A comprehensive kinetic model for high‐temperature free radical production of styrene/methacrylate/acrylate resins

Abstract

in Wiley Online Library (wileyonlinelibrary.com).n-Butyl methacrylate/styrene/n-butyl acrylate (BMA/ST/BA) high-temperature starved-feed solution semibatch copolymerization and terpolymerization experiments with varying monomer feed composition, final polymer content, monomer feed time, and reaction temperature were carried out. A comprehensive mechanistic terpolymerization model implemented in PREDICI includes methacrylate depropagation, acrylate backbiting, chain scission, and macromonomer propagation, as well as penultimate chain-growth and termination kinetics. The generality of the model was verified by comparison with terpolymerization data sets from two laboratories that demonstrate the impact of high-temperature secondary reactions on polymerization rate and polymer molecular weight.

Modeling of Functional Group Distribution in Copolymerization: A Comparison of Deterministic and Stochastic Approaches

“…The profiles shown in Figure are typical of starved‐feed operation: monomer concentrations remain low and polymer average MWs quickly attain constant values due to the fixed ratio of initiator to monomer that is fed . The feeding strategy minimizes copolymer composition drift, with the instantaneous composition of the polymer formed controlled by the monomer ratios in the feed.…”

Copolymerization of n‐Butyl Acrylate and Styrene: Terminal vs Penultimate Model

“…These values were used to provide a good description of the high temperature semibatch copolymerization system and also terpolymerization propagation kinetics with butyl methacrylate as a third monomer. [8][9][10] In another work, Garcia et al [ 1 ] investigated the ability of the terminal and implicit penultimate models to represent experimental conversions and compositions of the St/ n-BA system. The authors concluded that the terminal model was not able to predict well the copolymerization rate, which was then fi t using the penultimate model with s 1 = 0.009 and s 2 = 1.153 for radical reactivity ratios of n -BA and St, respectively.…”

Computer‐Aided Optimization of Conditions for Fast and Controlled ICAR ATRP of n‐Butyl Acrylate

“…For the reactions common with FRP, intrinsic rate coefficients reported in literature are used. [68][69][70][71] For activation of the ATRP initiator a value of 3.1 L Á mol À1 Á s À1 is considered based on the experimental study of Seeliger and Matyjaszewski. [72] The remaining secondary and tertiary activation and deactivation intrinsic rate coefficients are adjusted according to the experimental data of Ahmad et al [32] As discussed below, the obtained values are consistent with literature values and confirm the higher stability of tertiary macrospecies.…”