CN109400781B - Preparation method and application of super-crosslinked porous polyion liquid material - Google Patents
Preparation method and application of super-crosslinked porous polyion liquid material Download PDFInfo
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- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 43
- 239000011344 liquid material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 38
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- -1 alkenyl tertiary amine Chemical class 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 24
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 150000001993 dienes Chemical class 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 9
- 239000011592 zinc chloride Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical compound C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 claims description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013315 hypercross-linked polymer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
- C08F126/02—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 single or double bond to nitrogen
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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Abstract
The invention provides a method for preparing a super-crosslinked porous polyion liquid material by ionothermal polymerization and application thereof. The invention has the advantages that: (1) the yield is high and is 92-97%; (2) the specific surface area of the prepared material is large and is 200m2More than g; (3) the material has a full ionic liquid framework and high active component content; (4) the preparation process is simple and convenient, and the raw materials are easy to obtain; (5) the material has wide application, can effectively adjust the material structure by adjusting the raw materials, the complex anions and the polymerization conditions, and can be used for catalysisGas adsorption, wastewater treatment, separation and other fields; (6) the material is easy to recycle and can be recycled by filtration.
Description
Technical Field
The invention relates to a preparation method and application of a super-crosslinked porous polyion liquid material, belonging to the technical field of high polymer chemical synthesis.
Background
The ionic liquid has excellent performance and wide application, but has the defects of difficult recovery, high price, high viscosity, poor degradation, incapability of forming and the like. The immobilization can better solve the problems, but the traditional loading method grafts the large-volume ionic liquid on the carrier, which is easy to cause pore channel blockage and has low loading capacity. The porous polyion liquid combines the specific performance of the ionic liquid and the advantages of polymer processability, stability, durability, adjustable structure and the like, and is widely applied to the fields of catalysis, adsorption separation, electrochemistry and the like.
Porous polyionic liquids, particularly pure polyionic liquid skeleton porous materials, are less researched, and the most common synthetic method is composite copolymerization. Han Buxing topic group [ Y.Xie, Angew.chem.int.Ed.2007,46:7255]The vinyl imidazole ionic liquid and divinylbenzene are copolymerized to prepare the cross-linked polymeric material with better catalytic performance than the ionic liquid and the self-polymerization thereof. Subject group of Xiaofengshou (F. Liu, J. Am. chem. Soc.2012,134: 16948)]By adopting the copolymerization, quaternization and ion exchange of the vinylimidazole and the divinylbenzene, the synthetic material has better sulfuric acid activity for the preparation of the biodiesel. However, the pore channel of the copolymerization material is derived from polydivinylbenzene, ionic liquid is grafted on a polymer chain, and a nonionic liquid framework still belongs to a load type. Yuan et al [ Q.ZHao, adv.Mater.2015,27:2913]The polyion liquid and organic polyacid are subjected to ion crosslinking to form the porous polyion liquid composite material, and the carboxylic acid structure are adjustedThe synthesis process can regulate and control the pore structure and morphology of the material, and the material can be successfully used for CO2Adsorption, catalysis, high-sensitivity sensors, etc. However, the material is a polyion liquid compound, the ion crosslinking stability is unknown, and the ion exchange capacity is not available. The direct polymerization of the monomer is the simplest method for synthesizing the porous polyion liquid material, but because the polarity of the ionic liquid monomer is higher, the polarity among chains is enhanced along with the growth of a polymerization chain in the polymerization process, and the precipitation is easy to separate out, so that the key of the preparation of the hypercrosslinked polyion liquid is to form a hypercrosslinked polymerization network with high swelling rigidity. The hypercrosslinked polymer network is formed under the action of strong solvation, so that the polymer chain is fully swelled, after the solvent is volatilized, the polymer chain tends to shrink and tightly stack, the surface energy is reduced, but the rigid hypercrosslinked structure limits the conformational transformation and prevents shrinkage, and the original solvent occupies space to form a pore structure]. Unlike neutral polymers, polyion chains have large polarity, which is continuously increased along with the reaction, and are easily precipitated out from a solvent too early to form a closely-packed non-porous structure. In order to solve the problems, the invention quaternizes alkenyl tertiary amine and thionyl chloride to form a symmetrical rigid diene ionic liquid monomer, selects low-melting-point zinc chloride/potassium chloride composite molten salt as a reaction medium, utilizes the strong electrostatic coulombic effect between the ionic monomer and the molten salt and ionic heat strengthening conditions to ensure the formation of a high-swelling rigid super-crosslinked polyion liquid network, and regulates the solubility of the ionic liquid monomer and the swelling condition of the polymeric network by matching anions to prepare the super-crosslinked porous polyion liquid.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide a preparation method of a hypercrosslinked porous polyion liquid material.
