligomeric epoxy chain extender, 2% of polyethylene glycol, 3% of citric acid, 14.7% of maleic anhydride, 20% of nano plant fiber powder and 0.3% of nano anatase titanium dioxide;
the preparation method of the titanium dioxide modified biodegradable composite material comprises the following steps:
(1) mixing the dried bagasse, the bean curd residue and the coffee grounds in a high-grade grinder, and grinding into nanometer plant fiber powder with nanometer fineness;
(2) adding 30 percent of polybutylene adipate/terephthalate, 10 percent of polylactic acid, 10 percent of glycidyl methacrylate, 10 percent of oligomeric epoxy chain extender, 2 percent of polyethylene glycol, 3 percent of citric acid, 14.7 percent of maleic anhydride, 20 percent of nano plant fiber powder and 0.3 percent of nano anatase titanium dioxide into a mixer by weight percent for uniform mixing to obtain a mixture;
(3) adding the uniformly mixed mixture into a double-screw extruder, and extruding the mixture at a certain extrusion temperature (170 ℃ C. and 220 ℃ C.), thereby obtaining the titanium dioxide modified biodegradable composite material.
When in specific application, the titanium dioxide modified biodegradable composite material is processed by film blowing according to different purposes to be made into various disposable packaging materials (such as food fresh-keeping bags and medical article packaging bags) or food fresh-keeping films and the like.
Example 4
The titanium dioxide modified biodegradable composite material is prepared by mixing the following raw materials in percentage by weight: 20% of polybutylene adipate/terephthalate, 12% of polylactic acid, 6% of glycidyl methacrylate, 7.5% of acetylated triethyl citrate, 4% of maleic anhydride, 50% of nano plant fiber powder and 0.5% of nano anatase titanium dioxide;
the preparation method of the titanium dioxide modified biodegradable composite material comprises the following steps:
(1) mixing the dried sawdust, bamboo chips, fruit shells, rice hulls, peanut shells and soybean shells in a high-grade grinder and grinding the mixture into nano plant fiber powder with nanometer fineness;
(2) adding 20 percent of polybutylene adipate/terephthalate, 12 percent of polylactic acid, 6 percent of glycidyl methacrylate, 7.5 percent of acetylated triethyl citrate, 4 percent of maleic anhydride, 50 percent of nano plant fiber powder and 0.5 percent of nano anatase titanium dioxide into a mixer by weight percent for uniform mixing to obtain a mixture;
(3) adding the uniformly mixed mixture into a double-screw extruder, and extruding the mixture at a certain extrusion temperature (170 ℃ C. and 220 ℃ C.), thereby obtaining the titanium dioxide modified biodegradable composite material.
When in specific application, the titanium dioxide modified biodegradable composite material is processed by film blowing according to different purposes to be made into various disposable packaging materials (such as food fresh-keeping bags and medical article packaging bags) or food fresh-keeping films and the like.
The composite material of the embodiment is placed into an injection molding machine for manufacturing and molding, and the injection molding machine is used for injection molding into sample strips under the working conditions of 160T, 130 ℃ of sol, 150 ℃ and 2-4s of injection speed for performanceAnd (3) detecting, wherein the test result is as follows: 17.32MPa of tensile strength (GB/T1040-2And the water absorption (after drying at 50 ℃ for 24h, putting the mixture into water at 23 ℃ for 24h, GB/T1034-2008) is 0.963 percent. The result shows that the mechanical property of the biodegradable composite material is less influenced by adding 50% of the nano plant fiber powder into the biodegradable composite material.
