CN103160277B - Double-function light conversion agent and preparation method thereof - Google Patents

Double-function light conversion agent and preparation method thereof Download PDF

Info

Publication number
CN103160277B
CN103160277B CN201210335279.XA CN201210335279A CN103160277B CN 103160277 B CN103160277 B CN 103160277B CN 201210335279 A CN201210335279 A CN 201210335279A CN 103160277 B CN103160277 B CN 103160277B
Authority
CN
China
Prior art keywords
light
light conversion
double
agent
master batch
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210335279.XA
Other languages
Chinese (zh)
Other versions
CN103160277A (en
Inventor
胡广齐
刘晓瑭
方利浮
陈焰
郑明东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FOSHAN ONMILLION NANO MATERIALS Co Ltd
Original Assignee
FOSHAN ONMILLION NANO MATERIALS Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by FOSHAN ONMILLION NANO MATERIALS Co Ltd filed Critical FOSHAN ONMILLION NANO MATERIALS Co Ltd
Priority to CN201210335279.XA priority Critical patent/CN103160277B/en
Publication of CN103160277A publication Critical patent/CN103160277A/en
Application granted granted Critical
Publication of CN103160277B publication Critical patent/CN103160277B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a kind of double-function light conversion agent, it is characterized in that, its composition general formula is Ca 1-xn xf 2: Eu, TM, wherein: 0≤x≤1, N be selected from Ba, Zn, Sr, Mg, Hg and Fe one or more, TM be selected from Sm, Cu, Pr, Tb, Ce, La, Dy, Mn and Ag one or more.Double-function light conversion agent good stability in the present invention, luminous intensity are high, indigo plant/blood orange light intensity is adjustable, can be used for producing as regenerative ratio bifunctional light conversion thin film after Difunctional light conversion master batch.Make Difunctional light conversion master batch, can carry out pre-dispersed to ruddiness light-converting agent, improve the dispersiveness of ruddiness light-converting agent in film matrix, dust pollution during minimizing execute-in-place, make the light-converting film produced have the effect of the light that more takes a turn for the better.UV-light (300nm ~ 380nm) in sunlight and green glow (520nm-560nm) can be converted to the strong blue light (400nm ~ 500nm) and blood orange light (575nm ~ 630nm) that can promote crop growth by bifunctional light conversion thin film simultaneously.

