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Record for a UF thesis. Title & abstract won't display until thesis is accessible after 2014-12-31.

DARK ITEM
Permanent Link: http://ufdc.ufl.edu/UFE0043843/00001

Material Information

Title: Record for a UF thesis. Title & abstract won't display until thesis is accessible after 2014-12-31.
Physical Description: Book
Language: english
Creator: Vanderhenst, Rob
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2011

Subjects

Subjects / Keywords: Chemistry -- Dissertations, Academic -- UF
Genre: Chemistry thesis, M.S.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Statement of Responsibility: by Rob Vanderhenst.
Thesis: Thesis (M.S.)--University of Florida, 2011.
Local: Adviser: Miller, Stephen Albert.
Electronic Access: INACCESSIBLE UNTIL 2014-12-31

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2011
System ID: UFE0043843:00001

Permanent Link: http://ufdc.ufl.edu/UFE0043843/00001

Material Information

Title: Record for a UF thesis. Title & abstract won't display until thesis is accessible after 2014-12-31.
Physical Description: Book
Language: english
Creator: Vanderhenst, Rob
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2011

Subjects

Subjects / Keywords: Chemistry -- Dissertations, Academic -- UF
Genre: Chemistry thesis, M.S.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Statement of Responsibility: by Rob Vanderhenst.
Thesis: Thesis (M.S.)--University of Florida, 2011.
Local: Adviser: Miller, Stephen Albert.
Electronic Access: INACCESSIBLE UNTIL 2014-12-31

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2011
System ID: UFE0043843:00001


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CLEAN AND DIRECT SYNTHESIS OF POLYCARBONATES FROM BIORENEWABLE DIOLS VIA CARBONATE METATHESIS POLYMERIZATION (CAMP) BY ROB VANDERHENST A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFI LLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2011

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2 2011 Rob Vanderhenst

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3 To Rene and Henri, my grandfathers

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4 ACKNOWLEDGMENTS It is a pleasure to thank the many people who helped in the research and wri ting of this thesis I would have been able to do it without them This work would not have been possible without the support of Dr. Stephen A. Miller under whose guidance I worked on this topic for the last couple of years. I appreciate all his contr ibutions of time, ideas and funding to make this whole experience productive and stimulating. I am especially grateful for the fun group of original Miller Unit members, who have been a source of friendships as well as good advice and collaboration. Furt hermore I would like to thank all members of the Butler Polymer Research Laboratory for their help and advice. Very special thanks go out to the members of my committee : Dr. Eri c Enholm and Dr. Eri k Deumens, together with all the professors who gave me the opportunity to attend their class Not forgetting the University of Florida for all the great opportunities, the hi gh quality lectures it provided and the many friends I met Big thanks go out to my family, especially my mom and dad who always supported a nd encouraged me no matter what, Tom for the visits, good advice and late night phone calls and Nele for the always positive and happy attitude when calling on Skype. Last but not least, I want to thank Longchuan, who has been next to me for most of my ti me here and soon always will be there! Wo ai ni, qin ai da!

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5 TABLE OF CONTENTS page ACKNOWLEDGMENTS ................................ ................................ ................................ .. 4 LIST OF TABLES ................................ ................................ ................................ ............ 7 LIST OF FIGURES ................................ ................................ ................................ .......... 8 LIST OF SCHEMES ................................ ................................ ................................ ...... 20 LIST OF ABBREVIATIONS ................................ ................................ ........................... 21 ABSTRACT ................................ ................................ ................................ ................... 23 CHAPTER 1 AN INTRODUCTION TO PACKAGING ................................ ................................ .. 24 1.1 Packaging: Definition and Materials ................................ ................................ .. 24 1.2 Polymers in Packaging ................................ ................................ ..................... 26 1.2.1 Polymer Classes ................................ ................................ ...................... 26 1.2.1.1 Polyeth ylene terephthalate ................................ ............................. 26 1.2.1.2 Polyethylene ................................ ................................ .................. 27 1.2.1.3 Polyvinylchloride ................................ ................................ ............ 28 1.2.1.4 Polypropylene ................................ ................................ ................ 28 1.2.1.5 Polystyrene ................................ ................................ .................... 29 1.2.1.6 Polycarbonate ................................ ................................ ................ 29 1.3 Environmental Concerns ................................ ................................ ................... 30 2 POLYCARBONATES FROM A BIORENEWABLE FEEDSTOCK .......................... 32 2.1 Polycarbonates ................................ ................................ ................................ 32 2.1.1 Importance of Polycarbonates ................................ ................................ 32 2.1.2 Aromatic Polycarbonates ................................ ................................ ......... 32 2.1.2.1 BPA ................................ ................................ ................................ ...... 32 2.1.2.2 Polycondensation of BPA and Phosgene ................................ ....... 34 2.1.2.3 Transesterification of BPA and Diphenyl Carbonate (DPC) ........... 35 2.1.3 Aliphatic Polycarbonates ................................ ................................ ......... 36 2.2 Natural Molecules Giving New Polymers ................................ .......................... 37 2.2.1 Castor Oil as a Bio Renewable Feedstock ................................ .............. 37 2.2.2 DMC as a Green Carbonate Source ................................ ........................ 39 2.3 Synthesis and C haracterization of New Aliphatic Polycarbonates .................... 40 2.3.1 Carbonate Metathesis Polymerization ................................ ..................... 40 2.3.1.1 Monomer synthesis ................................ ................................ ........ 40 2.3.1.2 Polymer synthesis ................................ ................................ .......... 41 2.3.1.3 Proposed mechanism ................................ ................................ .... 45

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6 2.3.1.4 Conclusions ................................ ................................ ................... 45 2.3.2 Direct Synthesis ................................ ................................ ...................... 46 2.3.2.1 Polymer synthesis ................................ ................................ .......... 46 2.3.2.2 Proposed mechanism ................................ ................................ .... 48 2.3.2.3 Effect of methylene spacers ................................ ........................... 49 2.3.2.4 Conclusions ................................ ................................ ................... 51 2.4 Synthesis of Copolymers ................................ ................................ .................. 51 2.4.1 Monomer synthesis ................................ ................................ ................. 51 2.4.2 Polymer synthesis ................................ ................................ ................... 52 2.4.3 Incorporation study via NMR ................................ ................................ ... 54 2.4.4 Conclusions ................................ ................................ ............................. 55 2.5 New Ideas ................................ ................................ ................................ ......... 55 2.5.1. Coupling of Two Vanillin Alcohols ................................ .......................... 55 2.5.2. Sugar Derivatives ................................ ................................ ................... 56 2.6 Final Conclusions ................................ ................................ .............................. 56 3 EXPERIMENTAL PROCEDURES ................................ ................................ .......... 57 3.1 Molecular Characterizations ................................ ................................ ............. 57 3.2 Polymerizations Procedures ................................ ................................ ............. 57 3.3 Synthesis Procedures ................................ ................................ ....................... 58 APPENDIX A PROTON AND CARBON N MR ................................ ................................ .............. 79 B POLYMER DATA ................................ ................................ ................................ .. 136 LIST OF REFERENCES ................................ ................................ ............................. 204 BIOGRAPHICAL SKE TCH ................................ ................................ .......................... 207

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7 LIST OF TABLES Table page 1 1 Commercial classification of polyethylene resins ................................ ................ 28 2 1 Castor oil composition ................................ ................................ ........................ 38 2 2 CAMP, polymer synthesis reaction conditions ................................ ................. 42 2 3 CAMP, polymer synthesis catalyst s ................................ ................................ 43 2 4 Direct synthesis reaction conditions ................................ ................................ 47 2 5 Direct synthesis effect of methylene spacers ................................ ................... 49 2 6 Copolymers of compounds 2.22 and 2.57 ................................ .......................... 52

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8 LIST OF FIGURES Figure page 1 1 Worldwide packaging consumpti on for primary packaging ................................ 24 1 2 Worldwide packaging consumption by sector ................................ ..................... 25 1 3 Plastic Recycling Symbols ................................ ................................ .................. 26 1 4 Molecular structure of PET ................................ ................................ ................. 26 1 5 Molecular structure of PE ................................ ................................ ................... 27 1 6 Molecular s tructure of PVC ................................ ................................ ................. 28 1 7 Molecular structure of PP ................................ ................................ ................... 28 1 8 Molecular structure of PS ................................ ................................ ................... 29 1 9 Molecular structure of PC ................................ ................................ ................... 30 2 1 BPA synthesis ................................ ................................ ................................ .... 33 2 2 Mechanism of BPA synthesis ................................ ................................ ............. 34 2 3 Polycondensation process of PC ................................ ................................ ........ 34 2 4 Transesterification process for PC ................................ ................................ ...... 35 2 5 Synthesis of aliphatic polycarbonates ................................ ................................ 37 2 6 Castor oil plant ................................ ................................ ................................ .... 38 2 7 Non phosgene pathways for DMC production ................................ .................... 39 2 8 DMC as methoxycarbonylation agent ................................ ................................ 39 2 9 DMC as methylation agent ................................ ................................ ................. 40 2 10 Monomer synthesis starting with methyl chloroformate ................................ ...... 41 2 11 Monomer synthesis starting with DMC ................................ ............................... 41 2 12 Polymer morphology ................................ ................................ ........................... 44 2 13 Poly(decylene carbonate) film ................................ ................................ ............ 44 2 14 Possible mechanism for CAMP reaction ................................ ............................ 45

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9 2 15 One pot synthesis for polycarbonates ................................ ................................ 46 2 16 Proposed mechanism for alcoholic end chains ................................ ................... 48 2 16 Effect o f methylene spacers on T m ................................ ................................ ..... 50 2 17 Synthesis of resorcinol bis(2 hydroxyethyl) ether ................................ ............... 51 2 18 Synthesis of (1,3 phenylenebis(oxy)) bis(ethane 2,1 diyl)dimethyl dicarbonate .. 52 2 19 NMR spectra of polymers 2.9 2.61 and 2.67 for incorporation calculation ......... 54 A 1 1 H NMR spectra of compound 2.1 ................................ ................................ ...... 79 A 2 13 C NMR spectra of compound 2.1 ................................ ................................ ..... 79 A 3 1 H NMR spectra of compound 2.2 ................................ ................................ ...... 80 A 4 13 C NMR spectra of compound 2.2 ................................ ................................ ..... 80 A 5 1 H NMR spectra of compound 2.56 ................................ ................................ .... 81 A 6 13 C NMR spectra of compound 2.56 ................................ ................................ ... 81 A 7 1 H NMR spectra of compound 2.57 ................................ ................................ .... 82 A 8 13 C NMR spectra of compound 2.57 ................................ ................................ ... 82 A 9 1 H NMR spectra of compound 2.68 ................................ ................................ .... 83 A 10 13 C NMR spectra of compound 2.68 ................................ ................................ ... 83 A 11 1 H NMR spectra of polymer 2.5 ................................ ................................ .......... 84 A 12 13 C NMR spectra of polymer 2.5 ................................ ................................ ......... 84 A 13 1 H NMR spectra of polymer 2.6 ................................ ................................ .......... 85 A 14 13 C NMR spectra of polymer 2.6 ................................ ................................ ......... 85 A 15 1 H NMR spectra of polymer 2.7 ................................ ................................ .......... 86 A 16 13 C NMR spectra of polymer 2.7 ................................ ................................ ......... 86 A 17 1 H NMR spectra of polymer 2.8 ................................ ................................ .......... 87 A 18 13 C NMR spectra of polymer 2.8 ................................ ................................ ......... 87 A 19 1 H NMR spectra of polymer 2.9 ................................ ................................ .......... 88

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10 A 20 13 C NMR spectra of polymer 2.9 ................................ ................................ ......... 88 A 21 1 H NMR spectra of polymer 2.10 ................................ ................................ ........ 89 A 22 13 C NMR spectra of polymer 2.10 ................................ ................................ ....... 89 A 23 1 H NMR spectra of polymer 2.11 ................................ ................................ ........ 90 A 24 13 C NMR spectra of polymer 2.11 ................................ ................................ ....... 90 A 25 1 H NMR spectra of polymer 2.12 ................................ ................................ ........ 91 A 26 13 C NMR spectra of polymer 2.12 ................................ ................................ ....... 91 A 27 1 H NMR spectra of polymer 2.13 ................................ ................................ ........ 92 A 28 13 C NMR spectra of polymer 2.13 ................................ ................................ ....... 92 A 29 1 H NMR spectra of polymer 2.14 ................................ ................................ ........ 93 A 30 13 C NMR spectra of polymer 2.14 ................................ ................................ ....... 93 A 31 1 H NMR spectra of polymer 2.17 ................................ ................................ ........ 94 A 32 13 C NMR spectra of polymer 2.17 ................................ ................................ ....... 94 A 33 1 H NMR spectra of polymer 2 .18 ................................ ................................ ........ 95 A 34 13 C NMR spectra of polymer 2.18 ................................ ................................ ....... 95 A 35 1 H NMR spectra of polymer 2.21 ................................ ................................ ........ 96 A 36 13 C NMR spectra of polymer 2.21 ................................ ................................ ....... 96 A 37 1 H NMR spectra of polymer 2.23 ................................ ................................ ........ 97 A 38 13 C NMR spectra of pol ymer 2.23 ................................ ................................ ....... 97 A 39 1 H NMR spectra of polymer 2.24 ................................ ................................ ........ 98 A 40 13 C NMR spectra of polymer 2.24 ................................ ................................ ....... 98 A 41 1 H NMR spectra of polymer 2.25 ................................ ................................ ........ 99 A 42 13 C NMR spectra of polymer 2.25 ................................ ................................ ....... 99 A 43 1 H NMR spectra o f polymer 2.26 ................................ ................................ ...... 100 A 44 13 C NMR spectra of polymer 2.26 ................................ ................................ ..... 100

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11 A 45 1 H NMR spectra of polymer 2.27 ................................ ................................ ...... 101 A 46 13 C NMR spectra of polymer 2.27 ................................ ................................ ..... 101 A 47 1 H NMR spectra of polymer 2.28 ................................ ................................ ...... 102 A 48 13 C NM R spectra of polymer 2.28 ................................ ................................ ..... 102 A 49 1 H NMR spectra of polymer 2.30 ................................ ................................ ...... 103 A 50 13 C NMR spectra of polymer 2.30 ................................ ................................ ..... 103 A 51 1 H NMR spectra of polymer 2.31 ................................ ................................ ...... 104 A 52 13 C NMR spectra of polymer 2.31 ................................ ................................ ..... 104 A 53 1 H NMR spectra of polymer 2.35 ................................ ................................ ...... 105 A 54 13 C NMR spectra of polymer 2.35 ................................ ................................ ..... 105 A 55 1 H NMR spectra of polymer 2.36 ................................ ................................ ...... 106 A 56 13 C NMR spectra of polymer 2.36 ................................ ................................ ..... 106 A 57 1 H NMR spectra of polymer 2.37 ................................ ................................ ...... 107 A 58 13 C NMR spectra of polymer 2.37 ................................ ................................ ..... 107 A 59 1 H NMR spectra of polymer 2.38 ................................ ................................ ...... 108 A 60 13 C NMR spectra of polymer 2.38 ................................ ................................ ..... 108 A 61 1 H NMR spectra of polymer 2.39 ................................ ................................ ...... 109 A 62 13 C NMR spectra of polymer 2.39 ................................ ................................ ..... 109 A 63 1 H NMR spectra of polymer 2.40 ................................ ................................ ...... 110 A 64 13 C NMR spectra of polymer 2.40 ................................ ................................ ..... 110 A 65 1 H NMR spectra of pol ymer 2.41 ................................ ................................ ...... 111 A 66 13 C NMR spectra of polymer 2.41 ................................ ................................ ..... 111 A 67 1 H NMR spectra of polymer 2.42 ................................ ................................ ...... 112 A 68 13 C NMR spectra of polymer 2.42 ................................ ................................ ..... 112 A 69 1 H NMR spectra of polymer 2.43 ................................ ................................ ...... 113

