CN1781951A - High molecular samarium ligand, its preparing process and use - Google Patents
High molecular samarium ligand, its preparing process and use Download PDFInfo
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- CN1781951A CN1781951A CN 200510094313 CN200510094313A CN1781951A CN 1781951 A CN1781951 A CN 1781951A CN 200510094313 CN200510094313 CN 200510094313 CN 200510094313 A CN200510094313 A CN 200510094313A CN 1781951 A CN1781951 A CN 1781951A
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- samarium
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Abstract
The high molecular samarium complex is one ternary complex comprising macro molecular ligand, beta-diketone compound and trivalent samarium, and the macro molecular ligand is polyethylene with terminal radical containing 8-hydroxy quinoline unit. The preparation process includes: atom transferring free radical polymerization to synthesize polyethylene with terminal radical containing 8-hydroxy quinoline unit; synthesizing small molecular weight complex with trivalent samarium and beta-diketone; and final coordinating exchange reaction to synthesize the high molecular complex of trivalent samarium. The present invention is used as light converting agent with fluorescent emitting spectrum well fitting the absorption spectrum of chlorophyll, and the obtained high molecular complex of trivalent samarium is well compatible with polyethylene matrix, so that the present invention is especially suitable for use in preparing farm light converting film with high efficiency.
Description
Technical field
The present invention relates to macromolecule rare-earth complexe and preparation technology thereof, especially a kind of polymer-samaric ternary complex and preparation technology thereof, and its application in the preparation light conversion film.
Background technology
The growth of plant depends on absorption and the utilization of photosynthesis to sight, but is not that parts all in the sunlight can be by plant absorbing and utilization.Plant chlorophyll is main blue green light (400-500nm) and the blood orange light (625-700nm) that absorbs in the sunlight in the photosynthesis process.UV-light part in the sunlight not only can not be utilized by plant absorbing, and harmful to the growth of plant.What is more important, the UV-light in the sunlight has very strong Degradation to agricultural film, has a strong impact on the work-ing life of agricultural film.The effect of light conversion film is that the UV-light in the sunlight is converted into visible light, not only can prolong the work-ing life of plastic sheeting for farm use, and can improve the utilising efficiency of photosynthesis of plant to daylight, promote crop yield increase, precocious and improve nutritive ingredient in the crop.
Photothermal converting agent is the core technology in the light conversion film research, adds 1 ‰-8% and just can play significant light transition function in agricultural film.Photothermal converting agent adopts the material that possesses fluorescent characteristic usually, for example, Chinese invention patent CN1079407C discloses a kind of optical conversion agent for agricultural film, promptly be to utilize the fluorescent characteristic of aromatic series organic molecule to obtain, but this method is subjected to the influence of concentration, temperature, solvent purity and pH value of organic compound bigger, and product quality is difficult to guarantee.The photothermal converting agent that is occurred is based on the title complex of micromolecular trivalent europium and beta-diketon in recent years.The beta-diketon that is suitable for comprises (DBM) such as trifluoromethyl thiophene acetone (TTA), methyl ethyl diketone (ACAC), diphenylpropane-1,3-dione(DPPO) (DBM) and two naphthoyl methane.Also often use aromatic carboxylic acid as part in addition in the photothermal converting agent, as 2,6 dioctyl phthalate pyridines, 3 amino pyrazine-2-carboxylic acids etc., promptly disclose among the Chinese invention patent CN1060500C a kind of with the carboxylic acid be part contain the europium photothermal converting agent.
Effect often contains second part in the photothermal converting agent preferably.Second part has enlarged the whole conjugated degree of title complex, helps energy and shifts, and the fluorescence that strengthens title complex is had good synergistic.The second commonly used part comprises nitrogen heterocyclic ring as 1,10-phenanthroline, 22-dipyridyl and contain phosphorous oxides as three n-octyl phosphorus oxide, tributyl phosphate etc.
The small molecules title complex of trivalent europium has stronger fluorescent emission intensity and higher luminous efficiency, and being applied to is also having good effect aspect the raising crop yield in the agricultural film really.But also have problems in actual applications, as document Xue satellite, Li Jianyu, " to the just evaluation of matter of Eu (III) title complex photothermal converting agent spectrum ", spectroscopy and spectroscopic analysis, 2003,23 (4): 766-768 thinks that Eu (III) title complex maximum emission wavelength (614nm) and chlorophyll absorbing wavelength do not match, and this is its inherent defect as photothermal converting agent.On the other hand, micromolecular Eu (III) title complex can not homodisperse in polyethylene film, easily is separated, thereby produces the performance that fluorescent quenching influences material.And thereby the easy photochemical reaction that takes place causes the fluorescence intensity of photothermal converting agent to die down under sun exposure, therefore be that work-ing life of light conversion film of photothermal converting agent is not long with the small molecules title complex, generally can only reach 2-3 month, this point especially can not satisfy the requirement of canopy film.
