Synthesis of well‐defined pH‐responsive PPEGMEA‐g‐P2VP double hydrophilic graft copolymer via sequential SET‐LRP and ATRP

Abstract

A series of well‐defined double hydrophilic graft copolymers containing poly(poly(ethylene glycol) methyl ether acrylate) (PPEGMEA) backbone and poly(2‐vinylpyridine) (P2VP) side chains were synthesized by successive single electron transfer living radical polymerization (SET‐LRP) and atom transfer radical polymerization (ATRP). The backbone was first prepared by SET‐LRP of poly(ethylene glycol) methyl ether acrylate (PEGMEA) macromonomer using CuBr/tris(2‐(dimethylamino)ethyl)amine as catalytic system. The obtained homopolymer then reacted with lithium diisopropylamide and 2‐chloropropionyl chloride at −78 °C to afford PPEGMEA‐Cl macroinitiator. poly(poly(ethylene glycol) methyl ether acrylate)‐g‐poly(2‐vinylpyridine) double hydrophilic graft copolymers were finally synthesized by. ATRP of 2‐vinylpyridine initiated by PPEGMEA‐Cl macroinitiator at 25 °C using CuCl/hexamethyldiethylenetriamine as catalytic system via the grafting‐ from strategy. The molecular weights of both the backbone and the side chains were controllable and the molecular weight distributions kept relatively narrow (Mw/Mn ≤ 1.40). pH‐Responsive micellization behavior was investigated by 1H NMR, dynamic light scattering, and transmission electron microscopy and this kind of double hydrophilic graft copolymer aggregated to form micelles with P2VP‐core while pH of the aqueous solution was above 5.0. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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“…The progress in preparing transition‐metal‐containing polymers has also benefited from the development of these powerful synthetic methods 33, 47, 48. In particular, for the synthesis of graft copolymer, side chains can be formed in a well‐defined way via ATRP or SET‐LRP initiated by the pendant initiating groups on the backbone via the grafting‐from strategy,49–52 and the living characteristic of ATRP/SET‐LRP enabled it to control both molecular weights and polydispersities of side chains 53–57…”

“…Previous studies showed that the architecture of copolymers played an important role in the properties of micelles, because nonlinear block copolymers exhibited fundamentally different micellization properties compared with linear copolymers 51. In comparison with the corresponding linear counterpart with similar molecular weight, graft copolymers that contain a great quantity of side chains chemically attached onto a linear backbone are endowed with fascinating properties including worm‐like conformation, compact molecular dimension, and remarkable chain end effects that result from their confined and compact structures 51, 57. However, only a few reports were focused on the synthesis and self‐assembly behavior of well‐defined ferrocene‐based graft copolymers 33, 48.…”

Aqueous SET-LRP catalyzed with “in situ” generated Cu(0) demonstrates surface mediated activation and bimolecular termination

“…3 Subsequently, SET-LRP was expanded to acrylates, [4][5][6][7][8][9][10][11][12][13][14][15][16][17] methacrylates, 8,[18][19][20][21][22][23][24][25] acrylamides, [26][27][28][29][30][31] methacrylamide, 32 acrylonitrile, 33,34 and monomers containing more complex water soluble side groups, such as sugars, 35,36 N-(2-hydroxypropyl) methacrylamide, 32 dimethylacrylamide, 26 N-isopropylacrylamide, 26,[37][38][39] oligo(ethylene oxide) methyl ether acrylate, 40 oligo(ethylene oxide) methyl ether methacrylate, 41 hydroxyethyl acrylate, 10 hydroxyethyl methacrylate 23 and acryloyl morpholine. 42 At the same time as these developments, the list of solvents used in SET-LRP was expanded to other solvents that in combination with aliphatic N-donor ligands, such as tris[(2-dimethylaminoethyl)...…”

Synthesis and comparison of two poly (methyl methacrylate-b-3-(trimethoxysilyl)propyl methacrylate)/SiO 2 hybrids by “grafting-to” approach

“…As is known, atom transfer radical polymerization (ATRP) is suitable to develop this well-defined block copolymer [24][25][26]. Therefore, in this paper, the well-defined diblock copolymer containing PMPS segment is designed for facility the pendent RASi(OCH 3 ) 3 groups to hydrolyze easily into RASi(OH) 3 in a base or acid catalyst, which can subsequently react with TEOS to generate polymeric/silica hybrids [27,28].…”