CN116333216A - Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer - Google Patents
Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer Download PDFInfo
- Publication number
- CN116333216A CN116333216A CN202310213656.0A CN202310213656A CN116333216A CN 116333216 A CN116333216 A CN 116333216A CN 202310213656 A CN202310213656 A CN 202310213656A CN 116333216 A CN116333216 A CN 116333216A
- Authority
- CN
- China
- Prior art keywords
- imidazolyl
- pvdf
- zwitterionic polymer
- imidazole
- modifying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 122
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 122
- 239000012528 membrane Substances 0.000 title claims abstract description 70
- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 125000002883 imidazolyl group Chemical group 0.000 title claims abstract description 43
- 238000002715 modification method Methods 0.000 title description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 15
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 13
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 10
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 9
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 38
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 229960003638 dopamine Drugs 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 10
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- XRZVNIXEBCWMJE-UHFFFAOYSA-N ethanol;trihydrochloride Chemical compound Cl.Cl.Cl.CCO XRZVNIXEBCWMJE-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 26
- 230000004048 modification Effects 0.000 abstract description 16
- 238000012986 modification Methods 0.000 abstract description 16
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 13
- 239000002569 water oil cream Substances 0.000 abstract description 7
- 230000010069 protein adhesion Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000003921 oil Substances 0.000 description 28
- 235000019198 oils Nutrition 0.000 description 28
- 239000000839 emulsion Substances 0.000 description 13
- 241000894006 Bacteria Species 0.000 description 11
- 230000004907 flux Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 229920001690 polydopamine Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- -1 methacrylamido Chemical group 0.000 description 5
- 238000000089 atomic force micrograph Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 108091006146 Channels Proteins 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 108090000862 Ion Channels Proteins 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002073 fluorescence micrograph Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 235000019476 oil-water mixture Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000035587 bioadhesion Effects 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 230000032770 biofilm formation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides an imidazolyl zwitterionic polymer, which is synthesized by taking 1-vinylimidazole and vinyltrimethoxysilane as raw materials and AIBN as an initiator; then the sulfonate is introduced by using 1, 3-propane sultone to prepare the catalyst. Based on the imidazolyl zwitterionic polymer, sulfonate is introduced, and a two-step method is adopted to carry out hydrophilic modification on the surface and pore canal of the PVDF membrane, so that the modified PVDF membrane shows excellent super-hydrophilicity/underwater super-oleophobicity, has excellent antibacterial and protein adhesion resistance, and can realize high-efficiency oil-water emulsion separation under various severe environments. The invention also provides an imidazole-based zwitterionic polymer modified PVDF membrane prepared by the method.
Description
Technical Field
The invention relates to the technical field of separation membrane materials, in particular to an imidazolyl zwitterionic polymer, a PVDF membrane modified by the imidazolyl zwitterionic polymer and a modification method.
Background
With the continuous development of industrialization and city, the production of oily wastewater is explosively increased. During transportation and use, the oil and water mixture often forms emulsions due to vibration, agitation, and shearing. Therefore, under the current large background of pursuing green environmental protection, the oil-water emulsion separation by using the membrane technology, and particularly the oil-containing wastewater treatment by using the surface with special wettability has great significance and value.
At present, the surface super-hydrophilic/underwater super-oleophobic modified polyvinylidene fluoride (PVDF) membrane can be used for realizing oil-water separation and emulsion separation.
In the prior art, hydrophilic modification of a PVDF membrane by dopamine and diethylenetriamine and oil-water separation performance (functional materials, 2022,53 (10): 10222-10228, authors: du Guoyong, yuan Qiao) are carried out, and hydrophobic PVDF membrane is immersed in a mixed solution of dopamine hydrochloride (DA)/Diethylenetriamine (DETA) in a certain mass ratio, so that the super-hydrophilic-underwater super-oleophobic PVDF/polydopamine/diethylenetriamine (PVDF/PDA/DETA) membrane is prepared. Although the membrane can realize the separation of oil-water mixture, the membrane still has the defect in the separation performance of oil-water emulsion. For this reason, studies have shown that the introduction of micro-nano structures on super-hydrophilic surfaces can effectively achieve emulsion separation. For example, chinese patent No. CN109499393B prepares super-hydrophilic PVDF film through constructing surface micro-nano structure and amino polymer, and realizes the efficient separation of oil-water mixture and emulsified oil. In addition, preparation of the underwater super oleophobic PVDF film and research on the oil-water separation performance of the emulsion thereof (Chongqing university, 2020.004121, asAnd (2) the following: wang Deyong, etc.) to prepare tannic acid/polyvinylpyrrolidone/SiO 2 The PVDF film modified by the composite coating is used for realizing the separation of oil-in-water emulsion and has better oil stain resistance. Indeed, the above-mentioned studies and patent inventions show some oil-resistant adhesion while emulsion separation, but in practical applications, adhesion of microorganisms (bacteria, algae) and proteins is still an important cause of serious decrease in the separated water flux.
Zwitterionic polymers (zwitterionic polymers) are a class of materials having a pair of opposite charges on the repeat unit that can undergo hydration by ionic solvation and are stronger than the hydration effects of conventional nonionic hydrophilic materials by hydrogen bonding, generally exhibiting excellent anti-bioadhesion properties, including anti-nonspecific protein adsorption, anti-cell adhesion, anti-bacterial adhesion, biofilm formation, and the like. Therefore, the amphoteric ion polymer has better hydrophilicity on one hand, and can construct the super-hydrophilic/underwater super-oleophobic surface for super-efficient oil-water separation performance; on the other hand, excellent bioadhesive properties can be achieved by the formation of the hydration layer. However, the zwitterionic polymer material still faces the problems of complex preparation process, higher cost, insufficient antibacterial performance and the like when being applied to the oil-water separation membrane. For example, chinese patent No. CN114405287B first grafts a hydrophilic monomer containing hydroxyl groups onto the PVDF membrane surface to form a hydrophilic polymer gel layer, and then successfully grafts the zwitterionic monomer 3- (methacrylamido) propyl-dimethyl (3-thiopropyl) ammonium hydroxide inner salt (MPDSAH) onto the membrane surface by a surface initiated-atom transfer radical polymerization (SI-ATRP) reaction. Although the method enhances the hydrophilicity of the PVDF film and improves the anti-pollution capability, the hydrophilic film does not have sterilization performance and is difficult to maintain a long-acting anti-bioadhesion function, and in addition, the preparation process is long and the cost is high.
Therefore, how to prepare the amphoteric ion polymer with good hydrophilicity, antibacterial property and bioadhesion resistance, and modify the surface of the PVDF substrate by a simple and efficient method becomes a problem to be solved urgently.
Disclosure of Invention
The invention provides an imidazolyl zwitterionic polymer, which is modified by a PVDF membrane, has excellent super-hydrophilicity/underwater super-oleophobicity, has excellent antibacterial and protein adhesion resistance, and can realize high-efficiency oil-water emulsion separation in various severe environments.
The technical scheme of the invention is as follows:
an imidazolyl zwitterionic polymer having the structural formula:
the synthesis method of the imidazolyl zwitterionic polymer comprises the following steps:
1-vinylimidazole and vinyltrimethoxysilane are taken as raw materials, AIBN is taken as an initiator to synthesize an imidazole-based copolymer;
and then introducing sulfonate by using 1, 3-propane sultone to prepare the imidazolyl zwitterionic polymer.
The invention also provides a method for modifying the PVDF film by the imidazolyl zwitterionic polymer, which comprises the following steps:
s1, synthesizing an imidazolyl copolymer by taking 1-vinylimidazole and vinyltrimethoxysilane as raw materials and AIBN as an initiator;
s2, immersing the PVDF substrate in a Tris-HCl-ethanol solution of dopamine to enable dopamine monomers to be covered in a substrate pore channel;
step S3, immersing the PVDF substrate modified in the step S2 into Tris-HCl solution of dopamine hydrochloride monomer and ethanol solution of TEOS-imidazolyl copolymer for codeposition reaction, and then drying and curing the fully immersed PVDF substrate;
step S4, immersing the PVDF substrate of the step S3 in Fe 3+ In the aqueous solution of (2), the polymer on the surface of the PVDF substrate is reacted with Fe 3+ Crosslinking, taking out and drying;
s5, soaking the PVDF substrate in the step S4 in a methanol solution containing 1, 3-propane sultone, reacting for 6-8 hours at 60-80 ℃, taking out the PVDF substrate, cleaning and drying to prepare the imidazole-based zwitterionic polymer modified PVDF film; specifically, the reaction temperature may be 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, or may be other temperature values within the range; the reaction time may be 6h, 7h or 8h, or may be other values within this range.
Further, the specific process for synthesizing the imidazolyl copolymer in the step S1 is as follows:
mixing isopropanol, 1-vinyl imidazole and vinyl trimethoxy silane, adding azo-diisobutyronitrile for initiation, bubbling in a nitrogen atmosphere, heating in an oil bath for a period of time, transferring the reaction solution into diethyl ether for coagulation, and performing suction filtration and drying to obtain an imidazole-based copolymer;
wherein the mol ratio of the 1-vinylimidazole to the vinyltrimethoxysilane is 8-12:1; the addition amount of the initiator is 0.1-0.5% of the mass of the monomer; the volume ratio of the diethyl ether to the polymer reaction solution is 8-10:1. Specifically, the molar ratio of 1-vinylimidazole to vinyltrimethoxysilane may be 8: 1. 9: 1. 10:1, 11:1 or 12:1, other ratios within this range are also possible; the initiator may be added in an amount of 0.1%, 0.2%, 0.3%, 0.4% or 0.5% by mass of the monomer, or may be added in other amounts within the range; the volume ratio of diethyl ether to the polymer reaction solution may be 8:1, 9:1 or 10:1, or may be other values within this range.
Further, in the step S1, the temperature of the oil bath is 60-80 ℃, and the heating time of the oil bath is 8-16h. Specifically, the temperature of the oil bath may be 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, or may be other temperature values within the range; the oil bath heating time may be 8h, 10h, 12h, 14h or 16h, or may be other values within this range.
Further, in the step S2, the dopamine concentration is 2-5mg/mL, and the volume ratio of Tris-HCl to ethanol is 1:1, the soaking time is 1-10min. Specifically, the dopamine concentration may be 2mg/mL, 3mg/mL, 4mg/mL or 5mg/mL, or may be other values within this range.
Further, in the step S3, the concentration of the dopamine hydrochloride monomer in the Tris-HCl solution of the dopamine hydrochloride monomer is 2-5mg/mL, the concentration of the ethanol solution of the TEOS-imidazolyl copolymer is 30-40mg/mL, and the volume ratio of the Tris-HCl solution of the dopamine hydrochloride monomer to the ethanol solution of the TEOS-imidazolyl copolymer is 1:1-2:3. Specifically, the concentration of the dopamine hydrochloride monomer can be 2mg/mL, 3mg/mL, 4mg/mL or 5mg/mL, and can also be other values within the range; the ethanol solution concentration of the TEOS-imidazolyl copolymer can be 30mg/mL, 32mg/mL, 35mg/mL or 40mg/mL, and can also be other values within the range; the volume ratio of Tris HCl solution of dopamine hydrochloride monomer to ethanol solution of TEOS-imidazolyl copolymer may be 1: 1. 2:3. 3:4 or 4:5, other values within this range are also possible.
Further, in the step S3, the codeposition reaction is carried out on a shaker at room temperature for 8-15 hours. The reaction time is 8h, 10h, 12h or 15h, and may be any other value within the above range. Experiments show that the reaction time is shorter, the amount of the imidazolyl copolymer on the surface is smaller below 6 hours, and the thickness of the formed coating cannot lead the PVDF film to achieve super-hydrophilic performance; when the reaction time reaches a certain degree, the optimal time is 8-15h, the thickness of the coating is basically unchanged, and the PVDF film can reach a super-hydrophilic and underwater super-oleophobic state.
Further, in step S4, fe is contained 3+ The iron salt used in the aqueous solution of (2) is FeCl 3 Or Fe (Fe) 2 (SO 4 ) 3 ,Fe 3+ The concentration is 0.2-0.4mol/L, the infiltration time is 10-20min, and the drying temperature is 30-35 ℃. Specifically, fe 3+ The concentration may be 0.2mol/L, 0.3mol/L or 0.4mol/L, or other values within the range; the soaking time can be 10min, 15min or 20min, or can be other values in the range; the drying temperature is 30 ℃, 32 ℃ or 35 ℃, and other temperature values within the range can be adopted.
Further, in the step S5, the concentration of the 1, 3-propane sultone is 30-120mg/mL, and the drying temperature is 30-35 ℃. Specifically, the concentration of 1, 3-propane sultone may be 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL, 100mg/mL, 110mg/mL or 120mg/mL, or other values within the range; the drying temperature may be 30 ℃, 32 ℃ or 35 ℃, or may be other temperature values within the range.
The invention also provides an imidazole based zwitterionic polymer modified PVDF film prepared by the method.
Compared with the prior art, the imidazolyl zwitterionic polymer, the PVDF membrane modified by the imidazolyl zwitterionic polymer and the modification method have the beneficial effects that:
1. according to the PVDF membrane modified by the imidazolyl zwitterionic polymer and the modification method, the surface and the pore canal of the PVDF membrane are subjected to hydrophilic modification by adopting a two-step method, and the membrane pore canal is mainly made to contain dopamine hydrochloride monomers by utilizing a pre-soaking method so as to ensure the adsorption grafting of the imidazolyl copolymer in the pore canal in the later step. Wherein the interaction force between the substances comprises: adhesion of Polydopamine (PDA) to PVDF substrate surface and pore channels; PDA phenolic hydroxyl and toe silicon hydroxyl react with the chemical bond of trimethoxysilane in the copolymer; the interaction of the PDA and the imidazole ring, namely the cation-II interaction, the hydrogen bond interaction and the like. Finally, a hydrophilic coating with a micro-nano structure is formed on the surface of the substrate, so that the modified PVDF film shows excellent super-hydrophilicity/underwater super-oleophobicity, wherein the contact angle of water is below 10 degrees, and the contact angle of underwater oil is above 150 degrees.
2. According to the imidazolyl zwitterionic polymer modified PVDF membrane and the modification method, the modified polymer main chain has the characteristic functions of zwitterions due to the fact that the imidazole ring with positive charges and the sulfonic acid group with negative charges are simultaneously arranged in the modified polymer main chain. At the same time, compared with other common zwitterions, the positive charge on imidazole ring can effectively neutralize the negative charge of bacteria to inactivate the bacteria, and has excellent sterilization effect (the number of bacteria is 10 8 Down to 6X 10 3 CFU/mL); after sulfonate anions are introduced into the gel to become zwitterions, the gel reacts with water molecules to form a compact hydration layer, so that the gel has excellent antibacterial and protein adhesion resisting functions; in particular, the introduction of silane groups allows the polymer to better react with phenolic hydroxyl groups in the Polydopamine (PDA) groups, bind more firmly to the surface of the membrane, and react with Fe in polydopamine and in the presence of Fe 3+ Under the crosslinking action, the long-acting stability of the modified polyurethane can be obviously enhancedThe modified PVDF membrane can be subjected to efficient emulsion separation under various severe environments (pH: 1-13 and high-salt solution), and the separation efficiency is up to more than 99%.
3. The PVDF membrane modified by the imidazolyl zwitterionic polymer and the modification method thereof reduce the roughness of the membrane surface by introducing sulfonate anions, greatly enhance the anti-adhesion effect, and greatly improve the water flux of the membrane (reaching 4000Lm by enhancing the hydrophilicity of the membrane -2 h -1 bar -1 ) The flux of the emulsion reaches 1700Lm -2 h -1 bar -1 The filtration rate is increased, and the recovery rate after multiple cycles is more than 94%.
4. The PVDF membrane and the modification method for the modification of the oxazolyl zwitterionic polymer adopt a two-step method to carry out hydrophilic modification on the surface and pore canal of the PVDF membrane, wherein the zwitterionic polymer is prepared by coupling 1-vinylimidazole and vinyltrimethoxysilane with lower cost, an initiator AIBN is used as a raw material to synthesize an imidazole copolymer, and then 1, 3-propane sultone is used to introduce negative ion sulfonate, so that the multifunctional imidazolyl zwitterionic polymer is finally obtained.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared test chart of the imidazolyl zwitterionic polymer poly (VI-co-VTS) of the present invention;
FIG. 2 is a flow chart of an imidazolyl zwitterionic polymer modified PVDF membrane of the present invention;
FIG. 3 is an SEM image of an imidazolyl zwitterionic polymer modified PVDF membrane of the present invention with a PVDF membrane prior to modification;
FIG. 4 is an AFM image of an imidazolyl zwitterionic polymer modified PVDF film of the present invention with a PVDF film prior to modification;
FIG. 5 is a graph showing the comparison of water flux before and after modification of PVDF membrane pore passages;
FIG. 6 shows the presence or absence of Fe 3+ A PVDF membrane contact angle change comparison chart under the crosslinking modification condition;
FIG. 7 is a graph of water permeation of PVDF membrane dyed with methylene blue under different treatment conditions;
FIG. 8 is a schematic view of the submerged self-cleaning of an imidazolyl zwitterionic polymer modified PVDF film of the present invention;
FIG. 9 is an image of an antimicrobial experiment of PVDF film under different processing conditions;
FIG. 10 is an image of anti-adhesion fluorescence under different processing conditions;
FIG. 11 is a graph showing the emulsion separation effect of the modified PVDF film of example 2.
Detailed Description
In order to better understand the technical solution in the embodiments of the present invention and make the above objects, features and advantages of the present invention more obvious and understandable, the following detailed description of the present invention will be further described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
Example 1
An imidazolyl zwitterionic polymer having the structural formula:
the synthesis method of the imidazolyl zwitterionic polymer comprises the following steps:
mixing isopropanol, 1-vinyl imidazole and vinyl trimethoxy silane, adding azo-diisobutyronitrile for initiating, bubbling in nitrogen atmosphere, heating in an oil bath for a period of time, transferring the reaction solution into diethyl ether for coagulation, and carrying out suction filtration and drying to obtain an imidazole-based copolymer poly (VI-co-VTS), wherein an infrared test chart is shown in figure 1;
wherein, the mol ratio of the 1-vinylimidazole to the vinyltrimethoxysilane is 10:1; the addition amount of the initiator is 0.2% of the mass of the monomer; the volume ratio of the diethyl ether to the polymer reaction solution is 10:1;
the oil bath temperature is 65 ℃ and the oil bath time is 10 hours.
Example 2
A method for modifying PVDF membrane by imidazolyl zwitterionic polymer comprises the following steps:
referring to fig. 2, a flowchart of the modified PVDF membrane of the invention is shown, and the specific process includes the following steps:
membrane pore canal modification: repeatedly cleaning the PVDF substrate in ethanol and deionized water for 30min by using an ultrasonic cleaner; then soaking the membrane in a dopamine Tris-HCl-ethanol solution (the concentration of the dopamine is 2mg/mL, the volume ratio of the dopamine to the ethanol is 1:1), completely soaking the membrane in the dopamine solution for 5min, and repeating the operation for 3-4 times to ensure that the membrane pore canal is covered with dopamine monomers;
modification of imidazolyl polymers: the membrane pore modified PVDF substrate was completely immersed in 20mL of an equal volume of Tris-HCl solution of dopamine hydrochloride monomer (dopamine concentration of 2 mg/mL) and TEOS/poly (VI-co-VTS) in ethanol (TEOS concentration of 24mg/mL, poly (VI-co-VTS) concentration of 12 mg/mL) for co-deposition and reacted on a shaker at room temperature (25 ℃) for 10h. Placing the fully soaked PVDF substrate in a baking oven at 30 ℃ for curing for 15min;
Fe 3+ crosslinking treatment: impregnating the surface of PVDF substrate modified by imidazole-based polymer into FeCl of 0.2mol/L 3 Placing in solution for 15min, taking out, and oven drying at 30deg.CDrying for 5min;
introducing sulfonate anions: fe is added to 3+ The PVDF substrate after the crosslinking treatment is soaked in a solution containing 100mg/mL of 1, 3-propane sultone-methanol, and the reaction is carried out for 7 hours at the temperature of 65 ℃. And taking out the PVDF substrate, washing with deionized water, and then placing the PVDF substrate in a 30 ℃ oven for drying for 1min to obtain the imidazole-based zwitterionic polymer modified PVDF film capable of being used for emulsion separation.
Referring to fig. 3 and 4, fig. 3 is an SEM image of an imidazole-based zwitterionic polymer modified PVDF film of the invention and a PVDF film before modification, fig. 3 (a) shows an SEM image of a normal PVDF film, and fig. 3 (b) shows an SEM image of a modified PVDF film; fig. 4 is an AFM image of an imidazole-based zwitterionic polymer-modified PVDF film of the invention and a PVDF film before modification, fig. 4 (a) shows an AFM image of a normal PVDF film, and fig. 4 (b) shows an AFM image of a modified PVDF film. As can be seen from fig. 3 and fig. 4, the modified PVDF membrane pore channel forms a nano-structure of the polyimidazole zwitterionic polymer, so that it has good hydrophilicity and underwater super oleophobic ability.
Example 3
The process of the imidazole-based zwitterionic polymer modified PVDF film differs from example 2 in that: and the step of modifying the PVDF membrane pore canal by soaking the PVDF membrane pore canal with the dopamine Tris-HCl-ethanol solution is omitted. Referring to fig. 4, a comparison graph of water flux before and after modification of PVDF membrane channels is shown in fig. 5, and it can be seen from fig. 5 that the membrane channels are modified by using dopamine Tris-HCl-ethanol solution infiltration, so that the water flux is greatly increased.
Example 4
The process of the imidazole-based zwitterionic polymer modified PVDF film differs from example 2 in that: cancel Fe 3+ And a crosslinking treatment step. After the film was left for about 2 weeks, contact angle measurements were performed again, see FIG. 6, for the presence or absence of Fe 3+ Comparison of change in contact angle of PVDF film under crosslinking modification conditions, wherein 6 (a) represents that Fe was not used in the present example 3+ Change in PVDF film contact angle under crosslinking conditions, fig. 6 (b) shows a graph of change in PVDF film contact angle of example 2; as can be seen from FIG. 6, fe is used 3+ Oil/water connection of crosslinked PVDF membranesThe antenna is not changed obviously, and Fe is not used 3+ The cross-linked film water contact angle increases and the underwater oil contact angle decreases.
Example 5
Contact angle test
The water contact angle of the imidazolyl zwitterionic polymer modified PVDF film of example 2 in air was tested, and the instantaneous contact angle was less than 30℃and gradually decreased to 0℃in 5-10 seconds. The contact angle of the underwater oil can be greater than 150 degrees; the contact angle of the oil is tested by adopting different oils, and the test shows that the contact angle of the oil is larger than 150 degrees and the oil is super oleophobic whether the oil is light oil such as toluene, cyclohexane or heavy oil such as carbon tetrachloride; the modified PVDF film after repeated recycling can still achieve the super-oleophobic performance of multiple oils.
Meanwhile, the modified PVDF film has excellent hydrophilic capacity and underwater self-cleaning performance, the hydrophilic performance and the underwater self-cleaning performance are shown in figures 7 and 8, wherein figure 7 is a water permeation diagram of the PVDF film dyed with methylene blue under different treatment conditions, figure 7 (a) shows a water permeation diagram of the common PVDF film dyed with methylene blue, and figure 7 (b) shows a water permeation diagram of the modified PVDF film dyed with methylene blue; fig. 8 is a schematic view of underwater self-cleaning of an imidazole-based zwitterionic polymer-modified PVDF film of the invention, fig. 8 (a) showing heavy oil underwater self-cleaning ability, and fig. 8 (b) showing light oil underwater self-cleaning ability. As can be seen from fig. 7 and 8, the common PVDF film is hydrophobic, the modified PVDF film has excellent hydrophilic ability, and the modified PVDF film has efficient self-cleaning ability in heavy oil and light oil environments.
Example 6
Antibacterial test
Taking CFU as 10 8 100 microliters of staphylococcus aureus (MRSA) of (2) are respectively covered on a common PVDF membrane and a PVDF membrane modified in the example 2, the bacteria on the membrane are washed by quantitative PBS, the bacteria on the membrane are ultrasonically washed, and after the bacteria are coated on a suspension bacteria liquid for 24 hours, the growth conditions of the bacteria on the two membranes are recorded, so that the antibacterial effect of the membrane is observed.
Referring to fig. 9, an image of an antibacterial test of a PVDF film under different process conditions is shown, wherein fig. 9 (a) shows an antibacterial test of a general PVDF film, and fig. 9 (b) shows an antibacterial test of a modified PVDF film. As can be seen from FIG. 9, the modified PVDF membrane has obviously reduced bacterial cells compared with the common PVDF membrane, and has good antibacterial performance.
Example 7
Anti-adhesion test
Taking CFU as 10 8 20 microliter of staphylococcus aureus (MRSA) and adding 1980 microliter of LB medium, immersing PVDF membrane and modified membrane in bacterial solution, incubating for about 24 hours, then washing the bacteria on the membrane 3 times with quantitative PBS, then putting the membrane into quantitative PBS solution for ultrasonic oscillation, and recording the growth of bacteria on the two membranes after 24 hours by plating the suspension bacterial solution. Referring to fig. 10, the anti-adhesion fluorescence image under different processing conditions is shown in fig. 10 (a), and fig. 10 (b) shows the modified PVDF anti-bacterial anti-adhesion fluorescence image, and as can be seen from fig. 10, the modified PVDF film has good anti-adhesion performance.
Example 8
Emulsion separation test
1mL of light oil (toluene, cyclohexane, n-hexane and the like) is taken and dissolved in 99mL of water, 50-100ppm of Sodium Dodecyl Sulfate (SDS) surfactant is added, a cell breaker is used, ultrasonic treatment is carried out for 20-30min, so that an oil-water emulsion is obtained, the oil-water emulsion is subjected to suction filtration by using the PVDF film modified in the embodiment 2 under the condition of 1bar, clear water is obtained, the water flux is calculated, and TOC in the water is tested, so that the oil-water emulsion separation efficiency is obtained. Referring to fig. 11, an emulsion separation effect diagram of the modified PVDF membrane of example 2 is shown in fig. 11 (a), where fig. 11 (a) shows water and emulsion flux of the oil-water separation experiment after multiple cycles, and fig. 11 (b) shows water flux and separation efficiency of the oil-water separation experiment of different oils, and as can be seen from fig. 11, the modified PVDF membrane has higher stable water flux and separation efficiency in different emulsion environments.
The cost of the single membrane of the PVDF membrane modified by the imidazolyl zwitterionic polymer is calculated as follows:
in conclusion, the process for modifying the PVDF membrane by the imidazolyl zwitterionic polymer has the advantages of low cost, simple preparation method, low cost and good industrial application prospect.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.
Claims (10)
1. An imidazolyl zwitterionic polymer characterized by the structural formula:
the synthesis method of the imidazolyl zwitterionic polymer comprises the following steps:
1-vinylimidazole and vinyltrimethoxysilane are taken as raw materials, AIBN is taken as an initiator to synthesize an imidazole-based copolymer;
and then introducing sulfonate by using 1, 3-propane sultone to prepare the imidazolyl zwitterionic polymer.
2. A method for modifying a PVDF membrane with an imidazolyl zwitterionic polymer, comprising the steps of:
s1, synthesizing an imidazolyl copolymer by taking 1-vinylimidazole and vinyltrimethoxysilane as raw materials and AIBN as an initiator;
s2, immersing the PVDF substrate in a Tris-HCl-ethanol solution of dopamine to enable dopamine monomers to be covered in a substrate pore channel;
step S3, immersing the PVDF substrate modified in the step S2 into Tris-HCl solution of dopamine hydrochloride monomer and ethanol solution of TEOS-imidazolyl copolymer for codeposition reaction, and then drying and curing the fully immersed PVDF substrate;
step S4, immersing the PVDF substrate of the step S3 in Fe 3+ In the aqueous solution of (2), the polymer on the surface of the PVDF substrate is reacted with Fe 3+ Crosslinking, taking out and drying;
and S5, soaking the PVDF substrate in the step S4 in a methanol solution containing 1, 3-propane sultone, reacting for 6-8 hours at 60-80 ℃, taking out the PVDF substrate, cleaning and drying to prepare the imidazole-based zwitterionic polymer modified PVDF film.
3. The method for modifying a PVDF membrane by an imidazole-based zwitterionic polymer according to claim 2, wherein the specific process for synthesizing the imidazole-based copolymer in step S1 is as follows:
mixing isopropanol, 1-vinyl imidazole and vinyl trimethoxy silane, adding azo-diisobutyronitrile for initiation, bubbling in a nitrogen atmosphere, heating in an oil bath for a period of time, transferring the reaction solution into diethyl ether for coagulation, and performing suction filtration and drying to obtain an imidazole-based copolymer;
wherein the mol ratio of the 1-vinylimidazole to the vinyltrimethoxysilane is 8-12:1; the addition amount of the initiator is 0.1-0.5% of the mass of the monomer; the volume ratio of the diethyl ether to the polymer reaction solution is 8-10:1.
4. The method for modifying a PVDF film with an imidazolyl zwitterionic polymer according to claim 3, wherein in step S1, the oil bath temperature is 60-80℃and the oil bath heating time is 8-16h.
5. The method for modifying a PVDF membrane according to claim 2, wherein in step S2, the dopamine concentration is 2-5mg/mL, the volume ratio of Tris/HCl to ethanol is 1:1, the soaking time is 1-10min.
6. The method for modifying a PVDF membrane by an imidazolyl zwitterionic polymer according to claim 2, wherein in step S3, the concentration of dopamine hydrochloride monomer in Tris-HCl solution of dopamine hydrochloride monomer is 2-5mg/mL, the concentration of ethanol solution of TEOS-imidazolyl copolymer is 30-40mg/mL, and the volume ratio of Tris-HCl solution of dopamine hydrochloride monomer to ethanol solution of TEOS-imidazolyl copolymer is 1:1-2:3.
7. The method for modifying a PVDF film according to claim 2, wherein in step S3, the co-deposition reaction is carried out on a shaker at room temperature for 8 to 15 hours.
8. The method for modifying a PVDF film according to claim 2, wherein in step S4, fe is contained 3+ The iron salt used in the aqueous solution of (2) is FeCl 3 Or Fe (Fe) 2 (SO 4 ) 3 ,Fe 3+ The concentration is 0.2-0.4mol/L, the infiltration time is 10-20min, and the drying temperature is 30-35 ℃.
