Les revêtements poudres UV suscitent un développement croissant en raison, entre autres, de leurs qualités et de leur respect de la législation sur la minimisation des émissions polluantes. Un nouveau revêtement poudre UV à base de (co)polyamide de faible masse molaire et porteur de fonctions réactives sous UV a été élaboré en vue d'une application sur des supports sensibles aux hautes températures. Nous avons donc synthétisé un copolyamide 6/11/12 alpha, oméga-insaturé présentant une température de fusion de 107°C et une masse molaire moyenne en nombre de 7250 g/mol. L'irradiation sous UV de ce copolyamide, en présence de 4 % en masse de benzophénone, a permis, par polymérisation des doubles liaisons allyliques et formation des liaisons covalentes au niveau des ponts amide, de compenser la perte de cristallinité en le réticulant. Le revêtement obtenu, bien que restant à optimiser, a montré globalement de meilleures propriétés que celles des matériaux références fournis par Arkema.

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In the last two decades, hyperbranched (hb) polymers have drawn much attention and obtained intensive research activities both from industry and academia. They are known to have unique and interesting properties which derive from their three dimensional structure and the large number of functional groups. These structural characteristics provide high possibilities for controlling functional group interactions and modifications of other polymers in blends and therefore, they are expected to result in novel materials with desired properties. Furthermore, the easy synthetic accessibility of hb polymers by one-pot synthesis is advantageous as well and allows easy scale-up of laboratory reactions. Having the characteristics as mentioned above, hb polymers are considered good candidates for blend components or melt processing modifiers. In fact, hb polymers have already been used as blend components or additives aiming for different effects. In many cases, reduced viscosity and formation of miscible blends were observed by modification of a linear matrix polymer with hb polymers. More information will be introduced in the following theoretical section. In this work two hb polyester systems based on AB2 and A2+B3 approaches were synthesized and studied. Their possible applications as additives in the blends of linear polyamides were investigated.

Natural compounds have been the primary resource used to produce polymeric materials by humankind since the mid-1900s. Yet, progress in bio-based polymers from renewable feedstock has encountered some obstacles, mainly due to the low prices of petroleum-based monomers, compared to natural and sustainable materials. However, most commodity plastics are non-degradable materials, and solid plastic waste accumulation adversely affects the environment. As the world population is growing and demanding chemicals, energy, and plastics materials, polymer research is focusing on synthesizing bio-based and degradable polymers. Thus, biomass, a sustainable and inexpensive feedstock, is highly appropriate for designing alternative thermoplastics that are degradable to reduce the current environmental issues. In this dissertation, three different approaches were used to afford alternative thermoplastics to petroleum‐based commodities: bio-based poly(ether-amide)s, random aromatic copolyesters, and copoly(acetal triazole)s. In our first approach, two new lignin‐derived poly(ether‐amide)s (PEA)s were prepared. Their thermal properties showed high degradation temperature (Td) ranging from 330 °C to 380 °C, and glass transition temperature (Tg) between 100 °C and 120 °C. The chemical degradation studies revealed that the PEAs were degradable in 4 M H2SO4, HNO3, and TFA in 3 days. The second polymer group synthesized were semicrystalline bio-based aromatic copolyesters with tunable thermal properties. The thermal analysis of these copolyesters revealed high Td (413 °C to 446 °C) and Tg and Tm ranging from –36 °C to 67 °C and 60 °C to 267 °C, respectively. Their crystallization behavior showed a dependence on the comonomer composition, exhibiting a pseudo-eutectic region. Finally, furfural- and benzaldehyde-based copoly(acetal triazole)s (Td range 280–340 °C) were prepared by click polymerization at room temperature. Preliminary results showed that furfural-based copoly(acetal triazole)s were susceptible to hydrolytic degradation under neutral conditions after only 8 days at 40 °C. Overall, degradable and bio-based polymers were successfully synthesized as a potential thermoplastic alternative for packaging applications.

