CN114570337B - High-water-vapor-adsorption ionic liquid adsorbent and synthesis method and application thereof - Google Patents
High-water-vapor-adsorption ionic liquid adsorbent and synthesis method and application thereof Download PDFInfo
- Publication number
- CN114570337B CN114570337B CN202011402656.8A CN202011402656A CN114570337B CN 114570337 B CN114570337 B CN 114570337B CN 202011402656 A CN202011402656 A CN 202011402656A CN 114570337 B CN114570337 B CN 114570337B
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- vinyl
- methylimidazolium
- polymerization
- polyacetated
- 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.)
- Active
Links
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 61
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 37
- 239000003463 adsorbent Substances 0.000 title claims abstract description 19
- 238000001308 synthesis method Methods 0.000 title claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 7
- -1 acetic acid anions Chemical class 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- VPNMTSAIINVZTK-UHFFFAOYSA-N 1-ethenyl-3-methylimidazol-3-ium Chemical class C[N+]=1C=CN(C=C)C=1 VPNMTSAIINVZTK-UHFFFAOYSA-N 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 26
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 8
- WLWHLUQQCLCFNE-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole Chemical class CN1CN(C=C)C=C1 WLWHLUQQCLCFNE-UHFFFAOYSA-N 0.000 claims description 7
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 238000012719 thermal polymerization Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005956 quaternization reaction Methods 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 12
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 238000005338 heat storage Methods 0.000 abstract description 5
- 238000010612 desalination reaction Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000013535 sea water Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007791 dehumidification Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- USISIIYRINWYCM-UHFFFAOYSA-M 1-ethenyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CN1C=C[N+](C=C)=C1 USISIIYRINWYCM-UHFFFAOYSA-M 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QARDSQYLYGISQN-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole;hydrochloride Chemical compound [Cl-].CN1C[NH+](C=C)C=C1 QARDSQYLYGISQN-UHFFFAOYSA-N 0.000 description 1
- UHKIGXVNMXYBOP-UHFFFAOYSA-M 1-ethenyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].C[N+]=1C=CN(C=C)C=1 UHKIGXVNMXYBOP-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/26—Drying gases or vapours
- B01D53/261—Drying gases or vapours by adsorption
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种高水蒸气吸附聚离子液体吸附剂合成方法，属于吸附科学与技术领域。The invention relates to a method for synthesizing a high water vapor adsorption polyionic liquid adsorbent, which belongs to the field of adsorption science and technology.
背景技术Background technique
水蒸气吸附是干燥、海水淡化、吸附储热等领域的重要问题，开发具有高水蒸气吸附能力的吸附剂成为这些领域的主要目标。硅胶、分子筛、无机水合盐、金属有机骨架及离子液体等传统吸附剂在某些方面表现出优异的水蒸气吸附储热性能，但是同时存在的固有缺点极大限制了其发展与实际应用，因此亟需新型高效的水蒸气吸附剂体系。Water vapor adsorption is an important issue in the fields of drying, seawater desalination, and heat storage by adsorption, and the development of adsorbents with high water vapor adsorption capacity has become a major goal in these fields. Traditional adsorbents such as silica gel, molecular sieves, inorganic hydrated salts, metal-organic frameworks, and ionic liquids show excellent water vapor adsorption and heat storage performance in some aspects, but their inherent shortcomings greatly limit their development and practical application. New and highly efficient water vapor adsorbent systems are urgently needed.
离子液体是由阴阳离子组成的且在100℃以下呈现熔融状态的有机盐，被媒体认为是“未来最有潜力的新材料”之一。离子液体具有结构可调性，可以引入特定性能的官能团合成含有特定功能的离子液体，同时，无论是亲水性离子液体还是疏水性离子液体，它们中的大部分都具有极强的吸水性，而且离子液体具有良好的热稳定性和环境友好性，离子液体这些优异的物理化学性质有望使其成为理想的水蒸气吸附剂，因此近些年来备受吸附储热研究领域的关注。虽然离子液体具有较高的水蒸气吸附能力，但是其粘度大及与水蒸气接触面小，降低了离子液体体系中的传热传质甚至吸附速率，并且其液体形态容易和其他物质形成混合物而难以分离。Ionic liquids are organic salts composed of anions and cations and in a molten state below 100°C, and are considered by the media to be one of "the most promising new materials in the future". Ionic liquids have adjustable structure, and functional groups with specific properties can be introduced to synthesize ionic liquids with specific functions. Moreover, ionic liquids have good thermal stability and environmental friendliness. These excellent physical and chemical properties of ionic liquids are expected to make them ideal water vapor adsorbents, so they have attracted much attention in the field of adsorption heat storage research in recent years. Although ionic liquids have a high water vapor adsorption capacity, their high viscosity and small contact surface with water vapor reduce the heat and mass transfer and even the adsorption rate in the ionic liquid system, and their liquid form is easy to form a mixture with other substances. Difficult to separate.
聚离子液体是一种由不饱和离子液体单体通过聚合形成的固体聚合物材料，在聚合物电解质、CO2吸附、催化、导电及微波吸收等领域具有重要的应用价值和广泛的应用前景。聚离子液体不仅具有和离子液体相似的化学稳定性、热稳定性、高导电性和结构可调性，同时也表现出聚合物固有的机械稳定性、柔性、及孔隙结构可调节性，能够克服传统离子液体吸附剂水蒸气吸附量低及易泄露的缺点，极有希望应用于发展新型高效水蒸气吸附技术。Polyionic liquid is a solid polymer material formed by polymerization of unsaturated ionic liquid monomers. It has important application value and broad application prospects in the fields of polymer electrolytes, CO2 adsorption, catalysis, electrical conduction, and microwave absorption. Polyionic liquids not only have similar chemical stability, thermal stability, high electrical conductivity, and structural tunability to ionic liquids, but also exhibit inherent mechanical stability, flexibility, and pore structure tunability of polymers, which can overcome The shortcomings of traditional ionic liquid adsorbents, such as low water vapor adsorption capacity and easy leakage, are very promising for the development of new high-efficiency water vapor adsorption technologies.
发明内容Contents of the invention
针对已有技术不足，本发明提供了一种高水蒸气吸附聚离子液体吸附剂合成方法，其目的在于。Aiming at the deficiencies of the prior art, the invention provides a method for synthesizing a high water vapor adsorption polyionic liquid adsorbent, the purpose of which is to.
本发明的技术方案：Technical scheme of the present invention:
一种高水蒸气吸附聚离子液体吸附剂合成方法，主要包括以下步骤：A method for synthesizing a high water vapor adsorption polyionic liquid adsorbent, mainly comprising the following steps:
(1)离子化：以N-乙烯基咪唑和液化一卤甲烷为原料，通过季铵化反应制备卤化1-乙烯基-3-甲基咪唑离子液体，其中N-乙烯基咪唑和液化一卤甲烷的摩尔比为0.80-1，反应温度为50-100℃，反应时间为4小时-12小时；(1) Ionization: Using N-vinylimidazole and liquefied monohalomethane as raw materials, the halogenated 1-vinyl-3-methylimidazole ionic liquid is prepared by quaternization reaction, wherein N-vinylimidazole and liquefied monohalogen The molar ratio of methane is 0.80-1, the reaction temperature is 50-100°C, and the reaction time is 4 hours-12 hours;