In order to achieve the purpose, the preparation method of the hypercrosslinked porous polyion liquid material provided by the invention comprises the steps of carrying out quaternization on alkenyl tertiary amine and thionyl chloride to form a rigid diene ionic liquid monomer, introducing a proper complex anion through ion exchange, and then carrying out ionothermal polymerization in a zinc chloride/potassium chloride composite molten salt system to obtain the hypercrosslinked porous polyion liquid material.
The molar ratio of the thionyl chloride to the alkenyl tertiary amine is 1:2, so that the alkenyl tertiary amine is respectively connected to two sides of the sulfoxide to form the rigid diene ionic liquid monomer.
The molten salt is zinc chloride/potassium chloride composite molten salt, and has strong electrostatic coulombic effect with ionic liquid monomers, so that a cross-linked polyion liquid network can be well swelled to form cross-linked polyion liquid gel, and the mass ratio of zinc chloride to potassium chloride in the molten salt is 100: 3-35.
Preferably, the alkenyl tertiary amine is one of 4-vinylpyridine, 2-vinylimidazole and triallylamine.
Preferably, halogen ions can be exchanged into one of tetrafluoroborate, hexafluorophosphate, dicyanamide, trifluoromethanesulfonate and bistrifluoromethanesulfonimide ions through ion exchange, corresponding complex anions are adjusted, the swelling degree of ionic liquid monomers and a cross-linked polymerization network is changed, and the specific surface of the super-crosslinked polyionic liquid material is adjusted.
The preparation method of the super-crosslinked porous polyion liquid material comprises the following specific operation steps:
step one, preparing a rigid diene ionic liquid monomer;
adding ethyl acetate or tetrahydrofuran into alkenyl tertiary amine to prepare a 40% solution, then cooling in an ice-water bath, adding a polymerization inhibitor, wherein the dosage of the polymerization inhibitor is 1% of the total mass, stirring at the temperature below 5 ℃, slowly dropwise adding thionyl chloride, the dosage of which is half of that of the alkenyl amine substance, dropwise adding the thionyl chloride after about 60min, after dropwise adding, automatically heating to room temperature for reacting for 1-6 h, continuously heating to 60 ℃ for reacting for 5-24 h, sequentially washing with ethyl acetate and diethyl ether for 3 times, then carrying out vacuum drying at 60 ℃ to obtain a rigid diene ionic liquid monomer, dissolving the rigid diene ionic liquid monomer in an organic solvent, wherein the mass ratio of the monomer to the solvent is 1: 20-50, adding a complex anion salt for exchange, the molar dosage of the salt is 1.5 times of the monomer, heating and stirring at 25-80 ℃, and adding 1% of the polymerization inhibitor, filtering to remove corresponding salt after exchange, repeating the exchange for 3 times, and removing the solvent under reduced pressure to obtain a rigid diene ionic liquid monomer with corresponding complex anions;
step two, preparing a porous polyion liquid material;
grinding and mixing the ionic liquid monomer prepared in the first step and zinc chloride/potassium chloride composite salt with the mass ratio of 100: 3-35, grinding in a glove box for more than 30min, controlling the mass percentage of the monomer to the molten salt to be 1: 5-35, adding an initiator ammonium peroxysulfate with the amount of 1% of the ionic liquid monomer, uniformly mixing, transferring into a tubular muffle furnace, heating and polymerizing at 200-320 ℃ for 16-72 h under the protection of nitrogen, cooling to room temperature, adding a gel product into 10% diluted hydrochloric acid, heating and refluxing, removing the molten salt, washing the obtained polyionic liquid with ethyl acetate and ether for 3 times in sequence, and drying in an oven at 80 ℃ for 12h to obtain the porous polyionic liquid material.
