Diverse approaches to star polymers via cationic and radical RAFT cross-linking reactions using mechanistic transformation

2017 ◽  
Vol 8 (38) ◽  
pp. 5972-5981 ◽  
Author(s):  
Mineto Uchiyama ◽  
Kotaro Satoh ◽  
Thomas G. McKenzie ◽  
Qiang Fu ◽  
Greg. G. Qiao ◽  
...  

Core cross-linked star polymers were synthesizedviacationic RAFT polymerization and three different approaches in combination with a radical RAFT mechanism.

2020 ◽  
Vol 11 (2) ◽  
pp. 344-357 ◽  
Author(s):  
Thomas J. Gibson ◽  
Peter Smyth ◽  
Mona Semsarilar ◽  
Aidan P. McCann ◽  
William J. McDaid ◽  
...  

Facile low temperature aqueous heterogeneous RAFT polymerization for preparation of novel star polymers with acid-labile diacetal-based cores for DNA delivery.


2006 ◽  
Vol 59 (10) ◽  
pp. 719 ◽  
Author(s):  
Christopher Barner-Kowollik ◽  
Thomas P. Davis ◽  
Martina H. Stenzel

Various pathways to generate star polymers using reversible addition–fragmentation transfer (RAFT) are discussed. Similar to other polymerization techniques, star polymers can be generated using arm-first and core-first approaches. Unique to the RAFT process is the subdivision of the core-first approach into the R-group and Z-group approaches, depending on the attachment of the RAFT agent to the multifunctional core. The mechanism of the R- and Z-group approaches are discussed in detail and it is shown that both techniques have to overcome difficulties arising from termination reactions. Termination reactions were found to broaden the molecular weight. However, these side reactions can be limited by careful design of the synthesis. Considerations include RAFT and radical concentration, number of arms, type of RAFT agent and monomer. Despite obvious challenges, the RAFT process is highly versatile, allowing the synthesis of novel polymer architectures such as poly(vinyl acetate) and poly(vinyl pyrrolidone) star polymers.


2020 ◽  
Vol 11 (45) ◽  
pp. 7178-7184
Author(s):  
Jongmin Park ◽  
Stefan J. D. Smith ◽  
Colin D. Wood ◽  
Xavier Mulet ◽  
Myungeun Seo

Hyper-cross-linking of a core of block polymer micelles produces core cross-linked polymer with a spacious hyper-cross-linked core, which is solution-processible.


2015 ◽  
Vol 6 (45) ◽  
pp. 7871-7880 ◽  
Author(s):  
Sunirmal Pal ◽  
Megan R. Hill ◽  
Brent S. Sumerlin

Thermo- and redox-responsive hyperbranched copolymers were prepared by statistical copolymerization of N-isopropylacrylamide (NIPAM) and N,N′-bis(acryloyl)cystamine (BAC) by reversible addition–fragmentation chain transfer (RAFT) polymerization.


2012 ◽  
Vol 33 (9) ◽  
pp. 760-766 ◽  
Author(s):  
Jinna Liu ◽  
Hien Duong ◽  
Michael R. Whittaker ◽  
Thomas P. Davis ◽  
Cyrille Boyer

2011 ◽  
Vol 64 (6) ◽  
pp. 766 ◽  
Author(s):  
Bianca M. Blunden ◽  
Donald S. Thomas ◽  
Martina H. Stenzel

Amphiphilic block copolymers were prepared via reversible–addition fragmentation chain transfer (RAFT) polymerization and their synthesis, cross-linking, and degradation were studied using on-line monitoring. The focus of this work is the systematic alteration of the hydrophobic block using copolymers based on 5′-O-methacryloyluridine (MAU) and styrene at different compositions to determine the effect of the copolymer composition on the properties of the micelle. A poly(poly(ethylene glycol) methyl ether methacrylate) (PEGMA) macroRAFT agent was chain extended with a mixture of styrene and MAU. In both systems, an increasing fraction of styrene was found to reduce the rate of polymerization, but the functionality of the RAFT system was always maintained. The amphiphilic block copolymers were dialyzed against water to generate micelles with sizes between 17 and 25 nm according to dynamic light scattering (DLS). Increasing styrene content lead to smaller micelles (determined by DLS and transmission electron microscopy) and to lower critical micelle concentrations, which was measured using surface tensiometry. The micelles were further stabilized via core-cross-linking using bis(2-methacroyloxyethyl) disulfide as crosslinker. NMR analysis revealed a faster consumption of crosslinker with higher styrene content. These stable cross-linked micelles were investigated regarding their ability to degrade in the presence of dithiothreitol as a model reductant. Increasing the styrene content resulted in a faster degradation of the cross-linked micelles into unimers.


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