CN101381467A - Preparation method of biodegradable high molecule nano material by porous template and apparatus - Google Patents
Preparation method of biodegradable high molecule nano material by porous template and apparatus Download PDFInfo
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- CN101381467A CN101381467A CNA2008102012807A CN200810201280A CN101381467A CN 101381467 A CN101381467 A CN 101381467A CN A2008102012807 A CNA2008102012807 A CN A2008102012807A CN 200810201280 A CN200810201280 A CN 200810201280A CN 101381467 A CN101381467 A CN 101381467A
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Abstract
The invention discloses a method for preparing a biodegradable high molecular nano-material by porous template method and a device thereof. The method comprises the following steps: cleaning a porous template by deionized water; completely dissolving a degradable high molecular material in certain amount of solvent, and then dripping degradable high molecular solvent onto the porous template to ensure that the solvent is completely infiltrated into the porous template; sticking the porous template on a slide to be put in an oven for drying; and dissolving the porous template by an etching agent, and drying the solvent after cleaning so as to produce the degradable high molecular nano-material. The device consists of a sand core funnel, a mask, the porous template and a vacuum pump. The method and the device can easily prepare various biodegradable high molecular nano-materials, and have potential application value in medicine slow release, organizational projects and other fields.
Description
Technical field
The invention belongs to advanced biological nano technical field of material.Particularly a kind of preparation method and device of the biodegradable high molecule nano material based on foraminous die plate.
Background technology
In recent years, China scientist makes remarkable achievements repeatedly in the nanosecond science and technology field, and a series of important paper publishings are in world's authority's science publication or relevant international conference.In the many research field relevant with nanosecond science and technology, compare hot topic and might take the lead in obtaining having of practical application: nanometer preparation method, nano-device makes up, nanosecond medical science at present.Wherein the self-assembled nano structures material more and more receives people's concern, is becoming the new focus of nano materials research.Its basic intension is, and to be elementary cell with nano particle, nano wire and nanotube be arranged in the system with nanostructure in one dimension, the assembling of two and three dimensions space.The foraminous die plate method is a method of the extremely important and simple and easy easy control of assembling nanostructure material.
Utilize foraminous die plate to prepare metal, semi-conductor, polymer nano material in comparative maturity ground at present.These materials have special photoelectromagnetism functional performance after giving nanostructure, thereby lay a good foundation for the structure of photoelectromagnetism nano-device.In the nano pore of porous alumina, is electrolytic solution with dimethyl sulfoxide (DMSO) (DMSO) solution of metal chloride as [Appl.Phy.Lett., 2001,79 (7): 1039] such as A.J.Yin, makes metal nanometer line array by the alternating-current deposition.H.B.Xu etc. [Chem.Phy.Lett., 2005,412:294] electrophoretic deposition in porous alumina formwork has made organic CuPc nano wire.Steinhart etc. [Science, 2002,296 (14): 1997] utilize porous alumina formwork, have prepared the nanotube of polystyrene (PS), polytetrafluoroethylene (PTFE) by the fusion dampening.They utilize wide aperture silicon oxide template to prepare polymethylmethacrylate (PMMA) nanotube simultaneously.
Foraminous die plate is the effective ways that make up the degradable macromolecule nano material, but rarely has report.Because Biodegradable high-molecular is degradable in vivo, its degradation production can also finally excrete in metabolism, reducing the long-term effect of material to greatest extent, thereby will have broad prospect of application in fields such as medicament slow release and organizational projects by the Biodegradable high-molecular nano material of foraminous die plate method preparation to body.The conventional preparation method of high molecule nano material is scorification and solution impregnation method, and preceding kind of method can be accelerated material degradation, and back kind method can not be soaked into fully because solution viscosity is higher.
Summary of the invention
For addressing the above problem, we invent the method and apparatus that a kind of foraminous die plate prepares biodegradable high molecule nano material, again can be with its called after negative pressure leaching method.Biodegradable high molecule nano material based on foraminous die plate of the present invention comprises the preparation method and the device of nano wire and nanotube, by changing macromolecular solution concentration and template parameter, can regulate and control the nano material three-dimensional dimension according to actual needs.
