Mathematical Modeling of the Full Molecular Weight Distribution in ATRP Techniques

作者：Zapata Gonzalez Ivan; Hutchinson Robin A^*; Payne Kevin A; Saldivar Guerra Enrique^*

来源：AIChE Journal, 2016, 62(8): 2762-2777.

DOI：10.1002/aic.15232

• ATRP modeling
• slow initiation
• molecular weight distribution
• quasi-steady state approximation

In this work the molecular weight distribution (MWD) of several atom transfer radical polymerization (ATRP) techniques has been derived and solved using the Reduced Stiffness by Quasi Steady State Approximation (RSQSSA) methodology. The Quasi Steady State Approximation has been validated on the living radicals for normal, Simultaneous Reversible and Normal Initiation and Activators Regenerated by Electron Transfer (ARGET), and it is shown that the information lost due to its application is negligible. According to these results, RSQSSA shows the best performance in terms of wall-clock time and required memory in comparison to implicit techniques and Predici. In the case of the ARGET technique, the model predictions show good agreement with experimental data. Finally, an analysis on the impact of the slow and fast activation of the initiator on the MWD using ARGET has been carried out, indicating that the optimal initiator to control the MWD should exhibit activation-deactivation rates very similar to those of the polymeric equilibrium.

• 出版日期2016-8