Modeling and Simulation of Polymerization Processes

A special issue of Processes (ISSN 2227-9717). This special issue belongs to the section "Materials Processes".

Deadline for manuscript submissions: closed (31 March 2021) | Viewed by 27703

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Facultad de Química, Departamento de Ingeniería Química, Universidad Nacional Autónoma de México, 04510 Ciudad de México, Mexico
Interests: polymer science and engineering; polymer reaction engineering; modeling of polymerization processes; synthesis of materials for novel applications; development of biorefining processes

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Petrochemical Research and Technology Company (NPC-rt), National Petrochemical Company, P.O. Box 14358-84711, Tehran, Iran
Interests: macromolecular reaction engineering; molecular simulation; artificial intelligence; data mining; machine learning; process optimization; membrane science and technology; electrospinning and nanofiber technology

Special Issue Information

Dear Colleagues,

Polymer reaction engineering (PRE) is the branch of engineering that deals with the technology of large-scale polymer production and the manufacture of polymer products through polymerization processes. PRE is a broad and multidisciplinary area, relatively young and developing fast, which combines polymer science, chemistry, and technology with the principles of process engineering. The practical history of PRE started and evolved during the first half of the twentieth century. The 1930s were rich with theoretical findings in polymer science and engineering and with the commercial production of several new polymers. These investigations would transform our understanding of polymer manufacture and culminate in the development of several continuous polymerization processes and the establishment of PRE as a new area of research in the 1940s. The period from 1950 to 1990 saw the continued growth and evolution of process technologies, largely stimulated by the combination of PRE principles with the fundamental understanding of polymerization kinetics developed in the earlier years. These principles include the development of mathematical models for polymerization processes, and their solution using mathematical packages or specialized chemical engineering or polymerization software. The modeling and simulation of polymerization processes (MSPP) has been fundamental in the development of polymerization technologies since the early stages of PRE to date.

The importance of MSPP has already been recognized by MDPI Processes. A few related issues have been published in the last few years: “Computational Methods for Polymers”, Masoud Soroush, August 2019; “Modeling, Simulation and Control of Chemical Processes”, José Carlos Pinto, 2019; “Renewable Polymers: Processing and Chemical Modifications”, Marc A. Dubé and Tizazu Mekonnen, March 2019; “Process Modelling and Simulation: Cesar de Prada, Costas Pantelides and Jose Luis Pitarch, February 2019; and “Polymer Modeling, Control and Monitoring”, Masoud Soroush, February 2016.

The previous issues of Processes on related PRE topics have focused on recent specialized topics. This Special Issue on “Modeling and Simulation of Polymerization Processes” aims to address both new findings on basic topics as well as modeling of emerging aspects of product design and polymerization processes. Topics include but are not limited to:

  • Development of new aspects/models and/or improving the existing models on established polymerization processes;
  • Development of deterministic and stochastic mathematical methods for modeling of polymerization processes;
  • Modeling and simulation of reversible deactivation radical polymerization (RDRP) processes;
  • Modeling and simulation of dispersed-phase polymerization processes;
  • Modeling and simulation of step-growth polymerization processes;
  • Modeling and simulation of polymerization processes using bio-based monomers;
  • Modeling and simulation of nonlinear polymerization processes;
  • Modeling and simulation of catalytic and enzymatic polymerization processes;
  • Modeling of depolymerization and synthesis of hybrid materials;
  • Modeling and simulation of olefin polymerization processes
  • Modeling of novel polymerization processes;
  • Modeling and simulation of ultrasound-induced and radiation (light)-induced polymerization processes;
  • Molecular simulations in polymerization processes;
  • Data mining, artificial intelligence and machine learning in polymerization processes;
  • Classical and heuristic optimization algorithms in polymerization processes;
  • Modeling the recipe–microstructure–property interrelationships in polymerization processes.

Prof. Dr. Eduardo Vivaldo-Lima
Dr. Yousef Mohammadi
Guest editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Processes is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • reversible deactivation radical polymerization (RDRP)
  • dispersed-phase polymerization processes
  • catalytic and enzymatic polymerization processes
  • synthesis of hybrid materials
  • nonlinear polymerization processes
  • recipe–microstructure–property interrelationship
  • artificial intelligence, machine learning
  • data mining
  • process optimization
  • kinetic Monte Carlo
  • molecular simulation
  • polyolefin
  • light-induced polymerization

Published Papers (10 papers)

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Editorial

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4 pages, 190 KiB  
Editorial
Special Issue: Modeling and Simulation of Polymerization Processes
by Eduardo Vivaldo-Lima, Yousef Mohammadi and Alexander Penlidis
Processes 2021, 9(5), 821; https://doi.org/10.3390/pr9050821 - 8 May 2021
Cited by 4 | Viewed by 1687
Abstract
This Special Issue (SI) of Processes on Modeling and Simulation of Polymerization Processes (MSPP), and the associated Special Issue reprint, contain papers that deal with this very important area of scientific investigation in polymer science and engineering, both in academic and particularly industrial [...] Read more.
This Special Issue (SI) of Processes on Modeling and Simulation of Polymerization Processes (MSPP), and the associated Special Issue reprint, contain papers that deal with this very important area of scientific investigation in polymer science and engineering, both in academic and particularly industrial environments [...] Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymerization Processes)

Research

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9 pages, 5577 KiB  
Article
Molecular Simulation of Improved Mechanical Properties and Thermal Stability of Insulation Paper Cellulose by Modification with Silane-Coupling-Agent-Grafted Nano-SiO2
by Zhengxiang Zhang, Haibin Zhou, Wentao Li and Chao Tang
Processes 2021, 9(5), 766; https://doi.org/10.3390/pr9050766 - 27 Apr 2021
Cited by 6 | Viewed by 2293
Abstract
Cellulose is an important part of transformer insulation paper. Thermal aging of cellulose occurs in long-term operation of transformers, which deteriorates the mechanical properties and thermal stability of cellulose, resulting in a decrease in the transformer life. Therefore, improvement of the mechanical properties [...] Read more.
Cellulose is an important part of transformer insulation paper. Thermal aging of cellulose occurs in long-term operation of transformers, which deteriorates the mechanical properties and thermal stability of cellulose, resulting in a decrease in the transformer life. Therefore, improvement of the mechanical properties and thermal stability of cellulose has become a research hotspot. In this study, the effects of different silane coupling agents on the mechanical properties and thermal stability of modified cellulose were studied. The simulation results showed that the mechanical parameters of cellulose are only slightly improved by KH560 (γ-glycidyl ether oxypropyl trimethoxysilane) and KH570 (γ-methylacrylloxy propyl trimethoxy silane) modified nano-SiO2, while the mechanical parameters of cellulose are greatly improved by KH550 (γ-aminopropyl triethoxy silane) and KH792 (N-(2-aminoethyl)-3-amino propyl trimethoxy silane) modified nano-SiO2. The glass-transition temperature of the composite model is 24 K higher than that of the unmodified model. The mechanism of the change of the glass-transition temperature was analyzed from the point of view of free-volume theory. The main reason for the change of the glass-transition temperature is that the free volume abruptly changes, which increases the space for movement of the cellulose chain and accelerates the whole movement of the molecular chain. Therefore, modifying cellulose with KH792-modified nano-SiO2 can significantly enhance the thermal stability of cellulose. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymerization Processes)
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22 pages, 3159 KiB  
Article
Ethylene Polymerization via Zirconocene Catalysts and Organoboron Activators: An Experimental and Kinetic Modeling Study
by Luis Valencia, Francisco Enríquez-Medrano, Ricardo López-González, Priscila Quiñonez-Ángulo, Enrique Saldívar-Guerra, José Díaz-Elizondo, Iván Zapata-González and Ramón Díaz de León
Processes 2021, 9(1), 162; https://doi.org/10.3390/pr9010162 - 15 Jan 2021
Cited by 3 | Viewed by 4075
Abstract
Forty years after the discovery of metallocene catalysts, there are still several aspects that remain unresolved, especially when the “conventional” alkylaluminum activators are not used. Herein, we systematically investigated the synthesis of polyethylene (PE) via three different zirconocene catalysts, with different alkyl substituents, [...] Read more.
Forty years after the discovery of metallocene catalysts, there are still several aspects that remain unresolved, especially when the “conventional” alkylaluminum activators are not used. Herein, we systematically investigated the synthesis of polyethylene (PE) via three different zirconocene catalysts, with different alkyl substituents, activated via different organoboron compounds. The polymerization behavior, as well as the properties of the materials, were evaluated. The results demonstrate that the highest catalytic activity is shown by bis(cyclopentadienyl)dimethylzirconium activated by trityl tetra(pentafluorophenyl)borate. Additionally, it was found that toluene is the optimum solvent for these systems and at these reaction conditions. Moreover, to validate our experimental results, a comprehensive mathematical model was developed on the basis of thermodynamic and kinetic principles. The concentration of ethylene transferred to the solvent phase (toluene) in a liquid–vapor equilibrium (LVE) system was estimated based on Duhem’s theorem. Arrhenius expressions for the kinetic rate constants of a proposed kinetic mechanism were estimated by a kinetic model, in which the rate of polymerization was fitted by a least-square optimization procedure and the molecular weight averages by the method of moments. The simulations of the coordination polymerization suggest the presence of two types of active sites, principally at low temperatures, and the reactivation of the deactivated sites via a boron-based activator. However, the effect of the temperature on the reactivation step was not clear; a deeper understanding via designed experiments is required. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymerization Processes)
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33 pages, 28015 KiB  
Article
Mathematical Modeling of the Production of Elastomers by Emulsion Polymerization in Trains of Continuous Reactors
by Enrique Saldívar-Guerra, Ramiro Infante-Martínez and José María Islas-Manzur
Processes 2020, 8(11), 1508; https://doi.org/10.3390/pr8111508 - 20 Nov 2020
Cited by 6 | Viewed by 3137
Abstract
A mechanistic model is proposed to describe the emulsion polymerization processes for the production of styrene–butadiene rubber (SBR) and acrylonitrile–butadiene rubber (NBR) elastomers in trains of continuous stirred tank reactors (CSTRs). A single model was used to describe both processes by choosing the [...] Read more.
A mechanistic model is proposed to describe the emulsion polymerization processes for the production of styrene–butadiene rubber (SBR) and acrylonitrile–butadiene rubber (NBR) elastomers in trains of continuous stirred tank reactors (CSTRs). A single model was used to describe both processes by choosing the proper physicochemical parameters of each system. Most of these parameters were taken from literature sources or estimated a priori; only one parameter (the entry rate coefficient) was used as an adjustable value to reproduce the kinetics (mainly conversion), and another parameter (the transfer to polymer rate coefficient) was used to fit the molecular weight distribution (MWD) experimental values from plant data. A 0-1-2 model for the number of particles and for the moments of the MWD was used to represent with more fidelity the compartmentalization effects. The model was based on approaches used in previous emulsion polymerization models published in the literature, with the premise of reaching a compromise between the level of detail, complexity, and practical value. The model outputs along the reactor train included conversion, remaining monomer composition, instantaneous and accumulated copolymer composition, the number of latex particles and particle diameter, polymerization rate, the average number of radicals per particle, average molecular weights, and the number of branches per chain. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymerization Processes)
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18 pages, 2830 KiB  
Article
Kinetics and Modeling of Aqueous Phase Radical Homopolymerization of 3-(Methacryloylaminopropyl)trimethylammonium Chloride and its Copolymerization with Acrylic Acid
by Ikenna H. Ezenwajiaku, Emmanuel Samuel and Robin A. Hutchinson
Processes 2020, 8(11), 1352; https://doi.org/10.3390/pr8111352 - 26 Oct 2020
Cited by 6 | Viewed by 2481
Abstract
The radical homopolymerization kinetics of 3-(methacryloylaminopropyl) trimethylammonium chloride (MAPTAC) and its batch copolymerization with nonionized acrylic acid (AA) in aqueous solution are investigated and modeled. The drift in monomer composition is measured during copolymerization by in situ NMR over a range of initial [...] Read more.
The radical homopolymerization kinetics of 3-(methacryloylaminopropyl) trimethylammonium chloride (MAPTAC) and its batch copolymerization with nonionized acrylic acid (AA) in aqueous solution are investigated and modeled. The drift in monomer composition is measured during copolymerization by in situ NMR over a range of initial AA molar fractions and monomer weight fractions up to 0.35 at 50 °C. The copolymer becomes enriched in MAPTAC for monomer mixtures containing up to 60 mol% MAPTAC, but is enriched in AA for MAPTAC-rich mixtures; this azeotropic behavior is dependent on initial monomer content, as electrostatic interactions from the cationic charges influence the system reactivity ratios. Models for MAPTAC homopolymerization and AA-MAPTAC copolymerization are developed to represent the rates of monomer conversion and comonomer composition drifts over the complete range of experimental conditions. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymerization Processes)
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19 pages, 2760 KiB  
Article
Initiator Feeding Policies in Semi-Batch Free Radical Polymerization: A Monte Carlo Study
by Ali Seyedi, Mohammad Najafi, Gregory T. Russell, Yousef Mohammadi, Eduardo Vivaldo-Lima and Alexander Penlidis
Processes 2020, 8(10), 1291; https://doi.org/10.3390/pr8101291 - 15 Oct 2020
Cited by 9 | Viewed by 3212
Abstract
A Monte Carlo simulation algorithm is developed to visualize the impact of various initiator feeding policies on the kinetics of free radical polymerization. Three cases are studied: (1) general free radical polymerization using typical rate constants; (2) diffusion-controlled styrene free radical polymerization in [...] Read more.
A Monte Carlo simulation algorithm is developed to visualize the impact of various initiator feeding policies on the kinetics of free radical polymerization. Three cases are studied: (1) general free radical polymerization using typical rate constants; (2) diffusion-controlled styrene free radical polymerization in a relatively small amount of solvent; and (3) methyl methacrylate free radical polymerization in solution. The number- and weight-average chain lengths, molecular weight distribution (MWD), and polymerization time were computed for each initiator feeding policy. The results show that a higher number of initiator shots throughout polymerization at a fixed amount of initiator significantly increases average molecular weight and broadens MWD. Similar results are also observed when most of the initiator is added at higher conversions. It is demonstrated that one can double the molecular weight of polystyrene and increase its dispersity by 50% through a four-shot instead of a single shot feeding policy. Similar behavior occurs in the case of methyl methacrylate, while the total time drops by about 5%. In addition, policies injecting initiator at high monomer conversions result in a higher unreacted initiator content in the final product. Lastly, simulation conversion-time profiles are in agreement with benchmark literature information for methyl methacrylate, which essentially validates the highly effective and flexible Monte Carlo algorithm developed in this work. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymerization Processes)
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19 pages, 1010 KiB  
Article
Solution Polymerization of Acrylic Acid Initiated by Redox Couple Na-PS/Na-MBS: Kinetic Model and Transition to Continuous Process
by Federico Florit, Paola Rodrigues Bassam, Alberto Cesana and Giuseppe Storti
Processes 2020, 8(7), 850; https://doi.org/10.3390/pr8070850 - 16 Jul 2020
Cited by 8 | Viewed by 4504
Abstract
This work aims at modeling in detail the polymerization of non-ionized acrylic acid in aqueous solution. The population balances required to evaluate the main average properties of molecular weight were solved by the method of moments. The polymerization process considered is initiated by [...] Read more.
This work aims at modeling in detail the polymerization of non-ionized acrylic acid in aqueous solution. The population balances required to evaluate the main average properties of molecular weight were solved by the method of moments. The polymerization process considered is initiated by a persulfate/metabisulfate redox couple and, in particular, the kinetic scheme considers the possible formation of mid-chain radicals and transfer reactions. The proposed model is validated using experimental data collected in a laboratory-scale discontinuous reactor. The developed kinetic model is then used to intensify the discontinuous process by shifting it to a continuous one based on a tubular reactor with intermediate feeds. One of the experimental runs is selected to show how the proposed model can be used to assess the transition from batch to continuous process and allow faster scale-up to industrial scale using a literature approach. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymerization Processes)
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26 pages, 8074 KiB  
Article
Thermal Pyrolysis of Polystyrene Aided by a Nitroxide End-Functionality. Experiments and Modeling
by Almendra Ordaz-Quintero, Antonio Monroy-Alonso and Enrique Saldívar-Guerra
Processes 2020, 8(4), 432; https://doi.org/10.3390/pr8040432 - 5 Apr 2020
Cited by 12 | Viewed by 3737
Abstract
The thermal pyrolysis of polystyrene (PS) is gaining importance as the social pressure for achieving a circular economy is growing; moreover, the recovery of styrene monomer in such a process is especially relevant. In this study, a simple thermal pyrolysis process in the [...] Read more.
The thermal pyrolysis of polystyrene (PS) is gaining importance as the social pressure for achieving a circular economy is growing; moreover, the recovery of styrene monomer in such a process is especially relevant. In this study, a simple thermal pyrolysis process in the temperature range of 390–450 °C is developed. A working hypothesis is that by using a nitroxide-end functionalized PS (PS-T or dormant polymer), the initiation process for the production of monomer (unzipping) during the PS pyrolysis could be enhanced due to the tendency of the PS-T to activate at the nitroxide end. Two types of PS were used in this work, the first one was synthesized by free-radical polymerization (FRP-dead polymer) and the second by nitroxide-mediated polymerization (NMP) using three levels of nitroxide to initiator ratio: 1.3, 1.1, and 0.9. Analysis of the recovered products of the pyrolysis by gas-mass spectroscopy shows that the yield of styrene increases from ∼33% in the case of dead polymer to ∼38.5% for PS-T. A kinetic and mathematical model for the pyrolysis of dead and dormant polymer is proposed and solved by the method of moments. After a parameter sensitivity study and data fitting, the model is capable of explaining the main experimental trends observed. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymerization Processes)
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14 pages, 4606 KiB  
Article
New Aspects on the Modeling of Dithiolactone-Mediated Radical Polymerization of Vinyl Monomers
by Anete Joceline Benitez-Carreón, Jesús Guillermo Soriano-Moro, Eduardo Vivaldo-Lima, Ramiro Guerrero-Santos and Alexander Penlidis
Processes 2019, 7(11), 842; https://doi.org/10.3390/pr7110842 - 10 Nov 2019
Cited by 1 | Viewed by 2683
Abstract
A kinetic model for the dithiolactone-mediated radical polymerization of vinyl monomers based on the persistent radical effect and reversible addition (negligible fragmentation) was used to calculate the polymerization rate and describe molar mass development in the polymerization of methyl methacrylate at 60 °C, [...] Read more.
A kinetic model for the dithiolactone-mediated radical polymerization of vinyl monomers based on the persistent radical effect and reversible addition (negligible fragmentation) was used to calculate the polymerization rate and describe molar mass development in the polymerization of methyl methacrylate at 60 °C, using 2,2-azobisisobutyronitrile (AIBN) as an initiator, as well as dihydro-5-phenyl-2(3H)-thiophenethione (DTL1) and dihydro-2(3H)-thiophenethione (DTL2) as controllers. The model was implemented in the PREDICI commercial software. A good agreement between experimental data and model predictions was obtained. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymerization Processes)
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Review

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94 pages, 48213 KiB  
Review
A Review on the Synthesis, Characterization, and Modeling of Polymer Grafting
by Miguel Ángel Vega-Hernández, Gema Susana Cano-Díaz, Eduardo Vivaldo-Lima, Alberto Rosas-Aburto, Martín G. Hernández-Luna, Alfredo Martinez, Joaquín Palacios-Alquisira, Yousef Mohammadi and Alexander Penlidis
Processes 2021, 9(2), 375; https://doi.org/10.3390/pr9020375 - 18 Feb 2021
Cited by 35 | Viewed by 8441
Abstract
A critical review on the synthesis, characterization, and modeling of polymer grafting is presented. Although the motivation stemmed from grafting synthetic polymers onto lignocellulosic biopolymers, a comprehensive overview is also provided on the chemical grafting, characterization, and processing of grafted materials of different [...] Read more.
A critical review on the synthesis, characterization, and modeling of polymer grafting is presented. Although the motivation stemmed from grafting synthetic polymers onto lignocellulosic biopolymers, a comprehensive overview is also provided on the chemical grafting, characterization, and processing of grafted materials of different types, including synthetic backbones. Although polymer grafting has been studied for many decades—and so has the modeling of polymer branching and crosslinking for that matter, thereby reaching a good level of understanding in order to describe existing branching/crosslinking systems—polymer grafting has remained behind in modeling efforts. Areas of opportunity for further study are suggested within this review. Full article
(This article belongs to the Special Issue Modeling and Simulation of Polymerization Processes)
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