Facile and versatile synthesis of rod‐coil poly(3‐hexylthiophene)‐based block copolymers by nitroxide‐mediated radical polymerization

Abstract

A well-defined and monofunctional poly(3-hexylthiophene)-based (P3HT) macroinitiator has been obtained through a clean, simple, and an efficient multistep synthesis process. The macroinitiator is obtained via intermolecular radical 1,2addition onto an x-acrylate-terminated P3HT macromonomer. In a second step, well-defined rod-coil block copolymers were obtained by nitroxide-mediated radical polymerization (NMRP) using the so-called Blocbuilder V R . The polymerization was found to be controlled with various monomers such as styrene, isoprene, 4-vinylpyridine, or methyl acrylate. This process constitutes a very promising way to obtain versatile and clean materials for organic electronics. EXPERIMENTAL MaterialsAll reactions were carried out under a nitrogen atmosphere. Monomers (styrene, methyl acrylate (MA), 4-vinylpyridine (4VP), methyl methacrylate (MMA), isoprene) were distilled over calcium hydride under reduced pressure. BlocBuilder V R (MAMA-SG1) was kindly provided by Arkema (France).Additional Supporting Information may be found in the online version of this article.

Block Copolymer as a Nanostructuring Agent for High‐Efficiency and Annealing‐Free Bulk Heterojunction Organic Solar Cells

“…The rod–coil P3HT‐ b ‐P4VP copolymer utilized herein was synthesized according to a previously described strategy by Mougnier et al, using a synthetic route designed for organic electronic requirements 32. The synthesis procedure is presented in Scheme .…”

“…Synthesis of the Diblock P3HT‐b‐P4VP : ω‐MAMA‐SG1 terminated poly(3‐hexylthiophene) macroinitiator was synthesized according to the litterature 32. In a dried Schlenk, ω‐ Blocbuilder terminated P3HT (10 mg, 0.005 mmol) was dissolved in degassed toluene (0.1 mL) and stirred for 1 h. At this point, distilled 4‐vinylpyridine (0.9 mmol) was added to the reaction mixture.…”

Synthesis and structure–property relationship of carbazole‐alt‐benzothiadiazole copolymers

“…Among all π‐conjugated polymers, such as poly(1,4‐phenylene)s, poly(phenylene vinylene)s, and poly(thiophene)s that have been widely studied over the years, polyfluorenes and polycarbazoles have attracted specific attention for application in Organic Light Emitting Diodes (OLEDs) or in Organic Photovoltaic (OPV). Nevertheless, carbazole derivatives are somehow preferred as they show better stability (both chemically and environmentally), the 9‐position of carbazole being less sensitive than in the case of fluorene, and still allowing the grafting of a solubilizing group .…”

“…For instance, alternating electronrich and electron-deficient moieties in polymeric systems (pull-push copolymer) have shown promising properties especially for photovoltaic applications, since they favour the formation of an intramolecular charge transfer (ICT), which, among other parameters, allows a narrowing of the band-gap. 20 Among all p-conjugated polymers, such as poly(1,4-phenylene)s, 21 poly(phenylene vinylene)s, 22 and poly(thio-phene)s [23][24][25][26][27] that have been widely studied over the years, polyfluorenes 28 and polycarbazoles 29 have attracted specific attention for application in Organic Light Emitting Diodes (OLEDs) or in Organic Photovoltaic (OPV). Nevertheless, carbazole derivatives are somehow preferred as they show better stability (both chemically and environmentally), the 9position of carbazole being less sensitive than in the case of fluorene, 30,31 and still allowing the grafting of a solubilizing group.…”

Improving the control of styrene polymerization at 60 °C using a dialkylated α‐hydrogenated nitroxide

“…These features, together with the absence of cytotoxicity for nitroxides, alkoxyamines and polymers made by this method,11 have always clearly represented unquestionable advantages of NMP over other CLRP techniques 12, 13. In addition, in the last 15 years, significant efforts have allowed the main weaknesses of NMP to be efficiently solved, or at least significantly lowered12 as for instance the range of monomers14–19 or the range of macromolecular architecture20–23 that has been significantly extended. In particular, the use of additives to enhance the rate of polymerization,24, 25 the design of highly labile alkoxyamines based on highly crowded alkyl moieties,26 and the design of new nitroxides with enhanced structural features12 afforded a substantial decrease of the polymerization temperature.…”