CN118001949A - Polyquaternium modified polyether sulfone separation membrane and preparation method thereof - Google Patents
Polyquaternium modified polyether sulfone separation membrane and preparation method thereof Download PDFInfo
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- CN118001949A CN118001949A CN202410158984.XA CN202410158984A CN118001949A CN 118001949 A CN118001949 A CN 118001949A CN 202410158984 A CN202410158984 A CN 202410158984A CN 118001949 A CN118001949 A CN 118001949A
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- 239000012528 membrane Substances 0.000 title claims abstract description 134
- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 116
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 116
- 229920000289 Polyquaternium Polymers 0.000 title claims description 40
- 238000000926 separation method Methods 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000005266 casting Methods 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 238000007790 scraping Methods 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 14
- 150000003863 ammonium salts Chemical group 0.000 abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000002045 lasting effect Effects 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000000614 phase inversion technique Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 70
- 230000000052 comparative effect Effects 0.000 description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000001112 coagulating effect Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 239000004971 Cross linker Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000003385 bacteriostatic effect Effects 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 238000004848 nephelometry Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 229960003638 dopamine Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000008223 sterile water Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a polyquaternary ammonium salt modified polyethersulfone separating membrane and a preparation method thereof, wherein the polyquaternary ammonium salt modified polyethersulfone separating membrane comprises the following raw materials in parts by weight: 10-20 parts of polyether sulfone, 5-10 parts of pore-forming agent, 70-85 parts of solvent, 0.5-7.5 parts of polyquaternary ammonium salt-28 solution, 2-5 parts of cross-linking agent and 0.1-0.5 part of initiator. The preparation method of the polyquaternary ammonium salt modified polyethersulfone separating membrane comprises the steps of preparing a polyquaternary ammonium salt modified polyethersulfone solution, preparing a membrane by adopting a submerged precipitation phase inversion method, wherein the polyquaternary ammonium salt modified polyethersulfone solution is uniform and good in membrane forming property, and directly crosslinking a monomer in the polyquaternary ammonium salt-28 solution to a polyethersulfone network chain through stirring polymerization reaction, so that the polyquaternary ammonium salt modified polyethersulfone separating membrane is not easy to wash out, and has lasting and stable hydrophilicity and antibacterial and anti-pollution capabilities.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a polyquaternium modified polyether sulfone separation membrane and a preparation method thereof.
Background
Polyethersulfone is a thermoplastic polymer material excellent in comprehensive properties, has excellent heat resistance, physical and mechanical properties, insulation properties and the like, and particularly has the outstanding advantages of being capable of being continuously used at high temperature, maintaining stable properties in environments where temperature changes sharply and the like, and has been widely used in many fields.
The separation membrane prepared from the modified polyethersulfone has excellent hydrophilicity. There are a number of reports on antibacterial and anti-pollution modification of polymer separation membranes. For example, chinese patent publication No. CN109200835A discloses a preparation method of a bionic construction poly quaternary ammonium salt type antibacterial PVDF membrane, which utilizes the adhesiveness of dopamine oxidation self-polymerization crosslinking to form poly dopamine on the surface of the PVDF membrane, and grafts sulfhydrylation poly quaternary ammonium salt onto the surface of the membrane to realize secondary functional modification of the membrane, thereby obtaining the hydrophilic antibacterial membrane. Chinese patent publication No. CN108273398a discloses an antibacterial hollow fiber membrane, a preparation method and application thereof, the fiber yarn mixed with silver yarn is activated, then mixed with film-making liquid, the obtained mixture is woven to obtain a hollow fiber woven tube, and finally the woven tube is formed to obtain the antibacterial hollow fiber membrane.
However, the modification method is complex and is not beneficial to commercial production because inorganic micromolecule or organic macromolecule antibacterial agents are combined with membrane base materials with separation functions through grafting layer self-assembly or crosslinking and other means.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a polyquaternium modified polyethersulfone separating membrane with a simple preparation method and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
The polyquaternium modified polyethersulfone separating membrane comprises the following raw materials in parts by weight: 10-20 parts of polyether sulfone, 5-10 parts of pore-forming agent, 70-85 parts of solvent, 0.5-7.5 parts of polyquaternary ammonium salt-28 solution, 2-5 parts of cross-linking agent and 0.1-0.5 part of initiator.
As a further improvement to the above technical solution:
The cross-linking agent is glycidyl methacrylate and/or ethylene glycol dimethacrylate.
The initiator is dibenzoyl peroxide and/or azobisisobutyronitrile.
The polyquaternium-28 solution is a polymer of N, N, N-trimethyl-3- ((2-methyl-1-oxo-2-propenyl) amino) -1-propyl ammonium chloride and 1-vinyl-2-pyrrolidone or a polymer of N, N-dimethyl-N-2-propenyl-2-propylene ammonium chloride and acrylic acid.
The polyquaternium-28 solution is a polyquaternium-28 solution with a concentration of 20 wt.%.
The solvent is one or more of N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO) or N, N-dimethylacetamide (DMAc).
The pore-forming agent is one or more of polyethylene oxide, polyethylene glycol, polyvinylpyrrolidone, hydrophilic silicon dioxide and diethylene glycol.
The invention also provides a preparation method of the polyquaternium modified polyethersulfone separating membrane, which comprises the following steps:
A1, stirring and dissolving polyether sulfone, a pore-forming agent and a solvent, then adding a polyquaternium-28 solution, a cross-linking agent and an initiator, stirring and polymerizing to obtain a polyquaternium modified polyether sulfone solution, and standing and curing to obtain a modified polyether sulfone casting solution;
A2, scraping the casting film liquid to prepare a film, curing and forming, and cleaning to obtain the poly quaternary ammonium salt modified polyether sulfone separating film.
As a further improvement to the above technical solution:
In the step A1, the temperature of the stirring polymerization reaction is 50-90 ℃ and the time is 2-24h.
The method comprises the steps of scraping, forming, curing and forming, wherein a pre-evaporation step is further included between the scraping film and the curing and forming, and the pre-evaporation time is 30-50s.
In the step A2, solidification forming is carried out by adopting a solidification bath at the temperature of 30-80 ℃.
Compared with the prior art, the invention has the advantages that:
The polyquaternary ammonium salt modified polyether sulfone separating membrane is grafted to the polyether sulfone, so that the polyether sulfone has charges, has a bacterial inhibition effect, and solves the technical problem that the polyether sulfone membrane is easy to be polluted by bacteria, and the polyquaternary ammonium salt modified polyether sulfone separating membrane has good chemical stability, antibacterial property, good hydrophilicity and good mechanical property.
The preparation method of the polyquaternium modified polyethersulfone separating membrane is simple, efficient, easy to operate and low in cost, is beneficial to commercial production, prepares the polyquaternium modified polyethersulfone solution firstly, adopts a submerged precipitation phase inversion method to prepare the membrane, is uniform and good in membrane forming property, and directly crosslinks monomers in the polyquaternium-28 solution onto a polyethersulfone network chain through stirring polymerization reaction, is not easy to wash out, and has lasting and stable hydrophilicity and antibacterial and anti-pollution capabilities. In the preparation method, the stirring polymerization reaction is adopted, so that compared with physical stirring, the structure of the poly (quaternary ammonium salt) modified polyether sulfone separation membrane is more stable, particles are less prone to being generated relative to an active carrier, and compared with other polymerization reactions, the steps are simpler and easy to control.
Drawings
FIG. 1 is a graph showing the effect of nephelometry on the growth curve of E.coli of the unmodified/modified polyethersulfone separation membranes prepared in comparative example 1 and example 1 of the present invention.
FIG. 2 is a graph showing the effect of nephelometry on the growth curve of Staphylococcus aureus of the unmodified/modified polyethersulfone separation membranes prepared in comparative example 1 and example 1 of the present invention.
Detailed Description
The present invention will be described in further detail below. The instruments or materials used in the present invention are commercially available unless otherwise specified.
Example 1
The polyquaternium modified polyethersulfone separating membrane of the embodiment comprises the following raw materials in parts by weight: 10 parts of polyethersulfone, 5 parts of polyvinylpyrrolidone, 85 parts of N, N-dimethylacetamide, 5 parts of polyquaternium-28 solution with the concentration of 20wt.% and 2 parts of cross-linking agent and 0.1 part of initiator.
The preparation method of the polyquaternium modified polyether sulfone separation membrane comprises the following steps:
adding 10 parts of polyethersulfone, 5 parts of polyvinylpyrrolidone and 85 parts of N, N-dimethylacetamide into a reaction kettle, stirring and dissolving completely, adding 5 parts of polyquaternium-28 solution with the concentration of 20 wt%, 2 parts of cross-linking agent and 0.1 part of initiator, and carrying out polymerization reaction for 4 hours at the temperature of 50 ℃ under stirring to obtain a polyquaternium modified polyethersulfone solution, and standing and curing to obtain a modified polyethersulfone casting solution; the defoaming agent is not required to be added in the invention, so that the technical problem that impurities are introduced into the defoaming agent and remain in the membrane is avoided, and the defoaming process is completed by standing and defoaming in the standing process.
A2, scraping the casting solution under a greenhouse to prepare a flat membrane, pre-evaporating the flat membrane in air for 40s, immersing the flat membrane in a coagulating bath at 30 ℃, and keeping the flat membrane for 24 hours for curing and forming to obtain a formed membrane; and (3) washing the formed membrane with clear water to obtain the modified polyethersulfone separating membrane.
In this example, the crosslinker is glycidyl methacrylate and the initiator is dibenzoyl peroxide.
Comparative example 1
An unmodified polyethersulfone separating membrane of the comparative example comprises the following raw materials in parts by weight: 10 parts of polyethersulfone, 5 parts of polyvinylpyrrolidone and 85 parts of N, N-dimethylacetamide.
The preparation method of the unmodified polyethersulfone separation membrane of the comparative example comprises the following steps:
A1, adding 10 parts of polyethersulfone, 5 parts of polyvinylpyrrolidone and 85 parts of N, N-dimethylacetamide into a reaction kettle, stirring and dissolving completely at 50 ℃, and vacuum defoaming for 30min to obtain uniform and stable casting solution;
a2, scraping the casting solution under a greenhouse to prepare a flat membrane, pre-evaporating the flat membrane in air for 40s, immersing the flat membrane in a coagulating bath at 30 ℃, and keeping the flat membrane for 24 hours for curing and forming to obtain a formed membrane; and (3) washing the formed membrane with clear water to obtain the unmodified polyethersulfone separating membrane.
Antibacterial property test
The antibacterial properties of the unmodified/modified polyethersulfone separation membranes prepared in comparative example 1 and example 1 against Escherichia coli and Staphylococcus aureus were measured by nephelometry.
The operation steps are as follows: firstly, diluting the cultured bacterial liquid with a sterile PBS buffer solution in an ultra-clean workbench to ensure that the absorbance of the diluted bacterial suspension measured at the wavelength of 600 nm is 0.600-0.800. (zeroing in PBS buffer, as measured by a visible spectrophotometer); then, the unmodified/modified polyethersulfone separation membranes prepared in comparative example 1 and example 1 were each cut into 1cm discs with a puncher, immersed in sterile water for 24 hours, dried and placed in a multi-well plate for use, and 1 mL sterilized liquid medium and 1. Mu.L of the bacterial suspension were sucked by a pipette and added to the multi-well plate, followed by shaking culture in a constant temperature incubator at 37 ℃.
① Calculating the bacteriostasis rate: after 20h of cultivation, the culture medium is taken out and observed for turbidity, the OD630 value is measured, and the bacteriostasis rate is calculated (average of two parallel samples is measured). A positive control group was made without 20wt.% polyquaternium-28 solution.
The calculation formula of the bacteriostasis rate:
② Drawing a growth curve: OD630 values (averaged from two replicates) were measured every three hours up to 36 hours. After the experiment is completed, the data are processed and a growth curve corresponding to the time t-OD630 value is drawn.
As shown in FIGS. 1 and 2, the unmodified polyethersulfone separating membrane obtained in comparative example 1 had no remarkable inhibitory effect on Escherichia coli and Staphylococcus aureus, whereas the modified polyethersulfone separating membrane of example 1 had remarkable inhibitory effect on Escherichia coli and Staphylococcus aureus.
Example 2
The polyquaternium modified polyethersulfone separating membrane of the embodiment comprises the following raw materials in parts by weight: 14 parts of polyethersulfone, 6 parts of polyvinylpyrrolidone, 80 parts of dimethyl sulfoxide, 0.5 part of a polyquaternium-28 solution with the concentration of 20wt.% and 3 parts of a crosslinking agent and 0.5 part of an initiator.
The preparation method of the polyquaternium modified polyether sulfone separation membrane comprises the following steps:
Adding 14 parts of polyethersulfone, 6 parts of polyvinylpyrrolidone and 80 parts of dimethyl sulfoxide into a reaction kettle, stirring and dissolving completely, adding 0.5 part of polyquaternium-28 solution with the concentration of 20wt.%, 3 parts of cross-linking agent and 0.5 part of initiator, and carrying out polymerization reaction for 12 hours at the temperature of 70 ℃ under stirring to obtain a polyquaternium modified polyethersulfone solution, and standing and curing to obtain a modified polyethersulfone casting solution;
A2, scraping the casting solution under a greenhouse to prepare a flat membrane, pre-evaporating the flat membrane in air for 40s, immersing the flat membrane in a coagulating bath at 50 ℃, and keeping the flat membrane for 24 hours for curing and forming to obtain a formed membrane; and (3) washing the formed membrane with clear water to obtain the modified polyethersulfone separating membrane.
In this embodiment, the cross-linking agent is ethylene glycol dimethacrylate and the initiator is azobisisobutyronitrile.
Comparative example 2
The polyether sulfone separating membrane of the comparative example comprises the following raw materials in parts by weight: 14 parts of polyethersulfone, 6 parts of polyvinylpyrrolidone, 80 parts of dimethyl sulfoxide, 0 part of a polyquaternium-28 solution with the concentration of 20wt.% and 3 parts of a cross-linking agent and 0.5 part of an initiator.
The preparation method of the polyethersulfone separation membrane of the comparative example comprises the following steps:
Adding 14 parts of polyethersulfone, 6 parts of polyvinylpyrrolidone and 80 parts of dimethyl sulfoxide into a reaction kettle, stirring and dissolving completely, adding 0 part of polyquaternium-28 solution with the concentration of 20wt.%, 3 parts of cross-linking agent and 0.5 part of initiator, and carrying out polymerization reaction for 12 hours at the temperature of 70 ℃ under stirring to obtain a polyethersulfone solution, and standing and curing to obtain a polyethersulfone casting solution;
a2, scraping the casting solution under a greenhouse to prepare a flat membrane, pre-evaporating the flat membrane in air for 40s, immersing the flat membrane in a coagulating bath at 50 ℃, and keeping the flat membrane for 24 hours for curing and forming to obtain a formed membrane; and (3) washing the formed membrane with clear water to obtain the polyether sulfone separating membrane.
In this comparative example, the crosslinking agent and the initiator were the same as in example 2.
Comparative example 3
The polyquaternium modified polyethersulfone separating membrane of the comparative example comprises the following raw materials in parts by weight: 14 parts of polyethersulfone, 6 parts of polyvinylpyrrolidone, 80 parts of dimethyl sulfoxide, 0.25 part of a polyquaternium-28 solution with the concentration of 20wt.% and 3 parts of a crosslinking agent and 0.5 part of an initiator.
The preparation method of the polyquaternium modified polyether sulfone separation membrane of the comparative example comprises the following steps:
Adding 14 parts of polyethersulfone, 6 parts of polyvinylpyrrolidone and 80 parts of dimethyl sulfoxide into a reaction kettle, stirring and dissolving completely, adding 0.25 part of polyquaternium-28 solution with the concentration of 20wt.%, 3 parts of cross-linking agent and 0.5 part of initiator, and carrying out polymerization reaction for 12 hours at the temperature of 70 ℃ under stirring to obtain a polyquaternium modified polyethersulfone solution, and standing and curing to obtain a modified polyethersulfone casting solution;
A2, scraping the casting solution under a greenhouse to prepare a flat membrane, pre-evaporating the flat membrane in air for 40s, immersing the flat membrane in a coagulating bath at 50 ℃, and keeping the flat membrane for 24 hours for curing and forming to obtain a formed membrane; and (3) washing the formed membrane with clear water to obtain the modified polyethersulfone separating membrane.
In this comparative example, the crosslinking agent and the initiator were the same as in example 2.
Table 1 data sheet of bacteriostatic effects of example 2 and comparative example 2, 3
The following is noted: -clarification of the culture broth; + indicates that the culture solution is turbid; ++ indicates that the culture solution is very turbid
Through testing, when the solution with the concentration of 20wt.% of the polyquaternium-28 is added to be 0.5 part (example 2), the solution is in a clear state and has an antibacterial effect, and if the mass part of the solution with the concentration of 20wt.% of the polyquaternium-28 is added to be less than 0.25 part, the antibacterial effect is poor.
Example 3
The polyquaternium modified polyethersulfone separating membrane of the embodiment comprises the following raw materials in parts by weight: 14 parts of polyethersulfone, 6 parts of polyethylene glycol, 80 parts of N, N-dimethylacetamide, 3 parts of a polyquaternium-28 solution with the concentration of 20wt.% and 2 parts of a crosslinking agent and 0.1 part of an initiator.
The preparation method of the polyquaternium modified polyether sulfone separation membrane comprises the following steps:
Adding 14 parts of polyethersulfone, 6 parts of polyethylene glycol and 80 parts of N, N-dimethylacetamide into a reaction kettle, stirring and dissolving completely, adding 3 parts of polyquaternium-28 solution with the concentration of 20wt.%, 2 parts of a cross-linking agent and 0.1 part of an initiator, and carrying out polymerization reaction for 12 hours at the temperature of 60 ℃ under stirring to obtain a polyquaternium modified polyethersulfone solution, and standing and curing to obtain a modified polyethersulfone casting solution;
a2, scraping the casting solution under a greenhouse to prepare a flat membrane, pre-evaporating the flat membrane in air for 40s, immersing the flat membrane in a coagulating bath at 80 ℃, and keeping the flat membrane for 24h for curing and forming to obtain a formed membrane; and (3) washing the formed membrane with clear water to obtain the modified polyethersulfone separating membrane.
In this embodiment, the cross-linking agent is a mixture of glycidyl methacrylate and ethylene glycol dimethacrylate (in other embodiments, the mixture of any ratio of the two liquids can achieve the same or similar technical effects, the volume ratio of the two liquids is 1:1, and the initiator is a mixture of dibenzoyl peroxide and azobisisobutyronitrile (in other embodiments, the mixture of any ratio of the two liquids can achieve the same or similar technical effects, the volume ratio of the two liquids is 1:1).
Example 4
The polyquaternium modified polyethersulfone separating membrane of the embodiment comprises the following raw materials in parts by weight: 20 parts of polyethersulfone, 10 parts of polyethylene glycol, 70 parts of dimethyl sulfoxide, 5 parts of polyquaternium-28 solution with the concentration of 20wt.% and 3 parts of cross-linking agent and 0.5 part of initiator.
The preparation method of the polyquaternium modified polyether sulfone separation membrane comprises the following steps:
Adding 20 parts of polyethersulfone, 10 parts of polyethylene glycol and 70 parts of dimethyl sulfoxide into a reaction kettle, stirring and dissolving completely, adding 5 parts of polyquaternium-28 solution with the concentration of 20wt.%, 3 parts of cross-linking agent and 0.5 part of initiator, and carrying out polymerization reaction for 8 hours at the temperature of 80 ℃ under stirring to obtain a polyquaternium modified polyethersulfone solution, and standing and curing to obtain a modified polyethersulfone casting solution;
A2, scraping the casting solution under a greenhouse to prepare a flat membrane, pre-evaporating the flat membrane in air for 30s, immersing the flat membrane in a coagulating bath at 80 ℃, and keeping the flat membrane for 24h for curing and forming to obtain a formed membrane; and (3) washing the formed membrane with clear water to obtain the modified polyethersulfone separating membrane.
In this example, the crosslinker is glycidyl methacrylate and the initiator is dibenzoyl peroxide.
Example 5
The polyquaternium modified polyethersulfone separating membrane of the embodiment comprises the following raw materials in parts by weight: 20 parts of polyethersulfone, 10 parts of polyethylene glycol, 70 parts of dimethyl sulfoxide, 7.5 parts of polyquaternium-28 solution with the concentration of 20wt.% and 3 parts of cross-linking agent and 0.5 part of initiator.
The preparation method of the polyquaternium modified polyether sulfone separation membrane comprises the following steps:
Adding 20 parts of polyethersulfone, 10 parts of polyethylene glycol and 70 parts of dimethyl sulfoxide into a reaction kettle, stirring and dissolving completely, adding 7.5 parts of polyquaternium-28 solution with the concentration of 20wt.%, 3 parts of a cross-linking agent and 0.5 part of an initiator, and carrying out polymerization reaction for 8 hours at the temperature of 80 ℃ under stirring to obtain a polyquaternium modified polyethersulfone solution, and standing and curing to obtain a modified polyethersulfone casting solution;
a2, scraping the casting solution under a greenhouse to prepare a flat membrane, pre-evaporating the flat membrane in air for 40s, immersing the flat membrane in a coagulating bath at 80 ℃, and keeping the flat membrane for 24h for curing and forming to obtain a formed membrane; and (3) washing the formed membrane with clear water to obtain the modified polyethersulfone separating membrane.
In this example, the crosslinker is glycidyl methacrylate and the initiator is dibenzoyl peroxide.
Table 2 tables of antibacterial effect data for example 4 and example 5
The following is noted: -clarification of the culture broth; + indicates that the culture solution is turbid; ++ indicates that the culture solution is very turbid
Through tests, when the solution with the concentration of 20wt.% of polyquaternium-28 is added to be 5 parts and 7.5 parts, the antibacterial effect is relatively consistent and has no great change.
Example 6
The polyquaternium modified polyethersulfone separating membrane of the embodiment comprises the following raw materials in parts by weight: 20 parts of polyethersulfone, 10 parts of polyvinylpyrrolidone, 80 parts of N, N-dimethylformamide, 5 parts of polyquaternium-28 solution with the concentration of 20wt.% and 3 parts of cross-linking agent and 0.5 part of initiator.
The preparation method of the polyquaternium modified polyether sulfone separation membrane comprises the following steps:
Adding 20 parts of polyethersulfone, 10 parts of polyvinylpyrrolidone and 80 parts of N, N-dimethylformamide into a reaction kettle, stirring and dissolving completely, adding 5 parts of polyquaternium-28 solution with the concentration of 20wt.%, 3 parts of cross-linking agent and 0.5 part of initiator, and carrying out polymerization reaction for 8 hours at the temperature of 85 ℃ under stirring to obtain a polyquaternium modified polyethersulfone solution, and standing and curing to obtain a modified polyethersulfone casting solution;
a2, scraping the casting solution under a greenhouse to prepare a flat membrane, pre-evaporating the flat membrane in air for 40s, immersing the flat membrane in a coagulating bath at 80 ℃, and keeping the flat membrane for 24h for curing and forming to obtain a formed membrane; and (3) washing the formed membrane with clear water to obtain the modified polyethersulfone separating membrane.
In this example, the crosslinker is glycidyl methacrylate and the initiator is dibenzoyl peroxide.
Example 7
The polyquaternium modified polyethersulfone separating membrane of the embodiment comprises the following raw materials in parts by weight: 18 parts of polyethersulfone, 5 parts of polyethylene glycol, 77 parts of N, N-dimethylformamide, 5 parts of a polyquaternium-28 solution with the concentration of 20wt.% and 3 parts of a crosslinking agent and 0.5 part of an initiator.
The preparation method of the polyquaternium modified polyether sulfone separation membrane comprises the following steps:
Adding 18 parts of polyethersulfone, 5 parts of polyethylene glycol and 77 parts of N, N-dimethylformamide into a reaction kettle, stirring and dissolving completely, adding 5 parts of polyquaternium-28 solution with the concentration of 20wt.%, 3 parts of a cross-linking agent and 0.5 part of an initiator, and carrying out polymerization reaction for 24 hours at the temperature of 65 ℃ under stirring to obtain a polyquaternium modified polyethersulfone solution, and standing and curing to obtain a modified polyethersulfone casting solution;
a2, scraping the casting solution under a greenhouse to prepare a flat membrane, pre-evaporating the flat membrane in air for 40s, immersing the flat membrane in a coagulating bath at 80 ℃, and keeping the flat membrane for 24h for curing and forming to obtain a formed membrane; and (3) washing the formed membrane with clear water to obtain the modified polyethersulfone separating membrane.
In this example, the crosslinker is glycidyl methacrylate and the initiator is dibenzoyl peroxide.
Table 3 table of bacteriostatic effect data for example 4, example 6 and example 7
The following is noted: -clarification of the culture broth; + indicates that the culture solution is turbid; ++ indicates that the culture solution is very turbid
The bacteriostatic effect of examples 6 and 7 of the present invention is not much different from that of example 4.
While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art, or equivalent embodiments with equivalent variations can be made, without departing from the scope of the invention. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall fall within the scope of the technical solution of the present invention.
Claims (10)
1. A poly quaternary ammonium salt modified polyethersulfone separating membrane is characterized in that: the raw materials comprise the following components in parts by weight:
10-20 parts of polyether sulfone,
5-10 Parts of pore-forming agent,
70-85 Parts of a solvent,
0.5 To 7.5 parts of polyquaternium-28 solution,
2-5 Parts of cross-linking agent,
Initiator 0.1-0.5 parts.
2. The polyquaternium modified polyethersulfone separation membrane of claim 1, wherein: the cross-linking agent is glycidyl methacrylate and/or ethylene glycol dimethacrylate.
3. The polyquaternium modified polyethersulfone separation membrane of claim 1, wherein: the initiator is dibenzoyl peroxide and/or azobisisobutyronitrile.
4. The polyquaternium modified polyethersulfone separation membrane of claim 1, wherein: the solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or N, N-dimethylacetamide.
5. The polyquaternium modified polyethersulfone separation membrane of claim 1, wherein: the polyquaternium-28 solution is a polymer of N, N, N-trimethyl-3- ((2-methyl-1-oxo-2-propenyl) amino) -1-propyl ammonium chloride and 1-vinyl-2-pyrrolidone or a polymer of N, N-dimethyl-N-2-propenyl-2-propylene ammonium chloride and acrylic acid.
6. The polyquaternium modified polyethersulfone separation membrane of claim 1, wherein: the polyquaternium-28 solution is a polyquaternium-28 solution with a concentration of 20 wt.%.
7. A method for producing the polyquaternium modified polyethersulfone separation membrane according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
A1, stirring and dissolving polyether sulfone, a pore-forming agent and a solvent, then adding a polyquaternium-28 solution, a cross-linking agent and an initiator, stirring and polymerizing to obtain a polyquaternium modified polyether sulfone solution, and standing and curing to obtain a modified polyether sulfone casting solution;
A2, scraping the casting film liquid to prepare a film, curing and forming, and cleaning to obtain the poly quaternary ammonium salt modified polyether sulfone separating film.
8. The method of manufacturing according to claim 7, wherein: in the step A1, the temperature of the stirring polymerization reaction is 50-90 ℃ and the time is 2-24h.
9. The method of manufacturing according to claim 7, wherein: in the step A2, a pre-evaporation step is further included between the scraping film and the curing molding, and the pre-evaporation time is 30-50s.
10. The method of manufacturing according to claim 7, wherein: in the step A2, solidification forming is carried out by adopting a solidification bath at the temperature of 30-80 ℃.
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