CN114369300B - Low-mobility ultraviolet absorption small-molecule light conversion film and preparation method thereof - Google Patents
Low-mobility ultraviolet absorption small-molecule light conversion film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-mobility ultraviolet absorption small-molecule light conversion film, which comprises the following components in parts by weight: polymer resin: 89.97-99.99 parts; light conversion agent: 0.001-0.003 parts; an anti-aging agent: 0.001-5 parts; anti-fog drop agent: 0.001-5 parts; wherein the photo-conversion agent contains ketone group and hydroxyl group, and the general molecular formula of the structure of the photo-conversion agent is [ Eu ] 2 (TTA) x PA (4‑x) BDPA4]Or [ Eu ] 2 (TTA) x PA (4‑x) BDPA6]Wherein TTA is 2-thenoyltrifluoroacetone, PA is pyridine-2, 6-dicarboxylic acid, BDPA4 is 4,4'- (butane-1, 4-di (oxy) bis (pyridine-2, 6-dicarboxylic acid), BDPA6 is 4,4' - (butane-1, 6-di (oxy) bis (pyridine-2, 6-dicarboxylic acid). The invention also discloses a preparation method of the low-mobility ultraviolet absorption small-molecule light conversion film. The light conversion film has stronger absorption capability to ultraviolet light in a low frequency band, can convert the ultraviolet light in the band into red light required by photosynthesis of plants, and is beneficial to the growth of crops.
Description
Technical Field
The invention belongs to the technical field of agricultural light conversion films, and particularly relates to a low-mobility ultraviolet absorption small-molecule light conversion film and a preparation method thereof
Background
Light has a direct effect on crop growth. Wherein, blue-violet light (400-500 nm) and red-orange light (600-700 nm) can be absorbed by chlorophyll a, b and other pigments to enhance photosynthesis of plants. Yellow-green light (500-600 nm) is almost useless due to reflection from the leaves of the plant. While the effect of uv light on plants depends on their wavelength and dosage. Such as: the high-dose ultraviolet rays not only lead to the accelerated aging of the polyethylene film, but also can have adverse effects on the growth of crops; before harvesting, moderate supplementation of UV-A (315-400 nm) has important significance for promoting premature fruit and improving fruit quality; low doses of UV-B (280-315 nm) induce accumulation of secondary plant metabolites such as phenolic compounds, carotenoids and thioglucosides to improve fruit quality and reduce pest incidence; low doses of UV-C (< 280 nm) can also have beneficial effects on plants, increasing crop resistance to gray mold and fungal diseases. It can be seen that the conversion of part of the ultraviolet light into blue-violet light or red-orange light, while reducing the dosage of the ultraviolet light has important significance for plant growth.
The light conversion film is a functional agricultural film which improves the light transmittance and the light wavelength conversion by adding rare earth light conversion agent so as to improve the light utilization efficiency of plants. The light conversion film can be used for converting part of ultraviolet light into blue-violet light and red-orange light which can be utilized for photosynthesis of plants, so that photosynthesis of the plants is enhanced, and growth and development of crops, yield increase and quality improvement are promoted. The compound rare earth light conversion film disclosed in the patent CN 106349543A can promote the yield of crops such as tomatoes, cucumbers, strawberries and the like; patent CN 104108215A discloses a high light conversion rate greenhouse film, which can promote the growth and development of crops, improve the quality of fruits and reduce the occurrence rate of plant diseases and insect pests. Therefore, the use of light conversion films is of great importance for the development of agricultural production, especially greenhouse agriculture.
Currently, the type of light converting agent commonly used in light conversion films is usually europium ion (Eu 3+ ) The beta-diketone compound is a first ligand, the pyridine-2, 6-dicarboxylic acid and the derivative thereof are rare earth organic complexes (beta-DKs) synthesized by neutral ligands.
Document 2,Freund C,Porzio W,Giovanella U,Vignali F,Pasini M,Destri S,Mech A,Di P S,Di B L and Mineo P,2011.Thiophene based europium beta-diketonate complexes: effect of the ligand structure on the emission quantum yield.inorg Chem,50 (12): 5417-5429.
Document 3,Ugale A,Kalyani N T and Dhoble S J,2019.Reddish orange to blue tunable emission from rare earth beta-diketo Eu (TTA) 3dpphen complex for solid state lighting applications.Materials Science for Energy Technologies, 2 (1): 57-66.
