CN115368511B - A kind of aqueous phase preparation method of deep eutectic solvent-based imprinted polymer and its application - Google Patents
A kind of aqueous phase preparation method of deep eutectic solvent-based imprinted polymer and its application Download PDFInfo
- Publication number
- CN115368511B CN115368511B CN202211076420.9A CN202211076420A CN115368511B CN 115368511 B CN115368511 B CN 115368511B CN 202211076420 A CN202211076420 A CN 202211076420A CN 115368511 B CN115368511 B CN 115368511B
- Authority
- CN
- China
- Prior art keywords
- imprinted polymer
- eutectic solvent
- deep eutectic
- bisphenol
- hours
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 239000002904 solvent Substances 0.000 title claims abstract description 45
- 230000005496 eutectics Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000008346 aqueous phase Substances 0.000 title claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 40
- 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 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010828 elution Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000012719 thermal polymerization Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 24
- 239000000178 monomer Substances 0.000 description 11
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UMESNHVJZFCGBV-UHFFFAOYSA-N 2-methyl-4-[(2-methylphenyl)methylidene]-1,3-oxazol-5-one Chemical compound O=C1OC(C)=NC1=CC1=CC=CC=C1C UMESNHVJZFCGBV-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 2
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- -1 template molecule Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012420 spiking experiment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- 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
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- 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
- C08J9/26—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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种低共熔溶剂型印迹聚合物的水相制备方法及其应用，将低共熔溶剂和模板分子双酚A溶解到含有载体苯乙烯‑二乙烯基苯的纯水溶剂中，于20~40℃预聚合2~8h，再加入交联剂N,N’‑亚甲基双丙烯酰胺和引发剂偶氮二异丁腈，经超声和充氮气保护后，于50~70℃热聚合20~30h，经洗脱、干燥得到低共熔溶剂型印迹聚合物。本发明制备的印迹聚合物在水溶液中选择性吸附目标物双酚A的能力强且吸附量高，能够用于实际水样中双酚A的分离富集。
The invention discloses a water phase preparation method of a deep eutectic solvent-based imprinted polymer and its application. The deep eutectic solvent and template molecule bisphenol A are dissolved into a pure water solvent containing carrier styrene-divinylbenzene. , prepolymerize at 20~40℃ for 2~8h, then add cross-linking agent N,N'-methylene bisacrylamide and initiator azobisisobutyronitrile, after ultrasonic and nitrogen protection, polymerize at 50~70 Thermal polymerization at ℃ for 20 to 30 hours, followed by elution and drying to obtain a deep eutectic solvent-based imprinted polymer. The imprinted polymer prepared by the invention has strong ability to selectively adsorb the target bisphenol A in an aqueous solution and has a high adsorption capacity, and can be used for the separation and enrichment of bisphenol A in actual water samples.
Description
技术领域Technical field
本发明属于功能高分子聚合物的制备技术领域，具体涉及一种低共熔溶剂型印迹聚合物的水相制备方法及其应用。The invention belongs to the technical field of preparation of functional polymers, and specifically relates to a water phase preparation method and application of a deep eutectic solvent-based imprinted polymer.
背景技术Background technique
分子印迹聚合物（MIPs）是通过模板分子与功能单体形成高度交联的复合物，去除模板后，MIPs中的空间结构、大小、官能团等特异性识别位点与模板分子高度匹配，这种“记忆”能力能够选择性吸附识别与其他化合物共存的模板分子。在制备过程中，制孔剂作为分散介质，影响着功能单体和模板分子的非共价键强度和所形成的MIPs空间结构。但是，目前的分子印迹聚合物大多数还是在有机溶剂中制备的，可能会对环境带来二次污染。而且，由于“溶剂记忆”的存在，这些MIPs在水溶液中的吸附能力会受到很大影响。Molecularly imprinted polymers (MIPs) are highly cross-linked complexes formed by template molecules and functional monomers. After the template is removed, the spatial structure, size, functional groups and other specific recognition sites in MIPs are highly matched to the template molecules. This kind of The "memory" ability enables selective adsorption and recognition of template molecules that coexist with other compounds. During the preparation process, the pore-forming agent serves as a dispersion medium, affecting the non-covalent bond strength of functional monomers and template molecules and the spatial structure of the formed MIPs. However, most of the current molecularly imprinted polymers are prepared in organic solvents, which may cause secondary pollution to the environment. Moreover, due to the existence of "solvent memory", the adsorption capacity of these MIPs in aqueous solutions will be greatly affected.
