Show simple item record

dc.contributor.authorSantana Krishnan, Sandhya
dc.contributor.otherQueen's University (Kingston, Ont.). Theses (Queen's University (Kingston, Ont.))en
dc.date2011-12-21 16:05:14.904en
dc.date.accessioned2011-12-22T16:07:08Z
dc.date.available2011-12-22T16:07:08Z
dc.date.issued2011-12-22
dc.identifier.urihttp://hdl.handle.net/1974/6918
dc.descriptionThesis (Ph.D, Chemical Engineering) -- Queen's University, 2011-12-21 16:05:14.904en
dc.description.abstractFunctional water-soluble polymers find applications in a variety of fields including waste-water treatment, pharmaceuticals, cosmetics, drug delivery, and hygiene. Despite the increased demand for these products, understanding of their synthesis by free-radical aqueous-phase polymerization has lagged behind that of polymers produced in organic solvents. In this doctoral work, the free-radical batch and semibatch aqueous-phase polymerization of N-vinylpyrrolidone (NVP), N-vinylformamide (NVF), N-vinylimidazole (NVI) and quaternized vinylimidazole (QVI), as well as NVP polymerized in n-butanol, has been studied. Kinetic models are developed to describe monomer conversion and polymer molecular weight (MW) behaviour of these systems. The expressions developed from independent pulsed-laser studies for propagation (kp) and termination (kt) rate coefficients, including their variation with monomer concentration and conversion, are shown to provide an excellent description of aqueous-phase NVP polymerization. Polymerization of NVP in butanol and of NVF in water are well-represented by the base NVP model, with differences in polymerization rate and polymer MWs simply accounted for by the differences in kp for the systems, indicating that the kt behaviour must be quite similar. The NVI/QVI study demonstrates the importance of a pH-dependent degradative addition reaction to monomer for NVI, with polymerization behaviour identical to that of QVI for pH 1, an effect captured in the model developed to describe the system. The aqueous-phase copolymerization of NVP and NVF was also studied, and reactivity ratios were determined to be very close to unity. This information was combined with the kp and kt expressions used to describe NVP and NVF homopolymerizations, with no other additional parameters required to model the copolymerization rate, copolymer composition and copolymer MW. This result demonstrates that the improved homopolymerization knowledge of these water-soluble monomers can be easily extended to understand their behaviour in copolymerization.en_US
dc.languageenen
dc.language.isoenen_US
dc.relation.ispartofseriesCanadian thesesen
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.subjectQuaternized Vinylimidazoleen_US
dc.subjectN-vinylimidazoleen_US
dc.subjectFree-Radical Polymerizationen_US
dc.subjectAqueous-Phaseen_US
dc.subjectN-vinylpyrrolidoneen_US
dc.subjectKinetic Modelingen_US
dc.subjectN-vinylformamideen_US
dc.titleKinetic Modeling of Homo- and Co- Polymerization of Water-Soluble N-vinyl Monomersen_US
dc.typeThesisen_US
dc.description.degreePh.Den
dc.contributor.supervisorHutchinson, Robin A.en
dc.contributor.departmentChemical Engineeringen


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record