CN117861457B - Super-crosslinked polysulfate composite membrane and preparation method and application thereof - Google Patents
Super-crosslinked polysulfate composite membrane and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 239000002346 layers by function Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical class FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 238000005345 coagulation Methods 0.000 claims description 10
- 230000015271 coagulation Effects 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- -1 4, 1-phenylene Chemical group 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000007790 scraping Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000758 substrate Substances 0.000 abstract description 7
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 210000004379 membrane Anatomy 0.000 description 58
- 239000002585 base Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000004907 flux Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000001728 nano-filtration Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229940098773 bovine serum albumin Drugs 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 210000002469 basement membrane Anatomy 0.000 description 3
- 238000009295 crossflow filtration Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
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- 238000001471 micro-filtration Methods 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
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Abstract
The invention belongs to the field of membrane separation, and particularly relates to a super-crosslinked polysulfate composite membrane, and a preparation method and application thereof. The invention uses binaphthol and sulfonyl fluoride derivatives of bisphenol A to polymerize together to obtain binaphthyl polysulfate, the binaphthol is prepared into a substrate film, and the substrate film is subjected to Friedel-crafts alkylation reaction with aromatic derivative monomers in the presence of a cross-linking agent by adopting an interfacial polymerization method, so that a super cross-linked functional layer is successfully formed on the polysulfate substrate film, and a novel super cross-linked polysulfate composite film is obtained. The super-crosslinked polysulfate composite membrane prepared by the invention has a defect-free surface morphology and excellent separation performance, and is very suitable for membrane separation.
Description
Technical Field
The invention belongs to the field of membrane separation, and particularly relates to a super-crosslinked polysulfate composite membrane, and a preparation method and application thereof.
Background
The membrane separation technology is used as a novel separation technology, has the advantages of simple operation, high equipment filling density, mild working condition, energy conservation, no secondary pollution and the like, is an important technology for solving the problems of resource type water shortage and water quality type water shortage, and is also considered as a key technology of the chemical industry of the 21 st century. Membrane technologies can be divided into microfiltration, ultrafiltration, nanofiltration, reverse osmosis, pervaporation, gas separation, etc. according to different separation processes. The nanofiltration has the characteristic of between ultrafiltration and reverse osmosis, the aperture of the nanofiltration membrane is smaller than 2nm, and the nanofiltration membrane has wide application in the industrial processes of sea water desalination, resource recovery, sewage treatment and the like. Nanofiltration membranes generally consist of a porous support layer and a dense functional selective layer.
Porous support layers have a number of different options, with polysulfone membranes having a wide range of applications in water treatment and other toxic separations. Polysulfone is an important engineering plastic and has very wide application in automotive aerospace, sheet materials and electronic materials, but polysulfone cannot treat strong chemical substances (such as strong acid and strong alkali, corrosive raw materials and the like). The polysulfate as a novel special engineering plastic has excellent chemical resistance, even certain brands of polysulfate can be used in concentrated sulfuric acid and concentrated nitric acid, and in the field of membranes, the polysulfate has stronger wide-area property and pollution resistance to chemical environment than polysulfone, so that the development of polysulfate membrane materials has very important scientific research value and market application prospect.
The preparation of the functional selection layer determines the separation properties of the membrane. The Polyamide (PA) functional layer which is usually studied, however, is formed into a thicker, non-uniform pore size selective layer due to the uncontrollable monomer diffusion and reaction process, such selective layer cannot effectively achieve the balance between rejection and permeability, thus failing to meet the requirements of high performance nanofiltration membranes, and the chemical structure of the membrane with such functional selective layer is also easily damaged during long-term use. Therefore, it is important to design new materials with nano-porosity, structural integrity and chemical stability. In recent years, the use of metal organic frameworks, covalent organic frameworks, and graphene oxide materials has become a common method for preparing high performance separation membranes. However, the pore size of the structure of these materials is large (typically between 1-5 nm), and the effect of effective separation is not achieved for some contaminants with smaller molecular sizes.