(2)离子置换：向卤化1-乙烯基-3-甲基咪唑离子液体中加入乙酸铵，通过离子置换反应获得乙酸化1-乙烯基-3-甲基咪唑离子液体，其中卤化1-乙烯基-3-甲基咪唑离子液体和乙酸铵的摩尔比为0.85-1，反应温度为30-80℃，反应时间为1小时-6小时；(2) Ion replacement: Add ammonium acetate to the halogenated 1-vinyl-3-methylimidazolium ionic liquid, and obtain the acetic acidified 1-vinyl-3-methylimidazolium ionic liquid through ion replacement reaction, in which the halogenated 1-vinyl The molar ratio of base-3-methylimidazolium ionic liquid to ammonium acetate is 0.85-1, the reaction temperature is 30-80°C, and the reaction time is 1 hour-6 hours;
(3)聚合：将乙酸化1-乙烯基-3-甲基咪唑离子液体溶解在二甲基甲酰胺中，并加入偶氮二异丁腈，通过聚合反应将乙酸化1-乙烯基-3-甲基咪唑离子液体合成为聚乙酸化1-乙烯基-3-甲基咪唑离子液体，其中反应体系中二甲基甲酰胺的质量比例在10％-50％之间、偶氮二异丁腈的质量比例在0.5％-2％之间；(3) Polymerization: Dissolve the acetic acidified 1-vinyl-3-methylimidazolium ionic liquid in dimethylformamide, and add azobisisobutyronitrile, and the acetic acidated 1-vinyl-3- - Methylimidazole ionic liquid is synthesized into polyacetated 1-vinyl-3-methylimidazole ionic liquid, wherein the mass ratio of dimethylformamide in the reaction system is between 10%-50%, azobisisobutyl The mass proportion of nitrile is between 0.5%-2%;
(4)产品净化：将步骤(3)所得产物浸泡在乙醇中2-6小时，使得乙醇刚好没过该产物，利用乙醇替换产物中的二甲基甲酰胺和偶氮二异丁腈等杂质，然后进行过滤，将所得固体继续进行上述操作2次，然后将过滤后所得固体在50-100℃干燥4-8小时彻底去除残余的乙醇，得到纯净的聚乙酸化1-乙烯基-3-甲基咪唑离子液体。(4) Product purification: soak the product obtained in step (3) in ethanol for 2-6 hours, so that the ethanol just does not pass through the product, and use ethanol to replace impurities such as dimethylformamide and azobisisobutyronitrile in the product , and then filtered, the obtained solid continued to carry out the above operation twice, and then the filtered solid obtained was dried at 50-100°C for 4-8 hours to completely remove residual ethanol to obtain pure polyacetated 1-vinyl-3- Methylimidazolium Ionic Liquid.
其中，一卤甲烷包括一氯甲烷、一溴甲烷、一碘甲烷中的一种。Wherein, the monohalomethane includes one of monochloromethane, monobromethane and monoiodomethane.
其中，步骤(3)中的聚合反应可利用微波聚合、紫外聚合和热聚合等方式，紫外聚合条件为25℃，紫外有效波长为365nm，功率为6-12W，紫外光强度为200-600mW/cm2，紫外聚合时间为60-240min；微波聚合条件为微波功率为100-400W，微波辐射时间为60-120s，微波辐射程序为启停各5-10s交替进行；热聚合条件为60-100℃加热120-240min。Among them, the polymerization reaction in step (3) can use microwave polymerization, ultraviolet polymerization and thermal polymerization, etc., the ultraviolet polymerization condition is 25 ° C, the effective wavelength of ultraviolet is 365nm, the power is 6-12W, and the intensity of ultraviolet light is 200-600mW/ cm 2 , the UV polymerization time is 60-240min; the microwave polymerization condition is that the microwave power is 100-400W, the microwave radiation time is 60-120s, and the microwave radiation program is alternately started and stopped for 5-10s; the thermal polymerization condition is 60-100 Heating at ℃ for 120-240min.
其中，根据本发明技术方案制备的聚乙酸化1-乙烯基-3-甲基咪唑离子液体中乙酸阴离子和1-乙烯基-3-甲基咪唑阳离子的摩尔比为0.95-1.0，聚乙酸化1-乙烯基-3-甲基咪唑离子液体产物纯度大于90％。Wherein, the molar ratio of acetate anion and 1-vinyl-3-methylimidazolium cation in the polyacetated 1-vinyl-3-methylimidazolium ionic liquid prepared according to the technical scheme of the present invention is 0.95-1.0, and the polyacetated The purity of the 1-vinyl-3-methylimidazolium ionic liquid product is greater than 90%.
本发明的效果和益处是：一种高水蒸气吸附聚离子液体吸附剂合成方法，通过离子化、离子置换、聚合、产品净化四个步骤，实现了具有高水蒸气吸附能力的固体聚离子液体吸附剂的制备。有别于现有的聚离子液体，该聚离子液体单体具有较短的碳链和重复排列的醋酸负离子，具有较高的水蒸气吸附能力，可以广泛应用于干燥、除湿、吸附储热、吸附法海水淡化及污水处理等领域。该聚离子液体吸附剂作为一种多孔固体，克服了离子液体易泄露、易污染、易流动等缺点，适宜于大规模工业化应用。The effect and benefit of the present invention are: a high water vapor adsorption polyionic liquid adsorbent synthesis method, through four steps of ionization, ion replacement, polymerization, and product purification, a solid polyionic liquid with high water vapor adsorption capacity is realized Sorbent preparation. Different from the existing polyionic liquid, the polyionic liquid monomer has a shorter carbon chain and repeated arrangement of acetate anions, has a higher water vapor adsorption capacity, and can be widely used in drying, dehumidification, adsorption heat storage, Adsorption seawater desalination and sewage treatment and other fields. As a porous solid, the polyionic liquid adsorbent overcomes the disadvantages of easy leakage, easy pollution, easy flow and the like of the ionic liquid, and is suitable for large-scale industrial application.
具体实施方式detailed description
以下技术方案，进一步说明本发明的具体实施方式。The following technical schemes further illustrate the specific embodiments of the present invention.
实施例1Example 1
一种高水蒸气吸附聚离子液体吸附剂合成方法，主要包括以下步骤：A method for synthesizing a high water vapor adsorption polyionic liquid adsorbent, mainly comprising the following steps:
(1)离子化：以1摩尔(94.12g)N-乙烯基咪唑和1摩尔(50.49g)液化一氯甲烷为原料，通过季铵化反应制备氯化1-乙烯基-3-甲基咪唑离子液体，反应温度为80℃，反应时间为8小时；(1) Ionization: Using 1 mole (94.12g) of N-vinylimidazole and 1 mole (50.49g) of liquefied methylene chloride as raw materials, 1-vinyl-3-methylimidazole chloride was prepared by quaternization reaction Ionic liquid, the reaction temperature is 80°C, and the reaction time is 8 hours;
(2)离子置换：向所得氯化1-乙烯基-3-甲基咪唑离子液体中加入1摩尔(77.08g)乙酸铵，通过离子置换反应获得乙酸化1-乙烯基-3-甲基咪唑离子液体，反应温度为70℃，反应时间为3小时；(2) Ion replacement: Add 1 mole (77.08 g) of ammonium acetate to the obtained 1-vinyl-3-methylimidazolium chloride ionic liquid, and obtain acetic acidified 1-vinyl-3-methylimidazole through ion replacement reaction Ionic liquid, the reaction temperature is 70°C, and the reaction time is 3 hours;
(3)聚合：将所得乙酸化1-乙烯基-3-甲基咪唑离子液体(约170g)溶解在114g二甲基甲酰胺中，并加入1.43g偶氮二异丁腈，通过聚合反应将乙酸化1-乙烯基-3-甲基咪唑离子液体合成为聚乙酸化1-乙烯基-3-甲基咪唑离子液体，聚合方法采用热聚合法，热聚合条件为80℃加热180min，其中反应体系中二甲基甲酰胺的质量比例为40％、偶氮二异丁腈的质量比例为0.5％；(3) Polymerization: the obtained acetic acidified 1-vinyl-3-methylimidazolium ionic liquid (about 170g) was dissolved in 114g dimethylformamide, and 1.43g azobisisobutyronitrile was added, and the Acetated 1-vinyl-3-methylimidazolium ionic liquid is synthesized into polyacetated 1-vinyl-3-methylimidazolium ionic liquid. The polymerization method adopts thermal polymerization method. The mass proportion of dimethylformamide in the system is 40%, and the mass proportion of azobisisobutyronitrile is 0.5%;
(4)产品净化：将步骤(3)所得产物浸泡在300g乙醇中4小时，使得乙醇刚好没过该产物，利用乙醇替换产物中的二甲基甲酰胺和偶氮二异丁腈等杂质，然后进行过滤，将所得固体继续进行上述操作2次，然后将过滤后所得固体在80℃干燥6小时彻底去除残余的乙醇，得到纯净的聚乙酸化1-乙烯基-3-甲基咪唑离子液体。(4) Product purification: soak the product obtained in step (3) in 300g ethanol for 4 hours, so that the ethanol just does not pass through the product, and use ethanol to replace impurities such as dimethylformamide and azobisisobutyronitrile in the product, Then filter, and continue the above operation for the obtained solid twice, and then dry the obtained solid at 80°C for 6 hours to completely remove residual ethanol to obtain pure polyacetated 1-vinyl-3-methylimidazolium ionic liquid .
根据该实施例制备的聚乙酸化1-乙烯基-3-甲基咪唑离子液体产物中乙酸阴离子和1-乙烯基-3-甲基咪唑阳离子的摩尔比为0.99，聚乙酸化1-乙烯基-3-甲基咪唑离子液体产物纯度为98％。The molar ratio of acetate anion and 1-vinyl-3-methylimidazolium cation in the polyacetated 1-vinyl-3-methylimidazolium ionic liquid product prepared according to this embodiment is 0.99, and the polyacetated 1-vinyl -3-Methylimidazolium ionic liquid product purity is 98%.
利用动力蒸汽吸附仪对聚乙酸化1-乙烯基-3-甲基咪唑离子液体的水蒸气吸附能力进行了测试，测试条件为25摄氏度，本实施例制备的聚乙酸化1-乙烯基-3-甲基咪唑离子液体在90％相对湿度下的饱和吸附量为1.26g/g。The water vapor adsorption capacity of polyacetated 1-vinyl-3-methylimidazolium ionic liquid was tested using a dynamic steam adsorption instrument. The test condition was 25 degrees Celsius. The polyacetated 1-vinyl-3 prepared in this example - The saturated adsorption capacity of the methylimidazolium ionic liquid at 90% relative humidity is 1.26 g/g.
实施例2Example 2
一种高水蒸气吸附聚离子液体吸附剂合成方法，主要包括以下步骤：A method for synthesizing a high water vapor adsorption polyionic liquid adsorbent, mainly comprising the following steps:
(1)离子化：以0.5摩尔(47.06g)N-乙烯基咪唑和0.5摩尔(47.47g)液化一溴甲烷为原料，通过季铵化反应制备溴化1-乙烯基-3-甲基咪唑离子液体，反应温度为60℃，反应时间为10小时；(1) Ionization: Using 0.5 moles (47.06g) of N-vinylimidazole and 0.5 moles (47.47g) of liquefied bromomethane as raw materials, 1-vinyl-3-methylimidazolium bromide was prepared by quaternization reaction liquid, the reaction temperature is 60°C, and the reaction time is 10 hours;
(2)离子置换：向所得溴化1-乙烯基-3-甲基咪唑离子液体中加入0.5摩尔(38.54g)乙酸铵，通过离子置换反应获得乙酸化1-乙烯基-3-甲基咪唑离子液体，反应温度为40℃，反应时间为5小时；(2) Ion replacement: Add 0.5 moles (38.54 g) of ammonium acetate to the obtained 1-vinyl-3-methylimidazolium bromide ionic liquid, and obtain acetic acidated 1-vinyl-3-methylimidazolium by ion replacement reaction Ionic liquid, the reaction temperature is 40°C, and the reaction time is 5 hours;
(3)聚合：将所得乙酸化1-乙烯基-3-甲基咪唑离子液体(约85g)溶解在21.8g二甲基甲酰胺中，并加入2.18g偶氮二异丁腈，通过聚合反应将乙酸化1-乙烯基-3-甲基咪唑离子液体合成为聚乙酸化1-乙烯基-3-甲基咪唑离子液体，聚合方法采用紫外聚合法，紫外聚合条件为25℃，紫外有效波长为365nm，功率为8W，紫外光强度为400mW/cm2，紫外聚合时间为180min，其中反应体系中二甲基甲酰胺的质量比例为20％、偶氮二异丁腈的质量比例为2％；(3) Polymerization: Dissolve the obtained acetic acidified 1-vinyl-3-methylimidazolium ionic liquid (about 85 g) in 21.8 g of dimethylformamide, and add 2.18 g of azobisisobutyronitrile, through the polymerization reaction The acetic acidified 1-vinyl-3-methylimidazole ionic liquid is synthesized into polyacetated 1-vinyl-3-methylimidazolium ionic liquid, and the polymerization method adopts the ultraviolet polymerization method, and the ultraviolet polymerization condition is 25 ℃, and the ultraviolet effective wavelength 365nm, power 8W, ultraviolet light intensity 400mW/cm 2 , ultraviolet polymerization time 180min, wherein the mass proportion of dimethylformamide in the reaction system is 20%, and the mass proportion of azobisisobutyronitrile is 2%. ;
(4)产品净化：将步骤(3)所得产物浸泡在150g乙醇中4小时，使得乙醇刚好没过该产物，利用乙醇替换产物中的二甲基甲酰胺和偶氮二异丁腈等杂质，然后进行过滤，将所得固体继续进行上述操作2次，然后将过滤后所得固体在60℃干燥8小时彻底去除残余的乙醇，得到纯净的聚乙酸化1-乙烯基-3-甲基咪唑离子液体。(4) Product purification: soak the product obtained in step (3) in 150g ethanol for 4 hours, so that the ethanol just does not pass through the product, and use ethanol to replace impurities such as dimethylformamide and azobisisobutyronitrile in the product, Then filter, and continue the above-mentioned operation for the obtained solid twice, and then dry the obtained solid at 60°C for 8 hours to completely remove residual ethanol to obtain pure polyacetated 1-vinyl-3-methylimidazolium ionic liquid .
根据该实施例制备的聚乙酸化1-乙烯基-3-甲基咪唑离子液体产物中乙酸阴离子和1-乙烯基-3-甲基咪唑阳离子的摩尔比为0.96，聚乙酸化1-乙烯基-3-甲基咪唑离子液体产物纯度为95％。The molar ratio of acetate anion and 1-vinyl-3-methylimidazolium cation in the polyacetated 1-vinyl-3-methylimidazolium ionic liquid product prepared according to this embodiment is 0.96, and the polyacetated 1-vinyl -3-Methylimidazolium ionic liquid product purity is 95%.
利用动力蒸汽吸附仪对聚乙酸化1-乙烯基-3-甲基咪唑离子液体的水蒸气吸附能力进行了测试，测试条件为25摄氏度，本实施例制备的聚乙酸化1-乙烯基-3-甲基咪唑离子液体在90％相对湿度下的饱和吸附量为1.18g/g。The water vapor adsorption capacity of polyacetated 1-vinyl-3-methylimidazolium ionic liquid was tested using a dynamic steam adsorption instrument. The test condition was 25 degrees Celsius. The polyacetated 1-vinyl-3 prepared in this example - The saturated adsorption capacity of the methylimidazolium ionic liquid at 90% relative humidity is 1.18 g/g.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011402656.8A CN114570337B (en) | 2020-12-02 | 2020-12-02 | High-water-vapor-adsorption ionic liquid adsorbent and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011402656.8A CN114570337B (en) | 2020-12-02 | 2020-12-02 | High-water-vapor-adsorption ionic liquid adsorbent and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114570337A CN114570337A (en) | 2022-06-03 |
| CN114570337B true CN114570337B (en) | 2022-12-13 |
Family
ID=81768071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011402656.8A Active CN114570337B (en) | 2020-12-02 | 2020-12-02 | High-water-vapor-adsorption ionic liquid adsorbent and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114570337B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337938A (en) * | 2007-07-04 | 2009-01-07 | 中国纺织科学研究院 | The synthetic method of acetate ionic liquid |
| CN108273477A (en) * | 2018-02-07 | 2018-07-13 | 厦门大学 | A kind of porous poly ion liquid adsorbent and its application |
| CN109092265A (en) * | 2018-09-10 | 2018-12-28 | 陕西科技大学 | A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8734673B2 (en) * | 2008-08-08 | 2014-05-27 | The University Of Toledo | Boron selective ionic liquids and polymeric ionic liquids, methods of making and methods of use thereof |
| CN102481513B (en) * | 2009-06-25 | 2015-11-25 | Vtu控股有限责任公司 | Methods of use of ionic liquids and devices for gas sorption |
-
2020
- 2020-12-02 CN CN202011402656.8A patent/CN114570337B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337938A (en) * | 2007-07-04 | 2009-01-07 | 中国纺织科学研究院 | The synthetic method of acetate ionic liquid |
| CN108273477A (en) * | 2018-02-07 | 2018-07-13 | 厦门大学 | A kind of porous poly ion liquid adsorbent and its application |
| CN109092265A (en) * | 2018-09-10 | 2018-12-28 | 陕西科技大学 | A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified |
Non-Patent Citations (3)
| Title |
|---|
| Poly(ionic liquid)s: Polymers expanding classical property profiles;Jiayin Yuan 等;《Polymer》;20110128;第52卷;第1469-1482页 * |
| 聚离子液体作为吸附材料的研究进展;宋文琦 等;《材料导报Ａ：综述篇》;20160930;第30卷(第９期);第120-126、140页 * |
| 聚离子液体的合成及应用;何晓燕等;《高分子通报》;20130515(第05期);第17-28页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114570337A (en) | 2022-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Covalent triazine frameworks for carbon dioxide capture | |
| Wang et al. | Carbon dioxide capture in amorphous porous organic polymers | |
| Fu et al. | Fabrication of COF-MOF composite membranes and their highly selective separation of H2/CO2 | |
| Jiang et al. | Construction of a stable crystalline polyimide porous organic framework for C2H2/C2H4 and CO2/N2 separation | |
| Ma et al. | Mixed matrix membrane based on cross-linked poly [(ethylene glycol) methacrylate] and metal–organic framework for efficient separation of carbon dioxide and methane | |
| CN114177891B (en) | Preparation method of biochar composite metal organic framework adsorbing material | |
| CN108554387A (en) | A kind of beta cyclo dextrin polymer and preparation and the method for handling cationic dye wastewater using it | |
| CN114588879B (en) | An IL@MOFs composite material and its preparation method and application | |
| Wongsakulphasatch et al. | Effect of Fe open metal site in metal‐organic frameworks on post‐combustion CO2 capture performance | |
| Chen et al. | Mesoporous silica impregnated with organoamines for post‐combustion CO2 capture: a comparison of introduced amine types | |
| CN103908955B (en) | The preparation method of the superhigh cross-linking type polymeric adsorbent that a kind of acetamido is modified and application thereof | |
| CN116529207A (en) | Carbonaceous material, process for producing the same, fluorine-containing organic compound removing material, filter for water purification, and water purifier | |
| CN114570337B (en) | High-water-vapor-adsorption ionic liquid adsorbent and synthesis method and application thereof | |
| Lei et al. | Removal of furfural in wastewater by Al-MIL-53 prepared in various solvents | |
| Pourjavadi et al. | Improvement in oil absorbency by using modified carbon nanotubes in preparation of oil sorbents | |
| CN103418256B (en) | A kind of synthetic method of p-hydroxybenzoic acid blotting membrane and application thereof | |
| CN117732445A (en) | Preparation method of strong acid polymer-based ammonia adsorbent | |
| CN116333331B (en) | High-stability cage-based metal organic framework material and preparation method and application thereof | |
| CN117186481A (en) | A polyphenolic hydroxyl COFs aerogel rich in hydrogen bond donors and its preparation method and application | |
| CN106380604B (en) | A kind of preparation method of polycyclic phosphazene porous material and use thereof | |
| CN114573741B (en) | Polyacetylated imidazolyl ionic liquid for water vapor adsorption and preparation and application thereof | |
| CN110813260A (en) | A kind of preparation method of high-efficiency porous polymer solid acid adsorbing low-concentration ammonia gas | |
| CN110734404B (en) | Dicationic ionic liquid connected by polyethylene glycol chain, preparation method and method for capturing SO2 gas | |
| CN114805762B (en) | A kind of porous organic polymer containing azobenzene and its preparation method and application | |
| JP7316654B2 (en) | Ion mixture using silicon oxide as substrate having ammonia adsorption/desorption ability at high temperature, ammonia adsorption/desorption method using said ion mixture, and ammonia recovery device |
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 |