CN104209017A - Polyaniline in-situ autodoping PVDF (Polyvinylidene Fluoride) antifouling material and preparation method thereof - Google Patents
Polyaniline in-situ autodoping PVDF (Polyvinylidene Fluoride) antifouling material and preparation method thereof Download PDFInfo
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- CN104209017A CN104209017A CN201410425300.4A CN201410425300A CN104209017A CN 104209017 A CN104209017 A CN 104209017A CN 201410425300 A CN201410425300 A CN 201410425300A CN 104209017 A CN104209017 A CN 104209017A
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Abstract
The invention relates to a polyaniline in-situ autodoping PVDF (Polyvinylidene Fluoride) antifouling material and a preparation method thereof. The problem that the hydrophobic PVDF material is easy to pollute can be solved by utilizing the high-efficiency antifouling property of an amphoteric ionic polymer. According to the method, a sulfonated polyaniline material with the amphoteric ion characteristic is introduced into the surface of the PVDF material by adopting the method of firstly mixing and then sulfonating, the wettability and antifouling performance of the surface can be obviously improved, the static water contact angle on the surface can be reduced to 30 degrees below, the static adsorption amount of BSA on the surface of the material is lower than 4mu g/cm<2>, and the secondary water reflux recovery rate can achieve 95% when the polyaniline in-situ autodoping PVDF antifouling material is used as a separation membrane.
Description
Technical field
The invention belongs to technical field of material modification, relate to a kind of polyaniline original position auto-dope PVDF stain resistant material and preparation method thereof, particularly relate to a kind of polyaniline original position auto-dope PVDF stain resistant material utilizing polyaniline surface in situ sulfonation modifying PVDF and preparation method thereof, improve PVDF material surface hydrophily and promote its antifouling property.
Background technology
Various material in use its surface and interface is all inevitably faced with the problem of interface pollution, wherein pollutant comprises inorganic organic molecule, organic macromolecule, large biological molecule, biological pollutant etc., pollutant absorption is deposited in material surface, very serious impact is produced on material interface properties, while destruction material self character, shorten its service life, increase operation cost.Only for the marine pollution matter faced in various types of materials use procedure, multi-million dollar is lost every year in the whole world.The research of present stage to various pollution resistance material is varied; mainly comprise minimum living face energy material and hydrophilic material; utilize the fluorine-containing siliceous material with the ability polluting release realize the object of anti-soil and utilize hydrated sheath protection surface, interface respectively, suppress the adsorption fouling of each pollutant.
Interface pollution problem is ubiquitous, and in UF membrane industry, membrane pollution problem is particularly outstanding.Because it is efficient, energy-saving and environmental protection, molecule level filter, be easy to the advantages such as control in fact becomes one of most important means in separation science, water treatment, food, biology, environmental protection, chemical industry, the energy, oil, the field such as bionical are widely used in, create huge economy and social value, but fouling membrane can cause diffusion barrier separative efficiency decline rapidly and increase operation cost, in restriction film industry, there is the application of its further genralrlization.
Kynoar (PVDF) film has excellent heat endurance, chemical stability, weatherability and processability, is one of membrane material enjoying favor, but simultaneously because hydrophobic effect that its surface is stronger inevitably exists the problem of fouling membrane.Large quantity research shows, increase the hydrophily on film surface and be conducive to alleviating the membrane pollution problem that hydrophobic separation membrane faces in actual application, mainly through modified methods such as blended, surface grafting, surface physics process or coatings, introduce the antifouling property that pollution resistance material improves pvdf membrane.Present stage, antifouling effect best material was poly-amphion and polyethylene glycol (PEG) base polymer with bionical effect; based on stronger hydrogen bond action and hydration of ion; hydrophilic protective layer can be formed on film surface, hydrophobic contaminant be arranged, the adhesion of decreasing pollution thing.But poly-amphion is merely able to dissolve in aqueous due to stronger hydrophily; and cannot be dissolved in the cosolvent of PVDF, being incorporated into by poly-amphion can only by the method for surface grafting in pvdf membrane, and modified method is complicated; condition is harsh, is unsuitable for large-scale production.
Summary of the invention
The object of this invention is to provide a kind of polyaniline original position auto-dope PVDF stain resistant material and preparation method thereof, a kind of polyaniline original position auto-dope PVDF stain resistant material utilizing polyaniline surface in situ sulfonation modifying PVDF and preparation method thereof is particularly provided, improve PVDF material surface hydrophily and promote its antifouling property, poly-zwitterionic anti-soil properties can be shown after there is cosolvent and its auto-dope sulfonation based on PANI and PVDF, by the method for first blended post-modification, sulfonated polyaniline amphion is introduced in material surface original position, strengthen surface wettability and the antifouling property of PVDF material, method of modifying is simple and easy to realize, be suitable for large-scale production.
A kind of polyaniline original position auto-dope PVDF stain resistant material of the present invention; for polyaniline and PVDF blended shaping after form poly-zwitterionic original position auto-dope material through sulfonation process at material surface; in view of amphoteric ion polymer material and hydrophobic PVDF material do not exist cosolvent; the characteristic that amphoteric ion polymer is difficult to process with common used material simultaneously limits its scale and applies; the present invention can effectively address this problem; the method of first blended shaping rear sulfonation; original position introduces amphoteric ion polymer, effectively can improve the surface and interface characteristic of material.
As preferred technical scheme:
In a kind of polyaniline original position auto-dope PVDF stain resistant material as above, polyaniline quality and PVDF mass ratio are 0.5% ~ 5%.
A kind of polyaniline original position auto-dope PVDF stain resistant material as above, described polyaniline original position auto-dope PVDF stain resistant material is Flat Membrane or hollow-fibre membrane, for improving membrane pollution problem during diffusion barrier application.
A kind of polyaniline original position auto-dope PVDF stain resistant material as above, described Flat Membrane or hollow-fibre membrane, separation accuracy is ultrafiltration or micro-filtration, and PVDF stain resistant material surface static water contact angle is lower than 30 °, and static BSA adsorbance is lower than 5 μ g/cm
2, and secondary flux recovery rate reaches more than 95%, shows excellent antifouling property.
Present invention also offers a kind of preparation method of polyaniline original position auto-dope PVDF stain resistant material, 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: forming materials, second step gained solution is shaping by material forming process;
4th step: sulfonation, is placed in oleum fully sulfonation by shaping material;
5th step: cleaning, fully cleans the material deionized water after sulfonation, obtains polyaniline original position auto-dope PVDF stain resistant material.
The preparation method of a kind of polyaniline original position auto-dope PVDF stain resistant material as above, 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 and PVDF mass ratio are 0.5% ~ 15%.
The preparation method of a kind of polyaniline original position auto-dope PVDF stain resistant material as above, in the first step, crosses after dissolving and filters 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 oleum
3mass concentration is 5%-50%; In 5th step, fully cleaning refers to and to fall by the sulfuric acid cleaned of distilled water by film excess surface, and the distilled water to cleaning be neutrality.
The preparation method of a kind of polyaniline original position auto-dope PVDF stain resistant material as above, in second step, also adding pore-foaming agent, is PEG or PVP, and mass concentration is 2 ~ 30% of solution gross mass; Meanwhile, after stirring and dissolving, leave standstill more than 12h deaeration.
The preparation method of a kind of polyaniline original position auto-dope PVDF stain resistant material as above, described being referred to by material forming process utilizes conventional material forming method, and for casting, extruding, injection moulding or molding methods prepare all kinds of stain resistant material, comprises membrane material.
Described polyaniline original position auto-dope PVDF stain resistant material may be used for medical material, separation membrane material, coating, gel rubber material etc.
Polyaniline (PANI) is conventional conducting polymer composite, has special electricity, optical property, can have good electric conductivity, can be used for preparing the electrical devices and material with specific function after doping.But polyaniline is due to the strong interaction of its chain rigidity and interchain, make its solubility extreme difference, almost insoluble in the organic solvent that major part is conventional, be only partially soluble in N,, there is cosolvent with PVDF in dinethylformamide (DMF) and 1-METHYLPYRROLIDONE (NMP).Additional acid doping is carried out to PANI itself, can with H
+react, demonstrate charged negativity, and after sulfonation is carried out to PANI molecule, introduce sulfonate radical by auto-dope, again can with OH
-reaction; show lotus electropositive; after sulfonation auto-dope, existing positive charge in PANI strand unit, has negative electrical charge again, can show zwitterionic characteristic of birdsing of the same feather flock together; zwitterionic materials is gathered used as pollution resistance; present stage research surface, can assemble 21 hydrones around a pair negative ions electric charge in the amphoteric ion polymer unit chain link of bio-imitability, form hydrone protective layer; material and other pollution mediums are kept apart, superpower water and effect make it show excellent antifouling effect.
Beneficial effect:
Modified through the auto-dope of polyaniline original position, while pvdf membrane retains body elite clone performance, surface wettability and antifouling property significantly improve, and material surface Static water contact angles is lower than 30 °, and film surface BSA static adsorbance is lower than 5ug/cm
2; Prepare PVDF Flat Membrane or the hollow-fibre membrane of pollution resistance, for ultrafiltration micro-filtration separation field, its secondary flux recovery rate reaches 95%.
The method that poly-zwitterionic materials improves material antifouling property is introduced compared to other, prepare stain resistant material step by this method simple, be easy to realize, by first blended rear sulfonation, can poly-zwitterionic materials needed for film Surface Creation, prepare the membrane material of antifouling property excellence.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
A preparation method for polyaniline original position auto-dope PVDF stain resistant material, 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 the pore-foaming agent PEG 20000 that mass fraction is 2%, stirring and dissolving standing and defoaming;
3rd step: forming materials, second step gained solution is shaping by the material forming process of casting;
4th step: sulfonation, is placed in oleum fully sulfonation by shaping material; Abundant sulfonation refers to that the time of sulfonation is 1 hour, and sulfonating reaction temperature is 130 DEG C, SO in oleum
3mass concentration is 5%;
5th step: cleaning, fully cleans the material deionized water after sulfonation, and fully cleaning refers to and to fall by the sulfuric acid cleaned of distilled water by film excess surface, and the distilled water to cleaning be neutrality; Obtain polyaniline original position auto-dope PVDF stain resistant material, described polyaniline original position auto-dope PVDF stain resistant material be polyaniline and PVDF blended shaping after form poly-zwitterionic original position auto-dope material through sulfonation process at material surface; Separation accuracy is ultrafiltration, and PVDF stain resistant material surface static water contact angle is 28 °, and static BSA adsorbance is 4 μ g/cm
2, and secondary flux recovery rate reaches 96%.
Embodiment 2
A preparation method for polyaniline original position auto-dope PVDF anti-soil Flat Membrane, comprises the following steps:
The first step: polyaniline is dissolved in DMF solvent; The mass concentration of polyaniline is 5%; Cross after dissolving and filter undissolved component;
Second step: be dissolved in by PVDF in the solution that the first step obtains, polyaniline quality and PVDF mass ratio are 15%, add the pore-foaming agent PVP K30 that mass fraction is 20%, stirring and dissolving standing and defoaming;
3rd step: forming materials, is molded into hollow-fibre membrane by second step gained solution by the material forming process extruding TIPS method;
4th step: sulfonation, is placed in oleum fully sulfonation by shaping material; Abundant sulfonation refers to that the time of sulfonation is 20 hours, and sulfonating reaction temperature is 80 DEG C, SO in oleum
3mass concentration is 50%;
5th step: cleaning, fully cleans the material deionized water after sulfonation, and fully cleaning refers to and to fall by the sulfuric acid cleaned of distilled water by film excess surface, and the distilled water to cleaning be neutrality; Obtain polyaniline original position auto-dope PVDF anti-soil hollow-fibre membrane, described polyaniline original position auto-dope PVDF anti-soil hollow-fibre membrane be polyaniline and PVDF blended shaping after form poly-zwitterionic original position auto-dope Flat Membrane through sulfonation process at material surface; Separation accuracy is micro-filtration, and PVDF anti-soil Flat Membrane surface static water contact angle is 25 °, static BSA adsorbance 5 μ g/cm
2, and secondary flux recovery rate reaches 98%.
Embodiment 3
A preparation method for polyaniline original position auto-dope PVDF anti-soil Flat Membrane, 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%, stirring and dissolving standing and defoaming; Then add pore-foaming agent PEG400, mass concentration is 2% of solution gross mass; Meanwhile, after stirring and dissolving, leave standstill 20h deaeration;
3rd step: forming materials, is molded into Flat Membrane by second step gained solution by the material forming process of injection moulding;
4th step: sulfonation, is placed in oleum fully sulfonation by shaping material; Abundant sulfonation refers to that the time of sulfonation is 10 hours, and sulfonating reaction temperature is 30 DEG C, SO in oleum
3mass concentration is 10%;
5th step: cleaning, fully cleans the material deionized water after sulfonation, and fully cleaning refers to and to fall by the sulfuric acid cleaned of distilled water by film excess surface, and the distilled water to cleaning be neutrality; Obtain polyaniline original position auto-dope PVDF anti-soil Flat Membrane, described polyaniline original position auto-dope PVDF anti-soil Flat Membrane be polyaniline and PVDF blended shaping after form poly-zwitterionic original position auto-dope Flat Membrane through sulfonation process at material surface; Separation accuracy is micro-filtration, and PVDF anti-soil Flat Membrane surface static water contact angle is 20 °, and static BSA adsorbance is 3 μ g/cm
2, and secondary flux recovery rate reaches 95%.
Embodiment 4
A preparation method for polyaniline original position auto-dope PVDF anti-soil Flat Membrane, comprises the following steps:
The first step: polyaniline is dissolved in DMF solvent; The mass concentration of polyaniline is 2%; Cross after dissolving and filter undissolved component;
Second step: be dissolved in by PVDF in the solution that the first step obtains, polyaniline quality and PVDF mass ratio are 8%, stirring and dissolving standing and defoaming; Then add pore-foaming agent PVP K90, mass concentration is 30% of solution gross mass; Meanwhile, after stirring and dissolving, leave standstill 12h deaeration;
3rd step: forming materials, 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 shaping material; Abundant sulfonation refers to that the time of sulfonation is 15 hours, and sulfonating reaction temperature is 50 DEG C, SO in oleum
3mass concentration is 20%;
5th step: cleaning, fully cleans the material deionized water after sulfonation, and fully cleaning refers to and to fall by the sulfuric acid cleaned of distilled water by film excess surface, and the distilled water to cleaning be neutrality; Obtain polyaniline original position auto-dope PVDF anti-soil Flat Membrane, described polyaniline original position auto-dope PVDF anti-soil Flat Membrane be polyaniline and PVDF blended shaping after form poly-zwitterionic original position auto-dope Flat Membrane through sulfonation process at material surface; Separation accuracy is ultrafiltration, and PVDF anti-soil Flat Membrane surface static water contact angle is 15 °, static BSA adsorbance 2 μ g/cm
2, and secondary flux recovery rate reaches 99%.
Embodiment 5
A preparation method for polyaniline original position auto-dope PVDF anti-soil hollow-fibre membrane, comprises the following steps:
The first step: polyaniline is dissolved in DMF solvent; The mass concentration of polyaniline is 3%; Cross after dissolving and filter undissolved component;
Second step: be dissolved in by PVDF in the solution that the first step obtains, polyaniline quality and PVDF mass ratio are 10%, stirring and dissolving standing and defoaming; Then add pore-foaming agent PEG400, mass concentration is 20% of solution gross mass; Meanwhile, after stirring and dissolving, leave standstill 12h deaeration;
3rd step: forming materials, is molded into hollow-fibre membrane by second step gained solution by the material forming process extruded;
4th step: sulfonation, is placed in oleum fully sulfonation by shaping material; Abundant sulfonation refers to that the time of sulfonation is 16 hours, and sulfonating reaction temperature is 70 DEG C, SO in oleum
3mass concentration is 25%;
5th step: cleaning, fully cleans the material deionized water after sulfonation, and fully cleaning refers to and to fall by the sulfuric acid cleaned of distilled water by film excess surface, and the distilled water to cleaning be neutrality; Obtain polyaniline original position auto-dope PVDF anti-soil hollow-fibre membrane, described polyaniline original position auto-dope PVDF anti-soil hollow-fibre membrane be polyaniline and PVDF blended shaping after form poly-zwitterionic original position auto-dope material hollow-fibre membrane through sulfonation process at material surface; Separation accuracy is ultrafiltration, and PVDF anti-soil hollow-fibre membrane surface static water contact angle is 23 °, and static BSA adsorbance is 4.5 μ g/cm
2, and secondary flux recovery rate reaches 96%.
Embodiment 6
A preparation method for polyaniline original position auto-dope PVDF anti-soil hollow-fibre membrane, comprises the following steps:
The first step: polyaniline is dissolved in nmp solvent; The mass concentration of polyaniline is 2%; Cross after dissolving and filter undissolved component;
Second step: be dissolved in by PVDF in the solution that the first step obtains, polyaniline quality and PVDF mass ratio are 12%, stirring and dissolving standing and defoaming; Then add pore-foaming agent PVP K15, mass concentration is 18% of solution gross mass; Meanwhile, after stirring and dissolving, leave standstill 15h deaeration;
3rd step: forming materials, is molded into hollow-fibre membrane by second step gained solution by the material forming process extruded;
4th step: sulfonation, is placed in oleum fully sulfonation by shaping material; Abundant sulfonation refers to that the time of sulfonation is 5 hours, and sulfonating reaction temperature is 100 DEG C, SO in oleum
3mass concentration is 35%;
5th step: cleaning, fully cleans the material deionized water after sulfonation, and fully cleaning refers to and to fall by the sulfuric acid cleaned of distilled water by film excess surface, and the distilled water to cleaning be neutrality; Obtain polyaniline original position auto-dope PVDF anti-soil hollow-fibre membrane, described polyaniline original position auto-dope PVDF anti-soil hollow-fibre membrane be polyaniline and PVDF blended shaping after form poly-zwitterionic original position auto-dope material hollow-fibre membrane through sulfonation process at material surface; Separation accuracy is micro-filtration, and PVDF anti-soil hollow-fibre membrane surface static water contact angle is 30 °, and static BSA adsorbance is 5 μ g/cm
2, and secondary flux recovery rate reaches 98%.
Claims (9)
1. a polyaniline original position auto-dope PVDF stain resistant material, is characterized in that: described polyaniline original position auto-dope PVDF stain resistant material be polyaniline and PVDF blended shaping after form poly-zwitterionic original position auto-dope material through sulfonation process at material surface.
2. a kind of polyaniline original position auto-dope PVDF stain resistant material according to claim 1, is characterized in that, in described polyaniline original position auto-dope PVDF stain resistant material, polyaniline quality and PVDF mass ratio are 0.5% ~ 5%.
3. a kind of polyaniline original position auto-dope PVDF stain resistant material according to claim 1, is characterized in that, described polyaniline original position auto-dope PVDF stain resistant material is Flat Membrane or hollow-fibre membrane.
4. a kind of polyaniline original position auto-dope PVDF stain resistant material according to claim 3, it is characterized in that, described Flat Membrane or hollow-fibre membrane, separation accuracy is ultrafiltration or micro-filtration, PVDF stain resistant material surface static water contact angle is lower than 30 °, and static BSA adsorbance is lower than 5 μ g/cm
2, and secondary flux recovery rate reaches more than 95%.
5. the preparation method of a kind of polyaniline original position auto-dope PVDF stain resistant material according to any one of Claims 1 to 4, is characterized in that comprising 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: forming materials, second step gained solution is shaping by material forming process;
4th step: sulfonation, is placed in oleum fully sulfonation by shaping material;
5th step: cleaning, fully cleans the material deionized water after sulfonation, obtains polyaniline original position auto-dope PVDF stain resistant material.
6. the preparation method of a kind of polyaniline original position auto-dope PVDF stain resistant material according to claim 5, it is characterized 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 quality and PVDF mass ratio are 0.5% ~ 15%.
7. the preparation method of a kind of polyaniline original position auto-dope PVDF stain resistant material according to claim 5, is characterized in that, in the first step, crosses and filter undissolved component after dissolving; 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 oleum
3mass concentration is 5%-50%; In 5th step, fully cleaning refers to and to fall by the sulfuric acid cleaned of distilled water by film excess surface, and the distilled water to cleaning be neutrality.
8. the preparation method of a kind of polyaniline original position auto-dope PVDF stain resistant material according to claim 5, it is characterized in that, in second step, also add pore-foaming agent, is PEG or PVP, and mass concentration is 2 ~ 30% of solution gross mass; Meanwhile, after stirring and dissolving, leave standstill more than 12h deaeration.
9. the preparation method of a kind of polyaniline original position auto-dope PVDF stain resistant material according to claim 5, it is characterized in that, described being referred to by material forming process utilizes conventional material forming method, for casting, extruding, injection moulding or molding methods prepare all kinds of stain resistant material, and stain resistant material comprises membrane material.
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| CN102068925A (en) * | 2010-12-08 | 2011-05-25 | 天津大学 | Preparation method of polyaniline nano composite film |
| CN102343225A (en) * | 2011-09-28 | 2012-02-08 | 天津大学 | Preparation method of polyaniline (PANI) composite ultrafiltration membrane |
| CN102389722A (en) * | 2011-09-28 | 2012-03-28 | 天津大学 | Method for preparing nano composite ultrafiltration membrane by using polyaniline nano material |
| CN102716682A (en) * | 2012-06-29 | 2012-10-10 | 上海中科高等研究院 | Application of hollow fiber nano-filtration membrane in removal of As in water body |
-
2014
- 2014-08-26 CN CN201410425300.4A patent/CN104209017B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068925A (en) * | 2010-12-08 | 2011-05-25 | 天津大学 | Preparation method of polyaniline nano composite film |
| CN102343225A (en) * | 2011-09-28 | 2012-02-08 | 天津大学 | Preparation method of polyaniline (PANI) composite ultrafiltration membrane |
| CN102389722A (en) * | 2011-09-28 | 2012-03-28 | 天津大学 | Method for preparing nano composite ultrafiltration membrane by using polyaniline nano material |
| CN102716682A (en) * | 2012-06-29 | 2012-10-10 | 上海中科高等研究院 | Application of hollow fiber nano-filtration membrane in removal of As in water body |
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