The super-crosslinked microporous polymer is a polymer material with permanent micropores, and has the remarkable advantages of various synthetic methods, easy functionalization, large specific surface area, low reagent cost, mild operation conditions and the like, and is widely applied to the energy and environment fields such as gas storage, carbon capture, pollutant removal, molecular separation, catalysis, drug delivery, sensing and the like. At present, the super-crosslinked microporous polymer is not applied to the field of separation membranes, and the main reason is that the reaction process for obtaining the super-crosslinked microporous polymer by polymerization is a rapid dynamic process, and a highly crosslinked network can be formed in a short time, so that the growth morphology is difficult to control, and the finally formed membrane has poor morphology, defects and poor separation function. Thus, challenges remain in how to apply the super-crosslinked microporous polymer to the field of membrane separation.
Disclosure of Invention
In order to solve the above-mentioned drawbacks of the prior art, the present invention provides a method for preparing a super-crosslinked polysulfate composite membrane, which has a defect-free surface morphology and excellent separation performance.
Specifically, the invention provides a preparation method of a super-crosslinked polysulfate composite membrane, which comprises a binaphthyl-type polysulfate base membrane and a surface functional layer, and comprises the following steps of: (1) preparation of a polysulfate base film: under the protection of nitrogen, 1' -bi-2-naphthol and isopropyl bis (4, 1-phenylene) bis (sulfonyl fluoride) with the molar ratio of 1:1 are reacted for 6-12 hours at 140-220 ℃ in N, N-dimethylformamide in the presence of an acid neutralizer, and then reactants are cooled, poured into a precipitator, filtered, purified and dried to obtain binaphthyl polysulfate; dissolving the obtained binaphthyl type polysulfate in tetrahydrofuran, heating, stirring, dissolving, standing, defoaming to obtain casting solution, scraping and coating the casting solution on a supporting plate, immersing the supporting plate in a coagulating bath, and completely curing to obtain a binaphthyl type polysulfate base film; (2) preparation of a surface functional layer: and placing the binaphthyl type polysulfate base film at the two-phase interface of a catalytic phase and an organic phase, adding a reaction monomer and a crosslinking agent into the organic phase, so that Friedel-crafts alkylation reaction is carried out on the surface of the base film (wherein naphthalene groups in the polysulfate base film and the reaction monomer respectively carry out Friedel-crafts alkylation reaction with the crosslinking agent so as to crosslink with each other), and washing and drying the reacted base film to obtain the super-crosslinked polysulfate composite film.
The synthetic route of the binaphthyl polysulfate is shown below.
。
Further, the acid neutralizer is selected from one or more of sodium carbonate, silicon dioxide, potassium carbonate, lithium carbonate or cesium carbonate.
Further, the precipitant is selected from deionized water or ethanol.
Further, the mass-volume ratio of binaphthyl polysulfate to tetrahydrofuran in the casting solution is 1 g/5 mL.
Further, the coagulation bath is selected from deionized water or deionized water solution containing partial solvent, surfactant, polyelectrolyte or inorganic salt, and the temperature of the coagulation bath is 10-25 ℃.
Further, the catalytic phase is selected from at least one of concentrated H 2SO4 or trifluoromethanesulfonic acid.
Further, the organic phase is selected from at least one of n-hexane or n-heptane.
Further, the reaction monomer is at least one of benzene, biphenyl, diphenylmethane, diphenyl ether or any aromatic derivative which does not contain a strong electron withdrawing group.
Further, the crosslinking agent is at least one selected from the group consisting of dimethanol formal, 1, 4-p-dichlorobenzyl or ethylene glycol dimethyl ether.
Further, the feeding mole ratio of the reaction monomer to the cross-linking agent is 1:5-10.
The invention also provides a super cross-linked polysulfate composite membrane prepared by the method described herein.
The invention also provides the use of the super cross-linked polysulfate composite membranes prepared by the methods described herein in membrane separation.
