物理化学综合实验:g-C3N4/MIL-125(Ti)的制备表征及其光催化还原Cr(Ⅵ)性能测试

该综合实验制备了一种负载型催化剂，并对其光催化还原Cr（Ⅵ）性能进行测试。采用溶剂热法制备g-C3N4/MIL-125（Ti）催化剂，通过X射线粉末衍射（XRD）、透射电子显微镜（TEM）、N2-吸脱附曲线、固体紫外-可见漫反射光谱（DRS）、荧光光谱（PL）及交流阻抗谱（EIS）表征了催化剂的结构、形态以及光催化性能。结合材料的表征数据及性能测试结果分析探讨g-C3N4的负载量对光催化还原Cr（Ⅵ）活性的影响，进一步探究该催化反应的进行机制。该实验实现了光催化技术与物理化学实验教学的结合，可让学生获取催化学科的前沿知识，了解催化反应以及各种现代测试技术的基本原理。     

水杨酸甲酯制备实验的改进

"水杨酸甲酯的制备"是一个经典的有机化学实验，作为考核实验考查学生操作技能，并根据产品的质量和纯度给予学生成绩。教材中提供的实验方案不合理，导致学生制备产品的收率很低。对传统实验方法的不足之处进行分析，提出了先用碳酸钠中和硫酸（去除催化剂），再蒸馏分离甲醇的实验路线。改进的实验方案设计更合理，避免了水杨酸甲酯分解，提高了产品的收率，达到了良好的教学效果。     

4,4'-[(2,2-二苯乙烯)-1,1-双(4,1-亚苯基)]二吡啶的合成、表征及其聚集诱导发光性能研究

以提升学生的实验操作及创新能力为目的的综合化学实验，采用简单的2步法（缩合和Suzuki反应）合成了一种具有聚集诱导发光性能的化合物4，4'-[（2，2-二苯乙烯）-1，1-双（4，1-亚苯基）]二吡啶（简称2Py-TPE）。利用过滤、洗涤、萃取、干燥和柱层析等常用的有机分离操作手段对该化合物进行纯化；使用核磁共振仪、高分辨质谱仪、红外光谱仪及稳态瞬态荧光光谱仪对其进行结构表征和聚集诱导发光性能研究。该实验不仅可以促使学生了解以四苯乙烯衍生物为代表的聚集诱导发光材料的研究现状，而且能够培养学生的综合实验能力和科学探究能力。     

多相催化与材料表征技术应用于物理化学实验：Ag/SiO2催化剂的制备及其催化氧化CO实验

制备了一个贵金属负载型催化剂并对其催化氧化CO性能进行了测试。采用等体积浸渍法制备了Ag/SiO2催化剂,并通过X射线粉末衍射（XRD）、透射电子显微镜（TEM）、N2-吸脱附曲线及程序升温还原（H2-TPR）表征了催化剂的结构和形态。结合材料的表征数据及性能测试结果分析探讨银的负载量对催化氧化CO活性的影响,进一步探究该催化反应的进行机制。该实验将多相催化和现代测试技术与物理化学实验教学相结合,可以让学生获取催化学科的前沿知识,了解催化反应以及各种现代测试技术的基本原理,从而提高学生的综合实验能力,激发独立思考和创新的意识,有利于创新性人才的培养。     

结合理论课堂的知识点设计高分子材料合成实验课程

尝试在"高分子材料合成创新实验"课程中将理论课的知识点巧妙地融入到实验教学中，有目的地设置实验环节，通过对实验现象的分析，帮助学生巩固理论课知识点。为了充分利用实验的等待时间，在有目的地组织学生对实验进行预习的基础上，还尝试"激励学生参与"实验课的教学，鼓励学生以实验小组的形式讲解与实验相关联的理论知识，进一步巩固相关知识点，并扩充知识面。2年的实验教学反馈表明，这些尝试既有效巩固了理论课堂的知识点，做到了活学活用，又激发了学生的学习兴趣，提高了分析问题的能力。     

醋酸锰催化合成萘并噻唑衍生物研究型综合实验

设计了“醋酸锰（Ⅲ）催化合成2-邻氯苯甲酰氨基萘并[1,2-d]噻唑”研究型综合化学实验,以自制的醋酸锰（Ⅲ）为催化剂,催化氧化1-萘基-3-邻氯苯甲酰基硫脲合成2-邻氯苯甲酰氨基萘并[1,2-d]噻唑。通过该实验项目的教学,可使学生掌握醋酸锰（Ⅲ）、1-萘基-3-邻氯苯甲酰基硫脲和2-邻氯苯甲酰氨基萘并[1,2-d]噻唑的合成方法,掌握有机化合物结构表征的方法,可以培养学生的实践动手能力、科研创新能力以及综合运用知识的能力。该实验项目集无机合成实验、有机合成实验和仪器分析实验于一体,具有较强的可操作性和实用性,可作为基础化学研究型综合化学实验或开放性实验开设。     

二氧化碳共聚物为基的聚氨酯生物降解性能研究

以CO2为起始物合成出聚碳酸亚乙酯（PEC）二醇，进而合成以PEC为预聚物的聚氨酯。对该聚氨酶的力学性能、降解性能等进行了测试。结果表明，该聚氨酯同时具有良好的力学性能和良好的生物降解性能。     

直接甲醇燃料电池催化剂的制备与表征综合化学实验

将学科前沿领域的科研成果转化为研究型综合实验，结合新清洁能源发展介绍了直接甲醇燃料电池催化剂的制备与表征。采用液相还原取代法制备铂纳米管，通过XRD、TEM、XPS对材料进行形貌和结构表征，并以氢氧化钾溶液为电解质测试铂纳米管催化剂的电化学性能。通过开设该实验，不仅让学生了解直接甲醇燃料电池关键催化剂制备的实验原理、合成方法及数据分析，还可以更好地锻炼学生综合实验的操作技能，在培养研究兴趣的同时提升创新思维和创新能力。     

单金属位点催化剂的制备、表征及其在燃料电池中的应用

介绍了一个综合性较强的大学化学实验——单金属位点催化剂的制备及其在燃料电池中的应用。该实验是一个科研转化的综合化学实验，通过在氨气中简单热处理金属盐和氧化石墨烯，将金属原子单分散在氮掺杂的石墨烯骨架中（标记为M-NG）。通过XRD、TEM、SEM、HAADF-STEM等多种表征技术对催化材料进行结构表征，以碱性的氢氧化钾溶液为电解质测试催化剂在氧还原反应中的活性，从而开发单位点金属催化剂在燃料电池中的应用潜力。通过本实验将最前沿的学术研究成果和实践技能融入实验教学中，可以提高学生的综合实验操作技能，培养学生对科研的探究兴趣和探索能力。     

研究性综合化学实验：纳米级TS-1分子筛的合成、表征与催化性能的研究

介绍一个研究性综合化学实验--水热法合成纳米级TS-1分子筛及其表征与催化性能研究。实验通过传统的水热合成方法,制备了具有MFI拓扑结构的TS-1型分子筛。产物的结构通过X射线粉末衍射仪（XRD）、紫外-可见光谱仪（UV-Vis）进行了表征;产物的孔道性质通过N2吸附-脱附仪进行了表征,其形貌由透射电子显微镜（TEM）进行了表征。将所制备的钛硅分子筛材料用于二苯并噻吩的氧化脱硫反应的测试,表征了其催化活性。     

Emulsion polymerization of vinyl acetate using a polymerizable surfactant. II. Polymerization mechanism

The mechanism of growth of latex particles in the emulsion polymerization of vinyl acetate using a polymerizable surfactant, sodium dodecyl allyl sulfosuccinate (TREM LF-40; Henkel) was investigated. Both the aqueous phase and the particle/water interface were found to be loci for the copolymerization of TREM LF-40 with vinyl acetate. Competitive growth experiments using TREM LF-40 and its nonpolymerizable derivative were conducted to separate the effects of aqueous phase and particle surface. Particle size analysis of the seeded and unseeded polymerizations coupled with kinetic results suggested that the reactions at the particle/water interface are more important and that the particle size of the latexes is a key parameter controlling the polymerization rate through copolymerization and chain transfer to the polymerizable surfactant at the particle surface. A decrease in particle size lead to an increase in the amount of TREM LF-40 polymerized at the particle surface and to a decrease in polymerization rate. © 1992 John Wiley & Sons, Inc.     

Emulsion polymerization of vinyl acetate using a polymerizable surfactant. I. Kinetic studies

A polymerizable surfactant, sodium dodecyl allyl sulfosuccinate (TREM LF-40; Henkel) and its nonpolymerizable counterpart were used in comparative studies of the emulsion polymerization of vinyl acetate. The conversion-time behavior differed for the two surfactants; the TREM LF-40 showed a decrease in the polymerization rate with increasing concentration while its hydrogenated derivative showed the opposite behavior, the rate increasing with increasing surfactant. Particle size analysis revealed a decreasing particle size with increasing surfactant concentration for both series of reactions. An explanation for the seemingly ambiguous results obtained for the polymerizable surfactant was sought by examining the reactivity of its vinyl group in copolymerization with vinyl acetate and its allylic group in a chain transfer reaction. The results suggest that both the copolymerization and chain transfer reactions can lead to the observed reduction in polymerization rate with increasing TREM LF-40 concentration. © 1992 John Wiley & Sons, Inc.     

溴化铜对异丙醇铝存在下原子转移自由基聚合的影响

研究了以2-溴异丁酸乙酯为引发剂、溴化亚铜(CuX)/联二吡啶(bPy)/异丙醇铝[Al(OPrⁱ)₃]为三元复合催化体系,40℃下甲基丙烯酸甲酯(MMA)在环己酮中的原子转移自由基聚合,详细研究了溴化酮对聚合反应的影响.实验结果表明,以异丙醇铝为助催化剂,MMA可在较低温度下进行活性聚合;随着CuBr₂浓度的提高,自由基浓度降低,终止反应受到抑制;不加CuBr₂时,聚合物的分子量分布较宽(M_w/Mn);加入CuBr₂时,聚合物的分子量分布较窄(M_w/Mn=1.2～1.5),而且对数转化率与时间呈线性关系.     

N-杂环卡宾配体在聚合反应中的研究进展

N-杂环卡宾配体的优异催化性能引起了人们的广泛关注, 已成功应用于多种烯烃聚合反应。本文结合N-杂环卡宾的相关研究报道,首先简要介绍N-杂环卡宾,随后重点介绍N-杂环卡宾在开环易位聚合、烯烃配位聚合和原子转移自由基聚合等聚合反应的应用。在此基础上,指出了今后N-杂环卡宾配体在聚合反应研究的发展方向。     

"一锅法"N-(2-苯甲酰胺苯基)-水杨醛亚胺/TiCl4·2THF催化乙烯聚合

报道了4个含苯甲酰胺取代的水杨醛亚胺配体: N-(2-苯甲酰胺苯基)-水杨醛亚胺(L1)、 N-(2-苯甲酰胺苯基)-3-甲基水杨醛亚胺(L2)、 N-(2-苯甲酰胺苯基)-3-叔丁基水杨醛亚胺(L3)和N-(2-苯甲酰胺苯基)-3,5-二溴水杨醛亚胺(L4)的合成, 采用 ¹H NMR和HRMS对其结构进行了表征. 在助催化剂甲基铝氧烷(MAO)作用下, 以L3与TiCl₄·2THF为模型催化体系, 在最佳陈化条件(陈化温度为25 ℃, 陈化时间为30 min, 配体与TiCl₄·2THF的摩尔比3∶1)下, 考察了L1~L4/TiCl₄·2THF催化体系Al/Ti摩尔比、 反应时间、 反应温度和聚合压力, 以及配体结构等对乙烯聚合的影响. 结果表明, 随着在水杨醛骨架上氧原子邻位取代基位阻的增大, 催化体系的活性及所得聚乙烯的分子量均有增加, 其中以L3的催化活性最高, 达到224 kg PE/(mol Ti?h). 采用高温 ¹H NMR, ¹³C NMR, GPC-IR和DSC等对由不同配体L1~L4/TiCl₄·2THF得到的聚乙烯样品的微观结构与热性能进行了分析与表征, 结果显示样品为线性高密度聚乙烯, M_n=5.9×10 ⁴~11.9×10 ⁴, 分子量分布(PDI)为21.9~72.1.     

Butyl acrylate/methyl methacrylate latexes: adhesive properties

In this study, butyl acrylate/methyl methacrylate (BA/MMA) latexes of bimodal molecular weight and particle size distribution were prepared in a multi-step process by seeded conventional emulsion and seeded miniemulsion polymerization. For the conventional emulsion case, a BA/MMA batch copolymerization was conducted as a first step (seed generation) and was followed by a monomer addition step to ensure particle growth. In a third step, a BA/MMA pre-emulsified mixture was added to generate a second particle population. For the miniemulsion case, a BA/MMA copolymerization was carried out as a first step (seed generation) and was followed by a monomer addition step. The addition of a BA/MMA miniemulsion served to generate a bimodal particle size and molecular weight distribution. The final latexes were coated onto a polyethylene terephthalate carrier, dried and their performance as pressure-sensitive adhesives was evaluated using tack, peel and shear adhesion measurements. Structure-property relationships between the adhesive properties and the weight-average molecular weight and average particle size were examined. Even though the polymers obtained by miniemulsion showed better shear resistance, their shear resistance was low. There was no statistically significant difference in peel resistance of the polymers obtained by the two reactions. While a significant difference in tackiness between the two emulsion procedures was found when the adhesives were tested using the less sensitive, rolling ball test, no differences were found when they were tested using a loop tack test.     

Effect of the presence of polymer in miniemulsion droplets on the kinetics of polymerization

Solution of polystyrene in styrene were dispersed in an aqueous gel phase comprising sodium lauryl sulfate, cetyl alcohol, and water using an emulsification process known to produce monomer droplet sizes inthe submicron size range (referred to as miniemulsion droplets). The shelf-life stabilities of these miniemulsions were studied to determine their relative droplet sizes, and the emulsions were concommitantly polymerized in an isothermal batch reaction calorimeter. The polymerization kinetics and final particle sizes produced were compared with miniemulsion and conventional emulsion polymerizations prepared using equivalent recipes without the addition of polystyrene. The results indicate that polymerization of miniemulsions prepared from polymer solutions produce significantly different kinetics than both miniemulsion and conventional emulsion polymerizations. In general, a small amount of polymer greatly increases the rate of polymerization and the final number of particles produced in the polymerization to the extent where even conventional polymerizations carried out above the critical micelle concentration of the surfactant polymerize more slowly. The results are explained by considering the system to be comprised of small, stable pre-formed monomer-swollen polymer particles which are able to efficiently capture aqueous phase radicals. This enables the system to produce a large final number of particles, similar to the initial number of pre-formed polymer particles, as opposed to miniemulsions and micelles in which only a relatively small fraction of the initial number of species (droplets or micelles) become polymer particles. © 1994 John Wiley & Sons, Inc.     

Controlled random and alternating copolymerization of (meth)acrylates,acrylonitrile, and (meth)acrylamides with vinyl ethers by organotellurium‐, organostibine‐, and organobismuthine‐mediated living radical polymerization reactions

Random and alternating copolymerizations of acrylates, methacrylates, acrylonitorile, and acrylamides with vinyl ethers under organotellurium‐, organostibine‐, and organobismuthine‐mediated living radical polymerization (TERP, SBRP, and BIRP, respectively) have been studied. Structurally well‐controlled random and alternating copolymers with controlled molecular weights and polydispersities were synthesized. The highly alternating copolymerization occurred in a combination of acrylates and vinyl ethers and acrylonitorile and vinyl ethers by using excess amount of vinyl ethers over acrylates and acrylonitorile. On the contrary, alternating copolymerization did not occur in a combination of acrylamides and vinyl ethers even excess amount of vinyl ethers were used. The reactivity of polymer‐end radicals to a vinyl ether was estimated by the theoretical calculations, and it was suggested that the energy level of singly occupied molecular orbital (SOMO) of polymer‐end radical species determined the reactivity. By combining living random and alternating copolymerization with living radical or living cationic polymerization, new block copolymers, such as (PBA‐alt‐PIBVE)‐block‐(PtBA‐co‐PIBVE), PBA‐block‐(PBA‐alt‐PIBVE), and (PTFEA‐alt‐PIBVE)‐block‐PIBVE, with controlled macromolecular structures were successfully synthesized. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

用可聚合的眯唑型表面活性剂制备聚苯乙烯／粘土纳米复合材料

用本体聚合法制备了聚苯乙烯／粘土纳米复合材料,用傅里叶红外光谱（FTLR）对有机改性的蒙脱土进行了表征,用X-射线衍射（XRD）表征了纳米复合材料的结构,用热重分析（TGA）、微分热分析（DTA）表征了纳米复合材料的热稳定性。结果表明,聚苯乙烯可以插入含双键的咪唑盐表面活性剂改性的粘土中,形成部分剥离的结构;复合材料的热稳定性较高,开始分解的温度达到414．6℃。     

原位生成三苄氧基钇催化ε-己内酯可控开环聚合

本文研究了以烷基钇[Y(CH2SiMe3)3(THF)2]与苯甲醇原位反应生成的三苄氧基钇为引发剂的ε-己内酯(CL)可控开环聚合。研究结果表明,随着聚合体系中单体/引发剂摩尔比的增大,由1H-NMR计算和GPC测定得到的产物聚己内酯(PCL)的数均分子量均随之线性增加,且分子量分布(Mw/Mn =1.4～1.1)逐渐变窄;1H-NMR计算所得PCL的数均分子量与由单体/引发剂投料比计算得到的理论值一致,表明该体系催化的CL开环聚合具有很好的可控性。1H-NMR分析显示产物PCL的端基分别为苯甲醇酯和醇羟基,由此提出了可能的开环聚合机理。