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 ...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 IpOAl polar comonomer slowed down chain transfer rates obviously,rendering slightly higher molecular weights of the resultant PIps and smaller Np(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.展开更多
基金financially supported by the National Natural Science Foundation of China(No.U1862206)Jilin Province Department of Education(No.JJKH20200665KJ)+3 种基金Dr.W.Zhao thanks for the financial support from China Postdoctoral Science Foundation(No.2021M701818)Shandong Provincial Natural Science Foundation,China(No.ZR2022QE237)Qingdao Postdoctoral Applied Research Project,PetroChina Company Limited(No.2020B-2711)H.Liu sincerely acknowledges the financial support from the Taishan Scholars Program。
文摘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 IpOAl polar comonomer slowed down chain transfer rates obviously,rendering slightly higher molecular weights of the resultant PIps and smaller Np(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.