For addressing the above problem, we wish to adopt the title complex of samaric to prepare the photothermal converting agent that plastic sheeting for farm use is used.The maximum emission wavelength of the title complex of samaric is that 645 nanometers are (corresponding to Sm
3+ 4G
5/2→
6H
9/2Transition), its fluorescence emission peak and chlorophyllous absorption peak are identical substantially.And, the raw material Sm of Sm (III) title complex
2O
3Price only be Eu (III) title complex raw material Eu
2O
31/5.The title complex of Sm (III) and corresponding Eu (III) cooperate compare its fluorescence a little less than, but this shortcoming can remedy by the suitable amount of increase Sm (III) title complex.Yet, the difficulty that runs into is, micromolecular Sm (III) title complex is the same with micromolecular Eu (III) title complex, existing in polyethylene film can not homodisperse, easily be separated, thereby produce the performance that fluorescent quenching influence material, thereby and photochemical reaction easily takes place under sun exposure cause the fluorescence intensity of photothermal converting agent to die down, the problem that do not grow work-ing life.For this reason, need seek a kind of new samarium complex, to adapt to the requirement of the photothermal converting agent that uses as plastic sheeting for farm use.
Summary of the invention
The purpose of this invention is to provide a kind of new samarium complex, samarium complex can not be dispersed in the problem in the polyethylene film in the solution prior art;
Another goal of the invention of the present invention provides the preparation method of this samarium complex;
The 3rd goal of the invention of the present invention provides the purposes of this samarium complex.
For achieving the above object, the technical solution used in the present invention is: a kind of high molecular samarium ligand, it is the ternary complex that is made of macromolecular ligand, beta-diketone compounds and samaric, described macromolecular ligand is that end group contains the unitary polystyrene of oxine, and the molecular weight of polystyrene is between 2600-10000.
In the technique scheme, the molecular weight of polystyrene has a significant impact the samarium content in the polymer complex, and the fluorescence emission spectrum that therefore also influences the title complex product also has very big influence.The molecular weight of polystyrene is excessive, and the samarium content in the macromolecule ligand is on the low side, can become very weak at the emission peak of red light district.
The preparation method of above-mentioned high molecular samarium ligand comprises the following steps:
(1) with 5-chloromethyl-oxine as initiator, contain the unitary polystyrene of oxine by the synthetic end group of atom transfer radical polymerization;
(2) Samarium chloride and beta-diketone compounds carry out coordination, the small molecules title complex of synthetic samaric and beta-diketon;
(3) polystyrene that contains oxine with end group carries out the coordination permutoid reaction, the high molecular title complex of synthetic samaric as the small molecules title complex of macromolecular ligand and samaric.
In the technique scheme, described atom transition free radical polymerization reaction, coordination reaction are the common reactions in this area, and those skilled in the art can according to circumstances select corresponding reaction conditions.
Optimized technical scheme is, atom transfer radical polymerization in the described step (1) synthesizes, and constitutes polymerization system by initiator, styrene monomer, catalyzer and solvent, reacts 3-10 hour down at 90-130 ℃, resulting polymers is separated out in methyl alcohol, and removes catalyzer; Wherein, described catalyzer is selected from cuprous chloride, pentamethyl-diethylenetriamine or 2, the title complex of 2 '-dipyridyl, and described solvent is selected from cyclohexanone, methyl-phenoxide, N, the N-diformamide.
Coordination reaction in the described step (2) is, equimolar beta-diketone compounds and sodium hydroxide are dissolved in the ethanolic soln, be added drop-wise in the ethanolic soln of Samarium chloride in heating with under stirring, the mol ratio of Samarium chloride and beta-diketon is 1: 2, wherein, the ethanolic soln of Samarium chloride is dissolved in the acquisition of 95% ethanol by the hydrate of Samarium chloride, drip the back and continue heating 2 hours, produce a large amount of faint yellow precipitations, sedimentation and filtration, with absolute ethanol washing and dry getting final product, temperature of reaction is 60-80 ℃.
Coordination permutoid reaction in the described step (3) is, end group is that the polystyrene of oxine is dissolved in N, N-diformamide (DMF), regulating the pH value with aqueous sodium hydroxide solution is 8-9, then to the small molecules title complex that wherein adds excessive twice, reacted 1-7 hour down at 120 ℃, with mixing solutions precipitating in methyl alcohol, obtain the mixture of polymer complex and small molecules title complex, mixture is dissolved in ether, suction filtration is removed insoluble small molecules title complex, and filtrate is precipitating in methyl alcohol, obtains required high molecular samarium ligand.
The above-mentioned high molecular samarium ligand that the present invention obtains can be applied to prepare agricultural light conversion film.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the present invention has used the samaric title complex as photothermal converting agent, and its fluorescence emission spectrum and chlorophyllous absorption spectrum can better coincide;
2. the present invention is introducing the part that contains polystyrene chain in title complex, the polymer samaric title complex and the polyethylene base material that obtain have good consistency, can be even and stable be scattered in the polyethylene film, thereby be particularly suitable for preparing agricultural light conversion film;
3. the polymer samaric title complex that obtains of the present invention has the feature emission peak (645nm) of trivalent Sm title complex of red light district and the fluorescent emission (375-450nm) of blue light region macromolecular ligand simultaneously, better coincide with the absorption spectrum of chlorophyll to daylight, therefore high-molecular optical changing agent involved in the present invention has higher efficient.
Description of drawings
Accompanying drawing 1 is the fluorescence emission spectrum of photothermal converting agent 1 of the embodiment of the invention one and the comparison diagram of chlorophyllous absorption spectrum;
Accompanying drawing 2 is the fluorescence emission spectrum of photothermal converting agent 1 under filminess of embodiment one;
Accompanying drawing 3 is the fluorescence emission spectrum of photothermal converting agent 2 of the embodiment of the invention two and the comparison diagram of chlorophyllous absorption spectrum;
Accompanying drawing 4 is the fluorescence emission spectrum of photothermal converting agent 2 under filminess of embodiment two.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one:
1. end group contains polystyrene part synthetic of oxine
Initiator, monomer (vinylbenzene), catalyzer and solvent are added in the polymerizing pipe, by successive vacuumize-inflated with nitrogen is with the oxygen in the system of removing, and then polymerizing pipe inserted oil bath, 90-130 ℃ of reaction 3-10 hour down.After the reaction certain hour, resulting polymers is separated out in methyl alcohol, and removes catalyzer with 1: 1 salt acid elution.Get final product to such an extent that end group contains the polystyrene part of oxine by suction filtration, vacuum-drying, its molecular weight can be regulated by the ratio of control monomer and initiator.
The initiator that present embodiment uses is 5-chloromethyl-oxine; Catalyzer can be cuprous chloride and pentamethyl-diethylenetriamine or 2, the title complex of 2 '-dipyridyl; Solvent is pimelinketone, methyl-phenoxide, N, N-diformamide etc.
2.Sm (III) and the small molecules title complex of trifluoromethyl thiophene acetone synthetic
Under 60 ℃, trifluoromethyl thiophene acetone (TTA) 4.44g and 0.8g sodium hydroxide are dissolved in 95% ethanol of 50ml, under heating and the stirring condition TTA drips of solution are added to SmCl
3.6H
2In the ethanolic soln of O (3.66g is dissolved in 50ml 95% ethanol).Continue heating 2 hours after dripping, produce a large amount of faint yellow precipitations.Sedimentation and filtration, and with absolute ethanol washing for several times.Resulting pale yellow powder is in room temperature vacuum-drying.Product is the small molecules title complex SmCl (TTA) of samaric and TTA
22H
2O.
3.Sm high molecular title complex (III) is synthetic
With the 1g end group is the DMF that the polystyrene (molecular weight is 4022) of oxine is dissolved in 20ml, and regulating the pH value with aqueous sodium hydroxide solution is 8-9, then to the small molecules title complex SmCl (TTA) that wherein adds excessive twice
22H
2O reacted 1-7 hour down at 120 ℃.With mixing solutions precipitating in methyl alcohol, obtain the mixture of polymer complex and small molecules title complex.Mixture is dissolved in ether, and suction filtration is removed insoluble small molecules title complex, and with filtrate precipitating in methyl alcohol, also dry for several times with methanol wash, product is phototransformation agent 1 (PSt-Q-Sm-TTA
2).The fluorescence emission spectrum of photothermal converting agent 1 and the comparison of chlorophyllous absorption spectrum such as accompanying drawing 1.
