Additive manufacturing provides unmatched control and diversity over structural design of polymeric, ceramic and metallic parts. Nevertheless, until recently, the toolbox of polymeric feedstocks for light based additive manufacturing limited employment of printed parts for applications necessitating high thermomechanical performance. Development of synthetic pathways permitted the first additive manufacturing of high performance poly(amide imides) via ultraviolet assisted direct ink write (UV-DIW) printing. Precursor resins exhibited prerequisite rheology and reactivity for UV-DIW and produced organogels were well-defined and self-supporting. Thermal treatment induced drying and imidization of the precursor organogels to form the desired poly(amide imide) structures. During post-processing the parts displayed linear isotropic shrinkage as low as 26% and exhibited competitive thermomechanical properties. Following expansion of the high performance backbones available for additive manufacturing, simplification of synthetic rigors was undertaken. This investigation facilitated the evolution of the first photocurable and processable small molecule polyimide precursors. These supramolecular carboxylate ammonium nylon salts, coined polysalts, allowed for additive manufacturing of both high performance polyimides and polyetherimides using vat photopolymerization (VP). The use of small molecule precursors over previously investigated polymeric precursors displayed much lower solution viscosities yielding reduction of organic solvent loading, inducing lower overall shrinkage. Polysalts provide a stimulating platform for rapid and facile printing of high performance polyimides in the future. Surveying the excellent carbonization behavior for aromatic polyimides spurred translation of known 2D protocols to post-processing of printed polyimides. Applying pyrolysis methodologies to parts produced using VP and UV-DIW induced efficient carbonization at 1000 °C. Remarkably, the carbonized parts retained structure and did not display cracks or pore formation. Raman spectroscopy indicated production of disordered carbon via the utilized pyrolysis protocol, in line with literature on carbonization of PMDA-ODA polyimide at 1000 °C. Electrical testing indicated production of conductive materials following pyrolysis, with carbonization temperature modulating the performance. The excellent thermal stability, transport properties, and known mechanical performance of carbonaceous materials may enable application of these printed objects in customized electronics and aerospace environments. Exploration of drop-in monomeric units permitted a multi-pronged research program into augmentation of mechanical, rheological and transport properties of high performance polyetherimides (PEIs). Installation of sodium or lithium substituted disulfonated monomers via classical two-step polyimide synthesis afforded two series of sulfonated polyetherimides (sPEI). The sPEIs exhibited robust thermal properties, with high sulfonate mol% inducing Tg > 300 °C. X-ray scattering experiments revealed the development of domains via inclusion of the sulfonate moieties, with low mol% producing larger domain spacing. The larger domains present in the low mol% sPEIs yielded improved ionic liquid uptake within 2 d, yielding improved ionic conductivities at room temperature relative to high mol% samples. The observed conductivities indicated potential of the sPEIs as battery electrolytes, but further ionic liquid incorporation is required for competitive performance. Development of a poly(ethylene glycol) (PEG) bearing macromonomer facilitated synthesis of PEIs and PI graft copolymers. When coupled with 4,4'-(4,4'-isopropylidene-diphenoxy)diphthalic anhydride (BPADA) and meta-phenylene diamine (mPD), the PEG-grafted materials exhibited signs of phase mixing at low mol% incorporation of macromonomer, with a single observable Tg depressed from neat BPADA-mPD. Doping of the PEI-g-PEG with lithium salts allowed for production of polymeric films that displayed good ionic conductivities at room temperatures. Extension of the PEG macromonomer into fully aromatic PIs yielded phase separated materials even at modest loadings, >2.5 mol%. The formed PEG-g-PMDA-ODA contained thermally stable PI main-chains with thermally labile graft chains, which when thermally treated induced facile quantitative PEG removal. Remarkably, the thermally treated materials retained flexibility, even at >60 wt.% PEG removal. Further investigations aim to explore use of novel PEIs in energy storage as well as low density and dielectric materials. / Doctor of Philosophy / High performance polymers enjoy wide use in microelectronics and aerospace industries due to high thermal stability and excellent mechanical performance. However, processing restrictions hinder manufacturing of 3-dimensional objects of many high performance polymers suitable for extreme environments. Additive manufacturing, also known as 3D printing, has garnered attention in both academic and industrial settings over the last four decades due to the unmatched control over part design and internal structure, but the material arsenal for additive manufacturing of polymers lacks options for applications demanding high thermal stability. The first half of this dissertation aimed to promote translation of high performance polymeric chemistries to suitable feedstocks for additive manufacturing. By designing and developing novel chemical pathways, traditional processing limitations were circumvented and high performance polymers, such as poly(amide imides) and polyimides, were successfully processed via light based additive manufacturing. Likewise, by investigating carbonization dynamics of polyimides and expanding current additive manufacturing techniques for processing of fully aromatic polyimides, complex 3D carbonaceous materials were obtained. These carbon objects present extreme thermal stability and electrical conductivity, advantageous for aerospace and electronic industries. Additionally, investigations allowed for development of synthetically facile routes for expanding the available polyimide backbones for additive manufacturing via use of small molecule precursors. The second half of the dissertation explored novel polyetherimide and polyimide reagents for production of functional materials. Harnessing ionic building blocks permitted synthesis of a series of thermally robust polyetherimides displaying promise for energy storage. Similarly, coupling previous literature for ion conduction in solid polymer electrolytes for battery applications with thermally stable and flame resistant polyetherimides enabled synthesis of a series of innovative graft copolymers with good room temperature ionic conductivities. Lastly, pairing of thermally labile polymers with thermally resistant polyimide backbones allowed for development of an exciting platform for obtaining highly insulting and flexible films for electronics applications. Outlined future work aims to probe the formation of pores in the obtained polymer

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. / Doctor of Philosophy / 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.

Ce travail porte sur l'étude du mélange thermodurcissable - thermoplastique (époxyamine / polyetherimide avec séparation de phase) pour évaluer les performances électriques et thermiques. Ces matériaux seraient des nouveaux candidats pour remplacer la couche d'encapsulation dans les semi-conducteurs, par exemple ceux utilisés comme interrupteur dans les applications électroniques de puissance. Les mélanges de polymères seraient un nouveau candidat en tant qu'isolant pour le système. La matrice epoxy-amine seul et les melanges epoxy / Polyetherimide on été caractérisés par microscopie électronique à transmission, microscopie électronique à balayage, Calorimétrie différentielle à balayage, analyse thermogravimétrique, analyse mécanique dynamique, analyse diélectrique avec simulation analytique et des mesures de conductivité électrique et de tension de claquage ont également été entreprises. Ces techniques complémentaires ont d'abord été utilisées pour étudier la séparation de phases et ensuite pour quantifier la taille des nodules de thermoplastiques dans la matrice thermodurcissable. Cette séparation de phase a été examiné et a montré une diminution des valeurs diélectriques de 15% et une augmentation de la tension de claquage par rapport au système époxy-amine pur. / This work deals with the study of thermoset-thermoplastic blend (epoxy-amine/poly-etherimide phase separated) to assess the electrical and thermal performances. These materials would be new candidates to replace the encapsulation layer in semiconductors, for example ones used as switches in power electronic applications. Polymers blends would be a novel candidate as an insulator for the system. Pure epoxy system as well as Epoxy/Polyetherimide blends where characterized by transmission electron microscopy, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, dielectric analysis with analytical simulation, electrical conductivity and breakdown voltage measurements. These complementary techniques were used first to investigate the presence of the phase separation phenomenon and secondly to quantify the separated nodules size. The effect of this phase separation was examined and showed a decrease in the dielectric values of 15 % and an increase in the breakdown voltage compared to the pure epoxy system. It was finally simulated to show a close assumption of what is found experimentally.