CN105017554B - A method of preparing nanoporous polymeric thin-film material - Google Patents
A method of preparing nanoporous polymeric thin-film material Download PDFInfo
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- CN105017554B CN105017554B CN201410153125.8A CN201410153125A CN105017554B CN 105017554 B CN105017554 B CN 105017554B CN 201410153125 A CN201410153125 A CN 201410153125A CN 105017554 B CN105017554 B CN 105017554B
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Abstract
The invention discloses a kind of preparation methods of nanoporous polymeric thin-film material；By the way that polymer solution forms a film, is crosslinked, the thin polymer film with network structure is obtained, thin polymer film is swollen in processing solution later, is finally dried, obtains nanoporous polymeric film.This method is convenient, it is economical can largely use again, nanometer micropore film prepared by the present invention have height rough surface, nano-grade size, uniform dense distribution feature.
Description
Technical field
The invention belongs to surfacing fields, more particularly to a kind of side for preparing nanoporous polymeric thin-film material
Method.
Background technique
In recent years, microporous polymer film material, especially aperture nanometer scale microporous film material, because it has
Unique property and good application prospect have become the hot spot of research.They are widely used in separation and filter membrane, controllable
Drug, catalyst carrier, optical thin film, automatic cleaning coating, all various aspects such as template, tissue engineering bracket of materials synthesis.
Currently, the preparation method of microporous polymer film material can be generally divided into two classes：From top to bottom（top-down）
From bottom to top（bottom-up）.Photoetching and the relevant technologies are a kind of common methods, however are limited by optical diffraction, usually
Lithographic equipment is difficult to manufacture the poromerics less than sub-micron pore size（M Campbell et al,Nature2000,404,53;
JR Anderson et al, Electrophoresis2000,21,27-40）.Template is also a kind of common method, first prefabricated
Micropore template, then with polymer replication (Wang Jianying et al, Adv.Mater.2007,19,3865-3871)；But
Its process is complicated, and template construct is at high cost.Recently some other rule of thumbs are had also appeared, e.g., point
Sub- self-assembly method.It is to utilize the mutual insoluble in solid film of different blocks for example, synthesizing asymmetric amphiphilic block copolymer
Mutually separation occurs to generate subtle aggregation of different shapes, and nano-scale is further made by different processing methods
Microcellular structure（EJW Cross land et al,Soft Matter,2007,3,94-98）；However the cost of this method
Height, and have higher requirements to structure.Rubner develop it is a kind of utilize L-B-L method, by by cationic polyelectrolyte and yin
Cationic polyelectrolyte is alternately assembled into multilayer film, and nanometer micropore membrane material (JD is then obtained by aqueous solution processing
Mendelsohn, Langmuir2000,16,5017-5023)；However, not by electrostatic or the structure of interaction of hydrogen bond generation
Stablize, it is rotten to be easy to be protected from environmental generation.
It is simple therefore, it is necessary to develop a kind of preparation process, it is at low cost, and performance is stable, meets the new of environment protection requirement
The method for preparing polymer micro thin-film material.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of methods for preparing nanoporous polymeric thin-film material；Pass through
By polymer solution film forming, crosslinking, the thin polymer film with network structure is obtained, later by thin polymer film in processing solution
Middle swelling, is finally dried, and obtains nanoporous polymeric film.This method is convenient, economy can be used largely again, present invention preparation
Nanometer micropore film have height rough surface, nano-grade size, uniform dense distribution feature.
The present invention adopts the following technical solutions：
A method of nanoporous polymeric thin-film material is prepared, is included the following steps：
1）By polymer solution film forming, crosslinking, the thin polymer film with network structure is obtained；
2）Thin polymer film is swollen in processing solution；
3）It is dry, obtain nanoporous polymeric film.
Preferably, the step 1）In, polymer solution includes polymer, solvent and additive.The solvent is that can incite somebody to action
The substance of polymer dissolution, those skilled in the art can select as needed.In order to reach different applicabilities, polymer
Certain additive can be added in solution, including：Plasticizer, coloring agent, stabilizer, fire retardant, antioxidant, processing aid etc.
Deng those skilled in the art can select as needed.
The step 1）In, polymer is the polymer on main chain and/or side chain with activity of cross-linking reaction functional group.It is poly-
Closing object and being chemically crosslinked the thin polymer film to be formed by depth is highly cross-linked semi-rigid network structure, and thin polymer film passes through
Swelling processing occurs mutually to separate, and stable column shape microcellular structure is formd after drying.
The polymer type can for ionic or non-ionic, amphoteric or amphiphilic, linearly or nonlinearly framework
Homopolymer or copolymer.
Preferably, the step 1）In, polymer is water-soluble polymer.The water-soluble polymer is selected from following material
One of or it is a variety of：Ionic water-soluble polymers, non-ionic water-soluble polymer.
It is highly preferred that the Ionic water-soluble polymers contain carboxyl or quaternary ammonium salt group；It is described non-ionic water-soluble
Property polymer contains amide groups or hydroxyl group.
Most preferably, the step 1）In, polymer is selected from one of following material or a variety of：The homopolymer of acrylic acid
And its homopolymer and its copolymer, allyl of the homopolymer and its copolymer of copolymer, methacrylic acid, vinylbenzenesulfonic acid
The homopolymer and its copolymer, diallyl dimethyl of the homopolymer and its copolymer of sulfonic acid, 2- propionamido -2- methyl propane sulfonic acid
The homopolymer and its copolymer of ammonium chloride, the homopolymer of allyl amine and its copolymer, vinylpyridine homopolymer and its
Copolymer, the homopolymer of acrylamide and its copolymer, the homopolymer of Methacrylamide and its copolymer, vinylpyridine
Homopolymer and its copolymer, the homopolymer of vinyl pyrrole ketone and its copolymer, polyvinyl alcohol, polyoxyethylene.
The film forming is that polymer solution is coated on substrate.A variety of film forming processing methods, including rotation can be used to apply
It covers, dip-coating, roller coating, blade coating and spraying, those skilled in the art can select as needed.A variety of substrates can be used, including
Metal or nonmetallic materials, including glass, silicon wafer, quartz, polymer（PS,PVC,PE）And metal（Stainless steel, gold, silver, aluminium,
Copper）, those skilled in the art can select as needed.Before coating, base material is pre-processed, to guarantee substrate
The cleaning on surface.
The film forming and crosslinking can carry out simultaneously, and can also first form a film post-crosslinking.
When crosslinking, crosslinking agent can be added or not added.It is required according to the property of polymer and reaction to match crosslinking agent.
Preferably, when crosslinking, crosslinking agent is added；Wherein, the crosslinking agent is selected from living oligomer, organic crosslinking agent or nothing
Machine crosslinking agent；The living oligomer is selected from Lauxite, melamine resin, epoxy resin or isocyanate resin, organic friendship
Join agent and is selected from formaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, oxalic acid, succinic acid, maleic anhydride, terephthalic anhydride, second two
Amine or butanediamine；The inorganic crosslinking agent is selected from chromic salts, boron salt, zirconates, terbium salt or titanium salt.
Various ways, including normal temperature crosslinked, heating can be used according to type of crosslinking agent and materials'use condition in crosslinking method
Crosslinking, photo-crosslinking, crosslinking with radiation etc., those skilled in the art can select as needed.
Preferably, the degree of cross linking of thin polymer film is 10%~60%.
Preferably, step 2）In, when polymer is water-soluble polymer, the processing solution is aqueous solution.The present invention
In, aqueous solution refers to the solution with water as solvent, can be acidic aqueous solution, alkaline aqueous solution or neutral aqueous solution.It is acid water-soluble
PH=1~7 of liquid, pH=8~13 of alkaline aqueous solution.
It is highly preferred that the processing solution is the aqueous solution of salt.Most preferably, the processing solution be NaCl, KCl,
CaCl2Or Na2SO4Aqueous solution.
Preferably, the concentration of saline solution is 0.05M~2M.
Preferably, step 2）In, the processing solution is acid solution or alkaline solution；It is highly preferred that the processing is molten
Liquid one or more acid chosen from the followings or alkali：Hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide.
Swelling time is 10min~48h, and those skilled in the art can select as needed.
The processing solution refer to polymer matching it is good, have high-affinity and infiltrative solution, its essence is
The solution that raw polymer can be dissolved, but in this application due to being first crosslinked by polymer film forming and again, so that its
It is only capable of swollen polymer.Those skilled in the art can determine whether out the processing solution for being suitble to certain polymer according to existing literature.
The step 3）In, it is dry that dry blowing, vacuum drying, freeze-drying etc. can be used.To prevent high temperature from causing to become
Shape and rotten, generallys use room temperature blowing drying, not only simple but also rapidly.
The surface for the nanometer micropore thin-film material that the present invention obtains has vertical columnar microstructure, and the aperture of micropore is in 10-
200nm, surface roughness（RMS）Reach 1000nm or more.The aperture of micron, the pattern on surface can change crosslinking and post-processing
Condition implements modulation.
The principle of the present invention is that thin polymer film is chemically crosslinked to form the high rigid network being crosslinked by depth, then
Limited swelling occurs by swelling action, forms stable column shape microcellular structure after dry.
The chemical crosslinking of polymer film is to generate Covalent bonding together by chemical action to form network macromolecular structure.It
On the one hand make the interconnected network structure for forming high crosslinking of polymer chain, provide the rigid subtle network architecture.Another party
Face, it is insoluble that it is changed into polymer by solubility, prevents the loss of polymer during post-processing.
