Chemically initiated oxidative polymerization stands out as the most suitable method for the large-scale and controllable synthesis of perfluoropolyether (PFPE). However, the mechanism and related reaction kinetics of this synthesis reaction remain elusive. In this study, PFPE was synthesized through the copolymerization of hexafluoropropylene and oxygen, initiated by fluorine. Subsequently, the synthesis mechanism of this chemically initiated oxidative polymerization was first explored using density functional theory. Simulation results yielded a comprehensive reaction network of the synthesis process, including chain initiation, propagation, decomposition, transfer, and termination. Meanwhile, a detailed kinetic model was constructed based on theoretical reaction rates of relevant elementary reactions. The effects of reaction operating conditions on the molecular weight of PFPE were experimentally investigated, with results in good agreement with the kinetic model. This work stablishes a solid foundation for optimizing and controlling the PFPE synthesis process.

中文翻译：

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化学引发的六氟丙烯氧化聚合反应的机理和动力学研究


化学引发的氧化聚合是最适合大规模和可控合成全氟聚醚 （PFPE） 的方法。然而，这种合成反应的机制和相关反应动力学仍然难以捉摸。在本研究中，PFPE 是通过氟引发的六氟丙烯和氧的共聚反应合成的。随后，首先使用密度泛函理论探索了这种化学引发的氧化聚合的合成机制。仿真结果产生了合成过程的综合反应网络，包括链引发、传播、分解、转移和终止。同时，根据相关基本反应的理论反应速率构建了详细的动力学模型。通过实验研究了反应操作条件对 PFPE 分子量的影响，结果与动力学模型吻合较好。这项工作为优化和控制 PFPE 合成过程奠定了坚实的基础。