CN103285742B - Preparation method of quaternary ammonium salt type cationic polymer modified chitosan nanofiltration membrane - Google Patents
Preparation method of quaternary ammonium salt type cationic polymer modified chitosan nanofiltration membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a quaternary ammonium salt type cationic polymer modified chitosan nanofiltration membrane. The nanofiltration membrane comprises a porous polysulfone support layer and a quaternary ammonium salt type cationic polymer modified chitosan functional layer. The preparation process of the nanofiltration membrane comprises the following steps of: firstly carrying out solution polymerization reaction to obtain a quaternary ammonium salt type cationic polymer; then blending the quaternary ammonium salt type cationic polymer, chitosan and a cross-linking agent into a water solution with a certain concentration, and soaking a layer of the water solution on the surface of the porous polysulfone support film; and then carrying out curing cross-linking to obtain the nanofiltration membrane. The nanofiltration membrane achieves the water flux of 15-25 L.m<-2>.h<-1> under the operating pressure of 0.6 MPa, has very high interception rate on bivalent cations, achieves the maximal interception rate by 98.5%, achieves the interception rate of monovalent cations generally less than 60% and shows good pollution resistance, thus the prepared quaternary ammonium salt type cationic polymer modified chitosan nanofiltration membrane disclosed by the invention has the advantages of high permeation selectivity and pollution resistance; and the preparation method disclosed by the invention has the advantages of simplicity, easiness for operation, low cost and good industrialized application prospect.
Description
Technical field
The invention belongs to NF membrane separation field, relate in particular to a kind of preparation method of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane.
Background technology
Nanofiltration is a kind of novel pressure-actuated film separation process growing up phase late 1980s.The pore diameter range of NF membrane about 1～5nm left and right, 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 nanofiltration membrane with negative electric charge, positively charged nanofiltration membranes and charge embedded NF membrane.Commercialization NF membrane is mainly nanofiltration membrane with negative electric charge at present, as the CAM of Eastman Kodak E394-60, the PA membrane of the NF-40 of Film Tec company and the UTC-20HF of toray company, and the NFR-7400 series sulfonated polyether sulfone film of day eastern electrician's exploitation etc.But, along with the increase of actual separation system, positively charged nanofiltration membranes presents unique advantage 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 a kind of nature nitrogenous polysaccharose substance that extensively chitin (chitin) of existence 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 gradually.Huang etc. have synthesized 2-hydroxy-3-methyl amino-propyl group shitosan and shitosan-trimethylallylammonium chloride graft polymers, and prepared respectively the positively charged nanofiltration membranes of serial chitosan derivatives by apply-chemical crosslink technique of solution, this type of film is to Ca
2+, Mg
2+be greater than 95% Deng the rejection of polyvalent metal ion, water flux is less than 10 L.m
-2.h
-1, (Sep.Purif. Technol., 2008,58,393-399; Desalination, 2009,239,38-45).Boricha etc. have prepared the blended cross linking film of shitosan and cellulose acetate, and this film is to Cr
3+and Cu
2+rejection be less than 85%, water flux is about 16 L.m
-2.h
-1(Chem. Eng. J., 2010,157,393-400).Hence one can see that, and existing shitosan and derivative NF membrane thereof also fail to reach the separating property that simultaneously possesses high salt rejection and high water permeation flux; 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 there is good separating effect, high water permeation flux, also have strong anti-fouling performance.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane is provided.
The composite membrane that NF membrane is is functional layer by porous polysulfone supporting layer and Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan.
The preparation method's of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane step is as follows:
1) adding in 100ml water containing the third vinyl monomer of quaternary ammonium salt cationic group and the hydroxyalkyl acrylate monomer of 5～15 g 15～30 g, be made into the aqueous solution that mass percent concentration is 20～45wt%, pass into nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator of 1～3wt%, 30～50
ounder C, carry out polymerisation in solution, polymerization time is 2～6 hours, after organic solvent deposit, washing, in 40～60
odry 3～6 hours of C, vacuum drying, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use;
2) by the Cationic Polymers Containing Quaternary Ammonium Salts of 0.2～1.0 g, the polyaldehyde of 1.0～2.0 g shitosans and 0.1～0.45 g joins in 100 ml water and dissolves, then to add inorganic acid regulator solution pH value be 3.0～5.0,20～30
oat the temperature of C, stir 20～40 minutes, obtain the casting solution of clear;
3) 20～30
ounder the temperature of C and 50～60% relative air humidity condition, 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 Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane;
The third vinyl monomer containing quaternary ammonium salt cationic group described in step 1) is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, methacryloxypropyl trimethyl ammonium chloride, acrylyl oxy-ethyl dimethyl benzyl ammonium chloride or methylacryloxyethyldimethyl benzyl ammonium chloride; Hydroxyalkyl acrylate monomer described in step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
Oxidation-reduction initiator described in step 1) is that mass ratio is potassium peroxydisulfate and the sodium hydrogensulfite of 1:1.Organic solvent described in step 1) is acetone or n-hexane.
Step 2) described in shitosan weight average molecular weight be 5～200,000, deacetylation 85% or 95%.Step 2) described in polyaldehyde be MDA, glutaraldehyde or butanedial.Step 2) described in inorganic acid be sulfuric acid, hydrochloric acid or acetic acid.
The Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane of preparation.
The present invention is by adjusting the chemical composition of Cationic Polymers Containing Quaternary Ammonium Salts and the proportioning with shitosan thereof, obtain serial positively charged nanofiltration membranes, its rejection to divalent metal salt can reach 98.5%, and to the rejection of monovalent salt, generally lower than 60%, water flux is 15～25 L.m
-2.h
-1, this kind of composite nanometer filtering film shows long-term, good separating property and high water permeation flux to different valence state salt, the needs of realistic separation application.
The present invention is Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan as the material of film surface separating layer, copolymer is to be prepared by the method for free radical solution polymerization by the third vinyl monomer and hydroxyalkyl acrylate monomer containing quaternary ammonium salt cationic group, and the chemical composition of polymer and hydrophilic and hydrophobic can be realized by kind and the proportioning thereof of adjusting comonomer; Meanwhile, monomer used is conveniently easy to get, cheap; 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, and filming technology is simple, cost is low, has good industrial applicibility.
Brief description of the drawings
Fig. 1 is the infared spectrum of Cationic Polymers Containing Quaternary Ammonium Salts of the present invention and modification of chitosan NF membrane thereof.
Fig. 2 is the surface topography map of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane of the present invention.
Detailed description of the invention
The composite membrane that NF membrane is is functional layer by porous polysulfone supporting layer and Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan.
The preparation method's of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane step is as follows:
1) adding in 100ml water containing the third vinyl monomer of quaternary ammonium salt cationic group and the hydroxyalkyl acrylate monomer of 5～15 g 15～30 g, be made into the aqueous solution that mass percent concentration is 20～45wt%, pass into nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator of 1～3wt%, 30～50
ounder C, carry out polymerisation in solution, polymerization time is 2～6 hours, after organic solvent deposit, washing, in 40～60
odry 3～6 hours of C, vacuum drying, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use;
2) by the Cationic Polymers Containing Quaternary Ammonium Salts of 0.2～1.0 g, the polyaldehyde of 1.0～2.0 g shitosans and 0.1～0.45 g joins in 100 ml water and dissolves, then to add inorganic acid regulator solution pH value be 3.0～5.0,20～30
oat the temperature of C, stir 20～40 minutes, obtain the casting solution of clear;
3) 20～30
ounder the temperature of C and 50～60% relative air humidity condition, 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 Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane;
The third vinyl monomer containing quaternary ammonium salt cationic group described in step 1) is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, methacryloxypropyl trimethyl ammonium chloride, acrylyl oxy-ethyl dimethyl benzyl ammonium chloride or methylacryloxyethyldimethyl benzyl ammonium chloride; Hydroxyalkyl acrylate monomer described in step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
Oxidation-reduction initiator described in step 1) is that mass ratio is potassium peroxydisulfate and the sodium hydrogensulfite of 1:1.Organic solvent described in step 1) is acetone or n-hexane.
Step 2) described in shitosan weight average molecular weight be 5～200,000, deacetylation 85% or 95%.Step 2) described in polyaldehyde be MDA, glutaraldehyde or butanedial.Step 2) described in inorganic acid be sulfuric acid, hydrochloric acid or acetic acid.
The Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane of preparation.
The separating property method of testing of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane is as follows: NF membrane is placed in to the conventional nanofiltration testing arrangement in this area, and test cephacoria precompressed 1 h under 0.7 MPa operating pressure, then 25
ounder C and 0.6 MPa test condition, the water permeation flux (J) to film and the rejection (R) of material are measured, and its computing formula is suc as formula being: J=V/ (A.t); R=1-C
pc
f; Wherein, 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 subject to the restriction of embodiment:
Embodiment 1:
The hydroxy-ethyl acrylate of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 15 g and 5 g is added in 100ml water, be made into the aqueous solution that concentration is 20 wt%, pass into nitrogen, add potassium peroxydisulfate and the sodium hydrogensulfite (mass ratio is 1:1) of 1 wt%, 30
ounder C, carry out polymerisation in solution 6 hours, after acetone precipitation, washing, in 40
odry 6 hours of C, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use after vacuum drying; By above-mentioned 0.2g polymer, 1.0 g shitosans (molecular weight 50,000, deacetylation 85%) and 0.1 g glutaraldehyde join in 100 ml water and dissolve, then to add sulfuric acid regulation solution pH value be 5.0,20
othe lower stirring of C 20 minutes, obtains the casting solution of clear; 20
ounder the relative air humidity condition of the temperature 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 Cationic Polymers Containing Quaternary Ammonium Salts 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 45.2 % to the rejection of NaCl, water flux is 24.8L.m
-2.h
-1; To MgCl
2rejection be 96.5 %, water flux is 23.5L.m
-2.h
-1.
Embodiment 2:
The hydroxy-ethyl acrylate of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 30 g and 15 g is added in 100ml water, be made into the aqueous solution that concentration is 45 wt%, pass into nitrogen, add potassium peroxydisulfate and the sodium hydrogensulfite (mass ratio is 1:1) of 3 wt%, 50
ounder C, carry out polymerisation in solution 2 hours, after n-hexane precipitation, washing, in 60
odry 3 hours of C, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use after vacuum drying; By the above-mentioned polymer of 1.0 g, 2.0 g shitosans (molecular weight 200,000, deacetylation 95%) and 0.45 g glutaraldehyde join in 100 ml water and dissolve, then to add sulfuric acid regulation solution pH value be 3.0,30
othe lower stirring of C 40 minutes, obtains the casting solution of clear; 30
ounder the relative air humidity condition of the temperature 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 Cationic Polymers Containing Quaternary Ammonium Salts 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 40.5 % to the rejection of NaCl, water flux is 23.6L.m
-2.h
-1; To MgCl
2rejection be 97.5 %, water flux is 22.8L.m
-2.h
-1.
Embodiment 3:
The hydroxy-ethyl acrylate of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 20 g and 10 g is added in 100ml water, be made into the aqueous solution that concentration is 30 wt%, pass into nitrogen, add potassium peroxydisulfate and the sodium hydrogensulfite (mass ratio is 1:1) of 2 wt%, 40
ounder C, carry out polymerisation in solution 3 hours, after acetone precipitation, washing, in 50
odry 4 hours of C, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use after vacuum drying; By the above-mentioned polymer of 0.5 g, 1.5 g shitosans (molecular weight 100,000, deacetylation 95%) and 0.30 g glutaraldehyde join in 100 ml water and dissolve, then to add sulfuric acid regulation solution pH value be 4.0,25
othe lower stirring of C 30 minutes, obtains the casting solution of clear; 25
ounder the relative air humidity condition of the temperature of C and 50 %, 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 Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane.