低共熔溶剂（DES）是由氢键供体（如季铵盐等）和氢键受体（如羧酸、酰胺等）以一定摩尔比组成的低共熔混合物质，其凝固点低于其组分的纯物质熔点。DES也被称为一类新型离子液体，所以其不但具有熔点低、无蒸汽压、溶解性强等性质，而且还具有成本低、制备过程简单优点等优势。随着对DES的研究不断深入，其在分离、萃取和聚合物制备等领域的应用日益广阔。然而，目前以DES为功能单体的MIPs对识别生物分子的研究较多，缺乏对环境中污染物的识别吸附研究。Deep eutectic solvent (DES) is a deep eutectic mixture composed of hydrogen bond donors (such as quaternary ammonium salts, etc.) and hydrogen bond acceptors (such as carboxylic acids, amides, etc.) in a certain molar ratio. Its freezing point is lower than The melting point of a component's pure substance. DES is also known as a new type of ionic liquid, so it not only has properties such as low melting point, no vapor pressure, and strong solubility, but also has the advantages of low cost and simple preparation process. As the research on DES continues to deepen, its applications in the fields of separation, extraction and polymer preparation are becoming increasingly broad. However, at present, there are many studies on the recognition of biomolecules in MIPs with DES as the functional monomer, and there is a lack of research on the recognition and adsorption of pollutants in the environment.
发明内容Contents of the invention
本发明解决的技术问题是提供了一种低共熔溶剂型印迹聚合物的水相制备方法，该印迹聚合物在水溶液中选择性吸附目标物双酚A的能力强且吸附量高，能够用于实际水样中双酚A的分离富集。The technical problem solved by the present invention is to provide a water phase preparation method for a deep eutectic solvent-based imprinted polymer. The imprinted polymer has strong ability to selectively adsorb the target bisphenol A in an aqueous solution and has a high adsorption capacity, and can be used Separation and enrichment of bisphenol A in actual water samples.
本发明为解决上述技术问题采用如下技术方案，一种低共熔溶剂型印迹聚合物的水相制备方法，其特征在于：将低共熔溶剂和模板分子双酚A溶解到含有载体苯乙烯-二乙烯基苯的纯水溶剂中，于20~40℃预聚合2~8h，再加入交联剂N,N’-亚甲基双丙烯酰胺和引发剂偶氮二异丁腈，经超声和充氮气保护后，于50~70℃热聚合20~30h，经洗脱、干燥得到低共熔溶剂型印迹聚合物；In order to solve the above technical problems, the present invention adopts the following technical solution, an aqueous phase preparation method of a deep eutectic solvent-based imprinted polymer, which is characterized in that: the deep eutectic solvent and the template molecule bisphenol A are dissolved into a solution containing the carrier styrene- In the pure water solvent of divinylbenzene, prepolymerize at 20~40℃ for 2~8h, then add the cross-linking agent N,N'-methylenebisacrylamide and the initiator azobisisobutyronitrile. After ultrasonic and After nitrogen protection, thermal polymerization at 50~70°C for 20~30 hours, followed by elution and drying to obtain a deep eutectic solvent-based imprinted polymer;
所述低共熔溶剂为摩尔比0.5~2:1的甲基丙烯酸和苄基三甲基氯化铵混合溶剂、摩尔比0.5~2:1的甲基丙烯酸和苄基三乙基氯化铵混合溶剂、摩尔比0.5~2:1的甲基丙烯酸和苄基三丁基氯化铵混合溶剂、摩尔比0.5~2:1的甲基丙烯酸和正辛基三甲基氯化铵混合溶剂或摩尔比0.5~2:1的甲基丙烯酸和苄基三甲基溴化铵混合溶剂。The deep eutectic solvent is a mixed solvent of methacrylic acid and benzyltrimethylammonium chloride with a molar ratio of 0.5~2:1, and a mixed solvent of methacrylic acid and benzyltriethylammonium chloride with a molar ratio of 0.5~2:1. Mixed solvent, a mixed solvent of methacrylic acid and benzyltributylammonium chloride in a molar ratio of 0.5~2:1, a mixed solvent of methacrylic acid and n-octyltrimethylammonium chloride in a molar ratio of 0.5~2:1 or molar A mixed solvent of methacrylic acid and benzyltrimethylammonium bromide with a ratio of 0.5~2:1.
