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dc.contributor.authorLuk, Sharmaine
dc.contributor.otherQueen's University (Kingston, Ont.). Theses (Queen's University (Kingston, Ont.))en
dc.date.accessioned2017-08-22T23:21:59Z
dc.date.available2017-08-22T23:21:59Z
dc.identifier.urihttp://hdl.handle.net/1974/22035
dc.description.abstractIn this study, a bio-derived monomer, -methyl--methylene--butyrolactone (MeMBL) was saponified with sodium hydroxide (NaOH) to make the water-soluble monomer sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB), that was copolymerized via radical polymerization in aqueous solution with acrylamide (AM) and crosslinker to synthesize superabsorbent hydrogels. Absorbency of these hydrogels was shown to be much higher than sodium acrylate hydrogels, with mechanical properties varying with molar composition and crosslinking content. Reactivity ratio of SHMeMB:AM at 50C and 15 wt% were estimated using low conversion data (rSHMeMB=0.12 and rAM=1.10), and the integrated Mayo-Lewis equation (rSHMeMB=0.17 and rAM=0.95). However, in-situ NMR results showed that SHMeMB:AM copolymerizations proceed at a slower rate than of a similar system of AM copolymerized with sodium 4-hydroxy-2-methylene butanoate (SHMB), a similar monomer produced by ring-opening of -methylene--butyrolactone (MBL). Pulsed-laser polymerization coupled with size exclusion chromatography (PLP-SEC) studies were done for both systems at 60°C and 10 wt% monomer concentration. Homopolymerization kp values were estimated to be 25 and 165 L/mols for SHMeMB and SHMB, respectively, confirming that SHMeMB is less reactive than SHMB. Further kinetic studies of SHMeMB:AM copolymerization and homopolymerization of SHMeMB were conducted at elevated temperatures. SHMeMB conversions achieved a limiting value which decreased at higher temperatures, suggesting that polymerization rate was limited by depropagation. Comonomer composition drift also increased with temperature, with more AM incorporated into the polymer while SHMeMB underwent depropagation. Homopolymerization of SHMeMB with added sodium chloride (NaCl) showed a decrease in polymerization rate explained by an increase in propagation rate coefficient (kp) but an even greater increase in termination rate coefficient (kt) as supported by parameter estimation done using PREDICI. Even with added salt, however, depropagation was the dominant mechanism at higher temperatures. Lastly, the kinetic parameters estimated were implemented in a copolymerization model used to estimate the variation of kt with composition in SHMeMB:AM copolymerizations. It was found that the overall termination rate coefficient was dominated by the presence of SHMeMB, with as the estimate for kt,SHMeMB of the same order of magnitude as kt of another ionized water-soluble monomer, sodium methacrylic acid.en_US
dc.language.isoenen_US
dc.relation.ispartofseriesCanadian thesesen
dc.rightsQueen's University's Thesis/Dissertation Non-Exclusive License for Deposit to QSpace and Library and Archives Canadaen
dc.rightsProQuest PhD and Master's Theses International Dissemination Agreementen
dc.rightsIntellectual Property Guidelines at Queen's Universityen
dc.rightsCopying and Preserving Your Thesisen
dc.rightsThis 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.en
dc.subjectBio-Renewableen_US
dc.subjectSuperabsorbent Hydrogelsen_US
dc.subjectPolymerization Kineticsen_US
dc.titleRadical Polymerization of Bio-Renewable Butyrolactone Monomersen_US
dc.typeThesisen
dc.description.degreeMaster of Applied Scienceen_US
dc.contributor.supervisorHutchinson, Robin A.
dc.contributor.departmentChemical Engineeringen_US


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