Macromolecular Reaction Engineering

Cover image for Vol. 10 Issue 5

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. Development of an Elongational-Flow Microprocess for the Production of Size-Controlled Nanoemulsions: Application to the Preparation of Monodispersed Polymer Nanoparticles and Composite Polymeric Microparticles

      Wei Yu, Christophe A. Serra, Ikram U. Khan, Meriem Er-Rafik, Marc Schmutz, Isabelle Kraus, Shukai Ding, Lixiong Zhang, Michel Bouquey and René Muller

      Version of Record online: 21 NOV 2016 | DOI: 10.1002/mren.201600025

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      Composite polymeric microparticles doped with polymer nanoparticles are produced using a three-step microfluidic procedure: elongational-flow nanoemulsification of a monomer, polymerization of the nanodroplets, and emulsification of the resulting nanosuspension into microdroplets followed by the UV polymerization of the continuous phase.

    2. Chain-by-Chain Monte Carlo Simulation: A Novel Hybrid Method for Modeling Polymerization. Part I. Linear Controlled Radical Polymerization Systems

      Derya Demirel Özçam and Fouad Teymour

      Version of Record online: 16 NOV 2016 | DOI: 10.1002/mren.201600042

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      The Chain-by-Chain Monte Carlo simulation method (CBC-MC) is introduced as a novel hybrid deterministic/probabilistic technique for polymerization systems. In CBC-MC, nonspecific interactions are described through the use of deterministic equations, saving on ensemble size and computational time, and greatly enhancing convergence. In this article, CBC-MC is successfully tested in two case studies involving the synthesis of linear gradient copolymers.

    3. Ethylene Polymerization with a Hafnocene Dichloride Catalyst Using Trioctyl Aluminum and Borate: Polymerization Kinetics and Polymer Characterization

      Saeid Mehdiabadi, João B. P. Soares and Jeffrey Brinen

      Version of Record online: 11 NOV 2016 | DOI: 10.1002/mren.201600044

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      The polymerization of ethylene is investigated in a semibatch solution reactor using bis(n-propylcyclopentadienyl)hafnium dichloride and [B(C6F5)4][Me2NHPh]+. Trioctylaluminum (TOA) is used as impurity scavenger and alkylating agent. The figure shows the 3D response surface plot for the catalyst activity in terms of TOA, borate, and catalyst concentrations.

    4. Development of an Elongational-Flow Microprocess for the Production of Size-Controlled Nanoemulsions: Batch Operation

      Wei Yu, Christophe A. Serra, Ikram Ullah Khan, Shukai Ding, Rigoberto Ibarra Gomez, Michel Bouquey and René Muller

      Version of Record online: 11 NOV 2016 | DOI: 10.1002/mren.201600024

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      By passing alternatively through a restriction of 150, 250, or 500 μm in diameter, size-controlled nanoemulsions with narrow size distribution, viscosity ratio up to 14, and solid content up to 50% can be easily produced at low pressure. An empirical dimensionless correlation is provided to predict nanodroplet size.

    5. Copolymerization of 2,3,4,5,6-Pentafluorostyrene and Methacrylic Acid by Nitroxide-Mediated Polymerization: The Importance of Reactivity Ratios

      Nirmal B. Kannan and Benoît H. Lessard

      Version of Record online: 9 NOV 2016 | DOI: 10.1002/mren.201600052

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      Fluorinated amphiphilic block copolymers containing 2,3,4,5,6-pentafluorostyrene (PFS) and methacrylic acid (MAA) are synthesized using nitroxide-mediated polymerization. Unlike styrene the unfavored addition of PFS versus MAA results in poor copolymerization control at low PFS loadings (<50 mol%). However these reactivity ratios are exploited to synthesize one-pot block copolymers through the homopolymerization of PFS followed by the delayed one-shot addition of MAA.

    6. Molecular Architecture of Multi-Block Polymer Synthesized in a Dual-Catalyst Single CSTR

      Ivan Konstantinov, Carlos Villa, Tom Karjala and Pradeep Jain

      Version of Record online: 26 OCT 2016 | DOI: 10.1002/mren.201600047

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      This work provides analytical solutions for multi-block polymer synthesized in a dual-catalyst single CSTR. The molecular architecture is explored via four dimensionless numbers (XQ, Ω, DPnP, DPnQ) which quantify the interplay between propagation, chain shuttling and termination. Among the quantities investigated are polydispersity (PDI) and number average blocks per chain (Tn)

    7. Application of Polymer Reaction Modeling to Nonenzymatic Polynucleotide Replication

      Peter Mannion, Todd Zhen, Nathaniel Case and Francis Joseph Schork

      Version of Record online: 24 OCT 2016 | DOI: 10.1002/mren.201600034

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      Population balance methods are used to develop a mechanistic model of nonenzymatic polynucleotide replication. The model returns results in agreement with the previous models. In addition, the current model gives average lengths of polynucleotides and the average lengths of interior and terminal sequences of correct and incorrect insertions in a row not available from previous models.

