CN103316599A - Preparation method of glycine betaine colloid nano particle modified chitosan nanofiltration membrane - Google Patents
Preparation method of glycine betaine colloid nano particle modified chitosan nanofiltration membrane Download PDFInfo
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- CN103316599A CN103316599A CN2013102587260A CN201310258726A CN103316599A CN 103316599 A CN103316599 A CN 103316599A CN 2013102587260 A CN2013102587260 A CN 2013102587260A CN 201310258726 A CN201310258726 A CN 201310258726A CN 103316599 A CN103316599 A CN 103316599A
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Abstract
The invention discloses a preparation method of a glycine betaine colloid nano particle modified chitosan nanofiltration membrane which comprises a porous polysulfone support layer and a functional layer formed by glycine betaine colloid nano particle modified chitosan. The preparation method comprises the steps of: firstly, carrying out solution polymerization reaction to obtain a glycine betaine colloid nano particle; and then preparing the nano particle, chitosan and a cross-linking agent into a water solution with a certain concentration, dipping one layer of water solution on the surface of the porous polysulfone support layer, and then curing and crosslinking to obtain the nanofiltration membrane. According to the nanofiltration membrane, under the operation pressure of 0.6MPa, the water flux is 25-35L.m<-2>.h<-1>, the retention rate of divalent cations is generally higher than 97 percent, and the retention rate of monovalent salts is lower than 60 percent; meanwhile, the nanofiltration membrane shows good pollution resistance. Therefore, the prepared glycine betaine colloid nano particle modified chitosan nanofiltration membrane has high permeation selectivity and pollution resistance; the preparation method is simple and easy to operate and low in cost, and has a good industrialized application prospect.
Description
Technical field
The invention belongs to the NF membrane separation field, relate in particular to a kind of preparation method of betaine colloidal nanoparticles modification of chitosan NF membrane.
Background technology
Nanofiltration is a kind of novel pressure-actuated film separation process that grows up phase late 1980s.The pore diameter range of NF membrane about about 1～5nm, is a kind of diffusion barrier between reverse osmosis membrane and milipore filter greatly.According to the charge difference of membrane material, NF membrane can be divided into bear nanofiltration membrane, positively charged nanofiltration membranes and charge embedded NF membrane.The commercialization NF membrane is mainly PA membrane, CAM and the sulfonated polyether sulfone film etc. of bear electricity at present.Yet, increase along with the actual separation system, positively charged nanofiltration membranes presents special advantages in the separation of water softening, high valence state metal ion with fields such as separating of recovery, lotus positive electricity amino acid and protein, needs development of new high-performance positively charged nanofiltration membranes.
Shitosan is the nitrogenous polysaccharose substance that the extensive chitin (chitin) that exists of a kind of nature obtains after taking off acetyl, have good characteristics such as excellent biological compatibility, avirulence and biodegradability, now be widely used in applications such as medicine, food, chemical industry, water treatment and heavy metal recovery.Along with the development of membrane separation technique, shitosan develops into the important separation membrane material of a class (Sep.Purif. Technol., 2008,58,393-399 gradually; Desalination, 2009,239,38-45; Chem. Eng. J., 2010,157,393-400).Yet existing shitosan and derivative NF membrane thereof also fail to reach the separating property that possesses high salt rejection and high water permeation flux simultaneously; In addition, in the actual separation application process, the pollution problem of NF membrane is the key of its long-term stable operation of restriction.Therefore, be badly in need of developing a kind of novel chitosan positively charged nanofiltration membranes, make it not only have good separating effect, high water permeation flux, also have strong anti-fouling performance.
The betaine type polymer is that a class yin, yang ionic group is positioned at the amphoteric ion polymer on the same monomeric unit of macromolecular chain, and it is material modified now to become the novel film of a class gradually.Now existing report is incorporated into the betaine type polymer in the NF membrane by methods such as solution coating, interfacial polymerization and surface chemical modifications, can improve water flux and stain resistance (J. Membr. Sci., 2012,390-391, the 243-253 of film simultaneously; J. Membr. Sci., 2012,389,76-82; J. Membr. Sci., 2013,431,171-179).The betaine type polymer can form the aggregation that contains some macromolecular chains, i.e. the betaine colloidal nanoparticles by (interior) electrostatic attraction effect and hydrophilic, hydrophobic effect between strand.As this type of nano particle is incorporated in the chitosan film, not only can utilize its good hydrophilicity and strong stain resistance, also can rely on its unique nano aperture structure, when keeping the good separation selectivity of film, significantly improve water permeability and the stain resistance of film, can reach the needs that satisfy practical application better.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of betaine colloidal nanoparticles modification of chitosan NF membrane is provided.
NF membrane is to be the composite membrane of functional layer by porous polysulfone supporting layer and betaine colloidal nanoparticles modification of chitosan.
The preparation method's of betaine colloidal nanoparticles modification of chitosan NF membrane step is as follows:
1) is function monomer with beet base olefinic monomer and hydroxyalkyl acrylate monomer, is made into the aqueous solution, add water the dissolubility oxidation-reduction initiator, adopt the emulsifier-free emulsion polymerization method, preparation betaine colloidal nanoparticles;
2) shitosan and betaine colloidal nanoparticles are dispersed in contain in the inorganic aqueous acid, add crosslinking agent, be made into casting solution; 20～30
oUnder the temperature of C and 50～60% the relative air humidity condition, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, is positioned over 40～60
oIn the baking oven of C 2～4 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane;
The described beet base of step 1) olefinic monomer is 3-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] propane-1-acid inner salt, 2-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] ethane-1-carboxylic acid inner salt or 3-(4-vinylpridine) propane-1-carboxylic acid inner salt; Hydroxyalkyl acrylate monomer described in the step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
The mass percent concentration of beet base olefinic monomer is 15～35% in the aqueous solution described in the step 1).The mass percent concentration of hydroxyalkyl acrylate monomer is 5～15% in the aqueous solution described in the step 1).Oxidation-reduction initiator described in the step 1) is that mass ratio is persulfuric acid potassium sulfate and the sodium hydrogensulfite of 1:1, and total mass percent concentration is 1～3% in the aqueous solution.Emulsifier-free emulsion polymerization condition described in the step 1) is 30～50
oPolymerization is 2～6 hours under the C.
Step 2) the shitosan weight average molecular weight described in is 5～200,000, deacetylation 85% or 95%.Step 2) inorganic acid described in is sulfuric acid, hydrochloric acid or acetic acid.Step 2) crosslinking agent described in is MDA, glutaraldehyde or butanedial.Step 2) in the casting solution described in shitosan, betaine colloidal nanoparticles, inorganic acid and crosslinking agent mass percent concentration be respectively 0.5～2%, 0.1～1%, 0.1～0.3% and 0.2～0.5%.
The betaine colloidal nanoparticles modification of chitosan NF membrane of preparation.
The present invention is betaine colloidal nanoparticles modification of chitosan as the material of film surface isolation layer, colloidal nanoparticles is prepared by the emulsifier-free emulsion polymerization method by beet base olefinic monomer and hydroxyalkyl acrylate monomer, and the chemical composition of colloidal nanoparticles and hydrophilic and hydrophobic can be realized by kind and the proportioning thereof of adjusting comonomer; And then by adjusting the proportioning of betaine colloidal nanoparticles and shitosan, obtained serial nano hydridization chitosan nano filter membrane, and its rejection to divalent metal salt generally is higher than 97%, and the rejection of monovalent salt is lower than 60%, and water flux is 25～35 L.m
-2.h
-1, this kind composite nanometer filtering film has high permselective property and strong stain resistance; In addition, the present invention is raw materials used conveniently to be easy to get, cheap; The polymerization solvent for use is water, clean environment firendly, and preparation process is simple and safe.The preparation of composite membrane adopts simple dip-coating, the crosslinked processing of heat cure to get final product, and filming technology is simple, cost is low, has the favorable industrial practicality.
The specific embodiment
NF membrane is to be the composite membrane of functional layer by porous polysulfone supporting layer and betaine colloidal nanoparticles modification of chitosan.
The preparation method's of betaine colloidal nanoparticles modification of chitosan NF membrane step is as follows:
1) is function monomer with beet base olefinic monomer and hydroxyalkyl acrylate monomer, is made into the aqueous solution, add water the dissolubility oxidation-reduction initiator, adopt the emulsifier-free emulsion polymerization method, preparation betaine colloidal nanoparticles;
2) shitosan and betaine colloidal nanoparticles are dispersed in contain in the inorganic aqueous acid, add crosslinking agent, be made into casting solution; 20～30
oUnder the temperature of C and 50～60% the relative air humidity condition, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, is positioned over 40～60
oIn the baking oven of C 2～4 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane;
The described beet base of step 1) olefinic monomer is 3-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] propane-1-acid inner salt, 2-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] ethane-1-carboxylic acid inner salt or 3-(4-vinylpridine) propane-1-carboxylic acid inner salt; Hydroxyalkyl acrylate monomer described in the step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
The mass percent concentration of beet base olefinic monomer is 15～35% in the aqueous solution described in the step 1).The mass percent concentration of hydroxyalkyl acrylate monomer is 5～15% in the aqueous solution described in the step 1).Oxidation-reduction initiator described in the step 1) is that mass ratio is persulfuric acid potassium sulfate and the sodium hydrogensulfite of 1:1, and total mass percent concentration is 1～3% in the aqueous solution.Emulsifier-free emulsion polymerization condition described in the step 1) is 30～50
oPolymerization is 2～6 hours under the C.
Step 2) the shitosan weight average molecular weight described in is 5～200,000, deacetylation 85% or 95%.Step 2) inorganic acid described in is sulfuric acid, hydrochloric acid or acetic acid.Step 2) crosslinking agent described in is MDA, glutaraldehyde or butanedial.Step 2) in the casting solution described in shitosan, betaine colloidal nanoparticles, inorganic acid and crosslinking agent mass percent concentration be respectively 0.5～2%, 0.1～1%, 0.1～0.3% and 0.2～0.5%.
The betaine colloidal nanoparticles modification of chitosan NF membrane of preparation.
The separating property method of testing of betaine colloidal nanoparticles modification of chitosan NF membrane is as follows: NF membrane is placed the conventional nanofiltration testing arrangement in this area, and test cephacoria precompressed 1 h under 0.7 MPa operating pressure is then 25
oUnder C and the 0.6 MPa test condition, the water permeation flux (J) of film and the rejection (R) of material are measured, its computing formula is suc as formula being: J=V/ (A.t); R=1-C
pC
fWherein, the V-feed liquid sees through the volume of film, and the effective area of A-film is 22.4 cm
2, t-running time, C
p-penetrating fluid concentration, C
f-feeding liquid concentration; By measuring conductivity value, obtain inorganic salt solution concentration.
Provide embodiments of the invention below, but the present invention is not subjected to the restriction of embodiment:
Embodiment 1:
Get 15g 3-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] propane-1-acid inner salt and 5g hydroxy-ethyl acrylate add in the 100ml water, feed nitrogen, the adding mass percent concentration is 1% potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1), 30
oCarry out emulsifier-free emulsion polymerization under the C 6 hours, and through repeatedly centrifugal, washing, after the vacuum drying, obtained the betaine colloidal nanoparticles; With the above-mentioned nano particle of 0.1g, 0.5 g shitosan (molecular weight 50,000, deacetylation 85%), 0.1g hydrochloric acid and 0.2g glutaraldehyde join in the 100 ml water and dissolve, and obtain the casting solution of clear; 20
oUnder the relative air humidity condition of C and 50 %, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, again it is positioned over 40
oIn the baking oven of C 4 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane.This NF membrane is 25
oC is under the 0.6 MPa pressure, for 1 g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 51.2 %, and water flux is 28.5L.m
-2.h
-1To MgCl
2Rejection be 97.5 %, water flux is 27.6L.m
-2.h
-1
Embodiment 2:
Get 35g 3-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] propane-1-acid inner salt and 15g hydroxy-ethyl acrylate add in the 100ml water, feed nitrogen, the adding mass percent concentration is 3% potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1), 50
oCarry out emulsifier-free emulsion polymerization under the C 2 hours, and through repeatedly centrifugal, washing, after the vacuum drying, obtained the betaine colloidal nanoparticles; With the above-mentioned nano particle of 1g, 2 g shitosans (molecular weight 200,000, deacetylation 95%), 0.3g hydrochloric acid and 0.5g glutaraldehyde join in the 100 ml water and dissolve, and obtain the casting solution of clear; 30
oUnder the relative air humidity condition of C and 60 %, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, again it is positioned over 60
oIn the baking oven of C 2 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane.This NF membrane is 25
oC is under the 0.6 MPa pressure, for 1 g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 58.5 %, and water flux is 25.8L.m
-2.h
-1To MgCl
2Rejection be 98.7 %, water flux is 24.7L.m
-2.h
-1
Embodiment 3:
Get 25g 3-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] propane-1-acid inner salt and 10g hydroxy-ethyl acrylate add in the 100ml water, feed nitrogen, the adding mass percent concentration is 2% potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1), 40
oCarry out emulsifier-free emulsion polymerization under the C 4 hours, and through repeatedly centrifugal, washing, after the vacuum drying, obtained the betaine colloidal nanoparticles; With the above-mentioned nano particle of 0.5g, 1.5 g shitosans (molecular weight 100,000, deacetylation 95%), 0.2g hydrochloric acid and 0.3g glutaraldehyde join in the 100 ml water and dissolve, and obtain the casting solution of clear; 25
oUnder the relative air humidity condition of C and 55 %, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, again it is positioned over 50
oIn the baking oven of C 3 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane.
