Macromolecular Reaction Engineering

Cover image for Vol. 10 Issue 2

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

Special Series: Polyolefins—Catalyst and Process Innovations

Guest-edited by Joao Soares and Tim McKenna, this series publishes in an on-going fashion invited articles by leading researchers to document the rapid progress in this field.


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, Albert J. Van Reenen*

Solid state 13C NMR probes the changes in distribution of ethylene in rigid and amorphous domains of impact copolymers. In this publication, the observations from the perspective of the solid-state analyses are outlined and placed in the context of the evolution of microscopic, chemical, microstructural, and mechanical properties.

Macromol. React. Eng. DOI: 10.1002/mren.201400043


Thermal Behavior of Polyethylene Reactor Alloys Polymerized by Ziegler-Natta/Late Transition Metal Hybrid Catalyst

polyolefins_8_6_Mortazavi.jpgSaeid Ahmadjo, Samaneh Dehghani, Gholam Hossein Zohuri, Gholam Reza Nejabat, Hamed Jafarian, Mostafa Ahmadi and Seyed Mohammad Mahdi Mortazavi*

Ziegler-Natta (ZN) and late transition metal (LTM) hybrid catalysts were synthesized and utilized in preparation of polyethylene (PE) reactor alloys. By changing reaction parameters, versatile thermal behavior from LTM-PE to ZN-PE could be obtained. The proposed method seems to be a promising approach for synthesis of tailor-made polyethylene in a single reactor.

Macromol. React. Eng. DOI: 10.1002/mren.201400024


Preparation of Nanocomposites of Polypropylene with Carbon Nanotubes via Masterbatches Produced by In Situ Polymerization and by Melt Extrusion


Rafael S. Araujo, Renato J. B. Oliveira and Maria de Fátima V. Marques*

A new PP/multi-walled carbon nanotube (MWCNT) masterbatch is synthesized via in situ polymerization and compared with a masterbatch obtained by melt mixing. Both masterbatches are used for the realization of PP/MWCNT nanocomposites by mixing with a commercial PP in a extruder. It is shown that the use of the masterbatch synthesized in situ provides additional enhanced thermal stability and mechanical properties.

Macromol. React. Eng. DOI: 10.1002/mren.201400012


Catalytic Olefin Polymerization Process Modeling: Multi-Scale Approach and Modeling Guidelines for Micro-Scale/Kinetic Modeling


Vasileios Touloupidis

This work presents the basic framework for catalytic olefin polymerization kinetic modeling. It provides an insight for a better understanding of the kinetic models, offering the starter-kit tools for developing similar approaches in the complex but extremely interesting area of polymerization kinetic reaction engineering.

Macromol. React. Eng. DOI: 10.1002/mren.201300188


Kinetics and Growth of Polyethylene Nanofibrils over Metallocene Catalyst Supported on Flat Silica and Spherical

polyolefins_8_3_Choi.jpgSang Yool Lee and Kyu Yong Choi*

A catalyst loaded flat silica surface is deposited with methylaluminoxane (MAO) and a rac-Et(indenyl)2ZrCl2 catalyst. The polymer grows as nanofibrils of about 30-45 nm diameter. Some MAO clusters are formed and catalytic sites are concentrated in these clusters. The flat silica supported catalyst exhibit highest catalytic activity.

Macromol. React. Eng. DOI: 10.1002/mren.201400018


Condensed Mode Cooling for Ethylene Polymerization: The Influence of the Heat of Sorption

polyolefins_7_9_McKenna.jpgArash Alizadeh and Timothy F. L. McKenna*

The relative importance of the higher solubility of n-hexane and its associated heat of sorption on the thermal behavior of the polymer particles during gas phase ethylene polymerization is investigated. It is found that if a polymerizing particle begins to heat-up, the partial desorption of a condensable solute in a gaseous state helps to attenuate the temperature rise in the polymer particles, decreasing the risk of local hot spots.

Macromol. React. Eng. DOI: 10.1002/mren.201300165


Growth Kinetics Obtained from Single Particle Gas-Phase Ethene Homopolymerization with a Ziegler–Natta Catalyst

polyolefins_7_8_Paulik.jpgLeonhard Mayrhofer and Christian Paulik*

A micro-reactor, equipped with a video microscope is used for studying single particle gas-phase ethylene polymerization. Polymerization conditions are close to industrial set points. A standard 4th generation Ziegler–Natta catalyst system has been used. The rate of polymerization is calculated and related to SEM pictures to allow a deeper understanding of the gas-phase polymerization of ethylene. Different Al/Ti ratios and reaction temperatures are examined and explain the behavior of growing polyethylene-particles in a satisfying way.

Macromol. React. Eng. DOI: 10.1002/mren.201300153


Development of a Hetero-Bimetallic Phillips-Type Catalyst for Ethylene Polymerization

polyolefins_7_7_Terano.jpgYanning Zeng, Akanksha Matta, Sumant Dwivedi, Toshiaki Taniike, Minoru Terano*

The effects of various second metals in the impregnation solution have been investigated. The polymerization performance in terms of activity and branching is highly depended on the electronegativity of second metal. Bimetallic catalysts containing second metal with low electronegativity improved not only the activity but also the branching ability in ethylene polymerization.

Macromol. React. Eng. DOI: 10.1002/mren.201300119


Ethylene Polymerization Over Ph2C(Cp)(2,7-t-Bu2Flu)ZrCl2 Supported On SiO2-MAO

polyolefins_7_6_Escola.jpgEmilio Casas, Beatriz Paredes, Jose María Escola,* Carlos Martin, Rafael van Grieken

Ethylene polymerization over heterogeneous [Ph2C(Cp)(2,7-t-Bu2Flu)ZrCl2] supported on SiO2-MAO is investigated. At 8 bar, the polyethylenes show molecular weights above 400 000 g ⋅ mol-1. With hydrogen, the activity decreases while with 1-butene, the activity is higher than in the homopolymerization.

Macromol. React. Eng. DOI: 10.1002/mren.201300130


Controlling Polyolefin Properties by In-Reactor Blending: 3. Mechanical Properties

polyolefins_7_5_Ruff.jpgMartin Ruff,* Reinhold W. Lang, Christian Paulik

The effects of multi-stage (slurry) polymerization on mechanical properties of in-reactor blended UHMW-PE materials is presented, and it is shown that due to a controlled polymerized particle morphology, mechanical properties, such as impact properties can be regulated.

Macromol. React. Eng. DOI: 10.1002/mren.201200077


Analysis of Slurry-Phase Co-Polymerization of Ethylene and 1-Butene by Ziegler–Natta Catalysts Part 1: Experimental Activity Profiles

polyolefins_7_3_Rawatal.jpgJohn T. McCoy, Joao B. P. Soares, Randhir Rawatlal*

The activity of Ziegler–Natta catalysts for ethylene polymerization is studied, and a method developed to extract meaningful kinetic parameters from experimental data. Four model parameters are required to reproduce polymerization rate profiles for a range of laboratory experimental conditions.

Macromol. React. Eng. DOI: 10.1002/mren.201200078


Cycloolefin Copolymers by Early and Late Transition Metal Catalysts


Incoronata Tritto,* Laura Boggioni, Andrea Ravasio, Giulia Scalcione

Amorphous alternating E-co-N and E-co-NAC copolymers, in excellent yield, are synthesized with the palladium catalyst 1. N concentration allows for tuning molar mass values. Living E-co-N copolymerization with 2, at 50 °C, allows for efficient synthesis of PE-block-P(E-co-N)s, with crystalline PE and amorphous P(E-co-N) blocks, as well as P(E-co-N)1-block-P(E-co-N)2, with different Tg values.

Macromol. React. Eng. DOI: 10.1002/mren.201200056


Design and Synthesis of Olefin Copolymers with Tunable Amounts of Comonomers Bearing Stabilizing Functionalities


Maria Carmela Sacchi,* Simona Losio, Paola Stagnaro, Stefano Menichetti, Caterina Viglianisi

The present research proposes the design and synthesis of monomers bearing stabilizing functionalities and their copolymerization with ethylene to obtain non-releasing polymeric additives. Such materials can be added to commercial polyolefins to prepare films characterized by stability to auto- and photo-oxidation, with reduced, or eliminated risk, of migration of the stabilizer into the contact food.

Macromol. React. Eng. DOI: 10.1002/mren.201200055


Controlling Polyolefin Properties by In-Reactor Blending: 2. Particle Design


Martin Ruff*, Christian Paulik

Structure properties of in-reactor-blended ultra-high molecular weight polyethylene (UHMW-PE) reactor powders are presented, and it is shown that the particle morphology can be designed by precisely controlled multi-stage (slurry) polymerization. A novel kind of surface structure, named cocoon-structure, of bimodal PE reactor powders from multi-stage polymerizations is presented.

Macromol. React. Eng. DOI: 10.1002/mren.201200050


Controlling Polyolefin Properties by In-Reactor Blending, 1 - Polymerization Process, Precise Kinetics, and Molecular Properties of UHMW-PE Polymers

polyolefins_6_8_1_Ruff.jpgMartin Ruff*, Christian Paulik

A multi-stage polymerization method using a dynamic power-compensating reactor for preparing bimodal PE in-reactor blends is presented. Control of ultrahigh-molecular-weight fractions is achieved by isothermal, isobaric, and isoperibolic steady-state polymerization conditions in a slurry.

Macromol. React. Eng. DOI: 10.1002/mren.201200019


Simultaneous Deconvolution of Molecular Weight and Chemical Composition Distribution of Ethylene/1-Olefin Copolymers: Strategy Validation and Comparison

polyolefins_5_11_2_Anantawaraskul.jpgSiripon Anantawaraskul, Warawut Bongsontia, João B. P. Soares

Four simultaneous deconvolution strategies based on different microstructural information of ethylene/1-olefin copolymers were investigated. Deconvolution based on complete bivariate distribution of molecular weight and chemical composition was found to accurately identify the number of site type and provide best estimated mass fraction and kinetic parameters of each site type.