Thin polymer film, which is immersed in, in good affinity processing solution polymer, and processing solution can rapidly permeate into poly-
In polymeric network structure, swelling action occurs, polymer network structure is promoted to deform, generation mutually separates.But due to polymerization
The support and limitation of object rigidity network structure, the variation of space structure be it is limited and very subtle, still retain after dry micro-
The mutually framework of separation, to generate the stable microcellular structure for having certain shapes and size.
Beneficial effects of the present invention are as follows：
1, process is simple, easy to operate, applied widely；
2, environmentally protective, there is no by-product generation in production process, without the discharge of harmful substance waste liquid, is suitble to aqueous height
Molecule processing；
3, performance is stable, mechanical-physical character is strong, durability is good；
4, nanometer micropore film prepared by the present invention can assign film surface multi-functional property, for example, super affinity, absorption, from
Son exchange, catalyst and drag reduction etc., have important application meaning.
5, nanometer micropore film prepared by the present invention has openable invertibity, can be used for developing intellectual material；Have
Surface modified function can derive the functional polymer material of different application.
6, nanometer micropore film prepared by the present invention has height rough surface, nano-grade size, uniform dense distribution
Feature can regulate and control the structure and performance of microporous barrier by changing preparation condition, adapt to the demand of different application.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing；
The AFM figure that Fig. 1 is the copolymer coated 2D and 3D of acrylic acid and acrylamide in embodiment 1.
Fig. 2 is acrylic acid and acrylamide copolymer and diallyldimethylammonium chloride and acrylamide in embodiment 4
Copolymer mixed coating SEM figure.
Fig. 3 is acrylic acid and acrylamide copolymer and diallyldimethylammonium chloride and acrylamide in embodiment 5
Copolymer mixed coating by pH=2 acid solution processing after obtain SEM figure.
Fig. 4 is acrylic acid and acrylamide copolymer and diallyldimethylammonium chloride and acrylamide in embodiment 6
Copolymer mixed coating be by pH=11 alkaline solution processing after obtain SEM figure.
Fig. 5 be in embodiment 7 PVA by the AFM of NaCl solution treated the 2D and 3D of 0.2M.
Specific embodiment
For a better understanding of the invention, the solution of the present invention, this hair will be further illustrated by specific embodiment below
Bright protection scope should include the full content of claim, but not limited to this.
Embodiment 1
1）The copolymer for taking sodium acrylate and acrylamide, is configured to aqueous solution, and 1h is stirred at room temperature, matter is then added
Amount is the glutaraldehyde of polymer quality 3%, continues to stir 1h, obtains coating liquid.
2）Clean substrate used, such as silicon wafer, by H2O2And H2SO4（vH2O2/v H2SO4=1：3）Mixed liquor is at 80 DEG C
0.5h is managed, it is dry in 70 DEG C of baking oven after clear water rinses, with to be used.
3）Polymer solution is uniformly coated in substrate of glass using the method for rotary coating.
4）Then by the coating in 40 DEG C of film-formings, heating time is 5 hours, obtains smooth surface coating, thickness is about
It is 6 μm.
5）Above-mentioned coating is immersed in 1h in the sodium chloride solution of 0.2mol/l, after taking-up, uses N after rinsing 30s with clear water2
It dries up dry to get to anionic polymer microporous membrane coating.
6）Use AFM（Bruker Multimodoe8）Observe the surface microstructure of coating.And by computer disposal analysis-
The geometric parameter of micro-structure.
The AFM that Fig. 1 is the 2D and 3D of acrylic acid and acrylamide copolymer coating in embodiment 1 schemes.
Embodiment 2
1）The copolymer for taking methacrylic acid and acrylamide, is configured to aqueous solution, and 1h is stirred at room temperature, is then added
Quality is the glutaraldehyde of polymer quality 15%, continues to stir 1h, obtains coating liquid.
2）Clean substrate used, such as glass, by H2O2And H2SO4（vH2O2/v H2SO4=1：3）Mixed liquor is at 80 DEG C
0.5h is managed, it is dry in 70 DEG C of baking oven after clear water rinses, with to be used.
3）Polymer solution is uniformly coated in substrate of glass using the method for dip-coating.
4）Then by the coating in 80 DEG C of film-formings, heating time is 2 hours, obtains smooth surface coating, thickness is about
It is 10 μm.
5）By above-mentioned coating, it is immersed in the Na of 2mol/l2SO41h in solution after taking-up, uses vacuum after rinsing 30s with clear water
It dries to get anionic polymer microporous membrane coating is arrived.
6）Use AFM（Bruker Multimodoe8）It observes the surface microstructure of coating and is analyzed by computer disposal micro-
The geometric parameter of structure, experimental result are similar with embodiment 1.
Embodiment 3
1）The anionic copolymer for taking acrylic acid and acrylamide, is configured to aqueous solution, and 1h is stirred at room temperature, then plus
Enter the glutaraldehyde that quality is polymer quality 10%, continues to stir 1h, obtain coating liquid.
2）Clean substrate used, such as glass, by H2O2And H2SO4（vH2O2/v H2SO4=1：3）Mixed liquor is at 80 DEG C
0.5h is managed, it is dry in 70 DEG C of baking oven after clear water rinses, with to be used.
3）Polymer solution is uniformly coated in substrate of glass using the method for blade coating.
4）Then by the coating in 60 DEG C of film-formings, heating time is 3 hours, obtains smooth surface coating, thickness is about
It is 10 μm.
5）By above-mentioned coating, it is immersed in 1h in the KCL solution of 0.2mol/l, after taking-up, uses blowing after rinsing 30s with clear water
It dries to get anionic polymer microporous membrane coating is arrived.
6）With the surface microstructure of AFM observation coating and by the geometric parameter of computer disposal analysis micro-structure, experiment
As a result similar with embodiment 1.
Embodiment 4
1）Acrylic acid and acrylamide copolymer and diallyldimethylammonium chloride and acrylamide copolymer are taken, respectively
Aqueous solution is made, 1h is stirred at room temperature, 10% Lauxite is added thereto, continues to stir 1h, it is molten to obtain two kinds of polymer
Liquid；By above two polymer solution with volume ratio 1：2 mixing, are configured to coating liquid.
2）Clean substrate used, such as glass, by H2O2And H2SO4（vH2O2/v H2SO4=1：3）Mixed liquor is at 80 DEG C
0.5h is managed, it is dry in 70 DEG C of baking oven after clear water rinses, with to be used.
3) polymer is equably sprayed on the glass substrate by the way of spraying.
4) then by the coating in 60 DEG C of film-formings, heating time is 3 hours, obtains smooth surface coating, thickness is about
It is 10 μm.
5) by above-mentioned coating, 1h in sodium-chloride water solution (0.2mol/l) after taking-up, rinses 30s with clear water and uses room temperature
Blowing is dry to get the composition polymer nanometer micropore film coating made to different processing solutions.
6）By SEM image, analyze to obtain micro-structure geometric parameter by computer disposal.
Fig. 2 is acrylic acid and acrylamide copolymer and diallyldimethylammonium chloride and acrylamide in embodiment 4
The SEM of copolymer mixed coating schemes.
Embodiment 5
1）Acrylic acid and acrylamide copolymer and diallyldimethylammonium chloride and acrylamide copolymer are taken, respectively
It is configured to aqueous solution, 1h is stirred at room temperature, two kinds of polymer aqueous solution is mutually mixed（Volume ratio 4：1）, then it is added 10%
Glyoxal, continue stir 1h, obtain coating liquid.
2）Clean substrate used, such as silicon wafer, by H2O2And H2SO4（vH2O2/vH2SO4=1：3）Mixed liquor is handled at 80 DEG C
0.5h, it is dry in 70 DEG C of baking oven after clear water rinses, with to be used.
3）Polymer is equably sprayed on the glass substrate by the way of rotary coating.
4）Then by the coating in 60 DEG C of film-formings, heating time is 3 hours, obtains smooth surface coating, thickness is about
It is 10 μm.
5）Above-mentioned coating is immersed in acidity（pH=2）Aqueous solution in 1h, after taking-up, rinsed and 30s and blown with N2 with clear water
Drying is to get the composition polymer nanometer micropore film coating made to different processing solutions.
6）By SEM image, analyze to obtain micro-structure geometric parameter by computer disposal.By acid solution（pH=2）Place
The coating of reason, the column shape microcellular structure surface geometry form with dense distribution, micro-pore diameter are 20~30nm, averag density
It is 40~60（1/μm2）.
Fig. 3 is acrylic acid and acrylamide copolymer and diallyldimethylammonium chloride and acrylamide in embodiment 5
The SEM figure that the mixed coating of copolymer obtains after the processing of the acid solution of pH=2.
Embodiment 6
With embodiment 5, difference is above-mentioned coating being immersed in alkalinity（pH=11）Aqueous solution in 1h, after taking-up, with clear
Water rinses 30s and with blowing drying to get to the composition polymer nanometer micropore film coating of different processing solutions production, has
The column shape microcellular structure surface geometry form of dense distribution, micro-pore diameter are 10~25nm, and density is 800~1000（1/μ
m2）.
Fig. 4 is acrylic acid and acrylamide copolymer and diallyldimethylammonium chloride and acrylamide in embodiment 6
The mixed coating of copolymer is the SEM figure obtained after the processing of the alkaline solution of pH=11.
Embodiment 7
1）Take polyvinyl alcohol（Commercial goods PVA-2488）, it is configured to the aqueous solution 10ml that mass fraction is 8%, is added
The acetic acid solution of the 1mol/l of 0.5ml is as catalyst, and after mixing evenly, the potassium bichromate that the 0.01mol/l of 0.5ml is added is molten
Liquid stirs evenly, and is configured to coating liquid.
2）Substrate is cleaned, substrate is iron plate, and iron plate removes oxide by acid soak, using surfactant washing surface layer
Organic solvent.
3）Using the method for rotary coating, above-mentioned coating liquid is uniformly coated in substrate of glass.
4）Then the coating is solidified 2 hours at 80 DEG C, obtains the smooth coating in surface.
5）By above-mentioned PVA coating, it is immersed in 1h in the sodium chloride solution of 0.2M, after taking-up, 30s is rinsed with clear water and uses N2
It dries up dry to get to PVA polymer nanocomposite microporous membrane coating.
6）With the surface microstructure of AFM observation coating.Graphical analysis results show：By above-mentioned preparation method, obtain
Microcellular structure surface with dense distribution.Micro-pore diameter is 50~90nm, 2~3nm of depth, density 20~30（1/μm2）.
Fig. 5 be in embodiment 7 PVA by the AFM of NaCl solution treated the 2D and 3D of 0.2M.
Embodiment 8
1）Take polyvinyl alcohol（Commercial goods PVA-2488）, it is configured to the aqueous solution 10ml that mass fraction is 8%.
2）Substrate, substrate PVC are cleaned, substrate carries out chemical oxidation treatment using chromic acid.
3）Using the method for roller coating, above-mentioned coating liquid is uniformly coated in PVC substrate.
4）Then the coating is irradiated into 0.5 hour progress photocuring under ultraviolet light, obtains the smooth coating in surface.
5）By above-mentioned PVA coating, it is immersed in 1h in the sodium chloride solution of 0.2M, after taking-up, 30s is rinsed with clear water, is used in combination
N2 drying it is dry to get arrive PVA polymer nanocomposite microporous membrane coating.Use AFM（Bruker Multimode8）Observe the table of coating
Face microstructure, experimental result are similar with embodiment 1.
Embodiment 9
1）Acrylic acid and methacrylamide copolymer and diallyl dichloride ammonium and methacrylamide copolymer are taken,
It is uniformly mixed, is configured to aqueous solution, 1h is stirred at room temperature, obtain coating liquid.
2）Clean substrate used, such as silicon wafer, by H2O2And H2SO4（vH2O2/v H2SO4=1：3）Mixed liquor is at 80 DEG C
0.5h is managed, it is dry in 70 DEG C of baking oven after clear water rinses, with to be used.
3）Polymer solution is uniformly coated in substrate of glass using the method for blade coating.
4）Then by the coating in 60 DEG C of film-formings, heating time is 3 hours, obtains smooth surface coating, thickness is about
It is 10 μm.
5）By above-mentioned coating, it is immersed in 1h in the KCL solution of 0.2mol/l, after taking-up, uses blowing after rinsing 30s with clear water
It dries to get anionic polymer microporous membrane coating is arrived.
6）Use AFM（Bruker Multimodoe8）It observes the surface microstructure of coating and is analyzed by computer disposal micro-
The geometric parameter of structure, experimental result are similar with embodiment 1.
Embodiment 10
1）Acrylate homopolymer and allyl amine homopolymer are taken, is configured to aqueous solution respectively, mixes, is stirred at room temperature
1h continues to stir 1h, obtains coating liquid.
2）Clean substrate used, such as glass, by H2O2And H2SO4（vH2O2/v H2SO4=1：3）Mixed liquor is at 80 DEG C
0.5h is managed, it is dry in 70 DEG C of baking oven after clear water rinses, with to be used.
3）Method using dip-coating will respectively hand over polyacrylic acid homopolymerization and diallyl dimethyl ammoniumchloride solution
Alternately it is coated in substrate of glass.
4）By above-mentioned coating, it is immersed in 1h in the alkaline solution of pH=11, after taking-up, is rinsed with clear water dry with blowing after 30s
It is dry to get arrive anionic polymer microporous membrane coating.
5）Use AFM（Bruker Multimodoe8）It observes the surface microstructure of coating and is analyzed by computer disposal micro-
The geometric parameter of structure, experimental result are similar with embodiment 1.
Embodiment 11
1）It takes acrylate homopolymer and allyl amine homopolymer to be configured to aqueous solution respectively, mixes, 1h is stirred at room temperature,
Continue to stir 1h, obtains coating liquid.
2）Clean substrate used, such as glass, by H2O2And H2SO4（vH2O2/v H2SO4=1：3）Mixed liquor is at 80 DEG C
0.5h is managed, it is dry in 70 DEG C of baking oven after clear water rinses, with to be used.
3）Method using dip-coating will respectively hand over polyacrylic acid homopolymerization and diallyl dimethyl ammoniumchloride solution
Alternately it is coated in substrate of glass.
4）By above-mentioned coating, it is immersed in 1h in the alkaline solution of pH=11, after taking-up, is rinsed with clear water dry with blowing after 30s
It is dry to get arrive anionic polymer microporous membrane coating.
5）Use AFM（Bruker Multimodoe8）It observes the surface microstructure of coating and is analyzed by computer disposal micro-
The geometric parameter of structure, experimental result are similar with embodiment 1.
Embodiment 12
1）The mixture of the copolymer of acrylamide and methacrylic acid and the copolymer of acrylamide and allyl amine is taken,
It is configured to aqueous solution, 1h is stirred at room temperature, the glutaraldehyde that mass fraction is polymeric blends 5% is added, stirs 1h, obtains
Coating liquid.
2）Clean substrate used, such as glass, by H2O2And H2SO4（vH2O2/v H2SO4=1：3）Mixed liquor is at 80 DEG C
0.5h is managed, it is dry in 70 DEG C of baking oven after clear water rinses, with to be used.
3）Method using dip-coating will respectively hand over polyacrylic acid homopolymerization and diallyl dimethyl ammoniumchloride solution
Alternately it is coated in substrate of glass.
4）Then by the coating in 60 DEG C of film-formings, heating time is 3 hours, obtains smooth surface coating, thickness is about
It is 10 μm.
5）By above-mentioned coating, it is immersed in 1h in the acid solution of pH=2, after taking-up, is rinsed with clear water dry with blowing after 30s
It is dry to get arrive anionic polymer microporous membrane coating.
6）Use AFM（Bruker Multimodoe8）It observes the surface microstructure of coating and is analyzed by computer disposal micro-
The geometric parameter of structure, experimental result are similar with embodiment 1.
Embodiment 13
1）Take the mixing of the copolymer of acrylamide and methacrylic acid and the copolymer of acrylamide and vinylpyridine
Object is configured to aqueous solution, and 1h is stirred at room temperature, and the glutaraldehyde that mass fraction is polymeric blends 5% is added, stirs 1h, obtains
To coating liquid.
2）3）4）With embodiment 12.
5）By above-mentioned coating, it is immersed in 0.5h in the acid solution of pH=8, after taking-up, uses blowing after rinsing 30s with clear water
To get anionic polymer microporous membrane coating is arrived, experimental result is similar with embodiment 1 for drying.
Embodiment 14
1）It takes acrylate homopolymer and vinyl pyridine homo-polymer to be configured to aqueous solution respectively, mixes, be stirred at room temperature
1h continues to stir 1h, obtains coating liquid.
2）3）With embodiment 10.
4）By above-mentioned coating, it is immersed in 1h in the alkaline solution of pH=11, after taking-up, is rinsed with clear water dry with blowing after 30s
It is dry to get anionic polymer microporous membrane coating is arrived, experimental result is similar with embodiment 1.
Embodiment 15
1）Take the mixed of the copolymer of acrylamide and methacrylic acid and the copolymer of acrylamide and vinyl pyrrole ketone
It closes object and is configured to aqueous solution, 1h is stirred at room temperature, the glutaraldehyde that mass fraction is polymeric blends 5% is added, stirs 1h,
Obtain coating liquid.
2）3）4）With embodiment 12.
5）By above-mentioned coating, it is immersed in 0.5h in the acid solution of pH=8, after taking-up, uses blowing after rinsing 30s with clear water
To get anionic polymer microporous membrane coating is arrived, experimental result is similar with embodiment 1 for drying.
Embodiment 16
1）It takes acrylate homopolymer and vinyl pyrrole ketone homopolymer to be configured to aqueous solution respectively, 1h is stirred at room temperature,
Continue to stir 1h, obtains coating liquid.
2）3）With embodiment 10.
4）By above-mentioned coating, it is immersed in 1h in the alkaline solution of pH=11, after taking-up, is rinsed with clear water dry with blowing after 30s
It is dry to get anionic polymer microporous membrane coating is arrived, experimental result is similar with embodiment 1.
Embodiment 17
1）Take the copolymer and diallyldimethylammonium chloride and acrylamide of vinylbenzenesulfonic acid and acrylamide
The mixture of copolymer is configured to aqueous solution, and 1h is stirred at room temperature, and penta 2 that mass fraction is polymeric blends 5% are added
Aldehyde stirs 1h, obtains coating liquid.
2）3）4）With embodiment 12.
5）By above-mentioned coating, it is immersed in 0.5h in the acid solution of pH=8, after taking-up, uses blowing after rinsing 30s with clear water
To get anionic polymer microporous membrane coating is arrived, experimental result is similar with embodiment 1 for drying.
Embodiment 18
1）It takes vinylbenzenesulfonic acid homopolymer and diallyldimethylammonium chloride homopolymer to be configured to aqueous solution respectively, mixes
It closes, 1h is stirred at room temperature, continue to stir 1h, obtain coating liquid.
2）3）With embodiment 10.
4）By above-mentioned coating, it is immersed in 1h in the alkaline solution of pH=11, after taking-up, is rinsed with clear water dry with blowing after 30s
It is dry to get anionic polymer microporous membrane coating is arrived, experimental result is similar with embodiment 1.
Embodiment 19
1）Take the copolymer and Methacrylamide and methacryloxypropyl second of Methacrylamide and Sodium Allyl Sulfonate
The mixture of the copolymer of base trimethyl ammonium chloride is configured to aqueous solution, and 1h is stirred at room temperature, and it is polymerization that mass fraction, which is added,
The glutaraldehyde of object mixture 5% stirs 1h, obtains coating liquid.
2）3）4）With embodiment 12.
5）It by above-mentioned coating, is immersed in the KCl solution of 0.8mol/l for 24 hours, after taking-up, is rinsed after 30s with clear water with blowing
Air-dry dry to get to anionic polymer microporous membrane coating, experimental result is similar with embodiment 1.
Embodiment 20
1）Sodium Allyl Sulfonate homopolymer is taken to be configured to respectively with MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride homopolymer
Aqueous solution, mixing, is stirred at room temperature 1h, continues to stir 1h, obtains coating liquid.
2）3）With embodiment 10.
4）By above-mentioned coating, it is immersed in 10h in the alkaline solution of pH=11, after taking-up, uses blowing after rinsing 30s with clear water
To get anionic polymer microporous membrane coating is arrived, experimental result is similar with embodiment 1 for drying.
Embodiment 21
A method of nanoporous polymeric thin-film material is prepared, is included the following steps：
1）By polymer solution film forming, crosslinking, thin polymer film is obtained；
2）Thin polymer film is swollen in processing solution；
3）It is dry, obtain nanoporous polymeric film.
The polymer solution includes polymer, solvent and additive；The additive includes：It is plasticizer, coloring agent, steady
Determine agent, fire retardant, antioxidant and processing aid, experimental result is similar with embodiment 1.
Embodiment 22
With embodiment 21, difference is, the step 1）In, polymer is to have cross-linking reaction on main chain and/or side chain
The polymer of active function groups, the degree of cross linking of thin polymer film are 10%, and experimental result is similar with embodiment 1.
Embodiment 23
With embodiment 21, difference is, the step 1）In, polymer is water-soluble polymer.The water-soluble polymeric
Object is selected from one of following material or a variety of：Ionic water-soluble polymers, non-ionic water-soluble polymer, polymer thin
The degree of cross linking of film is 60%, and the processing solution is CaCl2, swelling time 10min, experimental result is similar with embodiment 1.
Embodiment 24
With embodiment 21, difference is, polymer is the Ionic water-soluble polymers containing carboxyl or quaternary ammonium salt group,
The degree of cross linking of thin polymer film is 45%, swelling time 48h, and the processing solution is hydrochloric acid, in experimental result and embodiment 1
It is similar.
Embodiment 25
With embodiment 21, difference is, polymer is to polymerize containing the non-ionic water-soluble of amide groups or hydroxyl group
Object, swelling time 2h, using vacuum drying, the processing solution is sulfuric acid, and experimental result is similar with embodiment 1.
Embodiment 26
With embodiment 21, difference is, the step 1）Middle polymer is the homopolymerization of 2- propionamido -2- methyl propane sulfonic acid
Object, the processing solution are phosphoric acid, and experimental result is similar with embodiment 1.
Embodiment 27
With embodiment 21, difference is, the step 1）Middle polymer is polyoxyethylene, and the processing solution is acetic acid,
Experimental result is similar with embodiment 1.
Embodiment 28
With embodiment 21, difference is, the step 1）When middle crosslinking, crosslinking agent is added, the crosslinking agent is melamine tree
Rouge, the processing solution are sodium hydroxide, and experimental result is similar with embodiment 1.
Embodiment 29
With embodiment 28, difference is, the crosslinking agent is epoxy resin, and the processing solution is potassium hydroxide, experiment
As a result similar with embodiment 1.
Embodiment 30
With embodiment 28, difference is, the crosslinking agent is isocyanate resin, and the processing solution is ammonium hydroxide, real
It is similar with embodiment 1 to test result.
Embodiment 31
With embodiment 28, difference is, the crosslinking agent is formaldehyde, and experimental result is similar with embodiment 1.
Embodiment 32
With embodiment 28, difference is, the crosslinking agent is glyoxal, and experimental result is similar with embodiment 1.
Embodiment 33
With embodiment 28, difference is, the crosslinking agent is terephthalaldehyde, and experimental result is similar with embodiment 1.
Embodiment 34
With embodiment 28, difference is, the crosslinking agent is succinic acid, and experimental result is similar with embodiment 1.
Embodiment 35
With embodiment 28, difference is, the crosslinking agent is maleic anhydride, and experimental result is similar with embodiment 1.
Embodiment 36
With embodiment 28, difference is, the crosslinking agent is terephthalic anhydride, and experimental result is similar with embodiment 1.
Embodiment 37
With embodiment 28, difference is, the crosslinking agent is ethylenediamine, and experimental result is similar with embodiment 1.
Embodiment 38
With embodiment 28, difference is, the crosslinking agent is butanediamine, and experimental result is similar with embodiment 1.
Embodiment 39
With embodiment 28, difference is, the crosslinking agent is chromic salts, and experimental result is similar with embodiment 1.
Embodiment 40
With embodiment 28, difference is, the crosslinking agent is boron salt, and experimental result is similar with embodiment 1.
Embodiment 41
With embodiment 28, difference is, the crosslinking agent is zirconates, and experimental result is similar with embodiment 1.
Embodiment 42
With embodiment 28, difference is, the crosslinking agent is terbium salt, and experimental result is similar with embodiment 1.
Embodiment 43
With embodiment 28, difference is, the crosslinking agent is titanium salt, and experimental result is similar with embodiment 1.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (8)
1. a kind of method for preparing nanoporous polymeric thin-film material, which is characterized in that include the following steps：
1) by polymer solution film forming, crosslinking, the thin polymer film with network structure is obtained；
2) thin polymer film is swollen in processing solution；
3) dry, obtain nanoporous polymeric film；
In the step 1), polymer solution includes polymer, solvent and additive；Polymer is water-soluble polymer；Polymerization
Object is the polymer on main chain and/or side chain with activity of cross-linking reaction functional group；
In the step 2), when polymer is water-soluble polymer, the processing solution be the aqueous solution of salt, acid solution or
Alkaline solution；
The degree of cross linking of the thin polymer film is 10%~60%.
2. the method according to claim 1 for preparing nanoporous polymeric thin-film material, which is characterized in that the step
1) in, the water-soluble polymer is selected from one of following material or a variety of：Ionic water-soluble polymers, non-ionic water
Soluble polymer.
3. the method according to claim 2 for preparing nanoporous polymeric thin-film material, which is characterized in that the ion
Type water-soluble polymer contains carboxyl or quaternary ammonium salt group；The non-ionic water-soluble polymer contains amide groups or hydroxyl base
Group.
4. the method according to claim 1 for preparing nanoporous polymeric thin-film material, which is characterized in that the step
1) in, polymer is selected from one of following material or a variety of：The homopolymer and its copolymer of acrylic acid, methacrylic acid it is equal
Polymers and its copolymer, the homopolymer of vinylbenzenesulfonic acid and its copolymer, the homopolymer of allyl sulphonic acid and its copolymer, 2-
Homopolymer and its copolymer, the homopolymer of diallyl alkyl dimethyl ammonium chloride and its copolymerization of propionamido- -2- methyl propane sulfonic acid
The homopolymer of object, the homopolymer of allyl amine and its copolymer, the homopolymer of acrylamide and its copolymer, Methacrylamide
And its homopolymer and its copolymer, polyethylene of the homopolymer and its copolymer of copolymer, vinylpyridine, vinyl pyrrole ketone
Alcohol, polyoxyethylene.
5. the method according to claim 1 for preparing nanoporous polymeric thin-film material, which is characterized in that when crosslinking,
Add crosslinking agent；Wherein, the crosslinking agent is selected from Lauxite, melamine resin, epoxy resin, isocyanate resin, formaldehyde, second two
Aldehyde, glutaraldehyde, terephthalaldehyde, oxalic acid, succinic acid, maleic anhydride, terephthalic anhydride, ethylenediamine, butanediamine, chromic salts, boron
Salt, zirconates, terbium salt or titanium salt.
6. the method according to claim 1 for preparing nanoporous polymeric thin-film material, which is characterized in that the salt
The concentration of aqueous solution is 0.05M~2M.
7. the method according to claim 1 for preparing nanoporous polymeric thin-film material, which is characterized in that the salt
Salt in aqueous solution is selected from following one or more：NaCl,KCl,CaCl2Or Na2SO4。
8. the method according to claim 1 for preparing nanoporous polymeric thin-film material, which is characterized in that the acidity
Acid or alkali in solution or alkaline solution are selected from following one or more：Hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, sodium hydroxide, hydrogen-oxygen
Change potassium, ammonium hydroxide.
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| CN102516583A (en) * | 2011-11-18 | 2012-06-27 | 南京工业大学 | Method for preparing antireflection film by selective swelling and pore-forming of amphipathic block copolymer |
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| CN102516583A (en) * | 2011-11-18 | 2012-06-27 | 南京工业大学 | Method for preparing antireflection film by selective swelling and pore-forming of amphipathic block copolymer |
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