Issue 2, 2020

Predictive design of polymer molecular weight distributions in anionic polymerization

Abstract

Molecular weight distributions (MWD) have a substantial impact on a diverse set of polymer physical and rheological properties, from processability and stiffness to many aspects of block copolymer microphase behavior. The precise MWD compositions of these polymers can be modularly controlled through temporal initiation in anionic polymerizations by metered addition of a discrete initiating species. With the technique described in this work, we identify initiator addition profiles through theoretical modeling which can be used to prepare any desired arbitrary MWD. This kinetic model reproduces experimental MWDs with high fidelity. Our modeling strategy incorporates a detailed kinetic description of polymer initiation and propagation, including the association and dissociation equilibria of the living polymer chain ends. We simplify the kinetic model by incorporating the aggregation phenomena into an effective propagation rate constant kp, allowing it to vary with the polymer chain length (i). Importantly, this model also yields the ability to predict MWDs at any arbitrary value of monomer conversion during the polymerization. Lastly, we simulate MWDs for a variety of new, yet unmeasured, initiator addition profiles, demonstrating the predictability of this approach.

Graphical abstract: Predictive design of polymer molecular weight distributions in anionic polymerization

Supplementary files

Article information

Article type
Paper
Submitted
10 جمادى الأولى 1440
Accepted
09 شوال 1440
First published
10 شوال 1440

Polym. Chem., 2020,11, 326-336

Author version available

Predictive design of polymer molecular weight distributions in anionic polymerization

S. Domanskyi, D. T. Gentekos, V. Privman and B. P. Fors, Polym. Chem., 2020, 11, 326 DOI: 10.1039/C9PY00074G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements