CN1320079C - Nano rare earth optical transfer agent in bionic state, Nano rare earth optical transfer agricultural film in bionic state, and preparation method thereof - Google Patents
Nano rare earth optical transfer agent in bionic state, Nano rare earth optical transfer agricultural film in bionic state, and preparation method thereof Download PDFInfo
- Publication number
- CN1320079C CN1320079C CNB2005100389326A CN200510038932A CN1320079C CN 1320079 C CN1320079 C CN 1320079C CN B2005100389326 A CNB2005100389326 A CN B2005100389326A CN 200510038932 A CN200510038932 A CN 200510038932A CN 1320079 C CN1320079 C CN 1320079C
- Authority
- CN
- China
- Prior art keywords
- light
- rare
- earth
- clay
- acid
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a nanometer rare earth light-converting agent in the bionic state, which is prepared by that the intercalation is carried out on a stable coordination compound formed by nitrate or hydrochloride of trivalent europium, nitrate or hydrochloride doped with lanthanum, samarium, gadolinium, yttrium and cerium, organic aromatic carboxylic acid and long-chain organic ligand, and clay; the chemical formula is M<1-x>Eu<x>L<m>N<n>clay, wherein M is lanthanum, samarium, gadolinium, yt or cerium, and N is long-chain organic ligand of which the structure is [(RO) [3]Si<y>R<1>NR<2>R<3>R<4>X<->. Clay is layer silicate. The light-converting agricultural film prepared by the light-converting agent comprises 100 of polyolefin and 0.005 to 5 of nanometer rare earth light-converting agent in bionic state. The present invention converts ultraviolet light to red orange light, bluish violet light and blue light having strong photosynthesis and infrared light increasing the temperature in sheds in order to adapt to the requirements of the growth of different crops. The luminous intensity of the light-converting film of the present invention can be enhanced by more than 100% even 129% to the utmost extent.
Description
Technical field
The present invention relates to a kind of agricultural polymer polyolefin film and used light-converting agent system thereof, and the preparation method of this optical transfer agricultural film, particularly a kind ofly convert UV-light the nano bionic attitude rare-earth light conversion agent system of blue red wave band and infrared light to and by nano bionic attitude Light Transform Farm Film Doped with Rare Earth of this light-converting agent preparation and preparation method thereof.
Background technology
Agricultural is related to national economy, is the basis of national economy, and the agricultural plastic film of one of China's agricultural three large-scale means of production is the industry of state key development.The application quantity of 2000 annual China agricultural films is about 930,000 tons, and expecting agricultural film in 2010 will be above 2,000,000 ton, and market outlook are very wide.Plastic sheeting for farm use light conversion designs principle is according to the light ecological principle, in agricultural film, introduce light-converting agent to realize transform light energy, optical transfer agricultural film can change into most of UV-light in the sunlight blood orange light (600-640-710nm) that helps crop growth and royal purple light and the blue or green light (480-450-400-380nm) with bionical attitude feature, improves light quality, raising luminous energy comprehensive utilization ratio, the growth that helps crop of moulding the canopy greenhouse and seeing through, the purpose that promotes the precocious volume increase of crop to reach.
Rare earth Eu (III) organic coordination compounds is a class light energy transforming composite, also is to study maximum classes at present both at home and abroad.The report of domestic and international relevant light-converting film, for example CN1105040A, CN1338500A, CN1491973A, CN1483786A patent application, point out that the rare optical transfer agricultural film of going up that contains light-converting agent Eu (III) title complex can strengthen the crop photosynthesis effect, make the plant development stalwartness, improve quality and volume increase.Increase production about 14% as tomato, cucumber, strawberry.Input-output ratio is 1: 2 ~ 12, but there is the problem of following several respects in this class light-converting film: the rare earth compounding light-converting agent only produces single light (as ruddiness), does not therefore have bionical completely attitude feature; Under action of ultraviolet ray, the light stability of light-converting film is relatively poor, and it is fast to change optical attenuation; Rare-earth light conversion agent and polymkeric substance are done the time spent at present, be that the light-converting agent powder is doped in the polymkeric substance mostly, form " doping type rare earth high polymer ", there are shortcomings such as dispersion is inhomogeneous, easy loss in light-converting agent in polymer matrix, some photothermal converting agent even and some auxiliary agent of plastic sheeting for farm use between have undesirable action, some physical and mechanical properties of plastic sheeting for farm use is had certain influence; There is the ruddiness effect in agricultural light-converting film, because the effect of atmospheric scattering, sunlight arrives the loss of royal purple light when moulding the canopy greenhouse apparently higher than blood orange light, and at present most agricultural light-converting film all is that UV-light is converted to blood orange light, and it is not very good to the photosynthesis of plants and the promoter action of growing only to increase blood orange light, and if blood orange light strong excessively, can produce the heat accumulation effect, make temperature of shed too high, hinder plant growth, even can burn out crop withered.
Summary of the invention
In order to overcome the problem that exists in the prior art, the invention provides a class nano bionic attitude rare-earth light conversion agent; And by the nano bionic attitude Light Transform Farm Film Doped with Rare Earth of this light-converting agent preparation, the infrared light (720～800nm) that this nano bionic attitude Light Transform Farm Film Doped with Rare Earth can become have the blood orange light (600-650-710nm) that helps crop growth of bionical attitude feature and royal purple light and blue or green light (480-450-400-380nm) with the phototransformation of sunlight medium ultraviolet and can improve the canopy temperature.
Nano bionic attitude rare-earth light conversion agent of the present invention (system), this light-converting agent is the compound light-converting agent of a kind of organic/inorganic (system), be nitrate or hydrochloride with the trivalent europium, the nitrate of doping lanthanum, samarium, gadolinium, yttrium, cerium or hydrochloride, organic aromatic carboxylic acid, the formed stable complex of long-chain organic ligand and clay carry out the formed light-converting agent of intercalation (system), it is characterized in that component constitutes:
M
1-xEu
xL
mN
n/ clay, 0＜X＜1 wherein, m=2-10, n=1-3; M is the arbitrary proportion combination of lanthanum La, samarium Sm, gadolinium Gd, yttrium Y, cerium Ce and one or two or three compositions in them; L is organic aromatic carboxylic acid class part, is C
1-C
18A kind of or the two or three composition combination of alkylbenzoic acid, benzaminic acid, salicylic acid or phthalic acid or styracin or naphthoic acid; N is that structure is [(RO)
3Si]
yR
1N
+R
2R
3R
4X
-The long-chain organic ligand, y=0-1; Clay is a layered silicate.
The long-chain organic ligand that the present invention was suitable for is that structure is [(RO)
3Si]
yR
1N
+R
2R
3R
4X
-The long-chain organic ligand.Wherein: R is CH
3Or C
2H
5R
1For-CH
2-or CH
3Or-C
3H
6-or C
3H
7R
2Be CH
3Or C
2H
5Or-CH
2CH
2OH; R
3Be CH
3Or C
2H
5Or-CH
2CH
2OH; R
4Can be chain alkyl, as dodecyl, hexadecyl, octadecyl; Can be aliphatics vinylformic acid and ester derivative thereof also, as CH
2=CHCOO C
2H
4-or CH
2=C (CH
3) COOC
2H
4-; X is Cl or Br.
The clay that the present invention was suitable for is inorganics-layered silicate that a class has laminate structure, and its cationic exchange total volume is 70～120meq/100g.
The polymkeric substance light-converting film (nano bionic attitude Light Transform Farm Film Doped with Rare Earth) that contains nano bionic attitude rare-earth light conversion agent of the present invention, its feed composition and weight part content are as follows:
Nano bionic attitude rare-earth light conversion agent (system) 0.005～5
The present invention can reach by following requirement:
The polyolefine that the present invention was suitable for is polyvinyl chloride (PVC) or polyethylene (PE) or ethylene-vinyl acetate copolymer (EVA).
The present invention is with light-converting agent M
1-xEu
xL
mN
nAs a kind of novel intercalator, the sheet interlayer that inserts layered silicate forms a class functional type polyorganosilicate mixture [nano bionic attitude rare-earth light conversion agent (system)]; Polymkeric substance being inserted nano bionic attitude rare-earth light conversion agent reacts again, the disperse phase that has light-converting agent is peeled off be nano level individual layer clay lamella, evenly be filled in the polymeric matrix, thereby strengthened the dispersiveness of powder and the mechanical property of fluorescence intensity and polymkeric substance also is improved.The infrared light that above-mentioned bionical attitude Light Transform Farm Film Doped with Rare Earth not only can be efficiently converts the UV-light of different-waveband the strongest blood orange light of light and effect and royal purple light and blue or green light to and can improve the canopy temperature, and by changeing the adjusting and the variation of light system, can obtain the light conversion agent of different blue red strength ratios, with the growth demand that adapts to Different Crop (emission band with plant chlorophyll absorb basic spectrum consistent) and can solve poor stability that agricultural light-converting film exists, change optical attenuation soon and the ruddiness effect.
The preparation method's of nano bionic attitude Light Transform Farm Film Doped with Rare Earth of the present invention step is as follows:
Nitrate or hydrochloride with the trivalent europium, the nitrate of doping lanthanum, samarium, gadolinium, yttrium, cerium or hydrochloride, organic aromatic carboxylic acid, long-chain organic ligand, (0.01～0.9) in molar ratio: (0.1～0.99): (2～10): (1～3) obtains the novel rare-earth light conversion agent of a class 20～200 ℃ of reactions 3～6 hours;
With 0.5～100 part of rare-earth light conversion agent and cation exchange capacity is 0.5～100 part of the clay of 70～120meq/100g, high-speed stirring in the presence of 20～2000 parts dispersion medium, form uniform material, 20～200 ℃ of reactions 3～6 hours, with the product of gained through washing, dry, pulverize after, obtain functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent);
0.005～5 part of above-mentioned nano bionic attitude rare-earth light conversion agent is scattered in 100 parts of polyolefine (polyvinyl chloride or polyethylene or ethylene-vinyl acetate copolymer) behind blowing or flow casting molding, just obtains nano bionic attitude Light Transform Farm Film Doped with Rare Earth.
The invention has the beneficial effects as follows: the rare-earth organic complex light conversion agent that the present invention adopts can not only improve the luminous efficiency of light-converting agent, but also can be used as a kind of novel intercalator, inserts the sheet interlayer of layered silicate, forms nano bionic attitude rare-earth light-converting system; The disperse phase that has light-converting agent is peeled off be nano level individual layer clay lamella, evenly be filled in the polymeric matrix, thereby strengthened the dispersiveness of powder, fluorescence intensity and fluorescence lifetime, the luminous intensity of the corresponding nano bionic attitude of the luminous strength ratio rare-earth light conversion agent of institute's synthetic nano bionic attitude rare-earth light-converting film improves more than 100%, through one batch field experiment (5 months), the optical transfer agricultural film fluorescence intensity still keeps 100%, more surprisingly because photocatalytic effect and special nanometer size effect, the prolongation in time of optical transfer agricultural film fluorescence intensity strengthens gradually, the highlyest strengthen 129%, later on fluorescence intensity descends again gradually, but button canopy optical transfer agricultural film fluorescence intensity the and just fluorescence intensity during the button canopy is suitable when finishing.
The auxiliary agent of nano bionic attitude rare-earth light conversion agent of the present invention and plastic sheeting for farm use has good matching, can not only be used for ordinary agricultural membrane and make optical transfer agricultural film, can also be widely used in do not have to drip, the plastic sheeting for farm use of anti-marquis; And the mechanical property of plastic sheeting for farm use can also improve, thereby prolonged the work-ing life of light-converting film.
The infrared light that the nano bionic attitude rare-earth light conversion agent that the present invention adopts can be efficiently converts the UV-light of different-waveband the strongest blood orange light of light and effect and royal purple light and blue or green light to and can improve the canopy temperature.And, can obtain the light conversion agent of different blue red strength ratios, to adapt to the growth demand of Different Crop by changeing the adjusting and the variation of light system.
The present invention has solved well how light-converting agent carries out nano-dispersed and the light-converting agent photostabilization is poor, has changeed a series of problems such as optical attenuation is fast, ruddiness effect, cost height owing to adopted nano-intercalation technology.
The present invention can impel farm crop to gather in the crops, make plant development stalwartness (plant dry substance accumulation increases, the flowers and fruits number improves, chlorophyll content rises, promote plant nutrient absorption etc.) ahead of time, quality improves (remarkable increase all being arranged as plant pigments, VITAMIN, solid, a sugar part equal size), increases output more than 20% (existing optical transfer agricultural film makes tomato, cucumber, strawberry increase production about 14%), input-output ratio high 1: 30 (existing optical transfer agricultural film input-output ratio is 1: 2～12).
Preparation method of the present invention is simple, is easy to suitability for industrialized production, has tangible economic benefit, ecological benefits and social benefit.
Description of drawings
The exciting light spectrogram of Fig. 1 nano bionic attitude rare-earth light-converting film
Fig. 2-1～2-6 is the emmission spectrum figure of the nano bionic attitude rare-earth light-converting film of different blue red strength ratios
The emmission spectrum figure of Fig. 3 different time nano bionic attitude rare-earth light-converting film
Among the figure, ordinate is a relative intensity, and abscissa is a wavelength.
Embodiment
In order to be illustrated more clearly in the present invention, enumerate following examples, but these there is not any restriction to scope of the present invention.
Embodiment 1
With (La
0.9Sm
0.09Eu
0.01) Cl
3, α-Nai Jiasuan, 3-triethoxysilylpropyl dimethyl dodecyl chlorination ammonium obtained a kind of novel rare-earth light-converting agent 20～40 ℃ of reactions 6 hours in 1: 4: 2 in molar ratio.With 0.5 part of light-converting agent and cation exchange capacity is 0.6 part of the clay of 80meq/100g, and high-speed stirring in the presence of 20 parts dispersion medium water forms uniform material, reacts 3～4 hours at 20～200 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 0.005 part of nano bionic attitude rare-earth light conversion agent is scattered in 100 parts of PVC polymkeric substance, just obtains nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 2
With (La
0.7Gd
0.1Eu
0.2) NO
3, p-methylbenzoic acid, 3-trimethoxy silicon propyl group methylethyl cetyl chloride ammonium obtained a kind of novel rare-earth light-converting agent 40～60 ℃ of reactions 4 hours in 1: 5: 1 in molar ratio.With 1 part of light-converting agent and cation exchange capacity is 10 parts of the clays of 90meq/100g, and high-speed stirring in the presence of 100 parts dispersion medium ethanol forms uniform material, reacts 3～5 hours at 60～70 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 5 parts of nano bionic attitude rare-earth light conversion agents are scattered among 100 parts of PE, just obtain nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 3
With (Ce
0.4Y
0.2Eu
0.4) Cl
3, β-naphthoic acid, 3-trimethoxy silicon propyl-dimethyl octadecyl bromination ammonium obtained a kind of novel rare-earth light-converting agent 150～200 ℃ of reactions 3 hours in 1: 8: 2 in molar ratio.With 6 parts of light-converting agents and cation exchange capacity is 7 parts of the clays of 80meq/100g, and high-speed stirring in the presence of 200 parts dispersion medium ethanol forms uniform material, reacts 4 hours at 80～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 4 parts of nano bionic attitude rare-earth light conversion agents are scattered among 100 parts of EVA, just obtain nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 4
With (La
0.4Y
0.2Eu
0.4) Cl
3, styracin, 3-triethoxysilylpropyl dimethyl dodecyl chlorination ammonium obtained the stable novel rare-earth light-converting agent of a class formation 60～80 ℃ of reactions 4 hours in 1: 6: 2 in molar ratio.With 4 parts of light-converting agents and cation exchange capacity is 6 parts of the clays of 80meq/100g, and high-speed stirring in the presence of 300 parts dispersion medium forms uniform material, reacts 3～5 hours at 80～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 3 parts of nano bionic attitude rare-earth light conversion agents are scattered among 100 parts of PE, just obtain nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 5
With (Gd
0.2Y
0.2Eu
0.6) Cl
3, to octadecyl phenylformic acid, octadecyl trimethylammonium bromide 1: 10: 3 in molar ratio 100～150 ℃ of reactions 3 hours, obtain the stable novel rare-earth light-converting agent of a class formation.With 10 parts of light-converting agents and cation exchange capacity is 10 parts of the clays of 100meq/100g, and high-speed stirring in the presence of 400 parts dispersion medium forms uniform material, reacts 3 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 2 parts of nano bionic attitude rare-earth light conversion agents are scattered among 100 parts of EVA, just obtain nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 6
With (Gd
0.6Eu
0.4) Cl
3, to hexadecyl phenylformic acid, cetyl trimethylammonium bromide 1: 8: 1 in molar ratio 80～100 ℃ of reactions 5 hours, obtain the stable novel rare-earth light-converting agent of a class formation.With 1 part of light-converting agent and cation exchange capacity is 30 parts of the clays of 70meq/100g, and high-speed stirring in the presence of 400 parts dispersion medium forms uniform material, reacts 4 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 1 part of nano bionic attitude rare-earth light conversion agent is scattered among 100 parts of PE, just obtains nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
With (La
0.8Eu
0.2) Cl
3, para-amino benzoic acid, 3-triethoxysilylpropyl dimethyl cetyl chloride ammonium obtained the stable novel rare-earth light-converting agent of a class formation 80～100 ℃ of reactions 4 hours in 1: 6: 2 in molar ratio.With 3 parts of light-converting agents and cation exchange capacity is 10 parts of the clays of 120meq/100g, and high-speed stirring in the presence of 100 parts dispersion medium forms uniform material, reacts 5 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 0.1 part of nano bionic attitude rare-earth light conversion agent is scattered among 100 parts of PVC, just obtains nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
With (Sm
0.9Eu
0.1) (NO
3)
3, to amylbenzene formic acid, 3-trimethoxy silicon propyl-dimethyl hexadecyl brometo de amonio 1: 7: 1 in molar ratio 30～60 ℃ of reactions 6 hours, obtain the stable novel rare-earth light-converting agent of a class formation.With 5 parts of light-converting agents and cation exchange capacity is 5 parts of the clays of 80meq/100g, and high-speed stirring in the presence of 100 parts dispersion medium forms uniform material, reacts 4 hours at 60～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 0.2 part of nano bionic attitude rare-earth light conversion agent is scattered among 100 parts of EVA, just obtains nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 9
With (Y
0.1Eu
0.9) Cl
3, terephthalic acid, 3-triethoxysilylpropyl methylethyl cetyl chloride ammonium obtained the stable novel rare-earth light-converting agent of a class formation 80～100 ℃ of reactions 6 hours in 1: 2: 1 in molar ratio.With 3 parts of light-converting agents and cation exchange capacity is 3 parts of the clays of 80meq/100g, and high-speed stirring in the presence of 60 parts dispersion medium forms uniform material, reacts 3～6 hours at 20～200 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 0.3 part of nano bionic attitude rare-earth light conversion agent is scattered among 100 parts of EVA, just obtains nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 10
With (La
0.7Sm
0.1Eu
0.2) Cl
3, to dodecyl phenylformic acid, dimethyl hydroxyethyl hexadecyl brometo de amonio mol ratio 1: 6: 3 20～200 ℃ of reactions 5 hours, obtain the stable novel rare-earth light-converting agent of a class formation.With 1 part of light-converting agent and cation exchange capacity is 100 parts of the clays of 90meq/100g, and high-speed stirring in the presence of 2000 parts dispersion medium forms uniform material, reacts 6 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 1.6 parts of nano bionic attitude rare-earth light conversion agents are scattered among 100 parts of EVA, just obtain nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 11
With (La
0.9Sm
0.09Eu
0.01) NO
3, to hexyl benzene formic acid, para-amino benzoic acid, 2-methylacryoyloxyethyl dimethyl 3-trimethoxy silicon propyl ammonium chloride 1: 3: 7 in molar ratio: 2 30～60 ℃ of reactions 6 hours, obtained a class formation and stablized the novel rare-earth light-converting agent.With 2 parts of light-converting agents and cation exchange capacity is 3 parts of the clays of 80meq/100g, and high-speed stirring in the presence of 30 parts dispersion medium forms uniform material, reacts 5 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 1 part of nano bionic attitude rare-earth light conversion agent is scattered among 100 parts of EVA, just obtains nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 12
With (La
0.7Sm
0.29Eu
0.01) Cl
3, to dodecyl phenylformic acid, 2-methylacryoyloxyethyl dimethyl 3-triethoxysilylpropyl brometo de amonio 1: 6: 1.5 in molar ratio 20～200 ℃ of reactions 5 hours, obtain the stable novel rare-earth light-converting agent of a class formation.With 1 part of light-converting agent and cation exchange capacity is 0.5 part of the clay of 90meq/100g, and high-speed stirring in the presence of 10 parts dispersion medium forms uniform material, reacts 6 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 2 parts of nano bionic attitude rare-earth light conversion agents are scattered among 100 parts of EVA, just obtain nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 13
With (La
0.7Sm
0.1Eu
0.2) Cl
3, to dodecyl phenylformic acid, 2-methylacryoyloxyethyl dimethyl 3-triethoxysilylpropyl ammonium chloride 1: 6: 1.5 in molar ratio 20～200 ℃ of reactions 5 hours, obtain the stable novel rare-earth light-converting agent of a class formation.With 1 part of light-converting agent and cation exchange capacity is 3 parts of the clays of 90meq/100g, and high-speed stirring in the presence of 20 parts dispersion medium forms uniform material, reacts 6 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; With 4 parts of nano bionic attitude rare-earth light conversion agents, be scattered among 100 parts of EVA, just obtain nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 14
With (Gd
0.4Y
0.2Eu
0.4) Cl
3, to dodecyl phenylformic acid, Dodecyl trimethyl ammonium chloride 1: 6: 2 in molar ratio 20～200 ℃ of reactions 5 hours, obtain the stable novel rare-earth light-converting agent of a class formation.With 5 parts of light-converting agents and cation exchange capacity is 10 parts of the clays of 120meq/100g, and high-speed stirring in the presence of 100 parts dispersion medium water formed uniform material, 60～80 ℃ of reactions 3 hours.The product of gained is functional type polyorganosilicate mixture after washing, drying, pulverizing; 1 part of mixture is scattered in the polymkeric substance of 100 parts of PE-EVA MULTILAYER COMPOSITE, just obtains nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 15
With (La
0.7Gd
0.1Eu
0.2) NO
3, to dodecyl phenylformic acid, methyl dihydroxy ethyl dodecyl chlorination ammonium 1: 6: 2 in molar ratio 20～200 ℃ of reactions 6 hours, obtain the stable novel rare-earth light-converting agent of a class formation.With 1 part of light-converting agent and cation exchange capacity is 3 parts of the clays of 90meq/100g, and high-speed stirring in the presence of 20 parts dispersion medium forms uniform material, reacts 6 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 1 part of nano bionic attitude rare-earth light conversion agent is scattered among 100 parts of PVC, just obtains nano bionic attitude Light Transform Farm Film Doped with Rare Earth behind blowing or the flow casting molding.
Embodiment 16
With (La
0.49Sm
0.5Eu
0.01) NO
3, to dodecyl phenylformic acid, dimethyl hydroxyethyl hexadecyl brometo de amonio mol ratio 1: 6: 3 20～200 ℃ of reactions 5 hours, obtain the stable novel rare-earth light-converting agent of a class formation.With 1 part of light-converting agent and cation exchange capacity is 100 parts of the clays of 90meq/100g, and high-speed stirring in the presence of 2000 parts dispersion medium forms uniform material, reacts 6 hours at 70～100 ℃.The product of gained is functional type polyorganosilicate mixture (nano bionic attitude rare-earth light conversion agent) after washing, drying, pulverizing; 0.02 part of nano bionic attitude rare-earth light conversion agent is scattered among 100 parts of PE, blow hope or flow casting molding after just obtain nano bionic attitude Light Transform Farm Film Doped with Rare Earth.
Embodiment 17
Basic identical with the foregoing description, but following change is arranged: the alkylbenzoic acid in wherein organic aromatic carboxylic acid class part adopts the undecyl phenylformic acid.
Embodiment 18
Basic identical with the foregoing description, but following change is arranged: the alkylbenzoic acid in wherein organic aromatic carboxylic acid class part adopts the certain herbaceous plants with big flowers yl benzoic acid.
Embodiment 19
Basic identical with the foregoing description, but following change is arranged: the alkylbenzoic acid in wherein organic aromatic carboxylic acid class part adopts nonyl benzene formic acid.
Basic identical with the foregoing description, but following change is arranged: the alkylbenzoic acid in wherein organic aromatic carboxylic acid class part adopts heptyl benzene formic acid.
Embodiment 21
Basic identical with the foregoing description, but following change is arranged: the alkylbenzoic acid in wherein organic aromatic carboxylic acid class part adopts butylbenzoic acid.
Embodiment 22
Basic identical with the foregoing description, but following change is arranged: the alkylbenzoic acid in wherein organic aromatic carboxylic acid class part adopts the n-propyl benzoate.
Embodiment 23
Basic identical with the foregoing description, but following change is arranged: the alkylbenzoic acid in wherein organic aromatic carboxylic acid class part adopts ethyl benzoate.
Embodiment 24
Basic identical with the foregoing description, but following change is arranged: the alkylbenzoic acid in wherein organic aromatic carboxylic acid class part adopts salicylic acid.
Embodiment 25
Basic identical with the foregoing description, but following change is arranged: wherein the dimethyl hydroxyethyl hexadecyl brometo de amonio in the long-chain organic ligand adopts 2-methylacryoyloxyethyl dimethyl 3-trimethoxy silicon propyl ammonium chloride.
Embodiment 26
Basic identical with the foregoing description, but following change is arranged: wherein the 2-methylacryoyloxyethyl dimethyl 3-trimethoxy silicon propyl ammonium chloride in the long-chain organic ligand adopts acrylyl oxy-ethyl dimethyl 3-triethoxysilylpropyl brometo de amonio.
Claims (5)
1, a kind of nano bionic attitude rare-earth light conversion agent, this light-converting agent is the compound light-converting agent of a kind of organic/inorganic, be nitrate or hydrochloride with the trivalent europium, the nitrate of doping lanthanum, samarium, gadolinium, yttrium, cerium or hydrochloride, organic aromatic carboxylic acid, the formed stable complex of long-chain organic ligand and clay carry out the formed light-converting agent of intercalation, it is characterized in that its feed composition and weight part content are as follows:
M
1-xEu
xL
mN
n/ clay, 0＜X＜1 wherein, m=2-10, n=1-3; M is the arbitrary proportion combination of lanthanum, samarium, gadolinium, yttrium, cerium and one or two or three compositions in them; L is organic aromatic carboxylic acid class part, and this organic aromatic carboxylic acid class part is C
1-C
18The combination of a kind of or two or three composition of alkylbenzoic acid, benzaminic acid, salicylic acid or phthalic acid or styracin or naphthoic acid; N is that structure is [(RO)
3Si]
yR
1N
+R
2R
3R
4X
-The long-chain organic ligand, y=0-1; Clay is a layered silicate;
Described long-chain organic ligand is that structure is [(RO)
3Si]
yR
1N
+R
2R
3R
4X
-The long-chain organic ligand, wherein: R is CH
3Or C
2H
5R
1For-CH
2-or CH
3Or-C
3H
6-or C
3H
7R
2Be CH
3Or C
2H
5Or-CH
2CH
2OH; R
3Be CH
3Or C
2H
5Or-CH
2CH
2OH; R
4It is chain alkyl; Or aliphatics vinylformic acid and ester derivative thereof; X is Cl or Br;
Described clay is the inorganics-layered silicate with laminate structure.
2,, it is characterized in that described chain alkyl is selected from dodecyl, hexadecyl or octadecyl according to the described nano bionic attitude of claim 1 rare-earth light conversion agent; Described aliphatics vinylformic acid and ester derivative thereof are selected from CH
2=CHCOOC
2H
4-or CH
2=C (CH
3) COOC
2H
4-;
Described clay, its cationic exchange total volume is 70～120meq/100g.
3, a kind of nano bionic attitude Light Transform Farm Film Doped with Rare Earth by the preparation of the described nano bionic attitude of claim 1 rare-earth light conversion agent is characterized in that the weight ratio of component and each component is as follows:
Polyolefine 100
Nano bionic attitude rare-earth light conversion agent 0.005～5
Wherein, polyolefine is polyvinyl chloride or polyethylene or ethylene-vinyl acetate copolymer.
4, the preparation method of the described nano bionic attitude of a kind of claim 3 Light Transform Farm Film Doped with Rare Earth, step is as follows:
Nitrate or hydrochloride with the trivalent europium, the nitrate of doping lanthanum, samarium, gadolinium, yttrium, cerium or hydrochloride, organic aromatic carboxylic acid, long-chain organic ligand, 0.01～0.09: 0.91～0.99: 2～10: 1～3 20～200 ℃ of reactions 3～6 hours in molar ratio, obtained rare-earth light conversion agent;
With 0.5～100 part of rare-earth light conversion agent and cation exchange capacity is 0.5～100 part of the clay of 70～120meq/100g, high-speed stirring in the presence of 20～2000 parts dispersion medium, form uniform material, 20～200 ℃ of reactions 3～6 hours, with the product of gained through washing, dry, pulverize after, obtain functional type polyorganosilicate mixture: nano bionic attitude rare-earth light conversion agent;
0.005～5 part of above-mentioned nano bionic attitude rare-earth light conversion agent is scattered in just obtains nano bionic attitude Light Transform Farm Film Doped with Rare Earth in 100 parts of polyolefine behind blowing or flow casting molding, described polyolefine is selected from: polyvinyl chloride or polyethylene or ethylene-vinyl acetate copolymer;
The component of described rare-earth light conversion agent constitutes:
M
1-xEu
xL
mN
n/ clay, 0＜X＜1 wherein, m=2-10, n=1-3; M is the arbitrary proportion combination of lanthanum, samarium, gadolinium, yttrium, cerium and one or two or three compositions in them; L is organic aromatic carboxylic acid class part, and this organic aromatic carboxylic acid class part is C
1-C
18The combination of a kind of or two or three composition of alkylbenzoic acid, benzaminic acid, salicylic acid or phthalic acid or styracin or naphthoic acid; N is that structure is [(RO)
3Si]
yR
1N
+R
2R
3R
4X
-The long-chain organic ligand, y=0-1; Clay is a layered silicate;
Described long-chain organic ligand is that structure is [(RO)
3Si]
yR
1N
+R
2R
3R
4X
-The long-chain organic ligand, wherein: R is CH
3Or C
2H
5R
1For-CH
2-or CH
3Or-C
3H
6-or C
3H
7R
2Be CH
3Or C
2H
5Or-CH
2CH
2OH; R
3Be CH
3Or C
2H
5Or-CH
2CH
2OH; R
4It is chain alkyl; Or aliphatics vinylformic acid and ester derivative thereof; X is Cl or Br;
Described clay is the inorganics-layered silicate with laminate structure.
According to the preparation method of the described nano bionic attitude of claim 4 Light Transform Farm Film Doped with Rare Earth, it is characterized in that 5, described chain alkyl is selected from dodecyl, hexadecyl or octadecyl; Described aliphatics vinylformic acid and ester derivative thereof are selected from CH
2=CHCOOC
2H
4-or CH
2=C (CH
3) COOC
2H
4-;
Described clay, its cationic exchange total volume is 70～120meq/100g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100389326A CN1320079C (en) | 2005-04-18 | 2005-04-18 | Nano rare earth optical transfer agent in bionic state, Nano rare earth optical transfer agricultural film in bionic state, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100389326A CN1320079C (en) | 2005-04-18 | 2005-04-18 | Nano rare earth optical transfer agent in bionic state, Nano rare earth optical transfer agricultural film in bionic state, and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1687305A CN1687305A (en) | 2005-10-26 |
| CN1320079C true CN1320079C (en) | 2007-06-06 |
Family
ID=35305347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100389326A Expired - Fee Related CN1320079C (en) | 2005-04-18 | 2005-04-18 | Nano rare earth optical transfer agent in bionic state, Nano rare earth optical transfer agricultural film in bionic state, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1320079C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994082A (en) * | 2012-12-13 | 2013-03-27 | 昆明理工大学 | Bismuth ion-doped germinate white light phosphor and preparation method thereof |
| CN105592702A (en) * | 2013-09-27 | 2016-05-18 | 骊住株式会社 | Antibacterial treating agent, antibacterial treatment method and plumbing member |
| US9943081B2 (en) | 2013-09-27 | 2018-04-17 | Lixil Corporation | Antibacterial/antiviral coating material, and method for forming antibacterial/antiviral coating film |
| US10550274B2 (en) | 2015-07-01 | 2020-02-04 | Lixil Corporation | Antibacterial/antiviral coating agent |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241175B (en) * | 2011-05-11 | 2013-11-27 | 沈阳市晨光塑料制品厂 | High-light-quality solar production-increasing greenhouse film and preparation method thereof |
| CN103087393B (en) * | 2013-02-19 | 2014-12-31 | 刘德元 | Converted blue light long-life-light-conversion multifunctional mulching film |
| CN103937493B (en) * | 2014-05-12 | 2016-01-06 | 福建师范大学 | A kind of preparation method of white light polynite fluorescent material of ultraviolet excitation |
| CN105038773A (en) * | 2015-08-07 | 2015-11-11 | 复旦大学 | High-luminescence-property silicon nanometer particle fluorescent powder and light-emitting film and preparing method thereof |
| CN106279224B (en) * | 2016-08-08 | 2018-07-17 | 洛阳师范学院 | A kind of doped yttrium dysprosium complex rareearth magnetic material and preparation method thereof |
| CN106279010B (en) * | 2016-08-08 | 2018-10-09 | 洛阳师范学院 | A kind of doped yttrium europium complex rareearth magnetic material and preparation method thereof |
| CN106279225B (en) * | 2016-08-08 | 2018-07-17 | 洛阳师范学院 | A kind of doped yttrium Gd coordination compound rareearth magnetic material and preparation method thereof |
| CN106279222B (en) * | 2016-08-08 | 2018-07-17 | 洛阳师范学院 | A kind of doped yttrium terbium coordination compound rare earth luminescent material and preparation method thereof |
| CN106947462A (en) * | 2017-05-11 | 2017-07-14 | 长春工业大学 | A kind of rare earth organic light conversion agents and preparation method thereof |
| CN109232930B (en) * | 2018-08-07 | 2021-04-27 | 陕西科技大学 | Polymer bionic texture film with excellent mechanical and tribological performances and preparation method thereof |
| US20240294828A1 (en) * | 2019-10-11 | 2024-09-05 | Solvay Sa | Use of silicates in a greenhouse film for increasing fruit development of plants |
| CN112715230A (en) * | 2020-12-29 | 2021-04-30 | 山东森博斯特塑胶科技有限公司 | Light adjusting film capable of promoting normal growth of crops in greenhouse and preparation method thereof |
| CN113480997A (en) * | 2021-07-09 | 2021-10-08 | 济南大学 | Multinuclear rare earth doped organic complex light conversion agent and light conversion master batch, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431255A (en) * | 2003-01-28 | 2003-07-23 | 南京师范大学 | Luminous nano composite material and its preparing method |
| CN1431254A (en) * | 2003-01-28 | 2003-07-23 | 南京师范大学 | Indoor temp prepared optical transfer film of polymer/polycaryon terrae rare organosilicon giving out light in mixed blue with red |
-
2005
- 2005-04-18 CN CNB2005100389326A patent/CN1320079C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431255A (en) * | 2003-01-28 | 2003-07-23 | 南京师范大学 | Luminous nano composite material and its preparing method |
| CN1431254A (en) * | 2003-01-28 | 2003-07-23 | 南京师范大学 | Indoor temp prepared optical transfer film of polymer/polycaryon terrae rare organosilicon giving out light in mixed blue with red |
Non-Patent Citations (4)
| Title |
|---|
| 我国稀土转光农膜的研究进展 王则民，稀土，第21卷第5期 2000 * |
| 我国稀土转光农膜的研究进展 王则民，稀土，第21卷第5期 2000;稀土配位化合物光转换剂的设计 李建宇等，中国塑料，第13卷第1期 1999;铕(III)多核配合物的形成及其荧光增强效应 刘德文等，发光学报，第20卷第3期 1999 * |
| 稀土配位化合物光转换剂的设计 李建宇等，中国塑料，第13卷第1期 1999 * |
| 铕(III)多核配合物的形成及其荧光增强效应 刘德文等，发光学报，第20卷第3期 1999 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994082A (en) * | 2012-12-13 | 2013-03-27 | 昆明理工大学 | Bismuth ion-doped germinate white light phosphor and preparation method thereof |
| CN102994082B (en) * | 2012-12-13 | 2014-07-02 | 昆明理工大学 | Bismuth ion-doped germinate white light phosphor and preparation method thereof |
| CN105592702A (en) * | 2013-09-27 | 2016-05-18 | 骊住株式会社 | Antibacterial treating agent, antibacterial treatment method and plumbing member |
| CN105592702B (en) * | 2013-09-27 | 2018-01-05 | 骊住株式会社 | Antibiosis additive, antibacterial processing method and sanitary ware part |
| US9943081B2 (en) | 2013-09-27 | 2018-04-17 | Lixil Corporation | Antibacterial/antiviral coating material, and method for forming antibacterial/antiviral coating film |
| US10550274B2 (en) | 2015-07-01 | 2020-02-04 | Lixil Corporation | Antibacterial/antiviral coating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1687305A (en) | 2005-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1320079C (en) | Nano rare earth optical transfer agent in bionic state, Nano rare earth optical transfer agricultural film in bionic state, and preparation method thereof | |
| CN1887942B (en) | Weather resistant light-converting luminous farm film and its making process | |
| CN101781431B (en) | Anti-aging light conversion film and preparation method thereof | |
| CN102775750A (en) | Degradable multiband light conversion ground film and preparation method thereof | |
| CN102250610A (en) | Preparation method of composite ZnO-mesoporous silica nanomaterial | |
| CN103172921B (en) | Bifunctional light conversion thin film and preparation method thereof | |
| CN101280070B (en) | Light conversion agent composition and preparation thereof, preparation of light conversion agricultural film | |
| CN103160010B (en) | Difunctional light conversion master batches and preparation method thereof | |
| CN101020820A (en) | Light transferring agent of bionic organic RE complex, farm light transferring agent therewith and their prpen | |
| CN101434725A (en) | Novel ecology imitating two band optical energy conversion agricultural film and technique for producing the same | |
| CN101434714B (en) | Nano red light conversion agent special for agricultural film and preparation thereof | |
| CN102161249A (en) | Light-splitting spectrum greenhouse film and preparation method thereof | |
| CN101358128A (en) | Rare earth organic complex light conversion agent and preparation method thereof | |
| CN107474353A (en) | A kind of conversion film and preparation method thereof | |
| CN105154069A (en) | Multi-colored adjustable light-emitting material of nitrogen-doped carbon dot coordination rare earth and preparation method thereof | |
| CN117285926B (en) | Alpha, alpha-terpyridyl rare earth organic red light conversion agent and preparation method and application thereof | |
| CN1200046C (en) | Luminous nano composite material and its preparing method | |
| CN1220721C (en) | Indoor temp prepared optical transfer film of polymer/polycaryon terrae rare organosilicon giving out light in mixed blue with red | |
| CN1201848A (en) | Mecerized fabrics and additives and production thereof | |
| CN1211305C (en) | Agricultural double-energy light-converting glass and its making process and usage | |
| CN1315981C (en) | Dual wave section fluorescent material and its preparaton method | |
| CN1286716A (en) | Light-converting material and composition for producing same | |
| CN1338482A (en) | Infrared barrier for high-molecular polymer | |
| CN1594499A (en) | Red long persistence luminescent materials and their synthesis process and use | |
| CN101676361A (en) | Europium-ion-doped barium molybdate nano luminescent powder 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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |