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Polymers 2019, 11(3), 487; https://doi.org/10.3390/polym11030487

Solvent Effects on Radical Copolymerization Kinetics of 2-Hydroxyethyl Methacrylate and Butyl Methacrylate

Department of Chemical Engineering, Queen’s University, 19 Division St., Kingston, ON K7L 3N6, Canada
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Received: 16 February 2019 / Revised: 7 March 2019 / Accepted: 8 March 2019 / Published: 13 March 2019
(This article belongs to the Special Issue Connecting the Fields of Polymer Reaction Engineering and Processing)
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Abstract

2-Hydroxyethyl methacrylate (HEMA) is an important component of many acrylic resins used in coatings formulations, as the functionality ensures that the chains participate in the cross-linking reactions required to form the final product. Hence, the knowledge of their radical copolymerization kinetic coefficients is vital for both process and recipe improvements. The pulsed laser polymerization (PLP) technique is paired with size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) to provide kinetic coefficients for the copolymerization of HEMA with butyl methacrylate (BMA) in various solvents. The choice of solvent has a significant impact on both copolymer composition and on the composition-averaged propagation rate coefficient (kp,cop). Compared to the bulk system, both n-butanol and dimethylformamide reduce the relative reactivity of HEMA during copolymerization, while xylene as a solvent enhances HEMA reactivity. The magnitude of the solvent effect varies with monomer concentration, as shown by a systematic study of monomer/solvent mixtures containing 50 vol%, 20 vol%, and 10 vol% monomer. The observed behavior is related to the influence of hydrogen bonding on monomer reactivity, with the experimental results fit using the terminal model of radical copolymerization to provide estimates of reactivity ratios and kp,HEMA. View Full-Text
Keywords: radical polymerization; polymerization kinetics; copolymerization; reactivity ratios; PLP-SEC; radical propagation; 2-hydroxyethyl methacrylate; hydrogen bonding; solvent effects. radical polymerization; polymerization kinetics; copolymerization; reactivity ratios; PLP-SEC; radical propagation; 2-hydroxyethyl methacrylate; hydrogen bonding; solvent effects.
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Idowu, L.A.; Hutchinson, R.A. Solvent Effects on Radical Copolymerization Kinetics of 2-Hydroxyethyl Methacrylate and Butyl Methacrylate. Polymers 2019, 11, 487.

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