The ultraviolet absorption wave band of the common beta-DKs is introduced in the documents 1-3, and the absorption wave band of the light conversion agent for ultraviolet rays is concentrated at 280-400 nm.
4,Yasuda N,Wang Y,Tsukegi T,Shirai Y and Nishida H,2010. Quantitative evaluation of photodegradation and racemization of poly (l-lactic acid) UV-C irradication. Polymer Degradation and Stability, 95 (7): 1238-1243.
Document 5,Yeh C C,Chen C N,Li Y T,Chang C W,Cheng M Y and Chang H I, 2011.The Effect of Polymer Molecular Weight and UV Radiation on Physical Properties and Bioactivities of PCL Films.Cllular Polymers,30 (261-276).
Document 6, zhang Jiang, 2019. Preparation of luminescent composite materials based on rare earth complexes, structure and fluorescence properties studies. University of vingilin.
Documents 4 to 6 find that the lack of the absorption of beta-DKs to low-frequency ultraviolet light is an important reason for limiting the further improvement of the light conversion efficiency of the agricultural film, and meanwhile, the phenomenon is unfavorable for shielding the greenhouse film from high-energy ultraviolet light, so that the service life of the greenhouse film and the growth of crops are influenced.
Therefore, the low-mobility ultraviolet absorbing light conversion film becomes a novel product which is urgently needed in the market.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the low-mobility ultraviolet absorption small-molecule light conversion film and the preparation method thereof, which have stronger absorption capability on ultraviolet light in a low frequency band, can convert the ultraviolet light in the frequency band into red light required by photosynthesis of plants, and are beneficial to the growth of crops.
In order to achieve the above object, the present invention provides the following technical solutions:
the low-mobility ultraviolet absorption small-molecule light conversion film comprises the following components in parts by weight:
polymer resin: 89.97-99.99 parts;
light conversion agent: 0.001-0.003 parts;
an anti-aging agent: 0.001-5 parts;
anti-fog drop agent: 0.001-5 parts;
wherein the photo-conversion agent contains ketone group and hydroxyl group, and the general molecular formula of the structure of the photo-conversion agent is [ Eu ] 2 (TTA) x PA (4-x) BDPA4]Or [ Eu ] 2 (TTA) x PA (4-x) BDPA6]Wherein TTA is 2-thenoyltrifluoroacetone, PA is pyridine-2, 6-dicarboxylic acid, BDPA4 is 4,4'- (butane-1, 4-di (oxy) bis (pyridine-2, 6-dicarboxylic acid), BDPA6 is 4,4' - (butane-1, 6-di (oxy) bis (pyridine-2, 6-dicarboxylic acid).
Further, the polymer resin comprises granular low-density polyethylene particles having a lipid solubility coefficient of 0.3 to 1.
Further, the light conversion agent has a structural formula:
the nuclear magnetic hydrogen spectrum data are as follows: 1 HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H), 8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H), 4.10(t,4H),1.94-1.69(m,8H),1.51(m,4H)。
further, the light conversion agent has a structural formula:
the nuclear magnetic hydrogen spectrum data are as follows: 1 HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H), 8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H), 4.10(t,4H),1.94-1.89(m,6H),1.69(m,2H)。
the invention also provides a preparation method of the low-mobility ultraviolet absorption small molecule light conversion film, which comprises the following steps:
step one, preparing a light conversion agent;
step two, weighing the polymer resin, the light conversion agent, the anti-fog drop and the anti-aging agent according to the required weight parts, and dividing the polymer resin into two parts for standby;
step three, uniformly mixing the light conversion agent with one part of the polymer resin obtained in the step two, and then melting, extruding and granulating to obtain light conversion master batch;
and fourthly, uniformly mixing the light conversion master batch obtained in the third step with polymer resin, anti-fog drops and an anti-aging agent, and then carrying out blow molding, cooling and traction to form a film.
Further, the method for preparing the light conversion agent in the first step specifically includes the following steps:
s1, dissolving 2-thiophenoyltrifluoroacetone, pyridine-2, 6-dicarboxylic acid, 4'- (butane-1, 4-di (oxy) group) bis (pyridine-2, 6-dicarboxylic acid) or 4,4' - (butane-1, 6-di (oxy) group) bis (pyridine-2, 6-dicarboxylic acid) and potassium hydroxide in an organic solvent to obtain a ligand solution;
s2, adding the ligand solution prepared in the previous step into a europium ion solution to obtain a mixed solution of the ligand and europium ion;
and S3, continuously stirring the ligand and europium ion mixed solution under the heating condition to obtain complex precipitate, filtering, washing and vacuum drying to obtain the light conversion agent.
Further, in the step S3, the heating temperature is 50-80 ℃ and the stirring time is 0.5-2h.
Further, the europium ion solution is prepared by mixing europium chloride hexahydrate (EuCl 3 ·6H 2 O) is dissolved in distilled water and heated to 50-80 ℃.
Further, in the ligand solution, the components comprise the following components in parts by weight:
2-thenoyl trifluoroacetone: 3.7-6.8 parts;
pyridine-2, 6-dicarboxylic acid: 2.8-5.1 parts;
4,4'- (butane-1, 4-di (oxy) bis (pyridine-2, 6-dicarboxylic acid) or 4,4' - (butane-1, 6-di (oxy) bis (pyridine-2, 6-dicarboxylic acid): 3.0-6.4 parts;
potassium hydroxide: 3.7-6.8 parts;
europium chloride hexahydrate: 6.1-11.2 parts;
ethanol: 18.4-30.0 parts;
water: 50.1-64.5 parts.
Further, in the third step, a double-screw extruder is adopted for extrusion, the extrusion temperature is 180-220 ℃, and the rotation speed of a host machine of the double-screw extruder is 50-100r/min; in the fourth step, the blowing temperature is 180-220 ℃.
According to the technical scheme, the invention has the following advantages: the light conversion film prepared by the invention has stronger absorption capability to ultraviolet light in a low frequency band, can convert the ultraviolet light in the band into red light required by photosynthesis of plants, and is beneficial to the growth of crops.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the UV-visible absorption spectra of light conversion films and conventional light conversion films (LCF-C) and polyethylene film (PE) of comparative groups in examples 1-5 of the present invention.
Fig. 2 is an emission spectrum of the light conversion film in example 1 of the present invention.
FIG. 3 is an emission spectrum of the light conversion film in example 2 of the present invention.
FIG. 4 is an emission spectrum of the light conversion film in example 3 of the present invention.
Fig. 5 is an emission spectrum of the light conversion film in example 4 of the present invention.
FIG. 6 is an emission spectrum of the light conversion film in example 5 of the present invention.
FIG. 7 is a graph showing the emission spectrum of a conventional light conversion film (LCF-C) control group in accordance with the present invention.
FIG. 8 is a graph showing the excitation spectra of light conversion films of examples 1-5 and a conventional light conversion film (LCF-C) control group according to the present invention.
FIG. 9 is a graph showing the mobility of the light conversion agent of the light conversion film and the conventional light conversion film (LCF-C) control group in examples 1 to 5 of the present invention.
Fig. 10 is the mobility of the light conversion agent of the light conversion film in example 1 of the present invention.
Fig. 11 is the mobility of the light conversion agent of the light conversion film in example 2 of the present invention.
Fig. 12 is the mobility of the light conversion agent of the light conversion film in example 3 of the present invention.
Fig. 13 is the mobility of the light conversion agent of the light conversion film in example 4 of the present invention.
Fig. 14 is the mobility of the light conversion agent of the light conversion film in example 5 of the present invention.
FIG. 15 is the mobility of the light converting agent of the conventional light conversion film (LCF-C) control group in the present invention.
Detailed Description
The invention will be further described in detail with reference to the drawings and specific examples for a clearer understanding of the type of construction and the manner of use thereof, but in no way limit the scope of protection of the patent.
The low-mobility ultraviolet absorption small-molecule light conversion film comprises the following components in parts by weight:
polymer resin: 89.97-99.99 parts;
light conversion agent: 0.001-0.003 parts;
an anti-aging agent: 0.001-5 parts;
anti-fog drop agent: 0.001-5 parts;
wherein the photo-conversion agent contains ketone group and hydroxyl group, and the general molecular formula of the structure of the photo-conversion agent is [ Eu ] 2 (TTA) x PA (4-x) BDPA4]Or [ Eu ] 2 (TTA) x PA (4-x) BDPA6]Wherein TTA is 2-thenoyltrifluoroacetone, PA is pyridine-2, 6-dicarboxylic acid, BDPA4 is 4,4'- (butane-1, 4-di (oxy) bis (pyridine-2, 6-dicarboxylic acid), BDPA6 is 4,4' - (butane-1, 6-di (oxy) bis (pyridine-2, 6-dicarboxylic acid).
