Living Polymer Chains with Predictable Molecular Weight and Dispersity via Carbanionic Polymerization in Continuous Flow: Mixing Rate as a Key Parameter

Aiming at systematic variation of the parameter dispersity, Đ (or “polydispersity”), living polymers with predictable dispersity (Đ = 1.15–2.20) and controlled molecular weights (Mn = 3200–18 500 g mol–1) were prepared via carbanionic polymerization. The approach relies on a continuous flow reactor equipped with a tangential four-way jet micromixing device. By varying the total flow rate, the mixing efficiency of the initiator (sec-BuLi) and the corresponding vinyl monomers is controlled, resulting in polymers with predefined dispersity, while the number-average molecular weight, Mn, is kept constant. In this manner living polystyrene (PS), poly(p-methylstyrene) (PpMeS), and poly(2-vinylpyridine) (P2VP) samples with systematically varied Đ (studied by SEC) were prepared. All polymerizations were carried out at room temperature in a 50:50 solvent mixture of THF with either hexane for PS and PpMeS or with benzene for the polymerization of 2VP. To prove the living character of all polymer chains of the distr...