四苯基乙烯基共轭微孔聚合物的制备及其气体吸附

共轭微孔聚合物由于其在气体吸附与分离、非均相催化和光电子等领域的巨大应用前景而广受关注. 本文以四苯基乙烯为基本构筑单元, 通过Sonogashira-Hagihara偶联反应制备了3种共轭微孔聚合物新材料, 研究了结构组成和构建模块对制备聚合物孔性能和气体吸附性能的影响. 氮气吸附测试结果表明, 由1,1,2,2-四炔四苯基乙烯自聚合制备的TPE-CMP1具有较大的比表面积, 为1096 m²·g^-1. 在1.13 bar/273 K条件下, TPE-CMP1的CO₂吸附能力为2.36 mmol·g^-1; 在1.13 bar/77.3 K条件下, TPE-CMP1对H₂的吸附能力为1.35 wt%. 另外, 制备的共轭微孔聚合物展示出较高的CO₂/N₂选择性吸附值. 由于这类多孔聚合物材料具有合成方法简单、优良的物理化学及热稳定性、高的比表面积和CO₂吸附性能, 因此将在气体吸附与分离方面具有潜在的应用前景.     

Hyper-crosslinked Conjugated Microporous Polymers with Increased Micropores Promotes Confining Polymerization for Electromagnetic Absorption Application

Conjugated microporous polymers have excellent skeleton structures but poor electrical conductivity limits their applications in microwave absorption. To solve this problem, a strategy of molecular expansion and confining polymerization is proposed in this work to synthesize conductive hyper-crosslinked conjugated microporous polymer. The topology of the conjugated microporous polymer is changed into a three-dimensional skeleton structure with high specific surface area by using molecular expans...     

Preparation and Adsorption Characteristics of Cordycepin Molecularly Imprinted Polymers

The separation of a molecularly imprinted polymer for cordycepin was investigated. The synthesis employed cordycepin as the molecular template, alpha-methylacrylic acid as the functional monomer, glycol dimethyl acrylate as the cross-linking agent, azobisisobutyronitrile as the initiator, and tetrahydrofuran as the solvent and pore-foaming agent. The interaction between cordycepin and the functional monomer was investigated by ultraviolet-visible and infrared spectroscopy. The properties of the molecularly imprinted polymer were analyzed by scanning electron microscopy, equilibrium adsorption experiments, and the Scatchard equation. Static adsorption, solid phase extraction, and high-performance liquid chromatography experiments were employed to evaluate the adsorption properties and selective recognition characteristics. The results showed that the molecularly imprinted polymer had specific adsorption with cordycepin, and the maximum absorption capacity was 1920 µg/g. Scatchard analysis suggested that high affinity and low affinity binding sites were present. For the high affinity case, the dissociation constant and apparent maximum numbers of the binding sites were 0.0089 mmol/L and 4.78 µmol/g, respectively. The dissociation constant and apparent numbers of binding sites were 0.035 mmol/L and 6.047 µmol/g for the low affinity sites. Compared with the corresponding nonimprinted polymer, the cordycepin molecularly imprinted polymer exhibited higher adsorption and selectivity for cordycepin than structural analogs.     

谷胱甘肽磁性分子印迹聚合物的制备及吸附性能研究

采用表面分子印迹技术,以谷胱甘肽（GSH）为模板分子,N-乙烯基吡咯烷酮（NVP）和丙烯酰胺（AM）为功能单体,N,N’-亚甲基双丙烯酰胺（MBA）为交联剂,γ-（甲基丙烯酰氧）丙基三甲氧基硅烷（KH570）改性的Fe₃O₄纳米颗粒为磁性载体,制备了对GSH有特异识别性的磁性分子印迹聚合物（GSH-MMIPs）. 利用X射线衍射仪（XRD）、透射电子显微镜（TEM）、红外光谱（FT-IR）和振动样品磁强计（VSM）对聚合物进行了表征,结果表明磁性载体表面成功地包覆了分子印迹聚合物薄层. 静态吸附平衡实验和Scatchard分析结果表明,GSH-MMIPs中存在两类不同的结合位点,平衡解离常数分别为8.786×10^-4 mol/L和5.424×10^-3 mol/L,最大吸附量分别为49.195 mg/g和155.003 mg/g. 与化学组成相同的磁性非印迹聚合物（GSH-MNIPs）相比,GSH-MMIPs对谷胱甘肽有较高的选择吸附性能.     

含氟共轭微孔聚合物的制备及其吸附应用研究

共轭微孔聚合物由于其高的比表面积、优良的物理化学稳定性、多样的合成方法以及沿分子骨架延伸的共轭结构等特点,近几年得到广泛关注和快速发展.本工作以1,3,5-三氟-2,4,6-三碘苯作为含氟单体与1,3,5-三乙炔基苯通过Sonogashira偶联反应聚合得到含氟共轭微孔聚合物F-CMP.通过把氟原子引入到共轭微孔聚合物骨架中,F-CMP显示出良好的疏水性能,与水的接触角达到145°.得益于良好的疏水性能和适宜的孔隙结构,相比于骨架结构相似的不含氟共轭微孔聚合物（H-CMP）,F-CMP对油和有机溶剂的吸附量得到大幅提高,且显示出高的吸附速率和良好的吸附循环性.     

槲皮素磁性分子印记聚合物的制备及其吸附性能

以槲皮素(Qu)为模板分子、N-乙烯基吡咯烷酮(NVP)和丙烯酸(AA)为功能单体、N,N′-亚甲基双丙烯酰胺(MBA)为交联剂、H2O2-Vc为引发剂、KH570修饰的Fe3O4纳米颗粒为磁性载体,借助表面分子印迹技术制备了能够对Qu进行特异性识别的槲皮素磁性分子印迹聚合物(Qu-MMIPs)。利用X射线衍射仪(XRD)、透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FT-IR)、振动样品磁强计(VSM)和紫外-可见分光光度计(UV-Vis)对样品进行了结构和性能表征。结果表明:Fe3O4磁性载体表面已成功包覆了分子印迹聚合物。与化学组成相同的磁性非印迹聚合物(Qu-MNIPs)相比,Qu-MMIPs对Qu有较高的吸附选择性。静态吸附平衡实验和Scatchard分析结果表明,Qu-MMIPs中存在两类不同的结合位点,平衡解离常数分别为1.646×10-6 mol/L和6.387×10-6 mol/L,最大吸附量分别为23.041mg/g和29.923mg/g。     

镓离子配合物印迹聚合物的研制及吸附性能研究

以8-羟基喹啉镓(Gaq3)为模板分子,丙烯酰胺为功能单体,二甲基丙烯酸乙二醇酯为交联剂,偶氮二异丁腈为引发剂,由沉淀聚合法在三氯甲烷和甲醇(体积比3:2)的混合溶剂中制备镓离子印迹聚合物.采用红外光谱和热重分析对其进行表征;采用等温平衡吸附实验和Langmuir吸附模型分析研究其吸附性能.以其作为固相萃取填料,应用于...     

苯甲酸分子印迹聚合物的制备及其吸附性能

以苯甲酸为模板分子,4-乙烯基吡啶为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用本体聚合法制备了高选择性识别的分子印迹聚合物。利用合成的聚合物作为吸附剂填充制备气体浓缩针装置,并用于挥发性有机化合物(VOCs)的气相色谱分析。实验结果表明:60℃下恒温聚合反应6h,模板分子、功能单体、交联剂的物质量比为1∶4∶20,预聚合时间为3h,溶剂为乙腈,模板分子为苯甲酸时,合成的分子印迹聚合物对苯系物的吸附量最大。     

胆固醇分子印迹聚合物的制备及其选择性吸附

随着人们生活水平的逐步提高,因人体内胆固醇过高所产生的疾病呈逐年增加的趋势.近年来的研究表明,胆固醇分子印迹聚合物对胆固醇具有良好的选择性吸附能力.将胆固醇分子印迹聚合物作为胆固醇的识别剂,提取食品中的胆固醇和治疔胆固醇有关的疾病,展现出了良好的应用前景.本文分别从胆固醇分子印迹聚合物的制备方法、识别机理、提高选择性识别途径以及新的印迹方法等方面进行了综述.     

石杉碱甲分子印迹聚合物的制备、表征及其吸附性能

以硅胶为牺牲载体,石杉碱甲为模板分子,甲基丙烯酸为功能单体,二乙烯基苯为交联剂,偶氮二异丁腈为引发剂,首次制备了石杉碱甲分子印迹聚合物,并用红外光谱、扫描电子显微镜和热重分析研究了印迹聚合物的结构特征,用静态吸附法和Scatchard分析法研究了印迹聚合物的识别效能和表面位点分布特征。 结果表明,石杉碱甲印迹聚合物对模板分子具有较好的选择吸附性能,选择系数为1.399。Scatchard分析表明,印迹聚合物基体中主要存有两类吸附位点,对高亲和位点：平衡离解常数Kd1=0.776 g/L,最大表观结合量Qmax1=0.213 mg/g;对低亲和位点：平衡离解常数Kd2=0.169 g/L,最大表观结合量Qmax2=0.832 mg/g。 当该聚合物用于微固相萃取蛇足石杉粗提液中的石杉碱甲时,石杉碱甲回收率为93.5%,显示了较好的富集效果。     

富羧酸基团的共轭微孔聚合物:结构单元对孔隙和气体吸附性能的影响

Polar groups in the skeletons of conjugated microporous polymers (CMPs) play an important role in determining their porosity and gas sorption performance. Understanding the effect of the polar group on the properties of CMPs is essential for further advances in this field. To address this fundamental issue, we used benzene, the simplest aromatic system, as a monomer for the construction of two novel CMPs with multi-carboxylic acid groups in their skeletons (CMP-COOH@1 and CMP-COOH@2). We then explored the profound effect the amount of free carboxylic acid in each polymer had on their porosity, isosteric heat, gas adsorption, and gas selectivity. CMP-COOH@1 and CMP-COOH@2 showed Brunauer-Emmett-Teller (BET) surface areas of 835 and 765 m²·g^-1, respectively, displaying high potential for carbon dioxide storage applications. CMP-COOH@1 and CMP-COOH@2 exhibited CO₂ capture capabilities of 2.17 and 2.63 mmol·g^-1 (at 273 K and 1.05 × 10⁵ Pa), respectively, which were higher than those of their counterpart polymers, CMP-1 and CMP-2, which showed CO₂ capture capabilities of 1.66 and 2.28 mmol·g^-1, respectively. Our results revealed that increasing the number of carboxylic acid groups in polymers could improve their adsorption capacity and selectivity.     

双酚F分子印迹聚合物的制备及其对水相中双酚F吸附性能的研究

以双酚F(4,4′-BPF)为模板分子,α-甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂,采用沉淀聚合法合成4,4′-BPF分子印迹聚合物(MIPs)。运用傅里叶红外(FT-IR)光谱对产物的结构进行表征,并对其吸附等温线、吸附动力学、吸附热力学及选择性识别性能进行研究。结果表明:MIPs对水相中4,4′-BPF具有特异性吸附,最大吸附容量为82.8 mg/g;Freundlich模型拟合吸附等温线的相关系数R2=0.995;热力学参数ΔG、ΔS、ΔH均小于0,表明此吸附过程是自发进行的、熵减的、放热的。     

双功能单体法制备磁性葡萄糖分子印迹聚合物及其吸附性能研究

采用表面分子印迹技术,以改性的磁纳米球作为载体,双功能单体分别为刀豆凝集素和3-氨基苯硼酸,交联剂为N,N'-亚甲基双丙烯酰胺,引发剂为过硫酸铵,采用二次接枝法成功合成了双功能单体的磁性葡萄糖分子印迹聚合物(MMIPs).通过多种表征技术:X射线衍射,扫描电子显微镜,红外光谱,振动样品磁强计,热重分析仪对合成的聚合物进行了表征分析.通过吸附动力学、热力学模型对实验数据进行拟合,探究了反应的吸附机理和吸附过程.合成的MMIPs的印迹因子能达到2.93,吸附量为9.112 mg/g.对其类特异性吸附的探索使得合成的聚合物还可应用于富含糖苷类化合物的提取与分离.     