Example 5
The titanium dioxide modified biodegradable composite material is prepared by mixing the following raw materials in percentage by weight: 70% of poly (butylene adipate/terephthalate), 5.5% of polylactic acid, 5% of glycidyl methacrylate, 5% of epoxidized soybean oil, 3% of maleic anhydride, 10% of nano plant fiber powder and 1.5% of nano anatase titanium dioxide;
the preparation method of the titanium dioxide modified biodegradable composite material comprises the following steps:
(1) mixing the dried sawdust, bamboo chips, corncob powder, bean curd residue and coffee grounds in a high-grade grinder, and grinding into nanometer plant fiber powder with nanometer fineness;
(2) adding 70 percent of poly (butylene adipate/terephthalate), 5.5 percent of polylactic acid, 5 percent of glycidyl methacrylate, 5 percent of epoxidized soybean oil, 3 percent of maleic anhydride, 10 percent of nano plant fiber powder and 1.5 percent of nano anatase titanium dioxide into a mixer by weight percent for uniform mixing to obtain a mixture;
(3) adding the uniformly mixed mixture into a double-screw extruder, and extruding the mixture at a certain extrusion temperature (170 ℃ C. and 220 ℃ C.), thereby obtaining the titanium dioxide modified biodegradable composite material.
When in specific application, the titanium dioxide modified biodegradable composite material is processed by film blowing according to different purposes to be made into various disposable packaging materials (such as food fresh-keeping bags and medical article packaging bags) or food fresh-keeping films and the like.
Comparative example 1
Based on example 5, the difference from example 5 is that: the ratio of polylactic acid becomes 16% without adding the nano plant fiber powder.
The biodegradable composite materials of examples 1-5 and comparative example 1 were blown and reprocessed to prepare packaging bags, which were then tested for degradability and antibacterial freshness-retaining properties.
Degradation Performance detection
The evaluation of the degradation performance of the composite material adopts a soil burying biodegradation experiment (the biodegradation experiment adopts a simpler outdoor soil burying method, the soil is common flower bed soil, the soil burying depth is about 10cm, a certain amount of water is added every 10 days after the degradation experiment is started, the soil is kept moist, after the first soil is buried for 30 days, a sample is taken out, the soil on the surface is washed away, the soil is placed in a 50 ℃ oven to be dried for 24 hours, and then the weight loss rate is calculated), and the experimental results are shown in table 1.
Detection of antibacterial and freshness-retaining properties
The fruits are very easy to be infected by pathogenic bacteria of the fruits and external pathogenic bacteria after being picked, the infection of the pathogenic bacteria is one of the main reasons for causing the fruit to go bad, the invention uses the rot index of the fruits to represent the fresh-keeping effect of different films, wherein the test method of the rot index comprises the following steps: put into constant temperature and humidity case (25 ℃, 50% RH) after packing with fresh strawberry with different freshness protection package, every freshness protection package selects 3, places 15 freshness protection packages altogether, places 15 strawberries in every freshness protection package, takes out after 120h, observes the rotten condition on strawberry surface, divides it into 4 levels according to rotten area size: grade 0, no rot; grade 1, rotting area is less than 10% of total area; 2, the rotten area accounts for 10 to 30 percent of the total area; grade 3, the rotten area is greater than 30% of the total area, and the rotten index is calculated according to the following formula:
TABLE 1
From the degradation test results of examples 1-5 and comparative example 1, it can be seen that, in the soil burying degradation test in the natural environment, when the composite material is degraded for 30 days, compared with comparative example 1, the degradation rate of the composite material of the invention is significantly improved by 11.51-57.56 times, which is an unexpected effect in the test process of the application.
After 90 days of second-batch soil burying, checking degradation conditions, wherein only a small amount of packaging bags are left in the soil burying area of the example 2, the weight loss rate is about 92.38%, the soil burying areas of the examples 1 and 3 are also provided with partial residual packaging bags, the weight loss rates are respectively about 82.57% and 79.25%, the soil burying area of the example 4 cannot find the packaging bags and is completely degraded, the soil burying area of the example 5 is also provided with the packaging bags, and the weight loss rate is about 49.57%; the buried area of comparative example 1 also had a large number of packages, and the loss of weight was measured to be about 7.19%, mainly the comparative example 1 was actually an unmodified biodegradable composite, and the degradation process was still longer, and the requirements for humidity, temperature, and microorganisms were higher in the degradation conditions.
The biodegradable effect of the titanium dioxide modified biodegradable composite material is obvious.
As can be seen from Table 1, compared with comparative example 1, the biodegradation efficiency of the material is remarkably improved, the fruit rot index is reduced, and the fruit rot indexes are respectively reduced by 60.84%, 59.82%, 61.07%, 62.35% and 63.00% compared with comparative example 1 in examples 1-5 of the invention. The titanium dioxide modified biodegradable composite material can better maintain the quality of foods such as fruits and the like and prolong the storage and preservation period. The antibacterial agent is added into the composite material in the comparative example 1, but the antibacterial performance of the composite material is far lower than that of the composite material in the examples 1-5 after tests, and the composite material is caused by the fact that the nano plant fiber powder is not added, and as the loose porous structure of the nano plant fiber powder has rich pore surfaces and has the largest specific surface area after nano grinding treatment, the organic antibacterial agent can be grafted better, and the antibacterial performance and the stability are further improved.
The invention has the beneficial effects
The invention adopts the synergistic effect of the degradable plastic, the nano plant fiber powder and the nano titanium dioxide to carry out functional modification on the biodegradable composite material, improves the application range of the modified degradable plastic, not only effectively reduces the production cost of the biodegradable composite material, but also has quick degradation performance after being used, can ensure the environmental protection property of the biodegradable composite material returning to nature after being used, simultaneously endows the biodegradable composite material with the antibacterial and bactericidal performance, and provides an excellent substitute product for food fresh-keeping materials and medical appliance packaging materials.
The nano anatase titanium dioxide is added into the biodegradable composite material modified by the nano plant fiber powder to prepare a film for food fresh-keeping packaging, the antibacterial fresh-keeping time of the film can be prolonged by more than 3 times compared with the fresh-keeping time of a common fresh-keeping film under the normal temperature condition, the film can also be used for packaging medical products, and the application range of the degradable material is expanded; the degradable plastic is buried in a farmland and a flower bed under natural conditions, the buried soil is completely decomposed in about three months after being 10cm thick, the natural environment is restored, the regression mode is simple, a large amount of manpower and material resources are saved, the environment is protected, the short-time complete degradation and the degradation conditions are simple, the application field of products is further widened, namely, the products can be directly composted or shallowly buried (namely, the soil layer of 10cm can be obtained) according to the collection of degradable plastic after being used, and the products can be decomposed into organic fertilizers in a short time; and the product cost is greatly reduced, the price of the common degradable plastic raw materials is more than twice that of common plastics such as PE, PP and the like, and the product cost is reduced by at least 30-50%, so that the cost performance has better competitiveness.
It should be understood that the above-described embodiments are only a part of the embodiments of the present application, and not all of the embodiments, and do not limit the scope of the present application. This application is capable of embodiments in many different forms and is provided for the purpose of enabling a thorough understanding of the disclosure of the application. Although the present application has been described in detail with reference to the foregoing embodiments, it will be apparent to one skilled in the art that the present application may be practiced without modification or with equivalents of some of the features described in the foregoing embodiments. All equivalent structures made by using the content of the specification of the present application are directly or indirectly applied to other related technical fields, and the same is within the protection scope of the present application.
Claims (10)
1. The titanium dioxide modified biodegradable composite material is characterized by being prepared by mixing the following raw materials in percentage by weight:
2. the titanium dioxide-modified biodegradable composite material according to claim 1, wherein said nano titanium dioxide is nano anatase titanium dioxide.
3. The titanium dioxide-modified biodegradable composite material according to claim 1, wherein the compatibilizer is one or a mixture of more than one of glycidyl methacrylate, an oligomeric epoxy chain extender, ethanolamine and tetrabutyl titanate.
4. The titanium dioxide-modified biodegradable composite material as claimed in claim 1, wherein the plasticizer is one or more selected from epoxidized soybean oil, white oil, glycerol, polyethylene glycol, citric acid, dimethyl phthalate, and acetylated triethyl citrate.
5. The titanium dioxide-modified biodegradable composite material according to claim 1, wherein said tackifier is maleic anhydride.
6. The titanium dioxide-modified biodegradable composite material according to claim 1, wherein the plant fiber of the nano plant fiber powder is at least one of wood chips, bamboo chips, fruit shells, rice hulls, wheat hulls, peanut shells, soybean shells, bagasse, rice straws, wheat straws, sorghum straws, cotton straws, hemp straws, corn cob meal, bean curd refuse, and coffee grounds.
7. A preparation method of a titanium dioxide modified biodegradable composite material is characterized by comprising the following steps:
(1) grinding the dried plant fiber powder into nanometer plant fiber powder with nanometer fineness in a high-grade grinder;
(2) adding 20-70 wt% of polybutylene adipate/terephthalate, 5-30 wt% of polylactic acid, 5-20 wt% of compatilizer, 5-15 wt% of plasticizer, 3-15 wt% of tackifier, 10-50 wt% of nano plant fiber powder and 0.2-1.5 wt% of nano titanium dioxide into a mixer for uniform mixing to obtain a mixture;
(3) and adding the uniformly mixed mixture into a double-screw extruder, and extruding the mixture at a preset extrusion temperature to obtain the titanium dioxide modified biodegradable composite material.
8. The method as claimed in claim 7, wherein the predetermined extrusion temperature is 170-220 ℃.
9. A food wrap film, characterized in that it is made using the titanium dioxide-modified biodegradable composite material according to any one of claims 1 to 6.
10. A medical or food packaging bag, characterized in that it is made of the titanium dioxide-modified biodegradable composite material according to any one of claims 1 to 6.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113265123A (en) * | 2021-04-26 | 2021-08-17 | 苏州赛荣建筑装饰工程有限公司 | Degradable thermal insulation plastic mulching film and preparation method thereof |
| CN114933815A (en) * | 2022-05-17 | 2022-08-23 | 江苏中科睿赛污染控制工程有限公司 | Straw composite material master batch and preparation method thereof |
| CN115028969A (en) * | 2022-05-05 | 2022-09-09 | 安徽万朗磁塑股份有限公司 | Biodegradable PBAT-based elastic sealing material and preparation method and application thereof |
| WO2024050726A1 (en) * | 2022-09-07 | 2024-03-14 | 扬州纳力新材料科技有限公司 | Flexible polyester film and preparation method therefor, composite current collector, battery and electronic product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033562A (en) * | 2016-11-28 | 2017-08-11 | 盐城工学院 | Root of kudzu vine nano-cellulose fiber polylactic acid plastic film and preparation method thereof |
| CN108440794A (en) * | 2018-03-12 | 2018-08-24 | 华侨大学 | A kind of preparation method of chitosan nano fiber element nanometer titanium dioxide composite membrane |
| CN109401246A (en) * | 2018-10-31 | 2019-03-01 | 安徽双平包装有限公司 | A kind of environment-protective food package bag material |
-
2019
- 2019-09-04 CN CN201910831647.1A patent/CN112442262A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033562A (en) * | 2016-11-28 | 2017-08-11 | 盐城工学院 | Root of kudzu vine nano-cellulose fiber polylactic acid plastic film and preparation method thereof |
| CN108440794A (en) * | 2018-03-12 | 2018-08-24 | 华侨大学 | A kind of preparation method of chitosan nano fiber element nanometer titanium dioxide composite membrane |
| CN109401246A (en) * | 2018-10-31 | 2019-03-01 | 安徽双平包装有限公司 | A kind of environment-protective food package bag material |
Non-Patent Citations (1)
| Title |
|---|
| 司鹏等: ""PLA/PBAT薄膜的制备及其降解性能研究"", 《塑料科技》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113265123A (en) * | 2021-04-26 | 2021-08-17 | 苏州赛荣建筑装饰工程有限公司 | Degradable thermal insulation plastic mulching film and preparation method thereof |
| CN115028969A (en) * | 2022-05-05 | 2022-09-09 | 安徽万朗磁塑股份有限公司 | Biodegradable PBAT-based elastic sealing material and preparation method and application thereof |
| CN115028969B (en) * | 2022-05-05 | 2024-02-20 | 安徽万朗磁塑股份有限公司 | Biodegradable PBAT-based elastic sealing material and preparation method and application thereof |
| CN114933815A (en) * | 2022-05-17 | 2022-08-23 | 江苏中科睿赛污染控制工程有限公司 | Straw composite material master batch and preparation method thereof |
| WO2024050726A1 (en) * | 2022-09-07 | 2024-03-14 | 扬州纳力新材料科技有限公司 | Flexible polyester film and preparation method therefor, composite current collector, battery and electronic product |
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Application publication date: 20210305 |