Des nanocomposites polyuréthane-argent (PU-Ag) ont été élaborés à l'aide de deux procédés respectueux de l'environnement et du manipulateur, dans le but de prévenir la colonisation microbienne de ces matériaux. Le premier consiste à incorporer une dispersion aqueuse de nanoparticules d'argent, réalisée ex situ, au cours du procédé de synthèse d'un PU en dispersion aqueuse. Une dispersion de nanoparticules d'argent obtenue par réduction chimique, sous micro-ondes, d'ions d'argent en présence de polyéthylèneglycol a été développée dans l'objectif d'intégrer chimiquement le PEG dans les chaînes de PU. Le second procédé réside dans la réduction photochimique, in situ, d'ions argent dans une matrice PU, en l'absence de tout autre composé chimique.La caractérisation des matériaux obtenus montre une dispersion homogène des nanoparticules d'argent avec des tailles de particules faibles (5 à 50 nm] et une activité biocide des surfaces vis-à-vis de deux souches bactériennes (Pseudomonas aeruginosa et Enterococcus faecalis) sans modification notable des propriétés physicochimiques intrinsèques du PU. / Two environment and human-friendly processes were developed to synthesize polyurethane-silver (PU-Ag) nanocomposites having biocide surfaces able preventing the microbial colonization.The first one, called ex-situ process, consists in incorporating a silver nanoparticles aqueous dispersion during the synthesis process of polyurethane, which is itself carried out in aqueous dispersion. In this case, the chemical reduction of silver ions under microwaves and in the presence of polyethyleneglycol was particularly developed with the aim to chemically incorporate the PEG in the PUchains. For the second process, silver ions dispersed inside a PU matrix were photochemically reduced in situ.The obtained materials exhibit a homogeneous dispersion of silver nanoparticles with small diameter (from 5 to 50 nm) without marked modification of the intrisic physomchemical properties of the PU. Lastly, the antibacterial properties of the surfaces aginst Pseudomonas aeruginosa and Enterococcus faecalis were confirmed.

Les bandes magnétiques sont des assemblages multicouches utilisant des réseaux polyuréthanes. Ces matériaux organiques sont utilisés en tant que revêtement protecteur contenant des pigments ou en tant que liant assurant la cohésion des charges magnétiques utilisées pour le codage d’informations. Parmi les défauts, dont l’apparition nécessite une meilleure compréhension des réactions chimiques mises en jeu lors de l’élaboration de ces assemblages, le développement d’une adhésion excessive entre les bandes et des plaques de PVC pouvant conduire à une dégradation par arrachement a été ciblé pour cette étude.L’influence des conditions de réactions (atmosphère, température et rapports molaires alcool/isocyanate) sur la cinétique de réticulation de systèmes polyuréthanes modèles a permis de quantifier les espèces réactives résiduelles à l’issue de la formation du réseau et de mettre en évidence l’implication des fonctions isocyanate dans des réactions secondaires, et une inhibition de leur réactivité lorsque les réactions ne sont pas conduites en conditions inertes. La présence d’eau dans le milieu réactionnel a été reliée l’implication des fonctions isocyanate dans la formation de liaisons urée. Enfin, la réalisation d’assemblages modèles n’a pas permis de reproduire les arrachements mais l’étude d’assemblages fournis par l’industriel suggère que le procédé utilisé pour la mise en forme de la couche de protection soit la cause de ce défaut. / Magnetic tapes are multilayer assemblies using polyurethane networks. These organic materials are used as a protective coating containing pigments or as a binder ensuring the cohesion of the magnetic charges used for the information coding. Among the defects, the appearance of which requires a better chemical reactions involved in these assemblies development understanding, an excessive adhesion development between the strips and PVC plates which can lead to degradation by tearing been targeted for this study.The reaction conditions influence (atmosphere, temperature and alcohol / isocyanate molar ratios) on the crosslinking kinetics of model polyurethane systems made it possible to quantify the residual reactive species at the network formation end and to prove the isocyanate functions involvement in side reactions, and their reactivity inhibition when the reactions are not conducted under inert conditions. The water presence in the reaction environment was related to the isocyanate functions involvement in the urea bonds formation. Finally, the model assemblies realization did not make it possible to reproduce the stripping but the assemblies provided by the industrialist study suggests that the process used for the protective layer shaping is the defect cause.

Polyurethanes (PU) are widely used synthetic polymers. The growing amount of PU used industrially has resulted in a worldwide increase of plastic wastes. The related environmental pollution as well as the limited availability of the raw materials based on petrochemicals requires novel solutions for their efficient degradation and recycling. The degradation of the polyester PU Impranil DLN by the polyester hydrolases LC cutinase (LCC), TfCut2, Tcur1278 and Tcur0390 was analyzed using a turbidimetric assay. The highest hydrolysis rates were obtained with TfCut2 and Tcur0390. TfCut2 also showed a significantly higher substrate affinity for Impranil DLN than the other three enzymes, indicated by a higher adsorption constant K. Significant weight losses of the solid thermoplastic polyester PU (TPU) Elastollan B85A-10 and C85A-10 were detected as a result of the enzymatic degradation by all four polyester hydrolases. Within a reaction time of 200 h at 70 °C, LCC caused weight losses of up to 4.9% and 4.1% of Elastollan B85A-10 and C85A-10, respectively. Gel permeation chromatography confirmed a preferential degradation of the larger polymer chains. Scanning electron microscopy revealed cracks at the surface of the TPU cubes as a result of enzymatic surface erosion. Analysis by Fourier transform infrared spectroscopy indicated that the observed weight losses were a result of the cleavage of ester bonds of the polyester TPU.

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This work reports the elucidation of the structure of a copolymer generated by the cross- catalyzed reactions of PF and pMDI prepolymers.  The electronic behavior of phenolic monomers as perturbed by alkali metal hydroxides in an aqueous environment was studied with 1H and 13C NMR.  Changes in electronic structure and thus reactivity were related to solvated ionic radius, solvent dielectric constant, and their effect on ion generated electric field strength. NMR chemical shifts were used to predict order of reactivity for phenolic model compounds with phenyl isocyanate with good success.  As predicted, 2-HMP hydroxymethyl groups were more reactive than 4-HMP in forming urethane bonds under neutral conditions and 2-HMP hydroxymethyl groups were more reactive than 4-HMP in forming urethane bonds under alkaline conditions. The structure of the reaction products of phenol, benzyl alcohol, 2-HMP, and 4-HMP with phenyl isocyanate were studied using 1H and 13C NMR under neutral organic and aqueous alkaline conditions.  Reactions in THF-d8 under neutral conditions, without catalyst, were relatively slow, resulting in residual monomer and the precipitation of 1,3-diphenyl urea from the carbamic acid reaction.  The reactions of phenol, 2-HMP, and 4-HMP in the presence of TEA catalyst favored the formation of phenyl urethanes (PU). Reactions with benzyl alcohol, 2-HMP, and 4-HMP in the presence of DBTL catalyst favored the formation of benzyl urethanes (BU).  Reactions of 2-HMP and 4-HMP led to formation of benzylphenyldiurethane (BPDU).  DBTL catalysts favored formation of BDPU strictly by a benzyl urethane pathway, while TEA favored its formation mostly via phenyl urethane, although some BU was also present.  Under aqueous alkaline conditions, 2-HMP was more reactive than 4-HMP, exhibiting an enhanced reactivity that was attributed to intramolecular hydrogen bonding and a resulting resonance stabilization of the phenolic aromatic ring. ATR-FTIR spectroscopic studies generated real time structural information for model compound reactions of the cross-catalyzed system, differentiating among reaction peaks generated by the carbamic acid reaction, PU and BU formation.  ATR-FTIR also permitted monitoring of propylene carbonate hydrolysis and accelerated alkaline PF resole condensation.  ATR-FTIR data also showed that the overall reaction stoichiometry between the PF and pMDI components drove copolymer formation.  Benzyl urethane formation predominated under balanced stoichiometric conditions in the presence of ammonium hydroxide, while phenyl urethane formation was favored in its absence.  Accelerated phenolic methylene bridge formation became more important when the PF component was in excess in the presence of sufficient accelerator.  A high percentage of free isocyanate was present in solid copolymer formed at ambient temperature. The combination of ammonium hydroxide and tin (II) chloride synergistically enhanced the reactivity of the materials, reducing the residual isocyanate. From 13C CP/MAS NMR of the copolymer, the presence of ammonium hydroxide and tin (II) chloride and the higher PF concentration resulted in substantial urethane formation.  Ammonium hydroxide favored formation of benzyl urethane from the 2-hydroxymethyl groups, while phenyl urethane formed in its absence.  The low alkalinity PF resole with ammonium hydroxide favored benzyl urethane formation.  Comparison of these results with the 13C NMR model compound reactions with phenyl isocyanate under alkaline conditions confirmed high and low alkalinity should favor phenyl and benzyl urethane formation respectively.  These cross catalyzed systems are tunable by formulation for type of co-polymer linkages, reactivity, and cost. / Ph. D.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18587号 / 工博第3948号 / 新制||工||1607(附属図書館) / 31487 / 京都大学大学院工学研究科機械理工学専攻 / (主査)教授 北條 正樹, 教授 北村 隆行, 教授 琵琶 志朗 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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During the last 50 years, plastic industry has grown exponentially with an estimated 8300 million metric tonnes of plastic produced to date. Regardless of the large variety of polymers available, 99% are entirely fossil-fuel based which compromises its degradability after use. Major synthetic polymers in use today are polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyurethane (PU) and polyethylene terephthalate (PET). The current methods for disposing of plastic waste mainly include landfilling, incineration, mechanical and chemical recycling. Despite of the significant improvement of these technologies, it is still necessary to overcome several limitations and deficiencies. Polyurethane (PU) is a synthetic polymer used as raw material in several industries. In 2015, PU global production reached 27 million metric tons, making the sixth most-used plastic worldwide. The main constituents of polyurethane are isocyanates, polyols and chain extenders. Unfortunately, the mismanaged plastic has spread out in different habitats across our planet including cold marine areas and uninhabited places, threatening wildlife and ecosystems. In order to avoid further contamination, it is necessary to transform plastic waste by restoring functional properties, providing added value and exploring new application areas that could provide economic benefits in a long- term perspective. In the last 10 years, a transition from a linear economy to a sustainable, bio-based circular economy has become fundamental to cope the fossil fuel-driven climate change and global plastic pollution. This transformation involves industrial and basic research strongly focused on biotechnology and bioprocesses. Within this transition, microorganisms are key players due to the wide diversity of enzymes and metabolic pathways that could be used for the development of sustainable processes and biomaterials. Recently, microorganisms with plastic-degrading potential have been regularly identified in different environments such as waste disposal, landfills, plastic refineries, open dumps, etc. Selective pressure and evolution of genetically flexible mechanisms have contribute to metabolize anthropogenic compounds, which it has been noted in several enzymatic reactions designed for the efficient degradation of a wide variety of recalcitrant substrates, leading to novel metabolic pathways. Even though several bacterial genera have been reported in the degradation of environmental pollutants, Pseudomonas species are amongst the most cited degraders of aromatic hydrocarbons and plastic polymers. The genus Pseudomonas incorporates one of the most complex, diverse, and ecologically significant group of bacteria on the planet. Members of this genus are found in large numbers in all the major natural environments (terrestrial, freshwater, and marine) and form intimate associations with plants and animals. This universal distribution suggests a remarkable degree of physiological and genetic adaptability. In fact, Pseudomonas have been most frequently linked with PU degradation. Chemically, polyester-based PUs are semi-crystalline structures containing hydrolysable ester and urethane bonds that are fragmented by extracellular enzymes (hydrolases), releasing oligomeric and monomeric building blocks. For instance, amines, alcohols, acids, aromatics, and other residues, such as EG (ethylene glycol), 1,4-butanediol (BDO), adipic acid (AA) ,4′-methylenedianiline (MDA) and 2,4- toluene diamine (2,4-TDA) are constantly present during PU degradation. However, MDA and 2,4-TDA are considered environmental pollutants, which represent a major risk for species in the aquatic and terrestrial areas. This fragmentation of the polymer is known as depolymerization and it is essential for strengthening recycling processes that use plastic waste as feedstock. The broad spectrum of building blocks might be used as carbon and energy source for microorganisms that degrade these compounds and/or use them for the production of higher-value elements. This latter is considered a promising upcycling strategy to reduce fossil-fuel plastic waste and promote new waste management strategies. Previous studies have revealed that extracellular enzymes are essential for biofilm formation on the polymer surface, reducing the resistance and durability of plastic materials. This first step promotes microbial attachment and further degradation. Enzymes with hydrolytic and proteolytic activity have been detected in spherical structures called outer membrane vesicles (OMVs) in several Pseudomonas species. Generally, OMVs play a key role in establishing inter- and intra-species communication, acquisition of nutrients, stress response, delivery of toxins, adhesion and virulence factors, biofilm formation, etc. Even though numerous bacterial strains and enzymes are involved in degradation processes, the complete catabolic mechanism is not totally understood yet. This thesis also centers on the characterization of outer membrane vesicles for extracellular degradation of a polyurethane oligomer and elucidation of the degradation pathway for the polyurethane monomer 2,4-diaminotoluene (2,4-TDA) by Pseudomonas capeferrum TDA1. In the first chapter, bacterial isolation from soil samples and the subsequent protocols to quantify biodegradation of polyurethane building blocks were fully described. The isolated strain was able to use a PU oligomer and 2,4-TDA as sole source of carbon. The latter compound also served as nitrogen source. These results provided a key insight into the catabolic mechanism of the soil bacterium as a potential PU monomer and oligomer-degrader. The second chapter described the identification of the isolated strain as Pseudomonas sp. by partial 16S rRNA gene sequencing, membrane fatty acid profile and structural gene for the cis/trans isomerase (cti). In addition, genomic DNA was isolated from bacterial cells grown on succinate and utilized for whole genome sequencing in order to detect catabolic genes related to aromatic compounds degradation. Preliminary, enzymes involved in the metabolic pathway were identified, which eventually led to a suggested degradation pathway for Pseudomonas sp. grown on 2,4-TDA. The strain was identified as Pseudomonas capeferrum (type strain WCS358) using the full 16S rRNA gene sequence. The third chapter reported a new method of RNA extraction from Pseudomonas capeferrum TDA1 growing on 2,4-TDA. Phenols and catechols are central intermediates of the aromatics biodegradation that can be easily oxidized to yield the corresponding quinones, which interfere with nucleic acids and tend to co- precipitate or degrade RNA. The chemical process is regulated by the activity of polyphenol oxidases enzymes, which have been identified in several Pseudomonas species previously. This optimized protocol incorporated several modifications including the use of a carrier, pooled samples and a final cleaning up step that could improve it significantly, yielded a high-quality RNA measured by A260/A280, A260/230 ratios (2.02 ± 0.16, 1.95 ± 0.01, respectively) from cells grown on 2,4-TDA compared to standard assays. Moreover, RIN (RNA integrity number) values were analyzed and samples with a RIN higher than 7.0 were selected for downstream applications, confirming the RNA quality. Finally, the fourth chapter evaluated the transcriptional changes in Pseudomonas capeferrum TDA1 grown on 2,4-TDA using RNA-seq. From all the expressed genes, one third were overexpressed in comparison to the control (succinate). These alterations in the gene expression demonstrates that aromatic compounds trigger adaptive responses that modify the transcriptional regulation mechanism including important changes not only in the catabolic system, but also in other patterns related to bacterial cell physiology and biofilm formation. In order to evaluate extracellular degradation, OMVs isolated from P. capeferrum TDA1 grown on a PU oligomer were tested for hydrolytic activity. Purified OMVs showed higher esterase activity compared to cell pellets. Relative OMV yields in TDA1 raised significantly in PU oligomer (0.28 ± 0.05%) compared to succinate (0.09 ± 0.01%). This three-fold increased activity could demonstrate that the release of OMV is part of the adaptive mechanisms of bacteria to stressful environmental conditions. The macromolecular degradation may occur through the action of both periplasmic and membrane-bound hydrolases harbored inside of OMVs and can be considered as a supporting mechanism for biodegradation. The results of this thesis present a further understanding of the transcriptome response in P. capeferrum TDA1 exposed to a PU monomer, suggest a model for extracellular degradation involving OMVs and propose a complete catabolic mechanism for the biodegradation of polyester-based PU containing intra and extracellular enzymes. Moreover, further studies on biological degradation of PU will contribute to redesign plastic polymers considering biodegradable building blocks and improving biocatalytic degradation, which could provide a sustainable use of PU plastic waste in the future.

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