    8. Bulk Free-Radical Copolymerization of n-Butyl Acrylate and n-Butyl Methacrylate: Reactivity Ratio Estimation

      Shanshan Ren, Laura Hinojosa-Castellanos, Lisha Zhang and Marc A. Dubé

      Version of Record online: 24 OCT 2016 | DOI: 10.1002/mren.201600050

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      The reactivity ratios are estimated for the bulk free-radical copolymerization of butyl acrylate and butyl methacrylate. High conversion experiments are performed to examine the composition drift, gel formation, and molecular weight development with conversion. The amount of gel polymer is greatly reduced in the presence of n-butyl methacrylate.

    9. Experimental and CFD Study of a Vertically Stirred Tubular Reactor Designed for Suspension Polymerization Reactions

      André L. Nogueira, Marintho B. Quadri, Ricardo A. F. Machado and Carlos A. Claumann

      Version of Record online: 24 OCT 2016 | DOI: 10.1002/mren.201600040

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      A stirred tubular reactor vertically installed is designed and constructed to produce suspension polymers. The behavior of the proposed reactor is investigated in this study experimentally and by using computational fluid dynamics techniques. An evaluation of the particles sedimentation kinetic throughout the reaction is also performed to generate information that can be useful to define strategies to continuously produce suspension polymers in the proposed reactor.

    10. Reactor Fouling by Preformed Latexes

      Jone Urrutia, Alberto Peña and José M. Asua

      Version of Record online: 13 OCT 2016 | DOI: 10.1002/mren.201600043

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      Fouling caused by latex deposition reduces the efficiency of the emulsion polymerization reactors and affects product quality. This work investigates the fouling created by preformed latexes both under perikinetic and orthokinetic conditions. The flow patterns determine the distribution of fouling in the reactor. A mechanism for fouling formation is proposed by combining computational fluid dynamics and experimental results.

    11. Activation and Deactivation of Phillips Catalyst for Ethylene Polymerization Using Various Activators

      Yanning Zeng, Patchanee Chammingkwan, Ryuki Baba, Toshiaki Taniike and Minoru Terano

      Version of Record online: 10 OCT 2016 | DOI: 10.1002/mren.201600046

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      Though not necessarily required, metal alkyl activators can modulate the performance of a Phillips catalyst in ethylene polymerization. The type of aluminum alkyl greatly affects a tradeoff between the catalyst activation and deactivation, where bulky alkyl groups exhibit preferential suppression of the deactivation to give the highest activity and the widest operation window.

  2. Communications

    1. Dependence of Propagation Rate Coefficients in Radical Polymerization on Solution Properties

      Peter Deglmann, Klaus-Dieter Hungenberg and Hugo M. Vale

      Version of Record online: 5 OCT 2016 | DOI: 10.1002/mren.201600037

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      The transition state theory has successfully been applied to quantitatively explain the solvent effect on the propagation rate coefficients in radical polymerization. The effect can entirely be explained by the degree of nonideality of the system and the thermodynamic activity of all species involved in the transition state.

  3. Full Papers

    1. Polystyrene Microstructured Foams Formed by Thermally Induced Phase Separation from Cyclohexanol Solution

      Andra Nistor, Michal Vonka, Adam Rygl, Malvina Voclova, Maria Minichova and Juraj Kosek

      Version of Record online: 26 SEP 2016 | DOI: 10.1002/mren.201600007

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      Polystyrene (PS) particles or microstructured PS materials with open pores, closed cells, or their combination can be prepared by thermally induced phase separation (TIPS). The TIPS for the PS-cyclohexanol system is studied experimentally and theoretically using the Cahn–Hilliard model. By incorporating polar interactions into the model the authors' previous work is extended and good agreement with experiments is observed.

    2. In Situ Use of Aqueous RAFT Prepared Poly(2-(diethylamino)ethyl methacrylate) as a Stabilizer for Preparation of CO2 Switchable Latexes

      Abbas Rezaee Shirin-Abadi, Philip G. Jessop and Michael F. Cunningham

      Version of Record online: 19 SEP 2016 | DOI: 10.1002/mren.201600035

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      CO2-switchable latexes are made using a poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA)-based stabilizer made in situ by reversible addition–fragmentation chain transfer (RAFT) polymerization. A PDEAEMA macroinitiator is first prepared in water by RAFT under CO2 atmosphere, and then used directly as a stabilizer in emulsion polymerization to yield the CO2-switchable latexes.

    3. Dynamic Monte Carlo Simulation of the l,l-Lactide Ring-Opening Polymerization

      Dimitrios Meimaroglou, Prokopios Pladis and Costas Kiparissides

      Version of Record online: 31 AUG 2016 | DOI: 10.1002/mren.201600039

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      In the present study, a comprehensive theoretical kinetic investigation of the homopolymerization of l,l-lactide in the presence of stannous octoate Sn(Oct)2 as initiator for the synthesis of high-molecular weight polylactide is carried out using the stochastic Monte Carlo numerical method.

    4. Modeling of Polyolefin Polymerization in Semibatch Slurry Reactors: Experiments and Simulations

      Tommaso Casalini, Frans Visscher, Erik Janssen, Francesco Bertola, Giuseppe Storti and Massimo Morbidelli

      Version of Record online: 30 AUG 2016 | DOI: 10.1002/mren.201600036

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      In this work, a single-particle model (the multigrain model) is applied to simulate polyethylene catalytic polymerization in slurry-phase semibatch reactor. It is shown that a simple two-site model for the catalyst is able to properly describe average polymer properties over different operative conditions (such as hydrogen partial pressure).

    5. Autoacceleration and Cyclization Effects on Styrene/Divinylbenzene Copolymerization

      Vinícius N. Santos, Leandro G. Aguiar and Reinaldo Giudici

      Version of Record online: 25 AUG 2016 | DOI: 10.1002/mren.201600021

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      The effect of cyclization reaction in styrene-divinylbenzene copolymerization is studied in diluted solution. Pendant double bond concentration is measured by Fourier transform infrared spectroscopy and the experimental results are interpreted by a kinetic model of this process. Rate constants for crosslinking and cyclization are estimated from the experiments.

    6. Origin of Chemical Composition of Ethylene/Propylene Copolymer Produced with Ziegler–Natta Catalyst

      Shougo Takahashi, Toru Wada, Patchanee Chammingkwan, Toshiaki Taniike and Minoru Terano

      Version of Record online: 25 AUG 2016 | DOI: 10.1002/mren.201600038

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      Copolymer composition in Ziegler–Natta catalyzed ethylene/propylene copolymerization tends to be dependent on the yield rather than the nature of active sites. The ethylene consumption easily overcomes its supply due to the comonomer effect as well as the high reactivity and poor solubility of ethylene. Low-yield polymerization is essential to study the influence of the active site nature on the copolymerization.

    7. Synthesis of Narrow Molecular Weight Distribution Copolymers for ArF Photoresist Materials by Nitroxide Mediated Polymerization

      Zi Jun Wang, Kevin Wylie and Milan Marić

      Version of Record online: 22 AUG 2016 | DOI: 10.1002/mren.201600029

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      Adamantyl-based methacrylic monomers are terpolymerized by NMP using low concentrations ≈5 mol% of various controlling comonomers in the initial mixture. Polymerizations are characterized by linear inline image versus conversion up to nearly 70% with low inline image. Low concentrations of styrenic controller comonomer do not affect the optical transparency (with exception of vinyl naphthalene) and thus these resins are promising for 193 nm photolithography resists.

  4. Reviews

    1. A Comprehensive Review on Controlled Synthesis of Long-Chain Branched Polyolefins: Part 3, Characterization of Long-Chain Branched Polymers

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

      Version of Record online: 22 AUG 2016 | DOI: 10.1002/mren.201600012

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      Long-chain branched polyolefins exhibit improved melt processability, such as higher melt strength and better shear thinning. In the previous papers, the catalyst systems and reaction conditions for the controlled synthesis of long-chain branched polyolefins have been reviewed. This paper summarizes the literatures pertinent to the precise characterization of long-chain branched polyolefins and provides perspectives about various characterization techniques.

  5. Full Papers

    1. Ethylene Polymerization over Metallocene Catalysts Supported on Highly Fibrous Silica Nanoparticles

      Sangyool Lee and Kyu Yong Choi

      Version of Record online: 17 AUG 2016 | DOI: 10.1002/mren.201600027

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      Electron dispersive X-ray scan of polyethylene synthesized over KCC-1 silica-supported catalyst shows silica core regions and polymer matrix as well as polymeric nanofibrils. No global fragmentation occurs during the polymerization as polymer grows directly from the active catalytic sites distributed on the external platelets of the KCC-1 silica particles.

    2. Anionic Polymerizable Surfactants and Stabilizers in Emulsion Polymerization: A Comparative Study

      Ziortza Aguirreurreta, José C. de la Cal and Jose R. Leiza

      Version of Record online: 16 AUG 2016 | DOI: 10.1002/mren.201600033

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      The feasibility of using commercially available polymerizable surfactants (LatemulPD-104 and SipomerPam-200) and polymerizable stabilizer (SipomerCops-1) in the batch emulsion copolymerization of model acrylic latexes is studied. The number of polymer particles and the polymer microstructure (gel fraction and sol molecular weight) are strongly affected by the surfactant/stabilizer used during the polymerization.

    3. 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.

    4. 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.

    5. 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.

    6. 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.

    7. 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.

    8. 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.

    9. 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.

    10. 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.

    11. 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.

    12. 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.

    13. 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.

  6. Reviews

    1. 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.


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