CN117285926B - Alpha, alpha-terpyridyl rare earth organic red light conversion agent and preparation method and application thereof - Google Patents
Alpha, alpha-terpyridyl rare earth organic red light conversion agent and preparation method and application thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 52
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
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- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 238000000498 ball milling Methods 0.000 claims description 27
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- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
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- 238000001354 calcination Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
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- 239000002243 precursor Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
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- 238000001914 filtration Methods 0.000 claims description 5
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
- 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
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/128—Borates containing plural metal or metal and ammonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
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Abstract
The invention relates to the field of organic luminescent material preparation, in particular to an alpha, alpha-terpyridyl rare earth organic red light conversion agent, a preparation method and application thereof. The red light conversion agent consists of a compound Y (1‑x) Eu x A 3 L and K 7 Mg(BO 3 ) 3 Composition of said Y (1‑x) Eu x A 3 The preparation method of L comprises the following steps: s1: by acid treatment of Y 2 O 3 And Eu 2 O 3 Dissolving; s2: adding alpha, alpha-terpyridine and 2-hydroxy-3-naphthoic acid into absolute ethyl alcohol; s3: adding ethanol solution containing alpha, alpha-terpyridine and 2-hydroxy-3-naphthoic acid into the solution in the step S1, adjusting the pH to 6-7, and reacting at 60-70 ℃ for 3-5h to obtain Y (1‑x) Eu x A 3 L. The alpha, alpha-terpyridyl rare earth organic red light conversion agent prepared by the invention has obvious yield increasing effect on plants when being applied to the field of agricultural films, and has excellent ageing resistance.
Description
Technical Field
The invention relates to the field of organic luminescent material preparation, in particular to an alpha, alpha-terpyridyl rare earth organic red light conversion agent, a preparation method and application thereof.
Background
The rare earth organic complex as an excellent light energy conversion material has become one of the research hot spots in the fields of chemistry and materials, and has attracted great research interest. The rare earth organic complex luminescent material has very wide application prospect in the fields of illumination materials, new energy sources, display materials, biological detection, light-conversion agricultural films and the like, wherein the application report of the rare earth organic complex luminescent material in the light-conversion agricultural films is widely focused. The problems of the existing rare earth organic complex luminescent material used as a light conversion agent applied to a light conversion agricultural film are as follows: the existing red light conversion agent has relatively poor spectrum absorption capability, can not achieve the expected yield increase effect on the agricultural plants, and has the ageing resistance to be further improved.
Chinese patent publication No. CN106967100A discloses a rare earth organic light conversion agent Eu (BMPD) n The agricultural film prepared by the light conversion agent has unexpected yield increasing effect on crops in practical application.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide an alpha, alpha-terpyridyl rare earth organic red light conversion agent, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
an alpha, alpha-terpyridyl rare earth organic red light conversion agent, which consists of a compound Y (1-x) Eu x A 3 L and Compound K 7 Mg(BO 3 ) 3 Composition of the compound Y (1-x) Eu x A 3 L hasThe following structural formula:；
wherein x is more than or equal to 0.1 and less than 1, eu 3+ 、Y 3+ Is a luminescence center, L is alpha, alpha-terpyridine, A is 2-hydroxy-3-naphthoic acid.
Further, the Y (1-x) Eu x A 3 L is prepared by the following method:
s1: by acid treatment of Y 2 O 3 And Eu 2 O 3 Dissolving;
s2: sequentially adding alpha, alpha-terpyridine and 2-hydroxy-3-naphthoic acid into absolute ethyl alcohol, stirring and dissolving;
s3: adding absolute ethanol solution containing alpha, alpha-terpyridine and 2-hydroxy-3-naphthoic acid into the solution in the step S1, stirring, adjusting pH to be 6-7 with sodium hydroxide, heating to 60-70 ℃, stirring for reaction for 3-5h, cooling to room temperature, filtering, washing with absolute ethanol, and drying to obtain Y (1-x) Eu x A 3 L。
In the step S1, the acid is one of hydrochloric acid and nitric acid, and the Y 2 O 3 With Eu 2 O 3 The mixing molar ratio is (1-x): x.
