Assessment of kinetics of photoinduced Fe‐based atom transfer radical polymerization under conditions using modeling approach

Abstract

Kinetic insight into photoinduced Fe‐based atom transfer radical polymerization (ATRP) involving monomer‐mediated photoreduction was performed by modeling approach for the first time. Preliminary numerical analysis of number‐average molar mass (Mn) derivation in this specific system was given. Simulation results provided a full picture of reactant concentration and reaction rate throughout the entire polymerization. Methyl 2,3‐dibromoisobutyrate (MibBr2) generated from methyl methacrylate (MMA)‐mediated photoreduction as the leading factor for the deviation of Mn from theoretical value was confirmed by reaction contributions in α‐bromophenylacetate (EBPA) containing system. Reasonable predictions were made with respect to the polymerizations under a variety of initial conditions. Results show that increasing light intensity will shorten transition period and increase steady state polymerization rate; decreasing catalyst loading will cause the decrease in polymerization rate and Mn deviation; varying initiation activity will slightly increase the time to attain steady state of dispersity (Mw/Mn) evolution and enormously change the fraction of reaction contributions; increasing targeted chain length will extend transition period, decrease steady state polymerization rate, increase Mn deviation degree with same reaction contributions, and decrease the time to attain the steady state of Mw/Mn. The numerical analysis presented in this work clearly demonstrates the unique ability of our modeling approach in describing the kinetics of photoinduced Fe‐based ATRP of MMA. © 2017 American Institute of Chemical Engineers AIChE J, 2017

Benchmarking Stochastic and Deterministic Kinetic Modeling of Bulk and Solution Radical Polymerization Processes by Including Six Types of Factors Two

“…reaction probabilities with sampled time steps (Δt). [1][2][3][4][5][6][7] One of the most employed deterministic methods is the method of moments (MoM) [8][9][10][11][12][13] although with the commercial implementation of the h-p Galerkin method, [14,15] and the development of the fixed-pivot [16] and Laplace-transformation regeneration [17] method MoM is not anymore the only way to proceed. Despite the aforementioned advanced deterministic developments one can still claim that for many research groups, specifically those with own code developments, MoM is or has been the starting point.…”

How the catalyst circulates and works in organocatalyzed atom transfer radical polymerization

“…The model-based methodology is a very effective strategy for conducting polymerization kinetic study. 41 In the present work, kinetic modeling based on the method of moments was employed to perform a thorough simulation of polymerization process for O-ATRP. [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] There have been growing interests in incorporating the utility of modeling into the RDRPs kinetics study.…”

“…39,40 Very recently, for example, the mass average molar mass (M n ) deviation in photoinduced Fe-based ATRP was studied through numerical simulation by our group. 41 In the present work, kinetic modeling based on the method of moments was employed to perform a thorough simulation of polymerization process for O-ATRP. The innovation lies in the accurate description of the detailed mechanism and the polymerization processes.…”

Mechanistic and kinetic investigation of Cu(II)‐catalyzed controlled radical polymerization enabled by ultrasound irradiation

“…External stimuli, such as light and electrical current, have been proved to be a powerful protocol in controlled radical polymerization (CRP) or reversible deactivation radical polymerization (recommended by IUPAC) by manipulating the electron transfer process . Recent advances in ultrasound as external stimuli for CRP offer a promising approach to synthesize well‐defined polymers under mild conditions and scale‐up of CRP .…”