نوع مقاله : پژوهشی
نویسندگان
تهران، دانشگاه صنعتی امیرکبیر، دانشکده مهندسی پلیمر و رنگ، صندوق پستی ۴۴۱۳-۱۵۸۷۵
چکیده
کلیدواژهها
موضوعات
عنوان مقاله [English]
نویسندگان [English]
Hypothesis
The complex photopolymerization kinetics of furfuryl acrylate are governed by the competitive interactions between its two distinct reactive site, the acrylic vinyl group and the furan ring. The formation of stable allylic radicals from the furan ring leads to their significant accumulation within the system, causing a fundamental deviation from classical free-radical polymerization kinetics.
Methods
A Kinetic Monte Carlo simulation was developed for the first time to simulate the photopolymerization of furfuryl acrylate at a molecular scale. The simulation was initialized with a system of 10¹¹ furfuryl acrylate molecules and incorporated a mechanism of 11 distinct reaction pathways. A custom C++ code, employing a Mersenne Twister random number generator for stochastic selection of reactions and time steps, was used to track the evolution of species concentrations, monomer conversion, and reaction probabilities over time.
Findings
The simulation results show excellent agreement with experimental data, confirming the accuracy of the simulation approach. One of the findings of this study was the identification of the pivotal role of stable allylic radicals and their gradual accumulation within the system. These radical species attained concentrations substantially exceeding those of acrylic radicals, thereby resulting in a deviation from classical polymerization kinetics. The intermolecular degradative chain transfer was identified as the most influential side reaction with a 30–39% probability, serving as the primary factor for the significant reduction in both molecular weight and polymerization rate. The ratio of the rate constant for intermolecular degradative chain transfer to propagation plays a significant role in controlling the final structure at different temperatures. This research not only provides a deep fundamental understanding of the polymerization mechanism of furanic monomers but also offers a computational framework for optimizing the synthesis of furfuryl acrylate-based polymers for advanced applications in areas such as biomaterials.
کلیدواژهها [English]
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