Macromolecular Reaction Engineering

Cover image for Vol. 9 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. Modeling Acrylic Acid Radical Polymerization in Aqueous Solution

      Nils F. G. Wittenberg, Calista Preusser, Hendrik Kattner, Marek Stach, Igor Lacík, Robin A. Hutchinson and Michael Buback

      Article first published online: 11 JUN 2015 | DOI: 10.1002/mren.201500017

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      The complexities of aqueous-phase polymerization of non-ionized acrylic acid are captured in a model that considers the formation of midchain radicals, the influence of radical chain length on termination kinetics, and the influence of monomer concentration on propagation kinetics. The model is verified against monomer conversion profiles, polymer branching levels, and molar mass distributions collected over a range of experimental conditions.

  2. Reviews

    1. Model-Based Production of Polymer Chains Having Precisely Designed End-to-End Gradient Copolymer Composition and Chain Topology Distributions in Controlled Radical Polymerization, A Review

      Xiaohui Li, Shaoning Liang, Wen-Jun Wang, Bo-Geng Li, Yingwu Luo and Shiping Zhu

      Article first published online: 15 MAY 2015 | DOI: 10.1002/mren.201500012

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      This article summarizes the recent development and application of the model-based monomer feeding strategies (MMFS) on precise production of polymer chains. With the MMFS method, a series of polymer products with predesigned copolymer composition distributions and chain topologies are successfully synthesized by semi-batch-controlled radical polymerization. Extending MMFS to heterogeneous systems and to continuous polymerization operations are encouraged in future research.

  3. Full Papers

    1. Kinetic Parameters of the Initiator Decomposition in Microwave and in Conventional Batch Reactors – KPS and V50-Case Studies

      Cristiane Costa, André L. Alberton, Alexandre F. Santos, Montserrat Fortuny, Pedro H. H. Araújo, Claudia Sayer and José Carlos Pinto

      Article first published online: 13 MAY 2015 | DOI: 10.1002/mren.201500013

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      This work presents a thorough statistical analysis of parameters used to describe the kinetic rate constants of microwave-assisted decomposition of initiators. The confidence regions of the estimated parameters confirm the difference for microwave and conventional heating. The relation of temperature and volume of hot spots can explain the increase of kinetic rate constants as a thermal effect.

    2. Novel SiO2-Supported Chromium Oxide(Cr)/Vanadium Oxide(V) Bimetallic Catalysts for Production of Bimodal Polyethylene

      Ruihua Cheng, Xin Xue, Weiwei Liu, Ning Zhao, Xuelian He, Zhen Liu and Boping Liu

      Article first published online: 12 MAY 2015 | DOI: 10.1002/mren.201400072

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      A series of SiO2-supported Cr–V bimetallic oxides catalysts were successfully synthesized through introduction of vanadium oxide into the traditional Phillips CrOx/SiO2 catalyst. Using these Cr/V bimetallic catalysts, one-pot synthesis of polyethylene and ethylene/1-hexene copolymers with bimodal MWD and improved short chain branch distribution together with enhancement of catalytic activity was achieved.

    3. Kinetics and Modeling of Ring-Opening Copolymerization of l-Lactide and ε-Caprolactone

      Feiyin Weng, Xiaohui Li, Yanjiao Wang, Wen-Jun Wang and Steven J. Severtson

      Article first published online: 27 APR 2015 | DOI: 10.1002/mren.201500009

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      A model for ring-opening copolymerization of l-lactide and ε-caprolactone based on coordination insertion mechanism, considering diffusion control in propagation and transesterification reactions is developed. It is successfully applied to predict monomer conversion, molecular weight and distribution, and cumulative polymer composition for copolymers with variable compositions as well as variable chain lengths.

    4. A Study on a Prepolymerization Process of Aromatic-Contained Polyamide Copolymers PA(66-co-6T) via One-Step Polycondensation

      Cai-Liang Zhang, Li Wan, Xue-Ping Gu and Lian-Fang Feng

      Article first published online: 16 APR 2015 | DOI: 10.1002/mren.201500006

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      A facile one-step polycondensation approach to prepare a prepolymer of aromatic-contained polyamide using terephthalic acid (PTA), adipic acid (ADA), hexamethylenediamine (HMDA) as raw materials was explored. The prepolymerization process was divided into four stages: formation of nylon salt, temperature rising, polycondensation, and venting.

    5. A Comparison of the Reactivity of Two Platinum Catalysts for Silicone Polymer Cross-Linking by UV-Activated Hydrosilation Reaction

      Sophie Marchi, Marco Sangermano, Patrick Meier and Xavier Kornmann

      Article first published online: 7 APR 2015 | DOI: 10.1002/mren.201500005

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      The photopolymerization of silicone polymers can be achieved in the presence of an appropriate transition-metal organometallic compounds. The reactivity of two different platinum catalysts is investigated for the formation of both thin and several centimeters thick materials. DSC analyses are performed to analyze the enthalpy of the different reactions.

    6. Modeling of Highly Branched Water-Soluble Polymers with Applications to Drug Delivery Model Extensions and Validation

      Seung Yeon Kim, Robert Van Dyke, Kai Chang, Lakeshia J. Taite and Francis Joseph Schork

      Article first published online: 7 APR 2015 | DOI: 10.1002/mren.201500010

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      The use of controlled polymerization of a polymer exhibiting a lower critical solution temperature and a polymerizable chain transfer agent to produce highly branched polymer for is explored via mathematical modeling. The application of such polymers is in drug delivery. The model is developed and compared with experimental data.

    7. A Novel Approval for Degradation of Polybutadiene and Synthesis of Diene-Based Telechelic Oligomers via Olefin Cross Metathesis

      Bin Jiang, Tian Wei, Ting-Ting Zou, Gary L. Rempel and Qin-Ming Pan

      Article first published online: 1 APR 2015 | DOI: 10.1002/mren.201500004

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      Synthesis of well-defined functionalized telechelic oligomers containing only a few butadiene repeating units is accomplished via metathetic degradation of polybutadiene in the presence of Grubbs second generation catalyst with selected monomers as chain transfer agents. The structures and compositions of metathesis products are acquired using 1H-NMR and GC-MS analysis.

    8. Investigating Effects of Using Mixtures of Two External Electron Donors on Microstructure and Properties of Polypropylene/Poly(ethylene-co-propylene) in-Reactor Blends Based on Ziegler–Natta Catalyst

      Leila Moballegh, Shokoufeh Hakim, Jalil Morshedian and Mehdi Nekoomanesh

      Article first published online: 1 APR 2015 | DOI: 10.1002/mren.201500002

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      The effects of using mixtures of two electron donors; phenyltriethoxysilane (donor A) and cyclohxylmethyldimethoxy silane (donor C) on activity, microstructure and mechanical properties have been shown. Mixture of electron donors has a synergistic effect on the molecular weight of the blends. The amount of block PP-PE copolymer and impact strength are higher in the case of the blend based on A/C:75/25 than other blends based on pure and mixture of donors.

    9. Modeling of the Dehydration Process Coupled with Solid-State Polymerization in Nylon 6 Drying Column

      Guojian Sun, Chunxi Qin, Zhenhao Xi, Zhimei Xu, Weizhen Sun and Ling Zhao

      Article first published online: 1 APR 2015 | DOI: 10.1002/mren.201400062

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      Nylon 6 drying is a gas–solid countercurrent process, containing both mass/heat transfer and solid-state polymerization (SSP) at relative low temperatures. In this paper, an integrated model combining the mass/heat transfer and polymerization reaction has been presented for Nylon 6 drying process. The influences of operation conditions on the moisture content and the degree of polymerization distribution profiles in industrial drying column have been discussed.

    10. Alternation of Pore Architecture of Ziegler–Natta Catalysts through Modification of Magnesium Ethoxide

      Toshiki Funako, Patchanee Chammingkwan, Toshiaki Taniike and Minoru Terano

      Article first published online: 27 MAR 2015 | DOI: 10.1002/mren.201400074

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      The modification of magnesium ethoxide with a small amount of i-propoxide caused the transformation of the crystalline phase and the particle densification, leading to significant alternation of the pore architecture of Ziegler–Natta catalysts.

  4. Reviews

    1. Encapsulation of PV Modules Using Ethylene Vinyl Acetate Copolymer as the Encapsulant

      Shan Jiang, Kemin Wang, Hongwen Zhang, Yonghong Ding and Qiang Yu

      Article first published online: 27 MAR 2015 | DOI: 10.1002/mren.201400065

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      This article pays special attention to research work on improving the performance of EVA encapsulation films of photovoltaic (PV) modules, including the aging resistance, adhesive strength, and energy conversion efficiency. β-Diketone macromolecular complexes are synthesized and doped into EVA film to increase the photovoltaic conversion efficiency and service life of EVA films.

  5. Feature Articles

    1. New Chemistries and Technologies Derived from a Common Reaction of α-Methylstyrene at 61 °C

      Yuhong Ma, Shan Jiang, Shujun Liang and Wantai Yang

      Article first published online: 25 MAR 2015 | DOI: 10.1002/mren.201400059

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      Free radical copolymerizations of styrene and (meth)acrylates with α-methylstyrene as the comonomer show that the molecular weights of the copolymers increase with the monomer conversion. The copolymers are able to generate chain free radicals when heated above 90 °C. These chain radicals have been applied to initiate vinyl monomers to prepare block and functional polymers. In addition, these chain radicals can act as in situ compatibilizers by forming graft polymers and can also modify MWCNTs by a grafting-onto mechanism.

    2. Polytrimethylene Terephthalate: An Example of an Industrial Polymer Platform Development in China

      Qiongdan Xie, Xilong Hu, Tengjiao Hu, Pan Xiao, Youyong Xu and Kenneth W. Leffew

      Article first published online: 24 MAR 2015 | DOI: 10.1002/mren.201400070

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      This short review introduces the industrial polymer platform of polytrimethylene terephthalate (Sorona) within DuPont China Research and Development Center founded in 2005. The R&D competencies and some of the research content on Sorona are briefly introduced in this paper. This platform continues to develop new applications for Sorona and provides technical support to the Chinese market for Sorona.

  6. Full Papers

    1. Tailor Made Products by Smart Processes

      Thomas Bott, Wolfgang Gerlinger and Johannes Barth

      Article first published online: 17 MAR 2015 | DOI: 10.1002/mren.201400069

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      Tailor made products by smart processes. From our industrial perspective, successful product development in the future will include more modeling starting at understanding of structure property relationships of a desired application rather than at synthesizing and screening new structures. Globalization in research will play an important role. BASF, being recognized as one of the leading employers in China, will be continuing to expand its research and development activities in Asia as well as in America in order to participate in regional innovation processes.

    2. Monte Carlo Modeling of Free Radical Polymerization in Microflow Reactors

      Zehui Gao and Junpo He

      Article first published online: 13 MAR 2015 | DOI: 10.1002/mren.201400061

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      Monte Carlo simulation is developed to model free radical polymerization in microflow reactor. The algorithm combines the stochastic process of the reactions with diffusion and flow, and is able to predict the polymerization rate, molecular weight, PDI, and copolymer sequence as a function of reaction time.

    3. 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.

    4. 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.

    5. 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.

    6. 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.

    7. 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. 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 ▪.

  8. 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.


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