CN112521738A - Degradable light conversion film and preparation method and application thereof - Google Patents

Degradable light conversion film and preparation method and application thereof Download PDF

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CN112521738A
CN112521738A CN202011479097.0A CN202011479097A CN112521738A CN 112521738 A CN112521738 A CN 112521738A CN 202011479097 A CN202011479097 A CN 202011479097A CN 112521738 A CN112521738 A CN 112521738A
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light conversion
degradable
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conversion agent
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CN112521738B (en
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叶炜浩
胡广齐
陈焰
梁敏婷
郑明东
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Foshan Onmillion Nano Materials Co ltd
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    • C08J5/18—Manufacture of films or sheets
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • A01G13/0256—Ground coverings
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    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
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Abstract

The invention belongs to the technical field of light conversion films, and discloses a degradable light conversion film and a preparation method and application thereof. The degradable light conversion film comprises the following components in parts by mass: 20-100 parts of degradable polymer base material, 0.1-1.2 parts of surface-modified light conversion agent, 0-80 parts of polyolefin film base material and 1-10% of solubilizer relative to the mass of the polyolefin film base material. The invention adopts a specific surface modification method to solve the problem of mixing and dispersing of the light conversion agent in the degradable polymer base material, and the obtained light conversion film has good uniformity, light transmittance and processability, and completely meets the use requirements of agricultural greenhouse films and agricultural mulching films. The greenhouse applying the light conversion film can effectively improve the yield and disease resistance of fruit and vegetable crops. And the degradable polymer substrate can be further compounded with the polyolefin film substrate, so that the degradable performance and the service life of the film can be considered.

Description

Degradable light conversion film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of light conversion films, and particularly relates to a degradable light conversion film and a preparation method and application thereof.
Background
Plant growth is closely related to photosynthesis, and the light emission spectrum of sunlight plays a crucial role in the growth and development of plants. The wavelength of light required by photosynthesis of plants is about 400-720 nm. Wherein the light of 440-480 nm (blue) and 640-680 nm (red) contribute the most to photosynthesis. Therefore, the conversion of other wavelength spectrums into blue light and red light as much as possible plays an important role in promoting plant growth, precocity and yield increase.
The light conversion film is a film which realizes light conversion by adding a light conversion agent, and ultraviolet light harmful to plant growth is converted into visible light beneficial to plant growth or yellow green light is converted into red orange light by the action of the added light conversion agent, so that the light quality after the film is penetrated is changed, the plant growth is promoted, and the yield and the income are increased.
The light conversion film in the current market generally adopts polyolefin materials such as polyethylene, polypropylene and polyvinyl chloride as substrates. Among them, polyethylene is a plastic variety with the largest production in the world at present, and is widely used for producing disposable plastic products such as agricultural mulching films, packaging materials and the like. However, the problem of "white pollution" to the ecological environment is becoming more and more serious due to the poor degradability of polyolefin materials. Therefore, the polyolefin material is subjected to substitution or composite modification, the degradability of the material is enhanced, the load generated to the environment is reduced, and the method has very important practical significance.
Patent CN 102775750 a discloses a degradable multiband light conversion mulching film and a preparation method thereof. The degradable polymer base material plastic master batch, the organic light conversion dye and the rare earth light conversion powder are weighed according to the percentage, are directly sent into a blown film extruder after being uniformly stirred, and the degradable light conversion mulching film is obtained after the film is extruded. The degradable polymeric substrate comprising: polylactic acid, poly beta-hydroxybutyrate, polyvinyl alcohol, polycaprolactone, cellulose, lignin, chitosan, a mixture of the degradable polymers according to any proportion or a mixture of the degradable polymers and non-degradable polymers such as polyethylene, polypropylene, polyvinyl chloride and the like according to any proportion; the organic light conversion dye comprises: molecular formula C28H31ClN2O3Called rhodamine B or molecular formula C20H6O5Br4Na2Weighing eosin; the rare earth light conversion powder comprises: rare earth silicate, rare earth phosphate, rare earth hydrochloride, rare earthNitrate, rare earth organic complex rare earth light conversion powder. However, the direct addition of organic or inorganic light conversion agents to degradable polymeric substrates has poor compatibility with film resins and is difficult to disperse. Resulting in the decrease of film uniformity and light transmittance and poor processability. And the light conversion performance of the film is difficult to be effectively exerted.