The invention has the beneficial effects that: the invention uses binaphthol and sulfonyl fluoride derivatives of bisphenol A to polymerize together to obtain binaphthyl polysulfate, and prepares the binaphthol and sulfonyl fluoride derivatives into a substrate membrane to be used as a support membrane of a super-crosslinking polysulfate composite membrane, and the binaphthol has excellent acid and alkali resistance, and the microporous structure can provide larger flux for the composite membrane, thereby being beneficial to forming a nanofiltration membrane with better separation performance. According to the invention, an interfacial polymerization method is further tried, naphthalene groups and aromatic derivative monomers in binaphthyl type polysulfate molecular chains are utilized to carry out Friedel-crafts alkylation reaction on the prepared polysulfate base film in the presence of a cross-linking agent, and as a result, a super-crosslinked functional layer is successfully formed on the polysulfate base film, and the base film and the functional layer are connected through chemical bonds (the naphthalene groups and the aromatic derivative monomers in the polysulfate base film are respectively subjected to Friedel-crafts alkylation reaction with the cross-linking agent so as to be crosslinked together), so that good interfacial compatibility can be realized, and the defect of poor stability of the functional layer on the surface of the base can be overcome; meanwhile, the super-crosslinked microporous polymer formed by the interfacial polymerization method is not the microsphere morphology which is usually present, but the surface structure without defects is realized; in addition, since the super-crosslinked structure is constructed by the connection of strong covalent bonds, the functional layer has excellent chemical and thermal stability.
Drawings
FIG. 1 shows the nuclear magnetic hydrogen spectrum (FIG. 1A) and the nuclear magnetic carbon spectrum (FIG. 1B) of binaphthyl polysulfate prepared in example 1 of the present invention.
FIG. 2 shows a scanning electron microscope image of a cross section of a binaphthyl-type polysulfate base film (FIG. 2A) and a super-crosslinked polysulfate composite film (FIG. 2B) prepared in example 1 of the present invention and a cross section of a super-crosslinked polysulfate composite film (FIG. 2C).
FIG. 3 shows scanning electron microscopy images of films prepared according to comparative example 1 (FIG. 3A) and comparative example 2 (FIG. 3B) of the present invention.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
A preparation method of a super-crosslinked polysulfate composite membrane, which comprises the following steps.
(1) Preparation of a polysulfate base film: under the protection of nitrogen, 0.05mol of R-1,1' -bi-2-naphthol and 0.05mol of isopropyl bis (4, 1-phenylene) bis (sulfonyl fluoride) are reacted in 50mL of N, N-dimethylformamide at 140 ℃ for 8 hours in the presence of 0.11mol of sodium carbonate, then the reactants are cooled and poured into hot deionized water (60 ℃) to be filtered, the precipitate is collected and subjected to soxhlet extraction with the hot deionized water and ethanol for 24 hours, and the precipitate is dried to obtain binaphthyl polysulfate (the number average molecular weight Mn is 172771 Da. FIG. 1 shows the nuclear magnetic hydrogen spectrum (FIG. 1A) and the nuclear magnetic carbon spectrum (FIG. 1B）：1H NMR (CDCl3,400 MHz) δH：8.03~8.05(m,2H),7.92~7.94 (m,2H),7.84~7.86 (m,1H),7.72~7.77(m,1H),7.59~7.66 (m,3H),7.43~7.51(m,4H),7.27~7.41(m,3H),6.93~7.21(m,9H),6.74~6.89(m,2H),6.54~6.68(m,2H),1.46~1.56(m,9H). nuclear magnetic carbon spectrum test results of the binaphthyl polysulfate prepared ：13C NMR (100 MHz,CDCl3) δC：149.56,149.51~149.49,146.80~146.46,133.21~131.02,128.78~126.46,121.26~120.65,120.62,120.06,120.03,119.13,42.75~42.59,30.79~30.74.
Dissolving 2g of the obtained binaphthyl type polysulfate in 10mL of tetrahydrofuran, heating to 80 ℃, stirring, dissolving, standing, defoaming to obtain casting solution, scraping and coating the casting solution on a glass plate, immersing the glass plate in a deionized water coagulation bath, standing for 20min at the coagulation bath temperature of 15 ℃, and drying in a hot air oven at 50 ℃ to obtain the binaphthyl type polysulfate substrate film after complete solidification.
