CN103172835B - A kind of preparation method of organic polymer MOPPV/PbSe nanocrystalline composite material - Google Patents
A kind of preparation method of organic polymer MOPPV/PbSe nanocrystalline composite material Download PDFInfo
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Abstract
The invention provides a kind of in situ chemical oxidation condensation polymerization legal system that utilizes for the method for polymkeric substance MOPPV/PbSe nanocrystalline composite material, selenium powder, sodium borohydride and anhydrous tetrahydro furan is added in three-necked bottle, ice bath reaction is to light yellow under nitrogen protection, obtains sodium hydrogen selenide solution; Then in another three-necked bottle, add potassium tert.-butoxide, anhydrous tetrahydro furan stirring makes it form solution; nitrogen is passed into get rid of dissolved oxygen to solution system; add the sodium hydrogen selenide solution of preparation under nitrogen protection; then drip and dissolve two benzyl chloride and plumbic acetate in anhydrous tetrahydrofuran solution; naturally cool to after room temperature until solution after reaction, with obtaining black powder shaped polymer MOPPV/PbSe nano composite material after absolute ethanol washing, suction filtration, vacuum-drying.This polymerization process is simple, and synthetic composite material can reach the requirement in photoelectric field application, has stronger practicality.
Description
Technical field
The present invention relates to a kind of in situ chemical oxidation condensation polymerization legal system that utilizes for the method for MOPPV/PbSe nano composite material, be different from the physical blending of simple organic/inorganic composite material, the method is simple and easy to do, and nano material and the large problem of organic materials compound difficulty can be solved, there is stronger practicality, can prepare fast and effectively in the lab, belong to Organic/Inorganic Composite Nanomaterials preparing technical field.
Background technology
Since the people such as Germany scientist Gleite in 1984 are first by inert gases agglomeration method successfully obtained nanoparticle, the research of each side such as preparation, properties and characterization of nano material achieves major progress.In recent years, crystalline state nanometer semiconductor particle causes the extensive concern of scientific circles because of optical property that it has large surface volume ratio, high activity, special electrical properties and uniqueness.The quantum size effect of based semiconductor nanoparticle and surface effects semi-conductor nano particles have broad application prospects in luminescent material, nonlinear optical material, photosensor material, photocatalyst material etc.How to realize the control of the size to semi-conductor nano particles, size-grade distribution and shape and finishing, find easier synthetic method and improvement and prepare the key that environment etc. is semi-conductor nano particles research.
Lead selenide is as a kind of important semiconductor nano material, and it is typical IV ~ VI race, and have the direct band-gap semicondictor of cube sodium chloride type structure, energy gap is little, and spectral absorption wide ranges has significant infrared absorption.Because energy gap is narrow, lead selenide can be used for producing many devices such as light detector, photoresistor, optical transmitting set, again due to the size adjustable of lead selenide nano particle, can effectively control its energy gap, thus better meet the lattice match requirement of each storeroom.At present, lead selenide nano material has been widely used in the field such as biophysics, fluorescence microscopy, especially enjoys favor at opto-electronics.Organic p-phenylene vinylene (PPV) is the photoelectric material of a class hole-transporting type, introduces alcoxyl functional group and the delocalization of PPV molecular backbone chain conjugated system can be made to strengthen, the solvability being conducive to exciton transfer and strengthening in organic solvent.In PPV, mix semiconductor nano material, be different from traditional organic/inorganic composite photoelectric material, not only can keep the excellent photoelectric properties of bi-material, the property such as Photo-induced electron transfer, spectral sensitization can also occur.At present, Polymer Nanocomposites has been widely used in the field such as biophysics, fluorescence microscopy, especially enjoys favor in organic optoelectronic field.
The method preparing polymkeric substance MOPPV/PbSe nano composite material at present has a variety of, comprise chemical Vapor deposition process, mechanical shock, microwave method, sonochemical method etc., the above method preparation condition is strict, complicated operation, though can prepare organic polymer/nano composite material, can not control its size, fail to solve nano material combines difficulty, nano material skewness in the polymer problem with organic polymer, in matrix material Application Areas, can not get good application.
Summary of the invention
The technical problem solved
In order to make up the deficiencies in the prior art part, solve the problem of nano material and the difficult compound of organic materials, the present invention proposes a kind of in situ chemical oxidation condensation polymerization legal system that utilizes for the method for polymkeric substance MOPPV/PbSe nano composite material, the method is simple and easy to do, can prepare fast and effectively in the lab, also can carry out suitability for industrialized production simultaneously.
Technical scheme
The invention provides a kind of original position condensation polymerization legal system that utilizes for the method for polymkeric substance MOPPV/PbSe nanocrystalline composite material, it is characterized in that step is as follows:
Step 1: selenium powder and sodium borohydride are put into container according to mol ratio 1:2, adds anhydrous tetrahydro furan THF and dissolves, then in container, be filled with nitrogen eliminating dissolved oxygen, and the sodium hydrogen selenide solution under the protection condition of ice bath of nitrogen required for reaction generation; Reaction principle is as follows:
4NaBH
4+2Se+7H
2O=2NaHSe+Na
2B
4O
7+14H
2
Step 2: potassium tert.-butoxide is put into container, adds anhydrous tetrahydro furan THF stirring and makes it form solution, pass into nitrogen 20min to get rid of dissolved oxygen, then add sodium hydrogen selenide solution prepared by step 1 under nitrogen protection to solution system;
Step 3: get two benzyl chloride and plumbic acetate is dissolved in anhydrous tetrahydrofuran solution, then after dripping in the solution made to step 2 with the speed of 1/s, after reaction 20min, be heated to 63 DEG C backflow 7h after stopped reaction, naturally cool to after room temperature until solution, with obtaining black powder shaped polymer MOPPV/PbSe nano composite material after absolute ethanol washing, suction filtration, vacuum-drying;
The mol ratio of described pair of benzyl chloride and potassium tert.-butoxide is 1:3;
The mol ratio of described plumbic acetate and selenium powder is 1:1.
Beneficial effect
The invention provides a kind of in situ chemical oxidation condensation polymerization legal system that utilizes for the method for polymkeric substance MOPPV/PbSe nano composite material, selenium powder, sodium borohydride and anhydrous tetrahydro furan is added in three-necked bottle, ice bath reaction is to light yellow under nitrogen protection, obtains sodium hydrogen selenide solution; Then in another three-necked bottle, add potassium tert.-butoxide, anhydrous tetrahydro furan stirring makes it form solution; nitrogen is passed into get rid of dissolved oxygen to solution system; add the sodium hydrogen selenide solution of preparation under nitrogen protection; then drip and dissolve two benzyl chloride and plumbic acetate in anhydrous tetrahydrofuran solution; naturally cool to after room temperature until solution after reaction, with obtaining black powder shaped polymer MOPPV/PbSe nano composite material after absolute ethanol washing, suction filtration, vacuum-drying.
The method preparation technology flow process is simple, does not need the conditions such as High Temperature High Pressure, and applicable continuous seepage, and compared with other technique existing, the present invention is practical, pollutes little, can also pass through Controlling Technology process, and then the form of control product.
Accompanying drawing explanation
The X-ray diffractogram of Fig. 1 MOPPV/PbSe nano composite material prepared by embodiment.
Scanning electronic microscope (SEM) figure of Fig. 2 MOPPV/PbSe nano composite material prepared by embodiment.
Transmission electron microscope (TEM) figure of Fig. 3 MOPPV/PbSe nano composite material prepared by embodiment.
Embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
The concrete preparation process of the present embodiment is as follows:
First take 0.14g sodium borohydride and put into three-necked bottle; add the appropriate anhydrous tetrahydro furan of 30ml, in container, be filled with nitrogen get rid of dissolved oxygen, after 20min, add 0.145g selenium powder; and ice bath reacts to pale yellow solution under the protection of nitrogen, the sodium hydrogen selenide solution required for generation.1.4g potassium tert.-butoxide is put into another three-necked bottle, adding 50ml anhydrous tetrahydro furan (THF) rapid stirring makes it form solution, nitrogen is passed into get rid of dissolved oxygen to solution system, freshly prepd sodium hydrogen selenide solution is added under nitrogen protection after 20min, then getting the two benzyl chloride (two benzyl chloride and potassium tert.-butoxide mol ratio are 1:3) of 0.7g and 0.596g plumbic acetate (plumbic acetate and selenium powder mol ratio are 1:1) to be dissolved in 20ml anhydrous tetrahydrofuran solution after ultrasonic disperse, slowly drip in above-mentioned solution with the speed of 1/s, after dripping, after reaction 20min, be heated to stopped reaction after 63 DEG C of return stirring 7h, naturally cool to after room temperature until solution, with absolute ethanol washing, suction filtration, black powder shaped polymer MOPPV/PbSe nano composite material is obtained after vacuum-drying.
Fig. 1 is X-ray diffraction (XRD-ADVANCE type) figure of MOPPV/PbSe nanocomposite films, can the structure of thing phase and element existence in qualitative analysis material.From figure, we can find out that polymkeric substance MOPPV/PbSe nano composite material is in 25.2 °, 29.3 °, 41.7 °, 49.1 °, 51.5 °, 60.4 °, 68.3 °, 76.1 ° appearance, 8 diffraction peaks, the diffraction peak corresponding to MOPPV and PbSe nano material contrasts, peak position becomes level and smooth and there occurs slight skew, there is no the appearance of impurity peaks compared with pure PbSe nano material characteristic peak, there is no the formation of other PbSe structures yet.In addition, diffraction peak in figure does not have obvious broadening phenomenon compared with body material, this is due to by home position polymerization reaction, PbSe quanta point material by well coated or be embedded in MOPPV polymeric matrix mutually in, this shows that PbSe is nanocrystalline and is effectively combined with each other with MOPPV polymkeric substance.
The nanocrystalline particle size of PbSe can be calculated by Debye-Scherrer formula.Debye-Scherrer formula is:
In formula: D is the thickness along crystal face vertical direction, is commonly considered as grain size; K is diffraction peak shape Scherrer constant, often gets 0.89; λ is X-ray wavelength (Cu, 0.154056nm); B
1/2for the halfwidth of diffraction peak, unit is radian; θ is Bragg diffraction angle.7.73nm is of a size of by calculating prepared PbSe nano-crystalline granule.
Fig. 2 is the scanning electronic microscope (SEM) of MOPPV/PbSe nanocomposite films, the film-forming properties of matrix material and the distribution of material can be observed, from figure, we can find out the overall film forming even compact of matrix material, in figure, white bright spot is the PbSe nano material be wrapped by or be embedded in polymkeric substance MOPPV, distributes comparatively even.
Fig. 3 is the transmission electron microscope image of MOPPV/PbSe composite material film, transmission electron microscope (TEM) not only can directly be observed the pattern of inorganic nano material, structure, obtaining information, can also be used to the distribution of the crystalline structure of the pattern of characterize polymers internal structure and polymkeric substance, shape and crystallization.From figure, we can see that the good spherical PbSe nano material of the dispersiveness prepared is evenly distributed in MOPPV polymeric matrix, size is about 8nm, match with the X Diffraction Calculation particle size out of pure PbSe nano material, tightly coated consistent with the coated or pattern structure that sem observation arrives by organic molecule around PbSe nano material.In addition, can also see that PbSe nano material has obvious lattice fringe, illustrate that PbSe material still keeps good crystallinity in the polymer.Formed in the color analysis of obvious contrast from the gray background figure, two integral parts can observing matrix material define clear and definite contact surface, and intert and form (MOPPV) alms giver/acceptor (PbSe) network system, the synthetic method of this Polymer Nanocomposites also reaches us in actual applications to the requirement of matrix material, for the separation of exciton and effective charge transport provide maximum separating interface and passage the most easily.
Claims (1)
1. utilize in situ chemical oxidation condensation polymerization legal system for a method for MOPPV/PbSe nano composite material, it is characterized in that step is as follows:
Step 1: selenium powder and sodium borohydride are put into container according to mol ratio 1:2, adds anhydrous tetrahydro furan THF and dissolves, then in container, be filled with nitrogen eliminating dissolved oxygen, and the sodium hydrogen selenide solution under the protection condition of ice bath of nitrogen required for reaction generation;
Step 2: potassium tert.-butoxide is put into container, adds anhydrous tetrahydro furan THF stirring and makes it form solution, pass into nitrogen 20min to get rid of dissolved oxygen, then add sodium hydrogen selenide solution prepared by step 1 under nitrogen protection to solution system;
Step 3: get 1, two (the chloromethyl)-2-methoxyl group-5-octyl group benzene of 4-and plumbic acetate are dissolved in anhydrous tetrahydrofuran solution, then after dripping in the solution made to step 2 with the speed of 1/s, after reaction 20min, be heated to 63 DEG C backflow 7h after stopped reaction, naturally cool to after room temperature until solution, with obtaining black powder shaped polymer MOPPV/PbSe nano composite material after absolute ethanol washing, suction filtration, vacuum-drying;
The mol ratio of described Isosorbide-5-Nitrae-bis-(chloromethyl)-2-methoxyl group-5-octyl group benzene and potassium tert.-butoxide is 1:3;
The mol ratio of described plumbic acetate and selenium powder is 1:1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1876695A (en) * | 2005-06-09 | 2006-12-13 | 中国科学院化学研究所 | Method for preparing polyphenylene ethenylene clay nanometer composite |
| WO2006135387A2 (en) * | 2004-08-06 | 2006-12-21 | University Of Massachusetts | Quantum dots tailored with electronically-active polymers |
| CN102617831A (en) * | 2012-03-22 | 2012-08-01 | 合肥工业大学 | Preparation method for chalcogenide semiconductor/carboxylation PPV (polyphenylene vinylene) electroluminescence composite material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006135387A2 (en) * | 2004-08-06 | 2006-12-21 | University Of Massachusetts | Quantum dots tailored with electronically-active polymers |
| CN1876695A (en) * | 2005-06-09 | 2006-12-13 | 中国科学院化学研究所 | Method for preparing polyphenylene ethenylene clay nanometer composite |
| CN102617831A (en) * | 2012-03-22 | 2012-08-01 | 合肥工业大学 | Preparation method for chalcogenide semiconductor/carboxylation PPV (polyphenylene vinylene) electroluminescence composite material |
Non-Patent Citations (3)
| Title |
|---|
| "Efficient conjugated polymer-ZnSeand-PbSe nanocrystals hybrid photovoltaic cells through full solar spectrum utilization";Daqin Yun等;《Solar Energy Materials & Solar Cells》;20090210;第93卷(第8期);第1208–1213页 * |
| "Optical properties of conjugated polymer-ZnSe nanocrystal nanocomposites";云大钦等;《Chinese Physics B》;20100115(第1期);第1-8页 * |
| "PMOCOPV/TiO2纳米复合材料的制备及发光性能";李宝铭等;《半导体光电》;20051030;第26卷(第5期);第415-417页 * |
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