Macromolecular Reaction Engineering

Cover image for Vol. 9 Issue 1

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


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  1. Full Papers

    1. Correlating Cobalt Net Charges with Catalytic Activities of the 2-(Benzimidazolyl)-6-(1-aryliminoethyl)pyridylcobalt Complexes toward Ethylene Polymerization

      Wenhong Yang, Yan Chen and Wen-Hua Sun

      Article first published online: 3 MAR 2015 | DOI: 10.1002/mren.201400064

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      DFT-QEq method was applied to study the catalytic activities for the series of 2-(Benzimidazolyl)-6-(1-aryliminoethyl)pyridyl cobalt complex pre-catalysts, which are analogues to iron systems reported previously. Good correlations were presented between experimental activities and calculated effective net charges. Comparisons with iron analogues indicated the variations of net charge on metal atoms are the same as a function of complex.

    2. Modeling of the ATRcoP Processes of Methyl Methacrylate and 2-(Trimethylsilyl) Ethyl Methacrylate in Continuous Reactors: From CSTR to PFR

      Wei Wang, Yin-Ning Zhou and Zheng-Hong Luo

      Article first published online: 26 FEB 2015 | DOI: 10.1002/mren.201400056

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      A tubular reactor model was developed to describe the ATRcoP of methyl methacrylate (MMA) and 2-(trimethylsilyl) ethyl methacrylate (HEMA-TMS) under different axial dispersions. The main ATRcoP behaviors and polymer micro-characteristics were obtained. Finally, the effects of flow patterns (including the CSTR and PFR modes) in different reactors on the ATRcoP characteristics were investigated using the model.

    3. Copolymerization of Limonene with n-Butyl Acrylate

      Shanshan Ren, Esther Trevino and Marc A. Dubé

      Article first published online: 24 FEB 2015 | DOI: 10.1002/mren.201400068

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      d-limonene, a renewable monoterpene derived from citrus fruit peels, is investigated to be used in polymer formulations. The copolymerization of d-limonene/n-butyl acrylate is evaluated by estimating the reactivity ratios and examining the composition drift with conversion. The incorporation of d-limonene into copolymer involves two routes: the normal propagation mechanism and a degradative chain transfer mechanism.

    4. D-Optimality in Model-Based Experimental Designs: Applications in NMRP of Styrene

      Alison J. Scott, Mark D. Hazlett, Eduardo Vivaldo-Lima and Alexander Penlidis

      Article first published online: 19 FEB 2015 | DOI: 10.1002/mren.201400060

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      Model-based D-optimal design of experiments is applied to the NMRP of styrene using three model levels: a fully mechanistic model, a refined mechanistic model, and a substantially reduced model. The D-optimal designs formulated using these models are compared to each other and are contrasted with additional optimality criteria (Bayesian design and anti-correlation criteria).

    5. Neodymium-Based Catalyst for the Coordination Polymerization of Butadiene: From Fundamental Research to Industrial Application

      Han Zhu, Ping Chen, Chang-Feng Yang and Yi-Xian Wu

      Article first published online: 19 FEB 2015 | DOI: 10.1002/mren.201400063

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      The neodymium-based catalyst system with high catalytic activity and stereoselectivity to butadiene polymerization was developed to produce polybutadiene with extremely high cis-1,4 configuration. The innovation technology has been achieved from fundamental research to industrial application.

    6. Comparison of RAFT Ab Initio Emulsion Polymerization of Methyl Methacrylate and Styrene Mediated by Oligo(methacrylic acid-b-methyl methacrylate) Trithiocarbonate Surfactant

      Yue Zhu, Shangyu Bi, Xiang Gao and Yingwu Luo

      Article first published online: 19 FEB 2015 | DOI: 10.1002/mren.201400058

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      MMA RAFT emulsion polymerization using oligo(MAA41-b-MMA8) RAFT as surfactant is conducted by comparison with the classical styrene systems. In MMA system, the coagulum-free latexes of high living polymers were achieved at 80 °C and low KPS concentrations, together with a broader final PDI than that in styrene system. The poorer polymerization performance of MMA RAFT emulsion polymerization is explained by the combination of the homogeneous nucleation mode of particles and the slow transportation rate of the oligomeric RAFT agent molecules from micelles to new-born particles.

    7. Design of Optimal Experiments for Terpolymerization Reactivity Ratio Estimation

      Niousha Kazemi, Thomas A. Duever and Alexander Penlidis

      Article first published online: 5 FEB 2015 | DOI: 10.1002/mren.201400048

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      This paper demonstrates that by implementing appropriate design of experiments and parameter estimation techniques, reliable reactivity ratios for terpolymerizations can be estimated from only three optimal feed compositions. The first ever model-based design of experiments criterion for terpolymerization reactivity ratio estimation is presented in this paper, which is as significant as the Tidwell-Mortimer criterion in copolymerization studies.

  2. Communications

    1. Effect of Diethylzinc on the Activity of Ethylene Polymerization by Metallocene Catalyst

      Wei Wang

      Article first published online: 4 FEB 2015 | DOI: 10.1002/mren.201400067

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      Adding a suitable amount of diethylzinc to a metallocene/MAO catalytic system for ethylene (co) polymerization results in a sharp increase in activity. Activities are enhanced 2∼5 times, and decrease when the amount of diethyl zinc is further increased. UV-vis analysis shows that the diethylzinc may react with MAO to generate a mixed aluminoxane, and form a more stable polymerization species ▪ author: please amend title of blue graph to read copolymerization ▪.

  3. Full Papers

    1. Effect of Monomer Concentration and pH on Reaction Kinetics and Copolymer Microstructure of Acrylamide/Acrylic Acid Copolymer

      Marzieh Riahinezhad, Neil McManus and Alexander Penlidis

      Article first published online: 28 JAN 2015 | DOI: 10.1002/mren.201400053

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      Water soluble acrylamide (AAm)/acrylic acid (AAc) copolymers are mainly used for enhanced oil recovery (EOR) applications. This requires the ability to design the copolymer structure and properties for the specific application. In this study, we investigated the effects of reaction factors such as total monomer concentration and solution pH on polymerization kinetics and copolymer microstructure characteristics.

  4. Special Article Series - Feature Articles

    1. The Use of Solid-State NMR to Investigate the Development of Segmental Mobility in Commercial Heterophasic Ethylene Propylene Copolymers (HEPCs)

      Linda Botha, Pritish Sinha, H. Duveskog and Albert J. Van Reenen

      Article first published online: 26 JAN 2015 | DOI: 10.1002/mren.201400043

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      Solid state 13C NMR probes the changes in distribution of ethylene in rigid and amorphous domains of impact copolymers.

  5. Full Papers

    1. Mathematical Modeling of Polyether Production from 1,3-Propanediol: Accounting for Linear Oligomers

      Wei J. Cui, Kimberley B. McAuley, Rupert E. Spence and Tuyu Xie

      Article first published online: 2 JAN 2015 | DOI: 10.1002/mren.201400038

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      A reactor model is developed to simulate the production of Cerenol® polyethers. The effects of super-acid catalyst and mass transfer of small species (water, monomer, propanal) and linear oligomers (dimer to heptamer) have been modeled. This model correctly predicts the dynamic trends in the concentration changes of linear oligomers, but the predicted maxima in these concentrations appear earlier compared with those from a previous model. The Dp is greatly improved compared with a previous model, where the evaporation of linear oligomers is not considered.

    2. Branching in RAFT Miniemulsion Copolymerization of Styrene/Triethylene Glycol Dimethacrylate and Control of Branching Density Distribution

      Xiaohui Li, Wen-Jun Wang, Bo-Geng Li and Shiping Zhu

      Article first published online: 29 DEC 2014 | DOI: 10.1002/mren.201400046

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      A model-based monomer feeding strategy is developed to achieve digital synthesis and precision production of polymer materials with targeted branching density distribution. For demonstration, a series of hyperbranched polystyrenes having uniform branching density distributions are synthesized via semibatch RAFT miniemulsion copolymerization of styrene and triethylene glycol dimethacrylate.

    3. Markovian Approach to Free-Radical Polymerization with Simultaneous Long-Chain Branching and Scission: Effect of Branching and Scission Kinetics

      Hidetaka Tobita

      Article first published online: 9 DEC 2014 | DOI: 10.1002/mren.201400042

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      The effect of branching and scission kinetics on the branched structure formation is investigated by using the analytic solution and the Monte Carlo simulation method. The illustrative calculations showed that the effect of different kinetics could be negligible when the final monomer conversion is smaller than about 25%, but may give significant differences at higher conversions as shown in the figure.

    4. Deterministic Modeling of Copolymer Microstructure: Composition Drift and Sequence Patterns

      Ivan Kryven and Piet D. Iedema

      Article first published online: 2 DEC 2014 | DOI: 10.1002/mren.201400047

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      The paper present a new deterministic approach allowing to study copolymer sequence distributions. The solution strategy is illustrated for styrene/acrylonitrile polymerization, highlighting the presence of different sequences, bimodalities, and a composition drift.

    5. Modeling of Polyamide 66 Solid State Polymerization: Drawing a Chemical Reaction Scheme

      Viviane Filgueiras, Stamatina N. Vouyiouka, Maria O. Konstantakopoulou, Anastasia C. Boussia, Constantine D. Papaspyrides, Enrique Luis Lima and José Carlos Pinto

      Article first published online: 13 NOV 2014 | DOI: 10.1002/mren.201400033

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      A chemical reaction scheme is proposed to describe polyamide 66 solid state polymerization using data measured under kinetic- and diffusion-controlled process conditions for reaction temperatures in the range of 160–200 °C and times up to 8 h. The obtained model can be correlated to industrial practice providing “safe” SSP conditions.


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