<p>A novel strategy for synthesising segmented poly(urethane urea) (PUU) without using a chain extender but nevertheless with the opportunity to vary the hard segment content has been developed. The strategy is based on amine formation from isocyanate upon reaction with water. By adding a dissolved soft segment to an excess of diisocyanate followed by the addition of water in the gas phase, amines are formed <i>in situ</i>. Urea linkages are then formed when these amines react with the excess of isocyanate groups. The gas phase addition facilitates addition in a slow and continuous manner. The hard segment content can easily altered by varying the diisocyanate/soft segment ratio. Even though the strategy is shown to be applicable to different diisocyanates, the focus has been on the potentially biodegradable methyl-2,6-diisocyanatehexanoate (LDI) and 1.4-butanediisocyanate (BDI) and various well known biodegradable polyesters and polycarbonates. </p><p>All the synthesised materials exhibited pronounced phase separation and hydrogen bonding within the hard domains. However, a major increase in hydrogen bonding strength was seen when a symmetric diisocyanate was used instead of an asymmetric. Based on FTIR measurements, PUUs with BDI and a polydisperse hard segment can exhibit the same degree of phase separation and hydrogen bonding as the monodisperse product.</p><p>The elastic properties of this new group of PUUs were exceptional with an elongation at break from 1600% to almost 5000% and the elastic modulus could be varied from a few MPa up to a couple of hundreds. </p><p>Hydrolytic degradation was greater in the polyester-based than in the polycarbonate-based PUUs due to the more reactive ester bonds. Low mass loss but a considerable loss in molecular weight was seen in the polyester PUUs. The tensile strength decreased dramatically due to the loss of strain hardening.</p><p>An MTT seeding assay using human fibroblasts and an in vivo biocompatibility study were performed and no signs of cytotoxicity were seen and the inflammatory response was comparable to other inert polymers.</p><p>A biodegradable PUU with properties that can be tailored through an easy synthesis is here presented. </p>

A novel strategy for synthesising segmented poly(urethane urea) (PUU) without using a chain extender but nevertheless with the opportunity to vary the hard segment content has been developed. The strategy is based on amine formation from isocyanate upon reaction with water. By adding a dissolved soft segment to an excess of diisocyanate followed by the addition of water in the gas phase, amines are formed in situ. Urea linkages are then formed when these amines react with the excess of isocyanate groups. The gas phase addition facilitates addition in a slow and continuous manner. The hard segment content can easily altered by varying the diisocyanate/soft segment ratio. Even though the strategy is shown to be applicable to different diisocyanates, the focus has been on the potentially biodegradable methyl-2,6-diisocyanatehexanoate (LDI) and 1.4-butanediisocyanate (BDI) and various well known biodegradable polyesters and polycarbonates. All the synthesised materials exhibited pronounced phase separation and hydrogen bonding within the hard domains. However, a major increase in hydrogen bonding strength was seen when a symmetric diisocyanate was used instead of an asymmetric. Based on FTIR measurements, PUUs with BDI and a polydisperse hard segment can exhibit the same degree of phase separation and hydrogen bonding as the monodisperse product. The elastic properties of this new group of PUUs were exceptional with an elongation at break from 1600% to almost 5000% and the elastic modulus could be varied from a few MPa up to a couple of hundreds. Hydrolytic degradation was greater in the polyester-based than in the polycarbonate-based PUUs due to the more reactive ester bonds. Low mass loss but a considerable loss in molecular weight was seen in the polyester PUUs. The tensile strength decreased dramatically due to the loss of strain hardening. An MTT seeding assay using human fibroblasts and an in vivo biocompatibility study were performed and no signs of cytotoxicity were seen and the inflammatory response was comparable to other inert polymers. A biodegradable PUU with properties that can be tailored through an easy synthesis is here presented.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A utilização de novos materiais aplicados aos processos de separação por membranas tem sido objeto de constante pesquisa acadêmica e tecnológica. Na permeação de gases petroquímicos, a modificação de estruturas poliméricas e o uso de membranas de transporte facilitado por adição de sais contendo metais ou nanopartículas destacam-se dentre as opções disponíveis. Os objetivos deste trabalho foram avaliar alterações químicas, estruturais e térmicas na matriz polimérica de poli(uretano-ureia) (PUU) provocadas pela adição de nanopartículas de prata (AgNps) e obter dados de pemeabilidade de gases petroquímicos (C2H4, C2H6, CO2 e N2) para avaliar a influência das AgNps no transporte desses gases através do filme polimérico. Alterações nos espectros de FTIR nas bandas de estiramento das ligações C-O-C e C=O (uretânica e ureica), e deslocamentos nos picos de difração, demonstram que houve interação entre as AgNps e o oxigênio éter do PUU. A interação com as AgNps diminuiu a estabilidade térmica dos domínios flexíveis do polímero, região onde são encontrados os grupos éteres. As imagens de TEM mostraram que houve baixa dispersão das Nps na matriz polimérica. A interação das AgNps com o grupo éter diminuiu a permeabilidade de todos os gases, porém a redução da permeabilidade do CO2 e do C2H4 foi muito mais significativa, mostrando a interferência das AgNps na sorção desses dois gases. O transporte facilitado de olefinas através dos filmes poliméricos não foi observado, em parte, causado pela baixa dispersão das AgNps na matriz polimérica. Apesar da interação, não foi possível responder se a superfície das Nps estava ativada para o transporte facilitado. Contudo, através dos resultados do trabalho foi possível propor um mecanismo de interação entre as AgNps e o PUU, e verificar como a presença das Nps pode alterar a interação da matriz polimérica com gases petroquímicos / The use of new materials applied to processes of membrane separation has been the target of constant academic and technological researches. In permeation of petrochemical gases, the modification of polymeric structure to form facilitated transport membranes are one of the worthy available options. In this sense, the goal of this work is, not only evaluate the influence of the addition of silver nanoparticles (AgNps) in the chemical, morphological and thermal properties of poly(urethane urea) (PUU) films, but also obtain permeability data for some petrochemical gases (C2H4, C2H6, CO2 e N2). FTIR spectra exhibited changes in the C-O-C and C=O stretching bands profile of (from urethane and urea groups) and XRD analyses exhibited shifts in peaks. These results demonstrate the AgNps interacted with the ether oxygen of PUU. The interaction with AgNps reduced the thermal stability of polymer soft segments, where the ether linkages are located. TEM images showed a lower dispersion of Np in the polymer matrix. The interaction between AgNps and ether groups also decreased the permeability of all gases. Reduction of CO2 and C2H4 permeability were clear, demonstrating the hindrance of AgNps in the sorption of both gases. The olefin transport facilitated through the polymeric films was not verified. . This is partially caused by the lower dispersion of AgNps in the polymer matrix. Although an interaction between the AgNps and ether oxygen was observed, it was not possible to confirm if the Nps surface was really activated to facilitated transport. However, considering the results obtained it was possible to propose the interaction mechanism between AgNps and PUU; and also to indicate how the presence of Nps can change the interaction between the polymeric matrix and the petrochemical gases

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A utilização de novos materiais aplicados aos processos de separação por membranas tem sido objeto de constante pesquisa acadêmica e tecnológica. Na permeação de gases petroquímicos, a modificação de estruturas poliméricas e o uso de membranas de transporte facilitado por adição de sais contendo metais ou nanopartículas destacam-se dentre as opções disponíveis. Os objetivos deste trabalho foram avaliar alterações químicas, estruturais e térmicas na matriz polimérica de poli(uretano-ureia) (PUU) provocadas pela adição de nanopartículas de prata (AgNps) e obter dados de pemeabilidade de gases petroquímicos (C2H4, C2H6, CO2 e N2) para avaliar a influência das AgNps no transporte desses gases através do filme polimérico. Alterações nos espectros de FTIR nas bandas de estiramento das ligações C-O-C e C=O (uretânica e ureica), e deslocamentos nos picos de difração, demonstram que houve interação entre as AgNps e o oxigênio éter do PUU. A interação com as AgNps diminuiu a estabilidade térmica dos domínios flexíveis do polímero, região onde são encontrados os grupos éteres. As imagens de TEM mostraram que houve baixa dispersão das Nps na matriz polimérica. A interação das AgNps com o grupo éter diminuiu a permeabilidade de todos os gases, porém a redução da permeabilidade do CO2 e do C2H4 foi muito mais significativa, mostrando a interferência das AgNps na sorção desses dois gases. O transporte facilitado de olefinas através dos filmes poliméricos não foi observado, em parte, causado pela baixa dispersão das AgNps na matriz polimérica. Apesar da interação, não foi possível responder se a superfície das Nps estava ativada para o transporte facilitado. Contudo, através dos resultados do trabalho foi possível propor um mecanismo de interação entre as AgNps e o PUU, e verificar como a presença das Nps pode alterar a interação da matriz polimérica com gases petroquímicos / The use of new materials applied to processes of membrane separation has been the target of constant academic and technological researches. In permeation of petrochemical gases, the modification of polymeric structure to form facilitated transport membranes are one of the worthy available options. In this sense, the goal of this work is, not only evaluate the influence of the addition of silver nanoparticles (AgNps) in the chemical, morphological and thermal properties of poly(urethane urea) (PUU) films, but also obtain permeability data for some petrochemical gases (C2H4, C2H6, CO2 e N2). FTIR spectra exhibited changes in the C-O-C and C=O stretching bands profile of (from urethane and urea groups) and XRD analyses exhibited shifts in peaks. These results demonstrate the AgNps interacted with the ether oxygen of PUU. The interaction with AgNps reduced the thermal stability of polymer soft segments, where the ether linkages are located. TEM images showed a lower dispersion of Np in the polymer matrix. The interaction between AgNps and ether groups also decreased the permeability of all gases. Reduction of CO2 and C2H4 permeability were clear, demonstrating the hindrance of AgNps in the sorption of both gases. The olefin transport facilitated through the polymeric films was not verified. . This is partially caused by the lower dispersion of AgNps in the polymer matrix. Although an interaction between the AgNps and ether oxygen was observed, it was not possible to confirm if the Nps surface was really activated to facilitated transport. However, considering the results obtained it was possible to propose the interaction mechanism between AgNps and PUU; and also to indicate how the presence of Nps can change the interaction between the polymeric matrix and the petrochemical gases

<p>U radu su prvi put za proveru teorija nastajanja i gumolike elastičnosti polimernih mreža primenjeni modelni poliuretanski sistemi čiji su čvorovi veoma stabilni izocijanurat(heksahidro-1,3,5-triazin- 2,4,6-trion) prstenovi. Rad obuhvata: (1) Sintetezu nekoliko serija homogenih poli(uretan-izocijanuratnih) mreža, na bazi 2.4-TDI i poli(oksipropilen)diola, dvoetapnim postupkom u masi, tj. ciklotrimerizacijom teleheličnih diizocijanata uz katalizator Polycat 41. (2) Sintezu manje savr&scaron;enih mreža sa nekom definisanom koncentracijom visećih lanaca koja je postignuta uvodenjem monoola dietilenglikol- monometiletra u toku pripreme prepolimera. (3) Odredivanje povoljnih reakcionih uslove svih etapa sinteze uz primenu i modifikaciju postojećih analitičkih postupaka za karakterizaciju svojstava reakcionih komponenti i praćenja reakcija umrežavanja. (4) Procenu mogućih bočnih reakcija u toku nastajanja mreža jer one mogu značajno uticati na raspodelu različitih fragmenata u mrežama praćenjem koncentracija reakcionih proizvoda kod modelnih reakcija u rastvoru uz isti diol i isti katalizator i odgovarajuće mono-funkcionalne izocijanatne komponente. (5) Karakterizaciju svojstava i strukturnih parametara modelnih mreža i to primenom postupaka ekstrakcije i bubrenja, diferencijalne skanirajuće kalorimetrije, fotoelastičnih merenja, dinamičko-mehaničke spektroskopije i merenja napon-istezanje. Izborom nominalne Mn diola od 400 do 4000 postigne gustina umreženja 0.1x10^-4mol/cm³ do 10x10^-4mol/cm³ sa rasponom temperatura staklastog prelaza od -60&deg;C do +30&deg;C. Za procenu strukturnih parametara mreža primenjena je teorija granajućih procesa sa kaskadnom zamenom za slučaj nastajanja mreža ciklotrimerizacijom i dvoetapni postupak. U zavisnosti od konverzije NCO grupa u mrežama izračunate su masa po monomernoj jedinici, maseni udeo, broj po monomernoj jedinici, koncentracija po jedinici zapremine, Mn, Mw, Mz i Mw/Mn kako za elastično aktivne, osnovne i viseće lance tako i zamolekule sola. Ključni ekspehmentalni podaci koji su kori&scaron;ćeni za proveru teorija nastajanja bio sadržaj gela dobijen vi&scaron;estrukim ekstrakcijama, a za teorije gumolike elastičnosti ravnotežni modul dobijen iz fotoelastičnih merenja. Provera teorija gumolike elastičnosti se zasnivala se u nalaženje vrednosti pred- faktora 3 (tzv. faktora pamćenja) u jednačini koja daje vezu ravnotežnog modula elastičnosti i koncentracije elastično aktivnih lanaca mreže koji ukazuje na način fluktuacije cvorova mreže. Fotoelastična merenja su omogućila da se preko njih parameter pred-faktor 3 proceni pri malim deformacijama. Potvrden je koncept stvarnih mreža sa delimično potisnutim fluktuacijama čvorova uz aditivni doprinos zapletenosti lanaca modulu elastičnosti prema Langley-Graesley konceptu zarobljenih prepletaja.</p> / <p>In this thesis polymer network formation theories and rubber elasticity of polymer networks on model polyurethane systems having as a junction very stable isocyanurate(hexahidro-1,3,5-tгiazin-2,4,6- trion) rings are for the first time investigated. The work contains: (1) Synthesis of homogenious series of several poly(urethane-isocyanurate) networks based on poly(oxypropylene)diol and 2.4-TDI by two stages procedures in bulk i.e. cyclotrimerization of telechelic diisoicyanates with Polycat 41 as catalyst. (2) Synthesis of less perfect networks with some concentration of dangling chains obtained by introduction of monofunctional component diethyleneglycolmonomethylether during prepolymer formation. (3) Determination of optimal reaction conditions for both stages of the synthesis. (4) Estimation of possible side reaction during network formation because of theirs important influence on nework fragment distribution. (5) Caracterization of networks structure and properties by swelling and multiply extraction, differential scanning calorimetry, photoelastical measurements, dynamic-mechanical spectroscopy and stress-strain measurements. By using the different Mn of diols (400 - 4000) the network density from<br />0.1x10^-4mol/cm³ to 10x10^-4mol/cm³ and glass transition temperatures from -60&deg;C to +30&deg;C was achieved. For network structure determinations the theory of branching processes with cascade substitution was used. Mass per monomer unit, mass fraction, number per monomer unit, concentration per unit volume, Mn, Mw, Mz and Mw/Mn for elastically active network chains, backbone chains, dangling chains and sol molecules In the dependence on NCO groups conversion are calculated. Crucial experimental data for examination of network formation theories was the gel content and for rubber<br />elasticity theories the equilibrium modulus received from photoelastical measurement. The estimation of rubber elasticity theories was based on the analysis of the front factor 3 in the equation which gives the relation between the equilibrium modulus and concentration of elastically active network chains. It is estimated the additive contribution of chain entanglements to the equilibrium modulus, especially in the case of high networks density according to Langley-Graesley theory of trapped entanglements.</p>

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Entre os polímeros considerados promissores para a remoção seletiva de CO2, destacam-se aqueles que contêm os grupos glicol etilênico (EG). Nesta dissertação, foram obtidos filmes a partir de dispersões aquosas de poliuretano (PU), sintetizadas em trabalho anterior, à base de poli(glicol propilênico) (PPG), copolímero em bloco à base de poli(glicol etilênico) (PEG) e PPG (EG-b-PG), ácido dimetilolpropiônico (DMPA), diisocianato de isoforona (IPDI) e etilenodiamina (EDA). PPG, EG-b-PG e DMPA formaram as regiões flexíveis nas proporções de: PPG 100% e 0% EG-b-PG, PPG 75% e 25% EG-b-PG, PPG 50% e 50% EG-b-PG e PPG 25% e 75% EG-b-PG em termos de equivalentes-gramas. A influência da quantidade dos segmentos de PEG foi avaliada por ensaios de permeação com os gases CO2, CH4 e N2. Os filmes obtidos das dispersões foram caracterizados por espectrometria de infravermelho com transformadas de Fourier (FTIR), análise termogravimétrica (TGA), difração de raios x (DRX) e espalhamento de raios X a baixo ângulo (SAXS). Espectros de FTIR mostraram que os segmentos de EG influenciaram a frequência da banda de carbonila. Curvas de perda de massa (TG) mostraram perfis semelhantes de degradação, enquanto que as curvas derivadas apresentaram diferenças. DRX e SAXS mostraram que os segmentos de PEG promoveram uma maior ordenação na estrutura da membrana. Testes de permeação de gases mostraram que o aumento do teor de PEG aumentou o valor da permeabilidade para o CO2, indicando que os segmentos de PEG interagiram favoravelmente com este gás. Em relação ao CH4 e N2, houve uma diminuição na permeabilidade quando comparados com os valores encontrados para o CO2, sendo atribuído a perda de mobilidade segmental. Em termos de seletividade, para o par CO2/CH4 foi obtido um valor médio de 61,7 para a membrana contendo o maior teor de PEG, e o par CO2/N2 um valor médio de 121,5, sendo superior aos valores encontrados na literatura, tornando o material promissor / Among the polymers considered promising for the selective removal of CO2 from natural gas, those containing ethylene glycol groups (EG) are the most distinguished. In this study cast films were obtained from aqueous dispersions of polyurethane (PU), synthesized in a previous work with poly (propylene glycol) (PPG), block copolymer based on poly(ethylene glycol) (PEG) and PPG, dimethylolpropionic acid (DMPA), isophorone diisocyanate (IPDI) and ethylenediamine (EDA). Segments of PPG, EG-b-PG and DMPA formed the flexible domains in the proportions of: PPG 100% and 0% EG-b-PG, PPG 75% and 25% EG-b-PG, PPG 50% and 50% EG-b-PG and PPG 25% and 75% EG-b-PG, in terms of equivalent-grams. The influence of the amount of PEG segments in permeation properties of CO2, CH4 and N2 was verified by permeability essays. The membranes were obtained as cast films from the dispersions and was characterized by infrared spectrometry (FTIR), termogravimetric analysis (TGA), X ray diffractometry (XRD) and small angle X ray scattering (SAXS). FTIR spectra showed that PEG segments influenced carbonyl band frequency. Loss of mass curves with temperature (TG) showed similar profiles of degradation, whereas DTG curves presented more stages. PEG segments conferred higher thermal stability for the materials. XRD and SAXS analysis showed that PEG promoted ordination to the membranes. In gas permeation tests, it was verified that the increase in copolymer amount increased permeability value for CO2, being attributed to the fact that the segments of poly(ethylene glycol) interacted favorably with this gas. In relation to CH4 and N2, there was a significant decrease in permeability when compared to the values found for CO2, being assigned to a loss of segmental mobility with increasing content of EG. In terms of selectivity, the pair CO2/CH4 had a mean value of 61,7 for the membrane containing the highest amount of EG groups, and the pair CO2/N2 produced a mean value of 121,5 for the same one, being superior than those found in the literature, making a promising material

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Entre os polímeros considerados promissores para a remoção seletiva de CO2, destacam-se aqueles que contêm os grupos glicol etilênico (EG). Nesta dissertação, foram obtidos filmes a partir de dispersões aquosas de poliuretano (PU), sintetizadas em trabalho anterior, à base de poli(glicol propilênico) (PPG), copolímero em bloco à base de poli(glicol etilênico) (PEG) e PPG (EG-b-PG), ácido dimetilolpropiônico (DMPA), diisocianato de isoforona (IPDI) e etilenodiamina (EDA). PPG, EG-b-PG e DMPA formaram as regiões flexíveis nas proporções de: PPG 100% e 0% EG-b-PG, PPG 75% e 25% EG-b-PG, PPG 50% e 50% EG-b-PG e PPG 25% e 75% EG-b-PG em termos de equivalentes-gramas. A influência da quantidade dos segmentos de PEG foi avaliada por ensaios de permeação com os gases CO2, CH4 e N2. Os filmes obtidos das dispersões foram caracterizados por espectrometria de infravermelho com transformadas de Fourier (FTIR), análise termogravimétrica (TGA), difração de raios x (DRX) e espalhamento de raios X a baixo ângulo (SAXS). Espectros de FTIR mostraram que os segmentos de EG influenciaram a frequência da banda de carbonila. Curvas de perda de massa (TG) mostraram perfis semelhantes de degradação, enquanto que as curvas derivadas apresentaram diferenças. DRX e SAXS mostraram que os segmentos de PEG promoveram uma maior ordenação na estrutura da membrana. Testes de permeação de gases mostraram que o aumento do teor de PEG aumentou o valor da permeabilidade para o CO2, indicando que os segmentos de PEG interagiram favoravelmente com este gás. Em relação ao CH4 e N2, houve uma diminuição na permeabilidade quando comparados com os valores encontrados para o CO2, sendo atribuído a perda de mobilidade segmental. Em termos de seletividade, para o par CO2/CH4 foi obtido um valor médio de 61,7 para a membrana contendo o maior teor de PEG, e o par CO2/N2 um valor médio de 121,5, sendo superior aos valores encontrados na literatura, tornando o material promissor / Among the polymers considered promising for the selective removal of CO2 from natural gas, those containing ethylene glycol groups (EG) are the most distinguished. In this study cast films were obtained from aqueous dispersions of polyurethane (PU), synthesized in a previous work with poly (propylene glycol) (PPG), block copolymer based on poly(ethylene glycol) (PEG) and PPG, dimethylolpropionic acid (DMPA), isophorone diisocyanate (IPDI) and ethylenediamine (EDA). Segments of PPG, EG-b-PG and DMPA formed the flexible domains in the proportions of: PPG 100% and 0% EG-b-PG, PPG 75% and 25% EG-b-PG, PPG 50% and 50% EG-b-PG and PPG 25% and 75% EG-b-PG, in terms of equivalent-grams. The influence of the amount of PEG segments in permeation properties of CO2, CH4 and N2 was verified by permeability essays. The membranes were obtained as cast films from the dispersions and was characterized by infrared spectrometry (FTIR), termogravimetric analysis (TGA), X ray diffractometry (XRD) and small angle X ray scattering (SAXS). FTIR spectra showed that PEG segments influenced carbonyl band frequency. Loss of mass curves with temperature (TG) showed similar profiles of degradation, whereas DTG curves presented more stages. PEG segments conferred higher thermal stability for the materials. XRD and SAXS analysis showed that PEG promoted ordination to the membranes. In gas permeation tests, it was verified that the increase in copolymer amount increased permeability value for CO2, being attributed to the fact that the segments of poly(ethylene glycol) interacted favorably with this gas. In relation to CH4 and N2, there was a significant decrease in permeability when compared to the values found for CO2, being assigned to a loss of segmental mobility with increasing content of EG. In terms of selectivity, the pair CO2/CH4 had a mean value of 61,7 for the membrane containing the highest amount of EG groups, and the pair CO2/N2 produced a mean value of 121,5 for the same one, being superior than those found in the literature, making a promising material