进一步限定，所述低共熔溶剂、模板分子、交联剂和引发剂的质量比为0.05~0.3:0.03:0.05~0.2:0.05。It is further limited that the mass ratio of the deep eutectic solvent, template molecule, cross-linking agent and initiator is 0.05~0.3:0.03:0.05~0.2:0.05.
进一步限定，所述洗脱过程具体为体积比9:1的甲醇和乙酸混合液索氏提取48h。It is further limited that the elution process is specifically Soxhlet extraction with a mixture of methanol and acetic acid in a volume ratio of 9:1 for 48 hours.
本发明所述低共熔溶剂型印迹聚合物用于实际水样中双酚A的分离富集。The deep eutectic solvent-based imprinted polymer of the present invention is used for the separation and enrichment of bisphenol A in actual water samples.
本发明与现有技术相比具有以下优点和有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
1、本发明提供了多种低共熔溶剂作为功能单体用以制备双酚A表面印迹聚合物，该印迹聚合物具有粒径均匀、吸附容量大、水中亲和力强等性能。1. The present invention provides a variety of deep eutectic solvents as functional monomers to prepare bisphenol A surface-imprinted polymers. The imprinted polymers have properties such as uniform particle size, large adsorption capacity, and strong affinity in water.
2、本发明采用纯水为制备溶剂，一方面减少了乙腈、甲醇等非极性溶剂对环境的二次破坏，另一方面提高了印迹聚合物在水介质中的吸附容量。2. The present invention uses pure water as the preparation solvent, which on the one hand reduces the secondary damage to the environment caused by non-polar solvents such as acetonitrile and methanol, and on the other hand increases the adsorption capacity of the imprinted polymer in the aqueous medium.
附图说明Description of the drawings
图1是本发明中低共熔溶剂的合成路线示意图。Figure 1 is a schematic diagram of the synthesis route of the deep eutectic solvent in the present invention.
图2是本发明中印迹聚合物的合成路线图。Figure 2 is a synthesis route diagram of the imprinted polymer in the present invention.
图3是本发明中载体、印迹聚合物和非印迹聚合物的电镜图。Figure 3 is an electron microscope image of the carrier, imprinted polymer and non-imprinted polymer in the present invention.
图4是本发明印迹聚合物和非印迹聚合物吸附动力学图。Figure 4 is a graph of adsorption kinetics of imprinted polymers and non-imprinted polymers of the present invention.
图5是本发明印迹聚合物和非印迹聚合物吸附等温线图。Figure 5 is an adsorption isotherm diagram of imprinted polymers and non-imprinted polymers of the present invention.
具体实施方式Detailed ways
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。The above-mentioned contents of the present invention will be further described in detail below through examples, but this should not be understood to mean that the scope of the above-mentioned subject of the present invention is limited to the following examples. All technologies implemented based on the above-mentioned contents of the present invention belong to the scope of the present invention.
