CN101328303B - Photoelectric nano composite material having push-and-pull electronic structure and preparation thereof - Google Patents
Photoelectric nano composite material having push-and-pull electronic structure and preparation thereof Download PDFInfo
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- CN101328303B CN101328303B CN2008100220059A CN200810022005A CN101328303B CN 101328303 B CN101328303 B CN 101328303B CN 2008100220059 A CN2008100220059 A CN 2008100220059A CN 200810022005 A CN200810022005 A CN 200810022005A CN 101328303 B CN101328303 B CN 101328303B
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Abstract
The invention discloses a photovoltaic nano composite material with pulling/pushing electronic structure and a preparation method thereof. The photovoltaic nano composite material is prepared by modifying 3- alkoxythiophene-3-paranitrobenzyloxythiophene alternating copolymer through one of nano cadmium selenide, cadmium sulfide and zinc sulphide; the nano material can be one of the nano cadmium selenide, the cadmium sulfide and the zinc sulphide. Compared with poly (3- alkylthrophene), the performances of the composite material such as the photoluminescence (PL), the electroluminescence (EL) and the cubic nonlinear optics (NLO) are greatly improved, and the composite material also has the characteristics of controllable content of nano particles, controllable particle diameter and strong optical performance, etc, so that the composite material has certain application potential in fields such as catalysis and photoelectric conversion, etc.
Description
Technical field
The present invention relates to a kind of photoelectric nano-composite material and preparation method thereof, be specifically related to a class and have photoelectric nano-composite material of electron donor-acceptor structure and preparation method thereof.
Background technology
Nano composite material has special conductive characteristic, photoelectric characteristic, photo-catalysis capability and with the absorption or the emmission spectrum of change of size, causes numerous scholars' concern.In the preparation process of nano composite material, polymkeric substance can improve the stability of nanoparticle widely as base material, makes nanoparticle controlled in very big size range simultaneously; Finishing coat structure that can the stabilized nanoscale particulate, and then realize microcosmic regulation and control to the nanoparticle special property; The optical property of polymer materials excellence provides good condition for developing novel composite non-linear optical material.There are some researches show that the main chain conjugated polymkeric substance with electron donor-acceptor structure has excellent performance and potential using value aspect photoelectricity conversion and conduction and the nonlinear optics.
Seek to have good photoluminescence, the photoelectric nano-composite material of electroluminescent and third-order nonlinear optical character, and seek to pass through the control proportioning raw materials, effectively control the preparation method of the nano-complex of the content of nanoparticle in the mixture, to obtain the matrix material of different performance, be those skilled in the art's continuous directions of effort.
Summary of the invention
The object of the invention provides a kind of photoelectric nano-composite material with electron donor-acceptor structure and preparation method thereof, to obtain good photoluminescence (PL), electroluminescent (EL) and third-order nonlinear optical (NLO) performance.
Another object of the present invention provides a kind of preparation method of photoelectric nano-composite material, adopts this method to realize that nanoparticle content is controlled, particle diameter is controlled.
For achieving the above object, the technical solution used in the present invention is: a kind of photoelectric nano-composite material with electron donor-acceptor structure, adopt nanometer-material-modified 3-alkoxy thiophene-3-with electron donor-acceptor structure that nitro benzyloxy thiophene alternating polymer is got, described nano material is selected from a kind of in nanometer cadmium selenide, Nano cadmium sulphide or the nano-zinc sulfide.
In the technique scheme, described 3-alkoxy thiophene-3-is in the nitro benzyloxy thiophene alternating polymer, described alkoxyl group be selected from propoxy-, butoxy, octyloxy, the last of the ten Heavenly stems oxygen base or dodecyloxy in a kind of.
Above-mentioned preparation method with photoelectric nano-composite material of electron donor-acceptor structure comprises the following steps:
(1) with alkyl alcohol and sodium according to 1.1: 1～1.2: 1 synthesis of alkyl sodium alkoxide in 1-methyl-2-pyrrolidone solution of mol ratio, again according to sodium alkyl alcohol: 3 bromo thiophene=1.1: 1～1.2: 1 (mol ratio) adds 3 bromo thiophene according to the amount of gained sodium alkyl alcohol and is prepared into the 3-alkoxy thiophene;
Wherein, described alkyl alcohol is selected from a kind of in methyl alcohol, n-Octanol, nonylcarbinol or the n-dodecanol;
According to nitrobenzyl alcohol: 3 bromo thiophene=1.1: 1～1.2: 1 (mol ratio), preparation 3-is to nitro benzyloxy thiophene under salt of wormwood catalysis;
(2) according to the 3-alkoxy thiophene: N-bromo-succinimide=1: 2 (mol ratio), in chloroformic solution with 3-alkoxy thiophene bromination, according to mol ratio 1: 2 bromination 3-alkoxy thiophene and Grignard reagent are carried out grignard reaction again, obtain the Grignard reagent of 3-alkoxy thiophene.
