Citation
An Alternative Approach for Synthesizing Polyglycolic Acid and Its Copolymers from C1 Feedstocks

Material Information

Title:
An Alternative Approach for Synthesizing Polyglycolic Acid and Its Copolymers from C1 Feedstocks
Creator:
Gokturk, Ersen
Publisher:
University of Florida
Publication Date:
Language:
English

Thesis/Dissertation Information

Degree:
Doctorate ( Ph.D.)
Degree Grantor:
University of Florida
Degree Disciplines:
Chemistry
Committee Chair:
MILLER,STEPHEN ALBERT
Committee Co-Chair:
POWELL,DAVID HINTON
Committee Members:
MCELWEE-WHITE,LISA ANN
APONICK,AARON
KAHVECI,TAMER
Graduation Date:
5/3/2014

Subjects

Subjects / Keywords:
Catalysts ( jstor )
Copolymerization ( jstor )
Epoxy compounds ( jstor )
Melting ( jstor )
Molecular weight ( jstor )
Oxides ( jstor )
Polymerization ( jstor )
Polymers ( jstor )
Recording instruments ( jstor )
Solvents ( jstor )
carbonmonoxide
polyglycolicacid
trioxane

Notes

General Note:
Over the last couple of years, replacing of petroleum-based products by biodegradable and biorenewable plastics has been burgeoning interests in polymer science. Large portions of trash in landfills are mostly petroleum based polymer materials, such as plastic bags and bottles. The degradability of these petroleum based materials takes a very long time, like thousands of years. Polyglycolic acid (PGA) is one of the most known biodegradable polymer, which is traditionally synthesized through anionic polymerization of glycolide (mostly with tin ocatanoate catalyst). Despite this route has been the best option for having higher yields and molecular weights; the need to use very expensive glycolide monomer is the limitation for the larger scale production of PGA for industry. The main objective of this research is to find an alternative way to synthesize Polyglycolic acid (PGA) and its copolymers that derive from sustainable C1 feedstocks, particularly formaldehyde and carbonmonoxide. The idea of the project consisted of the cationic alternating copolymerizations of trioxane (as a formaldehyde resource) and carbonmonoxide (CO) to produce PGA. This method constitutes cost-effective and efficient path for the synthesis of PGA from perfectly alternating copolymerizations of formaldehyde and CO. PGA was successfully synthesized up to 92% of yield by using triflic acid (TfOH) catalyst under 800 psi CO pressure at 170 oC in three days. Although very high conversion was observed from the copolymerization, the number average molecular weights of the products exhibited oligomeric glycolic acid (GA) structures. Therefore, polycondensation of oligoGA was applied by Zn(OAc)2.2H2O catalyst, and Mn was raised up to 700 KDa. The polymer from CO and H2CO is sufficiently similar to that prepared from glycolide that it can be readily substituted for the PGA prepared from glycolide. The products show nearly identical 13C NMR spectra, free of acetal carbon signals, are observed for commercial PGA and the PGA from the C1 feedstocks. To improve on the physical properties of PGA (such as melting temperature and appearance) terpolymerizations of trioxane, CO and a minor amount of epoxides were performed at the same reaction condition as PGA synthesis. By controlling the comonomer feed ratios and the polymerization temperatures, high quality PGA can be prepared. The method is extended to copolymers of PGA where alkylene oxides or cyclic ether comonomers are included into the polymerization mixture with the C1 monomers to yield polyester-ether thermoplastics. The melting temperatures of all terpolymers are also lower, and the colors have become lighter than the commercial PGA. Polymer solubility increased by increasing length of the side chains of epoxides. One of the products has indicated similar thermal properties to isotactic polypropylene. The PGA based copolymers will not only replace existing petroleum based materials, but will do so with improved thermal characteristics. The needs of applying very high CO pressure and high temperature for the polymerization directed us to discover transition metal assisted copolymerization of formaldehyde and CO. There is a need to find new catalyst systems that exhibit higher activity to decrease polymerization time, temperature or CO pressure. Some of our efforts involved Co2(CO)8/3-hydroxypyridine catalyst system for this copolymerization, but this catalyst system seems to be not an effective catalyst for the copolymerization. After testing several catalyst systems, scandium triflate [Sc(OTf)3] catalyst exhibited very good activity towards the cationic copolymerization of trioxane with carbonmonoxide (CO) for the production of PGA from up to 78 % of yield. Sc(OTf)3 is an environmentally friendly catalyst and can be recycled from the reaction media. These present important advantages for a catalyst system, and polymerization will be a very convenient alternative way to produce PGA.

Record Information

Source Institution:
UFRGP
Rights Management:
Copyright Gokturk, Ersen. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Embargo Date:
5/31/2016

Downloads

This item has the following downloads:


Full Text

PAGE 1

AN ALTERNATIVE APPROACH FOR SYNTHESIZING POLYGLYCOLIC ACID AND ITS COPOLYMERS FROM C1 FEEDSTOCKS By ERSEN GOKTURK A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2014

PAGE 2

2014 Ersen Gokturk

PAGE 3

To my parents: Erdal and Nesibe Gokturk, And my wife and my unborn son

PAGE 4

4 ACKNOWLEDGMENTS First and foremost I thank Dr. S tephen A. Miller this work would not have been possible without his guidance and encouragement I really appreciate his great project and interesting ideas to make this work more productive. I would also like to thank to Dr. L isa McElwee White, Dr. A aron Aponick, Dr. David Powell, and Dr. Tamer Kahveci, for their mentoring and support throughout my PhD progra m at the University of Florida. In addition I want to thank the members of the Miller research group especially Alex, Amr, Betsy, Emma, Ha, John, Matt, Mayra, Nicole, and Pengxu and to all members of the Butler Polymer Program for their help and encouragem ents. I cannot end without thanking to my wife Ilknur, and my parents for giving me the strength and encouragement to achieve my PhD. Last but not least I would also like to thank the Turkish Ministry of National Education that has given me the scholarship to study abroad and get to know the University of Florida.

PAGE 5

5 TABLE OF CONTENTS page ACKNOWLEDGMENTS ................................ ................................ ................................ .. 4 LIST OF TABLES ................................ ................................ ................................ ............ 8 LIST OF FIGURES ................................ ................................ ................................ .......... 9 ABSTRACT ................................ ................................ ................................ ................... 38 CHAPTER 1 A BIODEGRADABLE POLYMER: POLYGLYCOLIC ACID ................................ .... 40 Introduction ................................ ................................ ................................ ............. 40 Polyglycolic Acid ................................ ................................ ................................ ..... 41 The Most Commonly Used Synthetic Methods for PGA ................................ ......... 42 Polycondensation of Glycolic Acid ................................ ................................ .... 42 Ring Opening Polymerization of Glycolide ................................ ....................... 43 Solid State Polycondensation of Halogenoacetates ................................ ......... 46 2 THE SYNTHESIS OF POLYGLYCOLIC ACID FROM C1 FEEDSTOCKS ............. 47 Background ................................ ................................ ................................ ............. 47 Previous Work ................................ ................................ ................................ .. 47 Cationic Ring Opening Polymerization of Trioxane ................................ .......... 48 Copolymerizations of Trioxane and Carbon Monoxide ................................ ........... 49 Results and Discussion ................................ ................................ ........................... 50 Experi mental ................................ ................................ ................................ ........... 61 General Considerations and Instrumentation ................................ ................... 61 Representative Polymerization Procedure for Table 2 1 ................................ .. 62 General Polymerization Procedure for Table 2 2 ................................ ............. 63 General Polymerization Procedure for Table 2 3 ................................ ............. 63 The Production of PGA from Chain End Active POM ................................ ....... 64 Polycondensation of OligoGA (entry 5.1) ................................ ......................... 64 3 POLYGLYCOLIC ACID COPOLYMERS FOR REPLACING COMMODITY PLASTICS ................................ ................................ ................................ .............. 66 The Ring Opening Polymerizations of Epoxides ................................ ..................... 66 PGA Terpolymers with Epoxides ................................ ................................ ............ 67 Results and Discussion ................................ ................................ ........................... 68 Propylene oxide incorporation ................................ ................................ .......... 69 Conclusion ................................ ................................ ................................ .............. 75 Experimental ................................ ................................ ................................ ........... 76 General Considerations and Instrumentation ................................ ................... 76

PAGE 6

6 Representative Copolymerization Procedure for Epoxide Incorporation .......... 77 Butylene oxide incorporation ................................ ................................ ...... 77 Hexylene oxide incorporation ................................ ................................ ..... 78 Cyclohexene oxide incorporation ................................ ............................... 78 Epoxy octane incorporation ................................ ................................ ........ 79 Glycidol incorporation ................................ ................................ ................ 79 Epichlorohydrin incorporation ................................ ................................ ..... 80 4 PGA BASED COPOLYMERS FROM CYCLIC ETHERS ................................ ........ 81 Background ................................ ................................ ................................ ............. 81 Results and Discussion ................................ ................................ ........................... 81 Conclusion ................................ ................................ ................................ .............. 83 Experimental ................................ ................................ ................................ ........... 84 General Considerations and Instrumentation ................................ ................... 84 Preparation of Dioxolane ................................ ................................ ........... 85 Preparation of 1,3 Dioxane. ................................ ................................ ....... 85 Representative Terpolymerization Procedure for Cyclic Ether Incorporations 86 Dioxolane incorporation results ................................ ................................ .. 86 1,4 Dioxane incorporation results ................................ .............................. 87 1,3 Dioxane incorporation results ................................ .............................. 87 5 TRANSITION METAL CATALYZED COPOLYMERIZATION OF TRIOXANE AND CARBON MONOXIDE ................................ ................................ ................... 88 Introduction ................................ ................................ ................................ ............. 88 Results and Discussion ................................ ................................ ........................... 89 Co 2 (CO) 8 Catalyzed Copolymerization of Trioxane and CO ............................. 89 Sc(OTf) 3 Catalyst in Polymer Chemistry ................................ ........................... 93 Sc(OTf) 3 Catalyzed Copolymerization of Formaldehyde and CO ..................... 94 Experimental ................................ ................................ ................................ ......... 100 General Considerations and Instrumentation ................................ ................. 100 Representative Polymerization Procedure for Co 2 (CO) 8 Catalyzed Reactions (entries 1.1 1.5 in Table 5.1): ................................ ..................... 101 Representative Polymerization Procedure for Sc(OTf) 3 Catalyzed Reactions (entries 2.1 2.19 in Table 5.2): ................................ ................................ .... 102 6 CONCLUSION ................................ ................................ ................................ ...... 103 Summary of Results ................................ ................................ .............................. 103 Future D irections ................................ ................................ ............................ 104 How about using different aldehydes other than formaldehyde? ............. 106 APPENDIX A SUPPLEMENTARY INFORMATION FOR CHAPTER 2 ................................ ....... 108 FT IR Spectra ................................ ................................ ................................ ....... 108

PAGE 7

7 Thermogravimetric Analyses ................................ ................................ ................ 117 Differential Scanning Calorimetry Thermograms ................................ .................. 130 1 H NMR Spectra ................................ ................................ ................................ ... 143 13 C NMR Spec tra ................................ ................................ ................................ .. 152 Gel Permeation Chromatography (GPC) Data ................................ ...................... 161 A Picture of Our Product and Commercial PGA ................................ ................... 168 B SUPPLEMENTARY INFORMATION FOR CHAPTER 3 ................................ ....... 169 FT IR Spectra ................................ ................................ ................................ ....... 169 Thermogravimetric Analyses ................................ ................................ ................ 182 Differential Scanning Calorimetry Thermograms ................................ .................. 200 1 H NMR Spectra ................................ ................................ ................................ ... 219 13 C NMR Spec tra ................................ ................................ ................................ .. 231 Gel Permeation Chromatography (GPC) Data ................................ ...................... 243 C SUPPLEMENTARY INFORMATION FOR CHAPTER 4 ................................ ....... 253 FT IR Spectra ................................ ................................ ................................ ....... 253 Thermogravimet ric Analyses ................................ ................................ ................ 260 Differential Scanning Calorimetry Thermograms ................................ .................. 269 1 H NMR Spectra ................................ ................................ ................................ ... 279 13 C NMR Spectra ................................ ................................ ................................ .. 285 Gel Permeati on Chromatography (GPC) Data ................................ ...................... 291 D SUPPLEMENTARY INFORMATION FOR CHAPTER 5 ................................ ....... 298 FT IR Spectra ................................ ................................ ................................ ....... 298 Thermogravimet ric Analyses ................................ ................................ ................ 306 Differential Scanning Calorimetry Thermograms ................................ .................. 316 1 H NMR Spectra ................................ ................................ ................................ ... 327 13 C NMR Spectra ................................ ................................ ................................ .. 334 Gel Permeation Chromatography (GPC) Data ................................ ...................... 342 LIST OF REFERENCES ................................ ................................ ............................. 350 BIOGRAPHICAL SKETCH ................................ ................................ .......................... 353

PAGE 8

8 LIST OF TABLES Table page 2 1 Copolymerization results of trioxane and CO by Br nsted acid and Lewis acid catalysts. ................................ ................................ ................................ ..... 53 2 2 Cationic copolymerization results of trioxane and CO with addition of glycerol. ................................ ................................ ................................ .............. 55 2 3 Copolymerization results of paraformaldehyde and CO catalyzed by triflic acid. ................................ ................................ ................................ .................... 60 2 4 G3(MP2)/DFT calculation for gas phase copolymerization thermodynamics. a ... 61 3 1 Terpolymerization of trioxane, propylene oxide (PO) and CO. ........................... 69 3 2 Results of epoxide incorporation in the PGA backbone (see Tables 3 3 to 3 8 for additional information). ................................ ................................ .................. 71 3 3 Terpolymerization of trioxane, butylene oxide (BO) and CO. ............................. 77 3 4 Terpolymerization of trioxane, hexylene oxide (HO) and CO. ............................ 78 3 5 Terpolymerization of trioxane, cyclohexeneoxide (CHO) and CO. ..................... 78 3 6 Terpolymerization of trioxane, epoxyoctane (EO) and CO. ................................ 79 3 7 Terpolymerization of trioxane, glycidol (G) and CO. ................................ ........... 79 3 8 Terpolymerization of trioxane, epichlorohydrin (ECH) and CO. .......................... 80 4 1 Cyclic ether incorporation results in PGA backbone. ................................ .......... 83 4 2 Terpolymerization of trioxane, dioxolane and CO. ................................ .............. 86 4 3 Terpolymerization of trioxane, 1,4 dioxane and CO. ................................ .......... 87 4 4 Terpolymerization of trioxane, 1,3 dioxane a nd CO. ................................ .......... 87 5 1 Terpolymerization of propylene oxide, trioxane and CO by Co 2 (CO) 8 catalyst system. ................................ ................................ ................................ ............... 92 5 2 Copolymerization results of trioxane and CO by using Sc(OTf) 3 catalyst. .......... 95 5 3 Terpolymerization results of trioxane, propylene oxide and CO using Sc(OTf) 3 catalyst. ................................ ................................ ............................. 100 6 1 G3(MP2)/DFT calculation for gas phase copolymerization thermodynamics. a 107

PAGE 9

9 LIST OF FIGURES Figure page 1 1 The structure of the polyglycolic acid (PGA) repeat unit. ................................ .... 41 1 2 Three main synthesis methods for the preparation of PGA. ............................... 42 1 3 Polycondensation of glycolic acid. ................................ ................................ ...... 42 1 4 Three examples of ring opening polymerizations. 18 ................................ ........... 43 1 5 The mechanism of the ring opening polymerization of glycolide by Sn(II) octanoate catalyst. ................................ ................................ .............................. 45 1 6 Solid state polycondensation of halogenoacetates. ................................ ............ 46 2 1 Synthesis of Carilon and PGA. ................................ ................................ ........... 47 2 2 Cationic copolymerization of trioxane and CO in chlorosulfonic acid. 32 .............. 48 2 3 BF 3 .OEt 2 catalyzed copolymerization of trioxane and CO. 33 ............................... 48 2 4 Cationic polymerization mechanism of polyoxymethylene (POM). ..................... 49 2 5 Stepwise production of PGA via two different routes. ................................ ......... 50 2 6 Synthesis of PGA from trioxane and CO under Lewis acidic conditions. ............ 51 2 7 The possible side reaction of the cationic polymerization of trioxane, and the formation of polyoxymethylene. 38 ................................ ................................ ....... 51 2 8 High molecular weight PGA pr oduction from polycondensation of oligoGA. ...... 54 2 9 Utilization of glycerol as a branching agent for PGA production. ........................ 54 2 11 FT IR spectra of commercial PGA and entry 5.1 in Figure 2 8. .......................... 56 2 12 13 C NMR spectra of commercial PGA and entry 5.1 in Figure 2 8. ..................... 57 2 13 Dependence of the melting temperatures ( o C), and molecular weights (M n ) of PGA on increasing polymerization temperature. ................................ ................ 58 2 14 The possible polymerization mechanism of PGA synthesis. .............................. 59 2 15 PGA production from paraformaldehyde and CO. ................................ .............. 59 2 16 PGA production from chain end active po lyoxymethylene and CO. ................... 60

PAGE 10

10 2 17 High pressure polymerization vessel. ................................ ................................ 65 3 1 Anionic and cationic ring opening polymerizations of epoxides. ......................... 67 3 2 The possible polymerization mechanism for epoxide incorporation in PGA backbone. ................................ ................................ ................................ ........... 72 3 3 Comparative melting point trends for terpolymers prepared at 100 o C. .............. 73 3 4 HSQC NMR Spectrum of entry 6.2 in Table 3 6. ................................ ................ 74 5 1 The structures of a polyketone, polyester, and polycarbonate. ........................... 88 5 2 Synthesis of Carilon from the copoly merization of ethylene and CO. ................. 88 5 3 Polymerization of propylene oxide and CO by Co 2 (CO) 8 catalyst. ...................... 89 5 4 The possible polymerization mechanism of Co 2 (CO) 8 catalyzed synthesis of PGA. ................................ ................................ ................................ ................... 91 5 5 Effect of addition 1 mol % of Co 2 (CO) 8 catalyst into the triflic acid catalyzed polymerization of trioxane and CO. ................................ ................................ .... 91 5 6 Co 2 (CO) 8 catalyzed terpolymerization of propylene oxide, trioxane and CO. ..... 92 5 7 The effect of the formation of acylium ion as an initiator for trioxane and CO copolymerization. ................................ ................................ ................................ 93 5 8 Sc(OTf) 3 catalyzed aldol reaction of a silyl ether and formaldehyde. 59 ............... 93 5 9 Sc(OTf) 3 assisted polyester synthesis. 60 ................................ ............................ 94 5 10 The proposed mechanism for the copolymerization of trioxane and CO in Sc(OTf) 3 ................................ ................................ ................................ ............. 96 5 11 DSC analysis of the c ommercial PGA and polymer entry 2.16 in Table 5 2. ...... 97 5 12 13 C NMR spectra of the commercial PGA and polymer entry 2.16 in Table 5 2 98 5 13 FT IR spectra of the commercial PGA and polymer entry 2.16 in Table 5 2. ..... 99 5 14 Terpolymerization of trioxane, propylene oxide and CO by Sc(OTf) 3 ................ 99 6 1 The proposed terpolymerization of trioxane, CO and hexadecene oxide. ........ 105 6 2 The proposed PEG incorporation in PGA backbone. ................................ ....... 106 6 3 Unsuccessful attempts to produce PLA from the cationic copolymerization of Acetaldehyde an d CO. ................................ ................................ ..................... 107

PAGE 11

11 A 1 FT IR spectrum of polymer commercial polyglycolic acid. ................................ 108 A 2 FT IR spectrum of polymer 1.1 (Table 2 1, entry 1.1). ................................ ...... 108 A 3 FT IR spectrum of polymer 1.2 (Table 2 1, entry 1.2). ................................ ...... 109 A 4 FT IR spectrum of polymer 1.4 (Table 2 1, entry 1.4). ................................ ...... 109 A 5 FT IR spectrum of polymer 1.5 (Table 2 1, entry 1.5). ................................ ...... 109 A 6 FT IR spectrum of polymer 1.6 (Table 2 1, entry 1.6). ................................ ...... 110 A 7 FT IR spectrum of polymer 1.7 (Table 2 1, entry 1.7). ................................ ...... 110 A 8 FT IR spectrum of polymer 1.8 (Table 2 1, entry 1.8). ................................ ...... 110 A 9 FT IR spectrum of polymer 1.9 (Table 2 1, entry 1.9). ................................ ...... 111 A 10 FT IR spectrum of polymer 1.10 (Table 2 1, entry 1.10). ................................ .. 111 A 11 FT IR spectrum of polymer 1.11 (Table 2 1, entry 1.11). ................................ .. 111 A 12 FT IR spectrum of polymer 1.12 (Table 2 1, entry 1.12). ................................ .. 112 A 13 FT IR spectrum of polymer 1.13 (Table 2 1, entry 1.13). ................................ .. 112 A 14 FT IR spectrum of polymer 1.14 (Table 2 1, entry 1.14). ................................ .. 112 A 15 FT IR spectrum of polymer 1.15 (Table 2 1, entry 1.15). ................................ .. 113 A 16 FT IR spectrum of polymer 1.16 (Table 2 1, entry 1.16). ................................ .. 113 A 17 FT IR spectrum of polymer 1.17 (Table 2 1, entry 1.17). ................................ .. 113 A 18 FT IR spectrum of polymer 1.18 (Table 2 1, entry 1.18). ................................ .. 114 A 19 FT IR spectrum of polymer 1.19 (Table 2 1, entry 1.19). ................................ .. 114 A 20 FT IR spectrum of polymer 2.1 (Table 2 2, entry 2.1). ................................ ...... 114 A 21 FT IR spectrum of polymer 2.2 (Table 2 2, entry 2.2). ................................ ...... 115 A 22 FT IR spectrum of polymer 2.3 (Table 2 2, entry 2.3). ................................ ...... 115 A 23 FT IR spectrum of polymer 3.1 (Table 2 3, entry 3.1). ................................ ...... 115 A 24 FT IR spectrum of polymer 3.2 (Table 2 3, entry 3.2). ................................ ...... 116 A 25 FT IR spectrum of polymer 4.1 ( Figure 2 16, entry 4.1). ................................ .. 116

PAGE 12

12 A 26 FT IR spectrum of polymer 5.1 ( Figure 2 8, entry 5.1). ................................ .... 116 A 27 TGA Thermogram of commercial polyglycolic acid. ................................ .......... 117 A 28 TGA Thermogram of polymer 1.1 (Table 2 1, entry 1.1). ................................ .. 117 A 29 TGA Thermogram of polymer 1.2 (Table 2 1, entry 1.2). ................................ .. 118 A 30 TGA Thermogram of polymer 1.4 (Table 2 1, entry 1.4). ................................ .. 118 A 31 TGA Thermogram of polymer 1.5 (Table 2 1, entry 1.5). ................................ .. 119 A 32 TGA Thermogram of polymer 1.6 (Table 2 1, entry 1.6). ................................ .. 119 A 33 TGA Thermogram of polymer 1.7 (Table 2 1, entry 1.7). ................................ .. 120 A 34 TGA Thermogram of polymer 1.8 (Table 2 1, entry 1.8). ................................ .. 120 A 35 TGA Thermogram of polymer 1.9 (Table 2 1, entry 1.9). ................................ .. 121 A 36 TGA Thermogram of polymer 1.10 (Table 2 1, entry 1.10). .............................. 121 A 37 TGA Thermogram of polymer 1.11 (Table 2 1, entry 1.11). .............................. 122 A 38 TGA Thermogram of polymer 1.12 (Table 2 1, entry 1.12). .............................. 12 2 A 39 TGA Thermogram of polymer 1.13 (Table 2 1, entry 1.13). .............................. 123 A 40 TGA Thermogram of polymer 1.14 (Table 2 1, entry 1.14). .............................. 123 A 41 TGA Thermogram of polymer 1.15 (Table 2 1, entry 1.15). .............................. 124 A 42 TGA Thermogram of polymer 1.16 (Table 2 1, entry 1.16). .............................. 124 A 43 TGA Thermogram of polymer 1.17 (Table 2 1, entry 1.17). .............................. 125 A 44 TGA Thermogram of polymer 1.18 (Table 2 1, entry 1.18). .............................. 125 A 45 TGA Thermogram of polymer 1.19 (Table 2 1, entry 1.19). .............................. 126 A 46 TGA Thermogram of polymer 2.1 (Table 2 2, entry 2.1). ................................ .. 126 A 47 TGA Thermogram of polymer 2.2 (Table 2 2, entry 2.2). ................................ .. 127 A 48 TGA Thermogram of polymer 2.3 (Table 2 2, entry 2.3). ................................ .. 127 A 49 TGA Thermogram of polymer 3.1 (Table 2 3, entry 3.1). ................................ .. 128 A 50 TGA Thermogram of polymer 3.2 (Table 2 3, entry 3.2). ................................ .. 128

PAGE 13

13 A 51 TGA Thermogram of polymer 4.1 ( Figure 2 16, entry 4.1). .............................. 129 A 52 TGA Thermogram of polymer 5.1 ( Figure 2 8, entry 5.1). ................................ 129 A 53 DSC Thermogram of commercial polyglycolic acid. ................................ ......... 130 A 54 DSC Thermogram of polymer 1.1 (Table 2 1, entry 1.1). ................................ 130 A 55 DSC Thermogram of polymer 1.2 (Table 2 1, entry 1.2). ................................ 131 A 56 DSC Thermogram of polymer 1.4 (Table 2 1, entry 1.4). ................................ 131 A 57 DSC Thermogram of polymer 1.5 (Table 2 1, entry 1.5). ................................ 132 A 58 DSC Thermogram of polymer 1.6 (Table 2 1, entry 1.6). ................................ 132 A 59 DSC Thermogram of polymer 1.7 (Table 2 1, entry 1.7). ................................ 133 A 60 DSC Thermogram of polymer 1.8 (Table 2 1, entry 1.8). ................................ 133 A 61 DSC Thermogram of polymer 1.9 (Table 2 1, entry 1.9). ................................ 134 A 62 DSC Thermogram of polymer 1.10 (Table 2 1, entry 1.10). ............................. 134 A 63 DSC Thermogram of polymer 1.1 1 (Table 2 1, entry 1.11). ............................. 135 A 64 DSC Thermogram of polymer 1.12 (Table 2 1, entry 1.12). ............................. 135 A 65 DSC Thermogram of polymer 1.13 (Table 2 1, entry 1.13). ............................. 136 A 66 DSC Thermogram of polymer 1.14 (Table 2 1, entry 1.14). ............................. 136 A 67 DSC Thermogram of polymer 1.15 (Table 2 1, entry 1.15). ............................. 137 A 68 DSC Thermogram of polymer 1.16 (Table 2 1, entry 1.16). ............................. 137 A 69 DSC Thermogram of polymer 1.17 (Table 2 1, entry 1.17). ............................. 138 A 70 DSC Thermogram of polymer 1.18 (Table 2 1, entry 1.18). ............................. 138 A 71 DSC Thermogram of polymer 1.19 (Table 2 1, entry 1.19). ............................. 139 A 72 DSC Thermogram of polymer 2.1 (Table 2 2, entry 2.1). ................................ 139 A 73 DSC Thermogram of polymer 2 .2 (Table 2 2, entry 2.2). ................................ 140 A 74 DSC Thermogram of polymer 2.3 (Table 2 2, entry 2.3). ................................ 140 A 75 DSC Thermogram of polymer 3.1 (Table 2 3, entry 3.1). ................................ 141

PAGE 14

14 A 76 DSC Thermogram of polymer 3.2 (Table 2 3, entry 3.2). ................................ 141 A 77 DSC Thermogram of polymer 4.1 ( Figure 2 16, entry 4.1). .............................. 142 A 78 DSC Thermogram of polymer 5.1 ( Figure 2 8, entry 5.1). ................................ 142 A 79 1 H NMR spectrum of HFIP in CDCl 3 ................................ ................................ 143 A 80 1 H NMR spectrum of commercial polyglycolic acid in HFIP + CDCl 3 ............... 143 A 81 1 H NMR spectrum of polymer 1.1 in HFIP + CDCl 3 (Table 2 1, entry 1.1). ....... 143 A 82 1 H NMR spectrum of polymer 1.2 in HFIP + CDCl 3 (Table 2 1, entry 1.2). ....... 144 A 83 1 H NMR spectrum of polymer 1.4 in HFIP + CDCl 3 (Table 2 1, entry 1.4). ....... 144 A 84 1 H NMR spectrum of polymer 1.5 in HFIP + CDCl 3 (Table 2 1, entry 1.5). ....... 144 A 85 1 H NMR spectrum of polymer 1.6 in HFIP + CDCl 3 (Table 2 1, entry 1.6). ....... 145 A 86 1 H NMR spectrum of polymer 1.7 in HFIP + CDCl 3 (Table 2 1, entry 1.7). ....... 145 A 87 1 H NMR spectrum of polymer 1.8 in HFIP + CDCl 3 (Table 2 1, entry 1.8). ....... 145 A 88 1 H NMR spectrum of polymer 1.9 in HFIP + CDCl 3 (Table 2 1, entry 1.9). ....... 146 A 89 1 H NMR spectrum of polymer 1.10 in HFIP + CDCl 3 (Table 2 1, entry 1.10). ... 146 A 90 1 H NMR spectrum of polymer 1.11 in HFIP + CDCl 3 (Table 2 1, entry 1.11). ... 146 A 91 1 H NMR spectrum of polymer 1.12 in HFIP + CDCl 3 (Table 2 1, entry 1.12). ... 147 A 92 1 H NMR spectrum of polymer 1.13 in HFIP + CDCl 3 (Table 2 1, entry 1.13). ... 147 A 93 1 H NMR spectrum of polymer 1.14 in HFIP + CDCl 3 (Table 2 1, entry 1.14). ... 147 A 94 1 H NMR spectrum of polymer 1.15 in HFIP + CDCl 3 (Table 2 1, entry 1.15). ... 148 A 95 1 H NMR spectrum of polymer 1.16 in HFIP + CDCl 3 (Table 2 1, entry 1.16). ... 148 A 96 1 H NMR spectrum of polymer 1.17 in HFIP + CDCl 3 (Table 2 1, entry 1.17). ... 148 A 97 1 H NMR spectrum of polymer 1.18 in HFIP + CDCl 3 (Table 2 1, entry 1.18). ... 149 A 98 1 H NMR spectrum of polymer 1.19 in HFIP + CDCl 3 (Table 2 1, entry 1.19). ... 149 A 99 1 H NMR spectrum of polymer 2.1 in HFIP + CDCl 3 (Table 2 2, entry 2.1). ....... 149 A 100 1 H NMR spectrum of polymer 2.2 in HFIP + CDCl 3 (Table 2 2, entry 2.2). ....... 150

PAGE 15

15 A 101 1 H NMR spectrum of polymer 2.3 in HFIP + CDCl 3 (Table 2 2, entry 2.3). ....... 150 A 102 1 H NMR spectrum of polymer 3.1 in HFIP + CDCl 3 (Table 2 3, entry 3.1). ....... 150 A 103 1 H NMR spectrum of polymer 3.2 in HFIP + CDCl 3 (Table 2 3, entry 3.2). ....... 151 A 104 1 H NMR spectrum of polymer 4.1 in HFIP + CDCl 3 ( Figure 2 16, entry 4.1). .... 151 A 105 1 H NMR spectrum of polymer 5.1 in HFIP + CDCl 3 ( Figure 2 8, entry 5.1). ...... 151 A 106 13 C NMR spectrum of HFIP solvent in CDCl 3 ................................ .................. 152 A 107 13 C NMR spectrum of commercial polyglycolic acid in HFIP + CDCl 3 .............. 152 A 108 13 C NMR spectrum of polymer 1.1 in HFIP + CDCl 3 (Table 2 1, entry 1.1). ...... 152 A 109 13 C NMR spectrum of polymer 1.2 in HFIP + C 6 D 6 (Table 2 1, entry 1. 2). ....... 153 A 110 13 C NMR spectrum of polymer 1.4 in HFIP + CDCl 3 (Table 2 1, entry 1.4). ...... 153 A 111 13 C NMR spectrum of polymer 1.5 in HFIP + CDCl 3 (Table 2 1, entry 1.5). ...... 153 A 112 13 C NMR spectrum of polymer 1.6 in HFIP + CDCl 3 (Table 2 1, entry 1.6). ...... 154 A 113 13 C NMR spectrum of polymer 1.7 in HFIP + CDCl 3 (Table 2 1, entry 1.7). ...... 154 A 114 13 C NMR spectrum of polymer 1.8 in HFIP + CDCl 3 (Table 2 1, entry 1.8). ...... 154 A 115 13 C NMR spectrum of polymer 1.9 in HFIP + CDCl 3 (Table 2 1, entry 1.9). ...... 155 A 116 13 C NMR spectrum of polymer 1.10 in HFIP + C 6 D 6 (Table 2 1, entry 1.10). .... 155 A 117 13 C NMR spectrum of polymer 1.11 in HFIP + CDCl 3 (Table 2 1, entry 1.11). .. 155 A 118 13 C NMR spectrum of polymer 1.12 in HFIP + CDCl 3 (Table 2 1, entry 1.12). .. 156 A 119 13 C NMR spectrum of polymer 1.13 in HFIP + CDCl 3 (Table 2 1, entry 1.13). .. 156 A 120 13 C NMR spectrum of polymer 1.14 in HFIP + CDCl 3 (Table 2 1, entry 1.14). .. 156 A 121 13 C NMR spectrum of polymer 1.15 in HFIP + CDCl 3 (Table 2 1, entry 1.15). .. 157 A 122 13 C NMR spectrum of polymer 1.16 in HFIP + CDCl 3 (Table 2 1, entry 1.16). .. 157 A 123 13 C NMR spectrum of polymer 1.17 in HFIP + CDCl 3 (Table 2 1, entry 1.17). .. 157 A 124 13 C NMR spectrum of polymer 1.18 in HFIP + C 6 D 6 (Table 2 1, entry 1.18). .... 158 A 125 13 C NMR spectrum of polymer 1.19 in HFIP + CDCl 3 (Table 2 1, entry 1.19). .. 158