The degradable polymer base material is easy to be attacked by microorganisms or is promoted to degrade by other factors, the polyolefin material macromolecular chains are promoted to be broken at an accelerated speed by adding the materials, and the polyolefin material macromolecular chains are degraded into low-molecular-weight compound fragments which can be phagocytized by the microorganisms, so that the degradable polymer base material is a feasible direction for improving the degradability by composite modification. However, the degradable polymer substrate such as biomass polysaccharide compound is a strong polar natural polymer compound rich in hydroxyl, the chain structure of the nonpolar polyolefin material such as polyethylene and the compound is also very different, the miscibility of the two is very poor from the thermodynamic point of view, the direct mechanical blend will form a complete phase separation system, the two phases lack of adhesive force, and the uniformity, light transmittance and mechanical property of the film are reduced.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a degradable light conversion film.
The invention also aims to provide a preparation method of the degradable light conversion film.
The invention further aims to provide application of the degradable light conversion film in agricultural greenhouse films and agricultural mulching films.
The purpose of the invention is realized by the following technical scheme:
a degradable light conversion film comprises the following components in parts by mass:
Figure BDA0002837904020000021
Figure BDA0002837904020000031
further, the degradable polymer substrate comprises any one or a mixture of more than two of modified starch (such as methyl acrylate modified starch), cellulose ester, cellulose, chitosan, polyvinyl alcohol, polyhydroxyalkanoate, polybutylene succinate, polylactic acid and a copolymer thereof, polyhydroxyalkanoate, polypropylene succinate, caprolactam, terephthalate, polycaprolactone, polyhydroxybutyrate, valerate and aliphatic-aromatic copolyester.
Further, the surface-modified light conversion agent is a light conversion agent coated by silicon dioxide and surface-modified by a silane coupling agent.
Preferably, the silane coupling agent refers to a silane coupling agent containing an amino group, a mercapto group, a hydroxyl group or a carboxyl group. Wherein the silane coupling agent containing amino comprises aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane, tetraaminosilane, etc.; the silane coupling agent containing mercapto comprises 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and the like; the silane coupling agent containing hydroxyl comprises diphenyl dihydroxyl silane, triphenyl hydroxyl silane, 3-aminopropyl trihydroxy silane and the like; the silane coupling agent containing a carboxyl group includes 3- [ 3-carboxyallylamido ] propyltriethoxysilane, tetrakis (4-carboxyphenyl) silane, and the like. The strong polarity and reactivity of the active groups can further enhance the bonding force and dispersion stability between the light conversion agent and the degradable polymer substrate.
Further, the light conversion agent comprises at least one of an organic fluorescence light conversion agent, an inorganic salt light conversion agent, a rare earth organic complex light conversion agent and a quantum dot light conversion agent.
Further, the organic fluorescent light conversion agent includes any one of a fluorane-based fluorescent dye, a naphthalimide-based fluorescent dye, and a coumarin-based fluorescent dye. The fluoran fluorescent dye includes 3, 6-diethoxy fluoran, 3-diethylamino-7- (2' -chloroanilino) fluoran, rhodamine B, rhodamine 110, rhodamine 123, rhodamine 101 and the like. The naphthalimide fluorescent dye comprises 1, 8-naphthalimide, 4-amino-1, 8-naphthalimide, 1, 8-naphthalic anhydride and derivatives thereof.
Further, the inorganic salt light conversion agent comprises light conversion agents which are composed of activator ions and have blue light emitting wavelength of 440-460 nm and red light emitting wavelength of 640-660 nm, such as alkaline earth aluminate, oxide, sulfide, tungstate or silicate; the activator ion comprises Ce3+、Ce4+、Pr3+、Pr4+、Pr5+、Nd3+、Sm2+、Sm3+、Eu2+、Eu3+、Gd3+、Tb3+、Tb4+、Dy3+、Dy4+、Er3+、Tm3+、Yb2+、Yb3+Plasma rare earth ions or partial transition metal ions.
By way of example, among others, alkaline earth aluminates include CaAl2O4:Eu2+,Nd3+、SrAl2O4:Eu2+,Dy3+、Sr4Al14O25:Eu2+,Dy3+、SrAl4O7:Eu2+,Dy3+、SrAl2O4:Eu2+、Ca12Al14O33:Eu2+,Nd3+Etc.; the sulfide includes CaS Eu3+,Tm3+、CaS:Eu2+,Tm3+、ZnS:Cu2+、CaS:Bi3+Etc.; the silicate comprises Sr2MgSi2O7:Eu2+,Dy3+、CdSiO3:Sm3+、CdSiO3:Mn2+And the like.
Further, the rare earth organic complex light conversion agent comprises a monobasic or polybasic organic ligand compound formed by lanthanide rare earth metal ions and organic ligands containing beta-diketone groups, pyridyl groups, carboxyl groups, p-toluate groups, m-chlorobenzoate groups, sulfonic groups and the like; wherein the lanthanide rare earth metal ion comprises Ce3+、Ce4+、Pr3+、Pr4+、Pr5+、Nd3+、Sm2+、Sm3+、Eu2+、Eu3 +、Gd3+、Tb3+、Tb4+、Dy3+、Dy4+、Er3+、Tm3+、Yb2+、Yb3+And the like.
Further, the quantum dot light conversion agent comprises C, Si, Ge, CdSe, ZnSe, PbSe, CdTe, ZnO, InP, GaN, GaP, AlP, InN, ZnTe, InAs, GaAs, CaF2、Cd1-xZnxS、Cd1-xZnxSe、CdSeyS1-y、PbSeyS1-y、ZnXCd1-XTe、CdS/ZnS、Cd1-xZnxS/ZnS、Cd1-xZnxSe/ZnSe、CdSe1-xSx/CdSeyS1-y/CdS、CdSe/Cd1- xZnxSe/CdyZn1-ySe/ZnSe、Cd1-xZnxSe/CdyZn1-y Se/ZnSe、CdS/Cd1-xZnxS/CdyZn1-yS/ZnS、Cd1- xZnxSeyS1-y、CdSe/ZnS、Cd1-xZnxSe/ZnS、CdSe/CdS/ZnS、CdSe/ZnSe/ZnS、Cd1-xZnxSe/CdyZn1- yAt least one of S/ZnS and InP/ZnS equivalent sub-dots, wherein x and y have values ranging from 0 to 1.
Further, the solubilizer includes ethylene-acrylic acid copolymer, ethyl acrylate, maleic anhydride, and the like. The solubilizer is a series of polymers or polymer monomers containing carboxyl, and the carboxyl can be associated with the hydroxyl of the degradable material and has strong affinity with the degradable material; on the other hand, the chain structure of the solubilizer is similar to that of the polyethylene, which allows better compatibility of the blend.
Further, the polyolefin film substrate is selected from any one or more than two of polyethylene, polypropylene and polyvinyl chloride.
The preparation method of the degradable light conversion film comprises the following preparation steps:
(1) adding CTAB (cetyl trimethyl ammonium bromide) and ammonia water into a solvent, stirring and dissolving uniformly, then adding a light conversion agent, stirring and dispersing uniformly, then adding n-silane ethyl ester, stirring and reacting at 50-70 ℃, then adding a silane coupling agent, continuing stirring and reacting, washing and drying after the reaction is finished, and obtaining the light conversion agent with surface modification (silicon dioxide coating and silane coupling agent surface modification);
(2) mixing the surface-modified light conversion agent obtained in the step (1) and a degradable polymer base material, dispersing in a solvent, then dropwise adding an acid solution to adjust the pH value to 2-4, heating to 80-95 ℃, stirring for reaction, neutralizing, washing and drying after the reaction is finished, so as to obtain a degradable base material containing the light conversion agent;
(3) and (3) mixing, extruding and granulating the degradable base material containing the light conversion agent obtained in the step (2) with a solubilizer and a polyolefin film base material to obtain resin particles, and then putting the resin particles into a film blowing machine for film blowing to obtain the degradable light conversion film.
Preferably, the solvent in step (1) and step (2) is deionized water.
Preferably, the adding amount of the n-silane ethyl ester in the step (1) is 0.5 to 3 percent of the mass of the light conversion agent; the adding amount of the silane coupling agent is 0.5-3% of the mass of the light conversion agent.
Preferably, the n-silane ethyl ester is added in the step (1) and stirred for reaction for 20-30 hours; adding the silane coupling agent, and continuously stirring for 10-20 h.
Preferably, the acid solution in the step (2) is 1mol/L hydrochloric acid solution; the heating to 80-95 ℃ and stirring reaction time is 30-50 min.
The degradable light conversion film is applied to agricultural greenhouse films and agricultural mulching films.
