Synthesis of Highly Branched Comblike Polymers Having One Branch in Each Repeating Unit by Linking Reaction of Polystyryllithium with Well‐Defined New Epoxy‐Functionalized Polystyrene

Abstract

AbstractHighly branched comblike polymers having one branch in each repeating unit were successfully synthesized by the linking reaction of polystyryllithium (PSLi) with new epoxy‐functionalized polystyrenes, poly(4‐(3,4‐epoxybutyl)styrenes, (1). The reaction of PSLi with 1 proceeded very fast to reach 88 % efficiency after 1 h and was complete within 24 h under the conditions in THF at −78 °C. A high molecular weight PSLi (Mw = 56.2 kg/mol) could be completely reacted with 1 (Mw = 8.36 kg/mol) to introduce into each of all epoxy reaction sites. However, the linking efficiency decreased with increasing the molecular weights of PSLi and especially 1. With use of a high molecular weight 1 (Mw = 71.8 kg/mol), even a low molecular weight PSLi (Mw = 4.28 kg/mol) could not be quantitatively introduced into all epoxy functions, although a high efficiency of 88 % was achieved. The influence of both molecular weights on linking efficiency was examined in detail.