Under pressure: electrochemically-mediated atom transfer radical polymerization of vinyl chloride
Under pressure: electrochemically-mediated atom transfer radical polymerization of vinyl chloride
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DOI：
10.1039/d0py00995d
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发表时间：
2020-11-14
影响因子：
4.6
通讯作者：
Coelho, Jorge F. J.
中科院分区：
文献类型：
--
作者：
De Bon, Francesco;Ribeiro, Diana C. M.;Coelho, Jorge F. J.
对活性较低的单体的聚合的严格控制仍然是可逆失活自由基聚合（RDRP）（包括原子转移自由基聚合（ATRP））的一个主要挑战。首次采用不锈钢304（SS304）电化学反应器，采用简化的电化学装置，成功地实现了气态单体氯乙烯（VC）的电化学介导原子转移自由基聚合（eATRP）。控制聚合证实了理论和测量的分子量之间的良好协议，以及相对较窄的分子量分布。通过扩链实验验证了链端保真度的保持，产生聚氯乙烯（PVC）均聚物、嵌段共聚物和统计共聚物。通过eATRP合成PVC的可能性是一种有前途的替代方案，以提供更清洁的（共）聚合物，具有低催化剂浓度。反应器的金属体也成功地用作阴极。在这方面的贡献提出的设置开辟了其他气态单体的聚合途径。
The stringent control over the polymerization of less activated monomers remains one major challenge for Reversible Deactivation Radical Polymerizations (RDRP), including Atom Transfer Radical Polymerization (ATRP). Electrochemically mediated ATRP (eATRP) of a gaseous monomer, vinyl chloride (VC), was successfully achieved for the first time using a stainless-steel 304 (SS304) electrochemical reactor equipped with a simplified electrochemical setup. Controlled polymerizations were confirmed by the good agreement between theoretical and measured molecular weights, as well as the relatively narrow molecular weight distributions. Preservation of chain-end fidelity was verified by chain extension experiments, yielding poly(vinyl chloride) (PVC) homopolymers, block and statistical copolymers. The possibility of synthesizing PVC by eATRP is a promising alternative to afford cleaner (co)polymers, with low catalyst concentration. The metal body of the reactor was also successfully used as a cathode. The setup proposed in this contribution opens an avenue for the polymerization of other gaseous monomers.