Critically evaluated rate coefficients for free‐radical polymerization, 2.. Propagation rate coefficients for methyl methacrylate

Abstract

(1997). Critically evaluated rate coefficients for free-radical polymerization, 2. Propagation rate coefficients for methyl methacrylate. Macromolecular Chemistry and Physics, 198(5), 1545-1560. DOI: 10.1002/macp.1997 General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. SUMMARYPulsed-laser polymerization (PLP) in conjunction with molar mass distribution (MMD) measurement is the method of choice for determining the propagation rate coefficient kp in free-radical polymerizations. The authors, members of the IUPAC Working Party on Modeling of kinetics and processes of polymerization, collate results from using PLP-MMD to determine kp as a function of temperature T for bulk free-radical polymerization of methyl methacrylate at low conversions and ambient pressure. Despite coming from several different laboratories, the values of $ are in excellent agreement and obey consistency checks. These values are therefore recommended as constituting a benchmark data set, one that is best fitted by The 95% joint confidence interval for these Arrhenius parameters is also given. In so doing, we describe the most appropriate statistical methods for fitting k&") data and then obtaining a joint confidence interval for the fitted Arrhenius parameters. As well, we outline factors which impose slight limitations on the accuracy of the PLP-MMD technique for determining $, factors which may apply even when this technique is functioning well. At the same time we discuss how such systematic errors in kp can be minimized.

Kinetics of MMA and VAc Miniemulsion Polymerizations Using Miglyol and Castor Oil as Hydrophobe and Liquid Core

“…2a it can be observed that miniemulsion polymerization of VAc (R2) was much slower than that of MMA (R1), conducted with exactly the same formulation, except for the monomer type as shown in Tab. [25]). In addition, Figs.…”

On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

“…Nowadays, PLP coupled with size exclusion chromatography (SEC) is the method recommended by the International Union of Pure and Applied Chemistry (IUPAC) for the measurements of propagation rate coefficients [19][20][21][22]. The propagation rate coefficients for various important monomers evaluated by PLP are listed in Table 1.…”

Study of n-Butyl Acrylate Self-Initiation Reaction Experimentally and via Macroscopic Mechanistic Modeling

“…Pulsed-laser polymerization (PLP) and size exclusion chromatography have been used to study intra-molecular chain transfer to polymer (CTP) reactions in polymerization of alkyl acrylates [15,16]. The rate coefficients of the propagation reactions of styrene [17], and methyl methacrylate (MMA) [18], and chain transfer reactions of butyl methacrylate (BMA) [19] at temperatures above 30˝C have been estimated using PLP. Although the propagation rate coefficient of n-butyl acrylate (n-BA) at 70˝C has been calculated using PLP at 500 Hz [20], the presence of backbiting and β-scission reactions has hindered the prediction of alkyl acrylates' propagation rate coefficient at elevated temperatures [21][22][23].…”