Morphology control in metallocene-catalyzed polyolefin synthesis Dissertation zur Erlangung des Grades „Doktor der Naturwissenschaften“ am Fachbereich Chemie, Pharmazie und Geowissenschaften der Johannes Gutenberg-Universität Mainz Vorgelegt von Daejune Joe geboren in Seoul, Süd-Korea Mainz 2013 “An expert is a person who has made all the mistakes which can be made in a very narrow field.” Niels Bohr (1885-1962) Physicist Dekan: Herr Prof. Dr. H. Frey 1. Berichterstatter: Herr Prof. Dr. K. Müllen 2. Berichterstatter: Herr Prof. Dr. S. R. Waldvogel Tag der mündlichen Prüfung: 17.09.2013 Die vorliegende Arbeit wurde in der Zeit von April 2010 bis August 2013 am Max-Planck-Institut für Polymerforschung in Mainz unter Anleitung von Herrn Prof. Dr. K. Müllen ausgeführt. Herrn Professor Dr. Klaus Müllen danke ich für seine wissenschaftliche und persönliche Unterstützung sowie für zahlreiche motivierende Diskussionsbereitschaft. Copyright © 2013 by Daejune Joe, Mainz, Germany No part of this work may be reproduced by any means, nor transmitted, nor translated into machine language without a written permission from the author. Dedicated to my family members for their support Table of contents Table of contents 1 General Introduction ......................................................................... 2 1.1 Polyolefins ........................................................................................................ 2 1.2 General history of polyolefins ........................................................................... 3 1.3 Classification of polyethylenes ......................................................................... 6 1.3.1 Low density polyethylene (LDPE) ................................................................................................. 7 1.3.2 High density polyethylene (HDPE) ................................................................................................ 8 1.3.3 Linear low density polyethylene (LLDPE) ...................................................................................... 9 1.3.4 Ultra high molecular weight polyethylene (UHMWPE) ..................................................................... 9 1.4 Catalytic systems............................................................................................... 9 1.4.1 Phillips systems ........................................................................................................................ 10 1.4.2 Ziegler-Natta systems ................................................................................................................ 11 1.4.3 Metallocene and post-metallocene complexes .................................................................................... 13 1.5 Processes ......................................................................................................... 18 1.5.1 Radical process ......................................................................................................................... 18 1.5.2 Solution process ........................................................................................................................ 19 1.5.3 Slurry process .......................................................................................................................... 19 1.5.4 Gas-phase process ..................................................................................................................... 21 1.6 Support materials ............................................................................................ 21 1.6.1 Requirements for supports .......................................................................................................... 22 1.6.2 Inorganic supports ..................................................................................................................... 23 1.6.3 Organic supports ...................................................................................................................... 23 1.7 References ....................................................................................................... 28 2 Motivation and Objectives .............................................................. 34 3 Porous Polyurethane Particles ........................................................ 40 3.1 Introduction ..................................................................................................... 40 3.2 Objective ......................................................................................................... 43 3.3 Results and discussion .................................................................................... 44 3.3.1 Synthesis of porous polyurethane particles ....................................................................................... 44 3.3.2 Ethylene polymerization on polyurethane particles ............................................................................ 48 3.3.3 Morphology of the obtained polyolefin/polyurethane particles .............................................................. 52 3.4 Conclusion ...................................................................................................... 55 3.5 Experimental part ............................................................................................ 56 3.5.1 General procedures and materials ................................................................................................. 56 3.5.2 Preparation of the porous polyurethane particles ............................................................................... 56 3.5.3 Structural characterization of porous polyurethane particles ................................................................ 57 Table of contents 3.5.4 Staining the polyurethane particles with Rhodamine B ..................................................................... 57 3.5.5 Immobilization of the metallocene catalyst on the polyurethane particles ................................................ 58 3.5.6 Polymerization procedure in a gas phase reactor .............................................................................. 58 3.5.7 Characterization of polyethylene/polyurethane composites .................................................................. 59 3.6 References ....................................................................................................... 60 4 High Density Polyethylene Fibers ................................................. 64 4.1 Polyolefin fibers .............................................................................................. 64 4.2 Objectives ........................................................................................................ 67 4.3 Results and discussion ..................................................................................... 69 4.3.1 Synthesis of the anisotropic supports with polystyrene nanoparticles ..................................................... 69 4.3.2 Immobilizing metallocene on the electrospun fibers ........................................................................... 71 4.3.3 Ethylene polymerization of the electrospun fibers in a gas phase reactor ................................................ 72 4.3.4 Morphology of the polyolefin fibers ............................................................................................... 74 4.4 Outlook ............................................................................................................ 78 4.5 Conclusion ....................................................................................................... 80 4.6 Experimental part ............................................................................................ 81 4.6.1 General procedure and materials ................................................................................................. 81 4.6.2 Synthesis of styryl-boron-dipyrromethene (BODIPY) dye .................................................................. 81 4.6.3 Preparation of the PEO-functionalized PS nanoparticles with styryl BODIPY .................................... 82 4.6.4 Electrospinning of the PS nanoparticles ........................................................................................ 82 4.6.5 Immobilizing procedure for metallocene/MAO on the electrospun fibers ............................................... 83 4.6.6 Polymerization procedure in a gas-phase reactor .............................................................................. 84 4.6.7 Characterization of materials ..................................................................................................... 84 4.7 References ....................................................................................................... 85 5 Linear Low Density Polyethylene Fibers ....................................... 89 5.1 Linear low density polyethylene synthesis ...................................................... 89 5.2 Objective .......................................................................................................... 92 5.3 Results and discussion ..................................................................................... 94 5.4 Conclusion ....................................................................................................... 99 5.5 Experimental part .......................................................................................... 100 5.5.1 General procedures and materials .............................................................................................