PAGE 16

16 A 126 13 C NMR spectrum of polymer 2.1 in HFIP d 2 (Table 2 2, entry 2.1). ............... 158 A 127 13 C NMR spectrum of polymer 2.2 in HFIP + CDCl 3 (Table 2 2, entry 2.2). ...... 159 A 128 13 C NMR spectrum of polymer 2.3 in HFIP + CDCl 3 (Table 2 2, entry 2.3). ...... 159 A 129 13 C NMR spectrum of polymer 3.1 in HFIP + CDCl 3 (Table 2 3, entry 3.1). ...... 159 A 130 13 C NMR sp ectrum of polymer 3.2 in HFIP + CDCl 3 (Table 2 3, entry 3.2). ...... 160 A 131 13 C NMR spectrum of polymer 4.1 in HFIP + CDCl 3 ( Figure 2 16, entry 4.1). .. 160 A 132 13 C NMR spectrum of polymer 5.1 in HFIP + CDCl 3 ( Figure 2 8, entry 5.1). .... 160 A 133 GPC Chromatogram of commercial polyglycolic acid ................................ ..... 161 A 134 GPC Chromatogram of polymer 1.1 (Table 2 1, entry 1.1). .............................. 161 A 135 GPC Chromatogram of po lymer 1.2 (Table 2 1, entry 1.2). .............................. 161 A 136 GPC Chromatogram of polymer 1.4 (Table 2 1, entry 1.4). .............................. 162 A 137 GPC Chromatogram of polymer 1.5 (Table 2 1, entry 1.5). .............................. 162 A 138 GPC Chromatogram of polymer 1.6 (Table 2 1, entry 1.6). .............................. 162 A 139 GPC Chromatogram of polymer 1.7 (Table 2 1, entry 1.7). .............................. 163 A 140 GPC Chromatogram of polymer 1.8 (Table 2 1, entry 1.8). .............................. 163 A 141 GPC Chromatogram of polymer 1.9 (Table 2 1, entry 1.9). .............................. 163 A 142 GPC Chromatogram of polymer 1.10 (Table 2 1, entry 1.10). .......................... 164 A 143 GPC Chromatogram of polymer 1.11 (Table 2 1, entry 1.11). .......................... 164 A 144 GPC Chromatogram of polymer 1.12 (Table 2 1, entry 1.12). .......................... 164 A 145 GPC Chromatogram of polymer 1.13 (Table 2 1, entry 1.13). .......................... 165 A 146 GPC Chromatogram of polymer 1.14 (Table 2 1, entry 1.14). .......................... 165 A 147 GPC Chromatogram of polymer 1.15 (Table 2 1, entry 1.15). .......................... 165 A 148 GPC Chromatogram of polymer 1.16 (Table 2 1, entry 1.16). .......................... 166 A 149 GPC Chromatogram of polymer 1.17 (Table 2 1, entry 1.17). .......................... 166 A 150 GPC Chromatogram of polymer 1.18 (Table 2 1, entry 1.18). .......................... 166

PAGE 17

17 A 151 GPC Chromatogram of polymer 1.19 (Table 2 1, entry 1.19). .......................... 167 A 152 GPC Chromatogram of polymer 2.1 (Table 2 2, entry 2.1). .............................. 167 A 153 GPC Chromatogram of polymer 2.2 (Table 2 2, entry 2.2). .............................. 167 A 154 GPC Chromatogram of polymer 2.3 (Table 2 2, entry 2.3). .............................. 167 A 155 GPC Chromatogram of polymer 3.1 (Table 2 3, entry 3.1). .............................. 167 A 156 GPC Chromatogram of polymer 3.2 (Table 2 3, entry 3.2). .............................. 167 A 157 GPC Chromatogram of polymer 4.1 ( Figure 2 16, entry 4.1). ........................... 167 A 158 GPC Chromatogram of polymer 5.1 ( Figure 2 8, entry 5.1). ............................. 168 A 159 The pictures of commercial PGA and entry 1.17 at Table 2 1. ......................... 168 B 1 FT IR spectrum of polymer 1.4 (Table 3 1, entry 1.4). ................................ ...... 169 B 2 FT IR spectrum of polymer 1.5 (Table 3 1, entry 1.5). ................................ ...... 169 B 3 FT IR spectrum of polymer 1.6 (Table 3 1, entry 1.6). ................................ ...... 170 B 4 FT IR spectrum of polymer 1.7 (Table 3 1, entry 1.7). ................................ ...... 170 B 5 FT IR spectrum of polymer 1.8 (Table 3 1, entry 1.8). ................................ ...... 170 B 6 FT IR spectrum of polymer 1.9 (Table 3 1, entry 1.9). ................................ ...... 171 B 7 FT IR spectrum of polymer 1.10 (Table 3 1, entry 1.10). ................................ .. 171 B 8 FT IR spectrum of polymer 1.13 (Table 3 1, entry 1.13). ................................ .. 171 B 9 FT IR spectrum of polymer 1.14 (Table 3 1, entry 1.14). ................................ .. 172 B 10 FT IR spectrum of polymer 1.15 (Table 3 1, entry 1.15). ................................ .. 172 B 11 FT IR spectrum of polymer 1.16 (Table 3 1, entry 1.16). ................................ .. 172 B 12 FT IR spectrum of polymer 1.17 (Table 3 1, entry 1.17). ................................ .. 173 B 13 FT IR spectrum of polymer 1.18 (Table 3 1, entry 1.18). ................................ .. 173 B 14 FT IR spectrum of polymer 3.1 (Table 3 3, entry 3.1). ................................ ...... 173 B 15 FT IR spectrum of polymer 3 .2 (Table 3 3, entry 3.2). ................................ ...... 174 B 16 FT IR spectrum of polymer 3.3 (Table 3 3, entry 3.3). ................................ ...... 174

PAGE 18

18 B 17 FT IR spectrum of polymer 3.4 (Table 3 3, entry 3.4). ................................ ...... 174 B 18 FT IR spectrum of polymer 4.1 (Table 3 4, entry 4.1). ................................ ...... 175 B 19 FT IR spectrum of polymer 4.2 (Table 3 4, entry 4.2). ................................ ...... 175 B 20 FT IR spectrum of polymer 4.3 (Table 3 4, entry 4.3). ................................ ...... 175 B 21 FT IR spectrum of polymer 5.1 (Table 3 5, entry 5.1). ................................ ...... 176 B 22 FT IR spectrum of polymer 5.2 (Table 3 5, entry 5.2). ................................ ...... 176 B 23 FT IR spectrum of polymer 5.3 (Table 3 5, entry 5.3). ................................ ...... 176 B 24 FT IR spectrum of polymer 6.1 (Table 3 6, entry 6.1). ................................ ...... 177 B 25 FT IR spectrum of polymer 6.2 (Table 3 6, entry 6.2). ................................ ...... 177 B 26 FT IR spectrum of polymer 6.3 (Table 3 6, entry 6.3). ................................ ...... 177 B 27 FT IR spectrum of polymer 7.1 (Table 3 7, entry 7.1). ................................ ...... 178 B 28 FT IR spectrum of polymer 7.2 (Table 3 7, entry 7.2). ................................ ...... 178 B 29 FT IR spectrum of polymer 7.3 (Table 3 7, entry 7.3). ................................ ...... 178 B 30 FT IR spectrum of polymer 7.4 (Table 3 7, entry 7.4). ................................ ...... 179 B 31 FT IR spectrum of polymer 7.5 (Table 3 7, entry 7.5). ................................ ...... 179 B 32 FT IR spectrum of polymer 7.6 (Table 3 7, entry 7.6). ................................ ...... 179 B 33 FT IR spectrum of polymer 8.1 (Table 3 8, entry 8.1). ................................ ...... 180 B 34 FT IR spectrum of polymer 8.2 ( Table 3 8, entry 8.2). ................................ ...... 180 B 35 FT IR spectrum of polymer 8.3 (Table 3 8, entry 8.3). ................................ ...... 180 B 36 FT IR spectrum of polymer 8.4 (Table 3 8, entry 8.4). ................................ ...... 181 B 37 FT IR spectrum of polymer 8.5 (Table 3 8, entry 8.5). ................................ ...... 181 B 38 TGA Thermogram of polymer 1.4 (Table 3 1, entry 1.4). ................................ .. 182 B 39 TGA Thermogram of polymer 1.5 (Table 3 1, entry 1.5). ................................ .. 182 B 40 TGA Thermogram of polymer 1.6 (Table 3 1, entry 1.6). ................................ .. 183 B 41 TGA Thermogram of polymer 1.7 (Table 3 1, entry 1.7). ................................ .. 183

PAGE 19

19 B 42 TGA Thermogram of polymer 1.8 (Table 3 1, entry 1.8). ................................ .. 184 B 43 TGA Thermogram of polymer 1.9 ( Table 3 1, entry 1.9). ................................ .. 184 B 44 TGA Thermogram of polymer 1.10 (Table 3 1, entry 1.10). .............................. 185 B 45 TGA Thermogram of polymer 1.13 (Table 3 1, entry 1.13). .............................. 185 B 46 TGA Thermogram of polymer 1.14 (Table 3 1, entry 1.14). .............................. 186 B 47 TGA Thermogram of polymer 1.15 (Table 3 1, entry 1.15). .............................. 186 B 48 TGA Thermogram of polymer 1.16 (Table 3 1, entry 1.16). .............................. 187 B 49 TGA Thermogram of polymer 1.17 (Table 3 1, entry 1.17). .............................. 187 B 50 TGA Thermogram of polymer 1.18 (Table 3 1, entry 1.18). .............................. 1 88 B 51 TGA Thermogram of polymer 3.1 (Table 3 3, entry 3.1). ................................ .. 188 B 52 TGA Thermogram of polymer 3.2 (Table 3 3, entry 3.2). ................................ .. 189 B 53 TGA Thermogram of polymer 3.3 (Table 3 3, entry 3.3). ................................ .. 189 B 54 TGA Thermogram of polymer 3.4 (Table 3 3, entry 3.4). ................................ .. 190 B 55 TGA Thermogram of polymer 4.1 (Table 3 4, entry 4.1). ................................ .. 190 B 56 TGA Thermogram of polymer 4.2 (Table 3 4, entry 4.2). ................................ .. 191 B 57 TGA Thermogram of polymer 4.3 (Table 3 4, entry 4.3). ................................ .. 191 B 58 TGA Thermogram of polymer 5.1 (Table 3 5, entry 5.1). ................................ .. 192 B 59 TGA Thermogram of polymer 5.2 (Table 3 5, entry 5.2). ................................ .. 192 B 60 TGA Thermogram of polymer 5.3 (Table 3 5, entry 5.3). ................................ .. 193 B 61 TGA Thermogram of polymer 6.1 (Table 3 6, entry 6.1). ................................ .. 193 B 62 TGA Thermogram of polymer 6.2 (Table 3 6, entry 6.2). ................................ .. 194 B 63 TGA Thermogram of polymer 6.3 (Table 3 6, entry 6.3). ................................ .. 194 B 64 TGA Thermogram of polymer 7.1 (Table 3 7, entry 7.1). ................................ .. 195 B 65 TGA Thermogram of polymer 7.2 (Table 3 7, entry 7.2). ................................ .. 195 B 66 TGA Thermogram of polymer 7.3 (Table 3 7, entry 7.3). ................................ .. 196

PAGE 20

20 B 67 TGA Thermogram of polymer 7.4 (Table 3 7, entry 7.4). ................................ .. 196 B 68 TGA Thermogram of polymer 7.5 (Table 3 7, entry 7.5). ................................ .. 197 B 69 TGA Thermogram of polymer 7.6 (Table 3 7, entry 7.6). ................................ .. 197 B 70 TGA Thermogram of polymer 8.1 (Table 3 8, entry 8.1). ................................ .. 198 B 71 TGA Thermogram of polymer 8.2 (Table 3 8, entry 8.2). ................................ .. 198 B 72 TGA Thermogram of polymer 8.3 (Table 3 8, entry 8.3). ................................ .. 199 B 73 TGA Thermogram of polymer 8.4 (Table 3 8, entry 8.4). ................................ .. 199 B 74 TGA Thermogram of polymer 8.5 (Table 3 8, entry 8.5). ................................ .. 200 B 75 DSC Thermogram of polymer 1.4 ( Table 3 1, entry 1.4). ................................ 200 B 76 DSC Thermogram of polymer 1.5 (Table 3 1, entry 1.5). ................................ 201 B 77 DSC Thermogram of polymer 1.6 (Table 3 1, entry 1.6). ................................ 201 B 78 DSC Thermogram of polymer 1.7 (Table 3 1, entry 1.7). ................................ 202 B 79 DSC Thermogram of polymer 1.8 (Table 3 1, entry 1.8). ................................ 202 B 80 DSC Thermogram of polymer 1.9 (Table 3 1, entry 1.9). ................................ 203 B 81 DSC Thermogram of polymer 1.10 (Table 3 1, entry 1.10). ............................. 203 B 82 DSC Thermogram of polymer 1.13 (Table 3 1, entry 1.13). ............................. 204 B 83 DSC Thermogram of polymer 1.14 (Table 3 1, entry 1.14). ............................. 204 B 84 DSC Thermogram of polymer 1.15 (Table 3 1, entry 1.15). ............................. 205 B 85 DSC Thermogram of polymer 1.16 (Table 3 1, entry 1.16). ............................. 205 B 86 DSC Thermogram of polymer 1.17 (Table 3 1, entry 1.17). ............................. 206 B 87 DSC Thermogram of polymer 1.18 (Table 3 1, entry 1.18). ............................. 206 B 88 DSC Thermogram of polymer 3.1 (Table 3 3, entry 3.1). ................................ 207 B 89 DSC Thermogram of polymer 3.2 (Table 3 3, entry 3.2). ................................ 207 B 90 DSC Thermogram of polymer 3.3 (Table 3 3, entry 3.3). ................................ 208 B 91 DSC Thermogram of polymer 3.4 (Table 3 3, entry 3.4). ................................ 208

PAGE 21

21 B 92 DSC Thermogram of polymer 4.1 (Table 3 4, entry 4.1). ................................ 209 B 93 DSC Thermogram of polymer 4.2 (Table 3 4, entry 4.2). ................................ 209 B 94 DSC Thermogram of polymer 4.3 (Table 3 4, entry 4.3). ................................ 210 B 95 DSC Thermogram of polymer 5.1 (Table 3 5, entry 5.1). ................................ 210 B 96 DSC Thermogram of polymer 5.2 (Table 3 5, entry 5.2). ................................ 211 B 97 DSC Thermogram of polymer 5.3 (Table 3 5, entry 5.3). ................................ 211 B 98 DSC Thermogram of polymer 6.1 (Table 3 6, entry 6.1). ................................ 212 B 99 DSC Thermogram of polymer 6.2 (Table 3 6, entry 6.2). ................................ 212 B 100 DSC Thermogram of polymer 6.3 (Table 3 6, entry 6.3). ................................ 213 B 101 DSC Thermogram of polymer 7.1 (Table 3 7, entry 7.1). ................................ 213 B 102 DSC Thermogram of polymer 7.2 (Table 3 7, entry 7.2). ................................ 214 B 103 DSC Thermogram of polymer 7.3 (Table 3 7, entry 7.3). ................................ 214 B 104 DSC Thermogram of polymer 7.4 (Table 3 7, entry 7.4). ................................ 215 B 105 DSC Thermogram of polymer 7.5 (Table 3 7, entry 7.5). ................................ 215 B 106 DSC Thermogram of polymer 7.6 (Table 3 7, entry 7.6). ................................ 216 B 107 DSC Thermogram of polymer 8.1 (Table 3 8, entry 8.1). ................................ 216 B 108 DSC Thermogram of polymer 8.2 (Table 3 8, entry 8.2). ................................ 217 B 109 DSC Thermogram of polymer 8.3 (Table 3 8, entry 8.3). ................................ 217 B 110 DSC Thermogram of polymer 8.4 (Table 3 8, entry 8.4). ................................ 218 B 111 DSC Thermogram of polymer 8.5 (Table 3 8, entry 8.5). ................................ 218 B 112 1 H NMR spectrum of polymer 1.4 in HFIP + CDCl 3 (Table 3 1, entry 1.4). ....... 219 B 113 1 H NMR spectrum of polymer 1.5 in HFIP + CDCl 3 (Table 3 1, entry 1.5). ....... 219 B 114 1 H NMR spectrum of polymer 1.6 in HFIP + CDCl 3 (Table 3 1, entry 1.6). ....... 219 B 115 1 H NMR spectrum of polymer 1.7 in HFIP + CDCl 3 (Table 3 1, entry 1.7). ....... 220 B 116 1 H NMR spectrum of polymer 1.8 in HFIP + CDCl 3 (Table 3 1, entry 1.8). ....... 220

PAGE 22

22 B 117 1 H NMR spectrum of polymer 1.9 in HFIP + CDCl 3 (Table 3 1, entry 1.9). ....... 220 B 118 1 H NMR spectrum of polymer 1.10 in HFIP + CDCl 3 (Table 3 1, entry 1.10). ... 221 B 119 1 H NMR spectrum of polymer 1.13 in HFIP + CDCl 3 (Table 3 1, entry 1.13). ... 221 B 120 1 H NMR spectrum of polymer 1.14 in HFIP + CDCl 3 (Table 3 1, entry 1.14). ... 221 B 121 1 H NMR spectrum of polymer 1.15 in HFIP + CDCl 3 (Table 3 1, entry 1.15). ... 222 B 122 1 H NMR spectrum of polymer 1.16 in HFIP + CDCl 3 (Table 3 1, entry 1.16). ... 222 B 123 1 H NMR spectrum of polymer 1.17 in HFIP + CDCl 3 (Table 3 1, entry 1.17). ... 222 B 124 1 H NMR spectrum of polymer 1.18 in HFIP + CDCl 3 (Table 3 1, entry 1.18). ... 223 B 125 1 H NMR spectrum of polymer 3.1 in HFIP + CDCl 3 (Table 3 3, entry 3.1). ....... 223 B 126 1 H NMR spectrum of polymer 3.2 in HFIP + CDCl 3 (Table 3 3, entry 3.2). ....... 223 B 127 1 H NMR spectrum of polymer 3.3 in HFIP + CDCl 3 (Table 3 3, entry 3.3). ....... 224 B 128 1 H NMR spectrum of polymer 3.4 in HFIP + CDCl 3 (Table 3 3, entry 3.4). ....... 224 B 129 1 H NMR spectrum of polymer 4.1 in HFIP + CDCl 3 (Table 3 4, entry 4.1). ....... 224 B 130 1 H NMR spectrum of polymer 4.2 in HFIP + CDCl 3 (Table 3 4, entry 4.2). ....... 225 B 131 1 H NMR spectrum of polymer 4.3 in HFIP + CDCl 3 (Table 3 4, entry 4.3). ....... 225 B 132 1 H NMR spectrum of polymer 5.1 in HFIP + CDCl 3 (Table 3 5, entry 5.1). ....... 225 B 133 1 H NMR spectrum of polymer 5.2 in HFIP + CDCl 3 (Table 3 5, entry 5.2). ....... 226 B 134 1 H NMR spectrum of polymer 5.3 in HFIP + CDCl 3 (Table 3 5, entry 5.3). ....... 226 B 135 1 H NMR spectrum of polymer 6.1 in HFIP + CDCl 3 (Table 3 6, entry 6.1). ....... 22 6 B 136 1 H NMR spectrum of polymer 6.2 in HFIP + CDCl 3 (Table 3 6, entry 6.2). ....... 227 B 137 1 H NMR spectrum of polymer 6.3 in HFIP + CDCl 3 (Table 3 6, entry 6.3). ....... 227 B 138 1 H NMR spectrum of polymer 7.1 in HFIP + CDCl 3 (Table 3 7, entry 7.1). ....... 227 B 139 1 H NMR spectrum of polymer 7.2 in HFIP + CDCl 3 (Table 3 7, entry 7.2). ....... 228 B 140 1 H NMR spectrum of polymer 7.3 in HFIP + CDCl 3 (Table 3 7, entry 7.3). ....... 228 B 141 1 H NMR spectrum of polymer 7.4 in HFIP + CDCl 3 (Table 3 7, entry 7.4). ....... 228

PAGE 23

23 B 142 1 H NMR spectrum of polymer 7.5 in HFIP + CDCl 3 (Table 3 7, entry 7.5). ....... 229 B 143 1 H NMR spectrum of polymer 7.6 in HFIP + CDCl 3 (Table 3 7, entry 7.6). ....... 229 B 144 1 H NMR spectrum of polymer 8.1 in HFIP + CDCl 3 (Table 3 8, entry 8.1). ....... 229 B 145 1 H NMR spectrum of polymer 8.2 in HFIP + CDCl 3 (Table 3 8, entry 8.2). ....... 230 B 146 1 H NMR spectrum of polymer 8.3 in HFIP + CDCl 3 (Table 3 8, entry 8.3). ....... 230 B 147 1 H NMR spectrum of polymer 8.4 in HFIP + CDCl 3 (Table 3 8, entry 8.4). ....... 230 B 148 1 H NMR spectrum of polymer 8.5 in HFIP + CDCl 3 (Table 3 8, entry 8.5). ....... 231 B 149 13 C NMR spectrum of polymer 1.4 in HFIP + CDCl 3 (Table 3 1, entry 1.4). ...... 231 B 150 13 C NMR spectrum of polymer 1.5 in HFIP + CDCl 3 (Table 3 1, entry 1.5). ...... 231 B 151 13 C NMR spectrum of polymer 1.6 in HFIP + C 6 D 6 (Table 3 1, entry 1.6). ........ 232 B 152 13 C NMR spectrum of polymer 1.7 in HFIP + C 6 D 6 (Table 3 1, entry 1.7). ........ 232 B 153 13 C NMR spectrum of polymer 1.8 in HFIP + C 6 D 6 (Table 3 1, entry 1.8). ........ 232 B 154 13 C NMR spectrum of polymer 1.9 in HFIP + CDCl 3 (Table 3 1, entry 1.9). ...... 233 B 155 13 C NMR spectrum of polymer 1.10 in HFIP + CDCl 3 (Table 3 1, entry 1.10). .. 233 B 156 13 C NMR spectrum of polymer 1.13 in HFIP + C 6 D 6 (Table 3 1, entry 1.13). .... 233 B 157 13 C NMR spectrum of polymer 1.14 in HFIP + CDCl 3 (Table 3 1, entry 1.14). .. 234 B 158 13 C NMR spectrum of polymer 1.15 in HFIP + CDCl 3 (Table 3 1, entry 1.15). .. 234 B 159 13 C NMR spectrum of polymer 1.16 in HFIP + CDCl 3 (Table 3 1, entry 1.16). .. 234 B 160 13 C NMR spectrum of polymer 1.17 in HFIP + CDCl 3 (Table 3 1, entry 1.17). .. 235 B 161 13 C NMR spectrum of polymer 1.18 in HFIP + CDCl 3 (Table 3 1, entry 1.18). .. 235 B 162 13 C NMR spectrum of polymer 3.1 in HFIP + CDCl 3 (Table 3 3, entry 3.1). ...... 235 B 163 13 C NMR spectrum of polymer 3.2 in HFIP + CDCl 3 (Table 3 3, entry 3.2). ...... 236 B 164 13 C NMR spectrum of polymer 3.3 in HFIP + CDCl 3 (Table 3 3, entry 3.3). ...... 236 B 165 13 C NMR spectrum of polymer 3.4 in HFIP + CDCl 3 (Table 3 3, entry 3.4). ...... 236 B 166 13 C NMR spectrum of polymer 4.1 in HFIP + CDCl 3 (Table 3 4, entry 4.1). ...... 237

PAGE 24

24 B 167 13 C NMR spectrum of polymer 4.2 in HFIP + CDCl 3 (Table 3 4, entry 4.2). ...... 237 B 168 13 C NMR spectrum of polymer 4.3 in HFIP + CDCl 3 (Table 3 4, entry 4.3). ...... 237 B 169 13 C NMR spectrum of polymer 5.1 in HFIP + C 6 D 6 (Table 3 5, entry 5.1). ........ 238 B 170 13 C NMR spectrum of polymer 5.2 in HFIP + CDCl 3 (Table 3 5, entry 5.2). ...... 238 B 171 13 C NMR spectrum of polymer 5.3 in HFIP + CDCl 3 (Table 3 5, entry 5.3). ...... 238 B 172 13 C NMR spectrum of polymer 6.1 in HFIP + C 6 D 6 (Table 3 6, entry 6.1). ........ 239 B 173 13 C NMR spectrum of polymer 6.2 in HFIP + d DMSO (Table 3 6, entry 6.2). 239 B 174 13 C NMR spectrum of polymer 6.3 in HFIP + CDCl 3 (Table 3 6, entry 6.3). ...... 239 B 175 13 C NMR spectrum of polymer 7.1 in HFIP + CDCl 3 (Table 3 7, entry 7.1). ...... 240 B 176 13 C NMR spectrum of polymer 7.2 in HFIP + CDCl 3 (Table 3 7, entry 7.2). ...... 240 B 177 13 C NMR sp ectrum of polymer 7.3 in HFIP + CDCl 3 (Table 3 7, entry 7.3). ...... 240 B 178 13 C NMR spectrum of polymer 7.4 in HFIP + CDCl 3 (Table 3 7, entry 7.4). ...... 241 B 179 13 C NMR spectrum of polymer 7.5 in HFIP + CDCl 3 (Table 3 7, entry 7.5). ...... 241 B 180 13 C NMR spectrum of polymer 7.6 in HFIP + CDCl 3 (Table 3 7, entry 7.6). ...... 241 B 181 13 C NMR spectrum of polymer 8.1 in HFIP + CDCl 3 (Table 3 8, entry 8.1). ...... 242 B 182 13 C NMR spectrum of polymer 8.2 in HFIP + CDCl 3 (Table 3 8, entry 8.2). ...... 242 B 183 13 C NMR spectrum of polymer 8.3 in HFIP + CDCl 3 (Table 3 8, entry 8.3). ...... 242 B 184 13 C NMR spectrum of polymer 8.4 in HFIP + CDCl 3 (Table 3 8, entry 8.4). ...... 242 B 185 13 C NMR spectrum of polymer 8.5 in HFIP + CDCl 3 (Table 3 8, entry 8.5). ...... 242 B 186 GPC Chromatogram of polymer 1.4 (Table 3 1, entry 1.4). .............................. 243 B 187 GPC Chromatogram of polymer 1.5 (Table 3 1, entry 1.5). .............................. 243 B 188 GPC Chromatogram of polymer 1.6 (Table 3 1, entry 1.6). .............................. 243 B 189 GPC Chromatogram of polymer 1.7 (Table 3 1, entry 1.7). .............................. 244 B 190 GPC Chromatogram of polymer 1.8 (Table 3 1, entry 1.8). .............................. 244 B 191 GPC Chromatogram of polymer 1.9 (Table 3 1, entry 1.9). .............................. 244

PAGE 25

25 B 192 GPC Chromatogram of polymer 1.10 (Table 3 1, entry 1.10). .......................... 245 B 193 GPC Chromatogram of polymer 1.13 (Table 3 1, entry 1.13). .......................... 245 B 194 GPC Chromatogram of polymer 1.14 (Table 3 1, entry 1.14). .......................... 245 B 195 GPC Chromatogram of polymer 1.15 (Table 3 1 entry 1.15). ........................... 246 B 196 GPC Chromatogram of polymer 1.16 (Table 3 1, entry 1.16). .......................... 246 B 197 GPC Chromatogram of polymer 1.17 (Table 3 1, entry 1.17). .......................... 246 B 198 GPC Chromatogram of polymer 1.18 (Table 3 1, entry 1.18). .......................... 247 B 199 GPC Chromatogram of polymer 3.1 (Table 3 3, entry 3.1). .............................. 247 B 200 GPC Chromatogram of polymer 3.2 (Table 3 3, entry 3.2). .............................. 247 B 201 GPC Chromatogram of polymer 3.3 (Table 3 3, entry 3.3). .............................. 248 B 202 GPC Chromatogram of polymer 3.4 (Table 3 3, entry 3.4). .............................. 248 B 203 GPC Chromatogram of polymer 4.1 (Table 3 4, entry 4.1). .............................. 248 B 204 GPC Chromatogram of polymer 4.2 (Table 3 4, entry 4.2). .............................. 249 B 205 GPC Chromatogram of polymer 4.3 (Table 3 4, entry 4.3). .............................. 249 B 206 GPC Chromatogram of polymer 5.1 (Table 3 5, entry 5.1). .............................. 249 B 207 GPC Chromatogram of polymer 5.2 (Table 3 5, entry 5.2). .............................. 250 B 208 GPC Chromatogram of polymer 5.3 (Table 3 5, entry 5.3). .............................. 250 B 209 GPC Chromatogram of polymer 6.1 (Table 3 6, entry 6.1). .............................. 250 B 210 GPC Chromatogram of polymer 6.2 (Table 3 6, entry 6.2). .............................. 251 B 211 GPC Chromatogram of polymer 6.3 (Table 3 6, entry 6.3). .............................. 251 B 212 GPC Chromatogram of polymer 7.1 (Table 3 7, entry 7.1). .............................. 251 B 213 GPC Chromatogram of polymer 7.2 (Table 3 7, entry 7.2). .............................. 251 B 214 GPC Chromatogram of polymer 7.3 (Table 3 7, entry 7.3). .............................. 251 B 215 GPC Chromatogram of polymer 7.4 (Table 3 7, entry 7.4). .............................. 251 B 216 GPC Chromatogram of polymer 7.5 (Table 3 7, entry 7.5). .............................. 252

PAGE 26

26 B 217 GPC Chromatogram of polymer 7.6 (Table 3 7, entry 7.6). .............................. 252 B 218 GPC Chromatogram of polymer 8.1 (Table 3 8, entry 8.1). .............................. 252 B 219 GPC Chromatogram of polymer 8.2 (Table 3 8, entry 8.2). .............................. 252 B 220 GPC Chromatogram of polymer 8.3 (Table 3 8, entry 8.3). .............................. 252 B 221 GPC Chromatogram of polymer 8.4 (Table 3 8, entry 8.4). .............................. 252 B 222 GPC Chromatogram of polymer 8.5 (Table 3 8, entry 8.5). .............................. 252 C 1 FT IR spectrum of polymer 2.1 (Table 4 2, entry 2.1). ................................ ...... 253 C 2 FT IR spectrum of polymer 2.2 (Table 4 2, entry 2.2). ................................ ...... 253 C 3 FT IR spectrum of polymer 2.3 (Table 4 2, entry 2.3). ................................ ...... 254 C 4 FT IR spectrum of polymer 2.4 (Table 4 2, entry 2.4). ................................ ...... 254 C 5 FT IR spectrum of polymer 2.5 (Table 4 2, entry 2.5). ................................ ...... 254 C 6 FT IR spectrum of polymer 2.6 (Table 4 2, entry 2.6). ................................ ...... 255 C 7 FT IR spectrum of polymer 3.1 (Table 4 3, entry 3.1). ................................ ...... 255 C 8 FT IR spectrum of polymer 3.2 (Table 4 3, entry 3.2). ................................ ...... 255 C 9 FT IR spectrum of polymer 3.3 (Table 4 3, entry 3.3). ................................ ...... 256 C 10 FT IR spectrum of polymer 3.4 (Table 4 3, entry 3.4). ................................ ...... 256 C 11 FT IR spectrum of polymer 3.5 (Table 4 3, entry 3.5). ................................ ...... 256 C 12 FT IR spectrum of polymer 3.6 (Table 4 3, entry 3.6). ................................ ...... 257 C 13 FT IR spectrum of polymer 3.7 (Table 4 3, entry 3.7). ................................ ...... 257 C 14 FT IR spectrum of polymer 4.1 (Table 4 4, entry 4.1). ................................ ...... 257 C 15 FT IR spectrum of polymer 4.2 ( Table 4 4, entry 4.2). ................................ ...... 258 C 16 FT IR spectrum of polymer 4.3 (Table 4 4, entry 4.3). ................................ ...... 258 C 17 FT IR spectrum of polymer 4.4 (Table 4 4, entry 4.4). ................................ ...... 258 C 18 FT IR spectrum of polymer 4.5 (Table 4 4, entry 4.5). ................................ ...... 259 C 19 FT IR spectrum of polymer 4.6 (Table 4 4, entry 4.6). ................................ ...... 259

PAGE 27

27 C 20 FT IR spectrum of polymer 4.7 (Table 4 4, entry 4.7). ................................ ...... 259 C 21 TGA Thermogram of polymer 2.1 (Table 4 2, entry 2.1). ................................ .. 260 C 22 TGA Thermogram of polymer 2.2 (Table 4 2, entry 2.2). ................................ .. 260 C 23 TGA Thermogram of polymer 2.3 (Table 4 2, entry 2.3). ................................ .. 261 C 24 TGA Thermogram of polymer 2.4 (Table 4 2, entry 2.4). ................................ .. 261 C 25 TGA Thermogram of polymer 2.5 (Table 4 2, entry 2.5). ................................ .. 262 C 26 TGA Thermogram of polymer 2.6 (Table 4 2, entry 2.6). ................................ .. 262 C 27 TGA Thermogram of polymer 3.1 (Table 4 3, entry 3.1). ................................ .. 263 C 28 TGA Thermogram of polymer 3.2 (Table 4 3, entry 3.2). ................................ .. 263 C 29 TGA Thermogram of polymer 3.3 (Table 4 3, entry 3.3). ................................ .. 264 C 30 TGA Thermogram of polymer 3.4 (Table 4 3, entry 3.4). ................................ .. 264 C 31 TGA Thermogram of polymer 3.5 (Table 4 3, entry 3.5). ................................ .. 265 C 32 TGA Thermogram of polymer 3.6 (Table 4 3, entry 3.6). ................................ .. 265 C 33 TGA Thermogram of polymer 3.7 (Table 4 3, entry 3.7). ................................ .. 266 C 34 TGA Thermogram of polymer 4.1 (Table 4 4, entry 4.1). ................................ .. 266 C 35 TGA Thermogram of polymer 4.2 (Table 4 4, entry 4.2). ................................ .. 267 C 36 TGA Thermogram of polymer 4.3 (Table 4 4, entry 4.3). ................................ .. 267 C 37 TGA Thermogram of polymer 4.4 (Table 4 4, entry 4.4). ................................ .. 268 C 38 TGA Thermogram of polymer 4.5 (Table 4 4, entry 4.5). ................................ .. 268 C 39 TGA Thermogram of polymer 4.6 (Table 4 4, entry 4.6). ................................ .. 269 C 40 DSC Thermogram of polymer 2.1 (Table 4 2, entry 2.1). ................................ 269 C 41 DSC Thermogram of polymer 2.2 (Table 4 2, entry 2.2). ................................ 270 C 42 DSC Thermogram of polymer 2.3 (Table 4 2, entry 2.3). ................................ 270 C 43 DSC Thermogram of polymer 2.4 (Table 4 2, entry 2.4). ................................ 271 C 44 DSC Thermogram of polymer 2.5 (Table 4 2, entry 2.5). ................................ 271

PAGE 28

28 C 45 DSC Thermogram of polymer 2.6 (Table 4 2, entry 2.6). ................................ 272 C 46 DSC Thermogram of polymer 3.1 (Table 4 3, entry 3.1). ................................ 272 C 47 DSC Thermogram of polymer 3.2 (Table 4 3, entry 3.2). ................................ 273 C 48 DSC Thermogram of polymer 3.3 (Table 4 3, entry 3.3). ................................ 273 C 49 DSC Thermogram of polymer 3.4 (Table 4 3, entry 3.4). ................................ 274 C 50 DSC Thermogram of polymer 3.5 ( Table 4 3, entry 3.5). ................................ 274 C 51 DSC Thermogram of polymer 3.6 (Table 4 3, entry 3.6). ................................ 275 C 52 DSC Thermogram of polymer 3.7 (Table 4 3, entry 3.7). ................................ 275 C 53 DSC Thermogram of polymer 4.1 (Table 4 4, entry 4.1). ................................ 276 C 54 DSC Thermogram of polymer 4.2 (Table 4 4, entry 4.2). ................................ 276 C 55 DSC Thermogram of polymer 4.3 (Table 4 4, entry 4.3). ................................ 277 C 56 DSC Thermogram of polymer 4.4 (Table 4 4, entry 4.4). ................................ 277 C 57 DSC Thermogram of polymer 4.5 (Table 4 4, entry 4.5). ................................ 278 C 58 DSC Thermogram of polymer 4.6 (Table 4 4, entry 4.6). ................................ 278 C 59 1 H NMR spectrum of polymer 2.1 in HFIP + CDCl 3 (Table 4 2, entry 2.1). ....... 279 C 60 1 H NMR spectrum of polymer 2.2 in HFIP + CDCl 3 (Table 4 2, entry 2.2). ....... 279 C 61 1 H NMR spectrum of polymer 2.3 in HFIP + CDCl 3 (Table 4 2, entry 2.3). ....... 279 C 62 1 H NMR spectrum of polymer 2.4 in HFIP + CDCl 3 (Table 4 2, entry 2.4). ....... 280 C 63 1 H NMR spectrum of polymer 2.5 in HFIP + CDCl 3 (Table 4 2, entry 2.5). ....... 280 C 64 1 H NMR spectrum of polymer 2.6 in HFIP + CDCl 3 (Table 4 2, entry 2.6). ....... 280 C 65 1 H NMR spectrum of polymer 3.1 in HFIP + CDCl 3 (Table 4 3, entry 3.1). ....... 281 C 66 1 H NMR spectrum of polymer 3.2 in HFIP + CDCl 3 (Table 4 3, entry 3.2). ....... 281 C 67 1 H NMR spectrum of polymer 3.3 in HFIP + CDCl 3 (Table 4 3, entry 3.3). ....... 281 C 68 1 H NMR spectrum of polymer 3.4 in HFIP + CDCl 3 (Table 4 3, entry 3.4). ....... 282 C 69 1 H NMR spectrum of polymer 3.5 in HFIP + CDCl 3 (Table 4 3, entry 3.5). ....... 282

PAGE 29

29 C 70 1 H NMR spectrum of polymer 3.6 in HFIP + CDCl 3 (Table 4 3, entry 3.6). ....... 282 C 71 1 H NMR spectrum of polymer 3.7 in HFIP + CDCl 3 (Table 4 3, entry 3.7). ....... 283 C 72 1 H NMR spectrum of polymer 4.1 in HFIP + CDCl 3 (Table 4 4, entry 4.1). ....... 283 C 73 1 H NMR spectrum of polymer 4.2 in HFIP + CDCl 3 (Table 4 4, entry 4.2). ....... 283 C 74 1 H NMR spectrum of polymer 4.3 in HFIP + CDCl 3 (Table 4 4, entry 4.3). ....... 284 C 75 1 H NMR spectrum of polymer 4.4 in HFIP + CDCl 3 (Table 4 4, entry 4.4). ....... 284 C 76 1 H NMR spectrum of polymer 4.5 in HFIP + CDCl 3 (Table 4 4, entry 4.5). ....... 284 C 77 1 H NMR spectrum of polymer 4.6 in HFIP + CDCl 3 (Table 4 4, entry 4.6). ....... 285 C 78 13 C NMR spectrum of polymer 2.1 in HFIP + C 6 D 6 (Table 4 2, entry 2.1). ........ 285 C 79 13 C NMR spectrum of polymer 2.2 in HFIP + C 6 D 6 (Table 4 2, entry 2.2). ........ 285 C 80 13 C NMR spectrum of polymer 2.3 in HFIP + C 6 D 6 (Table 4 2, entry 2.3). ........ 286 C 81 13 C NMR spectrum of polymer 2.4 in HFIP + C 6 D 6 (Table 4 2, entry 2.4). ........ 286 C 82 13 C NMR spectrum of polymer 2.5 in HFIP + C 6 D 6 (Table 4 2, entry 2.5). ........ 286 C 83 13 C NMR spectrum of polymer 2.6 in HFIP + C 6 D 6 (Table 4 2, entry 2.6). ........ 287 C 84 13 C NMR spectrum of polymer 3.1 in HFIP + C 6 D 6 (Table 4 3, entry 3.1). ........ 2 87 C 85 13 C NMR spectrum of polymer 3.2 in HFIP + C 6 D 6 (Table 4 3, entry 3.2). ........ 287 C 86 13 C NMR spectrum of polymer 3.3 in HFIP + C 6 D 6 (Table 4 3, entry 3.3). ........ 287 C 87 13 C NMR spectrum of polymer 3.4 in HFIP + C 6 D 6 (Table 4 3, entry 3.4). ........ 288 C 88 13 C NMR spectrum of polymer 3.5 in HFIP + C 6 D 6 (Table 4 3, entry 3.5). ........ 288 C 89 13 C NMR spectrum of polymer 3.6 in HFIP + C 6 D 6 (Table 4 3, entry 3.6). ........ 288 C 90 13 C NMR spectrum of polymer 3.7 in HFIP + C 6 D 6 (Table 4 3, entry 3.7). ........ 289 C 91 13 C NMR spectrum of polymer 4.1 in HFIP + C 6 D 6 (Table 4 4, entry 4.1). ........ 289 C 92 13 C NMR spectrum of polymer 4.2 in HFIP + C 6 D 6 (Table 4 4, entry 4.2). ........ 289 C 93 13 C NMR spectrum of polymer 4.3 in HFIP + C 6 D 6 (Table 4 4, entry 4.3). ........ 290 C 94 13 C NMR spectrum of polymer 4.4 in HFIP + C 6 D 6 (Table 4 4, entry 4.4). ........ 290

PAGE 30

30 C 95 13 C NMR spectrum of polymer 4.5 in HFIP + C 6 D 6 (Table 4 4, entry 4.5). ........ 290 C 96 13 C NMR spectrum of polymer 4.6 in HFIP + C 6 D 6 (Table 4 4, entry 4.6). ........ 291 C 97 GPC Chromatogram of polymer 2.1 in HFIP solvent (Table 4 2, entry 2.1). ..... 291 C 98 GPC Chromatogram of polymer 2.2 in HFIP solvent (Table 4 2, entry 2.2). ..... 291 C 99 GPC Chromatogram of polymer 2.3 in HFIP solvent (Table 4 2, entry 2.3). ..... 292 C 100 GPC Chromatogram of polymer 2.4 in HFIP solvent (Table 4 2, entry 2.4). ..... 292 C 101 GPC Chromatogram of polymer 2.5 in HFIP solvent (Table 4 2, entry 2.5). ..... 292 C 102 GPC Chromatogram of polymer 2.6 in HFIP solvent (Table 4 2, entry 2.6). ..... 293 C 103 GPC Chromatogram of polymer 3.1 in HFIP solvent (Table 4 3, entry 3.1). ..... 293 C 104 GPC Chromatogram of polymer 3.2 in HFIP solvent (Table 4 3, entry 3.2). ..... 293 C 105 GPC Chromatogram of polymer 3.3 in HFIP solvent (Table 4 3, entry 3.3). ..... 294 C 106 GPC Chromatogram of polymer 3.4 in HFIP solvent (Table 4 3, entry 3.4). ..... 294 C 107 GPC Chroma togram of polymer 3.5 in HFIP solvent (Table 4 3, entry 3.5). ..... 294 C 108 GPC Chromatogram of polymer 3.6 in HFIP solvent (Table 4 3 entry 3.6). ..... 295 C 109 GPC Chromatogram of polymer 3.7 in HFIP solvent (Table 4 3, entry 3.7). ..... 295 C 110 GPC Chromatogram of polymer 4.1 in HFIP solvent (Table 4 4, entry 4.1). ..... 295 C 111 GPC Chromatogram of polymer 4.2 in HFIP solvent (Table 4 4, entry 4.2). ..... 296 C 112 GPC Chromatogram of polymer 4.3 in HFIP solvent (Table 4 4, entry 4.3). ..... 296 C 113 GPC Chromatogram of polymer 4.4 in HFIP solvent (Table 4 4, entry 4.4). ..... 296 C 114 GPC Chromatogram of polymer 4.5 in HFIP solvent (Table 4 4, entry 4.5). ..... 297 C 115 GPC Chromatogram of polymer 4.6 in HFIP solvent (Table 4 4, entry 4.6). ..... 297 D 1 FT IR spectrum of polymer 1 1 (Table 5 1, entry 1.1). ................................ ...... 298 D 2 FT IR spectrum of polymer 1 2 (Table 5 1, entry 1.2). ................................ ...... 298 D 3 FT IR spectrum of polymer 1 3 (Table 5 1, entry 1.3). ................................ ...... 299 D 4 FT IR spectrum of polymer 1 4 (Table 5 1, entry 1.4). ................................ ...... 299

PAGE 31

31 D 5 FT IR spectrum of polymer 1 5 (Table 5 1, entry 1.5). ................................ ...... 299 D 6 FT IR spectrum of polymer 2.1 (Table 5 2, entry 2.1). ................................ ...... 300 D 7 FT IR spectrum of polymer 2.2 (Table 5 2, entry 2.2). ................................ ...... 300 D 8 FT IR spectrum of polymer 2.3 (Table 5 2, entry 2.3). ................................ ...... 300 D 9 FT IR spectrum of polymer 2.4 (Table 5 2, entry 2.4). ................................ ...... 301 D 10 FT IR spectrum of polymer 2.5 (Ta ble 5 2, entry 2.5). ................................ ...... 301 D 11 FT IR spectrum of polymer 2.6 (Table 5 2, entry 2.6). ................................ ...... 301 D 12 FT IR spectrum of polymer 2.7 (Table 5 2, entry 2.7). ................................ ...... 302 D 13 FT IR spectrum of polymer 2.8 (Table 5 2, entry 2.8). ................................ ...... 302 D 14 FT IR spectrum of polymer 2.10 (Table 5 2, entry 2.10). ................................ .. 302 D 15 FT IR spectrum of polymer 2.11 (Table 5 2, entry 2.11). ................................ .. 303 D 16 FT IR spectrum of polymer 2.12 (Table 5 2, entry 2.12). ................................ .. 303 D 17 FT IR spectrum of polymer 2.13 (Table 5 2, entry 2.13). ................................ .. 303 D 18 FT IR spectrum of polymer 2.14 (Table 5 2, entry 2.14). ................................ .. 304 D 19 FT IR spectrum of polymer 2.15 (Table 5 2, entry 2.15). ................................ .. 304 D 20 FT IR spectrum of polymer 2.16 (Table 5 2, entry 2.16). ................................ .. 304 D 21 FT IR spectrum of polymer 2.17 (Table 5 2, entry 2.17). ................................ .. 305 D 22 FT IR spectrum of polymer 2.18 (Table 5 2, entry 2.18). ................................ .. 305 D 23 FT IR spectrum of polymer 2.19 (Table 5 2, entry 2.19). ................................ .. 305 D 24 TGA Thermogram of polymer 1.1 (Table 5 1, entry 1.1). ................................ .. 306 D 25 TGA Thermogram of polymer 1.2 (Table 5 1, entry 1.2). ................................ .. 306 D 26 TGA Thermogram of polymer 1.3 (Table 5 1, entry 1.3). ................................ .. 306 D 27 TGA Thermogram of polymer 1.4 (Table 5 1, entry 1.4). ................................ .. 307 D 28 TGA Thermogram of polymer 1.5 (Table 5 1, entry 1.5). ................................ .. 307 D 29 TGA Thermogram of polymer 2.1 (Table 5 2, entry 2.1). ................................ .. 307

PAGE 32

32 D 30 TGA Thermogram of polymer 2.2 (Table 5 2, entry 2.2). ................................ .. 308 D 31 TGA Thermogram of polymer 2.3 (Table 5 2, entry 2.3). ................................ .. 308 D 32 TGA Thermogram of polymer 2.4 (Table 5 2, entry 2.4). ................................ .. 309 D 33 TGA Thermogram of polymer 2.5 (Table 5 2, entry 2.5). ................................ .. 309 D 34 TGA Thermogram of polymer 2.6 (Table 5 2, entry 2.6). ................................ .. 310 D 35 TGA Thermogram of polymer 2.7 ( Table 5 2, entry 2.7). ................................ .. 310 D 36 TGA Thermogram of polymer 2.8 (Table 5 2, entry 2.8). ................................ .. 311 D 37 TGA Thermogram of polymer 2.10 (Table 5 2, entry 2.10). .............................. 311 D 38 TGA Thermogram of polymer 2.11 (Table 5 2, entry 2.11). .............................. 312 D 39 TGA Thermogram of polymer 2.12 (Table 5 2, entry 2.12). .............................. 312 D 40 TGA Thermogram of polymer 2.13 (Table 5 2, entry 2.13). .............................. 313 D 41 TGA Thermogram of polymer 2.14 (Table 5 2, entry 2.14). .............................. 313 D 42 TGA Thermogram of polymer 2.15 (Table 5 2, entry 2.15). .............................. 314 D 43 TGA Thermogram of polymer 2.16 (Table 5 2, entry 2.16). .............................. 314 D 44 TGA Thermogram of polymer 2.17 (Table 5 2, entry 2.17). .............................. 315 D 45 TGA Thermogram of polymer 2.18 (Table 5 2, entry 2.18). .............................. 315 D 46 TGA Thermogram of polymer 2.19 (Table 5 2, entry 2.19). .............................. 316 D 47 DSC Thermogram of polymer 1.1 (Table 5 1, entry 1.1). ................................ 316 D 48 DSC Thermogram of polymer 1 .2 (Table 5 1, entry 1.2). ................................ 316 D 49 DSC Thermogram of polymer 1.3 (Table 5 1, entry 1.3). ................................ 317 D 50 DSC Thermogram of polymer 1.4 (Table 5 1, entry 1.4). ................................ 317 D 51 DSC Thermogram of polymer 1.5 (Table 5 1, entry 1.5). ................................ 317 D 52 DSC Thermogram of polymer 2.1 (Table 5 2, entry 2.1). ................................ 318 D 53 DSC Thermogram of polymer 2.2 (Table 5 2, entry 2.2). ................................ 318 D 54 DSC Thermogram of polymer 2.3 (Table 5 2, entry 2.3). ................................ 31 9

PAGE 33

33 D 55 DSC Thermogram of polymer 2.4 (Table 5 2, entry 2.4). ................................ 319 D 56 DSC Thermogram of polymer 2.5 (Table 5 2, entry 2.5). ................................ 320 D 57 DSC Thermogram of polymer 2.6 (Table 5 2, entry 2.6). ................................ 320 D 58 DSC Thermogram of polymer 2.7 (Table 5 2, entry 2.7). ................................ 321 D 59 DSC Thermogram of polymer 2.8 (Table 5 2, entry 2.8). ................................ 321 D 60 DSC Thermogram of polymer 2.10 (Table 5 2, entry 2.10). ............................. 322 D 61 DSC Thermogram of polymer 2.11 (Table 5 2, entry 2.11). ............................. 322 D 62 DSC Thermogram of polymer 2.12 (Table 5 2, entry 2.12). ............................. 323 D 63 DSC Thermogram of polymer 2.13 (Table 5 2, entry 2.13). ............................. 323 D 64 DSC Thermogram of polymer 2.14 (Table 5 2, entry 2.14). ............................. 324 D 65 DSC Thermogram of polymer 2.15 (Table 5 2, entry 2.15). ............................. 324 D 66 DSC Thermogram of polymer 2.16 (Table 5 2, entry 2.16). ............................. 325 D 67 DSC Thermogram of polymer 2.17 (Table 5 2, entry 2.17). ............................. 325 D 68 DSC Thermogram of polymer 2.18 (Table 5 2, entry 2.18). ............................. 326 D 69 DSC Thermogram of polymer 2.19 (Table 5 2, entry 2.19). ............................. 326 D 70 1 H NMR spectrum of polymer 1.1 in CDCl 3 (Table 5 1, entry 1.1). ................... 327 D 71 1 H NMR spectrum of polymer 1.2 in CDCl 3 (Table 5 1, entry 1.2). ................... 327 D 72 1 H NMR spectrum of polymer 1.3 in CDCl 3 (Table 5 1, entry 1.3). ................... 327 D 73 1 H NMR spectrum of polymer 1.4 in CDCl 3 (Table 5 1, entry 1.4). ................... 328 D 74 1 H NMR spectrum of polymer 1.5 in CDCl 3 (Table 5 1, entry 1.5). ................... 328 D 75 1 H NMR spectrum of polymer 2.1 in HFIP + CDCl 3 (Table 5 2, entry 2.1). ....... 328 D 76 1 H NMR spectrum of polymer 2.2 in HFIP + CDCl 3 (Table 5 2, entry 2.2). ....... 328 D 77 1 H NMR spectrum of polymer 2.3 in HFIP + CDCl 3 (Tab le 5 2, entry 2.3). ....... 329 D 78 1 H NMR spectrum of polymer 2.4 in HFIP + CDCl 3 (Table 5 2, entry 2.4). ....... 329 D 79 1 H NMR spectrum of polymer 2.5 in HFIP + CDCl 3 (Table 5 2, entry 2.5). ....... 329

PAGE 34

34 D 80 1 H NMR spectrum of polymer 2.6 in HFIP + CDCl 3 (Table 5 2, entry 2.6). ....... 330 D 81 1 H NMR spectrum of polymer 2.7 in HFIP + CDCl 3 (Table 5 2, entry 2.7). ....... 330 D 82 1 H NMR spectrum of polymer 2.8 in HFIP + CDCl 3 (Table 5 2, entry 2.8). ....... 330 D 83 1 H NMR spectrum of polymer 2.10 in HFIP + CDCl 3 (Table 5 2, entry 2.10). ... 331 D 84 1 H NMR spectrum of polymer 2.11 in HFIP + CDCl 3 (Table 5 2, entry 2.11). ... 331 D 85 1 H NMR spectrum of polymer 2.12 in HFIP + CDCl 3 (Table 5 2, entry 2.12). ... 331 D 86 1 H NMR spectrum of polymer 2.13 in HFIP + CDCl 3 (Table 5 2, entry 2.13). ... 332 D 87 1 H NMR spectrum of polymer 2.14 in HFIP + CDCl 3 (Table 5 2, entry 2.14). ... 332 D 88 1 H NMR spectrum of polymer 2.15 in HFIP + CDCl 3 (Table 5 2, entry 2.15). ... 332 D 89 1 H NMR spectrum of polymer 2.16 in HFIP d 2 (Table 5 2, entry 2.16). ............ 333 D 90 1 H NMR spectrum of polymer 2.17 in HFIP + CDCl 3 (Table 5 2, entry 2.17). ... 333 D 91 1 H NMR spectrum of polymer 2.18 in HFIP + CDCl 3 (Table 5 2, entry 2.18). ... 333 D 92 1 H NMR spectrum of polymer 2.19 in HFIP + CDCl 3 (Table 5 2, entry 2.19). ... 334 D 93 13 C NMR spectrum of polymer 1.1 in HFIP + CDCl 3 (Table 5 1, entry 1.1). ...... 334 D 94 13 C NMR spectrum of polymer 1.2 in HFIP + CDCl 3 (Table 5 1, entry 1.2). ...... 335 D 95 13 C NMR spectrum of polymer 1.3 in HFIP + CDCl 3 (Table 5 1, entry 1.3). ...... 335 D 96 13 C NMR spectrum of polymer 1.4 in HFIP + CDCl 3 (Table 5 1, entry 1.4). ...... 335 D 97 13 C NMR spectrum of polymer 1.5 in HFIP + CDCl 3 (Table 5 1, entry 1.5). ...... 336 D 98 13 C NMR spectrum of polymer 2.1 in HFIP + CDCl 3 (Table 5 2, entry 2.1). ...... 336 D 99 13 C NMR spectrum of polymer 2.2 in HFIP + C 6 D 6 (Table 5 2, entry 2.2). ........ 336 D 100 13 C NMR spectrum of polymer 2.3 in HFIP + CDCl 3 (Table 5 2, entry 2.3). ...... 336 D 101 13 C NMR spectrum of polymer 2.4 in HFIP + CDCl 3 (Table 5 2, entry 2.4). ...... 337 D 102 13 C NMR spectrum of polymer 2.5 in HFIP + CDCl 3 (Table 5 2, entry 2.5). ...... 337 D 103 13 C NMR spectrum of polymer 2.6 in HFIP + CDCl 3 (Table 5 2, entry 2.6). ...... 337 D 104 13 C NMR spectrum of polymer 2.7 in HFIP + CDCl 3 (Table 5 2, entry 2.7). ...... 338

PAGE 35

35 D 105 13 C NMR spectrum of polymer 2.8 in HFIP d 2 (Table 5 2, entry 2.8). ............... 338 D 106 13 C NMR spectrum of polymer 2.10 in HFIP + CDCl 3 (Table 5 2, entry 2.10). .. 338 D 107 13 C NMR spectrum of polymer 2 11 in HFIP d 2 (Table 5 2, entry 2.11). ........... 339 D 108 13 C NMR spectrum of polymer 2.12 in HFIP + CDCl 3 (Table 5 2, entry 2.12). .. 339 D 109 13 C NMR spectrum of polymer 2.13 in HFIP + CDCl 3 (Table 5 2, entry 2.13). .. 339 D 110 13 C NMR spectrum of polymer 2.14 in HFIP + CDCl 3 (Table 5 2, entry 2.14). .. 340 D 111 13 C NMR spectrum of polymer 2.15 in HFIP + CDCl 3 (Table 5 2, entry 2.15). .. 340 D 112 13 C NMR spectrum of polymer 2.16 in HFIP d 2 (Table 5 2, entry 2.16). ........... 340 D 113 13 C NMR spectrum of polymer 2.17 in HFIP d 2 (Table 5 2, entry 2.17). ........... 341 D 114 13 C NMR spectrum of polymer 2.18 in HFIP + CDCl 3 (Table 5 2, entry 2.18). .. 341 D 115 13 C NMR spectrum of polymer 2.19 in HFIP + CDCl 3 (Table 5 2, entry 2.19). .. 341 D 116 GPC Chromatogram of polymer 1.1 (Table 5 1, entry 1.1). .............................. 342 D 117 GPC Chromatogram of polyme r 1.2 (Table 5 1, entry 1.2). .............................. 342 D 118 GPC Chromatogram of polymer 1.3 (Table 5 1, entry 1.3). .............................. 342 D 119 GPC Chromatogram of polymer 1.4 (Table 5 1, entry 1.4). .............................. 343 D 120 GPC Chromatogram of polymer 1.5 (Table 5 1, entry 1.5). .............................. 343 D 121 GPC Chromatogram of polymer 2.1 (Table 5 2, entry 2.1). .............................. 343 D 122 GPC Chromatogram of polymer 2.2 (Table 5 2, entry 2.2). .............................. 344 D 123 GPC Chromatogram of polymer 2.3 (Table 5 2, entry 2.3). .............................. 344 D 124 GPC Chromatogram of polymer 2.4 (Table 5 2, entry 2.4). .............................. 344 D 125 GPC Chromatogram of polymer 2.5 (Table 5 2, entry 2.5). .............................. 345 D 126 GPC Chromatogram of poly mer 2.6 (Table 5 2, entry 2.6). .............................. 345 D 127 GPC Chromatogram of polymer 2.7 (Table 5 2, entry 2.7). .............................. 345 D 128 GPC Chromatogram of polymer 2.8 (Table 5 2, entry 2.8). .............................. 346 D 129 GPC Chromatogram of polymer 2.10 (Table 5 2, entry 2.10). .......................... 346

PAGE 36

36 D 130 GPC Chromatogram of polymer 2.11 (Table 5 2, entry 2.11). .......................... 346 D 131 GPC Chromatogram of polymer 2.12 (Table 5 2, entry 2.12). .......................... 347 D 132 GPC Chromatogram of polymer 2.13 (Table 5 2, entry 2.13). .......................... 347 D 133 GPC Chromatogram of polymer 2.14 (Table 5 2, entry 2.14). .......................... 348 D 134 GPC Chromatogram of polymer 2.15 (Table 5 2, entry 2.15). .......................... 348 D 135 GPC Chromatogram of polymer 2.16 (Table 5 2, entry 2.16). .......................... 349 D 136 GPC Chromatogram of polymer 2.17 (Table 5 2, entry 2.17). .......................... 349 D 137 GPC Chromatogram of polymer 2.18 (Table 5 2, entry 2.18). .......................... 349 D 138 GPC Chromatogram of polymer 2.19 (Table 5 2, entry 2.19). .......................... 349

PAGE 37

37 LIST OF ABBREVIATIONS C1 A one carbon molecule CO Carbon monoxide DSC Differential Scanning Calorimetry FTIR Fourier Transform Infrared Spectroscopy GPC Gel Permeation Chromatography M n Number Average Molecular Weight NMR Nuclear Magnetic Resonance PDI Polydispersity Index PGA Polyglycolic acid POM Polyoxymethylene ROP Ring opening Polymerization T g Glass Transition Temperature T m Melting Temperature TfOH Triflic acid TGA Thermogravimetric analysis

PAGE 38

38 Abstract of Dissertation Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy AN ALTERNATIVE APPROACH FOR SYNTHESIZING POLYGLYCOLIC ACID AND ITS COPOLYMERS FROM C1 FEEDSTOCKS By Ersen Gokturk May 20 14 Chair: Stephen A. Miller Major: Chemistry Polyglycolic acid (PGA) is a well known biodegradable polymer, which is traditionally synthesized via anionic polymerization o f glycolide (mostly with tin oc tanoate catalyst). Although this route has been the best option in terms of high yields and molecular weights, the need to use very expensive glycolide monomer limit s the industrial scale production of PGA The main objective of this research is to find an alternative way to synthesize PGA and its copolymer s using materials derive d from potentially sustainable C1 feedstocks, particularly formaldehyde and carbon monoxide (CO) The new synthesis route involves c ationic alternating copolymerizations o f formaldehyde from trioxane and CO to produce PGA This meth od constitutes a cost effective and efficient path for the synthesis of PGA By using this method, PGA was successfully synthesized with yields up to 92% using triflic acid (TfOH) catalyst under 800 psi CO pressure at 170 o C in three days. T he polymer from CO and H 2 CO is sufficiently similar to that prepared from glycolide that it can be readily substituted for the PGA prepared by the glycolide route T he physical properties of PGA ( such as melting temperature and appearance ) could be tailored by a copolym erization strategy, in which a minor amount of a

PAGE 39

39 comonomer was added to the reaction system. By controlling the comonomer feed ratios and the polymerization temperatures, hig h quality PGA based copolymers were prepared. Furthermore, we used the method to m ake copolymers of PGA w ith alkylene oxides or cyclic ether comonomers included in the polymerization mixture with the C1 monomers to yield polyester ether thermoplastics. The melting temperatures of all terpolymers are lower, and the colors are lighter th an th ose of the commercial PGA. Polymer solubility can be increased by increasing the l ength of the side chain containing the alkylene oxide compound One of the products exhibited thermal properties similar to those of isotactic polypropylene suggesting that the ter polymer can be used as a replacement for this isotactic PP in some applications The need for very high CO pressure s and high temperature s for th e p roduction of PGA led us to discover transition metal assisted copolymeri zation of formaldehyde and CO. There is a need for new catalyst systems that exhibit higher activity to decrease polymerization time, temperature and/ or CO pressure. Some of our efforts involved the Co 2 (CO) 8 /3 hydroxypyridine catalyst system, but it did no t seem to be effective for the activation of trioxane or insertion of CO After testing several catalyst systems, scandium triflate [Sc(OTf) 3 ] exhibited very good activity towards the cationic copolymerization of formaldehyde and CO yield of PGA up to 78 % were produced in three days at 150 o C Sc(OTf) 3 is an environmentally friendly catalyst and can be recycled from the reaction media. These properties present important advantages for a catalyst system, and polymerization using Sc(OTf) 3 is a very convenien t alternative way for production of PGA.

PAGE 40

40 CHAPTER 1 A BIODEGRADABLE POLYMER: POLYGLYCOLIC ACID Introduction In recent years, research into biodegradable and biorenewable plastics to replace petroleum based products has increased dramatically. 1 Large portions o f trash in landfills are petroleum b ased polymer materials, including plastic bags, bottles etc 2 The d egradability of these petroleum based materials (such as polystyrene) takes a very long time, e.g., thousands of years, and increasing global pollution can be attributed is these non degradable materials; 3 Therefore, a switch fr om petroleum based plastics to degradable polymers is necessary. D egradable polymers contain hydrolytically unstable functional groups (su ch as esters, anhydrides, etc.) in their backbone s, but most petroleum based polymers do not. Because of hydrolytically unstable functional groups, these linkages can be hydrolyzed, or eaten by microorganisms, and degradability happens. 4 Biodegradable poly mers have gained considerable attention in two major areas: environmental protection and biomedical applications. In addition to addressing environmental concern s about managing plastic waste, 5 biodegradable polymers can be used for the medical applications as drug delivery systems, tissue engineering, surgical sutures, etc. 6,7 There are two main classifica tions of biodegradable polymers: natural and synthetic. Cellulose, starch, and etc. can b e given as examples of natural biodegradable polymers. Polyglycolic acid, polylactic acid, and etc. are the best known synthetic biodegradable polymers. Currently some implants for drug delivery, dental, and

PAGE 41

41 orthopedic applications, such as screws, nails, and etc., are prepared from polyglycolic acid and its copolymers because of their biocompatibility and biodegradability 8 Polyglycolic Acid Polyglycolic acid ( trade name Kuredux by Kureha corporation) 9 is the simplest biodegradable poly hydroxy acid) It has repeat units of glycolic acid and is found in some sugar crops (Figure 1 1) 10 Polyglycolic acid is a rigid, very crystalline thermoplastic polymer (45 55 %) 65 with a melting t emperature ( T m ) between 225 and 230 o C and a glass transition temperature ( T g ) around 35 40 o C 1 1 Because of its high crystallinity, it is not soluble in most solvents except highly fluorinated solvents such as hexafluoroisopropanol up to a molar mass of 45,000 g/mol. 1 2 Figure 1 1. The structure of the pol yglycol ic acid (PGA) repeat unit. There are three main types of processes to produce PGA: polycond ensation of glycolic acid, ring opening polymerization glycolide, and solid state polycondensation of halogenoacetates (Figure 1 2) Polycondensation methods give ri se to p olymers of low molecular weight ; however, higher molecular w eights can be obtained via ring opening polymerization of glycolide, the cyclic dimer form of glycolic acid. 13

PAGE 42

42 F igure 1 2 Three main synthesis methods for the preparation of PGA. The Most Commonly Used Synthetic Methods for PGA Po lycondensation of Glycolic Acid The e asiest way to produce PGA is by polycondensation of glycolic acid, but it always result s in low molecular weight product (Figure 1 3) Therefore it is not the most efficien t way to prepare PGA. Removal of water during the polycondensation drives the reaction but it is difficult to completely remove water from the waxy oligo GA mixture, due to the high boiling point of water. Another issue is the use of high temperature and l ow pressure for the polycondensation which promot es depolymerization of oligo GA to eliminate glycolide as a side product and interrupt the polymer chain growth. Taking into account these two drawbacks, low mole cular weight PGA is observed by polyc ondensa tion of glycolic acid. 1 4 Figure 1 3. Polycondensation of glycolic acid.

PAGE 43

43 To observe high molecular weight PGA, the azeotropic dehydration technique was also applied in the polycondensation of glycolic acid. W ater as a by product i s removed azeotropically by using a Dean S tark trap, and thus polycondensation of glycolic acid is driven to formation of very high molecular weight s up to M w = 300,000 g/mol. This method can be efficiently used below the ceiling temperatures of the polymers, thereby preventing depolymerization during the reaction. 1 5 Ring Open ing Polymerization of Glycolide Ring opening polymerization (ROP) is one of the most employed methods for polymerization including step and chain polymeriz ations. 1 6 Some cyclic monomers containing a functional group, such as ether, acetal, ester (lactone), amide (lactam) etc., can be successfully polymerized by the ring opening polymerization process to yield linear polymeric structures. Figure 1 4 illustrat es some examples of the ring opening polymerization. 1 7 Figure 1 4 Three examples of ring opening polymerizations. 1 8

PAGE 44

44 To convert a cyclic monomer to a linear polymer depends on thermodynamic and kinetic factors. While the relative stability of the cyclic monomer structure is the most important thermodynamic factor, a mechanism to open the ring and undergo a polymerization reaction count s as a kinetic factor. Thermodynamic factors generally play more important role s for ring opening polymerization than kin etic factors. Except for 5 and 6 membered rings, most cyclic monomers can be polymerize d by ROP and the polymerizations are t hermodynamically favorable. Six membered cyclic compounds have less ring strain ; therefore they are mostly unable to polymerize. Small rings, such as 3 and 4 membered rings, have very high ring strains; therefore, they undergo very exothermic ring opening polymerization s Large rings, such as between 7 to 9 membered rings, have le ss ring strain; therefore, the reaction enthalpy is very small, and polymerization becomes less favorable. For this case, entropic force s drive the reaction to open the rings. 1 9 There are several types of ring opening polymerization mechanism s such as rad ical metathesis, ionic (cationic and anionic), coordination, etc., depending on the structure of the monomer and the initiating system. O lefin metathesis, and ionic (cationic and anionic) mechanisms are the most applied methods for ROP. 20 The first prepar ation of a polyhydroxy acid using ring opening polymerization of lactones was achieve d by C arother s and cow orkers in the earlier 1930 s but with low molecular weights 21 T he ring strain of glycolide having two ester groups with a planar conformation become s a driving force for the ring opening polymerization of glycolide. Its estimated standard state enthalpy of polymerization reaction is around 20 KJ/mol, which is higher than that of normal lactones having one ester group. The most common

PAGE 45

45 catalyst to achi eve this polymerization is t in (II) bis(2 ethylhexanoate). Alternatively, a luminum alkoxides (especially Al(O i Pr) 3 ) or zinc catalysts can also be used as ring opening polymerization catalyst s for lactones. 2 2 Figure 1 5. The mechanism of the ring opening polymerization of glycolide by Sn(II) octanoate catalyst. Industrially, the most com mon strategy relies on the ring opening polymerization of glycolide. 13 Although this route has been the best option for producing high yields and molecular weights, the ve ry expensive glycolide monomer (Sigma Aldrich list price: 25 g is 90.98 $) 67 is limits large scale production of PGA. Another issue is that the ring opening polymerization of glycolide is mostly achieved anionically using tin octanoate catalyst and benzyl alcohol as a n initiator ( Figure 1 5 ). 2 3 Tin compounds are very toxic materials, and it is not easy to remove all tin compounds from the product. The high cost of glycolide and toxicity of the catalyst make it important to find an alternative route for synt hesizing PGA. 2 4 Recent ly, Bourissou and coworkers reported that PGA could also be prepared cationically from glyco lide In this case, a L ewis acid catalyst such as triflic acid initiates the polymerization at room temperature. 2 5 However, the resulting

PAGE 46

46 PGA mostly has a very low molecular weight and poor physical properties. 12 G lycolide is an expensive compound and therefore, the synthesis of PGA via these methods is not ideal for large scale production. Solid State Polycondensation of Halogenoacetates Therma lly induced s o lid state polycondensation of halogenoacetates, such as sodium chloroacetates, also produce PGA. Polymerization requires high temperatures between 160 180 o C under nitrogen atmosphere. During the polymerization, a salt as a side product is fo rmed, and it can be easily removed by washing with water (Figure 1 6) 26 Figure 1 6. Solid state polycondensation of h alogenoacetates

PAGE 47

47 CHAPTER 2 THE SYNTHESIS OF POLYGLYCOLIC ACID FROM C1 FEEDSTOCKS Background We were attracted to alternating copolymer izations of ethylene and carbon monoxide (CO) with Pd catalyst to produce Carilon ( Figure 2 1). 27 These polyketones are structurally similar to the PGA. Due to their structural similarity, the thermal properties of PGA are similar to those of Carilon, with glass transition temperatures ( T g ) around 35 o C and melting temperatures ( T m ) of 215 o C. 28 Instead of using ethylene, if formaldehyde can be polymerized with CO PGA may be observed. 29 The inexpensive C1 monomers formaldehyde and CO are potential ly ma de from methanol, which has been a very sustainable/green monomer for over 100 years, as it was produced via the destructive distillation of wood (hence its common name of wood alcohol). 3 0 B esid es methanol, CO is also a readily available C1 building block produced from agricultural waste, natural gas or coal. 31 Since methanol (wood alcohol) and CO can be obtained from biomass, this synthesis of PGA should be efficient, inexpensive, and potentially sustainable. Figure 2 1 Synthesis of Carilon and PGA Previous Work Masuda and coworkers reported on a copolymerization of trioxane as a formaldehyde source and CO in acidic condition using chlorosulfonic acid as the

PAGE 48

48 catalyst (Figure 2 2) They established that protonated formaldehyde in DCM at 800 psi CO at 180 o C reacted in two hours to yield a PGA based product. The product mainly consisted of two different parts that were acetone soluble and acetone insoluble respectively While the acetone soluble part had a molecular weight below 1000 g/mol, the acetone insoluble part had a molecular weight of 1200 g/mol or higher. 3 2 Figure 2 2. Cationic copolymerization of trioxane and CO in chlorosulfonic acid. 3 2 In the 197 0s, Cevidalli and coworkers patent ed the cationic copolymerization of formaldehyde and CO in L ewis acidic condition s at high temperature and pressure (F igure 2 3 ). The r eaction was carried out at 200 o C in 2500 psi CO in DCM with BF 3 OEt 2 as catalyst. As a product, low molecular weight polymer ( M n = 500 to 2000) was reported, and the product was ap parently a n o ligo glycolic acid microstructure. No melting temperatures were reported and other key characterization data were lacking. The product was poorly characterized. 3 3 Figure 2 3. BF 3 OEt 2 catalyzed copolymerization of trioxane and CO. 3 3 Cationic Ring Ope ning Polymerization of Trioxane Trioxane is the cyclic trimer form of formaldehyde. It can be synthesized by distillation of formaldehyde in acidic solution. Trioxane is commercially used to produce

PAGE 49

49 polyoxymethylene. Cationic ring opening polymerization of tr ioxane is achieved with strong L ewis acids like BF 3 or TiCl 4 and Br nsted acids. 3 4 As a reaction mechanism for the polymerization, the protonated acetal oxygen of trioxane is driven to a ring opening reaction through one of the O C bond s by adjacent oxygen atom resonance stabilization to yield carbocation oxonium ions. 3 5 The oxonium ion can either release a formaldehyde molecule or undergo an addition reaction with a new trioxane or a formaldehyde molecule to propagate the polymerization (Figure 2 4) Figure 2 4. Cationic polymerization mechanism of polyoxymethylene (POM). Copolymerizations of Trioxane and Carbon M onoxide W e first sought an appropriate catalyst and temperature that wou ld be amenable to cationic ring opening polymeriza tion (ROP) of trioxane and nucleophilic addition of CO ( Figure 2 5) 3 6 Without suitable catalyst, t he reaction requires a very high pressure of CO, which has poor nucleophilicity, and high temperatures and long reaction times are also required Our results have shown that cationic copolymerization of trioxane and CO is efficiently achieved in Br nsted acidic conditions at 170 o C in three days with 92% yield. The p oor nucleophilicity of CO is probably the rate limiting step for the polymerization The product exhibited characterization results similar to those of commercial PGA purchased from Polysciences I nc. (catalog# 06525). 37

PAGE 50

50 Figure 2 5 Stepwise production of PGA via two different routes. We have apparently for the first time definitively confirmed the identity of the PGA made via this route, and the polymers can be used for the same applications as commercial PGA. The number of synthetic steps from simple feedstocks is greatly reduced and the starting materials are all potenti ally sustaina ble from biomass. The methodology could potentially be utilized to m ake other important polyesters or copolymers from related starting materials. Results and Discussion Several acid catalysts, BF 3 OEt 2 p TSA, and triflic acid, were investigated for the copolymerization of trioxane and CO ( Figure 2 6 ). Different solvent systems, reaction temperatures and pressures were tried to determine the optimum polymerization condition s (Table 2 1).

PAGE 51

51 Figure 2 6 Synthesis of PGA from trioxane a nd CO under Lewis acidic condition s All reactions were carried out in a high pressure reactor, with catalyst loading kept 1 mol %. BF 3 .OEt 2 catalyzed reactions always yielded polyoxymethylene (POM) products, with no observable CO incorporation in the poly mer backbones even at higher temperatures and pressures. T rioxane can be polymeri zed in DCM with an appropriate L ewis acid catalyst to result in POM ( Figure 2 7 ). 38 Because t his reaction happens even at room temperature, a polyoxymethylene side product might also be formed during the polymerization. Polyoxymethylene is not soluble in most of the solvents due to its high crystallinity and strong anomeric interactions i n polymer backbones. 39 Figure 2 7. The possible side r eaction of the cationic polymerization of trioxane, and the formation of polyoxymethylene 38 Polymerization attempts using p TSA and triflic acid catalysts were very successf ul. Starting at 100 o C reaction temperature s CO incorporation was significant for both catalysts. However, triflic acid showed better catalytic activity than p TSA for the same reaction conditions. Therefore, triflic acid was chosen as the polymerization catalyst. For triflic acid catalyzed reactions, the CO pres sure was always kept at 800 psi, while reaction temperature reaction time and solvent systems were changed to determine their effect s on the polymerization. Efficient polymerization was accomplished in DCM with 1 % mol TfOH loading at 170 o C in three days (entry 1.17 in T able 2 1 )

PAGE 52

52 The thermal stability of PGA decreased with a degradation temperature at 245 o C (10% of degradation ), which is close to its melting temperature. 64 Because of degradation behavior of PGA at higher temperatures the yield dramatically decreased for reaction temperatures above 170 o C. If all the methylene groups in 0.1 mol (9.03 g) of trioxane had acquired a carbonyl group, the theoretical yield would have been 17.4 g PGA product. Accor ding to this fact, entry 1.17 in T able 2 1 produced the highe st yield at 92%. All polymer samples were insoluble in most of the solvents except HFIP (hexafluoro isopropanol). Because HFIP is v ery expensive and dangerous to the respiratory system, molar mass values of the products could not be determined by intrinsic viscosity values. Addition ally, to our knowledge, there are no Mark Houwink parameters for PGA in the literature to convert the data. 63 The po lymers with no CO incorporation (according to FT IR and 13 C NMR spectra) displayed higher molecular weights ( entri es 1.1 to 1.6 in T able 2 1). This is the reason of the formation of POM without having CO insertion As soon as CO incorporation was achieved, the molecular weights of the products interestingly decreased. We suspect that even if formaldehyde formaldehyde insertions may occur to form POM at high temperatures, the ce iling temperature of POM does not allow more acetal units in the polymer backbone. POM repeat units lose formaldehyde with heating, and only glycolic acid repeating units stay together to form PG A. Therefore, molecular weights of the products become lower. Even when we observed 92% yield, the molecular weight data showed only oligoglycolic acid formation.

PAGE 53

53 Table 2 1. Copolymerization results of trioxane and CO by Br nsted acid and Lewis acid catalysts. Entry a CO (psi) Catalyst b Solvent T p ( o C) Time Yield (g) Yield (%) M n (g/mol) PDI T g ( o C) T m ( o C) 1.1 250 BF 3 .OEt 2 DCM RT 1 day 4.76 28 9200 1.42 35.5 119.4 1.2 480 BF 3 .OEt 2 DCM RT 1 day 7.03 41 8700 1.76 42.2 119.5 1.3 800 BF 3 .OEt 2 DCM 100 1 day NR 0 1.4 800 TfOH DCM 50 1 day 4.09 24 13400 2.54 40.6 89.3 1.5 800 TfOH DCM 60 1 day 4.26 25 12400 3.05 41.1 129.2 1.6 800 TfOH DCM 80 1 day 2.63 15 4000 2.64 32.1 99.3 1.7 800 TfOH DCM 100 1 day 2.51 14 736 1.43 22.2 115.1 1.8 800 TfOH DCE 100 1 day 2.00 11 898 1.23 15.1 141.4 1.9 800 TfOH Heptane 100 1 day 3.50 20 825 1.32 17.9 118.6 1.10 800 TfOH DCM 105 1 day 2.58 15 546 2.04 17.1 159.5 1.11 800 TfOH DCM 130 1 day 3.53 20 1100 1.50 3.37 118.3 1.12 800 p TSA DCM 120 2 days 5.45 31 723 1.48 21.7 133.0 1.13 800 TfOH DCM 120 2 days 6.70 39 1000 1.48 38.8 143.0 1.14 800 TfOH DCM 110 3 days 8.25 47 1400 1.69 28.7 161.4 1.15 800 TfOH DCM 130 3 days 11.00 63 1000 1.48 15.1 163.7 1.16 800 TfOH DCM 150 3 days 14.40 83 1600 1.52 11.9 181.0 1.17 800 TfOH DCM 170 3 days 16.00 92 1800 1.73 13.0 191.9 1.18 800 TfOH DCM 180 3 days 9.80 56 1000 1.43 15.1 n.d. 1.19 c 800 TfOH HFIP 170 3 days 2.44 56 1400 1.59 38.1 n.d. 1.20 800 TfOH Xylenes 130 3 days NR 0 a Reactions conducted with 9.03 g (0.1 mol) of trioxane. b Catalyst loading was kept at 1 mol % of trioxane (0.001 mol TfOH ) c reaction conducted with 1.80 g of trioxane.

PAGE 54

54 To achieve higher molecular weights, we decided to use two different strategies: 1) polycondensation of oligoglycolic acid, and 2) addition of a branching agent (glycerol) to the reaction mixture. Polycondensation of oligoglycolic acid was prom oted by using Zn(OAc) 2 2H 2 O catalyst ( Figure 2 8 ). 40 In a typical run, a 2 g sample of o ligoglycolic acid (entry 1.17 in T able 2 1) was mixed with 0.5 wt % of the catalyst and heated to 200 o C with stirring for 2h. After that reduced pressure of 150 mmHg was applied for 12 h. We did not raise the temperature above 200 o C in order to prevent possible decomposition of PGA. After the polycondensation, the number average molecular weight of PGA reached up to about 600,000 g/mol. Since PGA is considered as soluble in hexafluoroisopropanol up to a molar mass of 45,000 g/mol due to its high crystallinity 1 2 this result might be the reason of aggregation of the product. Figure 2 8 High molecular weight PGA production f rom polycondensation of oligoGA. As a s econd strategy to increase the molecular weight of the PGA, we added 1 mol % of glycerol to the reaction mixture to observe branched PGA having high molecular weight. We expected to see hydroxyl ( OH) group addition to the acylium ion or protonated formald ehyde intermediates. If that occurred glycerol would behave as a terminator and help the formation of three armed PGA structures ( Figure 2 9 ). Figure 2 9 Utilization of glycerol as a branching agent for PGA production.

PAGE 55

55 Interestingly, the addition of 1 mol % of glycerol dramatically improved the reaction condition s (Table 2 2) The best yield was achieved at 150 o C in only one day as opposed to 170 o C in three days with a yield of 81 % which is much higher than the yields without addition of glycerol was incorporated in polymer backbone from 1 H NMR spectrum. Since HFIP proton peaks appeared at the same region as glycerol protons, they overlapped, and disappeared f rom the spectrum Table 2 2. Cationic c o pol ymer ization results of trioxane and CO with addition of glycerol. Entry a T p ( o C) Tim e Yield (g) Yield (%) M n (g/mol) PDI T g ( o C) T m ( o C) 2.1 100 1 day 7.1 40 44.6 172 2.2 150 1 day 14.2 81 50.3 206 2.3 170 1 day 5.0 28 51.4 198 a Reactions conducted wi th 9.03 g (0.1 mol) of trioxane, c atalyst loading was kept at 1 mol % of trioxane (0.001 mol TfOH ). The T g value of the oligomer entry 1.17 (Table 2 1) was measured at 13 o C, which is relatively close to the T g T g = 45 o C ) The T m value of the oligomer entry 1.17 (Table 2 1) was measured at 192 o C with the T m of commercial PGA ( purchased from Polysciences Inc. ); T m = 215 o C. Polycondensation of the oligomer s resulted in a T g value at 74 o C and T m at 218 o C (Figure 2 10 ). TGA results show ed the degradation of the PGA samples beginning at 210 o C under nitrogen atmosphere. The DSC results (Figure 2 10) indicated that the melting and glass transition temperatures for entry 5.1 are located a t 74 o C and 219 o C, respectively ( data presented refer to the second heating scans )

PAGE 56

56 Figure 2 10. DSC thermograms of c ommercial PGA and entry 5.1 in F igure 2 8. To prove CO incorporation into the polymer backbone, 13 C NMR and FT IR spectra we re measured. FT IR data confirmed the expected PGA structure. The band at 1750 cm 1 can be undoubtedly assigned to the ester carbonyl group (Figure 2 11). Figure 2 11. FT IR s pectra of c ommercial PGA and entry 5.1 in F igure 2 8.

PAGE 57

57 Figure 2 12. 13 C NMR spectra of c ommercial PGA and entry 5.1 in F igure 2 8. Figure 2 12 displays the 13 C NMR spectr a for a representative PGA sample and carbonyl carbon and methylene carbon, respectively. The 13 C NMR data confirmed that the polymer samples had perfect agreement with the expected PGA structure with no 13 C NMR and FT IR spectr a of the products are in good agreement with those of commercially available P GA. Figure 2 13 displays the dependence of PGA melting temperature and molecular weight as a function of reaction temp erature. Polymer melting temperatures and molecular weights of the polymers show a gradual overall increase for increasing polymerization temperature. Thus, for these PGA series, higher reaction temperatures result in higher polymer melting temperature, and hig her molecular weight. This may be the reason for increased CO incorporation with increasing reaction temperature.

PAGE 58

58 Figure 2 13. Depe ndence of t he melting temperatures ( o C), and molecular weights (M n ) of PGA on increasing polymerization temperature. Much attention has been dedicated to better understanding the copolymerization mechanism of CO and trioxane catalyzed by Br nsted acid cata lysts. Combining our experimental observations results, we propose the polymer ization mechanism depicted in F igure 2 14 P rotonated formaldehyde undergo es an intermolecular attack by CO to generate an acylium carbocation intermediate, followed by another attack on this intermediate by either a trioxane or a formaldehyde molecule to continue the polymerization. 0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 50 100 150 200 250 100 110 120 130 140 150 160 170 180 Molecular Weight (M n ) Polymer Melting Temperature ( C ) Reaction Temperature ( C )

PAGE 59

59 Figure 2 14. The possible polymerization mec hanism of PGA synthesis To provide support for this mechanism, copolymerization of paraformaldehyde and CO was tried using the same reaction condition s as mentioned for trioxane and CO ( Figure 2 15 ). After several experiments shown in T able 2 3, we observ ed the exact same polymeric structure of PGA, with no observable POM units in the polymer backbone. We also investigated formalin ( a solution of formaldehyde in water ) as a formaldehyde source. As expect ed copolymeriz ation of formalin and CO did not resul t in PGA due to the deactivation of cationic intermediates in water. Figure 2 15. PGA production from paraformaldehyde and CO.

PAGE 60

60 Table 2 3. Copolymerization results of paraformaldehyde and CO catalyzed by triflic acid Entry Formaldehyde (g) T p ( o C) Time Yield (g) M n (g/mol) PDI T g ( o C) T m ( o C) 3.1 3.0 100 1 day 4.4 1000 1.30 18.5 162 3.2 9.0 170 3 days 6.2 51.2 n.d. Previously, we mentioned that the side product might be POM, or polymers might contain acetal units in the PGA backbone having polyester acetals. To see the effect of the POM, we first polymerized trioxane with TfOH in DCM at room temperature to produce PO M. After 2 hours, we directly raised the CO pressure and reaction temperature without terminating the reaction, and we observed the same polymeric product in three days ( Figure 2 16 ). To verify that the structure contained no acetal functionality; we looke d at the 13 C NMR spectrum of the product, and no acetal functionality was observed at 90 ppm in the 13 C NMR spectrum ( see appendix A ). T hese results prove that the products do not have any POM units in the backbone. Figure 2 16. PGA production from c hain end active polyoxymethylene and CO. Table 2 4 reports the gas phase thermodynamic calculations for the 1:1 incorporation of carbon monoxide and formalde Despite the nominally favorabl G = 0.2 kcal/mol at 298K), we pursued this copolymerization without deterrence from previous studies that yielded small molecule heterocycles from CO and formaldehyde 66 or that generally afforded only low molecular weight material that was poorly character ized.

PAGE 61

61 Table 2 4 G3(MP2)/DFT calculation for gas phase copolymerization thermodynamics. a model copolymerization reaction H S G 298 25.1 83.8 0.2 a deter mined by DFT B3LYP 6 311++G**. are kcal/mol and the S are cal/molK. In conclusion, this method constitutes cost effective a convenient, and efficient path for the synthesis of PGA from perfectly alternating copolymerizations of formaldehyde and CO. The number of synthetic steps from simple feedstock is greatly reduced and the starting materials are all potentially sustainable from biomass Higher polymerization temperatures resulted in lower yields, but higher CO incorporation. 3 6 Triflic acid proved to be the best catalyst for the polymerization The key point for this polymerization was the reaction time; long standing reaction times alwa ys brought about higher yields. Experimental General Considerations and Instrumentation Unless otherwise noted, all solvents were purified by stirring over calcium hydride for 24 hours and then vacuum transfer into an oven dried Straus flask. Xylenes were purchased from Sigma Aldrich and stored over molecular sieves. S olvents were purchased from Sigma Aldrich and utilized after further purification P araformaldehyde was purchased from Sigma Aldrich. Trioxane was purchased from Acros Organics and used after recrystallization in CHCl 3 The catalyst s para toluenesulfonic acid ( p TSA), BF 3 .OEt 2 were purchased from Sigma Aldrich and used as received. Triflic acid (TfOH) was purchased from Oakwood Chemical and used as received A Parr 600 mL high pressure autoclave was used for the experiments with a magnetic stir bar

PAGE 62

62 Proton nuclear magnetic resonance ( 1 H NMR) spectra were recorded using a n Inova 5 00 MHz spectrometer NMR sample preparation: 0.5 g of sample was dissolved in 0.4 g of HFIP, and 1.0 g of CDCl 3 (or C 6 D 6 ) was added to the mixture.; HFIP d 2 was also used for some NMR spectra For 1 H NMR, number of scans = 32 with a 5 s relaxation delay. For 13 C; number of scans = 10000 with 3 s relaxation delay. Chemical shifts are reported in parts per million (pp m) downfield relative to tetramethylsilane (TMS, 0.0 ppm) or residual proton s in the specified solvent. Differential scanning calorimetry thermograms were obtained with a DSC Q1000 from TA instruments. About 1.5 3 mg of each sample was weighed and sealed in a pan Thermal history was established by a he at/cool/heat cycle at 10 C/min, and the data were obtained for the second heating ramp. Thermogravimetric analyses were performed under nitrogen with a TGA Q5000 from TA Instruments. About 5 10 mg of each sample was heated at 1 0 C/min from RT to 500 C. Gel permeation chromatography (GPC) was performed at 40 C using a Waters Associates GPCV2000 liquid chromatography system with an internal differential refractive index detector and two Waters Styragel HR i.d., 300 mm length) using hexafluoroisopropanol (HFIP) as the mobile phase at a flow rate of 1.0 mL/min. Calibration was performed with narrow polydispersity poly methyl methacrylate standards. Representative Polymerization Procedure for Table 2 1 Under nitrogen atmosphere, a mixture of trioxane (9.03 g, 0.1 mol), and an acid catalyst (1 mmol) in 100 mL of a solvent was placed in a 600 mL high pressure reactor, charged with desired pressure of CO and heated to the desired reaction temperature.

PAGE 63

63 The r eaction was stirred under CO pressure for desired reaction time at the same temperature. After cooling to room temperature, the pressure was released, and the mixture was poured into cold basic methano l. The product was washed with methanol a nd DCM, and dried under vacuum. PGA f ormation (Table 2 1 entry 1.17) = 1 H NMR (500 MHz, HFIP ppm 4. 84 (s, 2H). 13 C NMR (500 MHz, HFIP CDCl 3 POM formation (Table 2 1 entry 1.2) = 1 H NMR (5 00 MHz, HFIP ppm 5.18 (s, 2H) 4.98 (s, 2H) 4.94 (s, 2H). 13 C NMR (500 MHz, HFIP CDCl 3 89.9 General Polymerization Procedure for Table 2 2 Under nitrogen atmosphere, a mixture of trioxane (9.03 g, 0.1 mol), glycerol (0.073 mL, 1 mmol) and triflic acid ( 0.088 mL, 1 mmol) in 100 mL of DCM was placed in a 600 mL high pressure reactor charged with 800 psi CO, and heated to the desired reaction temperature. The r eaction was stirred under CO pressure for one day at the same temperature. After c ooling to room temperature, the pressure was released, and the mixture was poured into cold basic methanol. The product was washed with methanol a nd DCM, and dried under vacuum. 1 H NMR (500 MHz, HFIP ppm 4. 86 (s, 2H). 13 C NMR (500 MHz, HFIP CDCl 3 ) General Polymerization Procedure for Table 2 3 Under nitrogen atmosphere, a mixture of desired amount of paraformaldehyde and triflic acid ( 1 mol % ) in 100 mL of DCM was placed in a 600 mL high pressure reactor, charged with 800 psi CO, and heated to the desired reaction temperature. The r eaction was stirred under CO pressure for three days at the same temperature. After cooling to room temperature, the pressure was released, and the mixture was poured

PAGE 64

64 into cold basic methanol. The pr oduct was washed with methanol a nd DCM, and dried under vacuum. T he Production of PGA from Chain End Active POM Under nitrogen atmosphere, a mixture of trioxane (9.03 g, 0.1 mol), and triflic acid ( 0.088 mL, 1 mmol) in 100 mL of DCM was placed in a 600 mL high pressure reactor. Reaction stirred at room temperature for 12 hours. Then, without terminating the polymerization, the vessel was charged with 800 psi CO, and heated to 170 o C The r eaction was stirred under CO pressure for thr ee days After cooling to room temperature, the pressure was released, and the mixture was poured into cold basic methanol. The product was washed with methanol a nd DCM, and dried under vacuum. 1 H NMR (500 MHz, HFIP CDCl 3 ppm 4. 39 (s, 2H). 13 C NMR (500 MHz, HFIP CDCl 3 ) Polycondensation of OligoGA (entry 5.1) A 2 .0 g amount of oligo GA (Table 2 1 entry 1.17) was weighed into a 5 0 mL reaction flask equipped with a magnetic stirrer. Then, 0.5 wt % of Zn(OAc) 2 .2H 2 O relative to oligo GA was added in it. The mixture was heated at 20 0 o C with stirring under nitrogen for 2h then heating continued under reduced pressure for 1 2 h. Aft er cooling to room temperature, the mixture was poured into cold basic methanol. The product was isolated by filtr ation, and washed with methanol a nd DCM to remove oligomeric residuals, and dried under vacuum. Yield: 1.55 g brown solid 1 H NMR (500 MHz, HFIP 13 C NMR (500 MHz, HFIP CDCl 3

PAGE 65

65 Figure 2 17 High pressure p olymerization vessel.

PAGE 66

66 CHAPTER 3 POLYGLYCOLIC ACID COPOLYMERS FOR REPLACING COMMODITY PLASTICS The Ring Opening Polymerizations of Epoxides Epoxid es are cyclic ethers with three member ed rings which are traditionally produced by the reaction of alkenes with peroxide containing reagents. In polymer chemistry, e poxide s are mostly used as comonomer s to prepare resins and adhesives. 41 Besides that, epoxides can also be used for cationic or anionic ri ng openin g polymerizations to pr oduce polyethers, such as PEG (p olyethylene glycol). While cationic polymerization of epoxides results in low molecular weight polymers, anionic polymerization of epoxides can generate polymers having very high molecular weight s 4 2 Recently, epoxides also beca me very popular reagent s among polymer scientist s to synthesize metal catalyzed polyester and polycarbonate structures by copolymeriz ation with CO and CO 2 respectively 43 Anionic ring opening polymerization (ROP) of epoxides i nvolve s a nucleophilic attack to the less hindered carbon atom of the ring to produce the corresponding alkoxide intermediate (Figure 3 1) Then the polymer chain grows to yield linear polyether products Tertiary amines, imidazoles, or ammonium salts ser ve as the most common initiators for anionic ROP of epoxides. Anionic ROP pro pagates without side reactions, such as backbiting. It is the preferred method for the polymerization of epoxides. 4 4 In the case of cationic ring ope ning polymerization of epoxide s, Lewis acids, such as boron trifluoride complexes, are involved to initiate polymerization and activate the epoxy monomer by forming an oxonium active center. Formation of the oxonium intermediate propagates the polymerization cationically. Cationic initiators to polymerize

PAGE 67

67 epoxides generally require very high or low temperatures, and afford relatively low yields compared to the anionic polymerization. Significant backbiting reaction s may occur in the cationic RO P process due to the relatively high nucleophilicity of the oxygen atoms in the polymer ba ckbone. These oxygen atoms can react with cationic chain end s and terminate the polymerization to result in the formation of oligoethers (Figure 3 1) 45 Figure 3 1 A nionic and cationic ring opening polymerizations of epoxides PGA Terpolymers with Epoxides Recently, Miller and coworkers 4 6 reported that epoxides with long chains can be cationically copolymeriz ed with trioxane to produce Linear low density POM to tu ne the thermal properties of POM. Using this approach, they created a broad family of polyacetal ether copolymers having a var iety of branches. Branched POM wa s expected to disrupt the crystallinity of the polymer and consequently the melting temperature wa s anticipated to dec rease and copolymer solubility wa s expected to increase in common solvents. As predicted, the melting temperatures of the copolymers were depressed compared to that of POM homopolymer According to this report, the co polymerization strategy for PGA with epoxides may work to disrupt PGA crystallinity This approach may also help to increase the solubility of PGA in common solvents and to improve its physical properties The high

PAGE 68

68 T m and T g of PGA limit its utilization as a replac ement for a commodity plastic. The brown or beige color displayed by PGA also diminishes its use in m any packaging applications. In order to utilize PGA in other market ing materials such as packaging, the polymer should be specifically engineered t o improve the physical properties by a copolymerization strat egy utilizing appropriate comonomers Results and Discussion First, propylene oxide incorporation in the PGA backbone was attempted using the same reaction condition s as the PGA synthesis in Chapter 2 At 150 o C, small amounts of black solids were obtained for different propylene oxide feed ratios. These black solids w ere not soluble in any solvents, and t heir characterizations were not achieved as a result After trying several reaction t emperatures, the optimum tem perature for higher incorporation of propylene oxide in the PGA backbone was found to be 120 o C. At higher temperatures, the yield decreased and propylene oxide w as probably decomposing. O ptimization results also showed that wh en trioxane/propylene oxide feed ratios increased, the polymerization yield decreased If polymerization occurs at 100% yield, the theoretical yield must be 16.8 g of a ter polymer for 95/5 mol % of trioxane/propylene oxide entries (8.55 g tri oxane a nd 0.29 g prop. oxide). The maximum yiel d (77%) was obtained for entry 1.8 at T able 3 1. The i ncorporation percentage of propylene oxide in the polymer backbone was about two according to 1 H NMR result s In contrast to PGA synthesis, the terpolymerization temperature of the reaction is lower than that of PGA synthesis. All polymers, except black solids, were soluble in hexafluoroisopropanol, but not in any other solvents. The p olymer melting temperatures decreased with a minor amount of propyle ne oxide inco rporated in the polymer backbone.

PAGE 69

69 Propylene oxide incorporation Table 3 1 Terpolymerization of trioxane, propylene oxide (PO) and CO Entry a Trioxane /Propylene oxide % CO (psi) T p (C) Yield (g) Yield (%) Inc. ratio (%) of PO by 1 H NMR T g (C) T m (C) M n (g/mol) PDI 1 .1 95/5 800 150 0.27 2 1 .2 90/10 800 150 0.3 0 2 1 .3 80/20 800 150 0.35 2 1 .4 95/5 800 100 10.5 63 3.0 5.0 177 1300 1.34 1 .5 90/10 800 100 2.73 16 3.2 3 0 164 1200 1.36 1 .6 95/5 800 110 10.8 64 2.4 5.0 164 1300 1.33 1 .7 90/10 800 110 6.58 39 3.6 3. 0 175 1500 1.46 1 .8 95/5 800 120 12.9 77 2.1 8 0 180 1600 1.42 1 .9 90/10 800 120 5.1 0 30 1.0 12. 0 179 980 1.46 1 .10 95/5 800 130 8.6 0 51 0.9 8.0 175 1400 1.36 1 .11 80/20 800 120 0.2 0 1 1 .12 70/30 800 120 0 1 .13 95/5 1000 120 10.5 61 0.7 8.0 171 1300 1.36 1 .14 95/5 700 120 9.8 0 58 0.2 1. 0 181 1400 1.38 1 .15 96/4 800 120 8.7 0 52 0.6 21.0 179 1400 1.30 1 .16 97/3 800 120 12.6 75 1.8 23. 0 184 1500 1.35 1 .17 98/2 800 120 13.1 80 0.8 16 0 180 1400 1.32 1 .18 99/1 800 120 9.2 0 55 0.9 8. 0 170 1400 1.30 a a solvent, and a reaction time of 72 hours

PAGE 70

70 T he terpolymers also showed lighter colors than commercial PGA. The color and melting point change s again proved that the CO incorporation increased with increasing polymerization temperature as shown for PGA synthesis in Chapter 2 A terpolymer entry 1.6 i n T able 3 1 had thermal transition temperatures similar to those of isotactic polypropylene ( T g : 5 o C and T m : 166 o C ). Pressure optimization experiments showed that higher or lower pr essures did not affect the yield. After optimization of feed ratio and CO pressure parameters from propylene oxide incorporation experiments ( 95/5 mol % of trioxane/propylene oxide and 800 psi CO pressure) we decided to use T able 3 1 entry 1.8 condition s as an optimized ter polymerization condition for other epoxide inco rporations (butylene oxide, epoxy hexane, etc.), and changed only the polymerization temperatures. A series of ter polymers was synthesized with the same reaction condition s as entry 1.8 in T able 3 1. As shown in T able 3 2 (see also Tables 3 3 to 3 8) the ter polymerization of epoxides affords co polymers in very good yields between 50 92 %. Lower yields are probably related to leaving low molecular weight material in soluti on during the work up procedure, in which the reactions were cooled down to room tempe rature, CO was released, and products were precip itated with cold basic methanol, the precipitated polymer was collected by filtration and dried. The thermal properties of the obtained polymers can be correlated directly to their structures, their molecula r weights, and polymerization temperatures. C omparisons of the alkyl side chain length of the epoxide comonomers indicate that the melting temperature decreases with increasing alkyl chain length at the same polymerization temperature According to NMR results (see

PAGE 71

71 Appendix B) epoxides we re randomly copolymerized with the glycolic acid repeating units to produce polyester/ether structures Table 3 2 Results of e poxide incorporation in the PGA backbone (see Tables 3 3 to 3 8 for additional information) Entry Comonomer Copolymer T p ( o C) Yield (g) Yield (%) T g ( o C) T m ( o C) Color 2 1 120 12.9 77 5 166 2 2 100 9.20 54 8 170 2 3 110 9.00 53 14 178 2 4 110 11.8 69 32 182 2 5 110 9.80 57 13 176 2 6 100 12.4 73 30 154 2 7 110 12.4 73 28 180 a dichloromethane as solvent, 800 psi CO pressure, and a reaction time of 72 hours. The melting temperatures of the rest of the epoxide containing polymers decreased with a minor amount of the epoxide incorporation in the polymer backbone

PAGE 72

72 and the colors of the terpolymers again became lighter than commercial PGA a t lower polymerization temperatures. Figure 3 2. The possible polymerization mechanism for epoxide incorporation in PGA backbone. The possible incorporation of epoxide in to the PGA backbone is depicted in F igure 3 2. The polymerization reaction of trioxane, an epoxide and CO in acidic condition s has an entropic driving force. The trioxane ring can be ope ned by removal of formaldehyde. Then, the formation of protonated formaldehyde allows for the nucleophilic addition of CO to form a new acylium ion intermediate. A formaldehyde or an epoxide compound can attack the acylium ion to form a new intermediate; and reaction pro pagates to continue polymerization ( Figure 3 2 ).

