Structure-Property Relationships of Polyester Regioisomers and Pendant Functionalized Polyetherimides
| dc.contributor.author | Mondschein, Ryan Joseph | en |
| dc.contributor.committeechair | Long, Timothy E. | en |
| dc.contributor.committeemember | Turner, S. Richard | en |
| dc.contributor.committeemember | Moore, Robert Bowen | en |
| dc.contributor.committeemember | Cheng, Shengfeng | en |
| dc.contributor.department | Chemistry | en |
| dc.date.accessioned | 2021-01-02T07:00:28Z | en |
| dc.date.available | 2021-01-02T07:00:28Z | en |
| dc.date.issued | 2019-07-11 | en |
| dc.description.abstract | Step-growth polymerization enabled the synthesis of novel polyester regioisomers and pendant functionalized polyetherimides (PEI)s. Novel monomers incorporated at targeted mol % produced series of polyesters and PEIs, suitable for systematic analysis of key polymer properties. Subsequent compositional, thermal, mechanical, and rheological characterization forged structure-property relationships to further understand the influence of composition on performance. Altering regiochemistry is a subtle way to maintain the same polymer composition but tune desired properties. Similarly, introducing functional pendant groups expands the property profile of common industrial polymers and installs a handle for secondary chemistry after synthesizing the main polymer. Both altering regiochemistry and adding pendant groups alters polymer properties without the need for large changes in synthetic requirements or reaction conditions, ideal for industrial adoption. Incorporation of a kinked bibenzoate (BB)-based diester monomers into the commonly utilized linear regioisomer afforded processable amorphous and semi-aromatic (co)polyesters. BB-(co)polyesters with ethylene glycol (EG) possessed improved barrier performance compared to poly(ethylene terephthalate) (PET) while improving on mechanical properties, including tensile and flexural modulus/strength, rivaling bisphenol-A polycarbonate (BPA-PC). Replacement of EG with 1,4-cyclohexanedimethanol (CHDM) improved thermal properties closer to BPA-PC, while enabling melt rheological analysis due to its amorphous morphology. Time-temperature superposition (TTS) analysis produced master curves provided insight into the entanglement molecular weight (Me) and entanglement density. More kinked structures possessed a lower Me and more entanglements. Introducing kinked monomers posed the question of cyclic speices generation during polymerization, common in step-growth reactions. Thus, systematic incorporation of meta-substituted hydroxyethylresorcinol and para-substituted hydroxyethylhydroquinone regioisomers into PET analogues enabled the characterization of cyclic formation due to monomer regioisomers. Increased meta substitution produced increased amounts of cylic species, analyzed by size exclusion chromatography (SEC). Adding functionality to high performance polyetherimides (PEI)s is difficult due to the high temperatures required for processing. The lack of thermal stability for commonly utilized H-bonding/reactive groups limits viable moieties. Utilizing the high temperture processing, PEIs incorporating pendant carboxylic acids reacted in the melt to form branched PEIs. These branched PEIs exhibited steeper shear thinning as well as improved flame resistance, limited in thin film commercial PEIs. | en |
| dc.description.abstractgeneral | My research focused on making new plastics (polymers) for use in consumer and performance markets. Typical applications utilizing these plastics include food packaging, consumer goods, automotive, aerospace, microelectronics, construction, and medical devices. Large changes such as intricate new chemicals used to make the plastics increase the difficulty in incorporating these new materials into existing synthesis and processing techniques and infrastructure. Thus, my research revolved around subtle changes to the chemical structure of the plastic, suitable for easy industrial adoption while also improving targeted properties necessary for the aforementioned applications. Polyesters are a class of polymers commonly used for food packaging and consumer goods. Thus, improving gas barrier performance and mechanical integrity/strength is crucial when designing new polyesters. Changing the bond angles through the linear versus kinked nature of the polymer chain imparts processability and improved gas barrier, compared to commercial poly(ethylene terepthalate) (PET), commonly used in food packaging applications. The density of the polyesters is also increased, which improves mechanical strength. The specific structures used also increased the thermal resistivity compared to PET. This higher thermal resistivity enables use in applications where high temperature cleaning such as steam sterilization and dish-washing could deform products or processing such as filling food packaging containers with hot foods. Similar types of polymers which possess much higher thermal resistivity are classified as high performance polymers. One class of these include polyetherimides (PEIs). The specific chemical structures and their high thermal resistance makes them great candidates for applications in automotive, aerospace, and microelectronic applications; although, these same properties make these polymers very difficult and expensive to process into the desired parts. Thus, adding functionality to the polymer by putting specific chemical groups off of the main chain enabled easier processing and improved other polymer properties. Adding the functionality to these polymers allowed them to react and change structure at high temperatures (during processing) to achieve a different shape, thus improving desired properties, such as how easy they flow like liquids at high temperatures and processing conditions. Another benefit realized from this change during processing was the improvement of flame resistance. Due to the chemical structure of the PEIs, they inherently possess resistance to catching on fire, remaining on fire, and dripping flaming material. Although PEIs typically possess good flame resistance, thin films or small parts made from these polymers do not possess the same flame resistance and can produce flaming drips, undesirable for applications requiring flame resistance. Chemically modifying these polymers with the aforementioned functionality and processing them increased the flame resistance to eliminate flaming drips and lessen the amount of time the polymer was on fire. | en |
| dc.description.degree | Doctor of Philosophy | en |
| dc.format.medium | ETD | en |
| dc.identifier.other | vt_gsexam:18813 | en |
| dc.identifier.uri | http://hdl.handle.net/10919/101706 | en |
| dc.publisher | Virginia Tech | en |
| dc.rights | In Copyright | en |
| dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | en |
| dc.subject | polyester | en |
| dc.subject | regioisomers | en |
| dc.subject | barrier | en |
| dc.subject | permeability | en |
| dc.subject | cyclics | en |
| dc.subject | entanglement | en |
| dc.subject | polyetherimides | en |
| dc.subject | branching | en |
| dc.subject | flame resistance | en |
| dc.subject | processability | en |
| dc.subject | pendant groups | en |
| dc.title | Structure-Property Relationships of Polyester Regioisomers and Pendant Functionalized Polyetherimides | en |
| dc.type | Dissertation | en |
| thesis.degree.discipline | Chemistry | en |
| thesis.degree.grantor | Virginia Polytechnic Institute and State University | en |
| thesis.degree.level | doctoral | en |
| thesis.degree.name | Doctor of Philosophy | en |