Anionic alternating copolymerization of α-arylacrylates with methyl methacrylate: Effect of monomer sequence on fluorescence

Abstract

Anionic polymerizations of acrylates possessing 1‐pyrenyl (Py1), 1‐naphthyl (Np1), 2‐naphthyl (Np2), and 2‐fluorenyl (Fl2) groups as α‐substituents were investigated as well as the properties of the obtained polymers. Py1 and Np1 did not undergo polymerization, whereas Np2 and Fl2, annulated α‐phenylacrylates at 3,4‐position of the phenyl group, afforded homo‐oligomers and alternating copolymers with methyl methacrylate (MMA). The oligomer of Fl2 [oligo(Fl2)] exhibited strong excimer emission in diluted solution. In contrast, dominant monomer emission was observed for the alternating copolymer with MMA [poly(Fl2‐co‐MMA)]. In the alternating copolymer, MMA units could function as spacers preventing the association of pendant fluorene moieties to suppress the excimer formation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2806–2814

One-Pot Synthesis of α-Substituted Acrylates

“…The use of weak bases in the second step provided cleaner reactions and higher yields compared with strong bases, with the latter affording the product as a complex mixture. In the first step, NaH (entries 1 and 2) proved to be less suit- 3 for the second step (entry 4). Adding a phase-transfer catalyst (entry 5) did not improve the results significantly, nor did a change from K 2 CO 3 to the more DMF-soluble Cs 2 CO 3 (entry 6).…”

Precise Anionic Polymerization of Methyl Methacrylate: Simultaneous Control of Molecular Weight, Stereoregularity and End-Structure

“…The authors have recently conducted an extended study of the polymerisation of a-substituted acrylate esters [18, 19,31,32]. Part of this work explored block copolymerisation with an a-(alkoxymethyl)acrylate ester 2 added to a living anion of stereoregular PMMA.…”

α‐exomethylene lactone possessing acetal–ester linkage: Polymerization and postpolymerization modification for water‐soluble polymer

“…Recently, we have been interested in the polymerization chemistry of α‐functionalized acrylates, as the α‐functionality bound to the vinyl groups leads to unique polymerization behaviors that facilitate the controls of end‐functionality and monomer sequence as well as the excellent polymer properties, such as fluorescence and pH/temperature‐responsiveness . Along the line of this concept, herein, we have designed a new monomer; that is, an α‐functionalized acrylates which has a feature of EMLs possessing acetal–ester (A–E) linkage in its lactone skeleton.…”