Low-Dispersity Polymers in Ab Initio Emulsion Polymerization: Improved MacroRAFT Agent Performance in Heterogeneous Media

Low-Dispersity Polymers in Ab Initio Emulsion Polymerization: Improved MacroRAFT Agent Performance in Heterogeneous Media. Richardson, R. A. E., Guimaraes, T. R., Khan, M., Moad, G., Zetterlund, P. B., & Perrier, S. MACROMOLECULES, 53(18):7672–7683, September, 2020.
doi abstract bibtex

We demonstrate that the in-built monomer-feeding mechanism in an emulsion polymerization can be used to dramatically increase control (providing low molar mass dispersity (D) \textless= 1.15) over polymerizations mediated by reversible addition-fragmentation chain transfer (RAFT) agents with relatively low transfer constants (C-tr). An amphiphilic RAFT agent [RSC(= S)Z], based on a hydrophilic methacrylic R-group [(C) over dot(CH3)(2)CO2-PEG] and a hydrophobic Z group with C-tr approximate to 2, was used to mediate the polymerization of a range of methacrylate monomers under both heterogeneous and homogeneous conditions. Consistent with the low C-tr, batch miniemulsion or solution polymerizations did not provide polymers with low D. The issue of a low C-tr is overcome in an emulsion polymerization when the [monomer]/[RAFT agent] ratio at the locus of polymerization is substantially lower than the overall ratio, due to the presence of a discrete monomer droplet phase. The proposed mechanism is supported by a theoretical model. As a demonstration of the increased level of control achievable, the system has been exploited to generate methacrylate multiblock copolymers.

@article{richardson_low-dispersity_2020,
	title = {Low-{Dispersity} {Polymers} in {Ab} {Initio} {Emulsion} {Polymerization}: {Improved} {MacroRAFT} {Agent} {Performance} in {Heterogeneous} {Media}},
	volume = {53},
	issn = {0024-9297},
	doi = {10.1021/acs.macromol.0c01311},
	abstract = {We demonstrate that the in-built monomer-feeding mechanism in an emulsion polymerization can be used to dramatically increase control (providing low molar mass dispersity (D) {\textless}= 1.15) over polymerizations mediated by reversible addition-fragmentation chain transfer (RAFT) agents with relatively low transfer constants (C-tr). An amphiphilic RAFT agent [RSC(= S)Z], based on a hydrophilic methacrylic R-group [(C) over dot(CH3)(2)CO2-PEG] and a hydrophobic Z group with C-tr approximate to 2, was used to mediate the polymerization of a range of methacrylate monomers under both heterogeneous and homogeneous conditions. Consistent with the low C-tr, batch miniemulsion or solution polymerizations did not provide polymers with low D. The issue of a low C-tr is overcome in an emulsion polymerization when the [monomer]/[RAFT agent] ratio at the locus of polymerization is substantially lower than the overall ratio, due to the presence of a discrete monomer droplet phase. The proposed mechanism is supported by a theoretical model. As a demonstration of the increased level of control achievable, the system has been exploited to generate methacrylate multiblock copolymers.},
	number = {18},
	urldate = {2020-10-19},
	journal = {MACROMOLECULES},
	author = {Richardson, Robert A. E. and Guimaraes, Thiago R. and Khan, Murtaza and Moad, Graeme and Zetterlund, Per B. and Perrier, Sebastien},
	month = sep,
	year = {2020},
	pages = {7672--7683},
}

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