Comparative example 1
With reference to embodiment 3 steps, without preparation Cationic Polymers Containing Quaternary Ammonium Salts, directly taking shitosan as raw material, (each material adding proportion is with reference to embodiment 3) prepares NF membrane.
Comparative example 2
With reference to embodiment 3 steps, replace Cationic Polymers Containing Quaternary Ammonium Salts to add (adding proportion is with reference to embodiment 3) in chitosan film preparation process to polyvinyl alcohol (PVA-1788), preparation NF membrane.
Table 1 embodiment 3, the separating property comparison of the NF membrane of comparative example 1,2 preparation
| ? | MgCl 2Rejection (%) | Water flux (L.m -2.h -1） | NaCl rejection (%) | Water flux (L.m -2.h -1） |
| Embodiment 3 | 98.5 | 23.8 | 48.7 | 24.6 |
| Comparative example 1 | 97.5 | 6.5 | 61.2 | 7.8 |
| Comparative example 2 | 97.6 | 14.5 | 58.5 | 16.2 |
Table 1 result shows, 3 kinds of methods all can make NF membrane bivalent cation and monovalent salt to good separation performance, but its water flux has larger difference, and this is by cause different with hydrophily of charge of interpolation material of preparing chitosan film.
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, it be material modified adding polyvinyl alcohol (PVA-1788), introduces the macromolecular material flexible, hydrophily is strong in its chitosan film, the compactness of film is decreased, hydrophily increase.
In embodiment 3, taking Cationic Polymers Containing Quaternary Ammonium Salts as material modified, utilize its strong charge and good hydrophily, be introduced in chitosan film, not only can improve the hydrophily of film, can also strengthen the charge of film, promote that hydrone transmits in film, and the electrostatic repulsion of bivalent cation is strengthened, make film there is high water permeation flux and good separation selectivity simultaneously; In addition,, because Cationic Polymers Containing Quaternary Ammonium Salts has good stain resistance, can improve segregational stability and the stain resistance of film.Therefore,, taking Cationic Polymers Containing Quaternary Ammonium Salts as material modified, the chitosan nano filter membrane of preparation has high separation selectivity, high water permeability and strong stain resistance.
Embodiment 4:
The hydroxyethyl methacrylate of the acrylyl oxy-ethyl dimethyl benzyl ammonium chloride of 20 g and 10 g is added in 100ml water, be made into the aqueous solution that concentration is 30 wt%, pass into nitrogen, add potassium peroxydisulfate and the sodium hydrogensulfite (mass ratio is 1:1) of 1.5 wt%, 45
ounder C, carry out polymerisation in solution 4 hours, after acetone precipitation, washing, in 50
odry 3 hours of C, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use after vacuum drying; By the above-mentioned polymer of 0.5 g, 2.0 g shitosans (molecular weight 150,000, deacetylation 95%) and 0.35 g glutaraldehyde join in 100 ml water and dissolve, then to add sulfuric acid regulation solution pH value be 4.0,25
othe lower stirring of C 30 minutes, obtains the casting solution of clear; 25
ounder the relative air humidity condition of the temperature of C and 50 %, 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 Cationic Polymers Containing Quaternary Ammonium Salts 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 48.5 % to the rejection of NaCl, water flux is 23.8L.m
-2.h
-1; To MgCl
2rejection be 97.2 %, water flux is 22.5L.m
-2.h
-1.
