An Update on the Pivotal Role of Kinetic Modeling for the Mechanistic Understanding and Design of Bulk and Solution RAFT Polymerization

作者:De Rybel Nils; Van Steenberge Paul H M; Reyniers Marie Francoise; Barner Kowollik Christopher*; D'hooge Dagmar R*; Marin Guy B
来源:Macromolecular Theory and Simulations, 2017, 26(1): UNSP 1600048.
DOI:10.1002/mats.201600048

摘要

The importance of the development of kinetic modeling tools to mechanistically understand and design bulk and solution reversible addition fragmentation chain transfer (RAFT) polymerization is highlighted. Both deterministic and stochastic kinetic modeling methods are covered, considering a detailed reaction scheme and accounting for the impact of diffusional limitations on the reaction rates. A novel strategy is introduced to fundamentally calculate the diffusional contributions for the apparent RAFT addition and fragmentation rate coefficients. Next to literature examples, case studies are included to demonstrate that detailed theoretical studies are indispensable to completely map the effect of the polymerization conditions and RAFT agent reactivity on the control over microstructural properties and the overall polymerization time. Guidelines for future kinetic modeling activities are formulated to enhance joined theoretical and experimental research.

  • 出版日期2017-1