Solid‐supported synthesis of well‐defined amphiphilic block copolymer from methacrylates

Abstract

A new facile method for preparation of an amphiphilic block copolymer via a one‐pot sequential atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA) on solid support was developed. As a model homopolymerization for the solid‐supported block copolymerization, ATRPs of MMA and HEMA in toluene and in 2‐butanone/1‐propanol solvent system were carried out, respectively. Crosslinked polystyrene beads bearing 2‐bromoisobutyrate moieties successfully initiated the polymerizations of MMA and HEMA in controlled manner. On the basis of the successful results, the one‐pot synthesis of amphiphilic block copolymer by changing the reaction medium was performed. After the ATRP of MMA in toluene at 90 °C for 1 h, the poly(MMA) formed on the beads were washed by continuous flow of 2‐butanone/1‐propanol under nitrogen with the aid of a glass filter in a U‐shaped glass vessel. Then, 2‐butanone/1‐propanol, copper chloride (I), 2,2′‐bipyridyl, and HEMA were added and heated at 50 °C for 48 h with shaking the vessel, followed by treatment with trifluoroacetic acid to isolate the well‐defined amphiphilic block copolymer, poly(MMA‐b‐HEMA). These demonstrated the feasibility of the present strategy for well‐defined synthesis of amphiphilic block copolymers via a one‐pot procedure. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1990–1997, 2008

Polypeptoids: A perfect match for molecular definition and macromolecular engineering?

“…Accordingly, some researchers have studied the combination of SPPS and solid phase initiated polymerization . Very recently, Luxenhofer and coworkers have reported on the solid phase peptoid polymerization (SP3) using Rink‐type resins for initiators and N‐substituted NCA as monomers (Fig.…”

Synthesis, Assembled Structures, and Optoelectronic Properties of Amphiphilic Block Copolymers Containing Anthracene Units in the Main Chain

“…For size‐exclusion chromatography (SEC) measurements, the acetylation of poly(HEA) was conducted by treating the acetic anhydride according to a method reported previously with a slight modification 37. In this way, acetic anhydride (1 mL, 10.6 mmol) and pyridine (0.5 mL, 6.2 mmol) were added into the solution of poly(HEA) (40 mg, 0.34 HEA units per mmol) in DMF (0.5 mL).…”

An efficient, heterogeneous, reusable atom transfer radical polymerization catalyst

“…Atom transfer radical polymerization (ATRP) has attracted considerable attention in polymer and materials science. Without doubt, it is one of the most important synthetic methods due to its capability for synthesizing well‐defined polymers with a predetermined molecular weight, designed structure and tailor‐made functionalities . Traditionally, ATRP is performed using Cu(I) as catalyst with several ligands under an anaerobic atmosphere.…”

“…Without doubt, it is one of the most important synthetic methods due to its capability for synthesizing well-defined polymers with a predetermined molecular weight, designed structure and tailor-made functionalities. [1][2][3][4][5][6][7][8][9][10][11][12][13] Traditionally, ATRP is performed using Cu(I) as catalyst with several ligands under an anaerobic atmosphere. However, Cu(I) salts and their ligands (e.g.…”