Multifunctional agricultural greenhouse film and preparation method thereof

Abstract

The invention discloses a multifunctional agricultural greenhouse film and a preparation method thereof.The greenhouse film is beneficial to growth of crops, the carbon sequestration effect of the crops is improved, the output quality is improved, the greenhouse film further has a self-repairing function, the service life is prolonged, CQDS carbon quantum dots doped in a light conversion layer can be excited by sunlight to generate excitons, and the light conversion layer can be used for improving the light conversion effect of the crops. Light, which cannot be absorbed by leaf green, in sunlight is converted into absorbable light, so that photosynthesis of chlorophyll can be enhanced, and growth of crops is facilitated; the CU / WO3 quantum dots doped in the hydrolysis layer can be excited by sunlight to generate a catalyst capable of photolyzing water, condensate water attached to the greenhouse film can be decomposed into H2 / O, carbon sequestration is facilitated through photosynthesis of chlorophyll, and the generated sugar and carbohydrate are beneficial for increasing the output. The boron quantum dots doped in the self-repairing layer can generate covalent bonds with oxygen, and the early-stage damaged crazing of the film is re-crosslinked through the dynamic covalent bonds of boron, so that the self-repairing of the film can be realized, and the service life of the greenhouse film can be prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of agricultural greenhouses, and in particular to a multifunctional agricultural greenhouse film and a preparation method thereof. Background Art

[0002] Agricultural greenhouse is a facility used for agricultural planting, and greenhouse film is the most important component of agricultural greenhouse. The choice of agricultural greenhouse type will directly affect the function of agricultural greenhouse. The current greenhouse film mainly plays the role of heat preservation and moisture retention, light control, wind and rain protection, reducing water evaporation, and preventing soil loss. Chlorophylline photosynthesis, which is very important for crop growth, mainly absorbs red light and blue-violet light. These light energies are absorbed by chlorophyll molecules and converted into chemical energy, which in turn drives the photosynthesis. However, the current greenhouse film has not only red light and blue-violet light, but also other light, such as less ultraviolet light, and even green light that is not conducive to photosynthesis. However, the current greenhouse control of light is mainly to control the intensity of its sunlight, and the wavelength of light passing through the greenhouse film cannot be controlled. Carbon quantum dots (CQDs) are a carbon-based zero-dimensional material with many advantages such as excellent optical properties, good water solubility, low toxicity, environmental friendliness, wide source of raw materials, low cost, and good biocompatibility. However, carbon quantum dots have not yet been applied to greenhouse films to control and improve the different wavelengths of sunlight passing through the greenhouse films to enhance crop photosynthesis and facilitate crop growth. In addition, existing greenhouse films are easily damaged, which affects their service life. Summary of the invention

[0003] Therefore, based on the above background, the present invention provides a multifunctional agricultural greenhouse film and a preparation method thereof. The greenhouse film of the present invention is not only beneficial to the growth of crops, but also helps crops improve carbon fixation effects and improve output quality, but also has a self-repairing function, which helps to extend the service life.

[0004] The technical solution of the present invention is as follows:

[0005] A multifunctional agricultural greenhouse film, comprising a laminated functional layer and a base layer;

[0006] The functional layer comprises a light conversion layer, a hydrolysis layer, and a self-repairing layer stacked in sequence, wherein the self-repairing layer is located between the hydrolysis layer and the substrate layer;

[0007] The light conversion layer is doped with CQDS carbon quantum dots;

[0008] The hydrolysis layer is doped with CU / WO3 quantum dots;

[0009] The self-repairing layer is doped with boron quantum dots.

[0010] Furthermore, it also includes a blowing aid layer, and the base layer is located between the blowing aid layer and the self-repairing layer.

[0011] Furthermore, the light conversion layer, the hydrolysis layer, the self-repairing layer and the base layer are all made of PE as the base material.

[0012] Based on the same inventive concept, the present invention also provides a method for preparing a greenhouse film that is beneficial to crop growth, comprising the following steps:

[0013] 1) preparing a light conversion layer masterbatch, a hydrolysis layer masterbatch, and a self-repairing layer masterbatch by extrusion granulation respectively;

[0014] 2) Prepare the masterbatch particles of the matrix layer according to the quantity;

[0015] 3) The light conversion layer masterbatch, the hydrolysis layer masterbatch, the self-repairing layer masterbatch, the base layer masterbatch and the blow molding aid layer masterbatch of step 1) and step 2) are blow molded into a greenhouse film by co-extrusion composite blow molding.

[0016] Preferably, the amount of raw materials used in preparing the light conversion layer masterbatch in step 1) is as follows:

[0017] (0.1-0.5) wt% CQDS carbon quantum dots and (0-0.05) wt% maleic anhydride were added to every 50 kg PE powder.

[0018] Preferably, the amount of raw materials used in preparing the hydrolysis layer masterbatch in step 1) is as follows:

[0019] (0.1-0.5) wt% of CU / WO3 quantum dots and (0-0.05) wt% of maleic anhydride were added to every 50 kg of PE powder.

[0020] Preferably, the amount of raw materials used in preparing the self-repairing layer masterbatch in step 1) is as follows:

[0021] To every 50 kg of PE powder, (0.1-0.5) wt% of borate and (0-0.05) wt% of maleic anhydride were added.

[0022] Preferably, in step 3), the usage ratio of the base layer masterbatch, the light conversion layer masterbatch, the hydrolysis layer masterbatch and the self-healing layer masterbatch is (80-120):(2-10):(2-10):(2-10).

[0023] Based on the same inventive concept, the present invention applies the above-mentioned greenhouse film to the manufacture of greenhouses.

[0024] Based on the same inventive concept, the present invention also provides an agricultural greenhouse, which has a frame and a film. The film is stretched on the frame to form a space separated from the outside, and the film is made of the above-mentioned greenhouse film.

[0025] The beneficial effects achieved by the present invention are as follows:

[0026] The greenhouse film of the present invention comprises a functional layer and a substrate layer, wherein the CQDS carbon quantum dots doped in the light conversion layer in the functional layer can be excited by sunlight to generate excitons, converting the light in the sunlight that cannot be absorbed by chlorophyll into absorbable light, thereby enhancing the photosynthesis of chlorophyll and facilitating the growth of crops;

[0027] The CU / WO3 quantum dots doped in the hydrolysis layer can be excited by sunlight to generate catalysts for photolysis of water, which can decompose the condensed water attached to the greenhouse film into H2 / O. H2 is beneficial to the photosynthesis of chlorophyll for carbon fixation, and the generated sugars and carbohydrates are beneficial to increase output.

[0028] The boron quantum dots doped in the self-repairing layer can form covalent bonds with oxygen, and re-cross-link the early damaged silver lines of the membrane through the dynamic covalent bonds of boron, which can realize the self-repair of the membrane and help extend the service life of the greenhouse film. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Attached Figure 1 It is a schematic structural diagram of the greenhouse film of the present invention.

[0030] Attached Figure 2 It is a comparative bar chart of the fresh weight and dry weight of leek according to an embodiment of the present invention. DETAILED DESCRIPTION

[0031] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with its embodiments; it should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0032] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0033] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0034] Embodiment 1: A method for preparing a multifunctional agricultural greenhouse film, comprising the following steps:

[0035] 1) preparing a light conversion layer masterbatch, a hydrolysis layer masterbatch, and a self-repairing layer masterbatch by extrusion granulation respectively;

[0036] The raw materials for preparing the light conversion layer masterbatch are as follows:

[0037] 0.2 wt% of CQDS carbon quantum dots and 0.01 wt% of maleic anhydride were added to every 50 kg of PE powder.

[0038] The raw materials for preparing the hydrolysis layer masterbatch are as follows:

[0039] 0.3wt% of CU / WO3 quantum dots and 0.01wt% of maleic anhydride were added to every 50kg of PE powder.

[0040] The raw materials for preparing the self-repairing layer masterbatch are as follows:

[0041] 0.1 wt% borate and 0.01 wt% maleic anhydride are added to every 50 kg PE powder. In this step, borate is a polymerized organic complex of boron quantum dots, which can dynamically re-crosslink the damaged C=C bonds of the PE film to self-repair the film.

[0042] In a specific implementation, the molecular weight of the PE powder is 25000-50000.

[0043] 2) Prepare the masterbatch particles of the matrix layer according to the quantity;

[0044] The usage ratio of the base layer masterbatch, the light conversion layer masterbatch, the hydrolysis layer masterbatch and the self-repairing layer masterbatch is 100:5:5:5.

[0045] In specific applications, additives are added to the PE powder used for the light conversion layer masterbatch, the hydrolysis layer masterbatch, the self-repairing layer masterbatch, and the base layer masterbatch, and the additives include antioxidants, plasticizers, and lubricants, wherein the antioxidants include antioxidants and light stabilizers, wherein the antioxidant can be selected from at least one of antioxidant 1010, antioxidant 168, and antioxidant 1076. The antioxidant of this embodiment is antioxidant 1076, and its dosage is 0.1wt%-0.5wt% of the PE powder, that is, 1-5g is added to 1kg of PE powder;

[0046] The light stabilizer can be selected from at least one of UV-531, UV-327, UV-326, HALS, BAD and salicylate. In this embodiment, UV-531 is selected, and its dosage is 0.1wt%-0.3wt% of PE powder, that is, 1-3g is added to 1kg of PE powder.

