Reactive & Functional Polymers 50 (2001) 67–75 www.elsevier.com / locate / react Multifunctional ATRP macroinitiators for the synthesis of graft copolymers * ˇ ˇ ˇ ´ Miroslav Janata , Bohumil Masar, Ludek Toman, Petr Vlcek, Petra Policka, ˇ´ Jirı Brus, Petr Holler Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6, Czech Republic Received 11 March 2001; received in revised form 1 August 2001; accepted 6 August 2001 Abstract Multifunctional ATRP macroinitiators, polystyrene with 1-(2-bromopropionyloxy)ethyl or 1-(2-bromoisobutyryloxy)ethyl groups in the benzene rings and poly[4-methylstyrene-co-4-(bromomethyl)styrene], were synthesized. All the functionalized 1 13 polymers were characterized by IR, H and C NMR spectroscopy and by size exclusion chromatography.  2001 Elsevier Science B.V. All rights reserved. Keywords: ATRP macroinitiators; Functionalized polystyrene 1. Introduction groups bonded at the end(s) of the polymer chain or along it are used as powerful initiators Atom transfer radical polymerization (ATRP) for ATRP of (meth)acrylic monomers [2–4]. [1] is a new synthetic method which enables Benzyl halides and polymers with bonded preparation of well-defined polymers from radi- benzyl halide fragment(s) are also referred to as cally polymerizable monomers using halogen- suitable initiators for ATRP of methacrylates or containing initiators. Depending on the mono- styrene [2–4]. Depending on the structure of the mer to be polymerized, different types of initiator used, homopolymers, block or graft initiators are usually used to attain optimum copolymers can arise. polymerization conditions. Nevertheless, most We focused on the synthesis of graft co- of them contain a halogen atom bonded at the polymers by ATRP process using appropriate carbon atom activated in the a-position with polymers, functionalized with the mentioned carbonyl, alkoxycarbonyl, cyano or phenyl types of initiating groups along the polymer groups. chain, as multifunctional initiators [5]. There- Thus, esters of 2-halopropionic and 2- fore, the first aim of our project was to syn- haloisobutyric acid as well as polymers with thesize suitable ATRP macroinitiators. Low-mo- 2-halopropionyloxy or 2-haloisobutyryloxy lecular-weight polystyrene (PS) and poly(4- methylstyrene) [P(4-MS)], used as starting ma- terials, were functionalized by introducing the *Corresponding author. E-mail address: janata@imc.cas.cz (M. Janata). 2-bromopropionyloxy or 2-bromoisobutyryloxy 1381-5148 / 01 / $ – see front matter  2001 Elsevier Science B.V. All rights reserved. PII: S1381-5148(01)00091-8