Precision synthesis of graft copolymers via living cationic polymerization of p‐acetoxystyrene followed by friedel–crafts‐type termination reaction. Issue 21 (23rd August 2013)

• Record Type: Journal Article
• Authors: Shinke, Yu; Yamamoto, Hidehiro; Kanazawa, Arihiro; Kanaoka, Shokyoku; Aoshima, Sadahito
• Is Part Of: Journal of polymer science. Volume 51:Issue 21(2013:Nov.)
• Page Start: 4675
• Page End: 4683
• Publication Date: 2013-08-23
• Subjects: 547
• DOI: 10.1002/pola.26889
• Languages: English
• ISSNs: 0887-624X

Abstract

<abstract abstract-type="main"> <title>ABSTRACT</title> <p>This study describes a novel precision synthesis strategy for graft copolymers using Friedel–Crafts‐type termination reaction between a cationically prepared poly(styrene derivative) and the naphthyl side groups from a poly(vinyl ether) main chain. The pendant alkoxynaphthyl groups on the poly(vinyl ether) efficiently terminated the living cationic polymerization of <italic>p</italic>‐acetoxystyrene (AcOSt) with SnCl₄ in the presence of ethyl acetate as an added base. This research provides the first example of a well‐defined graft copolymer prepared using this method. The resulting polymer contained 40 poly‐(AcOSt) branches, as calculated from the <italic>M</italic>_w determined via gel permeation chromatography–MALS analysis, which was in good agreement with the estimated number of branches obtained from ¹H NMR analysis. The acetoxy groups in the grafted poly(AcOSt) chains were easily converted into phenolic hydroxy groups under basic conditions. The as‐obtained graft copolymer with poly(<italic>p</italic>‐hydroxystyrene) side chains exhibited a pH‐sensitive phase separation in water. The synthetic method for preparing the graft copolymers was also effective in the living cationic polymerizations of other styrene derivatives. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. <bold>2013</bold>, <italic>51</italic>, 4675–4683</p> </abstract>