CN105688693A - Preparation method of chitosan graft modification polyvinylidene fluoride (PVDF) separation membrane - Google Patents

Preparation method of chitosan graft modification polyvinylidene fluoride (PVDF) separation membrane Download PDF

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Publication number
CN105688693A
CN105688693A CN201610044016.1A CN201610044016A CN105688693A CN 105688693 A CN105688693 A CN 105688693A CN 201610044016 A CN201610044016 A CN 201610044016A CN 105688693 A CN105688693 A CN 105688693A
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pvdf
preparation
chitosan
paa
film
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冯霞
谢曼曼
夏伟伟
陈莉
赵义平
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Tianjin Polytechnic University
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Tianjin Polytechnic 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
    • B01D71/76Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/78Graft polymers
    • 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 manufacture
    • B01D67/0006Organic membrane manufacture 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
    • B01D69/06Flat membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2323/00Details relating to membrane preparation
    • B01D2323/38Graft polymerization
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/36Hydrophilic membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/48Antimicrobial properties

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The invention discloses a preparation method of a chitosan graft modification polyvinylidene fluoride (PVDF) separation membrane. The method firstly takes acrylic acid as a comonomer, and comprises the steps of enabling the acrylic acid to be grafted onto a main chain of PVDF by adopting a free radical graft copolymerization method to synthesize a PVDF-g-poly acrylic acid (PAA) copolymer, and preparing a PVDF-g-PAA copolymer flat sheet membrane by a phase inversion method; using carboxyl on the surface of the PVDF-g-PAA copolymer membrane to have a grafting reaction with chitosan in presence of a catalyst to enable the chitosan to be fixed on the surface of the PVDF membrane. The preparation method mainly adopts a surface grafting technology and comprises three preparation steps, i.e., preparation of the PVDF-g-PAA copolymer, preparation of the copolymer flat sheet membrane and preparation of a PVDF-g-PAA-chitosan (CTS) membrane. According to the preparation method of the chitosan graft modification PVDF separation membrane, the chitosan is grafted onto the surface of the PVDF separation membrane, so that the hydrophilia, contamination resistance and antibacterial property of the PVDF separation membrane are effectively improved.

