Polymerization-induced self-assembly via RAFT in emulsion: effect of Z-group on the nucleation step. Guimaraes, T. R., Bong, Y. L., Thompson, S. W., Moad, G., Perrier, S., & Zetterlund, P. B. POLYMER CHEMISTRY, 12(1):122–133, January, 2021.
doi  abstract   bibtex   
Polymerization-induced self-assembly (PISA) has emerged as one of the most powerful and widely employed techniques for preparation of block copolymer and polymeric nanoparticles in dispersed systems. Its success relies on a rapid, easily scalable and straightforward process, associated with the ability to readily control nanoparticle morphology. In the present work, we have investigated the effect of the Z-group of RAFT agents ZC(=S)-SR on the nucleation step of aqueous RAFT PISA performed in environmentally friendly emulsion polymerization. Seven different poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) macroRAFTs were synthesized using RAFT agents containing Z-groups of different hydrophilicity. Slow polymerizations and incomplete chain extension reactions were observed for systems with the most hydrophilic Z-group, while the more hydrophobic Z groups led to higher polymerization rates and very successful chain extensions. A mechanism based on Z-group induced RAFT exit is proposed to rationalize this surprising behaviour, providing important information on the mechanistic understanding and optimization of PISA in emulsion.
@article{guimaraes_polymerization-induced_2021,
	title = {Polymerization-induced self-assembly via {RAFT} in emulsion: effect of {Z}-group on the nucleation step},
	volume = {12},
	issn = {1759-9954},
	doi = {10.1039/d0py01311k},
	abstract = {Polymerization-induced self-assembly (PISA) has emerged as one of the most powerful and widely employed techniques for preparation of block copolymer and polymeric nanoparticles in dispersed systems. Its success relies on a rapid, easily scalable and straightforward process, associated with the ability to readily control nanoparticle morphology. In the present work, we have investigated the effect of the Z-group of RAFT agents ZC(=S)-SR on the nucleation step of aqueous RAFT PISA performed in environmentally friendly emulsion polymerization. Seven different poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) macroRAFTs were synthesized using RAFT agents containing Z-groups of different hydrophilicity. Slow polymerizations and incomplete chain extension reactions were observed for systems with the most hydrophilic Z-group, while the more hydrophobic Z groups led to higher polymerization rates and very successful chain extensions. A mechanism based on Z-group induced RAFT exit is proposed to rationalize this surprising behaviour, providing important information on the mechanistic understanding and optimization of PISA in emulsion.},
	number = {1},
	urldate = {2021-01-25},
	journal = {POLYMER CHEMISTRY},
	author = {Guimaraes, Thiago R. and Bong, Y. Loong and Thompson, Steven W. and Moad, Graeme and Perrier, Sebastien and Zetterlund, Per B.},
	month = jan,
	year = {2021},
	pages = {122--133},
}

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