Octafluorobiphenylene-linked bis(cyclopentadienone) was prepared bearing one perfluoro-4-tolyl and one tert-butyl substituent on the terminal diene rings. Polymerizations with 1,4- and 1,3-diethynylbenzene afforded linear Diels-Alder polyphenylenes (DAPPs) having lateral tert-butyl and perfluoro-4-tolyl substituents. The perfluoro-4-tolyl-substituted DAPPs are thermally stable, glassy solids (Tg ~ 230 deg C) that could not be cast into stable films (Mn ~ 10kDa, DPn ~ 10). New compounds perfluoro(1-phenyl-1-octanone) and perfluoro(1,1-diphenyl-1-octanol) were prepared from pentafluorophenylmagnesium bromide and perfluorooctanoyl chloride by nucleophilic acyl substitution and addition reactions. Diels-Alder reactions of 1,2-bis(nonafluorobiphenyl-4-yl)-4-tert-butylcyclopentadiene (CPD-1) with N-(4-fluorophenyl)maleimide (FMI) were explored as models for cyclopentadiene-maleimide-based Diels-Alder polymerizations. Mixtures of five endo/exo adducts were obtained, dependent upon CPD-1 tautomers present at reaction temperatures. The thermodynamic adduct (B3LYP/6-31G* geometry optimizations) was found to be the exo DA adduct of FMI and 2,3-bis(nonafluorobiphenyl-4-yl)-5-tert-butylcyclopentadiene. Five of the six possible isomers were observed and characterized including two by single-crystal X-ray diffraction. Parallel reactions of FMI and 1,2-bis(pentafluorophenyl)-4-tert-butylcyclopentadiene yielded three crystallographically characterized isomers, and with 1H NMR and 19F NMR spectrometry, including 1-D NOE, allowed five isomeric products to be identified. Diene CPD-1 is reactive toward nucleophiles (such as potassium 4-methylphenoxide) at the 4-positions of the C12F9 groups. Using this reactivity pattern, CPD-1 was polymerized with bis(phenol) A (BPA) and bis(phenol-A-6F) (BPAF) to form linear poly(arylene ethers) (Mn ~35 kDa) containing backbone cyclopentadienes. These polymers are glassy solids (Tg ~ 220 deg C) with good thermal stability (Td ~ 290 deg C), and they form stable, creaseable films cast from chloroform solutions. Treatment with 1.5-5.0% of 1,6-bis(N-maleimido)dodecane in N,N-dimethylacetamide (DMAc) at 165 deg C gave insoluble, solvent-swellable networks confirmed using ATR-FTIR. CPD-1 was also used as a cyclopentadiene-based linking group for chain extension of phenol-terminated methyl-PEEK oligomers (PEEKMOHs) with Mn values of 2, 5, and 10 kDa. These polymers are glassy solids (Tg ~ 156 deg C) with good thermal stability (Td ~ 400 deg C), that form stable, creaseable films from chloroform. Segmented polymers were treated with FMI in NMP, and showed functionalization density of approximately 50% by 19F NMR. Segmented polymers were also cross-linked by reaction of 1,6-bis(N-maleimido)hexane (cyclopentadiene to maleimide functional group ratio of 1:1) in NMP at 140 deg C. / Ph. D.

