CN1385490A - Blue light fluorescent powder converting agent for agricultural film and making method thereof - Google Patents
Blue light fluorescent powder converting agent for agricultural film and making method thereof Download PDFInfo
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- CN1385490A CN1385490A CN 02117295 CN02117295A CN1385490A CN 1385490 A CN1385490 A CN 1385490A CN 02117295 CN02117295 CN 02117295 CN 02117295 A CN02117295 A CN 02117295A CN 1385490 A CN1385490 A CN 1385490A
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- hydrazone
- blue light
- pyridine
- salicylic aldehyde
- converting agent
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Abstract
The present invention provides a method for preparing blue light fluorescent powder converting agent by using hydrazone or Schiff base metal complex, and is characterized by that it selects common metal ions of Al(3+), Ga(3+), In(3+), Sc(3+), Cd (2+), Be (2+), Zn(2+) and Zr (2+), etc. as centre ion, and uses the hydrazones having absorption in near ultraviolet region, including salicylal type hydrazones, pyridine aldehyde type hydrazones and pyridine diazane type hydrazones as ligand to synthesize new type agricultural film fluorescent popwder converting agent MLn (M: metal ion, L: ligand, n is less than or qual to 3 or greater than or equal to 1). Its excitation spectrum is wide-band UV 250-400 nm, emission spectrum is blue-violet region of 400-500 nm, in which violet emission of 400-420 nm is 12% of total emission intensity, so that it can absorb short-wave UV light and emit blue light.
Description
The invention belongs to the preparation method of blue light fluorescent powder converting agent for agricultural film.
Use the canopy film to carry out off-season cultivation and become the inundant trend of agricultural development.But existing ageing-resistant anti-droplet plastics film is used to seal booth and has only played the transparent heat insulating effect, and has ignored the photoproduction step response (the red blue light in the solar spectrum is photosynthetic effective spectrum composition) of crop, does not do any improvement to seeing through light quality.In order to utilize sun power more fully, according to the light ecological principle, daylight is changeed optical tech be applied in the macromolecule membrane, the development of new light conversion film will become the important development direction of functionalization canopy membrane technique.The key of this new and high technology then is the development of the light energy transforming composite of new and effective high stability." antenna effect " by being compound in the photothermal converting agent in the macromolecular material will not have sharp and deleterious UV-light converts ultramarine light (400-500nm) and the blood orange light (580-700nm) that photosynthesis needs most to crop.Increase the temperature of booth, humidity, illuminance, especially effectively spectral component.Thereby improve the output of crop, improve nutritive ingredient, shorten the ripening stage, reduce that due to illness insect pest is sprayed insecticide and the environmental pollution that causes.
Some rare earth inner complex is owing to have the luminous efficiency height, high color purity, characteristics such as stability is strong, and dispersiveness is good are suitable for doing the ruddiness changing agent, caused the great concern of scientists, development is more, as German Patent 3818986, and Chinese patent 1240105,1220279,1066857 etc.And obtained to a certain extent applying, as the multifunctional membrane of mixing the Eu-TTA-TOPO light-converting agent is used for the canopy film test, can make cucumber obtain the effect of average volume increase 15%.By contrast, the development of blue light changing agent is but lacked the people and is made inquiries, relevant coloring film-L-blue light film is to select blue section in the solar spectrum by add " tinting material " in resin, obviously its range of application is narrow, and similar cobalt aluminate, the mineral dye of chrome green etc. and the poor compatibility of resin, phthalocyanine blue, pigment dyestuffs such as phthalein viridescent are in next easy generation oxidation of action of ultraviolet ray and Degradation, photo and thermal stability is limited, work-ing life is shorter, and is not high to the absorption and the efficiency of conversion of sunlight, influences the light transmission features of plastic sheeting for farm use.The praseodymium title complex of being reported in other picture " plastics industry ", though blue light-emitting intensity is on the low side, the blue light-emitting naphthyl derivatives by the sol-gel method preparation that " Chinese plastics " are reported then prepares numerous and diverse, energy consumption is higher, so practical application all has big difficulty.The development that can predict high-performance high stability blue light changing agent will have broad application prospects in plastic sheeting for farm use market.
