The radical thiol–ene coupling of thiol-functionalized polystyrene (PS-SH) with dodecyl vinyl ether (DVE) and the polystyrene-b-poly(vinyl acetate) (PS-b-PVAc) polymer–polymer conjugation using 2,2-dimethoxy-2-phenylacetophenone (DMPA) as photoinitiator are modeled to assess the importance of diffusional limitations and side reactions. Intrinsic chemical rate coefficients are determined based on a kinetic study of the coupling of benzyl thiol (BT) and DVE. The addition and transfer reactions are chemically controlled, whereas diffusional limitations on termination slightly increase the coupling efficiency. Termination by recombination of carbon-centered radicals and addition of DMPA derived radicals to DVE are shown to be mainly responsible for the reduced coupling efficiency in case polymeric species are involved. The obtained results confirm the idea to disregard radical thiol–ene chemistry as a true member of the family of “click” chemistry techniques for polymer–polymer conjugation and show that the initial conditions have a significant impact on the coupling efficiency.

The performance of polymeric materials depends strongly on the control over the polymer microstructure during the synthesis step. In this review, attention is paid to the potential of microkinetic modelling to facilitate the identification of optimal reactants and reaction conditions to design the polymer microstructure in bulk and solution (post) polymerisation processes. Focus is on living polymerization, reversible deactivation radical polymerization (RDRP) and "click" chemistry techniques, covering both batch and continuous synthesis approaches. A description according to the increasing level of macromolecular detail and thus modelling complexity is provided, including not only the characterization of the polymer microstructure via a finite number of variates (e.g. chain length, overall composition and branching content) but also its explicit visualisation by the simulation of the architecture and monomer sequences of a representative number of individual polymer chains. Several complementary case studies are included to demonstrate the high relevance of model-based design for the development of improved and novel synthetic protocols for precision control

Precision functionality is the key feature of nextgeneration radical polymerization enabling the implementation of applications such as controlled drug delivery, self-healing material design, and optoelectronic materials. The incorporation of functionality is however diametrically opposed to diffusion-controlled growthinhibiting termination reactions. The fundamental bottleneck remains the identification of a generic and flexible protocol to accurately map the short−long termination reactivity. Herein, we introduce a unique framework based on the reversible addition−fragmentation chain transfer−chain length dependent−termination (RAFT-CLD-T) method that encompasses an extension of state-of-the-art fundamental theories and a correction for possible polymer matrix effects. Applied to methyl methacrylate (MMA) polymerization, the short−long termination reactivity is accurately quantified for the first time. Data analysis reveals the deficiency of currently used simplified models to describe the true short−long termination reactivity and the dominance of short-chain diffusivity. The proposed framework and insights are a turnkey prerequisite for the fundamental understanding of radical polymerization processes and to complete current macromolecular diffusion theories.