Preparation method for bismuth ion functional graphene agricultural film

Abstract

The present invention provides a preparation method for a bismuth ion functional graphene agricultural film, comprising the following steps: mixing: putting an oil-based bismuth ion graphene material and plastic granules into a blender for blending, and drying after the blending to obtain a mixture for later use; granulation: adding the mixture into an extruder, melting, mixing, extruding, cooling, pelletizing, and drying to obtain functional masterbatches; and film blowing: adding the functional masterbatches into a film blowing machine for film blowing to obtain a bismuth ion functional graphene agricultural film. The bismuth ion functional graphene agricultural film has a better heat insulation effect when being used as a greenhouse film, and can kill bacteria and harmful viruses on the ground when being used as a mulch film and a waterproof base film; moreover, bismuth ions effectively inhibit harmful fungi from infecting plant roots, and also achieve the function of preventing groundworm infestations.

Description

A method for preparing bismuth ion functional graphene agricultural film Technical Field

[0001] The invention belongs to the technical field of film material preparation, and particularly relates to a method for preparing a bismuth ion functional graphene agricultural film. Background Art

[0002] Following the preparation method of bismuth ion embedded graphene lattice, we applied the functional graphene material with bismuth ions embedded in the graphene lattice to agricultural film.

[0003] This invention combines functional graphene embedded with bismuth ions with plastic films for agricultural applications to create insulation films for greenhouses, planting films for the ground, and waterproof base films for trenches. These three types of films—sky films, ground films, and basement films—are manufactured using the same manufacturing method, but are applied to all three agricultural applications.

[0004] We've discovered that greenhouse films are the most widely used for insulation. Conventional greenhouse films provide the most economical insulation for winter crops and can also be used to grow or raise off-season produce. With this in mind, we've developed a method for applying functional graphene to agricultural films.

[0005] Materials incorporating bismuth ions embedded in a graphene lattice offer numerous advantages and are economically valuable. Previously, we have used thin films incorporating silver ions embedded in a graphene lattice. While these films are effective, offering sterilization and UV protection, they are still relatively expensive, making them unattainable for the average farmer. Only farmers with high-value crops and livestock will invest in them, though they also appreciate the high costs. Therefore, achieving economic value through improvement and optimization is essential.

[0006] Because bismuth ions are bound to graphene, the resulting film exhibits excellent light transmission. Compared to silver ions, bismuth ions are superior to silver ions in infrared and heat preservation. They are more effective than silver in trapping infrared and far-infrared radiation, a key goal of this research. The addition of graphene as an ion support allows graphene to amplify the bismuth ions. Tests have shown that bismuth ions have a stronger bactericidal effect than silver ions. Furthermore, bismuth-ion graphene exhibits a photocatalytic effect, achieving photocatalytic bactericidal activity without direct contact with bacteria and viruses. Even with direct contact, however, their bactericidal power is stronger than that of silver.

[0007] Bismuth ions offer numerous properties and excellent performance, making them a cost-effective material. Furthermore, bismuth-ion graphene not only locks in infrared radiation for thermal insulation but also filters ultraviolet light, providing radiation protection. Its ability to absorb X-rays and gamma rays also mitigates light pollution, making it an ideal material for environmentally friendly and green applications.

[0008] First, bismuth-ion graphene boasts a significant production cost advantage over silver-ion graphene. In the future, its applications in greenhouse films will be widespread. Besides serving as rooftop insulation and rain protection, bismuth-ion graphene films can also serve as ground films and waterproof base films. Furthermore, contact with the ground film through the soil can kill ground bacteria and harmful viruses. Furthermore, the bismuth ions effectively inhibit harmful fungi from infecting plant roots and are also used as base films to protect against groundworms. Summary of the Invention

[0009] In view of the shortcomings of the existing technology, the present invention provides a method for preparing a bismuth ion functional graphene agricultural film.