The preparation method who the purpose of this invention is to provide a kind of blue light fluorescent powder converting agent.By selecting that near-ultraviolet light is had the hydrazone of absorption or Schiff's base is part, common non-fluorescent emission metal ions M
N+Be central ion, the L of synthetic copline molecular structure
*→ L type binary fluorescence complex.Because the different sites of this atoms metal and organic ligand forms one or more additional rings, impels former ligand S
1(n, the π * of attitude
1) change S into
1(π, the π * of attitude
1), also strengthen the rigid planar structure of former ligand simultaneously, thereby can launch strong fluorescence.This title complex absorbs near-ultraviolet light, blue light-emitting, and have higher fluorescence quantum yield.The present invention uses common simple and easy chemical synthesis process, obtains high-level efficiency, high brightness, good stability, long service life, the blue light changing agent that has agricultural development to be worth.
The mold compound that the present invention is last, its general formula are MLn.M=Al wherein
3+, Ga
3+, In
3+, Sc
3+, Cd
2+, Be
2+, Zn
2+, Zr
2+Deng, 1≤n≤3.L=salicylic aldehyde type hydrazone class-salicylic aldehyde benzoyl hydrazone, salicylic aldehyde salicyloyl hydrazone, salicylic aldehyde-5-bromine water poplar acylhydrazone, salicylic aldehyde furoyl hydrazone; Pyridine aldehydes type hydrazone class-2-, pyridine aldehydes-2-furoyl hydrazone, 2-pyridine aldehydes-1-pyridine acetyl hydrazone, 3-hydroxyl-2-pyridine aldehydes-2-pyridine amine Schiff's base; Pyridine hydrazine type hydrazone class-salicylic aldehyde-2-pyridine hydrazone, m-hydroxybenzaldehyde-2-pyridine hydrazone etc.The reagent that uses is ethanol, acetone, ammonium acetate, common chemical reagent such as sodium formiate.In this three classes part, salicylic aldehyde type hydrazone class can be used as first-selected part because of its price is relatively low.
Take by weighing aldehyde and corresponding hydrazide compound according to 1: 1 stoichiometric ratio, they are dissolved in respectively in the ethanol of 50%-95%, under agitation mixed then fully reaction is handled the organic ligand that obtains having near ultraviolet absorption through conventional washing or recrystallization.
The gained part is dissolved in the ethanol of acetone or certain percentage, the salt of metal ion is dissolved in the distilled water.With the pH value of suitable buffered soln (pH=3-6) control agent, the two mixed reaction.The technical process of adopting is: dissolving → stirring → mixed → precipitation → filtration → washing → oven dry → grinding → finished product.
The present invention will be described in more detail below by embodiment, and technical scope of the present invention is not because of these
Embodiment and be subjected to any restriction.
Embodiment 1 AlL
3The preparation of (L=salicylic aldehyde benzoyl hydrazone)
The preparation of L takes by weighing 0.80 gram benzoyl hydrazine, and the 0.34ml salicylic aldehyde is dissolved in the ethanol of 10ml50% respectively, and the two is mixed in backflow 2h. cooling suction filtration in 90 ℃ of oil baths, and thick product is with 50% ethyl alcohol recrystallization, and infrared or vacuum-drying gets part.
AlL
3The preparation of (L=salicylic aldehyde benzoyl hydrazone) takes by weighing the 72mg part and is dissolved in the 15ml dehydrated alcohol; 24mgAlCl
36H
2O (or the KAl (SO of respective amount
4)
212H
2O) be dissolved in the 5ml distilled water, add the NH of 10mlpH=4.9
4Ac buffered soln.Stir the two mixing down, little backflow 1h down that boils.Suction filtration, water and ethanol respectively wash three times, and vacuum-drying gets bright orange green light-converting agent.At 280-400nm, particularly under the 280-350nm ultraviolet excitation, the blue light of the 446nm of emitting bright.