PAGE 73

73 The thermal properties of th ese polymers were evaluated, and are presented in Table 3 2. Important trends include: a decrease in the gla ss transition temperature with an increasing number of carbons in t he alkyl segment of the epoxide, and lower melting temperatures compared to PGA As expected, each additional methylene unit decreases the copolymer melting temperature. The dependence of t he chain length of epoxides on the terpolymerization melting temperature at a polymerization temperature of 100 o C is shown in F igure 3 3. As seen, melting points of the terpolymers gradually decrease with increasing alkylene chain length of the epoxide. Figure 3 3. C omparative melting point trends for terpolymers prepared at 100 o C. Increasing side chain length also led to increased solubility of the terpolymers For example, while propylene oxide incorporated terpolymer is not soluble in DMSO, epoxy oct ane incor porated polymer is moderately soluble in that solvent. In order to detect regioregularity of epoxide incorporation in the PGA backbone, we acquired the HSQ C (Heteronuclear single quantum coherence) NMR spectrum of entry 6.2 in T able 3 6 (Figure 3 4) which is sufficiently soluble in DMSO d 6 According to HSQC NMR, both epoxide carbons undergo nucleophilic attack and each carbon

PAGE 74

74 shows two different chemical shifts, around 60 and 52 ppm. Therefore, epoxide repeat units are written in two isomeric for ms. Figure 3 4 HSQC NMR Spectrum of entry 6.2 in T able 3 6. We also wanted to incorporate difunctional epoxide monomers in the PGA backbone such as glycidol and epichlorohydrin Difunctional epoxide compounds will behave as a versatile precursor for the copolymer synthesis. While the epoxide group undergoes cationic ring opening polymerization the other reactive group would be used either as crosslinking agent during the reaction or for further functionalization postpolymerization for access to a variety of functionalized PGA based copolymers Our preliminary results in chapter 2 proved that addition of a compound containing hydroxyl functional groups, s uch as glycerol, highly im proved our polymerization condition s and yield. Thus we first decided to use glycidol comonomer containing both epoxide and hydroxyl functionalities to observe both cationic ring opening polymerization of the epoxide ring and the crosslinking ability of t he free

PAGE 75

75 hydroxyl functionality. The results are summarized at Table 3 7. As expected, addition of a minor amount of glycidol highly improved the physical properties of PGA. The melting temperature of the copolymer giving the highest yield (73 %, entry 7.2 in Table 3 7) was detected at 154 o C, and it appeared as an off white solid. Epichlorohydrin incorporation in the PGA backbone was also achieved in high yields, with t he best yield (73%) prepared at 110 o C ( entry 8.3 in Table 3 8). The melting temperature of the observed copolymer, about 180 o C, was higher than that of other epoxide incorporated copolymers, and the product appeared as an off white powder. The copolymer was insoluble in common solvents and insolubility seems the biggest problem for further functionalization with pendant CH 2 Cl groups i n copolymer backbone Conclusion In conclusion, a new family of polyglycolic acid anologues has been synthesized and characterized. T he addition of minor quantities of epoxide c omonomers vastly improves the appearance of the PGA and allows for rational and programmed control of the polymeric properties, such as melting temperature and solubility W e are exploring new PGA based polymeric materials as novel commodity thermoplastics that mimic the thermal properties of commercially dominant polyolefins such as polypropylene. This method provides a cost effective and efficient path for synthesizing PGA based copolymers. The number of synthetic steps from simple feedstock is greatly re duced and the starting materials are potentially sustainable from biomass. The results have shown that optimal p olymerizations are obtained at temperatures lower than that of PGA synthesis. Higher reaction temperatures resulted in lower yields, but higher CO incorporation. Characterization of the terpolymers showed

PAGE 76

76 that decreased the melting temperature with an increasing number of alkyl units in the comonomer side chain. The solubilities of ter polymers increased with an increasing number of carbons in the alkyl side chains and the terpolymers were lighter in color than the commercial PGA. Experimental General Considerations and Instrumentation DCM was purified by stirring over calcium hydride for 24 hours and then vacuum transfer into an oven dried Straus flask. Epoxides were purchased from Sigma Aldrich and utilized after further purification Trioxane was purchased from Acros Organics and used after recrystallization in CHCl 3 Triflic acid (TfOH) was purchased from Oakwood Chemical and used as received A Parr 600 mL high pressure autoclave was used for the experiments. Proton nuclear magnetic resonance ( 1 H NMR) spectra were recorded using a n Inova 5 00 MHz spectrometer NMR sample preparation: 0.5 g of sample was dissolved in 0.4 g of HFIP, and 1.0 g of C DCl 3 (or C 6 D 6 ) was added to the mixture.; HFIP d 2 was also used for some NMR spectra For 1 H NMR, number of scans = 32 with a 5 s relaxation delay. For 13 C; number of scans = 10000 with 3 s relaxation delay. Chemical shifts are reported in parts per million (ppm) downfield relative to tetramethylsilane (TMS, 0.0 ppm) or residual proton s in the specified solvent. Differential scanning calorimetry thermograms were obtained with a DSC Q1000 from TA instruments. About 1.5 3 mg of each sample was weighed and sea led in a pan Thermal history was established by a he at/cool/heat cycle at 10 C/min, and the data were obtained for the second heating ramp.

PAGE 77

77 Thermogravimetric analyses were performed under nitrogen with a TGA Q5000 from TA Instruments. About 5 10 mg of each sample was heated at 1 0 C/min from RT to 500 C. Gel permeation chromatography (GPC) was performed at 40 C using a Waters Associates GPCV2000 liquid chromatography system with an internal differential refractive index detector and two Waters Sty ragel HR i.d., 300 mm length) using h exafluoroisopropanol (HFIP) as the mobile phase at a flow rate of 1.0 mL/min. Calibration was performed with narrow polydispersity poly methyl methacrylate standards. Representative Cop olymer ization Procedure for Epoxide Incorporation Under nitrogen atmosphere, a mixture of trioxane (95 mmol, 8.55 g) an epoxide compound (5 mmol), and TfOH catalyst ( 0.073 mL, 1 mmol) in 100 mL of DCM was placed in a 600 mL high pressure reactor charged with 8 00 psi CO, and heated to the desired reaction temperature. The r eaction was stirred under pressure for three days at the same reaction temperature. After cooling to room temperature, the pressure was released, and the mixture was poured into cold basic met hanol. The product was isolated by filtration, and washed with methanol and DCM, and dried under vacuum. Butylene oxide incorporation Table 3 3. Terpolymerization of trioxane, butylene oxide (BO) and CO Entry a Trioxane /Butylene oxide % T p ( o C) Yield (g) Yield (% ) Inc. ratio (%) of B O by 1 H NMR T g ( o C) T m ( o C) M n (g/mol) PDI

PAGE 78

78 Table 3 3. C ontinued. 3 .1 95/5 90 3.5 21 1.7 16.2 156 870 1.39 3 .2 95/5 100 9.2 54 1.8 8.2 176 1100 1.35 3 .3 95/5 110 8.5 50 2.4 16.5 181 1200 1.40 3 .4 95/5 120 5.8 34 0.9 2.0 187 1200 1.44 a All r dichloromethane as solvent, 800 psi CO pressure, and a reaction time of 72 hours. Hexylene oxide incorporation Table 3 4. Terpolymerization of trioxane, hexylene oxide (HO ) and CO Entry a Trioxane / Hexylene oxide % p ( o C) Yield (g) Yield (%) Inc. ratio (%) of HO by 1 H NMR T g ( o C) T m ( o C) M n (g/mol) PDI 4 .1 95/5 100 6.2 36 0.2 1.7 176 1100 1.44 4 .2 95/5 110 9.0 53 0.5 10.4 173 1200 1.67 4 .3 95/5 120 2.9 17 1.7 22 .0 179 530 2.10 a All r dichloromethane as solvent, 800 psi CO pressure, and a reaction time of 72 hours. Cyclohexene oxide incorporation Table 3 5. Terpolymerization of trioxane, cyclohexeneoxide (CHO) and CO Entry a Trioxane / CHO % p ( o C) Yield (g) Yield (%) Inc. ratio (%) of CHO by 1 H NMR T g ( o C) T m ( o C) M n (g/mol) PDI 5 .1 95/5 100 10.7 63 2.0 11.5 158 1100 1.65 5 .2 95/5 110 11.8 69 1.7 28.5 183 1000 1.59 5 .3 95/5 120 11.2 66 1.5 14.0 195 1500 2.20 a All r dichloromethane as solvent, 800 psi CO pressure, and a reaction time of 72 hours.

PAGE 79

79 Epoxy octane incorporation Table 3 6. Terpolymerization of trioxane, epoxyoctane (EO) and CO Entry a Trioxane / EO % T p ( o C) Yield (g) Yield (%) Inc. ratio (%) of EO by 1 H NMR T g ( o C) T m ( o C) M n (g/mol) PDI 6 .1 95/5 100 8.4 49 1.8 3.7 169 950 1.39 6 .2 95/5 110 9.8 57 2.0 7.7 177 1100 1.37 6 .3 95/5 120 9.6 56 1.3 15.9 179 1200 1.44 a All r dichloromethane as solvent, 800 psi CO pressure, and a reaction time of 72 hours. Glycidol incorporation Table 3 7. Terpolymerization of trioxane, glycidol (G) and CO Entry a Trioxane /Glycidol % T p ( o C) Yield (g) Yield (%) Inc. ratio (%) of G by 1 H NMR T g ( o C) T m ( o C) M n (g/mol) PDI 7 .1 95/5 90 11.7 69 1.5 16.3 142 7 .2 95/5 100 12.4 73 3.0 29.5 154 7 .3 95/5 110 11.2 66 2.4 30.3 177 7 .4 95/5 120 10.8 64 3.4 30.0 178 7 .5 95/5 130 8.20 49 2.8 39.1 209 7 .6 95/5 140 5.20 31 2.6 46.1 204 a All r g of trioxane, 1 mol% TfOH as initiator, dichloromethane as solvent, 800 psi CO pressure, and a reaction time of 72 hours.

PAGE 80

80 Epichlorohydrin incorporation Table 3 8. Terpolymerization of trioxane, epichlorohydrin (ECH) and CO Entry a Trioxane / ECH % T p ( o C) Yield (g) Yield (%) Inc. ratio (%) of ECH by 1 H NMR T g ( o C) T m ( o C) M n PDI 8 .1 95/5 90 9.40 55 1.5 43.6 189.3 8 .2 95/5 100 11.5 68 1.8 34.3 193.7 8 .3 95/5 110 12.4 73 2.3 27.6 179.6 8 .4 95/5 120 11.8 69 1.3 29.3 182.7 8 .5 90 / 10 110 10.0 59 3.9 17.3 173.5 a All r dichloromethane as solvent, 800 psi CO pressure, and a reaction time of 72 hours.

PAGE 81

81 CHAPTER 4 PGA BASED COPOLYMERS FROM CYCLIC ETHERS Background Cationic polymerization catalysis is generally more effective for cyclic ethers having three four and five membered rings. Six member ed cyclic ethers generally seem very stable, and do not give polymerization product. But larger membered ri ngs tend to polymerize. 4 7 Cyclic ethers are basically named by their ring size, oxirane for three membered, oxetane for four membered, oxolane for five membered an d oxane for six membered rings. 48 A variety of cyclic ethers can be successfully polymerized by the ring opening polymerization. Most cyclic ethers, except epoxides, are only polymerized cationically. Cyclic ether oxygen atom behaves as a L ewis base, and addition of initiator cation to the oxygen atom generates oxonium ion. Due to positively charg ed oxygen atom, the alpha carbon of the oxonium ion becomes electron deficient, and the polymerization propagates by the nucleophilic addition of the oxygen of another cyclic ether molecules to the alpha carbon of the oxonium ion. 49 The hydrolytic stabili ty of ether linkages in polyether products are generally more than that of the carbonate, ester or amide bonds, and this property makes them an important class of engineering thermoplastic. 5 0 In this chapter, the synthesis and characterization of new PGA based polyester ethers for which the comonomer is varied in structure of cyclic ethers, will be presented. Results and Discussion After we discovered the feasibility of the epoxide incorporation in PGA backbone to generate polyester ether product, we decid ed to incorporate minor amounts of cyclic

PAGE 82

82 ethers, such as dioxolane, 1,4 dioxane, and 1,3 dioxane, other than epoxides in PGA backbone The best y ields were obtained at 95/5 mol % of trioxane/dioxolane at 120 o C, 95/5 mol % of trioxane/1,4 dioxane at 140 o C and 95/5 mol % of trioxane/1,3 dioxane at 160 o C As we discussed for epoxide incorporations, the polymer melting temperatures decreased with a small amount of the cyclic ether colors of the terpolymers again became light er than commercial PGA at lower temperatures. But, the solubilities were almost the same as PGA; they were only soluble in hexafluoroisopropanol (HFIP). The polymerization reaction of trioxane, cyclic ether and carbon monoxide in acidic condition has entr opic driving force: trioxane ring can be opened by removal of formaldehyde; the formation of protonated formaldehyde allows for the nucleophilic addition of carbon monoxide to form a new acylium ion intermediate; a formaldehyde or an cyclic ether compound can attack to the acylium ion to form a new intermediate; and reaction proceeds in this fashion ( Figure 4 1 ). The thermal properties of these polymers were evaluated. Important trends include: a decrease in the glass transition temperature with an increasi ng number of carbons in the alkyl segment of the epoxide; all copolymers have lower melting temperatures than PGA. Table 4 1 displays the dependence of copolymer melting temperatures as functions of alkyl side chains in the comonomers. As expected, each ad ditional methylene unit decreases the copolymer melting temperature. According to 13 C NMR results, there is no appearance of the polyoxymethylene (acetal) spacers in the polymer backbones. Interestingly, acetal functionalities of

PAGE 83

83 dioxolane and 1,3 dioxane compounds were disappeared after the copolymerization. When their acetal oxygens were protonated, these rings can also form an oxonium intermediate. Addition of CO to these oxonium intermediates generates new glycolic acid repeating units. Therefore, acet al functionalities cannot be distinguished. Table 4 1. Cyclic ether incorporation results in PGA backbone. Entry Comonomer Copolymer T p ( o C) Yield (g) Yield (%) T g ( o C) T m ( o C) Color 1. 1 120 14.2 83 14 189 1. 2 140 15.8 92 n.d. 197 1. 3 160 9.20 54 6.3 141 a DCM as solvent, 800 psi CO pressure, and a reaction time of 72 hours. Although very high conversion was observed again from the ter polymerization s the number average molecular weights of the products exhibited oligomeric products that ranged between 1000 2000 g/mol Therefore, further polycondensation reaction might be applied for these products as mentioned in Chapter 2. Conclusion A new family of polyglycolic acid anologues as novel commodity thermoplastics has been synthesized and characterized. The addition of minor quantities of cyclic ether comonomers improve d the appearance and melting temperature of the PGA Despite having ve ry high conversions for cyclic ether incorporation in PGA backbone, the molecular weights of the terpolymers are still disappointing. For all oligo terpolymers,

PAGE 84

84 further polycondensation reaction should be applied to increase molecular weights. To see the e ffect of alkylene spacer in comonomer, different acetal contained comonomers having longer alkylene spacer, such as 1,3 dioxepane, could be tried. O xetane compounds have nearly th e same ring strain as epoxides, it will also be helpful to use this type of c omonomers in order to see the effect of alkylene spacer in PGA backbone. Experimental General Considerations and Instrumentation DCM was purified by stirring over calcium hydride for 24 hours and then vacuum transfer into an oven dried Straus flask. 1,4 Dioxane was purchased from Em Scientific and utilized after further purification Trioxane was purchased from Acros Organics and used after recrystallization in CHCl 3 Triflic acid (TfOH) was purchased from Oakwood Chemical and used as received A Parr 600 mL high pressure autoclave was used for the experiments. Proton nuclear magnetic resonance ( 1 H NMR) spectra were recorded using a n Inova 5 00 MHz spectrometer NMR sample preparation: 0.5 g of sample was dissolved in 0.4 g of HFIP, and 1.0 g of CDCl 3 ( or C 6 D 6 ) was added to the mixture.; HFIP d 2 was also used for some NMR spectra For 1 H NMR, number of scans = 32 with a 5 s relaxation delay. For 13 C; number of scans = 10000 with 3 s relaxation delay. Chemical shifts are reported in parts per million (ppm) downfield relative to tetramethylsilane (TMS, 0.0 ppm) or residual proton s in the specified solvent. Differential scanning calorimetry thermograms were obtained with a DSC Q1000 from TA instruments. About 1.5 3 mg of each sample was weighed and sealed in a pan Thermal history was established by a he at/cool/heat cycle at 10 C/min, and the data were obtained for the second heating ramp.

PAGE 85

85 Thermogravimetric analyses were performed under nitrogen with a TGA Q5000 from TA Instruments. About 5 10 mg of each sa mple was heated at 1 0 C/min from RT to 500 C. Gel permeation chromatography (GPC) was performed at 40 C using a Waters Associates GPCV2000 liquid chromatography system with an internal differential refractive index detector and two Waters Styragel HR 5E i.d., 300 mm length) using hexafluoroisopropanol (HFIP) as the mobile phase at a flow rate of 1.0 mL/min. Calibration was performed with narrow polydispersity poly methyl methacrylate standards. Preparation of Dioxolane A mix ture of 1 11.7 mL (124 g, 2 mol ) of ethylene glycol, 6 g (2 mol) of paraformaldehyde, and 6 g of p toluenesulfonic acid ( p TSA) in 500 ml of chloroform was boiled in a Dean S tark apparatus. When 40 ml of water had been removed, the chloroform was evaporated under reduced pressure, and the residue distilled to give 90 g (81 %) of product, bp: 75 o C. 1 H NMR (500 MHz, CDCl 3 ppm 4. 87 (s, 2H) 3.85 (s, 4H) 13 C NMR (500 MHz, CDCl 3 Preparation of 1,3 Dioxane. A mix ture of 143.4 mL (152 g, 2 mol ) of 1,3 propanediol, 6 g (2 mol ) of paraformaldehyde, and 6 g of p toluenesulfonic acid ( p TSA) in 500 ml of c hloroform was boiled in a Dean S tark apparatus. When 40 ml of water had been removed, the

PAGE 86

86 chloroform was evaporated under reduced p ressure, and the residue distilled to give 1 22 g ( 69 %) of product, bp: 105 106 o C. 1 H NMR (500 MHz, CDCl 3 ppm 4. 86 (s, 2H) 3.90 (t, 4H), 1.78 (q, 2H) 13 C NMR (500 MHz, CDCl 3 Representative Terp olymerization Procedure for Cyclic Ether Incorporations Under nitrogen atmosphere, a mixture of trioxane (X mol), a cyclic ether compound (100 X mol), and TfOH catalyst ( 0.073 mL, 1 mmol) in 100 mL of DCM was placed in a 600 mL high pressure reactor, charged with 800 psi CO, and heat ed to the desired reaction temperature. The r eaction was stirred under pressure for three days at the same reaction temperature. After cooling to room temperature, the pressure was released, and the mixture was poured into cold basic methanol. The product was isolated by filtration, and washed with methanol and DCM, and dried under vacuum. Dioxolane incorporation results Table 4 2 Terpolymerization of trioxane, dioxolane and CO Entry a Trioxane /Dioxolane % T p ( o C) Yield (g) Yield (%) Inc. ratio (%) of dioxolane by 1 H NMR T g ( o C) T m ( o C) M n (g/mol) PDI 2 .1 95/5 100 12.4 73 3.0 14 174 1200 1.38 2 .2 95/5 110 12.8 75 2.4 16 180 1400 1.49 2 .3 95/5 120 14.2 83 3.8 14 189 1300 1.47 2 .4 95/5 130 11.5 67 4.1 32 192 1400 1.37 2 .5 95/5 140 7.7 45 4.3 18 194 1300 1.48 2 .6 90/10 120 7.8 46 1.9 16 180 1500 1.37 2 .7 80/20 120 0 0 a All r DCM as solvent, 800 psi CO pressure, and a reaction time of 72 hours.

PAGE 87

87 1,4 D ioxane incorporation results Table 4 3 Terpolymerization of trioxane, 1,4 dioxane and CO Entry a Trioxane /1,4 dioxane % T p ( o C) Yield (g) Yield (%) Inc. ratio (%) of 1,4 dioxane by 1 H NMR T g ( o C) T m ( o C) M n (g/mol) PDI 3 .1 95/5 110 2.8 16 3.3 5 160 1000 1.35 3 .2 95/5 120 12.1 70 3.1 25 177 1400 1.42 3 .3 95/5 130 13.3 77 3.8 n.d. 189 1300 1.43 3 .4 95/5 140 15.8 92 3.9 n.d. 197 1500 1.43 3 .5 95/5 150 12.5 73 4.0 23 167 1500 1.32 3 .6 90/10 140 11.2 65 4.1 19 174 1300 1.37 3 .7 80/20 140 3.5 20 4.6 49 n.d. 1300 1.31 a All r DCM as solvent, 800 psi CO pressure, and a reaction time of 72 hours. 1,3 D ioxane i ncorporation results Table 4 4 Terpolymerization of trioxane, 1,3 dioxane and CO Entry a Trioxane /1,3 dioxane % T p ( o C) Yield (g) Yield (%) Inc. ratio (%) of 1,3 dioxane by 1 H NMR T g ( o C) T m ( o C) M n (g/mol) PDI 4 .1 95/5 140 5.2 30 1.8 34.3 188.3 1100 1.76 4 .2 95/5 150 8.3 49 2.1 18.5 159.3 1000 2.56 4 .3 95/5 160 9.2 54 2.3 6.30 141.0 1100 1.67 4 .4 95/5 170 3.0 18 1.9 3.30 n.d. 721 1.58 4 .5 90/10 160 6.2 36 0.7 8.10 151.9 928 1.90 4 .6 80/20 160 2.1 12 0.3 6.4 n.d. 667 1.59 4 .7 70/30 160 1.3 8 4 .8 60/40 160 0.45 3 4 .9 0/100 100 0 0 a All r DCM as solvent, 800 psi CO pressure, and a reaction time of 72 hours.

PAGE 88

88 CHAPTER 5 TRANSITION METAL CATALYZED COPOLYMERIZATION OF TRIOXANE AND CARBON MONOXIDE Introduction During the past few decades, metal complex catalyzed polymerizatio ns have played a leading role in producing polymers containing the carbonyl functionality in the poly mer backbone, such as polyketones, polyesters and polycarbonates (F igure 5 1 ). 5 1 F igure 5 1 The structures of a polyketone, polyester and polycarbonate. The first examples of polyketones were achieved with alternating copolymerization of ethylene and carbon monoxide by means of Pd catalyst. In addition to alkenes, alkynes and dienes were also successfully copolymerized with carbon monoxide by transition metal catalysts to prod uce the corresponding polyketones (F igure 5 2 ). 27 F igure 5 2 S ynthesis of Carilon from the copolymerization of ethylene and CO. U sing the same idea, it should also be possible to prepare polyesters by the copolymerization of carbon dioxide and an alkene, but there are currently no results to support this hypothesis However, as an alternative method, polyesters c an be successfully synthesized by the alternating copolymerization of small membered rings and CO Oxygen containing 3 and 4 membered rings (epoxide and oxetane) can

PAGE 89

89 polymerize with CO through ring opening polymerizat ion to give the corresponding polymers containing the carbonyl functionality. The best known example is the discovery of epoxide and CO polymerization to afford polyesters. 52 Metal complex catalyzed copolymerization of epoxide s and CO has been known to afford polyesters for many years The first discovery of the copolymerization of CO with alkylene oxides was reported by Furukawa and co workers in 1965. 5 3 It has been brought to the attention of the scientific community that copolymeriz ation of propylene oxide and CO by AlEt 3 /Co(acac) 3 as the catalytic system resulted in a polyester structure. A bout 30 years a fter this discovery, Drent and coworkers filled a patent that Co 2 (CO) 8 and 3 hydroxypy ridine mixtures can be used as catalyst s for the fo rmation of lactones by the c arbonylation of epoxides via CO. 5 4 F urther studies by other research groups proved that the same catalyst system produced pol yester as a major product, Lactone. 5 5 O bserved p olymer s were regioregular, but even isotactic if enantiomerically pure propylene oxide was used (Figure 5 3) Figure 5 3. Polymerization of propylene oxide and CO by Co 2 (CO) 8 catalyst. Results and Discussion Co 2 (CO) 8 Catalyzed Copolymerization of Trioxane and CO After the production of PGA from the cationic alternating copolymerization of formaldehyde and CO proved to be very successful with triflic acid catalyst, we started investigating the ability of transition metal species to catalyze the same reaction under milder condition s No reports of transition metals assisting this process have been made. Yet, it seems possible that certain transition metal species could enhance the

PAGE 90

90 electrophilicity of the acetal carbons on trioxane and facilitate attack of CO to form intermediate oxonium ions a step which is presumably rate limiting on account of the very high CO pressures needed to observe any CO incorporation. Some of our efforts involved the Co 2 (CO) 8 /3 hydroxypyridine catalyst system for this copolymerizat ion as il lustrated in F igure 5 4 In theory, a nionic cobalt ( 1 ox idation state) species would be generated in situ and should be suitable nucleophiles to attack formaldehyde, sourced from paraformaldehyde or trioxane under the reaction conditions. Migratory insert ion of a coordinated carbonyl group into the metal carbon bond is an established phenome non with this class of electron rich transition metal species. Cycling through these events would result in a polyglycolic acid chain appended to the metal, which might be isolable following a suitable workup. After we tested the possibility of this polymerization, this catalyst system did not seem to be an effective catalyst for the copolymerization. The results indicated that anionic cobalt species do not undergo a smo oth insertion of CO or trioxan e into the Co C bond (Figure 5 4 ). CO insertion did not occur in the acetal functionality by this catalytic system.

PAGE 91

91 Figure 5 4 The possible polymerization mechanism of Co 2 (CO) 8 catalyzed synthesis of PGA. To understand why we were unable to incorporate CO using this catalyt ic system, w e decided to a dd 1 mol % of cobalt catalyst to the triflic acid catalyzed system which had already been used successfully for the synthesis of PGA (Figure 5 5 ). We thought that the Co catalyst might help to increase the CO insertion rate in the polymer backbone, thereby allowing polymerization to proceed at lower temperature or in less time. Unfortunately, no CO insertion was observed again, and no yield was obtained. Figure 5 5 Effect of addition 1 mol % of Co 2 (CO) 8 catalyst into the triflic acid catalyzed polymerization of trioxane and CO.

PAGE 92

92 Following these unsuccessful attempts at polymerization using c obalt catalyst, we decided to add propylene oxide, which is readily polymerize d in cobalt catalyzed reaction condition s to the reaction mixture to increase the driving force for possible incorporation of glycolic acid units in the polymer backbone (Figure 5 6 ). We started observing some acetal functionality in the polymer backbone, but no PGA formation was detected. Somehow, the Co C bond can undergo insertion of formaldehyde or trioxane species, but do es not allow CO insertion for acetal intermediates. The results are shown in T able 5 1. Figure 5 6 Co 2 (CO) 8 catalyzed terpolymerization of propylene oxide, trioxane and CO. Table 5 1. T erpolymerization of propylene oxide, trioxane and CO by Co 2 (CO) 8 catalyst system Entry a Feed ratio (% PO/T ) Solvent T p ( o C) Time Yield (g) M n (g/mol) PDI T g ( o C) T m ( o C) 1.1 100/0 THF 75 1 day 6.20 3000 1.74 1.2 95/5 THF 75 1 day 5.60 2500 1.44 1.3 80/20 DCM 75 1 day 2.50 1100 1.43 24.5 n.d. 1.4 50/50 DCM 75 1 day 1.78 400 1.0 2.5 n.d. 1.5 20/80 DCM 75 1 day 0.40 1.6 0/100 DCM 75 1 day 0.40 1.7 0/100 THF 75 1 day 0.42 1.8 0/100 THF 100 3 days 0.38 a 2 (CO) 8 as initiator, and 1 mol % 3 hydroxypyridine as coinitiator 800 psi CO pressure. We also tested the formation of oxonium ion to initiate the polymerization from the reaction of acyl halides and aluminum chloride (Figure 5 7). Unfortunately, formation of acylium ions assisted by AlCl 3 did not work, and always yielded trace amount of solid

PAGE 93

93 side products. After the polymerizat ion, unreacted trioxane was evident in the NMR spectrum. Figure 5 7 The effect of the formation of acylium ion as an initiator for trioxane and CO copolymerization. Sc(OTf) 3 Cataly st in Polymer Chemistry Scandium trifluoromethanesulfonate Sc(OTf) 3 was first introduced by the Kobayashi group as a new type of a L ewis acid in organic chemistry in 1993. 5 6 Sc(OTf) 3 wa s found to be highly stable and active in wat er unlike some known L ewis acids such as AlCl 3 BF 3 etc., which require strictly anhydrous conditions for organic reactions. Because of the high solubility of Sc(OTf) 3 in water, it can be separated from the aqueous phase and t he recycled catalyst was found to be still effective for the 2 nd reaction. This type of a recyclable catalyst system provides two main benefits for organic transformations : 1) atom economy due to recyclability and reuse; 2) environmental ly friendly because of lacking toxicity after use. 57,5 8 Scandium triflate can be easily prepared f rom scandium oxide (Sc 2 O 3 ) and aqueous triflic acid (TfOH). 5 9 Figure 5 8. Sc(OTf) 3 catalyzed aldol reaction of a silyl ether and formaldehyde. 59

PAGE 94

94 Besides using Sc(OTf) 3 catalyst for some organic transformations, such as aldol reactions of silyl enol ethers with aldehydes and acetals, Michael reactions, and Friedel Crafts acylations (Figure 5 8 ) 6 0 t he catalyst was also used for polycondensation s of some diols and diacids to produce polyester s in polymer chemistry. 61 Sc(OTf) 3 catalyst enabled synthesiz ing aliphatic polyesters under milder conditions (Figure 5 9 ) 6 2 T aking into account the above advantages, Sc(OTf) 3 can be considered as a suitable catalyst Figure 5 9 Sc(OTf) 3 assisted polyester synthesis. 60 Sc(OTf) 3 Catalyzed Copolymerization of Formaldehyde and CO Seeking a more e ffective catalyst system for the copolymer ization of trioxane and CO, we were inspired by the studies mentioned above on environmentally friendly Sc(OTf) 3 catalyzed polycondensation reactions. We proposed synthesizing PGA without a metallic residue in one step by cationic copolymerization of formaldehyde and CO as C1 feed stocks using Sc(OTf) 3 as the polymerization catalyst. Using the Sc(OTf) 3 catalyst w e typically employ ed 800 psi CO and varied temperature ranges from 130 o C to 170 o C ; c atalyst loading for the polymerizations was kept from 0.5 t o 3 mol % with regard to trioxane. The best result was obtained in 55 % yield after three days reaction of trioxane with Sc(OTf) 3 catalyst under 800 psi CO pressure at 150 o C ( entry 2.3 in T able 5 2) It is worth mentioning that CO is a very weak nucleophile and longer reaction times for the polymerizations are understandable This reaction system opens the possibility of producing polyglycolic acid with different

PAGE 95

95 molecular weights, and hence different physical properties. The molecular weights of the synthesized PGA ranged between 1000 and 2400 g/mol Table 5 2. Cop olymeriza tion results of trioxane and CO by using Sc(OTf) 3 catalyst. Entry Solvent T p ( o C) Time Yield (g) Yield (%) M n (g/mol) PDI T g ( o C) T m ( o C) 2.1 DCM 130 3 days 0.3 8.60 1000 1.56 3.74 170.5 2.2 DCM 140 3 days 1.4 40.2 1400 1.47 22.8 188.4 2.3 DCM 150 3 days 1.9 55.0 1200 1.81 39.9 193.1 2.4 DCM 160 3 days 1.3 37.4 1400 1.45 45.7 194.0 2.5 DCM 170 3 days 0.95 27.3 1000 1.63 41.4 189.7 2.6 DCM 150 1 day 0.23 6.60 950 1.69 19.0 164.6 2.7 DCM 150 2 days 0.94 27.0 1400 1.66 48.6 191.2 2.8 HFIP 150 3 days 1.40 40.0 975 1.42 0.47 163.2 2.9 THF 150 3 days NR NR 2.10 Heptane 150 3 days 0.23 6.60 3.45 167.6 2.11 a DCM 150 3 days 2.45 70.0 1800 1.86 46.5 n.d. 2.12 b DCM 150 3 days 1.70 49.0 1600 1.71 29.6 197.4 2.13 c DCM 150 1 day 2.26 65.0 1800 1.79 17.5 191.9 2.14 d DCM 150 3 days 2.10 60.3 1600 2.28 47.1 194.4 2.15 DCM 150 4 days 2.68 77.0 2400 1.95 51.6 195.7 2.16 c DCM 150 2 days 2.71 78.0 2000 1.96 31.6 199.2 2.17 e DCM 150 3 days 0.71 1800 2.76 29.8 199.2 2.18 DCM 150 5 days 2.60 74.7 12.1 191.4 2.19 f DCM 150 1 day 1.70 49.0 29.8 192.4 a catalyst loading was kept as 2 mol % of trioxane, b catalyst loading was kept as 0.5 mol % of trioxane, c catalyst loading consisted of 1 mol % of Sc(OTf) 3 and 1 mol % of TfOH, d catalyst loading was kept as 3 mol % of trioxane, e p formaldehyde (0.6 g) was used as a formaldehyde source all other reactions conducted with 1.80 g of trioxane, and 800 psi CO pressure f 1 mol % of glycerol was added to the reaction mixture The react ion is further improved by increasing the catalyst ratio to 2 mol % of trioxane, and yield increased to 70 %, which is undoubtedly higher than that with 1 mol % of catalyst loading. Fu rther increase of the ratio showed no obvious change in yield. Compared to TfOH, Sc(OTf) 3 exhibited lower activity towards trioxane and CO copolymerization. Interestingly, th e addition of 1 mol % of TfOH to the catalytic system slightly improved the activity of Sc(OTf) 3 and resulted in 65 % of yield in one day at 150 o C (entry 2.13 at T able 5 2), which is considerably higher than that of TfOH alone for the

PAGE 96

96 same reaction in one day. By prolonging the polymerization time to two days for the same binary catalyst system, the polymerization yield increased to 78 % (entry 2.16 at T ab le 5 2) The proposed mechanistic pathway discovered for TfOH catalyzed copolymerization of formaldehyde and CO can be applied in the case of Sc(OTf) 3 catalyzed polymerizat ion as illustrated in Figure 5 10 Figure 5 10 The p roposed mechanism for the co polymerization of trioxane and CO in Sc(OTf) 3 I nitial testing results of the products were disappointing, as molecular weights seemed to be in a range of 1000 2400 g/mol. We hypothesize d t hat our system was preventing formation of high molecular weight po lymers resulting in oligomeric products. During the polymerization, crystalline PGA formation perhaps prevents the polymerization from going to completion, thereby limiting the molecular weight

PAGE 97

97 We also noticed that the glass transition and melting tempe ratures of these polymers showed to an upward trend with increasing reaction temperature and polymerization time, and we hypothesized that increasing molecular weight res ulted in these trends. Figure 5 11 directly compares the thermal properties of commercial PGA w ith our product (entry 2.16 in T able 5 2). The thermal stabilities of the products were also evaluated by TGA under inert (N 2 ) atmosphere. The degradation temperatures of the products begin appro ximately at 200 o C. Figure 5 11. DSC analysis of the commercial PGA and polymer entry 2.16 in T able 5 2. Polyglycolic acid is highly crystalline and insoluble in common organic solvents, and therefore particularly challenging to characterize using traditional solvated polymer characterization techniques like NMR or GPC. For NMR analysis, a mixture of HFIP and CDCl 3 (as a deuterated agent) was needed. The 13 C NMR spectrum of polymer entry

PAGE 98

98 2.16 in T able 5 2 indicate d units) (Figure 5 12) No significant differences were observed between the spectra of commer cial PGA and the product. The resonances of ester carbonyl and methylene carbons we Figure 5 12 13 C NMR spectra of the commercial PGA an d polymer entry 2.16 in T able 5 2. The FT IR spectra of entry 2.16 in T able 5 2 and commercial PGA (F igure 5 13 ) shows very close resemblance proving the similar polymeric structures of the commercial PGA and the product. The signal at 1743 cm 1 is characteristic of the C=O stretching vibration of the ester groups of the polymer structure.

