CN1569956A - Nano structural material model making method - Google Patents
Nano structural material model making method Download PDFInfo
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- CN1569956A CN1569956A CN 200410010817 CN200410010817A CN1569956A CN 1569956 A CN1569956 A CN 1569956A CN 200410010817 CN200410010817 CN 200410010817 CN 200410010817 A CN200410010817 A CN 200410010817A CN 1569956 A CN1569956 A CN 1569956A
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Abstract
The invention relates to a nano structural material model making method which mainly comprises the steps of, (1) dissolving amphipathic segmented copolymer into a solvent to obtain homogeneously dispersed macromolecular solution, (2) charging deionized water into the macromolecular solution so as to evoke self-assembly behavior for the segmented copolymer, (3) carrying out dialysis to the solvent by using deionized water as the dislysate, obtaining nanometer level macromolecular super molecule, coating the micelle diluted solution on the flat surface substrate and volatilizing the dissolvent.
Description
Technical field
The invention belongs to a kind of making method of nano structural material template, relate in particular to a kind of surface and have reactable group, the making method of the macromolecule micelle template of form, controllable size.
Background technology
Because the physical behavior of electronics in the material with sodium metrical scale compared with the physical behavior in the common material, very large change can take place in some character, system all can demonstrate usually such as small-size effect, quantum tunneling effect and table/interfacial effect etc., nano material is showing in fields such as electronics, optics, photoelectron, microdevice, transmitters that more and more important use is worth, so the preparation of nano structural material and performance study also become the focus of material science.In recent years, along with the develop rapidly of information technology, Materials science, biotechnology field technology, people press for that the preparation various size are controlled, form is various, are fit to the nano structural material of various demands.Usually, nano structural material is as nanometer rod or nano wire, nano particle can be by multiple different methods preparation.But, diameter long for length evenly, can be with the preparation report of the nanometer rod of metal composite also less.Most work is the preparation carbon nanotube, also has some successful job applications template synthetic methods to prepare the metal nano hybrid material.
Template is synthetic to be one of a kind of effective means of preparation nano structural material.The template of preparation nano structural material commonly used has hard template carbon nanotube and polymer template.Because but carbon nano tube surface do not have the reactive activity group, often diameter is inhomogeneous to use carbon nanotube and be the metal nanometer line that template makes.Work and the work reported in advanced Materials in 2003 of people such as Stamm M on Journal ofAmerican Chemical Society of people such as Massey J.A. calendar year 2001 all is to use the polymer template to have prepared successfully that length is long, diameter even metal hybridized nanometer rod.Prepare microphase-separated and the self-assembly behavior that all is based on segmented copolymer in the metal Nano structure material above as template about using polymer.Concrete grammar is to select to have the surface of the segment of active group as the macromolecule micelle template, prepares metal or organic-inorganic nano hybrid material by the surface being carried out chemically modified.Though the nano-hybrid material size of above method preparation is long, diameter is even, the method for making template is more numerous and diverse, and the length of nanometer rod, diameter is uncontrollable and the morphological structure that obtains is single.So just increased the cost of technology, limited the application in practice of this technology, and can not satisfy in the reality needs variform.
Summary of the invention
The making method that the purpose of this invention is to provide a kind of nano structural material micella template.
The preparation of nano-micelle template is based on the microphase-separated and the self-assembly behavior of amphipathic nature block polymer.Reach the morphological structure of adjusting micella template and the purpose of size by the character of regulating the used cosolvent of preparation nano-micelle.
