Radical Copolymerization of Hydroxy-Functional Monomers
Loading...
Authors
Idowu, Loretta
Date
Type
thesis
Language
eng
Keyword
Coatings , Pulsed Laser Polymerization , Modeling , Reactivity Ratio , Propagation Kinetics , HEMA , HEA , BMA , Semi-Batch , ESI-MS , Solvent Effects , Copolymerization
Alternative Title
Abstract
Solvent-borne acrylic resins are commonly used in automotive coatings formulations due to the superior characteristics they provide to the final products. Hydroxyl-functionality, incorporated by selection of 2-hydroxyethyl methacrylate (HEMA) or 2-hydroxyethyl acrylate (HEA) as monomers, is required to ensure that the low molecular weight chains produced by free radical copolymerization participate in the cross-linking reactions to form the final coating product. Hence, the knowledge of their copolymerization kinetic coefficients is vital for both process and recipe improvements.
In the first part of this work, 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. These experiments provide insights into the influence of solvent type on the copolymerization reactivity ratios and composition-averaged propagation rate coefficients.
In the second part of the study, small scale semi-batch reactions were conducted to investigate the influence of temperature, monomer composition and initiator content on the copolymerization of HEA with BMA. The effect of HEA content and copolymer molecular weight (MW) on resin performance was investigated by determining the amount and MWs of non-functional polymer that could be extracted after forming crosslinked films from the resins. Characterization of the extractable material by NMR, SEC, and by electrospray ionization mass spectrometry (ESI-MS) confirmed that the polymer extracted contained negligible levels of HEA. The experimental results were compared to Predici® and Monte Carlo simulations of the system
Description
Citation
Publisher
License
Queen's University's Thesis/Dissertation Non-Exclusive License for Deposit to QSpace and Library and Archives Canada
ProQuest PhD and Master's Theses International Dissemination Agreement
Intellectual Property Guidelines at Queen's University
Copying and Preserving Your Thesis
This publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.
ProQuest PhD and Master's Theses International Dissemination Agreement
Intellectual Property Guidelines at Queen's University
Copying and Preserving Your Thesis
This publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.