PAGE 99

99 Figur e 5 13 FT IR spectra of the commercial PGA and polymer entry 2.16 in T able 5 2. We also wanted to incorporate propylene oxide in to the PGA backbone using the Sc(OTf) 3 catalyst (Figure 5 14) Unfortunately, even mi nor amount s of propylene oxide in the reaction medium negatively a ffected the formation of PGA. No observable propylene oxide incorporation wa s achieved, and only trace amount s of PGA product were observed (Table 5 3). Figure 5 1 4 T erpolymerization of trioxane, propylene oxide and CO by Sc(OTf) 3

PAGE 100

100 Table 5 3. Terp olymerization results of trioxane propylene oxide and CO using Sc(OTf) 3 catalyst. Entry Feed ratio (% T/PO) T p ( o C) Yield (g) Yield (%) 3 .1 95/5 11 0 no rxn 3 .2 95/5 12 0 0.25 7 3 .3 95/5 13 0 0.30 8 a 3 as initiator, and 800 psi CO pressure. In conclusion, a new pathway to produce PGA has been introduced based on perfectly alternating cationic copolymerization of trioxane and CO catalyzed by Sc(OTf) 3 An additional benefit of this strategy is that Sc(OTf) 3 is an environmentally friendly catalyst and can be recycled from the reaction media. These present important advantages for a catalyst system, and polymerization using Sc(OTf) 3 will be a convenient alternative way to produce PGA. Obtained polymers confirm the previous investigation and opens up a new catalyst system for the preparation of PGA. Experimental General Considerations and Instrumentation Unless otherwis e noted, all solvents were purified by stirring over calcium hydride for 24 hours and then vacuum transfer into an oven dried Straus flask. Solvents were purchased from Sigma Aldrich and utilized after further purification Scandium triflate (Sc(OTf) 3 ) and Triflic acid (TfOH) were purchased from Oakwood Chemical and used as received. Trioxane was purchased from Acros Organics and used after recrystallization in CHCl 3 Co 2 (CO) 8 was purchased from Strem Chemicals and used as received. 3 hydroxy pyridine was purchased from Alfa Aesar and used as received. A Parr 600 mL high pressure autoclave was used for the experiments. Proton nuclear magnetic resonance ( 1 H NMR) spectra were rec orded using a n Inova 5 00 MHz spectrometer NMR sample preparation: 0.5 g of sample was dissolved

PAGE 101

101 in 0.4 g of HFIP, and 1.0 g of CDCl 3 (or C 6 D 6 ) was added to the mixture.; HFIP d 2 was also used for some NMR spectra For 1 H NMR, number of scans = 32 with a 5 s relaxation delay. For 13 C; number of scans = 10000 with 3 s relaxation delay. Chemical shifts are reported in parts per million (ppm) downfield relative to tetramethylsilane (TMS, 0.0 ppm) or residual proton s in the specified solvent. Differential scann ing calorimetry thermograms were obtained with a DSC Q1000 from TA instruments. About 1.5 3 mg of each sample was weighed and sealed in a pan Thermal history was established by a he at/cool/heat cycle at 10 C/min, and the data were obtained for the second heating ramp. Thermogravimetric analyses were performed under nitrogen with a TGA Q5000 from TA Instruments. About 5 10 mg of each sample was heated at 1 0 C/min from RT to 500 C. Gel permeation chromatography (GPC) was performed at 40 C using a Waters Associates GPCV2000 liquid chromatography system with an internal differential refractive index detector and two Waters Styragel HR i.d., 300 mm length) using hexafluoroisopropanol (HFIP) as the mobile phase at a flow rate of 1.0 mL/min. Calibration was performed with narrow polydispersity poly methyl methacrylate standards. Representative Polymerization Procedure for Co 2 (CO) 8 Catalyzed Reactions ( entries 1.1 1.5 in T able 5.1) : T o a THF solution of Co 2 (CO) 8 (0 .05 mmol, 17 mg) and 3 hydroxy pyridine (0.05 mmol, 15.5 mg) in a stainless steel autoclave under nitrogen atmosphere ; desired percent s of propylene oxide and trioxane were added, and the mixture was charged with 800 psi carbon monoxide and placed in an oi l bath ( 75 C). After stirring fo r 1 day

PAGE 102

102 the autoclave was cooled and CO was released. The reaction mixture was transferred into a flask, and about 1 mL of HCl was added. The mixture was washed with water, and polymer solution was extracted with DCM and then dried with MgSO 4 Solvent was evaporated under low pressure, giving of waxy polymer product. 1 H NMR (500 MHz, CDCl 3 13 C NMR (500 MHz, CDCl 3 Representa tive Polymerization Procedure for Sc(OTf ) 3 Catalyzed Reactions (entries 2.1 2.19 in T able 5.2) : Under nitrogen atmosphere, a mixture of trioxane (1.82 g, 20 mmol), and s candium triflate (Sc(OTf) 3 ) (0.098 g, 0.2 mmol) in 20 mL of a desired solvent was placed in a 600 mL high pressure reactor. Then, it was charged with CO, and heated to desired reaction temperature. Reaction was stirred under pressure for desired reaction time at the same temperature. After cooling to room temperature, the pressure was r eleased, and the mixture was poured into cold basic methanol. The isolated product was washed with methanol and DCM, and dried under vacuum. 1 H NMR (500 MHz, HFIP ppm 4.50 (s, 2H). 13 C NMR (500 MHz, HFIP CDCl 3

PAGE 103

103 CHAPTER 6 CONCLUSION Summary of Results It has been demonstrated that PGA can be produced from biorenewable C1 f eedstock s This method constitutes a cost effective and efficient pa th for the synthesis of PGA by perfectly alternating copolymerizations of formaldehy de and CO using a Br nsted acid catalyst. Compared to the ring opening polymerization method, t he number of synthetic steps from simple feedstock s is greatly reduced and the starting materials are all potentially sustainable from biomass. A variety of formaldehyde sources including t rioxane paraformaldehyde and polyoxymethylene can be polymerized in the presence of Br nsted acid catalysts to produce PGA Investigation of formalin solution as a formaldehyde source did not result in PGA due to the deacti vation of cationic intermediates in water. Triflic acid (TfOH) was determined to be the best catalyst for the polymerization. By using this method, PGA was successfully synthesized with yields up to 92% using triflic acid (TfOH) catalyst under 800 psi CO p ressure at 170 o C in three days. T he polymer from CO and H 2 CO is sufficiently similar to that prepared from glycolide that it can be readily substituted for the PGA prepared by the glycolide route Raising polymerization temperature and increasing reaction times brought about higher yields due to higher CO incorporation. To improve on the physical properties of PGA (such as melting temperature and appearance) we prepare d ter polymers of PGA with alkylene oxides or cyclic ethers include d in the polymerizatio n mixture. The resulting polyester ether thermoplastics constitute a new family of PGA analogues Addition of comonomers in the reaction system provided many possible polymeric structures. The results showed that optimal

PAGE 104

104 polymerizations we re obtained at te mperatures lower than that for the PGA synthesis. Higher reaction temperatures resulted in lower yields, but higher CO incorporation. The thermal properties of these copolymers were also evaluated. A decrease in the melting temperature with an increasing number of alkyl un its in the comonomer side chain and an increase in solubilities of copolymers with an increasing number of carbons in the alkyl side chains were observed. The color of the terpolymers was lighter than that of commercial PGA. The thermal t ransition temperature s ( T g and T m ) of one of the polymers were similar to those of isotactic polypropylene. A nother goal of the project was to perform the polymerization using milder conditions, due to the harshness of using very high temperature s and CO pressure s A new pathway to produce PGA was introduced based on perfectly alternating cationic copolymerization of trioxane and CO catalyzed by Sc(OTf) 3 An additional benefit of this strategy is that Sc(OTf) 3 is an environmentally friendly catalyst and ca n be recycled from the reaction media. These present important advantages for a catalyst system, and polymerization will be a convenient alternative way to produce PGA. The product confirm s the formation of PGA and provides a new catalyst system for the pr eparation of PGA. Future Directions Large scale production of PGA for commercial applications is suffering from three main drawbacks : production cost, insolubi lity in common solvents, and undesirable physical properties including color and melting temperat ure. The present study has shown that PGA can be prepared by the cationic alternating copolymerization of very cheap and abundant C1 feedstocks, formaldehyde and CO, in one step. I t has also been demonstrated that ter polymers of PGA w ith alkylene oxides display improved

PAGE 105

105 the physi cal properties. Addition of an epoxide as a comonomer allows the modulation of the melting temperature and improves the color to off white materials. However the al kylene chain length of epoxides was found to have only a slight effect on the solubility of PGA. As a future work, long chain epoxides derived from fatty acids such as hexadece ne oxide could be tried to improve the solubility of the PGA (Figure 6 1). Figure 6 1. The p roposed terpolymerization of trioxane, CO and he xadece ne oxide. Chapter 2 showed that addition of glycerol as a branching agent in the reaction mixture improved both reaction time and temperature for the production of PGA Glycerol has three hydroxyl group functionality, and we realized that addition of a minor amount of a compound containing hyd roxyl functionalities would lead to a nucleophilic attack on the oxonium ion intermediate to combine different active PGA polymer blocks. Polyethylene glycol (PEG) has been one of the most studied polymers and it is used commercially in numerous applications including biomedicine, pharmaceutics, etc. PEG can be considered as a macrodiol and is available in a wide range of molecular weights. It is soluble in a variety of solvents including water, methanol, ethanol, DCM, and etc. If we use a minor amount of PEG polymer as a comonomer in our polymerization, it may be possible to use PEG to join two different active PGA chains, thereby improving the physical properties of PGA, especially the solubilit y. P reliminary studies showed that this polymerization works perfectly to incorporate PEG in the PGA backbone. Addition of 1 mol % of PEG 400 in the

PAGE 106

106 polymerization at 110 o C in three days resulted in the formation of 13.1 g of the product containing PEG r epeat units (Figure 6 2) NMR and FT IR spectra also confirm ed the incorporation of PEG in PGA backbone. According to DSC analysis, the melting temperature( T m ) of the copolymer was 177 o C, which is much lower than PGA, and the glass transition temperature ( T g ) was 33 o C, which is close to the T g of PGA. Despite expecting to increase the solubility of PGA by addition of PEG 400, the product again did not show good solubility in common solvents. Perhaps u sing higher molecular weight PEG, such as PEG 8000, wou ld disrupt the crystallinity of PGA and improve its solubility. Figure 6 2. The p roposed PEG incorporation in PGA backbone. How about using different aldehydes other than f ormaldehyde? In efforts to make different polyesters using different aldehydes through the application of the same methodology was unfortunately unsuccessful. Our attempts mostly focused on the synthesis of polylactic acid (PLA) using cationic copolymerization of aceta ldehyde (or metaldehyde the cyclic tetramer of acetaldehyde as an acetaldehyde source) and CO in triflic acid catalyst (Figure 6 3) Failed polymerization attempts with acetaldehyde were disappointing. We think that the ceiling temperature of polyacetaldeh yde is very low (around 40 o C), therefore polymerizations must be conducted at very low temperatures. However, CO insertion in polymer backbone is not achieved at low temperatures. This fact might be the reason of failure co polymerization of acetaldehyde and CO.

PAGE 107

107 Table 6 1 reports the gas phase thermodynamic calculations for the 1:1 incorporation of carbon monoxide and acet Due to t he un favorabl G = +5.2 kcal/mol at 298K), the reaction is not able to proceed to yield the product. Besides that, t he steric effect of the methyl group on Acetaldehyde may also prevent nucleophilic attack of carbon monoxide to protonated acetaldehyde Table 6 1. G3(MP2)/DFT calculation for gas phase copolymerization thermodynamics. a model copolymerization reaction H S G 298 2 0.6 86.5 +5.2 a determined by DFT B3LYP 6 are cal/molK. Perhaps terpolymerization techniques with polymerizable formaldehyde could be employed to incorporate acetaldehyde units in PGA backbo ne, or instead of using TfOH, we might also use different acid catalyst to try this copolymerization. F igure 6 3. Unsuccessful attempt s to produce PLA from the cationic copolymerization of Acetaldehyde and CO.

PAGE 108

108 APPENDIX A SUPPLEMENTARY INFORMATION FOR CHAPTER 2 FT IR Spectr a Figure A 1. FT IR spectrum of polymer commercial polyglycolic acid. Figure A 2. FT IR spectrum of polymer 1.1 (Table 2 1 entry 1.1).

PAGE 109

109 Figure A 3. FT IR spectrum of polymer 1.2 (Table 2 1 entry 1.2). Figure A 4. FT IR spectrum of polymer 1.4 (Table 2 1 entry 1.4). Figure A 5. FT IR spectrum of polymer 1.5 (Table 2 1 entry 1.5).

PAGE 110

110 Figure A 6. FT IR spectrum of polymer 1.6 (Table 2 1 entry 1.6). Figure A 7. FT IR spectrum of polymer 1.7 (Table 2 1 entry 1.7). Figure A 8. FT IR spectrum of polymer 1.8 (Table 2 1 entry 1.8).

PAGE 111

111 Figure A 9. FT IR spectrum of polymer 1.9 (Table 2 1 entry 1.9). Figure A 10. FT IR spectrum of polymer 1.10 (Table 2 1 entry 1.10). Figure A 11. FT IR spectrum of polymer 1.11 (Table 2 1 entry 1.11).

PAGE 112

112 Figure A 12. FT IR spectrum of polymer 1.12 (Table 2 1 entry 1.12). Figure A 13. FT IR spectrum of polymer 1.13 (Table 2 1 entry 1.13). Figure A 14. FT IR spectrum of polymer 1.14 (Table 2 1 entry 1.14).

PAGE 113

113 Figure A 15. FT IR spectrum of polymer 1.15 (Table 2 1 entry 1.15). Figure A 16. FT IR spectrum of polymer 1.16 (Table 2 1, entry 1.16). Figure A 17. FT IR spectrum of polymer 1.17 (Table 2 1, entry 1.17).

PAGE 114

114 Figure A 18. FT IR spectrum of polymer 1.18 (Table 2 1, entry 1.18). Figure A 19. FT IR spectrum of polymer 1.19 (Table 2 1, entry 1.19). Figure A 20. FT IR spectrum of polymer 2.1 (Table 2 2, entry 2.1).

PAGE 115

115 Figure A 21. FT IR spectrum of polymer 2.2 (Table 2 2, entry 2.2). Figure A 22 FT IR spectrum of polymer 2 .3 (Table 2 2, entry 2 .3). Figure A 23 FT IR spectrum of polymer 3.1 (Table 2 3 entry 3.1).

PAGE 116

116 Figure A 24 FT IR spectrum of polymer 3.2 (Table 2 3 entry 3.2). Figure A 25. FT IR spectrum of polymer 4.1 (S cheme 2 16 entry 4.1). Figure A 26. FT IR spectrum of polymer 5.1 ( Figure 2 8 entry 5.1).

PAGE 117

117 Thermogravimetric Analyses Figure A 27. TGA Thermogram of commercial polyglycolic acid. Figure A 28. TGA Thermogram of polymer 1.1 (Table 2 1, entry 1.1).

PAGE 118

118 Figure A 29. TGA Thermogram of polymer 1.2 (Table 2 1, entry 1.2). Figure A 30. TGA Thermogram of polymer 1.4 (Table 2 1, entry 1. 4).

PAGE 119

119 Figure A 31. TGA Thermogram of polymer 1.5 (Table 2 1, entry 1.5). Figure A 32. TGA Thermogram of polymer 1.6 (Table 2 1, entry 1.6).

PAGE 120

120 Figure A 33. TGA Thermogram of polymer 1.7 (Table 2 1, entry 1.7). Figure A 34. TGA Thermogram of polymer 1.8 (Table 2 1, entry 1.8).

PAGE 121

121 Figure A 35. TGA Thermogram of polymer 1.9 (Table 2 1, entry 1.9). Figure A 36. TGA Thermogram of polymer 1.10 (Table 2 1, entry 1.10).

PAGE 122

122 Figure A 37. TGA Thermogram of polymer 1.11 (Table 2 1, entry 1.11). Figure A 38. TGA Thermogram of polymer 1.12 (Table 2 1, entry 1.12).

PAGE 123

123 Figure A 39. TGA Thermogram of polymer 1.13 (Table 2 1, entry 1.13). Figure A 40. TGA Thermogram of polymer 1.14 (Table 2 1, entry 1.14).

PAGE 124

124 Figure A 41. TGA Thermogram of polymer 1.15 (Table 2 1, entry 1.15). Figure A 42. TGA Thermogram of polymer 1.16 (Table 2 1, entry 1.16).

PAGE 125

125 Figure A 43. TGA Thermogram of polymer 1.17 (Table 2 1, entry 1.17). Figure A 44. TGA Thermogram of polymer 1.18 (Table 2 1, entry 1.18).

PAGE 126

126 Figure A 45. TGA Thermogram of polymer 1.19 (Table 2 1, entry 1.19). Figure A 46. TGA Thermogram of polymer 2.1 (Table 2 2, entry 2.1).

PAGE 127

127 Figure A 47. TGA Thermogram of polymer 2.2 (Table 2 2, entry 2.2). Figure A 48 TGA Thermogram of polymer 2.3 (Table 2 2, entry 2.3 ).

PAGE 128

128 Figure A 49 TGA Thermogram of polymer 3.1 (Table 2 3 entry 3.1). Figure A 50 TGA Thermogram of polymer 3.2 (Table 2 3 entry 3.2).

PAGE 129

129 Figure A 51. TGA Thermogram of polymer 4.1 ( Figure 2 16 entry 4.1). Figure A 52. TGA Thermogram of polymer 5.1 ( Figure 2 8 entry 5.1).

PAGE 130

130 Differential Scanning Calorimetry T hermograms Figure A 53. DSC Thermogram of commercial polyglycolic acid. Figure A 54. DSC Thermogram of polymer 1.1 (Table 2 1, entry 1.1).

PAGE 131

131 Figure A 55. DSC Thermogram of polymer 1.2 (Table 2 1, entry 1.2). Figure A 56. DSC Thermogram of polymer 1.4 (Table 2 1, entry 1.4).

PAGE 132

132 Figure A 57. DSC Thermogram of polymer 1.5 (Table 2 1, entry 1.5). Figure A 58. DSC Thermogram of polymer 1.6 (Table 2 1, entry 1.6).

PAGE 133

133 Figure A 59. DSC Thermogram of polymer 1.7 (Table 2 1, entry 1.7). Figure A 60. DSC Thermogram of polymer 1.8 (Table 2 1, entry 1.8).

PAGE 134

134 Figure A 61. DSC Thermogram of polymer 1.9 (Table 2 1, entry 1.9). Figure A 62. DSC Thermogram of polymer 1.10 (Table 2 1, entry 1.10).

PAGE 135

135 Figure A 63. DSC Thermogram of polymer 1.11 (Table 2 1, entry 1.11). Figure A 64. DSC Thermogram of polymer 1.12 (Table 2 1, entry 1.12).

PAGE 136

136 Figure A 65. DSC Thermogram of polymer 1.13 (Table 2 1, entry 1.13). Figure A 66. DSC Thermogram of polymer 1.14 (Table 2 1, entry 1.14).

PAGE 137

137 Figure A 67. DSC Thermogram of polymer 1.15 (Table 2 1, entry 1.15). Figure A 68. DSC Thermogram of polymer 1.16 (Table 2 1, entry 1.16).

PAGE 138

138 Figure A 69. DSC Thermogram of polymer 1.17 (Table 2 1, entry 1.17). Figure A 70. DSC Thermogram of polymer 1.18 (Table 2 1, entry 1.18).

PAGE 139

139 Figure A 71. DSC Thermogram of polymer 1.19 (Table 2 1, entry 1.19). Figure A 72. DSC Thermogram of polymer 2.1 (Table 2 2, entry 2.1).

PAGE 140

140 Figure A 73. DSC Thermogram of polymer 2.2 (Table 2 2, entry 2.2). Figure A 74 DSC Thermogram of polymer 2.3 (Table 2 2, entry 2.3 ).

PAGE 141

141 Figure A 75 DSC Thermogram of polymer 3.1 (Table 2 3 entry 3.1). Figure A 76 DSC Thermogram of polymer 3.2 (Table 2 3 entry 3.2).

PAGE 142

142 Figure A 77. DSC Thermogram of polymer 4.1 ( Figure 2 16 entry 4.1). Figure A 78. DSC Thermogram of polymer 5.1 ( Figure 2 8 entry 5.1).

PAGE 143

143 1 H NMR Spectra Figure A 79. 1 H NMR spectrum of HFIP in CDCl 3 Figure A 80. 1 H NMR spectrum of commercial polyglycolic acid in HFIP + CDCl 3 Figure A 81. 1 H NMR spectrum of polymer 1.1 in HFIP + CDCl 3 (Table 2 1, entry 1.1).

PAGE 144

144 Figure A 82. 1 H NMR spectrum of polymer 1.2 in HFIP + CDCl 3 (Table 2 1, entry 1.2). Figure A 83. 1 H NMR spectrum of polymer 1.4 in HFIP + CDCl 3 (Table 2 1, entry 1.4). Figure A 84. 1 H NMR spectrum of polymer 1.5 in HFIP + CDCl 3 (Table 2 1, entry 1.5).

PAGE 145

145 Figure A 85. 1 H NMR spectrum of polymer 1.6 in HFIP + CDCl 3 (Table 2 1, entry 1.6). Figure A 86. 1 H NMR spectrum of polymer 1.7 in HFIP + CDCl 3 (Table 2 1, entry 1.7). Figure A 87. 1 H NMR spectrum of polymer 1.8 in HFIP + CDCl 3 (Table 2 1, entry 1.8).

PAGE 146

146 Figure A 88. 1 H NMR spectrum of polymer 1.9 in HFIP + CDCl 3 (Table 2 1, entry 1.9). Figure A 89. 1 H NMR spectrum of polymer 1.10 in HFIP + CDCl 3 (Table 2 1, entry 1.10). Figure A 90. 1 H NMR spectrum of polymer 1.11 in HFIP + CDCl 3 (Table 2 1, entry 1.11).

PAGE 147

147 Figure A 91. 1 H NMR spectrum of polymer 1.12 in HFIP + CDCl 3 (Table 2 1, entry 1.12). Figure A 92. 1 H NMR spectrum of polymer 1.13 in HFIP + CDCl 3 (Table 2 1, entry 1.13). Figure A 93. 1 H NMR spectrum of polymer 1.14 in HFIP + CDCl 3 (Table 2 1, entry 1.14).

PAGE 148

148 Figure A 94. 1 H NMR spectrum of polymer 1.15 in HFIP + CDCl 3 (Table 2 1, entry 1.15). Figure A 95. 1 H NMR spectrum of polymer 1.16 in HFIP + CDCl 3 (Table 2 1, entry 1.16). Figure A 96. 1 H NMR spectrum of polymer 1.17 in HFIP + CDCl 3 (Table 2 1, entry 1.17).

PAGE 149

149 Figure A 97. 1 H NMR spectrum of polymer 1.18 in HFIP + CDCl 3 (Table 2 1, entry 1.18). Figure A 98. 1 H NMR spectrum of polymer 1.19 in HFIP + CDCl 3 (Table 2 1, entry 1.19). Figure A 99. 1 H NMR spectrum of polymer 2.1 in HFIP + CDCl 3 (Table 2 2, entry 2.1).

PAGE 150

150 Figure A 100. 1 H NMR spectrum of polymer 2.2 in HFIP + CDCl 3 (Table 2 2, entry 2.2). Figure A 101 1 H NMR spectrum of polymer 2.3 in HFIP + CDCl 3 (Table 2 2, entry 2.3 ). Figure A 102 1 H NMR spectrum of polymer 3.1 in HFIP + CDCl 3 (Table 2 3 entry 3.1).

PAGE 151

151 Figure A 103 1 H NMR spectrum of polymer 3.2 in HFIP + CDCl 3 (Table 2 3 entry 3.2). Figure A 104. 1 H NMR spectrum of polymer 4.1 in HFIP + CDCl 3 ( Figure 2 16 entry 4.1). Figure A 105. 1 H NMR spectrum of polymer 5.1 in HFIP + CDCl 3 ( Figure 2 8 entry 5.1).

PAGE 152

152 13 C NMR Spectra Figure A 106. 13 C NMR spectrum of HFIP solvent in CDCl 3 Figure A 107. 13 C NMR spectrum of commercial polyglycolic acid in HFIP + CDCl 3 Figure A 108. 13 C NMR spectrum of polymer 1.1 in HFIP + CDCl 3 (Table 2 1, entry 1.1).

PAGE 153

153 Figure A 109. 13 C NMR spectrum of polymer 1.2 in HFIP + C 6 D 6 (Table 2 1, entry 1.2). Figure A 110. 13 C NMR spectrum of polymer 1.4 in HFIP + CDCl 3 (Table 2 1, entry 1.4). Figure A 111. 13 C NMR spectrum of polymer 1.5 in HFIP + CDCl 3 (Table 2 1, entry 1.5).

PAGE 154

154 Figure A 112. 13 C NMR spectrum of polymer 1.6 in HFIP + CDCl 3 (Table 2 1, entry 1.6). Figure A 113. 13 C NMR spectrum of polymer 1.7 in HFIP + CDCl 3 (Table 2 1, entry 1.7). Figure A 114. 13 C NMR spectrum of polymer 1.8 in HFIP + CDCl 3 (Table 2 1, entry 1.8).

PAGE 155

155 Figure A 115. 13 C NMR spectrum of polymer 1.9 in HFIP + CDCl 3 (Table 2 1, entry 1.9). Figure A 116. 13 C NMR spectrum of polymer 1.10 in HFIP + C 6 D 6 (Table 2 1, entry 1.10). Figure A 117. 13 C NMR spectrum of polymer 1.11 in HFIP + CDCl 3 (Table 2 1, entry 1.11).

PAGE 156

156 Figure A 118. 13 C NMR spectrum of polymer 1.12 in HFIP + CDCl 3 (Table 2 1, entry 1.12). Figure A 119. 13 C NMR spectrum of polymer 1.13 in HFIP + CDCl 3 (Table 2 1, entry 1.13). Figure A 120. 13 C NM R spectrum of polymer 1.14 in HFIP + CDCl 3 (Table 2 1, entry 1.14).

PAGE 157

157 Figure A 121. 13 C NMR spectrum of polymer 1.15 in HFIP + CDCl 3 (Table 2 1, entry 1.15). Figure A 122. 13 C NMR spectrum of polymer 1.16 in HFIP + CDCl 3 (Table 2 1, entry 1.16). Figure A 123. 13 C NMR spectrum of polymer 1.17 in HFIP + CDCl 3 (Table 2 1, entry 1.17).

PAGE 158

158 Figure A 124. 13 C NMR spectrum of polymer 1.18 in HFIP + C 6 D 6 (Table 2 1, entry 1.18). Figure A 125. 13 C NMR spectrum of polymer 1.19 in HFIP + CDCl 3 (Table 2 1, entry 1.19). Figure A 126. 13 C NMR spectrum of polymer 2.1 in HFIP d 2 (Table 2 2, entry 2.1).

PAGE 159

159 Figure A 127. 13 C NMR spectrum of polymer 2.2 in HFIP + CDCl 3 (Table 2 2, entry 2.2). Figure A 128 13 C NMR spectrum of polymer 2.3 in HFIP + CDCl 3 (Table 2 2, entry 2.3 ). Figure A 129 13 C NMR spectrum of polymer 3.1 in HFIP + CDCl 3 (Table 2 3 entry 3.1).

PAGE 160

160 Figure A 130 13 C NMR spectrum of polymer 3.2 in HFIP + CDCl 3 (Table 2 3 entry 3.2). Figure A 131. 13 C NMR spectrum of polymer 4.1 in HFIP + CDCl 3 ( Figure 2 16 entry 4.1). Figure A 132. 13 C NMR spectrum of polymer 5.1 in HFIP + CDCl 3 ( Figure 2 8 entry 5.1).

PAGE 161

161 Gel Permeation Chromatography (GPC) Data Figure A 133. GPC Chromatogram of commercial polyglycolic acid Figure A 134. GPC Chromatogram of polymer 1.1 (Table 2 1, entry 1.1). Figure A 135. GPC Chromatogram of polymer 1.2 (Table 2 1, entry 1.2).

PAGE 162

162 Figure A 136. GPC Chromatogram of polymer 1.4 (Table 2 1, entry 1.4). Figure A 137. GPC Chromatogram of polymer 1.5 (Table 2 1, entry 1.5). Figure A 138. GPC Chromatogram of polymer 1.6 (Table 2 1, entry 1.6).

PAGE 163

163 Figure A 139. GPC Chromatogram of polymer 1.7 (Table 2 1, entry 1.7). Figure A 140. GPC Chromatogram of polymer 1.8 (Table 2 1, entry 1.8). Figure A 141. GPC Chromatogram of polymer 1.9 (Table 2 1, entry 1.9).

PAGE 164

164 Figure A 142. GPC Chromatogram of polymer 1.10 (Table 2 1, entry 1.10). Figure A 143. GPC Chromatogram of polymer 1.11 (Table 2 1, entry 1.11). Figure A 144. GPC Chromatogr am of polymer 1.12 (Table 2 1, entry 1.12).

PAGE 165

165 Figure A 145. GPC Chromatogram of polymer 1.13 (Table 2 1, entry 1.13). Figure A 146. GPC Chromatogram of polymer 1.14 (Table 2 1, entry 1.14). Figure A 147. GPC Chromatogram of polymer 1.15 (Table 2 1, entry 1.15).

PAGE 166

166 Figure A 148. GPC Chromatogram of polymer 1.16 (Table 2 1, entry 1.16). Figure A 149. GPC Chromatogram of polymer 1.17 (Table 2 1, entry 1.17). Figure A 150. GPC Chromatogram of polymer 1.18 (Table 2 1, entry 1.18).

PAGE 167

167 Figure A 151. GPC Chromatogram of polymer 1.19 (Table 2 1, entry 1.19). Figure A 152. GPC Chromatogram of polymer 2.1 (Table 2 2, entry 2.1). Figure A 153. GPC Chromatogram of polymer 2.2 (Table 2 2, entry 2.2). Figure A 154 GPC Chromatogram of pol ymer 2. 3 (Table 2 2, entry 2.3 ). Figure A 155 GPC Chromatogram of polymer 3.1 (Table 2 3 entry 3.1). Figure A 156 GPC Chromatogram of polymer 3.2 (Table 2 3 entry 3.2). Figure A 157. GPC Chromatogram of polymer 4.1 ( Figure 2 16 entry 4.1).

PAGE 168

168 Figure A 158. GPC Chromatogram of polymer 5.1 ( Figure 2 8 entry 5.1). A Picture of Our Product and Commercial PGA Figure A 159. The pictures of commercial PGA and entry 1.17 at T able 2 1.

PAGE 169

169 APPENDIX B SUPPLEMENTARY INFORMATION FOR CHAPTER 3 FT IR Spe ctr a Figure B 1. FT IR spectrum of polymer 1 4 (Table 3 1, entry 1. 4). Figure B 2. FT IR spectrum of polymer 1 .5 (Table 3 1, entry 1. 5).

PAGE 170

170 Figure B 3. FT IR spectrum of polymer 1 .6 (Table 3 1, entry 1. 6). Figure B 4. FT IR spectrum of polymer 1 .7 (Table 3 1, entry 1. 7). Figure B 5. FT IR spectrum of polymer 1 .8 (Table 3 1, entry 1. 8).

PAGE 171

171 Figure B 6. FT IR spectrum of polymer 1 .9 (Table 3 1, entry 1. 9). Figure B 7. FT IR spectrum of polymer 1 .10 (Table 3 1, entry 1. 10). Figure B 8. FT IR spect rum of polymer 1 .13 (Table 3 1, entry 1. 13).

PAGE 172

172 Figure B 9. FT IR spectrum of polymer 1 .14 (Table 3 1, entry 1. 14). Figure B 10. FT IR spectrum of polymer 1 .15 (Table 3 1, entry 1. 15). Figure B 11. FT IR spectrum of polymer 1 .16 (Table 3 1, entry 1. 16).

PAGE 173

173 Figure B 12. FT IR spectrum of polymer 1 .17 (Table 3 1, entry 1. 17). Figure B 13. FT IR spectrum of polymer 1 .18 (Table 3 1, entry 1. 18). Figure B 14. FT IR spectrum of polymer 3 .1 (Table 3 3, entry 3. 1).

PAGE 174

174 Figure B 15. FT IR spectrum of polymer 3 2 (Table 3 3, entry 3. 2). Figure B 16. FT IR spectrum of polymer 3 .3 (Table 3 3, entry 3. 3). Figure B 17. FT IR spectrum of polymer 3 .4 (Table 3 3, entry 3. 4).

PAGE 175

175 Figure B 18. FT IR spectrum of polymer 4 .1 (Table 3 4, entry 4. 1). Figure B 19. FT IR spectrum of polymer 4 .2 (Table 3 4, entry 4. 2). Figure B 20. FT IR spectrum of polymer 4 .3 (Table 3 4, entry 4. 3).

PAGE 176

176 Figure B 21. FT IR spectrum of polymer 5 .1 (Table 3 5, entry 5. 1). Figure B 22. FT IR spectrum of polymer 5 .2 (Table 3 5, entry 5. 2). Figure B 23. FT IR spectrum of polymer 5 .3 (Table 3 5, entry 5. 3).

PAGE 177

177 Figure B 24. FT IR spectrum of polymer 6 .1 (Table 3 6, entry 6. 1). Figure B 25. FT IR spectrum of polymer 6 .2 (Table 3 6, entry 6. 2). Figure B 26. FT IR spectrum of polymer 6 .3 (Table 3 6, entry 6. 3).

PAGE 178

178 Figure B 27 FT IR spectrum of polymer 7 .1 (Table 3 7, entry 7. 1). Figure B 28 FT IR spectrum of polymer 7 .2 (Table 3 7, entry 7. 2). Figure B 29 FT IR spectrum of polymer 7 .3 (Table 3 7, entry 7. 3).

PAGE 179

1 79 Figure B 30. FT IR spectrum of polymer 7 .4 (Table 3 7, entry 7. 4). Figure B 31. FT IR spectrum of polymer 7 .5 (Table 3 7, entry 7. 5). Figure B 32. FT IR spectrum of polymer 7 .6 (Table 3 7, entry 7. 6).

PAGE 180

180 Figure B 33 FT IR spectrum of polymer 8 .1 (Table 3 8, entry 8. 1). Figure B 34 FT IR spectrum of polymer 8 .2 (Table 3 8, entry 8. 2 ). Figure B 35 FT IR spectrum of polymer 8 .3 (Table 3 8, entry 8. 3 ).

PAGE 181

181 Figure B 36 FT IR spectrum of polymer 8 .4 (Table 3 8, entry 8. 4 ). Figure B 37 FT IR spectrum of polymer 8 .5 (Table 3 8, entry 8. 5 ).

PAGE 182

182 Thermogravimetric Analyses Figure B 38 TGA Thermogram of polymer 1 .4 (Table 3 1, entry 1. 4). Figure B 39 TGA Thermogram of polymer 1 .5 (Table 3 1, entry 1. 5).

PAGE 183

183 Figure B 40 TGA Thermogram of polymer 1 .6 (Table 3 1, entry 1. 6). Figure B 41 TGA Thermogram of polymer 1 .7 (Table 3 1, entry 1. 7).

PAGE 184

184 Figure B 42 TGA Thermogram of polymer 1 .8 (Table 3 1, entry 1. 8). Figure B 43 TGA Thermogram of polymer 1 .9 (Table 3 1, entry 1. 9).

PAGE 185

185 Figure B 44 TGA Thermogram of polymer 1 .10 (Table 3 1, entry 1. 10). Figure B 45 TGA Thermogram of polymer 1 .13 (Table 3 1, entry 1. 13).

PAGE 186

186 Figure B 46 TGA Thermogram of polymer 1 .14 (Table 3 1, entry 1. 14). Figure B 47 TGA Thermogram of polymer 1 .15 (Table 3 1, entry 1. 15).

PAGE 187

187 Figure B 48 TGA Thermogram of polymer 1 .16 (Table 3 1, entry 1. 16). Figure B 49 TGA Thermogram of polymer 1 .17 (Table 3 1, entry 1. 17).

PAGE 188

188 Figure B 50 TGA Thermogram of polymer 1 .18 (Table 3 1, entry 1. 18). Figure B 51 TGA Thermogram of polymer 3 .1 (Table 3 3, entry 3. 1).

PAGE 189

189 Figure B 52 TGA Thermogram of polymer 3 .2 (Table 3 3, entry 3. 2). Figure B 53 TGA Thermogram of polymer 3 .3 (Table 3 3, entry 3. 3).

PAGE 190

190 Figure B 54 TGA Thermogram of polymer 3 .4 (Table 3 3, entry 3. 4). Figure B 55 TGA Thermogram of polymer 4 .1 (Table 3 4, entry 4. 1).

PAGE 191

191 Figure B 56 TGA Thermogram of polymer 4 .2 (Table 3 4, entry 4. 2). Fig ure B 57 TGA Thermogram of polymer 4 .3 (Table 3 4, entry 4. 3).

PAGE 192

192 Figure B 58 TGA Thermogram of polymer 5 .1 (Table 3 5, entry 5. 1). Figure B 59 TGA Thermogram of polymer 5 .2 (Table 3 5, entry 5. 2).

PAGE 193

193 Figure B 60 TGA Thermogram of polymer 5 .3 (Table 3 5, entry 5. 3). Figure B 61 TGA Thermogram of polymer 6 .1 (Table 3 6, entry 6. 1).

PAGE 194

194 Figure B 62 TGA Thermogram of polymer 6 .2 (Table 3 6, entry 6. 2). Figure B 63 TGA Thermogram of polymer 6 .3 (Table 3 6, entry 6. 3).

PAGE 195

195 Figure B 64 TGA Thermogram of polymer 7 .1 (Table 3 7, entry 7. 1). Figure B 65 TGA Thermogram of polymer 7 .2 (Table 3 7, entry 7. 2).

PAGE 196

196 Figure B 66 TGA Thermogram of polymer 7 .3 (Table 3 7, entry 7. 3). Figure B 67 TGA Thermogram of polymer 7 .4 (Table 3 7, entry 7. 4).

PAGE 197

197 Figure B 68 TGA Thermogram of polymer 7 .5 (Table 3 7, e ntry 7. 5). Figure B 69 TGA Thermogram of polymer 7 .6 (Table 3 7, entry 7. 6).

PAGE 198

198 Figure B 70 TGA Thermogram of polymer 8 .1 (Table 3 8, entry 8. 1). Figure B 71 TGA Thermogram of polymer 8 2 (Table 3 8, entry 8. 2 ).

PAGE 199

199 Figure B 72 TGA Thermogram of polymer 8 3 (Table 3 8, entry 8. 3 ). Figure B 73 TGA Thermogram of polymer 8 4 (Table 3 8, entry 8. 4 ).

PAGE 200

200 Figure B 74 TGA Thermogram of polymer 8 5 (Table 3 8, entry 8. 5 ). Differential Scanning Calorimetry T hermograms Figure B 75 DSC Thermogram of polymer 1 .4 (Table 3 1, entry 1. 4).

PAGE 201

201 Figure B 76 DSC Thermogram of polymer 1 .5 (Table 3 1, entry 1. 5). Figure B 77 DSC Thermogram of polymer 1 .6 (Table 3 1, entry 1. 6).

PAGE 202

202 Figure B 78 DSC Thermogram of polymer 1 .7 (Table 3 1, entry 1. 7). Figure B 79 DSC Thermogram of polymer 1 .8 (Table 3 1, entry 1. 8).

PAGE 203

203 Figure B 80 DSC Thermogram of polymer 1 .9 (Table 3 1, entry 1. 9). Figure B 81 DSC Thermogram of polymer 1 .10 (Table 3 1, entry 1. 10).

PAGE 204

204 Figure B 82 DSC Thermogram of polymer 1 .13 (Table 3 1, entry 1. 13). Figure B 83 DSC Thermogram of polymer 1 .14 (Table 3 1, entry 1. 14).

PAGE 205

205 Figure B 84 DSC Thermogram of polymer 1 .15 (Table 3 1, entry 1. 15). Figure B 85 DSC Thermogram of polymer 1 .16 (Table 3 1, entry 1. 16).

PAGE 206

206 Figure B 86 DSC Thermogram of polymer 1 .17 (Table 3 1, entry 1. 17). Figure B 87 DSC Thermogram of polymer 1 .18 (Table 3 1, entry 1. 18).

PAGE 207

207 Figure B 88 DSC Thermogram of polymer 3 .1 (Table 3 3, entry 3. 1). Figure B 89 DSC Thermogram of polymer 3 .2 (Table 3 3, entry 3. 2).

PAGE 208

208 Figure B 90 DSC Thermogram of polymer 3 .3 (Table 3 3, entry 3. 3). Figure B 91 DSC Thermogram of polymer 3 .4 (Table 3 3, entry 3. 4).

PAGE 209

209 Figure B 92 DSC Thermogram of polymer 4 .1 (Table 3 4, entry 4. 1). Figure B 93 DSC Thermogram of polymer 4 .2 (Table 3 4, entry 4. 2).

PAGE 210

210 Figure B 94 DSC Thermogram of polymer 4 .3 (Table 3 4, entry 4. 3). Figure B 95 DSC Thermogram of polymer 5 .1 (Table 3 5, entry 5. 1).

PAGE 211

211 Figure B 96 DSC Thermogram of polymer 5 .2 (Table 3 5, entry 5. 2). Figure B 97 DSC Thermogram of polymer 5 .3 (Table 3 5, entry 5. 3).

PAGE 212

212 Figure B 98 DSC Thermogram of polymer 6 .1 (Table 3 6, entry 6. 1). Figure B 99 DSC Thermogram of polymer 6 .2 (Table 3 6, entry 6. 2).

PAGE 213

213 Figure B 100 DSC Thermogram of polymer 6 .3 (Table 3 6, entry 6. 3). Figure B 101 DSC Thermogram of polymer 7 .1 (Table 3 7, entry 7. 1).

PAGE 214

214 Figure B 102 DSC Thermogram of polymer 7 .2 (Table 3 7, entry 7. 2). Figure B 103 DSC Thermogram of polymer 7 .3 (Table 3 7, entry 7. 3).

PAGE 215

215 Figure B 104. DSC Thermogram of polymer 7 .4 (Table 3 7, entry 7. 4). Figure B 105 DSC Thermogram of polymer 7 .5 (Table 3 7, entry 7. 5).

PAGE 216

216 Figure B 106 DSC Thermogram of polymer 7 .6 (Table 3 7, entry 7. 6). Figure B 107 DSC Thermogram of polymer 8 .1 (Table 3 8, entry 8. 1).

PAGE 217

217 Figure B 108 DSC Thermogram of polymer 8 2 (Table 3 8, entry 8. 2 ). Figure B 109 DSC Thermogram of polymer 8 3 (Table 3 8, entry 8. 3 ).

PAGE 218

218 Figure B 110 DSC Thermogram of polymer 8 4 (Table 3 8, entry 8. 4 ). Figure B 111 DSC Thermogram of polymer 8 5 (Table 3 8, entry 8. 5 ).

PAGE 219

219 1 H NMR Spectra Figure B 112 1 H NMR spectrum of polymer 1 .4 in HFIP + CDCl 3 (Table 3 1, entry 1. 4). Figure B 113 1 H NMR spectrum of polymer 1 .5 in HFIP + CDCl 3 (Table 3 1, entry 1. 5). Figure B 114 1 H NMR spectrum of polymer 1 .6 in HFIP + CDCl 3 (Table 3 1, entry 1. 6).

PAGE 220

220 Figure B 115 1 H NMR spectrum of polymer 1 .7 in HFIP + CDCl 3 (Table 3 1, entry 1. 7). Figure B 116 1 H NMR spectrum of polymer 1 .8 in HFIP + CDCl 3 (Table 3 1, entry 1. 8). Figure B 117 1 H NMR spectrum of polymer 1 .9 in HFIP + CDCl 3 (Table 3 1, entry 1. 9).

PAGE 221

221 Figure B 118 1 H NMR spectrum of polymer 1 .10 in HFIP + CDCl 3 (Table 3 1, entry 1. 10). Figure B 119 1 H NMR spectrum of polymer 1 .13 in HFIP + CDCl 3 (Table 3 1, entry 1. 13). Figure B 120 1 H NMR spectrum of polymer 1 .14 in HFIP + CDCl 3 (Table 3 1, entry 1. 14).

PAGE 222

222 Figure B 121 1 H NMR spectrum of polymer 1 .15 in HFIP + CDCl 3 (Table 3 1, entry 1. 15). Figure B 122 1 H NMR spectrum of polymer 1 .16 in HFIP + CDCl 3 (Table 3 1, entry 1. 16). Figure B 123 1 H NMR spectrum of polymer 1 .17 in HFIP + CDCl 3 (Table 3 1, entry 1. 17).

PAGE 223

223 Figure B 124 1 H NMR spectrum of polymer 1 .18 in HFIP + CDCl 3 (Table 3 1, entry 1. 18). Figure B 125 1 H NMR spectrum of polymer 3 .1 in HFIP + CDCl 3 (Table 3 3, entry 3. 1). Figure B 126 1 H NMR spectrum of polymer 3 .2 in HFIP + CDCl 3 (Table 3 3, entry 3. 2).

PAGE 224

224 Figure B 127 1 H NMR spectrum of polymer 3 .3 in HFIP + CDCl 3 (Table 3 3, entry 3. 3). Figure B 128 1 H NMR spectrum of polymer 3 .4 in HFIP + CDCl 3 (Table 3 3, entry 3. 4). Figure B 129 1 H NMR spectrum of polymer 4 .1 in HFIP + CDCl 3 (Table 3 4, entry 4. 1).

PAGE 225

225 Figure B 130 1 H NMR spectrum of polymer 4 .2 in HFIP + CDCl 3 (Table 3 4, entry 4. 2). Figure B 131 1 H NMR spectrum of polymer 4 .3 in HFIP + CDCl 3 (Table 3 4, entry 4. 3). Figure B 132 1 H NMR spectrum of polymer 5 .1 in HFIP + CDCl 3 (Table 3 5, entry 5. 1).

PAGE 226

226 Figure B 133 1 H NMR spectrum of polymer 5 .2 in HFIP + CDCl 3 (Table 3 5, entry 5. 2). Figure B 134 1 H NMR spectrum of polymer 5 .3 in HFIP + CDCl 3 (Table 3 5, entry 5. 3). Figure B 135 1 H NMR spectrum of polymer 6 .1 in HFIP + CDCl 3 (Table 3 6, entry 6. 1).

PAGE 227

227 Figure B 136 1 H NMR spectrum of polymer 6 .2 in HFIP + CDCl 3 (Table 3 6, entry 6. 2). Figure B 137 1 H NMR spectrum of polymer 6 .3 in HFIP + CDCl 3 (Table 3 6, entry 6. 3). Fig ure B 138 1 H NMR spectrum of polymer 7 .1 in HFIP + CDCl 3 (Table 3 7, entry 7. 1).

PAGE 228

228 Figure B 139 1 H NMR spectrum of polymer 7 .2 in HFIP + CDCl 3 (Table 3 7, entry 7. 2). Figure B 140 1 H NMR spectrum of polymer 7 .3 in HFIP + CDCl 3 (Table 3 7, entry 7. 3). F igure B 141 1 H NMR spectrum of polymer 7 .4 in HFIP + CDCl 3 (Table 3 7, entry 7. 4).

PAGE 229

229 Figure B 142 1 H NMR spectrum of polymer 7 .5 in HFIP + CDCl 3 (Table 3 7, entry 7. 5). Figure B 143 1 H NMR spectrum of polymer 7 .6 in HFIP + CDCl 3 (Table 3 7, entry 7. 6). Fig ure B 144 1 H NMR spectrum of polymer 8 .1 in HFIP + CDCl 3 (Table 3 8, entry 8. 1).

PAGE 230

230 Fig ure B 145 1 H NMR spectrum of polymer 8 .2 in HFIP + CDCl 3 (Table 3 8, entry 8. 2 ). Fig ure B 146 1 H NMR spectrum of polymer 8 .3 in HFIP + CDCl 3 (Table 3 8, entry 8. 3 ). Fig ure B 147 1 H NMR spectrum of polymer 8 .4 in HFIP + CDCl 3 (Table 3 8, entry 8. 4 ).

PAGE 231

231 Fig ure B 148 1 H NMR spectrum of polymer 8 .5 in HFIP + CDCl 3 (Table 3 8, entry 8. 5 ). 13 C NMR Spectra Figure B 149 13 C NMR spectrum of polymer 1 .4 in HFIP + CDCl 3 (Table 3 1, entry 1. 4). Figure B 150 13 C NMR spectrum of polymer 1 .5 in HFIP + CDCl 3 (Table 3 1, entry 1. 5).

PAGE 232

232 Figure B 151 13 C NMR spectrum of polymer 1 .6 in HFIP + C 6 D 6 (Table 3 1, entry 1. 6). Figure B 152 13 C NMR spectrum of polymer 1 .7 in HFIP + C 6 D 6 (Table 3 1, entry 1. 7). Figure B 153 13 C NMR spectrum of polymer 1 .8 in HFIP + C 6 D 6 (Table 3 1, entry 1. 8).

PAGE 233

233 Figure B 154 13 C NMR spectrum of polymer 1 .9 in HFIP + CDCl 3 (Table 3 1, entry 1. 9). Figure B 155 13 C NMR spectrum of polymer 1 .10 in HFIP + CDCl 3 (Table 3 1, entry 1. 10). Fi gure B 156 13 C NMR spectrum of polymer 1 .13 in HFIP + C 6 D 6 (Table 3 1, entry 1. 13).

PAGE 234

234 Figure B 157 13 C NMR spectrum of polymer 1 .14 in HFIP + CDCl 3 (Table 3 1, entry 1. 14). Figure B 158 13 C NMR spectrum of polymer 1 .15 in HFIP + CDCl 3 (Table 3 1, entry 1. 15). Figure B 159 13 C NMR spectrum of polymer 1 .16 in HFIP + CDCl 3 (Table 3 1, entry 1. 16).

PAGE 235

235 Figure B 160 13 C NMR spectrum of polymer 1 .17 in HFIP + CDCl 3 (Table 3 1, entry 1. 17). Figure B 161 13 C NMR spectrum of polymer 1 .18 in HFIP + CDCl 3 (Table 3 1, entry 1. 18). Figure B 162 13 C NMR spectrum of polymer 3 .1 in HFIP + CDCl 3 (Table 3 3, entry 3. 1).

PAGE 236

236 Figure B 163 13 C NMR spectrum of polymer 3 .2 in HFIP + CDCl 3 (Table 3 3, entry 3. 2). Figure B 164 13 C NMR spectrum of polymer 3 .3 in HFIP + CDCl 3 (Table 3 3, entry 3. 3). Figure B 165 13 C NMR spectrum of polymer 3 .4 in HFIP + CDCl 3 (Table 3 3, entry 3. 4).

PAGE 237

237 Figure B 166 13 C NMR spectrum of polymer 4 .1 in HFIP + CDCl 3 (Table 3 4, entry 4. 1). Figure B 167 13 C NMR spectrum of polymer 4 .2 in HFIP + CDCl 3 (Table 3 4, entry 4. 2). Figure B 168 13 C NMR spectrum of polymer 4 .3 in HFIP + CDCl 3 (Table 3 4, entry 4. 3).

PAGE 238

238 Figure B 169 13 C NMR spectrum of polymer 5 .1 in HFIP + C 6 D 6 (Table 3 5, entry 5. 1). Figure B 170 13 C NMR spectrum of polymer 5 .2 in HFIP + CDCl 3 (Table 3 5, entry 5. 2). Figure B 171 13 C NMR spectrum of polymer 5 .3 in HFIP + CDCl 3 (Table 3 5, entry 5. 3).

PAGE 239

239 Figure B 172 13 C NMR spectrum of polymer 6 .1 in HFIP + C 6 D 6 (Table 3 6, entry 6. 1). Figure B 173 13 C NMR spectrum of polymer 6 .2 in HFIP + d DMSO (Table 3 6, entry 6. 2). Figure B 174 13 C NMR spectrum of polymer 6 .3 in HFIP + CDCl 3 (Table 3 6, entry 6. 3).

PAGE 240

240 Figure B 175 13 C NMR spectrum of polymer 7 .1 in HFIP + CDCl 3 (Table 3 7, entry 7. 1). F igure B 176 13 C NMR spectrum of polymer 7 .2 in HFIP + CDCl 3 (Table 3 7, entry 7. 2). Figure B 177 13 C NMR spectrum of polymer 7 .3 in HFIP + CDCl 3 (Table 3 7, entry 7. 3).

PAGE 241

241 Figure B 178 13 C NMR spectrum of polymer 7 .4 in HFIP + CDCl 3 (Table 3 7, entry 7. 4). Figure B 179 13 C NMR spectrum of polymer 7 .5 in HFIP + CDCl 3 (Table 3 7, entry 7. 5). Figure B 180 13 C NMR spectrum of polymer 7 .6 in HFIP + CDCl 3 (Table 3 7, entry 7. 6).

PAGE 242

242 Figure B 181 13 C NMR spectrum of polymer 8 .1 in HFIP + CDCl 3 (Table 3 8, entry 8. 1). Figure B 182 13 C NMR spectrum of polymer 8 .2 in HFIP + CDCl 3 (Table 3 8, entry 8. 2 ). Figure B 183 13 C NMR spectrum of polymer 8 .3 in HFIP + CDCl 3 (Table 3 8, entry 8. 3 ). Figure B 184 13 C NMR spectrum of polymer 8 .4 in HFIP + CDCl 3 (Table 3 8, entry 8. 4 ). Figure B 185 13 C NMR spectrum of polymer 8 .5 in HFIP + CDCl 3 (Table 3 8, entry 8. 5 ).

PAGE 243

243 Gel Permeation Chromatography (GPC) Data Figure B 186 GPC Chromatogram of polymer 1 .4 (Table 3 1, entry 1. 4). Figure B 187 GPC Chromatogram of polymer 1 .5 (Table 3 1, entry 1. 5). Figure B 188 GPC Chromatogram of polymer 1 .6 (Table 3 1, entry 1. 6).

PAGE 244

244 Figure B 189 GPC Chromatogram of polymer 1 .7 (Table 3 1, entry 1. 7). Figure B 190 GPC Chromatogram of polymer 1 .8 (Table 3 1, entry 1. 8). Figure B 191 GPC Chromatogram of polymer 1 .9 (Table 3 1, entry 1. 9).

PAGE 245

245 Figure B 192 GPC Chromatogram of polymer 1 .10 (Table 3 1, entry 1. 10). Figure B 193 GPC Chromatogram of polymer 1 .13 (Table 3 1, entry 1. 13). Figure B 194 GPC Chromatogram of polymer 1 .14 (Table 3 1, entry 1. 14).

PAGE 246

246 Figure B 195 GPC Chromatogram of polymer 1 .15 (Table 3 1 entry 1.15). Figure B 196 GPC Chromatogram of polymer 1 .16 (Table 3 1, entry 1. 16). Figure B 197 GPC Chromatogram of polymer 1 .17 (Table 3 1, entry 1. 17).

PAGE 247

247 Figure B 198 GPC Chromatogram of polymer 1 .18 (Table 3 1, entry 1. 18). Figure B 199 GPC Chromatogram of polymer 3 .1 (Table 3 3, entry 3. 1). Figure B 200 GPC Chromatogram of polymer 3 .2 (Table 3 3, entry 3. 2).

PAGE 248

248 Figure B 201 GPC Chromatogram of polymer 3 .3 (Table 3 3, entry 3. 3). Figure B 202 GPC Chromatogram of polymer 3 .4 (Table 3 3, entry 3. 4). Figure B 203 GPC Chromatogram of polymer 4 .1 (Table 3 4, entry 4. 1).

PAGE 249

249 Figure B 204 GPC Chromatogram of polymer 4 .2 (Table 3 4, entry 4. 2). Figure B 205 GPC Chromatogram of polymer 4 .3 (Table 3 4, entry 4. 3). Figure B 206 GPC Chromatogram of polymer 5 .1 (Table 3 5, entry 5. 1).

PAGE 250

250 Figure B 207 GPC Chromatogram of polymer 5 .2 (Table 3 5, entry 5. 2). Figure B 208 GPC Chromatogram of polymer 5 .3 (Table 3 5, entry 5. 3). Figure B 209 GPC Chromatogram of polymer 6 .1 (Table 3 6, entry 6. 1).

PAGE 251

251 Figure B 210 GPC Chromatogram of polymer 6 .2 (Table 3 6, entry 6. 2). Figure B 211 GPC Chromatogram of polymer 6 .3 (Table 3 6, entry 6. 3). Figure B 212 GPC Chromatogram of polymer 7 .1 (Table 3 7 entry 7 .1). Figure B 213 GPC Chromatogram of polymer 7 2 (Table 3 7 entry 7 .2 ). Figure B 214 GPC Chromatogram of polymer 7 3 (Table 3 7 entry 7 .3 ). Figure B 215 GPC Chromatogram of polymer 7 4 (Table 3 7 entry 7 .4 ).

PAGE 252

252 Figure B 216 GPC Chromatogram of polymer 7 5 (Table 3 7 entry 7 .5 ). Figure B 217 GPC Chromatogram of polymer 7 6 (Table 3 7 entry 7 .6 ). Figure B 218 GPC Chromatogram of polymer 8 .1 (Table 3 8, entry 8. 1). Figure B 219 GPC Chromatogram of polymer 8 2 (Table 3 8, entry 8. 2 ). Figure B 220 GPC Chromatogram of polymer 8 3 (Table 3 8, entry 8. 3 ). Figure B 221 GPC Chromatogram of polymer 8 4 (Table 3 8, entry 8. 4 ). Figure B 222 GPC Chromatogram of polymer 8 5 (Table 3 8, entry 8. 5 ).

PAGE 253

253 APPENDIX C SUPPLEMENTARY INFORMATION FOR CHAPTER 4 FT IR Spectr a Figure C 1. FT IR spectrum of polymer 2 .1 (Table 4 2, entry 2. 1). Figure C 2 FT IR spectrum of polymer 2 .2 (Table 4 2, entry 2. 2).

PAGE 254

254 Figure C 3 FT IR spectrum of polymer 2 .3 (Table 4 2, entry 2. 3). Figure C 4 FT IR spectrum of polymer 2 .4 (Table 4 2, entry 2. 4). Figure C 5 FT IR spectrum of polymer 2 .5 (Table 4 2, entry 2. 5).

PAGE 255

255 Figure C 6 FT IR spectrum of polymer 2 .6 (Table 4 2, entry 2. 6). Figure C 7 FT IR spectrum of polymer 3 .1 (Table 4 3, entry 3. 1). Figure C 8 FT IR spectrum of polymer 3 .2 (Table 4 3, entry 3. 2).

PAGE 256

256 Figure C 9 FT IR spectrum of polymer 3 .3 (Table 4 3, entry 3. 3). Figure C 1 0 FT IR spectrum of polymer 3 .4 (Table 4 3, entry 3. 4). Figure C 1 1 FT IR spectrum of polymer 3 .5 (Table 4 3, entry 3. 5).

PAGE 257

257 Figure C 1 2 FT IR spectrum of polymer 3 .6 (Table 4 3, entry 3. 6). Figure C 1 3 FT IR spectrum of polymer 3 .7 (Table 4 3, entry 3. 7). Figure C 1 4 FT IR spectrum of polymer 4 .1 (Table 4 4, entry 4. 1).

PAGE 258

258 Figure C 1 5 FT IR spectrum of polymer 4 .2 (Table 4 4, entry 4. 2). Figure C 1 6 FT IR spectrum of polymer 4 .3 (Table 4 4, entry 4. 3). Figure C 1 7 FT IR spectrum of polymer 4 .4 (Table 4 4, entry 4. 4).

PAGE 259

259 Figure C 1 8 FT IR spectrum of polymer 4 .5 (Table 4 4, entry 4. 5). Figure C 1 9 FT IR spectrum of polymer 4 .6 (Table 4 4, entry 4. 6). Figure C 20 FT IR spectrum of polymer 4 .7 (Table 4 4, entry 4. 7).

PAGE 260

260 Thermogravimetric Analyses Figure C 21 TGA Thermogram of polymer 2 .1 (Table 4 2, entry 2. 1). Figure C 22 TGA Thermogram of polymer 2 .2 (Table 4 2, entry 2. 2).

PAGE 261

261 Figure C 23 TGA Thermogram of polymer 2 .3 (Table 4 2, entry 2. 3). Figure C 24 TGA Thermogram of polymer 2 .4 (Table 4 2, entry 2. 4).

PAGE 262

262 Figure C 25 TGA Thermogram of polymer 2 .5 (Table 4 2, entry 2. 5). Figure C 26 TGA Thermogram of polymer 2 .6 (Table 4 2, entry 2. 6).

PAGE 263

263 Figure C 27 TGA Thermogram of polymer 3 .1 (Table 4 3, entry 3. 1). Figure C 28 TGA Thermogram of polymer 3 .2 (Table 4 3, entry 3. 2).

PAGE 264

26 4 Figure C 29 TGA Ther mogram of polymer 3 .3 (Table 4 3, entry 3. 3). Figure C 30 TGA Thermogram of polymer 3 .4 (Table 4 3, entry 3. 4).

PAGE 265

265 Figure C 31 TGA Thermogram of polymer 3 .5 (Table 4 3, entry 3. 5). Figure C 32 TGA Thermogram of polymer 3 .6 (Table 4 3, entry 3. 6).

PAGE 266

266 Figure C 33 TGA Thermogram of polymer 3 .7 (Table 4 3, entry 3. 7). Figure C 34 TGA Thermogram of polymer 4 .1 (Table 4 4, entry 4. 1).

PAGE 267

267 Figure C 35 TGA Thermogram of polymer 4 .2 (Table 4 4, entry 4. 2). Figure C 36 TGA Thermogram of polymer 4 .3 (Table 4 4, entry 4. 3).

PAGE 268

268 Figure C 37 TGA Thermogram of polymer 4 .4 (Table 4 4, entry 4. 4). Figure C 38 TGA Thermogram of polymer 4 .5 (Table 4 4, entry 4. 5).

PAGE 269

269 Figure C 39 TGA Thermogram of polymer 4 .6 (Table 4 4, entry 4. 6). Differential Scanning Calorimetry T hermograms Figure C 40. DSC Thermogram of polymer 2 .1 (Table 4 2, entry 2. 1).

PAGE 270

270 Figure C 41 DSC Thermogram of polymer 2 .2 (Table 4 2, entry 2. 2). Figure C 42 DSC Thermogram of polymer 2 .3 (Table 4 2, entry 2. 3).

PAGE 271

271 Figure C 43 DSC Thermogram of polymer 2 .4 (Table 4 2, entry 2. 4). Figure C 44 DSC Thermogram of polymer 2 .5 (Table 4 2, entry 2. 5).

PAGE 272

272 Figure C 45 DSC Thermogram of polymer 2 .6 (Table 4 2, entry 2. 6). Figure C 46 DSC Thermogram of polymer 3 .1 (Table 4 3, entry 3. 1).

PAGE 273

273 Figure C 47 DSC Thermogram of polymer 3 .2 (Table 4 3, entry 3. 2). Figure C 48 DSC Thermogram of polymer 3 .3 (Table 4 3, entry 3. 3).

PAGE 274

274 Figure C 49 DSC Thermogram of polymer 3 .4 (Table 4 3, entry 3. 4). Figure C 5 0. DSC Thermogram of polymer 3 .5 (Table 4 3, entry 3. 5).

PAGE 275

275 Figure C 51 DSC Thermogram of polymer 3 .6 (Table 4 3, entry 3. 6). Figure C 52 DSC Thermogram of polymer 3 .7 (Table 4 3, entry 3. 7).

PAGE 276

276 Fig ure C 53 DSC Thermogram of polymer 4 .1 (Table 4 4, entr y 4. 1). Figure C 54 DSC Thermogram of polymer 4 .2 (Table 4 4, entry 4. 2).

PAGE 277

277 Figure C 55 DSC Thermogram of polymer 4 .3 (Table 4 4, entry 4. 3). Figure C 56 DSC Thermogram of polymer 4 .4 (Table 4 4, entry 4. 4).

PAGE 278

278 Figure C 57 DSC Thermogram of polymer 4 .5 (Table 4 4, entry 4. 5). Figure C 58 DSC Thermogram of polymer 4 .6 (Table 4 4, entry 4. 6).

PAGE 279

279 1 H NMR Spectra Figure C 59 1 H NMR spectrum of polymer 2 .1 in HFIP + CDCl 3 (Table 4 2, entry 2. 1). Figure C 60 1 H NMR spectrum of polymer 2 .2 in HFIP + CDCl 3 (Table 4 2, entry 2. 2). Figure C 61 1 H NMR spectrum of polymer 2 .3 in HFIP + CDCl 3 (Table 4 2, entry 2. 3).

PAGE 280

280 Figure C 62 1 H NMR spectrum of polymer 2 .4 in HFIP + CDCl 3 (Table 4 2, entry 2. 4). Figure C 63 1 H NMR spectrum of polymer 2 .5 in HFIP + CDCl 3 (Table 4 2, entry 2. 5). Figure C 64 1 H NMR spectrum of polymer 2 .6 in HFIP + CDCl 3 (Table 4 2, entry 2. 6).

PAGE 281

281 Figure C 65 1 H NMR spectrum of polymer 3 .1 in HFIP + CDCl 3 (Table 4 3, entry 3. 1). Figure C 66 1 H NMR spectrum of polymer 3 .2 in HFIP + CDCl 3 (Table 4 3, entry 3. 2). Figure C 67 1 H NMR spectrum of polymer 3 .3 in HFIP + CDCl 3 (Table 4 3, entry 3. 3).

PAGE 282

282 Figure C 68 1 H NMR spectrum of polymer 3 .4 in HFIP + CDCl 3 (Table 4 3, entry 3. 4). Figure C 69 1 H NMR spectrum of polymer 3 .5 in HFIP + CDCl 3 (Table 4 3, entry 3. 5). Figure C 70 1 H NMR spectrum of polymer 3 .6 in HFIP + CDCl 3 (Table 4 3, entry 3. 6).

