| Abstract
| - The synthesis of well-defined homopolymers and random, block, and gradient copolymersfrom octadecyl acrylate (OA) and octadecyl methacrylate (OMA) using atom transfer radical polymerization(ATRP) is reported. Random copolymers were synthesized by the one-pot copolymerization of either tert-butyl acrylate/octadecyl acrylate (Mn,p(tBA-r-OA) = 13 680; Mw/Mn = 1.13) or tert-butyl methacrylate/octadecylmethacrylate (Mn,p(tBMA-r-OMA) = 24 250; Mw/Mn = 1.14) monomer pairs. Additionally, gradient copolymerswere prepared by the simultaneous copolymerization of either tert-butyl acrylate/octadecyl methacrylate(Mn,p(tBA-co-OMA) = 21 790; Mw/Mn = 1.25) or tert-butyl methacrylate/octadecyl acrylate (Mn,p(tBMA-co-OA) =21 900; Mw/Mn = 1.20) monomer pairs. AB and ABA triblock copolymers containing octadecyl groupswere also prepared with controlled molar mass and composition. The sequence of blocking was variedstarting from either poly(tert-butyl (meth)acrylate) or poly(octadecyl (meth)acrylate) macroinitiators. Thehalogen-exchange technique allowed preparation of various well-defined polyacrylate−polymethacrylateblock copolymers. Furthermore, uniform phase-separated structures were formed in ultrathin films castfrom AB diblock copolymers of ptBMA-b-pOMA (Mn = 52 000; Mw/Mn = 1.12) and ptBA-b-pOMA (Mn =28 750; Mw/Mn = 1.20) as determined from AFM. ABA triblock copolymers of pOMA-b-ptBA-b-pOMA(Mn = 75 900; Mw/Mn = 1.14) and poly(octadecyl methacrylate)-block-poly(n-butyl acrylate)-block-poly(octadecyl methacrylate) (Mn = 74 400; Mw/Mn = 1.16) were also analyzed using AFM.
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