Photocontrolled iodine-mediated reversible-deactivation radical polymerization with a semifluorinated alternating copolymer as the macroinitiator

Abstract

A new photocontrolled iodine-mediated reversible-deactivation radical polymerization (RDRP) strategy to facilely prepare main-chain-type semifluorinated alternating block copolymers was successfully established under irradiation with blue LED light at room temperature, by...

Amine‐catalyzed Synthesis of Fluorine‐containing Polymers through Halogen Bonding

“…As a fluoropolymer with a ‐CF 2 I skeleton, polymerization from polymer‐end iodine obtained by polyaddition was also attempted. Photopolymerization of a general‐purpose polymer from polyaddition terminal iodide using a ruthenium catalyst has been reported by Cheng et al [14] . If both the sequential and chain polymerization reactions proceed in the same visible light‐induced reaction catalyzed by the same amine, one‐pot successive polymerization will be availble (Scheme 1 (d)).…”

“…As a fluoropolymer with a -CF 2 I skeleton, polymerization from polymer-end iodine obtained by polyaddition was also attempted. Photopolymerization of a general-purpose polymer from polyaddition terminal iodide using a ruthenium catalyst has been reported by Cheng et al [14] If both the sequential and chain polymerization reactions proceed in the same visible light-induced reaction catalyzed by the same amine, one-pot successive polymerization will be availble (Scheme 1 (d)). Then in this study, we have investigate the amine catalyzed polyaddition minutely although there is a precedent, [9m] and an unprecedented chain polymerization of general-purpose monomers from -CF 2 I structure, and by combining them, one-pot successive polymerization was achieved.…”

Facile grafting modification of main-chain-type semi-fluorinated alternating fluoropolymersviasimultaneous CuAAC reaction and ATRP in one pot at ambient temperature

“…[18][19][20] Meanwhile, the development of various reversible deactivation radical polymerization (RDRP) methods provides new approaches for the precision synthesis of fluorinated copolymers with controlled macromolecular architectures, predictable molar mass and high chain-end fidelity. [21][22][23][24][25][26][27] Atom transfer radical polymerization (ATRP) as one of the RDRP methods is a powerful technique in polymer chemistry [28][29][30] that is often employed to synthesize fluorinated graft copolymers. [31][32][33][34] For example, chlorine on the main-chain-type polychlorotrifluoroethylene (PCTFE) backbone is utilized as an initiator and various side chains can be introduced into the PCTFE backbone via ATRP.…”

Hierarchical Self‐Assembly of Triphilic Main‐Chain‐Type Semifluorinated Alternating Graft Copolymers in Aqueous Solution

“…Different from the graft copolymers based on the traditional fluorinated graft copolymers with the backbone such as polyvinylidene fluoride or polychlorotrifluoroethylene , [9] the final fluorinated graft copolymers (AB) n A-g-mOEG x could be designed as diverse structures since the structure of the main-chain type semifluorinated (AB) n A is with powerful designability. [10] It's worth noting that the grafting density of (AB) n A-g-mOEG x is relatively low due to its special structure as compared with the typical grafting copolymers, [11] which could lead to the contact of the hydrophobic segments with the solvent molecules at some sites and the micelles tend to aggregate and fuse to form larger micelles through hierarchical self-assembly. [12] Furthermore, with semifluorinated alternating backbone, the number of interfaces between fluorinated segments and lipophilic segments increases, thereby enhancing the contribution of interfacial tension to the overall free energy, [5b] so we can explore the process of the self-assembly of final fluorinated graft copolymers (AB) n A-g-mOEG x containing fluorophilic, lipophilic and hydrophilic components and propose the possible mechanism of self-assembly.…”