Collaborative Research: GOALI: Design of Chemically Self-Regulated, Acrylic Coatings Processes through Iterative Use of Chemical Quantum Calculations and Spectroscopic Methods

合作研究：GOALI：通过迭代使用化学量子计算和光谱方法设计化学自调节丙烯酸涂料工艺

• 批准号: 0932882
• 负责人: Masoud Soroush
• 金额: $ 26.54万
• 依托单位: Drexel University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-09-01 至 2013-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0932882&HistoricalAwards=false
• 关键词: Collaborative; Research; GOALI; Design; Chemically

0932882SoroushIntellectual Merit The PIs' previous study of free-radical solution homo-and co-polymerization of a class of alkyl acrylates, such as ethyl and n-butyl acrylates, revealed very substantial, spontaneous thermal polymerization at 120-180oC in the absence of added thermal initiators. Monomers such as styrene and many methacrylates, not alkyl acrylates, had been known to undergo spontaneous polymerization. In their work, they carried out laboratory experiments and identified several factors influencing the initiation step in the spontaneous polymerization. They have also made advances in efficiently using chemical quantum-level computations on supercomputers to study the kinetics of polymerization reactions.Building on these successes, they plan to employ an iterative research strategy that includes first-principles density functional theory (DFT) calculations, design of experiments, batch laboratory experiments, and spectroscopic analyses. It is aimed at quantitatively understanding the kinetics, the reaction mechanisms, and the relevant intermediates and transition states for initiation and chain transfer in spontaneous thermal polymerization of methyl, ethyl, and n-butyl acrylates using this integrated research strategy, with the ultimate goal of designing 'gchemically self'regulated' polymerization processes for the production of high-performance acrylic resins. It will involve a broad spectrum of activities such as: (i) proposing initiation model mechanisms, (ii) estimating molecular geometries of reactants, transitions states, intermediates, and products using DFT calculations on supercomputers, (iii) validating and calculating reliable thermo chemistry using Gaussian-n theory, (iv) designing laboratory batch polymerization experiments to capture the initiating and product species and to verify the controlling nature of the species and mechanisms, (v) conducting polymerization experiments, (vi) conducting spectroscopic analyses, (vii) comparing end group structures from the chemical quantum calculations and spectroscopic analyses, (viii) calculating reaction rate coefficients from the quantum chemical data, (ix) comparing the theoretical predictions with values obtained from the experiments, and (x) validating the control living species.Broader Impacts The potential impacts of this project are societal (through improved safety), environmental, economic, and in human resource development. Spontaneous thermal polymerization allows for the production of higher quality, environmentally-friendlier solvent-borne paints and coatings at lower operating costs. Low molecular weight, polymer and oligomer solutions even at high weight percent solids have adequately low viscosity, thus requiring less organic solvents to be sprayable and brushable. The use of less or no added thermal initiators (normally the most expensive component of a resin formula) and significantly shorter reaction times lower the operating costs. The presence of less residual groups from azonitrile and organic peroxides thermal initiators (which adversely affect polymer properties such as resistance to UV radiation) in the final product and the use of the quantitative understanding in optimal control of molecular properties improve the resin quality. The PI and Co-PIs will train and mentor two doctoral research assistants as well as six undergraduate (REU) students, who will participate in broad range of research activities from quantum-level computations and supercomputing to laboratory experiments and spectroscopic methods, some of which will be conducted at DuPont Marshall Laboratory. The project results will be released to the public at conferences and in journal and conference proceedings papers. Students from under-represented groups will be selected, trained and mentored in this project.

0932882 ssosorhintelectual值得PIS对自由基溶液的先前研究，同类的烷基丙烯酸酯（例如乙基和N-丁基丙烯酸酯）的共聚合，在120-180oc中添加的情况下揭示了非常实质性的自发热聚合，热启动器。已知苯乙烯和许多甲基丙烯酸酯（而不是烷基丙烯酸酯）等单体会经历自发聚合。在他们的工作中，他们进行了实验室实验，并确定了影响自发聚合的启动步骤的几个因素。他们还取得了进步，可以在超级计算机上有效地使用化学量子级计算来研究聚合反应的动力学。建立这些成功，他们计划采用一个迭代研究策略，其中包括第一原则的功能理论（DFT）计算，设计，设计，设计实验，批处理实验实验和光谱分析。它旨在定量理解动力学，反应机制以及相关的中间体和过渡状态，用于使用这种综合研究策略的甲基，乙基和N-丁基丙烯酸酯的自发热聚合中的起始和链转移，并具有最终的目标。为高性能丙烯酸树脂的生产设计“ gchemny“自我调节”聚合过程。它将涉及一系列活动，例如：（i）提出启动模型机制，（ii）使用超级计算机上的DFT计算估算反应物，过渡状态，中间体和产品的分子几何形状，（iii）验证和计算可靠的热疗法化学性质使用高斯-N理论，（IV）设计实验室批次聚合实验，以捕获启动和产品物种并验证物种和机制的控制性质，（v）进行聚合实验，（VI）进行光谱分析，（VII）（VII）（VII）比较了从化学量子计算和光谱分析的最终组结构，（viii）从量子化学数据中计算反应速率系数，（IX）将理论预测与从实验获得的值进行比较，以及（x）验证对照生物。更广泛的影响该项目的潜在影响是社会（通过改善的安全性），环境，经济和人力资源开发。自发的热聚合可以以较低的运营成本生产更高质量，环保溶剂植物的油漆和涂料。低分子量，聚合物和低聚物溶液即使在高重量百分比的固体中也具有足够低的粘度，因此需要更少的有机溶剂可喷涂和刷牙。使用较少或没有添加的热启动器（通常是树脂配方中最昂贵的组件），并且反应时间明显降低了运营成本。在最终产物中存在来自偶氮腈和有机过氧化物的热启动器（不利影响聚合物耐药性）的残留组较少的基团（对聚合物的耐药性产生了不利影响），并且在对分子特性的最佳控制中使用定量理解可以提高树脂质量。 PI和Co-Pis将培训和指导两名博士研究助理以及六名本科生（REU）学生，他们将参加从量子级计算和超级计算到实验室实验和光谱方法的广泛研究活动，其中一些将在杜邦马歇尔实验室进行。该项目结果将在会议以及期刊和会议论文文件中向公众发布。将在该项目中选择，培训和指导来自代表性不足的小组的学生。