High permeability puncture resistant film material, method of making and use in rice cultivation

Abstract

The application relates to the technical field of plastic materials, in particular to a high-permeability puncture-resistant film material, a preparation method and application in rice planting. The film material is prepared by taking PBAT as a base material, and the PBAT base film material has the characteristics of good biodegradability and high water vapor permeability; a toughening material is introduced into the PBAT, which can effectively provide the toughness of the film material, and further improve the puncture resistance of the film material; the toughening material includes organic toughening material and inorganic toughening material, the organic toughening material and the inorganic toughening material are connected to polylactic acid molecules through stable chemical bonds, and the toughening effect is good; the inorganic toughening material, i.e. silicon-based mesoporous material, has a porous structure, small permeation resistance to gas, is beneficial to the diffusion and transmission of gas, and can improve the permeability of the film material. When the film material is applied to rice planting, not only can the temperature be increased and the water be preserved, but also the nutrient exchange, respiration and photosynthesis of rice seedlings can be efficiently carried out.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of plastic materials, in particular to a high-permeability puncture-resistant film material, a preparation method and application in rice planting. BACKGROUND

[0002] Rice has a long growth cycle. For rice in cold northern regions, the sowing and seedling raising is usually carried out before and after Tomb Sweeping Day, and the air temperature is relatively low. The seedling raising process generally needs to be carried out in a shed to effectively increase the temperature of the seedbed and facilitate the cultivation of strong seedlings. In order to seize the agricultural time, shorten the seedling raising time and increase the temperature of the seedbed, a seedbed covering and field film covering method is used for rice seedling raising. However, in the process of seedling growth, in order to ensure the normal performance of the respiration and photosynthesis of seedlings, the oxygen, carbon dioxide and water vapor content in the film needs to be maintained within a certain range. Similarly, the application of the film covering technology in the water field with straw returning to field will cause the gas exchange not timely in the process of accelerating the straw decomposition of the straw, which is easy to cause the hydrogen sulfide poisoning of rice and even the phenomenon of rotten roots, and thus the permeability of the film material is required to be high. The permeability of the film material itself is required to realize the permeation and diffusion of oxygen, carbon dioxide, methane and water vapor in and out of the film. In addition, if the film material is punctured and damaged, it will affect the normal growth of seedlings, and thus the film material is required to have good puncture resistance.

[0003] Chinese patent CN107469640B discloses a preparation method of a high-gas-permeability carbon film. The carbon film has a pore structure, and the high gas permeability of the carbon film is realized. However, the carbon film is mainly applied to the separation of small molecule gases, and the mechanical properties such as strength and toughness of the carbon film are far inferior to those of a plastic film, and thus the carbon film is difficult to be used as a film covering material. Chinese patent CN115558139B discloses a preparation process of an antibacterial puncture-resistant PBAT composite film. The toughness of the prepared composite film is improved by adding a styrene-maleic anhydride copolymer and polyether sulfone, and thus the puncture resistance of the composite film is improved. However, the components in the preparation process are physically blended, and the dispersion uniformity and compatibility are poor. The puncture resistance needs to be improved. In addition, the permeability of the antibacterial puncture-resistant PBAT composite film is poor. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application provides a high-permeability puncture-resistant film material and a preparation method to solve the problems that the permeability and puncture resistance of the film material in the prior art need to be improved.

[0005] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0006] A preparation method of a high-permeability puncture-resistant film material, comprising the following steps:

[0007] Step 1: Add maleic anhydride-grafted modified PBAT to chloroform and stir until dissolved. Add terminal amino liquid nitrile rubber dropwise. After the addition is complete, allow the reaction to proceed. After the reaction is complete, precipitate the precipitate, filter, wash, and dry to obtain nitrile rubber-modified PBAT.

[0008] Step 2: Add the silica-based mesoporous material to toluene, disperse it by ultrasonication, add γ-glycidoxypropyltrimethoxysilane, continue ultrasonication and reaction, after the reaction is completed, centrifuge, purify, and dry to obtain epoxy-modified silica-based mesoporous material;

[0009] Nitrile rubber-modified PBAT, epoxy-modified silica-based mesoporous material, antioxidant, and lubricant are mixed and melted to obtain modified PBAT melt.

[0010] Step 3: Extrude the modified PBAT melt and blow it into a film to obtain a highly permeable puncture-resistant membrane material.

[0011] Preferably, the maleic anhydride-grafted modified PBAT used in step one is prepared by the following steps:

[0012] PBAT (a copolymer of butylene adipate and butylene terephthalate), maleic anhydride, and dicumyl peroxide initiator were mixed, melted, extruded, and granulated. The melting, extrusion, and granulation processes were repeated three times, and the mixture was dried to obtain maleic anhydride-grafted modified PBAT.

[0013] Furthermore, the mass ratio of PBAT, maleic anhydride, and initiator dicumyl peroxide is 100:(5-10):(1.5-3); the melting temperature is 135-155℃.

[0014] Preferably, in step one, the mass ratio of maleic anhydride-grafted modified PBAT, chloroform, and amino-terminated liquid nitrile rubber is (100.5-101.5):(1000-1200):(15-25), and the reaction conditions are reflux reaction at 50-60℃ for 2-3 hours.

[0015] Preferably, in step two, when preparing the epoxy-modified silicon-based mesoporous material, the mass ratio of the silicon-based mesoporous material, toluene, and γ-glycidoxypropyltrimethoxysilane is (5-10):200:(2-5), and the reaction conditions are to react at 85-95℃ for 5-10 hours.

[0016] Preferably, in step two, the ultrasonic dispersion is performed at 300W power for 20-40 minutes, and the ultrasonic dispersion is continued at 300W power for 5-10 minutes.

[0017] Preferably, in step two, purification includes adding toluene to the centrifuged precipitate, ultrasonically dispersing it, centrifuging it, taking the centrifuged precipitate, and repeating the ultrasonic dispersion and centrifugation process six times.

[0018] Preferably, in step two, when preparing the modified PBAT melt, the mass ratio of nitrile rubber modified PBAT, epoxy modified silicon-based mesoporous material, antioxidant, and lubricant is 100:(3-5):(0.5-1):(0.5-1), and the melting temperature is 160-170℃.

[0019] Preferably, in step two, the antioxidant includes any one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0020] The lubricant includes either calcium stearate or zinc stearate.

[0021] In step three, the extrusion die temperature is 165-175℃.

[0022] The present invention also discloses a high-permeability puncture-resistant membrane material prepared by the preparation method of the high-permeability puncture-resistant membrane material described above.

[0023] Preferably, the application of a highly permeable and puncture-resistant membrane material as described above in rice cultivation.

[0024] Furthermore, the specific process of its application in rice cultivation includes: preparing ridges before flooding the field, digging furrows 20-30cm deep every 100cm, spraying microbial agents into the field after flooding for 3-5 days, letting the field rest for 2 days after fertilization, and covering the ridges with a highly permeable and puncture-resistant film material, ensuring the film material adheres tightly to the soil surface to prevent weed growth; during rice transplanting, planting two rows of rice per ridge, keeping the furrows watery but the film surface dry after transplanting, and spraying microbial agents multiple times after rice transplanting and before and after heading, and evenly spreading fertilizer in the furrows during topdressing; draining and drying the field 15 days before harvest, and the film material does not need to be recycled as it can be naturally degraded.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] In this invention, PBAT is used as the matrix material. PBAT has the characteristics of both PBA and PBT, and has good mechanical properties and biodegradability. PBAT base film material also has the characteristics of high water vapor permeability and good carbon dioxide adsorption and diffusion.

[0027] A method for preparing a highly permeable, puncture-resistant membrane material includes the following steps:

[0028] In this invention, toughening materials are introduced into PBAT, including organic toughening materials such as nitrile rubber and inorganic toughening materials such as silica-based mesoporous materials. These materials effectively improve the toughness of the membrane material, thereby enhancing its puncture resistance. During the introduction of the toughening materials, PBAT is grafted with maleic anhydride. The maleic anhydride-grafted PBAT first undergoes a ring-opening reaction with the amino groups on the terminal amino-terminated liquid nitrile rubber molecules, generating carboxyl groups and amide bonds connecting PBAT and nitrile rubber, thus obtaining a nitrile rubber complex. Acrylonitrile rubber modified PBAT; the pores of the silica-based mesoporous material are modified with γ-glycidyl etheroxypropyltrimethoxysilane. The introduced epoxy groups undergo ring-opening reactions with the carboxyl groups generated by the ring-opening reaction of maleic anhydride and the imino groups on the amide bonds, thus chemically bonding the silica-based mesoporous material to the acrylonitrile rubber modified PBAT molecules; both organic and inorganic toughening materials are stably chemically bonded to the PBAT molecules, exhibiting good compatibility with PBAT resin and good dispersion uniformity in PBAT resin, resulting in good toughening effect;

[0029] In addition, silicon-based mesoporous materials are porous silica materials with pore sizes between 2-50 nm. Due to their porous structure, when added to PBAT resin to prepare membrane materials, they have low resistance to gas permeation, which is conducive to gas diffusion and transport, and can effectively improve the permeability of the membrane material. When the membrane material is used as a seedling membrane in rice cultivation, it not only has a good heat preservation effect, but its high permeability can also ensure the normal respiration and photosynthesis of rice seedlings. Attached Figure Description

[0030] Figure 1 This is a flowchart illustrating the preparation process of the high-permeability, puncture-resistant membrane material in this invention.

