Nanostructured functional materials prepared by atom transfer radical polymerization

Abstract

Atom transfer radical polymerization (ATRP) is the most extensively studied controlled/living radical polymerization (CRP) method, with the interest originating primarily in its simplicity and broad applicability, and in the ability to prepare previously inaccessible well-defined nanostructured polymeric materials. This review illustrates the range of well-defined advanced functional materials that can be prepared by ATRP. We detail the precise synthesis of macromolecules with predetermined molecular weight, designed molecular weight distribution, controlled topology, composition and functionality. The materials include polymers with site-specific functionalities and novel architectures that are starting to find commercial application--such as stars, bottle brushes, block and gradient copolymers. This is followed by discussing their self-assembly into materials with nanoscale morphologies. These macromolecular engineering procedures provide new avenues to nanostructured functional materials for many high-value applications, for example as thermoplastic elastomers, coatings, surfactants, dispersants and as optoelectronic and biomedical materials.

Solid Phase Synthesis of Lysine-exposed Peptide-Polymer Hybrids by Atom Transfer Radical Polymerization

“…3 Indeed, ATRP could be a facile technique for preparing welldefined polymers with narrow molecular weight distribution, predictable chain length, controlled microstructure, defined chain-ends, and controlled architecture. 19 Moreover, the chemistry of ATRP is tolerant of many functional groups, thereby permitting the controlled synthesis of a broad range of polymers. The ATRPs of various monomers from different particles were studied extensively for surface modification.…”

Conjugation of siRNA with Comb‐Type PEG Enhances Serum Stability and Gene Silencing Efficiency

“…[18][19][20] When compared to the linear PEG with equivalent molecular weights, the comb-like PEG displays greater steric hindrance, thus potentially enhancing biostability and lowering clearance rates of the conjugated biotherapeutics. Moreover, comb-shaped PEG-(meth)acrylate polymers can be prepared by reversible addition fragmentation chain transfer (RAFT) polymerization [21][22][23][24][25] and atom transfer radical polymerization (ATRP) techniques, [26][27][28][29] which offer facile synthetic routes to the generation of polymers with controlled molecular weight, varying macromolecular architectures and defined endgroup functionalities. While control over the molecular weight and macromolecular structure of the conjugated polymer is crucial for improved pharmacokinetic properties of the bioconjugates, the defined end-group functionality enables varying synthetic strategies to be implemented for site-specific PEGylation.…”

Recent developments in metal-catalyzed living radical polymerization

“…Thus, a wide variety of conjugated monomers, such as methacrylates, acrylates, styrenes (Sts), acrylamides and acrylonitrile, can now be polymerized in a controlled fashion, although a truly well-controlled radical polymerization of unconjugated monomers such as vinyl acetate (VAc) is still one of the most challenging topics in metal-catalyzed living radical polymerizations. [6][7][8][9][10][11][12][13][14][15][16][17] In addition, the amounts of the metal catalyst used in the polymerizations have decreased owing to the evolution of the active catalysts or the addition of reducing agents for the oxidized metal catalysts. However, these are still challenges for industrial applications.…”

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] Besides these metal catalytic systems, there have also been substantial developments in various living radical polymerizations, such as nitroxide-mediated polymerizations, reversible addition fragmentation chain-transfer polymerizations and others, and in all of these, there are characteristic features of the mechanisms and components. [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] The metal-catalyzed living radical polymerization was originally discovered via evolution of the metal-catalyzed Kharasch or atom transfer radical addition reaction 35 to the chain-growth polymerization of vinyl monomers ( Figure 1).…”

“…The details on how we discovered the catalytic systems can be found in our previous reviews. 7,9 In contrast, the most extensively used catalysts are based on copper with nitrogen ligands, which were separately developed by many research groups, including Matyjaszewski, Percec, Haddleton and others [2][3][4][12][13][14][15][16][17] (The reaction mechanisms for the metal-catalyzed living radical polymerization and ATRP are supposed to be the same. Although the former name is mostly used in this review, it never intends to exclude the latter.…”