Description

The preparation method that the modified PVDF of a kind of chitosan graft separates film
Technical field
The invention belongs to technical field of membrane, particularly to the modified PVDF of a kind of chitosan graft preparation method separating film, belong to environmental technology field。
Background technology
Chitosan, also known as chitosan, chemistry (Isosorbide-5-Nitrae)-2-amino-2-deoxidation-β-D-Glucose by name, typical chemical formula is (C6H11NO4)n(161.2)n。As the deacetylated product of chitin, chitosan is unique alkaline polysaccharide in nature, has that cheap and easy to get, nontoxic, odorlessness, easily processing, biological degradability be good and the advantage such as recyclability, is widely used as fiber or film material。-NH on C-2 in chitosan2Increase make it rare cationic polymer, and be therefore widely applied in antibacterial, absorption etc.。
Kynoar (PVDF) has the features such as good chemical stability, radiation hardness characteristic, thermostability and film property, is that a kind of combination property is good and be widely used in the macromolecular material in membrance separation field。But its stronger hydrophobic performance so that it is be in use highly susceptible to the pollution of Organic substance, inorganic matter and microorganism。Utilize chitosan that PVDF separation membrane material is modified, can effectively strengthen the hydrophilic of PVDF, resistance tocrocking and anti-microbial property。In recent years, many research workers attempt being incorporated in pvdf membrane by chitosan, to improve the hydrophilic of film, resistance tocrocking and antibiotic property, such as Daraei et al. is in order to increase the active force between chitosan and PVDF in the situation without cross-linking agent, the solution of chitosan adds organic clay, then chitosan/organic clay solution is coated to pvdf membrane surface to reach the effect of modified PVDF;The modified chitosan of Zhao et al. chitosan solution, the chitosan of glutaraldehyde cross-linking and terephthaloyl chloride is coated modifiying on the PVDF surface of Static Spinning;The Nano chitosan modified PVDF membrane such as Jia Qian;Boributh et al. is immersed into chitosan solution pvdf membrane, with chitosan solution through pvdf membrane, and by submergence, infiltration in combination with in the way of modified PVDF membrane。
As naturally occurring unique alkaline polysaccharide, chitosan can be dissolved in mineral acid and the most organic acid such as rare hydrochloric acid, nitric acid, but insoluble in rare sulphuric acid, phosphoric acid and majority of organic solvent, limit it and be applied on tradition separation film by blending method。Therefore, in order to chitosan being incorporated into pvdf membrane surface to improve the hydrophilic of pvdf membrane, resistance tocrocking and antibiotic property, this invention first by alkali-treated PVDF and acrylic acid copolymer to introduce carboxyl, then copolymer is scraped and make Flat Membrane, utilize the carboxyl on co-polymer membrane surface by chitosan graft to pvdf membrane surface under catalyst action, to improve the antifouling property of pvdf membrane。
Summary of the invention:
The technical problem that the present invention intends to solve is to provide the modified PVDF of a kind of chitosan graft preparation method separating film, by alkali-treated PVDF is introduced carboxyl functional group with acrylic acid copolymer, then copolymer Flat Membrane is prepared, utilize the grafted chitosan under catalyst action of the carboxyl on co-polymer membrane surface, chitosan is incorporated into pvdf membrane surface and separates film with modified PVDF。The chitosan that product of the present invention adopts has the excellent properties such as good hydrophilic and biocidal property, it is possible under the premise not affecting PVDF premium properties, be effectively improved the hydrophilic of pvdf membrane, resistance tocrocking and antibiotic property。
Product of the present invention is prepared by following steps:
1.PVDF-g-PAA copolymer prepare reference literature [Jiang Zhixu. the preparation of Kynoar anticoagulation film and blood compatibility Journal of Sex Research [M]. Tianjin: Tianjin University of Technology, 2014]。
2. the preparation of copolymer Flat Membrane: weigh PVDF-g-PAA and join containing N, in the container of dinethylformamide (DMF), add Polyethylene Glycol (PEG), making PVDF-g-PAA mass ratio in DMF is 15wt%~20wt%, PEG mass ratio in DMF is 5wt%~10wt%, said vesse is placed in 50 DEG C~70 DEG C water-baths, stirring and dissolving obtains casting solution, casting solution is inclined to glass plate and scrapes film forming, immerse in the coagulating bath thermostatic water bath of 20 DEG C~30 DEG C, until co-polymer membrane after glass plate shaping and comes off, place 24h~36h in deionized water again, deionized water is cleaned and is namely obtained copolymer Flat Membrane。
The preparation of 3.PVDF-g-PAA-CTS film: be immersed in by the co-polymer membrane prepared in 2-(N-morpholine) ethyl sulfonic acid-hydrate (MES) buffer containing 1-ethyl-3-(3-dimethylamine propyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), carries out activation 1h~5h at 1 DEG C~10 DEG C。Then the film activated is placed in the borate buffer solution containing chitosan, under room temperature, reacts 12h~36h, finally, by the PVDF-g-PAA-CTS film deionized water rinsing of formation and be held in deionized water, stand-by。
In described step 3, EDC concentration in MES buffer is 0.01mol/L~0.1mol/L。
In described step 3, NHS concentration in MES buffer is 0.01mol/L~o.1mol/L。
In described step 3, the concentration of MES buffer is 0.05mol/L~0.5mol/L。
In described step 3, the concentration of borate buffer solution is 0.05mol/L~0.5mol/L
In described step 3, the molecular weight of chitosan is 5000~50000。
In described step 3, chitosan concentration in borate buffer solution is 1mg/mL~100mg/mL。
Detailed description of the invention
Embodiment 1:
(1) preparation of PVDF-g-PAA copolymer: the PVDF weighing alkali process joins in the container being placed with DMF, and making PVDF mass ratio in DMF is 16wt%, is placed in by this container in 60 DEG C of water-baths, constant temperature stirring 6h, at N2Under protection, being added thereto to acrylic acid and AIBN, making PVDF and acrylic acid mass ratio is 1: 1, and the mass ratio of PVDF and AIBN is 50: 1, continues logical N2After 0.1h, stop stirring after airtight stirring 10h, products therefrom absolute methanol is precipitated, cools down sucking filtration, and use deionized water wash post-drying, obtain PVDF-g-PAA copolymer;
(2) preparation of copolymer Flat Membrane: weigh in the pVDF-g-PAA container joined containing DMF, add PEG, making PVDF-g-PAA mass ratio in DMF is 15wt%, PEG mass ratio in DMF is 8wt%, this container is placed in 60 DEG C of water-baths, stirring and dissolving obtains casting solution, casting solution is inclined to glass plate and scrapes film forming, immerse in the coagulating bath thermostatic water bath of 25 DEG C, until co-polymer membrane after glass plate shaping and comes off, placing 36h in deionized water again, deionized water is cleaned and is namely obtained copolymer Flat Membrane;
(3) preparation of PVDF-g-PAA-CTS film: the co-polymer membrane prepared is immersed in the MES buffer containing EDC and NHS, and to make EDC concentration in MES buffer be 0.05mol/L, NHS concentration in MES buffer is 0.05mol/L, the concentration of MES buffer is 0.1mol/L, activation 2h is carried out at 4 DEG C, then the film activated is placed in the borax solution containing chitosan, the concentration making borax solution is 0.1mol/L, the concentration of chitosan is 20mg/mL, 12h is reacted under room temperature, finally, by the PVDF-g-PAA-CTS film deionized water rinsing of formation and be held in deionized water, stand-by。
Embodiment 2:
(1) with embodiment 1;
(2) preparation of copolymer Flat Membrane: weigh in the PVDF-g-PAA container joined containing DMF, add PEG, making PVDF-g-PAA mass ratio in DMF is 16wt%, PEG mass ratio in DMF is 9wt%, this container is placed in 60 DEG C of water-baths, stirring and dissolving obtains casting solution, casting solution is inclined to glass plate and scrapes film forming, immerse in the coagulating bath thermostatic water bath of 25 DEG C, until co-polymer membrane after glass plate shaping and comes off, placing 24h in deionized water, deionized water is cleaned and is namely obtained copolymer Flat Membrane;
(3) preparation of PVDF-g-PAA-CTS film: the co-polymer membrane prepared is immersed in the MES buffer containing EDC and NHS, and to make EDC concentration in MES buffer be 0.1mol/L, NHS concentration in MES buffer is 0.1mol/L, the concentration of MES buffer is 0.2mol/L, activation 3h is carried out at 4 DEG C, then being placed in the borax solution containing chitosan by the film activated, the concentration making borax solution is 0.1mol/L, and the concentration of chitosan is 35mg/mL。14h is reacted under room temperature, finally, by the PVDF-g-PAA-CTS film deionized water rinsing of formation and be held in deionized water, stand-by。
Embodiment 3:
(1) with embodiment 1;
(2) preparation of copolymer Flat Membrane: weigh in the PVDF-g-PAA container joined containing DMF, add PEG, making PVDF-g-PAA mass ratio in DMF is 17wt%, PEG mass ratio in DMF is 10wt%, this container is placed in 60 DEG C of water-baths, stirring and dissolving obtains casting solution, casting solution is inclined to glass plate and scrapes film forming, immerse in the coagulating bath thermostatic water bath of 25 DEG C, until co-polymer membrane after glass plate shaping and comes off, placing 36h in deionized water again, deionized water is cleaned and is namely obtained copolymer Flat Membrane;
(3) preparation of PVDF-g-PAA-CTS film: the co-polymer membrane prepared is immersed in the MES buffer containing EDC and NHS, and to make EDC concentration in MES buffer be 0.15mol/L, NHS concentration in MES buffer is 0.15mol/L, the concentration of MES buffer is 0.3mol/L, carries out activation 4h at 4 DEG C。Then being placed in the borax solution containing chitosan by the film activated is that the concentration making borax solution is 0.1mol/L, and the concentration of chitosan is 50mg/mL, 24h is reacted under room temperature, finally, by the PVDF-g-PAA-CTS film deionized water rinsing of formation and be held in deionized water, stand-by。
(4) in example 3, PVDF-g-PAA-CTS film product carries out antifouling property test and anti-microbial property test, and result shows that the flux recovery rate of product of the present invention is 91.2%, and maximum bacteriostasis rate is 89.6%。

