Synthesis of polymeric organic semiconductors using semifluorinated polymer precursors

The transesterification of 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) homopolymers and block copolymers with methyl acrylate (MA) or n-butyl acrylate (n-BuA) were investigated for the efficient synthesis of p-type and n-type organic semiconductor acrylates. HFIPA, MA, and n-BuA are readily prepared in a one-pot synthesis by Cu(0) reversible deactivation radical polymerization in high yield with low dispersity to give poly(HFIPA)₁₀₀, PMA₁₀₀-b-poly(HFIPA)_x, and PnBuA₁₀₀-b-poly(HFIPA)_x (x = 100, 50,25). The transesterification of poly(HFIPA)₁₀₀ was also studied using ¹⁹F NMR spectroscopy. Based on this method, a series of eight homopolymers and three copolymers based on semiconductor motifs commonly found in organic light-emitting diodes, organic thin-film transistors, and organic photovoltaics were synthesized with narrow dispersity and conversions up to 99%. These experiments demonstrate that poly(HFIPA) can provide a useful building block in the synthesis of organic electronic materials, providing a simpler route to complex materials which may be challenging to access directly via controlled radical polymerization. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2183–2191