Sulfonated polyaromatic hydrocarbon membranes have emerged as desirable candidates for proton exchange membranes (PEMs) due to their excellent mechanical properties, high thermal and chemical stability, and low cost. Specifically, sulfonated multiblock copolymers are attractive because their phase-separated morphologies aide in facile proton transport. In this work, the functionalization of semicrystalline gels of poly(ether ether ketone) (PEEK) is explored as a novel post-polymerization method to prepared blocky copolymers, and the effect of copolymer architecture on membrane physical properties, structure, and performance is extensively investigated. First, the blocky sulfonation of PEEK was explored to prepare blocky copolymers (SPEEK) with densely sulfonated domains and unfunctionalized, crystallizable domains. Compared to random SPEEK ionomers at similar ion content, blocky SPEEK exhibited enhanced crystallizability, decreased melting point depression, and faster crystallization kinetics. Phase separation between the hydrophilic sulfonated blocks and hydrophobic PEEK blocks, aided by polymer crystallization, resulted in enhanced water uptake, superior proton conductivity, and more closely associated ionic domains than random SPEEK. Furthermore, the random and blocky bromination of PEEK was investigated to prepare PEEK derivatives (BrPEEK) with reactive aryl-bromides. Spectroscopic evidence revealed long domains of unfunctionalized homopolymer for blocky BrPEEK, and this translated to an increased degree of crystallinity, higher melting temperature, and more rapid crystallization kinetics than random BrPEEK at similar degrees of bromination. The subsequent sulfonation of blocky BrPEEK resulted in a hydrophilic-hydrophobic blocky copolymer with clear multi-phase behavior. The phase-separated morphology contributed to decreased water uptake and areal swelling compared to random SPEEK and resulted in considerably higher proton conductivity at much lower hydration levels. Moreover, Ullmann coupling introduced superacidic perfluorosulfonic acid side chains to the BrPEEK backbone, which yielded membranes with less water content and less dimensional swelling than random SPEEK. Superior proton transport than random SPEEK was observed due to the superacid side chain and wider hydrophilic channels within the membranes, resulting in more continuous pathways for proton transport. Overall, this work provided a novel platform for the preparation of functionalized PEEK membranes using a simple post-polymerization functionalization procedure. The established methods produced blocky-type copolymers with properties reminiscent of multiblock copolymers prepared by direct polymerization from monomers/oligomers. / PHD / Block copolymers are an important class of polymers that are composed of two or more blocks of distinct polymeric segments covalently tethered to one another. Dissimilarity in the chemical nature of the blocks leads to self-organization into well-defined structures, and this unique structural order imparts material properties that are different from (and often superior to) the properties of the individual blocks alone. Thus, block copolymers are advantageous for a diverse array of applications including membranes, gas separation, water purification, medical devices, etc. Although considerable synthetic progress has been made towards discovering novel methods to prepare block copolymers, their widespread use is somewhat limited by the complex, energy-intensive procedures necessary to precisely control the block sequencing during polymerization. In this dissertation, a straightforward, inexpensive physical procedure is explored to synthesize blocky copolymers with controlled sequencing from commercially available polymers. This process relies on performing reactions in the gel state, whereby segments of the polymer chain are effectively shielded from the functionalizing chemistry. In particular, the gel state sulfonation and bromination of poly(ether ether ketone), a high performance polymer, is investigated to develop novel, blocky materials for membrane applications. This work not only expands the methodology towards the synthesis of block copolymers, but alaso provides critical insight into the effect of copolymer architecture on membrane physical properties, structure, and performance. Furthermore, this work provides an economically feasible method to prepare blocky copolymers from commercially derived materials, thereby providing a means to progress the widespread use of block copolymers in industry.

