Tesis sobre el tema "Furanic polymers"

Cette thèse de doctorat s'est déroulée dans le cadre du projet ANR FUTURES (Furanic TUnable REsins for Sustainable materials, i.e., Résines furaniques modulables et durables). L'alcool polyfurfurylique est un polymère thermodurcissable biosourcé qui possède d'excellentes propriétés chimiques et thermiques malgré un comportement cassant. L'objectif de ce projet est d'ouvrir la voie à de nouvelles applications pour l'alcool polyfurfurylique en exploitant les réactions secondaires qui ont lieu lors de la polymérisation. Cela permettra d'apporter de nouvelles fonctionnalités au matériau réticulé et de jouer sur la fragilité du matériau.Premièrement, les groupements carbonyls résultants de l'ouverture du cycle furanique lors de la polymérisation de l'alcool polyfurfurylique ont été quantifiés par potentiométrie et RMN quantitative. Les facteurs influençant le taux de carbonyls dans le polymère ont été évalués et la présence additionnelle d'eau au cours de la polymérisation s'est révélé être un facteur capital. Ensuite, l'environnement chimique des carbonyls a été apprécié par l'utilisation de RMN bidimensionnelle et un nouveau phénomène de réticulation de surface a été identifié et expliqué. L'impact de cette réticulation de surface sur les propriétés finales du matériau a été également mis en avant. Enfin, la présence de carbonyls résultant de l'ouverture de cycle a été exploitée pour fonctionnaliser le polymère post-réticulation. En utilisant des amines flexibles, le matériau passe progressivement d'un comportement cassant à un comportement plus ductile, permettant ainsi d'entrevoir de nouvelles applications. Les facteurs gouvernant les propriétés des matériaux fonctionnalisés par les amines ont également été étudiés<br>This doctoral project was conducted within the ANR FUTURES (FUranic TUnable REsins for Sustainable materials) project.Poly(furfuryl alcohol) is a bio-based thermoset with excellent chemical and thermal properties. Yet, it may mechanically behave in a brittle manner. The aim of the project was to pave the way for new applications of poly(furfuryl alcohol) by exploiting side reactions occurring during polymerization. This leads to additional functionalities that could be exploited to, among others, reduce the brittleness of the material.First, the reactive carbonyl resulting from the furan ring opening side reaction were quantified by potentiometry and quantitative NMR. The key factors that were influencing the carbonyl content were assessed and water proved to be the main one. The chemical nature of the carbonyls was thoroughly investigated by 2D NMR and a new surface crosslinking phenomenon was identified and explained. The impact of this surface crosslinking on the materials' properties was evaluated. Finally, the presence of carbonyls due to the ring-opening side reaction was exploited to functionalize the polymer. The use of large flexible amines allowed to shift the materials properties from brittle to ductile therefore paving to way to new applications for poly(furfuryl alcohol). Finally, factors governing the properties of the amine-functionalized materials were studied

Le travail de cette these a concerne la synthese, la caracterisation et l'etude de proprietes d'usage de structures oligomeres et polymeres conjuguees. L'originalite de ces travaux reside d'une part dans l'utilisation d'heterocycles furaniques et thiopheniques comme elements constitutifs des chaines et d'autre part, dans le fait que de nombreux composes oligomeres ont ete cibles, isoles et caracterises. Les possibilites d'application de ces materiaux dans les domaines touchant a l'electronique (conducteurs ou semi-conducteurs), a l'optique (cristaux liquides) et a la luminescence photo- et electroinduite, ont ete ensuite explorees. Ces recherches se divisent en cinq themes : (i) etude des reactions de polycondensation en milieu basique du 5-methyl furfural et du 5-2-(5-methyl furyl vinylene)furfural, avec caracterisation precise des oligo(furylene vinylene)s resultants et des polymeres correspondants. Etude des proprietes de conduction electronique apres dopage a l'iode. Etude de la photoluminescence. (ii) synthese et caracterisation d'oligo(heteroarylene vinylene)s furaniques, thiopheniques et mixtes par condensation en milieu basique de monomeres furaniques et/ou thiopheniques. (iii) synthese et caracterisation de bases de schiff ene-heterocycliques/aromatiques mono- et difonctionnelles. Etudes des proprietes thermiques et plus particulierement du comportement mesogene de ces structures. (iv) preparation d'electrolytes polymeres reticules (macrobases de schiff) : formation photochimique du reseau via la presence intrinseque d'unites -2,5-fu-ch = ch-fu-2,5-chromophores. Etude de la conductivite ionique apres dopage avec des sels de lithium. (v) preparation de polyacetylenes monosubstitues par des esters 2-furoiques dans le but d'obtenir des materiaux solubles et possedant, sous forme de membrane des proprietes de permeabilite selective des fluides.

In the current context of oil resources rarefaction, the development of biobased polymers is of major importance. The present work focused on the development of a biobased amorphous polyphthalamide, based on furan-2,5-dicarboxylic acid. The first part of the study was devoted to the development of a molecular modelling protocol that could calculate the glass transition temperature of polyphthalamides with accuracy. In order to do this, model polyphthalamides based on isophthalic, terephthalic acid and hexamethylene diamine were synthesized and characterized as well as simulated. By comparison between simulated and measured Tg, the protocol was validated. In a second part of the study, this protocol was applied to FDCA based polyphthalamides. These PPA were also synthesized. It was found that the PA 6-F undertakes a decarboxylation, preventing it from reaching high a molar mass. It was also found that the mechanical and thermal properties decrease as the amount of FDCA in the copolymers increases.

In this study, a novel series of conjugated monomers containing furan and fluorene units<br>2,7-di(furan-2-yl)-9H-fluoren-9-one (FOF), 2-(2-(furan-2-yl)-9H-fluoren-7-yl)furan (FFF), and 2-(2-(furan-2-yl)-9,9-dihexyl-9H-fluoren-7-yl)furan (FHF) were synthesized and their electrochemical polymerization were achieved via potential cycling. Optical and electrochemical properties of the polymers, poly(2,7-di(furan-2-yl)-9H-fluoren-9-one) (PFOF), poly(2-(2-(furan-2-yl)-9H-fluoren-7-yl)furan (PFFF) and poly(2-(2-(furan-2-yl)-9,9-dihexyl-9H-fluoren-7-yl)furan) (PFHF) were investigated and it was found that polymer films exhibit reversible redox behavior (Epox = 1.083 V for PFOF, Epox= 0.915 V for PFFF and Epox= 0.985 V for PFHF) accompanied with a reversible electrochromic behavior, orange to green for PFOF, yellow to dark blue for PFFF and orange to green for PFHF during oxidation. Their band gap values (Eg) were found to be 2.32, 2.49 and 2.61 eV for PFOF, PFFF and PFHF, respectively.

Ce travail est développé dans le but d’élaborer, caractériser et mettre en œuvre de matériaux polymères à base de polysemicarbazides et polyesters furaniques bio-sourcés. L’étude comporte trois grandes parties : la synthèse et l’optimisation du procédé de synthèse de poly(acylsemicarbazide)s, la préparation de quelques mélanges de polymères en mini-bivis de polymères furaniques (PEF ou PSC) avec le PET, le PLA et le PHA et l’élaboration de nouveaux copolyesters furano-aliphatiques par polymérisation par ouverture de cycle (PEF/PCL) ou par réactions d’interéchanges à l’état fondu de mélange d’homopolymères (PEF/PCL, PEF/PLA et PEF/PHA). Nous rapportons dans le premier chapitre de ce mémoire la synthèse d’une série de dihydrazides bifuraniques et l’étude de leur réactivité vis-à-vis de divers diisocyanates aromatiques afin d’élaborer des polyacylsemicarbazides furano-aromatiques. Notre étude est abordée en examinant le comportement d’un système de monomères modèle dans différentes conditions expérimentales afin d’optimiser le procédé de polycondensation avant de l’appliquer à diverses combinaisons de monomères. Nous traitons dans le deuxième chapitre l’élaboration de nouveaux matériaux à base de polymères furaniques (PEF ou PSC) par mélange de polyesters à l’état fondu. Pour cela, nous avons élaboré 3 types de mélanges polyester furaniques / polyesters aliphatiques et aromatiques. Enfin, nous nous intéressons dans le troisième chapitre à la synthèse de divers polyesters furaniques à extrémités contrôlées : PEF-dihydroxy (PEF di-OH), PEF-dicarboxylé (PEF di-COOH), PEF-diéthylester (PEF di-COOEt) et PEF à extrémités mixtes (PEF di-OH/COOEt). Ces derniers ont été utilisés pour l’élaboration de nouveaux polyesters furano-aliphatiques par la technique de polymérisation par ouverture de cycle (PEF /PCL) ou suite à des réactions d’interéchange à l’état fondu à partir de mélanges d’homopolymères (PEF/PLA, PEF/PHA et PEF/PCL)<br>This work aims at elaborating, characterising and processing polymer materials based on bio-sourced polysemicarbazides and furanic polyesters. The study has three main parts : Synthesis and optimisation of the synthesis of poly(acylsemicarbazide)s, elaboration of polymer blends based on furanic polymers (PEF or PSC) with PET, PLA and PHA and elaboration of new furano-aliphatic copolyesters by ring opening polymerisation (PEF/PCL) or by inter-exchange reactions between ’homopolymers (PEF/PCL, PEF/PLA et PEF/PHA) in the melt. The first chapter reports on the synthesis of a serie of bifuranic dihydrazides and on the study of their reactivity with several aromatic diisocyanates in order to elaborate furano-aromatic polyacylsemicarbazides. The behaviour of model monomer systems in various experimental conditions is studied in order to d’optimise the polycondensation processbefore transfering it to several monomer combinations. In the second chapter, we study the elaboration of new materials based on furanic polymers (PEF or PSC) blended with polyesters in the melt. 3 kinds of blends based on furanic polyesters / aliphatic and aromatic polyesters. The third chapter is devoted to the synthesis of furanic polyesters with controlled ends : dihydroxy-PEF (PEF di-OH), dicarboxylate-PEF (PEF di-COOH), diethylester-PEF (PEF di-COOEt) as well as PEF with mixed ends (PEF di-OH/COOEt). The latest have been used for the elaboration of new furano-aliphatic polyesters by ring opening polymerisation (PEF /PCL) or after interexchange reaction in melt homoplymer blends (PEF/PLA, PEF/PHA and PEF/PCL)

Cette these s'insere dans le contexte general d'une strategie visant a valoriser des materiaux issus de ressources renouvelables et traite plus specifiquement de la synthese et de la caracterisation de nouveaux oligomeres et polymeres furaniques photoactifs, notamment, des polymeres photoreticulables et des polymeres photodegradables. On a ainsi obtenu une nouvelle famille de materiaux dans laquelle l'heterocycle furanique est l'element original par rapport a des materiaux connus (aliphatiques ou aromatiques) issus de la petrochimie. La premiere partie de ce travail consiste en la synthese de nombreuses structures qui a l'etat solide, reagissent sous l'action de rayonnements uv, en formant soit des cyclobutanes pour les composes comportant une insaturation, soit des cyclophanes dans le cas ou les composes comportent deux insaturations non conjuguees. Ensuite, ces structures ont ete accrochees sur l'alcool polyvinylique donnant lieu a des materiaux photosensibles en vue d'une application industrielle ulterieure. Ce travail a montre que l'introduction du noyau furanique dans des structures photosensibles peut constituer une nouvelle famille de materiaux polymeres avec des proprietes prometteuses.

La polymérisation catalysée par des enzymes a fait l'objet d'une attention croissante ces dernières années en tant qu’alternative écologique à la catalyse à base de métal. L'objectif de notre travail est de synthétiser une série de polyesters par catalyse enzymatique basée sur différents diols et diesters aliphatiques et aromatiques, où nous nous sommes concentrés sur l'influence des paramètres de réaction, des structures de monomères et avons décrit les avantages et les limites de la catalyse enzymatique dans la synthèse de polymères. L'enzyme utilisée tout au long de nos travaux était Novozym 435, une lipase de Candida antarctica, immobilisée sur une résine acrylique. Dans le Chapitre 1, nous avons passé en revue les différentes méthodes et approches utilisées dans la littérature pour synthétiser des polymères par catalyse enzymatique. Dans le Chapitre 2, nous avons effectué la réaction entre l’hexane-1,6-diol et l'adipate de diéthyle via une approche de polycondensation en deux étapes où nous avons évalué l'effet de certains paramètres sur la masse molaire moyenne en nombre (Mn). L'effet de la température, du vide et de la charge enzymatique a été déterminé à l'aide d'un plan d’expérience de type plan composite centré. D'autres facteurs tels que le milieu réactionnel, le temps d'oligomérisation et la recyclabilité de l’enzyme ont également été évalués. Dans le Chapitre 3, des copolyesters à base de furane ont été synthétisés, où nous avons montré que nous pouvons incorporer des quantités plus élevées de dérivés furaniques lors de l'utilisation de diols aliphatiques avec des chaînes plus longues tels que le dodécane-1,12-diol. Dans le Chapitre 4, le lévoglucosan, une structure cyclique anhydre à 6 carbones et un produit de pyrolyse d'hydrates de carbone tels que l'amidon et la cellulose, a réagi avec des diesters de différentes longueurs de chaîne en présence de diols aliphatiques et de Novozym 435 comme catalyseur. Les polyesters produits étaient limités en terme de masse molaire moyenne en nombre (Mn) et de quantité de lévoglucosan incorporée. En augmentant la longueur du diester, nous avons augmenté la quantité de lévoglucosan incorporée ainsi que la masse molaire moyenne en nombre<br>Enzyme-catalyzed polymerization have been witnessing a growing attention in recent years as an eco-friendly substitute to metal-based catalysis. The objective of our work is to synthesize a series of polyesters via enzymatic catalysis based on different aliphatic and aromatic diols and diesters, where we focused on the influence of reaction parameters, monomer structures, and depicted the advantages and limitation of enzymatic catalysis in polymer synthesis. The enzyme used throughout our work was Novozym 435, a lipase from Candida antarctica, immobilized on an acrylic resin. In Chapter 1, we reviewed the different methods and approaches used in the literature to synthesize polymers via enzymatic catalysis. In Chapter 2, we performed the reaction between hexane-1,6-diol and diethyl adipate via a two-step polycondensation approach where we monitored the effect of certain parameters on the number average molecular weight (Mn). The influence of temperature, vacuum, and the amount of enzyme loading were determined using a central composite design. Other factors such as the reaction media, oligomerization time, and catalyst recyclability were also assessed. In Chapter 3 furan-based copolyesters were synthesized, where we showed that we can incorporate higher amounts of furan when using aliphatic diols with longer chains such as dodecane-1,12-diol. In Chapter 4, levoglucosan, an anhydrous 6-carbon ring structure and a pyrolysis product of carbohydrates such as starch and cellulose, was reacted against different chain length diesters in the presence of aliphatic diols and Novozym 435 as a catalyst. The polyesters produced were limited in their number average molecular weight (Mn) and the amount of levoglucosan that was successfully incorporated into the polymeric structure. Nevertheless, by increasing the chain length of the diester, we were able to produce a copolymer containing higher amounts of levoglucosan and a higher molecular weight

La recherche scientifique concernant les polymères biosourcés augmente rapidement pendant les dernières années, poussée par des croissantes préoccupations écologiques et économiques, ainsi que par l'incertitude sur la disponibilité future de ressources pétrochimiques limitées. Durabilité est un mot-clé de ce processus. Dans ce cadre, des produits respectueux de l'environnement, y compris des molécules et des additifs eco-compatibles, sont maintenant recherchés pour remplacer les polymères à base de pétrole par ceux dérivés de matières premières naturelles.Les résines époxydes sont des polymères thermodurcissables très polyvalents, extrêmement résistants à la corrosion, à l'humidité et aux produits chimiques, avec une bonne force d'adhérence à la plupart des matériaux et un faible retrait lors du durcissement. En raison de leurs températures de transition vitreuse élevées et de leur excellente résistance mécanique, les résines époxydes sont largement utilisées dans une large gamme d'applications, telles que l'électronique, les adhésifs structuraux, les composites pour l'aérospatiale et les revêtements protecteurs.Actuellement, plus des deux tiers des résines époxydes sont à base de diglycidyl éther de Bisphénol A. Dans cette industrie, la tendance à remplacer les matériaux dérivés du pétrole par des matériaux biosourcés est également liée à la nécessité de remplacer le bisphénol A (BPA), une molécule controversée, reconnu comme un perturbateur endocrinien et une substance reprotoxique. En particulier en application comme revêtement, l'utilisation de BPA présente un risque pour les utilisateurs d'aliments et de boissons conditionnés dans des récipients traités avec des résines époxydes. Les effets de la contamination du corps humain causée par le BPA sont le diabète, maladies cardiovasculaires, modification des enzymes hépatiques et les lésions de l'appareil reproducteur. Pour ces raisons, cette molécule a été interdite dans de nombreux pays pour la fabrication de produits pour enfants, ainsi qu'en France et au Canada de tous les matériaux en contact direct avec les aliments. La nécessité de développer de nouvelles résines époxy est donc urgente.Les molécules bio-dérivées développées depuis maintenant présentent des structures chimiques les plus diverses, chacune d’elles produisant des propriétés différentes des polymères finaux. Les caractéristiques particulières des résines époxydes sont liées à la structure aromatique de ses composants. Les molécules aromatiques présentes dans les matières premières naturelles proviennent principalement de la lignine, un des principaux constituants des parois cellulaires naturelles. Cependant, pour extraire des fragments aromatiques de la lignine, des procédés difficiles et consommateurs d’énergie sont nécessaires. Un substitut précieux des molécules aromatiques, facilement récupérables du glucose, sont les molécules furaniques ; leur validité a été étayée par plusieurs études.À la lumière de ce qui précède, les travaux présentés ici sont focalisés sur la production de résines époxyde à base de furane comme substitut potentiel de DGEBA dans l’industrie du revêtement de boîtes de conserve. Le cycle complet du matériau a été étudié : des synthèses de monomères époxydes furaniques ont été proposées, puis des thermodurcis époxydes ont été obtenus et caractérisés à la fois dans leurs propriétés chimiques et physiques (étude de la cinétique de durcissement, des propriétés mécaniques et thermiques). En outre, l’application des matériaux thermodurcissables époxydes proposés comme revêtement interne des boîtes de conserve a été testée<br>Research on bio-based polymers is rapidly increasing in last years, pushed by growing environmental and economic concerns, as well as by the uncertainty about future availability of finite petrochemical resources. Sustainability is a keyword in this process. In this frame, products that are respectful towards the environment, including eco-compatible building blocks and additives, are now researched to replace petroleum-based polymers with those derived from naturally occurring feedstocks. Epoxy resins are very versatile thermosetting polymers, extremely resistant to corrosion, moisture and chemicals, with good adhesive strength toward most materials (wettability) and low shrinkage upon curing. Due to their high glass transition temperatures and excellent mechanical strength, epoxy resins are widely employed in a broad range of applications, such as electronics, structural adhesives, aerospace composites and protective coatings. More than two-thirds of epoxy resins nowadays are based on diglycidyl ether of bisphenol A. In this industry the trend to replace petrol-derived materials with bio-based ones is related also to the necessity to substitute the Bisphenol A (BPA), a controversial building block recognized as an endocrine disrupter and reprotoxic substance. In particular in application as coating, the use of BPA results in hazard for customers of food and beverage products packed into containers treated with epoxy resins. The effects of human body contamination caused by BPA are diabetes, cardiovascular diseases, altered liver enzymes and reproductive apparatus damages. For these reasons, this molecule has been banned in many countries for the manufacturing of child products, and in France and Canada from all the materials in direct contact with food. The necessity to develop new epoxy resins results therefore urgent.Bio-derived molecules since now developed show the most various chemical structure, each of them producing different properties of final polymers. Peculiar characteristic shown by epoxy resins are related to the aromatic structure of its components. Aromatic molecules present in natural feedstock are mainly derived from lignin, one of the principal constituents of natural cell walls. However, to extract aromatic moieties from lignin, difficult and energy consuming processes are required. A valuable replacement of aromatic molecules, easily recoverable from glucose, are furanic molecules; their validity has been supported by several studies. In the light of the above, the work here presented is focused on production of furanic bio-based epoxy resins as potential substitute of DGEBA in can coating industry. The complete cycle of the material has been studied: the synthesis of furanic epoxy monomers and epoxy thermosets, the characterization of their chemical and physical properties (study of curing kinetics, mechanical and thermal properties). Furthermore, the application of bio-based epoxy thermosets as cans internal lining has been evaluated. Experimental results demonstrated that the obtained resins have good potential to be proposed as good alternatives to the traditional BPA-containing epoxy resins

Dans le but de la valorisation non-alimentaire de la biomasse vegetale, nous avons prepare de nouveaux materiaux furaniques: (i) des oligomeres et copolymeres polyconjugues de type poly(2,5-furylene vinylene) (pfv) a partir de monomeres furaniques (et/ou thiopheniques) ainsi que (ii) des polybases de schiff furaniques et/ou aromatiques, et (iii) des polyacetylenes substitues par des groupes furaniques. Tous ces produits ont ete synthetises et caracterises par diverses methodes physico-chimiques (ir, rmn, dsc, atg, conductivite electrique. . . ) en vue de l'obtention de materiaux potentiellement conducteurs electroniques, electroluminescents, ou encore a permeabilite selective aux fluides

Etude des proprietes mecaniques, de la stabilite thermique de la diffusion de l'eau et de sels radioactifs dans des polyurethannes. Les polyetherurethannes souples ont un comportement moyen a la temperature et a la diffusion. Les polyesterurethannes ont un meilleur comportement mais sont hydrolyses rapidement les polyetherurethannes rigides (tv=20 a 40#oc) sont le meilleur compromis; amelioration de la tenue en temperature vers 350-500#oc par addition de derives furanniques

Ce travail de thèse s’est inscrit au sein du projet européen Ecobinders dont l’objectif est le développement de nouveaux matériaux valorisant des produits dérivés de la biomasse tels que l’alcool furfurylique et/ou la lignine. De manière à comprendre les phénomènes physico-chimiques complexes mis en jeu lors des procédés d’élaboration et afin d’optimiser les propriétés de ces nouveaux matériaux, plusieurs approches originales ont été envisagées. Des études théoriques, comme l’analyse cinétique « sans modèle », u des techniques de pointe comme la calorimétrie multifréquence, la rhéométrie dynamique ont apporté un éclairage nouveau sur certains aspects fondamentaux. Lors de la polymérisation de l’alcool furfurylique, différentes étapes cinétiquement déterminantes ont mises en évidence et ont été attribuées soit à un contrôle par les mécanismes réactionnels ou à un contrôle par la diffusion. La polymérisation combinée alcool furfurylique / lignine a été étudiée et a permis l’élaboration de résines et de matrices thermodurcies. Les phénomènes de relaxation de la lignine ont été approfondis. Ceci a permis d’expliquer plus en détails le rôle de l’eau adsorbée, du vieillissement thermique et de mettre en évidence les aspects cinétiques. Enfin, des nano-hybrides ont été développés par deux voies distinctes. La voie sol-gel a été envisagée pour élaborer un nanocomposite alcool polyfurfurylique / silice qui a montré une amélioration de certaines propriétés mécaniques et thermiques. Un nouveau nano-composite argile / lignite / fibres naturelles a été développé par dispersion mécanique. Les propriétés barrières des feuillets d’argile ont amélioré la résistance thermique de ce matériau<br>This doctoral project has been conducted within the Ecobinders project which aims to develop new binders based on renewable resources such as furfuryl alcohol and/or lignin. Model-free kinetic and chemorheological analysis of furfuryl alcohol polymerisation have highlighted the different rate determing steps and the phase transitions (gelation, vitrification). The VOC’s released during polymerization have been identified. The influence of lignin incorporation on FA polymerization has been studied and oxidized or plasticized lignins have shown improved reactivity. Lab-scale polyfurfuryl alcohol or polyfurfuryl alcohol / lignin resins and thermoset have been elaborated on the basis of kinetic predictions. Evaluation of thermal instability, relaxation behaviour and morphological aspects of these lab-scale thermosets has highlighted a good compatibility between lignin and furanic network. Moreover, a polyfurfuryl alcohol / silica hybrid synthesized via sol-gel process has shown improved thermal performances as the consequence of nanoscales dispersion of silica particles. The quality control on new Ecobinders prototypes has been established. Dynamic aspects of lignin glass transition have been analyzed with multifrequency DSC together with other techniques. The influence of water sorption, thermal annealing, plasticization and fractionation has been considered. New layered silicate nanocomposite has been elaborated with lignin / natural fibres and improved thermal resistance has been shown

Les travaux de recherche réalisés, dans le cadre de la préparation de cette thèse consiste à préparer une nouvelle famille de polyesters ionomères furanique incorporant dans leur structure d’une part des unités aromatiques sulfonées et d’autre part des unités pyridiniques. Ce Choix est justifié principalement par les trois considérations suivantes : (i) la présence d’unités sulfonées dans la structure du poly (téréphtalate d’éthylène) confère à ce genre de polymère des propriétés physico-chimiques spécifiques favorisant son utilisation dans divers secteurs industriels dont principalement celui du détergents et celui des textiles, (ii) la présence d’unité furanique pourrait conduire à la biodégradabilité des matériaux dont on envisage leur préparation, (iii) la présence d’unités pyridiniques confère à ce genre de polymère des propriétés optoélectroniques (conductivité électrique, photoconductivité et propriétés luminescentes) permettant son utilisation dans diverses applications dont principalement le secteur spatiale et aéronautique<br>The research conducted for the preparation of this thesis is devoted to develop a new family of furanic copolyesters incorporating in their structure sulfonated and pyridinic units. This choice is justified mainly by the following three considerations: (i) the presence of sulfonated units in the poly(ethylene-terephthalate) structure gives to this kind of polymer a specific physicochemical properties favoring its use in various industrial sectors in a detergents and in textiles domains (ii) the presence of furanic unit could lead to the biodegradability of these materials (iii) Pyridinic units confer to these polymers an optoelectronic properties (electrical conductivity, photoconductivity and luminescent properties) favoring its use in various applications , in the space and aeronautics fields

Certains derives furaniques, obtenus a partir de la biomasse, se comportent comme d'excellents dienes vis a vis de la reaction de diels-alder. Dans cette perspective, l'application de cette reaction aux polymeres furaniques peut etre envisagee sous deux aspects. Le premier consiste en la modification de polymeres tels l'alcool polyvinylique ou le polystyrene par greffage de groupements pendants furaniques, qui seront ensuite mis en reaction avec des mono ou bismaleimides conduisant respectivement a des polyadduits ou des gels. Le second concerne la synthese et la polycondensation de monomeres possedant des extremites dieniques et/ou dienophile (aa + bb et ab). Cette these decrit l'elaboration et la caracterisation de divers materiaux bases sur l'application de ces differents concepts. La reversibilite de la reaction de diels-alder sur ce type de composes a egalement ete etudiee.

Hydrolyse de polymeres solubles (di-, tri-, oligosaccharides) ou insolubles (cellulose-beta -mannane, chitine) en presence de polymeres acides solubles ou insolubles. Emploi de resines acides solubles ou insolubles comme agent de deshydratation du fructose pour obtenir l'hydroxymethyl-5 furfural

Doutoramento em Química<br>A futura e inevitável escassez dos recursos fósseis, juntamente com o aumento imprevisível dos seus preços, levou, nas últimas décadas, a um aumento impressionante de iniciativas dedicadas não só à procura de fontes alternativas de fornecedores de energia, mas também de produtos químicos e polímeros a partir de fontes renováveis, em particular da biomassa vegetal. Entre estes, os polímeros derivados de monómeros furânicos constituem uma classe única de materiais cujas estruturas podem, em princípio, simular virtualmente os seus homólogos actualmente derivados de recursos fósseis. O anel furânico é uma estrutura heterocíclica com um carácter diénico pronunciado, o que torna-o um dieno particularmente apropriado para a reacção de Diels-Alder (DA) com dienófilos como a maleimida. Um dos aspectos mais relevantes da reacção de DA é a sua reversibilidade em função da temperatura, a qual permite que os aductos sejam facilmente revertidos nos seus precursores por aumento da temperatura (reacção de retro-DA). No caso específico da combinação furano-maleimida, a formação do aducto predomina até cerca de 60ºC, enquanto a reacção inversa é dominante acima de 100ºC. A combinação desta característica da reacção de DA com a química de compostos furânicos pode abrir um novo caminho para a preparação de materiais macromoleculares funcionais com base em fontes renováveis e com aplicações promissoras como auto-reparação e reciclabilidade. O principal objectivo desta Tese, é a síntese e caracterização de novos materiais poliméricos termo-reversíveis, aplicando a reacção de DA a monómeros complementares com estruturas dos tipos furânico (o dieno, designado por A) e de maleimida (o dienófilo, designado por B). A primeira etapa neste trabalho envolveu a síntese, purificação e caracterização de novos monómeros furânicos e de maleimida do tipo AA, A3, BB, B3, AB, AB2, cada um com diferentes grupos separadores das funções reactivas. Posteriormente, estes monómeros foram polimerizados e despolimerizados por ciclos de DA/retro-DA utilizando diferentes combinações. A formação e dissociação de todos os aductos de DA foram seguidas por ambas espectroscopias de UV e RMN de 1H. O primeiro sistema de DA estudado foi uma combinação modelo entre reagentes mono-funcionais (-A+-B), nomeadamente o acetato furfurílico (FA) e a N-metilmaleimida (MM), ambos comercialmente disponíveis. O objectivo desta abordagem foi estudar a cinética e o equilíbrio da formação/dissociação dos aductos de DA e obter indicações sobre as condições mais adequadas a serem usadas na preparação dos correspondentes novos materiais macromoleculares. Além disso, pretendia-se verificar a presença ou ausência de reacções secundárias que poderiam intervir em ambas as vias directa e inversa das reacções, mesmo após vários ciclos. A espectroscopia de UV forneceu informação quantitativa sobre a cinética de formação do aducto através da diminuição progressiva da absorvência máxima a 293 nm correspondente ao grupo maleimida, a diferentes temperaturas (35, 50, 65 ºC) Reciprocamente, a correspondente reacção de retro-DA foi seguida a 90 ºC através do aumento do mesmo pico. A reversibilidade destes sistemas foi verificada com sucesso após uma sequência de ciclos de DA/retro-DA. Adicionalmente, verificou-se que os espectros originaram um ponto isosbéstico, provando que estes sistemas não envolvem quaisquer reacções secundárias. Uma vez que foi usado um excesso de FA, as reacções de DA modelo apresentaram um comportamento cinético de pseudo-primeira ordem, com a constante de velocidade k mais alta (2.1x10-5 dm3mol-1s-1) para T=65 ºC. A correspondente energia de activação foi de 39.0 kJ.mol-1. A reacção de retro-DA seguiu um comportamento de primeira ordem, com constante de velocidade de 1.6x10-6 s-1. A evolução deste sistema por RMN de 1H a 65ºC deu-nos informações mais detalhadas sobre a sua evolução estrutural, ou seja, à medida que a intensidade dos picos atribuídos à formação do aducto aumentaram progressivamente ao longo do tempo, os pertencentes aos reagentes iniciais diminuiram proporcionalmente. O “rendimento final”, calculado após 20 dias à temperatura ambiente, foi de aproximadamente 70%. A reacção de retro-DA foi depois seguida a 90ºC, observando-se tal como na espectroscopia de UV, o deslocamento da reacção no sentido da regeneração dos reagentes de partida. A viabilidade de múltiplos ciclos de DA/retro-DA estabelecidos pela espectroscopia de UV foi igualmente confirmada por RMN de 1H. O passo seguinte envolveu o estudo de um sistema de policondensação linear baseado no crescimento gradual por reacção de DA entre um monómero bisfurânico A-A e um do tipo bismaleimida B-B, seguindo a mesma abordagem que no sistema modelo. O poliaducto linear foi obtido a partir de soluções equimolares dos monómeros, por reacção de DA a 65ºC. O progresso desta polimerização foi seguido por espectroscopia de UV e RMN de 1H e, mais qualitativamente, pelo aumento da viscosidade do meio. A reacção seguiu um comportamento de segunda ordem, com uma constante de velocidade de 9.4x10-6 dm3mol-1s-1, e observou-se novamente um ponto isosbéstico nos dados de UV. Os espectros de RMN apresentaram o padrão esperado, nomeadamente o aumento progressivo dos sinais associados ao aducto e a correspondente diminuição dos grupos furano e maleimida livres. A despolimerização do poliaducto através da reacção de retro-DA foi seguida a 110ºC usando as mesmas técnicas. Os dados de UV mostraram o retorno progressivo da absorção dos grupos de maleimida, seguindo um comportamento cinético de primeira ordem, com constante de velocidade de 2.5x10-6 s-1, até à completa regeneração de ambos os monómeros. Os espectros de RMN providenciaram mais uma vez informação estrutural sobre o progresso da despolimerização, a qual foi acompanhada por uma diminuição progressiva da viscosidade. Adicionalmente, para seguir a retro- DA, adicionou-se um excesso de composto furânico monofuncional, nomeadamente o 2,5-dimetilfurano (DMFu), ao sistema de modo a bloquear as funções maleimida complementares, evitando assim a repolimerização após arrefecimento. Os productos isolados foram então o monómero bisfurânico AA, DMFu que não reagiu e o bisaducto não-polimerizável de BB com DMFu. Este resultado indicou claramente que o polímero foi de facto revertido nos seus monómeros durante a reacção de retro-DA. O terceiro sistema estudado foi outra polimerização linear, seguindo as mesmas condições experimentais que os anteriores, mas com uma estratégia diferente de modo a contornar o problema clássico de assegurar a estequiometria exacta dos monómeros. As estruturas dos monómeros utilizados incorporam ambos os grupos reactivos, i.e, moléculas do tipo A-B. A polimerização prematura destes monómeros intrinsecamente reactivos foi evitada com a protecção do grupo maleimida na forma de um aducto de DA com furano, até a incorporação do substituinte furânico na outra extremidade. Portanto, a policondensação destes monómeros foi iniciada após a desprotecção in situ deste composto mediante aquecimento, seguido de arrefecimento até à temperatura adequada para polimerizar. Os resultados obtidos por UV e RMN sugerem que de facto o uso de monómeros do tipo A-B oferece um melhor sistema linear. Em seguida, foram estudados sistemas de policondensação não-linear por reacção de DA, entre monómeros (um ou ambos) com funcionalidade superior a dois, nomeadamente sistemas do tipo A3+B-B ou A-A+B3, seguindo mais uma vez as mesmas condições experimentais. Uma vez que utilizam monómeros complementares contendo, em média, mais de duas funcionalidades, estes sistemas conduzem a materiais reticulados. Nestes estudos, foram usadas três razões molares de [maleimida]/[furano], nomeadamente 1.0, 0.75 e 0.5, de modo a estudar ambas as situações de não-gelificação e reticulação. Ambos sistemas apresentaram um comportamento regular e boa reciclabilidade quer para gerar situações que possam conduzir à formação de redes a diferentes graus de conversão, ou que possam parar antes da sua obtenção, conforme previsto pela equação de Flory-Stockmayer. Como esperado, a utilização de grupos complementares em quantidades estequiométricas produziu o espessamento mais rápido e a reticulação quase completa; à medida que a quantidade relativa de monómero trifuncional decresceu, as reacções pararam antes da reticulação, ou seja, originaram meios altamente viscosos contendo polímeros solúveis altamente ramificados. As reacções de retro-DA a 110 ºC conduziram à gradual dissolução das partículas de gel (quando presentes), tendo sido comprovado pelos espectros de UV e de RMN de 1H, evidenciado a regeneração dos monómeros. Tal como no sistema do tipo A-A+B-B, a reacção de retro-DA foi seguida adicionando um excesso de DMFu ao sistema reaccional. Como esperado, os produtos finais foram os monómeros furânicos, o DMFu em excesso e o trisaducto ou o bisaducto maleimida-DMFu, o que confirma a eficiência da despolimerização com regeneração dos monómeros iniciais. O último sistema de policondensação por reacção de DA envolveu um monómero assimetricamente substituído do tipo AB2, capaz de originar estruturas macromoleculares hiper-ramificadas que não reticulam. Este estudo preliminar deste sistema foi seguido nas mesmas condições experimentais que os anteriores, apresentando um comportamento com as características esperadas.<br>The inevitable future scarcity of fossil resources, together with their skyrocketting prices, has led in the last decades to a dramatic increase of initiatives devoted not only to the search for alternative sources of energy providers, but also to the search for chemical commodities and polymers from renewable resources, namely the vegetable biomass. Among these, polymers from furan monomers constitute a unique class of materials whose structures can in principle simulate virtually all their current fossil-derived counterparts. The furan heterocycle displays a pronounced dienic character, which makes it highly suitable as diene in the Diels-Alder (DA) reaction, with dienophiles like maleimide. One of the most relevant aspects of the DA reaction is its thermal reversibility, which allows the adducts to be readily reverted to their precursors as the temperature is raised (retro-DA reaction). In the specific case of the furan-maleimide combination, the adduct formation dominates up to ca. 60ºC, whereas the reverse reaction is overwhelming above ca. 100ºC. The coupling of this DA feature with the furan chemistry can open a new way to prepare functional macromolecular materials based on renewable resources with novel properties and promising applications like mendability and recyclability. In this Thesis, the main goal is the synthesis and characterisation of novel thermoreversible polymer materials by means of the DA reaction, using complementary monomers bearing furan (the diene, assigned as A) and maleimide (the dienophile, assigned as B) moieties. The first step in this study was the synthesis, purification and characterization of new furan and maleimide monomers, viz. AA, A3, BB, B3, AB, AB2, each bearing different spacing moieties separating the reactive functions. They were then polymerized and depolymerised using different modes of DA/retro-DA cycles. The formation and decoupling of all the DA adducts were followed by both UV and 1H NMR spectroscopy. The first DA system investigated was on a model combination of monofunctional reagents (-A+-B), namely the commercially available furfuryl acetate (FA) and N-methylmaleimide (MM). The purpose of this approach was to study the kinetics and the equilibrium of the formation/decoupling of the DA adducts and to provide clear indications about the most appropriate conditions to be applied in the preparation of the corresponding novel macromolecular materials. Additionally, it aimed at verifying that no detectable side reactions intervened in both forward and backward pathways, even after several cycles. The UV spectroscopy provided quantitative information on the kinetics of the DA adduct formation by monitoring the progressive decrease in the maximum absorbance at 293 nm related to the maleimide moiety, at different temperatures (35, 50, 65ºC). Conversely, the corresponding retro-DA reaction was followed at 90ºC through the increase of the same peak. The reversibility of these systems was successfully checked over a couple of cycles. Additionally, all set of spectra gave rise to an isosbestic point, which proved that these systems did not involve any side reactions.Since an excess of FA was used here, these model DA reactions displayed a pseudo-first order behaviour, with the highest rate constant k (2.1x10-5 M-1.s-1) for T= 65ºC. The corresponding activation energy was found to be 39.0 kJ.mol-1. The retro-DA reaction followed a first order behaviour, with a rate constant of 1.6x10-6s-1.The evolution of the same system followed by 1H NMR spectroscopy at 65ºC gave a detailed insight into its structural evolution, viz. as the intensity of the peaks assigned to the adduct formation progressively increased with time, those belonging to the initial reagents decreased correspondingly. The “final yield” taken after 20 days at room temperature, was approximately 70%. The retro- DA reaction was then carried out at 90ºC, and showed the same features as its UV counterparts, namely the displacement of the reaction towards the regeneration of the initial reagents. The feasibility of multiple DA/retro-DA cycles established by UV spectroscopy was confirmed here. The subsequent stage involved the study of a linear polycondensation system based on the stepwise DA growth between a difuran monomer A-A and a complementary bismaleimide B-B, following the same approach as the model system. The formation of the linear DA polyadduct was achieved by letting equimolar solutions evolve at 65 ºC. The progress of this polymerization was followed by UV and 1H NMR spectroscopy and, more qualitatively, by the increase in the viscosity of the medium. The reaction followed a second order behaviour, with a rate constant of 9.4x10-6 M-1.s-1, and again, a characteristic isosbestic point was observed in the UV data. The NMR spectra gave the expected pattern, namely the progressive increase in the signals associated with the adduct and the corresponding decrease of those attributed to the unreacted furan and maleimide cycles. The depolymerization of the polyadduct through the retro-DA reaction was followed at 110ºC by the same techniques. The UV time scans showed the progressive return of the absorption due to maleimide moieties following a first-order kinetic pattern, with a rate constant of 2.5x10-6 s-1, until both monomers were fully regenerated. The 1H NMR spectra provided once more structural information about the course of this depolymerization, which was accompanied by a progressive decrease in viscosity. Additionally to follow the retro-DA, an excess of a monofunctional furan compound, namely 2,5-dimethylfurfural (DMFu), was added to the system in order to block the complementary maleimide functions, thus avoiding the repolymerisation after cooling. The isolated products were then the difuran monomer AA, the unreacted DMFu and the non-polymerizable bisadduct of BB with DMFu. This result clearly indicated that the polymer had indeed reverted to its monomers during the retro-DA. The third system studied was another linear polymerization, following the same experimental conditions as the previous, but with a different strategy, in order to avoid the classical problem of ensuring the exact monomer stoichiometry. Here, the monomers incorporated both reactive moieties in their structures, i.e. A-B molecules. Here, the premature polymerization of these intrinsically reactive monomers was avoided by protecting the maleimide group in the form of a furan-DA adduct, until the incorporation of the furan moiety. Therefore, the polycondensation of these monomers was initiated after the in situ deprotection of this compound through heating, followed by the cooling to appropriate temperature for polymerization. The results obtained by both UV and NMR spectroscopy suggested that indeed the use of an A-B monomer provides a better linear system. Non-linear DA polycondensations between monomers (one or both) with functionality higher than two, viz. A-A+B3 or A3+B-B systems, were then studied, following once more the same experimental conditions. The use of complementary monomers bearing on average more than two functionalities lead to crosslinked materials. In these systems, three [maleimide]/[furan] molar ratios, viz. 1.0, 0.75 and 0.50, were applied in order to examine both nongelling and crosslinking situations. Both types of systems displayed a clean-cut behaviour and good recyclability to generate situations either leading to the formation of a network at different degrees of conversions, or ending before its attainment, as predicted by the Flory-Stockmayer equation. As expected, the use of complementary moiety stoichiometry produced the most rapid thickening and near-complete crosslinking, whereas as the relative amount of trifunctional monomer was decreased, the reactions stopped short of crosslinking, i.e. gave highly viscous media containing soluble highly branched polymers. The retro-DA reactions at 110ºC revealed the gradual dissolution of the gel particles (when present), while the UV and 1H NMR spectra gave, once more, the details of the depolymerization processes leading the systems steadily back to the monomers. As in A-A+B-B depolymerization, to follow the retro-DA, an excess of DMFu DA trap, was added to the systems under the same conditions. As expected, the final products were the furan monomers, the unreacted DMFu and the non-polymerizable trisadduct or the bisadduct of maleimide-DMFu, confirming the efficiency of the retro-DA depolymerisation in the regeneration of the starting monomers. The last DA polycondensation system involved an assymmetrically substituted monomer of the AB2 type, capable of generating hyperbranched macromolecular structures that do not crosslink. This preliminary study was followed by the experimental approach applied above and the behaviour of the system displayed the expected features.<br>POCTI; FCT; FSE - SFRH/BD/28271/2006

Les réactions de Diels-Alder (DA) sont connues pour leur thermo-réversibilité. A basse température, le diène et les fonctions réactives diénophiles réagissent ensemble par la réaction de (DA) pour donner l'adduit. Le but de notre thèse est d'élaborer des réseaux réticulés thermoréversibles à base époxy-amine en utilisant des réactions de Diels-Alder. La thèse est composée de cinq chapitres dont le premier est consacré à la partie bibliographique. Celle-ci résume une partie des travaux réalisés sur la synthèse d'adduits et expose les différentes conditions utilisées pour aboutir à la synthèse, ainsi que les différentes méthodes d'analyse pour la caractérisation de ces adduits. Le deuxième chapitre est consacré à la synthèse et caractérisations des pré-polymères multi-diéne furanne ester. La synthèse de ces pré-polymères a été réalisée et confirmée par la RMN-1H, avec l'apparition de nouveaux signaux entre 4 et 5 ppm prouvant l'estérification. L'analyse IR- TF confirme l'apparition des deux bandes de vibration correspondantes à la fonction ester. Le troisième chapitre est consacré à la synthèse et caractérisations des pré-polymères acides multi-diénophiles (diénophiles ouverts) et une tri-maléimide diénophile (diénophile fermé). Les analyses RMN-1H et IR-TF confirment, respectivement, la disparition des protons de la fonction amine et les deux bandes anhydride, avec ouverture de la fonction époxy. Le quatrième chapitre est consacré à la synthèse et caractérisations de pré-polymères multi-diène furane. Ceux-ci ont été réalisés par la réaction de copolymérisation entre les fonctions époxydes de la DGEBA et la phényl diglycidyl éther (PGE) avec la furfurylamine (FAM). La RMN-1H a permis de calculer la fonctionnalité en fonction furane des diènes et de déterminer leur masse molaire moyenne en nombre. L'analyse thermogravimétrie (ATG) et l'analyse thermique par DSC ont montré que ces diènes sont des composés amorphes présentant une Tg de l'ordre de 20°C et restent stables thermiquement jusqu'à une température de 230°C. Enfin, dans le cinquième et dernier chapitre, la synthèse de réseaux thermoréversibles formés par la réaction de Diels-Alder entre les pré-polymères diène et la tri-maléimide diénophile sera présentée. La thermoréversibilité, les propriétés thermiques et d'autoréparation des réseaux seront étudiées

Le travail de recherche présenté dans ce manuscrit fait partie intégrante d’un projet de recherche collaborative financé par l’Union-Européenne (Il s’agit d’un projet H2020 de type « Marie-Curie Action »), dénommé HUGS (pour « HUmins as Green and Sustainable precursors for eco-friendly building-blocks and materials »). Ce projet de recherche implique 5 partenaires (INERIS/UTC, France, Avantium, Pays-Bas, Université de Sophia Antipolis/CNRS, France, l’université de Cordoue, Espagne et le LIKAT de l’université de Rostock en Allemagne). La recherche menée dans ce projet est essentiellement structurée via la mise en place de 5 programmes sous-jacents de doctorat (intitulé « Doctorat industriel européen » dans l’appel d’offre H2020 (H2020-MSCA-ITN-2015) auquel a répondu le consortium de recherche), mis en place lors du lancement du projet « HUGS » en 2016. L’objectif premier du projet HUGS concerne l’étude de divers chemins de valorisation à haute valeur ajoutée des humines. Ces résidus de biomasse, à l’instar des lignines se présentent comme des sources de carbone renouvelable à faible coût, en émergence dans nombre de bioraffineries modernes. Les humines sont des résidus complexes résultant du procédé de déshydratation par catalyse acide des polysaccharides (sucres en C5 et C6) contenus dans la biomasse lignocellulosique, ayant des cycles furaniques dans sa structure polymère. Le travail présenté ici est centré essentiellement sur les questionnements de sécurité soulevés par la phase de développement du projet. De manière plus ciblée, des actions prioritaires ont été définies, à savoir l’obtention d’un premier profilage des risques à caractère physicochimique des humines, ainsi qu’une première évaluation des risques des composés furaniques, lesquels constituent une famille de composés potentiellement très grande et représentent une voie encourageante vers le développement de nouveaux synthons au service d’une économie biosourcée. Les humines étant des résidus fatals, leur réutilisation sure et durable constitue aussi une étape stratégique dans le contexte de l’économie circulaire. De manière opérationnelle, le travail a compris les principaux axes de recherche suivants : • Revue bibliographique continue tout au long du travail de thèse concernant les humines, les composés furaniques et les matériaux associés (polymères) en termes de données relatives à la sécurité et ayant conduit aux principales informations suivantes: o Rareté /absence d’études sur les dangers physiques des humines et nombres de composés furaniques, car ces produits sont souvent au premier stade de leur développement o Malgré une la disponibilité très limitée de données pertinentes sur la sécurité, le constat est fait que les aspects de toxicité (par ingestion) sont le plus souvent le point focal des études, au détriment de l’examen des dangers physiques.o Seuls quelques composés furaniques (ethers, esters) ont spécifiquement fait l’objet de l’étude de certaines caractérisations en lien avec la sécurité (par exemple en termes de stabilité thermique), dans le cas d’application comme composants biosourcés de carburants innovants o De nombreuses variables influent sur les caractéristiques des humines et notamment leur méthode de production : ce qui signifie que les résultats obtenus sur les humines dans le cadre de ce projet (une seule source d’approvisionnement) mériteraient des travaux de consolidation dans le futur • Développements analytiques intégrant un premier examen de la distribution des points d’éclair en fonction des chaleurs de combustion des composés furaniques et une analyse des chaleurs de combustion de ces mêmes composés furaniques<br>The present research work was integrated as part of the EU-funded project named HUGS (HUmins as Green and Sustainable precursors for eco-friendly building blocks and materials), involving 5 main partners (Institut national de l'environnement industriel et des risques - France, Avantium - the Netherlands, Institut de Chimie de Nice - France, Universidad De Cordoba- Spain and Leibniz - Institut Fur Katalyse Ev An Der Universitat Rostock- Germany). The project is essentially supported through five European Industrial Doctorate fellowships put in place when the HUGS-MSCA-ITN-2015 program was launched in 2016. The primary objective of the HUGS project was to explore several valorization pathways of so-called “humins” in order to add value and create better business cases. Humins (and similarly lignins) are the side products that may become low-cost feedstock resulting from a number of future biorefineries and sugar conversion processes. Humins are complex residues resulting from the Acid-Catalyzed Dehydration and condensation of sugars, having furan-rings in their polymeric structures. The work presented in this specific part of the HUGS project is essentially focusing on safety-related topics of all components and subsequent applications related to sugar dehydration technology. Priority actions were devoted to a first insight on the characterization of physicochemical safety profiles of the side-product humins and main (parent) furanic products. Some members of this large family of compounds (e.g. RMF and FDCA) have high volume potential which results in opening new doors towards the development of furanbased building blocks and a bio-based economy. Humins are residues or side products which can be burnt for energy. However, its safe and sustainable use in high-value applications could also become a key milestone in the so-called circular economy. In practice, the work has been developed in two main locations: primarily at the INERIS lab, located in Verneuil-en-Halatte and at Avantium, located in Amsterdam. Nearly all experimental research after the production of the components at Avantium was performed at INERIS. This involved the evaluation of physicochemical hazards of both humins (crude industrial humins and humin foams obtained by thermal curing) and a series of furanic compounds. Avantium is involved in the commercialization of humins, furanics and furanic polymers/materials as novel chemicals and materials. The work has encompassed: An extensive bibliographical review of humins, furanics, and their related products (polymers, composites) resulted in the following main conclusions o A lack of physicochemical safety-oriented studies for many furanic compounds and for humins was observed as these products are still in the early stage of development and only a few may be commercialized in the next 5 years.o Despite the limited availability of safety-related data, more studies on toxicity aspects have been conducted for a selected number of furanics than physicochemical safety-related aspects. o A few furanic family members that have been evaluated as biofuel components were found to have given better emphasis on addressing some physicochemical safety attributes. o Every modification of the process for acid-catalyzed sugar dehydration (such as solvent, temperature, residence time and sugar concentration) will result in different humins, which would certainly demand further characterization and safety profiling of the resulting humins. • Analytical development integrating the first examination of flash point distribution versus the Net Heating Values, and analysis of total heats of combustion of furanic compounds. • Design and development of experimental plan addressing the safety-related key parameters such as thermal stability, self-heating risks, fire-risk-assessment and flammability limits depending on the need for specific tests and availability of the test samples

In der vorliegenden Arbeit wurde die kationische Polymerisation der heterocyclischen Monomere 2-Vinylfuran, 5-Methyl-2-vinylfuran und 2-Vinylthiophen in der Gegenwart silikatischer Partikel untersucht. Produkte dieser Reaktion sind Polymer/SiO2-Hybridpartikel und lösliche Polymere. Zu ihrer Untersuchung wurden NMR-spektroskopische Verfahren, IR-, UV/Vis-, MALDI TOF-Spektroskopie, Elementaranalyse und GPC angewandt. Damit gelang es, die Struktur der Polymere weitgehend aufzuklären. Der Einfluß der Reaktionsbedingungen auf die Ergebnisse der kationischen Oberflächenpolymerisation wurde untersucht und diskutiert. Die Ausbildung vernetzter Polymere bei der kationischen Polymerisation von 2-Vinylfuran bewirkte eine besonders starke Anbindung der Poly(2-vinylfuran)-Schicht und hohe Polymergehalte an den SiO2-Partikeln. Im Falle des Poly(2-vinylthiophens) (PVT) waren die Polymergehalte der Hybridpartikel deutlich niedriger. Es wurde eine lineare Polymerstruktur vorgeschlagen. Poly(2-vinylthiophen) und Poly(2-vinylthiophen)/Kieselgel-Hybridpartikel wurden in polymeranalogen Reaktionen mit Hydridakzeptoren und FeCl3 umgesetzt. Ziele dieser Reaktionen waren die Erzeugung von konjugierten Strukturelementen und die kontrollierte Vernetzung des Polymers über Bisthiopheneinheiten. Der Einfluß der Reaktionszeit und der Natur der eingesetzten Reagenzien auf die Reaktion von PVT mit Hydridakzeptoren wurde ausführlich studiert. Der Einfluß der Reaktionsbedingungen auf die Vernetzungsreaktion mit FeCl3 wurde mit Hilfe von GPC, IR- und 13C{1H}-CP/MAS-NMR-Spektroskopie untersucht<br>The following work examines the cationic polymerization of the heterocyclic monomers 2-vinylfuran, 5-methyl-2-vinylfuran und 2-vinylthiophen mediated by silica particles. The products of this reaction are polymer/SiO2-hybridpartikels and a soluble polymer part. For characterization of the products NMR-spectroscopical methods, IR-, UV/Vis-, MALDI TOF-spectroscopy, elemental analysis and GPC were used. With the help of this methods it succeeded to clear up the polymer structure. The influence of the reaction conditions on the results of the cationic polymerization was examined and discussed. Extensive crosslinking of the 2-vinylfuran monomer during cationic polymerization causes a very strong linkage of the poly(2-vinylfuran)-layer and a hight polymer content of the poly(2-vinylfuran)/SiO2-hybridpartikels. In case of poly(2-vinylthiophen) (PVT) the polymer content of the hybrid particles was notedly lower. A linear polymer structure was supposed. The reaction of poly(2-vinylthiophen) and poly(2-vinylthiophen)/silica hybrid particles with hydridacceptors and FeCl3 was studied. The objectives of this reactions were to generate conjugated structures and to cross-link the polymer by creating bisthiophene structures in a controlled manner. The influence of the reaction time and the nature of the acceptors on the reaction of PVT with the hydride acceptors was examined in detail. The influence of the reaction conditions on the cross-linking reaction with FeCl3 was studied with the help of GPC, IR- und 13C{1H} CP/MAS NMR spectroscopy

Ce travail porte sur l'élaboration et la caractérisation de plusieurs séries de systèmes hybrides du tetrathiafulvalène (HTTFS). Ces systèmes sont construits par le greffage de deux motifs 1,3-dithiole-2-ylidene aux deux extrémités d'un espaceur conjugué. Apres une première étape consacrée à l'analyse des différentes possibilités d'insertion d'espaceurs benzéniques, plusieurs séries de HTTFS dérivées d'hétérocycles aromatiques, thiophène, furanne et n-méthyl pyrrole, ont été synthétisées, l'analyse des propriétés électrochimiques de ces derniers montre qu'ils conduisent à un abaissement du potentiel d'oxydation avec une réduction des repulsions coulombiennes au stade dicationique. Sur la base des résultats obtenus, nous avons cherché à accroitre l'extension spatiale de ces systèmes en utilisant un oligomère conjugué. Ainsi, l'oxydation chimique et électrochimique des 2-(1,4-dithiafulven-6-yl)thiophène a permis d'accéder facilement à des analogues étendus du tetrathiafulvalène (ETTFS) symétriques. Cependant, l'augmentation du nombre d'hétérocycles s'est révélée limitée, ces résultats nous ont amenés à la synthèse de nouveaux espaceurs: dithiényl- et difurylpolyènes dont les propriétés optiques et électrochimiques révèlent que l'augmentation du nombre de doubles liaisons diminue les valeurs des potentiels d'oxydation et conduit à un déplacement bathochrome du maximum d'absorption, avec une diminution importante du gap homo-lumo. Enfin, les enseignements tirés de cette dernière phase de ce travail ont permis de définir des précurseurs dont l'électropolymérisation a conduit à de nouveaux polymères conjugues dérivés du furanne qui sont les plus conducteurs connus jusqu'à présent.

