A starlike amphiphilic graft copolymer with hydrophilic poly(acrylic acid) backbones and hydrophobic polystyrene side chains

Abstract

A well‐defined starlike amphiphilic graft copolymer bearing hydrophilic poly(acrylic acid) backbones and hydrophobic polystyrene side chains was synthesized by successive atom transfer radical polymerization followed by the hydrolysis of poly‐(methoxymethyl acrylate) backbone. A grafting‐from strategy was employed for the synthesis of a graft copolymer with narrow molecular weight distribution. Hydrophobic polystyrene side chains were connected to the backbones through stable CC bonds. The poly(methoxymethyl acrylate) backbones can be easily hydrolyzed with HCl without affecting the hydrophobic polystyrene side chains. This kind of amphiphilic graft copolymer can form stable sphere micelles in water. The sizes of the micelles were dependent on the ionic strength and pH value. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3687–3697, 2007

Synthesis of amphiphilic copolymer brushes possessing alternating poly(methyl methacrylate) and poly(N‐isopropylacrylamide) grafts via a combination of ATRP and click chemistry

“…In general, comb‐shaped polymer brushes can be categorized into homopolymer brushes and copolymer brushes. Since the pioneering work reported by Tsukahara et al3, 4 in 1989, extensive investigations have been devoted to the synthesis of homopolymer brushes mainly via three approaches including grafting‐through,5–20 grafting‐from,21–39 and grafting‐onto 40–46. In the past decade, the advent of controlled polymerization techniques, such as ring‐opening polymerization (ROP),5, 24, 25, 30, 37, 43 nitroxide‐mediated polymerization (NMP),47–49 atom transfer radical polymerization (ATRP),16, 31–33, 35, 39 and reversible addition‐fragmentation chain transfer (RAFT) polymerization,50, 51 have rendered the grafting‐from approach more appealing, starting with macroinitiators with the initiating sites distributed on every repeating unit.…”

Methods of controlled radical polymerization for the synthesis of polymer brushes

“…Of interest is the series of papers [104][105][106][107][108][109] devoted to the synthesis of brushes with a hydrophilic backbone (poly(acrylic acid) and hydrophobic side chains [poly(methyl methacrylate) [104,108], poly(n butyl methacrylate) [105], polystyrene [106,107], and poly(vinyl acetate) [109]). The scheme of synthesis of brushes with a hydrophilic backbone of poly(acrylic acid) and side chains of poly(n butyl methacrylate) applied in [104][105][106][107][108] Poly(methoxymethyl acrylate)-a precursor of poly(acrylic acid)-was synthesized for further use as a backbone.…”

“…The scheme of synthesis of brushes with a hydrophilic backbone of poly(acrylic acid) and side chains of poly(n butyl methacrylate) applied in [104][105][106][107][108] Poly(methoxymethyl acrylate)-a precursor of poly(acrylic acid)-was synthesized for further use as a backbone. This polymer was lithiated at the α carbon atom of the main polymer chain by lithium isopropyla mide in THF and then modified at the α carbon atom with 2 Br isobutyroyl (or 2 Br propionyl) bromide.…”

Well‐defined amphiphilic graft copolymer consisting of hydrophilic poly(acrylic acid) backbone and hydrophobic poly(vinyl acetate) side chains

“…In our previous studies, we utilized the grafting‐from approach to synthesize well‐defined amphiphilic linear and star‐like graft copolymers containing hydrophilic poly(acrylic acid) backbone and hydrophobic polystyrene, poly(methyl methacrylate), and poly(butyl methacrylate) side chains by successive ATRP 44–48. However, it is difficult to apply ATRP technique to vinyl acetate due to the low equilibrium constant49 and the presence of side reactions, such as the decomposition of dormant species and possible transformation of growing radicals to cations through an outer sphere electron‐transfer process 50.…”