Macromolecular Reaction Engineering

Cover image for Vol. 10 Issue 3

Early View (Online Version of Record published before inclusion in an issue)

Editor-in-Chief: Kirsten Severing, Editor: Stefan Spiegel

Online ISSN: 1862-8338

Associated Title(s): Macromolecular Chemistry and Physics, Macromolecular Materials and Engineering, Macromolecular Rapid Communications, Macromolecular Theory and Simulations


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  1. Full Papers

    1. Design of Tailor-Made Water-Soluble Copolymers for Enhanced Oil Recovery Polymer Flooding Applications

      Marzieh Riahinezhad, Laura Romero-Zerón, Neil McManus and Alexander Penlidis

      Version of Record online: 26 JUL 2016 | DOI: 10.1002/mren.201600020

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      Acrylamide/acrylic acid copolymers are extensively used in polymer flooding applications. However, the procedure to design and make this water-soluble copolymer with required desirable properties is not clear. The target here is to apply the knowledge of copolymer structure/property relationships in order to design AAm/AAc copolymers with tailor-made properties appropriate for polymer flooding applications.

  2. Essays

  3. Full Papers

    1. Multiscale Modeling of Mixing Behavior in a 3D Atom Transfer Radical Copolymerization Stirred-Tank Reactor

      Le Xie, Li-Tao Zhu, Zheng-Hong Luo and Chong-Wen Jiang

      Version of Record online: 11 JUL 2016 | DOI: 10.1002/mren.201600022

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      A computational fluid dynamics model combining the moment method used in the polymerization engineering field is implemented and validated using open data. Multiscale properties are characterized in terms of macroscopic mixing fields and the poly­mer microscopic structure. The simulated results highlight the function of stirring and provide useful guidelines for the scale-up of stirred-tank polym­erization reactors.

    2. Bulk Free Radical Polymerization of Methyl Methacrylate and Vinyl Acetate: A Comparative Study

      David Victoria-Valenzuela, Jorge Herrera-Ordonez, Gabriel Luna-Barcenas, George D. Verros and Dimitris S. Achilias

      Version of Record online: 11 JUL 2016 | DOI: 10.1002/mren.201600008

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      The kinetic behavior of the bulk methyl methacrylate and vinyl acetate polymerization is studied with the aid of a novel methodology for estimating kinetic rate coefficients and calorimetric measurements of the rate of polymerization. Similarities and differences between both systems as those shown in the figure are discussed. The results highlight the importance of the segmental motion of long radical chain-ends.

    3. Effect of Acid Treatment of Montmorillonite on “Support-Activator” Performance to Support Metallocene for Propylene Polymerization Catalyst

      Takao Tayano, Hideshi Uchino, Takehiro Sagae, Katsuyuki Yokomizo, Koji Nakayama, Shigeki Ohta, Hiroshi Nakano and Masahide Murata

      Version of Record online: 5 JUL 2016 | DOI: 10.1002/mren.201600017

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      Acid-treated montmorillonite is commonly used as a “support-activator” (S-A) for metallocene-catalyzed olefin polymerization. The activation mechanism for the catalysis process is investigated. Highly active catalysts are achieved when the S-A possesses strong acid sites (pKa < −8.2), which are located in small pores at the edge of the clay mineral as opposed to the interlayer.

    4. Mathematical Modeling of the Internal Surface Area of Copolymer Particles Based on Elementary Gel Structures

      Leandro G. Aguiar

      Version of Record online: 30 JUN 2016 | DOI: 10.1002/mren.201600023

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      A mathematical modeling concerning the dynamics of surface area formation during a copolymerization is presented. The internal surface area of the copolymer particles is predicted through numerical fractionation and the concept of elementary gel structure.

    5. Transfer of Emulsion Polymerization of Styrene and n-Butyl Acrylate from Semi-Batch to a Continuous Tubular Reactor

      Kristina Rossow, Peter Bröge, Fabian Gabriel Lüth, Preet Joy, Adel Mhamdi, Alexander Mitsos, Hans-Ulrich Moritz and Werner Pauer

      Version of Record online: 29 JUN 2016 | DOI: 10.1002/mren.201500077

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      The transfer of a semi-batch emulsion copolymerization (styrene/n-butyl acrylate) to a single feed continuous tubular reactor is investigated. It is shown that a direct transfer is advantageous compared to an intermediate step via a batch reactor in which the specific heat transfer is much more limited than in a tubular reactor.

    6. Miniemulsion Polymerization Monitoring Using Off-Line Raman Spectroscopy and In-Line NIR Spectroscopy

      Paula Maria Nogueira Ambrogi, Maria Magdalena Espinola Colmán and Reinaldo Giudici

      Version of Record online: 29 JUN 2016 | DOI: 10.1002/mren.201600013

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      Miniemulsion polymerization of styrene is studied using on-line monitoring with near-infrared spectroscopy and at-line Raman spectroscopy. Monomer conversion and average particle size can be monitored in real time. Detection of the changes in variables is important to understand unexpected behavior of the system.

    7. Transfer of Semibatch Processes to Continuous Processes with Side Injections—Opportunities and Limitations

      Thilo Goerke, Daniel Kohlmann and Sebastian Engell

      Version of Record online: 20 JUN 2016 | DOI: 10.1002/mren.201500070

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      The transferability from semibatch to continuous mode of operation is investigated by the detection of the ranges of feasible processes in both modes of operation. A comparison of the resulting ranges in terms of certain product qualities enables the prediction of transferable reaction systems.

    8. A Study of the Gas Phase Polymerization of Propylene: The Impact of Catalyst Treatment, Injection Conditions and the Presence of Alkanes on Polymerization and Polymer Properties

      Ana R. Martins, Aarón J. Cancelas and Timothy F. L. McKenna

      Version of Record online: 17 JUN 2016 | DOI: 10.1002/mren.201600011

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      An experimental study of the gas phase polymerization of propylene reveals that the reaction rate and final particle morphology are sensitive to the injection conditions of the catalyst. Injecting the catalyst in an oil suspension provides more favorable catalyst behavior.

    9. Understanding the Formation of Linear Olefin Block Copolymers with Dynamic Monte Carlo Simulation

      Tiprawee Tongtummachat, Siripon Anantawaraskul and João B. P. Soares

      Version of Record online: 10 JUN 2016 | DOI: 10.1002/mren.201600002

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      Dynamic Monte Carlo model is developed to describe the kinetics of chain-shuttling copolymerization and the microstructural evolution of olefin block copolymers (OBCs) with different numbers of blocks per chain. Effects of chain-shuttling rate constants and concentration of chain-shuttling agent are investigated. The results provide guidelines for producing OBCs with controlled microstructures.

    10. UV-Free Microfluidic Particle Fabrication at Low Temperature Using ARGET-ATRP as the Initiator System

      Lukas B. Braun, Tristan Hessberger, Christophe A. Serra and Rudolf Zentel

      Version of Record online: 9 JUN 2016 | DOI: 10.1002/mren.201600015

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      Activator regeneration by electron transfer - atom transfer radical polymerization is used as a new initiator system for the fabrication of monodisperse poly(methyl methacrylate) particles in a microfluidic device. The size of the particles is well adjustable. Applying this way of polymerization, particles can be produced without UV-light or high temperatures that make an incorporation of sensitive substances possible.

    11. Optimization of the Preparation Temperature for the Novel (SiO2/MgO/MgCl2)⋅TiClx Ziegler–Natta Polyethylene Catalyst

      Fan Huang, Jingwen Wang, Ruihua Cheng, Xuelian He, Zhen Liu, Ning Zhao and Boping Liu

      Version of Record online: 3 JUN 2016 | DOI: 10.1002/mren.201600005

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      The series of (SiO2/MgO/MgCl2)TiClx Ziegler-Natta polyethylene catalysts have been synthesized with magnesium acetate as Mg-source at different TiCl4 treating temperatures. The catalyst shows the highest homopolymerization activity when preparation temperature is 120 °C with only 1.25 of optimal Al/Ti molar ratio, which is much lower than industrial value, resulting in much lower cost for catalyst preparation and polyethylene production.

    12. Estimation of Apparent Kinetic Constants of Individual Site Types for the Polymerization of Ethylene and α-olefins with Ziegler–Natta Catalysts

      Keran Chen, Saeid Mehdiabadi, Boping Liu and João B. P. Soares

      Version of Record online: 2 JUN 2016 | DOI: 10.1002/mren.201600003

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      In this paper, it is shown that how to determine the apparent olefin polymerization kinetics constants of multisite catalysts, such as heterogeneous Ziegler-Natta catalysts. This novel method fits simultaneously the molecular weight distribution, instantaneous ethylene uptake profile and cumulative polymer yield in a semi-batch reactor to determine the activation, deactivation, and pseudopropagation constants per site type in these catalysts.

    13. Modular, Flexible, and Continuous Plant for Radical Polymerization in Aqueous Solution

      Daniel Kohlmann, Marie-Claire Chevrel, Sandrine Hoppe, Dimitrios Meimaroglou, David Chapron, Patrice Bourson, Christian Schwede, Wolfgang Loth, Achim Stammer, James Wilson, Patrick Ferlin, Laurent Falk, Sebastian Engell and Alain Durand

      Version of Record online: 28 APR 2016 | DOI: 10.1002/mren.201500079

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      A continuous and flexible pilot-scale plant is designed for the production of acrylic acid homo- and copolymer in aqueous solution. On the basis of previous experimental lab-scale studies the plant is built and equipped with Raman probes for monitoring the consumption of monomers. Demonstration experiments are carried out and results are satisfactorily depicted by theoretical calculations.

  4. Reviews

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      State-of-the-Art and Progress in Method of Moments for the Model-Based Reversible-Deactivation Radical Polymerization

      Yin-Ning Zhou and Zheng-Hong Luo

      Version of Record online: 13 APR 2016 | DOI: 10.1002/mren.201500080

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      There are numerous literatures on the kinetic and reactor models for reversible-deactivation radical polymerization (RDRP) processes, which show the accessibility on polymerization kinetics insight, process optimization, and controlling over chain microstructure. This work highlights the facility of the method of moments in the modeling field and presents a summary of the present state-of-the-art and future perspectives focusing on the model-based RDRP processes based on the method of moments. Summary on the current status and challenges is discussed briefly.

  5. Full Papers

    1. Dispersion Photopolymerization of Acrylated Oligomers Using a Flexible Continuous Reactor

      Patrice Roose, Michel Berlier, Roberto Lazzaroni and Philippe Leclère

      Version of Record online: 6 APR 2016 | DOI: 10.1002/mren.201500078

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      A flexible continuous photoreactor is introduced for the preparation of crosslinked colloids using dispersion photopolymerization. The performance of the reactor is established as functional conversion per particle following a detailed light scattering and infrared analysis. Crosslinked particles are visualized by peak force tapping atomic force microscopy.

    2. Operation of Flexible Multiproduct Modular Continuous Polymerization Plants

      Christian Schoppmeyer, Henry Vermue, Subanatarajan Subbiah, Daniel Kohlmann, Patrick Ferlin and Sebastian Engell

      Version of Record online: 6 APR 2016 | DOI: 10.1002/mren.201500044

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      The operation of modular flexible continuous polymerization plants is investigated for an industrial defined benchmark problem with two production lines with modules that can be physically moved. The campaign planning problem is solved, minimizing the cost of cleaning and waste production.

    3. Modeling the Radical Batch Homopolymerization of Acrylamide in Aqueous Solution

      Calista Preusser, Anna Chovancová, Igor Lacík and Robin A. Hutchinson

      Version of Record online: 15 MAR 2016 | DOI: 10.1002/mren.201500076

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      The complexities of aqueous-phase polymerization of acrylamide are captured in a model that considers the formation of midchain radicals and the influence of monomer concentration on propagation kinetics. The model is verified against batch polymerization monomer conversion profiles and molar mass distributions collected over a range of experimental conditions, as well as previous published data.

    4. CFD Analysis of Gas–Particle Heat Transfer in Gas-Phase Olefin Polymerizations

      Icaro Pianca Guidolini, Carlos Eduardo Fontes, Paulo Laranjeira da Cunha Lage and José Carlos Pinto

      Version of Record online: 8 MAR 2016 | DOI: 10.1002/mren201500062

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      Heat transfer between the particle and the medium in the gas-phase polymerization is analyzed using computational fluid dynamics tools. It is shown that the particle rotational speed is a very important variable, as well as the growth dynamics of the particles and should not be ignored in modeling the heat transfer particles.

    5. On the Modeling of Acrylic Acid Copolymerization in an Aqueous Solution: A Modular, Integrated Approach

      Dimitrios Meimaroglou, Marie-Claire Chevrel, Sandrine Hoppe, Alain Durand, Laurent Falk, James Wilson and Patrick Ferlin

      Version of Record online: 7 MAR 2016 | DOI: 10.1002/mren.201500036

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      A mechanistic mathematical model of the free-radical copolymerization of acrylic acid in an aqueous solution, taking place in a pilot-scale tubular reactor equipped with static mixers, is presented. A powerful and flexible coupled deterministic/stochastic simulator, combining the advantages of speed, efficiency, and increased predictive capabilities, is developed on the basis of the proposed mathematical model. These advantages are proven through a series of comparisons with experimental measurements, under a wide range of process conditions, as well as through a thorough analysis of the compositional characteristics of the produced copolymer in terms of different bivariate distributed properties.

