Synthesis of α-, ω-, and α,ω-End-Functionalized Poly(<i>n</i>-butyl acrylate)s by Organocatalytic Group Transfer Polymerization Using Functional Initiator and Terminator

Abstract

The α-functionalized (hydroxyl, ethynyl, vinyl, and norbornenyl), ω-functionalized (ethynyl, vinyl, hydroxyl, and bromo), and α,ω-functionalized polyacrylates were precisely synthesized by the N -(trimethylsilyl)bis(trifluoroethanesulfonyl)imide (Me 3 SiNTf 2 )-catalyzed group transfer polymerization (GTP) of n -butyl acrylate ( n BA). The α-functionalization and ω-functionalization were carried out using the functional triisopropylsilyl ketene acetal as the initiator (initiation approach) and 2-phenyl acrylate derivatives as the terminator (termination approach) for the organocatalytic GTP, respectively. All the polymerizations precisely occurred and produced well-defined end-functionalized poly( n -butyl acrylate)s which had predictable molecular weights and narrow molecular weight distributions. High-molecular-weight polyacrylates were easily synthesized using both approaches. In addition, the α,ω-functionalized (hetero)telechelic polyacrylates were synthesized by the combination of the initiation and termination approaches. The structure of the obtained polyacrylates and degree of functionalization were confirmed by the 1 H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS) measurements. The spectra of the 1 H NMR and MALDI-TOF MS showed that the end-functionalization quantitatively proceeded without any side reactions.