Claims (9)

1. the PVDF separation film that a chitosan graft is modified, it is characterised in that described modified PVDF separation membrane surface is grafted with chitosan。
2. chitin modified PVDF as claimed in claim 1 separates film, it is characterised in that the mass ratio of described PVDF and chitosan is 1: 0.01~1: 0.1。
3. the preparation method that the modified PVDF of described chitosan graft separates film, it is characterised in that the method comprises the following steps:
(1) preparation of PVDF-g-PAA copolymer: the PVDF powder weighing alkali process joins in the container being placed with N, dinethylformamide (DMF), is placed in by said vesse in 40 DEG C~70 DEG C water-baths, stirs 4h~12h, at N under constant temperature2Under protection, it is added thereto to acrylic acid and azodiisobutyronitrile (AIBN), continues logical N2After 0.1h~1h, airtight stirring 10h~14h stops stirring, is precipitated by products therefrom absolute methanol, cools down sucking filtration, and use deionized water wash post-drying, obtain PVDF-g-PAA copolymer;
(2) preparation of copolymer Flat Membrane: weigh in the PVDF-g-PAA container joined containing DMF, add Polyethylene Glycol (PEG), making PVDF-g-PAA mass ratio in DMF is 15wt%~20wt%, PEG mass ratio in DMF is 5wt%~10wt%, said vesse is placed in 50 DEG C~70 DEG C water-baths, stirring and dissolving obtains casting solution, casting solution is inclined to glass plate and scrapes film forming, immerse in the coagulating bath thermostatic water bath of 20 DEG C~30 DEG C, until co-polymer membrane after glass plate shaping and comes off, place 24h~36h in deionized water again, deionized water is cleaned and is namely obtained copolymer Flat Membrane;
(3) preparation of PVDF-g-PAA-CTS film: the co-polymer membrane prepared is immersed in 2-(N-morpholine) ethyl sulfonic acid-hydrate (MES) buffer containing 1-ethyl-3-(3-dimethylamine propyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), activation 1h~5h is carried out at 1 DEG C~10 DEG C, the film activated is placed in the borate buffer solution containing chitosan, 12h~36h is reacted under room temperature, finally, by the PVDF-g-PAA-CTS film deionized water rinsing of formation and be held in deionized water, stand-by。
4. the preparation method that the modified PVDF of chitosan graft separates film as claimed in claim 3, it is characterised in that in described step (3), EDC concentration in MES is 0.01mol/L~0.1mol/L。
5. the preparation method that the modified PVDF of chitosan graft separates film as claimed in claim 3, it is characterised in that in described step (3), NHS concentration in MES is 0.01mol/L~0.1mol/L。
6. the preparation method that the modified PVDF of chitosan graft separates film as claimed in claim 3, it is characterised in that in described step (3), the concentration of MES buffer is 0.05mol/L~0.5mol/L。
7. the preparation method that the modified PVDF of chitosan graft separates film as claimed in claim 3, it is characterised in that in described step (3), the concentration of borate buffer solution is 0.05mol/L~0.5mol/L。
8. the preparation method that the modified PVDF of chitosan graft separates film as claimed in claim 3, it is characterised in that in described step (3), the molecular weight of chitosan is 5000~50000。
9. the preparation method that the modified PVDF of chitosan graft separates film as claimed in claim 3, it is characterised in that in described step (3), chitosan concentration in borate buffer solution is 1mg/mL~100mg/mL。
CN201610044016.1A 2016-01-22 2016-01-22 Preparation method of chitosan graft modification polyvinylidene fluoride (PVDF) separation membrane Pending CN105688693A (en)

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CN106362601A (en) * 2016-09-28 2017-02-01 扬州云彩新材料科技有限公司 Nano fiber membrane filtering material with antibacterial function and preparation method thereof
CN109316986A (en) * 2018-11-07 2019-02-12 中南大学 A kind of acrylic acid and sulfonation dihydroxypropylchitosan modified polysulfone film and preparation method thereof
CN110548423A (en) * 2019-08-28 2019-12-10 陈泉学 Modified ultrafiltration membrane and modification method thereof
CN110772662A (en) * 2019-11-30 2020-02-11 山东百多安医疗器械有限公司 Antibacterial expanded polytetrafluoroethylene facial implant material and preparation process thereof
CN111808425A (en) * 2020-07-31 2020-10-23 西北师范大学 Preparation and application of chitosan/carboxylated polyphenylene sulfide composite material
CN111939773A (en) * 2020-08-18 2020-11-17 武汉高正新材料科技有限公司 Preparation method of PVDF (polyvinylidene fluoride) film
CN113914013A (en) * 2021-11-23 2022-01-11 华东理工大学 Electrostatic spinning forming method of cationic nanofiber membrane
CN116272434A (en) * 2023-05-26 2023-06-23 清华大学深圳国际研究生院 Anti-pollution film and preparation method thereof

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CN106362601A (en) * 2016-09-28 2017-02-01 扬州云彩新材料科技有限公司 Nano fiber membrane filtering material with antibacterial function and preparation method thereof
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CN109316986A (en) * 2018-11-07 2019-02-12 中南大学 A kind of acrylic acid and sulfonation dihydroxypropylchitosan modified polysulfone film and preparation method thereof
CN109316986B (en) * 2018-11-07 2021-09-21 中南大学 Acrylic acid and sulfonated dihydroxypropyl chitosan modified polysulfone membrane and preparation method thereof
CN110548423A (en) * 2019-08-28 2019-12-10 陈泉学 Modified ultrafiltration membrane and modification method thereof
CN110548423B (en) * 2019-08-28 2022-04-01 陈泉学 Modified ultrafiltration membrane and modification method thereof
CN110772662A (en) * 2019-11-30 2020-02-11 山东百多安医疗器械有限公司 Antibacterial expanded polytetrafluoroethylene facial implant material and preparation process thereof
CN111808425A (en) * 2020-07-31 2020-10-23 西北师范大学 Preparation and application of chitosan/carboxylated polyphenylene sulfide composite material
CN111808425B (en) * 2020-07-31 2023-06-06 西北师范大学 Preparation and application of chitosan/carboxylated polyphenylene sulfide composite material
CN111939773A (en) * 2020-08-18 2020-11-17 武汉高正新材料科技有限公司 Preparation method of PVDF (polyvinylidene fluoride) film
CN113914013A (en) * 2021-11-23 2022-01-11 华东理工大学 Electrostatic spinning forming method of cationic nanofiber membrane
CN116272434A (en) * 2023-05-26 2023-06-23 清华大学深圳国际研究生院 Anti-pollution film and preparation method thereof

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Application publication date: 20160622