实施例1Example 1
低共熔溶剂的制备：将甲基丙烯酸和苄基三甲基氯化铵按摩尔比2:1混合后于80℃搅拌反应得到澄清均一的液体。Preparation of deep eutectic solvent: Mix methacrylic acid and benzyltrimethylammonium chloride in a molar ratio of 2:1, stir and react at 80°C to obtain a clear and uniform liquid.
印迹聚合物的制备：以30mL水为溶剂，将0.10g苯乙烯-二乙烯基苯（载体），0.10g上述自制低共熔溶剂（功能单体）与0.03g双酚A（模板分子）于30℃预聚合4h，然后加入0.10g交联剂N,N’-亚甲基双丙烯酰胺和0.05g引发剂偶氮二异丁腈，经超声、充N2后于60℃热引发聚合24h得到产物，再用体积比为9:1的甲醇/乙酸混合液索氏提取48h后真空干燥得到印迹聚合物。Preparation of imprinted polymer: Using 30 mL of water as the solvent, mix 0.10 g of styrene-divinylbenzene (carrier), 0.10 g of the above-mentioned self-made deep eutectic solvent (functional monomer) and 0.03 g of bisphenol A (template molecule) in Prepolymerize at 30°C for 4 hours, then add 0.10g of cross-linking agent N,N'-methylenebisacrylamide and 0.05g of initiator azobisisobutyronitrile. After ultrasonic and N2 filling, thermally initiate polymerization at 60°C for 24 hours. The product was obtained, then Soxhlet extracted with a methanol/acetic acid mixture with a volume ratio of 9:1 for 48 hours and then vacuum dried to obtain the imprinted polymer.
实施例2Example 2
低共熔溶剂的制备：将甲基丙烯酸和苄基三乙基氯化铵按摩尔比2:1混合后于80℃搅拌反应得到澄清均一的液体。Preparation of deep eutectic solvent: Mix methacrylic acid and benzyltriethylammonium chloride in a molar ratio of 2:1, stir and react at 80°C to obtain a clear and uniform liquid.
印迹聚合物的制备：以30mL水为溶剂，将0.10g苯乙烯-二乙烯基苯（载体），0.10g上述自制低共熔溶剂（功能单体）与0.03g双酚A（模板分子）于30℃预聚合4h，然后加入0.10g交联剂N,N’-亚甲基双丙烯酰胺和0.05g引发剂偶氮二异丁腈，经超声、充N2后于60℃热引发聚合24h得到产物，再用体积比为9:1的甲醇/乙酸混合液索氏提取48h后真空干燥得到印迹聚合物。Preparation of imprinted polymer: Using 30 mL of water as the solvent, mix 0.10 g of styrene-divinylbenzene (carrier), 0.10 g of the above-mentioned self-made deep eutectic solvent (functional monomer) and 0.03 g of bisphenol A (template molecule) in Prepolymerize at 30°C for 4 hours, then add 0.10g of cross-linking agent N,N'-methylenebisacrylamide and 0.05g of initiator azobisisobutyronitrile. After ultrasonic and N2 filling, thermally initiate polymerization at 60°C for 24 hours. The product was obtained, then Soxhlet extracted with a methanol/acetic acid mixture with a volume ratio of 9:1 for 48 hours and then vacuum dried to obtain the imprinted polymer.
实施例3Example 3
低共熔溶剂的制备：将甲基丙烯酸和苄基三丁基氯化铵按摩尔比2:1混合后于80℃搅拌反应得到澄清均一的液体。Preparation of deep eutectic solvent: Mix methacrylic acid and benzyltributyl ammonium chloride in a molar ratio of 2:1, stir and react at 80°C to obtain a clear and uniform liquid.
印迹聚合物的制备：以30mL水为溶剂，将0.10g苯乙烯-二乙烯基苯（载体），0.10g上述自制低共熔溶剂（功能单体）与0.03g双酚A（模板分子）于30℃预聚合4h，然后加入0.10g交联剂N,N’-亚甲基双丙烯酰胺和0.05g引发剂偶氮二异丁腈，经超声、充N2后于60℃热引发聚合24h得到产物，再用体积比为9:1的甲醇/乙酸混合液索氏提取48h后真空干燥得到印迹聚合物。Preparation of imprinted polymer: Using 30 mL of water as the solvent, mix 0.10 g of styrene-divinylbenzene (carrier), 0.10 g of the above-mentioned self-made deep eutectic solvent (functional monomer) and 0.03 g of bisphenol A (template molecule) in Prepolymerize at 30°C for 4 hours, then add 0.10g of cross-linking agent N,N'-methylenebisacrylamide and 0.05g of initiator azobisisobutyronitrile. After ultrasonic and N2 filling, thermally initiate polymerization at 60°C for 24 hours. The product was obtained, then Soxhlet extracted with a methanol/acetic acid mixture with a volume ratio of 9:1 for 48 hours and then vacuum dried to obtain the imprinted polymer.
实施例4Example 4
低共熔溶剂的制备：将甲基丙烯酸和正辛基三甲基氯化铵按摩尔比2:1混合后于80℃搅拌反应得到澄清均一的液体。Preparation of deep eutectic solvent: Mix methacrylic acid and n-octyltrimethylammonium chloride in a molar ratio of 2:1, stir and react at 80°C to obtain a clear and uniform liquid.
印迹聚合物的制备：以30mL水为溶剂，将0.10g苯乙烯-二乙烯基苯（载体），0.10g上述自制低共熔溶剂（功能单体）与0.03g双酚A（模板分子）于30℃预聚合4h，然后加入0.10g交联剂N,N’-亚甲基双丙烯酰胺和0.05g引发剂偶氮二异丁腈，经超声、充N2后于60℃热引发聚合24h得到产物，再用体积比为9:1的甲醇/乙酸混合液索氏提取48h后真空干燥得到印迹聚合物。Preparation of imprinted polymer: Using 30 mL of water as the solvent, mix 0.10 g of styrene-divinylbenzene (carrier), 0.10 g of the above-mentioned self-made deep eutectic solvent (functional monomer) and 0.03 g of bisphenol A (template molecule) in Prepolymerize at 30°C for 4 hours, then add 0.10g of cross-linking agent N,N'-methylenebisacrylamide and 0.05g of initiator azobisisobutyronitrile. After ultrasonic and N2 filling, thermally initiate polymerization at 60°C for 24 hours. The product was obtained, then Soxhlet extracted with a methanol/acetic acid mixture with a volume ratio of 9:1 for 48 hours and then vacuum dried to obtain the imprinted polymer.
实施例5Example 5
低共熔溶剂的制备：将甲基丙烯酸和苄基三甲基溴化铵按摩尔比2:1混合后于80℃搅拌反应得到澄清均一的液体。Preparation of deep eutectic solvent: Mix methacrylic acid and benzyltrimethylammonium bromide in a molar ratio of 2:1, stir and react at 80°C to obtain a clear and uniform liquid.
印迹聚合物的制备：以30mL水为溶剂，将0.10g苯乙烯-二乙烯基苯（载体），0.10g上述自制低共熔溶剂（功能单体）与0.03g双酚A（模板分子）于30℃预聚合4h，然后加入0.10g交联剂N,N’-亚甲基双丙烯酰胺和0.05g引发剂偶氮二异丁腈，经超声、充N2后于60℃热引发聚合24h得到产物，再用体积比为9:1的甲醇/乙酸混合液索氏提取48h后真空干燥得到印迹聚合物。Preparation of imprinted polymer: Using 30 mL of water as the solvent, mix 0.10 g of styrene-divinylbenzene (carrier), 0.10 g of the above-mentioned self-made deep eutectic solvent (functional monomer) and 0.03 g of bisphenol A (template molecule) in Prepolymerize at 30°C for 4 hours, then add 0.10g of cross-linking agent N,N'-methylenebisacrylamide and 0.05g of initiator azobisisobutyronitrile. After ultrasonic and N2 filling, thermally initiate polymerization at 60°C for 24 hours. The product was obtained, then Soxhlet extracted with a methanol/acetic acid mixture with a volume ratio of 9:1 for 48 hours and then vacuum dried to obtain the imprinted polymer.