For achieving the above object, the preparation method of nano structural material template provided by the invention, its key step is as follows:
1) preparation of macromolecular solution: be weight percentage 1～3% polyvinylpyridine and the triblock copolymer of polystyrene of concentration is dissolved in the cosolvent, cosolvent is tetrahydrofuran (THF), dimethyl formamide or dioxane one or both a mixed solvent wherein, mixed solvent mixed in 30: 70 by volume～90: 10, stirred and obtained homodisperse macromolecular solution in 3～12 hours;
2) making of macromolecule micelle: under the agitation condition, in macromolecular solution, drip the precipitation agent deionized water of polystyrene segment PS, induce segmented copolymer generation microphase-separated, be self-assembled into the micella of nanoscale, the precipitation dosage that drips is 6～25% of macromolecular solution volume, stirs under normal temperature condition 2～48 hours, and then adds deionized water, add-on is 4～6 times of macromolecular solution volume, promptly obtains the frozen micella coarse fodder of form;
3) making of nano-high molecule template: the above-mentioned micella coarse fodder that obtains is put into dialysis tubing, molecular weight can freely be passed through at the small molecules below 12000, in deionized water, dialyse 3～7 angel's macromolecule micelle morphological structures, fixed size, promptly obtain the high molecular nanometer micella template that nucleocapsid structure and shell contain active group, the micella template has nanometer ball, nanometer rod, nano-rings or nano vesicle; The micella dilute solution is spin-coated on the planar substrates, treats promptly to obtain after the solvent evaporates template of nano structural material.
Because the cosolvent character that the present invention adopts can be regulated very easily, the micella template that obtains can be nanometer ball, nanometer rod, nano-rings or nano vesicle.And the size of these structures, can regulate by the ratio that changes two kinds of cosolvent in the mixed solvent as the length and the diameter of rod.Make like this nano-micelle template size and the form variable range is wide, form is abundant; Simultaneously, one deck pyridine group is contained on the nano-micelle surface of these nucleocapsid structures, because pyridine has lone-pair electron, can be easy to and have the metal ion or the mineral ion complexing of unoccupied orbital, like this for further carry out chemically modified, the preparation nano structural material provides good template.
Description of drawings
Figure 1A/A ' adopts cosolvent dimethyl formamide DMF, is to stir the atomic force microscope (A) of the finely dispersed nanometer ball that obtained in 48 hours and transmission electron microscope photo (A ') at 6% o'clock at the content of water, and the diameter of ball is 20 ± 1nm.
Figure 1B/B ' adopts cosolvent dioxane Dioxane, the content of water be stirred in 18% o'clock the diameter that obtained in 2 hours evenly (31 ± 1nm), length grows the scanning electron microscope (B) of nanometer rod of (the longest is 5 microns) and transmission electron microscope photo (B ').
Fig. 1 C/C ' is for adopting the cosolvent tetrahydrofuran THF, is to stir the atomic force microscope (C) of nano vesicle of the monodispersity that obtained in 3 hours and transmission electron microscope photo (C ') at 17% o'clock at the content of water, and the diameter of vesica is 80 ± 5nm.
Fig. 2 is for adopting cosolvent dioxane Dioxane, is to stir the atomic force microscope photo of the nano-rings that obtained in 48 hours at 25% o'clock at the content of water.The block copolymer nano ring micella that accounts for main ingredient is to obtain for the first time, does not see bibliographical information.
Fig. 3 A is for adopt mixing cosolvent Dioxane/THF=90/10, is to stir the atomic force microscope photo of the nanometer rod that obtained in 3 hours at 22% o'clock at the content of water.
Fig. 3 B is for adopt mixing cosolvent Dioxane/THF=80/20, is to stir the atomic force microscope photo of short nanometer rod of the length that obtained in 4 hours at 25% o'clock at the content of water.
Fig. 3 C is for adopting cosolvent Dioxane/THF=30/70, is to stir the atomic force microscope photo of the nanometer rod that length is short, diameter is bigger that obtained in 10 hours at 23% o'clock at the content of water.
Embodiment
The model that the amphipathic nature block polymer that uses among following each embodiment is produced as Canada is the triblock copolymer of P1643-4VPS4VP.Precipitation agent is a deionized water.Cosolvent is analytically pure DMF, THF, Dioxane.
Embodiment 1: with weight percent is that 3% segmented copolymer is dissolved among the cosolvent DMF, stirs 12 hours, slowly adds the precipitation agent deionized water of polystyrene PS then, induces segmented copolymer generation microphase-separated, is self-assembled into micella.Until the content of water is 6% o'clock of liquor capacity, stops to add water.Continuously stirring 48 hours adds deionized water then, and add-on is 5 times of total liquor capacity, and the macromolecule micelle form is freezed, and keeps existing form and size.The above-mentioned solution for preparing is put into dialysis tubing, molecular weight can freely be passed through at the small molecules below 12000, dialysis is 3 days in the deionized water environment, changes water every day 1 time.Promptly obtain the nanometer ball micella, see Figure 1A/A '.The above-mentioned micella that obtains is spun on the silicon substrate for 4 times with the deionized water dilution, treats promptly to have formed nanometer ball macromolecule micelle template after the solvent evaporates, the diameter of ball is about 20 nanometers.
Embodiment 2: with weight percent is that 1% segmented copolymer is dissolved among the cosolvent Dioxane, stirs 3 hours, slowly adds polystyrene PS segmental precipitation agent deionized water then, induces segmented copolymer generation microphase-separated, is self-assembled into micella.Until the content of water is 18% o'clock of liquor capacity, stops to add water.Continuously stirring 2 hours adds deionized water then, and add-on is 5 times of total liquor capacity, and the macromolecule micelle form is freezed, and keeps existing form and size.The above-mentioned solution for preparing is put into dialysis tubing, the small molecules of molecular weight under 12000 molecular weight can freely be passed through, dialysis is 5 days in the deionized water environment, changes water every day 1 time.Promptly obtain diameter uniformly, the nanometer rod micella of longer dimension, the longest is 5 microns, sees Figure 1B/B '.The above-mentioned micella that obtains is spun on the silicon substrate for 4 times with the deionized water dilution, treats promptly to have formed nanometer rod polymer template after the solvent evaporates.
Embodiment 3: with weight percent is that 1% segmented copolymer is dissolved among the cosolvent THF, stirs 5 hours, slowly adds the precipitation agent deionized water of PS then, induces segmented copolymer generation microphase-separated, is self-assembled into micella.Until the content of water is 17% o'clock of liquor capacity, stops to add water.Continuously stirring 3 hours.Add deionized water then, add-on is 6 times of total liquor capacity, and the macromolecule micelle form is freezed, and keeps existing form and size.The above-mentioned solution for preparing is put into dialysis tubing, the small molecules of molecular weight below 12000 can freely be passed through, dialysis is 7 days in the deionized water environment, changes water every day 1 time.Promptly obtain the nano vesicle micella, see Fig. 1 C/C '.The above-mentioned micella that obtains is spun on the silicon substrate for 5 times with the deionized water dilution, treats promptly to have formed nano vesicle macromolecule micelle template after the solvent evaporates.
Embodiment 4: with weight percent is that 1% segmented copolymer is dissolved among the cosolvent Dioxane, stirs 10 hours, slowly adds the precipitation agent deionized water of PS then, induces segmented copolymer generation microphase-separated, is self-assembled into micella.Until the content of water is 25% o'clock of liquor capacity, stops to add water.Continuously stirring 48 hours.Add deionized water then, add-on is 5 times of total liquor capacity, and the macromolecule micelle form is freezed, and keeps existing form and size.The above-mentioned solution for preparing is put into dialysis tubing, the small molecules of molecular weight below 12000 can freely be passed through, dialysis is 4 days in the deionized water environment, changes water every day 1 time.Promptly obtain novel nano-rings micella, see Fig. 2.The above-mentioned micella that obtains is spun on the silicon substrate for 5 times with the deionized water dilution, treats promptly to have formed novel nano ring macromolecule micelle template after the solvent evaporates.
