CN105148750A - Method for modifying surface of polyamide composite film - Google Patents
Method for modifying surface of polyamide composite film Download PDFInfo
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- CN105148750A CN105148750A CN201510518201.5A CN201510518201A CN105148750A CN 105148750 A CN105148750 A CN 105148750A CN 201510518201 A CN201510518201 A CN 201510518201A CN 105148750 A CN105148750 A CN 105148750A
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Abstract
The invention discloses a method for modifying the surface of a polyamide composite film. The method comprises steps as follows: (1), copolymers containing nitrogen heterocylic groups such as imidazole, pyridine and the like are dissolved in a solvent, and a coating solution is prepared; (2), the to-be-modified polyamide composite film is soaked in the coating solution for a certain period of time and then is taken out and dried, and a coating is formed on the surface of the film; (3), the polyamide composite film with the surface coated with the coating is subjected to surface quaternization crosslinking treatment, a nitrogen heterocylic zwitterionic polymer gel layer is formed on the surface of the film. The anti-pollution capacity and the anti-chlorine performance of the surface modified polyamide composite film are remarkably improved, and the service life of the polyamide composite film in applications of nanofiltration separation, reverse osmosis seawater desalination and the like is prolonged. The process is simple, the reaction condition is mild, and the method plays an important role in improvement of comprehensive performance of the polyamide composite film.
Description
Technical field
The invention belongs to functional material and technical field of membrane separation, relate to a kind of method of polyamide composite film surface modification.
Background technology
UF membrane occurs in 20 beginnings of the century, the new technology emerged rapidly after the sixties in 20th century.Membrane separation technique had both had separation, concentrated, purifying and refining function concurrently, has again efficient, energy-saving and environmental protection, molecule level is filtered and filter process is simple, be easy to the features such as control.At present, membrane separation technique has been widely used in food, medicine, biology, environmental protection, chemical industry, metallurgy, the energy, oil, water treatment, electronics, the field such as bionical, create huge economic benefit and social benefit, become one of most important means in current separation science.
The PA membrane generated based on interfacial polymerization is that composite membrane selects one of the most frequently used material of layer, it possesses height and retains, the advantages such as high flux and relatively low operating pressure for drink water purifying, desalinization, environmental wastewater process, the every field such as catalyst separation circulation.
But for the nanofiltration separation that relative high pressure drives, one needs the major issue solved to be fouling membrane.Fouling membrane refers to particle, colloid, large molecule, the deposition on film surface or fenestra inwall such as salt.Pollutant is mainly divided into inorganic, organic, biological three major types.Film in running, the pollutant such as protein or colloidal particle by the hydrophobic interaction with film surface, be adsorbed on film surface securely or fenestra inner, cause the temporary or permanent decay of membrane flux to cause membrane lifetime to reduce.In addition, before use NF membrane separating treatment, due in feeding liquid containing more bacterial micro-organism, usually can adopt and add oxidant such as the mode of clorox pretreatment is carried out to feeding liquid.But due to the avtive spot of polyamide existence to Active Chlorine attack sensitivity, therefore its chlorine-resistant property is very poor, Rotating fields selected by the polyamide of Active Chlorine meeting heavy damage composite membrane residual in material liquid, and as the chlorination of amido link, the Orton of chlorination on aromatic rings resets, cause the destruction of polyamide interchain hydrogen bond, the transformation of Molecular connectivity indices, the increase of film surface hydrophobic, the fracture of final or even amido link, the separating property of composite membrane is greatly declined, reduces its service life.Common business polyamide composite film requires that the active chlorine concentrations in material liquid is less than 0.1ppm, then additionally can increase the operating cost of separation process to the further pretreatment of the removal chlorine residue of stoste.Therefore, the antipollution and the chlorine-resistant property that improve film imperative simultaneously.
The antifouling property of usual raising film is applied by surface, surface grafting, blended physico-chemical process of Denging is to improving the hydrophily of film, and the roughness of reduction film and the distribution of change film surface charge realize.As patent CN101462024 proposes polyamide composite film to apply PVA solution, and PVA anti-soil layer is formed, to improve water flux and the contamination resistance of film to its crosslinked mode.Recent study shows, introduces amphion, forms water and ion, can improve the hydrophilicity of film by itself and water, and effectively hinders the absorption of protein, substantially increases the antifouling property of film.Such as An etc. are using amphion as a kind of aqueous phase monomers, by carrying out interfacial polymerization with oil phase monomer TMC, prepare the Nano filtering composite membrane of high flux height anti-soil.For the chlorine-resistant property improving film, generally the means of sacrifice layer are protected to realize Active Chlorine sensitivity site as changed monomeric species, grafting or coating by eliminating or protecting.Such as patent CN104023830A, use to comprise and there is epoxy-terminated fluorine compounds and polyamine as aqueous phase solution, porous supporting body is formed aqueous phase monomers layer, contact with described aqueous phase monomers layer by making oil-phase solution, form the aramid layer comprising fluorine compounds, obtain the aramid layer of high flux height chlorine-resistant property.But, not yet there is the report simultaneously improving polyamide composite film antipollution and chlorine-resistant property by introducing azacyclo-amphion gel layer at present.
Summary of the invention
The present invention is directed to existing technical problem, a kind of method of polyamide composite film surface modification is provided.Technical solution of the present invention is summarized as follows:
A method for polyamide composite film surface modification, comprises the steps:
(1) by azacyclo-dissolution of polymer in deionized water, the mass percentage concentration of azacyclo-polymer is 0.01% ~ 10%, is mixed with the coating liquid of stable homogeneous;
(2) dissolved in a solvent by quaternizing agent, the mass percentage concentration of quaternary ammonium reagent is 0.1% ~ 10%, obtains quaterisation liquid;
(3) polyamide composite film is soaked in coating liquid after 1 ~ 24 hour and take out, thoroughly clean by deionized water, dry in atmosphere;
(4) polyamide composite film after being applied on surface soaks in quaternary ammonium reaction liquid, carry out cross-linking reaction 1 ~ 48 hour, reaction temperature is 30 ~ 70 C, the azacyclo-polymer gel of bisexual ion purification is formed on film surface, finally by deionized water, polyamide composite film is thoroughly cleaned, obtain the polyamide composite film of surface modification.
The shape of described polyamide composite film is Flat Membrane or hollow-fibre membrane.
Described azacyclo-copolymer is poly-(N-vinyl imidazole-acrylic acid), poly-(N-vinyl imidazole-2-acrylamide-2-methyl propane sulfonic), poly-(2-vinylpyridine-acrylic acid) or poly-(N-vinylpyridine-2-acrylamide-2-methyl propane sulfonic);
Described quaternizing agent is 1,3-dibromopropane, Isosorbide-5-Nitrae-dibromobutane or to dibenzyl chlorine.
Described solvent is methyl alcohol, ethanol, n-hexane or normal heptane.
After surface modification, the contamination resistance of polyamide composite film and chlorine resistance can significantly strengthen, and extend the service life of polyamide composite film in the application such as nanofiltration separation and reverse osmosis seawater desalting.Present invention process is simple, reaction condition is gentle, significant to the combination property improving polyamide composite film.
Detailed description of the invention
Embodiment hereafter will make more detailed description to the present invention, but described embodiment is not construed as limiting the invention.From disclosed by the invention content associated to or derive all distortion, all think protection scope of the present invention.
Comparative example 1
Adopt former polyamide flat composite membrane as comparative example 1, test the performances such as its flux retains respectively.
Comparative example 2
Adopt former polyamide hollow composite membrane as comparative example 2, test the performances such as its flux retains respectively.
Embodiment 1
(N-vinyl imidazole-acrylic acid) will be gathered dissolve in deionized water, be mixed with the coating liquid that mass percentage concentration is the stable homogeneous of 0.01%.Polyamide flat composite membrane is soaked in coating liquid after 1 hour and take out, thoroughly clean by deionized water, dry in atmosphere;
By 1,3-dibromopropane is dissolved in methyl alcohol, obtain the quaternary ammonium reaction liquid that mass percentage concentration is 0.1%, polyamide flat composite membrane after being applied on surface soaks in quaternary ammonium reaction liquid, carry out cross-linking reaction 1 hour, reaction temperature is 30 C, forms the azacyclo-polymer gel of bisexual ion purification on film surface, finally by deionized water, polyamide flat composite membrane is thoroughly cleaned, obtain the polyamide flat composite membrane of surface modification.
Embodiment 2
(N-vinyl imidazole-2-acrylamide-2-methyl propane sulfonic) will be gathered dissolve in deionized water, be mixed with the coating liquid that mass percentage concentration is the stable homogeneous of 1%.Polyamide hollow fiber composite membrane is soaked in coating liquid after 6 hours and take out, thoroughly clean by deionized water, dry in atmosphere;
By 1,4-dibromobutane dissolves in ethanol, obtain the quaternary ammonium reaction liquid that mass percentage concentration is 0.5%, polyamide hollow fiber composite membrane after being applied on surface soaks in quaternary ammonium reaction liquid, carry out cross-linking reaction 12 hours, reaction temperature is 50 C, forms the azacyclo-polymer gel of bisexual ion purification on film surface, finally by deionized water, polyamide hollow fiber composite membrane is thoroughly cleaned, obtain the polyamide hollow fiber composite membrane of surface modification.
Embodiment 3
(N-vinylpyridine-acrylic acid) will be gathered dissolve in deionized water, be mixed with the coating liquid that mass percentage concentration is the stable homogeneous of 5%.Polyamide flat composite membrane is soaked in coating liquid after 12 hours and take out, thoroughly clean by deionized water, dry in atmosphere;
To be dissolved in n-hexane to dibenzyl chlorine, obtain the quaternary ammonium reaction liquid that mass percentage concentration is 5%, polyamide flat composite membrane after being applied on surface soaks in quaternary ammonium reaction liquid, carry out cross-linking reaction 24 hours, reaction temperature is 40 C, form the azacyclo-polymer gel of bisexual ion purification on film surface, finally by deionized water, polyamide flat composite membrane is thoroughly cleaned, obtain the polyamide flat composite membrane of surface modification.
Embodiment 4
(N-vinylpyridine-2-acrylamide-2-methyl propane sulfonic) will be gathered dissolve in deionized water, be mixed with the coating liquid that mass percentage concentration is the stable homogeneous of 10%.Polyamide hollow fiber composite membrane is soaked in coating liquid after 24 hours and take out, thoroughly clean by deionized water, dry in atmosphere;
To be dissolved in normal heptane to dibenzyl chlorine, obtain the quaternary ammonium reaction liquid that mass percentage concentration is 10%, polyamide hollow fiber composite membrane after being applied on surface soaks in quaternary ammonium reaction liquid, carry out cross-linking reaction 48 hours, reaction temperature is 70 C, form the azacyclo-polymer gel of bisexual ion purification on film surface, finally by deionized water, polyamide hollow fiber composite membrane is thoroughly cleaned, obtain the polyamide hollow fiber composite membrane of surface modification.
Film properties is tested:
Water flux and salt rejection: film is tested by cross-flow devices, flux be the film of unit area within the unit interval through the volume of water, unit L/m
2h, salt rejection is the ratio of penetrating fluid and stoste electrical conductivity.Test condition: feeding liquid is water or 2000ppm magnesium sulfate solution, and operating temperature is 25 C, and operating pressure is 0.4MPa, and pH value of solution is 7.0.
Antipollution is tested: the parameter being evaluated polyamide composite film antifouling property by resistance to protein contamination.With cross-flow devices test 100ppmBSA and 2000ppm magnesium sulfate mixed solution, test run is membrane flux after 12 hours, and calculates flux depression rate.
Chlorine-resistant property is tested: with the aqueous sodium hypochlorite solution of 2000ppm, be that aqueous sodium hypochlorite solution pH is adjusted to 4.0 by the hydrochloric acid solution of 1mol/L by molar fraction, composite membrane is soaked after 40 hours and take out, thoroughly clean by deionized water, evaluate its water flux and salt rejection.
Table 1 lists antipollution and the chlorine-resistant property of the compound nanometer filtering membrane of polyamide of comparative example 1 and the antipollution chlorine-resistant compound nanometer filtering membrane of polyamide of embodiment 1 ~ 4 preparation.
Table 1
。
Claims (5)
1. a method for polyamide composite film surface modification, is characterized in that, comprises the steps:
(1) by azacyclo-dissolution of polymer in deionized water, the mass percentage concentration of azacyclo-polymer is 0.01% ~ 10%, is mixed with the coating liquid of stable homogeneous;
(2) dissolved in a solvent by quaternizing agent, the mass percentage concentration of quaternary ammonium reagent is 0.1% ~ 10%, obtains quaterisation liquid;
(3) polyamide composite film is soaked in coating liquid after 1 ~ 24 hour and take out, thoroughly clean by deionized water, dry in atmosphere;
(4) polyamide composite film after being applied on surface soaks in quaternary ammonium reaction liquid, carry out cross-linking reaction 1 ~ 48 hour, reaction temperature is 30 ~ 70 C, the azacyclo-polymer gel of bisexual ion purification is formed on film surface, finally by deionized water, polyamide composite film is thoroughly cleaned, obtain the polyamide composite film of surface modification.
2. the method for a kind of polyamide composite film surface modification according to claim 1, is characterized in that, the shape of described polyamide composite film is Flat Membrane or hollow-fibre membrane.
3. the method for a kind of polyamide composite film surface modification according to claim 1, it is characterized in that, described azacyclo-copolymer is poly-(N-vinyl imidazole-acrylic acid), gathers (N-vinyl imidazole-2-acrylamide-2-methyl propane sulfonic), poly-(2-vinylpyridine-acrylic acid) or poly-(N-vinylpyridine-2-acrylamide-2-methyl propane sulfonic).
4. the method for a kind of polyamide composite film surface modification according to claim 1, is characterized in that, described quaternizing agent is 1,3-dibromopropane, Isosorbide-5-Nitrae-dibromobutane or to dibenzyl chlorine.
5. the method for a kind of polyamide composite film surface modification according to claim 1, is characterized in that, described solvent is methyl alcohol, ethanol, n-hexane or normal heptane.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106268375A (en) * | 2016-08-14 | 2017-01-04 | 太原市晋华恒远科技有限公司 | A kind of preparation method of ion liquid functionalization polyphenylene sulfide porous film |
| CN108114612A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Stratiform MOF nanometer sheet composite membranes |
| CN110354692A (en) * | 2018-04-10 | 2019-10-22 | 武汉大学深圳研究院 | The pressure retardation of amphoteric ion random copolymer modification permeates membrane preparation method |
| CN113720761A (en) * | 2021-09-09 | 2021-11-30 | 东风汽车集团股份有限公司 | Chlorine resistance test method for polyamide automobile parts |
| CN114053886A (en) * | 2021-11-18 | 2022-02-18 | 万华化学集团股份有限公司 | Polyamide composite reverse osmosis membrane and preparation method thereof |
| CN115121126A (en) * | 2022-07-18 | 2022-09-30 | 中国科学院赣江创新研究院 | Structure for regulating and controlling interfacial polymerization nanofiltration membrane by rare earth recovery hydrogel layer and preparation method of structure |
| CN115228291A (en) * | 2022-08-10 | 2022-10-25 | 万华化学集团股份有限公司 | Anti-pollution, antibacterial and large-flux reverse osmosis membrane and preparation method and application thereof |
| CN115414791A (en) * | 2022-08-15 | 2022-12-02 | 华中科技大学 | Surface quaternization modified nanofiltration membrane and application of surface quaternization modified nanofiltration membrane in preparation of surface quaternization modified nanofiltration membrane and separation of surface quaternization modified nanofiltration membrane from magnesium and lithium in salt lake |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268375A (en) * | 2016-08-14 | 2017-01-04 | 太原市晋华恒远科技有限公司 | A kind of preparation method of ion liquid functionalization polyphenylene sulfide porous film |
| CN106268375B (en) * | 2016-08-14 | 2018-09-11 | 太原市晋华恒远科技有限公司 | A kind of preparation method of ion liquid functionalization polyphenylene sulfide porous film |
| CN108114612A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Stratiform MOF nanometer sheet composite membranes |
| CN108114612B (en) * | 2016-11-26 | 2021-04-20 | 中国科学院大连化学物理研究所 | Layered MOF nanosheet composite membrane |
| CN110354692A (en) * | 2018-04-10 | 2019-10-22 | 武汉大学深圳研究院 | The pressure retardation of amphoteric ion random copolymer modification permeates membrane preparation method |
| CN110354692B (en) * | 2018-04-10 | 2021-09-14 | 武汉大学深圳研究院 | Preparation method of pressure retardation permeable membrane modified by zwitter-ion random copolymer |
| CN113720761A (en) * | 2021-09-09 | 2021-11-30 | 东风汽车集团股份有限公司 | Chlorine resistance test method for polyamide automobile parts |
| CN114053886A (en) * | 2021-11-18 | 2022-02-18 | 万华化学集团股份有限公司 | Polyamide composite reverse osmosis membrane and preparation method thereof |
| CN115121126A (en) * | 2022-07-18 | 2022-09-30 | 中国科学院赣江创新研究院 | Structure for regulating and controlling interfacial polymerization nanofiltration membrane by rare earth recovery hydrogel layer and preparation method of structure |
| CN115228291A (en) * | 2022-08-10 | 2022-10-25 | 万华化学集团股份有限公司 | Anti-pollution, antibacterial and large-flux reverse osmosis membrane and preparation method and application thereof |
| CN115414791A (en) * | 2022-08-15 | 2022-12-02 | 华中科技大学 | Surface quaternization modified nanofiltration membrane and application of surface quaternization modified nanofiltration membrane in preparation of surface quaternization modified nanofiltration membrane and separation of surface quaternization modified nanofiltration membrane from magnesium and lithium in salt lake |
| CN115414791B (en) * | 2022-08-15 | 2024-04-19 | 华中科技大学 | Surface quaternization modified nanofiltration membrane, preparation and application of surface quaternization modified nanofiltration membrane in separation of magnesium and lithium in salt lake |
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