Tromp Dorette S, Lankelma Marianne, de Valk Hannah, de Josselin de Jong Emile, de Bruin Bas
Van 't Hoff Institute for Molecular Sciences (HIMS), Department of Homogeneous and Supramolecular Catalysis, Universiteit van Amsterdam, P.O. Box 94720, 1090 GS Amsterdam, Netherlands.
Macromolecules. 2018 Sep 25;51(18):7248-7256. doi: 10.1021/acs.macromol.8b01150. Epub 2018 Sep 11.
Herein we describe the Rh-catalyzed C1 polymerization of silyl-protected diazoacetates of the general formula HC(=N)C(=O)O(CH) OSiR, where = 2-5. After polymerization and subsequent desilylation, polymers bearing a hydroxy-containing side group on backbone carbon are obtained. The molecular weight of the desired polymers can be controlled via chain transfer with methanol during the polymerization. The produced polymers are compared to atactic analogues formed by [(η-CH)PdCl]-catalyzed polymerization of silyl-protected diazoacetates with the same general formula. While the polymers produced by the Rh and Pd catalysts have the same hydrophilic/hydrophobic balance, the stereoregularity of the polymers formed by the Rh catalyst was found to be of influence on the thermoresponsive behavior of the polymer. The effect of this stereoregularity on the thermoresponsive phase separation behavior of the produced polymers in aqueous solution was investigated.
在此，我们描述了铑催化的通式为HC(=N)C(=O)O(CH) OSiR（其中 = 2 - 5）的甲硅烷基保护的重氮乙酸酯的C1聚合反应。聚合反应及随后的脱甲硅烷基化反应之后，得到了主链碳上带有含羟基侧基的聚合物。所需聚合物的分子量可通过聚合过程中与甲醇的链转移来控制。将所制备的聚合物与由[(η-CH)PdCl]催化的具有相同通式的甲硅烷基保护的重氮乙酸酯聚合反应形成的无规类似物进行比较。虽然铑和钯催化剂制备的聚合物具有相同的亲水/疏水平衡，但发现铑催化剂形成的聚合物的立构规整性对聚合物的热响应行为有影响。研究了这种立构规整性对所制备的聚合物在水溶液中的热响应相分离行为的影响。
