Method for manufacturing bismuth ion functional graphene agricultural film

Abstract

The present invention provides a method for producing a bismuth ion functional graphene agricultural film. The method includes a mixing step of feeding an oil-based bismuth ion graphene material and colloidal particles into a mixer, stirring, and drying after stirring to obtain and prepare a mixed material; a granulation step of feeding the mixed material into an extruder, melting, kneading, extruding, cooling, cutting, and drying to obtain a functional master batch; and a film inflation step of feeding the functional master batch into an inflation film molding machine to perform film inflation to obtain a bismuth ion functional graphene agricultural film. If this is used as a roof film among agricultural films, it will have a better heat retention effect. In addition, if it is used as a ground film and a waterproof underground film, it will be possible to kill bacteria and harmful viruses on the ground. In addition, the action of bismuth ions can effectively suppress the infection of harmful fungi on the roots of plants, thereby preventing damage caused by insects underground.

Description

【Technical Field】 【0001】 The present invention belongs to the technical field of film material manufacturing, and specifically relates to a method for manufacturing a bismuth ion-functionalized graphene agricultural film. 【Background Art】 【0002】 Following the method for manufacturing a bismuth ion-embedded graphene lattice, we decided to apply a functional graphene material with bismuth ions embedded in the graphene lattice to agricultural films. 【0003】 In the present invention, functional graphene embedded with bismuth ions is combined with agricultural plastic films to manufacture heat-insulating films for greenhouses, cultivation films for the ground, and waterproof underground films for trenches, etc. That is, three types of application films, namely roof films, ground films, and underground films, are manufactured, but these are merely applications of the same manufacturing method to three uses in agriculture. 【0004】 We noticed that greenhouse films are very widely used for heat insulation purposes. General greenhouse films can exhibit the most economical heat insulation effect in winter cultivation, and also enable the cultivation and breeding of out-of-season agricultural products in greenhouses, so their uses are very wide. Therefore, we utilized the characteristics of functional graphene to research and develop its application to agricultural films. 【0005】 Materials with bismuth ions embedded in the graphene lattice have various advantages and economic value. So far, we have used a material film with silver ions embedded in the graphene lattice, which of course was easy to use and could perform functions such as sterilization and ultraviolet prevention. However, due to the high manufacturing cost, it was difficult for ordinary farmers to accept, and only farmers with high cultivation and breeding value invested in it, but even they felt that the cost was slightly high. Therefore, we need to rationalize through improvement and pursue the achievement of economic value. 【0006】 When bismuth ions are bound to graphene, the resulting film exhibits superior light transmission properties. Furthermore, bismuth ions perform better than silver ions in terms of infrared radiation and heat retention, resulting in superior infrared and far-infrared retention compared to silver. This is also an objective of this research and development. In addition, graphene acts as a support for the ions, increasing their concentration. Moreover, tests have shown that the bactericidal power of bismuth ions is stronger than that of silver ions. Furthermore, bismuth ion graphene also possesses photocatalytic properties, allowing it to exhibit bactericidal capabilities through photocatalysis even without direct contact with bacteria or viruses. Naturally, when in direct contact with bacteria or viruses, its bactericidal power is stronger than that of silver. 【0007】 Bismuth ions possess numerous properties, offering excellent effectiveness and versatility, and are cost-effective as a material. Furthermore, bismuth ion graphene not only retains infrared radiation for heat retention but also exhibits the ability to block ultraviolet rays and shield against radiation. In addition, bismuth ion graphene has the advantage of absorbing X-rays and gamma rays, and can also prevent light pollution, making it an excellent material for environmental protection and green applications. 【0008】 First, bismuth ion graphene has a significant advantage over silver ion graphene in terms of production cost. Therefore, its application to greenhouse films is expected to expand considerably in the future. In addition, bismuth ion graphene film can be used not only as a roofing film for insulation and rain protection, but also as a ground film and a waterproof underground film. Furthermore, ground films using bismuth ion graphene can kill bacteria and harmful viruses on the surface when they come into contact with soil. Moreover, because bismuth ions effectively suppress infection of plant roots by harmful fungi, it can also be applied to underground films to prevent damage from underground insects. [Overview of the project] [Problems that the invention aims to solve] 【0009】 In response to the shortcomings of conventional technologies, the present invention provides a method for manufacturing bismuth ion functional graphene agricultural films. [Means for solving the problem] 【0010】 To achieve the above objectives, the present invention provides the following technical means. 【0011】 A method for manufacturing bismuth ion functional graphene agricultural film includes the following steps. 【0012】 (1) Mixing: Oily bismuth ion graphene material and colloidal particles are placed in a mixer and stirred. After stirring is complete, the mixture is dried to obtain and prepare the mixed material. 【0013】 (2) Granulation: The mixed material obtained in step (1) is put into an extruder and melted, kneaded, extruded, cooled, cut, and dried to obtain a functional masterbatch. 【0014】 (3) Film inflation: The functional masterbatch obtained in step (2) is put into an inflation film molding machine to perform film inflation and obtain a bismuth ion functional graphene agricultural film. 【0015】 Preferably, the colloidal particles in step (1) are PVC, EVA, PET, PO, or PP. 【0016】 Preferably, the mass ratio of the oily bismuth ion graphene material to the colloidal particles in step (1) is 1:100 to 250. 【0017】 Preferably, the stirring time in step (1) is 1 to 2 hours, and the stirring speed is 60 to 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, in the preparation of the oily bismuth ion graphene material in step (1), 100 parts by weight of natural scaly graphite powder and 4 parts by weight of chelating bismuth ion solution are placed in a reaction vessel, then 776 parts by weight of DTPA is added as an osmotic buffer to adjust the pH to 6, the reaction gas pressure is set to 0.1 MPa, and the reaction is carried out at 30°C for 8 hours. After the reaction is complete, 100 parts by weight of EDTA solution is added as a buffer, and the reaction is continued at 30°C for 4 hours. In this way, an oily bismuth ion graphene material is obtained after the reaction is complete. 【0020】 Preferably, the particle size of the natural scaly graphite powder is 300 to 15,000 mesh, and the mass concentration of chelating bismuth ions is 10,000 ppm. 【0021】 Preferably, the buffer is an EDTA solution with a concentration of 1 mol / L. 【0022】 The present invention further protects applications of the method for manufacturing the bismuth ion functional graphene agricultural film. The bismuth ion functional graphene agricultural film can be used for three types of application films: roofing films, above-ground films, and underground films. [Effects of the Invention] 【0023】 Compared to conventional technology, the present invention has the following beneficial effects. 【0024】 (1) First, the present invention provides the application of bismuth ion functional graphene material to agricultural films. In terms of infrared radiation and heat retention, bismuth ions have better functionality than silver ions, and therefore have a superior infrared and far-infrared retention effect than silver in terms of heat retention. 【0025】 (2) The bactericidal power of bismuth ions is stronger than that of silver ions. Moreover, since bismuth ion graphene also has a photocatalytic effect, it can exhibit bactericidal ability by photocatalysis without directly contacting bacteria and viruses. In addition, bismuth ion graphene can not only retain infrared rays for heat preservation, but also exhibit the ability to remove ultraviolet rays and prevent radiation. Further, bismuth ion graphene has the advantage of being able to absorb X-rays, gamma rays, etc. 【0026】 (3) If the bismuth ion-functional graphene material is applied to a ground film and a waterproof underground film, when the soil contacts the ground film using bismuth ion graphene, it becomes possible to kill bacteria and harmful viruses on the ground. Moreover, due to the action of bismuth ions, the infection of harmful fungi to the roots of plants is effectively suppressed, so that it plays a role in preventing damage by underground insects. 【Embodiments for Carrying out the Invention】 【0027】 Hereinafter, the technical means of the present invention will be described clearly and concisely in combination with specific examples. Needless to say, the described examples are only some examples of the present invention, not all examples. Further, based on the examples of the present invention, all other examples obtained on the premise that those skilled in the art do not perform creative labor all belong to the protection scope of the present invention. 【0028】 All raw materials in the examples of the present invention can be obtained from commercially available products, among which non-ionic chelating agents (EDTA, DTPA) and chelating bismuth ions can be purchased from Asia Group. 【0029】 Example 1: The manufacturing method of the bismuth ion-functional graphene agricultural film included the following steps. 【0030】 (1) Preparation of oily bismuth ion graphene material: 100 g of natural scaly graphite powder and 4 g of 10,000 ppm chelate bismuth ion solution were placed in a reaction vessel. Then, 776 g of 1 mol / L DTPA was added as an osmotic buffer to adjust the pH to 6, and the reaction gas pressure was set to 0.1 MPa. The reaction was carried out at 30°C for 8 hours. After the reaction was complete, 100 g of 1 mol / L EDTA solution was added as a buffer, and the reaction was continued at 30°C for 4 hours. In this way, an oily bismuth ion graphene material was obtained after the reaction was complete. 【0031】 (2) Mixing: 100 g of oily bismuth ion graphene material and 10 kg of PVC colloidal particles were placed in a mixer and stirred at a speed of 60 r / min for 1 hour. After stirring was complete, the mixture was dried at 60°C for 3 hours to obtain the mixed material, which was then prepared. 【0032】 (3) Granulation: The mixed material obtained in step (2) was fed into a twin-screw extruder and melted, kneaded, extruded, cooled, cut, and dried to obtain a functional masterbatch. 【0033】 (4) Film inflation: The functional masterbatch obtained in step (3) was put into an inflation film molding machine to perform film inflation and obtain a bismuth ion functional graphene agricultural film. 【0034】 Example 2: A method for producing a bismuth ion functional graphene agricultural film included the following steps. 【0035】 (1) Preparation of oily bismuth ion graphene material: 100 g of natural scaly graphite powder and 4 g of 10,000 ppm chelate bismuth ion solution were placed in a reaction vessel. Then, 776 g of 1 mol / L DTPA was added as an osmotic buffer to adjust the pH to 6, and the reaction gas pressure was set to 0.1 MPa. The reaction was carried out at 30°C for 8 hours. After the reaction was complete, 100 g of 1 mol / L EDTA solution was added as a buffer, and the reaction was continued at 30°C for 4 hours. In this way, an oily bismuth ion graphene material was obtained after the reaction was complete. 【0036】 (2) Mixing: 100 g of oily bismuth ion graphene material and 15 kg of PET colloidal particles were placed in a mixer and stirred at a speed of 60 r / min for 1 hour. After stirring was complete, the mixture was dried at 60°C for 3 hours to obtain the mixed material, which was then prepared. 【0037】 (3) Granulation: The mixed material obtained in step (2) was fed into a twin-screw extruder and melted, kneaded, extruded, cooled, cut, and dried to obtain a functional masterbatch. 【0038】 (4) Film inflation: The functional masterbatch obtained in step (3) was put into an inflation film molding machine to perform film inflation and obtain a bismuth ion functional graphene agricultural film. 【0039】 Example 3: A method for producing a bismuth ion functional graphene agricultural film included the following steps. 【0040】 (1) Preparation of oily bismuth ion graphene material: 100 g of natural scaly graphite powder and 4 g of 10,000 ppm chelate bismuth ion solution were placed in a reaction vessel. Then, 776 g of 1 mol / L DTPA was added as an osmotic buffer to adjust the pH to 6, and the reaction gas pressure was set to 0.1 MPa. The reaction was carried out at 30°C for 8 hours. After the reaction was complete, 100 g of 1 mol / L EDTA solution was added as a buffer, and the reaction was continued at 30°C for 4 hours. In this way, an oily bismuth ion graphene material was obtained after the reaction was complete. 【0041】 (2) Mixing: 100 g of oily bismuth ion graphene material and 10 kg of PP colloidal particles were placed in a mixer and stirred at a speed of 60 r / min for 1.5 hours. After stirring was complete, the mixture was dried at 60°C for 3 hours to obtain the mixed material, which was then prepared. 【0042】 (3) Granulation: The mixed material obtained in step (2) was fed into a twin-screw extruder and melted, kneaded, extruded, cooled, cut, and dried to obtain a functional masterbatch. 【0043】 (4) Film inflation: The functional masterbatch obtained in step (3) was put into an inflation film molding machine to perform film inflation and obtain a bismuth ion functional graphene agricultural film. 【0044】 Example 4: A method for producing a bismuth ion functional graphene agricultural film included the following steps. 【0045】 (1) Preparation of oily bismuth ion graphene material: 100 g of natural scaly graphite powder and 4 g of 10,000 ppm chelate bismuth ion solution were placed in a reaction vessel. Then, 776 g of 1 mol / L DTPA was added as an osmotic buffer to adjust the pH to 6, and the reaction gas pressure was set to 0.1 MPa. The reaction was carried out at 30°C for 8 hours. After the reaction was complete, 100 g of 1 mol / L EDTA solution was added as a buffer, and the reaction was continued at 30°C for 4 hours. In this way, an oily bismuth ion graphene material was obtained after the reaction was complete. 【0046】 (2) Mixing: 100 g of oily bismuth ion graphene material and 15 kg of PP colloidal particles were placed in a mixer and stirred at a speed of 100 r / min for 2 hours. After stirring was complete, the mixture was dried at 70°C for 3 hours to obtain the mixed material, which was then prepared. 【0047】 (3) Granulation: The mixed material obtained in step (2) was fed into a twin-screw extruder and melted, kneaded, extruded, cooled, cut, and dried to obtain a functional masterbatch. 【0048】 (4) Film inflation: The functional masterbatch obtained in step (3) was put into an inflation film molding machine to perform film inflation and obtain a bismuth ion functional graphene agricultural film. 【0049】 Example 5: A method for producing a bismuth ion functional graphene agricultural film included the following steps. 【0050】 (1) Preparation of oily bismuth ion graphene material: 100 g of natural scaly graphite powder and 4 g of 10,000 ppm chelate bismuth ion solution were placed in a reaction vessel. Then, 776 g of 1 mol / L DTPA was added as an osmotic buffer to adjust the pH to 6, and the reaction gas pressure was set to 0.1 MPa. The reaction was carried out at 30°C for 8 hours. After the reaction was complete, 100 g of 1 mol / L EDTA solution was added as a buffer, and the reaction was continued at 30°C for 4 hours. In this way, an oily bismuth ion graphene material was obtained after the reaction was complete. 【0051】 (2) Mixing: 100 g of oily bismuth ion graphene material and 10 kg of EVA colloidal particles were placed in a mixer and stirred at a speed of 60 r / min for 1 hour. After stirring was complete, the mixture was dried at 60°C for 2 hours to obtain the mixed material, which was then prepared. 【0052】 (3) Granulation: The mixed material obtained in step (2) was fed into a twin-screw extruder and melted, kneaded, extruded, cooled, cut, and dried to obtain a functional masterbatch. 【0053】 (4) Film inflation: The functional masterbatch obtained in step (3) was put into an inflation film molding machine to perform film inflation and obtain a bismuth ion functional graphene agricultural film. 【0054】 The bismuth ion functional graphene agricultural films obtained in Examples 1-5 above were applied to roofing films for agricultural use, and their light transmission performance was tested. The results are shown in Table 1. 【0055】 [Table 1] 【0056】 The bismuth ion functional graphene agricultural films obtained in Examples 1-5 above were applied to ground-mounted agricultural films, and their antibacterial performance was tested. The test standard was ASTM E2315-2016, and the deposit numbers for the E. coli used for testing were ATCC8739 and for Staphylococcus aureus ATCC6538. The results are shown in Table 2. 【0057】 [Table 2] 【0058】 While embodiments of the present invention have been presented and described, those skilled in the art will understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. Therefore, the scope of the present invention is limited by the appended claims and equivalents.

Claims

[Claim 1] A method for manufacturing a bismuth ion functional graphene agricultural film, (1) Preparation of oily bismuth ion graphene material: After adding 100 parts by weight of natural scaly graphite powder and 4 parts by weight of a chelating bismuth ion solution with a mass concentration of 10,000 ppm to a reaction vessel, 776 parts by weight of 1 mol / L DTPA solution is added to adjust the pH to 6 and the reaction is carried out, and then 100 parts by weight of 1 mol / L EDTA solution is added as a buffer and the reaction is carried out to obtain an oily bismuth ion graphene material, (2) Mixing: The oily bismuth ion graphene material obtained in step (1) is mixed with colloidal particles which are PVC, EVA, PET, PO, or PP in a mass ratio of 1:100 to 250, stirred, and dried after stirring is complete to obtain a mixed material. (3) Granulation: This step involves feeding the mixed material obtained in step (2) into an extruder and performing granulation to obtain a functional masterbatch. (4) Film inflation: The functional masterbatch obtained in step (3) is fed into an inflation film molding machine to perform film inflation and obtain a bismuth ion functional graphene agricultural film. A method characterized by including the following. [Claim 2] In step (1), A method for producing a bismuth ion functional graphene agricultural film according to claim 1, characterized by adding the DTPA solution to adjust the pH, setting the reaction gas pressure to 0.1 MPa and reacting at 30°C for 8 hours, and after the reaction is complete, adding the EDTA solution and continuing to react at 30°C for 4 hours. [Claim 3] The method for producing a bismuth ion functional graphene agricultural film according to Claim 1, characterized in that the particle size of the natural scaly graphite powder is 300 to 15,000 mesh. [Claim 4] The method for producing a bismuth ion functional graphene agricultural film according to claim 3, characterized in that the stirring time in step (2) is 1 to 2 hours and the stirring speed is 60 to 150 r / min. [Claim 5] The method for producing a bismuth ion functional graphene agricultural film according to claim 3, characterized in that the drying temperature in step (2) is 60 to 70°C and the drying time is 2 to 3 hours.

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