New Polymer Synthesis by Radical/ion Transformation Polymerization

在电子受体Ph_2I^+PF_6^-存在下，以偶氮引发剂AIBN为引发剂，对甲氧基苯乙烯（MOS）、正丁基乙烯基醚（BVE）和N-乙烯基咔唑（VCZ）进行了高收率聚合。ESR研究的模型自由基的增长端和传播自由基表明，在电子受体的存在下，自由基转化为相应的阳离子。在BVE的情况下，聚合物的形成是由引发自由基转化产生的阳离子物种引起的。MOS和VCZ的聚合反应是由于增长自由基在增长过程中转化为相应的阳离子，属于自由基/阳离子转化聚合。在电子受体和CHO存在下，MOS和VCZ分别与偶氮二异丁腈（AIBN）进行自由基/阳离子转化聚合，有效地制备了MOS/环氧环己烷（CHO）和VCZ/CHO嵌段共聚物。

p-Methoxystirene (MOS), n-butyl vinyl ether (BVE), and N-vinylcarbazole (VCZ) were polymerized in high yield by azoinitiators such as AIBN in the presence of electron acceptors such as Ph_2I^+PF_6^-. ESR study of the model radicals of the growing ends and the propagating radical showed the transformation of the radical to the corresponding cation in the presence of the electron acceptors. In the case of BVE,the polymer formation was caused by cationic species produced by the transformation of initiating radical. The polymerizations of MOS and VCZ were ascribed to the transformation of the growing radical to the corresponding cation during the propagation step which was classified as the radical/cation transformation polymerization. Block copolymers of MOS/cyclohexene oxide (CHO) and VCZ/CHO were effectively prepared by the radical/cation transformation polymerization of MOS and VCZ,respectively, with AIBN in the presence of electron acceptor and CHO.The formation of block copolymers was characterized by turbidmetry, thin-layr chromatography, and solubility test.