Further, the polymer resin comprises granular low-density polyethylene particles having a lipid solubility coefficient of 0.3 to 1.
Further, the light conversion agent has a structural formula:
the nuclear magnetic hydrogen spectrum data are as follows: 1 HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H), 8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H), 4.10(t,4H),1.94-1.69(m,8H),1.51(m,4H)。
further, the light conversion agent has a structural formula:
the nuclear magnetic hydrogen spectrum data are as follows: 1 HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H), 8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H), 4.10(t,4H),1.94-1.89(m,6H),1.69(m,2H)。
the invention also provides a preparation method of the low-mobility ultraviolet absorption small molecule light conversion film, which comprises the following steps:
step one, preparing a light conversion agent;
step two, weighing the polymer resin, the light conversion agent, the anti-fog drop and the anti-aging agent according to the required weight parts, and dividing the polymer resin into two parts for standby;
step three, uniformly mixing the light conversion agent with one part of the polymer resin obtained in the step two, and then melting, extruding and granulating to obtain light conversion master batch;
and fourthly, uniformly mixing the light conversion master batch obtained in the third step with polymer resin, anti-fog drops and an anti-aging agent, and then carrying out blow molding, cooling and traction to form a film.
Further, the method for preparing the light conversion agent in the first step specifically includes the following steps:
s1, dissolving 2-thiophenoyltrifluoroacetone, pyridine-2, 6-dicarboxylic acid, 4'- (butane-1, 4-di (oxy) group) bis (pyridine-2, 6-dicarboxylic acid) or 4,4' - (butane-1, 6-di (oxy) group) bis (pyridine-2, 6-dicarboxylic acid) and potassium hydroxide in an organic solvent to obtain a ligand solution;
s2, adding the ligand solution prepared in the previous step into a europium ion solution to obtain a mixed solution of the ligand and europium ion;
and S3, continuously stirring the ligand and europium ion mixed solution under the heating condition to obtain complex precipitate, filtering, washing and vacuum drying to obtain the light conversion agent.
Further, in the step S3, the heating temperature is 50-80 ℃ and the stirring time is 0.5-2h.
Further, the europium ion solution is prepared by mixing europium chloride hexahydrate (EuCl 3 ·6H 2 O) is dissolved in distilled water and heated to 50-80 ℃.
Further, in the ligand solution, the components comprise the following components in parts by weight:
2-thenoyl trifluoroacetone: 3.7-6.8 parts;
pyridine-2, 6-dicarboxylic acid: 2.8-5.1 parts;
4,4'- (butane-1, 4-di (oxy) bis (pyridine-2, 6-dicarboxylic acid) or 4,4' - (butane-1, 6-di (oxy) bis (pyridine-2, 6-dicarboxylic acid): 3.0-6.4 parts;
potassium hydroxide: 3.7-6.8 parts;
europium chloride hexahydrate: 6.1-11.2 parts;
ethanol: 18.4-30.0 parts;
water: 50.1-64.5 parts.
Further, in the third step, a double-screw extruder is adopted for extrusion, the extrusion temperature is 180-220 ℃, and the rotation speed of a host machine of the double-screw extruder is 50-100r/min; in the fourth step, the blowing temperature is 180-220 ℃.
Example 1
The embodiment provides a low-mobility ultraviolet absorption small molecule light conversion film, which comprises the following components:
polyethylene: 89.998 parts (PO, EVA may be used instead of polyethylene);
light conversion agent: 0.002 parts;
an anti-aging agent: 5 parts of (selected from polypropylene resin produced by Shandong white cloud plastic Co., ltd.);
anti-fog drop agent: 5 parts of sorbitan monostearate (selected from Shandong white cloud plastic Co., ltd.);
the synthesis method of the light conversion agent comprises the following steps:
(1) Synthesizing a light conversion agent; 0.2mol of EuCl is taken 3 ·6H 2 O was dissolved in 20ml of distilled water to obtain europium ion solution, and 0.2mol of 2-thenoyltrifluoroacetone, 0.2mol of pyridine-2, 6-dicarboxylic acid, 0.1mol of 4,4' - (butane-1, 4-di (oxy) bis (pyridine-2, 6-dicarboxylic acid) were each dissolved in 15ml of ethanol to obtain ligand solution. The europium ion solution is heated to 60℃and 2-thenoyltrifluoroacetone, pyridine-2, 6-dicarboxylic acid, 4' - (butane-1, 4-di (oxy) bis (pyridine-2, 6-dicarboxylic acid) ligand solution are added sequentially. Heating at 60deg.C, and stirring for 60min to obtain complex precipitate. Filtering, washing and vacuum drying at 60 ℃ for 12 hours to obtain the light conversion agent. The molecules of the light conversion agent are: [ Eu ] 2 (TTA) x PDA (4-x) BPDA4]The structural formula is as follows:
the nuclear magnetic hydrogen spectrum data are as follows: 1 HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H), 8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H),4.10(t,4H), 1.94-1.89(m,6H),1.69(m,2H)。
(2) Preparing a light conversion master batch; mixing 60g of the light conversion agent in the step (1), 14.94kg of granular LLDPE and the light conversion agent, and uniformly mixing by a high-speed stirrer to obtain a mixture, wherein the stirring speed is 1200r/min, and the stirring time is 2min. And (3) putting the mixture into a double-screw extruder, setting the temperature of the double-screw extruder to be 180 ℃, setting the screw rotating speed to be 100r/min, carrying out melt blending on the mixture by the extruder, and granulating after air cooling or water cooling to room temperature to obtain the light conversion master batch.
(3) Preparing a light conversion film; and (3) uniformly mixing 15kg of the light conversion master batch obtained in the step (2) with 2kg of LLDPE, 10kg of LDPE, 1.5kg of anti-aging agent and 1.5kg of anti-fogging agent to obtain a blow molding mixture. And (3) performing blow molding film forming on the mixture by using a film blowing machine to obtain a light conversion film with the low-frequency ultraviolet absorption capability and the thickness of 100+/-10 mu m. Wherein the melt blown film is divided into three temperature areas, the temperature of the first area is 180 ℃, the temperature of the second area is 190 ℃, and the temperature of the third area is 200 ℃.
The ultraviolet absorption spectrum, excitation spectrum and emission spectrum of the light conversion film in example 1 are shown in fig. 1, 2 and 3, respectively, and the comparison is beta-DKs conventional light conversion film (LCF-C). As can be seen from fig. 1, 2 and 8, the light conversion film can effectively absorb 230-400 nm ultraviolet light and is excited to emit red light with a main emission peak of 615 nm. As can be seen from fig. 7, the light conversion film of example 1 is more easily excited by low frequency uv light than the control.
Example 2
The embodiment provides a low-mobility ultraviolet absorption small molecule light conversion film, which comprises the following components:
polyethylene: 89.998 parts (PO, EVA can be used instead of polyethylene)
Light conversion agent: 0.002 parts
An anti-aging agent: 5 parts (Polypropylene resin produced by Shandong white cloud Plastic Co., ltd.)
Anti-fog drop agent: 5 parts (sorbitol anhydride monostearate manufactured by Shandong white cloud plastic Co., ltd.)
The synthesis method of the light conversion agent comprises the following steps:
(1) Synthesizing a light conversion agent; 0.2mol of EuCl is taken 3 ·6H 2 O was dissolved in 20ml of distilled water to give a europium ion solution, and 0.2mol of 2-thenoyltrifluoroacetone, 0.2mol of pyridine-2, 6-dicarboxylic acid, 0.1mol of 4,4' - (butane-1, 6-di (oxy) bis (pyridine-2)6-dicarboxylic acid) was dissolved in 15ml of ethanol, respectively, to obtain ligand solutions. The europium ion solution is heated to 60℃and 2-thenoyltrifluoroacetone, pyridine-2, 6-dicarboxylic acid, 4' - (butane-1, 6-di (oxy) bis (pyridine-2, 6-dicarboxylic acid) ligand solution are added sequentially. Heating at 60deg.C, and stirring for 60min to obtain complex precipitate. Filtering, washing and vacuum drying at 60 ℃ for 12h to obtain the light conversion agent. The molecules of the light conversion agent are: [ Eu ] 2 (TTA) x PDA (4-x) BPDA6]The structural formula is as follows:
the nuclear magnetic hydrogen spectrum data are as follows: 1 HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H), 8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H),4.10(t,4H), 1.94-1.69(m,8H),1.51(m,4H)。
(2) Preparing a light conversion master batch; mixing 60g of the light conversion agent in the step (1), 14.94kg of granular LLDPE and the light conversion agent, and uniformly mixing by a high-speed stirrer to obtain a mixture, wherein the stirring speed is 1200r/min, and the stirring time is 2min. And (3) putting the mixture into a double-screw extruder, setting the temperature of the double-screw extruder to be 180 ℃, setting the screw rotating speed to be 100r/min, carrying out melt blending on the mixture by the extruder, and granulating after air cooling or water cooling to room temperature to obtain the light conversion master batch.
(3) Preparing a light conversion film; and (3) uniformly mixing 15kg of the light conversion master batch obtained in the step (2) with 2kg of LLDPE, 10kg of LDPE, 1.5kg of anti-aging agent and 1.5kg of anti-fogging agent to obtain a blow molding mixture. And (3) performing blow molding film forming on the mixture by using a film blowing machine to obtain a light conversion film with the low-frequency ultraviolet absorption capability and the thickness of 100+/-10 mu m. Wherein the melt blown film is divided into three temperature areas, the temperature of the first area is 180 ℃, the temperature of the second area is 190 ℃, and the temperature of the third area is 200 ℃.
The ultraviolet absorption spectrum, excitation spectrum and emission spectrum of the light conversion film of example 2 are shown in fig. 1, 3 and 8, respectively, and the comparison is beta-DKs conventional light conversion film (LCF-C). As can be seen from fig. 1, 3 and 8, the light conversion film can effectively absorb 230-400 nm ultraviolet light and is excited to emit red light with a main emission peak of 615 nm. As can be seen from fig. 7, the light conversion film of example 2 is more easily excited by low frequency uv light than the control.
Example 3
The embodiment provides a low-mobility ultraviolet absorption small molecule light conversion film, which comprises the following components:
the preparation process of the light conversion agent, the light conversion master batch and the light conversion film in this example is the same as that of example 2, wherein the addition ratio of the light conversion agent in the light conversion master batch is 0.6%, and the addition ratio in the light conversion film is 0.3%.
The ultraviolet absorption spectrum, excitation spectrum and emission spectrum of the light conversion film in example 3 are shown in fig. 1,4 and 8, respectively. As can be seen from fig. 1, fig. 4 and fig. 8, the light conversion film can effectively absorb 230-400 nm ultraviolet light and is excited to emit red light with a main emission peak of 615 nm. As can be seen from fig. 7, the light conversion film in this embodiment is more susceptible to excitation by low frequency uv light relative to the control.
Example 4
The embodiment provides a low-mobility ultraviolet absorption small molecule light conversion film, which comprises the following components:
polyethylene: 94.998 parts
Light conversion agent: 0.002 parts
An anti-aging agent: 2.5 parts of
Anti-fog drop agent: 2.5 parts of
The preparation process of the light conversion agent, the light conversion master batch and the light conversion film in this example is the same as that of example 2, wherein the addition ratio of the light conversion agent in the light conversion master batch is 0.4%, and the addition ratio in the light conversion film is 0.2%.
The ultraviolet absorption spectrum, excitation spectrum and emission spectrum of the light conversion film in example 4 are shown in fig. 1, 5 and 8, respectively. As can be seen from fig. 1, 5 and 8, the light conversion film can effectively absorb 230-400 nm ultraviolet light and is excited to emit red light with a main emission peak of 615 nm. As can be seen from fig. 7, the light conversion film of example 4 is more easily excited by low frequency uv light than the control.
Example 5
The embodiment provides a low-mobility ultraviolet absorption small molecule light conversion film, which comprises the following components:
polyethylene: 99.998 parts
Light conversion agent: 0.002 parts
An anti-aging agent: 0 part of
Anti-fog drop agent: 0 part of
The preparation process of the light conversion agent, the light conversion master batch and the light conversion film in this example is the same as that of example 2, wherein the addition ratio of the light conversion agent in the light conversion master batch is 0.4%, the addition ratio in the light conversion film is 0.2%, and no anti-aging agent or anti-fog drop is present.
The ultraviolet absorption spectrum, excitation spectrum and emission spectrum of the light conversion film in example 5 are shown in fig. 1,6 and 8, respectively. As can be seen from fig. 1,6 and 8, the light conversion film can be effectively excited by ultraviolet light and generate red light with a main emission peak of 615 nm. As can be seen from fig. 7, the light conversion film in this embodiment is more susceptible to excitation by low frequency uv light relative to the control.
Next, the field application effect of the light conversion films (experimental groups) in examples 1 to 5 was analyzed and evaluated by using strawberry as a test crop, polyethylene film (PE), and conventional light conversion film (LCF-C) as a control group. The soil conditions and field management measures of the two groups are consistent. The effect of the experimental and control groups on strawberry biomass is shown in table 1.
TABLE 1
As shown in table 1, compared with the polyethylene film (PE), the light conversion film provided by the invention can effectively promote accumulation of biomass on the strawberry, wherein the effects of example 2 and example 3 are more remarkable; compared with the conventional light conversion film (LCF-C), the effect of the light conversion film of the embodiment 1-5 on promoting the accumulation of the biomass on the strawberry ground is weaker, because the nutrition growth and the reproduction growth of the strawberry are related to the temperature, and the light conversion film of the embodiment 1-5 has stronger conversion capability to low-frequency ultraviolet light, so that the temperature in a greenhouse is higher, and the reproduction growth of the strawberry is promoted.
The effect of the experimental and control groups on strawberry yield is shown in table 2.
TABLE 2
As can be seen from Table 2, the light conversion films of examples 1-5 all promote improved early-picking yield of strawberries, especially example 3, with the highest early-stage yield, as compared to the conventional light conversion film (LCF-C), indicating that the light conversion films of examples 1-5 promote premature ripening of strawberries.
Migration rate of uv absorber in light conversion film:
to investigate the migration of the UV absorber, PE/[ Eu ] containing the same amount of the UV absorber was used 2 (TTA) x PA (4-x) BDPA4]、PE/[Eu 2 (TTA) x PA (4-x) BDPA6]And a conventional light conversion film (LCF-C) sample film were placed in absolute ethanol, 5ml of the solution after soaking for 6, 12, 18, 24, 48, 72 hours was taken, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet spectrophotometer, as shown in FIGS. 10 to 15. According to the lambert law, in a certain concentration range, the absorbance of a substance is in a proportional relation with the concentration, and the absorbance at the wavelength of 287nm is selected in the experiment to represent the concentration change of a light conversion agent in a solution for soaking a sample in different time. As can be seen from FIG. 9, PE/[ Eu ] 2 (TTA) x PA (4-x) BDPA4]、PE/[Eu 2 (TTA) x PA (4-x) BDPA6]The transfer rate of the transfer agent in the film is approximately the same, the transfer rate can be almost negligible before 12 hours, the transfer rate rises from 12 hours to 48 hours, and the transfer rate tends to be unchanged from 48 hours to 144 hours. PE/[ Eu ] within 144 hours 2 (TTA) x PA (4-x) BDPA4]、 PE/[Eu 2 (TTA) x PA (4-x) BDPA6]The transfer of the transfer agent in the film was far lower than that of LCF-C, indicating [ Eu ] 2 (TTA) x PA (4-x) BDPA4]And [ Eu ] 2 (TTA) x PA (4-x) BDPA6]The two light conversion agents can solve the problem that the light conversion agent is easy to migrate and separate out in the long-term use process of the light conversion film, thereby effectively prolonging the service life of the light conversion film.
The invention is of course also subject to other similar structural compositions and uses than the embodiments described above. In summary, the present invention also includes other variations and alternatives that will be apparent to those skilled in the art.
Claims (10)
1.The low-mobility ultraviolet absorption small-molecule light conversion film is characterized by comprising the following components in parts by weight:
polymer resin: 89.97-99.99 parts;
light conversion agent: 0.001-0.003 parts;
an anti-aging agent: 0.001-5 parts;
anti-fog drop agent: 0.001-5 parts;
wherein the photo-conversion agent contains ketone group and hydroxyl group, and the general molecular formula of the structure of the photo-conversion agent is [ Eu ] 2 (TTA) x PA (4-x) BDPA4]Or [ Eu ] 2 (TTA) x PA (4-x) BDPA6]Wherein TTA is 2-thenoyltrifluoroacetone, PA is pyridine-2, 6-dicarboxylic acid, BDPA4 is 4,4'- (butane-1, 4-di (oxy) bis (pyridine-2, 6-dicarboxylic acid), BDPA6 is 4,4' - (butane-1, 6-di (oxy) bis (pyridine-2, 6-dicarboxylic acid).
2. The low mobility uv absorbing small molecule light converting film of claim 1, wherein said polymer resin comprises granular low density polyethylene particles having a lipid solubility coefficient of 0.3 to 1.
3. The low mobility uv absorbing small molecule light conversion film of claim 1 wherein the light conversion agent has the formula:
the nuclear magnetic hydrogen spectrum data are as follows: 1 HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H),8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H),4.10(t,4H),1.94-1.69(m,8H),1.51(m,4H)。
4. the low mobility uv absorbing small molecule light conversion film of claim 1 wherein the light conversion agent has the formula:
the nuclear magnetic hydrogen spectrum data are as follows: 1 HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H),8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H),4.10(t,4H),1.94-1.89(m,6H),1.69(m,2H)。
5. the method for preparing the low-mobility ultraviolet absorption small molecule light conversion film according to claim 1, which is characterized by comprising the following steps:
step one, preparing a light conversion agent;
step two, weighing the polymer resin, the light conversion agent, the anti-fog drop and the anti-aging agent according to the required weight parts, and dividing the polymer resin into two parts for standby;
step three, uniformly mixing the light conversion agent with one part of the polymer resin obtained in the step two, and then melting, extruding and granulating to obtain light conversion master batch;
and fourthly, uniformly mixing the light conversion master batch obtained in the third step with polymer resin, anti-fog drops and an anti-aging agent, and then carrying out blow molding, cooling and traction to form a film.
6. The method for preparing the low-mobility ultraviolet absorbing small molecule light conversion film according to claim 5, wherein the method for preparing the light conversion agent in the first step specifically comprises the following steps:
s1, dissolving 2-thiophenoyltrifluoroacetone, pyridine-2, 6-dicarboxylic acid, 4'- (butane-1, 4-di (oxy) group) bis (pyridine-2, 6-dicarboxylic acid) or 4,4' - (butane-1, 6-di (oxy) group) bis (pyridine-2, 6-dicarboxylic acid) and potassium hydroxide in an organic solvent to obtain a ligand solution;
s2, adding the ligand solution prepared in the previous step into a europium ion solution to obtain a mixed solution of the ligand and europium ion;
and S3, continuously stirring the ligand and europium ion mixed solution under the heating condition to obtain complex precipitate, filtering, washing and vacuum drying to obtain the light conversion agent.
7. The method according to claim 6, wherein in the step S3, the heating temperature is 50 ℃ to 80 ℃ and the stirring time is 0.5 to 2 hours.
8. The method according to claim 6, wherein the europium ion solution is prepared by mixing europium chloride hexahydrate (EuCl) 3 ·6H 2 O) is dissolved in distilled water and heated to 50-80 ℃.
9. The method for preparing the low-mobility ultraviolet absorption small molecule light conversion film according to claim 6, wherein the ligand solution comprises the following components in parts by weight:
2-thenoyl trifluoroacetone: 3.7-6.8 parts;
pyridine-2, 6-dicarboxylic acid: 2.8-5.1 parts;
4,4'- (butane-1, 4-di (oxy) bis (pyridine-2, 6-dicarboxylic acid) or 4,4' - (butane-1, 6-di (oxy) bis (pyridine-2, 6-dicarboxylic acid): 3.0-6.4 parts;
potassium hydroxide: 3.7-6.8 parts;
europium chloride hexahydrate: 6.1-11.2 parts;
ethanol: 18.4-30.0 parts;
water: 50.1-64.5 parts.
10. The method for preparing a low-mobility ultraviolet absorbing small molecule light conversion film according to claim 5, wherein in the third step, a twin-screw extruder is adopted for extrusion, the extrusion temperature is 180-220 ℃, and the host rotation speed of the twin-screw extruder is 50-100r/min; in the fourth step, the blowing temperature is 180-220 ℃.
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