The technical solution adopted in the present invention is as follows:
A kind of foraminous die plate prepares the method for biodegradable high molecule nano material, it is characterized in that this method is to be filled into Biodegradable high-molecular solution in the foraminous die plate behind negative pressure leaching, obtain the nano material of degradable macromolecule after with the foraminous die plate etching with etching agent, concrete steps are as follows:
A. open vacuum pump (8), locate to put foraminous die plate (5), be added drop-wise to foraminous die plate (5) with deionized water earlier and go up the washing foraminous die plate 2～3 times in the mask aperture (7) of mask (3);
B. degradable high polymer material fully is dissolved in the proper amount of solvent, then 2～3 degradable macromolecule drips of solution is added on the foraminous die plate (5), treat to stop to vacuumize after degradable macromolecule solution all infiltrates foraminous die plate (5);
C. careful takes out foraminous die plate (5) and with double faced adhesive tape foraminous die plate (5) is affixed on the slide with tweezers, puts into 40 ℃ of baking oven bakings 15 minutes;
D. use etching agent in 40 ℃ of baking ovens foraminous die plate (5) to be dissolved, remove remaining salinity with a large amount of washed with de-ionized water, 40 ℃ of baking ovens dried by the fire 15 minutes, promptly got the nano material of degradable macromolecule.
Described Biodegradable polymer material is natural degradable macromolecular material such as chitosan, starch, Mierocrystalline cellulose, protein, perhaps is synthesized degradable macromolecular material such as polyglutamic acid, poly(lactic acid), poly butyric ester, poly-hydroxyl valerate.
Described foraminous die plate is to have inorganic or organic porous material template in void channels aperture such as anodic oxidation aluminium formwork, nano aperture glass template, mesoporous zeolite template, porous silicon template, metal form, polycarbonate template.
Used solvent does not possess the ability of dissolving foraminous die plate and sand core funnel among the described method steps b, solvent is a water, perhaps is one or more the mixed solvents in more volatile solvent such as chloroform in paraffinic hydrocarbons, alkene, alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, hydrogenate hydrocarbon, terpene hydrocarbon, halohydrocarbon, heterocyclization thing, nitrogenous compound and the sulfocompound, tetrahydrofuran (THF), toluene, ethanol, the ether.
Etching agent used among the described method steps d is strong base solution such as NaOH or KOH solution etc. for not possessing the solution that dissolves Biodegradable polymer material but possess dissolving foraminous die plate ability.
A kind ofly be used for the device that foraminous die plate prepares the biodegradable high molecule nano material method, form by sand core funnel (1), mask (3), foraminous die plate (5) and vacuum pump (8), it is characterized in that core (2) is positioned at the middle part of sand core funnel (1), mask (3) is close to above the core (2), there is an endoporus in mask (3) central authorities, be mask aperture (7), the aperture of foraminous die plate (5) is slightly larger than the aperture of mask aperture (7) in the mask (3), and foraminous die plate (5) is close to above the mask (3) and covers mask aperture (7); Outlet (6) is arranged at sand core funnel (1) bottom, and outlet (6) connects vacuum pump (8).
The concrete structure of negative pressure leaching device of the present invention is noted following 2 points:
1) select suitable sand core funnel as the suction filtration supportive body.Be chosen as the undissolved thin-film material of macromolecule solvent (selecting water-fast polyethylene film in the example for use) as mask (3).
2) according to required nano material macro-size cutting mask (3): mask (3) center mask aperture (7) is consistent with the nano material macro-size, and mask (3) diameter is consistent with sand core funnel (1) interior diameter.Mask (3) is close to sand core funnel.
The mechanism that the foraminous die plate legal system is equipped with polymer nano material is as follows: when being placed on solution and being placed on the matrix surface with high surface energy, its can scatter as the liquid of lower concentration and form precursor film.Because foraminous die plate also has high surface energy, when polymers soln or melt are in contact with it, also similar wetting phenomena can take place.In the wetting starting stage, hole wall can be covered by a kind of thin surface film.This is because form the motivating force of the motivating force of surface film much larger than the completely filled micropore at the micropore inwall.In addition, hole wall is wetting to be taken place in wetting different time sections with the completely filled phenomenon, and the evaporation of solvent can stop liquid completely filled micropore in the solution, thereby makes polymer nanotube.And when macromolecular solution concentration relative with viscosity higher or pore size of template is less relatively or infiltration situation repeatedly under just can obtain polymer nano-wire.
Enumerate preparation biodegradable natural polymer chitosan and biological degradable synthesized polymer polyglutamic acid nano material preparation process in the example of the present invention.Foraminous die plate is selected anodic oxidation aluminium formwork for use, and mask is selected polyethylene film, and selecting solvent for use is water.Preparation biodegradable natural polymer chitosan dissolves etching with strong base solution (as the NaOH of 1～4mol/L or KOH etc.) with template, and preparation biodegradable polyglutamic acid nano material usefulness strong acid solution is (as HCl or the H of 1～4mol/L
3PO
4Deng) template is dissolved etching.
The present invention has successfully prepared the nano material of Biodegradable high-molecular chitosan (Fig. 2) and polyglutamic acid (Fig. 3) by the negative pressure leaching device with foraminous die plate.Has potential using value in fields such as medicament slow release and organizational projects after giving nanostructure with Biodegradable high-molecular.
Description of drawings
Fig. 1: self-control negative pressure leaching method Experimental equipment
Each digital code is expressed as follows among Fig. 1: 1. sand core funnel 2. cores 3. masks 4. degradable macromolecule solution droppings place 5. foraminous die plates 6. export 7. mask aperture, 8. vacuum pumps.
Fig. 2: the biodegradable chitosan nano material SEM figure of foraminous die plate method preparation
Fig. 3: the biodegradable polyglutamic acid nano material SEM figure of foraminous die plate method preparation
Embodiment
Further set forth the present invention below by embodiment.
Negative pressure leaching method legal system is equipped with the chitosan nano material.
I. make negative pressure leaching method experimental installation such as accompanying drawing 1 by oneself, open vacuum pump, put anodic oxidation aluminium formwork, be added drop-wise on the anodic oxidation aluminium formwork with deionized water earlier and wash template 2～3 times at the mask aperture place of polyethylene mask.
Ii. the chitosan solution of water preparation massfraction 1% is added drop-wise to 2～3 chitosan solutions on the anodic oxidation aluminium formwork, treats to stop to vacuumize after chitosan solution solution all infiltrates anodic oxidation aluminium formwork.
Iii. careful takes out anodic oxidation aluminium formwork and with double faced adhesive tape anodic oxidation aluminium formwork is affixed on the slide with tweezers, puts into 40 ℃ of baking oven bakings 15 minutes.
Iv. the NaOH solution with etching agent 4mol/L dissolves anodic oxidation aluminium formwork in 40 ℃ of baking ovens, and a large amount of washed with de-ionized water are removed remaining salinity, and 40 ℃ of baking ovens dried by the fire 15 minutes, promptly got the nano material of chitosan.
Negative pressure leaching method legal system is equipped with the chitosan nano material.
I. make negative pressure leaching method experimental installation such as accompanying drawing 1 by oneself, open vacuum pump, put anodic oxidation aluminium formwork, be added drop-wise on the anodic oxidation aluminium formwork with deionized water earlier and wash template 2～3 times at the mask aperture place of polyethylene mask.
Ii. the chitosan solution of water preparation massfraction 1% is added drop-wise to 2～3 chitosan solutions on the anodic oxidation aluminium formwork, treats to stop to vacuumize after chitosan solution solution all infiltrates anodic oxidation aluminium formwork.
Iii. careful takes out anodic oxidation aluminium formwork and with double faced adhesive tape anodic oxidation aluminium formwork is affixed on the slide with tweezers, puts into 40 ℃ of baking oven bakings 15 minutes.
Iv. the KOH solution with etching agent 3mol/L dissolves anodic oxidation aluminium formwork in 40 ℃ of baking ovens, and a large amount of washed with de-ionized water are removed remaining salinity, and 40 ℃ of baking ovens dried by the fire 15 minutes, promptly got the nano material of chitosan.
The negative pressure leaching legal system is equipped with the polyglutamic acid nano material.
I. make negative pressure leaching method experimental installation such as accompanying drawing 1 by oneself, open vacuum pump, put anodic oxidation aluminium formwork, be added drop-wise on the anodic oxidation aluminium formwork with deionized water earlier and wash template 2～3 times at the mask aperture place of polyethylene mask.
Ii. the polyglutamic acid solution of water preparation massfraction 3% is added to 2～3 polyglutamic acid drips of solution on the anodic oxidation aluminium formwork, treats to stop to vacuumize after polyglutamic acid solution all infiltrates anodic oxidation aluminium formwork.
Iii. careful takes out anodic oxidation aluminium formwork and with double faced adhesive tape anodic oxidation aluminium formwork is affixed on the slide with tweezers, puts into 40 ℃ of baking oven bakings 15 minutes.
Iv. use the H of etching agent 1mol/L
3PO
4With the anodic oxidation aluminium formwork dissolving, a large amount of washed with de-ionized water are removed remaining salinity to solution in 40 ℃ of baking ovens, and 40 ℃ of baking ovens dried by the fire 15 minutes, promptly got the nano material of polyglutamic acid.
The negative pressure leaching legal system is equipped with the polyglutamic acid nano material.
I. make negative pressure leaching method experimental installation such as accompanying drawing 1 by oneself, open vacuum pump, put anodic oxidation aluminium formwork, be added drop-wise on the anodic oxidation aluminium formwork with deionized water earlier and wash template 2～3 times at the mask aperture place of polyethylene mask.
Ii. the polyglutamic acid solution of water preparation massfraction 1% is added to 2～3 polyglutamic acid drips of solution on the anodic oxidation aluminium formwork, treats to stop to vacuumize after polyglutamic acid solution all infiltrates anodic oxidation aluminium formwork.
Iii. careful takes out anodic oxidation aluminium formwork and with double faced adhesive tape anodic oxidation aluminium formwork is affixed on the slide with tweezers, puts into 40 ℃ of baking oven bakings 15 minutes.
Iv. the HCl solution with etching agent 2mol/L dissolves anodic oxidation aluminium formwork in 40 ℃ of baking ovens, and a large amount of washed with de-ionized water are removed remaining salinity, and 40 ℃ of baking ovens dried by the fire 15 minutes, promptly got the nano material of polyglutamic acid.
Above-mentioned description to example is can understand and apply the invention method for the ease of those skilled in the art.Those of ordinary skill in the art can make various modifications to these embodiments easily, and needn't pass through performing creative labour being applied in the general principle of this explanation in other application examples.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention to improvement and modification that the present invention makes according to announcement of the present invention.
Claims (6)
1. a foraminous die plate prepares the method for biodegradable high molecule nano material, it is characterized in that this method is to be filled into Biodegradable high-molecular solution in the foraminous die plate behind negative pressure leaching, obtain the nano material of degradable macromolecule after with the foraminous die plate etching with etching agent, concrete steps are as follows:
A. open vacuum pump (8), locate to put foraminous die plate (5), be added drop-wise to foraminous die plate (5) with deionized water earlier and go up the washing foraminous die plate 2～3 times in the mask aperture (7) of mask (3);
B. degradable high polymer material fully is dissolved in the proper amount of solvent, then 2～3 degradable macromolecule drips of solution is added on the foraminous die plate (5), treat to stop to vacuumize after degradable macromolecule solution all infiltrates foraminous die plate (5);
C. careful takes out foraminous die plate (5) and with double faced adhesive tape foraminous die plate (5) is affixed on the slide with tweezers, puts into 40 ℃ of baking oven bakings 15 minutes;
D. use etching agent in 40 ℃ of baking ovens foraminous die plate (5) to be dissolved, remove remaining salinity with a large amount of washed with de-ionized water, 40 ℃ of baking ovens dried by the fire 15 minutes, promptly got the nano material of degradable macromolecule.