    6. Modeling of the Methyl Methacrylate Atom Transfer Radical Suspension Polymerization Process: Polymerization and Particle Kinetics

      Le Xie and Zheng-Hong Luo

      Version of Record online: 7 MAR 2016 | DOI: 10.1002/mren201500074

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      The first time, the morphological and molecular properties of particles, as well as their dynamics in the methyl methacrylate atom transfer radical batch suspension polymerization can be simultaneously simulated by solving the model that consists of polymerization kinetic equations, moment equations, a phase equilibrium equation and a particle population balance model in this work.

    7. Continuous Pilot-Scale Tubular Reactor for Acrylic Acid Polymerization in Solution Designed Using Lab-Scale Rheo-Raman data

      Marie-Claire Chevrel, Sandrine Hoppe, Dimitrios Meimaroglou, Laurent Falk and Alain Durand

      Version of Record online: 23 FEB 2016 | DOI: 10.1002/mren201500058

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      A continuous pilot-scale tubular reactor equipped with CSE-X static mixers from Fluitec is designed for polymerization of acrylic acid in aqueous solution. Experimental results are satisfactorily described by the model of perfect plug-flow reactor. This work provides the first demonstration of applicability of CSE-X static mixer elements in a continuous process producing high molar mass water-soluble polymer.

    8. Effect of Prepolymerization on the Kinetics of Ethylene Polymerization and Ethylene/1-Hexene Copolymerization with a Ziegler–Natta Catalyst in Slurry Reactors

      Keran Chen, Boping Liu and João B. P. Soares

      Version of Record online: 29 JAN 2016 | DOI: 10.1002/mren.201500066

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      The effect of prepolymerization conditions is quantified on ethylene homopolymerization and ethylene/1-hexene copolymerization using a lumped-parameter polymerization kinetics model. The apparent kinetic constants correlates not only to the prepolymerization conditions, but also to the morphology of the prepolymer particles: prepolymer particles with better fragmentation and less polymer fibrils activate faster and polymerize at higher rates in the main polymerization reactor.

    9. Optimizing Control and State Estimation of a Continuous Polymerization Process in a Tubular Reactor with Multiple Side-Streams

      Reza Hashemi, Daniel Kohlmann and Sebastian Engell

      Version of Record online: 29 JAN 2016 | DOI: 10.1002/mren.201500034

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      Production of polymers in modular continuous reactors was one of the goals of the European F3-factory project. The control of such plants is not an easy task as the process is described by nonlinear complex partial differential equations and the available measurements are few. In this work, we propose an optimizing control scheme to control such plants and maximize the plant throughput, while the product quality constraints are met.

    10. Application of Raman Spectroscopy to Characterization of Residence Time Distribution and Online Monitoring of a Pilot-Scale Tubular Reactor for Acrylic Acid Solution Polymerization

      Marie-Claire Chevrel, Sandrine Hoppe, Dimitrios Meimaroglou, David Chapron, Patrice Bourson, James Wilson, Patrick Ferlin, Laurent Falk and Alain Durand

      Version of Record online: 4 JAN 2016 | DOI: 10.1002/mren.201500055

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      A pilot-scale tubular reactor containing static mixers is equipped with Raman probes for online monitoring of radical copolymerization of acrylic acid in aqueous solution. Using sodium nitrate as a tracer, residence time distribution is established in reactive and nonreactive media with viscosities up to 1 Pa s. Calculations assuming a perfect plug flow are in good agreement with experimental results.

    11. Challenges and Opportunities in Continuous Production of Emulsion Polymers: a Review

      José M. Asua

      Version of Record online: 14 JUL 2015 | DOI: 10.1002/mren.201500032

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      Profit margin reduction and global competition are pushing emulsion polymer producers to consider process intensification that mainly relies on the replacement of semicontinuous reactors by continuous ones. In this work, the challenges in the continuous production of emulsion polymers are discussed and ways in which the challenges can be transformed in opportunities are reviewed.


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