RAFT step-growth polymerization <i>via</i> the Z-group approach and deconstruction by RAFT interchange

Li, Jiajia; Tanaka, Joji; Li, Qing; Jing Wang, Claire Jing; Sheiko, Sergei; Clouthier, Samantha Marie; Zhu, Jian; You, Wei

doi:10.1039/d3sc06736j

Chem. Sci.

2024

DOI: 10.1039/d3sc06736j

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RAFT step-growth polymerization via the Z-group approach and deconstruction by RAFT interchange

Jiajia Li,

Joji Tanaka,

Qing Li

et al.

Abstract: Recycling vinyl polymers is essential to mitigate the environmental impact of plastic waste. However, typical polymerization strategies to construct vinyl polymers lack the ability to incorporate degradable linkers throughout the...

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Cited by 2 publications

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RAFT Polymerization for Advanced Morphological Control: From Individual Polymer Chains to Bulk Materials

Hakobyan,

Ishizuka,

Corrigan

et al. 2024

Advanced Materials

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Control of the morphology of polymer systems is achieved through reversible‐deactivation radical polymerization techniques such as Reversible Addition‐Fragmentation chain Transfer (RAFT). Advanced RAFT techniques offer much more than just “living” polymerization — the RAFT toolkit now enables morphological control of polymer systems across many decades of length‐scale. Morphological control is explored at the molecular‐level in the context of syntheses where individual monomer unit insertion provides sequence‐defined polymers (single unit monomer insertion, SUMI). By being able to define polymer architectures, the synthesis of bespoke shapes and sizes of nanostructures becomes possible by leveraging self‐assembly (polymerization induced self‐assembly, PISA). Finally, it is seen that macroscopic materials can be produced with nanoscale detail, based on phase‐separated nanostructures (polymerization induced microphase separation, PIMS) and microscale detail based on 3D‐printing technologies. RAFT control of morphology is seen to cross from molecular level to additive manufacturing length‐scales, with complete morphological control over all length‐scales.

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RAFT Polymerization for Advanced Morphological Control: From Individual Polymer Chains to Bulk Materials

Hakobyan,

Ishizuka,

Corrigan

et al. 2024

Advanced Materials

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Step-growth irreversible deactivation radical polymerization: synergistic developments with chain-growth reversible deactivation radical polymerization

Kamigaito

2024

Bulletin of the Chemical Society of Japan

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Recent advances in chain-growth reversible deactivation radical polymerization (CG-RDRP), i.e. the so-called “living radical polymerization”, have synergistically developed step-growth radical polymerizations via controlled formation of radical species from covalent bonds followed by irreversible deactivation of the resulting radical species. The monomers for radical polyaddition are thus designed to possess carbon–halogen or thioester bonds, which can generate radical species in the presence of transition metal catalysts and radical initiators, as well as carbon‒carbon double bonds, which will irreversibly form carbon–halogen or thioester bonds. Radical polycondensations are achievable via radical coupling reactions of carbon-centered radicals generated from carbon–halogen bonds or radical quenching reactions with nitroxides. Furthermore, radical addition-condensation polymerizations are achieved by a sequence of reactions, i.e. the formation of radical species from carbon–halogen bonds, radical addition to nitroso or thiocarbonylthio compounds, and coupling or quenching reactions with the resulting stable radical. These step-growth irreversible deactivation radical polymerizations (SG-IDRP) enable the synthesis of a variety of polymers, such as polyethers, polyesters, polyamides, and polyimides, which have aliphatic, aromatic, polar, and degradable groups in their main chains. Sequence-regulated vinyl polymer structures can also be constructed by designing monomers. Combinations with CG-RDRPs further lead to unique hybrid block, multiblock, graft, hyperbranched, and network polymers.

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RAFT step-growth polymerization via the Z-group approach and deconstruction by RAFT interchange

Abstract: Recycling vinyl polymers is essential to mitigate the environmental impact of plastic waste. However, typical polymerization strategies to construct vinyl polymers lack the ability to incorporate degradable linkers throughout the...

Cited by 2 publications

References 70 publications

RAFT Polymerization for Advanced Morphological Control: From Individual Polymer Chains to Bulk Materials

RAFT Polymerization for Advanced Morphological Control: From Individual Polymer Chains to Bulk Materials

Step-growth irreversible deactivation radical polymerization: synergistic developments with chain-growth reversible deactivation radical polymerization

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