Presented herein is an operationally simple and reliable approach to the determination of comonomer reactivity ratios using continuous flow. The benefits of continuous-flow chemistry include the precise control of reaction time, heat transfer, and the ability to dynamically alter continuous variables within a single experiment. The flow system produces nine samples reacted to low conversions with systematically varied comonomer compositions in under one hour. The polymer compositions were fit to a model of terminal copolymerization resulting in point estimates for comonomer reactivity ratios. The continuous-flow system was validated by the determination of five comonomer reactivity ratios that provided good agreement with literature values. The method is demonstrated to streamline the determination of especially challenging comonomer systems, such as those with fast kinetics or disparate reactivity. Using sustainably-derived lignin-based methacrylates, our continuous-flow approach enabled the determination of reactivity ratios for three comonomer pairs that have not been previously reported. We envision the continuous-flow method will catalyze the further exploration of statistical copolymers in both batch and continuous flow.

中文翻译：

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连续流化学法测定共聚单体的反应比†

本文介绍的是一种使用连续流确定共聚单体反应比的操作简单可靠的方法。连续流化学的好处包括精确控制反应时间，传热以及在单个实验中动态更改连续变量的能力。流动系统在一小时内产生了9个样品，这些样品在系统转化为共聚单体的情况下发生了低转化率反应。使聚合物组合物适合于末端共聚的模型，从而得出共聚单体反应性比率的点估计值。通过测定五个共聚单体的反应比来验证连续流系统，这与文献值具有很好的一致性。实践证明，该方法可简化对特别具有挑战性的共聚单体体系的测定，例如动力学快或反应性差的那些。使用可持续衍生的木质素基甲基丙烯酸酯，我们的连续流方法能够确定以前未报道的三个共聚单体对的反应率。我们设想，连续流方法将促进批量和连续流统计共聚物的进一步探索。