Free Radical Polymerizations: LDPE and EVA

This chapter provides an in-depth exploration of the modeling of high-pressure manufacturing processes for low-density polyethylene (LDPE) and polyethylene-vinyl acetate (EVA) copolymer, utilizing free radical polymerization in stirred autoclave and tubular reactors. The chapter integrates conceptual development, modeling methodologies, illustrative examples, and practical workshops, offering a comprehensive learning experience. Key topics include the kinetics of free radical polymerization and copolymerization, the selection of appropriate thermodynamic methods, and the estimation of essential property parameters for simulating polyolefin processes. A novel contribution is the methodology for estimating kinetic parameters based on plant data, enabling the development of accurate simulation and optimization models for commercial polyolefin processes. Hands-on workshops are incorporated throughout the chapter to simulate both autoclave and tubular reactor processes, emphasizing practical applications in high-pressure LDPE and EVA copolymerization processes. This chapter serves as a critical resource for professionals and researchers seeking to optimize polyolefin production through advanced modeling and simulation techniques. The integration of theoretical and practical elements sets the foundation for enhanced process design and optimization. This is a preprint version of a chapter from our book-Integrated Process Modeling, Advanced Control and Data Analytics for Optimizing Polyolefin Manufacturing [39,43]. Please cite the original work if referenced 4.1 Polymers by Free Radical Polymerization We cover conceptual development, modeling methodology, illustrative examples, and hands-on workshops. Section 4.1 introduces polymers by free radical polymerization. Section 4.2 covers the kinetics of free radical polymerization and copolymerization. Section 4.3 explains the selection of appropriate thermodynamic methods and estimation of essential property parameters for simulating polyolefin processes produced by free radical polymerization. Section 4.4 presents a hands-on workshop for simulating an autoclave high-pressure (HP) LDPE process. We present an effective methodology for estimating the kinetic parameters based on plant data in the development of simulation and optimization models for commercial polyolefin processes involving free radical polymerization. Section 4.5 is another hands-on workshop for simulating tubular reactors for a high-pressure LDPE process. Section 4.6 presents a hands-on workshop for simulating an autoclave EVA copolymerization process. Section 4.7 is the bibliography.