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首页> 外文会议>AIChE Annual Meeting >Improved Mechanistic Models for the High-Temperature Free-Radical Production of Acrylic Copolymers
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Improved Mechanistic Models for the High-Temperature Free-Radical Production of Acrylic Copolymers

机译：改进了丙烯酸共聚物高温自由基生产的机械模型

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摘要

Polymeric binders in many high-solids solvent-borne automotive coatings formulations consist of functionalized low molecular weight acrylic copolymers. These materials, developed to meet the stringent environmental legislation to reduce solvent content in coatings, require narrow copolymer composition and molecular weight distributions in order to cure uniformly and completely on the vehicle surface. The necessary level of control is achieved through high-temperature starved-feed free radical semibatch solution polymerization. However, these reaction conditions also promote poorly understood secondary reactions (methacrylate depropagation; acrylate back-biting, branching, and scission) that make process development for new resins more of an art than a science. Combining recent advances in kinetic measurement techniques with detailed analysis of acrylate and methacrylate homopolymerizations, we have developed a mechanistic model that successfully captures the polymerization behavior of a butyl methacrylate / butyl acrylate copolymer system over the complete range of composition. This success, coupled with increased knowledge of the structure-reactivity relationship of acrylic monomers, points the way to a generalized modeling framework to guide process optimization and scale-up of new polymer compositions.
机译：许多高固体溶剂的汽车涂料配方中的聚合物粘合剂由官能化的低分子量丙烯酸共聚物组成。开发出满足严格的环境法律以降低涂料中的溶剂含量的这些材料需要窄的共聚物组合物和分子量分布，以便在车辆表面上均匀和完全固化。通过高温饥饿的自由基半液溶液聚合来实现必要的控制水平。然而，这些反应条件也促进了较差的二次反应（甲基丙烯酸酯脱落;丙烯酸酯背刺，分支和裂殖），其使新的树脂的过程开发更加艺术而言。在丙烯酸​​酯和甲基丙烯酸酯均聚的详细分析中结合了动力测量技术的最新进展，我们开发了一种机械模型，其成功地捕获甲基丙烯酸丁酯/丁基丙烯酸丁酯共聚物系统的聚合行为在全系列组合物上。这种成功与丙烯酸单体结构反应性关系的增加相结合，指向通用建模框架的方式，以引导新的聚合物组合物的过程优化和扩大。

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