Heterocyclic organic and organometallic compounds (i.e. polypyrrole), and their derivatives, have been of great interest for conductive polymers due to their novel properties and environmental stability as compared to their non-aromatic analogs (i.e. polyacetylene). Our current interest focus upon the potential role of metal ligand bound pyridazines as the next generation of electronic devices that utilize the metal ligands bound to organics as the semiconducting material. Pyridazine is a 6-membered aromatic ring with two adjacent nitrogen atoms. These are promising candidates for a variety of materials and commercial applications; but they are difficult to get a metal ligand to fuse to the aromatic ring. Our recent efforts focused in attaching Rhenium and Manganese ligands/substituents (process in which is called doping) that would cause oxidation to occur to our polymer making it a p-type polymer. Since p-type polymers charge carriers leave a vacancy that does not delocalize completely. This vacancy (known as a hole) or a radical cation that only partially delocalizes over several monomeric units causing them to be structurally deformed. This deformed structure is at a higher energy than that of an undoped polymer. Typical carriers in organic semiconductors are holes and electrons in a π-orbital. So when these molecules of π-conjugated systems have a π-bond overlap (or π- stacking), electrons can move via these π-electron clouds overlapping thus causing an electrical current. Our worked focused on the synthesis of pyridazines and their organometallic rhenium complexes and polymer research. Several aryl-substituted 5,6-fused pyridazines have been synthesized but none have been documented until this study. The main goal of the research was to fully characterize the general synthesis of furan containing organometallic complexes, [M(CO)3{η5-1,2-C5H3(CC4H3ON)(CC4H3ON)}] (M = Re or Mn) (4B). We successfully characterized the ability to attach a metal organic ligand to pyridazine though IR and NMR. However, when attempts were made to recrystallize our product, we yielded an orange-brown, block like crystal of 1,2- C5H3(CC4H3ONH)(CC4H3ON) (5) in which our metal ligand group fell off and we were left with pyridazine and inorganics. Though, we successfully got an X-ray characterization and electronic studies of compound 5 which are reported herein.

L'utilisation des composés furaniques comme matières premières est largement justifiée par la disponibilité et l'aspect renouvelable de ces sources (biomasse végétale). Dans ce projet, nous nous sommes intéressés au caractère photosensible des composés furaniques pour l'élaboration de nouveaux polymères photo-réticulables en vue de leur application sur plaques d'impression Offset. Des structures photosensibles simples ont été synthétisées et caractérisées afin d'étudier la synthèse et le comportement photochimique du photopolymère final. Lors de l'irradiation dans un milieu concentré, ces composés subissent une [pi2+pi2] cycloaddition entre un chromophore à l'état excité et un chromophore à l'état stable formant des motifs cyclobutanes. Les composés les plus prometteurs ont été utilisés comme monomères pour la préparation des photopolymères, basés sur une structure polyester, contenant le groupement chromophore dans la chaîne principale. Après une étude structurelle et thermique, ces polymères photosensibles ont été étudié photochimiquement et ont montré une bonne aptitude à induire la réticulation des matériaux initiaux.

Im Rahmen der vorliegenden Arbeit werden die Synthese und Charakterisierung eines thermisch-kontrollierten und eines photochemisch-kontrollierten reversiblen Polymersystems vorgestellt. Weiterhin werden Poly(dimethyl)siloxan-Oberflächen mit Amino-, Isocyanat-, Furan-, Maleimid- und Cumarin-Gruppen funktionalisiert. Hierbei werden sowohl bekannte als auch neuartige Wege der Oberflächenmodifizierung vergleichend untersucht und bewertet. Ausgehend von den hergestellten Cumarin-funktionalisierten Poly(dimethyl)siloxan-Oberflächen wird eine Anbindung des synthetisierten photochemisch-kontrollierten reversiblen Polymersystems an diese Oberflächen untersucht. Des Weiteren wird die Anbindung des synthetisierten thermisch kontrollierten reversiblen Polymersystems sowohl an den hergestellten Maleimid- als auch an den Furan-funktionalisierten Poly(dimethyl)siloxan-Oberflächen analysiert. Basierend auf den vorgestellten Cumarin-Funktionalisierungen werden photoaktive Oberflächen beschrieben und mittels ATR-IR-spektroskopischer und UV/Vis-spektroskopischer Methoden analysiert.

Nowadays environmental problems, climate changes, limited fossil resources and their price fluctuation, associated with industrial activity (often ecologically unsound) are the strong driving forces for governments, companies and scientists to find alternatives to the fossil-based materials. In this scenario 2,5- furandicarboxylic acid (FDCA), a renewable platform chemical has emerged as the most promising substitute to terephtalic acid for the synthesis of several materials, particularly polyesters, which possess similar thermal and mechanical proprieties. These materials could be applied to current applications and, could even be applied in new, innovative and high value applications. In this context, the development of sustainable FDCA-based polymers and materials is timely and quite relevant. Precisely, the main objective of this thesis is the development of more sustainable polymers and composites based on FDCA and a wide panoply of aliphatic compounds selected for their renewable origin (PART B) and/or the improved thermal and mechanical properties they can impart the ensuing materials. Furthermore, the potential of a new FDCA-based ester monomer as plasticiser for partial replacement of the non-renewable di(2- ethylhexyl) terephthalate on PVC formulations was also evaluated (PART C). In the first study, a partially renewable polyester based on FDCA and 1,4- cyclohexanediol, namely poly(1,4-cyclohexylene 2,5-furandicarboxylate) (PCdF) was prepared aiming at preparing a new material with enhanced thermal properties. Its synthesis was performed by two distinct approaches, namely via solution polycondensation and bulk polytransesterification. For comparative purposes, poly(1,4-cyclohexanedimethylene 2,5-furandicarboxylate) (PCF) homopolyester was also synthesised, due to their related structural resemblance. Homopolyesters with different molecular weights (Mn and Ð values ranging between 4 300-14 100 g/mol and 1.2-1.7, respectively) were obtained, depending on the synthesis approach and catalyst used. The resulting materials revealed to possess semi-crystalline character with high glass transition temperatures (Tg values of 175 and 105 ºC for PCdF and PCF, respectively), and thermal stablility up to 377 ºC. It was also found that, the absence of the methylene group on PCdF homopolyester, lead to a more rigid polymer chain backbone, and accordingly to a highest Tg. Other studies, focused on the development of copolyesters enterelly based on renewable-based monomers, namely those based on FDCA, 1,4-butanediol and poly(propylene oxide) or diglycolic acid were performed. In a second study, several poly(1,4-butylene 2,5-furandicarboxylate)-copoly( poly(propylene oxide) 2,5-furandicarboxylate) (PBF-co-PPOF) poly(esterether) s copolymers were synthesised using dimethyl 2,5-furandicarboxylate and different molar ratios of 1,4-butanediol and poly(propylene oxide). The ensuing copolyesters presented either semi-crystalline character when using higher PBF feed amounts, or completely amorphous viscous liquid was obtained instead when using a PBF/PPOF ratio equal to 1 . Moreover, these materials presented high thermal stability (maximum degradation temperatures between 340-365 ºC), and low Tgs (values ranging from -42.3 to -32.6 ºC), facilitating their processability at lower temperatures. Further, in a third stud, comprised the preparation of a series of FDCA-based nanocomposites were prepared using poly(1,4-butylene 2,5-furandicarboxylate)- co-poly(1,4-butylene diglycolate) (PBF-co-PBDG) copolyesters and acetylated bacterial cellulose (Ac-BC). In a first step, PBF-co-PBDG (co)polyesters were synthesised; followed, in a second step, by the preparation of nanocomposites films obtained by solvent-casting approach. Interestingly, for higher incorporation of BDG moieties, these reinforced materials showed an increased stiffness (Young’s modulus up to 1239 MPa) and reasonable elasticity (elongation at break values between 0.6 to 25.0 %) compared to their neat (co)polyester counterparts. Furthermore, similar values of oxygen permeability of nanocomposites and (co)polyesters were observed, expanding the exploitation of these materials for packaging applications. Finnaly, a fourth study, addressed the possibility of using a furanic ester as an additive for poly(vinyl chloride) (PVC). A combination of di(2-ethylhexyl) 2,5- furandicarboxylate (DEHF) and di(2-ethylhexyl) terephthalate (DEHT) plasticisers was performed into an attempt to increase the ‘green content’ of PVC formulations. These materials have shown to possess higher compatibility with the PVC matrix compared with DEHF as single plasticizer, confirmed by FTIR spectroscopy. Furthermore, they displayed thermal features comparable to those prepared with DEHT as single plasticizer (Tg’s between 19.2 to 23.8 ºC), and increased elongation at break (up to 330%). Moreover, migration tests revealed very low weight loss percentages, not exceeding ca. 0.3 and 0.2%, for water and PBS solution, respectively. More important, preliminary results of in vitro cell viability tests (concentrations up to 500 μM for a maximum of 72 h) revealed a non-toxic profile (around 100 %) for both DEHF and DEHT plasticisers. All FDCA-based materials and chemicals prepared under the scope of this dissertation are an important contribute for the increasing demand for new renewable-based products, within a sustainable approach. Further, these materials and chemicals, presented similar or improved properties to those prepared from petroleum-based resources.<br>Nos dias de hoje, os problemas ambientais, as mudanças climáticas, os recursos fósseis limitados e sua flutuação de preço, associados à atividade industrial (muitas vezes muito pouco ecológicas) são as forças motrizes para governos, empresas e cientistas encontrarem alternativas para os materiais preparados a partir de recursos fosséis. Neste cenário, o ácido 2,5- furandicarboxílico (FDCA), em produto químico de origem renovável, surgiu como o substituto mais promissor do ácido tereftálico na síntese de diversos materiais, particularmente poliésteres, que possuem propriedades térmicas e mecânicas semelhantes. Estes materiais podem ser utilizados nas aplicações existentes, e em outras novas aplicações, inovadoras e de alto valor. Neste contexto, o desenvolvimento de polímeros e materiais sustentáveis a partir dos furanos é oportuno e bastante relevante. Precisamente, esta tese tem como principal objetivo o desenvolvimento polímeros e materiais compósitos mais sustentáveis a partir do FDCA e uma panóplia de compostos alifáticos selecionados pela sua origem renovável. Posteriormente, foi ainda avaliado o potencial de um novo monómero éster preparado a partir do FDCA como plastificante para a substituição parcial do não renovável tereftalato de di(2- etilhexilo) em formulações de cloreto de polivínilo (PVC). No primeiro estudo, foi preparado um poliéster parcialmente renovável a partir do FDCA e do 1,4-ciclohexanodiol, nomeadamente o poli(2,5- furanodicarboxilato de 1,4-ciclohexileno) (PCdF) com o objectivo de se obter um novo material com propriedades térmicas melhoradas. A sua síntese foi efetuada a partir de duas abordagens distintas, nomeadamente via policondensação em solução e politransesterificação em estado sólido. Por motivos comparativos, foi ainda sintetizado o homopolímero poli(2,5- furandicarboxilato de 1,4-ciclohexanodimetileno) (PCF), devido à semelhança estrutural entre ambos. Homopolímeros com pesos moleculares diferentes foram obtidos de acordo com a abordagem de síntese e catalisadores utilizados (valores de Mn e Ð variando entre 4 300-14 100 g/mol e 1.2-1.7, respetivamente). Os materiais resultantes revelaram possuir carácter semi-cristalino com elevadas temperaturas de transição vítrea (valores de Tg de 175 e 105 ºC, para o PCdF e PCF, respetivamente) e estabilidade térmica até aos 377 ºC. Verificouse ainda que, a ausência do grupo metileno no homopolímero PCdF, deu origem a um material com estrutura de cadeia polimérica mais rígida, e consequentemente um valor de Tg mais elevado. Num segundo estudo, vários copolímeros do poli(2,5-furanodicarboxilato de 1,4- butileno)-co-poli(2,5-furanodicarboxilato de poli(óxido de propileno)) (PBF-co- PPOF) poli(éster-éter)s foram sintetizados a partir do 2,5-furanodicarboxilato de dimetilo e diferentes rácios molares do 1,4-butanodiol e do poli(óxido de propileno. Os copolímeros resultantes apresentaram caráter semi-cristalino quando quantidades superiores de PBF foram usadas, líquidos viscosos completamente amorfos quando o rácio PBF/PPOF usado foi igual a 1. Mais ainda, estes materiais apresentaram elevada estabilidade térmica (temperaturas de degradação máxima entre 340-365 ºC, e baixas Tg´s (valores a variar entre os - 42.3 a -32.6 ºC), facilitando desta forma o seu processamento a mais baixas temperaturas. Adicionalmente, num terceiro estudo, abrangendo a preparação de uma série de nanocompósitos à base de FDCA, preparados usando os copolímeros poli(2,5-furanodicarboxilato de 1,4-butileno)-co-poli(diglicolato de 1,4-butileno) (PBF-co-PBGD e celulose bacteriana acetilada (Ac-BC). Numa primeira etapa, os copolímeros foram sintetizados; seguida da preparação de filmes de nanocompósitos, obtidos através da abordagem de evaporação de solvente. Curiosamente, para uma maior incorporação de unidades de BDG, estes materiais reforçados demonstraram um aumento de rigidez (módulo de Young até 1239 MPa) e elasticidade aceitável (valores alongamento até à ruptura entre 0.6 até 25.0 %) quando comparados com os seus (co)polímeros homólogos puros. Além disso, foram observados valores similares para as permeabilidade ao oxigénio dos nanocompósitos e (co)polímeros, expandindo a exploração destes materiais para aplicações como embalagens. Finalmente, um quarto estudo, abordou a possibilidade de usar um éster furânico como aditivo para formulações de poli(cloreto de vinilo) (PVC) (Capítulo VI). A combinação dos plastificantes 2,5-furanodicarboxilato de di(2-etilhexilo) (DEHF) com o tereftalato de di(2-etilhexilo) (DEHT) foi efetuada de forma a aumentar o ‘conteúdo verde’ das formulações de PVC. Estes materiais demostraram possuir maior compatibilidade com a matriz do PVC comparativamente com os preparados apenas com o DEHF. Mais ainda, apresentaram características térmicas comparáveis aos preparados apenas com o DEHT (Tg’s entre 19.2 e 23.8 ºC) e um aumento do alongamento até à rutura (até 330%). Além disso, os testes de migração revelaram muito baixas percentagens de perda de massa, não excedendo os 0.3% e os 0.2%, respetivamente, para a água e para a solução PBS. Mais importante, resultados preliminares em testes de viabilidade celular in vitro (concentrações até 500 μM e máximo de 72 h) revelaram um perfil não-tóxico para ambos os plastificantes, DEHF e DEHT. Todos os materiais e químicos preparados a partir do FDCA dentro do âmbito desta dissertação são uma importante contribuição para a crescente procura por novos materiais de origem renovável, dentro de uma abordagem sustentável. Mais, estes materiais e químicos apresentaaram propriedades semelhantes ou melhoradas às dos preparados a partir de recursos petrolíferos.<br>Programa Doutoral em Química Sustentável

博士<br>臺灣大學<br>化學研究所<br>96<br>A range of oligoaryls having alternating para- or meta-benzene-furan rings is synthesized by rapid convergent/divergent method from the annlation of a propargylic dithioacetal and an aldehyde having a propargylic dithioacetal moiety as the substituent. This route provides a useful procedure toward the synthesis of monodisperse oligoaryls without repetitive units. Systematic investigation on the photophysical properties and molecular folder phenomenon of these oligomers are also explored. A series of dithiolated alternating benzene-furan oligoaryls was synthesized. IRAS (infrared reflection-absorption spectroscopy) and STM (scanning tunneling microscopy) experiments revealed that single-component monolayers of these oligoaryls have lattice packing of crystalline by pi-pi interaction and each distance between two single molecules is about 0.51 nm. The conductance of single molecule was decreased with the conjugated length of alternating benzene-furan oligoaryls increased. In addition, a series of double stranded polymers by using furan-containing oligoaryls as linkers was synthesized. Conformational change of the norbornene moiety after ROMP (ring opening metathesis polymerization) lead chormophores aggregated and quenched the fluorescent intensity. The first oxidation potential of polymers were conformably lower than corresponding monomers, and the difference of first oxidation potential between monomer and polymer was increased with the conjugated length of chormophores increased.

碩士<br>中原大學<br>化學工程研究所<br>99<br>In this study,a novel benzoxazine monomer FDP-FBz was synthesized using furfurylamine, formaldehyde and 4,4’-(9-Fluorenylidene) diphenol(FDP) as reactants. The chemical structure of 9,9-Bis(3- furfuryl-3,4-dihydro-2H-1,3- benzoxazinyl)fluorine (FDP-FBz) was characterized with FT-IR, 1H-NMR amd elemental analysis, proving that we synthesized high-purity FDP-FBz monomer successfully. 　　First part, PFBz possessing benzoxazine group in the mainchain was prepared through the Diels-Alder reaction using FDP-FBz and 1,1’-(Methylenedi-4,1-phenylene) bismaleimide (DDM-BMI) as monomers. After thermal ring opening polymerziation, poly(PFBz) showed a high Tg at 360℃, and good thermal stability. 　　Second part, two kind of hyperbranched polymers, TMI-BFBz and TMI-FFBz were prepared from bis(3- furfuryl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropane(BPA-FBz) and Trimaleimidophenyl phosphine oxide(TMPPO), FDP-FBz and TMPPO as monomer, respectively. After thermal ring opening polymerziation, poly(TMI-BFBz)and poly(TMI-FFBz) showed high Tgs at 350℃ and 330 ℃, respectively, and good thermal stability.

碩士<br>高雄醫學大學<br>職業安全衛生研究所<br>88<br>A side chain liquid crystalline polysiloxane polymer(PS3DBDE1) with high purity and high isotropic transition temperature served as a stationary phase in an attempt to chromatographize the dioxin/furan compounds. The polymer was coated on the inner surface of a 0.25(i.d.) capillary column by using the static coating method, forming a film with its thickness of df  0.25 m. A commercial standard solution (US EPA1613 standard solution 1613CS4) containing polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans(PCDFs) was used to test the chromatographic behavior of homemade capillar column. Two commerical capillary columns HP-5MS(Hewlett-Packard Co.) and RTX-5MS(RTX Co.) were choosen to compare their chromatographic behavior. The results show that the isomeric pair compounds 1,2,3,4-TCDD vs 2,3,7,8-TCDD and 1,2,3,4,7,8-HxCDD vs 1,2,3,6,7,8-HxCDD and the same substituted-chlorine number compounds 1,2,3,4,6,7,8-HpCDF vs 1,2,3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8,9-HpCDD vs 1,2,3,4,6,7,8,9-HpCDF had higher resolution than HP-5MS(Hewlett-Packard Co.) and RTX-5MS(RTX Co.) suggested by the column makers.

In der vorliegenden Arbeit wurde die kationische Polymerisation der heterocyclischen Monomere 2-Vinylfuran, 5-Methyl-2-vinylfuran und 2-Vinylthiophen in der Gegenwart silikatischer Partikel untersucht. Produkte dieser Reaktion sind Polymer/SiO2-Hybridpartikel und lösliche Polymere. Zu ihrer Untersuchung wurden NMR-spektroskopische Verfahren, IR-, UV/Vis-, MALDI TOF-Spektroskopie, Elementaranalyse und GPC angewandt. Damit gelang es, die Struktur der Polymere weitgehend aufzuklären. Der Einfluß der Reaktionsbedingungen auf die Ergebnisse der kationischen Oberflächenpolymerisation wurde untersucht und diskutiert. Die Ausbildung vernetzter Polymere bei der kationischen Polymerisation von 2-Vinylfuran bewirkte eine besonders starke Anbindung der Poly(2-vinylfuran)-Schicht und hohe Polymergehalte an den SiO2-Partikeln. Im Falle des Poly(2-vinylthiophens) (PVT) waren die Polymergehalte der Hybridpartikel deutlich niedriger. Es wurde eine lineare Polymerstruktur vorgeschlagen. Poly(2-vinylthiophen) und Poly(2-vinylthiophen)/Kieselgel-Hybridpartikel wurden in polymeranalogen Reaktionen mit Hydridakzeptoren und FeCl3 umgesetzt. Ziele dieser Reaktionen waren die Erzeugung von konjugierten Strukturelementen und die kontrollierte Vernetzung des Polymers über Bisthiopheneinheiten. Der Einfluß der Reaktionszeit und der Natur der eingesetzten Reagenzien auf die Reaktion von PVT mit Hydridakzeptoren wurde ausführlich studiert. Der Einfluß der Reaktionsbedingungen auf die Vernetzungsreaktion mit FeCl3 wurde mit Hilfe von GPC, IR- und 13C{1H}-CP/MAS-NMR-Spektroskopie untersucht.<br>The following work examines the cationic polymerization of the heterocyclic monomers 2-vinylfuran, 5-methyl-2-vinylfuran und 2-vinylthiophen mediated by silica particles. The products of this reaction are polymer/SiO2-hybridpartikels and a soluble polymer part. For characterization of the products NMR-spectroscopical methods, IR-, UV/Vis-, MALDI TOF-spectroscopy, elemental analysis and GPC were used. With the help of this methods it succeeded to clear up the polymer structure. The influence of the reaction conditions on the results of the cationic polymerization was examined and discussed. Extensive crosslinking of the 2-vinylfuran monomer during cationic polymerization causes a very strong linkage of the poly(2-vinylfuran)-layer and a hight polymer content of the poly(2-vinylfuran)/SiO2-hybridpartikels. In case of poly(2-vinylthiophen) (PVT) the polymer content of the hybrid particles was notedly lower. A linear polymer structure was supposed. The reaction of poly(2-vinylthiophen) and poly(2-vinylthiophen)/silica hybrid particles with hydridacceptors and FeCl3 was studied. The objectives of this reactions were to generate conjugated structures and to cross-link the polymer by creating bisthiophene structures in a controlled manner. The influence of the reaction time and the nature of the acceptors on the reaction of PVT with the hydride acceptors was examined in detail. The influence of the reaction conditions on the cross-linking reaction with FeCl3 was studied with the help of GPC, IR- und 13C{1H} CP/MAS NMR spectroscopy.

Submitted in part fulfilment of the requirements for the Master's Diploma of Technology: Chemistry, M. L. Sultan Technikon, 1992.<br>2- Vinylfuran has been synthesised from furan, obtained from furfural a degradation product of bagasse, and has the potential to be used as a monomer in the Polymer Industry. Furan was successfully reacted with ethylene under catalytic conditions of palladium (II) acetate and copper (II) acetate to produce 2-vinylfuran, via a direct substitution reaction, at atmospheric pressure and a temperature of 9Y C for two hours in dimethylformamide.<br>M

Im Rahmen der vorliegenden Arbeit werden die Synthese und Charakterisierung eines thermisch-kontrollierten und eines photochemisch-kontrollierten reversiblen Polymersystems vorgestellt. Weiterhin werden Poly(dimethyl)siloxan-Oberflächen mit Amino-, Isocyanat-, Furan-, Maleimid- und Cumarin-Gruppen funktionalisiert. Hierbei werden sowohl bekannte als auch neuartige Wege der Oberflächenmodifizierung vergleichend untersucht und bewertet. Ausgehend von den hergestellten Cumarin-funktionalisierten Poly(dimethyl)siloxan-Oberflächen wird eine Anbindung des synthetisierten photochemisch-kontrollierten reversiblen Polymersystems an diese Oberflächen untersucht. Des Weiteren wird die Anbindung des synthetisierten thermisch kontrollierten reversiblen Polymersystems sowohl an den hergestellten Maleimid- als auch an den Furan-funktionalisierten Poly(dimethyl)siloxan-Oberflächen analysiert. Basierend auf den vorgestellten Cumarin-Funktionalisierungen werden photoaktive Oberflächen beschrieben und mittels ATR-IR-spektroskopischer und UV/Vis-spektroskopischer Methoden analysiert.:Inhaltsverzeichnis 6 Abkürzungsverzeichnis 10 Kapitel I Einleitung und Zielstellung 13 I.I Poly(dimethyl)siloxan 13 I.II Funktionalisierung von Oberflächen 15 I.III Reversible Polymere an Oberflächen 18 I.IV Photoaktive Oberflächen 20 Kapitel II Sauerstoffplasma-Modifizierung 21 II.I Vorbetrachtung 21 II.I. a) Plasmen – Definition und Charakterisierung 21 II.I. b) Technisch angewandte Plasmaprozesse 24 II.II Hintergrund und Motivation Sauerstoffplasma-modifizierter PDMS-Oberflächen 27 II.II. a) ATR-IR-spektroskopische Charakterisierung von Sauerstoffplasma-modifizierten PDMS-Oberflächen 28 II.II. b) Rasterkraftmikroskopische Charakterisierung von Sauerstoffplasma-modifizierten PDMS-Oberflächen 34 II.II. c) Untersuchungen zum Quellverhalten von PDMS 35 II.III Zusammenfassung 38 II.IV Experimenteller Teil 39 II.IV. a) Herstellung von Substraten aus Poly(dimethyl)siloxan 39 II.IV. b) Sauerstoffplasma-Modifikation von Poly(dimethyl)siloxan 39 Kapitel III Amino-funktionalisierte Oberflächen 40 III.I Hintergrund und Motivation Amino-funktionalisierter Oberflächen 40 III.I. a) Amino-Funktionalisierung mittels 3 Aminopropyltriethoxysilan (APTES) 41 III.I. b) Amino-Funktionalisierung nach Balachander & Sukenik 43 III.I. c) Amino-Funktionalisierung mittels Phenylendiisocyanat (PDI) 45 III.II Kontaktwinkelanalyse von unterschiedlichen Amino-Beschichtungen 48 III.III Zusammenfassung 49 III.IV Experimenteller Teil 50 III.IV. a) Amino-Funktionalisierung von PDMS-Substraten mittels APTES 50 III.IV. b) Amino-Funktionalisierung von PDMS-Substraten nach Balachander & Sukenik 50 III.IV. c) Amino-Funktionalisierung von PDMS-Substraten mittels PDI 51 Kapitel IV Maleimid-funktionalisierte Oberflächen 52 IV.I Hintergrund und Motivation Maleimid-funktionalisierter Oberflächen 52 IV.II Synthese Maleimid-funktionalisierter PDMS-Oberflächen 53 IV.II. a) Syntheseroute via Maleinsäureanhydrid (MSA-Route) 53 IV.II. b) Trichlorosilyl-funktionalisierte Maleimid-Derivate 56 IV.III Experimenteller Teil 59 IV.III. a) Synthese eines furangeschützten Maleimids 59 IV.III. b) Synthese eines furangeschützten Undec-10-enyl-1-maleimids (13) 59 IV.III. c) Synthese eines furangeschützten 11-Trichlorosilyl-undecyl-1-maleimids (14) 60 IV.III. d) Maleimid-Funktionalisierung von PDMS-Substraten mittels MSA 61 IV.III. e) Maleimid-Funktionalisierung von PDMS-Substraten mittels trichlorosilyl-funktionalisierter Maleimid-Derivate 62 Kapitel V Furan-funktionalisierte Oberflächen 63 V.I Hintergrund und Motivation Furan-funktionalisierter Oberflächen 63 V.II Herstellung Furan-funktionalisierter PDMS-Oberflächen 65 V.II. a) Trichlorosilyl-funktionalisierte Furan-Derivate an Hydroxyl-Oberflächen 65 V.II. b) Furfural an Amino-Oberflächen 67 V.II. c) Furfurylalkohol an Isocyanat-Oberflächen 69 V.III Zusammenfassung 71 V.IV Experimenteller Teil 72 V.IV. a) Synthese von Undec-10-enyl-furan-2-carboxylat (15) vgl. 72 V.IV. b) Synthese von 11-(Trichlorosilyl)undecyl- furan-2-carboxylat (16) vgl. 72 V.IV. c) Furan-Funktionalisierung mittels 11 (Trichlorosilyl)undecyl furan 2 carboxylat (16) 73 V.IV. d) Furan-Funktionalisierung mittels Furfural nach 74 V.IV. e) Furan-Funktionalisierung mittels Furfurylalkohol vgl. 74 Kapitel VI Reversible Polymere 75 VI.I Hintergrund und Motivation reversibler Polymere 75 VI.II Thermisch-kontrollierte reversible Polymerisation (DIELS-ALDER-Reaktion) 77 VI.II. a) Hintergrund thermisch-kontrollierter reversibler Polymerisationen 77 VI.II. b) DIELS-ALDER-AB-Monomer mit flexiblem Spacer 80 VI.II. c) Charakterisierung der thermisch-kontrollierten Polymerisation 83 VI.III Zusammenfassung 96 VI.IV Photochemisch-kontrollierte reversible Polymerisation 97 VI.IV. a) Hintergrund photochemisch-kontrollierter reversibler Polymerisationen 97 VI.IV. b) Synthese geeigneter Biscumarine 101 VI.V Experimenteller Teil 108 VI.V. a) Thermisch-kontrollierte reversible Polymerisationen 108 VI.V. b) Photochemisch-kontrollierte reversible Polymerisationen 114 Kapitel VII Reversible Polymere an Oberflächen 117 VII.I Anbinden von DIELS-ALDER-AB-Polymeren an Maleimid- und Furan-Oberflächen 117 VII.I. a) ATR-IR-spektroskopische Charakterisierung 119 VII.II Zusammenfassung 121 VII.III Anbinden von Biscumarinen an Cumarin-Oberflächen 122 VII.III. a) ATR-IR-spektroskopische Charakterisierung 123 VII.IV Zusammenfassung 125 VII.V Experimenteller Teil 126 VII.V. a) Anbinden von DIELS-ALDER-AB-Polymeren an Maleimid-Oberflächen 126 VII.V. b) Anbinden von DIELS-ALDER-AB-Polymeren an Furan-Oberflächen 126 VII.V. c) Anbinden von Biscumarin an Cumarin-Oberflächen 126 Kapitel VIII Photoaktive Oberflächen 127 VIII.I Hintergrund und Motivation Cumarin-funktionalisierter Oberflächen 127 VIII.II Synthese Cumarin-funktionalisierter PDMS-Oberflächen 129 VIII.II. a) Funktionalisierung von PDMS-Oberflächen mit Cumarin-Gruppen 129 VIII.II. b) Allgemeine Bemerkung zur Wahl des Lösungsmittels 130 VIII.II. c) Photochemie von Cumarin-funktionalisierten PDMS-Oberflächen 131 VIII.II. d) ATR-IR-spektroskopische Charakterisierung photoaktiver Cumarin-Beschichtungen 132 VIII.III UV/Vis-spektroskopische Charakterisierung photoaktiver Cumarin-Beschichtungen 137 VIII.III. a) Belichtung mit UVA-Strahlung 137 VIII.III. b) Belichtung mit UVC-Strahlung 140 VIII.IV Zusammenfassung 142 VIII.V Experimenteller Teil 144 VIII.V. a) Funktionalisierung von PDMS-Substraten mit Isocyanat 144 VIII.V. b) Funktionalisierung von PDMS-Substraten mit Cumarin 144 VIII.V. c) Photochemisch-kontrollierte Modifikation von PDMS-Substraten mit Cumarin-Beschichtung 144 Kapitel IX Zusammenfassung und Ausblick 145 Kapitel X Anhang 150 X.I Messmethoden 150 X.I. a) ATR-IR-Spektroskopie 150 X.I. b) UV/Vis-Spektroskopie 150 X.I. c) Kontaktwinkelanalyse 151 X.I. d) Rasterkraftmikroskopie (AFM) 151 X.I. e) NMR-Spektroskopie 152 X.I. f) Größenausschluss-Chromatographie (SEC) 152 X.I. g) Thermoanalyse (TA) 152 X.I. h) Thermogravimetrie (TGA) 153 X.I. i) Dynamische Differenzkalorimetrie (DSC) 153 X.II Trocknen von Lösungsmitteln , 153 Kapitel XI Literatur 154 Selbstständigkeitserklärung 161 Lebenslauf 162 Danksagung 163