Abstract A novel route to prepare fluorinated grafted copolymers via the use of nitroxides and under mild conditions is described. First, iodine transfer polymerization of vinylidene fluoride (VDF) in the presence of 1-iodoperfluorohexane led to two PVDFs (average molar masses of 1700 and 4000 g mol−1 and dispersities of 1.2). Then, the grafting of nitroxide moieties onto PVDF backbone was achieved in solution without any polymer activation. The obtained PVDF-g-nitroxide polymers acted as efficient macroinitiators for the polymerization of styrene leading to PVDF-g-PS graft copolymers with styrene content ranging from 17 to 40 w.% and PS molar masses varying from 1000 to 1500 g mol−1. It was experimentally evidenced that the grafting took place from methylenic protons, especially from tail-to-tail addition, and theoretical calculations of bond dissociation energies confirmed such a finding. It was also demonstrated that the nature of the solvent had a great influence on the success of the grafting mechanism as the reaction was only efficient in N-methyl pyrrolidone. Considering the high chemical stability of PVDF, this chemical route paves the way towards the synthesis of various valuable graft copolymers.

中文翻译：

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含氮氧化物的 PS 接枝 PVDF 的制备

摘要 描述了通过使用硝基氧在温和条件下制备氟化接枝共聚物的新途径。首先，在 1-碘全氟己烷存在下，偏二氟乙烯 (VDF) 的碘转移聚合产生两种 PVDF（平均摩尔质量为 1700 和 4000 g mol-1，分散度为 1.2）。然后，在没有任何聚合物活化的情况下，在溶液中实现了硝基氧部分接枝到 PVDF 主链上。获得的 PVDF-g-硝基氧化物聚合物作为有效的大分子引发剂，用于苯乙烯聚合，形成 PVDF-g-PS 接枝共聚物，苯乙烯含量为 17 至 40 w.%，PS 摩尔质量为 1000 至 1500 g mol-1 . 实验证明，接枝发生于亚甲基质子，尤其是尾对尾加成，键解离能的理论计算证实了这一发现。还表明溶剂的性质对接枝机制的成功有很大影响，因为该反应仅在 N-甲基吡咯烷酮中有效。考虑到 PVDF 的高化学稳定性，这种化学途径为合成各种有价值的接枝共聚物铺平了道路。