CN113480997A - Multinuclear rare earth doped organic complex light conversion agent and light conversion master batch, and preparation method and application thereof - Google Patents

Multinuclear rare earth doped organic complex light conversion agent and light conversion master batch, and preparation method and application thereof Download PDF

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CN113480997A
CN113480997A CN202110777471.3A CN202110777471A CN113480997A CN 113480997 A CN113480997 A CN 113480997A CN 202110777471 A CN202110777471 A CN 202110777471A CN 113480997 A CN113480997 A CN 113480997A
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light conversion
rare earth
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earth doped
organic complex
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蒋绪川
周明明
刘威
杨成祥
游淇
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University of Jinan
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    • 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
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    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
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Abstract

The invention discloses a multinuclear rare earth doped organic complex light conversion agent and a preparation method thereof, a light conversion master batch and a preparation method and application thereof. The molecular formula of the prepared multinuclear rare earth doped organic complex light conversion agent is EuxSm1‑x‑zYzI3And L, wherein z is 0.01-0.3, and x + z is 1.The multinuclear rare earth doped organic complex light conversion agent obtained by the invention has stable structure and strong weather resistance; the light conversion master batch prepared by the light conversion agent is used in a light conversion agricultural film, can absorb ultraviolet light of 200-400 nm and convert the ultraviolet light into red orange light with the wavelength of 620-650 nm, can effectively promote the growth and development of crops and improve the yield, enables the crops, fruits and vegetables and the like to be harvested in advance, can improve the quality of the crops, fruits and vegetables, and effectively solves the defects of the existing common agricultural film.

Description

Multinuclear rare earth doped organic complex light conversion agent and light conversion master batch, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of agricultural films, and particularly relates to a multinuclear rare earth doped organic complex light conversion agent and a preparation method thereof, a light conversion master batch and a preparation method and application thereof.
Background
The plant can not grow away from the sun, sunlight is the energy source for photosynthesis of the plant, however, different light substances have different effects on the growth and development of the plant, such as: blue light is beneficial to the growth of plant stems and leaves, and red light is beneficial to improving the taste and quality of fruits and vegetables. Photosynthesis of plants occurs in chloroplasts, pigments in the chloroplasts absorb blue light with the wavelength of 400-480 nm and red orange light with the wavelength of 600-680 nm at the maximum, and ultraviolet light with the wavelength of 380nm or less and green light with the wavelength of 500-580 nm are reflected without being absorbed basically. Therefore, it is necessary to develop an efficient light conversion material, which converts green light and ultraviolet light, which are harmful or harmful to plants, into red light and blue light required for photosynthesis, so as to improve the utilization efficiency of light energy of plants, and thus, the purpose of increasing the yield of crops, promoting the early ripening and improving the nutrient content is achieved.
The rare earth organic complex light conversion agent is a common light energy conversion material, and is more and more valued by more and more people due to the advantages of stable structure, excellent fluorescence property, long luminescence life, high compatibility with a film and the like. However, since the f-f electron transition of the rare earth ion is forbidden transition, the absorption intensity is very low, and the rare earth ion is difficult to excite to emit light. However, some organic matters have higher light absorption coefficients, so that the organic matters can be combined with rare earth ions, absorbed energy is effectively transferred to the rare earth ions through intramolecular energy transfer, the rare earth ions can emit light, and the light emitting range of a spectrum can be adjusted by adjusting the proportion of rare earth central ions. The energy transfer efficiency between the ligand and the rare earth central ion is improved by using the first ligand, and the second ligand can also play a role in stabilizing the structures of the ligand and the rare earth central ion in the process of assisting the energy transfer of the first ligand, so that the ligand and the rare earth ion are better combined to improve the stability. Thus, the light energy conversion material with good stability and high luminous efficiency is obtained.
