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首页> 外文学位 >Modeling of kinetic complexities in high temperature free radical polymerization for production of acrylic coatings resins.
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Modeling of kinetic complexities in high temperature free radical polymerization for production of acrylic coatings resins.

机译：用于生产丙烯酸涂料树脂的高温自由基聚合中动力学复杂性的建模。

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Copolymers of methacrylate, acrylate and styrene produced via high-temperature solution polymerization are the base resin component for many automotive coatings. These materials are often manufactured using a semibatch starved-feed reactor policy in order to reduce the solvent level while tightly controlling polymer composition and molecular weight. Methacrylates are known to undergo depropagation reactions at these conditions, while acrylates are affected by backbiting followed by beta-scission and slowed monomer addition to the tertiary radicals. Both mechanisms have a significant impact on polymer molecular weights and free monomer concentrations in the reactor. Meanwhile, a strong penultimate effect has been observed for some of these binary systems at lower temperatures, also affecting the polymerization rate.; The objective of this work is to formulate a generalized model for the terpolymerization of methacrylate, acrylate and styrene, building from our knowledge of mechanisms in the homo- and co-poIymerizations. As part of this investigation, we answered specific questions about penultimate effects at higher temperature, and how they interact with depropagation for the butyl methacrylate/styrene (BMA/ST) system. It is found that penultimate kinetics have a strong impact on the copolymer-averaged propagation rate coefficient at the elevated temperatures at which depropagation is important. The Lowry Case 1 depropagation model adequately describes the effect of methacrylate deproagation over the range of conditions examined. The mechanistic models, implemented in PrediciRTM for high temperature semibatch BMA/ST copolymerization and BMA/ST/butyl acrylate terpolymerization, provide good predictions of monomer conversion and MW.
机译：通过高温溶液聚合生产的甲基丙烯酸酯，丙烯酸酯和苯乙烯的共聚物是许多汽车涂料的基础树脂组分。这些材料通常使用半间歇饥饿式进料反应器策略制造，以便在严格控制聚合物组成和分子量的同时降低溶剂含量。已知甲基丙烯酸酯在这些条件下会发生脱繁殖反应，而丙烯酸酯会受到咬合，β-断链和减慢单体向叔自由基的添加的影响。两种机理均对反应器中的聚合物分子量和游离单体浓度具有显着影响。同时，在较低的温度下观察到某些二元体系的强烈倒数第二个作用，也影响了聚合速率。这项工作的目的是根据我们对均聚和共聚机理的了解，为甲基丙烯酸酯，丙烯酸酯和苯乙烯的三元聚合建立一个通用模型。作为这项研究的一部分，我们回答了有关高温下的倒数第二个作用以及它们如何与甲基丙烯酸丁酯/苯乙烯（BMA / ST）系统的脱附相互作用的具体问题。已发现倒数第二动力学对在高温下对共聚物的平均传播速率系数有重要影响，在该温度下，重要的是不扩散。 Lowry Case 1繁殖模型充分描述了甲基丙烯酸酯在所研究条件范围内的繁殖作用。在PrediciRTM中实现的用于高温半间歇BMA / ST共聚和BMA / ST /丙烯酸丁酯三聚的机理模型，提供了单体转化率和MW的良好预测。

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