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El consum de tèxtil per habitant creix de manera exponencial, de manera que, el desenvolupament de nous processos sobre la gestió i els tractaments de residus tèxtils resulta una oportunitat clau per aconseguir models integrals d’economia circular que assegurin el tancament dels cicles. Actualment, es calcula que aproximadament un 80% dels residus tèxtils generats estan constituïts per fibres de cotó (CO) i polièster (PES). L’heterogeneïtat en els residus tèxtils és tot un repte per a la indústria tèxtil, per la qual cosa en aquest projecte s’estudia la recuperació de la cel·lulosa provinent de teixits PES/CO a partir de l’ús de líquids iònics (ILs). Inicialment s’analitza l’efecte dels líquids iònics sobre la superfície del teixit, determinant els factors influents referents a l’entrada del IL a l’interior del teixit i el mecanisme químic que governa el sistema. En aquest projecte es contempla l’estudi de les variables de temps, ràtio i temperatura del sistema, amb l’objectiu de definir quina d’elles té una major influència sobre el procés. S’avalua la capacitat dels líquids iònics, en concret de l’AmimCl, per a dissoldre la cel·lulosa i posteriorment regenerar la matèria mitjançant una simulació del procés wet spinning. El medi d’inflament de la fibra, aigua o DMSO, també ha estat un altre factor estudiat, examinant així la influència de cada dissolvent i les interaccions quan entren en contacte amb el líquid iònic. Finalment, de la matèria regenerada es caracteritza la seva estructura superficial a partir del microscopi electrònic d’escombratge (SEM), la seva estructura molecular mitjançant un anàlisis d’espectroscòpia infraroja (FTIR) i la seva estabilitat tèrmica amb un anàlisi termogravimètric (TGA). El consumo de textil por habitante crece de manera exponencial, de manera que, el desarrollo de nuevos procesos sobre la gestión y los tratamientos de residuos textiles resulta una oportunidad clave para conseguir modelos integrales de economía circular que aseguren el cierre de ciclos. Actualmente, se calcula que aproximadamente un 80% de los residuos textiles generados están constituidos por fibras de algodón (CO) y poliéster (PES). La heterogeneidad en los residuos textiles es todo un reto para la industria textil, por lo que en este proyecto se estudia la recuperación de la celulosa proveniente de tejidos PES/CO a partir del uso de líquidos iónicos (ILs). Inicialmente se analiza el efecto de los líquidos iónicos sobre la superficie del tejido, determinando los factores influyentes referentes a la entrada del IL en el interior del tejido y el mecanismo químico que gobierna el sistema. En este proyecto se contempla el estudio de las variables de tiempo, ratio y temperatura del sistema, con el objetivo de definir cuál de ellas tiene una mayor influencia sobre el proceso. Se evalúa la capacidad de los líquidos iónicos, en concreto del AmimCl, para disolver la celulosa y posteriormente regenerar la materia mediante una simulación del proceso wet spinning. El medio de inflamiento de la fibra, agua o DMSO, también ha sido otro factor estudiado, examinando así la influencia de cada disolvente y las interacciones cuando entran en contacto con el líquido iónico. Finalmente, de la materia regenerada se caracteriza su estructura superficial a partir del microscopio electrónico de barrido (SEM), su estructura molecular mediante un analisis de espectroscopia infrarroja (FTIR) y su estabilidad térmica con un analisis termogravimétrico (TGA). Textile consumption per inhabitant is growing exponentially, and therefore the development of new processes related to the management and treatment of textile waste is a key opportunity to achieve comprehensive circular economy models that ensure the closure of cycles. Nowadays, it has been estimated that approximately an 80% of the textile waste generated is composed of cotton (CO) and polyester (PES) fibers. The heterogeneity in the textile waste is a huge challenge for the textile industry, and for this reason this project studies the recovery of cellulose coming from textile fabrics composed of PES/CO making use of ionic liquids (ILs). Initially, the effect of ionic liquids on the surface of the textile is analyzed, determining the influencing factors related to the entry of IL inside the textile and the chemical mechanism that controls the system. This project considers the study of the time, ratio, and temperature variables of the system, with the aim of defining which of them has a greater influence on the process. The ability of ionic liquids, specifically AmimCl, to dissolve cellulose and subsequently regenerate the material through a simulation of the wet spinning process is evaluated. The responsible for the fiber’s inflation, water or DMSO, has also been another factor of study, analyzing the influence of each solvent and the interactions when in contact with the ionic liquid. Finally, the regenerated substance is characterized by: its surface structure using the scanning electron microscope (SEM), its molecular structure by infrared spectroscopy analysis (FTIR) and its thermal stability by thermogravimetric analysis (TGA).

A series of poly(butylene succinate) (PBS) ionomers containing up to 14 mol%of sulfonated succinate units have been synthesized by polycondensation in the melt-phase. The copolyesters were obtained with weight average molecular weights oscillating between 33,000 and 72,000 g·mol-1. All copolyesters were semicrystalline with melting temperatures and enthalpies decreasing and glass transition temperatures increasing with the content of ionic units. The thermal stability of PBS was slightly reduced by the incorporation of these units, and it was also found that the copolyesters were stiffer but also more brittle than PBS. The hydrolytic degradability of PBS was enhanced by copolymerization, an effect that was much more pronounced in basic media.

Metal-free catalysis was successfully applied to polymerize ω-pentadecalactone (PDL) by ring-opening polymerization (ROP) using several amino-ended initiators, namely hexylamine, allylamine and O,O′-bis(3-aminopropyl)diethylene glycol. This polymerization method was suitable to prepare telechelic polyesters carrying functional-end groups. The technique was then extended to the synthesis of block copolymers by ROP of PDL using bisamino-ended poly(ethylene glycol) (Mn = 2600) as macroinitiator. PPDLx-PEG56-PPDLx triblock copolymers with Mn ranging between ∼4000 and ∼90,000 g ·mol−1 were synthesized and extensively characterized by NMR, DSC, TGA and XRD. The amphiphilic copolymers thus produced were demonstrated to be able to self-assemble in nanoparticles with average diameters of ∼100–200 nm and morphologies highly depending on blocks lengths. The described synthetic route distinguishes in providing “clean” amphiphilic copolymers, which are attractive candidates for biomedical applications. Ministerio de Economía y Competitividad MAT-2016- 77345-CO3-01, MAT-2016-77345-CO3-02

In this paper, the preparation of PBS-ran-PCL copolyesters by enzymatic ring opening polymerization is presented for the first time. The copolyesters were produced in a wide composition range and free of metallic contaminants, so they may be regarded as potential biomaterials. The copolymers have been characterized by proton and carbon nuclear magnetic resonance (H and C NMR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), polarized light optical microscopy (PLOM) and wide angle X-ray scattering (WAXS). The PBS-ran-PCL copolyesters were able to crystallize in the entire composition range and displayed a pseudo-eutectic region. Most copolymers away from the pseudo-eutectic region exhibited a single crystalline phase (PBS-rich or PCL-rich crystalline phase), while within the pseudo-eutectic region the copolymers were double crystalline. Observations by PLOM, during isothermal crystallization showed that both nucleation density and spherulitic growth rate of the copolyesters are determined by the component that constitutes the majority phase. WAXS studies revealed that d spacings of selected crystallographic planes depend on composition. Therefore, both DSC and WAXS results suggest that the copolymers are probably isodimorphic, as the PBS-rich crystalline phase may contain small inclusions of PCL co-units, while the PCL-rich crystalline domains may also contain a minor quantity of PBS co-units inside., This work received financial support from Ministerio de Economia y Competitividad (MINECO) of Spain with Grant MAT2012-38044-C03-03 and MAT2016-77345-C3-1-P and from Agència de Gestió d'Ajuts Universitaris i de Recerca (AGAUR) (Catalonia, Spain) with grant 2009SGR1469. The POLYMAT/UPV/EHU team would like to acknowledge funding from the following projects: “UPV/EHU Infrastructure: INF 14/38”; “MINECO/FEDER: SINF 130I001726XV1/Ref.: UNPV13-4E-1726” and “MINECO MAT2014-53437-C2-P”. A.A. and A.I. acknowledge financial support from the Spanish Ministry (MINECO), Ref: MAT2015-63704-P (MINECO/FEDER, UE) and by the Eusko Jaurlaritza (Basque Government), Ref: IT-654-13. C.C. wishes to acknowledge CNPq (National Research Council) Brazil for the financial support. M.S. gratefully acknowledges the award of a PhD fellowship by POLYMAT Basque Center for Macromolecular Design and Engineering. JC M-H thanks to Consejo Nacional de Ciencia y Tecnología (CONACYT) (Mexico) for the awarded PhD grant.

Poly(ester amide)s are an emerging group of biodegradable polymers that may cover both commodity and speciality applications. These polymers have ester and amide groups on their chemical structure which are of a degradable character and provide good thermal and mechanical properties. In this sense, the strong hydrogen‑bonding interactions between amide groups may counter some typical weaknesses of aliphatic polyesters like for example poly(e-caprolactone). Poly(ester amide)s can be prepared from different monomers and following different synthetic methodologies which lead to polymers with random, blocky and ordered microstructures. Properties like hydrophilic/hydrophobic ratio and biodegradability can easily be tuned. During the last decade a great effort has been made to get functionalized poly(ester amide)s by incorporation of a-amino acids with hydroxyl, carboxyl and amine pendant groups and also by incorporation of carbon-carbon double bonds in both the polymer main chain and the side groups. Specific applications of these materials in the biomedical field are just being developed and are reviewed in this work (e.g., controlled drug delivery systems, hydrogels, tissue engineering and other uses like adhesives and smart materials) together with the main families of functionalized poly(ester amide)s that have been developed to date.

Polyalkylene dicarboxylates derived from 1,9-nonanediol and mixtures with different ratios of pimelic acid and azelaic acid were synthesized by thermal polycondensation. All samples had a high degree of crystallinity although it was found to decrease with the comonomer content. Crystallization kinetics of the two homopolymers and the copolymer with the eutectic composition was studied by calorimetric and optical microscopy techniques. Similar Avrami parameters were determined for the three samples and a spherulitic growth with heterogeneous nucleation was deduced. Spherulites showed negative birefringence and a fibrillar or ringed texture depending on the sample. Furthermore, clear differences were found in the primary nucleation density, the spherulitic growth rate and even in the secondary nucleation constant deduced from the Lauritzen-Hoffman treatment. The three studied samples had a similar arrangement of molecular chains, and consequently their WAXD patterns showed the same strong reflections related to the molecular packing. SAXS data revealed that a lamellar insertion mechanism was characteristic for non-isothermal crystallization from the melt. In addition, significant differences were found between the crystal lamellar thicknesses of the homopolymer and copolymer samples. Diffraction and spectroscopic data suggested that the lamellar crystals of the eutectic copolymer were mainly constituted by azelate units whereas the pimelate units were preferentially located in the amorphous regions including the interlamellar amorphous layer associated with the chain folds.

[eng] The presence of volatile fragrant molecules is generally associated with a feeling of pleasantness or cleanness in consumer products. Because of their high volatilities, the perception of fragrances is limited over time. Therefore, various delivery systems have been developed by the industry to control and extend the release of volatile ingredients by diffusion and also to protect active molecules against degradation. A promising encapsulation technique is the formation of capsules with tunable permeability, so-called colloidosomes. These are generally formed by locking the nanoparticles at the interface of a Pickering emulsion. However, there are very few articles concerning colloidosomes stabilized by covalent cross-linking. In addition, although Pickering emulsions have been known for over a century, the range of nanoparticles used to stabilize emulsions has been limited to silica, clays, polystyrene, polyacrylate latexes or metallic nanoparticles. Within the aim to apply colloidosomes or Pickering emulsions as delivery systems, the use of biodegradable and biocompatible polymeric nanoparticles such as polyester nanoparticles is of major interest. Polyester nanoparticles are solid colloidal particles with sizes generally between 20 and 500 nm that can be prepared in colloidal systems by polymerization of monomers in nano-emulsions which act as template for the nanoparticle formation. Nano-emulsions are emulsions with extremely small droplet size, typically in the range of 20-500 nm. Due to their small droplet size, nano-emulsions are transparent and present a better stability against gravitational separation than conventional emulsions. Nano-emulsions can be prepared by low-energy methods taking advantage of the internal energy of the system components which is released during the emulsification process. Despite the large number of articles describing the polymerization of monomers in nano-emulsions, only few articles refer to this process in nano-emulsions obtained by low-energy methods (Spernath, 2007). Therefore, studies on the preparation of polymeric nanoparticles from nano-emulsion droplets obtained by low-energy methods are of great interest. Concerning in-situ polymerization of monomers in nano-emulsions, many types of reactions have been reported generally requiring harsh conditions (low pH, toxic initiator, high temperature) to obtain polymers with acceptable yield and molecular weight. A research effort is needed to obtain polyester nanoparticles by polymerization under mild conditions. The global objective of this research work was the design, characterization and applications of polyester nanoparticles obtained by polymerization in mild conditions of monomer-in-water nano-emulsions obtained by low-energy methods. In a first step, bluish transparent lactone-in-water nano-emulsions are formed using either the PIT or the PIC methods at various O/S ratios and high water content. Nano-emulsions presented a good stability at room temperature and at 45ºC to carry out the polymerization in the droplet of the nano-emulsions. The formation of polyester nanoparticles was achieved by ring-opening polymerization of a lactone at 45ºC in nano-emulsions obtained by low-energy methods. The properties of the obtained nanoparticles such as size or crystallinity were optimized by varying the composition of the nano-emulsions template and/or the reaction parameters. Furthermore, the functionalization of the nanoparticles was confirmed by synthesizing nanoparticles by ring-opening polymerization of a hydroxy functionalized monomer or by copolymerization of two lactone monomers thereby controlling the degree of functionalization. The stabilization of emulsions of perfume-in-water by polyesters nanoparticles was investigated. Parameters such as the wettability of the nanoparticles, the concentration of nanoparticles, the ratio of each phase as well as the addition of electrolytes were studied These emulsions have been used as controlled release systems for model fragrance, but could not effectively control the release. Furthermore, in order to avoid the rapid evaporation of the perfume, the nanoparticles at the oil/water Pickering emulsions interface were covalently cross-linked leading to the formation of core-shell microcapsules, allowing the controlled release of perfume., [spa] En la presente tesis, se ha estudiado la formación de nanopartículas de poliésteres por polimerización por apertura de anillo de una lactona (catalizada por enzima y baja temperatura) usando nano-emulsiones obtenidas por métodos de baja energía. Se han optimizado las propiedades de las nanopartículas obtenidas tales como el tamaño o la cristalinidad mediante la variación de la composición de las nano-emulsiones plantilla y/o de los parámetros de reacción. Además, se ha confirmado la posibilidad de funcionalizar las nanopartículas mediante la adición de un grupo hidroxilo en su estructura o mediante la copolimerización de monómeros cíclicos controlando así el grado de funcionalización. Se ha estudiado también la estabilización de emulsiones de Pickering de un perfume-en-agua por las nanopartículas de poliésteres. Se han utilizado estas emulsiones como sistemas de liberación controlada de una fragancia modelo, pero no se pudo controlar eficientemente su liberación. Asimismo, con el objetivo de evitar la rápida evaporación del perfume, se han reticulado covalentemente las nanopartículas en la interfase aceite/agua de las emulsiones de Pickering conduciendo a la formación de microcápsulas con estructura núcleo-coraza, permitiendo un mayor control de la liberación de perfume.

Conselho Nacional de Desenvolvimento Científico e Tecnológico This works investigated the curing reaction of epoxidized oleic acid starshaped with different anhydrides, forming product as oligoésteres and polyesters. Oleic acid modified was obtained by esterification of oleic acid with an aminoalcohol to the resulting aminoester, followed by epoxidation of the double bond. The polymerization reactions were carried out from the opening of epoxy rings in the presence of different cyclic acid anhydrides: phthalic anhydride (PA), maleic anhydride (MA) and succinic anhydride (SA). The structures of the products in these reactions were elucidated by nuclear magnetic resonance (NMR) 1H and 13C and infrared spectroscopy (FT-IR). The technique of Differential Scanning Calorimetry (DSC) allowed the study of the crosslinking process of the different systems studied, allowing the determination of kinetic and thermodynamic parameters. The kinetic parameters of curing reaction systems of ME/AM and ME/AS were determined by methods Osawa, Kissinger and Barret. The thermal behavior of the products obtained was analyzed using thermogravimetric analysis (TGA). It was evident that the nature of anhydrides affects the thermodynamic and kinetics parameters of the crosslinking reaction. Values of DH for the reactions of epoxy ring opening are related to factors such as the steric size of the molecule and the position of the oxirane ring in the structure of the ME. The addition of BADGE in the mixture ME/anhydride increased molar mass and improves thermal and mechanical properties of polyester. By varying the composition of the system characteristics of the samples obtained were thermoplastic or crosslinked materials. The GPC results showed that the materials in the absence of BADGE are essentially oligomers. The rheology results indicated that all samples exhibit Newtonian fluid behavior. The viscosity values of the samples without BADGE indicated that these materials exhibited characteristics of highly viscous fluids and the samples in the presence of BADGE exhibited characteristics typical of solid. Este trabalho investigou a reação de cura do ácido oleico epoxidado (ME) com forma estrela com diferentes anidridos, originando oligoésteres e poliésteres. O ácido oleico modificado foi obtido pela esterificação do ácido oleico com um aminoálcool dando origem ao aminoéster, seguido da epoxidação da dupla ligação. As reações de polimerização foram realizadas a partir da abertura dos anéis epóxi na presença de diferentes anidridos de ácido cíclico: anidrido ftálico (AF), anidrido maleico (AM) e anidrido succínico (AS). As estruturas dos produtos das reações foram elucidadas por Ressonância Magnética Nuclear (RMN) de 1H e 13C e Espectroscopia de Infravermelho (FT-IR). A técnica de Calorimetria Exploratória Diferencial (DSC) permitiu o estudo do processo de reticulação dos diferentes sistemas estudados, possibilitando a determinação de parâmetros cinéticos e termodinâmicos. Os parâmetros cinéticos da reação de cura dos sistemas ME/AM e ME/AS foram determinados pelos métodos Osawa, Kissinger e Barret. O comportamento térmico dos produtos obtidos foi estudado utilizando a técnica de DSC e Análise Termogravimétrica (TGA). Evidenciou-se que a natureza dos anidridos influencia nos parâmetros termodinâmicos e cinéticos da reação de reticulação. Os valores de DH para as reações de abertura do anel epóxi estão relacionados a fatores estéricos como o tamanho da molécula e a posição do anel oxirano na estrutura do ME. A adição de BADGE na mistura ME/anidrido aumentou a massa molar e melhorou as propriedades térmicas e mecânicas dos poliésteres. Variando a composição do sistema as características dos materiais obtidos passaram de termoplásticos a termorrígidos. Os resultados de GPC mostraram que os materiais sem BADGE consistem essencialmente de oligômeros e as resinas com BADGE se apresentaram insolúveis e com aspecto de resinas poliméricas sólidas. Os resultados de reologia indicaram que, todas as amostras apresentaram comportamento de fluido newtoniano. Os valores de viscosidade das amostras sem BADGE indicaram que estes materiais apresentaram características de fluidos altamente viscosos e as amostras na presença de BADGE apresentaram características típicas de sólido.

Random poly(hexamethylene terephthalate-co-galactarate) s and poly(dodecamethylene terephthalate-co-galactarate) s copolyesters covering the whole range of compositions were obtained with weight-average molecular weights of 30,000–50,000 g mol 1 by melt polycondensation. They were thermally stable above 300 C, and displayed Tg in the þ20 to 20 C range with values steadily decreasing with the content in galactarate units. All the copolyesters were semicrystalline with Tm between 50 and 150 C and those made from dodecanediol were able to crystallize from the melt at a crystallization rate depending on composition. Copolyesters containing up to 50% of galactaric units retained the crystal structure of their respective polyterephthalate homopolyesters, whereas they adopted the structure of the respective polygalactarates when the content in Galx units reached 70%. Stress-strain essays revealed decay in the mechanical parameters as the aromatic units were replaced by Galx. Incubation in aqueous buffer revealed that hydrolysis of the polyesters were largely enhanced by copolymerization and evidenced the capacity of the Galx unit for making aromatic polyesters susceptible to biodegradation. A detailed NMR analysis complemented by SEM observations indicated that hydrolysis took place by preferred splitting of galactarate ester bonds with releasing of alkanediol and Galx-diacid.

Bu çalışmada ozonun tekstil terbiye işletmelerine entegrasyonunda boyama atık sularının renksizleştirilmesi ve yeniden kullanılması olanakları araştırılmıştır.Literatürde ozonlamayla renk giderimi konusunda oldukça fazla bilgi birikimi olup bu bilgi birikiminin tekstile entegrasyonunda boya banyolarının geri kazanım tekrar kullanımları önem taşımaktadır.Ozon, oksijenin 3 atom içeren bir allotropu olup, 2,07 V` luk oksidasyon potansiyeline sahiptir. Ozon gazı endüstriyel ölçekte ozon jeneratörlerinde üretilir. Ozon jeneratörlerinin yerli ve yabancı birçok üreticisi ve birçok modeli ticari olarak mevcuttur.Ozon gazı endüstriyel olarak; su ve meşrubat şişelemede, gıda endüstrisinde dezenfeksiyon amaçlı, su dezenfeksiyonunda ve atık su arıtımında kullanılmaktadır.Tekstil boyama atık sularının ozonlama ile renk giderimi üzerine birçok bilimsel çalışma mevcuttur. Kuvvetli bir oksidan olan ozon yardımıyla atık suyun sadece rengi uzaklaştırılmamakta aynı zamanda organik kirlilik miktarı da azaltılmaktadır. Rengi giderilmiş atık suyun tekrar kullanımının mümkün kılınması çevresel faydayı arttıracaktır.Çalışma kapsamında, ilk olarak; pH, sıcaklık, atık su bileşenleri ve ozon dozu gibi proses parametrelerinin ozonlamaya etkisi ve ozonlamanın renk giderimindeki etkinliği deneysel çalışmalar yapılarak incelenmiştir.İkinci olarak yapılan deneysel çalışmada, Dispers Blue 56, Dispers Blue 60 ve Dispers Blue 79 boyarmaddeleriyle hazırlanmış belirli konsantrasyondaki boyama atık sularına ozonlama yapılarak renk giderimindeki verimleri araştırılmıştır. Deneysel çalışmanın sonucunda boyarmaddelere HPLC analizi uygulanarak sonuçlar değerlendirilmiştir.Yapılan üçüncü çalışmada, ikinci çalışmada kullanılan üç boyarmaddeden biri olan Dispers Blue 60 boyarmaddesiyle boyama gerçekleştirilmiştir. Yapılan boyamalar sonucunda, boyama atık sularıyla üçerli gruplar oluşturularak ilk grupta ozonla renk gideriminin sağlandığı boya banyosuyla beş tekrarlı boyamalar gerçekleştirilmiş; oluşturulan diğer iki kontrol grubuyla ozonla renk giderimi sonucu geri kazanım tekrar kullanım olanakları karşılaştırılmıştır. Boyamalar sonucunda elde edilen kumaş numunelerinin renk ve haslık sonuçları birbiriyle karşılaştırılmıştır.Yapılan çalışma, 00688. STZ. 2010- 2 nolu Tekstil Terbiye İşletmesinde Ozon Kullanımı Ve Entegrasyonu konu başlıklı SANTEZ projesi kapsamında SANTEZ projesi olarak yürütülmüştür. Projede 7 iş paketi mevcut olup bu tezde iş paketlerinden birisi olan ozonla geri kazanım çalışmaları yapılmıştır. Projede kalan iş paketleri ayrı bir doktora tezi olarak sürmektedir.Sonuç olarak, ciddi bir üretim oranıyla karşımıza çıkan poliesterin boyanmasında oluşan tekstil atık suyunun renginin giderilmesinin ve buradan yola çıkılarak aynı atık suyun tekrarlı kullanımlarının olabileceğini ortaya koyan sonuçlara ulaşılmış, ozonun desteklenecek yeni yöntemlerle tekstilin birçok alanında ekolojik ve ekonomik çözümlere olanak sağlayacağı anlaşılmıştır.Anahtar Sözcükler: Ozon, dispers boyarmaddeler, poliester, poliester boyama, renk giderimi, geri kazanım Ozone (O3) is an allotrope of oxygen with 3 atoms which has an oxidation potential of 2,07 V. Ozone is generated in ozone generators by feeding air usually oxygen into the generator. Ozone generators are available in various models from local or international suppliers. Industrial uses are present in food industry, water treatment and waste water treatment for disinfection purposes.There are various scientific researches for decolorization of textile dyeing waste waters. With the help of ozone, which is a powerful oxidant, not only the waste water is decolorized but also organic pollution is also reduced.Within the context of this study, effect of process parameters such as pH, temperature, waste water content and ozone dose on ozonization analyzed with experimental studies.Findings of the second phase of the study are, efficiency of decolorization with ozonization is high for waste water of textile dyeing, prepared at a specific concentration with Dispers Blue 56, Dispers Blue 60 and Dispers Blue 79. After the experimental studies, HPLC analysis has been done on dyestuffs.In the third phase of the study, one of the three dyestuffs of second study, Dispers Blue 60, is used for dyeing. With the waste water of dyeing, 3 different groups are prepared, with the first group 5 consecutive dyeing is realized after decolorization with ozone at each step. With the remaining two groups, different ozonization methods are applied to support the decolorization study. After dyeing, color fastness results of fabric samples are compared. Color fastness results of fabric samples for each dyeing shows that this method is generally fine.The study is conducted as a SANTEZ Project, 00688.STZ.2010-2 Ozone Use And Integration For Textile Finishing Industry. There are 7 different studies in the project and one of them is investigated in this study. Remaining studies are under research as a Ph.D thesis.As a result of the study, ozone could be utilized for decolorization and multiple reuse of waste water of polyester dyeing. With new studies, ozone could help finding ecological and economical solutions for textile industry in various areas.Keywords: Ozone, dispers dyeing, polyester, polyester dyeing, decolorisation, treatment of wastewater, recovery 110

The dimethyl ester of 2,3:4,5-di-O-methylene-galactaric acid (Galx) was made to react in the melt with 1,n-alkanediols HO(CH2)nOH containing even numbers of methylenes (n from 6 to 12) to produce linear polycyclic polyesters. Two sets of poly(alkylene 2,3:4,5-di-O-methylenegalactarate) polyesters (PE-nGalx) with weight-average molecular weights in the ∼5000 - 10000 and ∼35000 - 45000 ranges were obtained using TBT and DBTO catalysts, respectively. For comparative purposes a set of poly(alkylene adipate) polyesters (PE-nAd) was also synthesized with molecular weights in the higher range using a similar procedure. The thermal stability of PE-nGalx was greater than that of PE-nAd although it notably decayed as molecular weight decreased. The replacement of Ad by Galx in the polyesters caused increases in Tg of up to 70ºC, and almost doubled the tensile mechanical parameters. All PE-nGalx were semicrystalline but only those made from 1,12-dodecanediol were able to crystallize from the melt with a crystallization rate that diminished as the molecular weight increased. In general, the galactarate containing polyesters displayed higher solubility and wettability than polyadipates, they hydrolyzed faster and exhibited comparable sensitivity to the action of lipases.

En este trabajo se investiga la influencia del procesado y del contenido de nanoarcilla en las propiedad mecánicas de láminas obtenidas por extrusión-calandra a partir de un grado comercial de PLA y una nanoarcilla organomodificada. El estudio de la morfologia se realizó mediante difracción de rayos-X de grandes ángulos y microscopía electrónica de transmisión, revelando el desarrollo de estructuras intercaladas, aunque tambien se observaron laminillas exfoliadas y particulas aglomeradas. La caracterización mecánica se realizó mediante ensayos a tracción uniaxial. Así mismo, se aplicó un tratamiento térmico a todas las láminas preparadas que permitió el estudio de los materiales en dos estados diferentes: rejuvenecido y envejecido. El comportamiento mecánico se vió afectado por el procesado sólo cuando el PLA se encuentra en estado envejecido, mientras que el contenido de arcilla únicamente produce algún efecto cuando está presente en un 2,5% en masa. El tratamiento de rejuvenecimiento provocó una transición frágil-dúctil que se manifestó en un aumento significativo de la ductilidad.

En este estudio, se prepararon microfibras de los polímeros polilactida y policaprolactona, y también de mezclas de ambos en distintas proporciones. Se determinaron las condiciones óptimas (solvente, potencial, flujo, etc.) para el electrohilado de los polímeros. Las microfibras obtenidas fueron analizadas mediante microscopia óptica y microscopía electrónica de barrido para determinar su morfología y sus diámetros. Las propiedades térmicas de las microfibras fueron estudiadas mediante calorimetría diferencial de barrido (DSC). Las características microestructurales fueron estudiadas mediante difracción de rayos-X a bajo y alto ángulo, utilizando la instalación de sincrotrón de Grenoble (línea BM16). Las microfibras preparadas en las condiciones que se consideraron óptimas fueron cargadas con el agente antibacteriano triclosán y posteriormente se estudio su cinética de liberación en distintos medios. También se evaluó el efecto antibacteriano del triclosán liberado. Finalmente, se realizaron estudios de biocompatibilidad in-vitro de scaffolds preparados a partir de las microfibras producidas con el objetivo de determinar su comportamiento como matrices tridimensionales para la adhesión y proliferación celular.

ÖZET Bu çalışmada Ring iplik makinalannda Sargılı iplik (core yarn) üretiminde bazı üretim parametrelerinin değişiminin iplik özelliklerine olan etkileri incelenmiştir. Öncelikle pamuk sargılı - poliester filaman özlü Sargılı iplik (core yarn) eğirme tekniği kullanılarak konvansiyonel Ring iplik makinasında Sargılı iplik (core yarn) üretiminde çekim ve büküm parametreleri değiştirilmiştir. Bu değişimler neticesinde üretilen her iplik tipinin doğrusal yoğunluk, enine kesit ve iplik bileşen oranlarının tespit edilmesinin yanı sıra, çekim ve büküm gibi üretim parametrelerinin değişiminin iplik kopma mukavemeti, kopma anındaki uzama miktarı, iplik düzgünsüzlüğü, ince yer, kaim yer ve neps miktarı üzerindeki etkileri incelenmiştir. ikinci adımda pamuk sargı - poliester filaman özden oluşan Sargılı iplik (core yarn) özellikleri konvensiyonel pamuk ring ipliğinin özellikler ile mukayese edilmiştir. Sargılı iplik yapısının iplik kopma mukavemeti ve kopma anındaki uzama ve iplik düzgünsüzlüğü değerleri üzerine olan etkisi incelenmiştir. Yapılan bu çalışmanın neticesinde aşağıdaki sonuçlar elde edilmiştin. Sargılı iplik eğirme tekniği ile % 100 pamuk ipliğine kıyasla iplik özelliklerinde iyileşme gözlenmiştir,. Çekim ve büküm parametrelerinin değişiminin sargılı iplik özellikleri üzerinde etkili olduğu görülmüştür. Anahtar Kelimeler : Sargılı iplik, Ring iplik, Ring iplik makinası, Pamuk, Poliester, Karışım iplik, Pamuk sargılı iplik. ABSTRACT The subject of this study is, to examine the effects of changing some of the production parameters on the properties of core yarns produced on a Ring Spinning Machine. Firstly, draft and twist parameters are changed in the production of core yarn on conventional ring spinning machine by using cotton covered - polyester filament core yarn spinning technique. As a result of these changes, linear density, cross-section and fibre composition are determined for produced all types of yarns. In addition, effects of changing draft and twist parameters are examined on yarn breaking strength, breaking extension, yarn irregularity and IPI values. Secondly, the properties of cotton covered polyester filament core yarn are compared with properties of conventional ring yarn. The effects of structure of core yarn are examined on yarn breaking strength, breaking extension and yarn irregularity. At the end of the study, the following results have been observed:. Increased yarn properties are observed in using core yarn technique is compared to 100% cotton yarn,. Changing twist and draft parameters affect core yarn structure. Key Words: Core Yarn, Ring Spun Yarn, Ring Spinning Machine, Cotton, Polyester, Blend yarn, Cotton covered yarn. 75

Cyclic oligo(butylene 2,5-furandicarboxylate) and e-caprolactone were copolymerized in bulk at 130-150 ºC by enzymatic ring opening polymerization using CALB as catalyst. Copolyesters within a wide range of compositions were thus synthesized with weight-average molecular weights between 20,000 and 50,000, the highest values being obtained for equimolar or nearly equimolar contents in the two components. The copolyesters consisted of a blocky distribution of the e-oxycaproate (CL) and butylene furanoate (BF) units that could be further randomized by heating treatment. The thermal stability of these copolyesters was comparable to those of the parent homopolyesters (PBF and PCL), and they all showed crystallinity in more or less degree depending on composition. Their melting and glass-transition temperatures were ranging between those of PBF and PCL with values increasing almost linearly with the content in BF units. The ability of these copolyesters for crystallizing from the melt was evaluated by comparative isothermal crystallization and found to be favored by the presence of flexible e-oxycaproate blocks. These copolyesters are essentially insensitive to hydrolysis in neutral aqueous medium but they became noticeably

A cyclic acetal of dimethyl l-tartrate (dimethyl 2,3-di-O-methylene l-threarate, Thx) was used as comonomer of dimethyl terephthalate (DMT) in the polycondensation with 1,6-hexanediol (HD) in the melt. Random copolyesters PHTxThxy with contents in tartrate units up to 50% were obtained with satisfactory molecular weights (Mw between 20,000 and 50,000) and dispersities slightly above 2, and without apparent discoloration. The copolyesters started to decompose above 300 °C. The Tg of the copolyesters oscillated between +9 and −9 °C with values steadily decreasing with increasing contents in Thx units. All the copolyesters as well as the homopolyester entirely made of tartrate units were semicrystalline with Tm falling from ∼145 °C for PHT to ∼70 °C for PHThx with intermediate values decreasing as the content in Thx increased. Copolyesters containing up to 30% of tartrate units were able to crystallize from the melt at crystallization rates that were delayed by the presence of tartrate units. The PHT70Thx30 copolyester displayed significant hydrodegradability when incubated in aqueous buffer and also certain biodegradability when subjected to the action of porcine pancreas lipases.

L’electrospinning és una técnica que permet obtener fibres de diàmetres de nanometres fins a micres. Consteix en aplicar una diferencia de potencial en una gota de dissolució de polímer que flueix al llarg del injector. En aquest projecte s’ha realitzat un estudi exhaustiu sobre la formació de fibres a partir de les poliesteramides PADAS i PGBGS. S’ha investigat la relació entre les característiques de les fibres obtingudes amb el dissolvent fet servir, el fluxe d’injecció, la distancia injector-col.lector i la concentració polímer/dissolvent.