This work reports a facile strategy for the preparation of a novel well-defined brush copolymer with two different grafts distributed on the same unit along the backbone via combination of three controlled polymerization methods, ring-opening polymerization (ROP), ring-opening metathesis polymerization (ROMP), and atom transfer radical polymerization (ATRP) based on the synthesis of the heterotrifunctional inimer, 2-hydroxymethyl-3-(2-bromoisobutyryloxymethyl)-5-norbornene (NBE-OH/Br). ROP of ε-caprolactone initiated by NBE-OH/Br was carried out to generate macroinimer, norbornene-graft-poly(ε-caprolactone)/Br (NBE-g-PCL/ Br). The grafting-through strategy was then employed to construct the polymer backbone, poly(norbornene)graft-poly(ε-caprolactone)/Br (PNBE-g-PCL/Br) via ROMP of the norbornene-terminated macroinimer NBE-g-PCL/Br. Finally, the grafting-from route was used for the synthesis of amphiphilic grafted brush copolymer, poly(norbornene)-graft-poly(ε-caprolactone)/poly(2-(dimethylamino)ethyl methacrylate) (PNBE-g-PCL/PDMAE-MA) by ATRP of 2-(dimethylamino)ethyl methacrylate using bromo-functionalized ROMP product PNBE-g-PCL/Br as macroinitiators, containing one hydrophobic PCL graft and one hydrophilic PDMAEMA graft on each unit of the backbone.

This paper describes the synthesis of a novel monomer of 5‐substituted cyclooctene with the pendant of imidazolium salt (7) and the ring‐opening metathesis polymerization of the functionalized cyclooctenes (4 and 7) in CH2Cl2 and ionic liquid [bmim][PF6] by a ruthenium‐based catalyst RuCl2(PCy3)(SIMes)(CHPh) (2). The polymerization, which was carried out in ionic liquid, afforded improved control over the molecular weight (Mn) and polydispersity of the resultant products (PDI <1.4). Furthermore, to facilitate the GPC measurement for molecular weight of polymers, the charged polymers (poly‐7) were hydrolyzed to give uncharged polymers (poly‐4*) by removing the imidazolium pendant from the polymer chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3986–3993, 2007

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