Cationic polymerizations of vinyl ethers have gained recent attention due to their ability to produce robust,biorenewable materials.These developments have been largely enabled by the advent of cationic reversible add...Cationic polymerizations of vinyl ethers have gained recent attention due to their ability to produce robust,biorenewable materials.These developments have been largely enabled by the advent of cationic reversible addition−fragmentation chain-transfer(RAFT)polymerization;however,the scalability and sustainability of this method are hindered by current chain-transfer agents(CTAs),which exist as viscous,colored oils requiring complex syntheses and solvent-intensive purification.Herein,we produce a solid,colorless CTA through a green synthetic route in 83%yield on a 50-gram scale.We investigate the utility of this CTA in chemical,electrochemical,photochemical,and acid-initiated methods,revealing that it achieves efficient polymerization with excellent control over molecular weight,low dispersity values,high chain end fidelity,and temporal control in cationic RAFT polymerizations.展开更多
基金This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No.DGE-1650441This work was supported by the National Science Foundation Center for Sustainable Polymers at the University of Minnesota,a Center for Chemical Innovation(CHE-1901635)This work made use of the NMR Facility at Cornell University that is supported,in part,by the NSF under the award number CHE-1531632.
文摘Cationic polymerizations of vinyl ethers have gained recent attention due to their ability to produce robust,biorenewable materials.These developments have been largely enabled by the advent of cationic reversible addition−fragmentation chain-transfer(RAFT)polymerization;however,the scalability and sustainability of this method are hindered by current chain-transfer agents(CTAs),which exist as viscous,colored oils requiring complex syntheses and solvent-intensive purification.Herein,we produce a solid,colorless CTA through a green synthetic route in 83%yield on a 50-gram scale.We investigate the utility of this CTA in chemical,electrochemical,photochemical,and acid-initiated methods,revealing that it achieves efficient polymerization with excellent control over molecular weight,low dispersity values,high chain end fidelity,and temporal control in cationic RAFT polymerizations.
