M.Sc. / Natural Organic Matter (NOM) is a complex of organic material present in a natural surface water. Odour, taste and acidity are some of the problems associated with NOM in water systems. Futhermore, it causes the yellow or brown colour of water, whic is aesthetically unpleasant to consumers. NOM is also the energy source of bacterial re-growth and aids in the transportation of metal ions in the distribution system.Moreover, NOM in water can react with disinfectants, e.g. chlorine, to form disinfection by products (DBPs) such as trihalomethanes (THMs) and habacetic acids (HAAs). DBPs have recently been found to have adverse effects in humans. This study was undertaken in order to assess the effectiveness of some of the water treatment techniques employed by selected water supplying companies in dealing with NOM. To achive this, the water treatment processes used by these companies to reduce NOM and metal ions were coagulation, sand filtration, the use of granular activated carbon, ozonation and chlorination. In addition, β-cyclodextrin (β-CD) polyurethanes synthesized in our laboratories were used to remove the DBPs present in the water samples.

Actuellement, les polyuréthanes (PUs) sont produits industriellement par polyaddition entre un diisocyanate et un polyol. Le caractère fortement sensibilisant des isocyanates, mettent ces composés sous forte pression réglementaire au niveau européen (REACH) et ont créé le besoin d'obtenir des PUs ne provenant pas d'isocyanates, lesquels sont plus communément appelés Non-Isocyanate PolyUréthanes (NIPUs). Les travaux de cette thèse visent ainsi à établir de nouvelles voies d'accès à des NIPUs. Des pré-polymères téléchéliques ont été synthétisés via la réaction de métathèse. Plusieurs groupements terminaux (jusqu'à 16), réagissant à température ambiante avec une amine primaire, ont été greffés avec succès à ces pré-polymères. La réaction avec plusieurs diamines a conduit à la synthèse de nouveaux matériaux NIPUs entièrement caractérisés. Les stratégies de synthèses développées au cours de ces travaux de thèse ouvrent de nouvelles perspectives quant à l'industrialisation de NIPUs. / Conventional polyurethanes (PUs) involve the use of isocyanates, which are considerably toxic and require phosgene for their manufacture. To tackle environmental issues, it is necessary to elaborate different routes to PUs. In this context, two isocyanate-free strategies towards the preparation of polythiourethanes (PTUs), i.e. non-isocyanate polyurethanes (NIPUs), have being developed. The first way involves the synthesis of α,ω-di(dithiocyclocarbonate) telechelic poly(propylene glycol) (bis(5DTCC)-PPG), poly(tetrahydrofurane diglycidyl ether) (bis(5DTCC)-PTG), upon chemical modification of the corresponding α,ω-diepoxide telechelic polymers (PPG, PTG, respectively) through cycloaddition of carbon disulfide. The second approach involves the ring-opening metathesis polymerization (ROMP), using Grubbs’ 2nd generation ruthenium catalyst, of cycloolefins using 16 differents chain-transfer agents. Bis(5DTCC) telechelic copolyolefins are thus synthesized. Reaction of the end-capping 5DTCC moieties with a diamine by ring-opening polyaddition ultimately affords at room temperature the corresponding NIPTU.

Les huiles végétales et leurs dérivés ont conduit à de nouveaux précurseurs agro-ressourcés utilisés pour la synthèse de polymères. Grâce au couplage thiol-ène, des polyols ont été obtenus par greffage du mercaptoéthanol directement sur les triglycérides insaturés. De la même manière, les esters méthyliques des huiles végétales ont permis la synthèse d'esters et d'amides diols pseudo-téléchéliques. Des polyols ont également été obtenus grâce à la réaction d'ouverture des cycles oxirane présents sur des huiles végétales époxydées. Différents acides carboxyliques ont permis d'introduire des fonctions hydroxyle sur les triglycérides. Ces différents synthons ont conduit à l'élaboration d'une large gamme de matériaux polyuréthanes, présentant des Tg variant de -10 °C à 100 °C. Le carbonate de glycérol, issu du glycérol agro-ressourcé, a également été utilisé pour l'élaboration de dicyclocarbonates, soit par estérification/trans-estérification à partir de diacides obtenus par greffage de l'acide thioglycolique sur plusieurs acides gras, soit par dimérisation à partir d'un dithiol commercial. Des polyuréthanes sans isocyanate ont ainsi été formulés à partir de ces nouveaux dicyclocarbonates, ouvrant la voie vers des polyhydroxyuréthanes totalement agro-ressourcés. Les précurseurs, ainsi que les matériaux qui en découlent, ont été caractérisés et certains ont fait l'objet de tests à l'échelle pré-industrielle. / Vegetable oils and their derivatives were used to synthesize new precursors suitable for polymer synthesis. Mercaptoethanol was grafted onto unsaturated triglycerides by thiol-ene coupling to yield polyols. This functionalization was also applied to vegetable oil methyl esters, yielding ester and amide containing pseudo-telechelic diols. The second synthetic strategy used ring opening of epoxydized vegetable oils. The reaction between vegetable oil oxiranes and several carboxylic acids afforded a range of polyester polyols. Thus, the synthesized intermediates allowed to formulate various polyurethanes, which exhibited glass transition temperatures ranging from -10 °C to 100 °C. Moreover, either esterification/trans-esterification with fatty acid based diacids, synthesized by thioglycolic acid addition onto different fatty acids, or thiol-ene coupling with a commercial dithiol, were performed on glycerin carbonate, leading to new dicyclocarbonates. Isocyanate free polyurethanes were then obtained from those dicyclocarbonates, opening the way for fully biobased polyhydroxyurethanes. The new precursor, and the polymers therefrom, were deeply characterized and some of them were tested at a pilot scale.

No description available.

The aim of this work is focused on biodegradability study of modified polyurethane materials (foams and foils) in glukose medium and biodegradation of whey. The biodegradability was tested with using mixed thermophilic aerobic bacterial culture of the Bacillus and Thermus genera. The cultivations were practised in the fermentor and in Erlenmayer flasks in a heated shaker. Maximal reduction of COD and culture growth has been achieved by biodegradation of polyuretane in the fermentor. Main effect of degradation was abiotic destruction of PUR materials and consequent utilization of degradation products by bacterial culture. These tests indicated that the best modification agent for biodegradation was 10% carboxymethyl cellulose. The polyurethane foam was more decomposed then the polyurethane foil. Biodegradation of whey without proteins in the fermentor was detected decrease of CHSK and lactose concentration about 50 % in 20th hour. Optimal conditions for whey biodegradation with the thermophilic bacterial culture were pH 6,5 and temperature 60 °C.

Confidentiel. Résumé non fourni. / Confidentiel. Résumé non fourni

Presented diploma thesis focuses on a new type of lightweight polyurethane foam (PUR), which has been manufactured with the intention of it being biodegradable within currently valid norms on biodegradation of plastic materials. The future use of said polyurethane foam is as carrier for odor repellent to avoid wildlife-vehicle collisions in agriculture landscape, where, after the end of its lifespan it could be left to biodegrade in soil the environment. The examined material, PUR BIO-10, was tested for biodegradability in laboratory microcosms according to standardized method ASTM D5988-03. Biodegradability was tested in two separate soil types - forest soil and agricultural soil, which have been selected with the future use of the material in mind. According to the method biodegradability was measured as mineralization of the material by capturing evolved carbon dioxide. During the first trial the mineralization of polyurethane foam was 10.65 ± 2.54 % in the forest soil and 20.48 ± 9.18 % in the agricultural soil. During the second trial the mineralization was 3.88 ± 3.42 % in the forest soil and 8.96 ± 1.79 % in the agricultural soil. In the second trial the difference between the soils was statistically significant. After the end of the biodegradation experiments the tested material was...

Decreasing the carbon footprint through use of renewable materials has environmental and societal impact. Foams are a valuable constituent in buildings by themselves or as a core in sandwich composites. Kenaf is a Southeast USA plant that provides renewable filler. The core of the kenaf is porous with a cell size in a 5-10 micrometer range. The use of kenaf core in foams represents a novel multiscalar cellular structural composite. Rigid polyurethane foams were made using free foaming expansion with kenaf core as filler with loadings of 5, 10 and 15 %. Free foaming was found to negatively affect the mechanical properties. An innovative process was developed to introduce a constraint to expansion during foaming. Two expansion ratios were examined: 40 and 60 % (decreasing expansion ratio). MicroCT and SEM analysis showed a varying structure of open and closed cell pores. The mechanical, thermal insulation, acoustic properties were measured. Pure PU foam showed improved cell size uniformity. Introducing kenaf core resulted in decreasing the PU performance in the free expansion case. This was reversed by introducing constraints. To understand the combined impact of having a mixed close cell and open cell architecture, finite element modeling was done using ANSYS. Models were created with varying percentages of open, closed, and bulk cells to encompass entire range of foam porosities. Net zero energy building information modelling was conducted using EnergyPlus was conducted using natural fiber composite skins. Environmental impacts for instance global warming potential, acidification, eutrophication, fossil fuel consumption, ozone depletion, and smog potential of the materials used in construction was studied using life cycle assessment. The results showed improvement on energy consumption and carbon footprint.

No description available.

Presented diploma thesis focuses on a new type of lightweight polyurethane foam (PUR), which has been manufactured with the intention of it being biodegradable within currently valid norms on biodegradation of plastic materials. The future use of said polyurethane foam is as carrier for odor repellent to avoid wildlife-vehicle collisions in agriculture landscape, where, after the end of its lifespan it could be left to biodegrade in soil the environment. The examined material, PUR BIO-10, was tested for biodegradability in laboratory microcosms according to standardized method ASTM D5988-03. Biodegradability was tested in two separate soil types - forest soil and agricultural soil, which have been selected with the future use of the material in mind. According to the method biodegradability was measured as mineralization of the material by capturing evolved carbon dioxide. Two trials with different treatments were executed. In the first trial the material was introduced directly into the soil and in the second trial the material was tested in a litterbag to avoid soil contamination which was problematic for further analysis. During the first trial, after 90 days, the mineralization of polyurethane foam was 10.65 ± 2.54 % in the forest soil and 20.48 ± 9.18 % in the agricultural soil. During the...