Structural Variability and Gas Adsorption Properties of Coordination Polymers Constructed with Aromatic Multicarboxylic and Bidentate Ligands

The self‐assembly reactions of transition metal ions and 1,3,5‐benzenetricarboxylic acid (H₃btc) in the presence of auxiliary aromatic bidentate ligands 1,10‐phenanthroline (1,10‐phen) or 4,4′‐bipyridine‐N,N′‐dioxide (4,4′‐bpdo) have isolated four coordination polymers [Co₁₈(btc)₁₀(H₂O)₆(OH)₆(1,10‐phen)₆] · 14H₂O · 3DMF ( 1 ) and [M₃(btc)₂(H₂O)₄(4,4′‐bpdo)] · 2H₂O · 2DMF [M = Co ( 2 ), Mn ( 3 ), Ni ( 4 )]. Single‐crystal X‐ray diffraction analysis revealed that the M₃ clusters in the structure of 1 – 4 are connected by hydroxyl group oxygen atoms (or oxygen atoms from 4,4′‐bpdo ligands) and carboxyl groups to generate a three‐dimensional framework. The network of final assemblies can be adjusted by varying the type of auxiliary ligands (1,10‐phen, 4,4′‐bpdo). In addition, the gas adsorption properties of 2 are also investigated.     

杯芳烃-壳聚糖聚合物的合成与吸附性能

杯芳烃聚合物常常表现出优异的离子选择性识别性能,在离子交换与吸附、离子萃取与分离、离子传感器和离子色谱等方面有较好的应用前景,但这类聚合物的吸附能力一般较低。壳聚糖是甲壳素的脱乙酰衍生物,是具有广泛用途的天然生物高分子材料,其分子内有氨基和羟基,     

新型金属有机气凝胶的合成、 表征及气体吸附性能

利用高稳定性的UiO-66系列金属有机骨架多孔材料制备金属有机气凝胶材料, 制得的UiO-66系列金属有机气凝胶材料具有多级孔结构和较高的比表面积, 在气体吸附分离领域具有较大应用潜力. 气体吸附实验结果表明, UiO-66-NH₂金属有机气凝胶材料具有极佳的CO₂吸附性能和CO₂/CH₄分离性能, 通过理想吸附溶液理论计算得出其吸附选择性高达18.3.     

Gas Adsorption Equilibria

Gas adsorption is a process for purification or separation of gas mixtures. Distillation is usually the first choice for bulk separations when liquefaction can be accomplished conveniently and when the relative volatilities of the materials to be separated do not approach or equal unity (azeotropy). If these conditions are not met, adsorption may offer an advantage, either by avoiding high or low temperatures or by providing higher separation factors and lower energy costs. Therefore the first step in the consideration of adsorption for a particular separation is the identification of a suitable adsorbent.     

蒸馏沉淀法制备扑热息痛亲水核-壳分子印迹微球及其吸附性能研究

选取扑热息痛(PR)作为模板分子,甲基丙烯酸(MAA)为功能单体,通过蒸馏沉淀聚合制得聚合物内核;以丙烯酰胺(AM)作为亲水单体,采用不同的壳交联剂,乙二醇二甲基丙烯酸酯(EGDMA)、3-羟甲基丙烷三甲基丙烯酸酯(TRIM)、Ⅳ,Ⅳ'-亚甲基双丙烯酰胺(MBA)通过自由基聚合枝接亲水层外壳,成功制得一系列亲水核-壳分子印迹聚合物微球(CS-MIPs),并对比其对聚合物性能的影响.通过紫外光谱(UV)、红外(FT-IR)光谱、扫描电镜(SEM)以及吸附实验进行表征,并进行了亲水性能测试.结果表明,采用MBA作交联剂的印迹微球吸附性能以及亲水性能最好,吸附量达120 μmol/g,接触角23.3°.本研究为检测水溶液中扑热息痛含量,提供了一种新思路.     

丙烯酰胺类聚合物合成方法研究进展

丙烯酰胺类聚合物具有优异的增稠、絮凝、吸湿特性,是水溶性聚合物中重要的品种之一.本文从水溶液聚合、分散聚合、反相悬浮聚合、反相微乳液聚合、胶束共聚合、双水相聚合、模板聚合、超临界CO2中聚合、离子液体中聚合和活性/可控自由基聚合等方面对丙烯酰胺类聚合物的合成方法研究作了全面的总结,同时简要评述了各种合成方法的特点,认为反相微乳液聚合、离子液体中聚合及活性/可控自由基聚合等方法具备独特的优势,并对丙烯酰胺类聚合物今后的发展前景作出了预测.