(2) Preparation of a surface functional layer: the binaphthyl-type polysulfate base film is placed in the center of a diffusion pool and is isolated into two chambers, a catalytic phase and an organic phase are respectively placed on two sides of the film, concentrated sulfuric acid is selected as the catalytic phase, normal hexane is selected as the organic phase, benzene and dimethanol formal are added into the organic phase, the benzene content is 2 mu mol/cm 2, the dimethanol formal content is 15 mu mol/cm 2, the polymerization is carried out for 3 days at 35 ℃, the reaction solution is fully washed by methanol after the completion, the reaction solution is dried at room temperature to obtain the super-crosslinked polysulfate composite film, and FIG. 2 shows a scanning electron microscope image of the binaphthyl-type polysulfate base film (FIG. 2A) and the super-crosslinked polysulfate composite film (FIG. 2B), the macroporous structure of the surface of the binaphthyl-type polysulfate base film disappears after the interfacial polymerization, the surface is covered by the super-crosslinked functional layer, and FIG. 2C shows a scanning electron microscope image of the cross section of the super-crosslinked polysulfate composite film, and the thickness of the super-crosslinked functional layer is about 100 nm.
The membrane was tested using a membrane, and the resulting membrane was tested in a cross-flow filtration apparatus at 25℃and 4bar operating pressure, as follows.
1. The pure water flux is 69 L.m -2·h-1·bar-1, which shows that the polysulfate composite membrane prepared by the invention has an ultra-crosslinking structure and still has excellent water permeability.
2. The membrane separation determination is carried out by using Congo red aqueous solution and bovine serum albumin aqueous solution, and the retention rates are respectively 95.3% and 99.3%, which shows that the super-crosslinking polysulfate composite membrane can efficiently separate pollutants in water.
3. After the super-crosslinked polysulfate composite membrane is soaked in an acid solution with the pH value of 1 and a sodium hydroxide alkali solution with the concentration of 1mol/L, the water flux and the pollutant adsorptivity are measured, the pure water flux is 57 L.m -2·h-1·bar-1 and 63 L.m -2·h-1·bar-1 respectively, and the rejection rate of Congo red is 90.3 percent and 92.5 percent respectively, which shows that the membrane performance is basically kept stable.
4. To evaluate the thermal stability of the super-crosslinked polysulfate composite membranes, the membranes were tested in a cross-flow filtration apparatus at 60 ℃ and 4bar operating pressure with a pure water flux of 62l·m -2·h-1·bar-1 and rejection rates of 94.5% and 99.2% for congo red and bovine serum albumin, respectively, indicating that the super-crosslinked polysulfate composite membranes of the invention have stable performance at elevated temperatures.
5. To evaluate the long-term stability of the super-crosslinked polysulfate composite membrane, the membrane was measured for pure water flux and congo red rejection every 2 hours, and the pure water flux and congo red rejection were found to remain substantially unchanged for 24 hours, indicating that the super-crosslinked polysulfate composite membrane of the invention has excellent mechanical stability.
Example 2
A preparation method of a super-crosslinked polysulfate composite membrane, which comprises the following steps.
(1) Preparation of a polysulfate base film: under the protection of nitrogen, 0.05mol of R-1,1' -bi-2-naphthol and 0.05mol of isopropyl bis (4, 1-phenylene) bis (sulfonyl fluoride) are reacted in 50mL of N, N-dimethylformamide at 180 ℃ for 10 hours in the presence of 0.11mol of sodium carbonate, then the reactants are cooled, poured into hot deionized water (60 ℃), filtered, and after precipitation is collected, the mixture is subjected to soxhlet extraction with hot deionized water and ethanol for 24 hours and dried, so that binaphthyl polysulfate is obtained.
Dissolving 2g of the obtained binaphthyl type polysulfate in 10mL of tetrahydrofuran, heating to 80 ℃, stirring, dissolving, standing, defoaming to obtain casting solution, scraping and coating the casting solution on a glass plate, immersing the glass plate in a deionized water coagulation bath, standing for 10min at the coagulation bath temperature of 25 ℃, and drying in a hot air oven at 50 ℃ to obtain the binaphthyl type polysulfate substrate film after complete solidification.
(2) Preparation of a surface functional layer: the binaphthyl type polysulfate basement membrane is placed in the center of a diffusion pool and is isolated into two chambers, a catalytic phase and an organic phase are respectively placed on two sides of the membrane, trifluoromethanesulfonic acid is selected as the catalytic phase, n-heptane is selected as the organic phase, biphenyl and ethylene glycol dimethyl ether are added into the organic phase, the content of biphenyl is 2 mu mol/cm 2, the content of ethylene glycol dimethyl ether is 15 mu mol/cm 2, polymerization is carried out for 3 days at 35 ℃, methanol is used for fully cleaning after the completion, and the super-crosslinked polysulfate basement membrane is obtained after the completion of room temperature drying.
Taking a membrane for testing, and testing the obtained membrane in a cross-flow filtering device at 25 ℃ and 4bar operating pressure, wherein the pure water flux is 61 L.m -2·h-1·bar-1; membrane separation was performed with an aqueous congo red solution and an aqueous bovine serum albumin solution, with rejection rates of 94.5% and 99.2%, respectively.
Comparative example 1
Attempts are made to prepare the super-crosslinked polysulfate composite membrane by an in-situ growth method, and the specific implementation method is as follows: clamping binaphthyl type polysulfate basement membrane in two tetrafluoro plate molds, preparing polymerization solution with the same monomer concentration, adding monomer benzene, catalyst aluminum chloride and crosslinking agent dimethoxy methane into 3mL of normal hexane solvent, and pouring the mixture on the surface of the membrane for reaction for 3 days at 35 ℃ after ultrasonic mixing is uniform. After the completion of the reaction, the reaction mixture was thoroughly washed with methanol. The surface morphology of the film is observed by a scanning electron microscope, as shown in fig. 3A, the surface of the base film after polymerization reaction does not change, and the surface does not form a super-crosslinking functional layer, which proves that the interface method adopted by the invention is essential for successfully preparing the super-crosslinking polysulfate composite film.
Comparative example 2
This comparative example provides a method for preparing a polysulfate composite membrane, which is different from example 1 in that bisphenol A is used instead of R-1,1' -bi-2-naphthol, including the following steps.
(1) Preparation of a polysulfate base film: under the protection of nitrogen, 0.05mol of bisphenol A and 0.05mol of isopropyl bis (4, 1-phenylene) bis (sulfonyl fluoride) are reacted in 50mL of N, N-dimethylformamide in the presence of 0.11mol of sodium carbonate at 180 ℃ for 10 hours, then the reactants are cooled, poured into hot deionized water (60 ℃), filtered, collected and subjected to soxhlet extraction with hot deionized water and ethanol for 24 hours, and dried, thereby obtaining bisphenol A polysulfate.
Dissolving 2g of the obtained bisphenol A type polysulfate in 10mL of tetrahydrofuran, heating to 80 ℃, stirring, dissolving, standing, defoaming to obtain casting solution, scraping and coating the casting solution on a glass plate, immersing the glass plate in a deionized water coagulation bath, standing for 10min at the coagulation bath temperature of 25 ℃, and drying in a hot air oven at 50 ℃ to obtain the bisphenol A type polysulfate substrate film after complete solidification.
(2) Preparation of a surface functional layer: the bisphenol A type polysulfate base film is placed in the center of a diffusion tank and is isolated into two chambers, a catalytic phase and an organic phase are respectively placed on two sides of the film, trifluoromethanesulfonic acid is selected as the catalytic phase, n-heptane is selected as the organic phase, biphenyl and ethylene glycol dimethyl ether are added into the organic phase, the content of biphenyl is 2 mu mol/cm 2, the content of ethylene glycol dimethyl ether is 15 mu mol/cm 2, the polymerization is carried out for 3 days at 35 ℃, methanol is used for fully cleaning after the completion, and the obtained film is subjected to scanning electron microscope observation after being dried at room temperature, as shown in fig. 3B, the formation of a super-crosslinking functional layer is not found on the surface of the base film of the bisphenol A type polysulfate base film, which proves that binaphthyl polysulfate adopted by the invention is essential for successfully preparing the super-crosslinking polysulfate composite film.
Comparative example 3
This comparative example tested the filtration performance of the binaphthyl-type polysulfate base membrane prepared in example 1, specifically, the binaphthyl-type polysulfate base membrane was tested in a cross-flow filtration apparatus at 25 ℃ under 4bar operating pressure, and the pure water flux was 89l·m -2·h-1·bar-1, indicating that the porous structure of the binaphthyl-type polysulfate base membrane can well permeate water therethrough; further, the membrane separation determination is carried out by using bovine serum albumin aqueous solution, the retention rate is 84.7%, which shows that the porous structure of the binaphthyl polysulfate base membrane has a certain separation effect on macromolecular pollutants in water, and the membrane separation determination is carried out by using Congo red aqueous solution, so that Congo red cannot be retained, the retention rate is only 6.8%, which shows that the porous structure of the binaphthyl polysulfate base membrane cannot effectively separate pollutants with smaller molecular weight, and the membrane separation application with wider application can still be realized by using the composite super-crosslinked polymeric membrane.
It should be noted that while the present invention has been described in connection with the preferred embodiments thereof, it should be understood that the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but are to be construed as providing a full breadth of the disclosure. The above-described features are further combined with each other to form various embodiments not listed above, and are considered to be the scope of the present invention described in the specification; further, modifications and variations of the present invention may be apparent to those skilled in the art in light of the foregoing teachings, and all such modifications and variations are intended to be included within the scope of this invention as defined in the appended claims.
Claims (7)
1. The preparation method of the super-crosslinked polysulfate composite membrane is characterized by comprising a binaphthyl-type polysulfate base membrane and a surface functional layer, and comprises the following steps of:
(1) Preparation of a polysulfate base film: under the protection of nitrogen, 1' -bi-2-naphthol and isopropyl bis (4, 1-phenylene) bis (sulfonyl fluoride) with the molar ratio of 1:1 are reacted for 6-12 hours at 140-220 ℃ in N, N-dimethylformamide in the presence of an acid neutralizer, and then reactants are cooled, poured into deionized water, filtered, purified and dried to obtain binaphthyl polysulfate;
Dissolving the obtained binaphthyl type polysulfate in tetrahydrofuran, heating, stirring, dissolving, standing, defoaming to obtain casting solution, scraping and coating the casting solution on a supporting plate, immersing the supporting plate in a coagulating bath, and completely curing to obtain a binaphthyl type polysulfate base film;
(2) Preparation of a surface functional layer: placing a binaphthyl type polysulfate base film at a two-phase interface of a catalytic phase and an organic phase, adding a reaction monomer and a crosslinking agent into the organic phase to enable Friedel-crafts alkylation reaction to occur on the surface of the base film, and washing and drying the reacted base film to obtain the super-crosslinked polysulfate composite film;
The catalytic phase is selected from at least one of concentrated H 2SO4 or trifluoromethanesulfonic acid;
the organic phase is selected from at least one of n-hexane or n-heptane;
the reaction monomer is at least one of benzene, biphenyl, diphenylmethane or diphenyl ether;
The cross-linking agent is at least one selected from dimethanol formal, 1, 4-p-dichlorobenzyl or ethylene glycol dimethyl ether.
2. The preparation method according to claim 1, wherein the acid neutralizer is one or more selected from sodium carbonate, potassium carbonate, lithium carbonate and cesium carbonate.
3. The method according to claim 1, wherein the mass-to-volume ratio of binaphthyl polysulfate to tetrahydrofuran in the casting solution is 1 g/5 ml.
4. The method of claim 1, wherein the coagulation bath is selected from deionized water and the temperature of the coagulation bath is 10-25 ℃.
5. The preparation method of claim 1, wherein the feeding molar ratio of the reaction monomer to the crosslinking agent is 1:5-10.
6. A super cross-linked polysulfate composite membrane prepared by the method of any one of claims 1-5.
7. Use of a super cross-linked polysulfate composite membrane prepared by the method of any one of claims 1-5 in membrane separation.
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