CN109400771B - Preparation method and application of super-crosslinked porous polyion liquid material - Google Patents
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Abstract
The invention provides a method for preparing a super-crosslinked porous polyion liquid material by ionic thermal crosslinking and application thereof. The method has the advantages that: (1) the yield is high and is 94-99%; (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.
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 the organic polyacid are subjected to ionic crosslinking to form the porous polyion liquid composite material, and the structure and the appearance of the material pore can be regulated and controlled by regulating the structure and the synthesis process of the carboxylic acid, so that the polyion liquid composite material can be successfully applied to 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 chains are fully swelled, after the solvent is volatilized, the polymer chains tend 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, polyionic chain polesThe performance is high, the polarity is continuously increased along with the reaction, and the solvent is easily precipitated and separated out too early to form a closely-packed non-porous structure. In order to solve the problems, alkenyl tertiary amine and allyl halide or styrene benzyl halide are polymerized to form a rigid diene ionic liquid monomer, proper complex anions are introduced through ion exchange, then, ionothermal polymerization is carried out in a zinc chloride/sodium chloride composite molten salt system to obtain a super-crosslinked porous polyion liquid material, a high-swelling rigid super-crosslinked polyion liquid network is guaranteed to be formed by utilizing strong electrostatic coulombic action between the ionic liquid center and molten salt and the ionothermal strengthening condition, and the structural performance of the material is adjusted through the complex 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 invention provides a preparation method of a hypercrosslinked porous polyion liquid material, which comprises the steps of polymerizing alkenyl tertiary amine and one of bromopropyl bromide, allyl chloride, 2-vinylbenzyl chloride, 4-vinylbenzyl chloride and 4-vinylbenzyl bromide to form a rigid diene ionic liquid monomer, introducing a complex anion through ion exchange, and then carrying out ionothermal polymerization in a zinc chloride/sodium chloride composite molten salt system to obtain the hypercrosslinked porous polyion liquid material.
Preferably, the alkenyl tertiary amine is one of 4-vinylpyridine, 2-vinylimidazole and triallylamine.
Preferably, the molten salt is zinc chloride/sodium chloride composite molten salt, can form a strong electrostatic coulomb effect with the polyion network, well swells the cross-linked polyion liquid network to form cross-linked polyion liquid gel, and the mass ratio of zinc chloride to sodium chloride in the molten salt is 100: 5-30.
Preferably, halogen ions are exchanged into tetrafluoroborate, hexafluorophosphate, dicyanamide, trifluoromethanesulfonate and bistrifluoromethanesulfonimide ions through ion exchange, corresponding complex anions are adjusted, and the specific surface and hydrophilicity and hydrophobicity of the super-crosslinked polyion liquid material are 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 and one of bromopropyl bromide, allyl chloride, 2-vinyl benzyl chloride, 4-vinyl benzyl chloride and 4-vinyl benzyl bromide to prepare a 40% solution, adding a polymerization inhibitor with the dosage of 1% of the total mass, stirring and reacting for 5-48 h at 55-85 ℃, washing for 3 times by ethyl acetate and diethyl ether in sequence, vacuum drying at 60 deg.c to obtain rigid diene ionic liquid monomer, dissolving the rigid diene ionic liquid monomer in organic solvent, preparing a solution with the mass ratio concentration of 10-50%, adding the solution into a salt containing complex anions for exchange, wherein the molar amount of the salt is 1.5 times of that of a monomer, heating and stirring at 25-80 ℃, adding 1% of 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 previous step and zinc chloride/sodium chloride composite salt with the mass ratio of 100: 5-30, grinding in a glove box for more than 30min, controlling the mass percentage of the monomer to the molten salt to be 1: 5-40, 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 requirements of practical application, the corresponding complex anions are introduced, so that the application in the aspects of catalysis, gas adsorption, wastewater treatment, separation and the like can be performed; the material can be filtered and recycled and can be reused.
Compared with the background art, the invention has the advantages that: (1) the yield is high and is 94-99%; (2) the specific surface area of the prepared material is large and is more than 200m 2/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
A preparation method of a hypercrosslinked porous polyion liquid material comprises the following specific steps:
step one, preparing a rigid diene ionic liquid monomer;
weighing 2-vinylimidazole and 4-chloromethyl styrene, mixing according to the mass ratio of 1: 1, adding a polymerization inhibitor, wherein the dosage of the polymerization inhibitor is 1 percent of the total mass, adding tetrahydrofuran, preparing into a 40 percent solution, stirring for 48 hours at 60 ℃ to obtain corresponding ionic liquid, washing for 3 times by using ethyl acetate, diethyl ether and petroleum ether in sequence, and then drying in vacuum at 60 ℃ to obtain a rigid diene ionic liquid monomer;
dissolving a rigid diene ionic liquid monomer in acetone, adding potassium hexafluorophosphate for exchange, heating and stirring at 60 ℃ until the molar amount of salt is 1.5 times that of the monomer, adding 1% of polymerization inhibitor, filtering to remove corresponding salt after exchange, repeating the exchange for 3 times, and removing the solvent under reduced pressure to obtain the rigid diene ionic liquid monomer of hexafluorophosphate radical complex anion;
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: 10, grinding and mixing the zinc chloride/sodium 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 1:25, adding an initiator ammonium peroxysulfate, and using the amount of the initiator ammonium peroxysulfate1% of ionic liquid monomer, evenly mixing, transferring into a tubular muffle furnace, heating and polymerizing at 230 ℃ for 24h under the protection of nitrogen, cooling to room temperature, adding the gel product into 10% diluted hydrochloric acid, heating and refluxing, removing 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 with the specific surface area of 326m2/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 7
The same procedure as in example 1 was repeated except that allyl halides or styrylbenzyl halides shown in Table 2 were used.
TABLE 2
Examples 8 to 12
The same as in example 1 except for the following differences, the complex anions shown in Table 3 were used.
TABLE 3
Examples 13 to 15
The mass percentages of the monomers and the molten salt shown in Table 4 were used as in example 1 except for the following.
TABLE 4
Example 16
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 17
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 28 mg/g.
Example 18
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 (5)
1. A preparation method of a super-crosslinked porous polyion liquid material is characterized by comprising the following steps: polymerizing alkenyl tertiary amine and one of allyl bromide, allyl chloride, 2-vinyl benzyl chloride, 4-vinyl benzyl chloride and 4-vinyl benzyl bromide to form a rigid diene ionic liquid monomer, introducing a complex anion through ion exchange, and then performing ionothermal polymerization in a zinc chloride/sodium chloride composite molten salt system 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: the molten salt is zinc chloride/sodium chloride composite molten salt, wherein the mass ratio of zinc chloride to sodium chloride is 100: 15-40.
4. The preparation method of the hypercrosslinked porous polyion liquid material as claimed in claim 1, wherein: halogen ions are exchanged into tetrafluoroborate, hexafluorophosphate, dicyanamide, trifluoromethanesulfonate and bistrifluoromethylsulfonimide ions through ion exchange.
5. The preparation method of the hypercrosslinked porous polyion liquid material as claimed in any one of claims 1-4, 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 and one of bromopropyl bromide, allyl chloride, 2-vinyl benzyl chloride, 4-vinyl benzyl chloride and 4-vinyl benzyl bromide to prepare a 40% solution, adding a polymerization inhibitor with the dosage of 1% of the total mass, stirring and reacting for 5-48 h at 55-85 ℃, washing for 3 times by ethyl acetate and diethyl ether in sequence, vacuum drying at 60 deg.c to obtain rigid diene ionic liquid monomer, dissolving the rigid diene ionic liquid monomer in organic solvent, preparing a solution with the mass ratio concentration of 10-50%, adding the solution into a salt containing complex anions for exchange, wherein the molar amount of the salt is 1.5 times of that of a monomer, heating and stirring at 25-80 ℃, adding 1% of 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 previous step and zinc chloride/sodium chloride composite salt with the mass ratio of 100: 5-30, grinding in a glove box for more than 30min, controlling the mass percentage of the monomer to the molten salt to be 1: 5-40, 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.
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| CN109400923B (en) * | 2018-10-26 | 2021-05-14 | 绍兴文理学院 | Preparation method and application of super-crosslinked porous polyion liquid material |
| CN109400922B (en) * | 2018-10-26 | 2021-05-14 | 绍兴文理学院 | Preparation method and application of super-crosslinked porous polyion liquid material |
| CN113144816A (en) * | 2021-03-12 | 2021-07-23 | 华侨大学 | Metal complex ion functionalized polyion liquid and preparation method and application thereof |
| CN114426680B (en) * | 2021-12-07 | 2024-03-22 | 北京东方雨虹防水技术股份有限公司 | Thermal response polyionic liquid hydrogel for desalting brine |
| CN114456295B (en) * | 2022-01-27 | 2023-11-24 | 西北师范大学 | Preparation method of porous polyion liquid |
| 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 |
| CN115715926B (en) * | 2022-11-30 | 2023-09-26 | 烟台盛泽环保科技有限公司 | Novel high-performance porous polyion liquid filler and preparation method and application thereof |
| CN116284524A (en) * | 2023-01-10 | 2023-06-23 | 合肥学院 | Super-crosslinked porous polyionic liquid with high ionic liquid content, preparation method and application |
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| CN101723852A (en) * | 2008-10-20 | 2010-06-09 | 浙江医药股份有限公司新昌制药厂 | Novel method for condensing aromatic aldehydes and active methylene compounds through catalysis of functional ionic liquid |
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