Consequences of End-Group Fidelity for the Quantitative Analysis of Surface Grafting of Polymers.

End-functional polymers are employed in a wide range of functionalization reactions, including, among others, polymer surface grafting. Herein, kinetic (PREDICI) simulations are used to investigate to what extent the molar mass distribution (MMD) of α-end-functional polymers derived from RAFT polymerization may differ from the MMD of nonfunctional chains and the overall polymeric material. The results indicate that the MMD of the overall polymeric material (as commonly accessed in experiments) may not provide a good estimate for the MMD of α-end-functional chains, if polymerization conditions deviate strongly from pseudoliving conditions. Careful consideration of this behavior is required when using α-end-functional RAFT polymers in quantitative studies.