9. The method for modifying a PVDF film according to claim 2, wherein the concentration of 1, 3-propane sultone in step S5 is 30-120mg/mL and the drying temperature is 30-35 ℃.
10. An imidazolyl zwitterionic polymer modified PVDF membrane, prepared by the method of any of claims 2-9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310213656.0A CN116333216A (en) | 2023-03-07 | 2023-03-07 | Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310213656.0A CN116333216A (en) | 2023-03-07 | 2023-03-07 | Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116333216A true CN116333216A (en) | 2023-06-27 |
Family
ID=86894103
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310213656.0A Pending CN116333216A (en) | 2023-03-07 | 2023-03-07 | Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116333216A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116836605A (en) * | 2023-08-11 | 2023-10-03 | 四川大学 | Antibacterial and antifouling self-healing material, coating and preparation method thereof |
CN118105538A (en) * | 2024-03-07 | 2024-05-31 | 常州集硕医疗器械有限公司 | Modified fiber reinforced PEEK bone scaffold material and preparation method thereof |
-
2023
- 2023-03-07 CN CN202310213656.0A patent/CN116333216A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116836605A (en) * | 2023-08-11 | 2023-10-03 | 四川大学 | Antibacterial and antifouling self-healing material, coating and preparation method thereof |
CN116836605B (en) * | 2023-08-11 | 2024-04-26 | 四川大学 | Antibacterial and antifouling self-healing material, coating and preparation method thereof |
CN118105538A (en) * | 2024-03-07 | 2024-05-31 | 常州集硕医疗器械有限公司 | Modified fiber reinforced PEEK bone scaffold material and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109224873B (en) | Method for enhancing hydrophilic stability of polymer membrane by complexing polyphenol with metal ions | |
CN116333216A (en) | Imidazolyl zwitterionic polymer, PVDF membrane modified by imidazolyl zwitterionic polymer and modification method of imidazolyl zwitterionic polymer | |
CN108905653B (en) | Preparation method and application of hyperbranched zwitterion modified polyvinylidene fluoride oil-water emulsion separation membrane | |
US11458440B2 (en) | Thin-film composite polyamide reverse osmosis membrane with anti-bacterial and anti-biofouling effects and preparation method thereof | |
CN103691328A (en) | Method for preparing contamination-resistant composite reverse osmosis membrane | |
JP5837480B2 (en) | Composite semipermeable membrane | |
CN111437741B (en) | Mussel bionic auxiliary polyelectrolyte layer-by-layer self-assembled nanofiltration membrane and application thereof | |
CN110066415B (en) | Preparation method of porous membrane with functionalized surface | |
KR20130028850A (en) | Reverse osmosis comprising ultra ultra-hydrophilic protective layer | |
CN112646095A (en) | Dopamine-modified diatomite-adsorbed heavy metal hydrogel and preparation method and application thereof | |
CN109647218B (en) | Modified polyvinylidene fluoride membrane with efficient pollution resistance and bacteriostasis and preparation method thereof | |
CN111644081A (en) | Preparation method of novel high-stability composite nanofiltration membrane | |
CN110538579B (en) | Preparation method and application of porous composite membrane | |
CN110743383B (en) | Modification method for improving permeation flux of polyamide composite membrane | |
CN113019142A (en) | Post-treatment modification method of polyamide composite nanofiltration membrane | |
CN115364702B (en) | Method for modifying organic film by nano hydrogel particles | |
CN115197419A (en) | Imidazole zwitterionic polymer and synthesis method and application thereof | |
CN114768555B (en) | Modified polyamide separation membrane and preparation method thereof | |
CN114471198B (en) | Preparation method of non-solvent induced anti-oil stain polyethersulfone ultrafiltration membrane and coating | |
CN108993174B (en) | Sodium hypochlorite-resistant ePTFE hydrophilic membrane and preparation method and application thereof | |
CN114713044B (en) | Method for improving pollution resistance of composite nanofiltration membrane | |
Wang et al. | Polyurea nanofiltration membranes with extreme-pH stability and high separation performance | |
CN111363185A (en) | Preparation method and application of molecularly imprinted composite membrane initiated by surface functional monomer prepolymerization system | |
CN114618328B (en) | Preparation method of PVDF (polyvinylidene fluoride) membrane with emulsion separation and dye adsorption performances | |
KR102061179B1 (en) | High adsorption capability polymer brush-foam composite and manufacturing method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |