O amido, encontrado abundantemente na natureza, é formado por dois polímeros: a amilopectina e a amilose. Ambos polímeros possuem excelentes qualidades industriais tais como, a biodegradabilidade e o baixo custo de obtenção. Entretanto, a amilopectina possui baixa solubilidade em solução aquosa. Para expandir a gama de aplicações deste polímero como, por exemplo, a produção de filmes biodegradáveis solúveis em água e que possam ser usados como revestimento de proteção no transporte de alimentos, ainda se fazem necessários alguns estudos. Um deles é tentar correlacionar como a funcionalização do seu esqueleto polimérico pode afetar a reação de formação destes filmes. Neste sentido, o objetivo desta Dissertação de Mestrado foi estudar a síntese da carboximetil amilopectina (CMAm) variando-se a pressão, temperatura e razão entre água e solvente orgânico. Sintetizamos várias CMAm a partir da amilopectina de milho ceroso, por meio de uma reação heterogênea utilizando hidróxido de sódio e ácido cloroacético. Empregou-se uma mistura de dimetilsulfóxido (DMSO) e água como solvente, com uma proporção variável entre 0 a 50% de água, para as pressões ambiente (758,3 mmHg) e reduzida (80 ± 20 mmHg) e para as temperaturas 70 e 80 ºC. Para cada uma das condições sintéticas estudadas, obtivemos CMAm com graus de substituição (GS) diversos. Os GS foram determinados por titulações condutimétricas com hidróxido de amónio e para as amostras sintetizadas com 0 a 40% de água foram confirmados por cromatografia líquida de alta eficiência (HPLC), obtendo-se uma boa correlação entre estes valores (R2 de 0,94263). Atribuiu-se os picos referentes às estruturas monossubstituídas (2-; 3- ou 6-mono-O-carboximetil glicose), dissubstituídas (2,3-; 2,6- ou 3,6-di-O carboximetil glicose) e trissubstituídas (2,3,6-tri-O-carboximetil glicose) por meio da cromatografia líquida acoplada a espectrometria de massa (LC-MS). A síntese realizada a 70 oC, pressão reduzida apresenta uma distribuição de CMAm substituída mais homogênea do que as demais condições sintéticas estudadas. Por medidas de potencial zeta em função do pH, determinaram-se para as CMAm de GS 0,86 e 0,43 o ponto isoelétrico no pH de 3,6 e 4,6; respectivamente. O espalhamento dinâmico de luz mostrou que a funcionalização da amilopectina com grupos carboximetílicos levou a abertura da sua estrutura inicial, extremamente ramificada, permitindo a formação de agregados maiores em solução aquosa para as amostras sintetizadas a 80 ºC sob pressão reduzida. Em contraste, as sínteses a 70 ºC nas pressões ambiente e reduzida provocaram uma diminuição no tamanho dos agregados em solução aquosa em função do GS. Por fim, a análise por microscopia ótica e eletrônica de varredura dos filmes de CMAm sintetizadas neste trabalho mostraram que são totalmente dependentes do GS, tipo de substituinte e o tamanho dos agregados em solução aquosa. / Starch is abundant in nature and composed by two polymers: amylopectin and amylose. Both biopolymers have excellent industrial characteristics, such as biodegradability and low cost. However, amylopectin has a very low solubility in aqueous solution. In order to expand the uses this biopolymer, for instance, the production of aqueous soluble and biodegradable films for food packing, there are still many open fields to study. One of them is to find the correlation between how the functionalization of the polymer backbone can affect the film formation process. For this reason, the goal of this work was to study the synthesis of carboxymethyl amylopectin (CMAm) varying the employed pressure, temperature and the ratio of water and organic solvent. Several CMAm were synthetized using amylopectin from maize, by means of an heterogeneous reaction using sodium hydroxide and chloroacetic acid. We have used a mixture of dimethyl sulfoxide (DMSO) and water as reaction solvent with variable ratio of 0 to 50% of water, employed ambient (758,3 mmHg) or reduced (80 ± 20 mmHg) pressure and temperatures of 70 and 80 ºC. The degree of substitution (DS) were determined for every synthetic condition studied in this work. The DS were determined through conductometric titration with ammonium hydroxide. The DS of the samples synthesized with 0 to 40% of water, were confirmed by high performance liquid chromatography (HPLC), with good correlation between these values (R2 of 0,94263). The peaks of the monosubstituted structures (2-; 3- ou 6-mono-O-carboxymethyl glucose), disubstituted (2,3-; 2,6- ou 3,6-di-O carboxymethyl glucose) e trisubstituted (2,3,6-tri-Ocarboxymethyl glucose) were attributed by liquid chromatography coupled with mass spectrometry (LC-MS). The synthesis made at 70 oC, reduced pressure, showed a more even distribution of substituted CMAm than the other synthetic conditions analyzed in this work. The isoelectric point of CMAm of DS of 0.86 and 0.43 were determined by zeta potential as function of pH. They were, respectively of pH 3.6 and 4.6. The dynamic light scattering showed that the funcionalization of the amylopectin with carboxymethyl groups has opened the initial branched polymer backbone, for samples synthesized at 80 ºC under reduced pressure, forming large aggregates in aqueous solution. On the other hand, the synthesis at 70 ºC at ambient and reduced pressures has caused a reduction of the aggregates sizes in aqueous solution as function of increasing DS. The optic and electronic scan microscopies of the CMAm films showed that they are completely dependent on DS, sort of susbstituents and sizes of the aggregates in aqueous solution.