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12 A 70 13 C NMR spe ctra of polymer 2.43 ................................ ................................ ..... 113 A 71 1 H NMR spectra of polymer 2.44 ................................ ................................ ...... 114 A 72 13 C NMR spectra of polymer 2.44 ................................ ................................ ..... 114 A 73 1 H NMR spectra of polymer 2.45 ................................ ................................ ...... 115 A 74 13 C NMR spectra of polymer 2.45 ................................ ................................ ..... 115 A 75 1 H NMR spectra of polymer 2.46 ................................ ................................ ...... 116 A 76 13 C NMR spectra of polymer 2.46 ................................ ................................ ..... 116 A 77 1 H NMR spectra of polymer 2.47 ................................ ................................ ...... 117 A 78 13 C NMR spectra of polymer 2.47 ................................ ................................ ..... 117 A 79 1 H NMR spectra of polymer 2.48 ................................ ................................ ...... 118 A 80 13 C NMR spectra of polymer 2.48 ................................ ................................ ..... 118 A 81 1 H NMR spectra of polymer 2.49 ................................ ................................ ...... 119 A 82 13 C NMR spectra of polymer 2.49 ................................ ................................ ..... 119 A 83 1 H NMR spectra of polymer 2.50 ................................ ................................ ...... 120 A 84 13 C NMR spectra of polymer 2.50 ................................ ................................ ..... 120 A 85 1 H NMR spectra of polymer 2.51 ................................ ................................ ...... 121 A 86 13C NMR spectra of polymer 2.51 ................................ ................................ ... 121 A 87 1 H NMR spectra of polymer 2.52 ................................ ................................ ...... 122 A 88 13 C NMR spectra of polymer 2.52 ................................ ................................ ..... 122 A 89 1 H NMR spectra of polymer 2.53 ................................ ................................ ...... 123 A 90 13C NMR spectra of polymer 2.53 ................................ ................................ ... 123 A 91 1 H NMR spectra of polymer 2.54 ................................ ................................ ...... 124 A 92 13 C NMR spectra of polymer 2.54 ................................ ................................ ..... 124 A 93 1 H NMR spectra of polymer 2.55 ................................ ................................ ...... 125 A 94 13 C NMR spectra of polymer 2.55 ................................ ................................ ..... 125

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13 A 95 1 H NMR spectra of polymer 2.58 ................................ ................................ ...... 126 A 96 13 C NMR spectra of polymer 2.58 ................................ ................................ ..... 126 A 97 1 H NM R spectra of polymer 2.59 ................................ ................................ ...... 127 A 98 13 C NMR spectra of polymer 2.59 ................................ ................................ ..... 127 A 99 1 H NMR spectra of polymer 2.60 ................................ ................................ ...... 128 A 100 13 C NMR spectra of polymer 2.60 ................................ ................................ ..... 128 A 101 1 H NMR spectra of polymer 2.61 ................................ ................................ ...... 129 A 102 13 C NMR spectra of polymer 2.61 ................................ ................................ ..... 129 A 103 1 H NMR spectra of polymer 2.62 ................................ ................................ ...... 130 A 104 13 C NMR spectra of polymer 2.62 ................................ ................................ ..... 130 A 105 1 H NMR spectra of polymer 2.63 ................................ ................................ ...... 131 A 106 13 C NMR spectra of polymer 2.63 ................................ ................................ ..... 131 A 107 1 H NMR spectra of polymer 2.64 ................................ ................................ ...... 132 A 108 13 C NMR spectra of polymer 2.64 ................................ ................................ ..... 132 A 109 1 H NMR spectra of pol ymer 2.65 ................................ ................................ ...... 133 A 110 13 C NMR spectra of polymer 2.65 ................................ ................................ ..... 133 A 111 1 H NMR spectra of polymer 2.66 ................................ ................................ ...... 134 A 112 13 C NMR spectra of polymer 2.66 ................................ ................................ ..... 134 A 113 1 H NMR spectra of polymer 2.67 ................................ ................................ ...... 135 A 114 13C NM R spectra of polymer 2.67 ................................ ................................ ... 135 B 1 TGA of polymer 2.9 ................................ ................................ .......................... 136 B 2 DSC of polymer 2.9 ................................ ................................ .......................... 136 B 3 TGA of polymer 2.17 ................................ ................................ ........................ 137 B 4 DSC of polymer 2.17 ................................ ................................ ........................ 137 B 5 TGA of polymer 2.18 ................................ ................................ ........................ 138

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14 B 6 DSC of polymer 2.18 ................................ ................................ ........................ 138 B 7 TGA of polymer 2.21 ................................ ................................ ........................ 139 B 8 DSC of polymer 2.21 ................................ ................................ ........................ 139 B 9 TGA of polymer 2.23 ................................ ................................ ........................ 140 B 10 DSC of polymer 2.23 ................................ ................................ ........................ 140 B 11 TGA of polymer 2.24 ................................ ................................ ........................ 141 B 12 DSC of polymer 2.24 ................................ ................................ ........................ 141 B 13 TGA of polymer 2.25 ................................ ................................ ........................ 142 B 14 DSC of polymer 2.25 ................................ ................................ ........................ 142 B 15 TGA of polymer 2.26 ................................ ................................ ........................ 143 B 16 DSC of polymer 2.26 ................................ ................................ ........................ 143 B 17 TGA of polymer 2.27 ................................ ................................ ........................ 144 B 18 DSC of polymer 2.27 ................................ ................................ ........................ 144 B 19 TGA of polymer 2.28 ................................ ................................ ........................ 145 B 20 DSC of polymer 2.28 ................................ ................................ ........................ 145 B 21 TGA of polymer 2.31 ................................ ................................ ........................ 146 B 22 DSC of polymer 2.31 ................................ ................................ ........................ 146 B 23 TGA of polymer 2.35 ................................ ................................ ........................ 147 B 24 DSC of polymer 2.35 ................................ ................................ ........................ 147 B 25 TGA of polymer 2.36 ................................ ................................ ........................ 148 B 26 DSC of polymer 2.36 ................................ ................................ ........................ 148 B 27 TGA of polymer 2.37 ................................ ................................ ........................ 149 B 28 DSC of polymer 2.37 ................................ ................................ ........................ 149 B 29 TGA of polymer 2.38 ................................ ................................ ........................ 150 B 30 DSC of polymer 2.38 ................................ ................................ ........................ 150

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15 B 31 TGA of polymer 2.39 ................................ ................................ ........................ 151 B 32 DSC of polymer 2.39 ................................ ................................ ........................ 151 B 33 TGA of p olymer 2.40 ................................ ................................ ........................ 152 B 34 DSC of polymer 2.40 ................................ ................................ ........................ 152 B 35 TGA of polymer 2.41 ................................ ................................ ........................ 153 B 36 DSC of polymer 2.41 ................................ ................................ ........................ 153 B 37 TGA of polymer 2.42 ................................ ................................ ........................ 154 B 38 DSC of polymer 2.42 ................................ ................................ ........................ 154 B 39 TGA of polymer 2.43 ................................ ................................ ........................ 155 B 40 DSC of polymer 2.43 ................................ ................................ ........................ 155 B 41 TGA of polymer 2.44 ................................ ................................ ........................ 156 B 42 DSC of polymer 2.44 ................................ ................................ ........................ 156 B 43 TGA of polymer 2.45 ................................ ................................ ........................ 157 B 44 DSC of po lymer 2.45 ................................ ................................ ........................ 157 B 45 TGA of polymer 2.46 ................................ ................................ ........................ 158 B 46 DSC of polymer 2.46 ................................ ................................ ........................ 158 B 47 TGA of polymer 2.47 ................................ ................................ ........................ 159 B 48 DSC of polymer 2.47 ................................ ................................ ........................ 159 B 49 TGA of polymer 2.48 ................................ ................................ ........................ 160 B 50 DSC of polymer 2.48 ................................ ................................ ........................ 160 B 51 TGA of polymer 2.49 ................................ ................................ ........................ 161 B 52 DSC of polymer 2.49 ................................ ................................ ........................ 161 B 53 TGA of polymer 2.50 ................................ ................................ ........................ 162 B 54 DSC of polymer 2.50 ................................ ................................ ........................ 162 B 55 TGA of pol ymer 2.51 ................................ ................................ ........................ 163

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16 B 56 DSC of polymer 2.51 ................................ ................................ ........................ 1 63 B 57 TGA of polymer 2.52 ................................ ................................ ........................ 164 B 58 DSC of polymer 2.52 ................................ ................................ ........................ 164 B 59 TGA of polymer 2.53 ................................ ................................ ........................ 165 B 60 DSC of polymer 2.53 ................................ ................................ ........................ 165 B 61 TGA of polymer 2.54 ................................ ................................ ........................ 166 B 62 DSC of polymer 2.54 ................................ ................................ ........................ 166 B 63 TGA of polymer 2.55 ................................ ................................ ........................ 167 B 64 TGA of polymer 2.55 ................................ ................................ ........................ 167 B 65 TGA of polymer 2.58 ................................ ................................ ........................ 168 B 66 DSC of poly mer 2.58 ................................ ................................ ........................ 168 B 67 TGA of polymer 2.59 ................................ ................................ ........................ 169 B 68 DSC of polymer 2.59 ................................ ................................ ........................ 169 B 69 TGA of polymer 2.60 ................................ ................................ ........................ 170 B 70 DSC of polymer 2.60 ................................ ................................ ........................ 170 B 71 TGA of polymer 2.61 ................................ ................................ ........................ 171 B 72 DSC of polymer 2.61 ................................ ................................ ........................ 171 B 73 TGA of polymer 2.62 ................................ ................................ ........................ 172 B 74 DSC of polymer 2.62 ................................ ................................ ........................ 172 B 75 TGA of polymer 2.63 ................................ ................................ ........................ 173 B 76 DSC of polymer 2.63 ................................ ................................ ........................ 173 B 77 TGA of polym er 2.64 ................................ ................................ ........................ 174 B 78 DSC of polymer 2.64 ................................ ................................ ........................ 174 B 79 TGA of polymer 2.65 ................................ ................................ ........................ 175 B 80 DSC of polymer 2.65 ................................ ................................ ........................ 175

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17 B 81 TGA of polymer 2.66 ................................ ................................ ........................ 176 B 82 DSC of polymer 2.66 ................................ ................................ ........................ 176 B 83 TGA of polymer 2.67 ................................ ................................ ........................ 177 B 84 DSC of polymer 2.67 ................................ ................................ ........................ 177 B 85 GPC analysis of polymer 2.5 ................................ ................................ ............ 178 B 86 GPC analysis of polymer 2.6 ................................ ................................ ............ 178 B 87 GPC analysis of polymer 2.7 ................................ ................................ ............ 179 B 88 GPC analysis of polymer 2.8 ................................ ................................ ............ 179 B 89 GPC analysis of polymer 2.9 ................................ ................................ ............ 180 B 90 GPC analysis of polymer 2.10 ................................ ................................ .......... 180 B 91 GPC analysis of polymer 2.11 ................................ ................................ .......... 181 B 92 GPC analysis of polymer 2.12 ................................ ................................ .......... 181 B 93 GPC analysis of polymer 2.13 ................................ ................................ .......... 182 B 94 GPC analysis of polymer 2.14 ................................ ................................ .......... 182 B 95 GPC analysis of polymer 2.17 ................................ ................................ .......... 183 B 96 GPC analysis of polymer 2.18 ................................ ................................ .......... 183 B 97 GPC analysis of polymer 2.21 ................................ ................................ .......... 184 B 98 GPC analysis of polymer 2.23 ................................ ................................ .......... 184 B 99 GPC analysis of polymer 2.24 ................................ ................................ .......... 185 B 100 GPC analysis of polymer 2.25 ................................ ................................ .......... 185 B 101 GPC analysis of polymer 2.26 ................................ ................................ .......... 186 B 102 GPC analysis of polymer 2.28 ................................ ................................ .......... 186 B 103 GPC analysis of polymer 2.30 ................................ ................................ .......... 187 B 104 GPC analysis of polymer 2.31 ................................ ................................ .......... 187 B 105 GPC analysis of polymer 2.35 ................................ ................................ .......... 188

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18 B 106 GPC analysis of polymer 2.36 ................................ ................................ .......... 188 B 107 GPC analysis of polymer 2.37 ................................ ................................ .......... 189 B 108 GPC analysis of polymer 2.38 ................................ ................................ .......... 189 B 109 GPC analysis of polymer 2.39 ................................ ................................ .......... 190 B 110 GPC analysis of polymer 2.40 ................................ ................................ .......... 190 B 111 GPC analysis of polymer 2.41 ................................ ................................ .......... 191 B 112 GPC analysis of polymer 2.42 ................................ ................................ .......... 191 B 113 GPC analysis of polymer 2.43 ................................ ................................ .......... 192 B 114 GPC analysis of polymer 2.44 ................................ ................................ .......... 192 B 115 GPC analysis of polymer 2.45 ................................ ................................ .......... 193 B 116 GPC analysis of polymer 2.46 ................................ ................................ .......... 193 B 117 GPC analysis of polymer 2.47 ................................ ................................ .......... 194 B 118 GPC analysis of polymer 2.48 ................................ ................................ .......... 194 B 119 GPC analysis of polymer 2.49 ................................ ................................ .......... 195 B 120 GPC analysis of polymer 2.50 ................................ ................................ .......... 195 B 121 GPC analysis of polymer 2.51 ................................ ................................ .......... 196 B 122 GPC analysis of polymer 2.52 ................................ ................................ .......... 196 B 123 GPC analysis of polymer 2.53 ................................ ................................ .......... 197 B 124 GPC analysis of polymer 2.54 ................................ ................................ .......... 197 B 125 GPC analysis of polymer 2.55 ................................ ................................ .......... 198 B 126 GPC analysis of polymer 2.58 ................................ ................................ .......... 198 B 127 GPC analysis of polymer 2.59 ................................ ................................ .......... 199 B 128 GPC analysis of polymer 2.60 ................................ ................................ .......... 199 B 129 GPC analysis of polymer 2.61 ................................ ................................ .......... 200 B 130 GPC analysis of polymer 2.62 ................................ ................................ .......... 200

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19 B 131 GPC analysis of polymer 2.63 ................................ ................................ .......... 201 B 132 GPC analysis of polymer 2.64 ................................ ................................ .......... 201 B 133 GPC analysis of polymer 2.65 ................................ ................................ .......... 202 B 134 GPC analysis of polymer 2.66 ................................ ................................ .......... 202 B 135 GPC analysis of polymer 2 .67 ................................ ................................ .......... 203

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20 LIST OF SCHEMES Scheme page 2.1 Vanillin coupling 1 ................................ ................................ ............................... 55 2.2 Vanillin coupling 2 ................................ ................................ ............................... 56 2.3 Diol from D Glucono 1,5 lactone ................................ ................................ ........ 56 2.4 Diol from erythriol ................................ ................................ ............................... 56 2.5 Diol from L Tartaric acid ................................ ................................ ..................... 56 3. 1 2.1 decane 1,10 diyl dimethyl dicarbonate ................................ ......................... 58 3.2 2.2 decane 1 ,10 diyl dimethyl dicarbonate ................................ ......................... 59 3.3 2.5 2.34 poly(decylene carbonate) ................................ ................................ ..... 59 3.4 2.34 2.49 poly(decylene carbonate) ................................ ................................ 6 5 3.5 2.50 poly(pentylene carbonate) ................................ ................................ .......... 70 3.6 2.51 poly(hexylene carbonate) ................................ ................................ ........... 70 3.7 2.52 poly(heptylene carbonate) ................................ ................................ .......... 71 3.8 2.53 poly(octylene carbonate) ................................ ................................ ............ 71 3.9 2.54 poly(nonylene carbonate) ................................ ................................ ........... 72 3.10 2.55 poly(dodecylene carbonate) ................................ ................................ ....... 72 3.11 2.56 resorcinol bis(2 hydroxyethyl) ether ................................ ............................ 73 3.12 2.57 (1,3 phenylenebis(oxy))bis(ethane 2,1 diyl)dimethyl dicarbonate .............. 73 3.13 2.58 2.65 copoly[decylene resorcinol bis(2 hydroxyethyl) ether carbonate] .... 74 3.14 2.67 poly(resorcinol bis(2 hydroxyethyl) ether carbonate] ................................ 77 3.15 2.68 ((ethane 1,2 diylbis(oxy))bis(3 methoxy 4,1 phenylene))dimethanol .......... 77

