University of North Dakota UND Scholarly Commons Theses and Dissertations Theses, Dissertations, and Senior Projects January 2019 The ffecE t Of Different Dianhydride Precursors On The yS nthesis, Characterization And Gas Separation Properties Of PI And PBO Derived From BisAPAF Maram Abdulhakim Qasem Al-Sayaghi Follow this and additional works at: https://commons.und.edu/theses Recommended Citation Al-Sayaghi, Maram Abdulhakim Qasem, "The Effect Of Different Dianhydride Precursors On The yS nthesis, Characterization And Gas Separation Properties Of PI And PBO Derived From BisAPAF" (2019). Theses and Dissertations. 2445. https://commons.und.edu/theses/2445 This Thesis is brought to you for free and open access by the Theses, Dissertations, and Senior Projects at UND Scholarly Commons. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of UND Scholarly Commons. For more information, please contact [email protected]. THE EFFECT OF DIFFERENT DIANHYDRIDE PRECURSORS ON THE SYNTHESIS, CHARACTERIZATION AND GAS SEPARATION PROPERTIES OF PI AND PBO DERIVED FROM BISAPAF By Maram Abdulhakim Qasem Al-Sayaghi Bachelor of Engineering, University of Leeds, UK, 2016 A Thesis Submitted to the Graduate Faculty of the University of North Dakota In partial fulfillment of the requirements for the degree of Master of Science Grand Forks, North Dakota May 2019 Copyright 2019 Maram Al-Sayaghi ii PERMISSION Title The effect of different dianhydride precursors on the synthesis, characterization and gas separation properties of PI and PBO derived from BisAPAF Department Chemical Engineering Degree Master of Science In presenting this thesis in partial fulfillment of the requirements for a graduate degree from the University of North Dakota, I agree that the library of this University shall make it freely available for inspection. I further agree that permission for extensive copying for scholarly purposes may be granted by the professor who supervised my thesis work or, in his absence, by the Chairperson of the department or the dean of the School of Graduate Studies. It is understood that any copying or publication or other use of this thesis or part thereof for financial gain shall not be allowed without my written permission. It is also understood that due recognition shall be given to me and to the University of North Dakota in any scholarly use which may be made of any material in my thesis. Maram Al-Sayaghi April, 15th, 2019 iv TABLE OF CONTENT ACKNOWLEDGEMENTS ............................................................................................................... xv ABSTRACT ........................................................................................................................................ xvi CHAPTER 1: EXECUTIVE SUMMARY ......................................................................................... 1 CHAPTER 2: A REVIEW OF THE FUNDAMENTALS OF POLYIMIDE MEMBRANES FOR NATURAL GAS SEPARATION ........................................................................................................ 5 2.1 Introduction ............................................................................................................... 5 2.2 Polymeric Membranes ............................................................................................ 11 2.2.1 Mass transfer principles in membranes .................................................................. 13 2.3 Polyimide Membranes ............................................................................................ 19 2.3.1 Properties of polyimides membranes .............................................................. 19 2.3.2 Chemistry & synthesis of polyimides membranes .......................................... 23 2.3.3 Thermal rearrangement of polyimides membranes ........................................ 33 2.4 Polyimide membranes for gas separation ............................................................... 35 2.5 Surface modification of polyimides ........................................................................ 40 2.5.3 Ion Irradiation ........................................................................................................ 43 2.6 Conclusions ................................................................................................................... 44 References ........................................................................................................................... 44 Appendix. 1 ......................................................................................................................... 55 References ........................................................................................................................... 58 CHAPTER 3: PHYSICOCHEMICAL AND THERMAL EFFECTS OF PENDANT GROUPS, SPATIAL LINKAGES AND BRIDGEING GROUPS ON THE FORMATION AND PROCESSING OF POLYIMIDES ................................................................................................... 60 3.1 Abstract ......................................................................................................................... 60 v 3.2 Introduction ................................................................................................................... 60 3.3 Experimental section ..................................................................................................... 63 3.2.1 Materials ................................................................................................................ 63 3.2.2 Polymer synthesis .................................................................................................. 65 3.2.3 Characterizations .................................................................................................... 66 3.4 Results and discussion .................................................................................................. 68 3.4.1 Solubility ................................................................................................................ 68 3.4.2 FTIR analysis ......................................................................................................... 71 3.4.3 Proton NMR analysis ............................................................................................ 73 3.4.4 GPC, DSC, TGA & XRD analyses ....................................................................... 76 3.5 Conclusions ................................................................................................................... 78 Acknowledgements ............................................................................................................. 79 References ........................................................................................................................... 79 CHAPTER 4: GAS SEPRATION USING POLYBENZOXAZOLE (PBO) MEMBRANES DERIVED FROM BISAPAF POLYIMIDES AND THE INFLUENCE OF DIANHYDRIDE PENDANT GROUPS ......................................................................................................................... 82 4.1 Abstract ......................................................................................................................... 82 4.2 Introduction ................................................................................................................... 82 4.3 Experimental Section .................................................................................................... 85 4.3.1 Materials ................................................................................................................ 85 4.3.2 Materials Preparation ............................................................................................. 86 4.4 Polymer Synthesis ......................................................................................................... 87 4.4.1 Hydroxyl polyamicacid (HPAA) synthesis ........................................................... 87 4.4.2 Hydroxyl polyimide (HPI) synthesis ..................................................................... 88 vi 4.5 Membrane Formation & Thermal Rearrangement ....................................................... 89 4.6 Characterization ............................................................................................................ 90 4.7 Gas Permeation Measurements ............................................................................... 92 4.8 Results and Discussion ................................................................................................. 93 4.9 Conclusions ................................................................................................................. 105 Reference .......................................................................................................................... 106 CHAPTER 5: SUPPLEMENTARY INFORMATION ................................................................. 109 5.1 Stage (1): Synthesis issues .......................................................................................... 109 5.1.1 Changing the amount of solvent .......................................................................... 110 5.1.2 Changing the reactant ratios ................................................................................. 112 5.1.3 Diamine purification ............................................................................................ 113 5.1.4 Precipitation method ...........................................................................................