The principle of the invention is as follows: firstly, the light conversion agent is mixed with CTAB and ammonia water to form a molecular layer on the surface of the light conversion agent, which is favorable for being combined with subsequent n-silane ethyl ester. Then adding n-silane ethyl ester, heating and stirring for reaction, forming a silicon dioxide coating structure on the surface of the light conversion agent, improving the modifiability of the surface of the light conversion agent, and increasing the connection sites of the surface ligand; and adding a silane coupling agent for continuous stirring reaction, wherein one function of the silane coupling agent is to prevent the silica from continuously growing, the other function of the silane coupling agent is to enhance the compatibility with the degradable polymer base material through an organic group on the coupling agent, and the third function of the silane coupling agent is to further enhance the binding force and the dispersion stability between the light conversion agent and the degradable polymer base material through the reaction between an active group on the coupling agent and the degradable material. And then mixing the obtained surface-modified light conversion agent with the degradable polymer base material for reaction, compounding the surface-modified light conversion agent with the degradable polymer base material by utilizing the surface modification effect of a coupling agent or the reaction of amino, carboxyl, hydroxyl or sulfydryl on a surface ligand and the hydroxyl and carboxyl of the branched chain of the degradable material, and uniformly dispersing the light conversion agent or connecting the light conversion agent into the polymer base material through a chemical bond to obtain the degradable base material containing the light conversion agent. And finally, mixing the degradable base material containing the light conversion agent, the solubilizer and the polyolefin film base material, extruding and granulating, and adding the compatibilizer during mixing, so that the blend has better compatibility, the bonding force of a two-phase interface is increased, the mechanical property and the transparency are obviously improved, and the degradable light conversion film obtained by film blowing has good comprehensive performance and good application prospect in agricultural greenhouse films and agricultural mulching films.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) the invention adopts a specific surface modification method to solve the problem of mixing and dispersing of the light conversion agent in the degradable polymer base material, and the obtained light conversion film has good uniformity, light transmittance and processability, and completely meets the use requirements of agricultural greenhouse films and agricultural mulching films.
(2) The degradable light conversion film has good light conversion performance, and the light conversion film greenhouse applying the light conversion film can effectively improve the plant height, the length, the width, the product of leaves, the yield and the disease resistance of fruit and vegetable crops.
(3) The degradable light conversion film can further compound the degradable polymer substrate and the polyolefin film substrate, solves the compounding problem between the degradable substrate and the polyolefin film substrate by adding the specific solubilizer, can give consideration to the degradable performance and the service life of the film, and meets the use requirements of agricultural films with different service periods.
Drawings
FIG. 1 and FIG. 2 are graphs showing the results of the comparison of the plant variation and yield of pepper plants during the testing of the effect of the degradable light-converting film obtained by the present invention in the agricultural greenhouse film;
FIG. 3 and FIG. 4 are graphs showing the variation of the length-width product of eggplant plant height and leaves and the comparison of yield during the testing of the application effect of the degradable light conversion film obtained by the present invention in an agricultural greenhouse film;
FIG. 5 and FIG. 6 are graphs showing the comparative results of the high variation and yield of tomato plants during the testing of the effect of the degradable light-converting film in agricultural greenhouse;
FIG. 7 and FIG. 8 are graphs showing the comparative results of the high variation and yield of sweet pepper plants during the testing of the effect of the degradable light-converting film obtained by the present invention applied to agricultural greenhouse films;
FIG. 9 is a graph showing the results of comparing the disease resistance of the degradable light conversion film obtained by the present invention in the test of the application effect in agricultural greenhouse films.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The degradable light conversion film comprises the following components in parts by mass:
100 parts of polylactic acid;
silicon dioxide coated and silane coupling agent surface modified light conversion agent Sr2MgSi2O7:Eu2+,Dy3+
0.8 part.
The degradable light conversion film of the embodiment is prepared by the following method:
(1) taking 0.75mmol CTAB, 2mL of 0.1mol/L ammonia water and 15mL of deionized water in a round-bottom flask, stirring to completely dissolve CTAB, and adding 2g of light conversion agent Sr2MgSi2O7:Eu2+,Dy3+Stirring for 30min to disperse the light conversion agent completely in the solution, then quickly injecting 15 μ L of n-silane ethyl ester, stirring at 60-70 deg.C for reaction for 24h, and then adding 15 μ L of silane coupling agent 3- [ 3-carboxyl allyl amide]Propyl triethoxy siliconAnd (4) continuously stirring the alkane for reaction for 12 hours, and washing and drying after the reaction is finished to obtain the light conversion agent coated by the silicon dioxide and modified by the surface of the silane coupling agent.
(2) Mixing and dispersing 0.8g of the surface-modified light conversion agent obtained in the step (1) and 100g of polylactic acid in 100ml of deionized water, stirring at room temperature for 10min to fully mix, dropwise adding 1mol/L hydrochloric acid solution into the mixed solution, and adjusting the pH value to 3; then stirring and reacting for 30min under the condition of heating in water bath at 85-90 ℃, and neutralizing, washing and drying after the reaction is finished to obtain the degradable base material containing the light conversion agent.
(3) And (3) extruding and granulating the degradable base material containing the light conversion agent obtained in the step (2) in a double-screw extruder to obtain resin particles, and then putting the resin particles into a film blowing machine for film blowing to obtain the degradable light conversion film.
Example 2
The degradable light conversion film comprises the following components in percentage by mass:
30 parts of methyl acrylate modified starch;
light conversion agent CaAl coated with silicon dioxide and surface modified by silane coupling agent2O4:Eu2+,Nd3+
0.6 part;
3 parts of ethylene-acrylic acid copolymer;
70 parts of polyethylene.
The degradable light conversion film of the embodiment is prepared by the following method:
(1) 0.75mmol CTAB, 2mL of 0.1mol/L ammonia water and 15mL of deionized water are put into a round-bottom flask, stirred to completely dissolve CTAB, and then 2g of light conversion agent CaAl is added2O4:Eu2+,Nd3+Stirring for 30min to disperse the light conversion agent completely in the solution, then quickly injecting 15 μ L of n-silane ethyl ester, stirring at 60-70 deg.C for reaction for 24h, and then adding 15 μ L of silane coupling agent 3- [ 3-carboxyl allyl amide]Continuously stirring and reacting the propyl triethoxy silane for 12 hours, and washing and drying after the reaction is finished to obtain the silicon dioxide packageA light conversion agent coated with silane coupling agent surface modification.
(2) Mixing and dispersing 0.6g of the surface-modified light conversion agent obtained in the step (1) and 30g of methyl acrylate modified starch in 50ml of deionized water, stirring for 10min at room temperature to fully mix the mixture, dropwise adding 1mol/L hydrochloric acid solution into the mixed solution, and adjusting the pH value to 3; then stirring and reacting for 30min under the condition of heating in water bath at 85-90 ℃, and neutralizing, washing and drying after the reaction is finished to obtain the degradable base material containing the light conversion agent.
(3) And (3) extruding and granulating the degradable base material containing the light conversion agent obtained in the step (2), 3g of solubilizer ethylene-acrylic acid copolymer and 70g of polyethylene in a double-screw extruder to obtain resin particles, and then putting the resin particles into a film blowing machine for film blowing to obtain the degradable light conversion film.
Example 3
The degradable light conversion film comprises the following components in parts by mass:
Figure BDA0002837904020000091
the degradable light conversion film of the embodiment is prepared by the following method:
(1) and (2) putting 0.5mmol of CTAB, 1mL of 0.1mol/L ammonia water and 20mL of deionized water in a round-bottom flask, stirring to completely dissolve the CTAB, adding 1g of carbon quantum dot light conversion agent, continuously stirring for 30min to completely disperse the carbon quantum dot light conversion agent in the solution, quickly injecting 5 mu L of N-silane ethyl ester, stirring and reacting at 50-60 ℃ for 30h, then adding 5 mu L of silane coupling agent N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, continuously stirring and reacting for 10h, washing and drying after the reaction is finished, thus obtaining the silica-coated and silane coupling agent surface modified light conversion agent.
(2) Mixing and dispersing 0.2g of the surface-modified light conversion agent obtained in the step (1) and 70g of the cellulose/chitosan compound in 100ml of deionized water, stirring for 10min at room temperature to fully mix the mixture, dropwise adding 1mol/L hydrochloric acid solution into the mixed solution, and adjusting the pH value to 2; then stirring and reacting for 30min under the condition of heating in water bath at the temperature of 80-85 ℃, and neutralizing, washing and drying after the reaction is finished to obtain the degradable base material containing the light conversion agent.
(3) And (3) extruding and granulating the degradable base material containing the light conversion agent obtained in the step (2) with 1g of solubilizer maleic anhydride and 30g of polyethylene in a double-screw extruder to obtain resin particles, and then putting the resin particles into a film blowing machine for film blowing to obtain the degradable light conversion film.
Example 4
The degradable light conversion film comprises the following components in percentage by mass:
50 parts of polylactic acid;
1 part of silica-coated and silane coupling agent surface modified light conversion agent 3-diethylamino-7- (2' -chloroanilino) fluorane;
5 parts of ethyl acrylate;
50 parts of polyethylene.
The degradable light conversion film of the embodiment is prepared by the following method:
(1) taking 1mmol of CTAB, 5mL of 0.1mol/L ammonia water and 20mL of deionized water, stirring to completely dissolve the CTAB, adding 2g of light conversion agent 3-diethylamino-7- (2' -chloroanilino) fluorane, continuously stirring for 30min to completely disperse the light conversion agent in the solution, then quickly injecting 30 mu L of n-silane ethyl ester, stirring and reacting for 24h at 60-65 ℃, then adding 30 mu L of silane coupling agent 3-mercaptopropyltrimethoxysilane, continuously stirring and reacting for 20h, washing and drying after the reaction is finished, and obtaining the light conversion agent coated by silicon dioxide and modified by the surface of the silane coupling agent.
