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Photocontrolled Iodine-Mediated Green Reversible-Deactivation Radical Polymerization of Methacrylates: Effect of Water in the Polymerization System
摘要： Photocontrolled iodine-mediated reversible-deactivation radical polymerization (RDRP) is a facile and highly efficient access to precision polymers. Herein, a facile photocontrolled iodine-mediated green RDRP strategy was successfully established in water by using 2-iodo-2-methylpropionitrile (CP-I) as the initiator and water-soluble functional monomers including poly(ethylene glycol) methyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA), and 2-hydroxypropyl methacrylate (HPMA) as the model monomers under blue-light-emitting diode (LED) irradiation at room temperature. Well-defined polymers (PPEGMA, PHEMA, PHPMA) with narrow polydispersities (1.09?1.21) were obtained, and amphiphilic block copolymers which can form nanospheres in situ in water (PPEGMA-b-poly(benzyl methacrylate) (PPEGMA-b-PBnMA) and PPEGMA-b-PHPMA) were prepared. To explore the role of water in our polymerization, control experiments were successfully carried out by using oil-soluble monomer methyl methacrylate (MMA) with the help of trace amounts of water. Notably, the green solvent—water—has an additionally positive effect in accelerating the polymerization and makes our polymerization system an environmentally friendly polymerization system. Therefore, this simple strategy conducted in the presence of water enables the green preparation of well-defined water-soluble or water-insoluble polymers and clean synthesis of amphiphilic copolymer nanoparticles in situ.
关键词： blue-light-emitting diode,water-soluble functional monomers,amphiphilic block copolymers,green solvent,RDRP,Photocontrolled iodine-mediated reversible-deactivation radical polymerization
更新于2025-09-19 17:13:59
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Effective utilization of NIR wavelengths for photo-controlled polymerization - penetration through thick barriers and parallel solar syntheses
摘要： This contribution details an efficient and controlled photopolymerization regulated by far-red (λ = 680 nm) and NIR (λ = 780 and 850 nm) light in the presence of aluminum phthalocyanine and aluminum naphthalocyanine. Initiating radicals are generated by photosensitization of peroxides affording an effective strategy that provides controlled polymerizations of a variety of monomers with excellent living characteristics. Critically, long wavelength irradiation provides penetration through thick barriers, affording unprecedented rates of controlled polymerization that can open new and exciting applications. Furthermore, a more optimized approach to performing solar syntheses is presented. By combining the narrow Q-bands of these PCs with others possessing complementary absorptions, layered, independent polymerizations and organic transformations may be performed in parallel under a single broadband emission source such as sunlight.
关键词： Reversible-deactivation radical polymerization,Photochemistry,Photopolymerization,Solar synthesis,NIR
更新于2025-09-12 10:27:22
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The Impact of Polymer Grafting from a Graphene Oxide Surface on Its Compatibility with a PDMS Matrix and the Light-Induced Actuation of the Composites
摘要： Poly(dimethyl siloxane) (PDMS)-based materials with improved photoactuation properties were prepared by the incorporation of polymer-grafted graphene oxide particles. The modification of the graphene oxide (GO) surface was achieved via a surface initiated atom transfer radical polymerization (SI ATRP) of methyl methacrylate and butyl methacrylate. The modification was confirmed by thermogravimetric analysis, infrared spectroscopy and electron microscopy. The GO surface reduction during the SI ATRP was investigated using Raman spectroscopy and conductivity measurements. Contact angle measurements, dielectric spectroscopy and dynamic mechanical analyses were used to investigate the compatibility of the GO filler with the PDMS matrix and the influence of the GO surface modification on its physical properties and the interactions with the matrix. Finally, the thermal conductivity and photoactuation properties of the PDMS matrix and composites were compared. The incorporation of GO with grafted polymer chains, especially poly(n-butyl methacrylate), into the PDMS matrix improved the compatibility of the GO filler with the matrix, increased the energy dissipation due to the improved flexibility of the PDMS chains, enhanced the damping behavior and increased the thermal conductivity. All the changes in the properties positively affected the photoactuation behavior of the PDMS composites containing polymer-grafted GO.
关键词： grafting method,reversible deactivation radical polymerization,smart polymers
更新于2025-09-09 09:28:46