Synthesis of Poly(Vinylcatechols). Saad Moulay Louisiana State University and Agricultural & Mechanical College
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Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1986 Synthesis of Poly(vinylcatechols). Saad Moulay Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Moulay, Saad, "Synthesis of Poly(vinylcatechols)." (1986). LSU Historical Dissertations and Theses. 4197. https://digitalcommons.lsu.edu/gradschool_disstheses/4197 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]. 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Other ___________________________________________________________________________ University M icrofilm s International SYNTHESIS OF POLY(VINYLCATECHOLS) A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The department of Chemistry by Saad Moulay B.S., University d'Alger (U.S.T.A.), 1979 August 1986 ACKNOWLEDGMENTS The author wishes to express his sincere gratitude to his major Professor, Dr.William H.Daly for his special guidance, understanding, and encouragement. His kindness, his help, and his patience will never be forgotten. The author acknowledges Dr.R.J.Gale for his helpful discussion and his assistance. Many thanks are extended to the faculty of the chemistry department from whom I learned the science of chemistry. The financial assistance received from Louisiana State University, Baton Rouge and from Dr. Charles E. Coates Memorial Foundation for the preparation of this dissertation is gratefully acknowl edged. The author also wishes to extend his gratitude to his beloved parents, his wife, and his children who patiently waited for the completion of this work. i i TABLE OF CONTENTS Page ACKNOWLEDGMENTS................................................................................................. i i LIST OF TABLES.................................................................................................. v i i i LIST OF FIGURES................................................................................................ X LIST OF SCHEMES...................................................................................... x i i i ABSTRACT................................................................................................................. xv INTRODUCTION......................................................................................... 1 A. Polymer Reagents in Organic Synthesis ............................ 1 I. Polymer Transfer Agents ................................................ 4 II. Polymer Catalysts ............................... 9 1. Polymer-bound transition metal complexes ...................................................................... 11 2. Immobilized enzymes ............................................... 19 III. Polymers as Protecting Groups .................................. 17 B. Redox Polymers ................................................................................. 22 I. Synthesis of Redox Polymers..... ........................... 24 1. Condensation polymers .......................................... 24 2. Attachment of redox units onto preformed polymers ................................................. 33 3. Vinyl polymers .......................................................... 40 II. Properties of Redox Polymers .................................... 54 1. Condensation polymers .......................................... 34 2. Vinyl polymers .......................................................... 36 III. Applications ......................................................................... 50 C. Objectives .......................................................................................... 60 RESULTS AND DISCUSSION................................................................................. 62 A. Monomer Syntheses ............................................................................ 6 ? B. Polymerization Reactions of Monomers ................................. 69 I. Homopolymerization ................... 69 1. Free radical initiation ..................................... 69 2. Dilatometric study of the homopolymerization of monomer 30................ 71 3. Cationic polymerization ..................................... 73 4. Anionic polymerization ........................................ 74 i i i II. Copolymerization Reactions of Monomers 30 and 31 with Styrene and Methyl Methacrylate.. 77 III. Graft Copolymerization on Poly( vinyl catechol) Precursors ................................... 90 C. Thermal Stability of the Poly(vinyl catechol) Precursors ........................................................................................... 94 D. Chemical Modification of Poly(vinyl catechol) Precursors ........................................................................................... 99 I. Chloromethylation Reaction ......................................... 100 II. Quaternization of Chloromethylated Poly(6-vi ny 1 -1 ,4-benzodi oxane) ................................. ■) q 2 III. Synthesis and Chloromethylation of Model Compounds ................................................................................. 103 IV. Lithiation Reaction ......................................................... 104 V. Bromination Reaction ........................................................ 105 VI. Cyanogenation Reaction ................................................... 116 VII. Ami nomethyl ation Reaction ............................................ 123 VIII. Sulfonation Reaction ........................................................ 128 IX. Sulfomethylation Reaction ............................................ 130 E. Removal of the Blocking Groups ........................................... 131 F. Oxidation of Poly(vinylcatechols) to the Corresponding Poly(benzoquinones) ...................................... 140 G. Potentiometric Titration of Poly(3-vinylcatechol). 141 EXPERIMENTAL METHODS...................................................................................... 1 54 A. General Information .................................................................... 154 B. Syntheses of Monomers. ............................................................. 155 Method A: Dehydration of 5-(l'-hydroxyethyl)- 1,3-benzodioxole 158 a. Preparation of 5-(l'-hydroxyethyl)- 1.3-benzodioxole ............................................... 158 b. Dehydration of 5-(l'-hydroxyethyl)- 1.3-benzodioxol e ...................................................... 158 Method B: Decarboxylation of 3,4- methyl enedioxycinnamic acid .......................... 159 Method C: Wittig methenation ofpiperonal 159 i v Method D: Wittig reaction