[0047] The plasticizer is selected from dibutyl phthalate (DBP) and diisobutyl adipate (DIBOPA), and its usage accounts for 5wt%-20wt% of the PE powder. The plasticizer of this embodiment is dibutyl phthalate (DBP), and its usage is 12wt% of the PE powder, that is, 120g is added to 1kg of PE powder;

[0048] The lubricant can be selected from fatty acid amide (such as oleic acid amide) and liquid paraffin. In this embodiment, oleic acid amide is selected, and its usage is 0.5wt%-1wt% of PE powder, that is, 5-10g is added to 1kg of PE powder.

[0049] Specifically, 1000 kg PE granules (base layer masterbatch) + 50 kg light conversion layer masterbatch + 50 kg hydrolysis layer masterbatch + 50 kg self-healing layer masterbatch.

[0050] 3) The light conversion layer masterbatch, hydrolysis layer masterbatch, self-repairing layer masterbatch and base layer masterbatch of step 1) and step 2) are blown into a greenhouse film by co-extrusion composite blow molding (ZQSJ-5FM1600 four-layer film blowing machine).

[0051] This embodiment prepares a greenhouse film with four layers in total. Figure 1 , which are a light conversion layer, a hydrolysis layer, a self-repairing layer and a matrix layer stacked in sequence.

[0052] Embodiment 2: A method for preparing a multifunctional agricultural greenhouse film, comprising the following steps:

[0053] 1) preparing a light conversion layer masterbatch, a hydrolysis layer masterbatch, and a self-repairing layer masterbatch by extrusion granulation respectively;

[0054] The raw materials for preparing the light conversion layer masterbatch are as follows:

[0055] 0.2wt% CQDS carbon quantum dots and 0.01wt% maleic anhydride are added to every 50kg PE powder. The raw materials for preparing the hydrolysis layer masterbatch are as follows:

[0056] 0.3wt% of CU / WO3 quantum dots and 0.01wt% of maleic anhydride were added to every 50kg of PE powder.

[0057] The raw materials for preparing the self-repairing layer masterbatch are as follows:

[0058] 0.1 wt% of borate and 0.01 wt% of maleic anhydride were added to every 50 kg of PE powder.

[0059] 2) Prepare the masterbatch particles of the base layer and the masterbatch particles of the blow molding auxiliary agent layer according to the amount;

[0060] The usage ratio of the masterbatch of the base layer, the masterbatch of the light conversion layer, the masterbatch of the hydrolysis layer, the masterbatch of the self-repairing layer and the masterbatch of the blow molding auxiliary agent layer is 100:5:5:5:1.

[0061] Specifically, 1000 kg PE granules (base layer masterbatch) + 50 kg light conversion layer masterbatch + 50 kg hydrolysis layer masterbatch + 50 kg self-repairing layer masterbatch + 10 kg blow molding additive layer masterbatch.

[0062] The blow molding auxiliary agent layer masterbatch comprises an antioxidant, an anti-aging agent, a plasticizer and a lubricant.

[0063] 3) The light conversion layer masterbatch, hydrolysis layer masterbatch, self-repairing layer masterbatch, base layer masterbatch and blowing aid layer masterbatch of step 1) and step 2) are blown into a greenhouse film by co-extrusion composite blow molding (ZQSJ-5FM1600 five-layer film blowing machine).

[0064] This embodiment prepares a greenhouse film with five layers in total. Figure 2 , which are a light conversion layer, a hydrolysis layer, a self-repairing layer, a base layer, and a blow molding auxiliary agent layer stacked in sequence.

[0065] Embodiment 3:

[0066] In this example, the greenhouse film prepared in Example 1 (hereinafter referred to as quantum dot film) and a blank film without quantum dots were compared in terms of their effects on the growth of leeks.

[0067] The blank film without quantum doping is co-extruded with the greenhouse film by blow molding into four layers, which respectively include a stacked first layer, a second layer, a third layer and a base layer.

[0068] The raw materials for preparing the first layer, the second layer and the third layer are: adding 0.01wt% of maleic anhydride into every 50kg of PE powder.

[0069] The base layer is the same as that in Example 1.

[0070] In this comparative example, the PE powder used in the first layer, the second layer, the third layer and the base layer has the same additives as in Example 1 added thereto.

[0071] In this embodiment, in March 2024, the greenhouse film of Example 1 and the blank film were used to build a quantum film greenhouse (experimental greenhouse) and a blank film greenhouse (control greenhouse) in Gaoliu Town, Qingzhou City, Shandong Province, and then Fusheng No. 1 leeks were planted in the quantum film greenhouse and the blank film greenhouse, respectively. The leeks in the two greenhouses were managed in the same way, such as watering and weeding.

[0072] Three months later, the plant heights of the leeks in the two greenhouses were counted, outliers were removed, and the other values ​​were averaged; the leeks were harvested for the first time, and the fresh weight and dry weight of the harvested leeks were counted. The results are shown in Table 1.

[0073] Table 1:

[0074] Plant height Fresh weight Dry weight Experimental Shed 40CM 3320 catties 855 catties Control shed 35CM 3000 catties 750 catties

[0075] The data in the above table are per mu yield data.

[0076] From the table above, the fresh weight of leeks in the quantum dot film greenhouse increased by 10.67%, the dry weight increased by 14%, and the plant height increased by 14.2% compared with those in the blank film greenhouse. It is obvious that the quantum film greenhouse of Example 1 can promote the growth of leeks.

[0077] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. Multifunctional agricultural greenhouse film, characterized in that: It includes a stacked functional layer and a base layer; The functional layer comprises a light conversion layer, a hydrolysis layer, and a self-repairing layer stacked in sequence, wherein the self-repairing layer is located between the hydrolysis layer and the substrate layer; The light conversion layer is doped with CQDS carbon quantum dots; The hydrolysis layer is doped with CU / WO3 quantum dots; The self-repairing layer is doped with boron quantum dots.

2. The multifunctional agricultural greenhouse film according to claim 1, characterized in that: The invention further comprises a blowing aid layer, and the base layer is located between the blowing aid layer and the self-repairing layer.

3. The multifunctional agricultural greenhouse film according to claim 1, characterized in that: The light conversion layer, the hydrolysis layer, the self-repairing layer and the base layer are all made of PE as the base material.

4. The method for preparing the multifunctional agricultural greenhouse film according to claim 1 or 3, characterized in that: The steps include: 1) preparing a light conversion layer masterbatch, a hydrolysis layer masterbatch, and a self-repairing layer masterbatch by extrusion granulation respectively; 2) Prepare the masterbatch particles of the base layer according to the amount; 3) The light conversion layer masterbatch, the hydrolysis layer masterbatch, the self-repairing layer masterbatch and the base layer masterbatch of step 1) and step 2) are blow-molded into a greenhouse film by co-extrusion composite blow molding.

5. The method for preparing the multifunctional agricultural greenhouse film according to claim 4, characterized in that: The raw materials for preparing the light conversion layer masterbatch in step 1) are as follows: (0.1-0.5) wt% CQDS carbon quantum dots and (0-0.05) wt% maleic anhydride were added to every 50 kg PE powder.

6. The method for preparing the multifunctional agricultural greenhouse film according to claim 5, characterized in that: The raw materials for preparing the hydrolysis layer masterbatch in step 1) are as follows: For every 50 kg of PE powder, (0.1-0.5) wt% of CU / WO3 quantum dots and (0-0.05) wt% of maleic anhydride were added.

7. The method for preparing the multifunctional agricultural greenhouse film according to claim 5, characterized in that: The raw materials for preparing the self-repairing layer masterbatch in step 1) are as follows: To every 50 kg of PE powder, (0.1-0.5) wt% of borate and (0-0.05) wt% of maleic anhydride were added.

8. The method for preparing the multifunctional agricultural greenhouse film according to claim 5, characterized in that: In step 3), the usage ratio of the base layer masterbatch, the light conversion layer masterbatch, the hydrolysis layer masterbatch and the self-healing layer masterbatch is (80-120):(2-10):(2-10):(2-10).

9. Use of the multifunctional agricultural greenhouse film according to any one of claims 1 to 3 or the greenhouse film prepared by the method for preparing a multifunctional agricultural greenhouse film according to any one of claims 4 to 8 in the manufacture of greenhouses.

10. An agricultural greenhouse, characterized in that: The agricultural greenhouse has a frame and a film, and the film is stretched on the frame to form a space separated from the outside. The film is the multifunctional agricultural greenhouse film described in any one of claims 1 to 3, or a greenhouse film prepared by the method for preparing a multifunctional agricultural greenhouse film described in any one of claims 4 to 8.

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