Embodiment 2 AlL
3The preparation of (L=salicylic aldehyde salicyloyl hydrazone)
The preparation of L takes by weighing 0.76 gram salicylyl hydrazine and is dissolved in the ethanol of 15ml95%, and stir down and drip the 0.61g salicylic aldehyde, backflow 2h. suction filtration, with the hot ethanol washing, infrared drying gets the white needles part.
AlL
3The preparation of (L=salicylic aldehyde salicyloyl hydrazone) takes by weighing the 70mg part and is dissolved in the 40ml acetone (but low-grade fever); 24mgAlCl
36H
2O is dissolved in the 30.5ml distilled water, adds the HCOONa buffered soln of 18mlpH=3.4.Stir the two mixing down, little backflow 1h down that boils.Suction filtration respectively washs three times with the boiling water and the ethanol that boils, and vacuum-drying gets bright yellow light-converting agent.At 290-400nm, particularly under the 340-400nm ultraviolet excitation, the blue light of the 453nm of emitting bright.
Embodiment 3 AlL
3The preparation of (L=salicylic aldehyde furoyl hydrazone)
The preparation of L takes by weighing 0.76g furans hydrazides and 0.73ml salicylic aldehyde, is dissolved in the ethanol of 10ml50% respectively, and the two mixes stirring, backflow 2h. cooling suction filtration in 90 ℃ of oil baths, and thick product water and absolute ethanol washing, infrared drying gets oyster white pinniform part.
AlL
3The preparation of (L=salicylic aldehyde furoyl hydrazone) takes by weighing the 68.8mg part and is dissolved in the 15ml dehydrated alcohol; 24mgAlCl
36H
2O is dissolved in the 5ml distilled water, adds the NH of 10mlpH=4.9
4Ac buffered soln.Stir the two mixing down, reflux 1h.Suction filtration, water and ethanol respectively wash three times, and vacuum-drying gets the glassy yellow light-converting agent.At 270-420nm, particularly under the 300-410nm ultraviolet excitation, emitting bright? the blue light of 446nm.
Embodiment of the invention gained fluorescence changing agent powder outward appearance is bright yellow, and its excitation spectrum is broadband 260-420nm, and the maximum excitation wavelength lays respectively at 318nm, 394nm, 393nm, emmission spectrum is positioned at 400-520nm, maximum value lays respectively at 446nm, 452nm, 446nm.Wherein the blue light of 420-500nm accounts for more than 85% of total emissive porwer.Therefore, it can absorb the short wave ultraviolet light in the solar radiation, and emission brightness is big, efficient height, the blue light of high color purity.
Three kinds of aluminum complex fluorescence changing agents (aluminium-salicylic aldehyde benzoyl hydrazone in the embodiment of the invention, aluminium-salicylic aldehyde salicyloyl hydrazone and aluminium-salicylic aldehyde furoyl hydrazone) compare with the europium complex that has been applied (Eu-thenoyltrifluoroacetone-triphenylphosphine oxide), be followed successively by 318 at separately maximum excitation wavelength, 394,393, under the 340nm, the relative brightness of blue light title complex is respectively 13.85 of Eu title complex sample, 7.67,8.82 times.Promptly with regard to relative luminosity, gained light-converting agent of the present invention obviously increases than the fluorescence quantum efficiency of conventional ruddiness light-converting agent, and embodiment one＞embodiment three＞embodiment two.
The rapid ageing of this light-converting agent is tested same and the Eu title complex compares, and with the high voltage mercury lamp ultraviolet light irradiation of 365nm, the distance of lamp and powder is 5cm, and irradiation time is for adding up effect.Comparing result shows: reach the ultraviolet lighting of 50h under normal temperature and pressure conditions after, be similar to the Eu title complex, the characteristic ultraviolet absorption of three kinds of blue light conversion agent is constant; Excitation spectrum only has salicylic aldehyde salicyloyl hydrazone-Al title complex that red shift is arranged slightly, but is in the ultraviolet region substantially, has only to move to purple district on a small quantity; Compare held stationary before the wave band feature of emmission spectrum and intensity and the illumination, illustrate that this light-converting agent has favorable photo-thermal stability.The TG-DTA test shows that before 200 ℃, the TG of this transforming agent presents platform trend substantially, and no water molecules or solvent molecule in the changing agent molecule are described.Its progressively the oxygenolysis temperature be positioned at about 400 ℃, its better heat stability is described, be suitable for the thermoplastic resin film forming.
Photothermal converting agent of the present invention is made its membrane production equipment of plastic sheeting for farm use, and technology is identical with normal film, is guaranteeing under the photothermal converting agent function, can be shared with other common function auxiliary agents, and the polyethylene that the long-lived nothing of preparation is dripped, polyvinyl chloride plastic sheeting for farm use.
Claims (7)
1. the preparation method of a blue light fluorescent powder converting agent for agricultural film.The raw material that is characterised in that selection is made of following component, and its general formula is: MLn.M=Al wherein
3+, Ga
3+, In
3+, Sc
3+, Cd
2+, Be
2+, Zn
2+, Zr
2+Deng, 1≤n≤3.L=salicylic aldehyde type hydrazone class-salicylic aldehyde benzoyl hydrazone, salicylic aldehyde salicyloyl hydrazone, salicylic aldehyde-5-bromine water poplar acylhydrazone, salicylic aldehyde furoyl hydrazone; Pyridine aldehydes type hydrazone class-2-pyridine aldehydes-2-furoyl hydrazone, 2-pyridine aldehydes-1-pyridine acetyl hydrazone, 3-hydroxyl-2-pyridine aldehydes-2-pyridine amine Schiff's base; Pyridine hydrazine type hydrazone class-salicylic aldehyde-2-pyridine hydrazone, m-hydroxybenzaldehyde-2-pyridine hydrazone etc.The reagent that uses is ethanol, acetone, ammonium acetate, common chemical reagent such as sodium formiate.
2. in the described part of claim 1, consider that from the angle of marketing salicylic aldehyde type hydrazone class is relatively low as first-selected part because of its price.
3. according to the preparation method of the described part of claim 1: the aldehyde of equimolar amount and hydrazine (or hydrazides) are dissolved in respectively in the aqueous ethanolic solution of 50%-95%, little boiling (70-90 ℃) backflow 1-3 hour, the gained crude product gets part with the ethyl alcohol recrystallization of hot ethanol or certain percentage, vacuum or infrared drying.
4. according to the preparation method of the described blue light fluorescent powder converting agent of claim 1: the amount of substance of gained part in the claim 3 with 1-3 times of metal ion is dissolved in dehydrated alcohol or the acetone, get solution I, corresponding metal salt is dissolved in and gets solution II in the distilled water, and the ammonium acetate of pH=3-6 or sodium formiate buffered soln are III.The three presses the order of I+ (II+III) and mixes with the certain volume ratio, little boiling backflow 1-3 hour down.Crude product water and dehydrated alcohol wash 2-4 time respectively, dry bright orange green light-converting agent.
5. according to the agent of claim 4 gained blue light conversion, absorb the UV-light of 280-400nm, emission 400-500nm and maximum intensity are at the blue light of 440-480nm.
6. according to according to claim 1 and 2 described blue light fluorescent powder converting agents, can be at the optothermal stabilizer that guarantees under the prerequisite of its effective luminous intensity with routine, auxiliary agents such as antifogging agent are shared, have anti-aging concurrently with preparation, the multi-functional plastic sheeting for farm use of high-tech of anti-droplet and commentaries on classics optical property.
7. range of application of the present invention comprises base of leaf type crop.Use jointly with the ruddiness changing agent, applicable to all crops (because say that with regard to photosynthetic angle red blue light is the most effective spectral component.Wherein blue light helps the growth of vegetable nutritorium-Ye and stem etc., and ruddiness helps reproductive growth-seed germination of plant and fruit etc.)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021172951A CN1176178C (en) | 2002-04-25 | 2002-04-25 | Blue light fluorescent powder converting agent for agricultural film and making method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021172951A CN1176178C (en) | 2002-04-25 | 2002-04-25 | Blue light fluorescent powder converting agent for agricultural film and making method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1385490A true CN1385490A (en) | 2002-12-18 |
| CN1176178C CN1176178C (en) | 2004-11-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009115574A1 (en) | 2008-03-19 | 2009-09-24 | Grow Foil B.V. | Greenhouse for enhanced plant growth |
| CN101434725B (en) * | 2008-12-12 | 2011-02-16 | 山东师范大学 | Novel ecology imitating two band optical energy conversion agricultural film and technique for producing the same |
| WO2015168439A1 (en) | 2014-04-30 | 2015-11-05 | Nitto Denko Corporation | Inorganic oxide coated fluorescent chromophores for use in highly photostable wavelength conversion films |
| US9960294B2 (en) | 2013-01-04 | 2018-05-01 | Nitto Denko Corporation | Highly fluorescent and photo-stable chromophores for wavelength conversion |
| CN108395555A (en) * | 2018-03-12 | 2018-08-14 | 苏州科技大学 | A kind of blue violet light conversion film and preparation method thereof |
| CN108440821A (en) * | 2018-03-12 | 2018-08-24 | 苏州科技大学 | A kind of blue violet light conversion film and the preparation method and application thereof |
| CN111039964A (en) * | 2018-10-12 | 2020-04-21 | 南京工业大学 | Tetrahedral cage-like structure complex and preparation method thereof |
| CN115057832A (en) * | 2022-05-13 | 2022-09-16 | 江苏聚泰科技有限公司 | Acylhydrazone derivatives, and preparation method and application thereof |
-
2002
- 2002-04-25 CN CNB021172951A patent/CN1176178C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009115574A1 (en) | 2008-03-19 | 2009-09-24 | Grow Foil B.V. | Greenhouse for enhanced plant growth |
| CN101434725B (en) * | 2008-12-12 | 2011-02-16 | 山东师范大学 | Novel ecology imitating two band optical energy conversion agricultural film and technique for producing the same |
| US9960294B2 (en) | 2013-01-04 | 2018-05-01 | Nitto Denko Corporation | Highly fluorescent and photo-stable chromophores for wavelength conversion |
| US10461201B2 (en) | 2013-01-04 | 2019-10-29 | Nitto Denko Corporation | Highly-fluorescent and photo-stable chromophores for wavelength conversion |
| US10840397B2 (en) | 2013-01-04 | 2020-11-17 | Nitto Denko Corporation | Highly-fluorescent and photo-stable chromophores for wavelength conversion |
| WO2015168439A1 (en) | 2014-04-30 | 2015-11-05 | Nitto Denko Corporation | Inorganic oxide coated fluorescent chromophores for use in highly photostable wavelength conversion films |
| CN108395555A (en) * | 2018-03-12 | 2018-08-14 | 苏州科技大学 | A kind of blue violet light conversion film and preparation method thereof |
| CN108440821A (en) * | 2018-03-12 | 2018-08-24 | 苏州科技大学 | A kind of blue violet light conversion film and the preparation method and application thereof |
| CN111039964A (en) * | 2018-10-12 | 2020-04-21 | 南京工业大学 | Tetrahedral cage-like structure complex and preparation method thereof |
| CN115057832A (en) * | 2022-05-13 | 2022-09-16 | 江苏聚泰科技有限公司 | Acylhydrazone derivatives, and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1176178C (en) | 2004-11-17 |
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