Embodiment 5:
The hydroxy propyl methacrylate of the methacryloxypropyl trimethyl ammonium chloride of 20 g and 5 g is added in 100ml water, be made into the aqueous solution that concentration is 25 wt%, pass into nitrogen, add potassium peroxydisulfate and the sodium hydrogensulfite (mass ratio is 1:1) of 1.0 wt%, 45
ounder C, carry out polymerisation in solution 5 hours, after acetone precipitation, washing, in 50
odry 4 hours of C, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use after vacuum drying; By the above-mentioned polymer of 0.8 g, 1.5 g shitosans (molecular weight 150,000, deacetylation 95%) and 0.25 g glutaraldehyde join in 100 ml water and dissolve, then to add sulfuric acid regulation solution pH value be 3.5,25
othe lower stirring of C 30 minutes, obtains the casting solution of clear; 25
ounder the relative air humidity condition of the temperature of C and 50 %, 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 Cationic Polymers Containing Quaternary Ammonium Salts 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 47.5 % to the rejection of NaCl, water flux is 24.3L.m
-2.h
-1; To MgCl
2rejection be 97.5 %, water flux is 23.9L.m
-2.h
-1.
Embodiment 6:
The hydroxyethyl methacrylate of the acrylyl oxy-ethyl-trimethyl salmiac of 20 g and 5 g is added in 100ml water, be made into the aqueous solution that concentration is 25 wt%, pass into nitrogen, add potassium peroxydisulfate and the sodium hydrogensulfite (mass ratio is 1:1) of 1.0 wt%, 45
ounder C, carry out polymerisation in solution 4 hours, after acetone precipitation, washing, in 50
odry 5 hours of C, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use after vacuum drying; By above-mentioned 0.5g polymer, 1.5 g shitosans (molecular weight 200,000, deacetylation 85%) and 0.30 g glutaraldehyde join in 100 ml water and dissolve, then to add sulfuric acid regulation solution pH value be 3.5,25
othe lower stirring of C 30 minutes, obtains the casting solution of clear; 25
ounder the relative air humidity condition of the temperature of C and 50 %, 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 Cationic Polymers Containing Quaternary Ammonium Salts 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 46.8% to the rejection of NaCl, water flux is 23.6L.m
-2.h
-1; To MgCl
2rejection be 96.9 %, water flux is 22.7L.m
-2.h
-1.
Embodiment 7:
The hydroxy-ethyl acrylate of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 20 g and 10 g is added in 100ml water, be made into the aqueous solution that concentration is 30 wt%, pass into nitrogen, add potassium peroxydisulfate and the sodium hydrogensulfite (mass ratio is 1:1) of 2 wt%, 40
ounder C, carry out polymerisation in solution 3 hours, after acetone precipitation, washing, in 50
odry 4 hours of C, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use after vacuum drying; By the above-mentioned polymer of 1.0 g, 1.0 g shitosans (molecular weight 150,000, deacetylation 95%) and 0.30 g glutaraldehyde join in 100 ml water and dissolve, then to add sulfuric acid regulation solution pH value be 3.0,25
othe lower stirring of C 30 minutes, obtains the casting solution of clear; 25
ounder the relative air humidity condition of the temperature of C and 50 %, 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 Cationic Polymers Containing Quaternary Ammonium Salts 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 46.5 % to the rejection of NaCl, water flux is 25.7L.m
-2.h
-1; To MgCl
2rejection be 97.6 %, water flux is 24.8L.m
-2.h
-1.
Embodiment 8:
The hydroxy-ethyl acrylate of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 30 g and 10 g is added in 100ml water, be made into the aqueous solution that concentration is 40 wt%, pass into nitrogen, add potassium peroxydisulfate and the sodium hydrogensulfite (mass ratio is 1:1) of 2 wt%, 40
ounder C, carry out polymerisation in solution 3 hours, after acetone precipitation, washing, in 50
odry 4 hours of C, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use after vacuum drying; By the above-mentioned polymer of 0.8 g, 1.5 g shitosans (molecular weight 150,000, deacetylation 95%) and 0.35 g butanedial join in 100 ml water and dissolve, then to add sulfuric acid regulation solution pH value be 3.0,25
othe lower stirring of C 30 minutes, obtains the casting solution of clear; 25
ounder the relative air humidity condition of the temperature of C and 50 %, 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 Cationic Polymers Containing Quaternary Ammonium Salts 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 48.1 % to the rejection of NaCl, water flux is 24.2L.m
-2.h
-1; To MgCl
2rejection be 97.4 %, water flux is 23.7L.m
-2.h
-1.