PAGE 283

283 Figure C 7 1. 1 H NMR spectrum of polymer 3 .7 in HFIP + CDCl 3 (Table 4 3, entry 3. 7). Figure C 7 2. 1 H NMR spectrum of polymer 4 .1 in HFIP + CDCl 3 (Table 4 4, entry 4. 1). Figure C 7 3. 1 H NMR spectrum of polymer 4 .2 in HFIP + CDCl 3 (Table 4 4, entry 4. 2).

PAGE 284

284 Figure C 7 4. 1 H NMR spectrum of polymer 4 .3 in HFIP + CDCl 3 (Table 4 4, entry 4. 3). Figure C 75 1 H NMR spectrum of polymer 4 .4 in HFIP + CDCl 3 (Table 4 4, entry 4. 4). Figure C 76 1 H NMR spectrum of polymer 4 .5 in HFIP + CDCl 3 (Table 4 4, entry 4. 5).

PAGE 285

285 Figure C 77 1 H NMR spectrum of polymer 4.6 in HFIP + CDCl 3 (Table 4 4, entry 4.6 ). 13 C NMR Spectra Figure C 78 13 C NMR spectrum of polymer 2 .1 in HFIP + C 6 D 6 (Table 4 2, entry 2. 1). Figure C 79 13 C NMR spectrum of polymer 2 .2 in HFIP + C 6 D 6 (Table 4 2, entry 2. 2).

PAGE 286

286 Figure C 80 13 C NMR spectrum of polymer 2 .3 in HFIP + C 6 D 6 (Table 4 2, entry 2. 3). Figure C 81 13 C NMR spectrum of polymer 2 .4 in HFIP + C 6 D 6 (Table 4 2, entry 2. 4). Figure C 82 13 C NMR spectrum of polymer 2 .5 in HFIP + C 6 D 6 (Table 4 2, entry 2. 5).

PAGE 287

287 Figure C 83 13 C NMR spectrum of polymer 2 .6 in HFIP + C 6 D 6 (Table 4 2, entry 2. 6). Figure C 84 13 C NMR spectrum of polymer 3 .1 in HFIP + C 6 D 6 (Table 4 3, entry 3. 1). Figure C 85 13 C NMR spectrum of polymer 3 .2 in HFIP + C 6 D 6 (Table 4 3, entry 3. 2). Figure C 86 13 C NMR spectrum of polymer 3 .3 in HFIP + C 6 D 6 (Table 4 3, entry 3. 3).

PAGE 288

288 F igure C 87 13 C NMR spectrum of polymer 3 .4 in HFIP + C 6 D 6 (Table 4 3, entry 3. 4). Figure C 88 13 C NMR spectrum of polymer 3 .5 in HFIP + C 6 D 6 (Table 4 3, entry 3. 5). Figure C 89 13 C NMR spectrum of polymer 3 .6 in HFIP + C 6 D 6 (Table 4 3, entry 3. 6).

PAGE 289

289 Figure C 90 13 C NMR spectrum of polymer 3 .7 in HFIP + C 6 D 6 (Table 4 3, entry 3. 7). Figure C 9 1 13 C NMR spectrum of polymer 4 .1 in HFIP + C 6 D 6 (Table 4 4, entry 4. 1). Figure C 92 13 C NMR spectrum of polymer 4 .2 in HFIP + C 6 D 6 (Table 4 4, entry 4. 2).

PAGE 290

290 Figure C 93 13 C NMR spectrum of polymer 4 .3 in HFIP + C 6 D 6 (Table 4 4, entry 4. 3). Figure C 94 13 C NMR spectrum of polymer 4 .4 in HFIP + C 6 D 6 (Table 4 4, entry 4. 4). Figure C 95 13 C NMR spectrum of polymer 4 .5 in HFIP + C 6 D 6 (Table 4 4, entry 4. 5).

PAGE 291

291 Figure C 96 13 C NMR spectrum of polymer 4 6 in HFIP + C 6 D 6 (Table 4 4, entry 4.6 ). Gel Permeation Chromatography (GPC) Data Figure C 97 GPC Chromatogram of polymer 2 .1 in HFIP solvent (Table 4 2, entry 2. 1). Figure C 98 GPC Chromatogram of polymer 2 .2 in HFIP solvent (Table 4 2, entry 2. 2).

PAGE 292

292 Figure C 99 GPC Chromatogram of polymer 2 .3 in HFIP solvent (Table 4 2, entry 2. 3). Figure C 100 GPC Chromatogram of polymer 2 .4 in HFIP solvent (Table 4 2, entry 2. 4). Figure C 101 GPC Chromatogram of polymer 2 .5 in HFIP solvent (Table 4 2, entry 2. 5).

PAGE 293

293 Figure C 102 GPC Chromatogram of polymer 2 .6 in HFIP solvent (Table 4 2, entry 2. 6). Figure C 103 GPC Chromatogram of polymer 3 .1 in HFIP solvent (Table 4 3, entry 3. 1). Figure C 10 4 GPC Chromatogram of polymer 3 .2 in HFIP solvent (Table 4 3, entry 3. 2).

PAGE 294

294 Figure C 10 5 GPC Chromatogram of polymer 3 .3 in HFIP solvent (Table 4 3, entry 3. 3). Figure C 10 6 GPC Chromatogram of polymer 3 .4 in HFIP solvent (Table 4 3, entry 3. 4). Figure C 107 GPC Chromatogram of polymer 3 .5 in HFIP solvent (Table 4 3, entry 3. 5).

PAGE 295

295 Figure C 108 GPC Chromatogram of polymer 3 .6 in HFIP solvent (Table 4 3, entry 3. 6). Figure C 109 GPC Chromatogram of polymer 3 .7 in HFIP solvent (Table 4 3, entry 3. 7). Figure C 110 GPC Chromatogram of polymer 4 .1 in HFIP solvent (Table 4 4, entry 4. 1).

PAGE 296

296 Figure C 111 GPC Chromatogram of polymer 4 .2 in HFIP solvent (Table 4 4, entry 4. 2). Figure C 112 GPC Chromatogram of polymer 4 .3 in HFIP solvent (Table 4 4, entry 4. 3). Figure C 113 GPC Chromatogram of polymer 4 .4 in HFIP solvent (Table 4 4, entry 4. 4).

PAGE 297

297 Figure C 114 GPC Chromatogram of polymer 4 .5 in HFIP solvent (Table 4 4, entry 4. 5). Figure C 115 GPC Chromatogram of polymer 4 .6 in HFIP solvent (Table 4 4, entry 4. 6).

PAGE 298

298 APPENDIX D SUPPLEMENTARY INFORMATION FOR CHAPTER 5 FT IR Spectr a Figure D 1 FT IR spectrum of polymer 1 1 (Table 5 1, entry 1.1). Figure D 2 FT IR spectrum of polymer 1 2 (Table 5 1, entry 1.2).

PAGE 299

299 Figure D 3 FT IR spectrum of polymer 1 3 (Table 5 1, entry 1.3). Figure D 4 FT IR spectrum of polymer 1 4 (Table 5 1, entry 1.4). Figure D 5 FT IR spectrum of polymer 1 5 (Table 5 1, entry 1.5).

PAGE 300

300 Figure D 6 FT IR spectrum of polymer 2.1 (Table 5 2, entry 2.1). Figure D 7 FT IR spectrum of polymer 2.2 (Table 5 2, entry 2.2). Figure D 8 FT IR spectrum of polymer 2.3 (Table 5 2, entry 2.3).

PAGE 301

301 Figure D 9 FT IR spectrum of polymer 2.4 (Table 5 2, entry 2.4). Figure D 10 FT IR spectrum of polymer 2.5 (Table 5 2, entry 2.5). Figure D 11 FT IR spectrum of polymer 2.6 (Table 5 2, entry 2.6).

PAGE 302

302 Figure D 12 FT IR spectrum of polymer 2.7 (Table 5 2, entry 2.7). Figure D 13 FT IR spectrum of polymer 2.8 (Table 5 2, entry 2.8). Figure D 14 FT IR spectrum of polymer 2.10 (Table 5 2, entry 2.10).

PAGE 303

303 Figure D 15 FT IR spectrum of polymer 2.11 (Table 5 2, entry 2.11). Figure D 16 FT IR spectrum of polymer 2.12 (Table 5 2, entry 2.12). Figure D 17 FT IR spectrum of polymer 2.13 (Table 5 2, entry 2.13).

PAGE 304

304 Figure D 18 FT IR spectrum of polymer 2.14 (Table 5 2, entry 2.14). Figure D 19 FT IR spectrum of po lymer 2.15 (Table 5 2, entry 2.15). Figure D 20 FT IR spectrum of polymer 2.16 (Table 5 2, entry 2.16).

PAGE 305

305 Figure D 21 FT IR spectrum of polymer 2.17 (Table 5 2, entry 2.17). Figure D 22 FT IR spectrum of polymer 2.18 (Table 5 2, entry 2.18). Figure D 23 FT IR spectrum of polymer 2.19 (Table 5 2, entry 2.19).

PAGE 306

306 Thermogravimetric Analyses Figure D 24 TGA Thermogram of polymer 1.1 (Table 5 1, entry 1.1). Figure D 25 TGA Thermogram of polymer 1.2 (Table 5 1, entry 1.2). Figure D 26 TGA Thermogram of polymer 1.3 (Table 5 1, entry 1.3).

PAGE 307

307 Figure D 27 TGA Thermogram of polymer 1.4 (Table 5 1, entry 1.4). Figure D 28 TGA Thermogram of polymer 1.5 (Table 5 1, entry 1.5). Figure D 29 TGA Thermogram of polymer 2.1 (Table 5 2, entry 2 .1).

PAGE 308

308 Figure D 30 TGA Thermogram of polymer 2.2 (Table 5 2, entry 2.2). Figure D 31 TGA Thermogram of polymer 2.3 (Table 5 2, entry 2.3).

PAGE 309

309 Figure D 32 TGA Thermogram of polymer 2.4 (Table 5 2, entry 2.4). Figure D 33 TGA Thermogram of polymer 2.5 (Table 5 2, entry 2.5).

PAGE 310

310 Figure D 34 TGA Thermogram of polymer 2.6 (Table 5 2, entry 2.6). Figure D 35 TGA Thermogram of polymer 2.7 (Table 5 2, entry 2.7).

PAGE 311

311 Figure D 36 TGA Thermogram of polymer 2.8 (Table 5 2, entry 2.8). Figure D 37 TGA Thermogram of polymer 2.10 (Table 5 2, entry 2.10).

PAGE 312

312 Figure D 38 TGA Thermogram of polymer 2.11 (Table 5 2, entry 2.11). Figure D 39 TGA Thermogram of polymer 2.12 (Table 5 2, entry 2.12).

PAGE 313

313 Figure D 40 TGA Thermogram of polymer 2.13 (Table 5 2, entry 2.13). Figure D 4 1 TGA Thermogram of polymer 2.14 (Table 5 2, entry 2.14).

PAGE 314

314 Figure D 42 TGA Thermogram of polymer 2.15 (Table 5 2, entry 2.15). Figure D 43 TGA Thermogram of polymer 2.16 (Table 5 2, entry 2.16).

PAGE 315

315 Figure D 44 TGA Thermogram of polymer 2.17 (Table 5 2, entry 2.17). Figure D 45 TGA Thermogram of polymer 2.18 (Table 5 2, entry 2.18).

PAGE 316

316 Figure D 46 TGA Thermogram of polymer 2.19 (Table 5 2, entry 2.19). Differential Scanning Calorimetry T hermograms Figure D 47 DSC Thermogram of polymer 1.1 (Table 5 1, entry 1.1). Figure D 48 DSC Thermogram of polymer 1.2 (Table 5 1, entry 1.2).

PAGE 317

317 Figure D 49 DSC Thermogram of polymer 1.3 (Table 5 1, entry 1.3). Figure D 50 DSC Thermogram of polymer 1.4 (Table 5 1, entry 1.4). Figure D 51 DSC Thermogram of polymer 1.5 (Table 5 1, entry 1.5).

PAGE 318

318 Figure D 52 DSC Thermogram of polymer 2.1 (Table 5 2, entry 2.1). Figure D 53 DSC Thermogram of polymer 2.2 (Table 5 2, entry 2.2).

PAGE 319

319 Figure D 54 DSC Thermogram of polymer 2.3 (Table 5 2, entry 2.3). Figure D 55 DSC Thermogram of polymer 2.4 (Table 5 2, entry 2.4).

PAGE 320

320 Figure D 56 DSC Thermogram of polymer 2.5 (Table 5 2, entry 2.5). Figure D 57 DSC Thermogram of polymer 2.6 (Table 5 2, entry 2.6).

PAGE 321

321 Figure D 58 DSC Thermogram of polymer 2.7 (Table 5 2, entry 2.7). Figure D 59 DSC Thermogram of polymer 2.8 (Table 5 2, entry 2.8).

PAGE 322

322 Figure D 60 DSC Thermogram of polymer 2.10 (Table 5 2, entr y 2.10). Figure D 61 DSC Thermogram of polymer 2.11 (Table 5 2, entry 2.11).

PAGE 323

323 Figure D 62 DSC Thermogram of polymer 2.12 (Table 5 2, entry 2.12). Figure D 63 DSC Thermogram of polymer 2.13 (Table 5 2, entry 2.13).

PAGE 324

324 Figure D 64 DSC Thermogram of polymer 2.14 (Table 5 2, entry 2.14). Figure D 65 DSC Thermogram of polymer 2.15 (Table 5 2, entry 2.15).

PAGE 325

325 Figure D 66 DSC Thermogram of polymer 2.16 (Table 5 2, entry 2.16). Figure D 67 DSC Thermogram of polymer 2.17 (Table 5 2, entry 2.17).

PAGE 326

326 Figure D 68 DSC Thermogram of polymer 2.18 (Table 5 2, entry 2.18). Figure D 69 DSC Thermogram of polymer 2.19 (Table 5 2, entry 2.19).

PAGE 327

327 1 H NMR Spectra Figure D 70 1 H NMR spectrum of polymer 1.1 in CDCl 3 (Table 5 1, entry 1.1). Figure D 71 1 H NMR spectrum of polymer 1.2 in CDCl 3 (Table 5 1, entry 1.2). Figure D 72 1 H NMR spectrum of polymer 1.3 in CDCl 3 (Table 5 1, entry 1.3).

PAGE 328

328 Figure D 73 1 H NMR spectrum of polymer 1.4 in CDCl 3 (Table 5 1, entry 1.4). Figure D 74 1 H NMR spectrum of polymer 1.5 in CDCl 3 (Table 5 1, entry 1.5). Figure D 75 1 H NMR spectrum of polymer 2.1 in HFIP + CDCl 3 (Table 5 2, entry 2.1). Figure D 76 1 H NMR spectrum of polymer 2.2 in HFIP + CDCl 3 (Table 5 2, entry 2.2).

PAGE 329

329 Figure D 77 1 H NMR spectrum of polymer 2.3 in HFIP + CDCl 3 (Table 5 2, entry 2.3). Figure D 78 1 H NMR spectrum of polymer 2.4 in HFIP + CDCl 3 (Table 5 2, entry 2.4). Figure D 79 1 H NMR spectrum of polymer 2.5 in HFIP + CDCl 3 (Table 5 2, entry 2.5).

PAGE 330

330 Figure D 80 1 H NMR spectrum of polymer 2.6 in HFIP + CDCl 3 (Table 5 2, entry 2.6). Figure D 81 1 H NMR spectrum of polymer 2.7 in HFIP + CDCl 3 (Table 5 2, entry 2.7). Figure D 82 1 H NMR spectrum of polymer 2.8 in HFIP + CDCl 3 (Table 5 2, entry 2.8).

PAGE 331

331 Figure D 83 1 H NMR spectrum of polymer 2.10 in HFIP + CDCl 3 (Table 5 2, entry 2.10). Figure D 84 1 H NMR spectrum of polymer 2.11 in HFIP + CDCl 3 (Table 5 2, entry 2.11). Figure D 85 1 H NMR spectrum of polymer 2.12 in HFIP + CDCl 3 (Table 5 2, entry 2.12).

PAGE 332

332 Figure D 86 1 H NMR spectrum of polymer 2.13 in HFIP + CDCl 3 (Table 5 2, entry 2.13). Figure D 87 1 H NMR spectrum of polymer 2.14 in HFIP + CDCl 3 (Table 5 2, entry 2.14). Figure D 88 1 H NMR spectrum of polymer 2.15 in HFIP + CDCl 3 (Table 5 2, entry 2.15).

PAGE 333

333 Figure D 89 1 H NMR spectrum of polymer 2.16 in HFIP d 2 (Table 5 2, entry 2.16). Figure D 90 1 H NMR spectrum of polymer 2.17 in HFIP + CDCl 3 (Table 5 2, entry 2.17). Figure D 91 1 H NMR spectrum of polymer 2.18 in HFIP + CDCl 3 (Ta ble 5 2, entry 2.18).

PAGE 334

334 Figure D 92 1 H NMR spectrum of polymer 2.19 in HFIP + CDCl 3 (Table 5 2, entry 2.19). 13 C NMR Spectra Figure D 93 13 C NMR spectrum of polymer 1.1 in HFIP + CDCl 3 (Table 5 1, entry 1.1).

PAGE 335

335 Figure D 94 13 C NMR spectrum of polymer 1.2 in HFIP + CDCl 3 (Table 5 1, entry 1.2). Figure D 95 13 C NMR spectrum of polymer 1.3 in HFIP + CDCl 3 (Table 5 1, entry 1.3). Figure D 96 13 C NMR spectrum of polymer 1.4 in HFIP + CDCl 3 (Table 5 1, entry 1.4).

PAGE 336

336 Figure D 97 13 C NMR spectrum of polymer 1.5 in HFIP + CDCl 3 (Table 5 1, entry 1.5). Figure D 98 13 C NMR spectrum of polymer 2.1 in HFIP + CDCl 3 (Table 5 2, entry 2.1). Figure D 99 13 C NMR spectrum of polymer 2.2 in HFIP + C 6 D 6 (Table 5 2, entry 2.2). Fig ure D 100 13 C NMR spectrum of polymer 2.3 in HFIP + CDCl 3 (Table 5 2, entry 2.3).

PAGE 337

337 Figure D 101 13 C NMR spectrum of polymer 2.4 in HFIP + CDCl 3 (Table 5 2, entry 2.4). Figure D 102 13 C NMR spectrum of polymer 2.5 in HFIP + CDCl 3 (Table 5 2, entry 2.5). Figure D 103 13 C NMR spectrum of polymer 2.6 in HFIP + CDCl 3 (Table 5 2, entry 2.6).

PAGE 338

338 Figure D 1 04 13 C NMR spectrum of polymer 2.7 in HFIP + CDCl 3 (Table 5 2, entry 2.7). Figure D 105 13 C NMR spectrum of polymer 2.8 in HFIP d 2 (Table 5 2, entry 2.8). Figure D 106 13 C NMR spectrum of polymer 2.10 in HFIP + CDCl 3 (Table 5 2, entry 2.10).

PAGE 339

339 Figure D 107 13 C NMR spectrum of polymer 2 11 in HFIP d 2 (Table 5 2, entry 2.11). Figure D 108 13 C NMR spectrum of polymer 2.12 in HFIP + C DCl 3 (Table 5 2, entry 2.12). Figure D 109 13 C NMR spectrum of polymer 2.13 in HFIP + CDCl 3 (Table 5 2, entry 2.13).

PAGE 340

340 Figure D 110 13 C NMR spectrum of polymer 2.14 in HFIP + CDCl 3 (Table 5 2, entry 2.14). Figure D 111 13 C NMR spectrum of polymer 2.15 in HFIP + CDCl 3 (Table 5 2, entry 2.15). Figure D 112 13 C NMR spectrum of polymer 2.16 in HFIP d 2 (Table 5 2, entry 2.16).

PAGE 341

341 Figure D 113 13 C NMR spectrum of polymer 2.17 in HFIP d 2 (Table 5 2, entry 2.17). Figure D 114 13 C NMR spectrum of polymer 2.18 in HFIP + CDCl 3 (Table 5 2, entry 2.18). Figure D 115 13 C NMR spectrum of polymer 2.19 in HFIP + CDCl 3 (Table 5 2, entry 2.19).

PAGE 342

342 Gel Permeation Chromatography (GPC) Data Figure D 116 GPC Chromatogram of polymer 1.1 (Ta ble 5 1, entry 1.1). Figure D 117 GPC Chromatogram of polymer 1.2 (Table 5 1, entry 1.2). Figure D 118 GPC Chromatogram of polymer 1.3 (Table 5 1, entry 1.3).

PAGE 343

343 Figure D 119 GPC Chromatogram of polymer 1.4 (Table 5 1, entry 1.4). Figure D 120. GPC Chromatogram of polymer 1.5 (Table 5 1, entry 1.5). Figure D 121 GPC Chromatogram of polymer 2.1 (Table 5 2, entry 2.1).

PAGE 344

344 Figure D 122 GPC Chromatogram of polymer 2.2 (Table 5 2, entry 2.2). Figure D 123 GPC Chromatogram of polymer 2.3 (Table 5 2, entry 2.3). Figure D 124 GPC Chromatogram of polymer 2.4 (Table 5 2, entry 2.4).

PAGE 345

345 Figure D 125 GPC Chromatogram of polymer 2.5 (Table 5 2, entry 2.5). Figure D 126 GPC Chromatogram of polymer 2.6 (Table 5 2, entry 2.6). Figure D 127 GPC Chromatogram of polymer 2.7 (Table 5 2, entry 2.7).

PAGE 346

346 Figure D 128 GPC Chromatogram of polymer 2.8 (Table 5 2, entry 2.8). Figure D 129 GPC Chromatogram of polymer 2.10 (Table 5 2, entry 2.10). Figure D 130 GPC Chromatogram of polymer 2.11 (Table 5 2, entry 2.11).

PAGE 347

347 Figure D 131 GPC Chromatogram of polymer 2.12 (Table 5 2, entry 2.12). Figure D 132 GPC Chromatogram of polymer 2.13 (Table 5 2, entry 2.13).

PAGE 348

348 Figure D 133 GPC Chromatogram of polymer 2.14 (Table 5 2, entry 2.14). Figure D 134 GPC Chromatogram of polymer 2.15 (Table 5 2, entry 2.15).

PAGE 349

349 Figure D 135 GPC Chromatogram of polymer 2.16 (Table 5 2, entry 2.16). Figure D 136 GPC Chromatogram of polymer 2.17 (Table 5 2, entry 2.17). Figure D 137 GPC Chromatogram of polymer 2.18 (Table 5 2, entry 2.18). Figure D 138 GPC Chromatogram of polymer 2.19 (Table 5 2, entry 2.19).

PAGE 350

350 LIST OF REFERENCES (1) Kolybaba, M.; Tabil, L. G.; Panigrahi, S.; Crerar, W. J.; Powel l, T.; Wang, B. Paper Number: RRV03 0007 An ASAE Meeting Presentation (2) Williams, C. K. Chem. Soc. Rev. 2007 36, 1573 1580. (3) Lucas, N.; Bienaime, C.; Belloy, C.; Queneudec, M.; Silvestre F.; Nava Saucedo, J. E. Chemosphere 2008 73, 429 442. (4) Avrous L.; Pollet, E. Environmental Silicate Nano Biocomposites, Green Energy and Technology ; Springer Verlag, London, 2012 D OI: 10.1007/978 1 4471 4108 2_2 (5) Mayer, J. M.; Kaplan, D. L. Trends. Polym. Sci. 1994 2, 227. (6) Dobrzynski, P.; Li, S.; Dasperczyk, J.; Bero, M.; Gase F.; and Vert, M. Biomacromolecules 2004 6 (1), 483 488. (7) Dunn, R. L.; Vert, M. The Encyclopedia of Controlled Drug Delivery 1999 1, 71 93. (8) Singh V.; Tiwari, M. Int. J. of Polym. Sci. 2010 Article ID 652719, 23 pages. (9) Kuredux Polyglycolic Acid (PGA) Resin, A New Polymer Option, http://www.kureha.com/product groups/pga.htm (10) Gilding, D. K.; Reed, A. M. Polymer 1979 20 (12), 1459 1464 (11) Gautier, E.; Fuertes, P.; Cassagnau, P.; Pascault J. P.; Fleury, E. Journal of Polymer Science: Part A: Polymer Chemistry 2009 Vol. 47, 1440 1449 (12) A) Gautier, E.; Fuertes, P.; Cassagnau, P.; Pascault J. P.; Fleury, E. World forum on Advanced Polymeric Mat erials Synthesis, Properties, Characterisation. POLYCHAR 18. April 7 10, 2003 (page A 33 ) B) Gautier, E.; Fuertes, P.; Cassagnau, P.; Pascault J. P.; Fleury, E. V Argentine Chilean Polymer Symposium ARCHIPOL 09 2009 O.2.B.01 GP (page 84). (13) Maciej, B.; Dobrzynski P.; Kasperczyk, J. Macromolecules 1999 32 (14), 4735 4737. (14) Nieuwenhuis, J. Clinical Materials 1992 10 59 67 (15) Ajioka, M.; Enomoto, K.; Suzuki, K.; and Yamaguchi, A. Journal of Environmental Polymer Degradation 1995, vol. 3, no. 4, pp. 225 234 (16) A ) Ivin, K. J.; Saegusa, T. Ring Opening Polymerization ; Elsevier Applied Science, London, 1984 Vols. 1 3. B ) McGrath, J. E. Ring Opening Polymerization: Kinetics, Mechanisms, and Synthesis ; American Chemical Society, Washington, DC, 1985 C ) Brunelle, D. J. Ring Opening Polymerization / Mechanisms, Catalysis, Structure, Utility ; Hanser Publisher, 1993 (17) Dubois, P.; C oulembie r, O.; R aquez J M. Handbook of Ring opening polymerization ; Wiley VCH, 2009 (18) Chujo, K.; Kobayashi, J.; Tokuhara, H.; Ta nabe, M. volume 100, issue 1, pages 262 266. (19) Donghang Xie thesis Dissertation submitted to the Faculty of the Virginia Polytechnic Institute and State, January 14, 1997 (20) McGrath, J. E. ed. Ring Opening Polymerization: Kinetics, Mechanisms, and Synthesis ; American Chemical Society, Washington, DC, 1985 (21) Schwarz, K.; Epple, M. Macromol. Chem. Phys., 1999 200, 2221 2229 (22) Piskin, E. J. Biomater. Sci. Polym. Ed. 1995 6 775

PAGE 351

351 (23) Dechy Cabaret, O.; Martin Vaca, B.; Bourissou, D. Chem Rev. 2004 104, 6147 6176. (24) Ga rlotta, D. Journal of Polymers and the Environment 2001 9, No. 2. (25) Bourisso, D.; Martin Vaca, B.; Dumitrescu, A.; Graullier, M.; Lacombe, F. Macromolecules 2005 38, 9993 9998. (26) Pinkus, A. G.; Subramanyam, R. Journal of Polymer Science Part A 1984 vol. 22 no. 5, pp. 1131 1140 (27) A ) Drent, E.; Budzelaar, P. H. M. Chem. Rev. 1996 96, 663 681. B ) Belov, G. P.; Novikova, E. V. Russ. Chem. Rev. 2004 73, 267 (28) Nakafuku, C.; Yoshimura, H. Polymer 2004 45(11) 3583 3585 (29) Miller, S. A., Chemistry & Industry Magazine 2013 7 20 23. (30) Miller, S. A. ACS Macro Lett. 2013 (31) Rowley, J. M.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2007 128, 4948 4960. (32) A ) Masuda, T.; Matsuda, A.; Murata, K.; Yamazaki; S. U.S. Patent 5,227,415, 1993 B ) Masuda, T. ; Kagami, K.; Murata, K.; Matsuda, A.; Takami, Y. Nippon Kagaku Kaishi 1982 2 257 262 (33) Cevidalli, G.; Ragazzini, M.; Modena, M. U.S. Patent 3,673,156, 1972 (34) Matyjaszewki, K. Cationic Polymerizations: Mechanisms, Synthesis & Applications ; Marcel Dekker, New York, 1996 (35) A ) Weissermel, K.; Fischer, E.; Gutweiler, K.; Hermann, H. D.; Cherdron, H. Angew. Chem. Int. Ed. Engl. 1967 6, 526. B ) Masamoto, J. Prog. Polym. Sci. 1993 18, 1. C ) Kern, W.; Jaacks, V. J. Polym. Sci. 1960 48, 399. (36) Gktrk, E.; Pemba, A. G.; Miller, S. A. Provisional U.S. Patent Application, Serial No. 61/608,196, March 8 th 2012 (37) http://www.polysciences.com/Catalog/Department/Product/98/categoryid -286/productid -447/search -06525/ (38) A ) Carothers W. H.; Dorough G. L.; V an Natta F. J., J. Am. Chem. Soc. 1932 54, 761. B ) Van Natta F. J.; Hill J. W.; Carothers W. H., J. Am. Chem. S oc. 1934 56, 455. C ) Hill J. W., J. Am. Chem. Soc. 1930 52, 4110. D ) Carothers W. H.; V an Natta F. J., J. Am. Chem. Soc. 1930 52, 314. (39) Martin, R. T.; Miller, S. A. Macromol. Symp. 2009 279, 72 78 (40) Takahashi, K.; Taniguchi, I.; Miyamoto, M.; Kimura, Y. Polymer 2000 41, 8725 8728. (41) Kricheldorf, H. R. Handbook of Polymer Synthesis, Part A ; Marcel Dekker, 1992 (42) Ebewele, R. O. Polymer Science and Technology ; Chapman & Hall/CRC, 2000 (43) Kumbar, S.; Laurencin, C.; Den M. Natural and Synthetic Biomedical Polymers ; Elsevier, 2014 (44) A) Pascault, J P.; Williams, J. J. Epoxy polymers New Materials and innovations ; Wiley VCH, 2010 B) Jihean, Lee. Doctor of Philosophy Thesis, July 2007. (45) A) Dubois, P.; C oulembie r, O.; R aquez J M. Handbook of R ing opening polymerization ; Wiley VCH, 2009 B) Yahiaoui, A.; Belbachir, M .; Hachemaoui, A Int. J. Mol. Sci. 2003 4, 572 585 (46) Ilg, A. D.; Price, C. J.; Miller, S. A. Macromolecules 2007 40, 7739 7741 (47) Sandler, S. R.; Karo W. Polymer S yntheses ; volume III second edition Academic press, 199 6

PAGE 352

352 (48) Braun, D.; Cherdron, H.; Ritter H. Polymer Synthesis: Theory and Practice: Fundamentals, Methods, Experiments ; Third. Springer: New York, 2001 (49) Odian, G. Principles of Polymerization ; Fourth. John Wiley & Sons: New Y ork, 2004 (50) Jurek, M. J.; McGrath, J. E., Polymer (London) 1989 30, 1552 (51) Nakano, K.; Kosaka, N.; Hiyama T.; Nozaki K. Dalton Trans 2003 4039 4050 (52) A) Drent, E.; Kragtwijk, E. Eur. Pat. Appl. EP 577,206, 1993 B) Lee, J. T.; Thomas, P. J.; Alper, H. J. Org. Chem. 2001 66, 5424 (53) Furukawa, J.; Iseda, Y.; Saegusa T.; Fujii, H. Makromol. Chem. 1965 89 263 (54) Drent, E. ; Kragtwijk, E. Eur. Pat. Appl. 1994 EP 577,206 (55) A) Lee, J. T.; Thomas P. J.; Alper, H. J. Org. Chem. 2001 66 5424 B ) Allmendinger, M.; Eberhardt, R.; Luinstra G.; Rieger, B. J. Am. Chem. Soc. 2002 124 5646 (56) Kobayashi, S. Eur. J. Org. Chem. 1999 15 27 (57) Takasu, A.; Iio, Y.; Oishi, Y.; Narukawa, Y.; Hirabayashi T. Macromolecules 2005 38, 1048 1050. (58) Park, B, Y.; Ryu, K. Y.; Park, J. H.; Lee, S. Green Chem. 2009 11 946 948. (59) Longbottom, D. Synlett 1999 No. 12, 2023 (60) A ) Qin, H.; Lowe, J. T.; Panek, J. S. J. Am. Chem. Soc 2007 129, 38 39. B ) Kang, Y. B.; Tang, Y.; Sun, X. Org. Biomol. Chem. 2006 4 299 301. (61) Kricheldorf, H. R.; Yashiro, T.; Weidner, S. Macromolecules 2009 42, 6433 6439. (62) Takasu, A.; Oishi, Y.; Iio, Y.; Inai, Y.; Hirabayashi T. Macromolecules 2003 36, 1772 1774 (63) Schwarz K.; Epple, M. Macromol. Chem. Phys. 199 9 200 2221 2229. (64) Chujo, K.; Kobayashi, H.; Suzuki, J.; Tokuhara, S. Die Makromol Chem 1967 100, 267 270 (65) Middleton J.; Tipton, A. Medical Plastics and Biomaterials Magazine March 1998 (66) Sano, T.; Sekine, T.; Wang, Z.; Soga, K.; Takahashi, I.; Masuda, T. Chem. Commun. 1997 19 1827 1828 (67) http://www.sigmaaldrich.com/catalog/product/sigma/g1796?lang=en®ion=US

PAGE 353

353 BIOGRAPHICAL SKETCH Ersen Gokturk was born in Hatay, Turkey. H e attended the Nigde University in Nigde to begi n his undergraduate studies in C hemistry in 1999 H e obtained his Master of Science in organic chemistry in August 2003 His master education was directed and mentore d by Dr. Aydin Demircan in the field of organic synt hesis, specifically radical and Heck type of cyclization reactions. H e was rewarded a PhD scholarship from Turkish Ministry of National E ducation in 2007. He joined the University of Florida in 2009. His research at the University of Florida dealt with the synthesis of degradable p olymers from bio renewable feed stocks. It was directed and mentored by Dr. Stephen A. Miller.


xml version 1.0 encoding UTF-8
REPORT xmlns http:www.fcla.edudlsmddaitss xmlns:xsi http:www.w3.org2001XMLSchema-instance xsi:schemaLocation http:www.fcla.edudlsmddaitssdaitssReport.xsd
INGEST IEID EP5JBKXTS_BENRS8 INGEST_TIME 2014-10-03T22:16:26Z PACKAGE UFE0046674_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES