Conventional studies of ionomers have focused on ionomers bearing monovalent carboxylate or sulfonate pendant ions. There are relatively fewer studies on ionomers containing multivalent pendant ions, such as divalent phosphonate. In this dissertation, poly(ethylene terephthalate) (PET) and polystyrene ionomers with divalent phosphonate pendant ions have been synthesized, and the influence of divalent phosphonate pendant ions on the structure-morphology-property relationship has been compared to the ionomers with monovalent sulfonate pendant ions. The phosphonate groups generated a stronger physically crosslinked network in phosphonated ionomers as compared to sulfonated analogues. Higher plateau modulus, longer relaxation time, and significantly higher zero-shear viscosity were noted for phosphonated ionomers by a dynamic melt rheology study. Compared to the ionic aggregates generated from sulfonate groups, larger ionic aggregates with associated phosphonate groups have been observed. Furthermore, phosphonated ionomers displayed significantly higher glass transition temperatures than sulfonated ionomers.
Ionomers have proven to be attractive, interfacially active compatibilizers for a number of polymer blend systems because of specific interactions that may develop between the ionic groups and complementary functional groups on other polar polymers within the blends. The successful compatibilization of polyester/polyamide blends (prepared by solution mixing and melt blending methods) using phosphonated PET ionomers as a minor-component compatibilizer has been demonstrated. The phase-separated polyamide domain dimension decreased with increasing mol % phosphonated monomers and this decrease was attributed to the specific interactions between the ionic phosphonate groups on the polyester ionomer and the amide linkages of polyamide. More importantly, the divalent phosphonate pendant ions are more effective at compatibilizing polyester/polyamide blends in comparison to the monovalent sulfonate pendant ions. Phosphonated PET ionomer-compatibilized polyester/polyamide blends required 6 times fewer ionic monomers to achieve domain dimension < 1 μm as compared to sulfonated PET-containing blends.
Deep eutectic solvents (DES) have been reported to be the next generation solvents due to the superior biocompatibility, biodegradability, and sustainability as compared to ionic liquids. Two types of deep eutectic solvents, choline chloride : malic acid (ChCl:MA) and L-arginine : levulinic acid (Arg:LA), have been demonstrated as effective plasticizers for poly(vinyl alcohol) (PVOH) films. The plasticization effects on the properties of PVOH films were evidenced by lower crystallizability and improved film ductility. In addition, ChCl:MA deep eutectic solvent was more effective in plasticizing PVOH as compared to propylene glycol, one of the most widely studied alcohol-type plasticizers. From an applied perspective, DES-plasticized PVOH film is a promising candidate in the packaging market of heath-related products. / Doctor of Philosophy / Non-covalent interactions play an important role on the structure-morphology-property relationship of polymeric materials. Divalent phosphonate pendant ions provide interesting effects on the properties of ionomer and polymer blends as compared to the monovalent sulfonate pendant ions. Ionomers containing phosphonate pendant ions exhibit a significantly stronger physically crosslinked network as compared to sulfonated ionomers. Compared to monovalent sulfonate groups, the divalent phosphonate groups are more effective at compatibilizing polymer blends. Furthermore, the compatibilized poly(ethylene terephthalate)-based blends exhibit improved optical and oxygen barrier properties compared to the base blend without compatibilizer, signifying potential benefits in packaging industry.
Poly(vinyl alcohol) is one of the most widely used packaging materials for food, medicine, detergent, etc. The incorporation of deep eutectic solvents as plasticizers significantly improved film ductility. In addition, the plasticization effect for choline chloride-based deep eutectic solvent is more profound than one of the most widely studied alcohol-type plasticizers, propylene glycol. The effective plasticization of poly(vinyl alcohol) using deep eutectic solvents confirmed the potential for future applications in the packaging market of health-related product.
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/102651 |
| Date | 17 September 2019 |
| Creators | Ju, Lin |
| Contributors | Chemistry, Moore, Robert Bowen, Long, Timothy E., Bortner, Michael J., Matson, John B. |
| Publisher | Virginia Tech |
| Source Sets | Virginia Tech Theses and Dissertation |
| Detected Language | English |
| Type | Dissertation |
| Format | ETD, application/pdf, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
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