According to the application of the super-crosslinked porous polyion liquid material, corresponding complex anions are introduced according to the requirements of practical application, the application in the aspects of catalysis, gas adsorption and wastewater treatment is carried out, and the material can be reused after being filtered and recovered.
Compared with the background art, the invention has the advantages that: (1) the yield is high and is 92-97%; (2) the specific surface area of the prepared material is large and is 200m2More than g; (3) the material has a full ionic liquid framework and high active component content; (4) the preparation process is simple and convenient, and the raw materials are easy to obtain; (5) the material has wide application, can effectively adjust the structure of the material by adjusting the raw material, the complex anion and the polymerization condition, and can be used in the fields of catalysis, gas adsorption, wastewater treatment, separation and the like; (6) the material is easy to recycle and can be recycled by filtration.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The preparation method of the super-crosslinked porous polyion liquid material provided by the embodiment comprises the following specific operation steps:
step one, preparing a rigid diene ionic liquid monomer;
adding ethyl acetate into 1-vinylimidazole to prepare 40 percentCooling the solution in an ice-water bath, adding a polymerization inhibitor, wherein the amount of the polymerization inhibitor is 1 percent of the total mass, stirring at the temperature of below 5 ℃, slowly dropwise adding thionyl chloride, the amount of which is half of that of the vinyl imidazole substance, dropwise adding the polymerization inhibitor after about 60min, automatically heating the solution to room temperature after the dropwise adding is finished, reacting for 2h, continuously heating the solution to the temperature of 60 ℃, reacting for 4h, washing the solution for 3 times by using ethyl acetate and ethyl ether in sequence, performing vacuum drying at the temperature of 60 ℃ to obtain a rigid diene ionic liquid monomer, dissolving the rigid diene ionic liquid monomer in a certain acetone solvent, adding the solution containing potassium hexafluorophosphate for exchange, wherein the molar amount of salt is 1.5 times that of the monomer, heating and stirring at the temperature of 40 ℃, adding 1 percent of the polymerization inhibitor, filtering and removing corresponding salt after the exchange, repeatedly exchanging for 3 times, and removing the solvent under reduced pressure to obtain corresponding PF6 -The rigid diene ionic liquid monomer;
step two, preparing a porous polyion liquid material;
mixing the ionic liquid monomer prepared in the first step with the ionic liquid monomer prepared in the first step in a mass ratio of 100: 25, grinding and mixing the zinc chloride/potassium chloride composite salt, grinding the mixture in a glove box for more than 30min, controlling the mass percentage of the monomer to the molten salt to be 1:20, adding an initiator ammonium peroxysulfate, wherein the dosage of the ammonium peroxysulfate is 1% of that of the ionic liquid monomer, uniformly mixing, transferring the mixture into a tubular muffle furnace, heating and polymerizing the mixture at 260 ℃ for 48h under the protection of nitrogen, cooling the mixture to room temperature, adding a gel product into 10% diluted hydrochloric acid, heating and refluxing the mixture, removing the molten salt, washing the obtained polyion liquid for 3 times by ethyl acetate and diethyl ether in sequence, and drying the polyion liquid in an oven at 80 ℃ for 12h to obtain the porous polyion liquid material, wherein the specific surface area of the porous polyi2/g。
Examples 2 to 4
The tertiary amine compounds shown in Table 1 were used in the same manner as in example 1 except for the following differences.
TABLE 1
Examples 5 to 9
The same as in example 1 except for the following differences, the complex anions shown in Table 2 were used.
TABLE 2
Examples 10 to 12
The mass percentages of the monomers and the molten salt shown in Table 3 were used as in example 1 except for the following.
TABLE 3
Example 13
The super-crosslinked polyion liquid material of example 11 is used for catalyzing the brain text reaction of benzaldehyde and ethyl cyanoacetate. Mixing benzaldehyde and ethyl cyanoacetate according to a molar ratio of 1: 1.5, adding 1 percent of catalyst by mass, heating and stirring for 4 hours at 70 ℃, and determining the yield to 99 percent by GC. The catalyst is filtered, recovered, washed and dried, and reused for 8 times, and the catalytic activity is unchanged.
Example 14
The hypercrosslinked polyionic liquid material of example 1 was used for adsorption of carbon dioxide. A certain amount of the super-crosslinked polyion liquid material is taken, after vacuum pumping, carbon dioxide gas is introduced to the atmosphere, and then after nitrogen purging, GC measures the adsorption quantity of the carbon dioxide on line. The result shows that the material has good performance for adsorbing carbon dioxide, and the adsorption amount is up to 30 mg/g.
Example 15
The super-crosslinked polyion liquid material of example 10 was used for methyl orange dye wastewater treatment. Adding 3% of super-crosslinked polymeric ionic liquid adsorbent into wastewater with methyl orange content of 40mg/L, stirring at room temperature for 30min, and testing with an ultraviolet spectrophotometer to obtain colorless transparent aqueous solution with methyl orange removal rate of 99%. After ethanol washing is carried out for a plurality of times, the adsorbent can be recycled.
The above is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art of polymer chemical synthesis technology, several modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A preparation method of a super-crosslinked porous polyion liquid material is characterized by comprising the following steps: quaternizing alkenyl tertiary amine and thionyl chloride, wherein the molar ratio of the thionyl chloride to the alkenyl tertiary amine is 1:2, forming a rigid diene ionic liquid monomer, introducing complex anions through ion exchange, and then performing ionothermal polymerization in a zinc chloride/potassium chloride composite molten salt system, wherein the mass ratio of zinc chloride to potassium chloride in the molten salt is 100: 3-35, so as to obtain the super-crosslinked porous polyionic liquid material.
2. The preparation method of the hypercrosslinked porous polyion liquid material as claimed in claim 1, wherein: the alkenyl tertiary amine is one of 4-vinylpyridine, 2-vinylimidazole and triallylamine.
3. The preparation method of the hypercrosslinked porous polyion liquid material as claimed in claim 1, wherein: and exchanging halogen ions into one of tetrafluoroborate, hexafluorophosphate, dicyanamide, trifluoromethanesulfonate and bistrifluoromethanesulfonimide ions through ion exchange.
4. The preparation method of the hypercrosslinked porous polyion liquid material as claimed in any one of claims 1-3, characterized by comprising the following specific steps:
step one, preparing a rigid diene ionic liquid monomer;
adding ethyl acetate or tetrahydrofuran into alkenyl tertiary amine to prepare a 40% solution, then cooling in an ice-water bath, adding a polymerization inhibitor, wherein the dosage of the polymerization inhibitor is 1% of the total mass, stirring at the temperature below 5 ℃, slowly dropwise adding thionyl chloride, the dosage of which is half of that of the alkenyl amine substance, dropwise adding the thionyl chloride after about 60min, after dropwise adding, automatically heating to room temperature to react for 1-6 h, continuously heating to 60 ℃ to react for 5-24 h, sequentially washing with ethyl acetate and diethyl ether for 3 times, then carrying out vacuum drying at 60 ℃ to obtain a rigid diene ionic liquid monomer, dissolving the rigid diene ionic liquid monomer in an organic solvent, wherein the mass ratio of the monomer to the solvent is 1: 20-50, adding a complex anion salt to exchange, the molar dosage of the salt is 1.5 times of the monomer, heating and stirring at 25-80 ℃, and adding 1% of the polymerization inhibitor, filtering to remove corresponding salt after exchange, repeating the exchange for 3 times, and removing the solvent under reduced pressure to obtain a rigid diene ionic liquid monomer with corresponding complex anions;
step two, preparing a porous polyion liquid material;
grinding and mixing the ionic liquid monomer prepared in the first step and a composite salt with the mass ratio of zinc chloride to potassium chloride being 100: 3-35, grinding in a glove box for more than 30min, controlling the mass percentage of the monomer to the molten salt to be 1: 5-35, adding an initiator ammonium peroxysulfate with the amount being 1% of that of the ionic liquid monomer, uniformly mixing, transferring into a tubular muffle furnace, heating and polymerizing at 200-320 ℃ for 16-72 h under the protection of nitrogen, cooling to room temperature, adding a gel product into 10% diluted hydrochloric acid, heating and refluxing to remove the molten salt, washing the obtained polyionic liquid with ethyl acetate and diethyl ether for 3 times in sequence, and drying in an oven at 80 ℃ for 12h to obtain the porous polyionic liquid material.
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