A series of well-defined poly[methyl(3,3,3-trifluoropropyl)siloxane]-b-polystyrene-b-poly(tert-butyl acrylate) (PMTFPS-b-PS-b-PtBA) triblock copolymers were prepared by a combination of anionic ring-opening polymerization of 1,3,5-trimethyl-1,3,5-tris(3′,3′,3′-trifluoropropyl)cyclotrisiloxane (F₃), and atom transfer radical polymerization (ATRP) of styrene (St) and tert-butyl acrylate (tBA), using the obtained α-bromoisobutyryl-terminal PMTFPS (PMTFPS-Br) as the macroinitiators. The ATRP of St from PMTFPS-Br, as well as the ATRP of tBA from the obtained PMTFPS-b-PS-Br macroinitiators, has typical characteristic of controlled/living polymerization. The results of contact angle measurements for the films of PMTFPS-b-PS-b-PtBA triblock copolymers demonstrate that the compositions have an effect on the wetting behavior of the copolymer films. For the copolymer films with different compositions, there may be different macroscale or nanoscale structures on the outmost layer of the copolymer surfaces. The films with high content of PtBA blocks exhibit almost no ordered microstructures on the outmost layer of the copolymer surfaces, even though they have microphase-separated structures in bulk. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Well-defined poly(tert-butyl methacrylate)-graft-poly (dimethylsiloxane) (PtBuMA-g-PDMS) graft copolymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) copolymerization of methacryloyl-terminated poly (dimethylsiloxane) (PDMS-MA) with tert-butyl methacrylate (tBuMA) in ethyl acetate, using 2,2′-azobis(isobutyronitrile) (AIBN) as the initiator and 2-cyanoprop-2-yl dithiobenzoate as the RAFT agent. The RAFT statistical copolymerization of PDMS-MA with tBuMA is shown to be azeotropic and the obtained PtBuMA-g-PDMS graft copolymers have homogeneously distributed branches because of the similar reactivity of monomers (r_tBuMA ≈ r_PDMS-MA ≈ 1). By the RAFT block copolymerization of PDMS-MA with tBuMA, moreover, narrow molecular weight distribution (M_w/M_n < 1.3) PtBuMA-g-PDMS graft copolymers with gradient or blocky branch spacing were synthesized. The graft copolymers exhibit the glass transitions corresponding to the PDMS and PtBuMA phase, respectively. However, the arrangement of monomer units in copolymer chains and the length of PtBuMA moieties have important effects on the thermal behavior of PtBuMA-g-PDMS graft copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011