Description

Double-function light conversion agent and preparation method thereof
Technical field
The present invention relates to double-function light conversion agent and preparation method thereof.
Background technology
So far, a large amount of research experiments proves, be irradiated in the spectrum of earth surface, and the light of the different wave length of not all is all favourable to plant-growth, really be conducive to the You Lianggefeng district of photosynthesis of plant: (1) blue light region (400 ~ 500nm), the strongest absorption peak of its Determination of Chlorophyll α is 425nm, chlorophyll β, and xenthophylls and the strongest absorption peak of alpha-carotene are 440nm; (2) blood orange district (600-680nm), wherein 645nm is the strongest absorption peak of chlorophyll β, and 660nm is the strongest absorption peak of chlorophyll α.By increasing the blue light of plant or red light irradiation degree, crop root can be made flourishing, and cauline leaf is luxuriant, increasing both production and income and quality superior.
But can for the manufacture of turning light master batch, and canopy membrane interaction can be produced in the most important material light-converting agent of crop growth, although have made some progress, but focus mostly in monochromatic light-converting agent, such as ruddiness light-converting agent mainly rare earth compounding light-converting agent, also there is a lot of problems in the research of this type of light-converting agent: (1) fluorescence lifetime short so far.Seldom there is document can report the fluorescence lifetime of organic coordination compound light-converting agent, even if report also only has effect in 3 months, for the production of turning light master batch, prepare light-converting film, at the button canopy initial stage, light conversion properties can be relatively good, but its light transition function very fast can decline very soon, cause it can not be synchronous with the life-span of film.(2) light function singleness.In the light-converting agent of rare earth organic complex, the ultraviolet of only having that can be used for light-converting film at present turns red function, seldom has the blue light reported and can be converted to needed for photosynthesis of plant.In addition, on light-use, can only UV-light be absorbed, and can not absorb green glow, reduce the utilising efficiency to daylight.(3) expensive.The price of its costliness, hinders its application on light-converting film; In addition, seldom see the report about blue light conversion agent, existing bibliographical information can by the green glow in sunlight and UV-light conversion position blue light and blood orange light, but the not easily compatible practical application of problem to light-converting agent of light-converting agent and polymer has manufactured a difficult problem.
Summary of the invention
First object of the present invention is to provide a kind of double-function light conversion agent, the UV-light (300nm ~ 380nm) in sunlight and green glow (520nm-560nm) can be converted simultaneously to the strong blue light (400nm ~ 500nm) and blood orange light (575nm ~ 630nm) that can promote crop growth.
For achieving the above object, the present invention is achieved through the following technical solutions:
Double-function light conversion agent, is characterized in that, its composition general formula is Ca 1-xn xf 2: Eu, TM, wherein: 0≤x≤1, N be selected from Ba, Zn, Sr, Mg, Hg and Fe one or more, TM be selected from Sm, Cu, Pr, Tb, Ce, La, Dy, Mn and Ag one or more.
Double-function light conversion agent in the present invention, with alkaline-earth metal fluoride Ca 1-xn xf 2for matrix, Eu are activator, remaining metal ion makes sensitizing agent.
Preferably, alkaline-earth metal fluoride Ca 1-xn xf 2for unitary alkaline-earth metal fluoride or binary alkaline-earth metal fluoride or polynary alkaline-earth metal fluoride.
Second object of the present invention is to provide a kind of preparation method of double-function light conversion agent simply and easily.
To achieve these goals, the present invention is by the following technical solutions:
The preparation method of aforementioned double-function light conversion agent, it is characterized in that, design according to molecular formula, rare earth ion and inorganic salt solution are mixed in molar ratio, under agitation condition, forms co-precipitation, centrifugation, after washing and drying, under reducing atmosphere, in microwave, high fire reacts 10 ~ 20 minutes or in 800 DEG C ~ 1200 DEG C high-temperature roastings 2 ~ 4 hours, namely obtains product.
Preferably, described reducing atmosphere is the mixture of carbon monoxide or hydrogen and nitrogen.
Preferably, by roasting under throw out and fusing assistant and reducing atmosphere; Described fusing assistant is NaF, CaF 2, BaF 2, Li 2cO 3, K 2cO 3, CaCl 2, KCl, NaCl, NH 4cl, H 3bO 3in one or more.
Preferably, the weight of described fusing assistant is 0.1 ~ 50% of weight of precipitate.More preferably, more preferably, the weight of described fusing assistant is 0.5 ~ 20% of weight of precipitate; Most preferably, the weight of fusing assistant is 2 ~ 15% of weight of precipitate.
Double-function light conversion agent good stability in the present invention, luminous intensity are high, indigo plant/blood orange light intensity is adjustable, can be used for producing as regenerative ratio bifunctional light conversion thin film after Difunctional light conversion master batch.
Make Difunctional light conversion master batch, can carry out pre-dispersed to ruddiness light-converting agent, improve the dispersiveness of ruddiness light-converting agent in film matrix, dust pollution during minimizing execute-in-place, make the light-converting film produced have the effect of the light that more takes a turn for the better.UV-light (300nm ~ 380nm) in sunlight and green glow (520nm-560nm) can be converted to the strong blue light (400nm ~ 500nm) and blood orange light (575nm ~ 630nm) that can promote crop growth by Difunctional light conversion light-converting film simultaneously.
The especially light-converting agent stable performance of Difunctional light conversion master batch material therefor, good weatherability, be prepared into light-converting film, effectively extend the work-ing life of light-converting film; Again due to low cost, good with farm crop photosynthesis Spectral matching, obviously can play the effect of volume increase, oil recovery enhancement for production estimation, and disease and pest obviously reduces, can apply on a large scale at production light-converting film, act on crop growth.
Accompanying drawing explanation
Fig. 1: the SEM figure of the double-function light conversion agent precursor in the embodiment of the present invention 1.
Fig. 2: the SEM figure of the double-function light conversion agent in the embodiment of the present invention 1.
Fig. 3: the embodiment of the present invention 1-9 exciting light spectrogram of double-function light conversion agent in ultraviolet region produced.
Fig. 4: the embodiment of the present invention 1-9 exciting light spectrogram of double-function light conversion agent in green Region produced.
The blue emission spectrum figure of Fig. 5: the embodiment of the present invention 1-9 double-function light conversion agent of producing.
The red emission spectrogram of Fig. 6: the embodiment of the present invention 1-9 double-function light conversion agent of producing.
Embodiment
Double-function light conversion agent in the present invention can first make Difunctional light conversion master batch, make double-function light conversion agent and macromolecular material consistency good, and do not reduce the mechanical property before not adding light-converting agent; And then make Bifunctional light conversion thin, for the plant such as Planting Crops, cash crop.
Difunctional light conversion master batch, by being prepared by the raw material comprising double-function light conversion agent, properties-correcting agent and organic polymer material, described double-function light conversion agent composition general formula is Ca 1-xn xf 2: Eu, TM, wherein: 0≤x≤1, N is one or more in Ba, Zn, Sr, Mg, Hg and Fe, TM be selected from Sm, Cu, Pr, Tb, Ce, La, Dy, Mn and Ag one or more.
