Polyisoprene Bearing Dual Functionalized Mini-Blocky Chain-Ends Prepared from Neodymium-mediated Coordinative Chain Transfer Polymerizations

Through neodymium-mediated coordinative chain transfer copolymerizaiton (CCTcoP), polyisoprenes bearing dual hydroxylated mini-blocky chain-ends were prepared via a three-step strategy. Kinetic studies revealed that, the polymerization demonstrated typical features of CCTcoP across the whole polymerization process, i.e. , quasi-living polymerization characteristic, tunable molecular weights, narrow molecular weight distributions, and atom economies. Comparing to previously reported CCTP homopolymerization systems, the presence of oxygen-containing Ip OAl polar comonomer slowed down chain transfer rates obviously, rendering slightly higher molecular weights of the resultant PIps and smaller N p (number of polymer chains per Nd atom) values. Moreover, to mimic the structure of natural rubber, the hydroxyl end groups can be facilely modified into phosphonate, amide, and UPy, whose structures were further confirmed by NMR spectra. Incorporation these functionalities could greatly improve the hydrophilic properties of the polymers, as revealed from the significantly reduced static water contact angles.