Abstract
Well-defined spheres, worms or vesicles are prepared via RAFT dispersion polymerization of benzyl methacrylate in n-dodecane at 90 °C using hydrogenated polybutadiene as a macro-RAFT agent.
Highlights
Polyethylene and polypropylene are ubiquitous in modern day life.[1]
The monohydroxy-capped PhBD (Mn = 4500 g mol−1, Đ = 1.09) was prepared via living anionic polymerization of butadiene initiated with sec-butyllithium at 26 °C in 90 : 10 w/w anhydrous cyclohexane/diethyl ether; the reaction temperature increased to approximately 40 °C owing to the exothermic nature of the polymerization
Exhaustive hydrogenation of the unsaturated groups was accomplished using a nickel/ aluminium catalyst prepared by the reaction of nickel 2-ethylhexanoate with triethylaluminium. This precursor was esterified using a carboxylic acid-based reversible addition–fragmentation chain transfer (RAFT) agent PETTC using via DCC/DMAP coupling chemistry (Scheme 1) to produce the desired macromolecular RAFT agent
Summary
Polyethylene and polypropylene are ubiquitous in modern day life.[1]. Such polyolefins dominate the global industrial production of synthetic polymers: they are utilized in many applications such as the manufacture of bags, pipes, automotive parts and electrical devices.[2]. Since Szwarc’s development of living anionic polymerization (LAP)[3,4] there has been considerable interest in the preparation of polyolefin-based block copolymers.[4,5,6,7,8] For example, Hillmyer et al prepared a monohydroxyl-capped polybutadiene (PBD) precursor via LAP, with the resulting hydrogenated polybutadiene (PhBD) being used to initiate the LAP of ethylene oxide to afford a series of near-monodisperse amphiphilic diblock copolymers.[9] More recently, reversible addition–fragmentation chain transfer (RAFT) polymerization[10,11,12] has been used to prepare well-defined polyolefin-based block copolymers. In 2000 De Brouwer et al.[13] esterified a monohydroxy-functional hydrogenated PhBD precursor using a carboxylic acid-containing dithiobenzoate chain transfer agent (CTA). The resulting polyisobutylene (PIB) was end-capped with a hydroxyl group before being esterified with a trithiocarbonate-based
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