Catalyst-free, aza-Michael polymerization of hydrazides: polymerizability, kinetics, and mechanistic origin of an α-effect.

ABSTRACT: Despite the powerful nature of the aza-Michael reaction for generating C-N linkages and bioactive moieties, the bis-Michael addition of 1° amines remains ineffective for the synthesis of functional, step-growth polymers due to the drastic reduction in reactivity of the resulting 2° amine mono-addition adduct. In this study, a wide range of commercial hydrazides are shown to effectively undergo the bis-Michael reaction with divinyl sulfone (DVS) and 1,6-hexanediol diacrylate (HDA) under catalyst-free, thermal conditions to afford moderate to high molecular weight polymers with M _n = 3.8-34.5 kg mol^-1. The hydrazide-Michael reactions exhibit two distinctive, conversion-dependent kinetic regimes that are 2^nd-order overall, in contrast to the 3^rd

SUBMITTER: Love D 

PROVIDER: S-EPMC6865069 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature