A novel fluorine‐containing graft copolymer bearing perfluorocyclobutyl aryl ether‐based backbone and poly(methyl methacrylate) side chains

Abstract

A series of novel graft copolymers consisting of perfluorocyclobutyl aryl ether-based backbone and poly(methyl methacrylate) side chains were synthesized by the combination of thermal [2p þ 2p] step-growth cycloaddition polymerization of aryl bistrifluorovinyl ether monomer and atom transfer radical polymerization (ATRP) of methyl methacrylate. A new aryl bistrifluorovinyl ether monomer, 2-methyl-1,4-bistrifluorovinyloxybenzene, was first synthesized in two steps from commercially available reagents, and this monomer was homopolymerized in diphenyl ether to provide the corresponding perfluorocyclobutyl aryl ether-based homopolymer with methoxyl end groups. The fluoropolymer was then converted to ATRP macroinitiator by the monobromination of the pendant methyls with N-bromosuccinimide and benzoyl peroxide. The grafting-from strategy was finally used to obtain the novel poly(2-methyl-1,4-bistrifluorovinyloxybenzene)-g-poly(methyl methacrylate) graft copolymers with relatively narrow molecular weight distributions (M w /M n 1.46) via ATRP of methyl methacrylate at 50 C in anisole initiated by the Br-containing macroinitiator using CuBr/dHbpy as catalytic system. These fluorine-containing graft copolymers can dissolve in most organic solvents. This is the first example of the graft copolymer possessing perfluorocyclobutyl aryl ether-based backbone.

AB-type monomers for the preparation of perfluorocycloalkene (PFCA) aryl ether polymers

“…The overall yield of TFVE monomers derived from bisphenols are reported to range from 27 to 55%: 54.5% [8]; 32.8%, 42.8% [29]; 60%, 81% [13]; 27% [10]; 23% [31]. The efficient preparation of TFVE monomers requires complete de-protonation and removal of produced water in the first step of synthesis (Scheme 4).…”

“…The synthesis of TFVE compounds (Scheme 4) involves fluoroalkyl incorporation in the first step, with reported yields for this first step ranging from 22 to 98%: 22%, 85.4%, 77.9%, 98% [8]; 41%, 42% [29]; 95% [30]; 50% [10]; 72% [9]; 70% [14]; 40.9% [31]. The overall yield of TFVE monomers derived from bisphenols are reported to range from 27 to 55%: 54.5% [8]; 32.8%, 42.8% [29]; 60%, 81% [13]; 27% [10]; 23% [31].…”

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)…”

“…GPC (A) and DSC (B) curves of ≡-PMBTFVB-≡ 4 (A) and c-PMBTFVB 5.Preparation of PMBTFVB-Br MacroinitiatorMono-bromination of pendant methyls of c-PMBTFVB 5 for introducingBr-containing ATRP initiating sites into cyclic backbone was conducted in CCl 4 by reacting with NBS and BPO according to our previous reports61,62 so that c-PMBTFVB 5 was transformed into c-PMBTFVB-Br 6 macroinitiator. The degree of bromination was…”

Synthesis and self-assembly of PMBTFVB-g-PNIPAM fluorine-containing amphiphilic graft copolymer

“…4 Therefore, many partially uorinated polymers such as uorine-containing poly(aryl ethers) and polyimides have been developed to improve their processability and properties. 21,22 Until now, none has studied the self-assembly behavior of amphiphilic gra copolymers that consist of a PFCB aryl etherbased backbone. In our group, a unique PFCB aryl ether-based polymer was used to prepare some novel semiuorinated copolymers by combining it with other commercial polymers, including PFCB aryl ether-based triblock copolymers, 17,18 copolymers with PFCB pendant side groups that were obtained by the copolymerization of new methacrylate monomers containing a PFCB unit and other comonomers, 19,20 and hydrophobic gra copolymers that bear a PFCB aryl ether-based backbone.…”