Abstract: Poly (vinylidene fluoride) (PVDF), thanks to its versatile properties, finds many applications ranging from water purification membranes (thermal and chemical stability) to electronic devices (piezoelectric, pyroelectric and ferroelectric properties). Block copolymers of PVDF with other polymers further expand its properties and, consequently, its applications. Toward this line, my thesis investigates the synthesis, molecular characterization and properties of novel PVDF-based copolymers mainly with poly(tert-butyl acrylate) (PtBuA), poly(methyl methacrylate) (PMMA) and polystyrene (PSt). To prepare the block copolymers a living polymerization is needed, which is compatible with the VDF and the comonomer (tBuA, MMA, St). For this purpose, we used iodine transfer polymerization (ITP) with the difunctional chain transfer agent (CTA) C4F8I2. Difunctional macroinitiator (I-PVDF-I) was first obtained by ITP of VDF monomer with C4F8I2, followed by addition of the comonomer tBuA, MMA or St to afford the triblock copolymers poly(tert-butyl acrylate)-block-poly(vinylidene fluoride)-block-poly(tert-butyl acrylate) (PtBuA-b-PVDF-b-PtBuA), poly(methyl methacrylate)-block-poly(vinylidene fluoride)-block-poly(methyl methacrylate) (PMMA-b-PVDF-b-PMMA) and polystyrene-block-poly(vinylidene fluoride)-block-polystyrene (PSt-b-PVDF-b-PSt). The structure of all intermediates and final products were characterized by Nuclear Magnetic Resonance (NMR) and Gel Permeation Chromatography (GPC). The microstructure and polymorphism of all triblock copolymers, characterized by XRD, shown that the PVDF in the first two copolymers exhibits the electroactive β-phase, while in the third copolymer there is the coexistence of α- and γ-phases. Linear PVDF homopolymers, using the free radical and IT polymerizations, were prepared for comparison purposes. All linear polymers possess the α-phase. The thesis is divided into the following five chapters: 1. Introduction, where the scope of this thesis is given with a brief background on PVDF; 2. Literature Review, where a summary of previously published works on PVDF synthesis and polymorphism is presented; 3. Experimental Section, where detailed procedures and characterization methods are given; 4. Results and Discussion, where outcomes of successful experiments are discussed; and 5. Conclusion and Perspective, where the outcomes of this work are summarized and perspective are discussed.

Recycling is one of the most important strategies for combating plastic pollution. However, before plastic waste can be converted into other items, the different types of plastic present in it must be sorted, a time-consuming and expensive process. Indeed, it is often more cost-effective to manufacture new plastic materials than to recycle existing plastic waste. Researchers are therefore attempting to eliminate the sorting process altogether and directly recycle the mixed plastic waste. While this would lead to phase-separated mixtures with temporally evolving domains and poor fracture toughness properties, these problems could be mitigated to some extent by incorporating surfactant-like macromolecular compatibilizers, such as block copolymers or random copolymers (RCPs). These compatibilizers preferentially localize at polymer/polymer interfaces, lowering droplet coalescence and interfacial tension in the process. Moreover, the macromolecular structure of these compatibilizers enables them to form entanglement networks across the interface, thus enhancing stress transfer and fracture toughness. Nanoparticle (NP)-based compatibilizers have recently attracted attention due to their significantly stronger suppression of droplet coalescence under certain conditions. Unfortunately, while these compatibilizers work relatively well in oil/water emulsions, they perform poorly in immiscible polymer blends. This is because most polymer blends consist of hydrophobic components, making the NPs gravitate toward one of the bulk phases rather than the interface. Moreover, their rigid cores function as stress concentrators in polymer matrices, causing further deterioration to the fracture toughness properties of the blend. In this dissertation, we construct hybrid compatibilizers consisting of NP cores and outer grafted polymer layers. In this manner, the desired features of both macromolecules and NPs are combined into a single compatibilizer: the NP cores suppress droplet coalescence, while the polymer grafts direct the NPs to the interface and form entanglements. We investigate the effectiveness of these hybrid compatibilizers in three critical areas: NP localization control, droplet coalescence suppression, and fracture toughness enhancement. In each area, we perform systematic studies using an immiscible polymer blend composed of poly(methyl methacrylate) (PMMA) and polystyrene (PS) in order to find the optimal compatibilizing effect as a function of graft chemistry, graft molecular weight, and grafting density. We demonstrate that the most efficient hybrid compatibilizers are those with a surfactant-like architecture. For example, silica NPs sparsely grafted with PS chains can form a dense monolayer packing at the immiscible PMMA/PS interface. In this example, surfactancy is derived from a balance of enthalpic interactions: the silica core strongly interacts with the PMMA phase, while the PS grafted layer mixes intimately with the PS phase. The hydrophilic–lipophilic balance is readily controlled by varying the contact area of each interaction through the grafting density or the graft molecular weight. Similarly, we show that silica NPs grafted with surfactant-like polymer chains, such as styrene–methyl methacrylate RCPs, can also localize at the PMMA/PS interface. Here, surfactancy is derived mainly from the RCP grafts. There are two advantages to using RCP grafts. First, it allows for interfacial localization even if the grafted layer completely encapsulates the silica core (i.e., at high grafting densities). Second, RCP grafts can entangle on both sides of the interface and thus transmit stress more efficiently than PS grafts, which only entangle on the PS side of the interface. There are two advantages to using this latter approach. First, RCP grafts can entangle on both sides of the interface and thus transmit stress more efficiently than PS grafts, which only entangle on the PS side of the interface. Second, it allows for interfacial localization even if the grafted layer completely encapsulates the silica core (i.e., at high grafting densities). Our research shows that both forms of hybrid compatibilizers significantly outperform conventional ungrafted macromolecular compatibilizers in droplet coalescence suppression. Interestingly, coalescence can be suppressed even when the hybrid compatibilizers only partially cover the dispersed droplets. We believe that this is due to the grafted layers forming strong entanglement networks around the droplets that function as barriers to coalescence. Linear rheology experiments corroborate this reasoning: the low-frequency storage moduli of the compatibilized blends approach a plateau when the NP grafting density is increased, suggesting the presence of a network structure at the interface. For fracture toughness experiments, we employ RCP-grafted NPs to exploit their entanglement on both sides of the interface. We show that when a moderate grafting density is used, the fracture toughness of the PMMA/PS interfaces exceeds that of the interfaces compatibilized with ungrafted RCP analogs. This again results from the brush entanglement network at the interface. Specifically, in the moderate grafting density zone, RCP brushes form a more connected entanglement network than ungrafted RCPs and are thus more efficient at transmitting stress across the interface. In summary, we have developed a method for accurately controlling the localization of NP-based compatibilizers in immiscible polymer blends. We have also identified the grafting conditions under which these hybrid compatibilizers outperform conventional macromolecular compatibilizers in both droplet coalescence suppression and fracture toughness enhancement.

L’électronique embarquée, notamment les modules de puissance, permet la gestion de l’énergie électrique et donc le développement de véhicules « décarbonés ». Toutefois, en vue d’être positionnés près du moteur thermique, ces composants électroniques devront résister à des environnements très divers et parfois à de sévères contraintes (humidité, agression chimique (huiles), vibrations…). Or, les matériaux d’encapsulation qui les protègent ne sont pas, aujourd’hui, assez performants pour répondre à ces nouvelles contraintes. Ainsi, le but de ces travaux de thèse est donc de développer de nouveaux polymères d’encapsulation. Pour cela, deux types de copolymères Silicone/Polyuréthane (Si/PU) réticulés ont été synthétisés, sans solvant, et avec des temps de polymérisation courts.Une première série de matériaux Si/PU contenant entre 55 et 76%m de motif silicone, a été synthétisée par polyaddition alcool-isocyanate à partir de précurseurs silicone, synthétisés ou commerciaux, et d’un pluriisocyanate, en présence d’un catalyseur. Une seconde série de copolymères Silicone/Polyhydroxyuréthane (Si/PHU) contenant 26 et 61%m de motif silicone a été obtenue sans isocyanate et sans catalyseur, à partir de poly(diméthylsiloxane) biscyclocarbonate et d’une triamine.Les propriétés mécaniques, thermiques et le caractère hydrophobe de tous ces matériaux ont été évalués. Dans le but d’améliorer les propriétés thermiques et de diminuer le coût de la résine d’encapsulation, des charges inorganiques ont été incorporées à certains polymères Si/PU.Les matériaux les plus intéressants ont été testés comme encapsulant dans des modules de puissance et les premières mesures électriques au cours de cyclages thermiques sont très prometteuses. / Embedded electronics, particularly power modules, allows management of electric energy and therefore development of “carbon-free” vehicle. However, these electronic components, will shortly be located near heat engine automotive, and they must withstand various environments and sometimes, hard stresses (humidity, chemical aggression (oil), vibrations…). But actual encapsulation materials are not today efficient enough to match with these future imposed stresses. Thus, the aim of this work is to develop new encapsulation polymers. For this, two types of crosslinked Silicone/Polyurethane (Si/PU) copolymers were “solvent-free” synthesized and with short polymerization times.A first series of materials Si/PU containing between 55 and 76%wt silicone units were synthesized by alcool-iscyanate polyaddition from silicone precursor, synthesized or commercial, and a pluri-isocyanate, in the presence of catalyst. A second series of copolymers, Silicone/Polyhydroxyurethane (Si/PHU) containing 26 and 61%wt silicone units, was obtained without isocyanate or catalyst from poly(dimethylsiloxane) biscyclocarbonate and a triamine.Mechanical and thermal properties as well as hydrophobic character of all materials were evaluated. In order to improve thermal properties and decrease the cost of encapsulation resin, inorganic fillers were blended in some of Si/PU polymers.The most interesting materials were tested as encapsulant in power modules, and the first electrical measurements during thermal cyclings were very promising

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17894号 / 工博第3803号 / 新制||工||1582(附属図書館) / 30714 / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 大嶋 正裕, 教授 山本 量一, 教授 宮原 稔 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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Ring opening metathesis polymerization (ROMP) is established as one of the efficient controlled living polymerization methods which have various applications in polymer science and technology fields. The research presented in this dissertation addresses several applications of multifunctional well-defined norbornene-based block copolymers synthesized by ROMP using ruthenium-based Grubbs catalysts. These novel block copolymers were applied to stabilize maghemite nanoparticles, creating the superparamagnetic polymeric nanocomposites. The Jaggregation properties of the porphyrin dyes were improved via self-assembly with a customized norbornene polymer. Novel multimodal copolymer probes were synthesized for two-photon fluorescence integrin-targeted bioimaging. In Chapter 1 a brief overview of ROMP along with ruthenium metal catalysts and selected applications of the polymers related to this research is presented. Superparamagnetic maghemite nanoparticles are important in biotechnology fields, such as enhanced magnetic resonance imaging (MRI), magnetically controlled drug delivery, and biomimetics. However, cluster formation and eventual loss of nano-dimensions is a major obstacle for these materials. Chapter 2 presents a solution to this problem through nanoparticles stabiulized in a polymer matrix. The synthesis and chracterization of novel diblock copolymers, consisting of epoxy pendant anchoring groups to chelate maghemite nanoparticles and steric stabilizing groups, as well as generation of nanocomposites and their characterization, including surface morphologies and iv magnetic properties, is discussed in Chapter 2. In Chapter 3, further improvement of the nanocomposites by ligand modification and the synthesis of pyrazole-templated diblock copolymers and their impact to stabilize the maghemite nanocomposite are presented. Additionally, the organic soluble magnetic nanocomposites with high magnetizations were encapsulated in an amphiphilic copolymer and dispersed in water to assess their water stability by TEM. To gain a preliminary measure of biocopatibility of the micelle-encapsulated polymeric magnetic nanocomposites, cell-viability was determined. In Chapter 4, aggregation behaviors of two porphyrin-based dyes were investigated. A new amphiphilic homopolymer containing secondary amine moieties was synthesized and characterized. In low pH, the polymer became water soluble and initiated the stable Jaggregation of the porphyrin. Spectroscopic data supported the aggregation behavior. Two photon fluorescence microscopy (2PFM) has become a powerful technique in bioimaging for non-invasive imaging and potential diagnosis and treatment of a number of diseases via excitation in the near-infrared (NIR) region. The fluorescence emission upon two-photon absorption (2PA) is quadratically dependent with the intensity of excitation light (compared to the linear dependence in the case of one-photon absoprtion), offering several advantages for biological applications over the conventional one-photon absorption (1PA) due to the high 3D spatial resolution that is confined near the focal point along with less photodamage and interference from the biological tissues at longer wavelength (~700-900 nm). Hence, efficient 2PA absorbing fluorophores conjugated with specific targeting moieties provides an even better bioimaging probe to diagnose desired cellular processes or areas of interest The αVβ3 integrin v adhesive protein plays a significant role in regulating angiogenesis and is over-expressed in uncontrolled neovascularization during tumor growth, invasion, and metastasis. Cyclic-RGD peptides are well-known antagonists of αVβ3 integrin which suppress the angiogenesis process, thus preventing tumor growth. In Chapter 5 the synthesis, photophysical studies and bioimaging is reported for a versatile norbornene-based block copolymer multifunctional scaffold containing biocompatible (PEG), two-photon fluorescent (fluorenyl), and targeting (cyclic RGD peptide) moieties. This water-soluble polymeric multi scaffold probe with negligible cytotoxicity exhibited much stronger fluorescence and high localization in U87MG cells (that overexpress integrin) compared to control MCF7 cells. The norbornene-based polymers and copolymers have quite remarkable versatility for the creation of advanced functional magnetic, photonic, and biophotonic materials.

Styrenic block copolymer thermoplastic elastomers are one of the most widely used thermoplastic elastomers (TPEs) today. The focus of this research is to fundamentally understand the structure-processs-property relationships in these materials. Deformation behavior of the block copolymers with cylindrical and lamellar morphologies has been investigated in detail using unique techniques like deformation calorimetry, transmission electron microscopy (TEM), combined in-situ small angle x-ray and wide angle x-ray scattering (SAXS/WAXS). The research involves the study of structural changes that occur at different length scales along with the energetics involved upon deformation. The structural changes in the morphology of these systems on deformation have been investigated using combined SAXS/WAXS setup. Small angle x-ray scattering probed the changes at the nano-scale of polystyrene (PS) cylinders, while wide angle x-ray scattering probed the changes at molecular length scales of the amorphous/crystalline domains of the elastomeric mid-block in these systems. TEM analysis of the crosslinked elastomers (by UV curing) further confirms the interpretation of structural details as obtained from SAXS upon deformation. New structural features at both these length scales have been observed and incorporated into the overall deformation mechanisms of the material. Characteristic structural parameters have been correlated to differences in their mechanical response in the commercially relevant cylindrical block copolymers. Effect of various process conditions and thermal treatments has been investigated. The process conditions affect the structure at both micro-scopic (grain size) and nano-scopic (domain size) length scales. A correlation has been obtained between a mechanical property (elastic modulus) and an easily measurable structural parameter (d-spacing). Effect of various phase transitions such as order-to-order transition has been studied. Selective solvents can preferentially swell one phase of the block copolymer relative to other and thus bring a change in morphology. Such kinetically trapped structures when annealed at higher temperature try to achieve their thermodynamic equilibrium state. Such changes in morphology significantly affect their tensile and hysteretic response. In another work it has been shown that by carefully compounding these styrenic block copolymers having different morphologies, it is possible to completely disrupt the local scale order and remove the grain boundaries present in these materials. Finally, a new test technique has been developed, by modifying an existing Charpy device to test polymeric films at a high strain rate. A custom designed load-cell is used for force measurements which imposes harmonic oscillations on a monotonic loading signal. The data obtained from this device can be used to analyze visco-elastic response of polymeric films at frequencies much higher than the conventional dynamic mechanical analyzer (DMA).