Este trabajo presenta los resultados de la investigación sobre la preparación y caracterización de las metilcelulosas a partir de las plantas anuales.Las pastas del miscanthus, el cardo, y el eucalipto, se prepararon mediante el proceso IRSP (Impregnation Rapid Steam Pulping) y se blanquearon con las secuencias del TCF (Total Chloride Free), que usan peróxido de hidrógeno y hidróxido de sodio (NaOH). Con el aumento de la severidad del proceso de obtención de las pastas, la accesibilidad y la reactividad de las pastas aumentaron mientras que la viscosidad y el número de la kappa disminuyeron. Se desarrolló un nuevo y sencillo método de metilación para preparar las metilcelulosas a partir de la madera y las plantas anuales en el laboratorio. Cada metilcelulosa de las pastas blanqueadas con las secuencias del TCF se sintetizó en una mezcla de isopropanol con metano de yodo a 600C durante 22 horas después la pasta del TCF se mercerizó en una solución del hidróxido de sodio al 40% durante 1 hora. La mercerización y la metilación se repitieron para obtener un grado de sustitución (DS) más alto. Los resultados de la espectroscopía infrarroja de transformada de Fourier (FTIR) (Fourier Transform Infrared Spectroscopy) mostraron que los grupos del OH de la celulosa habían sido sustituidos parcialmente por grupos del metoxil. Los modelos de sustitución supramolecular de las metilcelulosas se determinaron mediante espectroscopía de resonancia magnética nuclear del carbono-13. La viscosidad intrínseca de las metilcelulosas se midió con agua destilada, una solución al 4% de NaOH, o DMSO. Las propiedades reológicas de las metilcelulosas se midieron con DMSO, una solución al 4% de NaOH o agua destilada. Las metilcelulosas sintetizadas tenían unas propiedades similares a las metilcelulosas comerciales. Los volúmenes hidrosolubles y alcalinosolubles de la metilcelulosas se determinaron mediante extracción con disolventes.Las metilcelulosas se prepararon a partir de pastas de lino, yute, cáñamo, sisal, y abacá mediante metilaciones heterogéneas y homogéneas. Estas pastas se blanquearonmediante el proceso ECF (Elemental Chlorine Free). La mutilación inhomogénea de las pastas blanqueadas mediante el proceso ECF se sintetizó en una mezcla de isopropanol con metano de yodo a 600C durante 22 horas después la pasta del ECF se mercerizó durante 1 hora en una solución de NaOH al 50%. La mutilación homogénea de la pasta blanqueada mediante ECF se realizó en DMSO con metano de yodo a 300C durante 48 horas. Para esta metilación homogénea se usó una metilcelulosa con un grado de sustitución más bajo, que se disolvió completamente en DMSO. La espectroscopía infrarroja de transformada de Fourier (FTIR) de las metilcelulosas mostró la existencia de grupos de metoxiles sobre las moléculas de metilcelulosa. Se utilizó la espectroscopia de resonancia magnética nuclear del carbono 13 para medir los grados de sustitución de las metilcelulosas. Los pesos moleculares de las metilcelulosas hidrosolubles se determinaron con la cromotagrafía de exclusión por tamaños (SEC). Las viscosidades intrínsecas se midieron en una solución de NaOH al 4%. Las metilcelulosas preparadas a partir de pastas de elevadas accesibilidades y reactividades tenían las mejores grados de sustitución, pesos moleculares, viscosidades y viscosidades intrínsecas.Se investigaron las accesibilidades y reactividades de las pastas del ECF. Los volúmenes de glucosa y de xilosa de estas pastas se determinaron mediante HPLC (High performance liquid chromatography) después de la hidrólisis. Las accesibilidades de adsorción de yodo de estas pastas eran bajas y sus fragmentos accesibles estaban entre el 1,31% y el 5,16%. En la región amorfa, sus fragmentos accesibles estaban entre el 5% y el 24%. Las imágenes del SEM (Scanning Electrón Microscopy) mostraron que sus fibrillas tenían distintas estructuras morfológicas. Los resultados de la espectroscopía infrarroja de transformada de Fourier (FTIR) mostraron que, después de los pretratamientos, habían disminuido tanto la media de la intensidad de los enlaces de hidrógeno como los índices de cristalinidad relativos. Sus reactividades aumentaron significativamente después de la mercerización preliminar. Las accesibilidades y reactividades de la pasta del abacá se mejoraron con los tratamientos de impregnación con agua, la mercerización a 15 bares de presión, la explosión de vapor y la mercerización preliminar. La desintegración, el incremento de los huecos, el debilitamiento de la intensidad de los enlaces de hidrógeno, la depolimerización, y la decristalización son esenciales para mejorar las accesibilidades y las reactividades, pero el factor decisivo es la especie de la planta.Hemos estudiado los factores que influyen en el peso molecular (Mw) de las metilcelulosas hidrosolubles preparadas a partir de plantas anuales. El tiempo y la temperatura de impregnación y las condiciones de cocción influyeron de manera diferente en el peso molecular (Mw) de metilcelulosas preparadas a partir de los cardos recogidos en primavera y en verano, el miscanthus y el eucalipto. Se compararon los efectos de los pretratamientos (la impregnación con agua, la mercerización preliminar, la mercerización con presión y la explosión de vapor) en la pasta del abacá. Cuando se pretrató la pasta del abacá, su metilcelulosa hidrosoluble consiguió un peso molecular más alto. De entre los pretratramientos analizados, la explosión de vapor resultó el más adecuado. Para conseguir metilcelulosas con un peso molecular más alto deben perfeccionarse las condiciones de la preparación de las pastas blanqueadas mediante ECF. La especie de las plantas es el factor decisivo para conseguir el peso molecular más alto de las metilcelulosas y para seleccionar los pretratamientos más adecuados.Los parámetros del proceso de obtención de pastas, las condiciones de la metilación, las especies de las plantas, los pretratamientos, y la estructura morfológicas de las pastas influyó en los grados de sustitución de las metilcelulosas preparadas a partir de plantas anuales. Una severidad de impregnación más alta, una temperatura del proceso de obtención de pastas más alta y un incremento del tiempo del mismo proceso consiguieron grados de sustitución más altos. Un aumento de reactivos de la metilación causó un aumento de grado de sustitución. Las pastas obtenidas de distintas especies produjeron grados de sustitución diferentes, trabajando con las mismas condiciones de metilación. Los pretratamientos aumentaron el grado de sustitución de las metilcelulosas.Esta investigación contribuye a encontrar las condiciones apropiadas para metilcelulosas diseñadas a medida, sintetizadas a partir de plantas anuales. Esta investigación demuestra que estas plantas tienen la capacidad de ser preparadas para conseguir metilcelulosas de alta calidad y de alto valor aptas para distintas aplicaciones, como la industria alimentaria, la de la construcción o la farmacéutica. La industria puede utilizar estas plantas anuales de crecimiento rápido para producir metilcelulosas, con lo que, además, se evitará el uso de madera.Palabras clave: abacá, accessibilidad, blanqueo mediante TCF, cáñamo, cardo, eucalipto, grado de sustitución, lino, metilación, metilcelulosa, miscanthus, peso molecular, plantas anuales, proceso de obtención de pasta IRSP, sisal, yute. / Preparation and characterization of methylcelluloses from some annual plantswere investigated.Miscanthus, cardoon, and eucalyptus pulps were produced by Impregnation Rapid Steam Pulping (IRSP) process and bleached by Total Chloride Free (TCF) sequences using hydrogen peroxide and sodium hydroxide. With an increase of pulping severities, accessibilities and reactivities of bleached pulps increased while viscosities and kappa numbers decreased. A novel facile methylation was developed in order to prepare methylcelluloses from wood and annual plants. Each methylcellulose of TCF bleached pulps was synthesized in isopropanol slurry with iodomethane at 600C for 22 hours after the TCF bleached pulp was mercerized in 40% NaOH solution for 1 hour. The mercerization and methylation were repeated in order to obtain a higher degree of substitution (DS). Fourier Transform Infrared (FTIR) spectra showed OH groups of cellulose were partially substituted by methoxyl groups. Supramolecular substitution patterns of methylcelluloses were determined by 13C nuclear magnetic resonance (NMR) spectroscopy. Intrinsic viscosities of methylcelluloses were measured in distilled water, 4% NaOH solution, or dimethyl sulphoxide (DMSO). Rheological properties of methylcelluloses were measured in DMSO, 4% NaOH solution or distilled water, in which the synthesized methylcelluloses had similar properties as commercial methylcelluloses. Watersoluble and alkali-soluble contents of methylcelluloses were determined by solventextraction.We used iodomethane to synthesize methylcelluloses from Elemental Chloride Free (ECF) bleached abaca, hemp, flax, jute, and sisal pulps via heterogeneous and homogeneous methylations. The heterogeneous methylation was carried out in isopropanol with iodomethane at 600C for 22h after a ECF bleached pulp was mercerized in excessive 50% NaOH solution for one hour at ambient temperature. The homogeneous methylation was carried out in dimethyl sulfoxide with iodomethane at 300C for 48h using a methylcellulose of low degree of substitution. Fourier Transform Infrared (FTIR) spectra of the synthesized methylcelluloses showed the existence of methoxyl groups on methylcellulose molecules. The degrees of substitution of the synthesized methylcelluloses were measured by 13C Nuclear Magnetic Resonance (NMR) spectroscopy. The molecular weights of the waterVI soluble methylcelluloses were determined by Size Exclusion