Direct synthesis of light-emitting triblock copolymers from RAFT polymerization

Abstract

We introduce a straightforward and clean method to synthesize semiconducting triblockcopolymers (tri-BCPs) using RAFT polymerization.

The block copolymer shuffle in size exclusion chromatography: the intrinsic problem with using elugrams to determine chain extension success

“…If the molecular weight becomes significantly higher than 10 kg mol −1 , MS becomes, however, largely unsuitable. 72,73…”

Amphiphilic conjugated block copolymers as NIR-bioimaging probes

“…The reactivity of the styryl double bond is similar to that of the styrene monomer which has been studied extensively for RDRP. 19 In a typical RAFT process, polymerization starts with a 1,2 insertion (change from pre- to main equilibrium in the RAFT process). With styrene, this 1,2 insertion stage is often completely separated from the polymerisation and further chain growth, thus allowing use of this reaction for introduction only of the RAFT group itself.…”

“…The styryl-capped polymer was reacted with the RAFT agent DOPAT in the presence of AIBN resulting in the synthesis of di-DOPAT-p(IDT-NDI) macro initiator (P3). As described in the procedure by Ribeiro and co-workers, 19 an excess of RAFT agent must be employed, combined with a low concentration of AIBN, to drive the reaction to completion and to avoid termination of chains with AIBN-derived cyano-isopropyl radicals. Nonetheless, the synthesis of di-DOPAT-p(IDT-NDI) was successful as evidenced by the complete disappearance of the vinyl signals (5.31, 5.84 and 6.80 ppm) in the 1 H NMR spectrum depicted in Fig.…”

“…The flow method has shown to be effective for self-assembly of BCPS into nano-particles, which do not aggregate using classical batch procedures. 19 Micelles were made at a relatively low flowrate of 2 mL min −1 to balance the kinetic and thermodynamic stability of the particles during the self-assembly process. Making these micelles in flow ensures that despite using a weakly polar monomer as the building blocks for the corona of the micelle, stable particles were obtained.…”

“…Another synthesis method towards conjugated block copolymers was presented by Ribeiro and coworkers. 19 Here a reversible addition fragmentation transfer (RAFT)-functionality was incorporated at either end of the conjugated polymer after end capping in the step growth polymerization process followed by post-polymer modification. With this strategy, chain extension into a triblock copolymer was achieved.…”