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• W2095315093 abstract "Summary: The kinetics of solution free radical copolymerization of isobutyl methacrylate (i-BMA) and lauryl methacrylate (LMA) in benzene, initiated with 2,2-azoisobutyronitrile (AIBN) were studied at different monomer feed compositions at low conversion levels. In order to avoid the complications of copolymerization kinetics, the pseudo-kinetic rate constant method was applied in constant and variable volume polymerization systems. A two-step procedure based on interval analysis and the modified Rosenbrock method was used to estimate the kinetic parameters of copolymerization. In the first step, initiation, coupled propagation-termination and transfer rate parameters were determined from steady state kinetic equations using interval analysis. Since the objective function is non-linear, non-convex and has multiple local optima, a robust computational technique, based on the Interval Newton/Generalized Bisection (IN/GB) algorithm, was developed to solve this set of non-linear algebraic equations. This method was used with mathematical and computational guarantees of certainty to find the global optimum. In the second step, the system of mole balance, population balance and moment equations, which are highly stiff ordinary differential equations, were discritized and solved by the modified Rosenbrock method. The results of the first computational step were inserted as an active or equality constraint in the second step to calculate the individual elementary rate parameters of the reaction. Statistical analysis indicated that the copolymer composition is well described by the terminal unit model (TUM), but the implicit penultimate unit effect (IPUE) model of Fukuda and coworkers is more suitable for describing the rate data. In contrast to most previously studied systems, it was found that propagation and coupled rate parameters are greater than those predicted by the TUM. Variation of number average molecular weight of the copolymer in polymerization system for various initial monomer feed compositions at different reaction times (solid lines are computed results)." @default.
• W2095315093 created "2016-06-24" @default.
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• W2095315093 date "2004-07-21" @default.
• W2095315093 modified "2023-10-14" @default.
• W2095315093 title "A Two-Step Interval and Modified Rosenbrock Method for Kinetic Parameter Estimation in Copolymerization Systems: A Robust and Reliable Approach" @default.
• W2095315093 doi "https://doi.org/10.1002/mats.200300050" @default.
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