Macromolecular Reaction Engineering

Cover image for Vol. 10 Issue 2

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. 1 - 22
  1. Full Papers

    1. 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.

  2. Reviews

    1. A Comprehensive Review on Controlled Synthesis of Long-Chain-Branched Polyolefins: Part 2, Multiple Catalyst Systems and Prepolymer Modification

      Weifeng Liu, Pingwei Liu, Wen-Jun Wang, Bo-Geng Li and Shiping Zhu

      Version of Record online: 26 APR 2016 | DOI: 10.1002/mren.201500054

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      The literatures pertinent to controlled synthesis of long-chain-branched polyolefins through two-step processes with two or more catalysts are summarized and discussed. The two-step processes can be implemented either in single-reactor systems or in two-reactor setups.

    2. 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.

  3. 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. Analysis of Ethylene/1-Olefin Copolymers Made with Ziegler–Natta Catalysts by Deconvolution of Molecular Weight and Average Short Chain Branching Distributions

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

      Version of Record online: 7 MAR 2016 | DOI: 10.1002/mren.201500075

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      A method to deconvolute the gel permeation chromatographer equipped with infraredchromatograms measured at different times in a semibatch polymerization is proposed to estimate average molecular weights (Mn and Mw) and short chain branching frequencies (SCB/1000 C) per site type for olefin copolymers made with multisite Ziegler–Natta catalysts.

    7. 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.

    8. Ultra-High Molecular Weight Alpha-Amino Poly(Methyl Methacrylate) with High Tg through Emulsion Polymerization by Using Transition Metal Cation–Tertiary Amine Pairs as a Mono-Centered Initiator

      Jie Gao, Fengchi Jiang and Guangqun Zhai

      Version of Record online: 1 MAR 2016 | DOI: 10.1002/mren.201500067

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      FeCl3/EDTA and water-soluble tertiary amines form mono-centered redox pairs to initiate conventional radical ab initio emulsion polymerization of MMA, giving rise to PMMA with a 100% alpha-amino terminal functionality, an absolute MW > 106 g mol−1, syndiotactic-rich stereoregularity (rr > 55%), and a high Tg > 120 °C. PMMA chains may be in situ oxidized to mid-chain macro-radicals, and lead to loosely long-chain branched PMM.

  4. Reviews

    1. A Comprehensive Review on Controlled Synthesis of Long-Chain Branched Polyolefins: Part 1, Single Catalyst Systems

      Pingwei Liu, Weifeng Liu, Wen-Jun Wang, Bo-Geng Li and Shiping Zhu

      Version of Record online: 24 FEB 2016 | DOI: 10.1002/mren.201500053

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      Long-chain branching (LCB) represents one of the key chain microstructural parameters and has significant influence on polymer melt strength and shear thinning performance. Polyolefins having controlled LCB structure can be prepared using one-pot in-situ polymerization with single metallocene or late transition metal catalysts. The catalyst systems and the influences of various polymerization parameters on LCB structure are summarized and discussed in this review paper.

  5. Full Papers

    1. 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

      Thumbnail image of graphical abstract

      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.

    2. 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.

    3. 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.

    4. Vanadium Modification Effects on the (SiO2/MgO/MgCl2)•TiClx Ziegler–Natta Polyethylene Catalyst

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

      Version of Record online: 22 JAN 2016 | DOI: 10.1002/mren.201500056

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      Novel vanadium-modified (SiO2/MgO/MgCl2)·TiClx Ziegler–Natta ethylene polymerization catalysts with improved catalytic performance are successfully developed and systematically investigated. Proper addition amount of vanadium modification induce better catalytic performance with 27% higher activity, 48% higher hydrogen response, and 60% higher 1-hexene incorporation ability with better short chain branch distribution.

    5. Flash Latex Production in a Continuous Helical Photoreactor: Releasing the Brake Pedal on Acrylate Chain Radical Polymerization

      Abraham Chemtob, Emeline Lobry, Agnès Rannée, Florent Jasinski, Marta Penconi, Esther Oliveros, André M. Braun and Adrien Criqui

      Version of Record online: 21 JAN 2016 | DOI: 10.1002/mren.201500060

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      A novel continuous radical photopolymerization process enables to convert acrylate monomer emulsion with surprisingly high efficiency. The combination of a photochemical minireactor, the resulting very short polymerization times, low costs of production, and the simplicity of the equipment may be of interest to change the way emulsion polymerization is performed both at research and industrial levels.

    6. Effect of Droplet Size in Acrylamide-Based Microgel Formation by Microfluidics

      Fany Di Lorenzo and Sebastian Seiffert

      Version of Record online: 21 JAN 2016 | DOI: 10.1002/mren.201500061

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      Above-colloidal-scale microgel particles can be prepared with exquisite control by droplet-based microfluidic particle templating followed by droplet gelation. In this process, the success of droplet gelation depends on the concentration of reagents within the droplets, on temperature, and on droplet size, which this work assesses in a systematic fashion for two popular acrylamide-type monomers.

    7. 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.

    8. Estimation of Polymerization Conditions Needed to Make Ethylene/1-olefin Copolymers with Specific Microstructures Using Artificial Neural Networks

      Thanutchoke Charoenpanich, Siripon Anantawaraskul and João B. P. Soares

      Version of Record online: 22 DEC 2015 | DOI: 10.1002/mren.201500048

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      Two artificial neural network models are developed to describe ethylene/1-olefin copolymerization system: (1) a forward model for predicting the molecular weight and chemical composition distributions from a set of polymerization conditions and (2) an inverse model for determining the polymerization conditions to produce polymers with desired microstructures. The proposed model can be used as an efficient tool for material design.

    9. Molecular Weight Development of Surface and Solution Polymers in Surface-Initiated Atom Transfer Radical Polymerization and Their Dependence on Radical Termination Modes

      Dapeng Zhou, Zhiyang Bu, Dan Liu, Hongmei Wang, Huasheng Jiang and Luke Yan

      Version of Record online: 20 DEC 2015 | DOI: 10.1002/mren.201500049

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      This work reports a modeling study in the surface-initiated atom transfer radical polymerization, describing the growth of the molecular weight and polydispersity of polymer chain both on surface and in solution. Both surface radical termination and solution monomer consumption suppress the growth rate of polymer layer significantly.

    10. 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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