From the fluorescence emission spectrum of photothermal converting agent 1 and chlorophyllous absorption spectrum more as can be seen, PSt-Q-Sm-TTA
2The absorption spectrum of fluorescence emission spectrum and chlorophyll, especially chlorophyll b very identical.
4. the preparation of polymer complex film
(1cm * 1cm) water cleans quartz glass plate before use, and soaks after 24 hours in 50 ℃ of following vacuum-dryings in acetone.Polymer complex is dissolved in methylene dichloride.Polymers soln is dripped on the quartz glass plate, solution is dispersed on the sheet glass, treat that solvent evaporates just obtains being carried on afterwards the uniform thin film on the sheet glass by spin coating.Prepared polymeric film is preserved in exsiccator.The strength of solution of polymer complex is 2%-10%, controls the thickness that its concentration can be regulated prepared film.
Fig. 2 is the fluorescence emission spectrum of phototransformation agent 1 under filminess.
Embodiment two:
1. end group contains polystyrene part synthetic of oxine
Initiator, monomer (vinylbenzene), catalyzer and solvent are added in the polymerizing pipe, by successive vacuumize-inflated with nitrogen is with the oxygen in the system of removing, and then polymerizing pipe inserted oil bath, 90-130 ℃ of reaction 3-10 hour down.After the reaction certain hour, resulting polymers is separated out in methyl alcohol, and removes catalyzer with 1: 1 salt acid elution.Get final product to such an extent that end group contains the polystyrene part of oxine by suction filtration, vacuum-drying, its molecular weight can be regulated by the ratio of control monomer and initiator.
The initiator that present embodiment uses is 5-chloromethyl-oxine; Catalyzer can be cuprous chloride and pentamethyl-diethylenetriamine or 2,2 '-title complex of dipyridyl; Solvent is pimelinketone, methyl-phenoxide, N, N-diformamide etc.
2.Sm (III) and the small molecules title complex of diphenylpropane-1,3-dione(DPPO) synthetic
Diphenylpropane-1,3-dione(DPPO) (DBM) 4.48g (20mmol) and 0.8g sodium hydroxide add in 50ml 95% ethanol, and heating in flask, stirring under 60 ℃ treat that DBM continues to stir 30min after dissolving fully again.Solution with DBM under maintenance heating and the stirring condition drips SmCl
3.6H
2In the ethanolic soln of O (3.66g is dissolved in 50ml 95% ethanol).Continue heating 2 hours after dripping.Solid product is collected by suction filtration, and with absolute ethanol washing three times.Resulting pale yellow powder is in room temperature vacuum-drying, thick product recrystallization in the mixed solvent of ethyl acetate and sherwood oil.Products therefrom is the small molecules title complex (SmCl (DBM) of Sm (III) and DBM
22H
2O)
3.Sm polymer complex (III) is synthetic
The 1g end group is the DMF that the polystyrene (molecular weight is 4022) of oxine is dissolved in 20ml, and regulating the pH value with the NaOH aqueous solution is 8-9, then to the small molecules title complex SmCl (DBM) that wherein adds excessive twice
22H
2O reacted 1-7 hour down at 120 ℃.With mixing solutions precipitating in methyl alcohol, obtain the mixture of polymer complex and small molecules title complex.Mixture is dissolved in ether, and suction filtration is removed insoluble small molecules title complex, filtrate is precipitated out in methyl alcohol once more, and with methanol wash three times.Last product is dry in vacuum drying oven.Product is photothermal converting agent 2 (PSt-Q-Sm-DBM
2), the fluorescence emission spectrum of photothermal converting agent 2 and chlorophyllous absorption spectrum more as shown in Figure 3.
4. the preparation of polymer complex film
(1cm * 1cm) water cleans quartz glass plate before use, and soaks after 24 hours in 50 ℃ of following vacuum-dryings in acetone.Polymer complex is dissolved in methylene dichloride.Polymers soln is dripped on the quartz glass plate, solution is dispersed on the sheet glass, treat that solvent evaporates just obtains being carried on afterwards the uniform thin film on the sheet glass by spin coating.Prepared polymeric film is preserved in exsiccator.The strength of solution of polymer complex is 2%-10%, controls the thickness that its concentration can be regulated prepared film.Fig. 4 is the fluorescence emission spectrum of phototransformation agent 2 under filminess.
Claims (6)
1. high molecular samarium ligand, it is characterized in that: it is the ternary complex that is made of macromolecular ligand, beta-diketone compounds and samaric, described macromolecular ligand is that end group contains the unitary polystyrene of oxine, and the molecular weight of polystyrene is between 2600-10000.
2. the preparation method of a high molecular samarium ligand is characterized in that, comprises the following steps:
(1) with 5-chloromethyl-oxine as initiator, contain the unitary polystyrene of oxine by the synthetic end group of atom transfer radical polymerization;
(2) Samarium chloride and beta-diketone compounds carry out coordination, the small molecules title complex of synthetic samaric and beta-diketon;
(3) polystyrene that contains oxine with end group carries out the coordination permutoid reaction, the high molecular title complex of synthetic samaric as the small molecules title complex of macromolecular ligand and samaric.
3. the preparation method of high molecular samarium ligand according to claim 2, it is characterized in that: the atom transfer radical polymerization in the described step (1) synthesizes, constitute polymerization system by initiator, styrene monomer, catalyzer and solvent, reacted 3-10 hour down at 90-130 ℃, resulting polymers is separated out in methyl alcohol, and removes catalyzer; Wherein, described catalyzer is selected from cuprous chloride, pentamethyl-diethylenetriamine or 2, the title complex of 2 '-dipyridyl, and described solvent is selected from pimelinketone, methyl-phenoxide, N, the N-diformamide.
4. the preparation method of high molecular samarium ligand according to claim 2, it is characterized in that: the coordination reaction in the described step (2) is, equimolar beta-diketone compounds and sodium hydroxide are dissolved in the ethanolic soln, be added drop-wise in the ethanolic soln of Samarium chloride in heating with under stirring, the mol ratio of Samarium chloride and beta-diketon is 1: 2, drip the back and continue heating 2 hours, produce a large amount of faint yellow precipitations, sedimentation and filtration, with absolute ethanol washing and dry getting final product, temperature of reaction is 60-80 ℃.
5. the preparation method of high molecular samarium ligand according to claim 2, it is characterized in that: the coordination permutoid reaction in the described step (3) is, end group is that the polystyrene of oxine is dissolved in N, the N-diformamide, regulating the pH value with aqueous sodium hydroxide solution is 8-9, then to the small molecules title complex that wherein adds excessive twice, reacted 1-7 hour down at 120 ℃, with mixing solutions precipitating in methyl alcohol, obtain the mixture of polymer complex and small molecules title complex, mixture is dissolved in ether, and suction filtration is removed insoluble small molecules title complex, filtrate is precipitating in methyl alcohol, obtains required high molecular samarium ligand.
6. the application of the described high molecular samarium ligand of claim 1 in the agricultural light conversion film of preparation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962389A (en) * | 2010-09-13 | 2011-02-02 | 杭州师范大学 | Rare-earth compound olefin monomer and preparation method and application thereof |
| CN110950800A (en) * | 2019-10-12 | 2020-04-03 | 广西师范大学 | Rare earth complex constructed based on 2-methyl-5, 7-dibromo-8-hydroxyquinoline and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6388083B2 (en) * | 2000-07-07 | 2002-05-14 | Merck & Co., Inc. | Process for the synthesis of (2S)-phenyl-3-piperidone |
| EP1414927A1 (en) * | 2001-08-04 | 2004-05-06 | Elam-T Limited | Electroluminescent device |
| US20030003587A1 (en) * | 2002-06-28 | 2003-01-02 | Murray George M | Molecularly imprinted polymer based sensors for the detection of narcotics |
| CN1587346A (en) * | 2004-09-09 | 2005-03-02 | 徐良衡 | Non-conjugate high molecular electroluminescent material and its preparing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962389A (en) * | 2010-09-13 | 2011-02-02 | 杭州师范大学 | Rare-earth compound olefin monomer and preparation method and application thereof |
| CN101962389B (en) * | 2010-09-13 | 2012-12-19 | 杭州师范大学 | Rare-earth compound olefin monomer and preparation method and application thereof |
| CN110950800A (en) * | 2019-10-12 | 2020-04-03 | 广西师范大学 | Rare earth complex constructed based on 2-methyl-5, 7-dibromo-8-hydroxyquinoline and preparation method and application thereof |
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