Acrylate-methacrylate radical copolymerization kinetics of sparingly water-soluble monomers in polar and nonpolar solvents

The properties of waterborne polymer dispersions synthesized by emulsion radical polymerization are influenced by reactions in both the aqueous medium and the growing particles. Mathematical models representing the process often do not consider the difference in the propagation rate coefficient ( k...

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Bibliographic Details
Published in:Polymer chemistry 2024-11, Vol.15 (44), p.4542-4553
Main Authors: Rajabalinia, Noushin, Salarhosseini, Fatemeh, Hutchinson, Robin A
Format: Article
Language:English
Subjects:
Aqueous solutions
Chemical synthesis
Copolymerization
Copolymers
Emulsion polymerization
Ethylene glycol
Hydrogen bonding
Kinetics
Methacrylic acid
Monomers
Polymethyl methacrylate
Solvents
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Summary:The properties of waterborne polymer dispersions synthesized by emulsion radical polymerization are influenced by reactions in both the aqueous medium and the growing particles. Mathematical models representing the process often do not consider the difference in the propagation rate coefficient ( k p ) of monomers in the two phases, despite the body of evidence demonstrating that solvent polarity influences monomer-monomer and monomer-solvent hydrogen-bonding that affects both k p homopropagation values and copolymerization reactivity ratios. Therefore, it is vital to develop experimental approaches to systematically measure the influence of solvent on the copolymerization kinetics of hydrophobic monomers under conditions that are similar to emulsion systems. In this work, we study the copolymerization of methyl acrylate (MA) with di(ethylene glycol) methyl ether methacrylate (DEGMEMA) as models for the common emulsion monomers butyl acrylate and methyl methacrylate. As well as varying solvent choice and monomer concentration, MA/DEGMEMA copolymerization kinetics are compared to those of MA with methacrylic acid (MAA) to determine the influence of monomer functionality on its relative reactivity. The findings suggest that the copolymer composition of all methacrylate-acrylate systems - whether involving functional or non-functional monomers - converge to a single curve in protic polar aqueous solution. The influence of solvent on radical copolymerization kinetics is studied to provide insight to emulsion polymerization systems.
ISSN:1759-9954
1759-9962
DOI:10.1039/d4py01015a