CN114456295A - Preparation method of porous polyion liquid - Google Patents
Preparation method of porous polyion liquid Download PDFInfo
- Publication number
- CN114456295A CN114456295A CN202210097738.9A CN202210097738A CN114456295A CN 114456295 A CN114456295 A CN 114456295A CN 202210097738 A CN202210097738 A CN 202210097738A CN 114456295 A CN114456295 A CN 114456295A
- Authority
- CN
- China
- Prior art keywords
- cyanomethyl
- liquid
- polyion liquid
- porous
- poly
- 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.)
- Granted
Links
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 67
- 239000007788 liquid Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 24
- 125000002091 cationic group Chemical group 0.000 claims abstract description 19
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 6
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 5
- 231100000719 pollutant Toxicity 0.000 claims abstract description 5
- -1 1-cyanomethyl-3-vinylimidazole ammonium bromide Chemical compound 0.000 claims description 25
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 5
- KTIYLOCMYFVERP-UHFFFAOYSA-N 2-(3-ethenyl-2h-imidazol-1-yl)acetonitrile Chemical compound C=CN1CN(CC#N)C=C1 KTIYLOCMYFVERP-UHFFFAOYSA-N 0.000 claims description 5
- REXUYBKPWIPONM-UHFFFAOYSA-N 2-bromoacetonitrile Chemical compound BrCC#N REXUYBKPWIPONM-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 5
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical group OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005349 anion exchange Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 15
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- 239000002608 ionic liquid Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- WQJKNEGSMNNRLZ-UHFFFAOYSA-N 2-(3-ethenylimidazol-1-ium-1-yl)acetonitrile Chemical compound C=CN1C=C[N+](CC#N)=C1 WQJKNEGSMNNRLZ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UNJHYXSLULDQRA-UHFFFAOYSA-M 2-(3-ethenylimidazol-1-ium-1-yl)acetonitrile bromide Chemical compound [Br-].C=C[N+]=1C=CN(CC#N)C=1 UNJHYXSLULDQRA-UHFFFAOYSA-M 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001291 vacuum drying 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
- C08F126/00—Homopolymers 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
- C08F126/06—Homopolymers 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or 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; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method of porous polyion liquid, which comprises the following steps: under the action of tetraalkylammonium hydroxide, the cationic polyion liquid is self-assembled in a solvent to form the porous polyion liquid. Compared with the prior art, the method can prepare the porous polyion liquid with different pore sizes by regulating the concentration of the cationic polyion liquid in the system, has the characteristics of simple operation and controllable and easily-adjustable pore size, can flexibly, quickly and simply optimize the pore structure of the polyion liquid according to the size of pollutant molecules, and is a low-cost and green method for improving the adsorption performance of the porous polyion liquid.
Description
Technical Field
The invention particularly relates to a preparation method of porous polyion liquid.
Background
The ionic liquid is organic molten salt which is composed of positive ions and negative ions of the ionic liquid and is in a liquid state at or near room temperature. The polyion liquid is polymerized by an ionic liquid monomer, has a class of polymers of anionic and cationic groups on a repeating unit, has the characteristics of both the ionic liquid and the polymers, and overcomes the flowability of the ionic liquid. According to the charged ions of the main chain, the polyionic liquid can be divided into: 1. cationic polyion liquid, namely cations are connected with a polymer main chain through covalent bonds, 2, anionic polyion liquid, namely anions are connected with the polymer main chain through covalent bonds, and 3, amphoteric polyion liquid, namely cations and anions are connected with the polymer main chain through covalent bonds. The polyion liquid with different counter ions can be obtained through ion exchange (can be carried out before polymerization (monomer) or after polymerization (polymer)), so that the ionic conductivity, hydrophilicity and hydrophobicity and other properties of the polyion liquid can be adjusted, and the counter ions of common cationic polyion liquid have Cl-、Br-、I-、BF4 -、PF6 -、NO3 -、R’SO4 -、CF3SO3 -、PhSO3 -、Tf2N-、(CF3)2N- 、(CN)2N-And the like.
The porous polyion liquid not only has the characteristics of a pore structure, high specific surface area and the like of a traditional adsorbent, but also has the advantages of high conductivity, large polarity and the like, and the porous polyion liquid can be directly used for obtaining a corresponding porous structure during polymerization of an ionic liquid monomer or grafting the ionic liquid into the porous polyion liquidThe porous structure of the polymer, but the pore structure of the polyionic liquid is not easy to control and adjust in this way. Qiang Zhao et al, in the article "purified Structured Structure Nanoporous Poly (Ionic Liquid) Membranes: surface Preparation and Application in Fiber-optical pH Sensing", disclose a method for preparing Nanoporous polyionic Liquid Membranes by reacting Poly [ 1-cyanomethyl-3-vinylimidazole bis (trifluoromethanesulfonyl) imide]（PCMVImTf2N) and polyacrylic acid (PAA), drying at 80 deg.C for 1 hr, soaking in 0.2wt% ammonia water for 2 hr to deprotonate carboxyl group of PAA under the action of ammonia water, and reacting with PCMVImTf2And (3) performing electrostatic interaction on the imidazole cation of the N and generating phase separation in water to obtain the nano-porous polyion liquid membrane. Without ammonia treatment, a dense film without pores was obtained. The method can flexibly obtain the porous polyion liquid, but has the defects that the porous polyion liquid contains polyacrylic acid components and is not suitable for preparing the porous polyion liquid with the counter ion of halogen (such as Br)-、Cl-) The polyionic liquid of (1).
Water is one of the most important resources for human survival and ecosystem circulation. At present, a large amount of waste water is generated in various industries such as textile, food, cosmetics, pharmacy and the like, wherein a large amount of waste water contains phenols and azo organic pollutants, and potential harm is caused to human beings and the environment. Para-nitrophenol (PNP) is a typical representative of phenolic contaminants, and even at low concentrations these contaminant compounds can cause damage to organisms. As a result, the removal of organic contaminants from water bodies is becoming increasingly important. A Green synthesis, characterization and catalytic effectiveness of hypercross-linked porous polymeric ionic networks methods 4-nitrophenol reduction reported by Amutha Chinnappan et al, which synthesizes a porous polystyrene-ionic liquid material with a specific surface area of 541.13 m2And/g, using it as a catalyst to convert p-nitrophenol to p-aminophenol. In the text of "periodic porous polymeric compositions with an isolated adsorption performance for phenyl compositions" reported by Lili Zhang et al, imidazolyl polyions were preparedThe liquid can absorb p-nitrophenol to 460 mg/g, and is an adsorbent with application prospect. In a paper "high hly Salt Resistant Polymer Supported Ionic Liquid Adsorbent for ultra high Capacity Removal of p-Nitrophenol from Water" published by Meng Cheng et al, 1-amino-3 methyl imidazole bromide is grafted onto chloromethyl styrene to adsorb p-Nitrophenol, the adsorption Capacity can reach over 1269 mg/g, which is the substance with the highest adsorption Capacity of the currently reported polyion Liquid Adsorbent to p-Nitrophenol, but the product uses chloromethyl styrene, so that the manufacturing cost and process of the product are influenced.
Disclosure of Invention
In order to solve the problem that the pore size of the existing cationic porous polyion liquid is not easy to regulate, the invention provides a method for preparing the porous polyion liquid, and the method can simply and flexibly regulate the pore size of the porous polyion liquid.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows.
A preparation method of porous polyion liquid comprises the following steps:
under the action of tetraalkylammonium hydroxide, the cationic polyion liquid is self-assembled in a solvent to form the porous polyion liquid.
Preferably, the cationic polyionic liquid is an imidazole polyionic liquid.
Preferably, the imidazole-based polyionic liquid has the following chemical structure:
wherein R is alkyl or cyanoalkyl, A-Is Cl-、Br-、I-、BF4 -、PF6 -、NO3 -、R’SO4 -、CF3SO3 -、PhSO3 -、Tf2N-、(CF3)2N-、(CN)2N-R' is an alkyl group having 1 to 8 carbon atoms, and the cyanoalkyl group has 2 to 9 carbon atoms。
Alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, cyanoalkyl is cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, cyanohexyl, cyanoheptyl or cyanooctyl.
Preferably, the tetraalkylammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide.
Preferably, the concentration of the tetraalkylammonium hydroxide in the system is 1-10 wt%.
More preferably, the concentration of the tetraalkylammonium hydroxide is 2 to 5 wt%.
Preferably, the specific operation process of the method comprises the following steps:
(1) dissolving cationic polyion liquid to obtain solution A;
(2) dissolving tetraalkylammonium hydroxide to obtain a solution B;
(3) and (3) dropping the solution A into the solution B under stirring, and carrying out self-assembly to obtain the porous polyion liquid.
Preferably, the cationic polyionic liquid is poly [ 1-cyanomethyl-3-vinylimidazolium bis (trifluoromethanesulfonyl) imide ].
Preferably, the cationic polyionic liquid is dissolved with N, N-dimethyl imide (DMF).
Preferably, the tetraalkylammonium hydroxide is dissolved with ethylene glycol.
Preferably, the preparation process of the poly [ 1-cyanomethyl-3-vinylimidazolium bis (trifluoromethanesulfonyl) imide ] comprises the following steps:
synthesis of 1-cyanomethyl-3-vinylimidazole ammonium bromide monomer: reacting 1-vinyl imidazole and bromoacetonitrile in an acetone solvent to obtain 1-cyanomethyl-3-vinyl imidazole ammonium bromide;
synthesis of poly (1-cyanomethyl 3-vinylimidazole ammonium bromide): dissolving 1-cyanomethyl-3-vinyl imidazole ammonium bromide in a dimethyl sulfoxide (DMSO) solvent, and performing reflux reaction under the action of an initiator to obtain poly (1-cyanomethyl-3-vinyl imidazole ammonium bromide);
anion exchange: dissolving poly (1-cyanomethyl-3-vinylimidazole ammonium bromide) in water, adding lithium bistrifluoromethanesulfonylimide, and reacting to obtain poly [ 1-cyanomethyl-3-vinylimidazole bis (trifluoromethanesulfonyl) imide ].
Preferably, the 1-vinylimidazole and bromoacetonitrile are reacted at a molar ratio of 1:1 at room temperature.
Preferably, the initiator is Azobisisobutyronitrile (AIBN), the amount of the initiator is 1-3% of the mass of the monomer, and the temperature of the reflux reaction is 70-80 ℃.
Preferably, the amount of the lithium bistrifluoromethanesulfonimide salt is 1.2-1.5 times of the mass of the poly (1-cyanomethyl 3-vinylimidazole ammonium bromide), and the reaction is carried out at room temperature.
The porous polyion liquid is prepared by the method.
The porous polyion liquid is used as an adsorbent in the treatment of phenolic pollutant wastewater.
Preferably, the phenolic contaminant is nitrophenol.
More preferably, the nitrophenol is p-nitrophenol.
Advantageous effects
Compared with the prior art, the method can prepare the porous polyion liquid with different pore sizes by regulating the concentration of the cationic polyion liquid in the system, has the characteristics of simple operation and controllable and easily-adjustable pore size, and can flexibly, quickly and simply optimize the pore structure of the polyion liquid according to the size of pollutant molecules.
The porous polyion liquid can design proper pore distribution for the molecular size of the phenolic compound, and positive charges carried by the cationic polyion can form electrostatic interaction with the phenolic compound with negative charges, so that the porous polyion liquid is an excellent phenolic pollutant adsorbent.
With PCMVImTf2N is taken as an example, and after the optimization by the method, the PCMVImTf can be obviously obtained2The maximum adsorption capacity of N for adsorbing p-nitrophenol can reach 820.3mg/g, which shows that the method is a low-cost way for rapidly and effectively improving the adsorption performance of the porous polyion liquid.
Drawings
FIG. 1 is a scanning electron micrograph of a PILC according to the present invention.
Fig. 2 is an infrared spectrum of a PILC of the invention.
Fig. 3 is a graph of the adsorption kinetics of the PILCs of the invention.
FIG. 4 is a graph showing the effect of pH on the adsorption of p-nitrophenol by PILC of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments.
The tetraalkyl ammonium hydroxide is very easy to absorb moisture and can quickly absorb carbon dioxide in the air to generate carbonate. The commodity is usually an aqueous solution with the concentration of 10% -25%.
Example 1 treatment with PCMVImTf2N is an example
Synthesis of 1-cyanomethyl-3-vinylimidazole ammonium bromide monomer (CMVImBr): 5 g (0.106 mol) of 1-vinylimidazole and 6.37 g (0.106 mol) of bromoacetonitrile are introduced into a 100 mL round-bottomed flask containing 14 mL of acetone. The mixture was stirred at room temperature for 24 hours, filtered and washed three times with ether and finally dried under vacuum at room temperature for 24 hours.
Synthesis of poly (1-cyanomethyl 3-vinylimidazolium bromide) (PCAVImBr): 4g of CMVImBr and 80 mg of AIBN were added to a round-bottomed flask containing 40 mL of DMSO, stirred at 75 ℃ under nitrogen at reflux for 24 hours, the reaction mixture was added dropwise to excess THF (tetrahydrofuran) while cooling to room temperature, the precipitate was filtered and washed with a large amount of ethanol, and finally dried under vacuum at 60 ℃ until use.
Anion exchange: dissolving 10 g of PCAVImBr in 200 mL of deionized water, dropwise adding 100 mL of 13 g of lithium bistrifluoromethanesulfonylimide (LiTFSl) aqueous solution into the PCAVImBr solution, stirring the reaction mixture at room temperature for 2 hours, filtering the precipitate, washing the precipitate with deionized water for three times, and finally drying the precipitate in vacuum at 60 ℃ to obtain poly [ 1-cyanomethyl-3-vinylimidazolium bis (trifluoromethanesulfonyl) imide]（PCMVImTf2N, expressed as PIL).
Preparing a porous polyion liquid adsorbent: adding a certain amount of PCMVImTf2N was dissolved in DMF and stirred to form a homogeneous and transparent solution. 30 mL of ethylene glycol and 5 mL of 25% tetramethylammonium hydroxide solution were added to a beaker and placed in a 25 ℃ ultrasonic (model Sonifier W-450D) bath. 3 mL of PCMVImTf2The N solution was added drop-wise to the tetramethylammonium hydroxide solution with stirring (900 rpm) and sonication (40% sonication amplitude). Adding PCMVImTf2The solution N becomes turbid immediately, and the ultrasound treatment is continued for 5 min after the addition. Centrifuging, collecting, washing with ethanol for 4 times, vacuum drying at 50 deg.C until constant weight to obtain porous PCMVImTf2N (denoted by PILC). Nitrogen adsorption and desorption experiments show that the concentration of the PIL in the DMF is 15wt%, and the pore diameter of the obtained PILC is 59.76 nm. For other cationic polyionic liquids, pore size control can also be achieved according to this procedure.
The results of the pore volume of PILCs modulated by the concentration of PIL in DMF are shown in the following table:
FIG. 1 is a scanning electron micrograph of PILC as nanoscale particles.
FIG. 2 is an infrared spectrum of PILC, 1625 cm-1Is a stretching vibration peak of C = N bond on imidazole ring, 1328 cm-1Is a characteristic peak of S = O bond in anion, 1360--1Is a characteristic peak of C-N bonds in acetonitrile. These characteristic peaks indicate that the preparation of the porous polyionic liquid was successful.
Adsorption experiments
5 mg of PILC was weighed into 50 mL Erlenmeyer flasks containing 20 mL p-nitrophenol (PNP) at various concentrations, and the mixture was shaken by a shaker at 150 rpm. And taking out the mixture after a certain time, and measuring the absorbance of the mixture by using UV-vis to obtain the concentration of the p-nitrophenol residue.
(1) Study of adsorption kinetics
As can be seen from FIG. 3, the equilibrium time for PILC to adsorb PNP is 4h, and the maximum adsorption amount can reach 820.3 mg/g. Under the same adsorption condition, the maximum adsorption quantity of the PIL to the PNP before the regulation is only 87.1 mg/g.
(2) Effect of solution pH on adsorption Capacity
As can be seen from fig. 4, the adsorption of PNP by PILC is best under neutral conditions.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of porous polyion liquid comprises the following steps:
under the action of tetraalkylammonium hydroxide, the cationic polyion liquid is self-assembled in a solvent to form the porous polyion liquid.
2. The method of claim 1, wherein: the cationic polyionic liquid is imidazole polyionic liquid.
3. The method of claim 2, wherein: the imidazole polyionic liquid has the following chemical structure:
wherein R is alkyl or cyanoalkyl, A-Is Cl-、Br-、I-、BF4 -、PF6 -、NO3 -、R’SO4 -、CF3SO3 -、PhSO3 -、Tf2N-、(CF3)2N-、(CN)2N-R' is an alkyl group having 1 to 8 carbon atoms, and the cyanoalkyl group has 2 to 9 carbon atoms。
4. The method of claim 1, wherein: the tetraalkylammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide.
5. The method of claim 1, wherein: the concentration of the tetraalkylammonium hydroxide in the system is 1 to 10wt%, preferably, the concentration of the tetraalkylammonium hydroxide is 2 to 5 wt%.
6. The method of claim 1, wherein: the specific operation process comprises the following steps:
(1) dissolving cationic polyion liquid to obtain solution A;
(2) dissolving tetraalkylammonium hydroxide to obtain a solution B;
(3) and (3) dropping the solution A into the solution B under stirring, and carrying out self-assembly to obtain the porous polyion liquid.
7. The method of claim 6, wherein: the cationic polyion liquid is poly [ 1-cyanomethyl-3-vinyl imidazole bis (trifluoromethanesulfonyl) imide ];
preferably, the cationic polyionic liquid is dissolved with N, N-dimethyl imide and the tetraalkylammonium hydroxide is dissolved with ethylene glycol.
8. The method of claim 7, wherein: the preparation process of the poly [ 1-cyanomethyl-3-vinylimidazole bis (trifluoromethanesulfonyl) imide ] comprises the following steps:
synthesis of 1-cyanomethyl-3-vinylimidazole ammonium bromide monomer: reacting 1-vinyl imidazole and bromoacetonitrile in an acetone solvent to obtain 1-cyanomethyl-3-vinyl imidazole ammonium bromide;
synthesis of poly (1-cyanomethyl 3-vinylimidazole ammonium bromide): dissolving 1-cyanomethyl-3-vinyl imidazole ammonium bromide in a dimethyl sulfoxide solvent, and performing reflux reaction under the action of an initiator to obtain poly (1-cyanomethyl-3-vinyl imidazole ammonium bromide);
anion exchange: dissolving poly (1-cyanomethyl-3-vinylimidazole ammonium bromide) in water, adding lithium bistrifluoromethanesulfonylimide, and reacting to obtain poly [ 1-cyanomethyl-3-vinylimidazole bis (trifluoromethanesulfonyl) imide ];
preferably, the molar ratio of the 1-vinyl imidazole to the bromoacetonitrile is 1:1, and the reaction is carried out at room temperature;
preferably, the initiator is azobisisobutyronitrile, the amount of the initiator is 1-3% of the mass of the monomer, and the temperature of the reflux reaction is 70-80 ℃;
preferably, the amount of the lithium bistrifluoromethanesulfonimide salt is 1.2-1.5 times of the mass of the poly (1-cyanomethyl 3-vinylimidazole ammonium bromide), and the reaction is carried out at room temperature.
9. The porous polyion liquid prepared by the method of any one of claims 1 to 8.
10. Use of the porous polyionic liquid as an adsorbent in the treatment of wastewater containing phenolic pollutants as claimed in claim 9; preferably, the phenolic contaminant is nitrophenol; more preferably, the nitrophenol is p-nitrophenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210097738.9A CN114456295B (en) | 2022-01-27 | 2022-01-27 | Preparation method of porous polyion liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210097738.9A CN114456295B (en) | 2022-01-27 | 2022-01-27 | Preparation method of porous polyion liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114456295A true CN114456295A (en) | 2022-05-10 |
| CN114456295B CN114456295B (en) | 2023-11-24 |
Family
ID=81411304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210097738.9A Active CN114456295B (en) | 2022-01-27 | 2022-01-27 | Preparation method of porous polyion liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114456295B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716597A (en) * | 2022-05-18 | 2022-07-08 | 河北科技大学 | Solid ionic organic porous polymer and preparation method and application thereof |
| CN115193418A (en) * | 2022-07-26 | 2022-10-18 | 西北师范大学 | Preparation method of polyion liquid/attapulgite hybrid material and application of polyion liquid/attapulgite hybrid material in adsorption of p-nitrophenol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090266230A1 (en) * | 2004-08-05 | 2009-10-29 | Maciej Radosz | Poly(ionic liquid)s as new materials for co2 separation and other applications |
| CN105542048A (en) * | 2015-11-16 | 2016-05-04 | 浙江理工大学 | Polymeric ionic liquids ordered structure and preparation method thereof |
| CN109400771A (en) * | 2018-10-26 | 2019-03-01 | 绍兴文理学院 | The preparation method and applications of super cross-linked porous poly ion liquid material |
| CN110078702A (en) * | 2019-05-30 | 2019-08-02 | 中国科学院过程工程研究所 | A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate |
-
2022
- 2022-01-27 CN CN202210097738.9A patent/CN114456295B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090266230A1 (en) * | 2004-08-05 | 2009-10-29 | Maciej Radosz | Poly(ionic liquid)s as new materials for co2 separation and other applications |
| CN105542048A (en) * | 2015-11-16 | 2016-05-04 | 浙江理工大学 | Polymeric ionic liquids ordered structure and preparation method thereof |
| CN109400771A (en) * | 2018-10-26 | 2019-03-01 | 绍兴文理学院 | The preparation method and applications of super cross-linked porous poly ion liquid material |
| CN110078702A (en) * | 2019-05-30 | 2019-08-02 | 中国科学院过程工程研究所 | A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716597A (en) * | 2022-05-18 | 2022-07-08 | 河北科技大学 | Solid ionic organic porous polymer and preparation method and application thereof |
| CN114716597B (en) * | 2022-05-18 | 2023-04-11 | 河北科技大学 | Solid ionic organic porous polymer and preparation method and application thereof |
| CN115193418A (en) * | 2022-07-26 | 2022-10-18 | 西北师范大学 | Preparation method of polyion liquid/attapulgite hybrid material and application of polyion liquid/attapulgite hybrid material in adsorption of p-nitrophenol |
| CN115193418B (en) * | 2022-07-26 | 2023-09-26 | 西北师范大学 | Preparation method of polyion liquid/attapulgite hybrid material and application of polyion liquid/attapulgite hybrid material in adsorption of p-nitrophenol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114456295B (en) | 2023-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114456295A (en) | Preparation method of porous polyion liquid | |
| US20210171665A1 (en) | Porous polymeric cellulose prepared via cellulose crosslinking | |
| Ahmad et al. | Underwater suspended bifunctionalized polyethyleneimine-based sponge for selective removal of anionic pollutants from aqueous solution | |
| Wei et al. | Bidirectionally pH-responsive zwitterionic polymer hydrogels with switchable selective adsorption capacities for anionic and cationic dyes | |
| Wang et al. | Cellulose-based porous adsorbents with high capacity for methylene blue adsorption from aqueous solutions | |
| Lu et al. | Diallyl dimethyl ammonium chloride-grafted cellulose filter membrane via ATRP for selective removal of anionic dye | |
| İsmail et al. | Absorption and adsorption studies of polyacrylamide/sodium alginate hydrogels | |
| CN108905653B (en) | Preparation method and application of hyperbranched zwitterion modified polyvinylidene fluoride oil-water emulsion separation membrane | |
| EP3630352A1 (en) | A polymeric sorbent, preparation and use thereof | |
| Rabipour et al. | pH-sensitive nanocomposite hydrogels based on poly (vinyl alcohol) macromonomer and graphene oxide for removal of cationic dyes from aqueous solutions | |
| Bayat et al. | Electrospun chitosan/polyvinyl alcohol nanocomposite holding polyaniline/silica hybrid nanostructures: An efficient adsorbent of dye from aqueous solutions | |
| Dou et al. | Multifunctional Ag/AgCl decorated CO2-responsive cotton membranes with photo-induced self-cleaning property for efficient bidirectional oil/water separation and dyes removal | |
| CN109317115A (en) | By filtering the degerming from drinking water | |
| Li et al. | Preparation of an ionic liquid-based hydrogel with hyperbranched topology for efficient removal of Cr (VI) | |
| Ray et al. | Peptide-based surface modified silica particles: adsorption materials for dye-loaded wastewater treatment | |
| CN103962110A (en) | Multifunctional Fe3O4 magnetic nanometer material, as well as preparation method and application thereof | |
| Cao et al. | Synthesis of a perfluorooctanoic acid molecularly imprinted polymer for the selective removal of perfluorooctanoic acid in an aqueous environment | |
| CN111410723A (en) | Porous boron affinity imprinted polymer and preparation method and application thereof | |
| CN110327888B (en) | Difunctional sulfhydryl Schiff base metal organogel-nanocomposite material and preparation method and application thereof | |
| Zhang et al. | Tough poly (L-DOPA)-containing double network hydrogel beads with high capacity of dye adsorption | |
| Wang et al. | Preparation of inverse opal adsorbent by water-soluble colloidal crystal template to obtain ultrahigh adsorption capacity for salicylic acid removal from aqueous solution | |
| CN113122938B (en) | Preparation method and application of MOFs-containing chitosan/polyvinyl alcohol nanofiber membrane | |
| Almasian et al. | Grafting of polyamidoamine dendrimer on polyacrylonitrile nanofiber surface: synthesis and optimization of anionic dye removal process by response surface methodology method | |
| Sun | Molecularly imprinted polymer for 2, 4-dichlorophenoxyacetic acid prepared by a sol-gel method | |
| Singh et al. | Chitosan–poly (vinyl alcohol)–ionic liquid-grafted hydrogel for treating wastewater |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240221 Address after: 467000 north of middle section of Shahe Second Road, nylon industry cluster area, Gongdian Town, Ye County, Pingdingshan City, Henan Province Patentee after: Pingdingshan Deyuan Fine Chemicals Co.,Ltd. Country or region after: China Address before: 730050 no.967, Anning East Road, Anning District, Lanzhou City, Gansu Province Patentee before: Northwest Normal University Country or region before: China Patentee before: Baiyin division Innovation Research Institute of Northwest Normal University |