The agricultural film is introduced into China in the 80 s, the PE mulching film is taken as the main film, the function of the agricultural film is mainly heat preservation, the anti-aging PVC agricultural film and the LDPE dripping agricultural film are born under the study of scientists in China subsequently, the gradual multifunctional agricultural film is developed in succession, and various special greenhouse films and agricultural film varieties with attention paid to light quality study are attracted in the late 90 s. The light conversion agricultural film is taken as a control functional agricultural film, not only keeps the heat preservation and high light transmission of the traditional agricultural film, but also can convert partial ultraviolet light and green light in sunlight into blue light and red orange light required by plant growth, and improves the photosynthetic utilization rate of plants by improving the light quality. The covering of the light-conversion agricultural film not only promotes the growth and development of crops and improves the yield of the crops, so that the crops can be harvested in advance, but also improves the quality of the crops. Therefore, the development and research of light-converting agricultural films become one of the popular subjects in the agricultural film field of all countries in the world.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide a multinuclear rare earth doped organic complex light conversion agent and a preparation method thereof, a light conversion master batch and a preparation method thereof, and a light conversion agricultural film prepared from the light conversion master batch, which can promote the growth and development of crops, increase the yield of the crops, enable the crops to be harvested in advance, improve the quality of the crops, and effectively solve the defects of the existing agricultural film.
In order to achieve the above purpose or other purposes, the multinuclear rare earth doped organic complex light conversion agent and the preparation method thereof, the light conversion master batch and the preparation method thereof provided by the invention are mainly achieved through the following technical scheme.
Multinuclear rare earth doped organic complex light conversion agent with molecular formula of EuxSm1-x-zYzI3L, wherein z is 0.01-0.3, and x + z is 1;
eu is Eu3+A coordination center ion; sm is Sm3+A coordination center ion; y is Y3+Sensitizing ions;
i is a main ligand selected from any one of a-thenoyltrifluoroacetone, phthalic acid, salicylic acid, methacrylic acid, anthranilic acid, acetylacetone and benzoic acid;
l is an auxiliary ligand selected from any one of bipyridyl and phenanthroline.
The preparation method of the multinuclear rare earth doped organic complex light conversion agent comprises the following steps:
a) mixing EuCl3·6H2Dissolving O in organic solvent to obtain system A, and adding SmCl3·6H2Dissolving O in organic solvent to obtain system B, and dissolving YCl3·6H2Dissolving O in organic solvent to obtain a system C, and mixing and stirring the system A, B and the system C;
b) respectively dissolving a main ligand I and an auxiliary ligand L in an organic solvent to be used as a system E and a system F, and respectively adjusting the pH value to 6-7;
c) and (c) respectively dripping the solution obtained in the step b) into the mixed solution obtained in the step a) for reaction, and after the reaction is finished, carrying out post-treatment to obtain the multinuclear rare earth doped organic complex light conversion agent.
Further, EuCl3·6H2O、SmCl3·6H2O、YCl3·6H2The molar ratio of O is (0-0.99): (0-0.99): (0.01-0.3).
Further, EuCl in System A3·6H2The ratio of the molar weight of O (mmol) to the amount of organic solvent (ml) is 1: (5-15) fully dissolving the rare earth chloride. SmCl in System B3·6H2The ratio of the molar weight of O (mmol) to the amount of organic solvent (ml) is 1: (5-15). YCl in System C3·6H2The ratio of the molar weight of O (mmol) to the amount of organic solvent (ml) is 1: (5-15).
Further, the organic solvent is selected from absolute ethyl alcohol or absolute methyl alcohol.
Further, the molar ratio of the main ligand I to the auxiliary ligand L is 3: 1. preferably, the ratio of the molar amount (mmol) of the primary ligand I to the amount of organic solvent used (ml) in system E is 3: 10. in the system F, the ratio of the molar weight (mmol) of the auxiliary ligand L to the amount (ml) of the organic solvent is 1: 10.
preferably, the mixing and stirring temperature in the step a) is 60-65 ℃.