实施例6Example 6
低共熔溶剂的制备：将甲基丙烯酸和苄基三甲基氯化铵按摩尔比1:1混合后于80℃搅拌反应得到澄清均一的液体。Preparation of deep eutectic solvent: Mix methacrylic acid and benzyltrimethylammonium chloride in a molar ratio of 1:1, stir and react at 80°C to obtain a clear and uniform liquid.
印迹聚合物的制备：以30mL水为溶剂，将0.10g苯乙烯-二乙烯基苯（载体），0.10g上述自制低共熔溶剂（功能单体）与0.03g双酚A（模板分子）于30℃预聚合4h，然后加入0.10g交联剂N,N’-亚甲基双丙烯酰胺和0.05g引发剂偶氮二异丁腈，经超声、充N2后于60℃热引发聚合24h得到产物，再用体积比为9:1的甲醇/乙酸混合液索氏提取48h后真空干燥得到印迹聚合物。Preparation of imprinted polymer: Using 30 mL of water as the solvent, mix 0.10 g of styrene-divinylbenzene (carrier), 0.10 g of the above-mentioned self-made deep eutectic solvent (functional monomer) and 0.03 g of bisphenol A (template molecule) in Prepolymerize at 30℃ for 4h, then add 0.10g of cross-linking agent N,N'-methylenebisacrylamide and 0.05g of initiator azobisisobutyronitrile. After ultrasonic and N2 filling, thermally initiate polymerization at 60℃ for 24h. The product was obtained, then Soxhlet extracted with a methanol/acetic acid mixture with a volume ratio of 9:1 for 48 hours and then vacuum dried to obtain the imprinted polymer.
实施例7Example 7
低共熔溶剂的制备：将甲基丙烯酸和苄基三甲基氯化铵按摩尔比0.5:1混合后于80℃搅拌反应得到澄清均一的液体。Preparation of deep eutectic solvent: Mix methacrylic acid and benzyltrimethylammonium chloride at a molar ratio of 0.5:1, stir and react at 80°C to obtain a clear and uniform liquid.
印迹聚合物的制备：以30mL水为溶剂，将0.10g苯乙烯-二乙烯基苯（载体），0.10g上述自制低共熔溶剂（功能单体）与0.03g双酚A（模板分子）于30℃预聚合4h，然后加入0.10g交联剂N,N’-亚甲基双丙烯酰胺和0.05g引发剂偶氮二异丁腈，经超声、充N2后于60℃热引发聚合24h得到产物，再用体积比为9:1的甲醇/乙酸混合液索氏提取48h后真空干燥得到印迹聚合物。Preparation of imprinted polymer: Using 30 mL of water as the solvent, mix 0.10 g of styrene-divinylbenzene (carrier), 0.10 g of the above-mentioned self-made deep eutectic solvent (functional monomer) and 0.03 g of bisphenol A (template molecule) in Prepolymerize at 30°C for 4 hours, then add 0.10g of cross-linking agent N,N'-methylenebisacrylamide and 0.05g of initiator azobisisobutyronitrile. After ultrasonic and N2 filling, thermally initiate polymerization at 60°C for 24 hours. The product was obtained, then Soxhlet extracted with a methanol/acetic acid mixture with a volume ratio of 9:1 for 48 hours and then vacuum dried to obtain the imprinted polymer.
实施例8Example 8
分别将10mg实施例1制得的印迹聚合物（MIP）和非印迹聚合物（NIP），与10mL、50mgL-1的双酚A水溶液混合，室温振荡吸附一定时间后（0-180min），取上清液以紫外分光光度计检测277nm下的吸光度值。结果如图4所示。Mix 10 mg of the imprinted polymer (MIP) and the non-imprinted polymer (NIP) prepared in Example 1 with 10 mL and 50 mg L -1 of bisphenol A aqueous solution, and oscillate and adsorb at room temperature for a certain period of time (0-180 min). The absorbance value of the supernatant at 277 nm was detected with a UV spectrophotometer. The results are shown in Figure 4.
实施例9Example 9
分别将10mg实施例1制得的印迹聚合物（MIP）和非印迹聚合物（NIP），与10mL 的双酚A水溶液混合（0-1000mg L-1），室温振荡吸附3h后，取上清液以紫外分光光度计检测277nm下的吸光度值。结果如图5所示。Mix 10 mg of the imprinted polymer (MIP) and the non-imprinted polymer (NIP) prepared in Example 1 with 10 mL of bisphenol A aqueous solution (0-1000 mg L -1 ) respectively. After adsorption for 3 hours with shaking at room temperature, take the supernatant. The absorbance value of the liquid was measured at 277nm with a UV spectrophotometer. The results are shown in Figure 5.
实施例10Example 10
将实施例1中制得的印迹聚合物填充于装有筛板的聚丙烯小柱，用以对实际废水中双酚A的预处理，加标实验检测结果显示回收率达到90%以上，表明所得印迹聚合物对双酚A的分离富集具有良好的实用性；经过10次以上循环使用，该固相萃取小柱的吸附性能无明显下降，表明所得印迹聚合物具有优良的再生吸附性能。The imprinted polymer prepared in Example 1 was filled into a polypropylene column equipped with a sieve plate to pretreat bisphenol A in actual wastewater. The test results of the spiking experiment showed that the recovery rate reached more than 90%, indicating that The obtained imprinted polymer has good practicability for the separation and enrichment of bisphenol A; after more than 10 cycles of use, the adsorption performance of the solid-phase extraction cartridge has no significant decrease, indicating that the obtained imprinted polymer has excellent regeneration adsorption performance.
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。The above embodiments describe the basic principles, main features and advantages of the present invention. Those skilled in the industry should understand that the present invention is not limited by the above embodiments. What is described in the above embodiments and descriptions only illustrates the principles of the present invention. Without departing from the scope of the principle of the present invention, there will be various changes and improvements in the present invention, and these changes and improvements all fall within the scope of protection of the present invention.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211076420.9A CN115368511B (en) | 2022-09-05 | 2022-09-05 | A kind of aqueous phase preparation method of deep eutectic solvent-based imprinted polymer and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211076420.9A CN115368511B (en) | 2022-09-05 | 2022-09-05 | A kind of aqueous phase preparation method of deep eutectic solvent-based imprinted polymer and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115368511A CN115368511A (en) | 2022-11-22 |
| CN115368511B true CN115368511B (en) | 2024-01-26 |
Family
ID=84069918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211076420.9A Active CN115368511B (en) | 2022-09-05 | 2022-09-05 | A kind of aqueous phase preparation method of deep eutectic solvent-based imprinted polymer and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115368511B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177500A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing bisphenol A molecular engram polymer |
| CN107759736A (en) * | 2017-09-22 | 2018-03-06 | 河南师范大学 | A kind of preparation method of styrene divinylbenzene molecular imprinted polymer on surface for selective absorption Ciprofloxacin Hydrochloride |
| CN113171763A (en) * | 2021-05-24 | 2021-07-27 | 河南师范大学 | A method for preparing bisphenol A surface molecularly imprinted polymer in aqueous phase with MIL-100(Fe) as carrier |
| CN113248650A (en) * | 2021-06-18 | 2021-08-13 | 许昌学院 | Eutectic solvent type molecularly imprinted polymer with hydroxyapatite as carrier and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2935705B1 (en) * | 2008-09-05 | 2010-10-29 | Univ De Technologie De Compiegne | PROCESS FOR THE PREPARATION OF MOLECULAR IMPRESSION POLYMERS (PEM) BY RADICAL POLYMERIZATION |
-
2022
- 2022-09-05 CN CN202211076420.9A patent/CN115368511B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177500A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing bisphenol A molecular engram polymer |
| CN107759736A (en) * | 2017-09-22 | 2018-03-06 | 河南师范大学 | A kind of preparation method of styrene divinylbenzene molecular imprinted polymer on surface for selective absorption Ciprofloxacin Hydrochloride |
| CN113171763A (en) * | 2021-05-24 | 2021-07-27 | 河南师范大学 | A method for preparing bisphenol A surface molecularly imprinted polymer in aqueous phase with MIL-100(Fe) as carrier |
| CN113248650A (en) * | 2021-06-18 | 2021-08-13 | 许昌学院 | Eutectic solvent type molecularly imprinted polymer with hydroxyapatite as carrier and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115368511A (en) | 2022-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110479220A (en) | The method of molecularly imprinted polymer separating and enriching trace sulfamethoxazole pollutant based on supported ion liquid metal organic framework | |
| CN104945637B (en) | A kind of graft type retains by force the preparation method of anion chromatographic filling material | |
| Zhao et al. | Adsorption and recognition of protein molecular imprinted calcium alginate/polyacrylamide hydrogel film with good regeneration performance and high toughness | |
| CN110420627A (en) | A kind of preparation method of ion liquid functionalization metal organic framework-molecular imprinting composite material | |
| BR0113541B1 (en) | functionalized polymer beads, processes for preparing same and processes for separating an analyte from a solution and a mixture. | |
| Yang et al. | Molecularly imprinted polymers based on zeolite imidazolate framework-8 for selective removal of 2, 4-dichlorophenoxyacetic acid | |
| CN102350316A (en) | Preparation method of ultra-high crosslinking type adsorptive resin modified by N-methyl acetamido | |
| Li et al. | Preparation of high-performance chitosan adsorbent by cross-linking for adsorption of Reactive Red 2 (RR2) dye wastewater | |
| WO2021103622A1 (en) | Nicotinamide virtual template surface molecularly imprinted material and preparation method therefor and application thereof | |
| Ding et al. | Preparation and characterization of biocompatible molecularly imprinted poly (ionic liquid) films on the surface of multi-walled carbon nanotubes | |
| CN107118294B (en) | A kind of vinylpyridine modified pendant double bond post-crosslinking resin and its preparation method and application | |
| Li et al. | Rapid extraction of trace bisphenol A in real water samples using hollow mesoporous silica surface dummy molecularly imprinted polymers | |
| 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 | |
| CN115368511B (en) | A kind of aqueous phase preparation method of deep eutectic solvent-based imprinted polymer and its application | |
| Renkecz et al. | Preparation of molecularly imprinted microspheres by precipitation polymerization | |
| CN109021171B (en) | Aqueous preparation method of tylosin tartrate surface molecularly imprinted polymer and its application | |
| CN101053823A (en) | Poly (m-phenylene diamine) used as mercury ion adsorbent | |
| CN115368498A (en) | Preparation method and application of deep eutectic solvent-based molecularly imprinted polymer based on magnetic metal organic framework material carrier | |
| CN114014966B (en) | An amide group modified ultra-high cross-linked adsorption resin and its preparation method and application | |
| CN101591412B (en) | Method for preparing chloramphenicol molecularly imprinted polymeric microspheres | |
| Wang et al. | Caffeine molecular imprinted microgel spheres by precipitation polymerization | |
| CN108178810A (en) | The preparation and its application of a kind of reverse phase/anion exchange mixed mode polymer | |
| Li et al. | Preparation and evaluation of uniform-size (-)-ephedrine-imprinted polymeric microspheres by multi-step swelling and suspension polymerization | |
| CN100522346C (en) | Using sodium alginate to embed adsorbent of poly m-phenylene diamine, prepartion method and usage | |
| CN117756975A (en) | Preparation method and application of hierarchical pore metal organic framework surface molecularly imprinted polymer |
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 |