[0031] Figure 2 The above are bar graphs showing the O2 transmittance test results of the membrane materials prepared in Examples 1-6 and Comparative Examples 1-3 of the present invention.

[0032] Figure 3 The above are bar graphs showing the CO2 permeability test results of the membrane materials prepared in Examples 1-6 and Comparative Examples 1-3 of the present invention.

[0033] Figure 4 The above are bar graphs showing the water vapor transmission rate test results of the membrane materials prepared in Examples 1-6 and Comparative Examples 1-3 of the present invention.

[0034] Figure 5 The bar chart shows the puncture resistance test results of the membrane materials prepared in Examples 1-6 and Comparative Examples 1-3 of the present invention. Detailed Implementation

[0035] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0036] Example 1

[0037] A method for preparing a highly permeable, puncture-resistant membrane material includes the following steps:

[0038] Step 1: Mix PBAT, maleic anhydride, and initiator dicumyl peroxide in a mass ratio of 100:5:1.5. Melt, extrude, and granulate at 135℃. Repeat the melting, extrusion, and granulation process three times. Dry in a 70℃ oven for 24 hours to obtain maleic anhydride-grafted modified PBAT.

[0039] Step 2: Add maleic anhydride-grafted modified PBAT to chloroform and stir until dissolved. Add terminal amino-terminated liquid nitrile rubber dropwise. The mass ratio of maleic anhydride-grafted modified PBAT, chloroform, and terminal amino-terminated liquid nitrile rubber is 100.5:1000:15. The dropwise addition time of the terminal amino-terminated liquid nitrile rubber is 30 min. After the dropwise addition is complete, reflux the reaction at 50℃ for 3 h. After the reaction is complete, add 5 times the mass of deionized water to precipitate the precipitate. Filter, take the filter cake, wash it three times with ethanol, and dry it in a vacuum oven at 60℃ for 12 h to obtain nitrile rubber-modified PBAT.

[0040] Step 3: Add the silicon-based mesoporous material to toluene and ultrasonically disperse it for 20 min at 300 W. Add γ-glycidoxypropyltrimethoxysilane. The mass ratio of silicon-based mesoporous material, toluene, and γ-glycidoxypropyltrimethoxysilane is 5:200:2. Continue ultrasonication for 5 min at 300 W and react at 85℃ for 10 h. After the reaction is complete, centrifuge and add toluene to the centrifuged precipitate. After ultrasonic dispersion for 10 min at 300 W, centrifuge again. Take the centrifuged precipitate and repeat the ultrasonic dispersion and centrifugation process six times. Place it in a vacuum oven at 60℃ and dry for 12 h to obtain epoxy-modified silicon-based mesoporous material.

[0041] Nitrile-modified PBAT, epoxy-modified silica-based mesoporous material, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and calcium stearate were mixed in a mass ratio of 100:3:0.5:0.5 and melted at a melting temperature of 160℃ to obtain modified PBAT melt.

[0042] Step 4: Extrude the modified PBAT melt at a die temperature of 165°C and blow the film to obtain a high-permeability, puncture-resistant membrane material.

[0043] The thickness of the highly permeable puncture-resistant membrane material is 0.25 mm.

[0044] Example 2

[0045] A method for preparing a highly permeable, puncture-resistant membrane material includes the following steps:

[0046] Step 1: Mix PBAT, maleic anhydride, and initiator dicumyl peroxide in a mass ratio of 100:10:3. Melt, extrude, and granulate at 155℃. Repeat the melting, extrusion, and granulation process three times. Dry in a 70℃ oven for 24 hours to obtain maleic anhydride-grafted modified PBAT.

[0047] Step 2: Add maleic anhydride-grafted modified PBAT to chloroform and stir until dissolved. Add terminal amino-terminated liquid nitrile rubber dropwise. The mass ratio of maleic anhydride-grafted modified PBAT, chloroform, and terminal amino-terminated liquid nitrile rubber is 101.5:1200:25. The dropwise addition time of the terminal amino-terminated liquid nitrile rubber is 1 hour. After the dropwise addition is complete, reflux the reaction at 60°C for 2 hours. After the reaction is complete, add 5 times the mass of deionized water to precipitate the precipitate. Filter the precipitate, take the filter cake, wash it three times with ethanol, and dry it in a vacuum oven at 60°C for 12 hours to obtain nitrile rubber-modified PBAT.

