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Application of Barton Esters in Polymer Modification. Timothy S Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1999 Application of Barton Esters in Polymer Modification. Timothy S. Evenson Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Evenson, Timothy S., "Application of Barton Esters in Polymer Modification." (1999). LSU Historical Dissertations and Theses. 6887. https://digitalcommons.lsu.edu/gradschool_disstheses/6887 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 manuscript has been reproduced from the microfilm master. U M I films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type o f computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely afreet reproduction. In the unlikely event that the author did not send UM I a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note w ill indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back o f the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6” x 9” black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact U M I directly to order. UMI A Bell & Howell Information Company 300 North Zeeb Road, Ann Arbor M I 48106-1346 USA 313/761-4700 800/521-0600 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. APPLICATION OF BARTON ESTERS IN POLYMER MODIFICATION 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 o f Philosophy in The Department of Chemistry by Timothy S. Evenson B.S., University of Missouri-Rolla, 1994 May, 1999 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. DM1 Number: 9925528 UM I Microform 9925528 Copyright 1999, by U M I Company. A ll rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. UMI 300 North Zeeb Road Ann Arbor, M I 48103 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGMENTS A great deal of thanks to my major professor, Dr. William H. Daly. His advice and knowledge in polymer and organic chemistry have been extremely beneficial. I would also like to thank my committee members: Professors Mark L McLaughlin, Robert P. Hammer, James Melenkevitz, Robert Strongin, and special thanks to Professor Billie Collier. My gratitude to Paul Russo, loan Negulescu, Tracy McCarley, and Cindy Henk of LSU, and Drew Poche of Southeastern Louisiana University for their help and advice. I would like to thank the Graduate School for supporting me financially with a fellowship. Thanks also to the Department of Chemistry for providing teaching experience and further financial support. I would like to acknowledge the following research group members, fellow graduate students, and undergraduates: Jack Davies, Javier Macossay, Javier Nakamatsu, Xioalan Wang, Melissa Manuszak-Guerrini, Pei-Hung Yeh, Dewayne Logan, Loren Price, Sabrina Ratcliff, Elena Temyanko, Brian Fong, Garrett Doucet, Randy Cush, Patrick Lewis, Barry Misquitta, Stephanie Fredrickson, Kern Patteson, Holly Ricks, Tommy Menuet, Laura Wolf, Anthony and Earl. To all those who befriended me but were not mentioned here, I appreciate it. Finally, I would like to thank my family for their love, support, and encouragement. ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS ACKNOWLEDGMENTS.................................................................................ii LIST OF TA B LE S.......................................................................................... v LIST OF FIGURES....................................................................................... vi LIST OF ABBREVIATIONS.........................................................................viii ABSTRACT....................................................................................................ix CHAPTER 1 LITERATURE REVIEW.......................................................... 1 1.1. Polymer Architecture .................................................................. 1 1.2. Polymerization Mechanisms ..................................................... 2 1.3. Graft Copolymers ....................................................................... 4 1.4. Controlled Radical Polymerization ............................................ 8 1.5. Barton Esters ............................................................................15 CHAPTER 2 HOMOPOLYMERIZATION.................................................. 21 2.1. Barton Esters in Free Radical Polymerizations ......................21 2.2. Polymerization Mechanism ..................................................... 23 2.3. Polymerization Kinetics ........................................................... 29 2.4. Materials ....................................................................................34 2.5. Characterization .......................................................................35 2.6. Homopolymerizations .............................................................. 36 CHAPTER 3 GRAFT COPOLYMERIZATION...........................................39 3.1. Acryloyl Chloride Derivatives ...................................................39 3.2. Styrene Benzoate Derivatives ................................................ 42 3.3. Experimental ............................................................................ 48 3.3.1. Graft Copolymer Synthesis ....................................... 50 CHAPTER 4 POLY(ARYLENE ETHER SULFONE) MODIFICATION.....................................................................52 4.1. Introduction ............................................................................... 52 4.2. Poly(arylene ether sulfone)-gra/?-polystyrene ........................ 53 4.3. Other Grafts from Poly(arylene ether sulfone) ....................... 63 4.4. Experimental .............................................................................66 4.4.1. Additional Graft Copolymers .....................................69 4.4.2. Methyl Methacrylate Grafts ....................................... 69 4.4.3. Vinylpyridine Grafts ................................................... 70 4.4.4. Acrylamide Grafts ...................................................... 72 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CHAPTER 5 CELLULOSE MODIFICATION.............................................73 5.1. Introduction ................................................................................ 73 5.2. Grafting from Carboxymethyl Cellulose .................................. 73 5.3. Grafting from Hydroxypropyl Cellulose ....................................77 5.4. Experimental .............................................................................. 83 5.4.1. HPC-graff-polystyrene ............................................... 84 5.4.2. HPC-graft-polyacrylamide ..........................................86 CHAPTER 6 CONTROLLED RADICAL POLYMERIZATION................... 88 6.1. Synthesis of TEMPO Unimers ..................................................88 6.2. Controlled Grafting from Poly(arylene ether sulfone) ............ 90 6.3. Controlled Grafting from Hydroxypropyl Cellulose ................. 92 6.4. Experimental .............................................................................. 97 6.4.1. Unimer Preparation .................................................... 97 6.4.2. Poly(arylene ether sulfone)-TEMPO Adducts 99 6.4.3. HPC-TEMPO Adducts .............................................. 101 CHAPTER 7 CONCLUSIONS .................................................................. 103 7.1. Research Summary ............................................................... 103 7.2. Future W ork .............................................................................105 BIBLIOGRAPHY..........................................................................................107 VITA ..............................................................................................................111 iv Reproduced with permission of the copyright owner. Further
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