Center for Soft Condensed Matter Physics and Interdisciplinary Research, Soochow University, Suzhou, 215006, P. R. China.
State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry Engineering and Materials Science of Soochow University, Soochow University, Suzhou, 215123, China.
Macromol Rapid Commun. 2017 Nov;38(22). doi: 10.1002/marc.201700511. Epub 2017 Oct 10.
An ideal stimuli-responsive controlled/living radical polymerization should have the ability to manipulate the reaction through spatiotemporal "on/off" controls, achieving the polymerization under fully open conditions and allowing for precise control over macromolecular architecture with defined molecular weights and monomer sequence. In this contribution, the photo (sunlight)-induced electron transfer atom transfer radical-polymerization (PET-ATRP) can be realized to be reversibly activated and deactivated under fully open conditions utilizing one-component copper(II) thioxanthone carboxylate as multifunctional photocatalyst and oxygen scavenger. The polymerization behaviors are investigated, presenting controlled features with first-order kinetics and linear relationships between molecular weights and monomer conversions. More importantly, "CuAAC&ATRP" concurrent reaction combining PET-ATRP, photodriven deoxygenation, and photoactivated CuAAC click reaction is successfully employed to synthesize the sequence-defined multiblock functional copolymers, in which the iterative monomer additions can be easily manipulated under fully open conditions.
一种理想的刺激响应可控/活性自由基聚合应该具有通过时空“开/关”控制来操纵反应的能力，实现在完全开放条件下的聚合，并允许对具有确定分子量和单体序列的大分子结构进行精确控制。在本研究中，可以利用单组分铜（II）硫代酮羧酸作为多功能光催化剂和氧清除剂，在完全开放条件下实现光（阳光）诱导的电子转移原子转移自由基聚合（PET-ATRP）的可逆激活和失活。研究了聚合行为，呈现出具有一级动力学特征的可控特征，并且分子量和单体转化率之间存在线性关系。更重要的是，成功地将 PET-ATRP、光驱动脱氧和光激活 CuAAC 点击反应的“CuAAC&ATRP”并发反应结合起来，合成了序列定义的多嵌段功能共聚物，其中在完全开放条件下可以轻松地控制迭代单体的添加。
