Depolymerization of P(PDMS11MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration
Depolymerization of P(PDMS11MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration
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DOI：
10.1021/acs.macromol.1c00415
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发表时间：
2021-06-01
期刊：
影响因子：
5.5
通讯作者：
Matyjaszewski, Krzysztof
中科院分区：
文献类型：
--
作者：
Martinez, Michael R.;Dadashi-Silab, Sajjad;Matyjaszewski, Krzysztof
由于主链具有较高的热稳定性和化学稳定性，乙烯基聚合物解聚成单体是能源密集型的。甲基丙烯酸聚合物的解聚通常在最高温度和热降解温度之上进行，以通过键断裂降解聚合物。这项工作研究了在原子转移自由基聚合催化剂：氯化铜(II)/三(2-吡啶甲基)胺(CuCl2/TPMA)介导下，Cl封端的聚(聚(二甲基硅氧烷)甲基丙烯酸酯)(P(PDMS(11)MA-Cl))聚合物在170℃下的催化解聚。通过增加[TPMA]/[CuCl2]。紫外-可见光谱证明，配体的电子转移有助于高温（T > 130 摄氏度）下 Cu(I) 活化剂的（重新）生成。洗瓶刷可以在几个周期内部分解聚和重新聚合。
Depolymerization of vinyl polymers into monomers is energy-intensive due to the high thermal and chemical stability of the backbone. Depolymerizations of methacrylic polymers are typically conducted above the ceiling temperature and thermal degradation temperature to degrade polymers by bond scission. This work investigates the catalyzed depolymerization of a Cl-capped poly(poly(dimethylsiloxane) methacrylate) (P(PDMS(11)MA-Cl)) polymer mediated by an atom transfer radical polymerization catalyst: copper(II) chloride/tris(2-pyridylmethyl)amine (CuCl2/TPMA) at 170 degrees C. The depolymerization yield, rate, and selectivity were improved by increasing the ratio of [TPMA]/[CuCl2]. Electron transfer from the ligand contributed to the Cu(I) activator (re)generation at high temperature (T > 130 degrees C), as proven by ultraviolet-visible spectroscopy. The bottlebrush could be partially depolymerized and repolymerized over a few cycles.