Alkaline-earth metal fluoride Ca 1-xn xf 2for unitary alkaline-earth metal fluoride or binary alkaline-earth metal fluoride or polynary alkaline-earth metal fluoride.
Preferably, described double-function light conversion agent weight is the 0.1-90% turning light master batch weight.Preferably, double-function light conversion agent weight is the 0.1-80% turning light master batch weight; More preferably, double-function light conversion agent weight is the 5-60% turning light master batch weight.
Preferably, described properties-correcting agent is one or more the mixture be selected from resol, aminoresin, Synolac, epoxy resin, acrylic resin, silane coupling agent and titanate coupling agent.
Available resol includes but not limited to versatility resol and modified phenolic resins.Modified phenolic resins includes but not limited to water soluble phenol resin, rosin modified phenolic resin, nylon modified phenolic resin and aniline modified resol.
Available aminoresin includes but not limited to urea-formaldehyde resin, terpolycyantoamino-formaldehyde resin, aniline formaldehyde resin and water soluble amino resin.
Available Synolac includes but not limited to 300,310,341,342,343-3,343-4,355-5,389-8,3150,3247.
Available epoxy resin includes but not limited to bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy and acrylic acid epoxy resin.
Available acrylic resin includes but not limited to methyl methacrylate, β-dimethyl-aminoethylmethacrylate, poly-n-butyl methacrylate, n-BMA, Octyl methacrylate, methacrylic acid certain herbaceous plants with big flowers ester, phenyl methacrylate and lauryl methacrylate(LMA).
Available silane coupling agent includes but not limited to vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, Y-aminopropyl triethoxysilane, Y-glycidyl ether oxygen propyl trimethyl silane, Y-(methacryloxy) propyl trimethoxy silicane, Y-mercaptopropyl trimethoxysilane, N-β-aminoethyl-Y-aminopropyl trimethoxysilane, anilinomethyl triethoxysilane and anilinomethyl trimethoxy silane.
Available titanate coupling agent includes but not limited to the different capryloyl titanic acid ester of isopropoxy three, isopropoxy three isostearoyl base titanic acid ester, dioleoyl ethylene titanate, three oleoyl isopropyl titanate and tetrabutyl titanates.
Preferably, described properties-correcting agent weight is the 0.05-10% turning light master batch weight.
Preferably, described organic polymer material is the mixture of one or more be selected from Low Density Polyethylene, linear polyethylene, high density polyethylene(HDPE), polyvinyl chloride, polypropylene, polymeric amide, polystyrene, polyethylene terephthalate and polyvinyl acetate.
Preferably, also comprise the first auxiliary agent, described first auxiliary agent is photostabilizer and/or oxidation inhibitor.
Photostabilizer described in the present invention is selected from salol, p-t-butylphenyl salicylate, Resorcinol but benzoic ether, 2,4-dihydroxy benaophenonel, ESCALOL 567, dihydroxyphenyl propane sasapyrin and BP-3-5-sulfonic acid, (2,2,6,6-tetramethyl--4-piperidines) imines, succinic acid and (4-hydroxyl-2,2,6, the polymkeric substance of 6-tetramethyl--1-piperidine alcohols), sebacic acid two-2,2, the mixture of one or more in 6,6-tetramethyl piperidine alcohol ester.Preferably, photostabilizer is the mixture of (2,2,6,6-tetramethyl--4-piperidines) imines and succinic acid and (polymkeric substance of 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine alcohols).
Oxidation inhibitor described in the present invention is selected from irgasfos 168, antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant 300, antioxidant 330, antioxidant 3114, oxidation inhibitor 245,2,6-ditertbutylparacresol, 2, one or more in 4,6-tri-butyl-phenol.Irgasfos 168, i.e. three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester; Antioxidant 1010, i.e. four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Antioxidant 1076, i.e. β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid.Preferably, oxidation inhibitor is one or more mixture in three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Preferably, described first auxiliary agent weight is the 0.5-20% turning light master batch weight.
Preferably, also comprise the second auxiliary agent, described second auxiliary agent is lubricant, and described lubricant is selected from the mixture of one or more in polyethylene wax, vinyl bis-stearamides, Zinic stearas, stearic acid pentaerythritol ester, polyoxyethylene glycol and aluminate coupling agent.
Preferably, described second auxiliary agent weight is the 0.05-5% turning light master batch weight.
Difunctional light conversion agglomerate preparation method, is characterized in that, by the above-mentioned raw material by weight preparation, in 130 DEG C ~ 200 DEG C, rotating speed is under 100 ~ 500r/min condition, prepares through twin screw extruder.The method makes double-function light conversion agent scattered in organic polymer, and avoid double-function light conversion agent occur in preparation waste phenomenon.
First, by double-function light conversion agent, design according to molecular formula, raw material Rare Earth Ion and inorganic salt solution are mixed in molar ratio, under agitation condition, adds precipitation agent form co-precipitation, centrifugation, namely washing and drying obtains presoma, then, under reducing atmosphere, in microwave, high fire reaction 10 ~ 20 minutes or 800 DEG C ~ 1200 DEG C high-temperature roastings 2 ~ 4 hours, namely obtain the double-function light conversion agent of stable performance.Secondly, by the double-function light conversion agent of above-mentioned production, properties-correcting agent and organic polymer material and/or the first auxiliary agent and/or the second auxiliary agent, mix in proportion, under 130 DEG C ~ 200 DEG C service temperatures and rotating speed are 100 ~ 500r/min condition, extrude through twin screw extruder, air-cooled granulation, shear and obtain Difunctional light conversion master batch.When making different goods, the key points for operation of twin screw extruder are also different, the present invention adopts twin screw extruder to manufacture master batch, properties-correcting agent and double-function light conversion agent can be made through forcing machine, under 130 DEG C ~ 200 DEG C service temperatures and rotating speed are 100 ~ 500r/min condition, not only can realize carrying out effective modification to the surface of double-function light conversion agent, and better play the serviceability of twin screw extruder.
Embodiment 1
(1) the synthesis Ca of double-function light conversion agent 0.7ba 0.3f 2: Eu
Stoichiometrically take Ca (NO respectively 3) 24H 2o (14.8Kg), Ba (NO 3) 2(5Kg), Eu 2o 3(17.00g), NH 4f (11.5Kg), HNO 3(25ml).
A. first HNO is used 3dissolve Eu 2o 3, add Ca (NO 3) 24H 2o and Ba (NO 3) 2preparation 0.25mol/L solution A;
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.After drying, as shown in Figure 1, its material object is white chunks thing to the SEM shape characteristic of presoma.
C. by the throw out after above-mentioned oven dry, process adds the fusing assistant CaF of 0.5% of weight of precipitate 2grind, then under CO reducing atmosphere condition, 1200 DEG C of high-temperature roastings 2 hours, cool gradually, namely obtain sample.As shown in Figure 2, its material object is white powder to the SEM shape characteristic of described sample.
(2) production of light master batch is turned
Take 0.24kg double-function light conversion agent, high density polyethylene(HDPE) 20kg, vinyl bis-stearamides 0.4kg; photostabilizer salol 2kg; 1kg antioxidant 1010, the different capryloyl titanic acid ester 0.5kg of isopropoxy three, bisphenol A type epoxy resin 0.2kg; above-mentioned materials is sequentially added to high-speed mixer; after stirring with high-speed mixer, under the operational temperature conditions of 200 DEG C, the twin screw extruder being 500r/min through rotating speed is extruded; air-cooled granulation, shears and is prepared from master batch.
Embodiment 2
(1) the synthesis Ca of double-function light conversion agent 0.75zn 0.15f 2: Eu, Ce
Stoichiometrically take Ca (NO respectively 3) 24H 2o (17.6Kg), Zn (NO 3) 2, Ce 2o 3with MgO (altogether 3.2Kg), Eu 2o 3(17.00g), NH 4f (11.5Kg), HNO 3(25ml).
A. first HNO is used 3dissolve Eu 2o 3, Ce 2o 3and MgO, add Ca (NO 3) 24H 2o and Zn (NO 3) 2preparation 0.25mol/L solution A;
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the CaCl that fluxes of addition agent weight of precipitate 10% 2grind, then under nitrogen hydrogen mixeding gas reducing atmosphere condition, 800 DEG C of high-temperature roasting 4h hour, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) production of light master batch is turned
Take 25.4kg example 2(1) sample, linear polyethylene 20kg, polyethylene wax 0.8kg; photostabilizer Resorcinol but benzoic ether 2.5kg; 1.2kg antioxidant 2246, isopropoxy three isostearoyl base titanic acid ester 0.4kg, 0.5kg Synolac 342; above-mentioned materials is sequentially added to high-speed mixer; after stirring with high-speed mixer, under the operational temperature conditions of 130 DEG C, the twin screw extruder being 100r/min through rotating speed is extruded; air-cooled granulation, shears and is prepared from master batch.
Embodiment 3
(1) the synthesis Ca of double-function light conversion agent 0.65sr 0.30fe 0.05f 2: Eu
Stoichiometrically take Ca (NO respectively 3) 24H 2o (24.5Kg), Sr (NO 3) 2(11.2Kg), Fe 2o 3and Eu 2o 3(altogether 31.00g), NH 4f (21.2Kg), HNO 3(30ml).
A. first HNO is used 3dissolve Eu 2o 3, Fe 2o 3and Eu 2o 3, add Ca (NO 3) 24H 2o, Sr (NO 3) 2(11.2Kg) 0.25mol/L solution A is prepared;
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant of addition agent weight of precipitate 1% enters the capable grinding of NaF, then at H 2with N 2under mixture reducing atmosphere condition, 950 DEG C of high-temperature roastings 3 hours, cool gradually, namely obtain sample.
(2) production of light master batch is turned
Take 10kg example 3(1) sample; polyvinyl chloride 30kg; Zinic stearas 0.2kg, stearic acid pentaerythritol ester 0.3kg, polyethylene wax 1.0kg; photostabilizer dihydroxyphenyl propane sasapyrin 5kg; 2.5kg oxidation inhibitor 245; dioleoyl ethylene titanate 1.5kg; urea-formaldehyde resin 1.08kg; above-mentioned materials is sequentially added to high-speed mixer; after stirring with high-speed mixer, under the operational temperature conditions of 170 DEG C, the twin screw extruder being 250r/min through rotating speed is extruded; air-cooled granulation, is prepared from master batch.
Embodiment 4
(1) the synthesis Ca of double-function light conversion agent 0.75mg 0.25f 2: Eu, Sm, Pr
Stoichiometrically take Ca (NO respectively 3) 24H 2o (17.6Kg), Mg (NO 3) 2, Pr 2o 3and Sm 2o 3(altogether 3.2Kg), Eu 2o 3(14.00g), NH 4f (17.5Kg), HNO 3(25ml).
A. first HNO is used 3dissolve Eu 2o 3, Pr 2o 3and Sm 2o 3, add Ca (NO 3) 24H 2o, Mg (NO 3) 2preparation 0.25mol/L solution A;
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant CaCl of addition agent weight of precipitate 0.5% 2grind, then under CO reducing atmosphere condition, 900 DEG C of high-temperature roastings 3.5 hours, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) production of light master batch is turned
Take 8kg example 4(1) sample, high density polyethylene(HDPE) 20kg, polyethylene wax 1.0kg; photostabilizer ESCALOL 567 4kg; 2kg antioxidant 1076, dioleoyl ethylene titanate 1.89kg, novolac epoxy 2kg; above-mentioned materials is sequentially added to high-speed mixer; after stirring with high-speed mixer, under the operational temperature conditions of 170 DEG C, the twin screw extruder being 400r/min through rotating speed is extruded; air-cooled granulation, is prepared from master batch.
Embodiment 5
(1) the synthesis Ca of double-function light conversion agent 0.6sr 0.25zn 0.10f 2: Eu, Cu, Dy
Stoichiometrically take Ca (NO respectively 3) 24H 2o (17.6Kg), Sr (NO 3) 2, ZnO, CuO and Dy 2o 3(altogether 5.9Kg), Eu 2o 3(15.00g), NH 4f (18.5Kg), HNO 3(27ml).
A. first HNO is used 3dissolve Eu 2o 3, ZnO, CuO and Dy 2o 3, add Ca (NO 3) 24H 2o, Sr (NO 3) 2preparation 0.25mol/L solution A;
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant K of addition agent weight of precipitate 1.5% 2cO 3grind, then under CO reducing atmosphere condition, 900 DEG C of high-temperature roastings 4 hours, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) production of light master batch is turned
Take 8kg example 5(1) sample, polypropylene 30kg, polyethylene wax 0.5kg, photostabilizer 2,4-dihydroxy benaophenonel 1.1kg, 1.01kg antioxidant 2246, tetrabutyl titanate 0.8kg, versatility resol 0.2, terpolycyantoamino-formaldehyde resin 0.3,0.3kg Synolac 300, be sequentially added to high-speed mixer by above-mentioned materials, after stirring with high-speed mixer, under the operational temperature conditions of 175 DEG C, the twin screw extruder being 350r/min through rotating speed is extruded, and air-cooled granulation, is prepared from master batch.
Embodiment 6
(1) the synthesis Ca of double-function light conversion agent 0.6ba 0.25fe 0.15f 2: Eu, Mn
Stoichiometrically take Ca (NO respectively 3) 24H 2o (18.5Kg), Fe (NO 3) 2with MnO (altogether 2.4Kg), Ba (NO 3) 2(2.6Kg), Eu 2o 3(16.00g), NH 4f (21.5Kg), HNO 3(27ml).
A. first HNO is used 3dissolve Eu 2o 3, MnO, add Ca (NO 3) 24H 2o, Fe (NO 3) 2with Ba (NO 3) 2preparation 0.25mol/L solution A;
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant BaF of addition agent weight of precipitate 3.6% 2grind, then at H 2with N 2under mixture reducing atmosphere condition, 950 DEG C of high-temperature roasting 2.5h hour, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 6kg example 6(1) sample, high density polyethylene(HDPE) 30kg, polyethylene wax 0.6kg, photostabilizer ESCALOL 567 3kg, 1.5kg antioxidant 1010, tetrabutyl titanate 2.19kg, bisphenol f type epoxy resin 0.3, methyl methacrylate 0.2kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 185 DEG C, the twin screw extruder being 450r/min through rotating speed is extruded, air-cooled granulation, is prepared from master batch.
Embodiment 7
(1) the synthesis Ca of double-function light conversion agent 0.70sr 0.20ba 0.10f 2: Eu, Sm
Stoichiometrically take Ca (NO respectively 3) 24H 2o (18.5Kg), Sr (NO 3) 2, Sm 2o 3(altogether 4.5Kg), Ba (NO 3) 2(1.6Kg), Eu 2o 3(16.00g), NH 4f (21.5Kg), HNO 3(27ml).
A. first HNO is used 3dissolve Eu 2o 3, Sm 2o 3, add Ca (NO 3) 24H 2o, Sr (NO 3) 2with Ba (NO 3) 2preparation 0.25mol/L solution A;
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant NaCl of addition agent weight of precipitate 5.2% grinds, then at H 2with N 2under mixture reducing atmosphere condition, in microwave, high fire reaction is after 10 minutes, cools gradually, namely obtains sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 6kg example 7(1) sample, Low Density Polyethylene 30kg, polyethylene wax 1.2kg, photostabilizer p-t-butylphenyl salicylate 3kg, 1.5kg antioxidant 300, tetrabutyl titanate 0.3kg, methacrylic acid certain herbaceous plants with big flowers ester 0.5kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 185 DEG C, the twin screw extruder being 450r/min through rotating speed is extruded, air-cooled granulation, is prepared from master batch.
Embodiment 8
(1) the synthesis Ca of double-function light conversion agent 0.5sr 0.25ba 0.25f 2: Eu, La, Tb
Stoichiometrically take Ca (NO respectively 3) 24H 2o (12.5Kg), Sr (NO 3) 2, La 2o 3and Tb 2o 3(altogether 6.5Kg), Ba (NO 3) 2(5.6Kg), Eu 2o 3(16.00g), NH 4f (20.5Kg), HNO 3(27ml).
A. first HNO is used 3dissolve Eu 2o 3, La 2o 3and Tb 2o 3, add Ca (NO 3) 24H 2o, Sr (NO 3) 2preparation 0.25mol/L solution A;
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 2.4% grinds, and then under CO reducing atmosphere condition, in microwave, high fire reaction is after 20 minutes, cools gradually, namely obtains sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 7kg example 8(1) sample, linear low density polyethylene 28kg, polyethylene wax 1.4kg, photostabilizer p-t-butylphenyl salicylate 3.5kg, 1.6kg antioxidant 1010, vinyltrimethoxy silane 2.25kg, bisphenol A type epoxy resin 1.2kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 180 DEG C, the twin screw extruder being 350r/min through rotating speed is extruded, air-cooled granulation, is prepared from master batch.
Embodiment 9
(1) the synthesis Ca of double-function light conversion agent 0.70sr 0.10ba 0.10hg 0.10f 2: Eu, Mn
Stoichiometrically take Ca (NO respectively 3) 24H 2o (28.8Kg), Sr (NO 3) 2, MnO and HgO (altogether 5.5Kg), Ba (NO 3) 2(5.4Kg), Eu 2o 3(16.00g), NH 4f (25.6Kg), HNO 3(27ml).
A. first HNO is used 3dissolve Eu 2o 3, MnO, HgO, add Ca (NO 3) 24H 2o, Sr (NO 3) 2with Ba (NO 3) 2preparation 0.25mol/L solution A;
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 1.6% grinds, then at H 2with N 2under mixture reducing atmosphere condition, 1000 DEG C of high-temperature roastings 2 hours, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 10kg example 8(1) sample, high density polyethylene(HDPE) 40kg, polyoxyethylene glycol 0.2kg and aluminate coupling agent 0.8kg, photostabilizer Resorcinol but benzoic ether 5kg, 2.5kg antioxidant 330, tetrabutyl titanate 1.5kg, vinyltriethoxysilane 2.5kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 170 DEG C, the twin screw extruder being 380r/min through rotating speed is extruded, air-cooled granulation, is prepared into master batch.
Embodiment 10
(1) the synthesis Ca of double-function light conversion agent 0.7ba 0.25fe 0.05f 2: Eu, Ce
Stoichiometrically take Ca (NO respectively 3) 24H 2o (14.8Kg), Ba (NO 3) 2, CeO 2with FeO (altogether 5Kg), Eu 2o 3(17.00g), NH 4f (11.5Kg), HNO 3(25ml).
A. first HNO is used 3dissolve Eu 2o 3, CeO 2and FeO, add Ca (NO 3) 24H 2o and Ba (NO 3) 2preparation 0.25mol/L solution A.
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant of addition agent weight of precipitate 2.8% grinds, and then under reducing atmosphere hydrogen nitrogen mixed gas concrete conditions in the establishment of a specific crime, 1200 DEG C of high-temperature roastings 2 hours, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 0.241kg example 10(1) sample, high density polyethylene(HDPE) 20kg, polyethylene wax 0.4kg, photostabilizer salol 2kg, 1kg antioxidant 330, tetrabutyl titanate 0.5kg, novolac epoxy 0.2kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 130 DEG C, the twin screw extruder being 100r/min through rotating speed is extruded, air-cooled granulation, is prepared from master batch.
Embodiment 11
(1) the synthesis Ca of double-function light conversion agent 0.85ba 0.1fe 0.05f 2: Eu, Ce, Pr
Stoichiometrically take Ca (NO respectively 3) 24H 2o (17.6Kg), Ba (NO 3) 2, Pr 2o 3and CeO 2(altogether 3.2Kg), Eu 2o 3(17.00g), NH 4f (11.5Kg), HNO 3(25ml).
A. first HNO is used 3dissolve Eu 2o 3, Pr 2o 3and CeO 2, add Ca (NO 3) 24H 2o and Ba (NO 3) 2preparation 0.25mol/L solution A.
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant NaCl of addition agent weight of precipitate 8% grinds, and then under reducing atmosphere hydrogen nitrogen mixed gas concrete conditions in the establishment of a specific crime, 1100 DEG C of high-temperature roasting 2h hour, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 12.7kg example 11(1) sample, high density polyethylene(HDPE) 20kg, Zinic stearas 0.1kg, stearic acid pentaerythritol ester 0.2kg, polyoxyethylene glycol 0.1kg, aluminate coupling agent 0.5kg, photostabilizer ESCALOL 567 2.5kg, oxidation inhibitor 2, 6-ditertbutylparacresol 1.2kg, dioleoyl ethylene titanate 0.4kg, rosin modified phenolic resin 0.2kg, aniline formaldehyde resin 0.3kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 180 DEG C, the twin screw extruder being 300r/min through rotating speed is extruded, air-cooled granulation, be prepared from master batch.
Embodiment 12
(1) the synthesis Ca of double-function light conversion agent 0.6sr 0.35mg 0.05f 2: Eu, Mn, La
Stoichiometrically take Ca (NO respectively 3) 24H 2o (24.5Kg), Sr (NO 3) 2, MnO, La 2o 3with MgO (altogether 11.2Kg), Eu 2o 3(31.00g), NH 4f (21.2Kg), HNO 3(30ml).
A. first HNO is used 3dissolve Eu 2o 3, MnO, La 2o 3and MgO, add Ca (NO 3) 24H 2o and Sr (NO 3) 2preparation 0.25mol/L solution A.
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant KCl of addition agent weight of precipitate 7% grinds, and then under reducing atmosphere hydrogen nitrogen mixed gas concrete conditions in the establishment of a specific crime, 1200 DEG C of high-temperature roastings 3 hours, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 10kg example 12(1) sample, polyvinyl chloride 30kg, Zinic stearas 1.5kg, photostabilizer Resorcinol but benzoic ether 5kg, oxidation inhibitor 2,4,6-tri-butyl-phenol 2.5kg, tetrabutyl titanate 1.5kg, bisphenol A type epoxy resin 1.08kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 170 DEG C, the twin screw extruder being 250r/min through rotating speed is extruded, air-cooled granulation, is prepared from master batch.
Embodiment 13
(1) the synthesis Ca of double-function light conversion agent 0.75sr 0.15mg 0.05f 2: Eu, Sm, Dy
Stoichiometrically take Ca (NO respectively 3) 24H 2o (17.6Kg), Sr (NO 3) 2, Sm 2o 3and Dy 2o 3(altogether 3.2Kg), Eu 2o 3(14.00g), NH 4f (17.5Kg), HNO 3(25ml).
A. first HNO is used 3dissolve Eu 2o 3, Sm 2o 3and Dy 2o 3, add Ca (NO 3) 24H 2o and Sr (NO 3) 2preparation 0.25mol/L solution A.
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 6% grinds, and then under reducing atmosphere CO condition, in microwave, high fire reaction is after 10 minutes, cools gradually, namely obtains sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 8kg example 13(1) sample, high density polyethylene(HDPE) 20kg, polyoxyethylene glycol 1.0kg; photostabilizer dihydroxyphenyl propane sasapyrin 4kg; 2kg oxidation inhibitor 245, the different capryloyl titanic acid ester 1.09kg of isopropoxy three, bisphenol f type epoxy resin 2.8kg; above-mentioned materials is sequentially added to high-speed mixer; after stirring with high-speed mixer, under the operational temperature conditions of 170 DEG C, the twin screw extruder being 400r/min through rotating speed is extruded; air-cooled granulation, is prepared from master batch.
Embodiment 14
(1) the synthesis Ca of double-function light conversion agent 0.6sr 0.35zn 0.05f 2: Eu, Cu
Stoichiometrically take Ca (NO respectively 3) 24H 2o (17.6Kg), Sr (NO 3) 2, ZnO and CuO (altogether 5.9Kg), Eu 2o 3(15.00g), NH 4f (18.5Kg), HNO 3(27ml).
A. first HNO is used 3dissolve Eu 2o 3, ZnO and CuO, add Ca (NO 3) 24H 2o and Sr (NO 3) 2preparation 0.25mol/L solution A.
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant of addition agent weight of precipitate 5% grinds, and then under reducing atmosphere CO condition, in microwave, high fire reaction is after 20 minutes, cools gradually, namely obtains sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 0.32kg example 14(1) sample, high density polyethylene(HDPE) 30kg, polyethylene wax 0.5kg, photostabilizer salol 0.1kg, 0.1kg antioxidant 1010, tetrabutyl titanate 0.8kg, bisphenol A type epoxy resin 0.8kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 175 DEG C, the twin screw extruder being 350r/min through rotating speed is extruded, air-cooled granulation, is prepared from master batch.
Embodiment 15
(1) the synthesis Ca of double-function light conversion agent 0.7sr 0.15ba 0.1fe 0.05f 2: Eu
Stoichiometrically take Ca (NO respectively 3) 24H 2o (18.5Kg), Sr (NO 3) 2, FeO and Ba (NO 3) 2(altogether 2.6Kg), Eu 2o 3(16.00g), NH 4f (21.5Kg), HNO 3(27ml).
A. first HNO is used 3dissolve Eu 2o 3, FeO, add Ca (NO 3) 24H 2o, Sr (NO 3) 2with Ba (NO 3) 2preparation 0.25mol/L solution A.
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 5% grinds, and then under reducing atmosphere CO condition, 950 DEG C of high-temperature roasting 2.5h hour, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 41.38kg example 15(1) sample, high density polyethylene(HDPE) 30kg, polyethylene wax 0.6kg, photostabilizer dihydroxyphenyl propane sasapyrin 6.48kg, 3kg antioxidant 1076, tetrabutyl titanate 0.8kg, 0.5kg Synolac 3150, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 185 DEG C, the twin screw extruder being 450r/min through rotating speed is extruded, air-cooled granulation, is prepared from master batch.
Embodiment 16
(1) the synthesis Ca of double-function light conversion agent 0.75sr 0.15ba 0.1f 2: Eu
Stoichiometrically take Ca (NO respectively 3) 24H 2o (18.5Kg), Sr (NO 3) 2(4.5Kg), Ba (NO 3) 2(1.6Kg), Eu 2o 3(16.00g), NH 4f (21.5Kg), HNO 3(27ml).
A. first HNO is used 3dissolve Eu 2o 3, add Ca (NO 3) 24H 2o, Sr (NO 3) 2with Ba (NO 3) 2preparation 0.25mol/L solution A.
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 15% grinds, and then under reductibility CO atmospheric condition, 1000 DEG C of high-temperature roastings 1.5 hours, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 6kg example 7(1) sample, high density polyethylene(HDPE) 30kg, polyethylene wax 2.17kg, photostabilizer salol 3kg, 1.5kg antioxidant 1010, Y-aminopropyl triethoxysilane 0.3kg, terpolycyantoamino-formaldehyde resin 0.5kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 185 DEG C, the twin screw extruder being 450r/min through rotating speed is extruded, air-cooled granulation, is prepared from master batch.
Embodiment 17
(1) the synthesis Ca of double-function light conversion agent 0.55sr 0.25ba 0.2f 2: Eu
Stoichiometrically take Ca (NO respectively 3) 24H 2o (12.5Kg), Sr 2(NO 3) 3(6.5Kg), Ba (NO 3) 2(5.6Kg), Eu 2o 3(16.00g), NH 4f (20.5Kg), HNO 3(27ml).
A. first HNO is used 3dissolve Eu 2o 3, add Ca (NO 3) 24H 2o, Sr 2(NO 3) 3with Ba (NO 3) 2preparation 0.25mol/L solution A.
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant NaF of addition agent weight of precipitate 4% grinds, and then under reducing atmosphere hydrogen nitrogen mixed gas concrete conditions in the establishment of a specific crime, 1050 DEG C of high-temperature roastings 1 hour, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 7kg example 17(1) sample, high density polyethylene(HDPE) 28kg, polyethylene wax 1.4kg, photostabilizer p-t-butylphenyl salicylate 3.5kg, 1.6kg antioxidant 1010, vinyl trichloro silane 0.8kg, bisphenol A type epoxy resin 1.22kg, urea-formaldehyde resin 1.0kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 180 DEG C, the twin screw extruder being 350r/min through rotating speed is extruded, air-cooled granulation, is prepared from master batch.
Embodiment 18
(1) the synthesis Ca of double-function light conversion agent 0.65sr 0.17ba 0.18f 2: Eu, Tb
Stoichiometrically take Ca (NO respectively 3) 24H 2o (28.8Kg), Sr (NO 3) 2, and Tb 2o 3(altogether 5.5Kg), Ba (NO 3) 2(5.4Kg), Eu 2o 3(16.00g), NH 4f (25.6Kg), HNO 3(27ml).
A. first HNO is used 3dissolve Eu 2o 3and Tb 2o 3, add Ca (NO 3) 24H 2o, Ba (NO 3) 2, Sr (NO 3) 2preparation 0.25mol/L solution A.
The NH of preparation 1mol/L 4f solution B.
B. under agitation condition, solution A is added dropwise in solution B, continues stirring 1 hour, centrifugation, 100 DEG C of oven dry.
C. by the throw out after above-mentioned oven dry, the fusing assistant of addition agent weight of precipitate 5% grinds, and then under reducing atmosphere CO condition, 1000 DEG C of high-temperature roastings 2 hours, cool gradually, namely obtain sample.
As shown in Figure 3, as shown in Figure 4, as shown in Figure 5, the utilizing emitted light spectrogram in red light district as shown in Figure 6 for the utilizing emitted light spectrogram in blue light region for the exciting light spectrogram in green Region for the exciting light spectrogram of product in ultraviolet region.
(2) preparation of light master batch is turned
Take 10kg example 18(1) sample, polypropylene 40kg, polyethylene wax 1kg, photostabilizer salol 5kg, 2.5kg antioxidant 1010, tetrabutyl titanate 1.5kg, Synolac 0.5kg, 1.0kg epoxy resin 310, β-dimethyl-aminoethylmethacrylate 1.0kg, above-mentioned materials is sequentially added to high-speed mixer, after stirring with high-speed mixer, under the operational temperature conditions of 170 DEG C, the twin screw extruder being 380r/min through rotating speed is extruded, air-cooled granulation, is prepared from master batch.
The mode of production I of embodiment 19 Difunctional light conversion canopy film
Take Difunctional light conversion master batch 40kg, Low Density Polyethylene 200kg, linear low density polyethylene 800kg prepared by example 1 respectively, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, mix rear inflation film manufacturing machine blown film to form, wherein, film thickness is 80 microns, inflation film manufacturing machine melt temperature 175 DEG C, die head temperature about 165 DEG C.
The mode of production II of embodiment 20 Difunctional light conversion canopy film
Take Difunctional light conversion master batch 40kg, Low Density Polyethylene 200kg, linear low density polyethylene 800kg prepared by example 5 respectively, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, mix rear inflation film manufacturing machine blown film to form, wherein, film thickness is 80 microns, inflation film manufacturing machine melt temperature 175 DEG C, die head temperature about 165 DEG C.
The mode of production III of embodiment 21 Difunctional light conversion canopy film
Take Difunctional light conversion master batch 40kg, Low Density Polyethylene 200kg, linear low density polyethylene 800kg prepared by example 9 respectively, (2,2,6,6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2,2,6,6-tetramethyl piperidine alcohol ester 10kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, mix rear inflation film manufacturing machine blown film to form, wherein, film thickness is 80 microns, inflation film manufacturing machine melt temperature 175 DEG C, die head temperature about 165 DEG C.
The production of the blank canopy film of embodiment 22
Take Low Density Polyethylene 200kg respectively, linear low density polyethylene 800kg, (2, 2, 6, 6-tetramethyl--4-piperidines) imines 10kg, sebacic acid two-2, 2, 6, 6-tetramethyl piperidine alcohol ester 10kg, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 5kg, three [ 2.4-di-tert-butyl-phenyl ] phosphorous acid ester 5kg, 2kg photostabilizer ESCALOL 567, 1kg antioxidant 1010, mix rear inflation film manufacturing machine blown film to form, wherein, film thickness is 80 microns, inflation film manufacturing machine melt temperature 175 DEG C, die head temperature about 165 DEG C.
The contrast application of embodiment 23 Difunctional light conversion canopy film and blank film
First carry out two booths to build, each booth specification is length, width and height is 14m7m3.5m, then carry out bifunctional light conversion thin film and blank film two kinds of canopy films coverings, wherein light-converting film canopy is the light-converting film of above-mentioned example 19,20 and 21, and blank film is the blank film of above-mentioned example 22.Then according to the photosynthesis spectral signature of crop, have selected the crop relatively mated with above-mentioned light-converting film is: leaf class is milk Chinese cabbage, leaf mustard, Japanese Plantula Brassicae chinensis, romaine lettuce; Melon and fruit class is eggplant, capsicum and fresh kidney beans.Before plantation, in two canopies, soil has carried out abundant mixing, and the weight of fertilising completes the same, and the watering amount of every day is basically identical, does not carry out any pesticide application.Concrete test kind, data logging and comparing result see attached list 1 and table 2.Bifunctional light conversion thin film of the present invention is applied in the data logging of leafy vegetable plantation as following table 1; Bifunctional light conversion thin film of the present invention is applied in the data logging of leaf melon or fruit type crops plantation as following table 2.Stimulation ratio in table 1 and table 2 refers to the output increment rate using the output of bifunctional light conversion thin film relative to the output using blank film.
Table 1 leafy vegetable plantation Comparative result table
Table 2 melon-fruit-like vegetable plantation Comparative result table
Embodiment in the present invention, only for the present invention will be described, does not form the restriction to right, other equivalent in fact substituting, all in scope that those skilled in that art can expect.

