CN108837714A - A kind of poly-dopamine/manganese dioxide composite membrane and preparation method thereof - Google Patents
A kind of poly-dopamine/manganese dioxide composite membrane and preparation method thereof Download PDFInfo
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- CN108837714A CN108837714A CN201810659830.3A CN201810659830A CN108837714A CN 108837714 A CN108837714 A CN 108837714A CN 201810659830 A CN201810659830 A CN 201810659830A CN 108837714 A CN108837714 A CN 108837714A
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- dopamine
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- composite membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
Abstract
The invention discloses a kind of poly-dopamine/manganese dioxide composite membranes and preparation method thereof, belong to polymer modification field.The modification film of polyvinylidene fluoride of poly-dopamine surface coating is prepared first, it is then immersed in potassium permanganate and sulfuric acid mixed solution, using redox reaction between the two in film surface in-situ preparation manganese dioxide nano particle, a kind of poly-dopamine/manganese dioxide composite membrane is obtained.Material of the present invention is environmentally protective, and simple process is easily operated, low for equipment requirements, is easy to industrializing implementation, and a kind of poly-dopamine/manganese dioxide composite membrane of preparation has good hydrophilic and dyestuff degradation property.
Description
Technical field
The invention belongs to polymer modification fields, and in particular to a kind of preparation side of poly-dopamine/manganese dioxide composite membrane
Method.
Background technique
Kynoar（PVDF）There are many hydrophilic and functional modification method of film, and surface recombination modified is wherein critically important
A kind of method.It is surface recombination modified at present to be broadly divided into two classes：One kind is will be surface coating modified, and another kind of connect to surface
Branch is modified.It is surface coating modified easy to operate relative to surface graft modification, it is not necessarily to special installation, application trend is obvious.But
The problems such as less with modifying agent type there are coating.Currently, Organic inorganic film is because introducing hydrophily environment friendly inorganic on surface
Nano particle improves the hydrophily of film and increases the application function of film, more and more paid attention to.The study found that poly-
Dopamine not only has good Adhesion property to film, but also hydroxyl group rich in structure, can be very good to improve film
Hydrophilicity.In addition, generation is hydrophilic studies have found that poly-dopamine has reduction to potassium permanganate under acidic environment
Property and the manganese dioxide nano particle with catalytic performance.Based on this, the method comprises the steps of firstly, preparing the poly- of poly-dopamine surface coating
Vinylidene Modified Membrane, is then immersed in potassium permanganate and sulfuric acid mixed solution, is existed using redox reaction between the two
Film surface in-situ preparation manganese dioxide nano particle obtains a kind of poly-dopamine/manganese dioxide composite membrane.This is a kind of very simple
Single method of modifying not only increases the immobilized dispersibility of inorganic nanoparticles without expensive instrument, and to environment without dirt
Dye.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of poly-dopamine/manganese dioxide composite membrane and
Preparation method, preparation process of the invention is simple, easily operated, low for equipment requirements, is easy to industrializing implementation, and the one of preparation
Kind poly-dopamine/manganese dioxide composite membrane has good hydrophilic and dyestuff degradation property, and does not injure to human body.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of poly-dopamine/manganese dioxide composite membrane：The polyvinylidene fluoride of poly-dopamine surface coating is prepared first
Alkene Modified Membrane, is then immersed in potassium permanganate and sulfuric acid mixed solution, using redox reaction between the two in film surface
In-situ preparation manganese dioxide nano particle obtains a kind of poly-dopamine/manganese dioxide composite membrane.
More specifically, a kind of poly-dopamine/manganese dioxide composite membrane preparation method, includes the following steps：
1）The preparation of the modification film of polyvinylidene fluoride of poly-dopamine surface coating：
It is put into dopamine hydrochloride in the Tris solution of 10 mM, is settled to 200-400 mL, obtains mixed solution；Business is poly-
Vinylidene microfiltration membranes immerse in mixed solution, and 24 h are stirred at room temperature, and wash, and place 30-40 DEG C of drying in vacuum oven, obtain
The modification film of polyvinylidene fluoride of poly-dopamine surface coating, it is spare；
2）The preparation of poly-dopamine/manganese dioxide composite membrane
By step 1）Modification film of polyvinylidene fluoride obtained immerses in the mixed solution of liquor potassic permanganate and H2SO4 solution, often
Temperature concussion 2-5 minutes, takes out washing, and 50 DEG C of dryings obtain poly-dopamine/manganese dioxide composite membrane.
Step 1）In the mixed solution, the initial concentration of dopamine hydrochloride is 2-10mg/L.
Step 2）The concentration of the liquor potassic permanganate is 0.6-1.0 mM.
Step 2）The H2SO4 solution is 1-1.5 M.
The volume ratio of liquor potassic permanganate described in step 2) and H2SO4 solution is 20:1-100:1.
Poly-dopamine/manganese dioxide composite membrane made from a kind of preparation method as described above.
The beneficial effects of the present invention are：
The present invention innovatively utilizes poly-dopamine in the immobilized manganese dioxide nano particle of film surface in-situ reducing, this method preparation
Poly-dopamine/manganese dioxide composite membrane and preparation method thereof have the following advantages that：The film of preparation has good hydrophilic anti-pollution
Metachromia energy；Simple process, it is easily operated；It is low for equipment requirements, it is easy to industrializing implementation；The dyestuff degradation property of film is excellent；Increase
Add the uniformly dispersed of inorganic nanoparticles；Natural environment is not polluted.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further.But specific embodiment does not limit the claims in the present invention.
Embodiment 1
A kind of preparation method of poly-dopamine/manganese dioxide composite membrane, the specific steps are：
1）The preparation of poly-dopamine surface coating film：By dopamine hydrochloride（Initial concentration in mixed solution is 2 mg/L）
It is put into the Tris solution of 10 mM, constant volume 200mL obtains mixed solution；Business polyvinylidene fluoride microporous filtering film is immersed into mixed solution
In, 24 h are stirred at room temperature, wash, place in vacuum oven, 30 DEG C of dryings obtain poly-dopamine surface coating film, spare；
2）A kind of preparation of poly-dopamine/manganese dioxide composite membrane：Poly-dopamine surface coating film is immersed to 0.6 mM of 20 mL
Liquor potassic permanganate and 0.2mL 1 M H2SO4 mixed solution in, room temperature shakes 2 minutes, takes out washing, 50 DEG C of dryings obtain
Poly-dopamine/manganese dioxide composite membrane.
The contact angle of PVDF original film and water of the comparative experiments without blending and modifying reaches 102 °, the blended modification of the present embodiment
The contact angle of pvdf membrane and water drops to 48 ° afterwards, and contact angle declines rapidly at any time, until 20 seconds only have 10 °.With it is ultraviolet-
Visible spectrophotometer measurement discovery, to the removal rate of sodium indigotindisulfonate up to 93% or more.
Embodiment 2
A kind of preparation method of poly-dopamine/manganese dioxide composite membrane, the specific steps are：
1）The preparation of poly-dopamine surface coating film：By dopamine hydrochloride（Initial concentration in mixed solution is 4 mg/L）
It is put into the Tris solution of 10 mM, constant volume 200mL obtains mixed solution；Business polyvinylidene fluoride microporous filtering film is immersed into mixed solution
In, 24 h are stirred at room temperature, wash, place in vacuum oven, 30 DEG C of dryings obtain poly-dopamine surface coating film, spare；
2）A kind of preparation of poly-dopamine/manganese dioxide composite membrane：Poly-dopamine surface coating film is immersed to 0.6 mM of 20 mL
Liquor potassic permanganate and 0.3 mL 1 M H2SO4 mixed solution in, room temperature shake 2 minutes, take out washing, 50 DEG C of dryings,
Obtain poly-dopamine/manganese dioxide composite membrane.
Through detecting, the contact angle of the blended modified pvdf membrane of the present embodiment and water drops to 40 °, and contact angle is at any time
Between decline rapidly, until 20 seconds only 7 °.It is measured and is found with ultraviolet-visible spectrophotometer, to the removal rate of sodium indigotindisulfonate
Up to 97% or more.
Embodiment 3
A kind of preparation method of poly-dopamine/manganese dioxide composite membrane, the specific steps are：
1）The preparation of poly-dopamine surface coating film：By dopamine hydrochloride（Initial concentration in mixed solution is 6 mg/L）
It is put into the Tris solution of 10 mM, constant volume 200mL obtains mixed solution；Business polyvinylidene fluoride microporous filtering film is immersed into mixed solution
In, 24 h are stirred at room temperature, wash, place in vacuum oven, 30 DEG C of dryings obtain poly-dopamine surface coating film, spare；
2）A kind of preparation of poly-dopamine/manganese dioxide composite membrane：Poly-dopamine surface coating film is immersed to 0.6 mM of 20 mL
Liquor potassic permanganate and 0.4 mL 1 M H2SO4 mixed solution in, room temperature shake 2 minutes, take out washing, 50 DEG C of dryings,
Obtain poly-dopamine/manganese dioxide composite membrane.
Through detecting, the contact angle of the blended modified pvdf membrane of the present embodiment and water drops to 38 °, and contact angle is at any time
Between decline rapidly, until 20 seconds only 5 °.It is measured and is found with ultraviolet-visible spectrophotometer, to the removal rate of sodium indigotindisulfonate
Up to 94% or more.
Embodiment 4
A kind of preparation method of poly-dopamine/manganese dioxide composite membrane, the specific steps are：
1）The preparation of poly-dopamine surface coating film：By dopamine hydrochloride（Initial concentration in mixed solution is 10 mg/
L）It is put into the Tris solution of 10 mM, constant volume 200mL obtains mixed solution；It is molten that business polyvinylidene fluoride microporous filtering film is immersed into mixing
In liquid, 24 h are stirred at room temperature, wash, places 30 DEG C of dryings in vacuum oven, obtains poly-dopamine surface coating film, it is spare；
2）A kind of preparation of poly-dopamine/manganese dioxide composite membrane：Poly-dopamine surface coating film is immersed to 0.6 mM of 20 mL
Liquor potassic permanganate and 0.5 mL 1 M H2SO4 mixed solution in, room temperature shake 2 minutes, take out washing, 50 DEG C of dryings,
Obtain poly-dopamine/manganese dioxide composite membrane.
Through detecting, the contact angle of the blended modified pvdf membrane of the present embodiment and water drops to 35 °, and contact angle is at any time
Between decline rapidly, until 15 seconds only 5 °.It is measured and is found with ultraviolet-visible spectrophotometer, to the removal rate of sodium indigotindisulfonate
Up to 92% or more.
Embodiment 5
A kind of preparation method of poly-dopamine/manganese dioxide composite membrane, the specific steps are：
1）The preparation of poly-dopamine surface coating film：By dopamine hydrochloride（Initial concentration in mixed solution is 10 mg/
L）It is put into the Tris solution of 10 mM, constant volume 200mL obtains mixed solution；It is molten that business polyvinylidene fluoride microporous filtering film is immersed into mixing
In liquid, 24 h are stirred at room temperature, wash, places 30 DEG C of dryings in vacuum oven, obtains poly-dopamine surface coating film, it is spare；
2）A kind of preparation of poly-dopamine/manganese dioxide composite membrane：Poly-dopamine surface coating film is immersed to 0.6 mM of 20 mL
Liquor potassic permanganate and 0.8 mL 1 M H2SO4 mixed solution in, room temperature shake 2 minutes, take out washing, 50 DEG C of dryings,
Obtain poly-dopamine/manganese dioxide composite membrane.
Through detecting, the contact angle of the blended modified pvdf membrane of the present embodiment and water drops to 30 °, and contact angle is at any time
Between decline rapidly, until 10 seconds only 10 °.It is measured and is found with ultraviolet-visible spectrophotometer, to the removal rate of sodium indigotindisulfonate
Up to 91% or more.
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 poly-dopamine/manganese dioxide composite membrane preparation method, it is characterised in that：The painting of poly-dopamine surface is prepared first
The modification film of polyvinylidene fluoride covered, is then immersed in potassium permanganate and sulfuric acid mixed solution, utilizes redox between the two
Reaction obtains a kind of poly-dopamine/manganese dioxide composite membrane in film surface in-situ preparation manganese dioxide nano particle.
2. poly-dopamine according to claim 1/manganese dioxide composite membrane preparation method, it is characterised in that：Including with
Lower step：
1）The preparation of the modification film of polyvinylidene fluoride of poly-dopamine surface coating：
It is put into dopamine hydrochloride in the Tris solution of 10 mM, is settled to 200-400 mL, obtains mixed solution；Business is poly-
Vinylidene microfiltration membranes immerse in mixed solution, and 24 h are stirred at room temperature, and wash, and place in vacuum oven, dry in 30-40 DEG C
It is dry, the modification film of polyvinylidene fluoride of poly-dopamine surface coating is obtained, it is spare；
2）The preparation of poly-dopamine/manganese dioxide composite membrane
By step 1）Modification film of polyvinylidene fluoride obtained immerses liquor potassic permanganate and H2SO4In the mixed solution of solution, room temperature
Concussion 2-5 minutes, takes out washing, and 50 DEG C of dryings obtain poly-dopamine/manganese dioxide composite membrane.
3. poly-dopamine according to claim 2/manganese dioxide composite membrane preparation method, it is characterised in that：Step 1）
In the mixed solution, the initial concentration of dopamine hydrochloride is 2-10mg/L.
4. poly-dopamine according to claim 2/manganese dioxide composite membrane preparation method, it is characterised in that：Step 2）
The concentration of the liquor potassic permanganate is 0.6-1.0 mM, H2SO4The concentration of solution is 1-1.5 M.
5. poly-dopamine according to claim 4/manganese dioxide composite membrane preparation method, it is characterised in that：Step 2）
The liquor potassic permanganate and H2SO4The volume ratio of solution is 20:1-100:1.
6. a kind of prepare poly-dopamine made from preparation method as described in any one in claim 1-5/manganese dioxide composite membrane.
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Cited By (7)
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|---|---|---|---|---|
| CN110841628A (en) * | 2019-11-27 | 2020-02-28 | 清华大学 | Ozone decomposition catalyst and preparation method and application thereof |
| CN113289013A (en) * | 2021-04-08 | 2021-08-24 | 南京林业大学 | PDA-MnO2Film, preparation method and application thereof |
| CN114159984A (en) * | 2021-12-09 | 2022-03-11 | 武汉工程大学 | Containing MnO2Solar light driven water evaporation composite film of nano particles and preparation method thereof |
| CN115245741A (en) * | 2022-01-24 | 2022-10-28 | 江西博鑫环保科技股份有限公司 | Preparation method of polydopamine ceramic composite membrane |
| CN115475539A (en) * | 2022-08-22 | 2022-12-16 | 北方民族大学 | MnO 2 Nanowire modified PVDF (polyvinylidene fluoride) film as well as preparation method and application thereof |
| CN116116248A (en) * | 2023-01-19 | 2023-05-16 | 贵州省材料产业技术研究院 | PVDF composite ultrafiltration membrane with catalytic function and preparation method and application thereof |
| CN116116248B (en) * | 2023-01-19 | 2024-04-12 | 贵州省材料产业技术研究院 | PVDF composite ultrafiltration membrane with catalytic function and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110841628A (en) * | 2019-11-27 | 2020-02-28 | 清华大学 | Ozone decomposition catalyst and preparation method and application thereof |
| CN110841628B (en) * | 2019-11-27 | 2020-10-16 | 清华大学 | Ozone decomposition catalyst and preparation method and application thereof |
| CN113289013A (en) * | 2021-04-08 | 2021-08-24 | 南京林业大学 | PDA-MnO2Film, preparation method and application thereof |
| CN113289013B (en) * | 2021-04-08 | 2023-01-17 | 南京林业大学 | PDA-MnO 2 Film, preparation method and application thereof |
| CN114159984A (en) * | 2021-12-09 | 2022-03-11 | 武汉工程大学 | Containing MnO2Solar light driven water evaporation composite film of nano particles and preparation method thereof |
| CN114159984B (en) * | 2021-12-09 | 2024-04-23 | 武汉工程大学 | MnO-containing material2Solar light-driven water evaporation composite film with nanowires or nanotubes and preparation method thereof |
| CN115245741A (en) * | 2022-01-24 | 2022-10-28 | 江西博鑫环保科技股份有限公司 | Preparation method of polydopamine ceramic composite membrane |
| CN115475539A (en) * | 2022-08-22 | 2022-12-16 | 北方民族大学 | MnO 2 Nanowire modified PVDF (polyvinylidene fluoride) film as well as preparation method and application thereof |
| CN115475539B (en) * | 2022-08-22 | 2023-10-24 | 北方民族大学 | MnO 2 Nanowire modified PVDF (polyvinylidene fluoride) film and preparation method and application thereof |
| CN116116248A (en) * | 2023-01-19 | 2023-05-16 | 贵州省材料产业技术研究院 | PVDF composite ultrafiltration membrane with catalytic function and preparation method and application thereof |
| CN116116248B (en) * | 2023-01-19 | 2024-04-12 | 贵州省材料产业技术研究院 | PVDF composite ultrafiltration membrane with catalytic function and preparation method and application thereof |
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Application publication date: 20181120 |