[0048] Step 3: Add the silicon-based mesoporous material to toluene and ultrasonically disperse it for 40 min at 300 W. Add γ-glycidoxypropyltrimethoxysilane. The mass ratio of silicon-based mesoporous material, toluene, and γ-glycidoxypropyltrimethoxysilane is 10:200:5. Continue ultrasonication for 10 min at 300 W and react at 95℃ for 5 h. After the reaction is complete, centrifuge and add toluene to the centrifuged precipitate. After ultrasonic dispersion for 10 min at 300 W, centrifuge again. Take the centrifuged precipitate and repeat the ultrasonic dispersion and centrifugation process six times. Place it in a vacuum oven at 60℃ and dry for 12 h to obtain epoxy-modified silicon-based mesoporous material.

[0049] Nitrile-modified PBAT, epoxy-modified silica-based mesoporous material, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl alcohol, and zinc stearate were mixed in a mass ratio of 100:5:1:1 and melted at a melting temperature of 170℃ to obtain modified PBAT melt.

[0050] Step 4: Extrude the modified PBAT melt at an extrusion die temperature of 175°C and blow film to obtain a high-permeability, puncture-resistant membrane material.

[0051] The thickness of the highly permeable puncture-resistant membrane material is 0.25 mm.

[0052] Example 3

[0053] A method for preparing a highly permeable, puncture-resistant membrane material includes the following steps:

[0054] Step 1: Mix PBAT, maleic anhydride, and initiator dicumyl peroxide. The mass ratio of PBAT, maleic anhydride, and initiator dicumyl peroxide is 100:6:1.8. Melt, extrude, and granulate at 145℃. Repeat the melting, extrusion, and granulation process three times. Dry in a 70℃ oven for 24 hours to obtain maleic anhydride-grafted modified PBAT.

[0055] Step 2: Add maleic anhydride-grafted modified PBAT to chloroform and stir until dissolved. Add terminal amino-terminated liquid nitrile rubber dropwise. The mass ratio of maleic anhydride-grafted modified PBAT, chloroform, and terminal amino-terminated liquid nitrile rubber is 100.7:1040:17.5. The dropwise addition time of the terminal amino-terminated liquid nitrile rubber is 30 min. After the dropwise addition is complete, reflux the reaction at 55℃ for 2.5 h. After the reaction is complete, add 5 times the mass of deionized water to precipitate the precipitate. Filter, take the filter cake, wash it three times with ethanol, and dry it in a vacuum oven at 60℃ for 12 h to obtain nitrile rubber-modified PBAT.

[0056] Step 3: Add the silicon-based mesoporous material to toluene and ultrasonically disperse it for 40 min at 300 W. Add γ-glycidoxypropyltrimethoxysilane. The mass ratio of silicon-based mesoporous material, toluene, and γ-glycidoxypropyltrimethoxysilane is 6:200:2.5. Continue ultrasonication for 10 min at 300 W and react at 90 °C for 8 h. After the reaction is complete, centrifuge and add toluene to the centrifuged precipitate. After ultrasonic dispersion for 10 min at 300 W, centrifuge again. Take the centrifuged precipitate and repeat the ultrasonic dispersion and centrifugation process six times. Place it in a vacuum oven at 60 °C and dry for 12 h to obtain epoxy-modified silicon-based mesoporous material.

[0057] Nitrile-modified PBAT, epoxy-modified silica-based mesoporous material, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], and calcium stearate were mixed in a mass ratio of 100:3.5:0.6:0.6 and melted at a melting temperature of 165℃ to obtain modified PBAT melt.

[0058] Step 4: Extrude the modified PBAT melt at an extrusion die temperature of 170°C and blow film to obtain a high-permeability, puncture-resistant membrane material.

[0059] The thickness of the highly permeable puncture-resistant membrane material is 0.25 mm.

[0060] Example 4

[0061] A method for preparing a highly permeable, puncture-resistant membrane material includes the following steps:

[0062] Step 1: Mix PBAT, maleic anhydride, and initiator dicumyl peroxide in a mass ratio of 100:7:2.1. Melt, extrude, and granulate at 145℃. Repeat the melting, extrusion, and granulation process three times. Dry in a 70℃ oven for 24 hours to obtain maleic anhydride-grafted modified PBAT.

[0063] Step 2: Add maleic anhydride-grafted modified PBAT to chloroform and stir until dissolved. Add terminal amino-terminated liquid nitrile rubber dropwise. The mass ratio of maleic anhydride-grafted modified PBAT, chloroform, and terminal amino-terminated liquid nitrile rubber is 100.9:1080:20. The dropwise addition time of the terminal amino-terminated liquid nitrile rubber is 30 min. After the dropwise addition is complete, reflux the reaction at 55℃ for 2.5 h. After the reaction is complete, add 5 times the mass of deionized water to precipitate the precipitate. Filter, take the filter cake, wash it three times with ethanol, and dry it in a vacuum oven at 60℃ for 12 h to obtain nitrile rubber-modified PBAT.

