CN110614089A - Preparation method of functionalized polyamide-amine dendrimer adsorbent - Google Patents
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- 239000000412 dendrimer Substances 0.000 title claims abstract description 62
- 229920000736 dendritic polymer Polymers 0.000 title claims abstract description 62
- 239000003463 adsorbent Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- LGDSHSYDSCRFAB-UHFFFAOYSA-N Methyl isothiocyanate Chemical compound CN=C=S LGDSHSYDSCRFAB-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 triethoxysilyl Chemical group 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 19
- 238000000926 separation method Methods 0.000 abstract description 7
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 125000004354 sulfur functional group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 13
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004494 ethyl ester group Chemical group 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 230000003100 immobilizing effect Effects 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920000962 poly(amidoamine) Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012678 divergent method Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- RGKUKMROHWBUNQ-UHFFFAOYSA-N methanol;methyl prop-2-enoate Chemical compound OC.COC(=O)C=C RGKUKMROHWBUNQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
Description
技术领域technical field
本发明涉及一种功能化聚酰胺-胺树形分子吸附剂的制备方法,属于环境功能材料领域。The invention relates to a preparation method of a functionalized polyamide-amine tree molecular adsorbent, which belongs to the field of environmental functional materials.
背景技术Background technique
随着工业化的发展,工业废水排放量增加,其中金属离子引起的水污染已成为严重的环境问题。金属离子难以降解、具有毒性,对生态环境和人体造成严重的危害,因此如何有效去除水体中的金属离子具有重要的意义。With the development of industrialization, the discharge of industrial wastewater has increased, and the water pollution caused by metal ions has become a serious environmental problem. Metal ions are difficult to degrade, are toxic, and cause serious harm to the ecological environment and human body. Therefore, how to effectively remove metal ions in water is of great significance.
吸附法由于简单、高效等优点被广泛用作金属离子的分离去除。聚酰胺-胺树形大分子含有大量的氮、氧官能团及分子内空腔,易于实现对金属离子的吸附和分离。而且聚酰胺-胺树形大分子易于功能化,能够根据特定需求对其改性从而实现对特定金属离子的选择性吸附分离。然而聚酰胺-胺树形大分子及金属离子络合物在水溶液和大多数有机溶剂中都易溶解,这大大限制了其作为吸附剂的应用。通过将聚酰胺-胺树形大分子固载到特定的基团上是解决这一问题的有效途径。硅胶具有机械强度良好、热稳定性和化学稳定性好、孔结构丰富、比表面积大且表面富含硅羟基易进行改性等优点,常被用作固载聚酰胺-胺树形大分子的基体。目前,将聚酰胺-胺树形大分子固载到硅胶上通常有两种方法,一种是在硅胶表面引入反应活性点,然后通过发散法逐步合成聚酰胺-胺树形大分子;另一种是将合成好的聚酰胺-胺树形大分子通过功能基团间的偶联反应接到硅胶表面。第一种合成方法便于合成过程中产物的分离、提纯,但会导致聚酰胺-胺树形大分子在硅胶表面生长过程中形成分子内和分子间交联结构,以及硅胶孔道减少。第二种方法能够有效避免聚酰胺-胺树形大分子内部的结构缺陷,但由于空间位阻效应的存在,容易导致聚酰胺-胺树形大分子在硅胶表面负载量降低。以上存在的问题都会导致固载较高代数聚酰胺-胺树形大分子的吸附剂对金属离子的吸附量反而减小。Adsorption is widely used for the separation and removal of metal ions due to its simplicity and high efficiency. Polyamide-amine dendrimers contain a large number of nitrogen and oxygen functional groups and intramolecular cavities, which are easy to realize the adsorption and separation of metal ions. Moreover, polyamide-amine dendrimers are easy to be functionalized, and can be modified according to specific requirements to achieve selective adsorption and separation of specific metal ions. However, polyamide-amine dendrimers and metal ion complexes are easily soluble in aqueous solutions and most organic solvents, which greatly limits their application as adsorbents. Immobilizing polyamide-amine dendrimers on specific groups is an effective way to solve this problem. Silica gel has the advantages of good mechanical strength, good thermal and chemical stability, rich pore structure, large specific surface area, and the surface is rich in silanol and easy to modify. It is often used as a material for immobilizing polyamide-amine dendrimers. matrix. At present, there are usually two methods for immobilizing polyamide-amine dendrimers on silica gel, one is to introduce reactive sites on the surface of silica gel, and then gradually synthesize polyamide-amine dendrimers by the divergent method; the other The first is to attach the synthesized polyamide-amine dendrimer to the surface of silica gel through the coupling reaction between functional groups. The first synthesis method is convenient for the separation and purification of products during the synthesis process, but it will lead to the formation of intramolecular and intermolecular cross-linking structures of polyamide-amine dendrimers on the surface of silica gel, and the reduction of silica gel pores. The second method can effectively avoid structural defects inside the polyamide-amine dendrimer, but due to the existence of steric hindrance, it is easy to reduce the loading capacity of the polyamide-amine dendrimer on the surface of silica gel. The above existing problems will lead to the decrease of the adsorption capacity of metal ions by the adsorbent immobilized with higher generation polyamide-amine dendrimers.