In the step S2, the mixing mole ratio of the alpha, alpha-terpyridine and the 2-hydroxy-3-naphthoic acid is 1:3.
Further, the compound K 7 Mg(BO 3 ) 3 Prepared by the following method:
s1: weighing the raw materials according to the proportion of the chemical general formula, wherein the raw materials contain K + Compound (iv) containing Mg 2+ Compounds of (A) and BO-containing 3 3- Adding grinding aid into the mixture, and placing the mixture in a ball milling tank;
s2: placing the ball milling tank on a ball mill, and adding grinding balls for ball milling;
s3: after ball milling, centrifuging and drying to obtain a precursor;
s4: grinding the precursor, calcining, cooling and grinding after the calcining is finished, and obtaining the catalyst.
In step S1, the K-containing + The compound of (C) is K 2 CO 3 、KOH、K 2 (COO) 2 One of them contains Mg 2+ The compound of (2) is Mg (OH) 2 、Mg(NO 3 ) 2 One of them contains BO 3 3- The compound of (2) is H 3 BO 3 、K 2 B 4 O 7 ·10H 2 And one of O, wherein the grinding aid is one of absolute ethyl alcohol, methanol and deionized water.
In the step S2, the diameter of the grinding ball is 1-15 mm, the ball-material ratio is (1-4): 1, the ball milling time is 60-600 min, and the rotating speed is 100-300 rpm.
In the step S3, the drying temperature is 80-120 ℃; in the step S4, the calcination temperature is 500-900 ℃ and the calcination time is 4-12 h.
Further, the organic red light conversion agent is prepared by the following method: to compound Y (1-x) Eu x A 3 L, compound K 7 M(BO 3 ) 3 And (3) uniformly mixing deionized water according to the mass ratio of (3-5) to 1:5, grinding by a colloid mill, and drying to obtain the product.
Furthermore, the invention also provides application of the alpha, alpha-terpyridyl rare earth organic red light conversion agent in the field of light conversion agricultural films.
By adopting the technical scheme, the beneficial effects of the invention include:
the invention uses colloid mill to grind compound Y (1-x) Eu x A 3 L and Compound K 7 Mg(BO 3 ) 3 Grinding and mixing uniformly to prepare an alpha, alpha-terpyridyl rare earth organic red light conversion agent; the alpha, alpha-terpyridyl rare earth organic red light conversion agent prepared by the invention has obvious yield increasing effect on plants when being applied to the field of agricultural films, and has higher weightlessness temperature and excellent ageing resistance through a thermal stability test.
Drawings
FIG. 1 is an emission spectrum of an α, α, α -terpyridyl rare earth organic red light converter prepared in example 7;
fig. 2 shows the excitation spectrum of the α, α, α -terpyridyl rare earth organic red light converter prepared in example 7.
Detailed Description
The present invention will be further described with reference to examples and application examples, but the present invention is not limited to these examples.
Example 1
Compound Y 0.4 Eu 0.6 A 3 Preparation of L:
will be 0.1mol Y 2 O 3 And 0.15mol Eu 2 O 3 Adding the mixture into 0.4L 5M hydrochloric acid, and stirring and dissolving to obtain a hydrochloric acid solution containing rare earth ions; adding 0.5mol of alpha, alpha-terpyridine and 1.5mol of 2-hydroxy-3-naphthoic acid into 0.5L of absolute ethyl alcohol in sequence, stirring and dissolving, adding the mixture into a hydrochloric acid solution containing rare earth ions, adjusting pH to be 7 by using 2M sodium hydroxide, heating to 65 ℃, stirring and reacting for 4 hours, cooling to room temperature, filtering, washing by 0.2L of absolute ethyl alcohol, and drying at 100 ℃ to obtain a compound Y 0.4 Eu 0.6 A 3 L。
Example 2
Compound Y 0.2 Eu 0.8 A 3 Preparation of L:
will be 0.05mol Y 2 O 3 And 0.2mol Eu 2 O 3 Adding the mixture into 0.4L of 5M nitric acid, and stirring and dissolving the mixture to obtain a nitric acid solution containing rare earth ions; sequentially adding 0.5mol of alpha, alpha-terpyridine and 1.5mol of 2-hydroxy-3-naphthoic acid into 0.5L of absolute ethyl alcohol, stirring and dissolving, adding the mixture into a nitric acid solution containing rare earth ions, stirring, adjusting pH to be 7 by using 2M sodium hydroxide, heating to 70 ℃, stirring and reacting for 3 hours, cooling to room temperature, filtering, washing with 0.2L of absolute ethyl alcohol, and drying at 100 ℃ to obtain a compound Y 0.2 Eu 0.8 A 3 L。
Example 3
Compound Y 0.8 Eu 0.2 A 3 Preparation of L:
will be 0.2mol Y 2 O 3 And 0.05mol Eu 2 O 3 Adding the mixture into 0.4L 5M hydrochloric acid, and stirring and dissolving to obtain a hydrochloric acid solution containing rare earth ions; 0.5mol of alpha, alpha-terpyridine and 1.5mol of 2-hydroxy-3-naphthoic acid are added in sequence to 0.5Adding L absolute ethyl alcohol into hydrochloric acid solution containing rare earth ions after stirring and dissolving, regulating pH to be=6 by using 2M sodium hydroxide, heating to 60 ℃, stirring and reacting for 5 hours, cooling to room temperature, filtering, washing by 0.2L absolute ethyl alcohol, and drying at 100 ℃ to obtain a compound Y 0.8 Eu 0.2 A 3 L。
Example 4
Compound K 7 Mg(BO 3 ) 3 Is prepared from the following steps:
1mol Mg (OH) is taken 2 、3.5molK 2 CO 3 、3molH 3 BO 3 Placing 0.4L absolute ethyl alcohol in a ball milling tank, placing the ball milling tank on a ball mill, adding grinding balls for ball milling, wherein the diameter of the grinding balls is 5mm, the ball-to-material ratio is 3:1, the ball milling time is 100 min, and the rotating speed is 200 rpm; centrifuging after ball milling, and drying at 100 ℃ for 3 hours to obtain a precursor; grinding the precursor, calcining at 800 ℃ for 8 hours, cooling and grinding after the calcining is finished to obtain the compound K 7 Mg(BO 3 ) 3 。
Example 5
Compound K 7 Mg(BO 3 ) 3 Is prepared from the following steps:
taking 1mol Mg (NO) 3 ) 2 、7molKOH、3molH 3 BO 3 Placing 0.4L of methanol in a ball milling tank, placing the ball milling tank on a ball mill, adding grinding balls for ball milling, wherein the diameter of the grinding balls is 2 mm, the ball-to-material ratio is 1:1, the ball milling time is 60min, and the rotating speed is 300 rpm; centrifuging after ball milling, and drying at 80 ℃ for 3 hours to obtain a precursor; grinding the precursor, calcining at 900 ℃ for 4 hours, cooling and grinding after the calcining is finished to obtain the compound K 7 Mg(BO 3 ) 3 。
Example 6
Compound K 7 Mg(BO 3 ) 3 Is prepared from the following steps:
1mol Mg (OH) is taken 2 、2.75molK 2 (COO) 2 、0.75molK 2 B 4 O 7 ·10H 2 Placing O and 0.4L methanol into a ball milling tank, placing the ball milling tank on a ball mill, adding grinding balls for ball milling, wherein the diameter of the grinding balls is 15mm, the ball-to-material ratio is 4:1, the ball milling time is 600min,the rotating speed is 100 revolutions per minute; centrifuging after ball milling, and drying at 120 ℃ for 2 hours to obtain a precursor; grinding the precursor, calcining at 500 ℃ for 12 hours, cooling and grinding after the calcining is finished to obtain K 7 Mg(BO 3 ) 3 。
Example 7
2kg of Compound Y 0.4 Eu 0.6 A 3 L (prepared in example 1), 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
FIG. 1 shows the emission spectrum of the α, α, α -terpyridyl rare earth organic red light conversion agent prepared in this example, the excitation wavelength is 365nm, the main emission position is 606nm to 628nm, and the maximum emission is 615nm, which is matched with the absorption spectrum of plant photosynthesis in the red light region; fig. 2 shows the excitation spectrum of the α, α, α -terpyridyl rare earth organic red light conversion agent prepared in this embodiment, the emission wavelength is 615nm, the main excitation position is 250nm to 489nm, and the maximum excitation is 365nm, which indicates that the excitation light between 250nm and 489nm can excite the light conversion agent to emit light.
