Poly(bromoethyl acrylate): A Reactive Precursor for the Synthesis of Functional RAFT Materials

Abstract

Post-polymerization modification has become a powerful tool to create a diversity of functional materials. However, simple nucleophilic substitution reactions on halogenated monomers remains relatively unexplored. Here we report the synthesis of poly(bromoethyl acrylate) (pBEA) by reversible addition fragmentation chain transfer (RAFT) polymerization to generate a highly reactive polymer precursor for post-polymerization nucleophilic substitution. RAFT polymerization of BEA generated well-defined homopolymers and block copolymers over a range of molecular weights. The alkyl bromine containing homo-and block copolymer precursors were readily substituted by a range of nucleophiles in good to excellent conversion under mild and efficient reaction conditions without the need of additional catalysts. The broad range of nucleophilic species that are compatible with this post modification strategy enable facile synthesis of complex functionalities, from permanently charged polyanions to hydrophobic polythioethers to glycopolymers.

Branched poly (trimethylphosphonium ethylacrylate‐co‐PEGA) by RAFT: alternative to cationic polyammoniums for nucleic acid complexation

“…2, S4 and S6), which agrees with previously reported results, however it was not possible to be more precise than this due to the broad nature of the peaks. (Barlow et al, 2016) Phosphorous ( 31 P) NMR spectroscopy confirmed the presence of phosphonium moieties on the purified polymer (Fig. S8).…”

“…Bromoethyl acrylate was synthesised according to a previously published procedure. (Barlow et al, ) The chain transfer agent (CTA), 2‐(((Butylthio)‐carbonothioyl)thio) propanoic acid (PABTC) was prepared according to a previously reported procedure. (Ferguson et al, ) 50X Tris‐Acetate‐EDTA (TAE) buffer for gel electrophoresis was made up at concentration of 2.0 M Tris acetate (Sigma Aldrich) and 0.05 M EDTA (Sigma Aldrich) in deionised water, pH 8.2–8.4, and stored at room temperature.…”

“…Poly (bromo ethylacrylate) (pBEA) has recently been shown to be an excellent reactive precursor material for post polymerisation modification with a variety of functionalities, including phosphonium moeities. (Barlow et al, ) The monomer is compatible with controlled radical polymerisation techniques such as Reversible Addition Fragmentation chain Transfer (RAFT) polymerisation, which enable great control of molecular weight as well as access to complex architectures. (Boyer et al, ; Cobo et al, ) In addition, RAFT polymerisation with divinyl comonomers allows simple access to branched architectures,(Liu et al, ) which have been shown to be more efficient gene delivery vectors than linear polymers.…”

Switching Light Transmittance by Responsive Organometallic Poly(ionic liquid)s: Control by Cross Talk of Thermal and Redox Stimuli

“…[20][21][22] For example, protected sulfonate ester carbanions were used as nucleophiles in previous work. [24,25] Here we demonstrate a one-step synthetic approach to obtain thermoresponsive PILs via the Strecker reaction by choosing tetraalkylphosphonium sulfite as an effective and versatile nucleophile. This reaction has found application in the preparation of alkyl sulfonates via the S N 2 nucleophilic substitution reaction of sulfite with alkyl halides in aqueous solution almost one and a half century ago.…”

“…[23] Recently, in an attempt to overcome the limited solubility of alkali or ammonium sulfites in organic solvents, tetraalkylammonium sulfite has been utilized to create polyelectrolytes carrying sulfonate side groups with quantitative conversion under mild conditions. [24,25] Here we demonstrate a one-step synthetic approach to obtain thermoresponsive PILs via the Strecker reaction by choosing tetraalkylphosphonium sulfite as an effective and versatile nucleophile. Notably, this simple approach directly introduces sulfonate side groups with phosphonium counterions to a redox-active poly(ferrocenylsilane) polymer precursor bearing alkyl halide side groups and does not require deprotection steps or demanding reaction conditions.…”