Amphiphilic block copolymers featuring a reversible hetero Diels-Alder linkage

The present article reports the preparation of a novel class of switchable amphiphilic diblock copolymers with a temperature switchable linkage. Reversible addition fragmentation chain transfer (RAFT) polymerization was used to synthesize the individual blocks: for the preparation of the non-polar block{,} i.e. poly(isoprene-co-styrene) (P(I-co-S)) (9200 g mol-1 [less-than-or-equal] Mn [less-than-or-equal] 50 000 g mol-1{,} 1.22 [less-than-or-equal] D [less-than-or-equal] 1.36){,} a chain transfer agent (CTA{,} 3-((2-bromo-2-methylpropanoyl)oxy)propyl 2-(((dodecylthio)carbonothioyl)thio)-2-methylpropanoate) carrying a bromine group was employed{,} ready for subsequent cyclopentadienyl (Cp) transformation. For the preparation of the polar block{,} triethylene glycol methyl ether acrylate (TEGA) was polymerized (6600 g mol-1 [less-than-or-equal] Mn [less-than-or-equal] 35 000 g mol-1{,} 1.12 [less-than-or-equal] D [less-than-or-equal] 1.30) using a RAFT agent carrying a phosphoryl Z-group{,} which is able to undergo hetero Diels-Alder (HDA) ligation with Cp moieties. Both building blocks were conjugated at ambient temperature in the p ... mehrresence of ZnCl2 as catalyst yielding the amphiphilic block copolymer P(I-co-S)-b-PTEGA (16 000 g mol-1 [less-than-or-equal] Mn [less-than-or-equal] 68 000 g mol-1{,} 1.15 [less-than-or-equal] D [less-than-or-equal] 1.32). To investigate the bonding/debonding capability of the HDA linkage{,} high temperature nuclear magnetic resonance (HT-NMR) spectroscopy{,} high temperature dynamic light scattering (HT-DLS) and high temperature size exclusion chromatography (HT-SEC) were carried out{,} evidencing that efficiently switchable amphiphilic block copolymers were generated (>4 cycles).