Facile photochemical synthesis of main-chain-type semifluorinated alternating copolymers catalyzed by conventional amines or halide salts

Abstract

In this work, we report a much simple and low-cost method to prepare main-chain-type semifluorinated alternating copolymers by the formation of halogen bond (XB) complex between α,ω-diiodoperfluoroalkanes and amines/halide salts....

Synthesis and Phase Behavior of (Semifluorinated Alkane)‐Based Side‐Chain Liquid Crystalline Copolymers

“…Subsequently, it was connected with a rigid mesogen 4-methoxyphenyl benzoate to obtain LC monomers H 13 -H m M. Hereafter, we adopted TEA as a catalyst to synthesize regular alternating copolymers F n (I)H 13 (I)-H m M under irradiation with purple LED light at room temperature (25 °C). [47] Finally, in order to improve the structural regularity, F n H 13 -H m M was synthesized by iodine-hydrogen exchange using Zn and CH 3 COOH. See Figures S1-S15 (Supporting Information) for the 1 H NMR and 13 C NMR spectra for all the intermediates and resultants.…”

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

“…We have also reported the polyaddition of diiodoperfluoroalkane and dienes through UV light irradiation or visible light reactions catalyzed by eosin Y [9j] . Amine‐catalyzed polyaddition has been reported; however, this was accompanied by the hydrogenation of terminal iodide [9m] . In this study, a detailed investigation of visible light‐induced polyaddition reactions with amines without terminal hydrogenation was conducted (Scheme 1 (b)).…”

“…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

“…[1][2][3][4][5][6] However, fluoropolymers, especially perfluorinated homopolymers, also suffer from a few drawbacks, including poor solubility in organic solvents, high crystallinity due to high fluorine content and difficult post modification, which increase the processing costs and lead to limitations in the final materials. 1 To resolve these issues and retain the excellent properties of fluoropolymers, the incorporation of comonomers into the fluorinated backbone might be a viable solution [7][8][9][10][11][12][13][14][15][16][17] and grafting modification was proved to be an effective approach for the functionality of fluoropolymers. [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.…”

“…Recently, our group developed a new strategy to prepare main-chain-type semi-fluorinated copolymers under mild conditions, called step transfer-addition and radical-termination (START) polymerization. [7][8][9]43 Semi-fluorinated copolymers (AB) n A with various structures were synthesized via START polymerization of α,ω-diiodoperfluoroalkane (termed monomer A) and α,ω-unconjugated diene (termed monomer B), which can be designed with multiple structures. In addition, the periodic C-I groups on the fluorinated backbone are also able to undergo chemical modification, such as with the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, [44][45][46][47] while keeping the advantages of fluorinated copolymers.…”