1,1′- Thiocarbonyldiimidazole Radical Copolymerization for the Preparation of Degradable Vinyl Polymers

1,1 '-Thiocarbonyldiimidazole (TCDI) readily undergoes radical copolymerization with tert-butyl acrylate (tBA), N,N-dimethylacrylamide, and styrene. H-1 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 tBA 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-tBA) copolymer with styrene to form a diblock copolymer. The copolymers generated through this method contain TCDI-derived diimidazolyl thioether moieties, as established through H-1 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.