Embodiment 5: with weight percent is that 1.5% segmented copolymer is dissolved among the cosolvent Dioxane/THF=90/10, stirs 7 hours, slowly adds the precipitation agent deionized water of PS then, induces segmented copolymer generation microphase-separated, is self-assembled into micella.Until the content of water is 22% o'clock of liquor capacity, stops to add water.Continuously stirring 3 hours.Add deionized water then, add-on is 4 times of total liquor capacity, and the macromolecule micelle form is freezed, and keeps existing form and size.The above-mentioned solution for preparing is put into dialysis tubing, molecular weight can freely be passed through at the small molecules below 12000, dialysis is 6 days in the deionized water environment, changes water every day 1 time.Promptly obtain length than the nanometer rod micella that embodiment 2 is short slightly, diameter is big slightly, see Fig. 3 A.The above-mentioned micella that obtains is spun on the silicon substrate for 4 times with the deionized water dilution, treats promptly to have formed the nanometer rod macromolecule micelle template that length is short slightly, diameter is big slightly after the solvent evaporates.
Embodiment 6: with weight percent is that 2% segmented copolymer is dissolved among the cosolvent Dioxane/THF=80/20, stirs 8 hours, slowly adds the precipitation agent deionized water of PS then, induces segmented copolymer generation microphase-separated, is self-assembled into micella.Until the content of water is 25% o'clock of liquor capacity, stops to add water.Continuously stirring 4 hours.Add deionized water then, add-on is 4 times of total liquor capacity, and the macromolecule micelle form is freezed, and keeps existing form and size.The above-mentioned solution for preparing is put into dialysis tubing, the following small molecules of molecular weight 12000 molecular weight can freely be passed through, dialysis is 5 days in the deionized water environment, changes water every day 1 time.Promptly obtain the micella of nanometer stub, the longest is 2 microns, sees Fig. 3 B.The above-mentioned micella that obtains is spun on the silicon substrate for 3 times with the deionized water dilution, treats promptly to have formed nanometer stub macromolecule micelle template after the solvent evaporates.
Embodiment 7: with weight percent is that 1% segmented copolymer is dissolved among the cosolvent Dioxane/THF=30/70, stirs 12 hours, slowly adds the precipitation agent deionized water of PS then, induces segmented copolymer generation microphase-separated, is self-assembled into micella.Until the content of water is 23% o'clock of liquor capacity, stops to add water.Continuously stirring 10 hours.Add deionized water then, add-on is 5 times of total liquor capacity, and the macromolecule micelle form is freezed, and keeps existing form and size.The above-mentioned solution for preparing is put into dialysis tubing, the small molecules of molecular weight below 12000 can freely be passed through, dialysis is 3 days in the deionized water environment, changes water every day 1 time.Promptly obtain form fixed nanometer stub micella, 0.7 micron of maximum length, diameter is about 43 nanometers, sees Fig. 3 C.The above-mentioned micella that obtains is spun on the silicon substrate for 5 times with the deionized water dilution, treats promptly to have formed nanometer stub macromolecule micelle template after the solvent evaporates.
Claims (2)
1. the making method of a nano structural material template, key step is as follows:
The preparation of A, macromolecular solution: be weight percentage 1～3% polyvinylpyridine and the triblock copolymer of polystyrene of concentration is dissolved in the cosolvent, cosolvent is tetrahydrofuran (THF), dimethyl formamide or dioxane one or both a mixed solvent wherein, mixed solvent mixed in 30: 70 by volume～90: 10, stirred and obtained homodisperse macromolecular solution in 3～12 hours;
B, nano-high molecule micellar are made: under the agitation condition, in macromolecular solution, drip the precipitation agent deionized water of polystyrene segment PS, induce segmented copolymer generation microphase-separated, be self-assembled into the micella of nanoscale, the precipitation dosage that drips is 6～25% of macromolecular solution volume, stirs under normal temperature condition 2～48 hours, and then adds deionized water, add-on is 4～6 times of macromolecular solution volume, promptly obtains the frozen macromolecule micelle coarse fodder of form;
The making of C, nano-high molecule template: the micella coarse fodder that obtains is put into dialysis tubing, molecular weight can freely be passed through at the small molecules below 12000, in deionized water, dialyse 3～7 angel's macromolecule micelle morphological structures, fixed size, promptly obtain the nano-high molecule micella that nucleocapsid structure and shell contain active group, the micella dilute solution is spin-coated on the planar substrates, treats promptly to obtain after the solvent evaporates template of nano structural material.
2. the making method of a kind of nano structural material template as claimed in claim 1 is characterized in that described macromolecule micelle has nanometer ball, nanometer rod, nano-rings or nano vesicle.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305937C (en) * | 2005-02-25 | 2007-03-21 | 复旦大学 | Prepn process of metal coordinating polymer material in nanometer structure |
| CN100408626C (en) * | 2006-07-17 | 2008-08-06 | 南京大学 | Processing method of polystyrene at 10 to 60 deg.C |
| CN100506687C (en) * | 2005-06-20 | 2009-07-01 | 中国科学院化学研究所 | Method for forming two dimensional ordered lattice of metal or metal alloy quantum dots on solid interface, in which dot diameters are less than or equal to 5nm |
| CN102516564A (en) * | 2011-12-16 | 2012-06-27 | 华中科技大学 | Soap-free preparation method of biodegradable polymer nanoparticles |
| CN102604065A (en) * | 2012-03-27 | 2012-07-25 | 中国科学院长春应用化学研究所 | Cross-linked biologically degradable carrier polymer, micelle and vesicle, and preparation method and application of the cross-linked biologically degradable carrier polymer, micelle and vesicle |
| CN103043645A (en) * | 2012-12-12 | 2013-04-17 | 同济大学 | Method for inducing polymer to graft carbon nano tube in mixed solvent for self-assembly |
| CN104119763A (en) * | 2014-07-25 | 2014-10-29 | 西安交通大学 | Preparation method and application of lyophobic block copolymer/SiO2 sandstone protection hybrid material |
| CN108929447A (en) * | 2018-05-07 | 2018-12-04 | 复旦大学 | A kind of preparation method of core-shell structure polymer nanocomposite ring |
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2004
- 2004-04-23 CN CN 200410010817 patent/CN1257224C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305937C (en) * | 2005-02-25 | 2007-03-21 | 复旦大学 | Prepn process of metal coordinating polymer material in nanometer structure |
| CN100506687C (en) * | 2005-06-20 | 2009-07-01 | 中国科学院化学研究所 | Method for forming two dimensional ordered lattice of metal or metal alloy quantum dots on solid interface, in which dot diameters are less than or equal to 5nm |
| CN100408626C (en) * | 2006-07-17 | 2008-08-06 | 南京大学 | Processing method of polystyrene at 10 to 60 deg.C |
| CN102516564A (en) * | 2011-12-16 | 2012-06-27 | 华中科技大学 | Soap-free preparation method of biodegradable polymer nanoparticles |
| CN102516564B (en) * | 2011-12-16 | 2014-03-26 | 华中科技大学 | Soap-free preparation method of biodegradable polymer nanoparticles |
| CN102604065A (en) * | 2012-03-27 | 2012-07-25 | 中国科学院长春应用化学研究所 | Cross-linked biologically degradable carrier polymer, micelle and vesicle, and preparation method and application of the cross-linked biologically degradable carrier polymer, micelle and vesicle |
| CN103043645A (en) * | 2012-12-12 | 2013-04-17 | 同济大学 | Method for inducing polymer to graft carbon nano tube in mixed solvent for self-assembly |
| CN103043645B (en) * | 2012-12-12 | 2014-12-10 | 同济大学 | Method for inducing polymer to graft carbon nano tube in mixed solvent for self-assembly |
| CN104119763A (en) * | 2014-07-25 | 2014-10-29 | 西安交通大学 | Preparation method and application of lyophobic block copolymer/SiO2 sandstone protection hybrid material |
| CN108929447A (en) * | 2018-05-07 | 2018-12-04 | 复旦大学 | A kind of preparation method of core-shell structure polymer nanocomposite ring |
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