Claims (3)

1. double-function light conversion agent, is characterized in that, its composition general formula is Ca 1-xn xf 2: Eu, TM, wherein: 0<x≤1, N be selected from Zn, Hg and Fe one or more; Or N except comprise in Ba, Sr, Mg one or more, also comprise in Zn, Hg, Fe one or more, TM be selected from Sm, Cu, Pr, Tb, Ce, La, Dy, Mn and Ag one or more.
2. double-function light conversion agent according to claim 1, is characterized in that, alkaline-earth metal fluoride Ca 1-xn xf 2for unitary alkaline-earth metal fluoride or binary alkaline-earth metal fluoride or polynary alkaline-earth metal fluoride.
3. the preparation method of the double-function light conversion agent described in claim 1 or 2, it is characterized in that, design according to molecular formula, rare earth ion and inorganic salt solution are mixed in molar ratio, under agitation condition, forms co-precipitation, centrifugation, after washing and drying, under reducing atmosphere, in microwave, high fire reacts 10 ~ 20 minutes or in 800 DEG C ~ 1200 DEG C high-temperature roastings 2 ~ 4 hours, namely obtains product; Described reducing atmosphere is the mixture of carbon monoxide or hydrogen and nitrogen; By roasting under throw out and fusing assistant and reducing atmosphere; Described fusing assistant is NaF, CaF 2, BaF 2, Li 2cO 3, K 2cO 3, CaCl 2, KCl, NaCl, NH 4cl, H 3bO 3in one or more.
CN201210335279.XA 2012-09-11 2012-09-11 Double-function light conversion agent and preparation method thereof Active CN103160277B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210335279.XA CN103160277B (en) 2012-09-11 2012-09-11 Double-function light conversion agent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210335279.XA CN103160277B (en) 2012-09-11 2012-09-11 Double-function light conversion agent and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103160277A CN103160277A (en) 2013-06-19
CN103160277B true CN103160277B (en) 2015-08-19

Family

ID=48583820

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210335279.XA Active CN103160277B (en) 2012-09-11 2012-09-11 Double-function light conversion agent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103160277B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106941915A (en) * 2017-03-24 2017-07-14 滁州恒盛农业科技有限公司 A kind of method that Muscari botryoides is planted with Bifunctional light conversion thin
RU2715604C1 (en) * 2019-06-07 2020-03-02 Федеральное государственное бюджетное учреждение науки Сибирский федеральный научный центр агробиотехнологий Российской академии наук (СФНЦА РАН) Method of producing healthier potato minitubers

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1065527A2 (en) * 1999-07-02 2001-01-03 Agfa-Gevaert naamloze vennootschap Radiation image read-out method and apparatus
CN101845302A (en) * 2010-05-05 2010-09-29 华南农业大学 Difunctional light conversion agent for agricultural film and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1065527A2 (en) * 1999-07-02 2001-01-03 Agfa-Gevaert naamloze vennootschap Radiation image read-out method and apparatus
CN101845302A (en) * 2010-05-05 2010-09-29 华南农业大学 Difunctional light conversion agent for agricultural film and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Application of rare-earth complexes for photovoltaic precursors;Katsuyasu Kawano et. al.;《Solar Energy Materials and Solar Cells》;19971130;第48卷;35-41 *
Fluorescence properties of Eu2+ ions in mixed fluoride crystals M1-xNxF2(M,N=Ca,Sr,Ba);Christophe Dujardin et. al.;《Journal of Luminescence》;19921231;第53卷;444-446 *
Luminescence and energy transfer in CaF2 slightly doped with europium and manganese;U Galdi&ntilde;o G et al.;《J. Phys.: Condens. Matter》;19901231;第2卷;6071-6078 *
Photoionization yield in the doubly doped SrF2:Eu,Sm;Robert L. Fuller et al.;《PHYSICAL REVIEW B》;19901231;第43卷(第1期);27-35 *

Also Published As

Publication number Publication date
CN103160277A (en) 2013-06-19

Similar Documents

Publication Publication Date Title
CN103160010B (en) Difunctional light conversion master batches and preparation method thereof
CN103172921B (en) Bifunctional light conversion thin film and preparation method thereof
CN103160011B (en) Plant cultivation method
CN105295188A (en) Nitride red light conversion film and preparation method thereof
CN103709678B (en) Light-converting film and preparation method thereof
CN103710022B (en) Light-converting agent and preparation method thereof, turn light master batch and preparation method thereof
WO2022002217A1 (en) Light conversion film capable of promoting plant growth and preparation method therefor
Zhou et al. A potential red phosphor ZnMoO4: Eu3+ for light-emitting diode application
CN105713288B (en) One kind turns light conversion farm film and preparation method and application
JP2010511077A (en) Nitrogen oxide luminescent material, production method and application thereof
CN110157430A (en) One plant growth fluorescent powder and preparation method thereof
CN1887942B (en) Weather resistant light-converting luminous farm film and its making process
CN109874803B (en) Fluorescent powder capable of promoting plant growth and preparation method thereof
CN105482816A (en) Nitride red light conversion master batch and preparation method thereof
CN105400515A (en) Light emitting material and preparation method thereof
CN103160008A (en) Light conversion film and preparation method thereof
CN101280070B (en) Light conversion agent composition and preparation thereof, preparation of light conversion agricultural film
CN103160277B (en) Double-function light conversion agent and preparation method thereof
CN108864158A (en) A kind of four core rare-earth terbium complex and preparation method thereof and application as luminescent material
Yi et al. KGd (MoO4) 2: Eu3+ as a promising red phosphor for light-emitting diode application
CN103160009B (en) Turn light master batch and preparation method thereof
Haque et al. Eu3+-activated potential red-emitting phosphor for solid-state lighting
Ma et al. Study on synthesis and luminescent properties of Mn4+ doped (Gd, Y) 3Al5O12 phosphor
CN102618271B (en) A kind of white light LEDs single-matrix fluorescent material and preparation method thereof
CN103160276B (en) Ruddiness light-converting agent of ruddiness light-converting agent and preparation method thereof, coating and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant