Le polydicylopentadiène est un matériau aux propriétés d’usage remarquables. Il est obtenu par polymérisation par métathèse d’ouverture de cycle (ROMP) du dicyclopentadiène. Industriellement, les procédés de fabrication reposent sur le moulage à injection réactive de deux solutions de monomère: la première comprend une source de métal du groupe 6 (Mo, W), et la seconde un mélange de chloroalkyle aluminique, d’alcool et de différents additifs. Leur combinaison génère la formation in situ d’espèces actives en métathèse. Au cours de ces travaux, nous nous sommes focalisés sur la formulation à base d’aluminium. Dans un premier temps, nous avons étudié la chimie organométallique de l’aluminium en lien direct avec les formulations industrielles, ce qui nous a permis de comprendre et rationnaliser les observations faites sur ces systèmes. Puis, sur ces bases, nous avons développé de nouvelles formulations aluminiques pour l’obtention de polydicyclopentadiène en conditions industrielles, selon deux axes : modification du composant alcool, et modification du composant chloroalkyle aluminique. Certaines propriétés mécaniques des matériaux obtenus se sont avérées supérieures à celles obtenues à l’aide des procédés existants. De plus, l’apport de la chimie organométallique a été essentiel pour la compréhension de relations entre les modes de préparation et les performances des systèmes catalytiques. A l’issue de ces travaux, nous proposons une nouvelle solution industrielle pour la production de polydicyclopentadiène par moulage à injection réactive. / Polydicylopentadiene is a material featuring remarkable usage properties. It is obtained by ring opening metathesis polymerization (ROMP) of dicyclopentadiene. Industrial processes rely on the reactive injection molding of two monomer solutions: the first one contains a source of group 6 metal (Mo, W), and the second one, a mixture of chloroalkylaluminum, alcohol and various additives. Their combination generates in situ active species that perform metathesis. In the present work, we focused on the aluminum-based formulation. We have first studied the aluminum organometallic chemistry that is directly connected to the industrial formulations, which allowed us to understand and rationalize the observations made on these systems. Then, from this point on, we developed new aluminic formulations for polydicyclopentadiene preparation under industrially relevant conditions, working along two directions: modification avec the alcohol component, and modification of the chloroalkyl aluminum species. Some mechanical properties of the thus obtained materials proved to be better than those resulting from classical processes. Furthermore, the input from organometallic chemistry was critical to the understanding of the relationships between preparation modes and performances of the catalytic systems.From this study, we propose a new industrial solution for the production of polydicyclopentadiene by reactive injection molding.

This thesis discuses two very different projects. In the first project, synthesizing a polymer with the potential to release H2S. This was accomplished through the copolymerization of L-lactide and lactide monomers that has been functionalized with 4-hydroxythiobenzamide which is known to release H2S in vivo. The synthesis of the functionalized monomer required the development of a new method to attach functional groups to a derivative of L-lactide, which involved the addition of a thiol to an alpha- beta-unsaturated lactide using catalytic I2. After polymerization, the molecular weight of the copolymers ranged from 8 to 88 kg mol-1 with PDIs below 1.50. These polymers have the ability to be loaded with different amounts of thiobenzamide by controlling the ratio of the functionalized monomer with L-lactide during polymerization. The copolymers were fabricated into two sizes of microparticles with average diameters of 0.52 and 12 µm. The degradation of the smaller microparticles was studied in a PBS buffered solution at pH 7.4 which showed the slow release of the thiobenzamide over a 4 week period. These microparticles are the first to show potential to deliver H2S over a period of weeks. This research addresses a critical need in the field of H2S in medicine where no method exists to release H2S in vivo at times over a few hours. In the second project dicyclopentadiene was polymerized with Grubbs first generation catalyst and fabricated into highly cross-linked membranes with a thickness of 100 µm. The flux of twenty-one molecules with varying polarities and molecular weights ranging from 101 to 583 g mol-1 were studied. Molecules that permeated these membranes had flux rates of 10-5 to 10-6 mol cm-2 h-1 but molecules that did not permeate these membranes had flux rates 104 to 105 times slower. The large difference in flux did not have a strong correlation to molecular weight or solubility in the membrane. However, there was a strong correlation to the cross-sectional areas of the molecules. Cross-sectional area is the smallest two-dimensional rectangle determined by molecular modeling. The cross-sectional area cut-off of the membranes was determined to be between 0.38 and 0.50 nm2. This property gives these membranes the selectivity to successfully separate constitutional isomers, such as tributylamine and triisobutylamine. The membranes have also been used to separate organic products from expensive catalyst and ligands as well as different fatty acids from each other as their respective amine salts.

No / The cure of polydicyclopentadiene conducted by ring-opening metathesis polymerisation in the presence of a Grubbs catalyst was studied using non-invasive Raman spectroscopy. The spectra of the monomer precursor and polymerised product were fully characterised and all stages of polymerisation monitored. Because of the monomer's high reactivity, the cure process is adaptable to reaction injection moulding and reactive rotational moulding. The viscosity of the dicyclopentadiene undergoes a rapid change at the beginning of the polymerisation process and it is critical that the induction time of the viscosity increase is determined and controlled for successful manufacturing. The results from this work show non-invasive Raman spectroscopic monitoring to be an effective method for monitoring the degree of cure, paving the way for possible implementation of the technique as a method of real-time analysis for control and optimisation during reactive processing. Agreement is shown between Raman measurements and ultrasonic time of flight data acquired during the initial induction period of the curing process.

The formation of a functional surfaces combines the properties of a substrate and monolayer to produce a new hybrid that can combine aspects of each. Monolayers can be made on many surfaces, and well defined functionalized monolayers were assembled on for silicon(111) and polydicyclopentadiene (PDCPD). Acid terminated monolayers were assembled on silicon(111) and their functionalization chemistry explored. It was shown that using trifluoroacetic anhydride to generate an intermediate reactive anhydride, the surface could be functionalized with amines. It was further shown that using soft lithography these functionalized surfaces could be patterned. Mixed monolayers of methyl and olefin terminated surfaces on silicon(111) were used to develop a new soft lithographic technique with polydimethylsiloxane (PDMS). PDMS can be controllably etched using fluoride species. The surface is first activated by the attachment of the Grubbs' 1st generation catalyst. A PDMS microfluidic device is then placed on the surface. By using a cross metathesis reaction, the exposed channel can be pacified. The next step, a fluoride etchant is used to remove PDMS, exposing an unreacted surface. Polymer brushes were then grown by ring opening metathesis polymerization (ROMP) in this region. Functionalization of the emerging polymer PDCPD was conducted through two different routes. ROMP formed PDCPD has double bonds that can be functionalized. In the first process, the double bonds were reacted with bromine. This is a rapid reaction and proceeds to a significant depth in the material. Bromines can then be displaced with amines in a substitution reaction. This was demonstrated with a fluorinated amine that when examined by XPS were shown to be present only at the surface, further more we were able to pattern this surface too. Secondly, a process using epoxides was developed. The epoxidation reaction could not be quantified, but formation in the second step of an amine functionalized surfaces was observed by XPS. Further reaction of surface hydroxyls was also observed. This was also used to grow polyethylimine from the surface to sufficient thickness that it became observable by infrared spectroscopy.

Dicyclopentadiene (DCPD), a tricyclic olefin, is available from the C5 fraction of petroleum feedstocks. Owing to its high reactivity (due to the presence of a strained alkene), low cost, and lack of other commercial uses, DCPD has been extensively pursued as a monomer for use in ring-opening metathesis polymerization processes. The olefin metathesis reaction, for which Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock received the 2005 Nobel prize, is among the most attractive approaches to polymerize olefins, allowing production of high-molecular weight polymers including linear macromolecules, block copolymers, and crosslinked materials. Polydicyclopentadiene (PDCPD), which can be produced using a variety of early- and late-transition metal catalysts, is a thermoset polymer with a highly crosslinked structure. PDCPD has excellent impact strength, high storage modulus, good chemical resistance, wide service temperature range, and low density. As a result, it has found broad commercial utility in industrial manufacturing. Additionally, the reaction injecting molding (RIM) process used for DCPD polymerization makes it possible to precisely control the shape and dimensions of PDCPD products. Owing to its lack of chemical functionality, however, polydicyclopentadiene has many limitations. Previously, our research group developed a modified dicyclopentadiene monomer by adding an electron withdrawing group – a methyl ester functional group – on the pendent cyclopentene ring of the monomer. Polymerization of this functionalized monomer led to a novel thermoset material – methyl ester functionalized polydicyclopentadiene (fPDCPD) – that exhibits tunable surface hydrophobicity. In experiments described in this dissertation, my collaborators and I confirmed the thermal crosslinking mechanism of fPDCPD using a combination of solution-state and solid-state NMR, FTIR, and Raman spectroscopy. We also explored the surface chemistry of our novel material, by harnessing the embedded functional group in order to exert finer control over hydrophobicity, and to control interactions with biological organisms through the conjugation of biologically relevant functional groups. To further extend the utility of our functionalized dicyclopentadiene monomer, we synthesized a series of statistical polymers: fPDCPD-stat-PDCPD. Once again, we used a wide range of characterization methods, and showed that we can both tune the surface hydrophobicity of the copolymers and manipulate the mechanical properties by adjusting the molar fractions of functionalized and non-functionalized monomers. Chemical structures of these copolymers were interrogated by NMR, FTIR, and Raman spectroscopy. Frontal ring-opening metathesis polymerization was applied in an effort to study the kinetics of (co)polymerization. Finally, to lay the groundwork for future fPDCPD manufacturing, we successfully optimized the production of fDCPD monomers to half-kilo scale and fPDCPD polymers at 20-gram scale, while developing a reaction-injection molding process that permitted the production of dimensionally controlled fPDCPD objects. This in turn allowed us to conduct a rigorous assessment of the mechanical properties of our fDCPD through dynamic mechanical analysis (DMA), which established for the first time that our functionalized material has a comparable storage modulus to that of the parent (unmodified) PDCPD. The development of fPDCPD is approaching a new stage where it is ready to be commercialized and mass produced. We hope that our novel fPDCPD material will soon play a crucial role in replacing traditional metallic components in vehicle design and engineering material manufacturing. / Graduate / 2021-12-14

Le polydicyclopentadiène (PDCPD) est un polymère thermodurcissable synthétisé à partir de la polymérisation par métathèse par ouverture de cycle, qui présente l'avantage d'un temps de polymérisation court du fait de la présence de doubles liaisons et de l'utilisation de catalyseurs organométalliques. Dans cette thèse, PDCPD est considéré comme un candidat pour des applications en milieu marin, pour lesquelles la question de la durabilité doit être évaluée. L'objectif de ce travail est d'établir un modèle cinétique non empirique pour la prédiction de la durée de vie du PDCPD au cours de l'oxydation thermique. Tout d'abord, la caractérisation par spectroscopie Infrarouge et dosages des peroxydes au cours de l’oxydation a été réalisée afin de mettre en place un modèle cinétique pour le PDCPD sans stabilisant. En particulier, les constantes de vitesse d'initiation ont été identifiées par une étude de la thermolyse des hydroperoxydes; les constantes de vitesse de terminaison ont été obtenues par des expériences spécifiques sous différentes pressions d'oxygène. L'effet du catalyseur sur la cinétique d'oxydation a également été étudié dans ce travail. La consommation de doubles liaisons du polymère entraîne une augmentation significative de la concentration de nœuds de réticulation, puis une augmentation de la contrainte de rupture de PDCPD. Le modèle cinétique créé prédit ces tendances ainsi que l'épaisseur de la couche oxydée. L'effet des stabilisants visant à ralentir la vitesse d'oxydation a également étudié expérimentalement puis modélisé. En particulier, les amines encombrées (HALS) se sont révélées très efficaces et compatibles avec les catalyseurs de la ROMP. Dans la dernière partie, l’effet de l’oxydation thermique du PDCPD sur le comportement de sorption de l’eau a été étudié. Le PDCPD vierge présente une très faible absorption d'eau à cause de sa structure apolaire, alors que le PDCPD vieilli est plus hydrophile en raison de la formation de groupes polaires ce qui peut avoir une influence sur sa durée de vie en milieu marin. / Polydicyclopentadiene (PDCPD) is a thermoset polymer synthesized from ring opening metathesis polymerization with the advantage of short processing time due to the presence of double bonds and the use of organometallic catalysts. In this thesis, PDCPD is for example considered as a candidate for the field-joint in a marine environment. The question of the durability of PDCPD has to be assessed. The objective of this work is to establish a non-empirical kinetic model for the lifetime prediction of PDCPD during thermal oxidation. Firstly, the characterization by Infrared spectroscopy and peroxide titration of PDCPD during its thermal oxidation was conducted to set up a kinetic model for additive-free PDCPD. In particular, the initiation rate constants have been identified especially through hydroperoxide decomposition rates; the termination rate constants have been obtained by specific experiments under various oxygen pressures. The consumption of double bonds in the polymer causes a significant increase in crosslink concentration then increasing yield stress of PDCPD. The kinetic model predicts those trends as well as the thickness of the oxidized layer. The effect of stabilizer aimed at slowing down the oxidation rate was also experimentally studied and modeled. In particular, hindered amine stabilizers were shown to be promising candidates with good stabilizing properties and compatible with ROMP catalysts. Lastly, the effect of thermal oxidation of PDCPD on water sorption was investigated. Virgin PDCPD presents very low water absorption due to its apolar groups. Whereas, aged PDCPD shows increased hydrophilicity associated with polar groups build-up (which can probably impact its lifetime in marine conditions.

The use of plastic materials in the design of vehicle components is primarily driven by the need for vehicle weight and cost reduction. Additionally, these materials give design engineers freedom in creating appealing exterior designs. However, creating self-carrying exterior structures with polymers must fulfill long-term strength, creep and fatigue life requirements. Thus, the polymer polyDicyclopentadiene (pDCPD) has been chosen for this purpose. Its aging mechanics need to be understood by the design engineers to make the right decisions. This thesis has carried out mechanical tests such as uniaxial tensile testing, fatigue, and creep testing. Digital image correlation (DIC) system has been used to capture strain data from tensile tests. In the final analysis, DIC measurements proved more accurate than extensometer data retrieved from the testing machine. The rise in temperature has been captured using thermal imaging. Several degradation processes have been explored including physical aging, thermo-oxidation, photo-oxidation, chemical- and bio- degradations. Test results showed significant changes in mechanical properties after 17 years of aging. Additionally, severe thermal degradation has been observed in one of the tested panels of pDCPD. Temperature can rise to significant levels during cyclic loading at high stresses, which could have an impact on physical aging effects. Viscoelastic behavior has been explored and changes in dynamic and creep properties have been observed. The investigation also reviled that different defects caused by flawed manufacturing also can affect the material severely as one case has proved in this research.