1,1′- Thiocarbonyldiimidazole Radical Copolymerization for the Preparation of Degradable Vinyl Polymers
Oleksandr Ivanchenko, Mathias Destarac
Abstract
1,1′-Thiocarbonyldiimidazole (TCDI) readily undergoes radical copolymerization with tert -butyl acrylate ( t BA), N, N -dimethylacrylamide, and styrene. 1 H NMR monitoring of the comonomer reactivity revealed a notable compatibility between TCDI and comonomers, resulting in similar consumption rates when TCDI was introduced at a 10% feed ratio. Furthermore, trithiocarbonate-mediated RAFT copolymerization of TCDI with t BA gave polymers that exhibited a linear increase of molar mass ( M n th = 2–10 kg mol –1 ) with conversion with relatively low dispersities (1.2–1.4). Importantly, this process enabled a successful chain extension of the produced P(TCDI- co - t BA) copolymer with styrene to form a diblock copolymer. The copolymers generated through this method contain TCDI-derived diimidazolyl thioether moieties, as established through 1 H NMR spectroscopy. Additionally, degradation experiments using isopropylamine, benzoyl peroxide, sodium methoxide, and bleach have provided further confirmation of the presence of degradable TCDI moieties in the vinyl copolymer backbone.