Exploring the Full Potential of Reversible Deactivation Radical Polymerization Using Pareto-Optimal Fronts

Stijn Fierens,Marie-Françoise Reyniers,Guy Marin,Dagmar D'Hooge,Paul Van Steenberge

doi:10.3390/polym7040655

Stijn Fierens, Marie-Françoise Reyniers + Show 3 more

Open Access

https://doi.org/10.3390/polym7040655

Copy DOI

Journal: Polymers	Publication Date: Apr 9, 2015
Citations: 91	License type: CC BY 4.0

Affiliation: Ghent University

Abstract

The use of Pareto-optimal fronts to evaluate the full potential of reversible deactivation radical polymerization (RDRP) using multi-objective optimization (MOO) is illustrated for the first time. Pareto-optimal fronts are identified for activator regenerated electron transfer atom transfer radical polymerization (ARGET ATRP) of butyl methacrylate and nitroxide mediated polymerization (NMP) of styrene. All kinetic and diffusion parameters are literature based and a variety of optimization paths, such as temperature and fed-batch addition programs, are considered. It is shown that improvements in the control over the RDRP characteristics are possible beyond the capabilities of batch or isothermal RDRP conditions. Via these MOO-predicted non-classical polymerization procedures, a significant increase of the degree of microstructural control can be obtained with a limited penalty on the polymerization time; specifically, if a simultaneous variation of various polymerization conditions is considered. The improvements are explained based on the relative importance of the key reaction rates as a function of conversion.

Highlights

During the last two decades, reversible deactivation radical polymerization (RDRP), which is known as controlled radical polymerization (CRP), has shown to overcome disadvantages of conventional free radical polymerization (FRP), which allows mostly the synthesis of commodity polymer products [1,2,3,4,5,6,7], unless expensive functional monomers are used [8,9]
The listed kinetic parameters are adopted from Payne et al [64] and a distinction is made between ARGET ATRP specific and non-specific reaction steps
Two objectives are selected in this case study to illustrate the strength of Pareto-optimal fronts, taking into that the simulated end-group functionality (EGF) variation is rather limited (

Summary

Introduction

During the last two decades, reversible deactivation radical polymerization (RDRP), which is known as controlled radical polymerization (CRP), has shown to overcome disadvantages of conventional free radical polymerization (FRP), which allows mostly the synthesis of commodity polymer products [1,2,3,4,5,6,7], unless expensive functional monomers are used [8,9]. Under well-defined conditions, RDRP techniques are characterized by the establishment of a dynamic pseudo-equilibrium between propagating and dormant species, allowing the controlled incorporation of monomer units per activation-growth-deactivation cycle. This enables the production of polymers with a predetermined number average chain length and narrow chain length distribution (CLD; dispersity (Ð) < 1.3) that possess end-group functionality (EGF). This brings the synthesis of well-defined macromolecular architectures, such as block and star copolymers, within reach. Two important RDRP techniques, which are studied in this work, are activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) [10,11,12,13,14,15,16] and nitroxide mediated polymerization (NMP) [17,18,19,20,21].

Methods

Results

Conclusion