CN103316599B - A kind of preparation method of glycine betaine colloid nano particle modification of chitosan NF membrane - Google Patents
A kind of preparation method of glycine betaine colloid nano particle modification of chitosan NF membrane Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of glycine betaine colloid nano particle modification of chitosan NF membrane.NF membrane is that functional layer forms by porous polysulfone supporting layer and glycine betaine colloid nano particle modification of chitosan; Its preparation process is: first obtain glycine betaine colloid nano particle by solution polymerization, again above-mentioned nano particle, shitosan and crosslinking agent are made into the certain density aqueous solution, by it at porous polysulfones support membrane surface impregnation one deck, then curing cross-linked obtains NF membrane.This kind of NF membrane is under the operating pressure of 0.6MPa, and its water flux is 25 ~ 35 L.m
-2.h
-1, to the rejection of bivalent cation generally higher than 97%, to the rejection of monovalent salt lower than 60%; Meanwhile, good stain resistance is shown.Therefore, prepared glycine betaine colloid nano particle modification of chitosan NF membrane has high permselective property and stain resistance, and film-forming method is simple, with low cost, has good industrial applications prospect.
Description
Technical field
The invention belongs to NF membrane separation field, particularly relate to a kind of preparation method of glycine betaine colloid nano particle modification of chitosan NF membrane.
Background technology
Nanofiltration is a kind of novel pressure-actuated membrane separating process grown up phase late 1980s.The pore diameter range of NF membrane, greatly about about 1 ~ 5nm, is a kind of diffusion barrier between reverse osmosis membrane and milipore filter.Different according to the charge of membrane material, NF membrane can be divided into nanofiltration membrane with negative electric charge, positively charged nanofiltration membranes and charge embedded NF membrane.Current commercialization NF membrane is mainly PA membrane, the CAM and sulfonated polyether sulfone film etc. of bear electricity.But, along with the increase of actual separation system, positively charged nanofiltration membranes presents unique advantage in the field such as to be separated of separation and the recovery of water softening, high-valence state metal ion, 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 chitin (chitin) that extensively exists of a kind of nature obtains after de-acetyl, there is the good characteristics such as good biocompatibility, nontoxicity and biodegradability, be now widely used in the 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).But existing Chitosan-phospholipid complex NF membrane also fails to reach the separating property possessing high salt rejection and high water permeation flux simultaneously; In addition, in 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.
Betaine type polymer is the amphoteric ion polymer that a class anions and canons group is positioned on the same monomeric unit of macromolecular chain, now becomes the membrane modifying material that a class is novel gradually.Now have been reported and betaine type polymer is incorporated in NF membrane by methods such as solution coating, interfacial polymerization and surface chemical modifications, water flux and stain resistance (J. Membr. Sci., 2012,390-391,243-253 of film can be improved simultaneously; J. Membr. Sci., 2012,389,76-82; J. Membr. Sci., 2013,431,171-179).Betaine type polymer, by (interior) electrostatic attraction effect and hydrophilic, hydrophobic effect between strand, can form the aggregation containing some macromolecular chains, i.e. glycine betaine colloid nano particle.As this type of nano particle is incorporated in chitosan film, not only can utilize its good hydrophily and strong stain resistance, also can rely on the nano aperture structure of its uniqueness, while keeping the separation selectivity that film is good, significantly improve water permeability and the stain resistance of film, the needs of practical application can be met better.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of glycine betaine colloid nano particle modification of chitosan NF membrane is provided.
NF membrane is the composite membrane of functional layer by porous polysulfone supporting layer and glycine betaine colloid nano particle modification of chitosan.
The step of the preparation method of glycine betaine colloid nano particle modification of chitosan NF membrane is as follows:
1) with beet base olefinic monomer and hydroxyalkyl acrylate monomer for function monomer, be made into the aqueous solution, add water soluble oxidized-reduction initator, adopt surfactant-free emulsion polymerization, preparation glycine betaine colloid nano particle;
2) shitosan and glycine betaine colloid nano particle are dispersed in containing in inorganic aqueous acid, add crosslinking agent, be made into casting solution; 20 ~ 30
ounder the temperature of C and the relative air humidity condition of 50 ~ 60%, above-mentioned casting solution is evenly coated on polysulphone super-filter membrane, is positioned over 40 ~ 60
oin the baking oven of C 2 ~ 4 hours, obtain glycine betaine colloid nano particle modification of chitosan NF membrane;
Beet base olefinic monomer described in step 1) 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 step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
In the aqueous solution described in step 1), the mass percent concentration of beet base olefinic monomer is 15 ~ 35%.In the aqueous solution described in step 1), the mass percent concentration of hydroxyalkyl acrylate monomer is 5 ~ 15%.Persulfuric acid potassium sulfate and the sodium hydrogensulfite of to be mass ratio the be 1:1 of the oxidation-reduction initiator described in step 1), mass percent concentration total is in aqueous 1 ~ 3%.Emulsifier-free emulsion polymerization condition described in step 1) is 30 ~ 50
obe polymerized 2 ~ 6 hours under C.
Step 2) described in shitosan weight average molecular weight be 5 ~ 200,000, deacetylation 85% or 95%.Step 2) described in inorganic acid be sulfuric acid, hydrochloric acid or acetic acid.Step 2) described in crosslinking agent be MDA, glutaraldehyde or butanedial.Step 2) described in casting solution in shitosan, glycine betaine colloid nano particle, 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 glycine betaine colloid nano particle modification of chitosan NF membrane of preparation.
The material that the present invention is used as film surface separation layer is glycine betaine colloid nano particle modification of chitosan, colloidal nanoparticles is prepared by surfactant-free emulsion polymerization by beet base olefinic monomer and hydroxyalkyl acrylate monomer, and the chemical composition of colloidal nanoparticles and hydrophilic and hydrophobic realize by the kind and proportioning thereof adjusting comonomer; And then by adjustment glycine betaine colloid nano particle and the proportioning of shitosan, obtaining serial nano hydridization chitosan nano filter membrane, it is to the rejection of divalent metal salt generally higher than 97%, and to the rejection of monovalent salt lower than 60%, water flux is 25 ~ 35 L.m
-2.h
-1, this kind of composite nanometer filtering film has the selective and strong stain resistance of Thief zone; In addition, the present invention is raw materials used to be conveniently easy to get, cheap; Polymerization solvent for use is water, and clean environment firendly, preparation process is simple and safe.The process that preparation adopts simple dip-coating, heat cure is cross-linked of composite membrane, filming technology is simple, cost is low, has good industrial applicibility.
Detailed description of the invention
NF membrane is the composite membrane of functional layer by porous polysulfone supporting layer and glycine betaine colloid nano particle modification of chitosan.
The step of the preparation method of glycine betaine colloid nano particle modification of chitosan NF membrane is as follows:
1) with beet base olefinic monomer and hydroxyalkyl acrylate monomer for function monomer, be made into the aqueous solution, add water soluble oxidized-reduction initator, adopt surfactant-free emulsion polymerization, preparation glycine betaine colloid nano particle;
2) shitosan and glycine betaine colloid nano particle are dispersed in containing in inorganic aqueous acid, add crosslinking agent, be made into casting solution; 20 ~ 30
ounder the temperature of C and the relative air humidity condition of 50 ~ 60%, above-mentioned casting solution is evenly coated on polysulphone super-filter membrane, is positioned over 40 ~ 60
oin the baking oven of C 2 ~ 4 hours, obtain glycine betaine colloid nano particle modification of chitosan NF membrane;
Beet base olefinic monomer described in step 1) 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 step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
In the aqueous solution described in step 1), the mass percent concentration of beet base olefinic monomer is 15 ~ 35%.In the aqueous solution described in step 1), the mass percent concentration of hydroxyalkyl acrylate monomer is 5 ~ 15%.Persulfuric acid potassium sulfate and the sodium hydrogensulfite of to be mass ratio the be 1:1 of the oxidation-reduction initiator described in step 1), mass percent concentration total is in aqueous 1 ~ 3%.Emulsifier-free emulsion polymerization condition described in step 1) is 30 ~ 50
obe polymerized 2 ~ 6 hours under C.
Step 2) described in shitosan weight average molecular weight be 5 ~ 200,000, deacetylation 85% or 95%.Step 2) described in inorganic acid be sulfuric acid, hydrochloric acid or acetic acid.Step 2) described in crosslinking agent be MDA, glutaraldehyde or butanedial.Step 2) described in casting solution in shitosan, glycine betaine colloid nano particle, 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 glycine betaine colloid nano particle modification of chitosan NF membrane of preparation.
The separating property method of testing of glycine betaine colloid nano particle modification of chitosan NF membrane is as follows: NF membrane is placed in the conventional nanofiltration testing arrangement in this area, test cephacoria precompressed 1 h under 0.7 MPa operating pressure, then 25
ounder C and 0.6 MPa test condition, measure the water permeation flux (J) of film and the rejection (R) of material, its computing formula is such as formula being J=V/ (A.t); R=1-C
pc
f; Wherein, V-feed liquid is 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 by 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 100ml water, pass into nitrogen, add potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1) that mass percent concentration is 1%, 30
ocarry out emulsifier-free emulsion polymerization under C 6 hours, through repeatedly centrifugal, washing, after vacuum drying, obtain glycine betaine colloid nano particle; By above-mentioned for 0.1g nano particle, 0.5 g shitosan (molecular weight 50,000, deacetylation 85%), 0.1g hydrochloric acid and 0.2g glutaraldehyde join in 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 is evenly coated on polysulphone super-filter membrane, then is positioned over 40
oin the baking oven of C 4 hours, obtain glycine betaine colloid nano particle modification of chitosan NF membrane.This NF membrane is 25
oc, under 0.6 MPa pressure, for 1 g.L
-1naCl and MgCl
2the separating resulting of solution is: be 51.2 % to the rejection of NaCl, and water flux is 28.5L.m
-2.h
-1; To 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 100ml water, pass into nitrogen, add potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1) that mass percent concentration is 3%, 50
ocarry out emulsifier-free emulsion polymerization under C 2 hours, through repeatedly centrifugal, washing, after vacuum drying, obtain glycine betaine colloid nano particle; By above-mentioned for 1g nano particle, 2 g shitosans (molecular weight 200,000, deacetylation 95%), 0.3g hydrochloric acid and 0.5g glutaraldehyde join in 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 is evenly coated on polysulphone super-filter membrane, then is positioned over 60
oin the baking oven of C 2 hours, obtain glycine betaine colloid nano particle modification of chitosan NF membrane.This NF membrane is 25
oc, under 0.6 MPa pressure, for 1 g.L
-1naCl and MgCl
2the separating resulting of solution is: be 58.5 % to the rejection of NaCl, and water flux is 25.8L.m
-2.h
-1; To 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 100ml water, pass into nitrogen, add potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1) that mass percent concentration is 2%, 40
ocarry out emulsifier-free emulsion polymerization under C 4 hours, through repeatedly centrifugal, washing, after vacuum drying, obtain glycine betaine colloid nano particle; By above-mentioned for 0.5g nano particle, 1.5 g shitosans (molecular weight 100,000, deacetylation 95%), 0.2g hydrochloric acid and 0.3g glutaraldehyde join in 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 is evenly coated on polysulphone super-filter membrane, then is positioned over 50
oin the baking oven of C 3 hours, obtain glycine betaine colloid nano particle modification of chitosan NF membrane.
Comparative example 1
With reference to embodiment 3 step, without preparation glycine betaine colloid nano particle, be directly that NF membrane prepared by raw material (each material adding proportion is with reference to embodiment 3) with shitosan.
Comparative example 2
With reference to embodiment 3 step, glycine betaine colloid nano particle is replaced to add (adding proportion is with reference to embodiment 3) in chitosan film preparation process to, preparation NF membrane with polyvinyl alcohol (PVA-1788).
Table 1 embodiment 3, comparative example 1, the separating property of the NF membrane of 2 preparations compares
| 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 example 1 | 97.5 | 7.8 | 61.5 | 8.5 |
| Comparative example 2 | 97.8 | 15.6 | 57.2 | 16.5 |
Table 1 result shows, 3 kinds of methods all can obtain NF membrane bivalent cation and monovalent salt to good separation performance, but its water flux has larger difference, and this causes by the microstructure of the interpolation material preparing chitosan film is different with hydrophily.
