CN107486037B - A kind of PVDF/PDA composite membrane with super hydrophilicity - Google Patents

A kind of PVDF/PDA composite membrane with super hydrophilicity Download PDF

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CN107486037B
CN107486037B CN201710829883.0A CN201710829883A CN107486037B CN 107486037 B CN107486037 B CN 107486037B CN 201710829883 A CN201710829883 A CN 201710829883A CN 107486037 B CN107486037 B CN 107486037B
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pvdf
pda
film
composite membrane
membrane
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CN107486037A (en
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李建华
倪惺惺
郑徽
张德彬
张其清
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Fuzhou University
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Fuzhou University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/34Polyvinylidene fluoride
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane formation
    • B01D67/0006Organic membrane formation by chemical reactions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/58Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60Polyamines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2323/00Details relating to membrane preparation
    • B01D2323/40Details relating to membrane preparation in-situ membrane formation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/36Hydrophilic membranes

Abstract

The invention discloses a kind of PVDF/PDA composite membrane with super hydrophilicity, belongs to the compound membrane modifying field of high molecular functional.By the way that dopamine is added in buffer solution, after magnetic agitation 24-72h, addition pvdf membrane, magnetic agitation 3-5 days;A large amount of PDA microballoons in-situ preparation and modified obtained film entirety hydrophiling structure on film upper and lower surfaces and fenestra wall, wherein film section is the spongelike structure being interconnected between PDA microballoon tiling cover film hole wall but fenestra.Due to the presence of film microreactor effect in the good hydrophily of dopamine itself and modifying process, so that modified obtained PVDF/PDA composite membrane hydrophilicity and antifouling property when as water treatment applications film are greatly improved.Modified effect of the present invention is significant, and preparation process is simple, easily operated, low for equipment requirements, is easy to industrializing implementation, in fields such as water process, biomedicines there is potential be widely applied to be worth.

Description

A kind of PVDF/PDA composite membrane with super hydrophilicity
Technical field
The present invention relates to a kind of PVDF/PDA composite membrane with super hydrophilicity, belongs to the compound membrane modifying of high molecular functional Field.
Background technique
PVDF (Kynoar) is a kind of Crystalline plastics, crystallinity 30%-80%, white granular or powder Shape.PVDF has good thermal stability, and about 170 DEG C of crystalline melt point, thermal decomposition temperature is at 300 DEG C or more, long-term use temperature Range is -40 DEG C -150 DEG C;With excellent chemical stability, do not corroded by acid, alkali, oxidant and halogen under room temperature, to rouge The organic solvents such as fat hydrocarbon, aromatic hydrocarbon, alcohols and aldehydes are very stable, are only soluble in only a few polar solvent, oleum, highly basic etc.;It is mechanical Performance is prominent, has good impact strength, good toughness, hardness is big, and wear-resisting property is good;And also there is resistance to y outstanding to penetrate The performances such as line, ultraviolet radiation.Therefore, PVDF is a kind of relatively popular membrane material, and business pvdf membrane is in micro-filtration and ultrafiltration There is universal application in water process, be applied successfully to drinking water, gas filtration, pollutant removal, solvent refining and film The fields such as distillation.However, due to the stronger hydrophobicity of pvdf membrane itself, so that it is easy the albumen in absorption water in water process Matter, oil droplet, colloid or other organic substances and cause Pore Blocking, cause permeation flux, selection performance and service efficiency under Drop, and when as bio-separation and contacting blood material condensation easy to form, cause complication etc., limit it in water process And the application in the fields such as biomedicine.Therefore, hydrophilic modification is carried out to pvdf membrane material, pvdf membrane can be effectively improved Antifouling property, separating property and biological property, and practical application valence of pvdf membrane during socio-economic development will be promoted Value.
Catechol derivatives of the dopamine as L-3,4 dihydroxyphenylalanine, combine the catechol group of L-3,4 dihydroxyphenylalanine and the ammonia of lysine Base functional group is considered simulating the component of sticking of Mfp-5 in marine organisms mussel well, realizes in wet environment to matrix The attachment on surface.Dopamine can easily be dissolved oxygen in aqueous solution and be aoxidized, and then cause from poly- cross-linking reaction, almost Any solid material surface forms the composite layer of close attachment.The characteristics of dopamine is from poly- duplex surface modification technology: 1) Economical and efficient, environmentally protective, easy to operate, the surface for being suitable for almost any basis material is modified, and to the outer of material There is no limit for shape and size.2) there are catechol active function groups by the coated material surface of dopamine, can carries out Secondary response realizes the further functionalization of material surface.3) functional molecular synthesized according to bionic principle, can be by wherein Dopamine biomimetic features unit by its secure anchorage on the surface of the material, assign material surface more preferably performance.Therefore, dopamine Surface property can be optimized from the modified seperation film of poly- composite algorithm and assign film surface hydrophily, antifouling property, anti-microbial property, Biocompatibility etc. has wide application space and development in separation membrane surface modification or even the modified direction of solid material surface Prospect.
Summary of the invention
The purpose of the present invention is to provide a kind of PVDF/PDA composite membrane with super hydrophilicity.It is of the present invention multiple Close that membrane structure refers to due to a large amount of PDA microballoons the in-situ preparation on film upper and lower surfaces and fenestra wall and modified obtained film is whole Hydrophiling structure, wherein film section is the spongelike structure being interconnected between PDA microballoon tiling cover film hole wall but fenestra.Due to The presence of film microreactor effect in the good hydrophily of dopamine itself and modifying process, so that modified obtained PVDF/PDA Composite membrane has good hydrophily, antifouling property and biocompatibility, and maintains the backbone structure of Kynoar It is not destroyed, that is, remains the good physical property of polyvinylidene fluoride film, have in the fields such as water filtration, purification and biomedicine Wide application value.Preparation process of the present invention is simple, easily operated, and modified effect is significant, low for equipment requirements, is easy to industry Change and implements.
To achieve the above object, the present invention adopts the following technical scheme:
Utilize the adhesion property of dopamine and its complicated physics between pvdf membrane, chemical bond and dopamine The characteristics of polymerizeing balling-up in certain buffer solution pvdf membrane is added to the buffer solution and magnetic force of dopamine in different time points After stirring certain number of days, the modified PVDF/PDA structure of composite membrane of PDA microballoon in-situ preparation is obtained.
Preparation method specifically:
Dopamine is added in buffer solution, after magnetic agitation 24-72h, addition pvdf membrane, magnetic agitation 3-5 days.
Wherein the buffer solution of the dopamine is first by deionized water and ethyl alcohol, isopropanol or ethylene glycol with certain Ratio mixing, then it is configured to certain density Tris phosphate buffer.
Deionized water and the volume ratio of ethyl alcohol, isopropanol or ethylene glycol are 5:1-1 in the buffer solution of the dopamine: 1。
The concentration of dopamine is 1 ~ 10mg/mL in the dopamine buffer solution.
The partial size of PDA microballoon is 0.1-1 microns.
Remarkable advantage of the invention is:
(1) polyvinylidene fluoride material is modified using the dopamine with excellent hydrophily and biocompatibility, with Pure pvdf membrane is compared, and obtained PVDF/PDA composite membrane is former on film upper and lower surfaces and fenestra wall due to a large amount of PDA microballoons Position generates and modified obtained film entirety hydrophiling structure, and entire membrane structure is even up to super hydrophilic state, and because modified The presence of film microreactor effect in the process, so that obtained PVDF/PDA composite membrane hydrophily when as water treatment applications film It can be greatly improved with antifouling property, while the biocompatibility of film is also improved, and is remained and gathered inclined fluorine The good physical property of vinyl film is with a wide range of applications in the fields such as water filtration, purification and biomedicine;
(2) in previous study on the modification, PDA always plays the effect of intermediate, modified often as simple surface The method of additive in object or blending and modifying, surface coating PDA only gives only the preferable performance of film surface, but often film Properties can not be improved, limit film filtering etc. in application;Using the blending and modifying of PDA nano particle, PDA particle is easy to be embedded in film forming procedure is blended, and causes the performance of PDA that cannot embody completely;And in the present invention, directly It connects and comes Modified Membrane, the performance of PDA microballoon in-situ preparation and PDA in entire membrane structure for PDA as main " construction material " It is completely embodied, the overall performance for the PVDF/PDA composite membrane being prepared is preferable.In the present invention simultaneously, it will can control The PDA microballoon of size and uniform particle sizes are applied in the modification of pvdf membrane, the PDA microballoon of uniform particle sizes can for secondary response and Further functionalization provides a good platform;
(3) the PVDF/PDA structure of composite membrane of this method preparation has the advantage that 1. there is good hydrophily;2. having There is good antifouling property;3. energy with good stability;4. having good biocompatibility;5. modified effect is aobvious It writing, preparation process is simple, and it is easily operated, it is low for equipment requirements, it is easy to industrializing implementation.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the PVDF/PDA structure of composite membrane obtained with super hydrophilicity of embodiment 1;Wherein A, B, C respectively represent the front of PVDF original film, reverse side and section;D, E, F respectively represent the front of PVDF/PDA composite membrane, reverse side And section;
Fig. 2 is the contact angular data figure of the PVDF/PDA structure of composite membrane obtained with super hydrophilicity of embodiment 2;Its Middle M0-A and M0-B respectively represents the obverse and reverse contact angle size of PVDF original film;M1-A and M1-B respectively represent PVDF/PDA The obverse and reverse contact angle size of composite membrane;
Fig. 3 is the hemolysis rate figure of the PVDF/PDA structure of composite membrane obtained with super hydrophilicity of embodiment 1;Wherein M0 For PVDF original film;M1 is PVDF/PDA Composite Films Composite films.
Specific embodiment
In order to which the present invention is further explained, the present invention enumerates following embodiment, but the present invention is not limited to following embodiments.
Embodiment 1
First deionized water is mixed with dehydrated alcohol with the volume ratio of 5:1, then Tris phosphate buffer is dissolved in into ethyl alcohol In the mixed liquor of water, it is made into the solution that Tris concentration is 10 mmol/L, finally dopamine powder is dissolved into solution, is made Dopamine concentration is 1 mg/ml, and dopamine buffer solution first stirs for 24 hours after preparing, and continues stirring 3 after PVDF original film then is added It, is cleaned after the completion of stirring with deionized water, naturally dry, obtains modified PVDF/PDA composite membrane.
Embodiment 2
First deionized water is mixed with dehydrated alcohol with the volume ratio of 4:1, then Tris phosphate buffer is dissolved in into ethyl alcohol In the mixed liquor of water, it is made into the solution that Tris concentration is 10 mmol/L, finally dopamine powder is dissolved into solution, is made Dopamine concentration is 2 mg/ml, and dopamine buffer solution first stirs 48h after preparing, and continues stirring 4 after PVDF original film then is added It, is cleaned after the completion of stirring with deionized water, naturally dry, obtains modified PVDF/PDA composite membrane.
Embodiment 3
First deionized water is mixed with dehydrated alcohol with the volume ratio of 3:1, then Tris phosphate buffer is dissolved in into ethyl alcohol In the mixed liquor of water, it is made into the solution that Tris concentration is 10 mmol/L, finally dopamine powder is dissolved into solution, is made Dopamine concentration is 4 mg/ml, and dopamine buffer solution first stirs 72h after preparing, and continues stirring 3 after PVDF original film then is added It, is cleaned after the completion of stirring with deionized water, naturally dry, obtains modified PVDF/PDA composite membrane.
Embodiment 4
First deionized water is mixed with dehydrated alcohol with the volume ratio of 2:1, then Tris phosphate buffer is dissolved in into ethyl alcohol In the mixed liquor of water, it is made into the solution that Tris concentration is 10 mmol/L, finally dopamine powder is dissolved into solution, is made Dopamine concentration is 5 mg/ml, and dopamine buffer solution first stirs for 24 hours after preparing, and continues stirring 3 after PVDF original film then is added It, is cleaned after the completion of stirring with deionized water, naturally dry, obtains modified PVDF/PDA composite membrane.
Embodiment 5
First deionized water is mixed with dehydrated alcohol with the volume ratio of 5:4, then Tris phosphate buffer is dissolved in into ethyl alcohol In the mixed liquor of water, it is made into the solution that Tris concentration is 10 mmol/L, finally dopamine powder is dissolved into solution, is made Dopamine concentration is 6 mg/ml, and dopamine buffer solution first stirs 48h after preparing, and continues stirring 4 after PVDF original film then is added It, is cleaned after the completion of stirring with deionized water, naturally dry, obtains modified PVDF/PDA composite membrane.
Embodiment 6
First deionized water is mixed with dehydrated alcohol with the volume ratio of 4:3, then Tris phosphate buffer is dissolved in into ethyl alcohol In the mixed liquor of water, it is made into the solution that Tris concentration is 10 mmol/L, finally dopamine powder is dissolved into solution, is made Dopamine concentration is 8 mg/ml, and dopamine buffer solution first stirs 72h after preparing, and continues stirring 5 after PVDF original film then is added It, is cleaned after the completion of stirring with deionized water, naturally dry, obtains modified PVDF/PDA composite membrane.
Embodiment 7
First deionized water is mixed with dehydrated alcohol with the volume ratio of 3:2, then Tris phosphate buffer is dissolved in into ethyl alcohol In the mixed liquor of water, it is made into the solution that Tris concentration is 10 mmol/L, finally dopamine powder is dissolved into solution, is made Dopamine concentration is 10 mg/ml, and dopamine buffer solution first stirs for 24 hours after preparing, and continues to stir after PVDF original film then is added It 3 days, is cleaned after the completion of stirring with deionized water, naturally dry, obtains modified PVDF/PDA composite membrane.
Embodiment 8
First deionized water is mixed with dehydrated alcohol with the volume ratio of 1:1, then Tris phosphate buffer is dissolved in into ethyl alcohol In the mixed liquor of water, it is made into the solution that Tris concentration is 10 mmol/L, finally dopamine powder is dissolved into solution, is made Dopamine concentration is 4 mg/ml, and dopamine buffer solution first stirs 48h after preparing, and continues stirring 4 after PVDF original film then is added It, is cleaned after the completion of stirring with deionized water, naturally dry, obtains modified PVDF/PDA composite membrane.
Fig. 1 is the scanning electron microscope (SEM) photograph with the PVDF/PDA structure of composite membrane of super hydrophilicity;Wherein A, B, C are respectively represented The front of PVDF original film, reverse side and section;D, E, F respectively represent the front of PVDF/PDA composite membrane, reverse side and section;It can by figure Obtain, PDA microballoon is evenly distributed on the upper and lower surfaces and fenestra wall of pvdf membrane, but on fenestra wall PDA microballoon quantity it is remote Much larger than the upper and lower surfaces of film, while a large amount of existing PDA microballoons are not also complete by the fenestra on film upper and lower surfaces and section Full blocking;
Fig. 2 is the contact angular data figure with the PVDF/PDA structure of composite membrane of super hydrophilicity;It can be obtained from the figure that arriving, PVDF The obverse and reverse contact angle of former film is respectively 103.1 ° and 105.3 °, and the obverse and reverse contact angle of PVDF/PDA composite membrane Respectively 9.7 ° and 13.5 °, illustrates that the hydrophily of modified caudacoria has obtained significantly improving, reach super hydrophilic state;
Fig. 3 is the hemolysis rate figure with the PVDF/PDA structure of composite membrane of super hydrophilicity;Wherein M0:PVDF original film;M1: PVDF/PDA composite membrane;Eg1: the leaching liquor of film is all added in experimental group;Eg2: physiological saline and film leaching liquor in experimental group Volume ratio be 1:1;Eg3: the volume ratio of physiological saline and film leaching liquor is 4:1 in experimental group;It can be obtained from the figure that arriving, PVDF original film Hemolysis rate be all larger than 5%, there is a degree of haemolysis, and the hemolysis rate of PVDF/PDA composite membrane is both less than 5%, it is believed that There is no haemolysis, i.e., the biocompatibility of modified caudacoria is better than PVDF original film.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (6)

1. a kind of PVDF/PDA composite membrane with super hydrophilicity, it is characterised in that: the composite membrane is that PDA microballoon exists In-situ preparation on pvdf membrane upper and lower surfaces and fenestra wall and modified obtained film entirety hydrophiling structure, wherein film section is PDA The spongelike structure being interconnected between microballoon tiling cover film hole wall but fenestra;Preparation method are as follows: dopamine is added and is buffered In solution, after magnetic agitation 24-72h, addition pvdf membrane, magnetic agitation 3-5 days.
2. the PVDF/PDA composite membrane according to claim 1 with super hydrophilicity, it is characterised in that: dopamine is slow The concentration rushed in solution is 1 ~ 10mg/mL.
3. the PVDF/PDA composite membrane according to claim 1 with super hydrophilicity, it is characterised in that: the buffering Solution is first to mix deionized water in certain proportion with ethyl alcohol, isopropanol or ethylene glycol, then be configured to certain density Tris phosphate buffer.
4. the PVDF/PDA composite membrane according to claim 1 with super hydrophilicity, it is characterised in that: deionized water with The volume ratio of ethyl alcohol, isopropanol or ethylene glycol is 5:1-1:1.
5. the PVDF/PDA composite membrane according to claim 1 with super hydrophilicity, it is characterised in that: PDA microballoon is equal Be distributed on the upper and lower surfaces and fenestra wall of pvdf membrane evenly, but on fenestra wall the quantity of PDA microballoon be far longer than film it is upper, Lower surface.
6. the PVDF/PDA composite membrane according to claim 1 with super hydrophilicity, it is characterised in that: PDA microballoon Partial size is 0.1-1 microns.
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CN108752813B (en) * 2018-05-25 2020-08-07 福州大学 Polydopamine/ionic liquid/plant fiber blend membrane and preparation method thereof
CN108905647B (en) * 2018-06-19 2021-07-09 杭州安诺过滤器材有限公司 Preparation method of hydrophilic polyvinylidene fluoride microfiltration membrane
CN108816057B (en) * 2018-06-25 2021-04-27 福州大学 Polydopamine-ionic liquid composite membrane and preparation method thereof
CN110026092B (en) * 2019-04-17 2021-09-28 南京大学 Nano composite membrane for heavy metal interception and preparation method thereof
CN111701464A (en) * 2020-06-30 2020-09-25 福州大学 Super-hydrophilic beta-FeOOH/PDAus/PVDF composite membrane and preparation and application thereof
CN111701465A (en) * 2020-06-30 2020-09-25 福州大学 Super hydrophilic SiO2Preparation of/PDAus/PVDF composite membrane

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KR102080283B1 (en) * 2013-10-04 2020-02-21 주식회사 엘지화학 Surface-modified membrane and method of modifyng the membrane surface
CN107149881B (en) * 2016-03-02 2019-11-08 天津工业大学 A kind of dopamine modifying polymer film and preparation method thereof
CN105582822A (en) * 2016-03-10 2016-05-18 台州学院 Preparation method of dopamine-modified polysulfone membrane
CN106757789B (en) * 2017-01-11 2019-01-08 西南交通大学 A kind of preparation method of super hydrophilic polyvinylidene fluoride/poly-dopamine laminated film

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