Gradient graft copolymers derived from PEO‐based macromonomers

Atom transfer radical polymerization (ATRP) of two poly(ethylene oxide) (PEO) macromonomers, with different polymerization degrees (DP_n) and different end groups, was conducted in solution via the grafting through method. Selection of a PEO methacrylate with a methyl end‐group (PEOMeMA, DP_PEO = 23) and a PEO acrylate end‐capped by a phenyl ring (PEOPhA, DP_PEO = 4) for the copolymerization led to a spontaneous gradient of PEO grafts along the copolymer backbone. Such a composition was formed because of significantly different reactivities of the two PEO macromonomers. The resulting copolymer has PEOMeMA at one end of the polymer chain, gradually changing through hetero‐sequences of PEOPhA at the other chain end. An increase in the initial feed ratio of PEO acrylate reduced the rate of change in the shape of the gradient. Amorphous–crystalline structure in the copolymers was demonstrated by DSC and WAXS. The mechanical measurements of copolymers consisting of an amorphous PEOPhA and crystallizable PEOMeMA segments indicated elastomeric properties in the range of a soft rubber (G′ ～ 10⁴ Pa, G′ ? G″). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1347–1356, 2006