Organocatalyzed Photocontrolled Radical Polymerization of Semifluorinated (Meth)acrylates Driven by Visible Light

Abstract

Fluorinated polymers are important materials that are widely used in many areas. Herein, we report the development of a metal-free photocontrolled radical polymerization of semifluorinated (meth)acrylates with a new visible-light-absorbing organocatalyst. This method enabled the production of a variety of semifluorinated polymers with narrow molar-weight distributions from semifluorinated trithiocarbonates or perfluoroalkyl iodides. The high performance of "ON/OFF" control and chain-extension experiments further demonstrate the utility and reliability of this method. Furthermore, to streamline the preparation of semifluorinated polymers, a scalable continuous-flow approach has been developed. Given the broad interest in fluorinated materials and photopolymerization, we expect that this method will facilitate the development of advanced materials with unique properties.

Synthesis of Hyperbranched Polymers via Metal‐Free ATRP in Solution and Microemulsion

“…In contrast, the metal‐free ATRP of inimer 1 in microemulsion produced latex particles with small size and monomodal size distribution with complete conversion of inimer 1 in 2 h. This result was not very surprising because there is so far no literature report of metal‐free ATRP of acrylate monomers by using activated alkyl bromides as initiator and phenothiazine as photocatalyst, although the phenothiazine‐photocatalyzed polymerizations of acrylate monomers using trithiocarbonate iniferters and arylsulfonyl halide initiators have been recently reported. [ 71,72 ] Therefore, further exploration in this study only focused on the metal‐free ATRP of methacrylate‐based inimer 1 in microemulsion to investigate the effect of several experimental parameters on the hyperbranched structures.…”

Tuning the Conformation and Color of Conjugated Polyheterocyclic Skeletons by Installing ortho‐Methyl Groups

“…[9] As shown in Figure 5b,alinear increase in absorption at l = 855 nm was observed for M1-M1 and M2-M2,which indicates the formation of astable CTCs,whereas,because of the lower HOMO level, the formation of CTCs of DPAC and M0-M1 with F4-TCNQ are reversible,a ss hown by the nonlinear increase of absorption of CTCs,w ith binding constants of about 1.4 10 5 and 2.5 10 5 m À1 ,r espectively.Asimilar concept should be applicable for systematic tuning of the photoredox catalysts in photoinitiation reactions. [10] In summary,wehave designed and synthesized the model , which are ubiquitously applied in organic electronics. [11] Corresponding syntheses of the dibenzo[b,f]azepine derivatives are in progress (see Scheme S2) and the results will be published elsewhere.…”

Continuous Flow Photoinduced Reversible Deactivation Radical Polymerization

“…Chen and co‐workers reported photoinduced living radical polymerization of semifluorinated (meth)acrylates catalyzed by novel organocatalyst under the irradiation of visible light (Figure ). This technique allowed the synthesis of a range of semifluorinated polymers with narrow distributions initiated from iniferters of semifluorinated trithiocarbonates or initiators of perfluoroalkyl iodides.…”