|540. Wadkaonkar, S.; Wagner, M.; Müller, A.H.E.; Frey, H.: Anionic polymerization of 4-allyldimethylsilylstyrene: a versatile polymer scaffold for post-polymerization modifications, Macromolecules (2023)|
A facile synthesis using a Grignard reaction was employed to synthesize the silicon containing, functional monomer namely, 4-allyldimethylsilylstyrene (4ADSS). Detailed investigations regarding the living nature of anionic polymerization of 4ADSS and its polymerization via the styrene vinyl bond in cyclohexane at room temperature was conducted, and P4ADSS samples with Mn up to 80 kg mol-1 were accessible. Real-time 1H NMR kinetics of the statistical copolymerization of 4ADSS with styrene (r4ADSS = 3.55; rS = 0.047) revealed a remarkable gradient microstructure in the resulting copolymers. Consequently, a library of well-defined gradient copolymers P(4ADSS-co-S) with Mn in the range of 5 to 50 kg mol-1 by varying x4ADSS was synthesized. A comprehensive discussion regarding the glass transition temperatures, Tg, of the synthesized homo- and copolymers is presented. Furthermore, thiol-ene click reactions were explored on the pendent allyl moiety of P(4ADSS-co-S) to introduce functional groups. Likewise, P(4ADSS-co-S) copolymers were subject to hydrosilylation reactions, and the impact of the introduced siloxane moieties on the glass transition of the resulting copolymers is presented. Copolymerization of 4ADSS provides a promising access to design functional materials with specific applications.