[0064] Step 3: Add the silicon-based mesoporous material to toluene and ultrasonically disperse it for 40 min at 300 W. Add γ-glycidoxypropyltrimethoxysilane. The mass ratio of silicon-based mesoporous material, toluene, and γ-glycidoxypropyltrimethoxysilane is 7:200:3. Continue ultrasonication for 10 min at 300 W and react at 90℃ for 8 h. After the reaction is complete, centrifuge and add toluene to the centrifuged precipitate. After ultrasonic dispersion for 10 min at 300 W, centrifuge again. Take the centrifuged precipitate and repeat the ultrasonic dispersion and centrifugation process six times. Place it in a vacuum oven at 60℃ and dry for 12 h to obtain epoxy-modified silicon-based mesoporous material.

[0065] Nitrile-modified PBAT, epoxy-modified silica-based mesoporous material, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and zinc stearate were mixed in a mass ratio of 100:4:0.7:0.7 and melted at a melting temperature of 165℃ to obtain modified PBAT melt.

[0066] Step 4: Extrude the modified PBAT melt at an extrusion die temperature of 170°C and blow film to obtain a high-permeability, puncture-resistant membrane material.

[0067] The thickness of the highly permeable puncture-resistant membrane material is 0.25 mm.

[0068] Example 5

[0069] A method for preparing a highly permeable, puncture-resistant membrane material includes the following steps:

[0070] Step 1: Mix PBAT, maleic anhydride, and initiator dicumyl peroxide in a mass ratio of 100:8:2.4. Melt, extrude, and granulate at 145℃. Repeat the melting, extrusion, and granulation process three times. Dry in a 70℃ oven for 24 hours to obtain maleic anhydride-grafted modified PBAT.

[0071] Step 2: Add maleic anhydride-grafted modified PBAT to chloroform and stir until dissolved. Add terminal amino-terminated liquid nitrile rubber dropwise. The mass ratio of maleic anhydride-grafted modified PBAT, chloroform, and terminal amino-terminated liquid nitrile rubber is 101.1:1120:20. The dropwise addition time of the terminal amino-terminated liquid nitrile rubber is 30 min. After the dropwise addition is complete, reflux the reaction at 55℃ for 2.5 h. After the reaction is complete, add 5 times the mass of deionized water to precipitate the precipitate. Filter, take the filter cake, wash it three times with ethanol, and dry it in a vacuum oven at 60℃ for 12 h to obtain nitrile rubber-modified PBAT.

[0072] Step 3: Add the silicon-based mesoporous material to toluene and ultrasonically disperse it for 40 min at 300 W. Add γ-glycidoxypropyltrimethoxysilane. The mass ratio of silicon-based mesoporous material, toluene, and γ-glycidoxypropyltrimethoxysilane is 8:200:4. Continue ultrasonication for 10 min at 300 W and react at 90℃ for 8 h. After the reaction is complete, centrifuge and add toluene to the centrifuged precipitate. After ultrasonic dispersion for 10 min at 300 W, centrifuge again. Take the centrifuged precipitate and repeat the ultrasonic dispersion and centrifugation process six times. Place it in a vacuum oven at 60℃ and dry for 12 h to obtain epoxy-modified silicon-based mesoporous material.

[0073] Nitrile-modified PBAT, epoxy-modified silica-based mesoporous material, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and zinc stearate were mixed in a mass ratio of 100:4:0.8:0.8 and melted at a melting temperature of 165℃ to obtain modified PBAT melt.

[0074] Step 4: Extrude the modified PBAT melt at an extrusion die temperature of 170°C and blow film to obtain a high-permeability, puncture-resistant membrane material.

[0075] The thickness of the highly permeable puncture-resistant membrane material is 0.25 mm.

[0076] Example 6

[0077] A method for preparing a highly permeable, puncture-resistant membrane material includes the following steps:

[0078] Step 1: Mix PBAT, maleic anhydride, and initiator dicumyl peroxide in a mass ratio of 100:9:2.7. Melt, extrude, and granulate at 145℃. Repeat the melting, extrusion, and granulation process three times. Dry in a 70℃ oven for 24 hours to obtain maleic anhydride-grafted modified PBAT.

[0079] Step 2: Add maleic anhydride-grafted modified PBAT to chloroform and stir until dissolved. Add terminal amino-terminated liquid nitrile rubber dropwise. The mass ratio of maleic anhydride-grafted modified PBAT, chloroform, and terminal amino-terminated liquid nitrile rubber is 101.3:1160:22.5. The dropwise addition time of the terminal amino-terminated liquid nitrile rubber is 30 min. After the dropwise addition is complete, reflux the reaction at 55℃ for 2.5 h. After the reaction is complete, add 5 times the mass of deionized water to precipitate the precipitate. Filter, take the filter cake, wash it three times with ethanol, and dry it in a vacuum oven at 60℃ for 12 h to obtain nitrile rubber-modified PBAT.

[0080] Step 3: Add the silicon-based mesoporous material to toluene and ultrasonically disperse it for 40 min at 300 W. Add γ-glycidoxypropyltrimethoxysilane. The mass ratio of silicon-based mesoporous material, toluene, and γ-glycidoxypropyltrimethoxysilane is 9:200:4.5. Continue ultrasonication for 10 min at 300 W and react at 90 °C for 8 h. After the reaction is complete, centrifuge and add toluene to the centrifuged precipitate. After ultrasonic dispersion for 10 min at 300 W, centrifuge again. Take the centrifuged precipitate and repeat the ultrasonic dispersion and centrifugation process six times. Place it in a vacuum oven at 60 °C and dry for 12 h to obtain epoxy-modified silicon-based mesoporous material.

[0081] Nitrile-modified PBAT, epoxy-modified silica-based mesoporous material, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and zinc stearate were mixed in a mass ratio of 100:4.5:0.9:0.9 and melted at a melting temperature of 165℃ to obtain modified PBAT melt.

[0082] Step 4: Extrude the modified PBAT melt at an extrusion die temperature of 170°C and blow film to obtain a high-permeability, puncture-resistant membrane material.

[0083] The thickness of the highly permeable puncture-resistant membrane material is 0.25 mm.

[0084] Comparative Example 1

[0085] A method for preparing a highly permeable, puncture-resistant membrane material includes the following steps:

[0086] Step 1: Mix PBAT, maleic anhydride, and initiator dicumyl peroxide in a mass ratio of 100:5:1.5. Melt, extrude, and granulate at 135℃. Repeat the melting, extrusion, and granulation process three times. Dry in a 70℃ oven for 24 hours to obtain maleic anhydride-grafted modified PBAT.

[0087] Step 2: Add maleic anhydride-grafted modified PBAT to chloroform and stir until dissolved. Add terminal amino-terminated liquid nitrile rubber dropwise. The mass ratio of maleic anhydride-grafted modified PBAT, chloroform, and terminal amino-terminated liquid nitrile rubber is 100.5:1000:30. The dropwise addition time of the terminal amino-terminated liquid nitrile rubber is 30 min. After the dropwise addition is complete, reflux the reaction at 50℃ for 3 h. After the reaction is complete, add 5 times the mass of deionized water to precipitate the precipitate. Filter, take the filter cake, wash it three times with ethanol, and dry it in a vacuum oven at 60℃ for 12 h to obtain nitrile rubber-modified PBAT.

[0088] Step 3: Mix nitrile rubber modified PBAT, silica-based mesoporous material, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and calcium stearate. The mass ratio of nitrile rubber modified PBAT, silica-based mesoporous material, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and calcium stearate is 100:2.8:0.5:0.5. Melt the mixture at a melting temperature of 160℃ to obtain modified PBAT melt.

[0089] Step 4: Extrude the modified PBAT melt at a die temperature of 165°C and blow the film to obtain a high-permeability, puncture-resistant membrane material.

[0090] The thickness of the highly permeable puncture-resistant membrane material is 0.25 mm.

[0091] Comparative Example 2

[0092] A method for preparing a highly permeable, puncture-resistant membrane material includes the following steps:

[0093] Step 1: Mix PBAT, amino-terminated liquid nitrile butadiene rubber, silica-based mesoporous material, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and calcium stearate. The mass ratio of PBAT, amino-terminated liquid nitrile butadiene rubber, silica-based mesoporous material, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and calcium stearate is 90:10:2.8:0.5:0.5. Melt the mixture at a melting temperature of 160℃ to obtain modified PBAT melt.

[0094] Step 4: Extrude the modified PBAT melt at a die temperature of 165°C and blow the film to obtain a high-permeability, puncture-resistant membrane material.

[0095] The thickness of the highly permeable puncture-resistant membrane material is 0.25 mm.

[0096] Comparative Example 3

[0097] A method for preparing a highly permeable, puncture-resistant membrane material includes the following steps:

[0098] Step 1: Mix PBAT, maleic anhydride, and initiator dicumyl peroxide in a mass ratio of 100:5:1.5. Melt, extrude, and granulate at 135℃. Repeat the melting, extrusion, and granulation process three times. Dry in a 70℃ oven for 24 hours to obtain maleic anhydride-grafted modified PBAT.

[0099] Step 2: Add maleic anhydride-grafted modified PBAT to chloroform and stir until dissolved. Add terminal amino-terminated liquid nitrile rubber dropwise. The mass ratio of maleic anhydride-grafted modified PBAT, chloroform, and terminal amino-terminated liquid nitrile rubber is 100.5:1000:50. The dropwise addition time of the terminal amino-terminated liquid nitrile rubber is 30 min. After the dropwise addition is complete, reflux the reaction at 50℃ for 3 h. After the reaction is complete, add 5 times the mass of deionized water to precipitate the PBAT. Filter, take the filter cake, wash it three times with ethanol, and dry it in a vacuum oven at 60℃ for 12 h to obtain nitrile rubber-modified PBAT.

[0100] Step 3: Mix nitrile rubber modified PBAT, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and calcium stearate. The mass ratio of nitrile rubber modified PBAT, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and calcium stearate is 102.8:0.5:0.5. Melt the mixture at a melting temperature of 160℃ to obtain the modified PBAT melt.

[0101] Step 4: Extrude the modified PBAT melt at a die temperature of 165°C and blow the film to obtain a high-permeability, puncture-resistant membrane material.

[0102] The thickness of the highly permeable puncture-resistant membrane material is 0.25 mm.

[0103] In the above embodiments and comparative examples, PBAT was purchased from Xinjiang Lanshan Tunhe Chemical Co., Ltd., model: TH801T, melting temperature: 110-120℃, tensile stress: 20-25MPa; amino-terminated liquid nitrile rubber was purchased from Jingjiang Tonggao Chemical Co., Ltd., effective substance content: 99.5%, average molecular weight: 10000; the silicon-based mesoporous material was mesoporous silica MCM-41, purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd., pore size: 3-5nm.

[0104] Test case

[0105] The performance of the membrane materials prepared in Examples 1-6 and Comparative Examples 1-3 was tested:

[0106] (1) Permeability test: The permeability of the membrane material for oxygen (O2), carbon dioxide (CO2), and water vapor was tested. The test methods for O2 and CO2 permeability were based on standard GB / T1038.1-2022 "Test methods for gas permeability of plastic films and sheets - Part 1: Pressure difference method". The membrane material was cut into 150mm × 95mm samples, and the O2 and CO2 permeability of the membrane material were tested using a GTR-701M gas permeability tester in an environment with a temperature of 23℃ and a humidity of 50±5%. The permeation area was 40cm². 2The test method for water vapor transmission rate refers to standard GB / T1037-2021 "Determination of Water Vapor Transmission Performance of Plastic Films and Sheets - Cup Weight Gain and Loss Method". The film material is cut into circular samples with a diameter of 6.5 cm. The samples are placed over the mouth of a permeation cup and sealed with molten sealing wax. The permeation cup is then placed in a constant temperature and humidity chamber at 23±0.6℃ and 90±2% humidity. The water vapor transmission rate is calculated based on the mass of the permeation cup before and after the test. The test results for O2 transmission rate, CO2 transmission rate, and water vapor transmission rate are shown in Table 1.

[0107] Table 1

[0108]

[0109]

[0110] As shown in Table 1, the membrane material prepared by this invention has good permeability. The PBAT-based membrane material has good water vapor permeability, as well as good adsorption and diffusion properties for CO2, resulting in high CO2 gas permeability. The introduced inorganic toughening material, silicon-based mesoporous material, has a porous structure, which reduces the permeation resistance of the membrane material to gas, facilitating gas diffusion and transport, and effectively improving the permeability of the membrane material. Compared to Example 1, in Comparative Example 1, the silicon-based mesoporous material was not epoxy-modified, resulting in decreased compatibility with PBAT resin and reduced dispersion uniformity within the PBAT resin, leading to a decrease in the membrane material's permeability. In Comparative Example 2, the silicon-based mesoporous material was also not epoxy-modified, resulting in decreased compatibility with PBAT resin and reduced dispersion uniformity within the PBAT resin, further reducing the membrane material's permeability. The terminal amino-terminated liquid nitrile rubber, lacking chemical bonds to the PBAT molecules, primarily affected the membrane material's puncture resistance, having no significant impact on its permeability; the membrane material's permeability was comparable to that of Comparative Example 1. In Comparative Example 3, the absence of silicon-based mesoporous material had the most significant impact on the membrane material's permeability, resulting in the worst permeability.

[0111] (2) Puncture resistance test: The puncture resistance of the film material was tested. The test method was based on the standard GB / T37841-2019 "Test method for puncture resistance of plastic films and sheets". The test results are shown in Table 2.

[0112] Table 2

[0113]

[0114] As shown in Table 2, the membrane material prepared by this invention exhibits good puncture resistance. The introduction of nitrile rubber-based organic toughening materials and inorganic toughening materials, specifically silicon-based mesoporous materials, effectively improves the toughness of the membrane material, thereby enhancing its puncture resistance. Compared to Example 1, in Comparative Example 1, the silicon-based mesoporous material was not epoxy-modified, resulting in decreased compatibility with PBAT resin and reduced dispersion uniformity within the resin, leading to a decrease in the membrane material's puncture resistance. In Comparative Example 2, the silicon-based mesoporous material was also not epoxy-modified, further reducing its compatibility with PBAT resin and dispersion uniformity. Furthermore, the terminal amino-terminated liquid nitrile rubber lacked chemical bonds to the PBAT molecules, further decreasing the membrane material's puncture resistance. In Comparative Example 3, the absence of silicon-based mesoporous material had the most significant impact on the membrane material's permeability, resulting in the worst puncture resistance.

[0115] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a highly permeable, puncture-resistant membrane material, characterized in that, Includes the following steps: Step 1: Add maleic anhydride-grafted modified PBAT to chloroform and stir until dissolved. Add terminal amino liquid nitrile rubber dropwise. After the addition is complete, allow the reaction to proceed. After the reaction is complete, precipitate the precipitate, filter, wash, and dry to obtain nitrile rubber-modified PBAT. Step 2: Add the silica-based mesoporous material to toluene, disperse it by ultrasonication, add γ-glycidoxypropyltrimethoxysilane, continue ultrasonication and reaction, after the reaction is completed, centrifuge, purify, and dry to obtain epoxy-modified silica-based mesoporous material; Nitrile rubber-modified PBAT, epoxy-modified silica-based mesoporous material, antioxidant, and lubricant are mixed and melted to obtain modified PBAT melt. Step 3: Extrude the modified PBAT melt and blow it into a film to obtain a highly permeable puncture-resistant membrane material.

2. The method for preparing a highly permeable, puncture-resistant membrane material according to claim 1, characterized in that, The maleic anhydride-grafted modified PBAT used in step one is prepared by the following steps: PBAT, maleic anhydride, and initiator dicumyl peroxide were mixed, melted, extruded, and granulated. The melting, extrusion, and granulation process was repeated three times, and then dried to obtain maleic anhydride-grafted modified PBAT.

3. The method for preparing a highly permeable, puncture-resistant membrane material according to claim 2, characterized in that, The mass ratio of PBAT, maleic anhydride, and initiator dicumyl peroxide is 100:(5-10):(1.5-3); the melting temperature is 135-155℃.

4. The method for preparing a highly permeable, puncture-resistant membrane material according to claim 1, characterized in that, In step one, the mass ratio of maleic anhydride-grafted modified PBAT, chloroform, and amino-terminated liquid nitrile rubber is (100.5-101.5):(1000-1200):(15-25), and the reaction conditions are reflux reaction at 50-60℃ for 2-3 hours.

5. The method for preparing a highly permeable, puncture-resistant membrane material according to claim 1, characterized in that, In step two, when preparing the epoxy-modified silicon-based mesoporous material, the mass ratio of the silicon-based mesoporous material, toluene, and γ-glycidoxypropyltrimethoxysilane is (5-10):200:(2-5), and the reaction conditions are to react at 85-95℃ for 5-10 hours.

6. The method for preparing a highly permeable, puncture-resistant membrane material according to claim 1, characterized in that, In step two, when preparing the modified PBAT melt, the mass ratio of nitrile rubber modified PBAT, epoxy modified silicon-based mesoporous material, antioxidant, and lubricant is 100:(3-5):(0.5-1):(0.5-1), and the melting temperature is 160-170℃.

7. The method for preparing a highly permeable, puncture-resistant membrane material according to claim 1, characterized in that, In step two, the antioxidant includes any one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], and the lubricant includes any one of calcium stearate and zinc stearate.

8. The method for preparing a highly permeable, puncture-resistant membrane material according to claim 1, characterized in that, In step three, the extrusion die temperature is 165-175℃.

9. A highly permeable puncture-resistant membrane material prepared by the preparation method of the highly permeable puncture-resistant membrane material as described in any one of claims 1-8.

10. The application of a highly permeable, puncture-resistant membrane material as described in claim 9 in rice cultivation.

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