Selective Frustrated/Nonfrustrated Anion-Migrated Ring-Opening Polymerization of 1-Cyclopropylvinylbenzene

Exploring novel polymerization mechanisms for the preparation of switchable isomers in chains from homopolymerization with only monomers is undoubtedly an exhilarating and challenging pursuit in polymer chemistry. Therefore, this work presents a novel strategy for realizing reversible cycle anion migrated ring-opening polymerization (AMROP) and general anionic polymerization (thermodynamics limits the further ring-opening reaction of the 1-cyclopropylvinylbenzene (CPVB) unit, and this process is defined as frustrated AMROP). By employing alkali metal alkoxides (potassium tert-butoxide (t-BuOK) and sodium 2,3-dimethylpentan-3-olate (NaODP)) as additives, the opening of the cyclopropyl group in CPVB can be controlled during homopolymerization. Additionally, the structure and sequence distribution of inserted CPVB units are determined by distinct selective polymerization mechanisms. Thus, the synthetic polymer includes two structural units, i.e., ring-opened CPVB (ro), which is generated from AMROP, and nonopened CPVB (ga), which results from frustrated AMROP (F-AMROP). Furthermore, in view of steric hindrance from the penultimate-unit effect during chain growth of CPVB, the process of F-AMROP cannot continuously occur and requires the AMRO process of CPVB to decrease the steric hindrance around active centers. Therefor; under the influence of steric hindrance from the penultimate unit, AMRO, and thermodynamics, a reversible cycle of frustrated and nonfrustrated AMROP can be activated during the polymerization process, which further realizes a single monomer to prepare an alternating polymer with different isomers. Ultimately, the mechanisms for AMROP and F-AMROP are explored deeply with density functional theory calculations. This intriguing mechanistic finding will become a pioneering and innovative strategy for development of polymerization mechanisms and unprecedented polymer structures in polymer synthesis.