Macromol. React. Eng. DOI: 10.1002/mren.201100032


Thermodynamic Data of Ethylene-Propane Mixtures in Condensed and Supercritical State

polyolefins_5_11_n_Bartke.jpgSebastian Kröner, Wang Minjiong, Michael Bartke

Experimental thermodynamic data of the system ethylene/propane in condensed and supercritical state is presented in this work. Experiments and simulations are focused on temperature and pressure conditions relevant for heterogeneous polymerization of polyethylene as applied in industry. Good description of the experimental data could be achieved by simulations using the Peng-Robinson EOS with a liquid phase density correction.

Macromol. React. Eng. DOI: 10.1002/mren.201100014


Bimodality Criterion for the Chemical Composition Distribution of Ethylene/1-Olefin Copolymers: Theoretical Development and Experimental Validation

polyolefins_5_5_n_Anantawaraskul.jpgKanyanut Narkchamnan, Siripon Anantawaraskul,* João B.P. Soares

The bimodality criterion for chemical composition distribution of ethylene/1-olefin copolymers is developed and validated theoretically with simulation data and experimentally with crystallization analysis fractionation (CRYSTAF) and crystallization elution fractionation (CEF). The CCD bimodality criterion derived herein could be useful for determining the appropriate recipe to synthesize copolymer blends with desired CCD characteristics.

Macromol. React. Eng. DOI: 10.1002/mren.201100002


Hard versus Soft Materials as Supports for Metallocene and Post-Metallocene Catalysts

polyolefins_3_8_4_Klapper.jpgCorinna Naundorf, Daniela Ferrari, Giovanni Rojas, Gerhard Fink,* Markus Klapper,* Klaus Müllen

The influence of organic supports on the polymerization behavior of post-metallocene catalysts is studied and compared with similarly supported titanium and zirconium metallocenes. The effects of the immobilization, activation, and polymerization process were studied by video microscopy, laser confocal fluorescence microscopy, SEM, and TEM. A model for the polymerization process for a catalyst supported on latex particles was developed from the results obtained. Organic supports based on latex particles are easily adjustable for different catalysts due to the versatile functionalization of the surfaces and can be applied to different types of olefin polymerization catalysts. They can be considered as an alternative to SiO2 or MgCl2 supports.

Macromol. React. Eng. DOI: 10.1002/mren.200900026


Characteristics of Bimodal Polyethylene Prepared via Co-Immobilization of Chromium and Iron Catalysts on an MgCl2-Based Support

polyolefins_3_8_3_Chadwick.jpgNileshkumar Kukalyekar, Luigi Balzano, Gerrit W. M. Peters, Sanjay Rastogi*, John C. Chadwick*

Bimodal polyethylenes comprising varying proportions of high- and low-molecular-weight fractions are synthesized in a single polymerization stage, via the co-immobilization of a chromium and an iron catalyst on an MgCl2/AlEtn(OEt)3-n support. Changes observed in the viscoelastic response of the polymer melt with increasing content of the high-molecular-weight fraction indicate effective mixing in the bimodal blend. In flow, chains in the high-molecular weight fraction tend to orient and stretch under shear. Due to the longer relaxation time of the high-molecular-weight component, X-ray diffraction and scattering reveal that shear-induced crystallization takes place at temperatures close to the equilibrium melting point of linear polyethylene. The so-crystallized high-molecular-weight component suppresses the nucleation barrier for further crystallization, leading to the formation of a "shish-kebab" polymer morphology.

Macromol. React. Eng. DOI: 10.1002/mren.200900021


Metallocene-Catalyzed Gas-Phase Ethylene Copolymerization: Kinetics and Polymer Properties

polyolefins_3_8_2_Bergstra.jpgMichiel F. Bergstra*, Günter Weickert, Gerben B. Meier

The influence of 1-hexene is examined on the kinetics of ethylene copolymerization with a metallocene catalyst in gas phase. A model is derived, which is able to describe a large reaction rate increase due to a small amount of incorporated comonomer. This complexation model describes the measured reaction rates for ethylene and 1-hexene, and the co-monomer incorporation. Polymer properties were analyzed, such as comonomer weight fraction. The density, melting point, and molecular weight of the produced polymer decreased with increase in 1-hexene gas concentration. The in situ 1-hexene sorption is estimated and follows Henry's law, but seems much higher than reported in the literature.

Macromol. React. Eng. DOI: 10.1002/mren.200900019


Special Article Series on 'Polyolefins - Catalyst and Process Innovations'

polyolefins_3_8_1_Chadwick.jpgJohn C. Chadwick

This Essay inaugurates a Special Article Series called "Polyolefins - Catalyst and Process Innovations". Examples illustrating recent progress in both the fundamental understanding and application of Ziegler-Natta and single-centre catalysts in polyolefin production are given.

Guest-edited by John C. Chadwick (Dutch Polymer Institute), the new article series will highlight new developments in olefin polymerization catalysis and how increased control over polymer structure and properties can be achieved by catalyst and process modifications.

Macromol. React. Eng. DOI: 10.1002/mren.200900043