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The objective of the research described in this thesis has been to improve the toughness of phenolic networks while maintaining flame resistance. A four step synthetic scheme has been developed to prepare 4,4′-Bis(3,4-dicyanophenoxy)biphenyl(biphenoxyphthalonitrile). A 700 g mol-1 novolac oligomer was cured with relatively low concentrations of this reagent (~20 wt %) into high Tg (~190 °C) networks. The curing reaction was attrubuted to nucleophilic attack of the phenolic hydroxyl on the nitrile groups of the phthalonitrile resulting in the formation of heterocylic rings. TGA and cone calorimetry demonstrated that these networks have excellent thermo-oxidative stability. Further goals were to develop halogen-free, flame retardant monomers for improving the thermo-oxidative resistance of polystyrene and dimethylacrlyate/styrene(vinyl ester) networks. 4-Vinylphenoxyphthalonitrile, a phthalonitrile derivative of styrene, was synthesized. FTIR has been utilized to demonstrate this new monomer co-cured into vinyl ester networks in free radical thermosetting polymerizations. Upon post-curing the networks between 200-260 °C for ~1.5 h, the nitrile groups reacted to form heterocyclic crosslinks. TGA and cone calorimetry demonstrated that the 4-vinylphenoxyphthalonitrile substantially improved the flame resistance of vinyl ester networks. Copolymerizations of styrene and 4-vinylphenoxyphthalonitrile were conducted at 75 °C for 24 h using 0.5 wt % AIBN in chlorobenzene. Dynamic TGA at 10 °C min-1 in air showed that copolymers containing 10 and 25 mole % of 4-vinylphenoxyphthalonitrile had increased initial weight loss temperatures in air by (~50 °C higher) and increased the char yield between 400-600 °C. High molecular weight nitrile-functional, (hexafluoroisopropylidene)diphenol based aromatic poly(arylene ether)s with pendent sulfonic acid groups were prepared by nucleophilic step copolymerization of 4,4′-(hexafluoroisopropylidene)diphenol, 2,6-dichlorobenzonitrile, and 3,3′-disulfonate-4,4′-dichlorodiphenylsulfone under basic conditions in N-methyl-2-pyrrolidinone at 200 °C. A series of these materials with systematically varied concentrations of the sulfonic acid moieties showed increased glass transition temperatures, proton conductivities, and hydrophilicities as a function of disulfonation. Atomic force microscopy (AFM) demonstrated that the acidified copolymer with 35 mole % of disulfonated units was phase separated into a co-continuous morphology of hydrophobic and hydrophilic domains. / Ph. D.

Rotational-translational decoupling, a phenomenon commonly observed in supercooled liquids, has been a topic of great interest. Despite its prevalence, the underlying cause of this phenomenon, often attributed to dynamic heterogeneity, has not been conclusively elucidated. This thesis investigates and evaluates how dynamic heterogeneity may lead to this decoupling using simultaneous single-molecule rotational and translational measurements. In the experimental study, single molecule fluorescence imaging experiments are performed on the ideal probe N,N’-dipentyl-3,4,9,10-perylenedicarboximide in high molecular weight polystyrene near its glass transition temperature. A novel trajectory linking method based on hierarchical clustering is developed to facilitate single molecule tracking even in imaging data where specific molecules cannot be observed visually for a substantial number of frames. This linking algorithm then allows molecules to be localized over full movies, such that rotational and translational measurements can be compared over comparable timespans. The investigation of translational dynamics using such long trajectories, which was not previously achieved, reveals that both rotational-translational decoupling and translational enhancement persist on the single molecule level, supporting the hypothesis that temporally heterogeneous dynamics experienced by the probe molecules is a contributing factor in observed rotational-translational breakdown in both ensemble and single molecule studies. A tendency towards dynamical convergence between subgroups with fast and slow dynamics is observed, demonstrating temporal heterogeneity at the single molecule level. In comparison to rotational dynamics, translational dynamics was discovered to have a longer lifetime. Other key observations facilitated by the linked trajectory analysis include that apparent diffusion coefficient of probe molecules decreases with longer observation time, a finding inconsistent with normal diffusive behavior. To investigate the origin of this anomalous slowing in single molecule studies existing alongside the observed overall enhancement in translational motion, temporally heterogeneous models with multiple types of correlation were studied via simulations. The results emphasize the critical role that bias in translational and rotational measurements can play when investigating and observing dynamic heterogeneity, as nearly all models including dynamic heterogeneity show increasing diffusion coefficient with increasing number of dynamic environments explored. Strikingly, translational enhancement is evident in single molecule translational simulations even when slow dynamics are reinforced via positive correlation in the models. A comparison of the diffusion coefficient evolution between simulations and experiments reveals that the sub-diffusive continuous time random walk model is the most plausible candidate to account for the set of observations seen in experiment.