(2) Mixing and dispersing 1g of the surface-modified light conversion agent obtained in the step (1) and 50g of polylactic acid in 50ml of deionized water, stirring at room temperature for 10min to fully mix the light conversion agent and the polylactic acid, dropwise adding 1mol/L hydrochloric acid solution into the mixed solution, and adjusting the pH value to 4; then stirring and reacting for 30min under the heating of water bath at 90-95 ℃, and neutralizing, washing and drying after the reaction is finished to obtain the degradable base material containing the light conversion agent.
(3) And (3) extruding and granulating the degradable base material containing the light conversion agent obtained in the step (2) with 5g of solubilizer ethyl acrylate and 50g of polyethylene in a double-screw extruder to obtain resin particles, and then putting the resin particles into a film blowing machine for film blowing to obtain the degradable light conversion film.
Comparative example 1
This comparative example is different from example 2 in that the light conversion agent CaAl without surface modification is used2O4:Eu2+,Nd3+And the rest is completely the same.
Comparative example 2
This comparative example is different from example 2 in that the light conversion agent CaAl without surface modification is used2O4:Eu2+,Nd3+And no ethylene-acrylic acid copolymer was added, the rest being identical.
Firstly, the mechanical properties and transparency of the degradable light conversion films obtained in the above examples and comparative examples are tested, and the results are shown in table 1 below.
TABLE 1
Figure BDA0002837904020000111
As can be seen from the results in Table 1, the invention can significantly improve the mechanical properties and transparency of the obtained film by performing specific surface modification on the light conversion material and adding the solubilizer.
And secondly, testing the application effect of the obtained degradable light conversion film in an agricultural greenhouse film, taking the degradable light conversion film in the embodiment 1 as an application example, and comparing and analyzing the changes and influences of the traditional film and the degradable light conversion film on the growth conditions and the yield of fruits and vegetables such as hot peppers, eggplants, tomatoes and sweet peppers during greenhouse planting by adopting a uniform field management technology through field planting.
(1) The results of the pepper plant changes and yield comparison during the experiment are shown in fig. 1 and fig. 2, respectively. The results in fig. 1 show that the plant height of the peppers keeps continuously increasing change during the planting test, the plant heights of the crops in the light conversion film greenhouse are all higher than those in the common film greenhouse, and the difference between the two greenhouses is more obvious as the planting time is longer; in the aspect of the length and width product of the blades, the data shows that the length and width product of the blades of the light conversion film greenhouse is also higher than that of the blades of crops in a common film greenhouse. The results in fig. 2 show that compared with the common film greenhouse, the yield of the peppers planted in the light conversion film greenhouse is obviously higher than that of the crops in the common film greenhouse, and the actual yield is increased by 26.91% compared with that in the common film greenhouse.
(2) The results of the changes of the length-width product of the eggplant plant and the leaves during the test and the comparison of the yield are shown in fig. 3 and fig. 4 respectively. The results in fig. 3 show that the plant height change of the eggplant is similar to that of the pepper during the planting test, namely the plant heights of the crops in the light conversion film greenhouse are all higher than those in the common film greenhouse, and the difference between the two greenhouses is more obvious as the planting time is longer; in the aspect of the length and width product of the blades, data show that the length and width product of the light conversion film greenhouse is higher than that of the blades of crops in a common film greenhouse, but the length and width product of the light conversion film greenhouse is slightly different from that of eggplants in the common film greenhouse in an ascending trend, and the length and width product of the blades of the light conversion film greenhouse is changed in a trend of ascending and then descending. The results in fig. 4 show that the yield of eggplants planted in the light conversion film greenhouse is obviously higher than that of eggplants planted in a common film greenhouse, and the actual yield is increased by 27% compared with that in the common film greenhouse during the whole experiment.
(3) The results of the high variation and yield comparison of tomato plants during the experiment are shown in FIGS. 5 and 6, respectively. The results in fig. 5 show that the plant heights of the tomatoes in the common film greenhouse and the light conversion film greenhouse are gradually changed during the planting test, the plant heights of the tomatoes in the light conversion film greenhouse are higher than those in the common film greenhouse at the same measurement time, and the difference between the two greenhouses is more obvious as the planting time in the early and middle periods is longer; however, the tomato is subjected to a measure of removing the growing point at the top in the middle and later stages, so that the subsequent plant height is not changed. The results in fig. 6 show that the yield of eggplants planted in the light conversion film greenhouse is obviously higher than that of eggplants planted in a common film greenhouse, and the actual yield is increased by 24.11 percent compared with that in the common film greenhouse in the whole experiment period.