Comparative Examples 1
With reference to embodiment 3 steps, without preparation betaine colloidal nanoparticles, directly be raw material (each material adding proportion is with reference to embodiment 3) preparation NF membrane with the shitosan.
Comparative Examples 2
With reference to embodiment 3 steps, replace the betaine colloidal nanoparticles to add (adding proportion is with reference to embodiment 3) in the chitosan film preparation process to polyvinyl alcohol (PVA-1788), the preparation NF membrane.
Table 1 embodiment 3, the separating property of the NF membrane of Comparative Examples 1,2 preparation relatively
| ? | MgCl 2Rejection (%) | Water flux (L.m -2.h -1） | NaCl rejection (%) | Water flux (L.m -2.h -1） |
| Embodiment 3 | 98.3 | 30.8 | 48.2 | 32.5 |
| Comparative Examples 1 | 97.5 | 7.8 | 61.5 | 8.5 |
| Comparative Examples 2 | 97.8 | 15.6 | 57.2 | 16.5 |
Table 1 is the result show, 3 kinds of methods all can make the NF membrane that bivalent cation and monovalent salt is had the good separation performance, but its water flux has bigger difference, and this is causes different with hydrophily of microstructure by the interpolation material of preparation chitosan film.
In the Comparative Examples 1, do not add that other is material modified, constitute by shitosan crystalline polymer chain is crosslinked, this film is fine and close; In the Comparative Examples 2, it be material modified adding polyvinyl alcohol (PVA-1788), introduces flexible good, macromolecular material that hydrophily is strong in its chitosan film, the compactness of film is decreased, the hydrophily increase.
Among the embodiment 3, be material modified with the betaine colloidal nanoparticles, utilize nanostructured and the good hydrophilicity of himself uniqueness, be introduced in the chitosan film, not only can improve the hydrophily of film, can also in film, form " aquaporin " structure, promote that hydrone transmits in film; Simultaneously, because betaine colloidal nanoparticles favorable dispersibility can guarantee that the compactness of film is unaffected, has high selection separation property; In addition, because the betaine colloidal particle has good stain resistance, can improve segregational stability and the stain resistance of film.Therefore, be material modified with the betaine colloidal nanoparticles, the chitosan nano filter membrane of preparation has high separation selectivity, high water permeability and strong stain resistance.