Preferably, in the step b), 2.5mol/L NaOH solution is adopted to adjust the pH of the systems E and F respectively to 6-7.
Preferably, the reaction temperature in the step c) is 70-80 ℃, and the reaction time is 3-4 h.
Preferably, the post-treatment in step c) includes, but is not limited to, washing the reaction product with water, then with alcohol, filtering with suction, and then drying at 80 ℃.
The invention also provides a light conversion master batch which comprises the multinuclear rare earth doped organic complex light conversion agent and a polymer material, wherein the polymer material is selected from one or more of polyethylene, polypropylene, polyolefin, ethylene-vinyl acetate copolyester and polyvinyl chloride.
Further, the mass ratio of the polynuclear rare earth doped organic complex light conversion agent to the polymer material is (0.1-0.3): 1.
the method for preparing the light conversion master batch comprises the following steps:
1) adding the multinuclear rare earth doped organic complex light conversion agent and the polymer material into an internal mixer for mixing to obtain a uniformly mixed massive polymer melt;
2) adding the block polymer melt into a forced feeder, and sequentially extruding strip polymers through a single-screw extruder;
3) and adding the strip polymer into a granulator, and granulating to obtain the light conversion master batch.
Further, the mass ratio of the polynuclear rare earth doped organic complex light conversion agent to the polymer material is (0.1-0.3): 1.
further, the temperature of the internal mixer in the step 1) is 130-200 ℃, and the mixing time is 0.5-2 h.
Further, the temperature of each temperature zone in the forced feeding machine in the step 2) is 160-180 ℃. The rotating speed of the single screw extruder in the step 2) is 300-500 rpm, and the die head temperature of the extruder is 200-300 ℃.
Further, the rotating frequency of the cut particles in the step 3 is 20.00-30.00 Hz.
The third aspect of the invention protects the application of the light conversion master batch in the light conversion agricultural film.
The light conversion agricultural film comprises a light conversion master batch and a polymer material, wherein the polymer material is selected from one or more of polyethylene, polypropylene, polyolefin, ethylene-vinyl acetate copolyester and polyvinyl chloride. The mass ratio of the light conversion master batch to the polymer material is (0.01-0.03): 1.
the method for preparing the light conversion agricultural film comprises the following steps:
mixing the light conversion master batch and the polymer material, adding the mixture into a film blowing machine for film blowing, and obtaining the light conversion agricultural film by using the traction auxiliary machine of the film blowing machine again for traction.
Preferably, the temperature of the film blowing machine is 170-230 ℃, and the rotation frequency of the screw is 10.00-16.00 Hz. The rotating speed of a traction auxiliary machine of the film blowing machine is 80-100 rpm.
The multinuclear rare earth doped organic complex light conversion agent provided by the invention adopts Eu3+、Sm3+And Y3+Codoping, I and L being organic ligands these ligands having the lowest triplet level with Eu3+And Sm3+The co-emission level has good matching property, and Y3+The energy transferred by the organic ligand obtained by adding the inert rare earth ions can not be transferred out for luminescence, and then the energy is transferred to the rare earth ions Eu3+And Sm3+. The organic ligand has better light absorption characteristic in an ultraviolet region, and the polynuclear rare earth doped organic complex has higher fluorescence quantum yield under the excitation of ultraviolet light, so that the organic ligand has good light conversion effect. The multinuclear rare earth doped organic complex light conversion agent obtained by the invention has stable structure and strong weather resistance; the light conversion master batch prepared by the light conversion agent is used in a light conversion agricultural film, can absorb ultraviolet light of 200-400 nm and convert the ultraviolet light into red orange light with the wavelength of 620-650 nm, can promote the growth and development of crops and improve the yield of the crops, enables the crops to be harvested in advance, improves the quality of the crops, and effectively solves the problems that the light conversion master batch is used in the light conversion agricultural film, the growth and development of the crops can be promoted, the yield of the crops is improved, the quality of the crops is improved, and the problem that the light conversion master batch is poor in quality is solvedThe existing agricultural film has defects.