(4) The results of the high variation of the sweet pepper plants and the yield comparison during the test are shown in fig. 7 and 8, respectively. The results in fig. 7 show that the plant height change of sweet peppers during the planting test is similar to that of peppers and eggplants, namely the plant heights of the crops in the light conversion film greenhouse are all higher than those in the common film greenhouse, and the difference between the two greenhouses is more obvious as the planting time is longer; in the aspect of the change of the length and width products of the blades, data show that the length and width products of the blades of the light conversion film greenhouse are also higher than those of the blades of crops in the common film greenhouse, but the changes of the length and width products of the blades of the common film greenhouse and the eggplant of the light conversion film greenhouse are in a trend of gradually descending at first. The results in fig. 8 show that the yield of eggplants planted in the light conversion film greenhouse is obviously higher than that of eggplants planted in a common film greenhouse, and the actual yield is increased by 22.26% compared with that of the common film greenhouse in the whole experiment period.
(5) The disease resistance comparison result shows that in the greenhouse planting management process, when normal pesticide application is maintained, but rainfall is continuously performed for multiple days from 2 months, serious diseases occur in the greenhouse from the end of 3 months to the beginning of 4 months, particularly pepper and tomato are obvious, so that the influence of the common film greenhouse and the light conversion film greenhouse on crops during the disease period is analyzed by taking the example as a comparison result, and the result is shown in fig. 9. As can be seen from FIG. 9, before the occurrence of diseases, compared with the common film greenhouse, the yield of the peppers and the tomato in the light conversion film is increased to different degrees, wherein the yield of the peppers is increased by about 13.22%, and the yield of the tomatoes is increased by 19.68%; after the disease occurs and pesticide is sprayed for treatment, the yield of the hot pepper in the light conversion film greenhouse is 61.88 percent higher than that in the common film greenhouse, and the yield of the tomato in the light conversion film greenhouse is 46 percent higher than that in the common film greenhouse. The results of the performance comparison of the pepper and the tomato plants after the disease occurs show that after the disease outbreak shows, the performances of the pepper and the tomato in the common film greenhouse are obviously different from those of the pepper and the tomato in the light conversion film greenhouse, the pepper leaves in the common film greenhouse obviously yellow or the yellow spots are obviously curled in the follow-up process, and the pepper in the light conversion film greenhouse normally shows although the leaf color of the later-stage leaves becomes light. In the aspect of tomatoes, yellow spots appear on tomato leaves in a common film greenhouse, the situation that main vines are withered is also caused along with the prolonging of time, the tomato leaves in a light conversion film greenhouse are often characterized by early diseases, but the gradual leaves are gradually restored to be normal.
From the above results, it can be seen that:
1. compared with a common film greenhouse, the light conversion film greenhouse can effectively improve the plant height and the length and width product of leaves of fruit and vegetable crops such as hot peppers, eggplants, tomatoes and sweet peppers, even if the improvement degree of the crops is different according to different varieties.
2. Compared with a common film greenhouse, the light conversion film greenhouse effectively improves the yield of fruit and vegetable crops, so that the yield of hot peppers is increased by 26.91%, the yield of eggplants is increased by 27%, the yield of tomatoes is increased by 24.11% and the yield of sweet peppers is increased by 22.26%.
3. Compared with the common film greenhouse, the light conversion film greenhouse has the advantages that the occurrence of diseases is effectively inhibited in the light conversion film greenhouse, and the disease condition of plants can be relieved even after the diseases occur, so that the plants can gradually recover to normal growth.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A degradable light conversion film is characterized by comprising the following components in parts by mass:
Figure FDA0002837904010000011
2. the degradable light conversion film of claim 1, wherein: the degradable polymer base material comprises any one or a mixture of more than two of modified starch, cellulose ester, cellulose, chitosan, polyvinyl alcohol, polyhydroxyalkanoate, polybutylene succinate, polylactic acid and a copolymer thereof, polyhydroxyalkanoate, polypropylene glycol succinate, caprolactam, terephthalate, polycaprolactone, polyhydroxybutyrate, valerate and aliphatic-aromatic copolyester.
3. The degradable light conversion film of claim 1, wherein: the surface modified light conversion agent is a light conversion agent coated by silicon dioxide and surface modified by a silane coupling agent.
4. The degradable light conversion film of claim 3, wherein: the silane coupling agent is a silane coupling agent containing amino, sulfydryl, hydroxyl or carboxyl; wherein the silane coupling agent containing amino comprises aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane or tetraaminosilane; the silane coupling agent containing mercapto comprises 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane; the silane coupling agent containing hydroxyl comprises diphenyl dihydroxysilane, triphenyl hydroxysilane or 3-aminopropyl trihydroxysilane; the silane coupling agent containing a carboxyl group includes 3- [ 3-carboxyallylamido ] propyltriethoxysilane or tetrakis (4-carboxyphenyl) silane.
5. The degradable light conversion film of claim 3, wherein: the light conversion agent comprises at least one of an organic fluorescence light conversion agent, an inorganic salt light conversion agent, a rare earth organic complex light conversion agent and a quantum dot light conversion agent.
6. The degradable light conversion film of claim 5, wherein: the organic fluorescent light conversion agent comprises any one of fluorane fluorescent dye, naphthalimide fluorescent dye and coumarin fluorescent dye; the inorganic salt light conversion agent comprises alkaline earth aluminate, oxide, sulfide, tungstate or silicate formed by activator ions, and the activator ions comprise Ce3+、Ce4+、Pr3+、Pr4+、Pr5+、Nd3+、Sm2+、Sm3+、Eu2+、Eu3+、Gd3+、Tb3+、Tb4+、Dy3+、Dy4+、Er3+、Tm3+、Yb2+Or Yb3+(ii) a The rare earth organic complex light conversion agent comprises a monobasic or polybasic organic ligand compound consisting of lanthanide rare earth metal ions and organic ligands containing beta-diketone group, pyridyl group, carboxyl group, p-toluate group, m-chlorobenzoate group or sulfonic group; wherein the lanthanide rare earth metal ion comprises Ce3+、Ce4+、Pr3+、Pr4+、Pr5+、Nd3+、Sm2+、Sm3+、Eu2+、Eu3+、Gd3+、Tb3+、Tb4+、Dy3+、Dy4+、Er3+、Tm3+、Yb2+Or Yb3+(ii) a The quantum dot light conversion agent comprises C, Si, Ge, CdSe, ZnSe, PbSe, CdTe, ZnO, InP, GaN, GaP, AlP, InN, ZnTe, InAs, GaAs, CaF2、Cd1-xZnxS、Cd1-xZnxSe、CdSeyS1-y、PbSeyS1-y、ZnXCd1-XTe、CdS/ZnS、Cd1-xZnxS/ZnS、Cd1-xZnxSe/ZnSe、CdSe1-xSx/CdSeyS1-y/CdS、CdSe/Cd1-xZnxSe/CdyZn1-ySe/ZnSe、Cd1-xZnxSe/CdyZn1-y Se/ZnSe、CdS/Cd1- xZnxS/CdyZn1-yS/ZnS、Cd1-xZnxSeyS1-y、CdSe/ZnS、Cd1-xZnxSe/ZnS、CdSe/CdS/ZnS、CdSe/ZnSe/ZnS、Cd1-xZnxSe/CdyZn1-yS/ZnS or InP/ZnS, wherein x and y have values ranging from 0 to 1.
7. The degradable light conversion film of claim 1, wherein: the solubilizer comprises ethylene-acrylic acid copolymer, ethyl acrylate or maleic anhydride; the polyolefin film base material is selected from any one or more than two of polyethylene, polypropylene and polyvinyl chloride.
8. The method for preparing a degradable light conversion film according to any one of claims 1 to 7, comprising the following steps:
(1) adding CTAB and ammonia water into a solvent, stirring and dissolving uniformly, then adding a light conversion agent, stirring and dispersing uniformly, then adding n-silane ethyl ester, stirring and reacting at 50-70 ℃, then adding a silane coupling agent, continuing stirring and reacting, washing and drying after the reaction is finished, and obtaining the surface-modified light conversion agent;
(2) mixing the surface-modified light conversion agent obtained in the step (1) and a degradable polymer base material, dispersing in a solvent, then dropwise adding an acid solution to adjust the pH value to 2-4, heating to 80-95 ℃, stirring for reaction, neutralizing, washing and drying after the reaction is finished, so as to obtain a degradable base material containing the light conversion agent;
(3) and (3) mixing, extruding and granulating the degradable base material containing the light conversion agent obtained in the step (2) with a solubilizer and a polyolefin film base material to obtain resin particles, and then putting the resin particles into a film blowing machine for film blowing to obtain the degradable light conversion film.
9. The method for preparing a degradable light conversion film according to claim 8, wherein: in the step (1) and the step (2), the solvent is deionized water; the adding amount of the n-silane ethyl ester in the step (1) is 0.5 to 3 percent of the mass of the light conversion agent; the adding amount of the silane coupling agent is 0.5 to 3 percent of the mass of the light conversion agent; adding n-silane ethyl ester in the step (1), and stirring for reaction for 20-30 h; adding a silane coupling agent, and continuously stirring for 10-20 h; the acid solution in the step (2) is 1mol/L hydrochloric acid solution; the heating to 80-95 ℃ and stirring reaction time is 30-50 min.
10. The use of the degradable light conversion film of any one of claims 1 to 7 in agricultural greenhouse films and agricultural mulching films.
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