Synthesis and Characterization of a Novel Perfluorocyclobutyl Aromatic Ether-Based ABA Triblock Copolymer

Abstract

A novel perfluorocyclobutyl aromatic ether-based ABA triblock copolymer (A: polystyrene block; B: perfluorocyclobutyl aromatic ether-based fluoropolymer block) was synthesized by combination of atom transfer radical polymerization (ATRP) of styrene and thermal step-growth cycloaddition polymerization of trifluorovinyl monomer. We first synthesized a new ATRP initiator containing the trifluorovinyl group, which can initiate ATRP of styrene in a controlled way to obtain well-defined polystyrene with narrow molecular weight distribution (Mw/Mn < 1.10). The apparent polymerization rate exhibited first-order relation with respect to the concentration of monomer and the molecular weight increases linearly with the conversion of monomer. Second, fluoropolymer containing a perfluorocyclobutyl aromatic ether unit was prepared by solution polymerization and followed by reacting with ATRP initiator containing a trifluorovinyl group to get ATRP macroinitiator with two initiation groups at both ends. The macroinitiator-initiated ATRP of styrene to obtain ABA triblock copolymer. The copolymer shows excellent solubility in conventional solvents.

Synthesis of a sun-shaped amphiphilic copolymer consisting of a cyclic perfluorocyclobutyl aryl ether-based backbone and lateral PMAA side chains

“…1 PMBTFVB 2 homopolymer was then obtained via thermal [2π + 2π] step-growth thermal cycloaddition polymerization of bifunctional monomer 1 in diphenyl ether at 200°C and both ends of the homopolymer were capped by mono-functional 4-methoxytrifluorovinyloxybenzene according to our previous reports. [61][62][63][64] It should be point out that because during the cyclization reaction, only chain ends took part in the reaction and 1 H and 13 C NMR analyses were employed to determine the transformation of end groups, thus PFCB aryl ether-based backbone with a relative low molecular weight was prepared on purpose for getting better 1 H and 13 C NMR spectra with high resolution. Figure 1A shows 1 (1)…”

Well‐Defined Triblock Copolymer Containing Perfluorocyclobutyl Aryl Ether and Poly(acrylic acid) Segments

“…Many methods can be employed to prepare block copolymers, mainly including two strategies, "sequential feeding" [7][8][9][10][11][12] and "mechanism transformation". [13][14][15][16][17][18][19][20][21][22][23] Sequential feeding refers to sequentially adding different monomer after complete consumption of the former monomer through the same polymerization mechanism to get block copolymer. While the living polymerization was used, the polymer chain with active initiative end in the end can further initiate another monomer available to be polymerized after the first monomer was completely converted.…”

Perfluorocyclobutyl-based methacrylate monomers: Synthesis and radical polymerization

“…Monomers containing two or three trifluorovinyl ethers were synthesized from different commercially available polyphenols and were polymerized to afford different thermoplastic or thermoset PFCB aryl ether polymers. However, only few literatures reported the synthesis of copolymers via trifluorovinyl aryl ether monomers and other commonly used monomers due to the normal high polymerization temperature (>150 8C) and unusual polymerization mechanism without any initiator [10][11][12][13]. The number of PFCB linkage in copolymers was very difficult to be tuned.…”