CN104209017B - A kind of polyaniline auto-dope PVDF stain resistant material and preparation method thereof in situ - Google Patents
A kind of polyaniline auto-dope PVDF stain resistant material and preparation method thereof in situ Download PDFInfo
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Abstract
The present invention relates to a kind of polyaniline auto-dope PVDF stain resistant material and preparation method thereof in situ, utilize the efficient anti-soil properties of amphoteric ion polymer, improve the problem that hydrophobicity PVDF material easily pollutes.By the method for sulfonation after being first blended in the method, the sulfonated polyaniline material with zwitterionic character is incorporated into PVDF material surface, its surface wettability and antifouling property be improved significantly, surface static water contact angle drops to less than 30 °, and material surface BSA static adsorbance is less than 5ug/cm2, when being used as to separate film, its secondary flux recovery rate reaches 95%.
Description
Technical field
The invention belongs to technical field of material modification, relate to a kind of polyaniline auto-dope PVDF stain resistant material and preparation method thereof in situ,
Particularly relate to a kind of polyaniline utilizing polyaniline surface in situ sulfonation modifying PVDF auto-dope PVDF stain resistant material in situ and
Its preparation method, improves PVDF material surface hydrophilic and promotes its antifouling property.
Background technology
Various materials in use its surface and interface is the most inevitably faced with the problem of interface pollution, and wherein pollutant include
Inorganic organic molecule, organic macromolecule, biomacromolecule, biological pollutant etc., pollutant absorption is deposited in material surface,
Material interface properties is produced the most serious impact, while destroying material self character, shortens its service life, increase fortune
Battalion's cost.Only as a example by the marine pollution matter faced during various types of materials uses, multi-million dollar is lost in the whole world every year.
Present stage is varied to the research of various pollution resistance materials, mainly includes minimum living face energy material and hydrophilic material, is utilized respectively
The fluorine-containing siliceous material with the ability polluting release realizes the purpose of anti-soil and utilizes hydrated sheath protection surface, interface, and suppression is each
The absorption of pollutant is polluted.
Interface pollution problem is ubiquitous, and in membrance separation industry, membrane pollution problem is especially prominent.Because of its efficiently, energy-saving and environmental protection,
Molecular level filters, the advantage such as easily controllable becomes one of most important means in separation science in fact, be widely used to water process,
Food, biology, environmental protection, chemical industry, the energy, oil, the field such as bionical, create huge economy and social value, but film
Pollution can cause separation membrance separation efficiency to decline rapidly and increase operation cost, and there is its further genralrlization in restriction film industry should
With.
Kynoar (PVDF) film has heat stability, chemical stability, weatherability and the processability of excellence, is to enjoy
One of membrane material of favor, but simultaneously because the stronger hydrophobic interaction in its surface problem that inevitably there is fouling membrane.In a large number
Research shows, increases the hydrophilic on film surface and is conducive to alleviating the fouling membrane that hydrophobic separation membrane faces in actual application and asks
Topic, main by modified methods such as blended, surface grafting, surface physics process or coatings, introduce pollution resistance material and improve PVDF
The antifouling property of film.The best material of present stage antifouling effect is poly-amphion and the Polyethylene Glycol (PEG) with bionical effect
Base polymer, based on stronger hydrogen bond action and hydration of ion, can form hydrophilic protective layer on film surface, and hydrophobicity is dirty
Dye thing arranges, and reduces the adhesion of pollutant.But poly-amphion is merely able to dissolve in aqueous due to stronger hydrophilic,
And cannot be dissolved in the cosolvent of PVDF, poly-amphion is incorporated in pvdf membrane can only by the method for surface grafting,
Modified method is complicated, and condition is harsh, is unsuitable for large-scale production.
Summary of the invention
It is an object of the invention to provide a kind of polyaniline auto-dope PVDF stain resistant material and preparation method thereof in situ, particularly provide
A kind of polyaniline auto-dope PVDF stain resistant material and preparation method thereof in situ utilizing polyaniline surface in situ sulfonation modifying PVDF,
Improve PVDF material surface hydrophilic and promote its antifouling property, there is cosolvent based on PANI with PVDF and it is from mixing
Poly-zwitterionic anti-soil properties can be shown after miscellaneous sulfonation, by the method that post-modification is first blended, draw in situ at material surface
Entering sulfonated polyaniline amphion, strengthen surface wettability and the antifouling property of PVDF material, method of modifying the most easily realizes,
Be suitable to large-scale production.