2. method according to claim 1, it is characterized in that Biodegradable polymer material is natural degradable macromolecular material such as chitosan, starch, Mierocrystalline cellulose, protein, perhaps is synthesized degradable macromolecular material such as polyglutamic acid, poly(lactic acid), poly butyric ester, poly-hydroxyl valerate.
3. method according to claim 1 is characterized in that foraminous die plate is to have inorganic or organic porous material template in void channels aperture such as anodic oxidation aluminium formwork, nano aperture glass template, mesoporous zeolite template, porous silicon template, metal form, polycarbonate template.
4. method according to claim 1, it is characterized in that the used solvent of step b does not possess the ability of dissolving foraminous die plate and sand core funnel, solvent is a water, perhaps is one or more the mixed solvents in more volatile solvent such as chloroform in paraffinic hydrocarbons, alkene, alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, hydrogenate hydrocarbon, terpene hydrocarbon, halohydrocarbon, heterocyclization thing, nitrogenous compound and the sulfocompound, tetrahydrofuran (THF), toluene, ethanol, the ether.
5. method according to claim 1 is characterized in that the used etching agent of steps d for not possessing the solution that dissolves Biodegradable polymer material but possess dissolving foraminous die plate ability, is strong base solution such as NaOH or KOH solution etc.
6. one kind is used for the device that the described foraminous die plate of claim 1 prepares the biodegradable high molecule nano material method, form by sand core funnel (1), mask (3), foraminous die plate (5) and vacuum pump (8), it is characterized in that core (2) is positioned at the middle part of sand core funnel (1), mask (3) is close to above the core (2), there is an endoporus in mask (3) central authorities, be mask aperture (7), the aperture of foraminous die plate (5) is slightly larger than the aperture of mask aperture (7) in the mask (3), and foraminous die plate (5) is close to above the mask (3) and covers mask aperture (7); Outlet (6) is arranged at sand core funnel (1) bottom, and outlet (6) connects vacuum pump (8).
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| CNA2008102012807A CN101381467A (en) | 2008-10-16 | 2008-10-16 | Preparation method of biodegradable high molecule nano material by porous template and apparatus |
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| CNA2008102012807A CN101381467A (en) | 2008-10-16 | 2008-10-16 | Preparation method of biodegradable high molecule nano material by porous template and apparatus |
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| CN104479088A (en) * | 2014-12-10 | 2015-04-01 | 郑州轻工业学院 | Method for preparing thermosetting polyurethane acrylate nano array by virtue of template in situ polymerization |
| CN104479088B (en) * | 2014-12-10 | 2017-01-25 | 郑州轻工业学院 | Method for preparing thermosetting polyurethane acrylate nano array by virtue of template in situ polymerization |
| CN109293944A (en) * | 2018-10-26 | 2019-02-01 | 浙江海洋大学 | A kind of preparation method of high-molecular polyivnyl alcohol nanometer grass |
| CN113244460A (en) * | 2021-04-29 | 2021-08-13 | 南开大学 | Oriented microchannel bracket for promoting tissue regeneration and preparation method thereof |
| CN114990664A (en) * | 2022-05-17 | 2022-09-02 | 山东建筑大学 | Elliptical-cylindrical-surface-shaped aluminum oxide template for preparing nano material, preparation method and application |
| CN114990663A (en) * | 2022-05-17 | 2022-09-02 | 山东建筑大学 | Parabolic cylindrical aluminum oxide template for preparing nano material, preparation method and application |
| CN114990664B (en) * | 2022-05-17 | 2024-04-16 | 山东建筑大学 | Elliptic cylindrical alumina template for preparing nano material, preparation method and application |
| CN114990663B (en) * | 2022-05-17 | 2024-06-07 | 山东建筑大学 | Parabolic cylindrical aluminum oxide template for preparing nano material, preparation method and application |
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