Chromatography (SEC). Intrinsic viscosities of the synthesized methylcelluloses were measured in 4% NaOH solution. Methylcelluloses with better properties, such as greater degrees of substitution, molecular weights, viscosities, and intrinsic viscosities, were prepared from the pulps with higher accessibilities and reactivities. The factors influencing the preparation of methylcelluloses from these pulps were discussed.Pretreatments (water-soaking, pre-mercerization, mercerization under a pressure of 15 bars, and steam explosion) were used to improve the accessibilities and reactivities of celluloses of bleached flax, hemp, sisal, abaca, and jute pulps for the synthesis of methylcellulose. Glucose and xylose contents of these pulps were determined by High Performance Liquid Chromatograph (HPLC) after hydrolysis. Degrees of crystallinity of these pulps were determined by X-ray Diffraction (XRD) spectra. Figures of Scanning Electron Microscope (SEM) showed that their fibrils had different morphological structures. The iodine adsorption accessibilities of these pulps were low and accessible fractions ranged from 1.3% to 5.2%. Accessible fractions in amorphous cellulose were calculated in the 5% to 18% range. The accessibilities of these pulps were hemp pulp > flax pulp > sisal pulp > jute pulp > abaca pulp. Fourier Transform Infrared (FTIR) spectra showed that mean hydrogen bond strengths were weakened and relative crystallinity indexes were decreased by pretreatments. The accessibility and reactivity of the abaca pulp were improved by water soaking, mercerization under 15 bars pressure, steam explosion and preliminary mercerization, of which steam explosion and pre-mercerization were thebest treatments. Species was the main factor for the accessibility and reactivity.We studied the factors that influenced the molecular weights (Mw) of watersolublemethylcelluloses prepared from annual plants and juvenile eucalyptus. Miscanthus and cardoon stalks, and bleached pulps of abaca, jute, sisal, hemp, and flax were used as the annual plant materials. A higher concentration of NaOH solution during the impregnation led to a spring cardoon methylcellulose having a lower molecular weight. As the impregnation times increased, so did the molecular weights of the water-soluble methylcelluloses of spring cardoon. The impregnation conditions had less influence on the methylcelluloses of summer cardoon than on the methylcelluloses of spring cardoon. As the cooking times increased, so did the molecular weights of miscanthus methylcelluloses. A lower pulping severity increased the molecular weight of eucalyptus methylcellulose. The preliminary treatments (water soaking, pre-mercerization, mercerization under pressure andsteam explosion) improved the molecular weights of water-soluble abaca methylcelluloses. The steam explosion method was the best of the preliminary treatments for the abaca pulp. Different species led to different molecular weights for methylcelluloses synthesized from ECF bleached pulps, and these were further improved by preliminary mercerization. The molecular weight of -cellulose methylcellulose changed as the ratio of the methylation reagent was varied. In order to synthesize an optimum Mw of methylcellulose, the different raw materials can be chosen, the pulping parameters adjusted (including impregnation and cooking), the cellulose pretreated, and the methylcellulose conditions changed. The plant species is the decisive factor for the Mw of methylcellulose.The pulping parameters, the methylation conditions, the species, the pretreatments, and the morphological structures of pulps influenced the degrees of substitution of the methylcelluloses prepared from the annual plants. A higher impregnation severity, a higher pulping temperature, and a longer pulping time caused a higher degree of substitution. An increase of methylation reagents led to an increase of degree of substitution. Methylcelluloses of different degrees of substitution were synthesized from the pulps of different species when a same methylation condition was used. The pretreatments increased the degrees of substitution of methylcelluloses.This investigation contributes to find appropriate conditions for the production of methylcellulose from annual plants. The present investigation demonstrates these annual plants have the capacities to produce upgraded and high quality methylcelluloses for varied applications, such as additives of foods, construction, pharmaceutics, polymerization, paints, and detergents etc. The industry can utilize these annual fast-growth plants to produce methylcelluloses. Therefore, a lot of wood will be saved.Keywords: abaca, accessibility, annual plants, cardoon, degree of substitution, eucalyptus, flax, hemp, IRSP pulping, jute, methylation, methylcellulose, miscanthus, molecular weight, sisal, steam explosion, TCF bleaching.

O amido, encontrado abundantemente na natureza, é formado por dois polímeros: a amilopectina e a amilose. Ambos polímeros possuem excelentes qualidades industriais tais como, a biodegradabilidade e o baixo custo de obtenção. Entretanto, a amilopectina possui baixa solubilidade em solução aquosa. Para expandir a gama de aplicações deste polímero como, por exemplo, a produção de filmes biodegradáveis solúveis em água e que possam ser usados como revestimento de proteção no transporte de alimentos, ainda se fazem necessários alguns estudos. Um deles é tentar correlacionar como a funcionalização do seu esqueleto polimérico pode afetar a reação de formação destes filmes. Neste sentido, o objetivo desta Dissertação de Mestrado foi estudar a síntese da carboximetil amilopectina (CMAm) variando-se a pressão, temperatura e razão entre água e solvente orgânico. Sintetizamos várias CMAm a partir da amilopectina de milho ceroso, por meio de uma reação heterogênea utilizando hidróxido de sódio e ácido cloroacético. Empregou-se uma mistura de dimetilsulfóxido (DMSO) e água como solvente, com uma proporção variável entre 0 a 50% de água, para as pressões ambiente (758,3 mmHg) e reduzida (80 ± 20 mmHg) e para as temperaturas 70 e 80 ºC. Para cada uma das condições sintéticas estudadas, obtivemos CMAm com graus de substituição (GS) diversos. Os GS foram determinados por titulações condutimétricas com hidróxido de amónio e para as amostras sintetizadas com 0 a 40% de água foram confirmados por cromatografia líquida de alta eficiência (HPLC), obtendo-se uma boa correlação entre estes valores (R2 de 0,94263). Atribuiu-se os picos referentes às estruturas monossubstituídas (2-; 3- ou 6-mono-O-carboximetil glicose), dissubstituídas (2,3-; 2,6- ou 3,6-di-O carboximetil glicose) e trissubstituídas (2,3,6-tri-O-carboximetil glicose) por meio da cromatografia líquida acoplada a espectrometria de massa (LC-MS). A síntese realizada a 70 oC, pressão reduzida apresenta uma distribuição de CMAm substituída mais homogênea do que as demais condições sintéticas estudadas. Por medidas de potencial zeta em função do pH, determinaram-se para as CMAm de GS 0,86 e 0,43 o ponto isoelétrico no pH de 3,6 e 4,6; respectivamente. O espalhamento dinâmico de luz mostrou que a funcionalização da amilopectina com grupos carboximetílicos levou a abertura da sua estrutura inicial, extremamente ramificada, permitindo a formação de agregados maiores em solução aquosa para as amostras sintetizadas a 80 ºC sob pressão reduzida. Em contraste, as sínteses a 70 ºC nas pressões ambiente e reduzida provocaram uma diminuição no tamanho dos agregados em solução aquosa em função do GS. Por fim, a análise por microscopia ótica e eletrônica de varredura dos filmes de CMAm sintetizadas neste trabalho mostraram que são totalmente dependentes do GS, tipo de substituinte e o tamanho dos agregados em solução aquosa. / Starch is abundant in nature and composed by two polymers: amylopectin and amylose. Both biopolymers have excellent industrial characteristics, such as biodegradability and low cost. However, amylopectin has a very low solubility in aqueous solution. In order to expand the uses this biopolymer, for instance, the production of aqueous soluble and biodegradable films for food packing, there are still many open fields to study. One of them is to find the correlation between how the functionalization of the polymer backbone can affect the film formation process. For this reason, the goal of this work was to study the synthesis of carboxymethyl amylopectin (CMAm) varying the employed pressure, temperature and the ratio of water and organic solvent. Several CMAm were synthetized using amylopectin from maize, by means of an heterogeneous reaction using sodium hydroxide and chloroacetic acid. We have used a mixture of dimethyl sulfoxide (DMSO) and water as reaction solvent with variable ratio of 0 to 50% of water, employed ambient (758,3 mmHg) or reduced (80 ± 20 mmHg) pressure and temperatures of 70 and 80 ºC. The degree of substitution (DS) were determined for every synthetic condition studied in this work. The DS were determined through conductometric titration with ammonium hydroxide. The DS of the samples synthesized with 0 to 40% of water, were confirmed by high performance liquid chromatography (HPLC), with good correlation between these values (R2 of 0,94263). The peaks of the monosubstituted structures (2-; 3- ou 6-mono-O-carboxymethyl glucose), disubstituted (2,3-; 2,6- ou 3,6-di-O carboxymethyl glucose) e trisubstituted (2,3,6-tri-Ocarboxymethyl glucose) were attributed by liquid chromatography coupled with mass spectrometry (LC-MS). The synthesis made at 70 oC, reduced pressure, showed a more even distribution of substituted CMAm than the other synthetic conditions analyzed in this work. The isoelectric point of CMAm of DS of 0.86 and 0.43 were determined by zeta potential as function of pH. They were, respectively of pH 3.6 and 4.6. The dynamic light scattering showed that the funcionalization of the amylopectin with carboxymethyl groups has opened the initial branched polymer backbone, for samples synthesized at 80 ºC under reduced pressure, forming large aggregates in aqueous solution. On the other hand, the synthesis at 70 ºC at ambient and reduced pressures has caused a reduction of the aggregates sizes in aqueous solution as function of increasing DS. The optic and electronic scan microscopies of the CMAm films showed that they are completely dependent on DS, sort of susbstituents and sizes of the aggregates in aqueous solution.

Content: Developing novel tanning agents from renewable biomass is regarded as an effective strategy for sustainable leather industry. In this study, a series of dialdehyde carboxymethyl cellulose (DCMC) were prepared by periodate oxidation of carboxymethyl cellulose (CMC) with varying degrees of substitution (DS: 0.7, 0.9 and 1.2). The structural properties of DCMC were characterized. Size Exclusive Chromatography measurements showed that CMC underwent severe degradation during periodate oxidation, resulting in the decline of weight-average molecular weight from 250,000 g/mol to around 13,000 g/mol. FT-IR analysis illustrated that aldehyde group was successfully introduced into DCMC. The aldehyde group content of DCMC decreased from 8.38 mmol/g to 2.95 mmol/g as the DS rose from 0.7 to 1.2. Interestingly, formaldehyde was found to be produced in DCMC, and its content was 159.4, 151.7 and 38.4 mg/L, respectively when the DS of CMC was 0.7, 0.9 and 1.2, respectively. Further analysis by HPLC found that fructose was formed during oxidative degradation, and was subsequently oxidized to generate formaldehyde. This was in accordance with the fact that higher DS resulted in lower formaldehyde content in DCMC. The whole reaction mechanism is still under investigation at the moment. Tanning trials showed that the shrinkage temperature and thickening rate of DCMC tanned leather decreased as the DS increased. This should be due to the difference in aldehyde content of DCMC. Leather tanned by DCMC-0.7 (DS of CMC was 0.7) had the highest shrinkage temperature of 81°C and thickening rate of 76%. It was noteworthy that the formaldehyde content in DCMC tanned leather was only 0.11-0.40 mg/kg even though DCMC contained a small amount of formaldehyde. In general, we hope the work on dialdehyde tanning agent derived from CMC could provide some essential data for the development of sustainable tanning material and process. Take-Away: 1. Higher degree of substitution (DS) of CMC resulted in lower aldehyde group content of DCMC. 2. The formaldehyde content of DCMC was negatively correlated with DS. 3. The tanning performance of DCMC with lower DS was better.

Submitted by Milena Rubi (milenarubi@ufscar.br) on 2017-05-22T18:06:39Z No. of bitstreams: 1 FREITAS_ Roberta_2016.pdf: 17970377 bytes, checksum: e39a9b30d7fa1b64129148265b79339d (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2017-05-22T18:06:48Z (GMT) No. of bitstreams: 1 FREITAS_ Roberta_2016.pdf: 17970377 bytes, checksum: e39a9b30d7fa1b64129148265b79339d (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2017-05-22T18:06:55Z (GMT) No. of bitstreams: 1 FREITAS_ Roberta_2016.pdf: 17970377 bytes, checksum: e39a9b30d7fa1b64129148265b79339d (MD5) / Made available in DSpace on 2017-05-22T18:07:05Z (GMT). No. of bitstreams: 1 FREITAS_ Roberta_2016.pdf: 17970377 bytes, checksum: e39a9b30d7fa1b64129148265b79339d (MD5) Previous issue date: 2016-04-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Currently, seek to technologies for new materials that minimize environmental problems, it leads researchers to develop polymers from renewable and biodegradab le sources, such as cellulose and its derivatives.The cellulose acetate is produced by replacing the hydroxyl groups present in the cellobiose by acetilas groups, one of the first man - made polymers.It is mainly used in membranes, films, fibers, filters, as component in adhesives and pharmaceuticals. In the present work , was studied deacetylationversus time of a commercial cellulose acetate , starting with 2.5 DS , by alkaline hydrolysis,was studied the kinetics of the reaction and determining the degree of sub stitution (DS) by Standard Test Methods of Testing Cellulose Acetate ASTM D 871 - 96.For comparison, the deacetylation was carried out in homogeneous and heterogeneous media.FTIR was used to characterize the typical functional groups in the samples. Samples of deacetylated CA with GS 1.8, 2.0, 2.2 together with the cellulose and the CA 2.5 were thermally characterized by the DSC technique , whereby it was obtained water desorption temperature, melting and Tg of the material.By DRX technique it was possible to assess morphological characteristics of the CA with different DS , as the crystallinity index ( Ic ) . The CA deacetylated (DS = 2,3) and the commercial CA (DS = 2.5) were analyzed in the DMA, which was determined storage modulus , loss modulus and glass transit ion temperature ( Tg ) of the material s. It was not ed that the Tg of the sample DS =2.3 is higher than DS =2.5 being more crystalline ; and this leads to increased rigidity, restricting the mobility of chains . Biodegradability of CA was analyzed, with DS 2,5 , in simulated soil with soil, manure, sand and demineralized water in times of 0 days and 6 months.To characterize the CA biodegraded was used DMA technique to test the tensile modulus and mechanical - dynamic thermal. By DMA analysis it was concluded that, as the AC is biodegraded, its mechanical properties are changed, like the storage module with increased biodegradation and loss modulus which decreased. The DSC analysis, XRD and FTIR were also performed to characterize the CA degradation , withDS 2,5 , and this ag ree with the DNA results . Through analyzes it can be concluded that the CA chains were degraded, but the mass loss was not significant.The CA,with GS2,3 , was biodegradation for 3 months and compared with the CA biodegradability , with GS 2.5 , by DMA technique . / Atualmente, buscam-se tecnologias para novos materiais capazes de minimizar os problemas ambientais, isso leva os pesquisadores a desenvolverem polímeros derivados de fontes renováveis. O acetato de celulose é produzido pela substituição dos grupos hidroxilas presente na celobiose por grupos acetilas , sendo um dos primeiros polímeros produzidos pelo homem. É usado principalmente em membranas, filmes , fibras, filtros , como componente em produtos adesivos e farmacêuticos . No presente trabalho foi estudada a desacetilação em função do tempo do acetato de celulose comercial, com GS inicial de 2,5 , por hidrólise alcalina , estudada a cinética da reação e determinado o grau de substituição (GS) pela norma Standard Test Methods of Testing Cellulose Acetate ASTM D 871 - 96. Para comparação, a desacetilação foi realizada em meio homogêneo e heterogêneo.O FTIR foi usad o para caracterização d os grupos funcionais típicos nas amostras. As amostras de AC desacetiladas com GS de 1,8, 2,0, 2,2 juntamente com a celulose e o AC 2, 5 for am caracterizadas termicamente pela técnica de DSC, onde se obteve a temperatura de dessorção de água, fusão e a Tg dos materiais. Pela técnica de DRX foi possivel avaliar caracteristicas morfológicas dos AC com diferentes GS, como o índice de cristalinida de (Ic). O AC desacetilado (GS=2, 3 ) e o AC comercial (GS=2, 5 ) foram analisados no DMA onde foi determinado o módulo de armazenamento, módulo de perda e a temperatura de transição vítrea ( Tg) dos materiais. Notou - se que a Tg da amostra com GS=2, 3 é maior do que a com GS=2, 5 por ser mais cristalino; o que leva a maior rigidez, restringindo a mobilidade das cadeias. Foi analisada a biodegradabilidade do AC , com GS 2,5, em solo simulado com terra (23%) , esterco (23%) , areia (23%) e água desmineraliza da (31%) nos tempos de 0 dias a 6 meses . Para caracterização do AC biodegradado foi usada a técnica de DMA com ensaio no módulo de tensão e térmico dinânico-mecânico. Pela análise de DMA foi possível concluir que conforme o AC é biodegradado suas propriedades mecânicas foram alteradas, como o módulo de armazenamento que aumentou com biodegradação e o módulo de perda que diminuiu . As análises de DSC, DRX e FTIR também foram realizadas para caracterização da biodegradação do AC, com GS 2,5, que corroboraram c om os resultados de DMA. Chegou - se a conclusão, pelas análises, que as cadeias do AC foram degradadas, porém a perda de massa não foi significativa. O AC, com GS 2,3, foi biodegradado por 3 meses e comparado com biodegradabilidad e do AC com GS 2,5 pela técnica de DMA.

This thesis deals with the preparation of chemically and/or enzymatically modified cellulose. This modification can be either irreversible or reversible. Irreversible modification is used to prepare cellulose derivatives as end products, whereas reversible modification is used to enhance solubility in the preparation of regenerated cellulose. The irreversible modification studied here was the preparation of carboxymethyl cellulose (CMC) using extended mercerization of a spruce dissolving pulp. More specifically the parameters studied were the effect of mercerization at different proportions of cellulose I and II in the dissolving pulp, the concentration of alkali, the temperature and the reaction time. The parameters evaluated were the degree of substitution, the filterability and the amount of gel obtained when the resulting CMC was dissolved in water. Molecular structures of CMC and its gel fractions were analysed by using NIR FT Raman spectroscopy. It was found that the alkali concentration in the mercerization stage had an extensive influence on the subsequent etherification reaction. FT Raman spectra of CMC samples and their gel fractions prepared with low NaOH concentrations (9%) in the mercerization stage indicated an incomplete transformation of cellulose to Na-cellulose before carboxymethylation to CMC. Low average DS values of the CMC, i.e. between 0.42 and 0.50 were obtained. Such CMC dissolved in water resulted in very thick and semi solid gum-like gels, probably due to an uneven distribution of substituents along the cellulose backbone. FT Raman spectra of CMC samples and their gel fractions mercerized at higher alkaline concentration, i.e. 18.25 and 27.5% in the mercerization stage, indicated on the other hand a complete transformation of cellulose to Na-cellulose before carboxymethylation to CMC. Higher average DS values of the CMC, i.e. between 0.88 and 1.05 were therefore obtained. When dissolved in water such CMC caused gel formation especially when prepared from dissolving pulp with a high fraction of cellulose II. The reversible modification studied was the dissolution of cellulose in NaOH/ZnO. Here the effect of enzyme pretreatment was investigated by using two mono-component enzymes; namely xylanase and endoglucanase, used in consecutive stages. It was found that although the crystallinity and the