A kind of polyaniline of present invention auto-dope PVDF stain resistant material in situ, is blended after molding through sulfonation for polyaniline and PVDF
Process and form poly-zwitterionic original position auto-dope material, in view of amphoteric ion polymer material is with hydrophobic at material surface
There is not cosolvent in PVDF material, the characteristic that amphoteric ion polymer is difficult to process with common used material simultaneously limits its scale
Application, the present invention can effectively solve this problem, molding after the method for sulfonation is first blended, introduces amphoteric ion polymer in situ,
The surface and interface characteristic of material can be effectively improved.
As preferred technical scheme:
In a kind of polyaniline auto-dope PVDF stain resistant material in situ as above, polyaniline quality with PVDF mass ratio is
0.5%～5%.
A kind of polyaniline auto-dope PVDF stain resistant material in situ as above, described polyaniline auto-dope PVDF in situ resists
Dirty material is Flat Membrane or hollow-fibre membrane, for improving membrane pollution problem when separating film application.
A kind of polyaniline auto-dope PVDF stain resistant material in situ as above, described Flat Membrane or hollow-fibre membrane, separate
Precision is ultrafiltration or microfiltration, and PVDF stain resistant material surface static water contact angle is less than 30 °, and static BSA adsorbance is less than
5μg/cm2, and secondary flux recovery rate reaches more than 95%, shows the antifouling property of excellence.
Present invention also offers the preparation method of a kind of polyaniline auto-dope PVDF stain resistant material in situ, comprise the following steps:
The first step: polyaniline is dissolved in NMP or DMF solvent；
Second step: PVDF is dissolved in the solution that the first step obtains, stirring and dissolving standing and defoaming；
3rd step: material molding, by second step gained solution by material forming process molding；
4th step: sulfonation, is placed in oleum fully sulfonation by the material of molding；
5th step: clean, fully cleaned by the material deionized water after sulfonation, obtains polyaniline auto-dope PVDF in situ and resists
Dirty material.
The preparation method of a kind of polyaniline as above auto-dope PVDF stain resistant material in situ, in the solution that the first step obtains,
The mass concentration of polyaniline is 0.1%～5%；In the solution that second step obtains, polyaniline quality with PVDF mass ratio is
0.5%～15%.
The preparation method of a kind of polyaniline as above auto-dope PVDF stain resistant material in situ, in the first step, filters after dissolving
Remove undissolved component；In 4th step, abundant sulfonation refers to that the time of sulfonation is 1～20 hour, and sulfonating reaction temperature is 0～130
DEG C, SO in oleum3Mass concentration is 5%-50%；In 5th step, fully clean and refer to film excess surface with distilled water
Sulfuric acid cleaned fall, to clean after distilled water be neutrality.
The preparation method of a kind of polyaniline as above auto-dope PVDF stain resistant material in situ, in second step, is additionally added pore
Agent, for PEG or PVP, mass concentration is the 2～30% of solution gross mass；Meanwhile, after stirring and dissolving, stand more than 12h
Deaeration.
The preparation method of a kind of polyaniline as above in situ auto-dope PVDF stain resistant material, described in pass through material forming process
Refer to utilize conventional material forming method, for casting, extrude, be molded or molding methods preparing all kinds of stain resistant material, including film material
Material.
Described polyaniline auto-dope PVDF stain resistant material in situ may be used for medical material, separation membrane material, coating, gel
Material etc..
Polyaniline (PANI) is conventional conducting polymer composite, has special electricity, an optical property, doped after can have
There is good electric conductivity, can be used for preparing electrical devices and the material with specific function.But polyaniline is due to its chain rigidity and chain
Between strong interaction, make its solubility extreme difference, the most insoluble in the organic solvent that major part is conventional, be only partially soluble in N, N-
, there is cosolvent with PVDF in dimethylformamide (DMF) and N-Methyl pyrrolidone (NMP).PANI itself is entered
The additional acid doping of row, can be with H+React, demonstrate charged negativity, and after PANI molecule is carried out sulfonation, pass through
Auto-dope introduces sulfonate radical, again can be with OH-Reaction, shows lotus electropositive, after sulfonation auto-dope in PANI strand unit
Existing positive charge, has again negative charge, can show zwitterionic characteristic of birdsing of the same feather flock together, and is used as the poly-zwitterionic materials of pollution resistance,
Present stage research surface, can assemble 21 around a pair negative ions electric charge in the amphoteric ion polymer unit chain link of bio-imitability
Hydrone, forms hydrone protective layer, is kept apart with other pollution mediums by material, and it is excellent that superpower water and effect make it show
Different antifouling effect.
Beneficial effect:
Modified through polyaniline in situ auto-dope, while pvdf membrane retains body elite clone performance, surface wettability and
Antifouling property significantly improves, and material surface Static water contact angles is less than 30 °, and film surface BSA static adsorbance is less than
5ug/cm2；Prepare PVDF Flat Membrane or the hollow-fibre membrane of pollution resistance, for ultrafiltration micro-filtration separation field, its secondary water
Flux recovery rate reaches 95%.
Introduce, compared to other, the method that poly-zwitterionic materials improves material antifouling property, prepare stain resistant material by this method and walk
It is rapid simple, it is easy to accomplish, by sulfonation after being first blended, can prepare anti-at the poly-zwitterionic materials needed for film Surface Creation
The membrane material of dirty excellent performance.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art
Can make various changes or modifications the present invention, these equivalent form of values fall within the model that the application appended claims is limited equally
Enclose.
Embodiment 1
The preparation method of a kind of polyaniline auto-dope PVDF stain resistant material in situ, comprises the following steps:
The first step: polyaniline is dissolved in nmp solvent；The mass concentration of polyaniline is 0.1%；
Second step: be dissolved in by PVDF in the solution that the first step obtains, polyaniline quality and PVDF mass ratio are 0.5%, add
Enter the porogen PEG 20000 that mass fraction is 2%, stirring and dissolving standing and defoaming；
3rd step: material molding, by the material forming process molding by casting of the second step gained solution；
4th step: sulfonation, is placed in oleum fully sulfonation by the material of molding；Fully sulfonation refers to that the time of sulfonation is 1
Hour, sulfonating reaction temperature is 130 DEG C, SO in oleum3Mass concentration is 5%；
5th step: clean, fully cleaned by the material deionized water after sulfonation, fully cleans and refers to film surface with distilled water
Unnecessary sulfuric acid cleaned is fallen, and the distilled water after cleaning is neutral；Obtain polyaniline auto-dope PVDF stain resistant material, institute in situ
Stating polyaniline auto-dope PVDF stain resistant material in situ is to process and at material surface through sulfonation after polyaniline is blended molding with PVDF
Form poly-zwitterionic original position auto-dope material；Separation accuracy is ultrafiltration, and PVDF stain resistant material surface static water contact angle is
28 °, static BSA adsorbance is 4 μ g/cm2, and secondary flux recovery rate reaches 96%.
Embodiment 2
The preparation method of a kind of polyaniline auto-dope PVDF anti-soil Flat Membrane in situ, comprises the following steps:
The first step: polyaniline is dissolved in DMF solvent；The mass concentration of polyaniline is 5%；It is filtered to remove insoluble after dissolving
The component solved；
Second step: be dissolved in by PVDF in the solution that the first step obtains, polyaniline quality and PVDF mass ratio are 15%, add
Enter the porogen PVP K30 that mass fraction is 20%, stirring and dissolving standing and defoaming；
3rd step: material molding, is molded into doughnut by second step gained solution by the material forming process of extrusion TIPS method
Film；
4th step: sulfonation, is placed in oleum fully sulfonation by the material of molding；Fully sulfonation refers to that the time of sulfonation is 20
Hour, sulfonating reaction temperature is 80 DEG C, SO in oleum3Mass concentration is 50%；
5th step: clean, fully cleaned by the material deionized water after sulfonation, fully cleans and refers to film surface with distilled water
Unnecessary sulfuric acid cleaned is fallen, and the distilled water after cleaning is neutral；Obtain polyaniline auto-dope PVDF anti-soil doughnut in situ
Film, described polyaniline in situ auto-dope PVDF anti-soil hollow-fibre membrane is polyaniline and PVDF is blended after molding at sulfonation
Manage and form poly-zwitterionic original position auto-dope Flat Membrane at material surface；Separation accuracy is microfiltration, PVDF anti-soil Flat Membrane
Surface static water contact angle is 25 °, static BSA adsorbance 5 μ g/cm2, and secondary flux recovery rate reaches 98%.