[0010] To achieve the above object, the present invention provides the following technical solutions:

[0011] A method for preparing a bismuth ion functional graphene agricultural film comprises the following steps:

[0012] (1) Mixing: Put the oily bismuth ion graphene material and the colloid particles into a blender and stir them. After stirring, dry them to obtain a mixture for later use;

[0013] (2) Granulation: Add the mixture obtained in step (1) into an extruder, perform melting, mixing, extrusion, cooling, pelletizing, and drying to obtain functional masterbatch;

[0014] (3) Film blowing: adding the functional masterbatch obtained in step (2) into a film blowing machine, and performing film blowing to obtain a bismuth ion functional graphene agricultural film.

[0015] Preferably, the colloid particles in step (1) are one of PVC, EVA, PET, PO or PP.

[0016] Preferably, in step (1), the mass ratio of the oily bismuth ion graphene material to the colloid particles is 1:100-250.

[0017] Preferably, the stirring time in step (1) is 1-2 h, and the stirring speed is 60-150 r / min.

[0018] Preferably, the drying temperature in step (1) is 60-70°C, and the drying time is 2-3 hours.

[0019] Preferably, the preparation of the oily bismuth ion graphene material in step (1) is as follows: 100 parts by weight of natural flake graphite powder and 4 parts by weight of chelated bismuth ion solution are added to a reactor, 776 parts by weight of DTPA are added as an infiltration buffer, the pH is adjusted to 6, the reaction pressure is 0.1 MPa, and the reaction is carried out at 30°C for 8 hours. After the reaction is completed, 100 parts by weight of EDTA solution is added as an impact agent, and the reaction is continued at 30°C for 4 hours. After the reaction is completed, the oily bismuth ion graphene material is obtained.

[0020] Preferably, the particle size of the natural flake graphite powder is 300-15000 mesh, and the mass concentration of the chelated bismuth ions is 10000 ppm.

[0021] Preferably, the impact agent is EDTA solution with a concentration of 1 mol / L.

[0022] The present invention also protects the application of the preparation method of the bismuth ion functional graphene agricultural film. The bismuth ion functional graphene agricultural film can be used in three application films: sky film, ground film and basement film.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) This invention proposes for the first time to apply bismuth ion functional graphene materials to agricultural films. Compared with silver ions, bismuth ions have better functions in infrared and heat preservation, so they have better heat preservation performance than silver in locking infrared and far infrared rays.

[0025] (2) Bismuth ions have stronger bactericidal ability than silver ions, and bismuth ion graphene has a stronger photocatalytic effect, which can play a photocatalytic bactericidal role without direct contact with bacteria and viruses; bismuth ion graphene can not only lock infrared rays and keep warm, but also filter ultraviolet rays and have the ability to protect against radiation. It can absorb x-rays and gamma rays and other advantages.

[0026] (3) When bismuth ion functional graphene materials are applied to ground membranes and waterproof base membranes, the ground membranes made of bismuth ion graphene can come into contact with the soil, which can kill the invasion of bacteria and harmful viruses on the ground. In addition, the bismuth ion can effectively inhibit harmful fungi from infecting plant roots, and also achieve the effect of blocking groundworm invasion. Implementation Method

[0027] The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0028] All raw materials in the examples of the present invention can be obtained commercially, among which non-ionic chelating agents (EDTA, DTPA) and chelated bismuth ions can be purchased from Asia Sky Group. Example

[0029] A method for preparing a bismuth ion functional graphene agricultural film comprises the following steps:

[0030] (1) Preparation of oily bismuth ion graphene material: 100 g of natural flake graphite powder and 4 g of chelated bismuth ion solution with a mass concentration of 10,000 ppm were added to the reactor, and then 776 g of 1 mol / L DTPA was added as an infiltration buffer. The pH was adjusted to 6 and the reaction pressure was 0.1 MPa. The reaction was carried out at 30°C for 8 h. After the reaction was completed, 100 g of 1 mol / L EDTA solution was added as an impact agent and the reaction was continued at 30°C for 4 h. After the reaction was completed, the oily bismuth ion graphene material was obtained.

[0031] (2) Mixing: 100 g of oily bismuth ion graphene material and 10 kg of PVC particles were placed in a blender and stirred at a speed of 60 r / min for 1 h. After stirring, the mixture was dried at 60 ° C for 3 h to obtain a mixture for standby use;

[0032] (3) Granulation: Add the mixture obtained in step (2) into a twin-screw extruder, perform melting, mixing, extrusion, cooling, pelletizing, and drying to obtain functional masterbatch;

[0033] (4) Film blowing: The functional masterbatch obtained in step (3) is added into a film blowing machine and film blowing is performed to obtain a bismuth ion functional graphene agricultural film. Example

[0034] A method for preparing a bismuth ion functional graphene agricultural film comprises the following steps:

[0035] (1) Preparation of oily bismuth ion graphene material: 100 g of natural flake graphite powder and 4 g of chelated bismuth ion solution with a mass concentration of 10,000 ppm were added to the reactor, and then 776 g of 1 mol / L DTPA was added as an infiltration buffer. The pH was adjusted to 6 and the reaction pressure was 0.1 MPa. The reaction was carried out at 30°C for 8 h. After the reaction was completed, 100 g of 1 mol / L EDTA solution was added as an impact agent and the reaction was continued at 30°C for 4 h. After the reaction was completed, the oily bismuth ion graphene material was obtained.

[0036] (2) Mixing: 100 g of oily bismuth ion graphene material and 15 kg of PET pellets were placed in a blender and stirred at a speed of 60 r / min for 1 h. After stirring, the mixture was dried at 60 ° C for 3 h to obtain a mixture for later use;

[0037] (3) Granulation: Add the mixture obtained in step (2) into a twin-screw extruder, perform melting, mixing, extrusion, cooling, pelletizing, and drying to obtain functional masterbatch;

[0038] (4) Film blowing: The functional masterbatch obtained in step (3) is added into a film blowing machine and film blowing is performed to obtain a bismuth ion functional graphene agricultural film. Example

[0039] A method for preparing a bismuth ion functional graphene agricultural film comprises the following steps:

[0040] (1) Preparation of oily bismuth ion graphene material: 100 g of natural flake graphite powder and 4 g of chelated bismuth ion solution with a mass concentration of 10,000 ppm were added to the reactor, and then 776 g of 1 mol / L DTPA was added as an infiltration buffer. The pH was adjusted to 6 and the reaction pressure was 0.1 MPa. The reaction was carried out at 30°C for 8 h. After the reaction was completed, 100 g of 1 mol / L EDTA solution was added as an impact agent and the reaction was continued at 30°C for 4 h. After the reaction was completed, the oily bismuth ion graphene material was obtained.

[0041] (2) Mixing: 100 g of oily bismuth ion graphene material and 10 kg of PP particles were placed in a blender and stirred at a speed of 60 r / min for 1.5 h. After stirring, the mixture was dried at 60 ° C for 3 h to obtain a mixture for later use;

[0042] (3) Granulation: Add the mixture obtained in step (2) into a twin-screw extruder, perform melting, mixing, extrusion, cooling, pelletizing, and drying to obtain functional masterbatch;

[0043] (4) Film blowing: The functional masterbatch obtained in step (3) is added into a film blowing machine and film blowing is performed to obtain a bismuth ion functional graphene agricultural film. Example

[0044] A method for preparing a bismuth ion functional graphene agricultural film comprises the following steps:

[0045] (1) Preparation of oily bismuth ion graphene material: 100 g of natural flake graphite powder and 4 g of chelated bismuth ion solution with a mass concentration of 10,000 ppm were added to the reactor, and then 776 g of 1 mol / L DTPA was added as an infiltration buffer. The pH was adjusted to 6 and the reaction pressure was 0.1 MPa. The reaction was carried out at 30°C for 8 h. After the reaction was completed, 100 g of 1 mol / L EDTA solution was added as an impact agent and the reaction was continued at 30°C for 4 h. After the reaction was completed, the oily bismuth ion graphene material was obtained.

[0046] (2) Mixing: 100 g of oily bismuth ion graphene material and 15 kg of PP particles were placed in a blender and stirred at a speed of 100 r / min for 2 h. After stirring, the mixture was dried at 70 ° C for 3 h to obtain a mixture for standby use;

[0047] (3) Granulation: Add the mixture obtained in step (2) into a twin-screw extruder, perform melting, mixing, extrusion, cooling, pelletizing, and drying to obtain functional masterbatch;

[0048] (4) Film blowing: The functional masterbatch obtained in step (3) is added into a film blowing machine and film blowing is performed to obtain a bismuth ion functional graphene agricultural film. Example

[0049] A method for preparing a bismuth ion functional graphene agricultural film comprises the following steps:

[0050] (1) Preparation of oily bismuth ion graphene material: 100 g of natural flake graphite powder and 4 g of chelated bismuth ion solution with a mass concentration of 10,000 ppm were added to the reactor, and then 776 g of 1 mol / L DTPA was added as an infiltration buffer. The pH was adjusted to 6 and the reaction pressure was 0.1 MPa. The reaction was carried out at 30°C for 8 h. After the reaction was completed, 100 g of 1 mol / L EDTA solution was added as an impact agent and the reaction was continued at 30°C for 4 h. After the reaction was completed, the oily bismuth ion graphene material was obtained.

[0051] (2) Mixing: 100 g of oily bismuth ion graphene material and 10 kg of EVA particles were placed in a blender and stirred at a speed of 60 r / min for 1 h. After stirring, the mixture was dried at 60 ° C for 2 h to obtain a mixture for standby use;

[0052] (3) Granulation: Add the mixture obtained in step (2) into a twin-screw extruder, perform melting, mixing, extrusion, cooling, pelletizing, and drying to obtain functional masterbatch;

[0053] (4) Film blowing: The functional masterbatch obtained in step (3) is added into a film blowing machine and film blowing is performed to obtain a bismuth ion functional graphene agricultural film.

[0054] The bismuth ion functionalized graphene agricultural films obtained in Examples 1-5 above were applied to agricultural skylights to test their light transmittance. The results are shown in Table 1 below:

[0055] Table 1 Light transmission properties of various examples

[0056] The bismuth ion functionalized graphene agricultural film obtained in Examples 1-5 was applied to agricultural mulch to test its antibacterial properties. The test standard was ASTM E2315-2016. The test was performed using the Escherichia coli accession number ATCC8739 and the Staphylococcus aureus accession number ATCC6538. The results are shown in Table 2 below:

[0057] Table 2 Antibacterial properties of various examples

[0058] Item Antibacterial rate of Escherichia coli % Antibacterial rate of Staphylococcus aureus % Example 1 99.93 99.91 Example 2 99.97 99.94 Example 3 99.91 99.97 Example 4 99.96 99.93 Example 5 99.92 99.95

[0059] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of a bismuth ion functional graphene agricultural film, comprising:(1) mixing: adding an oil-based bismuth ion graphene material and colloidal particles to a mixer, and then stirring the oil-based bismuth ion graphene material and the colloidal particles followed by drying to obtain a mixed material for later use;(2) granulating: adding the mixed material obtained in the step (1) to an extruder, and then melting the mixed material to obtain a melted material, compounding the melted material to obtain a compounded material, extruding the compounded material followed by cooling to obtain a cooled material, and granulating the cooled material followed by drying to obtain functional masterbatches; and(3) film blowing: adding the functional masterbatches to a film-blowing machine followed by blowing to obtain the bismuth ion functional graphene agricultural film;wherein a preparation method of the oil-based bismuth ion graphene material in the step (1) comprises:adding 100 parts by weight of natural flake graphite powder and 4 parts by weight of a chelated bismuth ion solution to a reaction kettle, and then adding 776 parts by weight of diethylenetriaminepentaacetic acid (DTPA) to the reaction kettle followed by adjusting a pH of 6 for reaction with a pressure of 0.1 megapascals (MPa) at a temperature of 30C for 8 h to obtain a reacted mixture, and adding 100 parts by weight of an ethylenediaminetetraacetic acid (EDTA) solution as an impact agent to the reacted mixture for reaction at 30C for 4 h to obtain the oil-based bismuth ion graphene material.

2. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 1, wherein the colloidal particles in the step (1) comprises one selected from the group consisting of polyvinyl chloride (PVC), ethylene-vinyl acetate copolymer (EVA), polyethylene terephthalate (PET), polyolefin (PO) and polypropylene (PP).

3. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 1, wherein a weight ratio of the oil-based bismuth ion graphene material to the colloidal particles in the step (1) is 1 : 100-250.

4. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 1, wherein time for the stirring in the step (1) is in a range of 1-2 hours (h), and a speed of the stirring in the step (1) is in a range of 60-150 revolutions per minute (r / min).

5. The preparation method of the bismuth ion functional graphene agricultural film as2023325977   28 Aug 2026claimed in claim 1, wherein a temperature of the drying in the step (1) is in a range of 60-70C, and time of the drying in the step (1) is in a range of 2-3 h.

6. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 1, wherein a particle size of the natural flake graphite powder is in a range of 300-15000 mesh, and a weight concentration of the chelated bismuth ion solution is 10000 parts per million (ppm).

7. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 1, wherein the EDTA solution is at a concentration of 1 mole per liter (mol / L).

8. An application method of the preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 1, comprising: applying the bismuth ion functional graphene agricultural film in three types of application films including: a top film, a ground film and an underground film.

9. A preparation method of a bismuth ion functional graphene agricultural film, comprising:(1) preparation of an oil-based bismuth ion graphene material: adding 100 grams (g) of flake graphite powder and 4 g of a chelated bismuth ion solution to a reaction kettle, and then adding 776 g of DTPA to the reaction kettle followed by adjusting a pH of6 for reaction with a pressure of 0.1 MPa at a temperature of 30oC for 8 h to obtain a reacted mixture, and adding 100 g of a EDTA solution as an impact agent to the reacted mixture for reaction at 30C for 4 h to obtain the oil-based bismuth ion graphene material;(2) mixing: adding the oil-based bismuth ion graphene material and colloidal particles to a mixer, and then stirring the oil-based bismuth ion graphene material and the colloidal particles followed by drying to obtain a mixed material for later use;(3) granulating: adding the mixed material obtained in the step (1) to an extruder, and then melting the mixed material to obtain a melted material, compounding the melted material to obtain a compounded material, extruding the compounded material followed by cooling to obtain a cooled material, and granulating the cooled material followed by drying to obtain functional masterbatches; and(4) film blowing: adding the functional masterbatches to a film-blowing machine followed by blowing to obtain the bismuth ion functional graphene agricultural film.

10. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 9, wherein a particle size of the natural flake graphite powder is in a range of 300-15000 mesh, and a weight concentration of the chelated bismuth ion solution is 100002023325977   28 Aug 2026ppm.

11. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 10, wherein a concentration of the EDTA solution is 1 mol / L.

12. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 9, wherein a weight ratio of the oil-based bismuth ion graphene material to the colloidal particles in the step (2) is 1 : 100-250.

13. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 9, wherein time for the stirring in the step (2) is in a range of 1-2 h, and a speed of the stirring in the step (2) is in a range of 60-150 r / min.

14. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 9, wherein a temperature of the drying in the step (2) is in a range of 60-70C, and time of the drying in the step (2) is in a range of 2-3 h.

15. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 9, wherein the colloidal particles in the step (2) are PVC, and a weight ratio of the oil-based bismuth ion graphene material to the colloidal particles in the step (2) is 1 : 100.

16. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 9, wherein the colloidal particles in the step (2) are PET, and a weight ratio of the oil-based bismuth ion graphene material to the colloidal particles in the step (2) is 1 : 150.

17. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 9, wherein the colloidal particles in the step (2) are PP, and a weight ratio of the oil-based bismuth ion graphene material to the colloidal particles in the step (2) is 1 : 150.

18. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 17, wherein time for the stirring in the step (2) is 2 h, and a speed of the stirring in the step (2) is 100 r / min; a temperature of the drying in the step (2) is 70C, and time of the drying in the step (2) is 3 h.

19. The preparation method of the bismuth ion functional graphene agricultural film as claimed in claim 9, wherein the colloidal particles in the step (2) are EVA, and a weight ratio of the oil-based bismuth ion graphene material to the colloidal particles in the step (2) is 1 : 100.