Acrylic resins, synthesized from a mixture of monomers selected from the methacrylate, acrylate and styrene families, are the base polymer components for many automotive coatings due to their excellent chemical and mechanical properties. The low molecular weight polymers with reactive functionalities are made via high-temperature starved-feed free-radical solution semibatch terpolymerization, operating conditions that greatly promote the importance of secondary reactions, such as methacrylate depropagation, and acrylate backbiting, chain scission and macromonomer propagation. In this work, a generalized model for styrene/methacrylate/acrylate terpolymerization has been developed and formulated in the PREDICI software package and poorly understood high temperature mechanisms have been studied. Unknown rate coefficients for methacrylate depropagation, reactivity of acrylate macromonomer and penultimate copolymerization kinetics were determined via separate kinetic experiments. The generality of the terpolymerization mechanistic model was verified against data obtained under a range of polymerization conditions, and provides an exclusive insight into the kinetic complexity of methacrylate/styrene/acrylate terpolymerization at high temperatures. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2010-04-28 19:56:36.906

OBJETIVO: caracterizar a interação entre tensão e cinética de polimerização e seus parâmetros determinantes, e avaliar a qualidade da rede polimérica e propriedades mecânicas de compósitos comerciais para dentes posteriores a base de dimetacrilato ou de silorano. A cinética de polimerização foi avaliada sob influência da intensidade da fonte de luz, da temperatura e da umidade. Por fim, o grau de conversão (GC) do compósito a base de silorano foi avaliado por espectroscopia e titulação. MÉTODOS: foram utilizados três compósitos de baixa contração: Kalore (KAL - GC America) e N´Durance (NDUR Septodont), a base de dimetacrilatos; e Filtek P90 (P90 - 3MESPE), a base de silorano. O EsthetX HD (EHD - Dentsply) foi utilizado como controle. A tensão de polimerização (TP) dos espécimes (n = 5; Ø = 5 mm; h = 1 mm, 10 min) foi obtida em máquina universal de ensaios mecânicos. A contração volumétrica (CVol) foi determinada em linômetro (n = 3; Ø = 6 mm; h = 1,5 mm; 10 min). O módulo de elasticidade em flexão (MeFlex) e a resistência à flexão (RFlex) (n = 10; 10 x 2 x 1 mm) foram obtidos através do teste de dobramento em três pontos (8 mm entre apoios; 0.5 mm/min). O GC e a taxa de polimerização (Rp) dos espécimes (n = 3; Ø = 6,5 mm; h = 0,8 mm) foram determinados por espectroscopia no NIR (banda em 6165 cm-1 para dimetacrilatos e em 4156 cm-1 e 4071 cm-1 para silorano). Para os testes acima descritos, a fotopolimerização foi realizada com 740 mW/cm2 x 27 s (Bluephase G2 Ivoclar). A temperatura de transição vítrea (Tg), a tangente de delta (tan delta), o grau de heterogeneidade e a densidade de ligações cruzadas de espécimes (n = 3; 15 x 3 x 1 mm) com o máximo de conversão foram obtidos em analisador dinâmico-mecânico. A análise dos extratos obtidos após imersão dos espécimes (Ø = 12 mm; h = 0,8 mm; 970 mW/cm2 x 30 s) em diclorometano foi realizada através de 1H-NMR para verificar monômeros residuais. A cinética de polimerização de espécimes (n = 3; Ø = 5,5 mm; h = 1 mm) de todos os materiais, fotopolimerizados com Acticure 4000 EXFO e filtro 320-500 nm, foi analisada sob variação de irradiância (3, 30 ou 200 mW/cm2) e de temperatura (23, 35 ou 60 °C) por espectroscopia no NIR (banda em 6165 cm-1 para dimetacrilatos e em 4156 cm-1 para silorano). A influência da umidade a 23, 35 ou 60 °C na cinética de polimerização foi verificada para Filtek P90 e EsthetX HD. Para auxiliar na identificação de bandas que possam ser utilizadas para o GC do Filtek P90, as conversões de bandas referentes a anéis epóxicos selecionadas com a caracterização espectroscópica (Mid-IR e NIR) de monômeros modelos e do Filtek P90 sem carga foram comparadas com os valores encontrados no teste de titulação ácido-base desses materiais. Os dados dos testes laboratoriais, quando necessário, foram submetidos à Anova e ao Teste de Tukey ( < 0,05). RESULTADOS: O EHD apresentou a maior TP, estatisticamente semelhante ao NDUR e maior que o KAL e o P90, estatisticamente semelhantes. A Cvol do EHD foi superior à do NDUR, e o P90 e o KAL obtiveram os menores valores, estatisticamente semelhantes. O P90 apresentou o maior MeFLex, sem diferença entre os outros materiais. O EHD obteve o maior valor de RFlex, e o KAL e o NDUR apresentaram os menores valores, sem diferença entre eles. O NDUR apresentou o maior GC, seguido do EHD e KAL, e o P90 apresentou o menor valor. O EHD apresentou a maior Tg, seguido de P90, KAL e NDUR. O NDUR e o P90 apresentaram, respectivamente, a maior e a menor tan delta. O NDUR e o KAL apresentaram a maior e a menor homogeneidade, respectivamente. O P90 apresentou a maior densidade de ligações cruzadas, sem diferença entre os outros compósitos. Diferentemente do EHD e do KAL, o P90 e o NUR não apresentaram lixiviação de monômeros residuais. O P90 mostrou cinética de polimerização semelhante aos compósitos dimetacrilatos, inclusive sob variação de irradiância e temperatura. A umidade aumentou ligeiramente o GCMáx do EHD a 23 e a 35 °C, porém a temperatura exerceu maior influência à 60° C. De uma maneira geral, a umidade não influenciou a cinética de polimerização do P90. Em Mid-IR, o P90 apresentou 60 % de conversão através da banda em 883 cm-1, próximo ao valor obtido com a titulação. Já em NIR, há conversão em duas bandas distintas: em 4156 cm-1 (42%) e em 4071 cm-1 (65%). CONCLUSÃO: o GC exerceu grande influência sobre os valores de TP. Altos valores de MeFlex e RFlex foram associados à alta densidade de ligações cruzadas. P90 e NDUR não apresentaram lixiviação de monômeros residuais. Um maior GC é obtido quando o compósito alcança alto valor de conversão até o ponto de vitrificação. O P90 mostrou comportamento semelhante aos compósitos baseados em dimetacrilatos quanto à cinética de polimerização, inclusive sob variação de irradiância e temperatura. De uma maneira geral, a umidade não exerceu grande influência na cinética de polimerização do P90 e do EHD. Como não se sabe a composição exata do Filtek P90, pode-se dizer apenas que a conversão deste material é cerca de 40 %. O teste de titulação precisa ser aperfeiçoado e são necessários estudos adicionais para se validar a metodologia FTIR X titulação utilizada. Como a composição monomérica exata do Filtek P90 não é conhecida, não foi possível precisar a conversão deste material com os métodos empregados, porém pode-se dizer que este material apresenta, no mínimo, cerca de 40 % de conversão, dada pela banda em 4156 cm-1. / OBJECTIVE: To characterize the interaction between polymerization kinetics and stress and its determining parameters, and evaluate polymer network quality and mechanical properties of commercial composites for posterior teeth based on dimethacrylate or silorane. Also, the influence of the intensity of the light source, temperature and humidity on the polymerization reaction was evaluated. Finally, the degree of conversion (DC) of the composite based on silorane was evaluated by spectroscopy and titration. METHODS: three \"low shrinkage\" composites were chosen: Kalore (KAL - GC America) and N\'Durance (NDUR - Septodont), based on dimethacrylates, and Filtek P90 (P90 - 3MESPE), based on silorane. EsthetX HD (EHD - Dentsply) was used as a control. Polymerization stress (PS) of samples (n = 5, Ø = 5 mm; h = 1 mm, 10 min) was obtained using a universal testing machine. Volumetric shrinkage (VS) was determined in a linometer (n = 3, Ø = 6 mm, h = 1.5 mm, 10 min). Elastic modulus (E) and flexural strength (FS) (n = 10; 10 x 2 x 1 mm) were obtained by three point bending test (8 mm between support, 0.5 mm/min). DC and polymerization rate (Rp) of specimen (n = 3, Ø = 6.5 mm, h = 0.8 mm) were determined by NIR spectroscopy (peak 6165 cm-1 for dimethacrylates and 4156 cm-1 and 4071 cm-1 for silorane). For these tests, photopolymerization was performed with 740 mW/cm2 x 27 s (Bluephase G2 - Ivoclar). Glass transition temperature (Tg), loss tangent (LT), degree of heterogeneity and crosslink density of specimens (n = 3, 15 x 3 x 1 mm) with maximum conversion was obtained in a dynamic mechanical analyzer. Analysis of extracts obtained after specimen immersion (Ø = 12 mm, h = 0.8 mm; 970 mW/cm2 x 30 s) in dichloromethane was carried out using 1H-NMR to determine residual monomers. Polymerization kinetics of specimens (n = 3; Ø = 5.5 mm, h = 1 mm) of all materials cured with Acticure 4000 - EXFO and 320-500 nm filter, was analyzed using different levels of irradiance (3, 30 or 200 mW/cm2) and temperature (23, 35 or 60 °C) by NIR spectroscopy (peak 6165 cm-1 for dimethacrylates and 4156 cm-1 for silorane). The influence of moisture at 23, 35 or 60 °C on polymerization kinetics was observed for Filtek P90 and EsthetX HD. To assist in the identification of peaks that can be used to calculate the conversion of Filtek P90, peaks related to epoxy rings selected with the spectroscopic characterization (Mid-IR and NIR) of model monomers and Filtek P90 (after filler extraction with acetone) were compared with the values found in acid-base titration test of these materials. Data were submitted to ANOVA and Tukey\'s test ( < 0.05). RESULTS: EHD showed the greatest TP, statistically similar to NDUR and greater than KAL and P90, statistically similar. EHD Cvol was superior to NDUR, and P90 and KAL had the lowest and statistically similar values. P90 had the highest MeFLex, with no difference between other materials. EHD had the highest RFlex value, and NDUR and KAL, the lowest one, with no difference between them. NDUR had the highest DC, followed by EHD and KAL, and P90 had the lowest value. EHD showed the highest Tg, followed by P90 and KAL and NDUR. NDUR and P90 showed respectively the highest and lowest LT. NDUR and KAL had the highest and the lowest homogeneity, respectively. P90 had the highest crosslink density, with no difference between other composites. Unlike EHD and KAL, NUR and P90 showed no leachable monomers. P90 showed similar polymerization kinetics to dimethacrylate composites, even with irradiation and temperature variation. Moisture slightly increased the DC of EHD at 23 and 35 °C, and temperature showed greater influence at 60 °C. In general, moisture did not influence P90 polymerization kinetics. P90 showed 60 % conversion in Mid-IR over the peak 883 cm-1, similar to the value obtained with titration. Two distinct peaks showed conversion in NIR: 4156 cm-1 (42 %) and 4071 cm-1 (65 %). CONCLUSION: DC had a great influence on PS values. Higher E and FS values were associated with higher crosslink density. NDUR and P90 showed no leachable monomers. A higher DC is obtained when the composite reaches high values of conversion before vitrification. P90 showed similar behavior to composites based on dimethacrylate regarding the polymerization kinetics, including under variation of irradiance and temperature. In general, moisture does not great influence P90 and EHD polymerization kinetics. As the exact composition of P90 is unknown, it was not possible to specify the conversion of this material with the methods employed, but it can be said that this material exhibits at least about 40 % conversion, provided by the peak 4156 cm-1.

No description available.

This thesis is focused on the determination of the propene polymerization kinetics on phthalate and nonphthalate diester Ziegler-Natta MgCl2-supported catalysts under the industrial conditions. The kinetic profiles were determined by various laboratory techniques for propene polymerization. For assessing the profiles were utilized batch gas and liquid polymerization modes in 2-litre and 4-litre reactors. Finally, the results were complemented with the runs performed in a unique Stopped-Flow apparatus, which allows polymerization of liquid propene at very short polymerization times. The kinetics profiles of both catalysts were determined and compared by combination of experimental data of these techniques. The basic properties of the synthesized polymeric powders were measured, such as the melt flow index, bulk density and amount of polypropene fraction soluble in cold xylene.

The aim of the study will be the determination of the kinetic profiles of the polymerization of propene, ethene and their mixtures with commercial Ziegler-Natta catalyst by application of two different experimental procedures. The prepared polymer material will be utilized for the SEC analysis and subsequent evaluation of the concentration of active sites. The determined molecular mass distribution curves will be further investigated by the application of the procedure, which deconvolute the overall profile on the basic Flory's distribution functions. Then the comprehensive study about character and behavior of various types of active centers in dependence on time and type of monomer will result from this investigation.

<p>Coated calcium-alginate beads are the basis of many encapsulation methods used in pursuit of cell-based enzyme and hormone replacement therapies. The standard alginate - poly-L-lysine - alginate (APA) capsules consist of a calcium-alginate hydrogel core containing cells designed to express a therapeutic product, coated with permeability controlling poly-L-lysine (PLL, a polycation) followed by an exterior layer of polyanionic alginate. Although this approach is promising, the required long-term survival of the implanted cells has remained largely elusive as the current APA capsules suffer from several biocompatibility and mechanical strength issues, one of which is the weakening of ionic crosslinks over time, exposing the encapsulated cells to the host.</p> <p>This thesis aims to replace the exterior layer of alginate with a Temporarily Reactive Polyelectrolyte (TPR) to reinforce AP capsules by forming covalently crosslinked shells. TRPs are polyanions that possess reactive electrophilic groups capable of forming permanent covalent crosslinks with the underlying polyamine (such as PLL), and subsequently hydrolyze, increasing the net negative charge of the polyanion. TRPs are thought to improve the biocompatibility and strength of the microcapsules by forming stable inert amide bonds, as well as increasing the net negative charge of the capsule through the liberation of carboxylates. This thesis will focus primarily on two TRPs: 50% hydrolyzed poly(methyl vinyl ether-<em>alt</em>-maleic anhydride), PMM₅₀ , and poly(methacrylic acid-co-2-vinyl-4,4-dimethylazlactone) with a 50:50 co-monomer ratio, PMV₅₀ . Their synthesis, rates of hydrolysis and capsule formation around encapsulated C2C12 cells for <em>in-vitro</em> and<em> in-vivo</em> studies will be described. Additionally the synthesis and rates of hydrolysis of other 2-vinyl-4,4-dimethylazlactone (VDMA)-copolymers are presented as potential candidates for future TRPs.</p> / Doctor of Philosophy (PhD)

This dissertation describes the essential modeling components and techniques for building comprehensive polymer process models for metal-catalyzed polyolefin processes. The significance of this work is that it presents a comprehensive approach to polymer process modeling applied to large-scale commercial processes. Most researchers focus only on polymerization mechanisms and reaction kinetics, and neglect physical properties and phase equilibrium. Both physical properties and phase equilibrium play key roles in the accuracy and robustness of a model. This work presents the fundamental principles and practical guidelines used to develop and validate both steady-state and dynamic simulation models for two large-scale commercial processes involving the Ziegler-Natta polymerization to produce high-density polyethylene (HDPE) and polypropylene (PP). It also provides a model for the solution polymerization of ethylene using a metallocene catalyst. Existing modeling efforts do not include physical properties or phase equilibrium in their calculations. These omissions undermine the accuracy and predictive power of the models. The forward chapters of the dissertation discuss the fundamental concepts we consider in polymer process modeling. These include physical and thermodynamic properties, phase equilibrium, and polymerization kinetics. The later chapters provide the modeling applications described above. / Ph. D.

The dissertation describes and assembles the building blocks for sound and accurate models for solid-state polymerization process systems of condensation polymers, particularly poly(ethylene terephthalate) and nylon-6. The work centers on an approach for modeling commercial-scale, as opposed to laboratory-scale, systems. The focus is not solely on coupled polymerization and diffusion, but extends to crystallization, physical properties, and phase equilibrium, which all enhance the robustness of the complete model. There are three applications demonstrating the utility of the model for a variety of real, industrial plant operations. One of the validated simulation models is for commercial production of three different grades of solid-state PET. There are also validated simulation models for the industrial leaching and solid-state polymerization of nylon-6 covering a range of operating conditions. The results of these studies justify our mixing-cell modeling approach as well as the inclusion of all relevant fundamental concepts. The first several chapters discuss in detail the engineering fundamentals that we must consider for modeling these polymerization process systems. These include physical properties, phase equilibrium, crystallization, diffusion, polymerization, and additional modeling considerations. The last two chapters cover the modeling applications. / Ph. D.

Made available in DSpace on 2017-07-24T19:22:04Z (GMT). No. of bitstreams: 1 Camilo Andres Pulido Mora.pdf: 15669266 bytes, checksum: ffecbe6f814025ea53601a49fb579e21 (MD5) Previous issue date: 2017-03-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The aims of the study were: 1) to evaluate the bond strength (μTBS) and light transmission (LT) of individualized posts with different composite resin translucency,as well as the Vickers microhardness (VHN) of a self-adhesive resin cement. 2) to compare the shrinkage strain (SS), shrinkage rate (SR) and VHN of a conventionalcement and a self-adhesive one in the apical and cervical thirds of the root canal. 3) to compare the μTBS, VHN and nanoinfiltration (NI) immediately and after 3 years of a conventional resin cement and a self-adhesive one used in fiberglass post cementation. For the experiment 1, 70 lower premolars (n = 10) were selected and divided into 5 groups according to the resin translucency used for the post individualization: ideal adaptation (Positive control), high translucency composite resin (HT), Medium translucency composite resin (MT), high opacity composite resin (RAO) and pooradaptation (Negative Control); and cemented with dual resin cement RelyX U200 (3M / ESPE). One week later the BS, VHN and LT were evaluated.For experiment 2, 56 lower premolars were selected and endodontically treated. The teeth were randomly divided into 2 groups (n = 28) according to the resin cement used: RelyX ARC Group (3M / ESPE) and U200 Group: RelyX U200 (3M /ESPE). After that, 28 specimens (n = 14 per group) were sliced and submitted to VHN, BS and NI tests; And the other 28 specimens were sliced and stored in distilled water at 37 ° C for testing after 3 years. For experiment 3, 34 lower premolar teeth were selected and endodontically treated; Were then randomly divided into two groups (n = 14) according to the resin cement used: RelyX ARC Group (3M / ESPE) and U200 Group: RelyX U200 (3M / ESPE). Before the insertion of the resin cement in the root canal, two fiber optic sensors with Bragg gratings were placed in the post to measure cement deformation in the coronary and apical regions of the root canal. Data from each group (n = 10) were kinetically analyzed for polymerization Shrinkage strain (PS). The Shrinkage rate (SR) was calculated by numerical differentiation of the shrinkage data as a function of time. The experiments were analyzed by ANOVA and Tukey's test (a= 0.05). Experiment 1 showed a significant influence of resin translucency on resin cement properties. High translucency, promoted high μTBS and VHN. Experiment 2 showed that ARC had higher values of μTBS and VHN in the cervical third, but U200 presented the highest values after 3 years. In experiment 3 there was no difference in PS between the cements analyzed, but the ARC presented higher SR in both thirds. For the VHN, no significant difference in the cervical third was found, but U200 presented higher values in the apical third. / Os objetivos do estudo foram: 1) avaliar a resistência de união (RU) e transmissão de luz (TL) de pinos individualizados com diferente translucidez de resina composta, assim como a microdureza Vickers (MDV) de um cimento resinoso autoadesivo. 2) comparar a contração, taxa de contração e microdureza de um cimento convencional e um autoadesivo nos terços apical e cervical do canal radicular. 3) comparar a RU, MDV e nanoinfiltração (NI) imediata e após 3 anos de um cimento dual convencional e um cimento dual autoadesivo utilizados na cimentação de pinos de fibra de vidro. Para o experimento 1 foram selecionados 70 pré-molares inferiores (n=10) e divididos em 5 grupos segundo o grau de translucidez de resina utilizada para a individualização do pino: adaptação ideal (Controle positivo), resina de alta translucidez (HT), resina de média translucidez (MT), resina composta de alta opacidade (HO) e adaptação inadequada (Controle negativo); e cimentados com cimento resinoso dual RelyX U200 (3M/ESPE). Uma semana depois foi avaliada a RU, MDV e TL dos mesmos. Para o experimento 2, foram selecionados 56 dentes pré-molares inferiores e tratados endodonticamente. Os dentes foram divididos aleatoriamente em 2 grupos (n=28) segundo o cimento resinoso utilizado: Grupo ARC: RelyX™ ARC (3M/ESPE) e Grupo U200: RelyX U200 (3M/ESPE). Depois disso, 28 corpos-de-prova (n=14 por grupo) foram armazenados em água destilada por 48 h e depois cortados em fatias e submetidos a teste de MDV, RU e NI; e os outros 28 corpos-de-prova foram cortados em fatias e armazenados em água destilada a 37°C a fim de serem testados após de 3 anos. Para o experimento 3 foram selecionados 34 dentes pré-molares inferiores e tratados ndodonticamente;depois foram aleatoriamente divididos em 2 grupos (n=17) segundo o cimento resinoso utilizado: Grupo ARC: RelyX ARC (3M/ESPE) e Grupo U200: RelyX U200 (3M/ESPE). Antes da inserção do cimento resinoso no canal radicular foram posicionados no pino dois sensores de fibra óptica com redes de Bragg para a mensuração das deformações do cimento na região coronária e apical do canal radicular. Os dados de cada grupo (n=10) foram analisados cineticamente e para analisar a contração de polimerização (CPO). A taxa de contração (TP) foi calculada por diferenciação numérica dos dados de contração em função do tempo. Os experimentos foram analisados por ANOVA e teste de Tukey (a=0,05). O experimento 1 mostrou que há uma influência significativa da translucidez da resina nas propriedades do cimento. Quanto maior a translucidez, maior a RU e MDV. O experimento 2 mostrou que o ARC teve maiores valores de RU e MDV no terço cervical, mas foi o U200 quem apresentou maiores valores de RU e MDV após 3 9 anos. No experimento 3 não houve diferença na CPO entre os cimentos analisados, mas o ARC apresentou maior TP em ambos os terços. Para a MDV, não houve diferença significativa no terço cervical, mas o U200 apresentou maiores valores no terço apical.

Made available in DSpace on 2014-12-17T15:01:46Z (GMT). No. of bitstreams: 1 JuceliaMER.pdf: 2171315 bytes, checksum: 6d1b358ee82a3e95a8b3fb30782bdf76 (MD5) Previous issue date: 2005-12-15 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Polyurethanes are very versatile macromolecular materials that can be used in the form of powders, adhesives and elastomers. As a consequence, they constitute important subject for research as well as outstanding materials used in several manufacturing processes. In addition to the search for new polyurethanes, the kinetics control during its preparation is a very important topic, mainly if the polyurethane is obtained via bulk polymerization. The work in thesis was directed towards this subject, particularly the synthesis of polyurethanes based castor oil and isophorone diisocianate. As a first step castor oil characterized using the following analytical methods: iodine index, saponification index, refraction index, humidity content and infrared absorption spectroscopy (FTIR). As a second step, test specimens of these polyurethanes were obtained via bulk polymerization and were submitted to swelling experiments with different solvents. From these experiments, the Hildebrand parameter was determined for this material. Finally, bulk polymerization was carried out in a differential scanning calorimetry (DSC) equipment, using different heating rates, at two conditions: without catalyst and with dibutyltin dilaurate (DBTDL) as catalyst. The DSC curves were adjusted to a kinetic model, using the isoconversional method, indicating the autocatalytic effect characteristic of this class of polymerization reaction / Poliuretanas s?o pol?meros de grande versatilidade, podendo ser usadas na forma de p?s, adesivos ou elast?meros. Por este motivo, as poliuretanas s?o amplamente pesquisadas e utilizadas nas ind?strias. Paralelamente ? busca por novas poliuretanas, ? importante o controle cin?tico durante sua obten??o, principalmente se estas s?o obtidas via polimeriza??o em massa. O trabalho desta tese aborda este problema, especificamente no caso da obten??o de poliuretanas derivadas do ?leo de mamona e diisocianato de isoforona. Para isto, primeiramente o ?leo de mamona foi caracterizado atrav?s dos seguintes m?todos anal?ticos: ?ndice de iodo, ?ndice de saponifica??o, ?ndice de refra??o, ?ndice de hidroxila, teor de umidade e espectroscopia de absor??o na regi?o do infravermelho (FTIR). Como segundo passo, os corpos de prova dessas poliuretanas foram obtidos atrav?s de polimeriza??o em massa e submetidos a ensaios de inchamento com diferentes solventes. A partir destes ensaios o par?metro de Hildebrand foi determinado para este material. Finalmente, a polimeriza??o em massa desse material foi executada em equipamento de calorimetria explorat?ria diferencial (DSC) a diferentes taxas de aquecimento sob duas condi??es: sem catalisador e com o catalisador, dibutil-dilaurato de estanho (DBTDL). As curvas de DSC foram ajustadas a modelos cin?ticos, usando o m?todo isoconversional, caracterizando o car?ter autocatal?tico da forma??o de poliuretanas