CN106279736A - A kind of hollow fiber polymer membrane composite and preparation method thereof - Google Patents
A kind of hollow fiber polymer membrane composite and preparation method thereof Download PDFInfo
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- CN106279736A CN106279736A CN201510299988.0A CN201510299988A CN106279736A CN 106279736 A CN106279736 A CN 106279736A CN 201510299988 A CN201510299988 A CN 201510299988A CN 106279736 A CN106279736 A CN 106279736A
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- hollow fiber
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Abstract
The present invention provides the preparation method of a kind of hollow fiber polymer membrane composite, it comprises the steps: that catalyst and electrolyte are added in a solvent by a, obtain living solution, wherein, it is 0.5%～2.0% that described catalyst accounts for the weight/mass percentage composition of described living solution, and it is 0.5%～2.0% that described electrolyte accounts for the weight/mass percentage composition of described living solution；One hollow fiber polymer membrane is immersed in described living solution by b, and keeps a period of time；C has addition reaction monomers in the living solution of hollow fiber polymer membrane to immersion, making this reaction monomers occur interface polymerization reaction to generate a conducting polymer coating on the surface of described hollow fiber polymer membrane, wherein said reaction monomers is one or more in aniline, pyrroles, thiophene and derivatives.The present invention also provides for a kind of hollow fiber polymer membrane composite.
Description
Technical field
The present invention relates to polymeric material field, particularly relate to a kind of hollow fiber polymer membrane composite and
Its preparation method.
Background technology
Use film to carry out water to process there is efficiency height, low cost, environmental protection, normal-temperature operation and without chemical change
Etc. advantage, thus attention.But, the method in use film is easily subject to protein, impurity
And the pollution of microorganism, and cause the problem that flux depression, separation efficiency reduce, service life shortens.
Then, people start film is modified research.Such as Application No. 201410457195.2 China
Providing a kind of conduction filter membrane and application thereof in patent application, it is by non-woven fabrics, stainless steel cloth and casting solution
Composition, concrete by making conducting film at the embedded stainless steel cloth of Flat Membrane.The method is due to stainless steel silk
Between net, non-woven fabrics and organic polymer, compatibility difference is big, thus is not easy to be combined with each other, through length
Time use is easily peeled off.Providing one in Application No. 201010160213.2 Chinese patent application can
Conductive reinforced tubular porous body composite film and preparation method thereof, its method is at conductive hollow fabric table
Topcoating is covered polymer material film and is obtained.Owing to using the method for coating to equally exist conductive fiber and macromolecule material
Poor compatibility between material film, the problem of easy ablation.
Summary of the invention
For the problems referred to above, it is an object of the invention to provide the high score that a kind of compatibility is preferable and is not easily stripped
Sub-doughnut film composite material and preparation method thereof.
The present invention provides the preparation method of a kind of hollow fiber polymer membrane composite, and it comprises the steps:
Catalyst and electrolyte are added in a solvent by a, obtain living solution, and wherein, described catalyst accounts for
The weight/mass percentage composition of described living solution is 0.5%～2.0%, and described electrolyte accounts for the matter of described living solution
Amount percentage composition is 0.5%～2.0%；
One hollow fiber polymer membrane is immersed in described living solution by b, and keeps a period of time；
C has addition reaction monomers in the living solution of hollow fiber polymer membrane to immersion so that this reaction list
Body occurs interface polymerization reaction to generate a conducting polymer and be coated with on the surface of described hollow fiber polymer membrane
Layer, wherein said reaction monomers is one or more in aniline, pyrroles, thiophene and derivatives.
The weight/mass percentage composition accounting for described living solution in catalyst described in step a is 0.8%～1.2%, institute
Stating electrolyte and accounting for the weight/mass percentage composition of described living solution is 0.8%～1.2%.
It is water or the mixed solvent being made up of water and organic solvent in solvent described in step a, described organic
Solvent is at least one in ethanol, methanol, ether or acetone, organic molten described in described mixed solvent
The weight/mass percentage composition of agent is 1%～50%, and the weight/mass percentage composition of described water is 50%～99%.
Described in described mixed solvent, the weight/mass percentage composition of organic solvent is 5%～35%, the matter of described water
Amount percentage composition is 65%～95%.
In catalyst described in step a is Iron trichloride hexahydrate, iron sulfate, aluminum sulfate, Alumen one
Planting or multiple, described electrolyte is tosilate, dodecane sulfonate, β-sulfonate, anthraquinone sulphur
One or more in hydrochlorate, 5-butyl naphthalene sulfonate.
The most described hollow fiber polymer membrane is politef, Kynoar, polysulfones, gathers
In ether sulfone, polrvinyl chloride, polyacrylonitrile, polyethylene, polyacrylic curtain type membrane and pillar film at least one
Kind.
The weight/mass percentage composition accounting for described living solution in reaction monomers described in step c is 0.5%～2.0%.
It is 0.8%～1.2% that described reaction monomers accounts for the weight/mass percentage composition of described living solution.
Reaction temperature in interface polymerization reaction described in step c is-1 degree Celsius～1 degree Celsius.
The present invention also provides for a kind of hollow fiber polymer membrane composite wood using method prepared as above to obtain
Material, it is high with the conduction on the surface being attached to described hollow fiber polymer membrane that it includes hollow fiber polymer membrane
Molecular coatings.
Compared to prior art, hollow fiber polymer membrane composite of the present invention and preparation method thereof has
Have the advantage that first, first hollow fiber polymer membrane is immersed in described living solution, in living solution
Catalyst can be evenly affixed in advance the surface of described hollow fiber polymer membrane, be subsequently adding reaction monomers,
Make this reaction monomers in surface generation circle of described hollow fiber polymer membrane under the catalytic action of catalyst
Face polyreaction, generates described conducting polymer coating, thus this conducting polymer coating can be firmly attached to
The compatibility of the surface of described hollow fiber polymer membrane, conducting polymer coating and hollow fiber polymer membrane
Preferably and be not easily stripped, thus substantially increase the service life of hollow fiber polymer membrane composite；The
Two, described electrolyte can enter among the skeleton of the macromolecular compound formed by reaction monomers as adulterant,
Thus its electric conductivity can be further enhanced, it is effectively increased electric conductivity and the pollution resistance of hollow fiber polymer membrane.
Detailed description of the invention
Technical scheme in embodiment of the present invention will be clearly and completely described below, it is clear that institute
The embodiment described is only a part of embodiment of the present invention rather than whole embodiments.Based on
Embodiment in the present invention, those of ordinary skill in the art are obtained under not making creative work premise
The every other embodiment obtained, broadly falls into the scope of protection of the invention.
The invention provides the preparation method of a kind of hollow fiber polymer membrane composite, it includes walking as follows
Rapid:
Catalyst and electrolyte are added in a solvent by a, obtain living solution, and wherein, described catalyst accounts for
The weight/mass percentage composition of described living solution is 0.5%～2.0%, and described electrolyte accounts for the matter of described living solution
Amount percentage composition is 0.5%～2.0%；
One hollow fiber polymer membrane is immersed in described living solution by b, and keeps a period of time；
C has addition reaction monomers in the living solution of hollow fiber polymer membrane to immersion so that this reaction list
Body occurs interface polymerization reaction to generate a conducting polymer and be coated with on the surface of described hollow fiber polymer membrane
Layer, wherein said reaction monomers is one or more in aniline, pyrroles, thiophene and derivatives.
In step a, described solvent can be water or the mixed solvent being made up of water and organic solvent.Described
Organic solvent is at least one in ethanol, methanol, ether or acetone.Have described in described mixed solvent
The weight/mass percentage composition of machine solvent is 1%～50%, and the weight/mass percentage composition of described water is 50%～99%.Excellent
Choosing, described in described mixed solvent, the weight/mass percentage composition of organic solvent is 5%～35%, described water
Weight/mass percentage composition is 65%～95%.
Described catalyst is the material with certain oxidisability, in order to reaction monomers in subsequent step c
Interface polymerization reaction.Described catalyst can be in Iron trichloride hexahydrate, iron sulfate, aluminum sulfate, Alumen
One or more.Preferably, described catalyst accounts for the weight/mass percentage composition of described living solution and is
0.8%～1.2%.
The effect of described electrolyte is to enter with the form of adulterant to be polymerized, by reaction monomers, the macromolecule obtained
Compound scaffold strengthens its electric conductivity.Described electrolyte can be tosilate, dodecyl sodium sulfonate
One or more in salt, β-sulfonate, anthraquinone sulphonates, 5-butyl naphthalene sulfonate.Described electrolyte accounts for
The weight/mass percentage composition of described living solution is 0.8%～1.2%, so that the conducting polymer finally given
The electric conductivity of coating reaches optimum.
In stepb, after hollow fiber polymer membrane is immersed described living solution, the sides such as concussion can be used
Method makes hollow fiber polymer membrane fully be infiltrated by described living solution, so that electrolyte and catalyst are equal
The even surface being attached to described hollow fiber polymer membrane.The time of concussion can be 20 minutes～120 minutes,
It is preferably 30 minutes～90 minutes.
Described hollow fiber polymer membrane does not limits with the mass ratio of living solution, as long as by polymeric hollow fiber
Film is immersed in described living solution.Described hollow fiber polymer membrane can be politef, gather partially
Fluorothene, polysulfones, polyether sulfone, polrvinyl chloride, polyacrylonitrile, polyethylene, polyacrylic curtain type membrane and
At least one in pillar film.
In step c, under the catalytic action of described catalyst, described reaction monomers is in described polymeric hollow
There is polyreaction in the surface of fibrous membrane.This polyreaction occur reaction monomers formed organic facies and solvent
Aqueous phase between, for chemical oxidation interface polymerization reaction.Owing to described reaction monomers is aniline, pyrroles, thiophene
One or more in fen and derivant thereof, thus the polyaniline obtained, polypyrrole, polythiophene etc. tool itself
Conductive macromolecular compound.Wherein said electrolyte is formed by reaction monomers as adulterant entrance
Among the skeleton of macromolecular compound, and its electric conductivity can be further enhanced.In the process, described high score
Itself there is not chemical reaction in sub-hollow-fibre membrane, and is only used as supporter, uniformly adheres to described on its surface
Conducting polymer coating.
The reaction temperature of described interface polymerization reaction can be-1 degree Celsius～1 degree Celsius.The described response time is 6
Hour～72 hours, preferably 8 hours～64 hours.Concrete, after adding reaction monomers, can lead to
The methods such as concussion, stirring of crossing make it react completely.In the present embodiment, after adding reaction monomers, use concussion
Method makes it react completely.The advantage of this concussion method is: will not destroy described hollow fiber polymer membrane
Structure, make its homogeneous response simultaneously, thus uniformly generate institute on the surface of described hollow fiber polymer membrane
State conducting polymer coating.
It is 0.5%～2.0% that described reaction monomers accounts for the weight/mass percentage composition of described living solution.Preferably, institute
Stating reaction monomers and accounting for the weight/mass percentage composition of described living solution is 0.8%～1.2%, so that reaction monomers has
Preferably concentration, thus the conducting polymer coating that reaction obtains has preferable electric conductivity.
It is appreciated that after step c, also includes step d, described hollow fiber polymer membrane is combined
Material takes out, and cleans with deionized water concussion and dry.The time of concussion is 1 hour～24 hours, excellent
Elect 2 hours～24 hours as.
The present invention also provides for a kind of hollow fiber polymer membrane composite using above-mentioned preparation method to obtain.
Described hollow fiber polymer membrane composite includes hollow fiber polymer membrane and is attached in described macromolecule
The conducting polymer coating on the surface of hollow fiber film.
Described hollow fiber polymer membrane primarily serves filtration and removes Organic substance and the effect of colloid in water body.?
Under the effect of extra electric field, described conducting polymer coating is with negative charge, thus can be subtracted by repulsive interaction
The absorption of electronegativity colloid in few water body, and under electric field action, produce H2O2, thus play oxidative degradation
The effect of pollutant in water body, substantially increases the water treatmenting performance of hollow fiber polymer membrane composite.
The thickness of described conducting polymer coating is 10 microns～100 microns.Described hollow fiber polymer membrane
The aperture that retains of composite is 1 nanometer～10 microns.
Hollow fiber polymer membrane composite of the present invention and preparation method thereof has the advantage that first,
First being immersed by hollow fiber polymer membrane in described living solution, the catalyst in living solution can be the most uniform
It is attached to the surface of described hollow fiber polymer membrane, is subsequently adding reaction monomers so that this reaction monomers exists
There is interface polymerization reaction under the catalytic action of catalyst in the surface of described hollow fiber polymer membrane, generate
Described conducting polymer coating, thus this conducting polymer coating can be firmly attached to described polymeric hollow fibre
The surface of dimension film, conducting polymer coating preferably and is not easily stripped with the compatibility of hollow fiber polymer membrane,
Thus substantially increase the service life of hollow fiber polymer membrane composite；Second, described electrolyte can
Enter among the skeleton of the macromolecular compound formed by reaction monomers as adulterant, thus can increase further
Its electric conductivity strong, is effectively increased electric conductivity and the pollution resistance of hollow fiber polymer membrane.
Below in conjunction with specific embodiment, the preparation method of the hollow fiber polymer membrane composite of the present invention is entered
Row explanation:
Embodiment 1:
Catalyst Iron trichloride hexahydrate and electrolyte anthraquinone disulfonic acid salt are sequentially added into and are made up of water and ethanol
Solvent in, stirring certain time make it dispersed, obtain living solution, ferric chloride in living solution
The weight/mass percentage composition of hydrate is 0.5%, and the weight/mass percentage composition of anthraquinone disulfonic acid salt is 0.5%；Described
In solvent, the weight/mass percentage composition of water is 75%, and the weight/mass percentage composition of ethanol is 25%；
Polytetrafluoroethylhollow hollow fiber membrane is immersed in described living solution, shake about 90 minutes；
There is addition reaction monomers aniline in the living solution of polytetrafluoroethylhollow hollow fiber membrane to immersion, take the photograph in 0
Family name's degree shakes about 36 hours so that this aniline is at the generation interface, surface of described polytetrafluoroethylhollow hollow fiber membrane
Polyreaction and generate an electrically conductive polyaniline coating, wherein reaction monomers aniline accounts for the percent mass of living solution
Content is 1%；
Polytetrafluoroethylhollow hollow fiber membrane composite is taken out, and cleans about 24 hours with deionized water concussion,
Dry.
Embodiment 2:
Catalyst Alumen and electrolyte β-sulfonate are sequentially added in the solvent being made up of water and ethanol, stirring
Certain time makes it dispersed, obtains living solution, and in living solution, the weight/mass percentage composition of Alumen is
The weight/mass percentage composition of 0.8%, β-sulfonate is 1.2%；In described solvent, the weight/mass percentage composition of water is
80%, the weight/mass percentage composition of ethanol is 20%；
Pvdf Microporous Hollow Fiber Membrane is immersed in described living solution, shake about 80 minutes；
There is addition reaction monomers pyrroles in the living solution of Pvdf Microporous Hollow Fiber Membrane to immersion, take the photograph in 0
Family name's degree shakes about 48 hours so that this pyrroles is at the generation interface, surface of described Pvdf Microporous Hollow Fiber Membrane
Polyreaction and generate an electric polypyrrole coating, wherein reaction monomers pyrroles accounts for the percent mass of living solution
Content is 1.8%；
Pvdf Microporous Hollow Fiber Membrane composite is taken out, and cleans about 20 hours with deionized water concussion,
Dry.
Embodiment 3:
Catalyst sulfuric acid aluminum and electrolyte tosilate are sequentially added into the solvent being made up of water and ethanol
In, stirring certain time makes it dispersed, obtains living solution, the quality hundred of aluminum sulfate in living solution
Dividing content is 0.8%, and the weight/mass percentage composition of tosilate is 1%；The quality hundred of water in described solvent
Dividing content is 90%, and the weight/mass percentage composition of ethanol is 10%；
Ps hollow fiber uf membrane is immersed in described living solution, shake about 75 minutes；
Addition reaction monomers thiophene in the living solution of ps hollow fiber uf membrane is had, in 0 degree Celsius of shake to immersion
Swing about 72 hours so that this thiophene occurs interfacial polymerization anti-on the surface of described polytetrafluoroethylhollow hollow fiber membrane
Should and generate a conductive polythiophene coating, wherein reaction monomers thiophene accounts for the weight/mass percentage composition of living solution and is
1.4%；
Ps hollow fiber uf membrane composite is taken out, and cleans about 18 hours with deionized water concussion, dry
?.
The above is the preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, this
A little improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a preparation method for hollow fiber polymer membrane composite, it comprises the steps:
Catalyst and electrolyte are added in a solvent by a, obtain living solution, and wherein, described catalyst accounts for
The weight/mass percentage composition of described living solution is 0.5%～2.0%, and described electrolyte accounts for the matter of described living solution
Amount percentage composition is 0.5%～2.0%；
One hollow fiber polymer membrane is immersed in described living solution by b, and keeps a period of time；
C has addition reaction monomers in the living solution of hollow fiber polymer membrane to immersion so that this reaction list
Body occurs interface polymerization reaction to generate a conducting polymer and be coated with on the surface of described hollow fiber polymer membrane
Layer, wherein said reaction monomers is one or more in aniline, pyrroles, thiophene and derivatives.
2. a preparation method for hollow fiber polymer membrane composite as claimed in claim 1, it is special
Levying and be, the weight/mass percentage composition accounting for described living solution in catalyst described in step a is 0.8%～1.2%,
It is 0.8%～1.2% that described electrolyte accounts for the weight/mass percentage composition of described living solution.
3. a preparation method for hollow fiber polymer membrane composite as claimed in claim 1, it is special
Levy and be, be water or the mixed solvent being made up of water and organic solvent in solvent described in step a, described
Organic solvent is at least one in ethanol, methanol, ether or acetone, has described in described mixed solvent
The weight/mass percentage composition of machine solvent is 1%～50%, and the weight/mass percentage composition of described water is 50%～99%.
4. a preparation method for hollow fiber polymer membrane composite as claimed in claim 3, it is special
Levying and be, described in described mixed solvent, the weight/mass percentage composition of organic solvent is 5%～35%, described water
Weight/mass percentage composition be 65%～95%.
5. a preparation method for hollow fiber polymer membrane composite as claimed in claim 1, it is special
Levy and be, in catalyst described in step a is Iron trichloride hexahydrate, iron sulfate, aluminum sulfate, Alumen
One or more, described electrolyte is tosilate, dodecane sulfonate, β-sulfonate, anthracene
One or more in quinone sulfonate, 5-butyl naphthalene sulfonate.
6. a preparation method for hollow fiber polymer membrane composite as claimed in claim 1, it is special
Levy and be, the most described hollow fiber polymer membrane be politef, Kynoar, polysulfones,
In polyether sulfone, polrvinyl chloride, polyacrylonitrile, polyethylene, polyacrylic curtain type membrane and pillar film at least
A kind of.
7. a preparation method for hollow fiber polymer membrane composite as claimed in claim 1, it is special
Levying and be, the weight/mass percentage composition accounting for described living solution in reaction monomers described in step c is
0.5%～2.0%.
8. a preparation method for hollow fiber polymer membrane composite as claimed in claim 7, it is special
Levying and be, it is 0.8%～1.2% that described reaction monomers accounts for the weight/mass percentage composition of described living solution.
9. a preparation method for hollow fiber polymer membrane composite as claimed in claim 1, it is special
Levying and be, the reaction temperature in interface polymerization reaction described in step c is-1 degree Celsius～1 degree Celsius.
10. one kind uses the hollow fiber polymer membrane obtained such as claim 1 to 9 any one preparation method
Composite, it is characterised in that it includes hollow fiber polymer membrane and is attached to described polymeric hollow fibre
The conducting polymer coating on the surface of dimension film.
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| CN201510299988.0A CN106279736A (en) | 2015-06-04 | 2015-06-04 | A kind of hollow fiber polymer membrane composite and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721594A (en) * | 2019-11-03 | 2020-01-24 | 江苏美能膜材料科技有限公司 | Hydrophilic polyvinylidene fluoride composite porous membrane and preparation method thereof |
| CN111484145A (en) * | 2020-04-24 | 2020-08-04 | 东南大学 | Membrane pollution prevention membrane bioreactor |
| CN111498980A (en) * | 2020-04-24 | 2020-08-07 | 东南大学 | Membrane pollution prevention MFC-AnMBR coupling device |
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| CN103255634A (en) * | 2013-05-23 | 2013-08-21 | 中原工学院 | Preparation method of polyacrylonitrile/polyaniline compound micro-nano conductive fiber |
| CN105013335A (en) * | 2015-06-29 | 2015-11-04 | 天津工业大学 | Polymer conductive composite membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103255634A (en) * | 2013-05-23 | 2013-08-21 | 中原工学院 | Preparation method of polyacrylonitrile/polyaniline compound micro-nano conductive fiber |
| CN105013335A (en) * | 2015-06-29 | 2015-11-04 | 天津工业大学 | Polymer conductive composite membrane and preparation method thereof |
Non-Patent Citations (1)
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| 邢明皓 等: "界面聚合法制备MABR中空纤维膜", 《化学工业与工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721594A (en) * | 2019-11-03 | 2020-01-24 | 江苏美能膜材料科技有限公司 | Hydrophilic polyvinylidene fluoride composite porous membrane and preparation method thereof |
| CN111484145A (en) * | 2020-04-24 | 2020-08-04 | 东南大学 | Membrane pollution prevention membrane bioreactor |
| CN111498980A (en) * | 2020-04-24 | 2020-08-07 | 东南大学 | Membrane pollution prevention MFC-AnMBR coupling device |
| CN111484145B (en) * | 2020-04-24 | 2022-11-08 | 东南大学 | Membrane pollution prevention membrane bioreactor |
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Application publication date: 20170104 |