发明内容Contents of the invention
本发明要解决的技术问题是克服现有技术的不足,提供一种功能化聚酰胺-胺树形大分子金属离子吸附剂的制备方法。本发明所制备的吸附剂以含硫聚酰胺-胺树形大分子为功能基,对Hg(II)具有良好的结合能力,可以实现对水体中Hg(II)的有效吸附和选择性分离。The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a preparation method of a functionalized polyamide-amine dendrimer metal ion adsorbent. The adsorbent prepared by the invention uses sulfur-containing polyamide-amine dendrimers as functional groups, has good binding ability to Hg(II), and can realize effective adsorption and selective separation of Hg(II) in water.
为解决上述技术问题,本发明采用如下技术方案:一种功能化聚酰胺-胺树形大分子吸附剂的制备方法,包括:In order to solve the above-mentioned technical problems, the present invention adopts the following technical scheme: a preparation method of functionalized polyamide-amine dendrimer adsorbent, comprising:
取异硫氰酸甲酯,加入第1.0或2.0代三乙氧基硅基聚酰胺-胺树形大分子,以150-300毫升无水乙醇为溶剂,加热搅拌反应制得第1.0或2.0代三乙氧基硅基含硫聚酰胺-胺树形大分子,然后冷却至25℃;再加入正硅酸乙酯、水和氟化铵,继续搅拌反应,反应结束后样品在50℃下陈化48小时,过滤出产物并用无水乙醇抽提至少12小时,干燥得到第1.0或2.0代功能化聚酰胺-胺树形大分子吸附剂。Take methyl isothiocyanate, add the 1.0th or 2.0th generation triethoxy silicon-based polyamide-amine dendrimer, use 150-300 ml of absolute ethanol as a solvent, heat and stir the reaction to obtain the 1.0th or 2.0th generation Triethoxy silicon-based sulfur-containing polyamide-amine dendrimers, then cooled to 25°C; then added tetraethyl orthosilicate, water and ammonium fluoride, and continued to stir the reaction. After the reaction, the samples were aged at 50°C After 48 hours, the product was filtered out and extracted with absolute ethanol for at least 12 hours, and dried to obtain the 1.0th or 2.0th generation functionalized polyamidoamine dendrimer adsorbent.
在上述技术方案的基础上,本发明还可以做如下改进。On the basis of the above technical solutions, the present invention can also be improved as follows.
进一步,整个制备过程均在氮气保护下进行;Further, the whole preparation process is carried out under nitrogen protection;
进一步,所述第1.0或2.0代三乙氧基硅基聚酰胺-胺树形大分子中氨基和异硫氰酸甲酯的摩尔比为1:(1.2-6),反应温度为50-70℃,时间为24-36小时;Further, the molar ratio of amino group to methyl isothiocyanate in the 1.0th or 2.0th generation triethoxysilyl polyamide-amine dendrimer is 1: (1.2-6), and the reaction temperature is 50-70 °C, the time is 24-36 hours;
进一步,所述第1.0或2.0代三乙氧基硅基含硫聚酰胺-胺树形大分子与正硅酸乙酯、水及氟化铵的摩尔比为1:(2-10):(1-12):(0.01-0.05),反应温度为25℃,反应时间为24-36小时。Further, the molar ratio of the 1.0th or 2.0th generation triethoxy silicon-based sulfur-containing polyamide-amine dendrimer to tetraethylorthosilicate, water and ammonium fluoride is 1: (2-10): ( 1-12): (0.01-0.05), the reaction temperature is 25°C, and the reaction time is 24-36 hours.
本发明所用第1.0或2.0代三乙氧基硅基聚酰胺-胺树形大分子通过发散合成法得到,具体制备方法参考文献Rongjun Qu, Xilu Ma, Minghua Wang, et al, Journal ofIndustrial and Engineering Chemistry, 2014, 20: 4382-4392。The 1.0th or 2.0th generation triethoxysilyl-based polyamide-amine dendrimers used in the present invention are obtained by a divergent synthesis method, and the specific preparation method refers to the literature Rongjun Qu, Xilu Ma, Minghua Wang, et al , Journal of Industrial and Engineering Chemistry , 2014, 20: 4382-4392.
第1.0代三乙氧基硅基酰胺-胺树形大分子的合成步骤如下:The synthesis steps of the 1.0th generation triethoxysilyl amide-amine dendrimer are as follows:
在氮气保护下,将160毫升丙烯酸甲酯的甲醇溶液(体积比为1:1)逐滴滴加到150毫升3-氨丙基三乙氧基硅烷的甲醇溶液中(体积比为1:1),反应混合物在0℃下搅拌反应0.5小时后升至25℃继续反应24小时。反应结束后用旋转蒸发仪在40℃下蒸出甲醇和过量的丙烯酸甲酯,得到第0.5代三乙氧基硅基聚酰胺-胺树形大分子。随后在0℃下,将第0.5代三乙氧基硅基聚酰胺-胺树形大分子的甲醇溶液(25克溶于30毫升甲醇中)逐滴滴加到240毫升乙二胺的甲醇溶液中(体积比为1:1),反应0.5小时后再升温至25℃反应96小时。反应结束后用旋转蒸发仪在70℃下蒸出甲醇和过量的乙二胺,制得第1.0代三乙氧基硅基酰胺-胺树形大分子。Under nitrogen protection, the methanol solution of 160 milliliters of methyl acrylate (volume ratio is 1:1) is added dropwise in the methanol solution of 150 milliliters of 3-aminopropyltriethoxysilane (volume ratio is 1:1 ), the reaction mixture was stirred at 0°C for 0.5 hour and then raised to 25°C to continue the reaction for 24 hours. After the reaction, use a rotary evaporator to distill off methanol and excess methyl acrylate at 40° C. to obtain the 0.5th generation triethoxysilyl polyamide-amine dendrimer. Subsequently, a methanol solution of the 0.5th generation triethoxysilylpolyamidoamine dendrimer (25 g dissolved in 30 ml of methanol) was added dropwise to a methanol solution of 240 ml of ethylenediamine at 0 °C (1:1 volume ratio), after 0.5 hours of reaction, the temperature was raised to 25°C for 96 hours. After the reaction, use a rotary evaporator to distill off methanol and excess ethylenediamine at 70° C. to obtain the 1.0th generation triethoxysilylamide-amine dendrimer.
第2.0代三乙氧基硅基酰胺-胺树形大分子的合成步骤如下:The synthesis steps of the 2.0th generation triethoxysilyl amide-amine dendrimer are as follows:
在氮气保护下,将40毫升丙烯酸甲酯的甲醇溶液(体积比为1:1)逐滴滴加到第1.0代三乙氧基硅基聚酰胺-胺树形大分子的甲醇溶液中(20克于30毫升甲醇中)中,混合物在0℃下搅拌反应0.5小时后至25℃继续反应24小时。反应结束后用旋转蒸发仪在40℃下蒸出甲醇和过量的丙烯酸甲酯,得到第1.5代三乙氧基硅基聚酰胺-胺树形大分子。随后在0℃下,将第1.5代三乙氧基硅基聚酰胺-胺树形大分子的甲醇溶液(12克溶于15毫升甲醇中)逐滴滴加到100毫升乙二胺的甲醇溶液中(体积比为1:1),反应0.5小时后再升温至25℃反应96小时。反应结束后用旋转蒸发仪在70℃下蒸出甲醇和过量的乙二胺,制得第2.0代三乙氧基硅基酰胺-胺树形大分子。Under nitrogen protection, 40 milliliters of methyl acrylate methanol solution (volume ratio is 1:1) was added dropwise in the methanol solution of the 1.0th generation triethoxysilyl polyamide-amine dendrimer (20 g in 30 ml of methanol), the mixture was stirred at 0°C for 0.5 hour and then continued to react at 25°C for 24 hours. After the reaction, use a rotary evaporator to distill off methanol and excess methyl acrylate at 40° C. to obtain the 1.5th generation triethoxysilyl polyamide-amine dendrimer. Subsequently, a methanol solution of the 1.5th generation triethoxysilyl polyamido-amine dendrimer (12 g dissolved in 15 ml of methanol) was added dropwise to a methanol solution of 100 ml of ethylenediamine at 0 °C (1:1 volume ratio), after 0.5 hours of reaction, the temperature was raised to 25°C for 96 hours. After the reaction, use a rotary evaporator to distill off methanol and excess ethylenediamine at 70° C. to obtain the 2.0th generation triethoxysilylamide-amine dendrimer.