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21 LIST OF ABBREVIATION S BPA Bisphenol A C Celsius CAMP Carbonate metathesis polymerization Cat. Catalyst CO 2 Carbon dioxide Da Dalton DMC Dimethyl carbonate DPC Diphenyl carbonate DSC Differential scanning calorimetry g Grams h Hours HDPE High density polyethylene Hz Hertz LDPE Low density polyethylene LLDPE Linear low density polyethylene MDPE Medium density polyethylene mg Milligram MHz Mega hertz mL Milliliter mmol Millimole mol Moles mol% Mole percent M w Weight average mole cular weight NMR Nuclear magnetic resonance

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22 N 2 Nitrogen gas PC Polycarbonate PDI Polydispersity index PE Polyethylene PET Polyethylene terephthalate PIC Plastic Identification Code PP Polypropylene ppm Parts per million PS Polystyrene PVC Polyvinyl chlorid e ROP Ring opening polymerization T g Glass transition temperature TGA Thermal gravimetric analysis THF Tetrahydrofuran T m Melting temperature T peak Temperature of TGA for 50% weight loss under N 2 VLDPE Very low density polyethylene

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23 Abstract of The sis Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master in Science CLEAN AND DIRECT SYNTHESIS OF POLY CARBONATES FROM BIORENEWABLE DIOLS VIA CARBONATE METATHESIS POLYMERIZATION (CAMP) By Rob Vanderhenst December 2011 Chair: Stephen A. Miller Major: Chemistry The worldwide annual waste production is estimated at more than 1 billion tons. A major cut is generated by plastic packaging. When this packaging enters the municipal waste stream, it becomes a major source of household refuse and it get s disposed to landfill sites. All over the world regulations have been introduced to promote the reuse and recycling of packaging materials and laws are enforced to increas e the use of bio renewable, compostable polymers in future packaging materials. This resea rch focuses on the usage of bio renewable feedstock s (castor oil, glucose building block s for polycarbonates. A n economic al and ecological method for producing aliphatic polycarbonates was After the optimization of this procedure, the chain length of the repeating unit w as altered and copolymers were produced bearing rigid structure s in the backb one. The thermal properties and the effects of the modifications were then studied for all obtained polymers.

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24 CHAPTER 1 AN INTRODUCTION TO PACKAGING 1.1 Packaging: Definition and M aterials ny nature to be used for the containment, protection, handling, delivery and preservation of goods from It is a most important tool for the well being and safety of people and commerce and because of its use in a wid e range of industries across food and drink, healthcare, cosmetics and other consumer goods as well as a range of industrial sectors, p ackaging has be come an essential everyday item Figure 1 1 Worldwide p ackaging consumption for primary packaging 2 With world population increasing and the world wide distribution chains becoming more sophisticated because of this growing demand, the Packaging industry is booming like never before This is confirmed by the numbers in the last decade; i n 2009, the prima ry packaging market was worth 564 billion US dollars an increase of almost 50% compared to 2000 and the market i s expected to grow at an annual rate of around 4 5% for the next 10 year s 2

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25 Packaging encompasses a wide range of material types across paper, board, plastic, metal, glass, wood and other materials. The largest share of global packaging is accounted for paper and board packaging (38 %). Plastic (34%), however, is the fastest growing sector i n the market and will close t he gap on paper soon to bec ome the biggest player in the packaging industry. Across other sectors, metal packaging (16%) and container glass (6%) sales are set to grow steadily, but will lose further share to plastics in beverage and food markets 2 Figure 1 2 Worldwide packaging consumption by sector Due to growing demand of plastics as a packaging material, the scarcity of oil and the growing public awareness of sustainability, there is an immense intere st in polymers derived from bio renewable feedstock s to mimic and eventually replace the commercial petro plastics. T he U.S. Department of Agriculture ha s targeted that 25% of U.S. chemical production should be bio based by the year 2030, a substantial inc rease from the current 5% share 3

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26 1.2 Polymers in P ackaging 1.2.1 Polymer C la sses Packaging represents the largest single sector of plastics use. The sector accounts for 35% of plastic consumption and plastic is the material of choice in nearly half of all packaged goods 4 A common feat ure of all these plastic materials is that th eir backbone is made of natural or synthetic macromolecules composed of thousands of atoms and having correspondingly high molecular masses commonly referred to as polymers Five groups of polymers each with its specific properties, are used worldwide for packaging applications and can be identified by its own Plastic Identify Code (PIC). Plastic R ecycle Symbols Figure 1 3 Plastic Recycling Symbols 1.2.1.1 Polyethylene terephthalate P olyethylene terephthalate (PET) is the third most produced polymer in the world after polyethylene and polypropylene. It represents about 18% of the worldwide polymer market and is mostly known for its use in bottles and fibers 5 Figure 1 4 Molecula r structure of PET

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27 The backbone of the polymer chain is made of aromatic units, giving stiffness to the polymer chain. The two methylene linkers provide some flexibility to the main chain, and are responsible for the relatively low glass transition tempera ture. PET can be semi rigid to rigid, is very lightweight and has excellent mechanical properties such as tensile and impact strength 6 It makes a good gas and fair moisture barrier, as well as a good barrier to alcohol and solvents It is strong and impact resistant It is naturally colorless with a high tr ansparency 7 1.2.1. 2 Polyethylene Polyethylene (PE) is probably the most popular plastic in the world. It is used to make grocery bags, milk and shampoo bottles, films and even toys Polyethylene is a low cost material that is flexible, chemic al resis tant, t ough and weatherproof but has poor barrier properties to gasses and limited heat resistance 8 Being such a versatile material, it has the simplest structure of all commercial polymers (Figure 1 5 ) PE is a semi crystalline thermoplastic pol ymer formed by the polymer ization of ethylene. Figure 1 5 Molecular structure of PE PE in general is characterized by an extremely regular and flexible molecular chain structure with no side groups other than branches of more polyethylene. Their de nsities and melting temperatures decrease wi th the increase of branching 8 Based on the density PE can be classified into the material types listed in Table 1 1 9

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28 Table 1 1 Commercial classification of polyethylene resins 9 Polyethylene product Density (g/mL) T m ( C) High density polyethylene (HDPE) 0.940 0.970 144 Medium density polyethylene (MDPE) 0.936 0.939 ~ 120 Low density polyethylene (LDPE) 0.915 0.940 108 Linear low density polyethylene (LLDPE) 0.915 0.926 135 Very low density po lyethylene (VLPDE) 0.890 0.940 ~ 105 1.2.1.3 Polyvinylchloride Polyvinyl c hloride (PVC) widely known as vinyl, is one of the largest volume synthetic thermoplastic used globally. It is constructed of repeating eth yl groups, having one hydrogen atom rep laced by chloride (Figure 1 6 ) Figure 1 6 Molecular structure of PVC S ince it is both rigid and flexible PVC is used for making pipes, frames, railing, wire, cable insulation, medical tubing and so on. It has g ood chemical resistance, stable elect rical properties and a superior fire performance 8 1.2.1.4 Polypropylene Isotactic p olypropylene is used in a wide variety of applications including medical and laboratory equipment, reusable containers, car batteries and diapers 10 It s molecular structur e is very similar to that of PE; however, on every other carbon in the backbone a meth yl group is attached (Figure 1 7 ). Figure 1 7 Molecular structure of PP

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29 Because of these methyl groups, rotation and flexibility of the chain are greatly restricte d, resulting in significantly greater stiffness than PE. Due to the flexibility of the backbone and the stereo regularity of the methyl groups, PP molecules coil into a helical shape. These coils crystallize to a high degree giving PP many of its desirable properties like chemical solvent resistance and opacity 8 1.2.1.5 Polystyrene Polystyrene (PS) is an aromatic vinyl polymer made from the monomer styrene Structurally, it is a long hydrocarbon chain, with a phenyl group attached to every other carbon at om (Figure 1 8 ) Due to this inflexibility PS is strong and brittle and may crack at room temperature. The only commercially interesting form of PS is atactic PS, which is a clear polymer that is used in protective packaging, bottles, food packaging 8 Figure 1 8 Molecular structure of PS Polystyrene is readily foamed or formed into beads. These foams and beads are excellent thermal insulators and are used to produce home insulation and containers for hot foods. Styrofoam TM is a tr ade name for foamed polystyrene 1 1 1.2.1. 6 Polycarbonate Polycarbonate (PC) gets its name from the carbonate group in its backbone. In packaging, PC is mostly identified with the polymer of bisphenol A (BPA) and phosgene (Figure 1 9 ) The ar yl groups in the backbone, togeth er with the two methyl side groups, contribute to significant inflexibility. It is this stiffness and the lack of mobility that

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30 prevents the polymer from developing any sign ificant crystal structure; it also has a major impact on the properties of the poly mer. Figure 1 9 Molecular structure of PC The unique combination of outstanding properties including strength, lightness, durability, high transparency (because of its amorphous nature) thermal stability, and good electrical insulation make PC a hig h quality plastic 1 2 Its application area extends from compact disks to insulating foils and from safety glass to astronaut helmets. 1.3 Environmental Concerns Although packaging have had a remarkable impact on our culture, it has become increasingly obvio us that the use of p ackaging has the potential of becoming as much a problem as a solution. In 2009, used packaging generate d a total of 71.75 million tons of waste in the US only, taking a 29.5% share of the market. Plastics represented 17.4 % of this tot al and with the re covery rate at only 13.7% the lowest in class; there is a lot of plastic waste left to dispose 1 3 Constrained landfill capacity and the low landfill decomposition rate (es timated at 500 to 1000 years) 1 4 combined with the debate about th e emissions caused by incineration 13 are pushing the need for packaging plastics that could be recycle d, or even better decomposed to higher levels. Although some materials can be recycled into products similar to the original ycling), the recycling process generally changes the recycled

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31 into materials that require less strength or different properties meaning the re is no need to dispose of them sinc e they could be re used as fibers for textile but it also does not help in decreasing the total amount of packaging waste. Composting however, is the biological decomposition of organic material by microorganisms such as bacteria and fungi. With proper t emperature and moisture controls, composting can quickly reduce the original volume of some materials by 50% Biodegradable organic materials such as leaves, grass, food wastes, and paper can be composted One way to ameliorate the waste problem would be t o develop new p olymers, which not only mimic the properties of the current commercial plastics but also help to reduc e the generation of total waste. I n order to have a high economic and ecological impact such a new p olymer should meet all of the followin g goals : (1) derive from biomass, preferable not from a food source; (2) be degradable under simple chemical processes or in nature; (3) have all needed properties to ensure its function as a packaging plastic; and (4) start from relatively cheap monomers with a simple production process.

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32 CHAPTER 2 POLYCARBONATES FROM A BIORENEWABLE FEEDSTOCK 2.1 Polycarbonates 2.1.1 Importance of Polycarbonates Polycarbonate is an important engineering plastic that has been widely use d since its development in 1953 15, 1 6 and first production in 1960. T he use of PC has become so common that almost every kind of product ranging from construction to electronics and even the simplest of accessories like bottles are made from this material. Polycarbonates are divided into two fields, the poly(aromatic carbonate)s and the poly(aliphatic carbonate)s Aromatic PCs are derived from rigid, aromatic monomers which provide the polymer with a balance of useful features including transparency, high impact resistance and heat deflection temperatures 12 Aliphatic PCs lack this rigidity in the backbone, but are very useful because of their biocompatibility, biodegradability and low toxicity 17,18 2.1.2 Aromatic Polycarbonates Aromatic polycarbonates are one of the most useful engineering pl astics due to their good heat resistance, mechanical properties, and transparency 12 Commonly, they are prepared by interfacial polycondensation of BPA with phosgene 1 5 but in response to safer and more environmentally conscious demands, the transesterific ation method with diphenyl carbonate (DPC) 1 6 is gaining popularity 2.1.2.1 BPA Although BPA or 2,2 bis(4 hydroxyphenyl) propane is said to be first synthesized in 1891 by the Russian chemist A.P. Dianin, it is Thomas Zincke who first report ed its synthes is in 1905 1 9 Later on, scientists discover ed that it is in fact an artificial estrogen

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33 and it was used as such until the invention of another, more potent synthetic estrogen named Diethylstilbestrol (DES) 20 Therefore BPA was shelved until polymer scient ist discovered it could be polymerized into a strong and transparent plastic. Unfortunately with time th e p lastic decay s releasing the BPA into the materials with which it comes in contact 21 Nowadays there is a growing concern about the harmful effects of BPA on our health 22 a nd although scientists do no t really seem to agree on t hose possible health risks, BPA remains controversial. W hile both sides are continuing studies, trying to prove the y are right, many countries went ahead and banned BPA from foo d and beverages packaging 23 ,24 Ever since, polymer chemists are trying to develop a new green polycarbonate with the similar characteristics to replace the BPA based plastic. Synthesis. BPA is produced by the condensation of phenol and acetone The react ion is acid catalyzed at 60 80 C with high molar proportions (up to 3 0:1) 2 5 of phenol to acetone to ensure total condensation and suppress the side reactions. Figure 2 1 BPA synthesis To isolate the bisphenol A, light boilers like acetone and wate r are separated by distillation and the crude bisphenol is then crystallized from cold pheno l to obtain high purity product. In an acidic medium, acetone is proton ated to a n oxonium ion ( 1 ) This ion then adds to the limiting quinonoid structure of phenol ( 2 ) to yield a protonated carbinol ( 3 )

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34 Rearrangement with the release of water yield s the protonated phenol ( 4 ) which adds to a second phenol molecule to yield BPA ( 5 ) Figure 2 2 Mechanism of BPA synthesis Because of the high performance, e xcellent BPA quality, lack of corrosivity and their safety and ease of handlin g 2 7 cation exchange resins (like Amberlyst TM ) replaced the acid catalyst s in all major BPA producers. 2.1.2.2 P olycondensation of BPA and P hosgene The mos t widely used commercia l process involves the interfacial reaction between phosgene and the sodium salt of BPA in a heterogeneous system (Figure 2 3). Figure 2 3 Polycondensati on process of PC Aqueous sodium hydroxide (NaOH) is added to an organic phase containing BPA and phosgene to create a liquid liquid system. The obtained sodium salts of BPA (in aq.

