Modeling of RAFT polymerization of MMA in supercritical carbon dioxide using the PC-SAFT equation of state

Abstract

The PC-SAFT equation of state was applied to the study of RAFT polymerization of methyl methacrylate in supercritical CO2.

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.…”

“…Numerical methods in the polymer reaction engineering (PRE) field are either deterministic based on differential equations with concentration as the dependent variable and time t as the independent variable or stochastic based on discrete reaction probabilities with sampled time steps (Δ t ). [ 1–7 ] One of the most employed deterministic methods is the method of moments (MoM) [ 8–13 ] 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.…”

Influence of structure and solubility of chain transfer agents on the RAFT control of dispersion polymerisation in scCO2

“…The presence of three regimes might not be so surprising, since the dispersion polymerisation of MMA in scCO 2 can be considered as a three stage polymerisation in terms of monomer conversion. 62 At the first stage, polymerisation can only occur in the continuous phase, then in two phases (continuous and dispersed) and, finally, polymerisation occurs only in the dispersed phase.…”

“…Even though, previous computational simulations assumed that mobility of the CTA was effectively the same as the monomer or that the CTA was completely and instantaneously transported into the dispersed phase. 51,[60][61][62] In the following section we try to identify the solvent factors that might tune the behaviour of the CTAs. Computational solvation models are used to probe the affinities of the different CTAs towards toluene and scCO 2 and we use the data to explain the disparity in control of our polymerisations.…”

“…67 Very few studies have tried to model RAFT dispersion polymerisation in scCO 2 . 51,60,62,68 In that study, the particles were assumed to be the main locus of the reaction as for conventional radical polymerisation. Predici® soware was used to study the RAFT polymerisation of styrene with AIBN initiator and S-thiobenzoyl thioglycolic acid (TBTGA) as the CTA in scCO 2 .…”