New Polymer Synthesis by Radical/ion Transformation Polymerization

在Ph_2I^+PF_6^-等电子受体的存在下，偶氮引发剂AIBN对甲氧基stirene （MOS）、正丁基乙烯醚（BVE）和n-乙烯基咔唑（VCZ）进行了高收率的聚合。对生长端和传播端模型自由基的ESR研究表明，在电子受体的存在下，自由基向相应的阳离子转变。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引起的。MOS和VCZ的聚合反应是由于增殖过程中生长的自由基向相应的阳离子转化而发生的聚合反应，可归类为自由基/阳离子转化聚合。在电子受体和CHO存在下，用AIBN分别对MOS和VCZ进行自由基/阳离子转化聚合，制备了MOS/环氧环己烯（CHO）和VCZ/CHO嵌段共聚物。用浊度法、薄层色谱法和溶解度法对嵌段共聚物的形成进行了表征。

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.