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A Flat Model Approach to Ziegler-Natta Olefin Polymerization Catalysts

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A Flat Model Approach to Ziegler-Natta Olefin Polymerization Catalysts A flat model approach to Ziegler-Natta olefin polymerization catalysts Citation for published version (APA): Andoni, A. (2009). A flat model approach to Ziegler-Natta olefin polymerization catalysts. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR638773 DOI: 10.6100/IR638773 Document status and date: Published: 01/01/2009 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license above, please follow below link for the End User Agreement: www.tue.nl/taverne Take down policy If you believe that this document breaches copyright please contact us at: [email protected] providing details and we will investigate your claim. Download date: 06. Oct. 2021 A FLAT MODEL APPROACH TO ZIEGLER-NATTA OLEFIN POLYMERIZATION CATALYSTS PROEFSCHRIFT ter verkrijging van de graad van doctor aan de Technische Universiteit Eindhoven, op gezag van de Rector Magnificus, prof.dr.ir. C.J. van Duijn, voor een commissie aangewezen door het College voor Promoties in het openbaar te verdedigen op woensdag 28 januari 2009 om 16.00 uur door Adelaida Andoni geboren te Fier, Albanië Dit proefschrift is goedgekeurd door de promotor: prof.dr. J.W. Niemantsverdriet Copromotoren: dr. P.C. Thüne en dr. J.C. Chadwick Adelaida Andoni Technische Universiteit Eindhoven, 2009 A catalogue record is available from the Eindhoven University of Technology Library ISBN: 978-90-386-1450-2 Copyright © 2009 by Adelaida Andoni The research described in this thesis forms part of the research programme of the Dutch Polymer Institute (DPI, P.O. Box 902, 5600 MB, Eindhoven, The Netherlands), Polyolefin Technology Area, DPI project #387. Cover design by Adelaida Andoni and Paul Verspaget (Verspaget & Bruinink) Printed at the Universiteitdrukkerij, Eindhoven University of Technology. Për prindërit e mi, motrën time dhe miket e mia më të mira. Table of contents 1. Introduction and scope 1 2. Experimental details 31 3. Ethylene polymerization over a planar Ziegler-Natta model catalyst 59 4. Propylene polymerization over a planar Ziegler-Natta model catalyst 81 5. A preparation method for well-defined crystallites of MgCl2-supported Ziegler- Natta catalysts and their observation by AFM and SEM 107 6. The role of electron donors on lateral surfaces of MgCl2-supported Ziegler-Natta catalysts; Observation by AFM and SEM 125 7. Attenuated total reflection infrared spectroscopy for studying planar Ziegler-Natta model catalysts 143 8. Conclusions and outlook 179 Summary 185 Samenvatting 187 Përmbledhje 189 Acknowledgments 191 List of publications 195 Cover on Macromolecular Rapid Communications (invited) 197 Curriculum Vitae 199 Chapter 1 Introduction and scope 1.1 Catalysis Catalysis has been, is and will continue to be indispensable for mankind. Given the fact that most products of the chemical industry are produced catalytically, catalysis can be regarded as the driving force of society. A catalyst basically boosts a chemical reaction, in other words it increases the reaction rate without being consumed itself. The word ‘catalysis’ originates from the Greek and means ‘down’ and ‘loosen’ [1]. Catalysis as the tool of performing reactions has been applied for thousands of years in processes such as fermentation. At the end of the eighteenth and the beginning of the nineteenth century, the influence of metals and oxides on the decomposition of several substances was investigated by many scientists. For example, it was observed that decomposition of alcohol in the presence of copper or iron produced carbon and a flammable gas [1]. Nowadays a very well-known example of catalysis is the way in which the three-way catalyst leads to a proficient decrease in pollution from car engines. To better understand how catalysis works, a simplified schematic representation of a catalytic * reaction has been depicted in Figure 1.1 . Let us consider a certain reaction, say A2+B2 → 2AB. Catalysis occurs on the surface of the catalyst, therefore the so-called catalytic cycle will begin with the adsorption of the molecules onto the surface. Upon adsorption the internal bonds of the molecule will be weakened or broken. As adsorption is always exothermic, the potential energy will decrease. In the next step, the molecule undergoes one or more reactions. This leads to the formation of the desired product, which is still bound to the catalyst. Finally, desorption of the product will occur, enabling the adsorption of new reagents on the catalyst. This step is enormously important, because without it there is no catalytic cycle and therefore no catalysis. A catalyst does not change the thermodynamics of a reaction, meaning that the equilibrium remains unchanged. The rate of the reaction is enhanced as a new and a more favorable reaction pathway is established. In other words the activation energy is now lower * The scheme in Figure 1.1 holds only for heterogeneous catalysis. Chapter 1 (Figure 1.1.) and as a result milder reaction conditions can be applied (lower temperatures and pressures). Figure 1.1: Schematic representation of a catalytic reaction (A2+B2 → 2AB) showing the potential energy diagram and displaying gas phase and catalytic reaction pathways. Generally speaking, catalysts are divided in two major groups: homogeneous and heterogeneous catalysts. In homogeneous catalysis all the reactants and the catalyst are in the same phase, which is commonly the liquid phase. The catalyst is usually a metal complex which dissolves in a solvent along with all the reactants. Homogeneous catalysts are frequently applied in batch processes, owing to the fact that volumes are small and the added value is high, e.g. in pharmaceuticals. Lastly, biocatalysis is an area of homogeneous catalysis where natural products (enzymes) are used in chemical reactions. In heterogeneous catalysis the catalyst is in a different phase than the reactants. The catalyst is in the solid phase, which can be a metal or a metal oxide, whereas the reactants are in the 2 Introduction and scope liquid or gas phase. Application of different types of reactions carried out in batch and continuous processes makes heterogeneous catalysis advantageous over homogeneous catalysis. Furthermore, the fairly easy separation of the catalyst from the reaction mixture offers the possibility of recycling the catalyst, lowering its costs. It is essential that the catalyst should consist of small particles with a high fraction of surface atoms (catalysis proceeds on the surface). Therefore, catalysts are usually supported i.e., dispersed on porous carriers with high surface area, such as silica, alumina, titania or carbon. However, unsupported catalysts are also in use (iron catalyst for ammonia synthesis) [2]. 1.2 Polyethylene and polypropylene Among the many different types of polymers, polyolefins such polyethylene (PE) and polypropylene (PP) have established a prominent position, attributable to their cost and performance balance, and their economical and environmentally friendly production. Polymers are large molecules which are made up of simple repeating units. Polyethylene is the most intensively used polymer worldwide [3]. The production of all synthetic polymers amounts to 220 Million tons per annum. Around 60 Million tons per annum are polyethylenes [3]. A polyethylene chain is a long chain of carbon atoms, with 2 hydrogen atoms attached to each carbon atom. The structure of polyethylene is depicted in Figure 1.2. Figure 1.2: The repeating of polyethylene. A single polyethylene chain can include thousands of its repeated units -CH2-. 3 Chapter 1 One also can describe polymers as linear, branched and network. The degree of branching has an enormous impact on the properties of a polymer [4]. The most important types are illustrated in Figure 1.3. High density polyethylene (HDPE) has little or no branching. HDPE has a high tensile strength and high density (≥ 0.94 g/cm3). HDPE is resistant to many solvents and has a wide variety of applications such as plastic bags, fuel tanks and water pipes. Low density polyethylene (LDPE) consists of chains with long and short branches. The density of LDPE ranges from 0.91 to 0.94 g/cm3. LDPE is broadly used for manufacturing various containers, plastic bags and computer components. Lastly, linear low density polyethylene (LLDPE) is essentially a linear polymer with significant short-chain branches (two to six atom carbons), resulting in a density in the range 0.915-0.925 g/cm3. Figure 1.3: Representation of the most common types of polyethylene. After ethylene, propylene is the simplest α-olefin, giving a polymer with methyl side-groups along the chain (Figure 1.4). The stereochemical configuration of the methyl groups determines the tacticity of polypropylene, which can be isotactic, syndiotactic or atactic, as shown in Figure 1.5.
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