Enhanced Preparation of Alkoxyamine‐Functionalized Poly(p‐phenylene)s and Their Use as Macroinitiators for the Synthesis of Stimuli‐Responsive Coil‐Rod‐Coil Block Copolymers

Herein, the enhanced preparation of alkoxyamine‐functionalized poly(p–phenylene)s (PPP) via Suzuki polycondensation (SPC) using microwave irradiation is described. Microwave heating effects a drastic decrease of reaction times compared to conventional heating. By varying the diboronic acid esters within the polymerization process different chain lengths of PPPs ( = 1900?3600 g mol^?1) could be prepared. In addition, by exchange of the catalyst and base either preferably mono‐ or bis‐alkoxyamine‐terminated PPPs could be obtained. These macroinitiators are then applied for the nitroxide‐mediated radical polymerization (NMRP) of N–isopropylacrylamide (NIPAAm) to form PNIPAAm‐b‐PPP‐b‐PNIPAAm block copolymers ( = 24 900–38 400 g mol^?1, / = 1.54–1.67).