Dataset Information

Light and magnetism dual-gated photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization.

ABSTRACT: A novel raspberry-like γ-Fe₂O₃@carbon dot (CD) nanocatalyst was prepared and applied for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. The nanocatalyst was found to be an efficient photocatalyst in visible light-regulated PET-RAFT polymerization owing to the oxidative quenching mechanism between the photoexcited γ-Fe₂O₃@CDs and the RAFT agent in the PET process. Notably, polymerization can be reversibly ceased in the absence of light or under an external magnetic field. The superparamagnetic nature and high saturation magnetization value (∼30.4 emu g^-1) of the nanocatalyst contribute to convenient recycling of the nanocatalyst after polymerization. The PET-RAFT polymerization with the nanocatalyst before and after recycling was investigated, which displayed all the characteristics of controlled/living polymerization systems.

SUBMITTER: Hu L

PROVIDER: S-EPMC9049777 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Light and magnetism dual-gated photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization.

Hu Lingjuan L Wang Qi Q Zhang Xiaomeng X Zhao Haitao H Cui Zhe Z Fu Peng P Liu Minying M Liu Nan N He Shengbao S Pang Xinchang X Qiao Xiaoguang X

RSC advances 20200213 12

A novel raspberry-like γ-Fe2O3@carbon dot (CD) nanocatalyst was prepared and applied for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. The nanocatalyst was found to be an efficient photocatalyst in visible light-regulated PET-RAFT polymerization owing to the oxidative quenching mechanism between the photoexcited γ-Fe2O3@CDs and the RAFT agent in the PET process. Notably, polymerization can be ...[more]

PMID: 35493912

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Project description:Polymerization-induced self-assembly (PISA) is a powerful platform technology for the rational and efficient synthesis of a wide range of block copolymer nano-objects (e.g., spheres, worms or vesicles) in various media. In situ small-angle X-ray scattering (SAXS) studies of reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization have previously provided detailed structural information during self-assembly (see M. J. Derry et al., Chem. Sci. 2016 , 7 , 5078 - 5090 ). However, conducting the analogous in situ SAXS studies during RAFT aqueous emulsion polymerizations poses a formidable technical challenge because the inherently heterogeneous nature of such PISA formulations requires efficient stirring to generate sufficiently small monomer droplets. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precursor block leads to the formation of sterically-stabilized PGMA-PMOEMA spheres, worms or vesicles, depending on the precise reaction conditions. Construction of a suitable phase diagram enables each of these three morphologies to be reproducibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids. High MOEMA conversions are achieved within 2 h at 70 °C, which makes this new PISA formulation well-suited for in situ SAXS studies using a new reaction cell. This bespoke cell enables efficient stirring and hence allows in situ monitoring during RAFT emulsion polymerization for the first time. For example, the onset of micellization and subsequent evolution in particle size can be studied when preparing PGMA29-PMOEMA30 spheres at 10% w/w solids. When targeting PGMA29-PMOEMA70 vesicles under the same conditions, both the micellar nucleation event and the subsequent evolution in the diblock copolymer morphology from spheres to worms to vesicles are observed. These new insights significantly enhance our understanding of the PISA mechanism during RAFT aqueous emulsion polymerization.

Dataset Information

Light and magnetism dual-gated photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization.

Publications

Light and magnetism dual-gated photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization.

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