HP-RAFT: A Free-Radical Polymerization Technique for Obtaining Living Polymers of Ultrahigh Molecular Weights


  • HP-RAFT: High-pressure reversible addition-fragmentation transfer polymerization. This work was funded by the N.S.F. through the Materials Research Science and Engineering Center at the University of Massachusetts (DMR-0213695). Additional general support came from the industrial sponsors of the Green Chemistry cluster at the Center for UMass/Industry Research on Polymers.


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Poly(methyl methacrylate)s of extremely high molecular weights (>106) and narrow molecular weight distributions (w/n<1.2:1) were easily obtained by living/controlled free-radical polymerization under high hydrostatic pressure (5 kbar; see scheme, AIBN=2,2′-azobis(isobutyronitrile)). This technique provides conditions amenable to industrial scale-up.