本发明与已有技术相比具有如下优势:Compared with the prior art, the present invention has the following advantages:
本合成方法所制备的功能化聚酰胺-胺树形大分子吸附剂中聚酰胺-胺树形大分子结构规整、功能基含量高、吸附位点分布均匀,对Hg(II)具有良好的结合能力,可以实现对水体中Hg(II)的有效吸附和选择性分离。In the functionalized polyamide-amine dendrimer adsorbent prepared by the synthesis method, the polyamide-amine dendrimer has a regular structure, a high content of functional groups, and uniform distribution of adsorption sites, and has good binding to Hg(II). Ability to achieve effective adsorption and selective separation of Hg(II) in water.
具体实施方式Detailed ways
以下对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。The principles and features of the present invention are described below, and the examples given are only used to explain the present invention, and are not intended to limit the scope of the present invention.
实施例1Example 1
在氮气保护下,将8毫摩尔的第1.0代三乙氧基硅基聚酰胺-胺树形大分子和24毫摩尔异硫氰酸甲酯加入到500毫升的三口烧瓶中,随后加入150毫升无水乙醇为溶剂,反应混合物在50℃下反应36小时,然后冷却至25℃得到第1.0代三乙氧基硅基含硫聚酰胺-胺树形大分子;随后加入16毫摩尔正硅酸乙酯、8毫摩尔水和0.08毫摩尔的氟化铵,反应混合物在25℃下反应24小时,反应结束后样品在50℃下陈化48小时,过滤出产物并用无水乙醇抽提12小时,干燥得到第1.0功能化聚酰胺-胺树形大分子吸附剂。Under nitrogen protection, 8 mmoles of the 1.0th generation triethoxysilyl polyamide-amine dendrimer and 24 mmoles of methyl isothiocyanate were added to a 500 ml three-necked flask, followed by 150 ml Anhydrous ethanol was used as a solvent, and the reaction mixture was reacted at 50°C for 36 hours, then cooled to 25°C to obtain the 1.0th generation triethoxysilyl-based sulfur-containing polyamide-amine dendrimer; then 16 mmoles of orthosilicic acid were added Ethyl ester, 8 mmol of water and 0.08 mmol of ammonium fluoride, the reaction mixture was reacted at 25 °C for 24 hours, after the reaction, the sample was aged at 50 °C for 48 hours, the product was filtered out and extracted with absolute ethanol for 12 hours , and dried to obtain the 1.0th functionalized polyamide-amine dendrimer adsorbent.
实施例2Example 2
在氮气保护下,将8毫摩尔的第1.0代三乙氧基硅基聚酰胺-胺树形大分子和48毫摩尔异硫氰酸甲酯加入到500毫升的三口烧瓶中,随后加入250毫升无水乙醇为溶剂,反应混合物在70℃下反应24小时,然后冷却至25℃得到第1.0代三乙氧基硅基含硫聚酰胺-胺树形大分子;随后加入32毫摩尔正硅酸乙酯、16毫摩尔水和0.16毫摩尔的氟化铵,反应混合物在25℃下反应36小时,反应结束后样品在50℃下陈化48小时,过滤出产物并用无水乙醇抽提12小时,干燥得到第1.0功能化聚酰胺-胺树形大分子吸附剂。Under nitrogen protection, 8 mmoles of the 1.0th generation triethoxysilyl polyamide-amine dendrimer and 48 mmoles of methyl isothiocyanate were added to a 500 ml three-necked flask, followed by 250 ml Anhydrous ethanol was used as a solvent, and the reaction mixture was reacted at 70°C for 24 hours, then cooled to 25°C to obtain the 1.0th generation triethoxysilyl-based sulfur-containing polyamide-amine dendrimer; then 32 mmoles of orthosilicic acid were added Ethyl ester, 16 mmoles of water and 0.16 mmoles of ammonium fluoride, the reaction mixture was reacted at 25°C for 36 hours, after the reaction, the sample was aged at 50°C for 48 hours, the product was filtered out and extracted with absolute ethanol for 12 hours , and dried to obtain the 1.0th functionalized polyamide-amine dendrimer adsorbent.
实施例3Example 3
在氮气保护下,将8毫摩尔的第2.0代三乙氧基硅基聚酰胺-胺树形大分子和48毫摩尔异硫氰酸甲酯加入到500毫升的三口烧瓶中,随后加入250毫升无水乙醇为溶剂,反应混合物在60℃下反应30小时,然后冷却至25℃得到第2.0代三乙氧基硅基含硫聚酰胺-胺树形大分子;随后加入32毫摩尔正硅酸乙酯、24毫摩尔水和0.16毫摩尔的氟化铵,反应混合物在25℃下反应32小时,反应结束后样品在50℃下陈化48小时,过滤出产物并用无水乙醇抽提12小时,干燥得到第2.0功能化聚酰胺-胺树形大分子吸附剂。Under nitrogen protection, 8 mmoles of the 2.0th generation triethoxysilyl polyamide-amine dendrimer and 48 mmoles of methyl isothiocyanate were added to a 500 ml three-necked flask, followed by 250 ml Anhydrous ethanol was used as a solvent, and the reaction mixture was reacted at 60°C for 30 hours, and then cooled to 25°C to obtain the 2.0th generation triethoxysilyl-based sulfur-containing polyamide-amine dendrimers; then 32 mmoles of orthosilicic acid were added Ethyl ester, 24 mmoles of water and 0.16 mmoles of ammonium fluoride, the reaction mixture was reacted at 25°C for 32 hours, after the reaction, the sample was aged at 50°C for 48 hours, the product was filtered out and extracted with absolute ethanol for 12 hours , and dried to obtain the 2.0th functionalized polyamide-amine dendrimer adsorbent.
实施例4Example 4
在氮气保护下,将8毫摩尔的第2.0代三乙氧基硅基聚酰胺-胺树形大分子和80毫摩尔异硫氰酸甲酯加入到500毫升的三口烧瓶中,随后加入300毫升无水乙醇为溶剂,反应混合物在70℃下反应24小时,然后冷却至25℃得到第2.0代三乙氧基硅基含硫聚酰胺-胺树形大分子;随后加入24毫摩尔正硅酸乙酯、16毫摩尔水和0.24毫摩尔的氟化铵,反应混合物在25℃下反应24小时,反应结束后样品在50℃下陈化48小时,过滤出产物并用无水乙醇抽提12小时,干燥得到第2.0功能化聚酰胺-胺树形大分子吸附剂。Under nitrogen protection, 8 mmoles of the 2.0th generation triethoxysilyl polyamide-amine dendrimer and 80 mmoles of methyl isothiocyanate were added to a 500 ml three-necked flask, followed by 300 ml Anhydrous ethanol was used as a solvent, and the reaction mixture was reacted at 70°C for 24 hours, then cooled to 25°C to obtain the 2.0th generation triethoxysilyl-based sulfur-containing polyamide-amine dendrimer; 24 mmol orthosilicic acid was then added Ethyl ester, 16 mmoles of water and 0.24 mmoles of ammonium fluoride, the reaction mixture was reacted at 25°C for 24 hours, after the reaction, the sample was aged at 50°C for 48 hours, the product was filtered out and extracted with absolute ethanol for 12 hours , and dried to obtain the 2.0th functionalized polyamide-amine dendrimer adsorbent.
