Poly (styrene - co - maleic anhydride) and Polystyrene Grafted with Poly(ether amines): Synthesis, Characterization and Gas Separation Performance Dissertation zur Erlangung des akademischen Grades Doktor der Naturwissenschaften (Dr. rer. nat) der Technischen Fakultät der Christian-Albrechts-Universität zu Kiel Diógenes Rojas Kiel 2010 Poly (styrene - co - maleic anhydride) and Polystyrene Grafted with Poly(ether amines): Synthesis, Characterization and Gas Separation Performance Dissertation zur Erlangung des akademischen Grades Doktor der Naturwissenschaften (Dr. rer. nat) der Technischen Fakultät der Christian-Albrechts-Universität zu Kiel Diógenes Rojas Kiel 2010 1. Gutachter Prof. Dr. Volker Abetz 2. Gutachter Prof. Dr. Klaus Rätzke Datum der mündlichen Prüfung 15.11.2010 Acknowledgement After a difficult but satisfactory challenge to complete my Ph.D. I would like to express my gratitude towards my supervisor Prof. Dr. Peter Simon. His kindness, suggestions, and observations have been an enormous contribution to my project; I hope to have a chance to continue in this productive exchange of ideas and experiences in the future. I am also thankful to Dr. Luis Antonio de Almeida Prado for the collaboration and fruitful discussion of ideas generating a better and qualified work. Special thanks go to my co-workers at GKSS- Institute of Polymer Research (Helmholtz-Zentrum Geesthacht) for having been helpful and contributing to my work; namely, Susanne Novak, Maren Brinkmann, Karen-Marita Prause, Silvio Neumann, Carsten Scholles and Brigitte Lademann. I also thank Dr. Wilfredo Yave and Dr. Carmen Nistor for the abundant information and discussion about the gas separation membrane. Furthermore, I am grateful to Connie Kampmann to have been a great spiritual support during my journey to complete my Ph.D. Finally, I would like to thank all of my family in Venezuela for understanding why I could not be near them during the last years. “Parao” “Sí; Pagué el precio que paga el que no vive arrodillao…” Rubén Blades Table of Contents Table of Contents ………………………………………………………………………….. i List of Figures ………………………………………………………………………… vii List of Tables ……………………………………………………………………….. xvi Chapter I Introduction ……………………………………………………….. 1 1.1 CO 2 and CH 4 : Emissions and Management ……………………………………..2 • Polymer Membranes for Gas Separation …………………………………2 1.2 Motivation of the Thesis ………………………………………………………….3 1.3 Outline of the Work ………………………………………………………….3 1.4 Objectives ………………………………………………………………………….4 1.5 References ………………………………………………………………………….5 Chapter II Theoretical Background ………………………………………….. 7 2.1 Polystyrene and Poly(styrene-co -maleic anhydride): History, Properties and Applications …………………………………………..8 2.1.1 Polystyrene ………………………………………………………………….8 2.1.2 Styrene-co -Maleic Anhydride……………………………………………….8 2.1.3 Properties of Polystyrene and Poly(styrene-co -maleic anhydride)……..9 2.2 Synthesis of PS, SMA and Polymer Structures …………………………………11 2.2.1 Synthesis of Polystyrene ………………………………………………...11 2.2.2 Synthesis of Poly(styrene-co -maleic Anhydride)………………………..14 2.2.3 Polymeric Structure of the PS and SMA …………………………………17 i 2.3 Chemical Modification of PS and SMA: Grafting - Functionalization …………18 2.3.1 Functionalization ………………………………………………………...18 2.3.2 Graft-Copolymers ………………………………………………………...19 2.4 Polyethylene Glycol: Structure and Characteristic………………………………20 2.5 Poly(ether amines): Jeffamine (Mono-functional) Applications, Properties and Reactions ………………………………………………………...21 2.5.1 Reactions of Poly(ether amines) (Jeffamine)…………………………….22 2.5.2 Direct Amidation…………………………………………………………….23 2.5.3 Properties and Applications of the Jeffamine……………………………24 2.6 Graft-Copolymers via Sulfonation ………………………………………………...25 • Challenges of the Synthesis of Graft-Copolymer via Sulfonation……..26 2.7 Membrane Based for Gas Separation. Theory Models…………………………26 2.7.1 Solution-Diffusion Model ………………………………………………...27 2.7.2 The Pore-Flow Model ………………………………………………...27 2.8 Polymers Structures, Materials and Types of Membranes…………………….33 2.9 Membranes Preparation and Classification by Morphology……………………36 • Flow Configurations of Membrane Processes …………………………37 2.10 Key Industrial Applications ………………………………………………………...40 • Carbon Dioxide Separation………………………………………………..42 2.11 Permeability: Definition - Models, Polymer Structure and Permeation……….43 2.11.1 Definition – Models ………………………………………………………...43 2.11.2 Relationship of Polymer Structure and Membrane Permeation……….45 2.12 Robeson Models ………………………………………………………………...51 2.13 References ………………………………………………………………...54 ii Chapter III Characterization and Instrumentation …………………………… 60 3.1 Thermal Analysis ……………………………………………………………………60 3.1.1 Differential Scanning Calorimetry (DSC) …………………………………………60 • DSC Measurements………………………………………………………..62 3.1.2 Thermogravinetric Analysis (TGA)………………………………………………..62 • TGA Measurements ………………………………………………………..63 3.2 Fourier Transform Infrared Spectroscopy (FT-IR)………………………………64 • FT-IR Measurements ………………………………………………………65 3.3 Nuclear Magnetic Resonance Spectroscpy (NMR)……………………………..65 • NMR Measurements………………………………………………………..67 3.4 Gel Permeation Chromatography (GPC)………………………………………...67 • Gel Permeation Chromatography Measurements………………………71 3.5 Scanning Electron Microscopy (SEM)……………………………………………72 • Electron Microscopy Images………………………………………………74 3.6 Elementary Analysis (EA) ………………………………………………………...74 • Elementary Analysis Measurements……………………………………...75 3.7 References ………………………………………………………………………...77 Chapter IV Grafting of Poly(styrene-co -maleic anhydride) via Maleic Anhydride with Poly(ether amines)…….………………… 79 4.1 Experimental Part ………………………………………………………………...80 4.1.1 Materials ………………………………………………………………...80 4.1.2 Preparation of Graft-Copolymers …………………………………………81 4.2 Results and Discussion…………………………………………………………….82 iii 4.2.1 1H-NMR and 13 C-NMR Analysis …………………………………………82 4.2.2 Gel Permeation Chromatography (GPC)………………………………...87 4.3.3 Thermal Properties of the Graft-Copolymers…………………………….92 4.3.3.1 Differential Scanning Calorimetric (DSC)……………………….. 92 4.3.3.2 Variation of Glass Transition Temperature with the [PEG]…… 97 4.3.3.3 Thermal Stability of the Graft-Copolymers (TGA)……………… 98 4.3 Conclusions ……………………………………………………………………….100 4.4 References ……………………………………………………………………….101 Chapter V Grafting of Poly(styrene) and Poly(styrene-co-maleic anhydride) via Sulfonation…………………………………………………………… 103 5.1. Experimental Part ……………………………………………………………….104 5.1.1. Materials ……………………………………………………………….104 5.1.2. Graft-Copolymer Synthesis………………………………………………104 5.1.2.1 Homogeneous Sulfonation of Polystyrene……………………. 104 5.1.2.2 Amidation of the Sulfonated Polymer………………………….. 106 5.2 Results and Discussion ……………………………………………………….109 5.2.1 Characterization. Evaluation of the Sulfonation ………………………..109 5.2.1.1 Sulfonation Degree by Elemental Analysis…………………… 109 5.2.1.2 Gel Permeation Chromatography Analysis…………………… 110 5.2.1.3 Thermal Analysis: DSC and TGA………………………………. 112 • Differential Scanning Calorimetric (DSC)………………………. 112 • Thermogravimetric Analysis (TGA)……………………………... 114 5.2.1.4 FT-IR Spectroscopy……………………………………………… 116 iv 5.2.2 Characterization of Graft-copolymer: SMA-SO 3H-Jeffamine and PS-SO 3H-Jeffamine……………………………………………………………….118 5.2.2.1 Analysis by 1H-NMR …………………………………………….. 118 5.2.2.2 FT-IR Spectroscopy …………………………………………….. 122 5.2.2.3 Gel Permeation Chromatography……………………………… 124 5.2.2.4 Thermal Analysis: DSC and TGA………………………………. 125 • Differential Scanning Calorimetric (DSC)………………………. 125 • Thermogravimetric Analysis (TGA)……………………………... 127 5.3 Conclusions ……………………………………………………………………….130 5.4 References ……………………………………………………………………….131 Chapter VI Membrane Properties of Series-ML,-MM and -MH and Series -GSMA and –GPSS……………………………………………... 133 6.1 Experimental Part ……………………………………………………………….134 6.1.1 Preparation of the Membrane……………………………………………134 6.1.2 Single Gas Measurements and Determination of Permeability………136 6.2 Results and Discussion ……………………………………………………….140 6.2.1 Characterization and Analysis of the Membranes Series-ML, -MM, -MH by SEM ……………………………………….140 6.2.1.1 Membranes Based on Series-L Graft-Copolymer, -ML……… 140 6.2.1.2 Membranes Based on Series-M Graft-Copolymer, -MM…….. 142 6.2.1.3 Membranes Based on Series-H Graft-Copolymer, -MH…….. 144 6.2.2 Characterization and Analysis of the Membranes Series-GSMA and -GPSS by SEM ……………………………………………………….147 v 6.2.3 Membranes Properties of Series-ML, Series-MM and Series-MH .....151 6.2.3.1 Analysis of CO 2 Permeability and the CO 2/N 2 Selectivity …… 152 6.2.3.2 Analysis of CH 4 Permeability and the CO 2/CH 4 Selectivity …160 6.2.3.3 Comparison of Membranes Performance between Series-ML, -MM and -MH, Polyimides and others Polymers Reported ………………………………………………. 162 6.2.5 Membranes Properties of Series-GSMA and Series-GPSS ………..170 6.2.5.1 Membranes Properties Dependency with the PEG Content ………………………………………………. 171 6.2.5.2 Membranes Properties Dependency with Tg ……………….. 173 6.3 Conclusions ……………………………………………………………………….176 6.4 References ……………………………………………………………………….178 Chapter VII Summary …………………………………………………………………. 181 7.1 Summary ……………………………………………………………………….181 7.2 Zusammenfassung ……………………………………………………………….184 Chapter VIII Appendix ………………………………………………………………. 189 vi List of Figures Figure 1.1: Schematic overview of the components of the global climate system that is relevant to climate changes, their processes and interactions, and some elements that may change, reproduced from IPCC-Technical paper II…….…………………………..1 Figure 1.2: Radiative