Biobaserade polymerer är en av möjligheterna för att uppnå mer hållbara plaster och produkter. Polyamider (PA) har mångsidiga tillämpningar alltifrån fibrer i kläder till tillämpningar som bildelar. De mest producerade polyamiderna (PA6 och PA66) står för en årlig fossilbränsleförbrukning på nästan 10 miljoner ton. Skadliga effekter berör inte bara produktionsfasen utan även konsumtionsfasen samt hanteringen av uttjänta produkter. Därför är det ett stort behov av att utveckla biobaserade polyamider som är kemiskt återvinningsbara, för att minska miljöpåverkan från dessa material. I detta arbete syntetiserades furanbaserade polyamider (FPA) genom en polykondensationsreaktion mellan hexametylendiamin (HMDA) och en biobaserad disyra, 2,5-furandikarboxylsyra (FDCA). Dessutom framställdes sampolymerer genom att använda olika förhållanden av C6- och C10-diaminer (HMDA och 1,10-dekandiamin). Strukturen och den kemiska sammansättningen av de syntetiserade polymererna och sampolymererna bekräftades med hjälp av Fourier-transform infraröd spektroskopi och kärnresonansspektroskopi. Den högsta molekylvikten som uppnåddes var 9900 g/mol, främst på grund av begränsningar i reaktoruppställningen (avsaknad av ett vakuumsystem och avsaknad av adekvat blandning). Utöver detta identifierades nedbrytningen av FDCA och förångningen av HMDA som potentiella faktorer som hämmade för högre molekylvikt. Baserat på de termiska analyserna visade sig FPA:erna vara amorfa, med en genomsnittlig glastemperatur på 102°C. Vidare visade de syntetiserade polyamiderna hög termisk stabilitet, med en initial nedbrytningstemperatur (motsvarande 5 % viktförlust) på 340°C. / Biobased polymers is one of the pathways to achieve more sustainable plastics and products. Polyamides (PA) are commodity polymers, having versatile applications from fibers in clothes to car parts. The most produced polyamides (PA6 and PA66) account for yearly fossil-fuel consumption of almost 10 million tonnes. The detrimental effects do not only concern the production phase, but also the consumption and end-of-life aspects. Hence, there is a crucial need to develop bio-based polyamides that are chemically recyclable to reduce the environmental impact of these materials.  In this work, furan-based polyamides (FPAs) were synthesized through a polycondensation reaction between hexamethylenediamine (HMDA) and a biobased diacid, 2,5-furandicarboxylic acid (FDCA). In addition, copolymers were made by using different ratios of C6 and C10 diamines (HMDA and 1,10-decanediamine). The structure and chemical composition of the synthesized polymers and copolymers were confirmed using Fourier-transform infrared spectroscopy, and proton nuclear magnetic resonance. The highest molecular weight attained was 9900 g/mol, mainly due to limitations from the reactor setup (absence of a vacuum system and lack of adequate mixing). Adding to this, the degradation of FDCA and the evaporation of HMDA were identified as potential factors inhibiting the increase in molecular weight. Based on the thermal analyses, the FPAs were found to be amorphous, with an average glass transition temperature of 102°C. Further, the synthesized polyamides showed high thermal stability, having an initial degradation temperature (corresponding to 5% weight loss) of 340°C.

É cada vez maior a utilização de polímeros reforçados com fibra de vidro no mercado nacional. Entre eles utiliza-se a poliamida 6 que apresenta ótima resistência à tração, ao impacto e à absorção de umidade comparada à poliamida 6 sem reforço de fibra de vidro, sendo atualmente utilizada na indústria automobilística em peças sob o capô, em especial em carcaças de radiadores. Este trabalho foi realizado com o objetivo de estudar o efeito da radiação ionizante nas propriedades mecânicas (resistência à tração, à flexão e ao impacto Izod) e térmicas (resistência ao fio incandescente e temperatura de fusão) da poliamida 6 com reforço de fibra de vidro, submetida à diferentes doses de radiação (100 a 600 kGy). As amostras foram preparadas e irradiadas em um acelerador JOB 188 com feixe de elétrons de energia de 1,5 MeV em diferentes doses e uma taxa de dose de 22,61 kGy/h. Após a irradiação, as propriedades das amostras da poliamida 6 com reforço de fibra de vidro irradiada foram determinadas e comparadas com as amostras não irradiadas e constatou-se que as propriedades mecânicas de resistência à flexão e à tração aumentaram e a de resistência ao impacto diminuiu. Em relação à propriedade térmica de temperatura de fusão diminuiu de 224,4ºC para 212,5ºC mas a perda de massa diante do aumento constante da temperatura também diminuiu. Em relação à propriedade de resistência ao fio incandescente a poliamida 6 com reforço de fibra de vidro irradiada teve um bom desempenho. As imagens captadas por Microscopia Eletrônica de Varredura mostram que a irradiação provocou uma boa integração entre a fibra de vidro e o polímero o que foi responsável pelo bom desempenho na propriedade de resistência ao fio incandescente. / It is each time more common the use of polymers reinforced with fibreglass in the domestic market. Between them it is used polyamide 6 that it presents good tension resistance, to the impact and the humidity absorption compared with non-reinforced, being also at the present time used in the automobile industry in parts underneath the hood, especially in the radiator frames. The aim of this work is to study the effect of ionizing radiation on properties of polyamide 6 with fibreglass reinforcement, undergone to different radiation doses. Samples were prepared and irradiated on JOB 188 accelerator with an electron beam energy of 1.5 MeV in air with different doses (100 to 600 kGy) and a dose rate of 22.61 kGy/h. Afterward the irradiation, the properties of the samples of irradiated polyamide 6 with fibreglass reinforcement were evaluated and compared with the samples non-irradiated. It evidenced that the mechanical properties flexural resistance and tension resistance increased and the resistance to the impact decreased. Regarding the thermal properties of the temperature of fusing decreased of 224,4ºC for 212,5ºC but the loss of mass ahead of the constant increase of the temperature also decreased. In the property of resistance to the glow wire the polyamide 6 with fibreglass reinforcement had a good performance. The images caught for Scanning Electronic Microscopy show that the irradiation provoked a good integration enters the fibreglass and polymer what was responsible for the good performance in the property of resistance to the glow wire.

Particles originating from bacteria, fungi (including mold spores, mildew, yeast), pollen, dust mites, and viruses can induce immune responses that trigger allergies and asthma. Carpeting is believed to act as a "sink" where bioparticulates are trapped via adhesive interactions and then are released by foot traffic or cleaning. This scenario can result in an accumulation of contaminants at higher levels than would be found outdoors or in a carpet-less environment. Numerous organizations (school districts, hospitals) have taken steps to remove carpeting, even though this hypothesis remains unproven. While statistical studies exist both in support and denial of the accumulation hypothesis, there is little fundamental understanding of the microscopic-level interactions between carpet and bioparticles. A fundamental understanding of particle affinities with polymers utilized in carpet would help to develop accurate models and address real problems in a rational and productive manner. In addition, a solution to the bioparticulate accumulation problem would have a profound impact on US health, resulting in significant economic savings. More than 20 million people suffer from asthma in the U.S., with children being the most vulnerable. In 2000 there were 9.3 million physician office visits and 1.8 million emergency room visits due to asthma alone, resulting in an estimated $9.4 billion in medical costs and $4.6 billion in lost productivity annually. In this thesis, two measurement techniques were developed to quantify the adhesive interactions between biological particulates and polymeric carpeting materials. Atomic force microscopy (AFM) was used to measure the adhesive interactions of relevant biological particulates (in this case the E. coli bacteria and A. artemisiifolia ragweed pollen grains) with Nylon-6 and Nylon-6,6, polyamide-12 and polystyrene. The adhesion force measurements were modeled using several adhesion theories. We found that the Hamaker models were sufficient for explaining the data, indicating the prominence of van der Waals forces in controlling bioparticle interactions with polyamides. In addition, the geometry of the pollen played a significant role: adhesion forces were approximately a multiple of the number of contact points the grain has with the surface. Forces for E. coli and polyamides were about the same magnitude as polyamide-polyamide surface self-interactions.

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Made available in DSpace on 2014-10-09T12:26:24Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:59Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP