Nous nous sommes attachés à trouver de nouvelles applications de la réaction de transfert O-N acylique pour la synthèse de peptides et de polypeptides. Nous avons mis au point une nouvelle voie pour la synthèse de peptide alcool sur support solide. Cette méthodologie a permis de préparer 3 peptides alcool modèles comme l'Octréotide avec de bons rendements et d'excellentes puretés. Nous avons développé une nouvelle stratégie pour la synthèse de polyamide à partir de polyester via une réaction de multi-transfert O-N acylique. Pour cela, nous avons isolé trois générations de polymères : les polyesters Z-protégés après polymérisation, les polyesters hydrosolubles après le clivage des groupements Z et les polyamides après multi-transfert O-N acylique dans des conditions basiques organiques et à pH physiologique. Cette stratégie a été appliquée à la synthèse de polyamide de sérine et de sérine gamma-homologuée. Maintenant, nous développons une nouvelle stratégie de polymérisation de séquence peptidique contenant une sérine N-protégée en position N-terminale. Comme décrit précédemment pour les polysérines, les objectifs de cette étude sont de synthétiser in fine des polypeptides à partir des polypeptides/esters correspondants. / We founded some news applications of the O-N acyl transfer, notably for the synthesis of peptides and polypeptides. We optimized a new general voice for the preparation of peptides alcohol on solid support. This methodology permits to synthesize 3 peptides alcohol with yield and purity, notably Octreotide. We developed a new strategy for the synthesis of polyamide from polyester using an O-N acyl multi-transfer reaction. We have isolated 3 generations of polymers: the Z-protected polyesters after polymerization (polycondensation and ROP), the unprotected water-soluble polyesters after the cleavage of the protection Z and the polyamides after the O-N acyl multi-transfer in basic organic condition or in phosphate buffer. This methodology was applied to the synthesis of the polyamide serine and gamma-homologated serine. Currently, we are developing a new methodology for the polymerization peptide sequence containing an N-protected serine in N-terminal position. As previously described on polyserine, the objectives of this polymerization are to generate polypeptides from the corresponding polypeptides/esters.

<p>U ovom radu vr&scaron;ena su istraživanja u cilju razvoja novih postupaka sinteze za nekoliko vrsta polimernih mreža i hibridnih biopolimernih materijala za specijalne primene. Cilj je bio da se razvije novi postupak sinteze rotaksana na bazi poli(etilen glikola) i &beta;-ciklodekstrina kaoprekursora mreža. Dobijeni prekursori mreža iskori&scaron;ćeni su za sintezu topolo&scaron;kih gelova koji su umreženi preko hidroksilnih grupa ciklodekstrinskih prstena. Analiziran je i uticaj količine umreživača, odnosno gustine umreženja, na svojstva bubrenja. Proučavan je i uticaj nanopunila na svojstva modelnih epoksi mreža na bazi bisfenola A i poli(oksi propilen) diamina. Kao punila kori&scaron;ćene su nanočestice nemodifikovanog i povr&scaron;inski modifikovanog titanijum(IV)oksida (TiO₂). Dinamičko-mehaničkom analizom potvrđen je ojačavajući efekat punila. Razvijen je postupak sinteze poli(D,L-laktida) u mikrotalasnom polju, čime je drastično smanjeno vreme polimerizacije (sa 150 sati na 15 minuta) u odnosu na klasičnu termosintezu. Sintezom poli(laktida) kao i kopolimera poli(laktida) sa biorazgradivim monomerima (na osnovu obnovljivih sirovina) dobijeni su materijali izuzetnih ekolo&scaron;kih svojstava. Poli(laktid) se odlikuje veoma dobrim mehaničkim svojstvima i biorazgradivo&scaron;ću, dok je blok-kopolimerizacijom sa drugim biorazgradivim monomerima vr&scaron;ena sinteza termoplastičnih poliestara. Variranje dužine segmenata je ostvareno sintezom adekvatnih oligomera kao prekursora za kopolimerizaciju. Vr&scaron;eno je projektovanje sirovinskog sastava segmentiranih elastomera kod kojih postojanje mekih i tvrdih segmenata ima za posledicu mikrofaznu separaciju faza &scaron;to u toku eksploatacije utiče na mehanička svojstva i mogućnost III razgradnje. Na taj način dobijeni su elastomerni materijali željenih svojstava. Metodama FTIC i 1H NMR spektroskopijom potvrđena je pretpostavljena struktura segmenata i finalnih termoplastičnih poliestara. Analizom molskih masa poliestara metodama gel propusne hromatografije, viskozimetrije i osmometrije napona pare, potvrđena je izuzetna kontrola reakcija polimerizacije i uspe&scaron;nost primenjenih metoda sinteze. Analiza toplotnih svojstava blok poliestara diferencijalno skenirajućom kalorimetrijom je pokazala da zbog neme&scaron;ljivosti faza, tvrdih i mekih segmenata, finalni blok poliestri mogu da pokažu razlike u temperaturama faznih transformacija u zavisnosti od dužine i udela segmenata. Termogravimetrijskom analizom je potvrđen uticaj dužine segmenata i faznog razdvajanja na toplotna svojstva termoplastičnih poliestara. Očekuje se da će sintetisani materijali biti podesni za primene u inženjerstvu tkiva, a posebno kao materijali za kontrolisano otpu&scaron;tanje lekova.</p> / <p>The primary goal of the work described in this thesis was to develop new methods for the<br />synthesis of polymer networks and hybrid biopolymers for special applications. The purpose was a development of synthesis procedure for the preparation of rotaxane based on poly(ethylene glycol) and &beta;-cyclodextrin, as network precursors. These network precursors were then cross-linked through hydroxy groups on cyclodextrine rings. Polyrotaxanes are intermediary products in the synthesis of topological gels and they are formed by the insertion of the linear polymer chains of poly(ethylene oxide) into the &beta;-CD cavities. In this work polyrotaxanes from acetylated-&beta;-CD and poly(ethylene oxide) were synthesized. The influence of crosslinker contents, and crosslink density on swelling properties was investigated. The influence of synthesis parameters and filler modification on reactions and final properties of organic-inorganic hybrid materials based on epoxy resin and an organically modified titanium(IV)oxide (TiO2) was investigated. Dynamic-mechanical analysis was used to determine reinforcement effect of nanofiller on the epoxy resin properties. The aim of this work was the investigation of microwave irradiation on the polymerization of D,L-lactide. It was found that if heating is carried out in the microwave field polymerization time of D,Llactide rapidly decreases from 150 hours to 15 minutes. Environmentally friendly materials were obtained from poly(lactide) and copolymers of poly(lactide) and monomers based on renewable resources. Poly(lactide) is biocompatible and biodegradable polymer with high stretching and low extension capacities. It has been used for the production of orthopedic fraction fixators and sutures surgery. Poly(lactide) was used for thermoplastic polyester (TPE) synthesis. Most thermoplastic polyesters derive their properties from segmented or block structures which are achieved by alternating hard and soft segments. FT-IR and 1H NMR spectroscopy were confirmed the assumed structure of segments and final thermoplastic polyesters. Since the properties of these materials strongly depend on the degree of phase separation, the influence of the lenghts of soft and hard segment on final properties of obtained TPEs was studied. Analysis of molecular mass of these polyesters by gel permeation chromatography, vapor pressure osmometry and viscozimetric analysis confirmed that good control of polymerization was achieved and that synthesis methods were successful. Thermal properties were characterized by means of differential scanning calorimetry (DSC) and thermo-gravimetric analysis (TGA). Phase separation had strong influences on thermal properties of obtained TPEs. DCS measurements showed that due to poor mixability of hard and soft segments, final block polyesters could have different temperatures of phase transitions depending on the length of the segments. Thermal degradation and the influence of phase separation on thermal stability of segmented thermoplastic polyesters were confirmed by nonisothermal analysis, using thermogravimetric analysis. It is expected that synthesized materials will be suitable for tissue engineering and as drug carriers.</p>

Zielsetzung dieser Arbeit war die Zähmodifizierung eines neuen besonders hochtemperaturbeständigen ungesättigten Polyesters, nachfolgend Referenz genannt. Im Rahmen dieser Arbeit wurden verschiedene konzeptionelle Ansätze verfolgt, um die Harz- und Duromer-Eigenschaften von hochtemperaturbeständigen ungesättigten Polyesterharzen (Unsaturated Polyester Resin, UPR) zu modifizieren und zu verstehen.:1. Einleitung 2. Motivation 3. Theoretischer Teil 4. Charakterisierungsmethoden 5. Ergebnisse und Diskussion 6. Zusammenfassung 7. Experimenteller Teil 8. Literaturverzeichnis 9. Anhang 10. Versicherung

In this work, hyperbranched aromatic polyesters-polyphenols based on 4,4-bis(4’ hydroxy¬phenyl)pentanoic acid (BHPPA) were prepared and, according to the authors knowledge, for the first time tested as precursors for polyurethane bulk resins and coatings. Comparison of poly-BHPPA with competing products The materials prepared in this work show better properties than their aliphatic polyester-polyol analoga based on 2,2-bis-(hydroxymethyl)propanoic acid (BHMPA). Especially, the solubility of poly-BHPPA in organic solvents is better and poly-BHPPAs also do not tend to microphase separation during their reaction with isocyanates, in contrast to poly-BHMPAs. The poly-BHPPA and the polyurethane networks made from them display higher Tg values than analogous poly- BHMPA compounds. Because of the high Tg of the reacting and final systems, curing must occur at elevated temperatures (90°C) in order to avoid undercure. The lower reactivity of phenolic OH groups prevents the reaction from being too fast at that temperature. A drawback of the polyurethanes based on the aromatic polyesters-polyols prepared is the lower thermal stability of their urethane bonds, if compared to aliphatic urethanes. An interesting possibility for future investigations would be the modification of the BHPPA monomer in order to change the OH functionality from phenolic to aliphatic OH, e.g. by replacement of the phenolic OH by hydroxymethyl or hydroxyethyl groups (requires a strong modification of the monomer synthesis) or simpler by reacting the phenolic OH of BHPPA with a suitable reagent like oxirane, which would lead to groups like O-CH2-CH2-OH in the place of the phenolic OH. Such a BHPPA modification should in turn yield modified “poly-BHPPA” polycondensates, which would combine the advantages of poly-BHPPA with those of aliphatic OH precursors of polyurethanes. Poly-BHPPA synthesis Hyperbranched polymers of the 4,4-bis-(4’-hydroxyphenyl)pentanoic acid (BHPPA) were synthesized successfully by the catalyzed (by dibutyltin diacetate) polycondensation of BHPPA. The products obtained were oligomers with number average molecular weight ranging from 1800 to 3400 g/mol (polymerization degree of ca. 6 to 12), displaying a first moment of functionality in the range 7 to 14. Such products were good OH precursors for the preparation of polyurethane coatings, because higher functional polymers would gel at low conversions. The analysis of the functional groups (determination of acid and hydroxyl numbers) and the 1H-NMR and the 13C-NMR spectroscopy were found to be good methods for the determination of molecular weights. The polydispersity of the poly-BHPPA products was in the range 3.5 to 6. Their degree of branching was found to be in the range 0.36 to 0.47. Poly-BHPPA containing aliphatic polyols as core monomers were also prepared successfully. Difunctional and trifunctional core monomers usually reached a full conversion of their OH groups, while the tetra- and hexafunctional core monomers were converted only to 89%. In all these products however, a considerable amount, usually even a majority, of the polymer molecules were core free. The poly-BHPPA products prepared displayed relatively high glass transition temperatures, in the range of 84°C to 114°C, obviously due to interactions between the phenol groups and to hydrogen bridging. The thermal stability of these products was also high, with decomposition occurring near 350°C (at a heating rate of 10°C / min) Kinetics investigations of the poly-BHPPA reactivity towards isocyanates The poly-BHPPA are polyphenols and were expectedly found to react significantly slower with isocyanates than aliphatic alcohols. The reactivity of poly BHPPA was also found to be somewhat lower than that of the monofunctional, low molar-mass 4 ethylphenol. Hexamethylene diisocyanate trimer, Desmodur N3300, was found to be more reactive than hexamethylene diisocyanate (HDI) or butyl isocyanate in all experiments, possibly due to a substitution effect. The substitution effect can be explained by a change of microenvironment caused by conversion of isocyanate group and OH group into urethane groups. The reactions of low-molecular-mass alcohols or phenols with low molecular weight isocyanates followed well the 2nd order kinetics, while the reactions of poly-BHPPA with isocyanates show deviations from ideal 2nd order kinetics at higher conversions. All the kinetics experiments were carried out under catalysis by dibutyltin dilaurate. This catalyst inhibits the undesired reaction of isocyanate groups with moisture. It was also found that the catalysis was necessary to reach reasonable curing times for poly-BHPPA based polyurethane networks. The uncatalyzed systems reacted extremely slowly. Preparation of polyurethane networks from poly-BHPPA The poly BHPPA products prepared were used successfully as OH functional precursors of polyurethane networks. The networks prepared contained only very low sol fractions. Acetone and also ethylene diglycol dimethylether (diglyme) were found to be good swelling solvents for the networks prepared, while methyl propyl ketone was a much poorer solvent and aromatic compounds like toluene or xylene practically did not swell the poly BHPPA based polyurethanes. The networks prepared contain a relatively high amount of cyclic bonds, 40 to 50% in the finally cured state, which is an expected result for systems with precursors of high functionality and with small distances between the functional groups. The temperature of glass transition (Tg) of the networks prepared (ranging from 68°C to 126°C) depends of the poly BHPPA precursor used: it increases with increasing molecular mass and with increasing core functionality. The choice of the isocyanate crosslinker also influences Tg: the networks made from HDI show higher Tg values, than networks made from the same poly BHPPA but crosslinked with Desmodur N3300 (Tri HDI). The urethane bonds in the networks prepared start to decompose near 140°C. The easier degradation of PU with aromatic urethane bonds is a disadvantage in comparison with aliphatic polyurethanes, whose decomposition starts at 200°C. The surfaces of polyurethane coatings prepared are smooth, displaying a roughness of ca. 20-25 nm, and relatively hydrophilic: the contact angle with water was found to be near 80°. The prepared networks are also relatively hard, possessing the Shore D hardness of 70.

Les filaments composites cœur/peau ont été développés dans le but de proposer des capteurs et de effecteurs textiles pour des applications « smart textiles ». Le filage des filaments a été effectué avec une technique de type extrudeuse à piston. Le travail a porté sur la modification d’une machine de filage par fusion, de la caractérisation de polymères, de la caractérisation des filaments développés et de l’optimisation des techniques d’obtention des filaments. La conception du procédé ainsi que son optimisation ont été effectués avec du PET. La modification de la machine a consisté à concevoir les filières, modifier le piston et à introduire un canal d’alimentation sous forme de tube en inox pour sécuriser le passage du filament métallique d’âme dans le four. Ainsi, 10 filières différentes et trois pistons ont été conçus en se fondant sur les règles industrielles puis leurs performances ont été optimisées. Les polymères ont été caractérisés par DSC, par rhéologie et par techniques analytiques. Ces résultats ont montré la forte influence de la température en particulier une forte réduction de la cristallinité du filament composite. L’optimisation des paramètres d’extrusion a pris en compte la vitesse du piston, la vitesse de bobinage, les modifications de la machine dont le nombre de trous des filières, la position du tube dans la filière, les dimensions internes du tube, le diamètre de sortie de la filière. Il a été montré que la conception de la filière a une influence significative sur la forme des filaments obtenus ainsi que sur la concentricité de l’âme. Les propriétés physiques, morphologiques, tribologiques et mécaniques des filaments ont été mesurés. Ainsi, les filaments ont des diamètres compris entre 350 et 500 µm et peuvent être de formes elliptique, triangulaire, rectangulaire ou circulaire et les meilleures propriétés mécaniques sont obtenues avec les filaments le plus réguliers tandis que les filaments irréguliers présentent un coefficient de frottement plus important. Les résultats concernant la rigidité en flexion se sont avérés peu fiables. A partir des paramètres optimisés, un filament composite de polymère ferroélectrique (PVDF 70%-TrFE 30%) avec une âme cuivre a été filé et a montré de parfaites caractéristiques de forme et de concentricité. Ce filament composite peut maintenant être utilisé pour développer des capteurs et des effecteurs, des transmetteurs de signaux, des boucliers électromagnétiques et de l’électronique intégrable dans les vêtements. / A coaxial composite fiber has been developed for the intended application in textile based sensors, actuators and eletric signal transmissions in wearable textile products. The work focuses on melt extrusion machine modification, characterization of polymers, characterization of developed filaments and optimization techniques for obtaining required results. Melt extrusion machine has been used having piston based mechanism. The process design and optimization was done using polyester polymer. The machine modification includes design of spinnert, piston end modification and introduction of separate feeding channel for core filament in the oven. A number of 10 spinnerets designs were developed according to industrial die design rules and optimized for their performance. The piston end designs developed were 3 in number. A stainless steel tube has been introduced into the oven for a separate secure passage of core filament. The polymer characterization was done by thermal, rheological and analytical techniques. The obtained results exhibited thermal attibutes of the polymer and showed reduction in degree of crystallanity in composite filament. The optimization of extrusion parameters including piston speed, winding speed ; and modifications in machine which includes design parameters of number of holes, tube position, tube internal diameter and spinneret exit diameter were done. It was observed that design parameters have significant effect on cross-sectional shape, eccentricity of core and morphology of filament. The characterization of composite filament has been carried out by physical, morphological, mechanical, tribology and bending techniques. The composite filaments developed were in range of 350-500 µm diameter. The filaments developed have elliptical, triangular, rectangular and circular shapes. The regular filaments showed higher tenacity and breaking strength than irregular shaped filaments. The frictional coefficient values were found higher for irregular shapes. Bending stiffness results obtained were not reliable for irregular cross-sectional shapes. The optimized parameters wers used to develop composite filament using ferroelectric polymer (PVDF-TrFE) having 70 :30 ratio copolymer. The developed filament was very regular in shape with good eccentricity of core. The developed Cu/PVDF-TrFE core/sheath filament can be used for development of sensors and actuators. The Cu/Polyester core/sheath filament can be used for electrical signal transmission lines in wearable electronic textiles and for development of electromagnetic shielding effectiveness fabrics.

Mikrofibersläpp vid tvätt lyfts ständigt som ett återkommande problem eftersom de små fragmenten leds ut i vattendragen och påverkar miljön negativt. Mängden mikroplaster är svåra att se och mäta vid endast visuell antydan. Med hjälp av en ny standard för bestämning av mikrofibersläpp finns det nu möjligheter till att bestämma mängden fibrer som lossnar påverkas vid tvätt. För att textilbranschen ska kunna bli mer hållbar krävs ytterligare undersökningar på huruvida teoretisk hållbara val av tillverkningsmetoder verkar i praktiken. Genom att använda sig av olika testmetoder för en simulerad åldring på textilier med olika infärgningsmetoder kan användningsfasens visuella och fysiska påverkan studeras, för att på så vis underlätta vid hållbara val i den textila värdekedjan. Den simulerade åldringen är anpassad efter användningsfasen av de material som används i denna studie. Skillnaden i resultat för vattenavvisningsförmåga, färghärdighet samt den mängd fibrer som lossnar under tvätt, jämförs före och efter den simulerade åldringen. Studien resulterade i att den mer hållbara metoden för infärgning av textil inte bara är teoretiskt bättre utan också genomgående presterade bättre i de tester som utförts på tygerna. Detta med undantag för resultatet i fibersläppsmetoden som efter genomförandet inte kunde jämföras enligt standarden då metoden inte kunde utföras helt korrekt. Problemet visade sig tillsynes vara värdefullt för studien då det resulterade i att det inte bara var fibrer som lossnade vid tvätt utan också beläggning, vilket ansågs vara ännu sämre. Metoden för den genomförda studien har varit användbar för att kunna dra slutsatsen att det spinnfärgade tyget fortsatt är ett mycket bättre val än det styckfärgade. Detta konstaterades efter en statistisk analysmetod av resultaten från de utförda testmetoderna men också genom den visuella indikationen. / Microfiber-pollution from washing is a recurring topic and problem because of the small fragments coming out into the water. The amount of microplastics is hard to see and measure with visual analysis, but by using the new standard method to determine the microfibres when collecting the loss of material it opens facilities to see what and how the quantity is affected. To make a more sustainable business in the textile industry, more studies about how the differences in the manufacturing processes affect the textiles have to be done. By using different test methods for a simulation of aging textiles with two different methods of coloring, the phase of use can be studied and in best case support sustainable choices in the textile value chain. The simulated aging is customized for the phase of use for the material used in this study. The results that will be analyzed are for the water repellency, color fastness and the loss of material, before and after the simulated aging. The study concluded that the more sustainable method for coloring the material is a better choice both theoretical and practical. This was found out from all the tests performed on the materials. Except for the results in the microfibre test that after being performed could not be compared according to the standard when the method could not be accomplished completely correct after problems with the filtration. Otherwise, the problem turned out to be useful for the study after being analyzed because it was not only fibers detached from the specimens but also the water repellency coating. The method for the study has been successfully useful to be able draw the conclusion that the solution dyed material is a better choice than the one being piece dyed. It was found out after the statistical analysis of the results from the performed test methods, but also through a visual indication.

This study has its background in the EU directive, the ‘Single-Use Plastics Directive’. The directive was initiated due to the environmental impacts that the oceans suffer due to plastic waste. The directive presents the most common single-use products found as waste in the oceans, including wipes and cloths. In collaboration with Essity, a global hygiene and health company, this study aims to find a replacement fibre for the currently used polyester fibre in Essity’s industrial cleaning cloths. To this end, we have evaluated the applicability of an agricultural fibre in the aspects of processability and sustainability. A theoretical part including a literature study of agricultural fibres is combined with a practical experimental part to evaluate a manufactured prototype. The theoretical part includes a compilation of the relevant parameters per fibre and the experimental part consists of laboratory tests and a panel test. On this basis, it was concluded that the first agricultural fibre, hemp, did not function adequately in the process due to the variations in fibre length and coarseness. A solution to this problem may be pre-treatments of the fibres. The second fibre, flax, functioned well in the process and may then be considered applicable in the aspect of process. The applicability of an agricultural fibre is possible in industrial cleaning cloths, but the geographical location of cultivation, transport, the chemicals used and irrigation should also be taken into account in the aspects of sustainability. / Bakgrunden till denna studie är EU-direktivet, ‘Single-Use Plastics Directive’. Direktivet har sitt ursprung i de miljöproblem som våra hav lider av på grund av nedskräpningen medplastavfall. Direktivet redovisar de engångsartiklar som återfinns allra mest i haven idag, däribland rengöringsdukar. På förekommen anledningen ska därför denna studie i samarbete med Essity, ett globalt hygien- och hälsoföretag, undersöka möjligheten att ersätta den befintliga polyesterfibern i deras industriella rengöringsdukar. Studien har utvärderat möjligheten att använda en naturlig fiber med avseende på tillverkningsprocess och hållbarhet. För att möjliggöra en utvärdering av en tillverkad prototyp, så har en teoretisk del med en litteraturstudie i kombination med en praktisk experimentell del genomförts. Den teoretiska delen består av en sammanställning av relevanta parametrar för varje fiber och den experimentella delen består av laboratorietester och ett paneltest. Slutsatserna från ett förstaförsök var att hampafibrer inte fungerade i processen på grund av variationer i hampansfiberlängd och grovlek. Att göra en förbehandling skulle kunna vara lösningen. I det andraförsöket med linfibrer, visade det sig att linfibrer fungerar i processen och därför kan vara applicerbar med avseende på tillverkningsprocess. En naturlig fiber kan användas i industriella rengöringsdukar, ur ett hållbarhetsperspektiv är det viktigt att beakta den geografiska platsen för odling, transporter, användning av kemikalier och konstbevattning.

Les polymères issus de la biomasse génèrent depuis quelques années un engouement certain puisqu’ils apparaissent comme de potentiels substituts aux polymères issus de l’industrie pétrolière. Parmi ces monomères récemment développés, l’acide succinique bio-sourcé a reçu une attention particulière notamment pour des applications dans le domaine des polyesters tels que le poly(butylène succinate). La présente thèse décrit la synthèse de ce polymère par estérification directe de l’acide succinique et du 1,4-butanediol dans un réacteur pilote de 7.5 L. Les principaux paramètres du procédé tels que l’excès de diol, la température de trans-estérification ainsi que la pureté de l’acide succinique ont été étudiés. Une attention particulière a été portée sur le choix du catalyseur (son type, la quantité utilisée …) afin d’observer son influence sur le procédé ainsi que sur la stabilité du polymère final. Puis différentes stratégies de modification du poly(butylene succinate) ont été testées pour améliorer à la fois sa mise en forme par extrusion gonflage et les propriétés des films obtenus. Dans ce but l’introduction d’agents de branchements, de silices nanométriques ainsi que des comonomères rigides a été étudiée. / Polymers issued from biomass present a growing interest, since they seem to be a suitable alternative to conventional petrochemical polymers. Among the newly developed monomers, bio-based succinic acid received a particular attention for its application in the synthesis of aliphatic polyesters such as poly(butylene succinate). The present thesis reports the synthesis of this polymer via the direct esterification of succinic acid and 1,4-butanediol in a 7.5 L pilote scale reactor. Main process parameters such as the diol exces, the trans-esterification temperature as well as the purity of succinic acid have been studied. In addition a special attention was taken to highlight the influence of the catalyst (its type, quantity ...) on the synthesis and on the stability of the resulting polymer. Then several strategies of modification of poly(butylene succinate) have been studied to improve the processability of the polymer via film extrusion blowing and to enhance the properties of polymer films. To that end the introduction of branching agents, silica nanofillers as well as rigid comonomers have been studied.

Ce travail s’inscrit dans le développement de formulations performantes et processables pour les liners de réservoirs de stockage hyperbare. Une large gamme de formulations à base polyamide et polyépoxyde a ainsi été synthétisée en conditions contrôlées, représentatives du procédé de rotomoulage. Les systèmes polyamide ont été modifiés par copolymérisation statistique et les polyépoxydes par une phase dispersée micro- ou nano-structurée avec des thermoplastiques de haute Tg ou des copolymères blocs. Les propriétés morphologiques, thermiques, mécaniques et barrière de chaque formulation ont été caractérisées et confrontées au cahier des charges du matériau. En parallèle, l’influence des conditions opératoires et de la formulation sur les rhéocinétiques de polymérisation, de cristallisation, de gélification et/ou de séparation de phase a ainsi été établie. L’ensemble de ces résultats a été mis à profit afin d’identifier des relations structures – propriétés – processabilité en vue de l’application. Afin de valider le potentiel des formulations retenues, ces dernières ont été rotomoulées en conditions opératoires variables avec un suivi in situ de l’écoulement et ex situ de la viscosité. Ce travail a permis d’établir les fenêtres de processabilité de chaque formulation et de comprendre l’origine des défauts d’écoulement. / The aim of this present study is to develop efficient and processable formulations for the liners of high pressure storage tank. A wide range of formulations based on polyamide and polyepoxide has been synthesized under controlled conditions representative of the rotomolding process. The polyamide system has been modified by copolymerization and the polyepoxyde system by a micro- or nano-structured dispersed phase with high Tg thermoplastics or block copolymers. The morphological, thermal, mechanical and barrier properties of each formulation were characterized and compared to the specifications of the material. In parallel, the influence of operating conditions and formulation on the rheokinetics of polymerization, crystallization, gelation and / or phase separation has been established. All of these results have been exploited to identify structure - property - processability relationships for the application. To validate the potential of selected formulations, they were rotationally molded in variable operating conditions with flow monitoring and rheological measure. This work has established the processing windows of each formulation and has allowed an understanding of the origin of flow defects.

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). / 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).