性能评价1:实施例2和实施例3制备的功能化聚酰胺-胺树形大分子吸附剂对Hg(Ⅱ)的吸附性能Performance Evaluation 1: The Adsorption Performance of the Functionalized Polyamide-Amine Dendrimer Adsorbent Prepared in Example 2 and Example 3 for Hg(II)
分别称取20毫克实施例2和实施例3制备的第1.0和2.0代功能化聚酰胺-胺树形大分子吸附剂,置于100毫升具塞锥形瓶中,分别加入20毫升0.001摩尔/升的Hg(II)溶液,置于气浴振荡器中并在25℃下振荡12小时。用原子吸收分光光度计测定溶液中剩余Hg(Ⅱ)的浓度,根据吸附前后Hg(Ⅱ)离子浓度的变化,计算出第1.0和2.0代功能化聚酰胺-胺树形大分子吸附剂对Hg(II)离子的吸附量分别为1.55和1.68毫摩尔/克。Weigh respectively 20 mg of the 1.0th and 2.0th generation functionalized polyamide-amine dendrimer adsorbents prepared in Example 2 and Example 3, place them in a 100 ml conical flask with a stopper, add 20 ml of 0.001 mol/ One liter of Hg(II) solution was placed in an air bath shaker and shaken at 25°C for 12 hours. The concentration of remaining Hg(II) in the solution was measured with an atomic absorption spectrophotometer, and the Hg(II) ion concentration of the 1.0th and 2.0th generation functionalized polyamide-amine dendrimers was calculated according to the change of Hg(II) ion concentration before and after adsorption. The adsorption amounts of (II) ions were 1.55 and 1.68 mmol/g, respectively.
性能评价2:实施例2和实施例3制备的功能化聚酰胺-胺树形大分子吸附剂对Hg(Ⅱ)的选择性吸附Performance Evaluation 2: Selective Adsorption of Hg(II) by the Functionalized Polyamide-Amine Dendrimer Adsorbent Prepared in Example 2 and Example 3
分别称取一系列质量约为20毫克的实施例2和实施例3制备的第1.0和2.0代功能化聚 酰胺-胺树形大分子吸附剂,置于100毫升具塞锥形瓶中,随后分别加入20毫升离子浓度均 为0.001 摩尔/升Hg( )-Co()、Hg()-Pb()、Hg()-Mn()、Hg()-Ni()、Hg()- Fe(III)、Hg()-Cu()、Hg()-Cd()的混合离子溶液,置于气浴振荡器中并在25℃下 振荡12小时。用原子吸收分光光度计分别测定溶液中剩余Hg(Ⅱ)的浓度及其他金属离子的 浓度,根据吸附前后金属离子浓度的变化,计算出对Hg(II)及共存离子的吸附量及选择性 系数,结果见表1和表2。可见功能化聚酰胺-胺树形大分子吸附剂对Hg(II)表现出良好的吸 附选择性,当Hg()与Co()、Pb()、Mn()、Ni()、Fe(III)等离子共存时,能够100%选 择性吸附Hg(II)。 Weigh a series of 1.0th and 2.0th generation functionalized polyamidoamine dendrimer adsorbents prepared in Example 2 and Example 3 with a mass of about 20 mg respectively, place them in a 100 ml conical flask with a stopper, and then Add 20 milliliters of ion concentration respectively and all are 0.001 mol/L Hg ( )-Co( ), Hg( )-Pb( ), Hg( )-Mn( ), Hg( )-Ni( ), Hg( )- Fe(III), Hg( )-Cu( ), Hg( )-Cd( ) mixed ion solution, placed in an air bath shaker and shaken at 25°C for 12 hours. Use an atomic absorption spectrophotometer to measure the concentration of remaining Hg(II) and other metal ions in the solution, and calculate the adsorption capacity and selectivity coefficient for Hg(II) and coexisting ions according to the changes in the concentration of metal ions before and after adsorption. , the results are shown in Table 1 and Table 2. It can be seen that the functionalized polyamide-amine dendritic macromolecular adsorbent shows good adsorption selectivity for Hg(II), when Hg( ) and Co( ), Pb( ), Mn( ), Ni( ), Fe(III) ions coexist, and can selectively adsorb Hg(II) with 100%.