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35 p hase) react with phosgene (in organic phase) on the interfacial border and mono and di chloroformates of BPA are formed. In the second stage of the process, a pha se transfer catalyst is added to condense the oligo carbonates to high molecular weight polycarbonate. The molecular weight, an average up to 200,000 g/ mol 15 is regulated by the addition of phenol or phenolic derivatives to end cap the polymer chains. 2. 1.2.3 T ransesterification of BPA and Diphenyl C arbonate (DPC) The second industrial route to synthesize PC uses a melt phase transesterification reaction between BPA and DPC. T his process is multi staged with a pre polymerization step of BPA and DPC, subs equent ly followed by a melt poly condensation of the oligomers Figure 2 4 Transesterification process for PC In a first stage BPA, DPC and the catalyst are heated up to 200 C under vacuum to form low molecular weight oligomers and remove most of the formed phenol. The temperature of the second stage is increased to 280 300 C to evaporate the remaining phenol and DPC and form an intermediate weight average molecular weight (~50,000 g/mol) 15 polycarbonate. For optimal molecular weight control two d ifferent catalysts are used ; alkali or alkaline earth metal hydroxides, carbonates or oxides for the lower temperature stage and transesterification catalysts such as quaternary phosphonium salts f or the higher temperature stage. The polymer prepared with th is melt process is exposed to high temperatures, which leads to instability and discoloration o f the product 15

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36 2.1.3 Aliphatic Polycarbonates Because of their poor physical properties, polycarbonates from aliphatic monomers attracted significantly less er attention as the above mention ed BPA based polymer. Their potential as biocompatible, biodegradable and non toxic materials 17,18 makes them however valuable candidates in the search for new green polymers which resulted in a rene wed interest in their synthes is Synthesis and previous studies T he development of suitable non phosgene routes for the production of aliphatic polycarbonates has been studied by many laboratories. Inoue and coworkers had a first big breakthrough in 1969 by copolymerizing alip hatic epoxides with CO 2 in the pre sence of a metal based catalyst 2 8 ,2 9 Although this approach is CO 2 consuming and high molecular weight polymer can be obtained, the re are some drawbacks prevent ing its application as a scaled up production for polycarbon ates. The polymerization process was feasible only for epoxides and oxetanes in the presence of an air sensitive catalyst and the obtained polymer chains contained ether linkages which weakens their thermal and mechanical properties. An alternative pathway for obtaining high molecular weight polycarbonates involves the ring opening polymerization (ROP) o f cyclic carbonates 30 3 2 Th e ring opening of these carbonates is thermodynamica lly favored at all temperatures, and has been w idely investigated by a varie ty of different mechanisms including cationic 3 3 anionic 3 4 and coordination insertion 3 5 pathways. Once again, several limitations to this process have been observed; besides the ether linkages in the backbone, the R OP of aliphatic PC is limited to six or seven membered cyclic carbonates. Considering this with t he low yield large quantities of catalyst and harmful solvents together with

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37 complicated purifications make it a n im practical application for commercial PC production Recently, there has been much research into the synthesis of aliphatic polycarbonates via a two step polycondensation of dialkyl carbonates and aliphatic diols 36 3 8 This melt polymerization gave decent yields, all being above 65% and produced polycarbonates without ether linkages in the backbone. T he shortcoming for this process however, was the low molecular weight of the o btained materials, which could therefore not be directly used as biodegradable plastics. Earlier this year, Li et all 3 9 were able to produce high molecular polycar bonates using a novel TiO 2 /SiO 2 based catalyst. Figure 2 5. Synthesis of aliphatic polycarbonates 2.2 Natural Molecules Giving New Polymers 2.2.1 Castor Oil as a Bio Renewable Feedstock The c astor oil plant (Ricinus C ommunis) is a native of tropica l Asia and Africa but nowadays it is naturalized and cultivated on commercial scale all around the world in temperate zones 40 It is a robust, branched annual herb that may grow 6 to 15 feet, with thick, hollow, herbaceous stems with a purplish bloom in t he upper part. The plant has large palm shaped leaves with, cluster like blossoms and spiny fruits, each carrying 3 seeds. All parts are poisonous, especially the beans 4 1

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38 F igure 2 6 Castor oil plant Like most plant oils, castor oil is obtained f rom the beans by a variety of processes such as different presses and solvent extraction. It has a relatively constant chemical composition, regardless its country of origin or season it was harvested 4 2 In accordance with most vegetable oils, castor oil i s a triacylglycerol composed of various fatty acids and glycerol (Table 2 1 ) The high ricinoleic acid content up to 90% is the reason for the high value of the oil and its versatile application potential in the chemical industry 4 3 Table 2 1 Cast or oil composition 4 3 Fatty Acid Molecular formula Percentage (%) Linoleic C 18 H 32 O 2 4.1 4.7 Linolenic C 18 H 3 0 O 2 0.5 0.7 Oleic C 18 H 3 4 O 2 2.2 3.3 Palmitic C 1 6 H 32 O 2 0.8 1.1 Ricinoleic C 18 H 3 4 O 3 87.7 90.4 Stearic C 18 H 36 O 2 0.7 1.0 Among other monomers, 1,12 o ctadecanediol, 1,10 decanediol and 9 octadecene 1,12 diol are interesting diols that could be obtained from castor oil by trans esterification and hydrogenation or by alkali splitting, e sterification and hydrogenation 4 4

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39 2.2.2 DMC as a Gre en Carbonate Source Dimethylcarbonate is achieving increasing attention in the chemical industry, mainly for two aspects: its versatility as a reagent and second ly its non toxicity for human health and the environment 4 5 Since DMC is the methyl ester of c arbonic acid, and therefore a derivative of CO 2 it is considered as an environmentally acceptable compound that does not ca use emissions in the atmosphere 4 6 Another reason why it i s referred to as a genuinely ocess no longer utilizes phosgene, but is based on the oxycarbonylation of methanol 4 7 Recently, alternative processes for DMC synthesis using methanol and urea have been reported 4 8 Figure 2 7 Non phosgene pathways for DMC production Be cause of its structure, DMC possesses two active centers (alkyl and carbonyl carbons), different processes can occur when reacti ng DMC with a n anionic nucleophile. The probability of the two different pathways can be tuned by controlling the temperature 4 6 At a temper ature below 90 C (boiling point of DMC), the methoxy carbonylation reaction will take place. Figure 2 8 DMC as methoxycarbonylation agent

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40 Higher temperatures ( 120 C) will cause DMC to act as a methylation agent. Figure 2 9 DMC as methylation agent Since both pathways generate a methoxy ion they can be carried out in the presence of catalytic amounts of base 4 6 These method s ha ve the advantages of avoid i ng t he formation of unwanted inorganic salts unlike most other methylation processes and the possibility to recycle the produced methanol for the production of DMC. 2 .3 Synthesis and Characterization o f New Aliphatic Polycarbonates 1,10 decanediol has been synthesized into polycarbonates in the past 4 9 50 None of those studies however, resulted in high molecular weight materials that could be used as a biodegradable thermoplastic by itself. The obtained oligomers were mostly used as pre polymer to produ ce poly urethanes 50 2.3 .1 Carbonate Metathesis Polymerization In this study we develop a pathway for the synthesis of high molecular weight polycarbonates via a carbonate interchange reaction, which hereafter is referred to as imply, CAMP. The projected work here focuses on development of the CAMP reaction by changing most of the reaction conditions. 2.3.1.1 Monomer synthesis The decane 1,10 diyl dimethyl dicarbonate wa s obtained by reacting 1,10 decanediol an d methyl chloroformate. After work up product 2.1 was obtained in a

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41 relatively good yield as white needle like crystals. The work up for this reaction involves a precipitation step to remove the unreacted pyridine filtration extraction, concentration und er reduced pressure and finally recrystallization; however no purification by column chromatography is necessary. Figure 2 10 Monomer synthesis starting with methyl chloroformate A greener pathway, avoiding the use of methyl chloroformate and pyrid ine was used as well to obtain the biscarbonate monomer The diol was heated together with DMC in a Dean Stark apparatus set up until the desired amount of methanol was collected. The excessive DMC was then removed under reduced pressure and the obtained s olid was recrystallized giving product 2.2 in small white crystals in a decent yield Once again there was no need for further purification. Figure 2 11 Monomer synthesis starting with DMC 2.3.1.2 Polymer synthesis A series of polymers w as synthesized in the melt under dynamic vacuum in order to remove DMC as a byproduct (Table 2 2.) The synthesis yields were close to 75 % for most the polymers. The moderate yield is probably due to the work up procedure in the sense that the melted polymer was cooled d own under nitrogen leaving a hard solid that was dissolved in an appropriate solvent such as chloroform or methylene chloride and then crashed out in cold methanol leaving the low molecular weight material in solution.

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42 Table 2 2 CAMP polymer synthesis reaction conditions Entry N 2 Vacuum Yield (%) M w PDI Temp. ( C) time (h) Temp. ( C) time (h) 2. 3 100 2 175 1.5 2. 4 125 2 175 1.5 2. 5 175 2 175 1.5 69 275 00 1.8 3 2. 6 125 12 175 1.5 77 127 00 1.6 2 2. 7 150 12 175 1.5 76 83300 1.78 2. 8 175 12 175 1.5 72 627 00 1.64 2. 9 200 2 200 1.5 78 749 00 1.63 2. 10 200 1 200 1.5 64 68600 2.14 2. 1 1 200 2 230 1.5 74 32000 2.14 2.1 2 a ) 200 2 200 1.5 72 61800 2.30 2.1 3 b ) 200 2 200 1.5 58 621 00 2.16 2.1 4 c ) 200 2 200 1.5 62 68600 2. 0 6 a ) ,b ) and c ) a re carried out with respectively 1,3 and 10 mol% of catalyst loading A study to investigate the effect of different catalysts on the CAMP reaction was conducted next. The polymerizations were carried out under the same optimal conditions found in previous assignment and the results are bundled in T able 2 3. Besides some common transesterification agents and widely used catalysts we focused on cheap, non toxic chemicals. The latter ones show ed the best results and produced high molecular weight polymers i n decent yields. We especially noticed zinc and sodium acetate and the potassium carbonates and therefore further research will be limited to those catalysts. The thermal characteristics of all these polymers were studied using thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC) under a nitrogen atmosphere.

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43 Table 2 3 CAMP, polymer synthesis catalysts Entry C atalyst Yield (%) M w PDI T g ( C) T peak ( C) 2. 9 Zn(OAc) 2 76 74900 1.63 60.41 377 2.15 No cat. 2.16 pTSA 2.17 KHCO 3 74 46000 1.74 59.70 368 2.18 K 2 CO 3 77 579 00 1.94 58.23 360 2.19 Co(OAc) 2 2.20 Mn(OAc) 2 2.21 Ti[OCH(CH 3 ) 2 ] 4 56 94 00 1.27 55.98 370 2.22 ZnO 2.23 Sn( Oct ) 2 63 219 00 1.73 56.99 353 2.24 SnCl 2 66 211 00 1.53 58.35 366 2.25 Cp 2 ZrCl 2 78 136 0 0 1.58 56.50 371 2.26 ZrCl4 35 620 0 1.23 52.45 347 2.27 Mn(acac ) 2 54 a ) a ) 57.36 343 2.28 NaOAc 70 659 00 1.70 59.67 380 2.29 V 2 O 5 2.30 Li 2 CO 3 20 21 00 1.34 b ) 2.31 ZnCl 2 78 380 00 1.71 59.73 381 2.32 NaHCO 3 2.33 Na 2 CO 3 2.34 CaCO 3 a) not soluble in THF b) too waxy for DSC Polymer chains generally pack together in a non uniform fashion, with ordered or crystalline like regions mixed together with disordered or amorphous domains (Figure 2 12A). The thermal properties of polyme rs are directly related to this macromolecular structure; the glass transition is associated with the amorphous part of the chain while the melting point correspon ds to the crystalline part of the polymer 5 1 Thermal analysis of the polymers did not show a pronounced glass transition temperature ( T g ) and s ince T g is correlated to the disordered, amorphous phase of the polymer, we might draw the conclusion that our polymers have a large amount of highly structured chains and therefore semi crystalline with a high crystalline fraction

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44 Figure 2 12. Polymer morphology A) Chain spatial arrangement 5 2 B) internal bonding for polycarbonate As poly(decylene carbonate) is comp osed of a n aliphatic chain with carbona te groups every ten carbons, it s flexibility and ability f or inter chain bonding because of the polar carbonate groups (Figure 2 12B ) together with the absence of disturbing branches make it indeed easier to slip into this structurally oriented matrix and form a crystalline material. The higher the molecular weight, or in other words the longer the chains, the less disruption in the structure and therefore we can see a slightly higher T m with increasing M w (Table 2 3.). Increased crystallinity is also associated with an increase in rigidity, tens ile strength and opacity. A plastic film, obtained by dissolving the polymer in chloroform followed by evaporation of the solvent (i.e. solution casting) shows this lack of flexibility and opacity (Figure 2 13). Figure 2 13. Poly(decylene carbona te) film A) B)

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45 2.3.1.3 Proposed mechanism In the CAMP reaction over K 2 CO 3 the carbonate group was coordinated with the catalyst to increase the positive character of its carbonyl group. The free electron pair on the oxygen of the alk yl group of another monomer then attack s the carbonyl carbon to fo r m the tetrahedral intermediate (Figure 2 14.). The thereafter released methoxy ion will re attack the carbonyl carbon to form DMC and the growing polycarbonate. Figure 2 14. P ossible mechanism for CAMP rea ction If the first step attack on the carbon yl carbon is done by the oxygen on the methyl group, the net result will give us the starting material again. However, since the R alkyl has a stronger electron donating effect than the methyl group, it i s believ ed that this oxygen w ill execute the attack because of its g r eater nucleophilic character. 2.3.1. 4 Conclusions An easy and green 2 step synthesis for aliphatic polycarbonates was developed and the reaction conditions were optimized to give high molecular w eight polymers. Poly (decylene carbonate)s were synthesized and their thermal characteristics were studied.

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46 2.3.2 Direct Synthesis To become a commercial ly available plastic, having all the necessary characteristics is critical ; having a cost effective m ass production, however, is at least as important. That i s why the industry is looking for simple and cheap production processes ; a one step synthesis w ith high yield outcome, using cheap catalysts would be perfect e specially when no solvents are needed a nd the formed byproducts could be recovered and reused in the process. This study aims to develop such a commercially applicable procedure for aliphatic polycarbonates. Figure 2 15. One pot synthesis for polycarbonates 2.3.2.1 Polymer synthesis A series of polymers w as synthesized from 1,10 decanediol and DMC in a one pot synthesis, applying reduced pressure to remove methanol and DMC as byproducts (Table 2 4.). Decent molecular weight materials were obtained in fairly good yields (70 80%). Afte r the melt polymerization, the polymers were dissolved in chloroform precipitated out in methanol and dried under reduced pressure.

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47 Table 2 4 Direct synthesis reaction conditions Entry N 2 Method N 2 Vacuum Yield (%) M w PDI Temp. ( C) time (h) Te mp. ( C) time (h) Temp. ( C) time (h) 2.35 85 12 1 200 6 200 2 57 258 00 2.12 2.36 85 12 1 200 12 200 2 59 21500 2.03 2.37 85 12 1 200 24 200 2 79 30100 2.08 2.38 85 24 1 200 6 200 2 77 401 00 2.07 2.39 85 24 1 200 12 200 2 63 268 00 2.07 2.40 85 24 1 200 24 200 2 65 151 00 1.86 2.41 85 12 2 200 6 200 2 62 396 00 2.45 2.42 85 12 2 200 12 200 2 81 560 00 1.80 2.43 85 12 2 200 24 200 2 75 467 00 2.26 2.44 85 24 2 200 6 200 2 79 90200 2.00 2.45 85 24 2 200 12 200 2 73 21100 1.88 2.46 88 24 2 200 24 200 2 78 41100 2.35 2.47 a ) 85 24 2 200 6 200 2 77 24000 1.59 2.48 b ) 85 24 2 200 6 200 2 68 52700 1.75 2.49 c ) 85 24 2 200 6 200 2 68 539 00 1.88 a ) ,b ) and c ) were carried out using Na 2 CO 3 Zn(OAc) 2 and Na(OAc) respectively. Method 1 removed the excess of DMC by increasing the heat to 125 C for 1h, method 2 skipped this step. The first phase in this one pot synthesis is the methoxy carbonylation of the diol with the removal of methanol. Since DMC has a boiling point of 90 C and methanol boils at 65 C the reaction was carried out in an excess (10:1 ratio) of DMC at 85 C under a N 2 atmosphere. In an attempt to get this conversion close to complete, the reaction was carried out for different durations Afterwards, the excess DMC was removed and the rea ction continued into phase 2: the melt polymerization. With a set temperature (at 200 C) and changing duration (6, 12 or 24 hours) of the polymerization reaction, poly(decylene carbonate)s were obtained in good yields with high molecular weights.

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48 Both m ethods show ed the best results when the first reaction step was carried out for 24 h, followed by 6 h stirring at 200 C under a n N 2 atmosphere and 2h under a vacuum atmosphere. This suggests that after a certain time at higher temperatures, the carbonate monomers and/or oligomers start to decompose, resulting in lower yields as well as lower M w Different catalysts were used under the same reaction conditions. Although Zn(OAc) 2 showed the best performance in the previous study its ability to produce the d ecylene bis carbonate was limited which lowered the overall performance for this one pot synthesis. K 2 CO 3 had a decent conversion rate for the first step and good yield for the polymerization, making it the preferred choice for this direct synthesis. Remar kably Na 2 CO 3 that failed to produce any polymers in the previous study, performed quite well this time ; this might be explained by a possible slightly different mechanism. 2.3.2.2 Proposed mechanism Because of the incomplete reaction between DMC and the diols there will be different end groups reacting with each other, which might explain the observed behavior of the catalysts. Figure 2 16. Proposed mechanism for alcoholic end chains 53 While the methyl carbonate chain ends react with each other via the previously described CAMP reaction, the unreacted alcohol ends will participate in a condensation reaction wit h the methyl carbonate ends and form methanol as a bypro duct 5 3

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49 The free electron pair on the aliphatic alcohol group will attack the carbony l carbon to form the tetrahedral intermediate (Figure 2 16.). A proton transfer from OH to the tetrahed ral intermediate on its methoxy oxygen forms the methanol and will give the oligo carbonate s 2.3 .2. 3 Effect of methylene spacers We studied how the ch ain length might have an influence on the thermal properties of the polycarbonates. When c hanging the number of carbons between the two carbonate groups within the polymer chain, i.e. decreasing the sp 3 carbon spacers should have an effect on the flexibil ity of the polymer chain. This implies several changes in the chain chain interactions and crystallization of the polymer and by consequence its thermal behavior as well. A series of polymers has been synthesized with diols ranging from pentane diol to dodecane diol using the same direct method as described above The obtained polymers were subjected to thermal analysis to compare their characteristics. Table 2 5 Direct synthesis effect of methylene spacers Entry x M w PDI T g ( C) T m ( C) 2.50 5 13900 1.48 48.49 40.06 2.51 6 26000 1.82 4.01 53.97 2.52 7 15400 2.27 45.44 2.53 8 13300 2.41 55.11 2.54 9 26 500 1.98 53.20 2. 44 10 90200 2.00 58.64 2.5 5 12 554 00 1. 82 68.35

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50 At first, it seems like there is only little or no direct correlation between the increasing temperatures and the growing chain lengths. When having a closer look and comparing the polymers with an odd or even number of carbon spacers to each other, we did notice that there is a clear relationship between chain length and m elting temperature (Figure 2 16 ) Figure 2 16 Effect of methylene spacers on T m Because of the different structure of the odd and even membered chains, the latter ones are able to pack together i n a uniform fashion more compactly than the odd membered ones 5 4 This denser compaction presumably has less free space and therefore results in higher melting temperatures In general, the melting points will increase as the strengths of the intermolecular forces increase 55 For this reason we see the increasing melting temperature with increasing chain lengths. Number of methylene spacers Tm ( C)

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51 2.3.2.4 Conclusions Because DMC has a boiling point around 90 C, all previous studies had the need for complicated equipment a nd set ups 36 39 We developed an easy, straight forward method that does no t require any of those fancy apparatus and produced high molecular weight aliphatic polycarbonates. The thermal properties of these polymers were modified by changing the number of carbon spacers in the backbone. 2.4 Synthesis of Copolymers Another way of controlling the thermal and mechanical behavior of materials consists of incorporation of ri gid structures in the backbone making copolymers of the diol and an aromatic repeat unit. The incorporatio n of such an aromatic unit into the aliphatic polycarbonate chain will increase the intermolecular forces giving the chain some stiffness and rigidity and changing its thermal / mechanical characteristics. 2.4 .1 Monomer synthesis Resorcinol or benzene 1,3 diol, is an aromatic diol that could be obtained from the distillation of Brazil wood extract 5 6 Frost et al who recently developed a green synthesis for catechol and hydroquinone from glucose 5 7 is currently focused on making resorcinol via a similar bi osynthesis. Figure 2 17. S ynthesis of resorcinol bis(2 hydroxyethyl) ether Because of the bulkiness and the fact that p henol is not a good nucleophile because its lone pairs are in conjugation with the benzene ring, t he resorcinol bis(2 hydroxyethyl) ether, compound 2.5 6 was synthesized to make a more suitable monomer for our reaction.

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52 Resorcinol was melted together with ethylene carbonate and a catalytic amount of tri phenyl phosphate and stirred overnight, the reaction was quenched with methanol and after rec rystallization in methanol the product was obtained as white crystals with a 78% yield. Compound 2.5 6 was then converted into the (bis) carbonate monomer 2.57 via the methoxy carbonylation reaction with DMC and catalytic amounts of Na 2 CO 3 Figure 2 18. S ynthesis of (1,3 phenyle nebis(oxy))bis(ethane 2,1 diyl) dimethyl dicarbonate 2.4 .2 Polymer synthesi s A set of polymers is synthesized by the CAMP reaction with different feed ratios of the monomers, as displayed in Table 2 6. Table 2 6 Copo lymers of compounds 2. 22 and 2. 57 Entry 2.2 (%) 2.5 7 (%) M w PDI T g ( C) T m ( C) 2.9 100 0 749 00 1. 63 60.41 2. 58 90 10 598 00 1.56 47.80 2. 59 80 20 36800 1.81 37.76 2.6 0 70 30 28300 1.93 26.99 59.74 2.6 1 60 40 30400 1.85 17.31 85.28 2.6 2 50 50 33 900 1.90 7.98 95.65 2.6 3 40 60 28800 1.71 2.10 2.6 4 30 70 19700 1.80 11.45 2.6 5 20 80 29900 2.26 17.26 2.66 10 90 10900 1.80 26.13 2.6 7 0 100 146 00 1.63 39.02

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53 Glass transition is directly correlated to the amorphous phase of the poly mer. Since this phase is not ordered, the space filling and conformational freedom is a determini ng factor for the characteristics of the material The more available free space the less heat it takes for the chains to break out of the rigid glassy state and into the soft rubbery state in other words a lower T g The flexible aliphatic backbone of our polyme r creates a large mobility which will result in lots of free space and therefore we were not able to determine a T g for these polymers When increasin g the feed ratio of our rigid co monomer enough to create rigid sequences, the chain loses some of its flexibility and a T g is noticed, further incorporation results in a growing rigid block that gradually immobilizes the chain movement, creating an increa se in T g In contradiction to the T g The melting point is connected with the crystalline phase of the polymer. Melting could be explained as the temperature at which crystalline domains lose their structure. So, a t first, the incorporation of the bulky monomer disrupts the chain packaging of our polymer The crystalline phase is no longer closely packed together which results in lower T m Increasing the feed of compound 2.57 will cause an increase in T m and a lthough the chain packaging becomes loose r wh en increasing the feed of compound 2.57 its rigid structure will cause the backbone to have strong er int e r chain forces ( e.g. stacking ) requiring more energy to break and therefore increasing the T m However, in the end the chain packing is completely disrupted as the polymers do es n o t show any melting points.

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54 2.4.3 Incorporation study via NMR To check the incorporation of compound 2.57 it i s most convenient to compare the NMR spectra of the monomers with that of the copolymer. Compound 2.2 has spec ific peaks in the 1.0 2.0 ppm region that match the 16 aliphatic CH 2 hydrogens in its backbone, where compound 2.57 show s peaks between 6.5 7.5 ppm corresponding to the 4 hydrogens in the aromatic part of the repeat unit. Copolymers should show peak s in both typical areas and by measuring the intensity of these peaks and calculate the ratio, we get the incorporation. Figure 2 19. NMR spectra of polymers 2.9 2.61 and 2.67 for incorporation calculation Figure 2 19. shows the spectra of the homo polymers and the 60/40 copolymer 2.61 Integration of the peaks for the copolymer spectra gives 41 aromatic protons and 260 aliphatic ones. Calculations lead to a 62.3/37.7 polymer composition, which is closely accordant to the initial 60/40 feed ratio. All the other compositions had a similar relation between the feed ratio and the actual incorporation. Polymer 2.9 Polymer 2.61 Polymer 2.67

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55 2.4.4 Conclusions This study showed that including a rigid structure in the backbone of the polymer change s its morphology and as a consequence th e thermal (and mechanical) properties are modified as well. When increasing the fraction of the rigid co monomer, the crystallinity decreases and ultimately the copolymer acts like an amorphous material. NMR studies demonstrated that the incorporation fra ction of monomer is nearly the same as the feed fraction 2.5 New Ideas Our experiments showed that the thermal behavior of the synthesized aliphatic polymers could be changed by incorporation of rigid structures in the backbone of the polymer. It would be interesting to see what the effect on those properties would be when using different bio renewable diols: 2.5.1. Coupling o f Two Vanillin Alcohols With 1,2 dibromo ethane: The two aromatic structures, together with the methoxy groups will provide rigidi ty to the chain. The methylene spacers however will provide some flexibility to the backbone. Scheme 2.1 Vanillin coupling 1 With isosorbide : th is compound might be a green alternative for BPA, i t bring s the same inflexibility and lack of mobility to the polymer but without the toxicity and harmful effects.

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56 Scheme 2.2. Vanillin coupling 2 2.5.2. Sugar Derivatives From D glucono 1,5 lactone Scheme 2.3. Diol from D Glucono 1,5 lactone From erythritol Scheme 2.4. Diol from erythriol L Tartaric acid Scheme 2. 5 Diol from L Tartaric acid 2.6 Final Conclusions Using cheap, abundant and relatively harmless catalysts like Zn(OAc) 2 and K 2 CO 3 a series of high molecular weight ( M w 70 000 Da) a liphatic polycarbonates were produced, first via a 2 s tep and later via a direct carbonate metathesi s polymerization of DMC and aliphatic diol s in decent yields ( 70%) Depending on the number of methylene groups of the repeat unit, the polymers showed diverse behavior in terms of melting, glass transitio n and thermal decomposition. Copolymers were made to introduce some rigidity to the backbone structure of the material and adjust its thermal properties. W e were able to increase both T g and T m by increasing the percentage of the rigid structure in our co polymer chains.

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57 CHAPTER 3 EXPERIMENTAL PROCEDURES 3.1 Molecular Characterizations Proton nuclear magnetic resonance ( 1 H NMR) spectra were recorded using a Varian Mercury 300 MHz spectrometer. Chemical shifts are reported in parts per million (ppm) downfiel d relati ve to tetramethylsilane (TMS, 0. 0 ppm) or residual proton in the specified solvent. Coupling constants ( J ) are reported in Hertz (Hz). Multiplicities are reported using the following abbreviations: s, singlet; d, doublet; t, triplet; q, quartet; qu in, quintuplet; m, multiplet; br, broad. Differential scanning chromatographs were obtained with a DSC Q1000 from TA instruments. About 3 5 mg of each sample were massed and added to a sealed pan that went through a heat/cool/heat /cool cycle at 10 C/min. Reported data are from the second full cycle. The temperature range depends on the experiment, but was limited to 300 C by the instrument. Thermogravimetric analyses were measured under a nitrogen atmosphere with a TGA Q5000 from TA Instruments. About 3 5 mg of each sample was heated at 2 0 C/min from 25 500 C. About 10 mg of each sample was dissolved in 10 m L THF and the molecular weight data w ere obtained by Gel Permeation Chromatography with polystyrene standards on a Waters Alliance GPCV 2000. 3.2 Polymerizations Procedures Two step s ynthese s. All the polymerizations were carried out in a close d flask connected to the Schlenk line with a b ump trap The fla s k loaded with monomer and the catalyst was purged with nitrogen and evacuated 3 times befor e melting the solid monomer by heating in a silicon e oil bath. Agitation was effected with a magnetic stir

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58 bar. The melt was kept under nitrogen to allow the formation of oligomers and limit the sublimation of the monomer. Dynamic vacuum was then applied o n the molten polymer to remove the produced dimethyl carbonate At the end of the polymerization the product was cooled under nitrogen leaving a solid that was dissolved in chloroform and then crashed in cold methanol. The polymer was obtained by filtratio n and dried on the Schlenk line overnight. Direct syntheses. For the one pot synthesis, the polymerization s w ere carried out in a closed flask connected to the Schlenk line with a bump trap. The flask was then loaded with the diol, an excess of dimethyl ca rbonate and catalyst. The mixture was heated to 85 C w ith magnetic stirring under a nitrogen atmosphere. Afterwards the temperature wa s raised to melt the monomers and remove the excess DMC The melt was kept under nitrogen to allow the formation of oligo mers and limit the sublimation of the monomer. Dynamic vacuum was then applied to remove the formed byproducts. When stirring stopped, the product was recovered with the same techniques used in the two step synthesis. 3.3 Synthesis Procedures Scheme 3 1. 2.1 decane 1,10 diyl dimethyl dicarbonate To a mixture of 5.0 2 g of 1,10 de canediol (30 mmol) and 0.1 7 g ( 1.4 mmol) of 4 d imethylaminopyridine in 200 mL dry dichloromethane was added 9.76 mL of pyridine (130 mmol) The flask was cooled down to 0 C i n an ice bath and 9.26 mL of methyl chloroformate (120 mmol) was added drop wise to the solution over a time span of 30 minutes After one additional hour of stirring, t he ice bath was removed and the reaction

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59 was continued overnight at room temperature un der a nitrogen atmosphere. Saturated CuSO 4 solution was poured into t h e reaction mixture and the formed copper salts were filtered off. The filtrate was extracted with di e thyl ether (3 x 20 mL) and the organic layer was concentrated in vacuo The remaining solids were recrystallized in methanol to give white needle like crystals. Filtration gave 6.6 7 g of 2.1 in 77% yield. 1 H NMR (CDCl3, 300 MHz): (ppm) = 4.13 (t, J = 6.6 Hz, 4H CH 2 O ), 3.78 (s, 6H OCO 2 CH 3 ), 1.55 1.80 (m, 4 H C H 2 CH 2 O ), 1.16 1.46 (m, 12 H CH 2 ) 13 (ppm) = 156.0, 68.3, 54.7, 29.5, 29.3, 28.8, 25.8 Scheme 3.2 2 2 decane 1,10 diyl dimethyl dicar bonate 8.7 0 g of 1,10 decanediol (0.05 mol) and 45. 0 g of dimethyl carbonate (0.50 mol) were added to a 250 mL RB flask. 0.1 6 g of sodium carbonate (1.5 mmol) was added and the mixture was heated at reflux wi th the removal of methanol (4 mL ). The excess of dimethyl carbonate was removed under reduced pressure and the resulting product was recrystallized in methanol to give 11. 7 g 2.2 as white crystals in 80% yield. 1 H NMR (CDCl3, 300 MHz): (ppm) = 4.13 (t, J = 6.7 Hz, 4H CH 2 O ), 3.78 (s, 6H OCO 2 CH 3 ), 1.58 1.75 (m, 4H C H 2 CH 2 O ), 1.18 1.43 (m, 12H CH 2 ) 13 (ppm) = 156.0, 68.3, 54.7, 29.5, 29.3, 28.8, 25.8 Scheme 3.3 2.5 2.34 poly(decylene carbonate)

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60 2. 9 poly(decylene carbonate) 200 C / 2h general procedure 2.0 0 g (6.9 mmol) of 2.1 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were me lted under nitrogen for 2h at 200 C and v acuum was applied for 1.5h at 200 C. The reaction was allowed to c ool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 1.1 2 g of white product was obtained by filtration in 78 % yield. 1 H NMR (CDCl 3 300 MHz): (ppm) = 4.12 (t, J = 6.8 Hz, 4H, CH 2 O ), 1.66 (quin, J=6.9 Hz, 4H, C H 2 CH 2 O ), 1.22 1.43 (m, 12H, CH 2 ) 13 C NMR (CDCl 3 (ppm) = 155.6, 68.2, 29.6, 29.4, 28.9, 25.9 2. 5 poly(decylene carbonate) 1 75 C / 2h 2.0 0 g (6.9 mmol) of 2.1 and 0 .07 5 g (0.34 mmol) of zinc acetate (5 mol%) were mel ted under nitrogen for 2h at 175 C and vacuum was applied for 1.5h at 175 C The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 0.9 9 g of white product was obtained by filtration in 6 9 % yield. 2. 6 poly(decylene carbonate) 1 2 5 C / 12h 2.0 0 g (6.9 mmol) of 2.1 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were melted under nitrogen for 12h at 12 5 C a nd vacuum was applied for 1.5h a t 175 C The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 1.1 0 g of white product was obtained by filtration in 77 % yield.

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61 2. 7 poly(decylene carbonate) 150 C / 12h 2.0 0 g (6.9 mm ol) of 2.1 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were mel ted under nitrogen for 12h at 150 C and vacuum was applied for 1.5h at 175 C The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated i n methanol. 1.0 9 g of white product was obtained by filtration in 76 % yield. 2. 8 poly(decylene carbonate) 175 C / 12h 2.0 0 g (6.9 mmol) of 2.1 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were me lted under nitrogen for 12h at 175 C and v acuum was a pplied for 1.5h at 175 C The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 1.0 3 g of white product was obtained by filtration in 72 % yield. 2. 10 poly(decylene carbonate) 200 C / 1h 2.0 0 g (6.9 mmol) of 2.1 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were me lted under nitrogen for 1h at 200 C and v acuum was applied for 1.5h at 200 C The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 0.9 2 g of white product was obtained by filtration in 64 % yield. 2. 11 poly(decylene carbonate) 230 C / 2h 2.0 0 g (6.9 mmol) of 2.1 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were me lted under nitrogen for 2h at 200 C an d v acuum was applied for 1.5h at 230 C The reaction was allowed to cool down and the obtained solid was dissolved in chloroform

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62 and precipitated in methanol. 1.0 1 g of white product was obtained by filtration in 70 % yield. 2. 12 poly(decylene carbonate) 1 mol% Zn(OAc) 2 2.0 0 g (6.9 mmol) of 2.1 and 0.01 5 g (0.068 mmol) of zinc acetate (1 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1. 5h at 200 C The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 0.9 9 g of white product was obtained by filtration in 72% yield. 2.1 3 poly(decylene carbonate) 3 mol% Zn(OAc) 2 2.0 0 g (6.9 mmol) of 2.1 and 0.04 5 g (0.20 mmol) of zinc acetate (3 mol%) were melted under nitroge n for 2h at 200 C and vacuum was applied for 1.5h at 200 C The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 0.8 2 g of white product was obtained by filtration in 58% yield. 2.1 4 poly (decylene carbonate) 10 mol% Zn(OAc) 2 2.0 0 g (6.9 mmol) of 2.1 and 0.1 5 0 g (0.67 mmol) of zinc acetate (10 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtaine d solid was dissolved in chloroform and precipitated in methanol. 0.9 4 g of white p roduct was obtai ned by filtration in 62 % yield. 2.17 poly(decylene carbonate) KHCO 3 2.0 0 g (6.9 mmol) of 2.1 and 0.03 4 g (0.34 mmol) of potassium bicarbonate (5 mol%) wer e melted under nitrogen for 2h at 200 C and vacuum was applied for 1. 5h at

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63 200 C The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 1.0 4 g of white product was obtained by filtration in 74% yield. 2.18 poly(decylene carbonate) K 2 CO 3 2.0 0 g (6.9 mmol) of 2.1 and 0.04 7 g (0.34 mmol) of potassium carbonate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 1.0 9 g of white product was obtained by filtration in 77% yield. 2.21 poly(decylene carbonate) Ti[OCH(CH 3 ) 2 ] 4 2.0 0 g (6.9 mmol) of 2.1 and 0. 0 9 6 g (0.34 mmol) of titanium isopropoxide (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 0.8 2 g of white product was obtained by filtration in 56% yield. 2.23 poly(decylene carbonate) Sn(Oct) 2 2.0 0 g (6.9 mmol) of 2.1 and 0.13 8 g (0.34 mmol) of tin 2 ethyl hexan oate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The rea ction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 0.9 5 g of white product was obtained by filtration in 63% yield.

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64 2.24 poly(decylene carbonate) SnCl 2 2.0 0 g (6.9 mmol) of 2.1 and 0.0 6 4 g ( 0.34 mmol) of tin(II) chloride (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 0.9 5 g of white product was obtained by filtration in 66% yield. 2.25 poly(decylene carbonate) Cp 2 ZrCl 2 2.0 0 g (6.9 mmol) of 2.1 and 0.0 9 9 g (0.34 mmol) of b is(cyclopentadienyl) zirconium dichloride (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 1. 1 5 g of white product was obtained by filtration in 78 % yield. 2.26 poly(decylene carbonate) ZrCl 4 2 .0 0 g (6.9 mmol) of 2.1 and 0.07 9 g (0.34 mmol) of zi rconium chloride ( 5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform a nd precipitated in methanol. 0.5 1 g of white product was obtained by filtration in 35 % yield. 2.27 poly(decylene carbonate) Mn(acac) 2 2.0 0 g (6.9 mmol) of 2.1 and 0.0 8 6 g (0.34 mmol) of manganese acetylacetonate (5 mol%) were melted under nitrogen for 2 h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved

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65 in chloroform and precipitated in methanol. 0.7 9 g of white product was obtained by filtration in 54 % yield. 2.28 poly(decylen e carbonate) NaOAc 2.0 0 g (6.9 mmol) of 2.1 and 0.0 2 8 g (0.34 mmol) of sodium acetate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C The reaction was allowed to cool down and the obtained solid was dissol ved in chloroform and precipitated in methanol. 0.9 8 g of white product was obtained by filtration in 70 % yield. 2.30 poly(decylene carbonate) Li 2 CO 3 2.0 0 g (6.9 mmol) of 2.1 and 0.02 5 g (0.34 mmol) of lithium carbonate (5 mol%) were melted under nitrog en for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 0.2 8 g of white product was obtained by filtration in 20 % yield. 2.31 poly (decylene carbonate) ZnCl 2 2.0 0 g (6.9 mmol) of 2.1 and 0.0 4 6 g (0.34 mmol) of zinc chloride (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid w as dissolved in chloroform and precipitated in methanol. 1.1 1 g of white product was obtained by filtration in 78% yield. Scheme 3.4 2.34 2.49 poly(decylene carbonate)

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66 2.44 poly(decylene carbonate) 24h/6h general procedure 4.3 5 g (25 mm ol) of 1,1 0 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. Afterwards t he temperature was raised to 200 C and stirred for another 6h under an inert atmospher e Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 3.9 7 g of product in 79% yield 1 H NMR (CDCl 3 300 MHz): (ppm) = 4.04 (t, J = 6.7 Hz, 4H, CH 2 O ), 1.44 1.74 (m, 4H, C H 2 CH 2 O ), 1.03 1.38 (m, 12H, CH 2 ) 13 C NMR (CD Cl 3 75 2.35 poly(decylene carbonate) method 1 12h/6h 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stirred at 85 C und er a nitrogen atmosphere for 12h. The excess of dimethyl carbonate is then boiled off at 125 C for 1h. Afterwards the temperature was raised to 200 C, and stirred for another 6h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic s tirring stopped. Work up gave 2.8 5 g of product in 57% yield 2.36 poly(decylene carbonate) method 1 12h/12h 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stirred at 85 C u nder a nitrogen atmosphere for 12h. The excess of dimethyl carbonate is then boiled off at 125 C for 1h. Afterwards the temperature was raised to 200 C and stirred for another 12h under an inert atmosphere. Vacuum was applied for 1.5h before the magnet ic stirring stopped. Work up gave 2.9 4 g of product in 59% yield

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67 2.37 poly(decylene carbonate) method 1 12h/24h 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stirred at 85 C under a nitrogen atmosphere for 12h. The excess of dimethyl carbonate is then boiled off at 125 C for 1h. Afterwards the temperature was raised to 200 C and stirred for another 24h under an inert atmosphere. Vacuum was applied for 1.5h before the ma gnetic stirring stopped. Work up gave 3.9 6 g of product in 79% yield 2.38 poly(decylene carbonate) method 1 24h/6h 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. The excess of dimethyl carbonate is then boiled off at 125 C for 1h. Afterwards the temperature was raised to 200 C and stirred for another 6h under an inert atmosphere. Vacuum was applied for 1.5h before the m agnetic stirring stopped. Work up gave 3.8 4 g of product in 77% yield 2.39 poly(decylene carbonate) method 1 24h/12h 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stirred a t 85 C under a nitrogen atmosphere for 24h. The excess of dimethyl carbonate is then boiled off at 125 C for 1h. Afterwards the temperature was raised to 200 C and stirred for another 12h under an inert atmosphere. Vacuum was applied for 1.5h before th e magnetic stirring stopped. Work up gave 3.1 4 g of product in 63% yield

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68 2.40 poly(decylene carbonate) method 1 24h/24h 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stir red at 85 C under a nitrogen atmosphere for 24h. The excess of dimethyl carbonate is then boiled off at 125 C for 1h. Afterwards the temperature was raised to 200 C and stirred for another 24h under an inert atmosphere. Vacuum was applied for 1.5h befo re the magnetic stirring stopped. Work up gave 3.2 7 g of product in 65% yield 2.41 poly(decylene carbonate) method 2 12h/6h 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were st irred at 85 C under a nitrogen atmosphere for 12h. Afterwards the temperature was raised to 200 C and stirred for another 6h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 3.1 2 g of product in 6 2% yield 2.42 poly(decylene carbonate) method 2 12h/12h 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stirred at 85 C under a nitrogen atmosphere for 12h. Afterwards the t emperature was raised to 200 C and stirred for another 12h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 4.0 4 g of product in 81 % yield 2.43 poly(decylene carbonate) method 2 12h/24h 4.3 5 g (25 mmol) of 1,10 d ecanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassi um carbonate were stirred at 85 C under a nitrogen atmosphere for 12h. Afterwards the temperature was raised to 200 C and stirred for

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69 another 24h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 3.7 6 g of product in 75 % yield 2.45 poly(decylene carbonate) method 2 24 h/ 12 h 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbona te and 0.17 5 g (5 mol%) of potassi um carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. Afterwards the temperature was raised to 200 C and stirred for another 12 h under an inert atmosphere. Vacuum was applied for 1.5h before the magneti c stirring stopped. Work up gave 3.6 3 g of product in 73 % yield 2.46 poly(decylene carbonate) method 2 24 h/ 24 h 4.3 5 g (25 mmol) of 1,10 decanediol, 25 mL (300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. Afterwards the temperature was raised to 200 C and stirred for another 24 h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 3.8 8 g of product in 78 % yield 2. 47 poly(decylene carbonate) Na 2 CO 3 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.13 2 g (5 mol%) of sodium carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. Afterwards the temperature was raised to 20 0 C and stirred for another 6h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 3.8 5 g of product in 77 % yield 2.48 poly(decylene carbonate) Zn(OAc) 2 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.27 5 g (5 mol%) of potassiu m carbonate were stirred at 85 C under a nitrogen

PAGE 70

70 atmosphere for 24h. Afterwards the temperature was raised to 200 C and stirred for another 6h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 3.3 8 g of product in 68 % yield 2.49 poly(decylene carbonate) NaOAc 4.3 5 g (25 mm ol) of 1,10 decanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.10 3 g (5 mol%) of potassi um carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. Afterwards the temperature was raised to 200 C and stirred for another 6h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 3.4 2 g of product in 68 % yield Scheme 3.5 2.50 poly(pentylene carbonate) 2.6 0 g (25 mm ol) of 1,5 pent anediol, 25 mL (300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassiu m carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. Afterwards the temp erature was raised to 200 C and stirred for another 6h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 1.8 6 g of product in 57 % yield. 1 H NMR (CDC l 3 300 MHz ) : (ppm) = 3.99 4.12 (t J = 6.45 Hz, 4 H CH 2 O ), 1.58 1.72 (m, 4 H C H 2 CH 2 O ), 1.32 1.47 (m, 2 H CH 2 ) 13 C NMR (CDCl 3 (ppm) = 153.4, 68.0 28.6, 22.2 Scheme 3.6 2.5 1 poly(hex ylene carbonate)

PAGE 71

71 2.95 g (25 mm ol) of 1,6 hex anediol, 25 mL (300 mmol) of dimethyl carbonat e and 0.17 5 g (5 mol%) of potassiu m carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. Afterwards the temperature was raised to 200 C and stirred for another 6h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 2.6 3 g of product in 73% yield. 1 H NMR (CDCl 3 300 MHz): 4.06 (t, J = 6.7 Hz, 4H, CH 2 O ), 1.62 (t, J = 6.7 Hz, 4H, C H 2 CH 2 O ) 1.27 1.44 (m, 4 H CH 2 ) 13 C NMR (CDCl 3 Scheme 3.7 2.5 2 poly(hep tylene carbonate) 3.3 1 g (25 mm ol) of 1,7 hept anediol, 25 mL (300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassi um carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. Afterwards the temperature was raised to 200 C and stirred for another 6h under an inert atmosphere. Vacuum was applie d for 1.5h before the magnetic stirring stopped. Work up gave 3.0 0 g of product in 7 6 % yield. 1 H NMR (CDCl 3 300 MHz): J = 6.7 Hz, 4H, CH 2 O ), 1.58 1.73 (m, 4H, C H 2 CH 2 O ), 1.28 1.45 (m, 6 H, CH 2 ) 13 C NMR (CDCl 3 Scheme 3.8 2.5 3 poly( octyl ene carbonate) 3.6 6 g (25 mmol) of 1,8 octanediol, 25 mL ( 300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassiu m carbonate were stirred at 85 C under a nitrogen

PAGE 72

72 atmosphere for 24h. Afterwards the temperature was raised to 200 C and stirred for another 6h under an inert atmosphere. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 2.9 7 g of product in 69% yield. 1 H NMR (CDCl 3 300 MHz): 4.12 (t, J = 6.7 Hz, 4H, CH 2 O ), 1.59 1.75 (m, 4H, C H 2 CH 2 O ), 1.34 (br. s., 8 H, CH 2 ) 13 C NMR (CDCl 3 156.1, 68.2, 29.3, 28.9, 25.8 Scheme 3.9 2.5 4 poly(non ylene carbonate) 4.0 1 g (25 mmol) of 1,9 nonanediol, 25 mL (30 0 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. Afterwards the temperature was raised to 200 C and stirred for another 6h under an inert atmosphere. Vacuum was applied f or 1.5h before the magnetic stirring stopped. Work up gave 3.4 5 g of product in 74% yield. 1 H NMR (CDCl 3 300 MHz): J = 6.8 Hz, 4H, CH 2 O ), 1.64 (quin, J = 6.9 Hz, 4H, C H 2 CH 2 O ), 1.18 1.45 (m, 1 0 H, CH 2 ) 13 C NMR (CDCl 3 155.6, 68.2, 29.5, 29.3, 28.9, 25.9 Scheme 3.10 2.5 5 poly(dodec ylene carbonate) 5.0 6 g (25 mmol) of 1,12 dodecanediol, 25 mL (300 mmol) of dimethyl carbonate and 0.17 5 g (5 mol%) of potassium carbonate were stirred at 85 C under a nitrogen atmosphere for 24h. Afterwards the temperature was raised to 200 C and stirred for

PAGE 73

73 another 6h under an inert atmospher e. Vacuum was applied for 1.5h before the magnetic stirring stopped. Work up gave 4.4 5 g of product in 78% yield. 1 H NMR (CDCl 3 300 MHz): J = 6.8 Hz, 9H), 1.51 1.71 (m, 4H, C H 2 CH 2 O ), 1.09 1.36 (m, 16 H, CH 2 ) 13 154 .9, 68.6, 29.75, 29.71, 29.5, 28.9, 25.9 Scheme 3.11 2.5 6 resorcinol bis(2 hydroxyethyl) ether 3 3 g ( 0.30 mol) of resor cinol and 5 4 g (0.60 mol) were added in a 500 mL round bottom flask together with 0.4 5 g (1.3 mmol) t riphenyl phosph ine The mixture was heated to 150 C in an inert atmosphere; after the CO 2 production decreased the temperature was raised to 160 C and st irred overnight. The reaction was allowed to cool down to 80 C and 100 mL methanol was added. This mixture was stirred for 12h and filtered to get the product. After recrystallization in toluene 44. 7 g of compound 2.56 was obtained as white crystals in 72 % yield. 1 H NMR (CDCl 3 (ppm) = 7.17 7.23 ( t, J = 8.21 Hz, 1H Ar H ), 6.38 6.62 ( m 3H, Ar H ), 4.38 4.52 ( J = 4.81 Hz, 4H, CH 2 ), 4.10 4.20 ( J = 4.81 Hz, 4H, CH 2 ), 3.81 ( s 2H, O H ) 13 C NMR ( CDCl 3 130. 1, 107 .7, 101 8 66. 4 65 .9 Scheme 3.12 2.5 7 (1,3 phenylenebis(oxy))bis(ethane 2,1 diyl)dimethyl dicarbonate To a mixture of 16.0 5 g (80 mmol) g of 2.5 6 and 0. 5 g (4.1 mmol) of 4 d imethylaminopyridine in 200 mL dry dichloromethane was added 29.25 mL of pyrid ine

PAGE 74

74 (390 mmol) The flask was cooled down to 0 C in an ice bath and 27.75 mL of methyl chloroformate (360 mmol) was added drop wise to the solution over a time span of 30 minutes. After one additional hour of stirring, the ice bath was removed and the re action was continued overnight at room temperature under a nitrogen atmosphere. Saturated CuSO 4 solution was poured into the reaction mixture and the formed copper salts were filtered off. The filtrate was extracted with diethyl ether (3 x 20 mL) and the o rganic layer was concentrated in vacuo. The remaining solids were recrystallized in methanol to give white needle like crystals. Filtration gave 18. 1 g of 2. 57 in 72% yield. 1 H NMR (CDCl 3 300 MHz), (ppm) = 7.09 7.14 ( t, J = 8.21 Hz, 1 H Ar H ), 6.35 6.52 (m, 3H, Ar H ), 4.33 4.49 (t J = 4.81 Hz, 4H, CH 2 ), 4.04 4.17 ( t, J = 4.53 Hz 4 H, CH 2 ), 3.74 ( s, 6 H, OCH 3 ) 13 C NMR (CDCl 3 65 .9, 55.1 Scheme 3.13 2.5 8 2.65 copoly[decylene resorcinol bis(2 hydroxyethyl) ether carbonate] 1 H NMR (CDCl 3 7.12 7.23 (t J = 8.8 Hz 1H Ar H ), 6.43 6.58 (m, 3H, Ar H ), 4.47 ( t J = 4.2 Hz 4H, CH 2 ) 4.03 4.22 (m, 8H ), 1.66 (quin, J = 6.9 Hz, 4H, C H 2 CH 2 O ), 1.22 1.44 (m, 16H C H 2 ) 13 68.6, 66.5, 65.9, 29.6, 29.3, 25.9

PAGE 75

75 2.58 copoly[decylene resorcinol bis(2 hydroxyethyl) ether carbonate] 90 10 1.8 0 g (6. 2 mmol) of 2.1 0.2 2 g (0.7 mmol) of 2.57 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 1.0 8 g of white product was obtained by filtration in 76 % yield. 2.59 copoly[decylene resorcinol bis(2 hydroxyethyl) ether carbonate] 80 20 1.6 0 g (5.5 mmol) of 2.1 0.4 4 g (1.4 mmol) of 2.57 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 1.0 2 g of white product was obtained by filtration in 77 % yield. 2.60 copoly[decylene resorcinol bis(2 hydroxyethyl) ether carbonate] 70 30 1.4 0 g (4.8 mmol) of 2.1 0.6 5 g (2.1 mmol) of 2.57 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were melted unde r nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 0.9 9 g of white product was obtained by filtration in 68 % yield. 2 .61 copoly[decylene resorcinol bis(2 hydroxyethyl) ether carbonate] 60 40 1.2 0 g (4.2 mmol) of 2.1 0.8 6 g (2.7 mmol) of 2.57 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained

PAGE 76

76 solid was dissolved in chloroform and precipitated in methanol. 1.0 1 g of white product was obtained by filtration in 69 % yield. 2.62 copoly[decylene resorcinol bis(2 hydroxyethyl) ether ca rbonate] 50 50 1.0 0 g (3.5 mmol) of 2.1 1.0 8 g (3.5 mmol) of 2.57 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtaine d solid was dissolved in chloroform and precipitated in methanol. 1.0 4 g of white product was obtained by filtration in 70 % yield. 2.63 copoly[decylene resorcinol bis(2 hydroxyethyl) ether carbonate] 40 60 0.8 0 g (2.8 mmol) of 2.1 1.3 1 g (4.2 mmol) of 2.57 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methan ol. 0.9 6 g of white product was obtained by filtration in 64 % yield. 2.64 copoly[decylene resorcinol bis(2 hydroxyethyl) ether carbonate] 30 70 0.6 0 g (2.1 mmol) of 2.1 1.5 2 g (4.9 mmol) of 2.57 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were mel ted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 1.0 2 g of white product was obtained by filtration in 67 % yield. 2.65 copoly[decylene resorcinol bis(2 hydroxyethyl) ether carbonate] 20 80 0.4 0 g (1.4 mmol) of 2.1 1.7 4 g (5.6 mmol) of 2.57 and 0.07 5 g (0.34 mmol) of zinc acetate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was

PAGE 77

77 applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 0.9 7 g of white product was obtained by filtration in 63 % yield. 2.66 copoly[decylene resorcinol bis(2 hydroxyethyl) e ther carbonate] 10 90 0.20 g (0.7 mmol) of 2.1 1.9 5 g (6.3 mmol) of 2.57 and 0.075 g (0.34 mmol) of zinc acetate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and th e obtained solid was dissolved in chloroform and precipitated in methanol. 1.01 g of white product was obtained by filtration in 65 % yield. Scheme 3.14 2.67 poly( resorcinol bis(2 hydroxyethyl) ether carbonate ) 2 .31 g (0.7 mmol) of 2.57 and 0.075 g (0.3 4 mmol) of zinc acetate (5 mol%) were melted under nitrogen for 2h at 200 C and vacuum was applied for 1.5h at 200 C. The reaction was allowed to cool down and the obtained solid was dissolved in chloroform and precipitated in methanol. 1.07 g of white p roduct was obtained by filtration in 6 4 % yield. 1 H NMR (CDCl 3 300 MHz), J = 8.3 Hz, 1H Ar H ), 6.48 (td, J = 7.7, 2.2 Hz, 3H, Ar H ), 4.39 4.65 (m, 4H, CH 2 ), 4.09 4.23 (m, 4 H, CH 2 ) 13 C NMR (CDCl 3 159.7, 155.1, 130.2, 108.0, 101.9, 66.5, 65.8 Scheme 3.15 2.68 ((ethane 1,2 diylbis (oxy))bis(3 methoxy 4,1 phenylene))dimethanol

PAGE 78

78 24.6 g (0.16 mol) vanill ol, 7 mL (0.08 mol) 1,2 dibromoethane and 13.6 mL (0.16 mol) of 12N NaOH solution were added to 300 mL ethanol in a 1 L round bottom flask. The mixture was refluxed under nitrogen for 48 hours. Ethanol was removed using reduced pressure and the remaining mixture was poured into a mixture of ether and water (50/50). After 1 h stirring, the insoluble product was filtered off, washed with ether and dried, giving 10.73 g product as a beige po wder ( 20% yield) 1 H NMR (CDCl 3 6.90 7.03 (m, 2 H Ar H), 6.76 6.87 (m, 4 H Ar H ), 5.07 (t, J = 5.7 Hz, 4H O CH 2 Ar), 4.42 (d, J = 5.9 Hz, 2 H O CH 2 ), 4.24 (s, 2 H O CH 2 ), 3.75 (s, 6 H O CH 3 ), 3.32 (s 2H OH ) 13 C NMR (CDCl 3 67.3, 62.8, 55.4

PAGE 79

79 APPENDIX A PROTON AND CARBON NM R SPECTRA Figure A 1 1 H NMR spectra of compound 2.1 Figure A 2 1 3 C NMR spectra of compound 2.1