Drawings
FIG. 1 is a normalized excitation spectrum of a light conversion agricultural film prepared by the polynuclear rare earth doped organic complex light conversion agent prepared in example 1 (the monitoring wavelength of an emission spectrum is Em 620nm, the selection parameters are 700V voltage and 1nm scanning step length);
FIG. 2 is a normalized emission spectrum of a light conversion agricultural film prepared by the polynuclear rare earth doped organic complex light conversion agent prepared in example 1 (the monitoring wavelength of the emission spectrum is Ex 340nm, the selected parameters are 700V voltage, and the scanning step length is 1 nm).
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
The main test instruments and production equipment adopted in the embodiment of the invention are as follows: a film blowing machine (luhua plastic machinery, ltd., lekume, Shandong); internal mixers (Nanjing national plastic extrusion Equipment Co., Ltd.); a pelletizer (Shanghai Jinshan switch plant); combined transient/steady state fluorescence spectrometer (FLS 920, edinburg instruments, uk).
Example 1
Preparing a multinuclear rare earth doped organic complex light conversion agent:
the molar ratio of the raw materials is 1: 8: 1 weighing EuCl3·6H2O and SmCl3·6H2O and YCl3·6H2And O accounts for 1mmol, the O is respectively dissolved in 10mL of absolute ethyl alcohol, the mixture is added into a three-neck flask after being mixed, the mixture is stirred until the O is completely dissolved, and the stirring is continued at 60 ℃ for 0.5h to obtain the rare earth mixed solution.
Respectively preparing 10mL of salicylic acid ethanol solution and 0.01mmol/L of phenanthroline ethanol solution, and respectively adjusting the pH value to 7 by using 2.5mol/L NaOH solution.
Respectively dropwise adding salicylic acid ethanol solution and phenanthroline ethanol into the rare earth mixed solution, reacting for 4 hours at 70 ℃, standing and cooling to room temperature, washing with water for three times, washing with alcohol for three times, performing suction filtration, and drying at 80 ℃ to obtain the multinuclear rare earth doped organic complex light conversion agent.
Preparing the light conversion master batch:
adding 300g of multinuclear rare earth doped organic complex light conversion agent and 1kg of polyethylene into an internal mixer, and carrying out internal mixing at 130 ℃ for 1h to obtain a uniformly mixed blocky polymer melt;
adding the block polyethylene melt into a forced feeder, adjusting the temperature to 180 ℃, and extruding a strip polymer by using a single-screw extruder (the rotating speed of the extruder is 300rpm, and the temperature of a die head of the extruder is 300 ℃);
and adding the strip-shaped polymer into a granulator, wherein the rotating frequency of the granulator is 20.00Hz, and obtaining the light conversion master batch.
Preparing a light conversion agricultural film:
mixing 33g of light conversion master batch and 2kg of polyethylene, adding the mixture into a hopper of a film blowing machine, wherein the temperature of a charging barrel in three temperature zones of the film blowing machine is 160 ℃, 180 ℃ and 220 ℃, the temperature of a machine head is 200 ℃, the rotating frequency of a screw rod is 12.00Hz, and the winding rotating speed is 160rpm, and preparing the light conversion agricultural film.
The obtained light conversion agricultural film is tested for the excitation range under the emission wavelength of 620nm by adopting a combined transient/steady state fluorescence spectrometer (FLS 920 of Edinburgh instruments, England), and the result is shown in figure 1, and the light conversion agricultural film has strong absorption under the wavelength of 400nm and has a maximum absorption peak under the wavelength of 340nm, and the absorption region is mainly in an ultraviolet region.
The emission range of the prepared light conversion agricultural film is tested under the condition that the excitation wavelength is 340nm, and the result is shown in figure 2, and it can be seen from the figure that the light conversion agricultural film can emit stronger red light (620-660 nm) under the excitation of ultraviolet light. Therefore, the light conversion agricultural film prepared by the embodiment can absorb ultraviolet light which is not beneficial to plant growth and convert the ultraviolet light into red light which is beneficial to plant growth.
Example 2
Preparing a multinuclear rare earth doped organic complex light conversion agent:
the molar ratio of the raw materials is 2: 6: 2 weighing EuCl3·6H2O and SmCl3·6H2O and YCl3·6H2Respectively dissolving 1mmol of O in 10mL of absolute ethyl alcohol, mixing, adding into a three-neck flask, and stirring until the O is completely dissolved; and continuously stirring for 0.5h at the temperature of 60 ℃ to obtain the rare earth mixed solution.
Respectively preparing 10mL of 0.03mmol/L benzoic acid ethanol solution and 0.01mmol/L o-phenanthroline ethanol solution, and then respectively adjusting the pH of the ligand solution to 7 by using 2.5mol/L NaOH solution.
Respectively dropwise adding a benzoic acid ethanol solution and a phenanthroline ethanol solution into the rare earth mixed solution, reacting for 4 hours at 70 ℃, standing and cooling to room temperature, washing with water for three times, washing with alcohol for three times, performing suction filtration, and drying at 80 ℃ to obtain the multinuclear rare earth doped organic complex light conversion agent.
Preparing the light conversion master batch:
200g of multinuclear rare earth doped organic complex light conversion agent and 1kg of polyethylene raw material are added into an internal mixer to be internally mixed for 1.5 hours at 140 ℃ to obtain a block-shaped polyethylene melt;
adding the block polyethylene melt into a forced feeder, adjusting the temperature of each temperature zone to 170 ℃, and extruding a strip polymer by using a single-screw extruder (the rotating speed of the extruder is 400rpm, and the die head temperature of the extruder is 300 ℃);
and adding the strip-shaped polymer into a granulator, wherein the rotating frequency of the granulator is 22.00Hz, and obtaining the light conversion master batch.
Preparing a light conversion agricultural film:
mixing 9g of light conversion master batch and 3kg of polyethylene, adding the mixture into a hopper of a film blowing machine, wherein the temperature of a charging barrel in three temperature zones of the film blowing machine is 170 ℃, 190 ℃ and 210 ℃, the temperature of a machine head is 210 ℃, the rotating frequency of a screw rod is 13.00Hz, and the winding rotating speed is 150rpm, and preparing the light conversion agricultural film.
Example 3
Preparing a multinuclear rare earth doped organic complex light conversion agent:
the molar ratio of the components is 3: 5: 3 weighing EuCl3·6H2O and SmCl3·6H2O and YCl3·6H2Respectively dissolving 1mmol of O in 10mL of absolute ethyl alcohol, mixing, adding into a three-neck flask, and stirring until the O is completely dissolved; and continuously stirring for 0.5h at the temperature of 60 ℃ to obtain the rare earth mixed solution.
10mL of each of a 0.03mmol/L ethanol solution of benzoic acid and a 0.01mmol/L ethanol solution of bipyridine was prepared, and then pH was adjusted to 6 with 2.5mol/L NaOH.
Respectively dropwise adding the benzoic acid ethanol solution and the bipyridyl ethanol solution into the rare earth mixed solution, reacting for 4h at 70 ℃, standing and cooling to room temperature, washing with water for three times, washing with alcohol for three times, filtering, and drying at 80 ℃ to obtain the multinuclear rare earth doped organic complex light conversion agent.
Preparing the light conversion master batch:
adding 300g of multinuclear rare earth doped organic complex light conversion agent and 3kg of polyethylene raw material into an internal mixer, and internally mixing for 1.2 hours at 148 ℃ to obtain a block polyethylene melt;
adding the block polyethylene melt into a forced feeder, adjusting the temperature of each temperature zone to be 175 ℃, and extruding a strip polymer by using a single-screw extruder (the rotating speed of the extruder is 480rpm, and the temperature of a die head of the extruder is 300 ℃);
and adding the strip-shaped polymer into a granulator, wherein the rotating frequency of the granulator is 22.00Hz, and obtaining the light conversion master batch.
Preparing a light conversion agricultural film:
mixing 2.5g of light conversion master batch and 2.5kg of polyethylene raw material, adding the mixture into a hopper of a film blowing machine, wherein the temperature of a charging barrel in three temperature zones of the film blowing machine is 180 ℃, 180 ℃ and 220 ℃, the temperature of a machine head is 220 ℃, the rotating frequency of a screw rod is 15.00Hz, and the winding rotating speed is 170rpm, so as to prepare the light conversion agricultural film.
Example 4
Preparing a multinuclear rare earth doped organic complex light conversion agent:
the molar ratio of the components is 8: 1: 1 weighing EuCl3·6H2O and SmCl3·6H2O and YCl3·6H2Dissolving 1mmol of O in 10mL of anhydrous methanol respectively, mixing, adding into a three-neck flask, and stirring until the O is completely dissolved; and continuously stirring for 0.5h at the temperature of 60 ℃ to obtain the rare earth mixed solution.
10mL of each of a 0.06mmol/L methanolic benzoic acid solution and a 0.02mmol/L methanol bipyridine solution was prepared, and then the pH was adjusted to 6 with 2.5mol/L NaOH.
And respectively dropwise adding the benzoic acid methanol solution and the bipyridyl methanol solution into the rare earth mixed solution, reacting for 4 hours at 70 ℃, standing and cooling to room temperature, washing for three times with water, washing for three times with alcohol, filtering, and drying at 80 ℃ to obtain the multinuclear rare earth doped organic complex light conversion agent.
Preparing the light conversion master batch:
400g of multinuclear rare earth doped organic complex light conversion agent and 1.6kg of ethylene-vinyl acetate copolyester raw material are added into an internal mixer to be internally mixed for 1.5 hours at 165 ℃ to obtain blocky ethylene-vinyl acetate copolyester melt;
adding the massive ethylene-vinyl acetate copolyester melt into a forced feeder, adjusting the temperature of each temperature zone to be 180 ℃, and extruding a strip-shaped polymer by a single-screw extruder at the rotating speed of 480 rpm;
and adding the strip-shaped polymer into a granulator, wherein the rotating frequency of the granulator is 23.00Hz, and obtaining the light conversion master batch.
Preparing a light conversion agricultural film:
4g of light conversion master batch and 2kg of ethylene-vinyl acetate copolyester raw materials are mixed and added into a hopper of a film blowing machine, the temperature of a charging barrel of three temperature zones of the film blowing machine is 180 ℃, 180 ℃ and 220 ℃, the temperature of a machine head is 220 ℃, the rotating frequency of a screw rod is 15.00Hz, and the winding rotating speed is 170rpm, so that the light conversion agricultural film is prepared.
Example 5
Preparing a multinuclear rare earth doped organic complex light conversion agent:
the molar ratio of the raw materials is 1: 8: 1 weighing EuCl3·6H2O and SmCl3·6H2O and YCl3·6H2Dissolving 1mmol of O in 10mL of anhydrous methanol respectively, mixing, adding into a three-neck flask, and stirring until the O is completely dissolved; and continuously stirring for 0.5h at the temperature of 60 ℃ to obtain the rare earth mixed solution.
10mL of each of a 0.06mmol/L methanolic benzoic acid solution and a 0.02mmol/L methanol bipyridine solution was prepared, and then the pH was adjusted to 6 with 2.5mol/L NaOH.
And respectively dropwise adding the benzoic acid methanol solution and the bipyridyl methanol solution into the rare earth mixed solution, reacting for 4 hours at 70 ℃, standing and cooling to room temperature, washing for three times with water, washing for three times with alcohol, filtering, and drying at 80 ℃ to obtain the multinuclear rare earth doped organic complex light conversion agent.
Preparing the light conversion master batch:
adding 330g of self-made polynuclear rare earth doped organic complex light conversion agent and 3.2kg of polyethylene raw material into an internal mixer, and internally mixing for 1 hour at 155 ℃ to obtain a block-shaped polyethylene melt;
adding the block polyethylene melt into a forced feeder, adjusting the temperature of each temperature zone to 170 ℃, and extruding a strip polymer by a single-screw extruder at the rotating speed of 480 rpm;
and adding the strip-shaped polymer into a granulator, wherein the rotating frequency of the granulator is 24.00Hz, and obtaining the light conversion master batch.
Preparing a light conversion agricultural film:
mixing 8g of light conversion master batch and 3.2kg of polyethylene raw material, adding the mixture into a hopper of a film blowing machine, wherein the temperature of a charging barrel in three temperature zones of the film blowing machine is 180 ℃, 180 ℃ and 220 ℃, the temperature of a machine head is 220 ℃, the rotating frequency of a screw rod is 15.00Hz, and the winding rotating speed is 170rpm, and preparing the light conversion agricultural film.
Example 6
Preparing a multinuclear rare earth doped organic complex light conversion agent:
the molar ratio of the raw materials is 2: 5: 3 weighing EuCl3·6H2O and SmCl3·6H2O and YCl3·6H2Dissolving 1mmol of O in 10mL of anhydrous methanol respectively, mixing, adding into a three-neck flask, and stirring until the O is completely dissolved; (ii) a And continuously stirring for 0.5h at the temperature of 60 ℃ to obtain the rare earth mixed solution.
10mL of each of a 0.05mmol/L methanol solution of a-thenoyltrifluoroacetone and a 0.03mmol/L methanol solution of bipyridine were prepared, and then pH was adjusted to 6 with 2.5mol/L NaOH.
And respectively dropwise adding the alpha-thenoyl trifluoroacetone methanol solution and the bipyridyl methanol solution into the rare earth mixed solution, reacting for 4h at 70 ℃, standing and cooling to room temperature, washing with water for three times, washing with alcohol for three times, filtering, and drying at 80 ℃ to obtain the multinuclear rare earth doped organic complex light conversion agent.
Preparing the light conversion master batch:
adding 750g of self-made polynuclear rare earth doped organic complex light conversion agent and 2.5kg of polyethylene raw material into an internal mixer, and internally mixing for 1h at 145 ℃ to obtain a block-shaped polyethylene melt;
adding the block polyethylene melt into a forced feeder, adjusting the temperature of each temperature zone to be 168 ℃, and extruding a strip polymer by a single-screw extruder at the rotating speed of 480 rpm;
and adding the strip-shaped polymer into a granulator, wherein the rotating frequency of the granulator is 30.00Hz, and obtaining the light conversion master batch.
Preparing a light conversion agricultural film:
mixing 7g of light conversion master batch and 2.8kg of polyethylene raw material, adding the mixture into a hopper of a film blowing machine, wherein the temperature of a charging barrel in three temperature zones of the film blowing machine is 180 ℃, 180 ℃ and 220 ℃, the temperature of a machine head is 220 ℃, the rotating frequency of a screw rod is 15.00Hz, and the winding rotating speed is 170rpm, and preparing the light conversion agricultural film.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. The multinuclear rare earth doped organic complex light conversion agent is characterized in that the molecular formula is EuxSm1-x-zYzI3L, wherein z is 0.01-0.3, and x + z is 1;
eu is Eu3+A coordination center ion; sm is Sm3+A coordination center ion; y is Y3+Sensitizing ions;
i is a main ligand selected from any one of a-thenoyltrifluoroacetone, phthalic acid, salicylic acid, methacrylic acid, anthranilic acid, acetylacetone and benzoic acid;
l is an auxiliary ligand selected from any one of bipyridyl and phenanthroline.
2. A method of making the polynuclear rare earth doped organic complex light conversion agent of claim 1, comprising the steps of:
a) mixing EuCl3·6H2Dissolving O in organic solvent to obtain system A, and adding SmCl3·6H2Dissolving O in organic solvent to obtain system B, and dissolving YCl3·6H2Dissolving O in organic solvent to obtain a system C, and mixing and stirring the system A, B and the system C;
b) respectively dissolving a main ligand I and an auxiliary ligand L in an organic solvent to be used as a system E and a system F, and respectively adjusting the pH value to 6-7;
c) and (c) respectively dripping the solution obtained in the step b) into the mixed solution obtained in the step a) for reaction, and after the reaction is finished, carrying out post-treatment to obtain the multinuclear rare earth doped organic complex light conversion agent.
3. The method of claim 2, wherein the EuCl3·6H2O、SmCl3·6H2O、YCl3·6H2The molar ratio of O is (0-0.99): (0-0.99): (0.01-0.3).
4. The method of claim 2, wherein the molar ratio of primary ligand I to ancillary ligand L is 3: 1.
5. a light conversion master batch, which is characterized by comprising the polynuclear rare earth doped organic complex light conversion agent as claimed in claim 1 and a polymer material, wherein the polymer material is selected from one or more of polyethylene, polypropylene, polyolefin, ethylene-vinyl acetate copolyester and polyvinyl chloride.
6. The method for preparing the light conversion master batch of claim 5, which comprises the following steps:
1) adding the multinuclear rare earth doped organic complex light conversion agent and the polymer material into an internal mixer for mixing to obtain a uniformly mixed massive polymer melt;
2) adding the block polymer melt into a forced feeder, and sequentially extruding strip polymers through a single-screw extruder;
3) and adding the strip polymer into a granulator, and granulating to obtain the light conversion master batch.
7. The method of claim 6, wherein the weight ratio of the polynuclear rare earth doped organic complex light conversion agent to the polymer material is (0.1-0.3): 1.
8. use of the light conversion master batch of claim 5 in light conversion agricultural films.
9. A light conversion agricultural film, which is characterized by comprising the light conversion master batch of claim 5 and a polymer material, wherein the polymer material is selected from one or more of polyethylene, polypropylene, polyolefin, ethylene-vinyl acetate copolyester and polyvinyl chloride.
10. The method for preparing the light-converting agricultural film according to claim 9, comprising the steps of:
mixing the light conversion master batch and the polymer material, adding the mixture into a film blowing machine for film blowing, and adjusting the rotating speed of a traction auxiliary machine of the film blowing machine for traction film blowing to obtain the light conversion agricultural film.
CN202110777471.3A 2021-07-09 2021-07-09 Multinuclear rare earth doped organic complex light conversion agent and light conversion master batch, and preparation method and application thereof Pending CN113480997A (en)

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CN1687305A (en) * 2005-04-18 2005-10-26 南京师范大学 Nano rare earth optical transfer agent in bionic state, Nano rare earth optical transfer agricultural film in bionic state, and preparation method thereof
CN105566365A (en) * 2016-01-29 2016-05-11 合肥工业大学 Double-central-ion rare earth organic complex light conversion agent and preparation method thereof
CN111621077A (en) * 2020-06-12 2020-09-04 济南大学 Light conversion master batch, preparation method thereof and light conversion agricultural film prepared from light conversion master batch

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CN1338500A (en) * 2000-08-10 2002-03-06 上海师范大学 Multi-kernel rare-earth light-converting powder, its preparing process and its application
CN1687305A (en) * 2005-04-18 2005-10-26 南京师范大学 Nano rare earth optical transfer agent in bionic state, Nano rare earth optical transfer agricultural film in bionic state, and preparation method thereof
CN105566365A (en) * 2016-01-29 2016-05-11 合肥工业大学 Double-central-ion rare earth organic complex light conversion agent and preparation method thereof
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