In comparative example 1, do not add that other is material modified, form by shitosan crystalline polymer chain is crosslinked, this film is finer and close; In comparative example 2, add polyvinyl alcohol (PVA-1788) for material modified, introduce the macromolecular material flexible, hydrophily is strong in its chitosan film, make that the compactness of film decreases, hydrophily increases.
In embodiment 3, be material modified with glycine betaine colloid nano particle, utilize the nanostructured of himself uniqueness and good hydrophily, be introduced in chitosan film, not only can improve the hydrophily of film, " aquaporin " structure can also be formed in film, promote that hydrone transmits in film; Meanwhile, due to glycine betaine colloid nano particle favorable dispersibility, can ensure that the compactness of film is unaffected, there is high selection separation property; In addition, because betaine colloidal particle has good stain resistance, segregational stability and the stain resistance of film can be improved.Therefore, be material modified with glycine betaine colloid nano particle, 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 100ml water, pass into nitrogen, add potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1) that mass percent concentration is 2%, 40
ocarry out emulsifier-free emulsion polymerization under C 4 hours, through repeatedly centrifugal, washing, after vacuum drying, obtain glycine betaine colloid nano particle; By above-mentioned for 0.5g nano particle, 1.5 g shitosans (molecular weight 100,000, deacetylation 85%), 0.2g hydrochloric acid and 0.3g glutaraldehyde join in 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 is evenly coated on polysulphone super-filter membrane, then is positioned over 50
oin the baking oven of C 3 hours, obtain glycine betaine colloid nano particle modification of chitosan NF membrane.This NF membrane is 25
oc, under 0.6 MPa pressure, for 1 g.L
-1naCl and MgCl
2the separating resulting of solution is: be 56.5 % to the rejection of NaCl, and water flux is 28.8L.m
-2.h
-1; To 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 adds in 100ml water, pass into nitrogen, add potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1) that mass percent concentration is 2%, 40
ocarry out emulsifier-free emulsion polymerization under C 4 hours, through repeatedly centrifugal, washing, after vacuum drying, obtain glycine betaine colloid nano particle; By above-mentioned for 0.5g nano particle, 1.5 g shitosans (molecular weight 100,000, deacetylation 95%), 0.2g acetic acid and 0.3g butanedial join in 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 is evenly coated on polysulphone super-filter membrane, then is positioned over 50
oin the baking oven of C 3 hours, obtain glycine betaine colloid nano particle modification of chitosan NF membrane.This NF membrane is 25
oc, under 0.6 MPa pressure, for 1 g.L
-1naCl and MgCl
2the separating resulting of solution is: be 57.6 % to the rejection of NaCl, and water flux is 30.8L.m
-2.h
-1; To 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 100ml water, pass into nitrogen, add potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1) that mass percent concentration is 2%, 45
ocarry out emulsifier-free emulsion polymerization under C 3 hours, through repeatedly centrifugal, washing, after vacuum drying, obtain glycine betaine colloid nano particle; By above-mentioned for 1g nano particle, 2 g shitosans (molecular weight 100,000, deacetylation 95%), 0.2g sulfuric acid and 0.3g glutaraldehyde join in 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 is evenly coated on polysulphone super-filter membrane, then is positioned over 50
oin the baking oven of C 3 hours, obtain glycine betaine colloid nano particle modification of chitosan NF membrane.This NF membrane is 25
oc, under 0.6 MPa pressure, for 1 g.L
-1naCl and MgCl
2the separating resulting of solution is: be 55.6 % to the rejection of NaCl, and water flux is 33.5L.m
-2.h
-1; To 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 100ml water, pass into nitrogen, add potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1) that mass percent concentration is 1%, 50
ocarry out emulsifier-free emulsion polymerization under C 3 hours, through repeatedly centrifugal, washing, after vacuum drying, obtain glycine betaine colloid nano particle; By above-mentioned for 1g nano particle, 1.5g shitosan (molecular weight 100,000, deacetylation 95%), 0.1g acetic acid and 0.25g glutaraldehyde join in 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 is evenly coated on polysulphone super-filter membrane, then is positioned over 50
oin the baking oven of C 3 hours, obtain glycine betaine colloid nano particle modification of chitosan NF membrane.This NF membrane is 25
oc, under 0.6 MPa pressure, for 1 g.L
-1naCl and MgCl
2the separating resulting of solution is: be 57.8 % to the rejection of NaCl, and water flux is 31.5L.m
-2.h
-1; To 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 100ml water, pass into nitrogen, add potassium peroxydisulfate and sodium hydrogensulfite (mass ratio 1:1) that mass percent concentration is 1%, 45
ocarry out emulsifier-free emulsion polymerization under C 3 hours, through repeatedly centrifugal, washing, after vacuum drying, obtain glycine betaine colloid nano particle; By above-mentioned for 1g nano particle, 2 g shitosans (molecular weight 150,000, deacetylation 95%), 0.2g sulfuric acid and 0.3g MDA join in 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 is evenly coated on polysulphone super-filter membrane, then is positioned over 50
oin the baking oven of C 4 hours, obtain glycine betaine colloid nano particle modification of chitosan NF membrane.This NF membrane is 25
oc, under 0.6 MPa pressure, for 1 g.L
-1naCl and MgCl
2the separating resulting of solution is: be 57.8 % to the rejection of NaCl, and water flux is 29.6L.m
-2.h
-1; To MgCl
2rejection be 98.4%, water flux is 28.7L.m
-2.h
-1.
Claims (9)
1. a preparation method for glycine betaine colloid nano particle modification of chitosan NF membrane, is characterized in that its step is as follows:
1) with beet base olefinic monomer and hydroxyalkyl acrylate monomer for function monomer, be made into the aqueous solution, add water soluble oxidized-reduction initator, adopt surfactant-free emulsion polymerization, preparation glycine betaine colloid nano particle;
2) shitosan and glycine betaine colloid nano particle are dispersed in containing in inorganic aqueous acid, add crosslinking agent, be made into casting solution; The temperature of 20 ~ 30 DEG C and 50 ~ 60% relative air humidity condition under, above-mentioned casting solution is evenly coated on polysulphone super-filter membrane, is positioned in the baking oven of 40 ~ 60 DEG C 2 ~ 4 hours, obtains glycine betaine colloid nano particle modification of chitosan NF membrane; Step 1) described in beet base olefinic monomer be 3 ?[N, N ?Er Jia Ji ?[2 ?(2 ?Jia Ji Bing ?2 ?alkene acyloxy) ethyl] and ammonium] Bing Wan ?1 ?acid inner salt, 2 ?[N, N ?Er Jia Ji ?[2 ?(2 ?Jia Ji Bing ?2 ?alkene acyloxy) ethyl] and ammonium] Yi Wan ?1 ?carboxylic acid inner salt or 3 ?(4 ?vinylpyridine) Bing Wan ?1 ?carboxylic acid inner salt; Step 1) described in hydroxyalkyl acrylate monomer be hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
2. preparation method as claimed in claim 1, is characterized in that step 1) described in the aqueous solution in the mass percent concentration of beet base olefinic monomer be 15 ~ 35%.
3. preparation method as claimed in claim 1, is characterized in that step 1) described in the aqueous solution in the mass percent concentration of hydroxyalkyl acrylate monomer be 5 ~ 15%.
4. preparation method as claimed in claim 1, is characterized in that step 1) described in persulfuric acid potassium sulfate and the sodium hydrogensulfite of oxidation-reduction initiator to be mass ratio be 1:1, mass percent concentration total is in aqueous 1 ~ 3%.
5. preparation method as claimed in claim 1, is characterized in that step 1) described in emulsifier-free emulsion polymerization condition for being polymerized 2 ~ 6 hours at 30 ~ 50 DEG C.
6. preparation method as claimed in claim 1, is characterized in that step 2) described in 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 or hydrochloric 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, glycine betaine colloid nano particle, 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%.
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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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| WO2011088505A1 (en) * | 2010-01-19 | 2011-07-28 | Flinders University Of South Australia | Low-fouling filtration membranes |
| CN101862610A (en) * | 2010-05-05 | 2010-10-20 | 大连理工大学 | Absorption film for eliminating bilirubin and preparation method thereof |
| CN102764594A (en) * | 2012-07-09 | 2012-11-07 | 东北大学 | Method for preparing chiral chitosan charged nanofiltration membranes |
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