PAGE 80

80 Fig ure A 3 1 H NMR spectra of compound 2.2 Figure A 4 1 3 C NMR spectra of compound 2.2

PAGE 81

81 Figure A 5 1 H NMR spectra of compound 2.56 Figure A 6 1 3 C NMR spectra of compound 2.5 6

PAGE 82

82 Figure A 7 1 H NMR spectra of compound 2 .57 Figure A 8 1 3 C NMR spectra of compound 2.57

PAGE 83

83 Figure A 9 1 H NMR spectra of compound 2.68 Figure A 10 1 3 C NMR spectra of compound 2.68

PAGE 84

84 Figure A 11 1 H NMR spectra of polymer 2.5 Figure A 12 1 3 C NMR spectra of polymer 2. 5

PAGE 85

85 Figure A 13 1 H NMR spectra of polymer 2.6 Figure A 14 1 3 C NMR spectra of polymer 2.6

PAGE 86

86 Figure A 15 1 H NMR spectra of polymer 2. 7 Figure A 16 1 3 C NMR spectra of polymer 2. 7

PAGE 87

87 Figure A 1 7 1 H NMR spectra of polymer 2. 8 Figure A 1 8 1 3 C NMR spectra of polymer 2. 8

PAGE 88

88 Figure A 19 1 H NMR spectra of polymer 2.9 Figure A 2 0 1 3 C NMR spectra of polymer 2.9

PAGE 89

89 Fi gure A 21 1 H NMR spectra of polymer 2.10 Figure A 2 2 1 3 C NMR spectra of polymer 2.10

PAGE 90

90 Figure A 23 1 H NMR spectra of polymer 2.11 Figure A 2 4 1 3 C NMR spectra of polymer 2.11

PAGE 91

91 Figure A 25 1 H NMR spectra of polymer 2.12 Figure A 26 1 3 C NMR spectra of polymer 2.12

PAGE 92

92 Figure A 27 1 H NMR spectra of polymer 2.13 Figure A 28 1 3 C NMR spectra of polymer 2.13

PAGE 93

93 Figure A 29 1 H NMR spectra of polymer 2.14 Figure A 30 1 3 C NMR spectra of polymer 2.14

PAGE 94

94 Figur e A 31 1 H NMR spectra of polymer 2.17 Figure A 32 1 3 C NMR spectra of polymer 2.17

PAGE 95

95 Figure A 33 1 H NMR spectra of polymer 2.18 Figure A 34 1 3 C NMR spectra of polymer 2.18

PAGE 96

96 Figure A 35 1 H NMR spectra of polymer 2.21 Figure A 36 1 3 C NMR spectra of polymer 2.21

PAGE 97

97 Figure A 37 1 H NMR spectra of polymer 2.23 Figure A 38 1 3 C NMR spectra of polymer 2.23

PAGE 98

98 Figure A 39 1 H NMR spectra of polymer 2.24 Figure A 4 0 1 3 C NMR spectra of polymer 2.24

PAGE 99

99 Figure A 41 1 H NMR spectra of polymer 2.25 Figure A 42 1 3 C NMR spectra of polymer 2.25

PAGE 100

100 Figure A 43 1 H NMR spectra of polymer 2.26 Figure A 44 1 3 C NMR spectra of polymer 2.26

PAGE 101

101 Figure A 45 1 H NMR spectra of polymer 2.27 Figure A 46 1 3 C NMR spectra of polymer 2.27

PAGE 102

102 Figure A 47 1 H NMR spectra of polymer 2.2 8 Figure A 48 1 3 C NMR spectra of polymer 2.28

PAGE 103

103 Figure A 49 1 H NMR spectra of polymer 2.30 Figure A 50 1 3 C NMR spectra of polymer 2.30

PAGE 104

104 Figure A 51 1 H NMR spectra of polymer 2.31 Figure A 52 1 3 C NMR spectra of polymer 2.31

PAGE 105

105 Figure A 53 1 H NMR spectra of polymer 2.35 Figure A 54 1 3 C NMR spectra of polymer 2.35

PAGE 106

106 Figure A 55 1 H NMR spectra of polymer 2.36 Figure A 56 1 3 C NMR spectra of poly mer 2.36

PAGE 107

107 Figure A 57 1 H NMR spectra of polymer 2.37 Figure A 58 1 3 C NMR spectra of polymer 2.37

PAGE 108

108 Figure A 59 1 H NMR spectra of polymer 2.38 Figure A 60 1 3 C NMR spectra of polymer 2.38

PAGE 109

109 Figure A 61 1 H NMR spectra of polymer 2.39 Figure A 62 1 3 C NMR spectra of polymer 2.39

PAGE 110

110 Figure A 63 1 H NMR spectra of polymer 2.40 Figure A 64 1 3 C NMR spectra of polymer 2.40

PAGE 111

111 Figure A 65 1 H NMR spectra of polymer 2.41 Figure A 66 1 3 C NMR spectra of polymer 2.41

PAGE 112

112 Figure A 67 1 H NMR spectra of polymer 2.42 Figure A 68 1 3 C NMR spectra of polymer 2.42

PAGE 113

113 Figure A 69 1 H NMR spectra of polymer 2.43 Figure A 70 1 3 C NMR spectra of polymer 2.43

PAGE 114

114 Figure A 71 1 H NMR spectra of polymer 2.44 Figure A 72 1 3 C NMR spectra of polymer 2.44

PAGE 115

115 Figure A 73 1 H NMR spectra of polymer 2.45 Figure A 74 1 3 C NMR spec tra of polymer 2.45

PAGE 116

116 Figure A 75 1 H NMR spectra of polymer 2.46 Figure A 76 1 3 C NMR spectra of polymer 2.46

PAGE 117

117 Figure A 77 1 H NMR spectra of polymer 2.47 Figure A 7 8 1 3 C NMR spectra of polymer 2.47

PAGE 118

118 Figure A 79 1 H NMR spectra of polymer 2.48 Figure A 80 1 3 C NMR spectra of polymer 2.48

PAGE 119

119 Figure A 81 1 H NMR spectra of polymer 2.49 Figure A 82 1 3 C NMR spectra of polymer 2.49

PAGE 120

120 Figure A 83 1 H NMR spectra of polymer 2.50 Figure A 84 1 3 C NMR spectra of polymer 2.50

PAGE 121

121 Figure A 85 1 H NMR spectra of polymer 2.51 Figure A 86 13C NMR spectra of polymer 2.51

PAGE 122

122 Figure A 87 1 H NMR spectra of polymer 2.52 Figure A 88 1 3 C NMR spectra of polymer 2.52

PAGE 123

123 Figure A 89 1 H NMR spectra of polymer 2.53 Figure A 90 13C NMR spectra of polymer 2.53

PAGE 124

124 Figure A 91 1 H NMR spectra of polymer 2.54 Figure A 9 2 1 3 C NMR spectra of polymer 2.54

PAGE 125

125 Figure A 93 1 H NMR spectra of polymer 2.55 Figure A 94 1 3 C NMR spectra of polymer 2.55

PAGE 126

126 Figure A 95 1 H NMR spectra of polymer 2.58 Figure A 96 1 3 C NMR spectra of polymer 2.58

PAGE 127

127 Figure A 97 1 H NMR spectra of polymer 2.59 Figure A 98 1 3 C NMR spectra of polymer 2.59

PAGE 128

128 Figure A 99 1 H NMR spectra of polymer 2.60 Figure A 100 1 3 C NMR spectra of polymer 2.60

PAGE 129

129 Figure A 101 1 H NMR spectra of polymer 2.61 Figure A 102 1 3 C NMR spectra of polymer 2.61

PAGE 130

130 Figure A 103 1 H NMR spectra of polymer 2.62 Figure A 104 1 3 C NMR spectra of polymer 2.62

PAGE 131

131 F igure A 105 1 H NMR spectr a of polymer 2.63 Figure A 106 1 3 C NMR spectra of polymer 2.63

PAGE 132

132 Figure A 107 1 H NMR spectra of polymer 2.64 Figure A 108 1 3 C NMR spectra of polymer 2.64

PAGE 133

133 Figure A 109 1 H NMR spectra of polymer 2.65 Figure A 110 1 3 C NMR spectra of polymer 2.65

PAGE 134

134 Figure A 111 1 H NMR spectra of polymer 2.66 Figure A 112 1 3 C NMR spectra of polymer 2.66

PAGE 135

135 Figure A 113 1 H NMR spectra of polymer 2.67 Figure A 114 13C NMR spectra of polymer 2.67

PAGE 136

136 APPENDIX B POLYMER CHARACTERIZATION DAT A Figure B 1 TGA of polymer 2.9 Figure B 2 DSC of polymer 2.9

PAGE 137

137 Figure B 3 TGA of polymer 2.17 Figure B 4 DSC of polymer 2. 1 7

PAGE 138

138 Figure B 5 TGA of polymer 2.18 Figure B 6 DSC of polymer 2. 18

PAGE 139

139 Figure B 7 TGA of polymer 2.21 Figure B 8 DSC of polymer 2. 21

PAGE 140

140 Figure B 9 TGA of polymer 2.23 Figure B 10 DSC of polymer 2.23

PAGE 141

141 Figure B 11 TGA of polymer 2.24 Figure B 12 DSC of polymer 2.24

PAGE 142

142 Figure B 13 TGA of polymer 2.25 Figure B 14 DSC of polymer 2.25

PAGE 143

143 Figure B 15 TGA of polymer 2.26 Figure B 16 DSC of polymer 2. 26

PAGE 144

144 Figure B 17 TGA of polymer 2.27 Figure B 18 DSC of polymer 2. 27

PAGE 145

145 Figure B 19 TGA of polymer 2.28 Figure B 20 DSC of polymer 2. 28

PAGE 146

146 Figure B 21 TGA of polymer 2. 31 Figure B 22 DSC of polymer 2.31

PAGE 147

147 Figure B 23 TGA of polymer 2.35 Figure B 24 DSC of polymer 2.35

PAGE 148

148 Figure B 25 TGA of polymer 2.36 Figure B 26 DSC of polymer 2.36

PAGE 149

149 Figure B 27 TGA of polymer 2 .37 Figure B 28 DSC of polymer 2.37

PAGE 150

150 Figure B 29 TGA of polymer 2.38 Figure B 30 DSC of polymer 2.38

PAGE 151

151 Figure B 31 TGA of polymer 2.3 9 Figure B 32 DSC o f polymer 2.39

PAGE 152

152 Figure B 33 TGA of polymer 2.4 0 Figure B 34 DSC of polymer 2.40

PAGE 153

153 Figure B 35 TGA of polymer 2.41 Figure B 36 DSC of polymer 2.41

PAGE 154

154 Figure B 37 TGA of polymer 2.42 Figure B 38 DSC of polymer 2.42

PAGE 155

155 Figure B 39 TGA of polymer 2.43 Figure B 40 DSC of polymer 2.43

PAGE 156

156 Figure B 41 TGA of polymer 2. 44 Figure B 4 2 DSC of polymer 2. 4 4

PAGE 157

157 Figure B 43 TGA o f polymer 2.45 Figure B 44 DSC of polymer 2.45

PAGE 158

158 Figure B 45 TGA of polymer 2.46 Figure B 46 DSC of polymer 2.46

PAGE 159

159 Figure B 47 TGA of polymer 2.47 Figure B 48 DSC of polymer 2.47

PAGE 160

160 Figure B 49 TGA of polymer 2.48 Figure B 50 DSC of polymer 2.48

PAGE 161

161 Figure B 51 TGA of polymer 2.49 Figure B 52 DSC of polymer 2.49

PAGE 162

162 Figure B 53 TGA of polymer 2. 50 Figure B 54 DSC of polymer 2. 50

PAGE 163

163 Figure B 55 TGA of polymer 2. 51 Figure B 56 DSC of polymer 2. 51

PAGE 164

164 Figure B 57 TGA of polymer 2. 52 Figure B 58 DSC of polymer 2. 52

PAGE 165

165 Figure B 59 TGA of polymer 2. 53 Figure B 60 DSC of polymer 2. 53

PAGE 166

166 Figure B 61 TGA of polymer 2. 54 Figure B 62 DSC of polymer 2. 54

PAGE 167

167 Figure B 63 TGA of polymer 2. 5 5 Figure B 64 TGA of polymer 2. 5 5

PAGE 168

168 Figure B 65 TGA of po lymer 2.58 Figure B 66 DSC of polymer 2.58

PAGE 169

169 Figure B 67 TGA of polymer 2.59 Figure B 68 DSC of polymer 2.59

PAGE 170

170 Figure B 69 TGA of polymer 2.60 Figure B 70 DSC of polymer 2.60

PAGE 171

171 F igure B 71 TGA of polymer 2.61 Figure B 72 DSC of polymer 2.61

PAGE 172

172 Figure B 73 TGA of polymer 2.62 Figure B 74 DSC of polymer 2.62

PAGE 173

173 Figure B 75 TGA of polymer 2.63 Figure B 76 DSC of poly mer 2.63

PAGE 174

174 Figure B 77 TGA of polymer 2.64 Figure B 78 DSC of polymer 2.64

PAGE 175

175 Figure B 79 TGA of polymer 2.65 Figure B 80 DSC of polymer 2.65

PAGE 176

176 Figure B 81 TGA of polymer 2.66 Fi gure B 82 DSC of polymer 2.66

PAGE 177

177 Figure B 83 TGA of polymer 2.67 Figure B 84 DSC of polymer 2.67

PAGE 178

178 Figure B 85 GPC analysis of polymer 2.5 Figure B 86 GPC analysis of polymer 2. 6

PAGE 179

179 Figure B 8 7 GPC analysis of polymer 2.7 Figure B 88 GPC analysis of polymer 2. 8

PAGE 180

180 Figure B 89 GPC analysis of polymer 2.9 Figure B 90 GPC analysis of polymer 2. 10

PAGE 181

181 Figure B 91 GPC analysis of polymer 2.11 Figure B 92 GPC analysis of polymer 2.1 2

PAGE 182

182 Figure B 93 GPC analysis of polymer 2.13 Figure B 94 GPC analysis of polymer 2.1 4

PAGE 183

183 Figure B 95 GPC analysis of polymer 2.17 Figure B 96 GPC analysis of p olymer 2.1 8

PAGE 184

184 Figure B 97 GPC analysis of polymer 2.21 Figure B 98 GPC analysis of polymer 2.23

PAGE 185

185 Figure B 99 GPC analysis of polymer 2.24 Figure B 100 GPC analysis of polymer 2.25

PAGE 186

186 Figure B 1 01 GPC analysis of polymer 2.26 Figure B 102 GPC analysis of polymer 2.28

PAGE 187

187 Figure B 103 GPC analysis of polymer 2.30 Figure B 104 GPC analysis of polymer 2.31

PAGE 188

188 Figure B 105 GPC analysis of polymer 2.3 5 Figure B 106 GPC analysis of polymer 2.36

PAGE 189

189 Figure B 107 GPC analysis of polymer 2.37 Figure B 108 GPC analysis of polymer 2.38

PAGE 190

190 Figure B 109 GPC analysis of polymer 2.39 Figure B 110 GPC analysis of polymer 2.40

PAGE 191

191 Figure B 111 GPC analysis of polymer 2.41 Figure B 112 GPC analysis of polymer 2.42

PAGE 192

192 Figure B 113 GPC analysis of polymer 2. 43 Figure B 114 GPC analysis of polymer 2. 44

PAGE 193

193 Figure B 115 GPC analysis of polymer 2.45 Figure B 116 GPC analysis of polymer 2. 46

PAGE 194

194 Figure B 117 GPC analysis of polymer 2.47 Figure B 118 GPC analysis of polymer 2. 48

PAGE 195

195 Figure B 119 GPC analys is of polymer 2. 49 Figure B 120 GPC analysis of polymer 2. 50

PAGE 196

196 Figure B 121 GPC analysis of polymer 2. 51 Figure B 122 GPC analysis of polymer 2. 52

PAGE 197

197 Figure B 123 GPC analysis of polymer 2. 53 F igure B 124 GPC analysis of polymer 2. 54

PAGE 198

198 Figure B 125 GPC analysis of polymer 2. 55 Figure B 126 GPC analysis of polymer 2.58

PAGE 199

1 99 Figure B 127 GPC analysis of polymer 2. 59 Figure B 128 GPC analysis of po lymer 2.60

PAGE 200

200 Figure B 129 GPC analysis of polymer 2.61 Figure B 130 GPC analysis of polymer 2.62

PAGE 201

201 Figure B 131 GPC analysis of polymer 2. 63 Figure B 1 3 2 GPC analysis of polymer 2.64

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202 Figure B 1 33 GPC analysis of polymer 2.65 Figure B 134 GPC analysis of polymer 2.66

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203 Figure B 135 GPC analysis of polymer 2.67

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204 LIST OF REFERENCES (1) European Parliament and Council Directive 94/62/EC Article 3 1994 (2) Market Statist ics and Future Trends in Global Packaging WPO/PIRA International Ltda. 2008 (3) U.S. Department of Energy /U.S. Department of Agriculture Biomass as Feedstock for a Bioenergy and Bioproducts Industry: The Technical Feasibility of a Billion Ton Annual Supply Ap ril 2009 (4) Pusch Thema Umwelt 1/2009 3 (5) GBI Research The Polyethylene Terephthalate (PET) Market to 2020 Carbonated Soft Drinks and Bottled Water Market in Asia Driving the Global Demand July 2010 (6) Caldicott, R. Plast. Eng. 1999 35 (7) Fakirov S. Handbook of Thermoplastic Polyesters Homopolymers, Copolymers, Blends and Composites Wiley VCH 2002 (8) Piringer, O.G.; Baner, A.L. Plastic packaging: interactions with food and pharmaceutical (2nd ed.) Wiley VCH 2008 (9) Peacock, A.J. Handbook of Polyethylene Structure Properties and Applications CRC PRESS 2000 (10) Maier, C.; Calafut, T. William Andrew 1998 (11) Mcintire, O.R. US Patent 2,450,436 Manufacture of Cellular Thermoplastic Products 1948 (12) Serini, V. Polycarbo nates in Ullmann's Encyclopedia of Industrial Chemistry 2000 (13) U.S. Environmental Protection Agency, Municipal Solid Waste in the United States: 2009 Facts and Figures December 2010 (14) Sinclair, R. J. Macromol. Sci. Part A: Pure Appl. Che m. 1996 A33,585 (15) Schne ll H.; Bottenbruch, H.; Krimm, H. US Patent 3,028,365 1962 (16) Fox, D.W. US Patent 3,153,008 1964 (17) Edlund, U.; Albertsson, A. C.; Singh, S.K.; Fogelberg, I.; Lundgren, B.O. Biomaterials 2000 21, 945 955

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206 (39) Zhu, W.; Huang, X.; Li, C.; Xiao, Y.; Zhang, D.; G uan G Polym. Int. 2011 60, 1060 1067 (40) Encyclopaedia Britannica Encyclopaedia Britannica Online Castor oil plant 2011 http://www.britannica.com (41) Grieve, M. A Modern Herbal Castor oil plant 1995 http://botanical.com/botanical/mgmh/c/casoil32.html (42) Binder, R.G.; Applewhite, T.H.; Kohler, G.O.; Goldblatt, L.A. J. Am. Oil Chem. Soc. 1962 39, 513 517 (43) Mutly, H.; Meier, M.A.R. Eur. J. Lipid Sci. Technol. 2010 112, 10 30 (44) Noweck, K.; Grafahrend, W. ylopedia of Industral Chemistry 2006 (45) Tundo, P.; Selva, M. Acc. Chem. Res. 2002 35, 706 716 (46) Tundo, P. Pure Appl. Chem. 2001 73, 1117 1124 (47) Kricsfalussy, Z.; Waldmann, H. ; Traenckner, H. J. Ind. Eng. Chem. Res. 1998 37, 865 866 (48) Sun et Al. US Patent 7,271,120 B2 2007 (49) Carothers, W.H.; Van Natta, F.J. J. Am. Chem. Soc. 1930 52, 314 324 (50) Tomczyk, K.; Parzuchowski, P.G.; Kozakiewicz, J. ; Przybylski, J ; Rokicki, G. Polymeri 20 10 55, 366 372 (51) Grellmann, W.; Seidler, S. Polymer Testing, Hanser Gardner Pubns, 2007 (52) Reusch, R.N. Polymers 2001 http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJm l/polymers.htm (53) Su, K.; Li, Z.; Cheng, B.; Liao, K.; Shen, D.; Wang, Y. J. Mol. Catal. A: Chem 2010 315, 60 68 (54) Muller, A. Proc. Roy. Soc. London A 1929 124, 317 321 (55) Kent, J.A. Handbook of Industrial Chemistry and Biotechnology Springer, 2006 (56) Watts, H.; Fownes, G.; Sir Tilden, W.A. Manual of chemistry: theoretical and practical, Volume 2 Blakiston, 1886 (57) Gibson, J.M.; Thomas, P.M.; Thomas, J.D.; Barker, J.L.; Chandran, S.S.; Harrup Draths, K.M.; Frost, J.W. Angew. Chemie, Int. Ed. 2001 ,40, 1945

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207 BIO GRAPHICAL SKETCH R ob V anderhenst was born in 1981 i n Neer pel t Belgium After finishing high school, h e attended the Xios Hogeschool Limburg where he obtained his d egree in Industrial Sciences Packaging Science with honors. During this study he worked 6 months as a research student at STFI Packforsk in Stockholm, Sweden o n a project on bio material films in order t o complete his thesis. After graduation he worked for 2 years as a packaging engineer at the R&D department of P rocter & G amble bef ore enroll ing in the chemistry program at the University of Florida in January 2009. His research there dealt with the synthesis of polymers f rom bio renewable feed stocks and was directed and mentored by Dr. Stephen A. Miller.