CN109575704A - The preparation method of the strong polyelectrolyte membrane of nanoporous - Google Patents
The preparation method of the strong polyelectrolyte membrane of nanoporous Download PDFInfo
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- CN109575704A CN109575704A CN201811518424.1A CN201811518424A CN109575704A CN 109575704 A CN109575704 A CN 109575704A CN 201811518424 A CN201811518424 A CN 201811518424A CN 109575704 A CN109575704 A CN 109575704A
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- polyelectrolyte
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- strong polyelectrolyte
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
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Abstract
The invention belongs to new material technology fields, and in particular to a kind of novel method for preparing the strong polyelectrolyte membrane of nanoporous.Using strong polyelectrolyte, LBL self-assembly prepares the strong polyelectrolyte membrane of nanoporous in ionic liquid aqueous solution.Compared with prior art, the invention has the benefit that 1) the present invention provides a kind of new methods for preparing nano-porous film, different from traditional preparation method, this method is independent of weak polyelectrolyte system but layer assembly prepares nano-porous film using strong polyelectrolyte PSS and PDADMAC in BMIMCl ionic liquid aqueous solution；2) method provided by the invention for preparing nano-porous film using strong polyelectrolyte is simple and effective；3) the strong polyelectrolyte membrane of nanoporous prepared by the present invention can be used for anti-reflection coating, the concentration and type of ionic liquid when passing through assembling, and assembling number of plies etc. accurately controls the hole size of porous membrane.
Description
Technical field
The invention belongs to new material technology fields, and in particular to a kind of novel to prepare the strong polyelectrolyte membrane of nanoporous
Method.
Background technique
To construct multi-layer polyelectrolyte membrane, laminated assembling technology is widely studied and is applied.By regulating and controlling poly- electricity
The condition (such as pH, ionic strength and temperature) of the property and assembling that solve matter adjusts the physicochemical properties of polyelectrolyte membrane.
And wherein nano-porous polymer film is because it is in nanofiltration, medicament transport, control delivery and anti-reflection coating and biology
The potential application of material etc. and be particularly important.
Rubner et al. prepares porous polyelectrolyte membrane layer by layer using weak polyelectrolyte for the first time.They use polypropylene
Acid and polyallylamine prepare multilayer weak polyelectrolyte, and these weak polyelectrolyte multilayer films are immersed in acid solution and prepare micropore
Film.To this day, researcher has carried out a large amount of research, but these research works in nanoporous polyelectrolyte membrane field
It is all based on weak polyelectrolyte system.It is reported that in the field about the research for preparing the strong polyelectrolyte membrane of nanoporous
So far or blank.Since weak polyelectrolyte film is very sensitive for outside stimulus (such as PH and ionic strength), the structure of film
Be easy to property it is impacted, so weak polyelectrolyte film application be restricted.And polyelectrolyte membrane is then external by force
The sensitivity of boundary's environment is lower, is more widely applied.Due to ionizing completely, strong polyelectrolyte molecules chain exists in an assembling process
Mobility in film is significantly lower than weak polyelectrolyte strand, so to frequently appear in weak polyelectrolyte thin for nano-porous structure
In film, without in strong polyelectrolyte membrane.And this method the result shows that being assembled in the aqueous solution of ionic liquid
When, strong polyelectrolyte molecules chain also has very high mobility in film, can also prepare the strong polyelectrolyte of nanoporous
Film.
Summary of the invention
The purpose of the present invention is to solve the shortcomings of the prior art and providing and a kind of preparing strong polyelectrolyte nanoporous
The new method of film, using strong polyelectrolyte PSS and PDADMAC, in BMIMCl ionic liquid aqueous solution prepared by layer assembly
The strong polyelectrolyte membrane of nanoporous.
The technical proposal adopted by the invention to solve the above technical problems is that: the preparation of the strong polyelectrolyte membrane of nanoporous
Method, it is characterised in that: LBL self-assembly gathers by force to prepare nanoporous in ionic liquid aqueous solution using strong polyelectrolyte
Electrolytic thin-membrane.
According to the above scheme, the strong polyelectrolyte is PSS (kayexalate, MW=70kDa) and PDADMAC
(polydimethyl diallyl ammonium chloride, MW < 100kDa).
According to the above scheme, the ionic liquid aqueous solution is BMIMCl (1- butyl -3- methylimidazole villaumite), HMIMCl
(1- hexyl -3- methylimidazole villaumite) or EMIMCl (1- ethyl-3-methylimidazole villaumite).
According to the above scheme, include following steps: preparing two kinds of concentration with BMIMCl aqueous solution is 0.5-1.0mg/mL
Polyelectrolyte PSS and PDADMAC solution, be then dipped through pretreated silicon wafer or glass substrate manually, make poly- electrolysis
Matter is continuously adsorbed on silicon wafer or glass substrate, after having deposited the required number of plies, is rinsed with water to eliminate film surface
The excessive salt particle of upper absorption.
According to the above scheme, the time of the silicon wafer or the glass substrate alternating impregnating in polyelectrolyte solution is 5-15 points
Clock is adopted be rinsed with water 2-4 times during this period.
According to the above scheme, the preprocess method of the silicon wafer or glass substrate is: being handled first with Piranha solution clear
Wash silicon wafer/glass substrate；Then, ultrasound 15-30 minutes in the mixture of the water of 1:1 and 2- propyl alcohol；Then, in 5:1:1
Water, 30% hydrogen peroxide and 29% ammonium hydroxide mixed solution in handle 10-30 minutes at 50-80 DEG C；Finally, with a large amount of water
Silicon wafer or glass substrate are rinsed, is dried up in nitrogen atmosphere.
Mechanism of the invention: the present invention with diameter cationic in ionic liquid be far longer than in common sodium chloride sodium from
The diameter of son, so that large-sized ionic liquid cation can be such that positive and negative polyelectrolyte more rolls up in molecular conformation when assembled
Song, so as to cause the appearance of nano aperture.
Compared with prior art, the invention has the benefit that
1) the present invention provides a kind of new methods for preparing nano-porous film, different from traditional preparation method, we
Method is independent of weak polyelectrolyte system but uses strong polyelectrolyte PSS and PDADMAC in BMIMCl ionic liquid aqueous solution
Middle layer assembly prepares nano-porous film；
2) method provided by the invention for preparing nano-porous film using strong polyelectrolyte is simple and effective；
3) the strong polyelectrolyte membrane of nanoporous prepared by the present invention can be used for anti-reflection coating, ionic liquid when passing through assembling
Concentration and type of body, and the assembling number of plies etc. accurately control the hole size of porous membrane.
Detailed description of the invention
Fig. 1 is the relation curve of strong the polyelectrolyte membrane number of plies and thickness that embodiment 1,2,3,4 is prepared；
Fig. 2 (a, b) is the AFM figure for the strong polyelectrolyte membrane of nanoporous that embodiment 3 is prepared, and (c, d) is to implement
The AFM for the strong polyelectrolyte membrane that example 4 is prepared schemes；
Fig. 3 is the transmission curve of the strong polyelectrolyte membrane of nanoporous that embodiment 3 is prepared and blank glass comparison.
Specific embodiment
Below with reference to embodiment, the present invention will be further described in detail.
The preprocess method of silicon wafer or glass substrate is: handling cleaning silicon wafer/glass substrate with Piranha solution first；
Then, ultrasound 15-30 minutes in the mixture of the water of 1:1 and 2- propyl alcohol；Then, the water of 5:1:1,30% hydrogen peroxide and
It is handled 10-30 minutes at 50-80 DEG C in the mixed solution of 29% ammonium hydroxide；Finally, silicon wafer or glass substrate are rinsed with a large amount of water,
It is dried up in nitrogen atmosphere.
Embodiment 1
With concentration be 0.1M BMIMCl ionic liquid aqueous solution prepare two kinds of concentration be 0.5mg/mL polyelectrolyte PSS
With the solution of PDADMAC.Then by being dipped through pretreated silicon or glass substrate manually, keep polyelectrolyte enterprising in substrate
The continuous absorption of row.Substrate alternating impregnating 10 minutes in both polymer solutions are rinsed with water 3 times during this period.Heavy
After having accumulated the required number of plies, it is rinsed with water to eliminate the excessive salt particle adsorbed in film surface.It is 0.1M in concentration such as Fig. 1
When BMIMCl ionic liquid aqueous solution prepares film, for the thickness of film as the increase of the number of plies is similar to linear increase, group installs 8
After bilayer, thickness is almost 30nm.
Embodiment 2
With concentration be 0.3M BMIMCl ionic liquid aqueous solution prepare two kinds of concentration be 0.5mg/mL polyelectrolyte PSS
With the solution of PDADMAC.Then by being dipped through pretreated silicon or glass substrate manually, keep polyelectrolyte enterprising in substrate
The continuous absorption of row.Substrate alternating impregnating 10 minutes in both polymer solutions are rinsed with water 3 times during this period.Heavy
After having accumulated the required number of plies, it is rinsed with water to eliminate the excessive salt particle adsorbed in film surface.It is 0.3M in concentration such as Fig. 1
When BMIMCl ionic liquid aqueous solution prepares film, for the thickness of film as the increase of the number of plies is similar to exponential increase, group installs 8
After bilayer, thickness is almost 80nm.
Embodiment 3
With concentration be 0.5M BMIMCl ionic liquid aqueous solution prepare two kinds of concentration be 0.5mg/mL polyelectrolyte PSS
With the solution of PDADMAC.Then by being dipped through pretreated silicon or glass substrate manually, keep polyelectrolyte enterprising in substrate
The continuous absorption of row.Substrate alternating impregnating 10 minutes in both polymer solutions are rinsed with water 3 times during this period.Heavy
After having accumulated the required number of plies, it is rinsed with water to eliminate the excessive salt particle adsorbed in film surface.It is 0.5M in concentration such as Fig. 1
When BMIMCl ionic liquid aqueous solution prepares film, the thickness of film is as the increase of the number of plies is in apparent exponential increase, assembling
After complete 8 bilayers, thickness reaches 120nm.This it appears that film surface has many nano apertures from the AFM figure of Fig. 2.
Meanwhile it can be seen that nano-porous film from the H103 resin of Fig. 3 and glass substrate significantly propose the permeability of light
It rises.
Embodiment 4
With concentration be 0.5M NaCl solution prepare two kinds of concentration be the molten of 0.5mg/mL polyelectrolyte PSS and PDADMAC
Liquid.Then by passing through pretreated dipping silicon or glass substrate manually, adsorb polyelectrolyte continuously on substrate.
Substrate alternating impregnating 10 minutes in both polymer solutions are rinsed with water 3 times during this period.Depositing the required number of plies
Afterwards, it is rinsed with water to eliminate the excessive salt particle adsorbed in film surface.It is that 0.5M NaCl solution prepares film in concentration such as Fig. 1
When, the thickness of film is as the increase of the number of plies is similar to exponential increase, and after group installs 8 bilayers, thickness is almost 90nm.But from
This it appears that film surface does not have nano aperture in the AFM figure of Fig. 2.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection scope of the invention.
Claims (6)
1. the preparation method of the strong polyelectrolyte membrane of nanoporous, it is characterised in that: using strong polyelectrolyte in ionic liquid water
LBL self-assembly prepares the strong polyelectrolyte membrane of nanoporous in solution.
2. the preparation method of the strong polyelectrolyte membrane of nanoporous according to claim 1, it is characterised in that: described is strong
Polyelectrolyte is PSS and PDADMAC.
3. the preparation method of the strong polyelectrolyte membrane of nanoporous according to claim 1 or 2, it is characterised in that: described
Ionic liquid aqueous solution be BMIMCl, HMIMCl or EMIMCl.
4. the preparation method of the strong polyelectrolyte membrane of nanoporous according to claim 3, it is characterised in that: include with
Lower step: the molten of the polyelectrolyte PSS and PDADMAC that two kinds of concentration are 0.5-1.0mg/mL is prepared with BMIMCl aqueous solution
Then liquid is dipped through pretreated silicon wafer or glass substrate manually, connect polyelectrolyte on silicon wafer or glass substrate
Continuous absorption is rinsed with water after having deposited the required number of plies to eliminate the excessive salt particle adsorbed in film surface.
5. the preparation method of the strong polyelectrolyte membrane of nanoporous according to claim 4, it is characterised in that: the silicon
The time of piece or the glass substrate alternating impregnating in polyelectrolyte solution is 5-15 minutes, adopts be rinsed with water 2-4 times during this period.
6. the preparation method of the strong polyelectrolyte membrane of nanoporous according to claim 3, it is characterised in that: the silicon
The preprocess method of piece or glass substrate is: handling cleaning silicon wafer/glass substrate with Piranha solution first；Then, in 1:1
Water and 2- propyl alcohol mixture in ultrasound 15-30 minutes；Then, in the water of 5:1:1,30% hydrogen peroxide and 29% ammonium hydroxide
It is handled 10-30 minutes at 50-80 DEG C in mixed solution；Finally, silicon wafer or glass substrate are rinsed with a large amount of water, in nitrogen atmosphere
Middle drying.
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