Kinetic Modeling of the Synthesis of Poly(4-vinylpyridine) Macro-Reversible Addition-Fragmentation Chain Transfer Agents for the Preparation of Block Copolymers

Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most common controlled polymerization techniques to prepare well-defined, rather narrow dispersed polymers due to reduced demands in reactant preparation. Despite these advantages, RAFT polymerization was so far primarily utilized on small laboratory scales. This study presents a first step to a scaled-up RAFT polymerization by developing and experimentally validating a kinetic model on the example of the polymerization of 4-vinylpyridine (4VP), which to date is not described in the literature. With the implementation of the results from modeling, the synthesis process was extended to a medium scale (from 6 to 36 g), while the same high conversions, molar mass, and low dispersity as in the smaller scale were achieved. The process is also optimized regarding the high degree of livingness necessary for using the 4VP polymers as a macro-RAFT agent in the subsequent reaction step for the synthesis of poly(4-vinylpyridine)-b-polystyrene diblock copolymers by RAFT dispersion polymerization.