Embodiment 3
The preparation method of a kind of polyaniline auto-dope PVDF anti-soil Flat Membrane in situ, comprises the following steps:
The first step: polyaniline is dissolved in nmp solvent；The mass concentration of polyaniline is 1%；
Second step: be dissolved in by PVDF in the solution that the first step obtains, polyaniline quality and PVDF mass ratio are 5%, stir
Mix dissolving standing and defoaming；Being subsequently adding porogen PEG400, mass concentration is the 2% of solution gross mass；Meanwhile, in stirring
After dissolving, stand 20h deaeration；
3rd step: material molding, is molded into Flat Membrane by second step gained solution by the material forming process of injection；
4th step: sulfonation, is placed in oleum fully sulfonation by the material of molding；Fully sulfonation refers to that the time of sulfonation is 10
Hour, sulfonating reaction temperature is 30 DEG C, SO in oleum3Mass concentration is 10%；
5th step: clean, fully cleaned by the material deionized water after sulfonation, fully cleans and refers to film surface with distilled water
Unnecessary sulfuric acid cleaned is fallen, and the distilled water after cleaning is neutral；Obtain polyaniline auto-dope PVDF anti-soil Flat Membrane in situ,
Described polyaniline auto-dope PVDF anti-soil Flat Membrane in situ is to process and at material through sulfonation after polyaniline is blended molding with PVDF
Surface forms poly-zwitterionic original position auto-dope Flat Membrane；Separation accuracy is microfiltration, PVDF anti-soil Flat Membrane surface static water
Contact angle is 20 °, and static BSA adsorbance is 3 μ g/cm2, and secondary flux recovery rate reaches 95%.
Embodiment 4
The preparation method of a kind of polyaniline auto-dope PVDF anti-soil Flat Membrane in situ, comprises the following steps:
The first step: polyaniline is dissolved in DMF solvent；The mass concentration of polyaniline is 2%；It is filtered to remove insoluble after dissolving
The component solved；
Second step: be dissolved in by PVDF in the solution that the first step obtains, polyaniline quality and PVDF mass ratio are 8%, stir
Mix dissolving standing and defoaming；Being subsequently adding porogen PVP K90, mass concentration is the 30% of solution gross mass；Meanwhile, stirring
After mixing dissolving, stand 12h deaeration；
3rd step: material molding, is molded into Flat Membrane by second step gained solution by the material forming process of molding；
4th step: sulfonation, is placed in oleum fully sulfonation by the material of molding；Fully sulfonation refers to that the time of sulfonation is 15
Hour, sulfonating reaction temperature is 50 DEG C, SO in oleum3Mass concentration is 20%；
5th step: clean, fully cleaned by the material deionized water after sulfonation, fully cleans and refers to film surface with distilled water
Unnecessary sulfuric acid cleaned is fallen, and the distilled water after cleaning is neutral；Obtain polyaniline auto-dope PVDF anti-soil Flat Membrane in situ,
Described polyaniline auto-dope PVDF anti-soil Flat Membrane in situ is to process and at material through sulfonation after polyaniline is blended molding with PVDF
Surface forms poly-zwitterionic original position auto-dope Flat Membrane；Separation accuracy is ultrafiltration, PVDF anti-soil Flat Membrane surface static water
Contact angle is 15 °, static BSA adsorbance 2 μ g/cm2, and secondary flux recovery rate reaches 99%.
Embodiment 5
The preparation method of a kind of polyaniline auto-dope PVDF anti-soil hollow-fibre membrane in situ, comprises the following steps:
The first step: polyaniline is dissolved in DMF solvent；The mass concentration of polyaniline is 3%；It is filtered to remove insoluble after dissolving
The component solved；
Second step: be dissolved in by PVDF in the solution that the first step obtains, polyaniline quality and PVDF mass ratio are 10%, stir
Mix dissolving standing and defoaming；Being subsequently adding porogen PEG400, mass concentration is the 20% of solution gross mass；Meanwhile, stirring
After mixing dissolving, stand 12h deaeration；
3rd step: material molding, is molded into hollow-fibre membrane by second step gained solution by the material forming process of extrusion；
4th step: sulfonation, is placed in oleum fully sulfonation by the material of molding；Fully sulfonation refers to that the time of sulfonation is 16
Hour, sulfonating reaction temperature is 70 DEG C, SO in oleum3Mass concentration is 25%；
5th step: clean, fully cleaned by the material deionized water after sulfonation, fully cleans and refers to film surface with distilled water
Unnecessary sulfuric acid cleaned is fallen, and the distilled water after cleaning is neutral；Obtain polyaniline auto-dope PVDF anti-soil doughnut in situ
Film, described polyaniline auto-dope PVDF anti-soil hollow-fibre membrane in situ is to process through sulfonation after polyaniline is blended molding with PVDF
And form poly-zwitterionic original position auto-dope material hollow-fibre membrane at material surface；Separation accuracy is ultrafiltration, PVDF anti-soil
Hollow-fibre membrane surface static water contact angle is 23 °, and static BSA adsorbance is 4.5 μ g/cm2, and secondary flux recovery rate
Reach 96%.
Embodiment 6
The preparation method of a kind of polyaniline auto-dope PVDF anti-soil hollow-fibre membrane in situ, comprises the following steps:
The first step: polyaniline is dissolved in nmp solvent；The mass concentration of polyaniline is 2%；It is filtered to remove insoluble after dissolving
The component solved；
Second step: be dissolved in by PVDF in the solution that the first step obtains, polyaniline quality and PVDF mass ratio are 12%, stir
Mix dissolving standing and defoaming；Being subsequently adding porogen PVP K15, mass concentration is the 18% of solution gross mass；Meanwhile, stirring
After mixing dissolving, stand 15h deaeration；
3rd step: material molding, is molded into hollow-fibre membrane by second step gained solution by the material forming process of extrusion；
4th step: sulfonation, is placed in oleum fully sulfonation by the material of molding；Fully sulfonation refers to that the time of sulfonation is 5
Hour, sulfonating reaction temperature is 100 DEG C, SO in oleum3Mass concentration is 35%；
5th step: clean, fully cleaned by the material deionized water after sulfonation, fully cleans and refers to film surface with distilled water
Unnecessary sulfuric acid cleaned is fallen, and the distilled water after cleaning is neutral；Obtain polyaniline auto-dope PVDF anti-soil doughnut in situ
Film, described polyaniline auto-dope PVDF anti-soil hollow-fibre membrane in situ is to process through sulfonation after polyaniline is blended molding with PVDF
And form poly-zwitterionic original position auto-dope material hollow-fibre membrane at material surface；Separation accuracy is microfiltration, PVDF anti-soil
Hollow-fibre membrane surface static water contact angle is 30 °, and static BSA adsorbance is 5 μ g/cm2, and secondary flux recovery rate reaches
To 98%.
Claims (8)
1. a polyaniline auto-dope PVDF stain resistant material in situ, is characterized in that: described polyaniline auto-dope PVDF anti-soil material in situ
Material through sulfonation process and forms poly-zwitterionic original position auto-dope at material surface after molding being blended for polyaniline with PVDF
Material；The surface static water contact angle of described polyaniline auto-dope PVDF stain resistant material in situ is less than 30 °, static BSA
Adsorbance is less than 5 μ g/cm2, and secondary flux recovery rate reaches more than 95%；Described polyaniline auto-dope PVDF in situ
In stain resistant material, polyaniline quality and PVDF mass ratio are 0.5%～5%.
A kind of polyaniline auto-dope PVDF stain resistant material in situ the most according to claim 1, it is characterised in that described polyphenyl
Amine auto-dope PVDF stain resistant material in situ is Flat Membrane or hollow-fibre membrane.
A kind of polyaniline auto-dope PVDF stain resistant material in situ the most according to claim 2, it is characterised in that described flat board
Film or hollow-fibre membrane, separation accuracy is ultrafiltration or microfiltration.
4. the preparation method of the auto-dope PVDF stain resistant material in situ of a kind of polyaniline as according to any one of claims 1 to 3, it is special
Levy is to comprise the following steps:
The first step: polyaniline is dissolved in NMP or DMF solvent；
Second step: PVDF is dissolved in the solution that the first step obtains, stirring and dissolving standing and defoaming；
3rd step: material molding, by second step gained solution by material forming process molding；
4th step: sulfonation, is placed in oleum fully sulfonation by the material of molding；
5th step: clean, fully cleaned by the material deionized water after sulfonation, obtains polyaniline auto-dope PVDF anti-soil in situ
Material.
The preparation method of a kind of polyaniline the most according to claim 4 auto-dope PVDF stain resistant material in situ, it is characterised in that
In the solution that the first step obtains, the mass concentration of polyaniline is 0.1%～5%；In the solution that second step obtains, polyaniline matter
Amount and PVDF mass ratio are 0.5%～15%.
The preparation method of a kind of polyaniline the most according to claim 4 auto-dope PVDF stain resistant material in situ, it is characterised in that
In the first step, after dissolving, it is filtered to remove undissolved component；In 4th step, abundant sulfonation refers to that the time of sulfonation is 1～20
Hour, sulfonating reaction temperature is 0～130 DEG C, SO in oleum3Mass concentration is 5%-50%；In 5th step, fully
Cleaning and refer to the sulfuric acid cleaned of film excess surface be fallen with deionized water, the deionized water after cleaning is neutral.
The preparation method of a kind of polyaniline the most according to claim 4 auto-dope PVDF stain resistant material in situ, it is characterised in that
In second step, being additionally added porogen, for PEG or PVP, mass concentration is the 2～30% of solution gross mass；Meanwhile, exist
After stirring and dissolving, stand more than 12h deaeration.
The preparation method of a kind of polyaniline the most according to claim 4 auto-dope PVDF stain resistant material in situ, it is characterised in that
Described refer to cast by material forming process, extrude, be molded or molding methods prepares all kinds of stain resistant material.
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