The effect of carrier concentration and dye type on carrier and dye uptake of Dacron type 54 yarn was determined. Disperse Red 60 and Disperse Yellow 54 dyes were used. 0-phenyl phenol was used with six different concentrations of this carrier (0, 1, 2, 3, 4 and 5 gm/l). Spun Dacron type 54 polyester yarn of 490 denier weighing ten grams was obtained. Dyeing was done using the Ahiba Texomat dyeing machine. The standard composite curves and equations were established for both dyes as well as the carrier. The dye in the yarn was extracted with dimethyl formamide as a solvent using the Fisher Shaking Water Bath. To measure the dye and carrier uptake of the polyester yarn, the extraction and dye bath solutions were analyzed spectrophotometrically. A two-way factorial Analysis of Variance (ANOVA) was used to test the hypotheses. The first null hypothesis indicating that there will be no difference in the uptake of disperse dye by polyester fiber due to initial carrier concentration was rejected. The second null hypothesis indicating that there will be no difference in the uptake of disperse dye by the polyester fiber due to dye type was also rejected. The third and fourth null hypotheses of no difference in the carrier uptake of polyester fiber due to initial carrier concentration and dye type respectively were likewise rejected. The results of this study indicated that both carrier concentration and dye type as well as their interaction have a significant effect on dye and carrier uptake of the polyester yarn. / Master of Science

Chemical grouting has been used to insure the stability of underground mine openings for more than twenty years. The polyurethane grout, which is currently being used, has a limited range of mechanical properties that restrict its utilization. Polyurethane also poses serious threats to miners' health due to its toxicity and flammability, To overcome many of these problems and limitations, research has been conducted on a newly developed polyester-based grout. The assessment of mechanical properties of polyester grout is the focus of this work. Field experiences and laboratory research have defined properties which an effective grouting material should possess. Experimental results indicate that the polyester grout meets or exceeds these recommended properties and has the potential to expand the applicability of chemical grouting in ground control. By adjusting its formulations, mechanical properties of polyester grout can be engineered to solve specific ground control problems. / Master of Science

Changes in nylon 6.6 and polyester filament yarns were determined after heat treatment with dry heat at various temperatures under constant length conditions. An attempt was made to relate structural changes and changes in physical properties due to heat setting. Density, obtained by the density gradient column technique, was used to calculate the degree of crystallinity as a structural parameter. Filament tensile strength and elongation at break were measured on a constant-rate-of-extension machine, and then toughness of the sample was obtained from the load elongation curve. The amount of dye uptake was estimated spectrophotometrically. Degree of crystallinity increased significantly as temperature increased for both nylon 6.6 and polyester fibers. Tenacity decreased substantially for nylon 6.6 and increased marginally for polyester. Elongation and toughness at break decreased for both nylon 6.6 and polyester. Tenacity of nylon 6.6 decreased despite an increase in degree of crystallinity. This suggests degradation of the fibers. Therefore, degree of crystallinity appeared to be of little importance as a contributor to change in tensile strength for degraded nylon 6.6. Tenacity of polyester was well predicted by degree of crystallinity. As crystallinity increased, tenacity of polyester increased. Elongation and toughness of both nylon 6.6 and polyester decreased as degree of crystallinity increased, but the relationship to crystallinity for polyester was not significant. Dyeability of both nylon 6.6 and polyester was well predicted by degree of crystallinity. In both cases, the amount of dye uptake decreased as crystallinity increased. This research suggests that determinations for structural changes such as degradation and orientation might be utilized in addition to crystallinity to predict tenacity of nylon 6.6 and elongation and toughness of polyester. / Ph. D.

Flamskyddande kemikalier används idag inom en hel del olika områden. Ett stort område är textil, där hemtextil är dominerande. Det finns en mängd olika typer av flamskydd på marknaden. Alla har till uppgift att sakta ner brandförloppet eller helt förhindra att en brand uppstår. De halogenerade flamskydden är de mest effektiva men har många kopplingar till miljöproblem. De fosforbaserade och kvävebaserade är snällare mot miljön med mindre effektiva än de halogenerade. Ofta kombineras de fosfor- och de kvävebaserade flamskydden för att få bättre egenskaper på slutprodukten.Denna rapport innehåller, på uppdrag av FOV Fabrics AB, en kartläggning av flamskyddsmarknaden i Europa, med fokus på de produkter som kan tillämpas på material av polyester och polyamid. Målet är att finna flamskyddsmedel för dessa som dessutom är tvättbeständiga samt relativt ofarliga för miljön. De produkter som anses relevanta testas sedan gentemot den internationella brandstandarden, ISO 6941, vilket innebär att en provbit belagd/impregnerad med kemikalien fästs vertikalt i en anordning. Tygprovet utsätts sedan för en horisontell låga i tio sekunder. Därefter görs mätningar på exempelvis den tid det tar tills tygprovet slocknat, samt andel skadat material. Rapporten innehåller även information om övriga tester som utförts, såsom drag- och rivstyrka, tvättbeständighet och färgförändringsmätningar på de produkter som visat tillfredsställande resultat i brandtesterna.Av de nio produkter vi testade fann vi varierade resultat. En del uppfyllde inte våra krav med avseende på flamskydd, och en del visade sig ha mycket dålig tvättbeständighet. Vi fann dock några produkter för båda materialen, två för polyester och fyra för polyamid, som är aktuella att göra vidare tester på. Eventuellt kvävs justering av koncentrationer och appliceringsrutiner för att möta FOV:s önskemål.Flame-retardant chemicals are used today in a lot of different areas. A large area is textiles, where upholstery textiles are dominant. There are many different types of flame retardants on the market, and the purpose is to slow down or completely prevent a fire. The halogenated flame retardant is the most effective but has many links to environmental problems. The phosphorous and nitrogen-based is kinder to the environment but often with less efficiency than the halogenated. When phosphorous and nitrogen flame retardants are combined, the two often get better features.This report, commissioned by the company FOV Fabrics AB, contains a scan of the flame retardant market in Europe, focusing on those products that can be applied to textiles of polyester and polyamide. The goal is to find the flame retardant for these materials, which are also wash resistant and has a relatively low environmental impact. The products that are deemed relevant are then tested against the international fire standard, ISO 6941, which means that a test piece, which has been coated/finished with the chemical, is fastened vertically on a device and then ignited by a horizontal flame for ten seconds. Thereafter, measurements are taken as regards to the amount of time before the test piece burns out and the proportion of damaged material. The report also includes information about other tests conducted, such as tensile- and tear strength, wash resistance and color change. These measurements are made on those products which have shown satisfactory performance in regards to the fire tests.Among the nine products we tested, we found varied results. Some did not meet our requirements for fire protection, and some were found to have very poor wash resistance. We found, however, a couple of products for polyester and four products for polyamide which showed such good results that they are relevant for further testing. Adjustment of concentration and application procedures may be adjusted to achieve the requirements of FOV's specifications. / Program: Textilingenjörsutbildningen

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.

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.

In unserem alltäglichen Leben nehmen Kunststoffe eine immer größere Rolle ein. Die organische Struktur dieser Materialien bedingt die Brennbarkeit derselbigen und birgt somit eine Gefahr, die allgegenwärtig ist. Flammschutz von Polymeren ist daher eine wichtige Eigenschaft. Der Markt an Flammschutzadditiven ist bereits sehr breit gefächert. Allerdings gibt es nur wenig Studien, die systematisch Struktur und Flammschutzwirkung betrachten. So war es das Ziel dieser Arbeit, durch die Untersuchung zweier systematisch variierter Polymergruppen Struktur-Eigenschafts-Beziehungen zu entwicklen, die das Verständnis von Flammschutzadditiven erweitern. Die erste Gruppe bestand aus Polyestern mit einem gleichbleibenden Polymerrückrat an dem phosphorhaltige Seitenketten systematisch variiert wurden. In der zweiten Gruppe wurde das Polymergrundgerüst bei gleichbleibendem Substituenten variiert. Die Strukturen wurden umfassend hinsichtlich ihres Abbaus untersucht, so das durch Korrelation von Abbauverhalten und erarbeiteten Abbaumechanismen Zusammenhänge zwischen der nativen Polymerstruktur und dem Flammschutzverhalten gefunden werden konnten. Es lässt sich nachweisen, dass das Hauptabbaumaximum fast vollständig durch die Polymergrundkette dirigiert wird. Der Substituent hat wenig Einflauss darauf, womit sich die Möglichkeit ergibt Flammschutzadditive gezielt and das Abbaumaximum des zu schützenden Matrixpolymers anzupassen. Die strukturelle Veränderung des phosphorhaltigen Substituenten hingegen ermöglich es das Flammschutzadditv in seiner Wirkungsweise, also Aktivität in der Gasphase oder kondensierten Phase, anzupassen. Sehr wesentlich, besonders mit Blick auf die Rückstandbildung, ist das Zusammenspiel zwischen Substituent und Polymerrückgrat. Bei geeigneter Wahl aliphatischer und aromatischer Anteile lassen sich so Flammschutzadditive herstellen, die einerseits gut zu verarbeiten sind, andererseits aber auch einen möglichst hohen Rückstand erzeugen. Mit Kenntnis dieser Struktur-Eigenschafts-Beziehungen ist es zukünftig möglich, polymere Flammschutzadditive zielgerichteter zu entwickeln. So lässt sich das Additiv in seiner Wirkung nicht nur an das Matrixpolymer anpassen, sondern auch an die primären Brandgefahren in dessen Endanwendung. Eine Under-the-hood-Anwendung im Automobilbau fordert andere Flammschutzeigenschaften als die Verwendung im häuslichen Küchenbedarf.

L'objectif de ce travail est de développer des catalyseurs originaux et performants à base de lipases immobilisées sur argiles pour la synthèse de biopolyesters et d’obtenir des nanohybrides organique/inorganique par greffage de chaînes polyesters sur les nanoparticules d'argiles. Deux argiles (sépiolite et montmorillonite) ont été utilisées pour l'immobilisation de Candida antarctica lipase B (CALB) et les catalyseurs obtenus ont été testés en polymérisation de l'ε-caprolactone et des isomères de lactide. Les cinétiques de polymérisation et la caractérisation des polyesters ont montré que les lipases immobilisées sur montmorillonite sont plus performantes que celles immobilisées sur sepiolite. L’organo-modification de ces argiles améliore l’activité catalytique des systèmes obtenus. L'utilisation de CALB immobilisée sur montmorillonite a permis l’élaboration de nanohybrides organique/inorganique via le greffage et la croissance des chaînes polyesters à partir de la surface de l’argile. Finalement, des copolyesters statistiques PCL/PLA ont été obtenus avec succès par polymérisation enzymatique du D-lactide avec l'ε-caprolactone. / This thesis aims at presenting the use and development of original catalytic systems based on lipases immobilized on clays which are efficient for the synthesis of biopolyesters and allowing the preparation of organic/inorganic nanohybrids based on clay nanoparticles (sepiolite and montmorillonite) grafted with such polyesters. These nanoclays were used as lipase supports and the clay-immobilized forms of Candida antarctica lipase B (CALB) were tested for ε-caprolactone and lactide isomers polymerization. Polymerization kinetics and characterization of resulting materials have shown that lipases immobilized on montmorillonite show better performances compared to the ones immobilized on sepiolite. Clay surface organo-modification has proved to greatly enhance the catalytic activity of the corresponding systems. CALB immobilized on montmorillonite allowed the elaboration of organic/inorganic nanohybrids as evidenced by the effective grafting of polyester chains from the clay surface. Finally, random PCL/PLA copolyesters were successfully obtained by lipase-catalyzed copolymerization of D-lactide with ε-caprolactone.

Dans le contexte du développement des bio-raffineries, le glycérol et ses dérivéssont des co-produits de l’oléochimie pour lesquels de nouvelles voies de valorisation doiventêtre trouvées. Cette thèse porte sur l’étude de la polymérisabilité d’un dérivé du glycérol, ledivinylglycol (DVG), monomère symétrique à 6 carbones qui possède un diol vicinal et deuxfonctions vinyliques. Dans ces travaux, la réactivité des fonctions hydroxyle et vinyliques duDVG dans des réactions de polycondensation et polyaddition a été investiguée. Dans unpremier temps, la synthèse de polyesters et de polyuréthanes a été réalisée par réaction duDVG avec des diesters biosourcés et des diisocyanates, respectivement. Les fonctionsvinyliques du DVG ont ensuite été mises à profit pour synthétiser des polymères originaux parpolymérisation par ADMET et addition thiol-ène. Enfin, des réseaux tridimensionnels époxyamineont été préparés par polymérisation entre une série de diamines et le DVG bis-époxydé,préalablement obtenu par oxydation des doubles liaisons. Ces différentes méthodes depolymérisation ont montré que les doubles liaisons du DVG étaient plus réactives que lesfonctions alcool et qu’un panel de polymères originaux pouvait être obtenu à partir de cesynthon bio-sourcé. / In the context of the development of bio-refineries, glycerol and its derivatives areco-products of oleochemistry for which new valorization routes must be found. This thesisdeals with the polymerizability study of a glycerol derivative, divinylglycol (DVG), asymmetrical C-6 monomer which bears a vicinal diol and two vinyl functions. In this work, thereactivity of the hydroxyl and vinyl functions of DVG in polycondensation and polyadditionreactions was studied. In a first step, the synthesis of polyesters and polyurethanes wascarried out by reaction of DVG with biosourced diesters and diisocyanates, respectively. Thevinyl functions of DVG were then used to synthesize original polymers by ADMETpolymerization and thiol-ene addition. Finally, three-dimensional epoxy-amine networkswere prepared by polymerization between a series of diamines and the bis-epoxidized DVG,previously obtained by oxidation of the double bonds. These different methods ofpolymerization showed that DVG double bonds were more reactive than the alcohol functionsand that a panel of original polymers could be obtained from this bio-sourced synthon.

Nanoparticles from biodegradable polymers are considered one of the most promising systems for biomedical application as drug delivery systems. Therefore, the synthesis and characterization of a new aliphatic biodegradable copolyester named PBS/PBDL (poly(butylene succinate-co- butylene dilinoleate)) intended to the application as drug delivery system is reported in the thesis. Surfactant-free biodegradable and narrowly distributed, nanosized spherical particles (RH < 60 nm) have been produced from the biodegradable material by applying a single-step nanoprecipitation protocol. The size of the generated polymer nanoparticles (PNPs) could be controlled by adjusting the polymer concentration, the choice of organic solvent, mixing different organic solvents or by changing temperature and ionic strength. By optimizing such parameters sub-100 nm uniform PNPs can be produced through this methodology including the advantage and ability to scale-up production. The nanoparticles structure was characterized in detail by employing a variety of scattering techniques and transmission electron microscopy (TEM). Combined static light scattering (SLS) and dynamic light scattering (DLS) measurements suggested that the nanoparticles comprise a porous core conferring them a non-compact characteristic. Their porosity...