specific surface area of the dissolving pulp sustained minimal change during the enzymatic treatment; the solubility of pulp increased in a NaOH/ZnO solution from 29% for untreated pulp up to 81% for enzymatic pretreated pulp. / Baksidetext Cellulose can be chemically and/or enzymatically modified. Irreversible modification is used to prepare cellulose derivatives as end products, reversible modification to enhance solubility in the preparation of regenerated cellulose. The irreversible modification studied here was the preparation of carboxymethyl cellulose (CMC) using extended mercerization of a spruce dissolving pulp. More specifically the parameters studied were the effect of mercerization at different proportions of cellulose I and II in the dissolving pulp, the concentration of alkali, the temperature and the reaction time. It was found that the alkali concentration in the mercerization stage had an extensive influence on the subsequent etherification reaction. The content of cellulose II had little effect on degree of substitution (DS) at low NaOH concentration, but tended to decrease DS at higher NaOH concentration in both cases compared with cellulose I. It was also found that the content of cellulose II correlates with the gel formation obtained when the CMC is dissolved in water. The reversible modification studied was the dissolution of cellulose in NaOH/ZnO. Here the effect of enzyme pretreatment was investigated by using two mono-component enzymes; namely xylanase and endoglucanase, used in consecutive stages. It was found that the solubility of pulp increased in a NaOH/ZnO solution from 29% for untreated pulp up to 81% for enzymatic pretreated pulp.

Ce travail est consacré à la synthèse de nouveaux polymères donneurs de liaison Hydrogène et à leur utilisation comme partenaire dans la construction de nouveaux films multicouches préparés par le procédé d’élaboration en couche-par-couche (LbL). Plus particulièrement, une nouvelle réaction impliquant des mercaptoalcools non protégés et le poly(2,3,4,5,6-pentafluorostyrène) (PPFS) a été développé et appliquée à la synthèse de nouveaux polymères donneurs de liaisons H. Ce couplage régiosélectif et chimiosélectif de type « click » avec un thiol hétérofonctionnel peut être utilisée pour préparer une bibliothèque de polymères qui diffèrent de par leur degré de substitution (DS) et/ou leur fonctionnalité en groupements associatifs. Le contrôle de ces paramètres structuraux permet de moduler leur force d’interactions avec des partenaires accepteurs de liaison H variés, comme la poly(4-vinyl pyridine) (P4VP), le poly(acrylate de n-butyle) (PBA) et le poly(oxyde d'éthylène) (PEO), de telle façon que tous les types de mélanges binaires (mélange non miscible, partiellement ou totalement miscible, ou complexe interpolymère) peuvent être obtenus. Ensuite, les dérivés de PPFS donneurs de liaisons H ont été utilisés en partenariat avec le P4VP pour élaborer avec succès de nouveaux films multicouche dont la force motrice est l’établissement de liaisons H. L'influence de nombreux paramètres relatifs à la structure des polymères donneurs (DS, structure chimique du groupement associatif), au type de modification chimique subie par le substrat sur lequel est élaboré le film multicouche (monocouche auto-assemblée vs. polymère greffée en conformation de type brosse) ou encore des paramètres expérimentaux liés aux conditions de dépôt (concentration des solutions de dépôt, nature du partenaire adsorbé en premier) a été étudiée. Plus particulièrement, le mécanisme de croissance ainsi que les caractéristiques de surface du film ont été évalués. / This work deals with the design of novel hydrogen-bond donor polymers and their use as partner in new tailor-made multilayered films prepared by the layer-by-layer (LbL) process. In this context, a novel regioselective and chemoselective “click-type” reaction of unprotected mercaptoalcohols onto poly(2,3,4,5,6-pentafluoro-styrene) (PPFS) has been developed, and applied to the synthesis of new hydroxylated H-bond donor polymers. This coupling with heterofunctional thiol is used to prepare a library of polymers differing in the degree of substitution (DS) and/or functionality. The fine control of these parameters makes it possible to tune their interaction ability with various acceptor polymers such as poly(4-vinyl pyridine) (P4VP), poly(n-butyl acrylate) (PBA) and poly(ethylene oxide) (PEO), such that all possible scenarios (immiscible blend, partially or totally miscible blend or interpolymer complex) can be achieved. Subsequently, the resulting H-bond donor polymers (PPFS derivatives) were used to successfully build-up multilayered films with using P4VP as partner via layer-by-layer (LbL) through the dip deposition process. The influence of various parameters related to structure of the partners (DS, nature of the PPFS derivatives), the chemical structure of the surface onto which the film is built-up (self-assembled monolayer vs. polymer brush) and the deposition process (concentration of deposition solutions, nature of the first deposited partner) was in-depth evaluated, on both the growth mechanism and on the surface features of the multilayered films.