The copper mediated reversible deactivation radical polymerization (Cu⁰‐RDRP) can realize the precise synthesis of vinyl polymers in aqueous media. To our best of knowledge, there are few hydrophobic initiators directly utilized to perform the aqueous Cu⁰‐RDRP because the heterogeneity usually causes the polymerization to go out of control. This article first describes a very small number of hydroxylpropyl β‐cyclodextrins (HP‐β‐CDs) enabling to solubilize a bifunctional hydrophobic initiator tetraethylene glycol bis(2‐bromoisobutyrate) (T2B) into water to initiate the homogeneous Cu⁰‐RDRP of N‐isopropylacrylamide (NIPAM) giving rise to well‐defined poly(N‐isopropylacrylamide) (PNIPAM). The solubilization action is arisen from the inclusion complexation of HP‐β‐CDs with T2B as evidenced by 2D NOESY and 2D DOSY NMR analyses. Furthermore these entrapped HP‐β‐CDs show little effect on the polymerization process as they all skip off the initiator at the very beginning of the polymerization as determined by GPC and ¹H NMR measurements.

中文翻译：

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羟丙基β-环糊精增溶疏水性引发剂，以引发NIPAM在水中的铜介导的RDRP

铜介导的可逆失活自由基聚合反应（Cu ⁰ ‐RDRP）可以实现水性介质中乙烯基聚合物的精确合成。据我们所知，很少有疏水性引发剂可直接用于执行Cu ⁰ -RDRP水溶液，因为非均质性通常会导致聚合反应失控。本文首先介绍了极少量的羟丙基β-环糊精（HP-β-CD），它们能够将双功能疏水性引发剂四甘醇双（2-溴异丁酸酯）（T2B）溶解到水中以引发均相Cu ⁰N-异丙基丙烯酰胺（NIPAM）的RDRP产生定义明确的聚N-异丙基丙烯酰胺（PNIPAM）。2D NOESY和2D DOSY NMR分析证明，增溶作用是由HP-β-CD与T2B的包合络合物产生的。此外，这些被捕获的HP-β-CD在聚合过程中几乎没有影响，因为它们在聚合开始时就通过GPC和¹ H NMR测量都跳过了引发剂。