Chemical Modifications of Condensation Polymers, Chloromethylation and Quaternization
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Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1983 Chemical Modifications of Condensation Polymers, Chloromethylation and Quaternization. Shih-jen Wu Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Wu, Shih-jen, "Chemical Modifications of Condensation Polymers, Chloromethylation and Quaternization." (1983). LSU Historical Dissertations and Theses. 3948. https://digitalcommons.lsu.edu/gradschool_disstheses/3948 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. 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Zeeb Road Ann Arbor, Ml 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 8413737 Wu, Shih’Jen CHEMICAL MODIFICATIONS OF CONDENSATION POLYMERS, CHLOROMETHYLATION AND QUATERNIZATION The Louisiana State University and Agricultural and Mechanical Col.Ph.D. 1983 University Microfilms International 300 N. Zeeb Road, Ann Arbor, Ml 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CHEMICAL MODIFICATIONS OF CONDENSATION POLYMERS, CHLOROMETHYLATION AND QUATERNIZATION A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College 1n partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Sh1h-Jen Uu B.S., Fu-Jen Catholic University, 1976 December 1983 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. To my mother, my family, and the memory of my father ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS The author would like to express his sincere appreciation to his major professor, William H. Daly, for his enthusiastic guidance and encouragement during the past years; his knowledge and Inspiration as a teacher w ill be remembered. Sincere thanks are given to professor Nikolaus H. Fischer and his wife Helga Fischer, and Dr. James Rlnker for their friendship and encouragement. The author thanks professors Dewey K. Carpenter and James G. Traynham for helpful discussions. The help and camaraderie of his laboratory partner, C. Rungaroonthaikul, 1s deeply esteemed. The author also wants to thank the Organic Division, Chemistry Department, for their assistance and friendship during his stay at Louisiana State University. The financial assistance received from Louisiana State Universlty-Baton Rouge and from Dr. Charles E. Coates Memorial Foundation for the preparation of this Dissertation are gratefully acknowledged. F in ally, the author would like to thank his family for their heartful encouragement and assistance. 11 i Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS page ACKNOWLEDGEMENTS..................................................................................... 1i1 LIST OF TABLES.................... v11 LIST OF FIGURES...................................................................................vi11 LIST OF SCHEMES xi 1 ABSTRACT...................................................................................................x111 Chapter 1. INTRODUCTION........................................................................... 1 1.1 Functionalization of Polymers ................................ 2 1.2 Chemical Reaction on Polymers ................................ 7 2. CHLOROMETHYLATION OF CONDENSATION POLYMERS.................... 13 2.1 Introduction........................................................................14 2.2 Chioromethylat1on ....................................................... 17 2.2.1 Reagents ....................................................................17 2.2.2 Catalyst Selection ................................................ 20 2.2.3 Reaction Conditions ....................................... 23 2.3 Synthesis and Chioromethylation of Polysulfone Model Compound ............................................ 40 2.4 Thermal Properties of Polysulfone Model .... 46 2.5 Experimental ........................................................................57 3. QUATERNIZATION OF CHLOROMETHYLATED CONDENSATION POLYMERS WITH TERTIARY AMINES........................................................................................... 68 3.1 Introduction........................................................................69 3.2 Quaternization of Polymeric Amines with Alkyl Halides............................................................70 3.3 Quaternization of Chioromethylated Polystyrene ...................................................... 75 1 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. page 3.4 Result and Discussion....................................................80 3.4.1 Quaternization of Chi oromethyl ated Polymers ................................ 87 3.4.2 Impact of Sterlc Hindrance ......................... 94 3.4.3 Impact of Added Electrolyte ............................. 97 3.4.4 Impact of Chain F le x ib ility ............................. 98 3.5 Experimental .......................................................... 109 4. QUATERNIZATION OF CHLOROMETHYLATED CONDENSATION POLYMERS WITH TERTIARY AMINES CONTAINING HYDROXYL GROUPS.................................. 113 4.1 Introduction................................................................. 114 4.2 Quaternization of Chioromethylated Polysulfone......................................................................115 4.3 Quaternization of Chioromethylated Acetylated Phenoxy Resin ....................................... 121 4.4 Summary Kinetic Results of Quaternization Chioromethylated Condensation Polymers .... 131 4.5 Experimental ................................................................. 135 5. PREPARATION AND CHARACTERIZATION OF QUATERNIZED CONDENSATION POLYMERS.................................. 136 5.1 Introduction.................................................................137 5.2 Preparation of Quaternlzed Polymers ......................137 5.3 Reaction of Chioromethylated Polysulfone with l,4-D1azabicyclo(2,2,2)octane .................... 155 5.4 Viscosity Study of Quaternlzed Polymers. 161 5.5 Experimental ................................................................ 167 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. page REFERENCES...............................................................................................170 VITA.......................................................................................................... 179 vi Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES Table page 2-1. Influence of Substrate:Catalyst Ratio on Chioromethylation of Poly [o*y-2,6-di methyl -1 ,4-phenylene] .................................... 25