Claims (6)
1. a preparation method for Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane, is characterized in that its step is as follows:
1) adding in 100ml water containing the third vinyl monomer of quaternary ammonium salt cationic group and the hydroxyalkyl acrylate monomer of 5～15 g 15～30 g, be made into the aqueous solution that mass percent concentration is 20～45wt%, pass into nitrogen, adding mass percent concentration is water soluble oxidized-reduction initator of 1～3wt%, 30～50
ounder C, carry out polymerisation in solution, polymerization time is 2～6 hours, after organic solvent deposit, washing, in 40～60
odry 3～6 hours of C, vacuum drying, obtains Cationic Polymers Containing Quaternary Ammonium Salts, for subsequent use;
2) by the Cationic Polymers Containing Quaternary Ammonium Salts of 0.2～1.0 g, the polyaldehyde of 1.0～2.0 g shitosans and 0.1～0.45 g joins in 100 ml water and dissolves, then to add inorganic acid regulator solution pH value be 3.0～5.0,20～30
oat the temperature of C, stir 20～40 minutes, obtain the casting solution of clear;
3) 20～30
ounder the temperature of C and 50～60% relative air humidity condition, 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 Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane;
The third vinyl monomer containing quaternary ammonium salt cationic group described in step 1) is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, methacryloxypropyl trimethyl ammonium chloride, acrylyl oxy-ethyl dimethyl benzyl ammonium chloride or methylacryloxyethyldimethyl benzyl ammonium chloride; Hydroxyalkyl acrylate monomer described in step 1) is hydroxy-ethyl acrylate, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
2. the preparation method of a kind of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane according to claim 1, is characterized in that the oxidation-reduction initiator described in step 1) is that mass ratio is potassium peroxydisulfate and the sodium hydrogensulfite of 1:1.
3. the preparation method of a kind of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane according to claim 1, is characterized in that the organic solvent described in step 1) is acetone or n-hexane.
4. the preparation method of a kind of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane according to claim 1, is characterized in that step 2) described in shitosan weight average molecular weight be 5～200,000, deacetylation 85% or 95%.
5. the preparation method of a kind of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane according to claim 1, is characterized in that step 2) described in polyaldehyde be MDA, glutaraldehyde or butanedial.
6. the preparation method of a kind of Cationic Polymers Containing Quaternary Ammonium Salts modification of chitosan NF membrane according to claim 1, is characterized in that step 2) described in inorganic acid be sulfuric acid or hydrochloric acid.
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| CN105949387B (en) * | 2016-05-16 | 2019-02-19 | 浙江大学 | A kind of preparation method of the cation type water-soluble aqueous polymer dispersion of no stabilizer |
| CN107754619B (en) * | 2017-11-12 | 2020-05-19 | 韦韬 | Preparation method of natural polyelectrolyte nanofiltration membrane |
| CN108014651A (en) * | 2017-12-21 | 2018-05-11 | 贵州省材料产业技术研究院 | The method that dopamine assistant depositing prepares antibacterial composite nanometer filtering film |
| CN108636140A (en) * | 2018-05-04 | 2018-10-12 | 烟台金正环保科技有限公司 | A kind of preparation method of the lotus positive electricity polyamide composite nanofiltration membrane based on Lactated chitosan |
| CN109316986B (en) * | 2018-11-07 | 2021-09-21 | 中南大学 | Acrylic acid and sulfonated dihydroxypropyl chitosan modified polysulfone membrane and preparation method thereof |
| CN112827360A (en) * | 2019-11-22 | 2021-05-25 | 宁波方太厨具有限公司 | Heavy metal adsorption membrane chromatographic ultrafiltration membrane, membrane component and manufacturing method thereof |
| CN113171693B (en) * | 2021-04-30 | 2022-12-06 | 中煤（北京）环保工程有限公司 | Chemical sewage treatment method based on polysulfone composite microfiltration membrane |
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