This work investigates the influence of microstructure and cooling and heating rates on the physical and chemical properties of fast crystallizing polymers. The primary objectives were to 1) utilize advanced methodologies to accurately determine the fundamental thermodynamic value of equilibrium melting temperature (Tmo) for the semi-crystalline polymer poly(ether ketone ketone) (PEKK), 2) increase understanding of the influence of microstructure (random versus blocky) of functionalized semi-crystalline polymers on physical and chemical properties, and 3) understand the influence of additive manufacturing process parameters on semi-crystalline polymer crystallization and final properties. All objectives utilized the advanced characterization technique of fast scanning calorimetry (FSC) using the Mettler Toledo Flash DSC 1. The first half of this work focuses on the high-performance semi-crystalline aromatic polymer poly(ether ketone ketone) (PEKK) with a copolymerization ratio of terephthalate to isophthalate moieties (i.e., T/I ratio) of 80/20. Due to the fast heating and cooling rates of the Flash DSC, PEKK underwent melt-reorganization upon heating at slow heating rates. This discovery resulted in utilizing a Hoffman-Weeks linear extrapolation of the zero-entropy production temperature to establish a new equilibrium melting temperature of 382 oC. Additionally, a new NMR solvent, dichloroacetic acid, was discovered for PEKK, allowing for comprehensive NMR analysis of PEKK for the first time. Diphenyl acetone (DPA) was discovered as a novel, benign gelation solvent for PEKK, enabling heterogeneous gel-state bromination and sulfonation to afford blocky microstructures. The gel state functionalization process resulted in a blocky microstructure with runs of pristine crystallizable PEKK retained within the crystalline domains, and amorphous domains containing the functionalized PEKK monomers. The preservation of the pristine crystalline domains resulted in enhanced physical and chemical properties compared to the randomly functionalized analogs. Additionally, heterogeneous gel state functionalization of PEKK gels prepared from different solvents and gelation temperatures resulted in differences in crystallization behavior between blocky microstructures of the same degree of functionalization. This result demonstrates that the blocky microstructure can be tuned through controlling the starting gel morphology. The second half of this work focuses on understanding the influence of cooling and heating rates on the melting, crystal morphology, and crystallization kinetics on isotactic polypropylene (iPP), iPP-polyethylene copolymers (iPP-PE), and iPP/iPP-PE blends and using this information to gain understanding of how these polymers crystallize during the additive manufacturing processes of powder bed fusion (PBF) and material extrusion (MatEx). The crystallization kinetics of iPP, iPP-PE copolymers, and iPP/iPP-PE blends exhibited bimodal parabolic-like behavior attributed to crystallization of the mesomorphic crystal polymorph at low temperatures and the α-form crystal at high temperatures. Incorporation of non-crystallizable polyethylene fractions both covalently and blended as a secondary component, resulted in decreasing crystallization rates, inhibition of crystallization, and decreased crystallizability. Additionally, the non-isothermal crystallization behavior of these systems shows that the non-crystallizable fractions influence the crystal nucleation density and temperature at which polymorphic crystallization occurs. Utilizing in-situ IR thermography in the PBF system, the heating and cooling rates observed for a single-layer PBF print were used to mimic the PBF process by FSC. Partial melting in the printing process leads to self-seeding and increased crystallization onset temperatures upon cooling, which influences the final part melting morphology. Nucleation from surrounding powder and partially melted crystals greatly influences the crystallization kinetics and crystal morphology of the final part. Utilizing rheological experiments and process-relevant cooling rates observed in the MatEx process, the miscibility of iPP/iPP-PE blends influenced the nucleation behavior and crystallization rates, subsequently leading to differences in printed part properties. / Doctor of Philosophy / The crystalline morphology of semi-crystalline polymers depends on their microstructure and thermal history. The resultant crystalline morphology greatly affects the physical and chemical properties. In the first part of this work, the effect of microstructure on material properties is explored. Block copolymer microstructures consist of two or more blocks of distinct polymer segments covalently bonded to one another. This leads to self-organization of the components into unique structural order that would not be attainable if the polymer segments were randomly bonded together. This structural order enhances material properties; thus, block copolymers are advantageous for many applications. However, synthesis of block copolymers can be tedious and expensive. Thus, additional methodologies for block copolymer synthesis are desired. In this work blocky (i.e., statistically non-random) copolymers are synthesized through a facile post-polymerization functionalization method. These blocky copolymers result in enhanced physical and chemical properties compared to the randomly synthesized analogs. This work shows blocky functionalization of a new polymer under new post-polymerization conditions and expands upon the synthesis methodology for block copolymers. In the second part of this work, the effect of heating and cooling rates on the formation of crystals during additive manufacturing is explored. Additive manufacturing modalities of powder bed fusion and material extrusion consist of rapid heating and cooling processes, which can affect how crystals form and ultimately affect the final printed part properties. Using a technique called fast scanning calorimetry, the different heating and cooling rates that the polymer witnesses during printing can be mimicked, and the formation of crystals under these different conditions can be replicated. This mimicking analysis can be related to the printing process and be used to help guide printing processes to enhance printed part properties.