Embodiment 4:
Get 25g 2-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] ethane-1-carboxylic acid inner salt and 10g hydroxyethyl methacrylate add in the 100ml water, feed nitrogen, the adding mass percent concentration is 2% potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1), 40
oCarry out emulsifier-free emulsion polymerization under the C 4 hours, and through repeatedly centrifugal, washing, after the vacuum drying, obtained the betaine colloidal nanoparticles; With the above-mentioned nano particle of 0.5g, 1.5 g shitosans (molecular weight 100,000, deacetylation 85%), 0.2g hydrochloric acid and 0.3g glutaraldehyde join in the 100 ml water and dissolve, and obtain the casting solution of clear; 25
oUnder the relative air humidity condition of C and 55 %, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, again it is positioned over 50
oIn the baking oven of C 3 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane.This NF membrane is 25
oC is under the 0.6 MPa pressure, for 1 g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 56.5 %, and water flux is 28.8L.m
-2.h
-1To MgCl
2Rejection be 98.2 %, water flux is 27.1L.m
-2.h
-1
Embodiment 5:
Get 25g 3-(4-vinylpridine) propane-1-carboxylic acid inner salt and 10g hydroxy propyl methacrylate and add in the 100ml water, feed nitrogen, the adding mass percent concentration is 2% potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1), 40
oCarry out emulsifier-free emulsion polymerization under the C 4 hours, and through repeatedly centrifugal, washing, after the vacuum drying, obtained the betaine colloidal nanoparticles; With the above-mentioned nano particle of 0.5g, 1.5 g shitosans (molecular weight 100,000, deacetylation 95%), 0.2g acetic acid and 0.3g butanedial join in the 100 ml water and dissolve, and obtain the casting solution of clear; 25
oUnder the relative air humidity condition of C and 55 %, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, again it is positioned over 50
oIn the baking oven of C 3 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane.This NF membrane is 25
oC is under the 0.6 MPa pressure, for 1 g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 57.6 %, and water flux is 30.8L.m
-2.h
-1To MgCl
2Rejection be 98.5%, water flux is 28.9L.m
-2.h
-1
Embodiment 6:
Get 25g 3-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] propane-1-acid inner salt and 5g hydroxy-ethyl acrylate add in the 100ml water, feed nitrogen, the adding mass percent concentration is 2% potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1), 45
oCarry out emulsifier-free emulsion polymerization under the C 3 hours, and through repeatedly centrifugal, washing, after the vacuum drying, obtained the betaine colloidal nanoparticles; With the above-mentioned nano particle of 1g, 2 g shitosans (molecular weight 100,000, deacetylation 95%), 0.2g sulfuric acid and 0.3g glutaraldehyde join in the 100 ml water and dissolve, and obtain the casting solution of clear; 25
oUnder the relative air humidity condition of C and 55 %, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, again it is positioned over 50
oIn the baking oven of C 3 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane.This NF membrane is 25
oC is under the 0.6 MPa pressure, for 1 g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 55.6 %, and water flux is 33.5L.m
-2.h
-1To MgCl
2Rejection be 98.7%, water flux is 32.1L.m
-2.h
-1
Embodiment 7:
Get 20g 3-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] propane-1-acid inner salt and 10g hydroxy-ethyl acrylate add in the 100ml water, feed nitrogen, the adding mass percent concentration is 1% potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1), 50
oCarry out emulsifier-free emulsion polymerization under the C 3 hours, and through repeatedly centrifugal, washing, after the vacuum drying, obtained the betaine colloidal nanoparticles; With the above-mentioned nano particle of 1g, 1.5g shitosan (molecular weight 100,000, deacetylation 95%), 0.1g acetic acid and 0.25g glutaraldehyde join in the 100 ml water and dissolve, and obtain the casting solution of clear; 25
oUnder the relative air humidity condition of C and 55 %, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, again it is positioned over 50
oIn the baking oven of C 3 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane.This NF membrane is 25
oC is under the 0.6 MPa pressure, for 1 g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 57.8 %, and water flux is 31.5L.m
-2.h
-1To MgCl
2Rejection be 97.6%, water flux is 29.8L.m
-2.h
-1
Embodiment 8:
Get 20g 3-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] propane-1-acid inner salt and 5g hydroxy-ethyl acrylate add in the 100ml water, feed nitrogen, the adding mass percent concentration is 1% potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1), 45
oCarry out emulsifier-free emulsion polymerization under the C 3 hours, and through repeatedly centrifugal, washing, after the vacuum drying, obtained the betaine colloidal nanoparticles; With the above-mentioned nano particle of 1g, 2 g shitosans (molecular weight 150,000, deacetylation 95%), 0.2g sulfuric acid and 0.3g MDA join in the 100 ml water and dissolve, and obtain the casting solution of clear; 25
oUnder the relative air humidity condition of C and 55 %, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, again it is positioned over 50
oIn the baking oven of C 4 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane.This NF membrane is 25
oC is under the 0.6 MPa pressure, for 1 g.L
-1NaCl and MgCl
2The separating resulting of solution is: the rejection to NaCl is 57.8 %, and water flux is 29.6L.m
-2.h
-1To MgCl
2Rejection be 98.4%, water flux is 28.7L.m
-2.h
-1
Claims (10)
1. the preparation method of a betaine colloidal nanoparticles modification of chitosan NF membrane is characterized in that its step is as follows:
1) is function monomer with beet base olefinic monomer and hydroxyalkyl acrylate monomer, is made into the aqueous solution, add water the dissolubility oxidation-reduction initiator, adopt the emulsifier-free emulsion polymerization method, preparation betaine colloidal nanoparticles;
2) shitosan and betaine colloidal nanoparticles are dispersed in contain in the inorganic aqueous acid, add crosslinking agent, be made into casting solution; 20～30
oUnder the temperature of C and 50～60% the relative air humidity condition, above-mentioned casting solution evenly is coated on the polysulphone super-filter membrane, is positioned over 40～60
oIn the baking oven of C 2～4 hours, obtain betaine colloidal nanoparticles modification of chitosan NF membrane;
The described beet base of step 1) olefinic monomer is 3-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] propane-1-acid inner salt, 2-[N, N-dimethyl-[2-(2-methyl-prop-2-alkene acyloxy) ethyl] ammonium] ethane-1-carboxylic acid inner salt or 3-(4-vinylpridine) propane-1-carboxylic acid inner salt; Hydroxyalkyl acrylate monomer described in the step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
2. preparation method as claimed in claim 1, the mass percent concentration that it is characterized in that beet base olefinic monomer in the aqueous solution described in the step 1) is 15～35%.
3. preparation method as claimed in claim 1, the mass percent concentration that it is characterized in that hydroxyalkyl acrylate monomer in the aqueous solution described in the step 1) is 5～15%.
4. preparation method as claimed in claim 1 is characterized in that the oxidation-reduction initiator described in the step 1) is that mass ratio is persulfuric acid potassium sulfate and the sodium hydrogensulfite of 1:1, and total mass percent concentration is 1～3% in the aqueous solution.
5. preparation method as claimed in claim 1, the emulsifier-free emulsion polymerization condition described in the step 1) that it is characterized in that is for 30～50
oPolymerization is 2～6 hours under the C.
6. preparation method as claimed in claim 1 is characterized in that step 2) described in the shitosan weight average molecular weight be 5～200,000, deacetylation 85% or 95%.
7. preparation method as claimed in claim 1 is characterized in that step 2) described in inorganic acid be sulfuric acid, hydrochloric acid or acetic acid.
8. preparation method as claimed in claim 1 is characterized in that step 2) described in crosslinking agent be MDA, glutaraldehyde or butanedial.
9. preparation method as claimed in claim 1, it is characterized in that step 2) described in casting solution in shitosan, betaine colloidal nanoparticles, inorganic acid and crosslinking agent mass percent concentration be respectively 0.5～2%, 0.1～1%, 0.1～0.3% and 0.2～0.5%.
10. as each described preparation method of claim 1～9, it is characterized in that the betaine colloidal nanoparticles modification of chitosan NF membrane for preparing.
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| CN104028114B (en) * | 2014-05-16 | 2016-01-13 | 浙江大学 | A kind of preparation method based on nanometer betaine type CMC filter membrane |
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| CN105727761B (en) * | 2016-03-10 | 2018-07-24 | 上海工程技术大学 | A kind of anti-protein-contamination amphoteric ion ultrafiltration membrane and preparation method thereof |
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| CN107029555A (en) * | 2017-04-19 | 2017-08-11 | 大连理工大学 | A kind of solvent resistant NF membrane and preparation method thereof |
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| CN111744373A (en) * | 2020-07-07 | 2020-10-09 | 杭州易膜环保科技有限公司 | Method for constructing amphoteric anti-pollution coating on polyamide surface |
| CN114682107A (en) * | 2022-04-07 | 2022-07-01 | 中山大学 | Anti-pollution ultrafiltration membrane and preparation method and application thereof |
| CN114682107B (en) * | 2022-04-07 | 2023-08-11 | 中山大学 | Anti-pollution ultrafiltration membrane and preparation method and application thereof |
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