This dissertation demonstrates the preparation of blocky brominated syndiotactic polystyrene (sPS-co-sPS-Br) copolymers with tailored chain sequences using a simple, post-polymerization functionalization method conducted in the heterogeneous gel state, and investigates the effect of sPS reaction state and sPS/solvent gel morphology on the copolymer microstructure and thermal properties. Gel-state (Blocky) brominated copolymers were prepared from a 10 w/v% sPS/carbon tetrachloride (CCl4) gel and a 10 w/v% sPS/chloroform (CHCl3) gel in a matched set containing 6−32 mol% p-bromostyrene (Br-Sty) units. For comparison, a matched set of randomly brominated copolymers was prepared using a homogeneous solution-state (Random) reaction method and a set of brominated copolymers was prepared using a heterogenous powder-state (Powder) reaction method. The degree of bromination was evaluated using 1H nuclear magnetic resonance (NMR) spectroscopy. Powder-state bromination produced copolymers with a limited degree of functionalization of up to 12 mol% Br and required a threefold longer reaction time than the gel-state method conducted on the sPS/CHCl3 gel, demonstrating that the powder-state method is time-consuming and the dense sPS powder is incapable of producing copolymers with high Br-content. Microstructural characterization provided by 13C NMR spectroscopy, showed that bromination of sPS produces multiple peaks in the quaternary carbon region of the NMR spectrum, signifying through-bond communication between neighboring styrene and Br-Sty monomers. This work provides the first high-resolution comonomer sequencing of brominated sPS copolymers. Characterization of the quaternary carbon spectrum, assisted by band selective gradient heteronuclear multiple bond correlation (bsgHMBC) spectroscopy, electronic structure calculations, and simulated statistically random copolymer chains, revealed that each resonance peak could be assigned to a styrene or Br-Sty unit that exists in the center of a unique sequence of five monomers (i.e., a pentad) along the copolymer chain (e.g., ssssb where s = styrene and b = brominated styrene). Our comonomer sequencing method demonstrated that the Blocky and Powder copolymers have block-like character. Remarkably, the Blocky copolymers exhibit notably higher degrees of blockiness and larger fractions of sssss and bbbbb pentads at low Br contents (i.e., 32 mol% Br), relative to the Powder copolymers, confirming their blocky microstructure. Quenched films of the Blocky copolymers, analyzed using ultra-small-angle (USAXS) and small-angle X ray scattering (SAXS), show micro-phase separated morphologies that are reminiscent of conventional block copolymer phase behavior, supporting that the Blocky copolymers contain distinct segments of pure sPS and segments of randomly brominated sPS. Crystallization behavior of the copolymers, examined using differential scanning calorimetry (DSC), demonstrates that the Blocky copolymers are more crystallizable and crystallize faster at lower supercooling compared to their Random analogs. Simulations of blocky copolymers were developed based on the semicrystalline gel morphology to rationalize the effect of gel-state functionalization on copolymer microstructure and crystallization behavior. The simulations confirm that restricting the accessibility of the brominating reagent to monomers well removed from the crystalline fraction of the gel network produces copolymers with a greater prevalence of long runs of pure sPS that is advantageous for preserving desired crystallizability of the resulting blocky copolymers. To investigate the effect of sPS/solvent gel morphology on copolymer microstructure and crystallization behavior, the sPS/CCl4 and sPS/CHCl3 copolymers were compared directly. Characterization of the sPS/solvent gels using USAXS/SAXS, revealed that the gels exhibit different morphologies and average lamella thicknesses. Microstructural analysis showed that the sPS/CHCl3 copolymers contain larger fractions of sssss pentad and a greater degree of blockiness. The sPS/CHCl3 copolymers contain larger phase domains, supporting that these copolymers contain longer distinct segments of pure sPS and randomly brominated sPS in a multiblock-like microstructure. In addition, the sPS/CHCl3 copolymers are more crystallizable during conditions of rapid cooling and crystallize faster at low supercooling relative to their sPS/CCl4 analogs. Simulated average chains of the Blocky copolymers, generated from the empirical pentad sequence distributions, provide strong evidence that the runs of pure sPS in the Blocky copolymers originate from the crystalline stems within the crystalline lamellae. Thus, the simulations support that semicrystalline blocky brominated copolymers with tailored chain sequences, phase behavior, and crystallization properties and can be prepared simply by changing the gelation solvent. / Doctor of Philosophy / Block copolymers are a class of large molecules (polymers) that are made up of two or more chains (blocks) of different smaller units (monomers) linked together at one of each of the chain ends. When the monomers that make up each block have distinctly different chemical properties, the blocks may be capable of self-assembling into well-ordered physical structures, which give the block copolymer unique material properties that are different, and often better than the properties of the individual blocks alone (homopolymers). Block cop olymers have thus received tremendous attention with respect to controlled preparation, tailored structure development, and customized physical properties, for their potential use in self-assembled, nanostructured materials. Nevertheless, the generally difficult procedures and conditions required to make (polymerize) block copolymers with controlled sequences limits the scope of their commercial application. As an alternative to conventional polymerization methods, this dissertation demonstrates a comparatively simple physical method to make copolymers that contain significantly non-random (blocky) monomer sequences, starting with a homopolymer and using a reagent to modify units along the polymer chain. This post-polymerization method is conducted in the homopolymer’s gel state, in which segments of the homopolymer chains are effectively shielded from the reagent. The homopolymer, syndiotactic polystyrene (sPS), was used as a model to conduct a fundamentical investigation into the effects of the polymer reaction state, i.e., gel, solution, or powder, and the gel structure (morphology) on the copolymer structure and properties. The gel-state was found to produce copolymers with a high degree of modification and a greater degree of blockiness than the solution-state and powder-state. Copolymers prepared from the gel state exhibited properties that are characteristic of conventional block copolymers. Furthermore, using the gel-state method, blocky copolymers with tailored chain sequences and properties were prepared by simply changing the gel morphology. Thus, reaction in the gel-state is demonstrated as a simple physical approach to polymer design and synthesis that will be useful in the development of next-generation functionalized materials through the modification of lowcost commodity polymers. As an advancement to the manner in which nanostructured materials are created, these tailored materials will greatly enhance the convenience of block copolymers for a wide variety of applications including structural and biomechanical materials, and polymeric membranes for energy conversion and water purification systems.

[ES] La revalorización del reciclado de plástico de envases se ha convertido en una de las prioridades ambientales más importantes a nivel mundial debido a que el plástico se ha convertido en uno de los materiales más utilizados en la fabricación de envases y productos, debido a sus propiedades de durabilidad, resistencia y bajo coste. Sin embargo, el plástico también es uno de los materiales más difíciles de reciclar debido a su resistencia a la degradación. La revalorización del reciclado de plástico de envases es una solución que puede ayudar a reducir la cantidad de plástico que termina en los vertederos y los océanos. La revalorización del reciclado de plásticos de envases puede ayudar a reducir el impacto ambiental de la producción de plástico. Esto se logra a través de la recogida, el procesamiento y el reciclaje de los plásticos usados. Esto reduce los costes de producción y preserva los recursos naturales. Además, para la revalorización del reciclado de plásticos de envases, se deben mejorar los procesos de reciclaje de plástico. Esto incluye la innovación de nuevas tecnologías y procesos de reciclaje, así como mejorar la eficiencia de los procesos existentes. Además, la revalorización del reciclado también puede ayudar a mejorar la calidad de los plásticos reciclados para que sean aptos para su reutilización. Por tanto, la revalorización del reciclado de plásticos de envases es una solución ecológica y económica para reducir el impacto ambiental de la producción de plásticos. Se ha estudiado la recuperación de materiales poliolefinicos y sus alternativas mediante el reciclado mecánico procedentes de residuos domésticos e industriales de diferente naturaleza, con el fin de conocer la posibilidad de obtener un material capaz de competir en algunos usos con el material virgen. En el trabajo se revisa de una manera inicial los dos principales problemas que nos vamos a encontrar a la hora de realizar el proceso de recuperación. De una parte, la presencia de impurezas de otros materiales plásticos y en otras ocasiones la degradación que sobre el material se ha producido en anteriores procesos o por acción de agentes externos como puede ser la luz solar. En ambos casos encontraremos que el material recuperado presenta una disminución de sus propiedades mecánicas y además dificultades en el proceso de recuperación. La utilización de técnicas de análisis instrumental como la calorimetría diferencial han sido las herramientas utilizadas para predecir la calidad del material recuperado a partir de las características del residuo. Otros de los problemas detectados a la hora de la revalorización del plástico son debido a que hay una amplia variedad de plásticos utilizados que son difícil de separar visualmente en el flujo de residuos, esto representa una diferencia con respecto a aquellos cuyos envases son fáciles de identificar. En aquellos casos que la separación del flujo de residuos es sencilla, obtenemos materiales reciclados de excelente calidad. Esto ocurre en la revalorización de residuos procedentes de la recogida selectiva. Pero esta situación no se puede extrapolar en aquellos casos que aparezcan impurezas. Por ejemplo, la existencia de los anillos aromáticos hace que el Poliestireno presente una baja compatibilidad incluso con polímeros derivados del estireno, como es el caso del Acrilonitrilo-Butadieno-Estireno (ABS), donde es recomendable el uso de compatibilizantes para sus mezclas.¿ / [CA] La revalorització del reciclatge de plàstic d'envasos s'ha convertit en una de les prioritats ambientals més importants a nivell mundial pel fet que el plàstic s'ha convertit en un dels materials més utilitzats en la fabricació d'envasos i productes, per les seves propietats de durabilitat, resistència i baix cost. Tot i això, el plàstic també és un dels materials més difícils de reciclar a causa de la seva resistència a la degradació. La revalorització del reciclatge de plàstic d'envasos és una solució que pot ajudar a reduir la quantitat de plàstic que acaba als abocadors i els oceans. La revalorització del reciclatge de plàstics d¿envasos pot ajudar a reduir l¿impacte ambiental de la producció de plàstic. Això s'aconsegueix a través de la recollida, processament i reciclatge dels plàstics usats. Això redueix els costos de producció i preserva els recursos naturals. A més, per a la revalorització del reciclatge de plàstics d'envasos, cal millorar els processos de reciclatge de plàstic. Això inclou la innovació de noves tecnologies i processos de reciclatge, així com millorar l'eficiència dels processos existents. A més, la revalorització del reciclatge també pot ajudar a millorar la qualitat dels plàstics reciclats perquè siguen aptes per a la seva reutilització. Per tant, la revalorització del reciclatge de plàstics d'envasos és una solució ecològica i econòmica per reduir l'impacte ambiental de la producció de plàstics. S'ha estudiat la recuperació de materials poliolefínics i les alternatives mitjançant el reciclatge mecànic procedents de residus domèstics i industrials de diferent naturalesa, per tal de conèixer la possibilitat d'obtindre un material capaç de competir en alguns usos amb el material verge. Per tant, es revisa d'una manera inicial els dos principals problemes que ens trobarem a l'hora de realitzar el procés de recuperació. D'una banda, la presència d'impureses d'altres materials plàstics i altres vegades la degradació que s'ha produït sobre el material en processos anteriors o per acció d'agents externs com pot ser la llum solar. Habitualment trobarem que el material recuperat presenta una disminució de les propietats mecàniques i més dificultats en el procés de recuperació. La utilització de tècniques d'anàlisi instrumental com la calorimetria diferencial han estat les eines utilitzades per predir la qualitat del material recuperat a partir de les característiques del residu. Altres dels problemes detectats a l'hora de la revalorització del plàstic és perquè hi ha una àmplia varietat de plàstics utilitzats que són difícils de separar visualment en el flux de residus, això representa una diferència respecte a aquells els envasos dels quals són fàcils d'identificar . En aquells casos que la separació del flux de residus és senzilla, obtenim materials reciclats de gran qualitat. Això passa en la revalorització de residus procedents de la recollida selectiva. Però aquesta situació no es pot extrapolar en aquells casos que apareguin impureses. Per exemple, l'existència dels anells aromàtics fa que el Poliestirè presenti una baixa compatibilitat fins i tot amb polímers derivats de l'estirè, com és el cas de l'Acrilonitril-Butadiè-Estirè (ABS), on és recomanable l'ús de compatibilitzants per a les mescles. / [EN] The revaluation of the recycling of plastic packaging has become one of the most important environmental priorities worldwide because plastic has become one of the most used materials in the manufacture of packaging and products, due to its properties of durability, resistance and low cost. However, plastic is also one of the most difficult materials to recycle due to its resistance to degradation. Upgrading plastic packaging recycling is one solution that can help reduce the amount of plastic that ends up in landfills and oceans. The revaluation of the recycling of packaging plastics can help reduce the environmental impact of plastic production. This is achieved through the collection, processing and recycling of used plastics. This reduces production costs and preserves natural resources. In addition, for the revaluation of the recycling of packaging plastics, the plastic recycling processes must be improved. This includes innovating new recycling technologies and processes, as well as improving the efficiency of existing processes. In addition, the revaluation of recycling can also help improve the quality of recycled plastics so that they are suitable for reuse. Therefore, the revaluation of the recycling of packaging plastics is an ecological and economic solution to reduce the environmental impact of plastic production. The recovery of polyolefin materials and their alternatives through mechanical recycling from domestic and industrial waste of different natures have been studied, in order to discover the possibility of obtaining a material capable of competing in some uses with virgin material. In the work, the two main problems that we are going to find when carrying out the recovery process are reviewed in an initial way. On the one hand, the presence of impurities from other plastic materials and on other occasions the degradation that has occurred on the material in previous processes or by the action of external agents such as sunlight. In both cases we will find that the recovered material presents a decrease in its mechanical properties and also difficulties in the recovery process. The use of instrumental analysis techniques such as differential calorimetry have been the tools used to predict the quality of the material recovered from the characteristics of the residue. Other problems detected when it comes to revaluing plastic is due to the fact that there is a wide variety of plastics used that are difficult to visually separate in the waste stream, this represents a difference with respect to those whose containers are easy to identify. . In those cases where the separation of the waste stream is simple, we obtain excellent quality recycled materials. This occurs in the revaluation of waste from selective collection. But this situation cannot be extrapolated in those cases where impurities appear. For example, the existence of aromatic rings means that Polystyrene has low compatibility even with polymers derived from styrene, such as Acrylonitrile-Butadiene-Styrene (ABS), where the use of compatibilizers is recommended for their mixtures. / Peinado López-Cepero, F. (2023). Sistemas de revalorización de poliolefinas procedentes de residuos sólidos urbanos [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/194553