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.

PIs先前对一类烷基丙烯酸酯（如乙基丙烯酸酯和正丁基丙烯酸酯）在自由基溶液中均聚和共聚的研究表明，在不添加热引发剂的情况下，在120-180℃下发生了非常明显的自发热聚合。单体，如苯乙烯和许多甲基丙烯酸酯，而不是烷基丙烯酸酯，已经知道进行自发聚合。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引发步骤的几个因素。他们还在超级计算机上高效地使用化学量子级计算来研究聚合反应动力学方面取得了进展。在这些成功的基础上，他们计划采用一种迭代研究策略，包括第一性原理密度泛函理论（DFT）计算、实验设计、批量实验室实验和光谱分析。它的目的是定量地了解动力学，反应机制，以及相关的中间体和过渡态的引发和链转移在丙烯酸甲酯，乙基和正丁基丙烯酸酯的自发热聚合使用这种集成的研究策略，最终目标是设计“地球化学自我”调节聚合工艺生产高性能丙烯酸树脂。它将涉及范围广泛的活动，例如：(i)提出引发模型机制，（ii）在超级计算机上使用DFT计算估计反应物，过渡态，中间体和产物的分子几何形状，（iii）使用高斯-n理论验证和计算可靠的热化学，（iv）设计实验室批量聚合实验以捕获引发和产物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）比较来自化学量子计算和光谱分析的端基结构，（viii）从量子化学数据计算反应速率系数，（ix）将理论预测与实验所得值进行比较，以及(x)验证对照生物物种。更广泛的影响该项目的潜在影响包括社会（通过提高安全性）、环境、经济和人力资源开发。自发热聚合可以以更低的运营成本生产出更高质量、更环保的溶剂型油漆和涂料。低分子量，聚合物和低聚物溶液即使在高质量百分比的固体也具有足够低的粘度，因此需要较少的有机溶剂来喷涂和刷。使用少量或不添加热引发剂（通常是树脂配方中最昂贵的成分）和显著缩短的反应时间降低了操作成本。最终产物中氮腈和有机过氧化物热引发剂的残余基团（对聚合物性能如抗紫外线辐射有不利影响）的减少，以及在分子性能的最佳控制中定量理解的使用，提高了树脂质量。PI和co -PI将培训和指导两名博士研究助理以及六名本科生（REU）学生，他们将参与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。项目结果将在会议上以及在期刊和会议论文集中向公众公布。来自弱势群体的学生将在这个项目中被挑选、培训和指导。