Modelagem da homopolimerização via radical livre controlada em presença de radicais nitroxido

AUTOR(ES)
DATA DE PUBLICAÇÃO

2003

RESUMO

A practical methodology for the computer modeling of number-and weight-averages molecular weight and molecular weight distribution of polymer with linear structure obtained from nitroxide mediated radical polymerization (NMRP) has been developed. Since free-radical polymerization (FRP) is one of the most important chain-growth polymerization, this work embraces a free-radical polymerization in homogeneous systems as reference point to model the "Iiving" free-radical polymerization. The "living" free-radical polymerization (LFRP) emphasizes the production of polymers with highly controlled structures, narrows MWD and polydispersity index closed to 1.0. Different mechanisms have been proposed to carry out LFRP, among them, Nitroxide-mediated radical po/ymerization (NMRP), which attains polymers with controlled molecular weight by mediated nitroxide radicais acting as trapping agent, in which the polymer chain that is growing are reversibly trapped. To obtain number- and weight-averages molecular weight and molecular weight distributions (MWD) for FRP process the instantaneous and moments methods were used. On the other hand, for the process NMRP the method of moments was used to obtain the number- and weight-averages molecular weight and polydispersity index. The mathematical model was based on kinetics constant rates and free-volume theory for FRP and kinetics constant rates for NMRP. Simulations were compared with experimental data to validate the model. Styrene and methylmethacrilate was analyzed as cases studies for FRP process and styrene polymerization for NMRP process. The model was able to modeling monomolecular and bimolecular NMRP process to different conditions of temperature and species concentrations. It showed the dead polymer chain appear by live polymeric chain not captured by nitroxide radicais in the NMRP processo. Then, NMRP can obtain "Iiving" characteristic if exists enough quantity of nitroxide radical. This permits the radicais created to be captured. Nitroxide radicais more unstable generate best results in relation to productivity and product quality

ASSUNTO(S)

polimerização radicais (quimica) simulação (computadores) reatores quimicos

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