(3) under the effect that accounts for amount of monomer 0.5% (mol ratio) coupling reaction catalyst, the 3-alkoxy thiophene of 1: 1 (mol ratio) and 3-to nitro benzyloxy thiophene polyreaction, are obtained having the 3-alkoxy thiophene-3-of electron donor-acceptor structure to nitro benzyloxy thiophene alternating polymer.
(4) according to the mole number of 3-alkoxy thiophene-3-to nitro benzyloxy thiophene alternating polymer repeating unit: the mole number of Cadmium chloride fine powder or zinc chloride=5: 1～1: 5 prepares polythiofuran derivative-Cd in DMF solution
2+(Zn
2+), with sodium sulphite or the reaction of sulfurous acid selenium sodium, original position generates the polythiofuran derivative nano-complex again.
Wherein, the described coupling reaction catalyst of step (3) is Ni (dppp) Cl
2
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. introduced polymkeric substance owing to nanoparticle, thereby increased the stability and the photoelectric conductivity of the coplanar structure of polymkeric substance, so this material has good photoluminescence, electroluminescent and third-order nonlinear optical character.
At 3-alkoxy thiophene-3-in nitro benzyloxy thiophene alternating polymer synthetic, owing to can therefore can improve the solvability of mixture by selecting the kind of monomer 3-alkoxy thiophene.
3. in the preparation of nano-complex, because can be by the mole proportioning of control 3-alkoxy thiophene-3-to nitro benzyloxy thiophene alternating polymer and nanoparticle, therefore can effectively control content, particle diameter and the dispersiveness thereof of nanoparticle, and then the optical property of regulating nano-complex.
4. owing to studied the influence of the factors such as content of monomer ratio, nanoparticle to the mixture optical property in great detail, that the present invention has is efficient, easy, reduce production costs and easy advantage such as industrializing implementation.
Description of drawings
Accompanying drawing 1 is a poly-alkoxy thiophene nano-complex preparation technology schema among the embodiment one.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one: shown in accompanying drawing 1,
The first step in 250 milliliters of there-necked flasks, is a solvent with the 1-methyl-2-pyrrolidone, and high purity nitrogen protective reaction system is with 10 gram sodium (0.44 mole) and excessive methyl alcohol reaction synthesizing methanol sodium.Reaction finishes the remaining methyl alcohol of back pressure reducing and steaming, adds 2.5 gram CuI and 15 milliliters of (0.16 mole) 3 bromo thiophenes preparation 3-methoxythiophene under 110 ℃ in solution again.
In 100 milliliters of there-necked flasks, put into 10 gram 3-methoxythiophene (0.088 mole) and 0.09 mole of n-Octanol and 0.2 gram anhydrous slufuric acid hydrogen sodium, be warmed up to 110 ℃ under the nitrogen protection and reacted 4 hours.Reaction finishes after-filtration and removes solid, and underpressure distillation obtains 3-octyloxy thiophene.Yield 50%.
15.3 grams (0.1 mole) to nitrobenzyl alcohol and 15.3 gram (0.1 mole) 3 bromo thiophenes, were prepared 3-in 48 hours to nitro benzyloxy thiophene in 120 ℃ of reactions under 8 gram salt of wormwood catalysis.Product is refining through ethyl alcohol recrystallization.Yield 30%.
Second step, in 100 milliliters of there-necked flasks, add 2.12 gram (0.01 mole) 3-octyloxy thiophene, 3.56 gram (0.02 mole) N-bromo-succinimides, in chloroformic solution, react 36 hours down with 3-octyloxy thiophene bromination in 70 ℃, according to mol ratio 1: 2 bromination 3-octyloxy thiophene and ethyl group magnesium bromide are carried out the grignard reaction again, obtain 3-octyloxy thiophene magnesium bromide grignard reagent.
Prepare 3-to nitro benzyloxy thiophene magnesium bromide grignard reagent with quadrat method.
The 3rd step, in 100 milliliters of there-necked flasks, add 3.95 gram (0.01 mole) 3-octyloxy thiophene magnesium bromides, 4.17 gram (0.01 mole) 3-to nitro benzyloxy thiophene magnesium bromide and 0.3 gram (0.0005 mole) 1, two (diphenylphosphine) propane nickelous chlorides of 3-, polymerization 1 hour under room temperature obtains having the 3-octyloxy thiophene-3-of push-and-pull electronics to nitro benzyloxy thiophene alternating polymer in tetrahydrofuran solution.Yield 70%.
In the 4th step, 4.46 gram (0.01 mole) 3-octyloxy thiophene-3-to nitro benzyloxy thiophene alternating polymer and 2.28 gram (0.01 mole) Cadmium chloride fine powdeies (2.5 crystal water), were refluxed 24 hours the poly-alkoxy thiophene-Cd of preparation in 100 milliliters of tetrahydrofuran solutions
2+, in sonic oscillation, to react 1 hour with excessive sodium sulphite again, original position generates polythiofuran derivative-cadmium sulfide nano mixture.Yield 80%.
Embodiment two:
The first step, second step prepared 3-dodecyloxy thiophene magnesium bromide and 3-to nitro benzyloxy thiophene magnesium bromide according to example 1 the first step, second one step process respectively.
In the 3rd step, in 100 milliliters of there-necked flasks, add 4.5 gram (0.01 mole) 3-dodecyloxy thiophene magnesium bromides, 4.17 gram (0.01 mole) 3-to nitro benzyloxy thiophene magnesium bromide and 0.3 gram (0.0005 mole) Ni (dppp) Cl
2, polymerization 1 hour under room temperature obtains having the 3-dodecyloxy thiophene-3-of push-and-pull electronics to nitro benzyloxy thiophene alternating polymer in THF solution.Yield 71%.
The 4th step, 5.02 gram (0.01 mole) 3-dodecyloxy thiophene-3-are restrained (0.01 mole) Cadmium chloride fine powdeies (2.5 crystal water) to nitro benzyloxy thiophene alternating polymer and 2.28, refluxed 24 hours in 100 milliliters of THF solution, the poly-3-dodecyloxy thiophene-3-of preparation is to nitro benzyloxy thiophene-Cd
2+, in sonic oscillation, to react 1 hour with the aqueous solution that contains 2.30 gram (0.012 mole) sulfurous acid selenium sodium again, original position generates polythiofuran derivative-cadmium selenide nano mixture.Yield 80%.
Claims (4)
1. photoelectric nano-composite material with electron donor-acceptor structure, it is characterized in that: adopt nanometer-material-modified 3-alkoxy thiophene-3-with electron donor-acceptor structure that nitro benzyloxy thiophene alternating polymer is got, described nano material is selected from a kind of in nanometer cadmium selenide, Nano cadmium sulphide or the nano-zinc sulfide.
2. the photoelectric nano-composite material with electron donor-acceptor structure according to claim 1, it is characterized in that: described 3-alkoxy thiophene-3-is in the nitro benzyloxy thiophene alternating polymer, described alkoxyl group be selected from propoxy-, butoxy, octyloxy, the last of the ten Heavenly stems oxygen base or dodecyloxy in a kind of.
3. the preparation method with photoelectric nano-composite material of electron donor-acceptor structure is characterized in that, comprises the following steps:
(1) with alkyl alcohol and sodium according to 1.1: 1～1.2: 1 synthesis of alkyl sodium alkoxide in 1-methyl-2-pyrrolidone solution of mol ratio, again according to sodium alkyl alcohol: 3 bromo thiophene=1.1: 1～1.2: 1 (mol ratio) adds 3 bromo thiophene according to the amount of gained sodium alkyl alcohol and is prepared into the 3-alkoxy thiophene;
Wherein, described alkyl alcohol is selected from a kind of in methyl alcohol, n-Octanol, nonylcarbinol or the n-dodecanol;
According to nitrobenzyl alcohol: 3 bromo thiophene=1.1: 1～1.2: 1 (mol ratio), preparation 3-is to nitro benzyloxy thiophene under salt of wormwood catalysis;
(2) according to the 3-alkoxy thiophene: N-bromo-succinimide=1: 2 (mol ratio), in chloroformic solution with 3-alkoxy thiophene bromination, according to mol ratio 1: 2 bromination 3-alkoxy thiophene and Grignard reagent are carried out grignard reaction again, obtain the Grignard reagent of 3-alkoxy thiophene;
(3) under the effect that accounts for amount of monomer 0.5% (mol ratio) coupling reaction catalyst, the Grignard reagent of the 3-alkoxy thiophene of 1: 1 (mol ratio) and 3-to the Grignard reagent polyreaction of nitro benzyloxy thiophene, are obtained having the 3-alkoxy thiophene-3-of electron donor-acceptor structure to nitro benzyloxy thiophene alternating polymer;
(4) according to the mole number of 3-alkoxy thiophene-3-to nitro benzyloxy thiophene alternating polymer repeating unit: the mole number of Cadmium chloride fine powder or zinc chloride=5: 1～1: 5 prepares polythiofuran derivative-Cd in DMF solution
2+Or polythiofuran derivative-Zn
2+, with sodium sulphite or the reaction of sulfurous acid selenium sodium, original position generates the polythiofuran derivative nano-complex again.
4. according to the preparation method of photoelectric nano-composite material described in the claim 3, it is characterized in that the described coupling reaction catalyst of step (3) is Ni (dppp) Cl
2
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Address after: Suzhou City, Jiangsu province 215131 Xiangcheng District Ji Road No. 8 Patentee after: Soochow University Address before: 215123 Suzhou City, Suzhou Province Industrial Park, No. love road, No. 199 Patentee before: Soochow University |