表1 第1.0代功能化聚酰胺-胺树形大分子吸附剂对Hg(II)的选择性吸附Table 1 Selective adsorption of Hg(II) by the 1.0th generation functionalized polyamide-amine dendrimers
表2 第2.0代功能化聚酰胺-胺树形大分子吸附剂对Hg(II)的选择性吸附Table 2 Selective adsorption of Hg(II) by the 2.0th generation functionalized polyamide-amine dendrimers
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within range.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114558551A (en) * | 2022-03-31 | 2022-05-31 | 陕西科技大学 | Magnetic composite adsorption material with sulfur-containing surface and preparation method thereof |
CN116813930A (en) * | 2023-08-29 | 2023-09-29 | 鲁东大学 | Preparation method of a high molecular weight hyperbranched dendritic macromolecule metal ion adsorbent |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006065266A2 (en) * | 2004-04-20 | 2006-06-22 | Dendritic Nanotechnologies, Inc. | Dendritic polymers with enhanced amplification and interior functionality |
CN101671554A (en) * | 2008-09-10 | 2010-03-17 | 首都医科大学 | Silica-coated fluorescent magnetic nanoparticle, preparation method and application |
CN102161758A (en) * | 2011-01-26 | 2011-08-24 | 大连理工大学 | Preparation method of novel silica gel-based hyperbranched PAMAM (polyamidoamine) chelating resin |
CN102302782A (en) * | 2011-07-08 | 2012-01-04 | 东华大学 | Preparation method of hepatoma carcinoma cell-targeted polyamido-amine dendrimer support |
CN102671710A (en) * | 2011-03-07 | 2012-09-19 | 河南科技大学 | Noble metal nanocatalyst loaded on dendritic macromolecule functionalized graphene and preparation method thereof |
CN102895958A (en) * | 2012-10-24 | 2013-01-30 | 常州大学 | Attapulgite clay based adsorbing material and preparation method thereof |
CN104130422A (en) * | 2014-07-25 | 2014-11-05 | 鲁东大学 | Preparation method of silica gel-bonded polyamidoamine (PAMAM) dendrimer adsorbent |
CN104645948A (en) * | 2015-02-12 | 2015-05-27 | 鲁东大学 | Preparation method of silica bonding sulfur-containing terminal group PAMAM dendrimer adsorption agent |
CN106589401A (en) * | 2017-01-04 | 2017-04-26 | 安庆师范大学 | Preparation method of P-containing silica gel-supported PAMAM type dendritic polymer |
-
2019
- 2019-10-23 CN CN201911011041.XA patent/CN110614089A/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006065266A2 (en) * | 2004-04-20 | 2006-06-22 | Dendritic Nanotechnologies, Inc. | Dendritic polymers with enhanced amplification and interior functionality |
CN101671554A (en) * | 2008-09-10 | 2010-03-17 | 首都医科大学 | Silica-coated fluorescent magnetic nanoparticle, preparation method and application |
CN102161758A (en) * | 2011-01-26 | 2011-08-24 | 大连理工大学 | Preparation method of novel silica gel-based hyperbranched PAMAM (polyamidoamine) chelating resin |
CN102671710A (en) * | 2011-03-07 | 2012-09-19 | 河南科技大学 | Noble metal nanocatalyst loaded on dendritic macromolecule functionalized graphene and preparation method thereof |
CN102302782A (en) * | 2011-07-08 | 2012-01-04 | 东华大学 | Preparation method of hepatoma carcinoma cell-targeted polyamido-amine dendrimer support |
CN102895958A (en) * | 2012-10-24 | 2013-01-30 | 常州大学 | Attapulgite clay based adsorbing material and preparation method thereof |
CN104130422A (en) * | 2014-07-25 | 2014-11-05 | 鲁东大学 | Preparation method of silica gel-bonded polyamidoamine (PAMAM) dendrimer adsorbent |
CN104645948A (en) * | 2015-02-12 | 2015-05-27 | 鲁东大学 | Preparation method of silica bonding sulfur-containing terminal group PAMAM dendrimer adsorption agent |
CN106589401A (en) * | 2017-01-04 | 2017-04-26 | 安庆师范大学 | Preparation method of P-containing silica gel-supported PAMAM type dendritic polymer |
Non-Patent Citations (2)
Title |
---|
YUZHONG NIU ET AL.: "Synthesis of Silica-Gel-Supported Sulfur-Capped PAMAM Dendrimers for Efficient Hg(II) Adsorption: Experimental and DFT Study", 《IND. ENG. CHEM. RES.》 * |
高丽花: "硅胶负载PAMAM树形大分子对金属离子的吸附", 《合成树脂及塑料》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114558551A (en) * | 2022-03-31 | 2022-05-31 | 陕西科技大学 | Magnetic composite adsorption material with sulfur-containing surface and preparation method thereof |
CN116813930A (en) * | 2023-08-29 | 2023-09-29 | 鲁东大学 | Preparation method of a high molecular weight hyperbranched dendritic macromolecule metal ion adsorbent |
CN116813930B (en) * | 2023-08-29 | 2023-12-15 | 鲁东大学 | Preparation method of a high molecular weight hyperbranched dendritic macromolecule metal ion adsorbent |
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