• graft copolymers;
  • grafting-from;
  • polyallene;
  • single electron transfer-living radical polymerization (SET-LRP);
  • synthesis


A well-defined amphiphilic graft copolymer, consisting of hydrophobic polyallene-based backbone and hydrophilic poly(N-isopropylacrylamide) (PNIPAM) side chains, was prepared by the combination of living coordination polymerization, single electron transfer-living radical polymerization (SET-LRP), and the grafting-from strategy. First, the double-bond-containing backbone was prepared by [(η3-allyl)NiOCOCF3]2-initiated living coordination polymerization of 6-methyl-1,2-heptadiene-4-ol (MHDO). Next, the pendant hydroxyls in every repeating unit of poly(6-methyl-1,2-heptadiene-4-ol) (PMHDO) homopolymer were treated with 2-chloropropionyl chloride to give PMHDO-Cl macroinitiator. Finally, PNIPAM side chains were grown from PMHDO backbone via SET-LRP of N-isopropylacrylamide initiated by PMHDO-Cl macroinitiator in N,N-dimethylformamide/2-propanol using copper(I) chloride/tris(2-(dimethylamino)ethyl)amine as catalytic system to afford PMHDO-g-PNIPAM graft copolymers with a narrow molecular weight distribution (Mw/Mn = 1.19). The critical micelle concentration (cmc) in water was determined by fluorescence probe technique and the effects of pH and salinity on the cmc of PMHDO-g-PNIPAM were also investigated. The micellar morphology was found to be spheres using transmission electron microscopy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013