Norovirus som orsakar vinterkräksjukan är en av de vanligaste vintersjukdomarna i Sverige. Sjukdomstiden varar generellt i en till tre dagar med symptomen kräkning och/eller diarré. Till den totala sjukdomsbilden världen över gällande akut gastroenterit, bidrar norovirus med 18 %. Trots att sjukdomen är mycket vanlig är kunskapen om norovirusets förfarande till stor del okänd.Syftet med studien var att göra en tidsserieanalys, även så kallad One-Step Growth analys, av koncentrationen minus-RNA i celler som infekterats med olika koncentrationer av murint norovirus (MNV). För att detektera minus-RNA användes RT-qPCR med SYBR Green. Målet var att se om startkoncentrationerna av virus vid någon tidpunkt korrelerar med mängden minus-RNA i cellerna. Efter 4 och 8 timmar fanns ett exponentiellt samband mellan den initiala viruskoncentrationen och minus-RNA-uttrycket i cellerna. Koncentrationen minus-RNA i de infekterade cellerna ökade mellan de undersökta tiderna 4, 8 och 24 timmar. Vidare visade resultaten att det krävs 4 timmar för att minus-RNA skulle vara kvantifierbar vid en högre infektionskoncentration av viruspartiklar, medan det krävs 24 timmar för den lägre infektionskoncentrationen av viruspartiklar. / Norovirus causes winter vomiting disease and is one of the commonest cause of winter illness in Sweden. The disease period generally lasts one to three days with symptoms like vomiting and/or diarrhea. To the disease burden of acute gastroenteritis worldwide, norovirus contributes with 18 %. Even though the illness is very common, the knowledge about norovirus is poor and largely unknown.The purpose of the study was to do a time series analysis, a so-called One-Step Growth analysis, of the minus-RNA concentration in cells infected with different concentrations of murine norovirus (MNV). For the detection of minus-RNA RT-qPCR was used with SYBR Green. The goal was to correlate start concentration of virus at any time with the amount of minus-RNA in the cells. At 4 and 8 hours there was an exponential connection by the initial virus concentration and minus-RNA development in the cells. The concentration of minus-RNA in the infected cells increased between 4, 8 and 24 hours. Further, the results can be interpreted as requiring 4 hours for the higher concentrations to become quantifiable, while requiring 24 hours for the lower concentrations to become quantifiable.

This thesis focuses on my endeavors to prepare new porous polymeric monoliths that are viable to use as supports in flow-through processes. Polymer monoliths of various porous properties and different chemical properties have been prepared utilizing the thermally induced phase separation (TIPS) phenomenon and step-growth polymerization reactions. The aim has been to find appropriate synthesis routes to produce separation supports with fully controlled chemical, physical and surface properties. This thesis includes preparation of porous monolithic materials from several non-cross-linked commodity polymers and engineering plastics by dissolution/precipitation process (i.e. TIPS). Elevated temperatures, above the upper critical solution temperature (UCST), were used to dissolve the polymers in appropriate solvents that only dissolve the polymers above this critical temperature. After dissolution, the homogeneous and clear polymer-solvent solution is thermally quenched by cooling. A porous material, of three dimensional structure, is then obtained as the temperature crosses the UCST. More than 20 organic solvents were tested to find the most compatible one that can dissolve the polymer above the UCST and precipitate it back when the temperature is lowered. The effect of using a mixture of two solvents or additives (co-porogenic polymer or surfactant) in the polymer dissolution/precipitation process have been studied more in depth for poly(vinylidine difluoride) (PVDF) polymers of two different molecular weight grades. Monolithic materials showing different pore characteristics could be obtained by varying the composition of the PVDF-solvent mixture during the dissolute­ion/precipitation process. Step-growth polymerization (often called polycondensat­ion reaction) combined with sol-gel process with the aid of porogenic polymer and block copolymer surfactant have also been used as a new route of synthesis for production of porous melamine-formaldehyde (MF) monoliths. In general, the meso- and macro-porous support materials, for which the synthesis/preparation is discussed in this thesis, are useful to a wide variety of applications in separation science and heterogeneous reactions (catalysis).

Phosphonium ions readily compare to ammonium ions in regards to their aggregate characteristics, thermal stability, and antibacterial activity. Ionic aggregation in phosphonium-based polymers provides thermoreversible crosslinks, ideal for reversible self-assembly, self-healing, and smart response. In polymers, these ionic functionalities aggregate, providing improved moduli, and altering the size and structure of ionic aggregates regulates polymer melt processability. This dissertation highlights phosphonium-based chemistry for the synthesis of novel step-growth ionomers and structure-property relationships in ionic polymers. The synthesis of phosphonium endcapping reagents for melt polyester reactions afforded a thermally stable ionic functionality that controlled molecular weight. Weak association was present with phosphonium ions at low ion concentrations below 7.7 mole %. The use of novel ionic bisacetoacetate monomers in the formation of networks from Michael addition reactions led to the synthesis of ionic networks with increased and broadened glass transitions and improved tensile stresses at break and strains at break compared to those in the non-ionic networks. The first electrospun fibers from Michael addition crosslinking reactions are reported, and equilibrium ionic liquid uptake experimental results indicated that ionic functional networks absorb close to three times the amount of ionic liquid as non-ionic, poly(ethylene glycol)-based films. Chain-extending polyurethanes with a phosphonium diol and subsequently varying the hard segment content led to changes in ionic aggregation, crystallinity, and thermal transitions in the polymers. Additionally, novel phosphonium-based methacrylate monomers incorporated into diblock copolymers with styrene exhibited microphase separation. Overall, the inclusion of phosphonium ions pendant to or in the main chain of various types of polymers led to changes in morphology, improved tensile properties, enhanced moduli, broadened transitions, changes in crystalline melting points, changes in solubility, and appearance of ionic aggregation. / Ph. D.

Ion-containing segmented polyurethanes exhibit unique morphology and physical properties due to synergistic interactions of electrostatic, hydrogen bonding, and hydrophobic interactions. A fundamental investigation on a series of well-defined ion-containing polyurethanes elucidated the influence of charge placement, charge density, and soft segment structure on physical properties, hydrogen bonding, and morphologies. An unprecedented comparison of poly(ethylene oxide)(PEO)-based sulfonated polyurethanes containing sulfonate anions either in the soft segments or hard segments revealed that sulfonate charge placement dramatically influenced microphase separation and physical properties of segmented polyurethanes, due to altered hydrogen bonding and thermodynamic immiscibility between soft and hard segments. Moreover, studies on sulfonated polyurethanes with identical sulfonated hard segments but different soft segment structures indicated that soft segment structure tailored sulfonated polyurethanes for a wide range of mechanical properties. Sulfonated polyurethanes incorporated with ammonium-functionalized multi-walled carbon nanotubes (MWCNTs) generated novel polyurethane nanocomposites with significantly enhanced mechanical performance. Modification of MWCNTs followed a dendritic strategy, which doubled the functionality by incorporating two ammonium cations per acid site. Complementary characterization demonstrated successful covalent functionalization and formation of surface-bound ammonium salts. Upon comparison with pristine MWCNTs, ammonium-functionalized MWCNTs exhibited significantly enhanced dispersibility in both DMF and sulfonated polyurethane matrices due to good solvation of ammonium cations and intermolecular ionic interactions between anionic polyurethanes and cationic MWCNTs. Segmented polyurethanes containing sulfonated PEO-based soft segments and nonionic hard segments were incorporated with various contents of room temperature ionic liquid, 1-ethyl-3-methylimidazolium ethylsulfate (EMIm ES), to investigate the influence of ionic liquid on physical properties, morphologies, and ionic conductivity. Results indicated that EMIm ES preferentially located in the sulfonated PEO soft phase, leading to significantly enhanced ionic conductivity and well-maintained mechanical properties. These properties are highly desirable for electromechanical transducer applications. Electromechanical actuators fabricated with sulfonated polyurethane/IL composite membranes exhibited effective response under a low applied voltage (4 V). However, in the case of an imidazolium-containing segmented polyurethane with imidazolium ionic hard segments and hydrophobic poly(tetramethylene oxide) (PTMO) soft segments, EMIm ES selectively located into the imidazolium ionic hard domains, as evidenced with a constant PTMO soft segment glass transition temperature (Tg) and systematically reduced imidazolium hard segment Tg. Dielectric relaxation spectroscopy demonstrated that ionic conductivity of imidazolium-containing segmented polyurethanes increased by five orders of magnitude upon incorporation of 30 wt% EMIm ES. Imidazolium-containing sulfonated pentablock copolymers were also investigated to elucidate the influence of imidazolium counter cation structures on solution rheology, morphology, and thermal and mechanical properties. Combination of living anionic polymerization and post functionalization strategies provided well-defined sulfonated pentablock copolymers containing structured imidazolium cations in sulfonated polystyrene middle block. Varying alkyl substitute length on imidazolium cations tailored physical properties and morphologies of sulfonated pentablock copolymers. Results indicated that long alkyl substitutes (octyl and dodecyl) on imidazolium cations significantly influenced solution rheological behavior, morphology, and water uptake properties of sulfonated pentablock copolymers due to the altered characteristic of imidazolium cations. Imidazolium-containing sulfonated pentablock copolymers exhibited systematically tailored mechanical properties due to the plasticizing effect of alkyl substitutes. In addition, incorporation of ionic liquids into sulfonated pentablock copolymers further tailored their mechanical properties and ionic conductivity, which made these materials suitable for electromechanical transducer applications. All sulfonated pentablock copolymers were successfully fabricated into actuator devices, which exhibited effective actuation under a low applied voltage (4 V). / Ph. D.

Des carbènes N-hétérocycliques (NHC)s ont été employés comme catalyseurs organiques de la polymérisation par étapes du téréphtaldéhyde. Cette partie est une application en chimie des polymères de la réaction de « condensation de la benzoïne » catalysée par les NHCs impliquant un mono-aldéhyde analogue. Des poly(1,4-phénylène-1-oxo-2-hydroxyéthylène)s ou « polybenzoïnes » ont ainsi été obtenus par polymérisation en solution dans le DMSO ou le THF comme solvant à une température inférieure à 40 °C. La présence de chaines de polybenzoïne cycliques a pu être mise en évidence. La proportion de ces cycles dépend de la nature du catalyseur carbénique et de la polarité du milieu réactionnel. Dans la deuxième partie du travail, des solutions simples ont été proposées pour manipuler les NHCs de manière plus aisée, en évitant leur dégradation prématurée. Pour ce faire, des supports polymères porteurs de sites carbéniques, c’est à dire des « poly(NHC)s », ont été développés et employés à des fins d’organocatalyse. Bien que recyclables, ces « poly(NHC)s » restent assez sensibles aux traces d’impuretés. Un moyen de les protéger est de les faire réagir avec le CO2. Les adduits ainsi formés, « poly(NHC-CO2)s », peuvent alors être employés comme précurseurs pour générer les « poly(NHC)s » in situ, par simple activation thermique, le retour aux « poly(NHC-CO2)s » pouvant être effectué par carboxylation des « poly(NHC)s ». Enfin, des méthodes de synthèse de composés de type imidazolium (version moléculaire) et polyimidazolium (version polymère supportée) à contre anion hydrogénocarbonate (HCO3-) ont été développées. De tels précurseurs peuvent eux-mêmes servir de pré-catalyseurs (moléculaires ou polymères) pour générer, par chauffage, des NHCs et poly(NHC)s, offrant un moyen très pratique de mener des réactions d’organocatalyse et de recycler les catalyseurs. / N-Heterocyclic carbenes (NHCs) have been employed as organic catalysts for the step-growth polymerization of terephtaldehyde. This part is an application to polymer chemistry of the so-called “benzoin condensation”, reaction catalyzed by NHCs involving a mono-aldehyde substrate. Poly(1,4-phenylene-1-oxo-2-hydroxyethylene)s or « polybenzoins » have thus been obtained by polymerization reactions conducted in DMSO or THF at temperatures below 40°C. Presence of cyclic polybenzoins has been put forward. The content of such cyclic species was found to vary as a function of the NHC catalyst employed and of the reaction media used. In a second part, simple solutions have been proposed to easily handle NHCs, by avoiding their degradation. For this purpose, polymer supports bearing NHCs moities, i.e “poly(NHC)s”, have been developed and employed for the purpose of organocatalysis. Even if “poly(NHC)s” were found to be recyclable, they still remain sensitive to impurities. Another way to protect the carbenic centers is to react “poly(NHC)s” with CO2. The adducts thus obtained, “poly(NHC-CO2)s”, can then be employed as precursors for the in situ generation of “poly(NHC)s”, by a simple thermal activation. A further carboxylation of such generated species allow for the recovering of “poly(NHC-CO2)s”. Finally, synthetic methods for the preparation of imidazolium (molecular version) and polyimidazolium (supported polymer version) salts with hydrogenocarbonate (HCO3-) as counter-anion have been developed. Such precursors can serve as precatalysts (molecular or supported) to generate, by heating, NHCs and poly(NHC)s, giving a practice way to conduct organocalysed reactions and recycle the catalysts.

Acid induced step-growth polymerizations of bis(p-methoxybenzyl) carbonate (pMBC), bis(m-methoxybenzyl) carbonate (mMBC) and difurfuryl carbonate (DFC) have been performed to produce resin-foams, because controlled release of carbon dioxide takes place during polymerization of those organic carbonates. The monomers are polymerized in bulk using p-toluene sulfonic acid (pTS) as a catalyst. The volume development of the foams is assisted by use of an appropriate surfactant and the crosslinking agent 1,3,5-trioxane as co-components. A portion of carbon dioxide release is a function of the carbenium stability of the reactive intermediate derived from the monomer; DFC > pMBC ≫ mMBC. Resins derived from mMBC can be post-treated to release carbon dioxide after polymerization. The molecular structures of the resulting materials are investigated by solid state 13C-NMR spectroscopy and IR spectroscopy. Scanning electron microscopy was used to study foam morphology. The carbon dioxide release was monitored with TG-MS analysis. Finally, the polymer foams have been converted into carbon foams and investigated by means of mercury porosimetry. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

La variété des structures colloïdales auto assemblées est principalement due à la présence d'interactions anisotropes. Nous présentons ici une méthode numérique pour étudier l'agrégation irréversible par patches de particules sphériques. Il s'agit d'une amélioration de la dynamique d’amas browniens prenant en compte les interactions par patches et les mouvements de rotation. Nous limitons notre étude aux particules à deux patches opposés de taille variable. Une interaction isotrope, faible, est également ajoutée pour modéliser une polymérisation par étape dans diverses conditions de solvant. Cet algorithme a été testé sur des chaînes isolées et nous avons retrouvé les propriétés statiques et dynamiques attendues. En jouant sur la balance entre la qualité du solvant et la taille des patches diverses morphologies hors-équilibres sont obtenues. Même dans la limite diluée, les collisions corrélées jouent un rôle important et une description de type Smoluchowski échoue. / The versatility of self assembling structures is mostly due to the presence of anisotropic interactions. We present a new simulation method to study irreversible patchy aggregation of spherical particles. It is a variation of the Brownian Cluster Dynamics method taking into account patchy interactions and rotational motions. We limit our case to particles with two oppositely located patches. The size of patches can vary and an isotropic interaction is superimposed around the particle to mimic step-polymerization with various solvent qualities. This new algorithm was successfully tested on single polymer chains and expected static and dynamic properties were recovered. Depending on the balance between solvent quality and patch size various out of equilibrium morphologies could be obtained. Even in the limit dilute solutions, correlated collisions play a key role and the Smoluchowski approach fails. We propose new directions for a better understanding of anisotropy effects on kinetics.

A busca por materiais derivados de fontes renováveis e com características como biocompatibilidade e biodegradabilidade tem crescido significativamente nos últimos anos. A utilização de enzimas na polimerização representa um grande passo para a obtenção destes, visto que possibilitam a produção de polímeros evitando a utilização de catalisadores tóxicos e, assim, melhorando sua biocompatibilidade. O presente trabalho descreve a utilização de monômeros funcionais derivados de fontes renováveis na produção de poliésteres hidrolisáveis via catálise enzimática. As sínteses de polímeros produzidos a partir de isosorbídeo e ácidos dicarboxílicos ou derivados - como seus ésteres alquílicos e vinílicos - foram feitas utilizando a lipase de Candida antarctica Fração B como catalisador. As polimerizações foram realizadas por policondensações em massa e em solução, utilizando-se diferentes solventes e diferentes técnicas para remoção de subprodutos de reação. A principal abordagem foi o estudo das diferentes condições reacionais realizadas, variando-se o tempo de reação, tipo do monômero, solvente utilizado (se for o caso) e tipo de técnica para remoção de subprodutos visando o aumento da massa molar dos polímeros. A condição que forneceu os materiais com maiores massas molares foi a policondensação em solução, utilizando a mistura cicloexano:benzeno como solvente. Tendo por objetivo investigar profundamente a condição ótima obtida, e estabelecer padrões de comparação com outros sistemas, foram estudados, nessa condição, parâmetros como tempo de reação, efeito do tamanho da cadeia carbônica do monômero, grupo de saída, solubilidade dos polímeros e diluição do sistema. Os materiais obtidos foram caracterizados por cromatografia por exclusão de tamanho (SEC), termogravimetria (TG), calorimetria exploratória diferencial (DSC), espectroscopia no infravermelho, difração de raios-X, e Ressonância Magnética Nuclear (RMN) de 1H e 13C. Através deste trabalho foi provado que, embora apresente uma cinética de reação lenta, a polimerização enzimática deste diol secundário estericamente impedido é possível, fornecendo poliésteres com massas molares similares às obtidas via catálise química. Todos os resultados obtidos neste trabalho são inéditos no que diz respeito à polimerização enzimática de dióis secundários impedidos, mais especificamente de isosorbídeo. / The search for materials derived from renewable sources, with characteristics such as biocompatibility and biodegradability has grown significantly in recent years. The use of enzymes in the polymerization is a major step for the attainment of these materials, since it allows the production of polymers while avoiding the use of toxic catalysts and thus improving its biocompatibility. This paper describes the use of functional monomers derived from renewable sources in the production of hydrolysable polyesters by enzyme catalysis The synthesis and characterization of polymers derived from isosorbide and dicarboxilic acids or derivatives - such as alkyl and vinyl esters - were carried out using the lipase from Candida antarctica - Fraction B as catalyst. The polymerizations were accomplished by polycondensations in bulk and in solution, using different solvents and different techniques for removal of reaction byproducts. The main approach was to study the different reaction conditions, by varying the reaction time, monomer type, solvent used (if applicable) and the type of technique for removal of byproducts, aiming at maximizing polymer molar mass. The condition that provided the material with higher molecular weight was the solution step-growth polymerization, using a mixture cyclohexane:benzene as solvents. Aiming to thoroughly investigate the optimum condition obtained, and to establish standards for comparison with other systems, it was studied, in this condition, parameters such as reaction time, effect of monomer carbon chain length , leaving group, polymers solubility of and dilution of the reaction system. The materials were characterized by gel permeation chromatography (SEC), thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy, X-ray diffraction and 1H and 13C Nuclear Magnetic Resonance (NMR). Through this work it was proved that, in spite of a slow reaction kinetics, the enzymatic polymerization of this hindered secondary diol is possible, providing polyester with molecular weight similar to those obtained by chemical catalysis. All results obtained in this work are unprecedented with respect to the enzymatic polymerization of hindered secondary diols, more specifically of Isosorbide.

A busca por materiais derivados de fontes renováveis e com características como biocompatibilidade e biodegradabilidade tem crescido significativamente nos últimos anos. A utilização de enzimas na polimerização representa um grande passo para a obtenção destes, visto que possibilitam a produção de polímeros evitando a utilização de catalisadores tóxicos e, assim, melhorando sua biocompatibilidade. O presente trabalho descreve a utilização de monômeros funcionais derivados de fontes renováveis na produção de poliésteres hidrolisáveis via catálise enzimática. As sínteses de polímeros produzidos a partir de isosorbídeo e ácidos dicarboxílicos ou derivados - como seus ésteres alquílicos e vinílicos - foram feitas utilizando a lipase de Candida antarctica Fração B como catalisador. As polimerizações foram realizadas por policondensações em massa e em solução, utilizando-se diferentes solventes e diferentes técnicas para remoção de subprodutos de reação. A principal abordagem foi o estudo das diferentes condições reacionais realizadas, variando-se o tempo de reação, tipo do monômero, solvente utilizado (se for o caso) e tipo de técnica para remoção de subprodutos visando o aumento da massa molar dos polímeros. A condição que forneceu os materiais com maiores massas molares foi a policondensação em solução, utilizando a mistura cicloexano:benzeno como solvente. Tendo por objetivo investigar profundamente a condição ótima obtida, e estabelecer padrões de comparação com outros sistemas, foram estudados, nessa condição, parâmetros como tempo de reação, efeito do tamanho da cadeia carbônica do monômero, grupo de saída, solubilidade dos polímeros e diluição do sistema. Os materiais obtidos foram caracterizados por cromatografia por exclusão de tamanho (SEC), termogravimetria (TG), calorimetria exploratória diferencial (DSC), espectroscopia no infravermelho, difração de raios-X, e Ressonância Magnética Nuclear (RMN) de 1H e 13C. Através deste trabalho foi provado que, embora apresente uma cinética de reação lenta, a polimerização enzimática deste diol secundário estericamente impedido é possível, fornecendo poliésteres com massas molares similares às obtidas via catálise química. Todos os resultados obtidos neste trabalho são inéditos no que diz respeito à polimerização enzimática de dióis secundários impedidos, mais especificamente de isosorbídeo. / The search for materials derived from renewable sources, with characteristics such as biocompatibility and biodegradability has grown significantly in recent years. The use of enzymes in the polymerization is a major step for the attainment of these materials, since it allows the production of polymers while avoiding the use of toxic catalysts and thus improving its biocompatibility. This paper describes the use of functional monomers derived from renewable sources in the production of hydrolysable polyesters by enzyme catalysis The synthesis and characterization of polymers derived from isosorbide and dicarboxilic acids or derivatives - such as alkyl and vinyl esters - were carried out using the lipase from Candida antarctica - Fraction B as catalyst. The polymerizations were accomplished by polycondensations in bulk and in solution, using different solvents and different techniques for removal of reaction byproducts. The main approach was to study the different reaction conditions, by varying the reaction time, monomer type, solvent used (if applicable) and the type of technique for removal of byproducts, aiming at maximizing polymer molar mass. The condition that provided the material with higher molecular weight was the solution step-growth polymerization, using a mixture cyclohexane:benzene as solvents. Aiming to thoroughly investigate the optimum condition obtained, and to establish standards for comparison with other systems, it was studied, in this condition, parameters such as reaction time, effect of monomer carbon chain length , leaving group, polymers solubility of and dilution of the reaction system. The materials were characterized by gel permeation chromatography (SEC), thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy, X-ray diffraction and 1H and 13C Nuclear Magnetic Resonance (NMR). Through this work it was proved that, in spite of a slow reaction kinetics, the enzymatic polymerization of this hindered secondary diol is possible, providing polyester with molecular weight similar to those obtained by chemical catalysis. All results obtained in this work are unprecedented with respect to the enzymatic polymerization of hindered secondary diols, more specifically of Isosorbide.