Macromolecular design with the use of acrylic monomers containing groups with mobile hydrogen atoms

Chemoselective Transesterification of Acrylate Derivatives for Functionalized Monomer Synthesis Using a Hard Zinc Alkoxide Generation Strategy

“…To facilitate Zn(OTf) 2 catalysis, the reaction was performed under neat conditions (Scheme , b). Whereas the combined use of Zn 4 (OCOCF 3 ) 6 O ( 1 ) and DMAP ( 5 ) provided the product in 99 % yield without undesired polymerization, Zn(OTf) 2 promoted only polymerization, presumably initiated by the conjugate addition of the alcohols,, which suggested that hard zinc alkoxide generation was crucial for highly chemoselective transesterification.…”

Step-Growth Polymerisation of Alkyl Acrylates via Concomitant Oxa-Michael and Transesterification Reactions

“…Again, DBU performed better than DMAP ( Table 2, to 2400 Da. [4][5][6][7][8][9] Thus, it can be assumed that by tuning the reaction conditions or changing the catalyst not only for the homopolymerisation of HEA but also for the herein presented auto-tandem polymerisation, higher molecular masses might be accessible. Mechanistically, the reaction is initiated either by deprotonation of the alcohol or by nucleophilic attack of the base/nucleophile on the Michael acceptor in a 1,4-or 1,2-fashion, generating a strongly basic zwitterion, which can subsequently deprotonate an alcohol.…”

“…Various di-alcohols(4)(5)(6)(7)(8) in the auto-tandem oxa-Michael addition and transesterification polymerisation of ethyl acrylate (2) catalysed with 5 mol% DBU crude yield after 24 h reaction time, calculated according to: massreaction mixture/(massmonomers + masscatalyst -massEtOH) x 100; b repeat units calculated from 1 H-NMR spectra; c number average molecular mass and dispersity determined by SEC in THF relative to poly(styrene) standards; d reaction performed with 5 mol% DMAP; e not determined due to overlapping signals.…”

Step-growth polymerisation of alkyl acrylates via concomitant oxa-Michael and transesterification reactions

“…Since then few studies on the polymerisation of hydroxy functionalized acrylates with base-or nucleophile-type catalysts have been reported. [4][5][6] Suzuki et al presented the homopolymerisation of hydroxy functionalized acrylate monomers, such as HEA, catalysed by N-heterocyclic carbenes (NHC) at room temperature. 7 Within the same group, stepgrowth polymerisation of acrylic acid catalysed by NHC ligands or PPh 3 was studied under harsh conditions (100°C) and oligomers with number average molecular masses (M n ) up to 400 Da were obtained.…”