Example 8
1.5kg of Compound Y 0.2 Eu 0.8 A 3 L (prepared in example 2), 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 5) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
Example 9
2.5kg of Compound Y 0.8 Eu 0.2 A 3 L (prepared in example 3), 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 6) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
Comparative example 1
2kg of Compound Y 0.4 Eu 0.6 A 3 L (examples)1), 0.5kg of Compound K 7 Ba(BO 3 ) 3 Mixing 2.5kg deionized water uniformly, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
Comparative example 2
2.5kg of Compound Y 0.4 Eu 0.6 A 3 L (prepared in example 1), 0.5kg of Compound K 7 Sr(BO 3 ) 3 Mixing 2.5kg deionized water uniformly, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
Comparative example 3
2.5kg of Compound Y 0.4 Eu 0.6 A 3 L (prepared in example 1), 0.5kg of Compound K 7 Ca(BO 3 ) 3 Mixing 2.5kg deionized water uniformly, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
Comparative example 4
2kg of Compound YA 3 L, 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
L is alpha, alpha-terpyridine, A is 2-hydroxy-3-naphthoic acid.
Comparative example 5
2kg of Compound EuA 3 L, 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
L is alpha, alpha-terpyridine, A is 2-hydroxy-3-naphthoic acid.
Comparative example 6
2kg of Compound Y 0.4 Eu 0.6 A 3 L (prepared in example 1), 0.5kg of Compound Na 7 Mg(BO 3 ) 3 Mixing 2.5kg deionized water, grinding with colloid mill, and drying at 120deg.CDrying for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
Comparative example 7
2kg of Compound Y 0.4 Eu 0.6 A 3 L (prepared in example 1), 0.5kg of Compound K 7 Mg(SiO 3 ) 4.5 Mixing 2.5kg deionized water uniformly, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
Comparative example 8
2kg of Compound Y 0.4 Sm 0.6 A 3 L, 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
L is alpha, alpha-terpyridine, A is 2-hydroxy-3-naphthoic acid.
Comparative example 9
2kg of Compound Y 0.4 Lu 0.6 A 3 L, 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
L is alpha, alpha-terpyridine, A is 2-hydroxy-3-naphthoic acid.
Comparative example 10
2kg of Compound Lu 0.4 Eu 0.6 A 3 L, 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
L is alpha, alpha-terpyridine, A is 2-hydroxy-3-naphthoic acid.
Comparative example 11
2kg of compound Sm 0.4 Eu 0.6 A 3 L, 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4), 2.5kg deionized water was mixed and then ground with a colloid millGrinding and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
L is alpha, alpha-terpyridine, A is 2-hydroxy-3-naphthoic acid.
Comparative example 12
2kg of Compound Y 0.4 Eu 0.6 A 3 L, 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
L is phenanthroline and A is 2-hydroxy-3-naphthoic acid.
Comparative example 13
2kg of Compound Y 0.4 Eu 0.6 A 3 L, 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
L is alpha, alpha-terpyridine, A is salicylic acid.
Comparative example 14
2kg of Compound Y 0.4 Eu 0.6 A 3 L, 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
L is phenanthroline, A is salicylic acid.
Comparative example 15
2kg of Compound Y 0.4 Eu 0.6 A 3 L, 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water, grinding by a colloid mill, and drying at 120 ℃ for 6 hours to obtain the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
L is 2,2':6', 2' -tripyridine-6-carboxylic acid, A is 1, 3-bis (4-methoxyphenyl) propane-1, 3-dione.
Comparative example 16
2kg of Compound Y 0.4 Eu 0.6 A 3 L (prepared in example 1), 0.5kg of Compound K 7 Mg(BO 3 ) 3 (prepared in example 4) and 2.5kg of deionized water are uniformly mixed, then grinding is carried out in a ball milling tank (grinding balls are put in according to the ball-material ratio of 4:1, the ball milling speed is 240 r/min) for 5h, and drying is carried out at 120 ℃ for 6h, thus obtaining the alpha, alpha-terpyridyl rare earth organic red light conversion agent.
Comparative example 17
Organic light conversion agent Eu (BMPD) nL prepared in Chinese patent publication No. CN106967100A in example 1.
Application example
Preparing a light conversion agricultural film:
respectively adding 30Kg of red light conversion agent, 15Kg of low density polyethylene (951-000), 50Kg of linear low density polyethylene (7042) and 5Kg of vinyl bis stearamide (EBS-SF) prepared in examples 7-9 and comparative examples 1-17 into a high-speed mixer, stirring by the high-speed mixer, wherein the stirring speed is 1200r/min, the stirring time is 2h, extruding by a double-screw extruder with the rotating speed of 300r/min at 160 ℃ after stirring uniformly, and granulating by air cooling to prepare light conversion master batch;
300Kg of low-density polyethylene (951-000) and 400Kg of linear low-density polyethylene (7042) are mixed uniformly, and then blown into a film by a film blowing machine, so that the agricultural film with the film thickness of 90 micrometers is prepared. Wherein the melting temperature of the film blowing machine is 180 ℃ and the die head temperature is 160 ℃.
Lettuce is planted in an open greenhouse (without covering an agricultural film), an agricultural film greenhouse without adding a light conversion agent and an agricultural film greenhouse with different light conversion agents, the specification of each greenhouse is 5 meters long, 5 meters wide and 3 meters high, lettuce is selected to be planted in the greenhouse, 3 areas are randomly selected for each greenhouse when planting and harvesting, and 10 samples are selected for each area.
The yield increase of lettuce covered by the agricultural film of different light conversion agents is shown in table 1:
TABLE 1
| Greenhouse | Number of plants | Total weight/g |
| Open greenhouse | 30 | 4328.15 |
| Agricultural film greenhouse without light conversion agent | 30 | 4935 .12 |
| Example 7 | 30 | 6047.10 |
| Example 8 | 30 | 5979.32 |
| Example 9 | 30 | 5938.79 |
| Comparative example 1 | 30 | 5809.73 |
| Comparative example 2 | 30 | 5818.96 |
| Comparative example 3 | 30 | 5794.37 |
| Comparative example 4 | 30 | 5614.38 |
| Comparative example 5 | 30 | 5710.61 |
| Comparative example 6 | 30 | 5900.14 |
| Comparative example 7 | 30 | 5789.26 |
| Comparative example 8 | 30 | 5514.72 |
| Comparative example 9 | 30 | 5418.26 |
| Comparative example 10 | 30 | 5610.74 |
| Comparative example 11 | 30 | 5674.10 |
| Comparative example 12 | 30 | 5573.18 |
| Comparative example 13 | 30 | 5689.75 |
| Comparative example 14 | 30 | 5548.79 |
| Comparative example 15 | 30 | 5718.67 |
| Comparative example 16 | 30 | 5876.54 |
| Comparative example 17 | 30 | 5798.05 |
Examples 7 to 9 of the present application are compounds Y (1-x) Eu x A 3 L and Compound K 7 Mg(BO 3 ) 3 As can be seen from table 1, the prepared red light conversion agent has a higher yield increasing effect when the agricultural film prepared by the red light conversion agent is used for lettuce growth; when the agricultural film prepared by using other types of red light conversion agents is used for lettuce growth, the agricultural film also has a yield increasing effect, but the yield increasing effect is not as good as that of the light conversion agents prepared by the application.
The light-converting agricultural film prepared in the application example is subjected to thermal stability performance test in an air atmosphere by adopting a thermogravimetric analyzer, wherein the temperature test range is 50-600 ℃, the temperature rising rate is 10 ℃/min, the test results are shown in table 2, the Td5% is the temperature at which the weight loss is 5%, and Tdmax% is the temperature at which the weight loss is maximum.
TABLE 2
| Light-converting agricultural film | Td5％/℃ | Tdmax％/℃ |
| Example 7 | 350 | 425 |
| Example 8 | 351 | 426 |
| Example 9 | 348 | 422 |
| Comparative example 1 | 345 | 420 |
| Comparative example 2 | 346 | 419 |
| Comparative example 3 | 340 | 409 |
| Comparative example 4 | 339 | 408 |
| Comparative example 5 | 341 | 410 |
| Comparative example 6 | 345 | 419 |
| Comparative example 7 | 346 | 421 |
| Comparative example 8 | 340 | 410 |
| Comparative example 9 | 342 | 414 |
| Comparative example 10 | 343 | 414 |
| Comparative example 11 | 343 | 416 |
| Comparative example 12 | 342 | 415 |
| Comparative example 13 | 340 | 412 |
| Comparative example 14 | 341 | 413 |
| Comparative example 15 | 345 | 419 |
| Comparative example 16 | 348 | 422 |
| Comparative example 17 | 343 | 413 |
Examples 7 to 9 are compounds Y (1-x) Eu x A 3 L and Compound K 7 Mg(BO 3 ) 3 As can be seen from the data in Table 2, the Td5% temperature and Tdmax% temperature of the agricultural film prepared by the red light conversion agent are higher than those of the agricultural films prepared by other types of light conversion agents.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention; however, those skilled in the art can make various changes, modifications and variations equivalent to the above-described embodiments without departing from the scope of the technical solution of the present invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the present invention.
Claims (8)
1. An alpha, alpha-terpyridyl rare earth organic red light conversion agent is characterized in that the red light conversion agent consists of a compound Y (1-x) Eu x A 3 L and Compound K 7 Mg(BO 3 ) 3 The composition of the composite material comprises the components,
the compound Y (1-x) Eu x A 3 L has the following structural formula:
wherein x is more than or equal to 0.1 and less than 1, eu 3+ 、Y 3+ Is a luminescence center, L is alpha, alpha-terpyridine, A is 2-hydroxy-3-naphthoic acid;
the organic red light conversion agent is prepared by the following method:
to compound Y (1-x) Eu x A 3 L, compound K 7 Mg(BO 3 ) 3 And (3) uniformly mixing deionized water according to the mass ratio of (3-5) to 1:5, grinding by a colloid mill, and drying to obtain the product.
2. The α, α, α -terpyridyl rare earth organic red light converter of claim 1, wherein Y (1-x) Eu x A 3 L is prepared by the following method:
s1: by acid treatment of Y 2 O 3 And Eu 2 O 3 Dissolving;
s2: sequentially adding alpha, alpha-terpyridine and 2-hydroxy-3-naphthoic acid into absolute ethyl alcohol, stirring and dissolving;
s3: adding absolute ethanol solution containing alpha, alpha-terpyridine and 2-hydroxy-3-naphthoic acid into the solution in the step S1, stirring, adjusting pH to be 6-7 with sodium hydroxide, heating to 60-70 ℃, stirring for reaction for 3-5h, cooling to room temperature, filtering, washing with absolute ethanol, and drying to obtain Y (1-x) Eu x A 3 L。
3. The α, α, α -terpyridyl rare earth organic red light conversion agent according to claim 2, wherein in step S1, the acid is one of hydrochloric acid and nitric acid, and the Y is 2 O 3 With Eu 2 O 3 The mixing molar ratio is (1-x): x.
4. The α, α, α -terpyridyl rare earth organic red light converter according to claim 2, wherein in step S2, the mixing molar ratio of α, α, α -terpyridyl to 2-hydroxy-3-naphthoic acid is 1:3.
5. The alpha, alpha-terpyridyl rare earth organic red light converting agent according to claim 1, characterized in that said compound K 7 Mg(BO 3 ) 3 Prepared by the following method:
s1: weighing the raw materials according to the proportion of the chemical general formula, wherein the raw materials contain K + Compound (iv) containing Mg 2+ Compounds of (A) and BO-containing 3 3- Adding grinding aid into the mixture, and placing the mixture in a ball milling tank;
s2: placing the ball milling tank on a ball mill, and adding grinding balls for ball milling;
s3: after ball milling, centrifuging and drying to obtain a precursor;
s4: grinding the precursor, calcining, cooling and grinding after the calcining is finished to obtain the catalyst;
wherein in step S1, the K-containing material + The compound of (C) is K 2 CO 3 、KOH、K 2 (COO) 2 One of them contains Mg 2+ The compound of (2) is Mg (OH) 2 、Mg(NO 3 ) 2 One of them contains BO 3 3- The compound of (2) is H 3 BO 3 、K 2 B 4 O 7 ·10H 2 And one of O, wherein the grinding aid is one of absolute ethyl alcohol, methanol and deionized water.
6. The alpha, alpha-terpyridyl rare earth organic red light conversion agent according to claim 5, wherein in the step S2, the diameter of the grinding ball is 1-15 mm, the ball-material ratio is (1-4): 1, the ball milling time is 60-600 min, and the rotating speed is 100-300 r/min.
7. The α, α, α -terpyridyl rare earth organic red light converter of claim 5, wherein in step S3, the drying temperature is 80-120 ℃; in the step S4, the calcination temperature is 500-900 ℃ and the calcination time is 4-12 h.
8. Use of an α, α, α -terpyridyl rare earth organic red light conversion agent according to any one of claims 1-7 in the field of light conversion agricultural films.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1317537A (en) * | 2001-02-12 | 2001-10-17 | 湖南师范大学 | Single-base dual-energy light-transforming agent and its preparing prcess and application |
| CN1557907A (en) * | 2004-02-03 | 2004-12-29 | 复旦大学 | Rare earth complexes containing dipyridyl derivatives and their use as electroluminescent materials |
| CN105482816A (en) * | 2015-11-17 | 2016-04-13 | 佛山安亿纳米材料有限公司 | Nitride red light conversion master batch and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317537A (en) * | 2001-02-12 | 2001-10-17 | 湖南师范大学 | Single-base dual-energy light-transforming agent and its preparing prcess and application |
| CN1557907A (en) * | 2004-02-03 | 2004-12-29 | 复旦大学 | Rare earth complexes containing dipyridyl derivatives and their use as electroluminescent materials |
| CN105482816A (en) * | 2015-11-17 | 2016-04-13 | 佛山安亿纳米材料有限公司 | Nitride red light conversion master batch and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Designing Cage-Supported Cluster-Organic Framework for Highly Efficient Optical Limiting;Rui-Yan Chen;ACS Materials Letters;第4卷(第8期);1397-1401 * |
| 光转换膜在农业上的应用概述;冯迎春;西北植物学报;第21卷(第3期);600-604 * |
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