Citation
Poly(Ethylene Terephthalate) Mimics from Biorenewable Feedstocks

Material Information

Title:
Poly(Ethylene Terephthalate) Mimics from Biorenewable Feedstocks
Creator:
Short, Gabriel N
Publisher:
University of Florida
Publication Date:
Language:
English

Thesis/Dissertation Information

Degree:
Master's ( M.S.)
Degree Grantor:
University of Florida
Degree Disciplines:
Chemistry
Committee Chair:
MILLER,STEPHEN ALBERT
Committee Co-Chair:
SUMERLIN,BRENT S
Committee Members:
CASTELLANO,RONALD K

Subjects

Subjects / Keywords:
biorenewable
ferulicacid
succinicacid
terephthalate

Notes

General Note:
Worldwide, an estimated 311 millions tons of plastics is produced annually and when disposed of, accumulate in landfills and waterways.1-3 To lessen environmental impact, biorenewable and degradable polymers that mimic commodity plastics are needed.4 Herein, two series of poly(ethylene terephthalate) mimics are reported. Copolymers derived from ferulic acid and coumaric acid utilize four monomers: acetyl-ferulic acid and acetyl-coumaric acid, as well as their hydrogenated forms. While the number average molecular weight (Mn) is low, initial thermal and physical data show that the copolymers are suitable mimics for a number of commercial polymers with glass transition temperatures (Tg) ranging from 60-177 C. While succinic acid (SA) is normally derived from petrochemicals, companies have recently synthesized bio-succinic acid through the fermentation of non-food biomass, industrial waste, and corn glucose.5,6 To form a PET mimic, SA is dimerized yielding dimethylsuccinylsuccinate (DMSS) and after three steps, 2,5-dimethoxyterephthalic acid (DMTA) is produced.7,8 Reacting DMTA with a number of alkyl diols, from n= 2-10, a series of PET mimics was formed with Mw above 10,000 g/mol and Tg ranging from 7-74 C.

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Source Institution:
UFRGP
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All applicable rights reserved by the source institution and holding location.
Embargo Date:
8/31/2018

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POLY(ETHYLENE T EREPHTHALA TE) MIMICS FROM BIORENEWABLE FEEDSTOCKS By GABRIEL SHORT A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE UNIVERSITY OF FLORIDA 2016

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2016 Gabriel Short

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To my family and friends who believed in me especiall y Kathryn Olsen for her support

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4 ACKNOWLEDGMENTS I would like to thank my committee memb ers: Dr. Sumerlin, Dr. Castellano, and especially Dr. Miller for their help and support. The University of Florida for the use of its helped guide me during these years. I would also like to thank my lab mates in the Miller lab as well as my friends in the department for their support during this time. Lastly, I would like to thank my parents who have unconditionally supported me and offered guidance throughout my time he re.

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5 TABLE OF CONTENTS page ACKNOWLEDGMENTS ................................ ................................ ................................ .. 4 LIST OF TABLES ................................ ................................ ................................ ............ 7 LIST OF FIGURES ................................ ................................ ................................ .......... 8 LIST OF ABBREVIATIONS ................................ ................................ ........................... 17 ABSTRACT ................................ ................................ ................................ ................... 19 CHAPTER 1 MOTIVATION FOR BIORENEWABLE POLYMERS ................................ ............... 20 1.1 What is the Problem with Current Polymers? ................................ ................... 20 ................................ .................... 20 1.3 Biore newable Starting Materials ................................ ................................ ....... 21 1.3.1 Ferulic and Coumaric Acid ................................ ................................ ...... 22 1.3.2 Succinic Acid ................................ ................................ ........................... 23 1.3.3 Aliphatic Diols ................................ ................................ .......................... 23 2 FERULIC ACID AND COUMARIC ACID BASED COPOLYMERS ......................... 24 2.1 Background and Introduction ................................ ................................ ............ 24 2.2 Copolymer Series ................................ ................................ ............................. 25 2.2.1 Synthesis and Characterization ................................ ............................... 27 2.2.2 Effects of Internal Alkene ................................ ................................ ......... 28 2.2.3 Glass Transition Temperature Comparison ................................ ............. 33 2.2.4 New Ideas and Conclusion ................................ ................................ ...... 35 3 SUCCINIC ACID BASED POLY(ETHYLENE TEREPHTHALATE) MIMIC ............. 37 3.1 Background and Introduction ................................ ................................ ............ 37 3.2 Dimethyl 2,5 dimethoxyterephthalate and Derivatives ................................ ...... 39 3.3 Polyester Copolymers From Diols and Succinic Acid Based Monomers .......... 40 3.3.1 Poly(alkylene dimethoxyterephthal a tes) Synthesis and Characterization ................................ ................................ ............................ 41 3.3.2 Comparison of Poly(alkylene dimethoxyterephthal a tes) with Poly(alkylene dihydroxyterephthal ates) ................................ ......................... 44 3.4 New Ideas and Conclusion ................................ ................................ ............... 45 4 EXPERIMENTAL ................................ ................................ ................................ .... 47 4.1 Molecular C haracterization ................................ ................................ ............... 47

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6 4.2 Synthesis of Ferulic and Coumaric Acid Based Polymers ................................ 48 4.2.1 Monomer Synthesis ................................ ................................ ................. 48 4.2.2 Polymer Synthesis ................................ ................................ ................... 51 4.2.3 Incorporation Ratio for Polymer Series From AFA, DHFA, and DHCA. ... 54 4.3 Succinic Acid Based Poly(ethylene terephthalate) Mimic Synthesis ................. 56 4.3.1 2,5 dimethoxyterephthalic Acid Synthesis ................................ ............... 56 4.3.2 Polymer Synthesis ................................ ................................ ................... 58 APPENDIX A PROTON AND C ARBON NMR ................................ ................................ ........... 62 B POLYMER CHARACTERIZATION DATA ................................ ........................... 88 LIST OF REFERENCES ................................ ................................ ............................. 135 BIOGRAPHICAL SKETCH ................................ ................................ .......................... 139

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7 LIST OF TABLES Table page 1 1 Concentration of ferulic acid from different sources ................................ ............ 22 2 1 Thermal and physical data obtai ned from copolymerization of DHCA ( 2.2 ) and DHFA ( 2.5 ) ................................ ................................ ................................ .. 29 2 2 Thermal and physical data obtai ned from copolymerization of DHCA ( 2.2 ) and AFA( 2.4 ) ................................ ................................ ................................ ...... 30 3 1 Thermal and physical data obtained from polymerizations of DMTA and d iols ... 42 3 2 Optimization of polymerization between DMTA and ethylene glycol .................. 44 3 3 Thermal property comparison between polymers with thr ee different diacids .... 45

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8 LIST OF FIGURES Figure page 1 1 Annual production of major commodity polymers 11 ................................ ........... 21 2 1 Synthesis of biorenewable monomers from FA ( 2.3 ) and CA ( 2 ) ....................... 26 2 2 The monomer AFA ( 2.4 ), DHCA ( 2.2 ), and DHFA ( 2.5 ) ................................ .... 27 2 3 Monomer synthesis starting with FA ( 2.3 ) and CA ( 2 ), acetylation to form AFA ( 2.4) and ACA ( 2.1 ), and hydrogenation to form DHFA ( 2.5 ) and DHCA ( 2.2 ) ................................ ................................ ................................ .................... 27 2 4 Copolymerizations ut ilizing DHCA ( 2.2 ), DHFA ( 2.5 ), and AFA ( 2.4 ) ................ 28 2 5 Secondary polymerization of polyhydroferulic acid. ................................ ........... 31 2 6 Large scale polymeriz ation of DHFA ( 2.5 ) forming polymer ( 2.27 ) .................... 32 2 7 Six different polymers available from the four monomers Poly(hydroferulic co hydrocoumaric) acid (a), poly(hydroferulic co coumaric) acid (b), po ly(hydroferulic co ferulic) acid (c), poly(hydrocoumaric co coumaric) acid (d), poly(hydrocoumaric co ferulic) acid (e), and poly(ferulic co coumaric) acid(f). ................................ ................................ ................................ ................ 33 2 8 T g of five copolymer series compaired to several commodity plastics ................ 34 3 1 Structure of poly(ethylene terephthalate) ................................ ............................ 37 3 2 Synthesis of 2,5 dimethoxyterephthalic acid ( 3.4 ), starting from succinic acid and progressing through dimethylsuccinylsuccinate ( 3 ) ................................ ..... 38 3 3 Proposed synthesis of DMSS ( 3 ) from SA ................................ .......................... 39 3 4 Possible biorenewable terephthalic acid mimics synthesized from DMSS ( 3 ) .... 40 3 5 General polymerization procedure for poly(alkylene dimethoxyterephthalate) series ................................ ................................ ................................ .................. 41 3 6 Comparison of T g and T m for poly(alkylene dimethoxyterephthalate) series ....... 43 4 1 Synthesis of acetyl ferulic acid ( 2.4 ) ................................ ................................ ... 49 4 2 Synthesis of acetyl coumaric acid ( 2.1 ) ................................ .............................. 49 4 3 Synthesis of acetyl dihydroferulic acid ( 2.5 ) ................................ ....................... 50 4 4 Synthesis of acetyl dihydrocoumaric acid ( 2.2 ) ................................ .................. 50

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9 4 5 Polymerization set up. An oil bath holding a round bottom flask with stirrer connected to a bump trap is set on a hot plate with tempe rature control. The apparatus is attached to a Schlenk line. ................................ ............................. 51 4 6 Synthesis of copolymers utilizing AFA ( 2.4 ), DHFA ( 2.5 ), and DHCA ( 2.2 ) ........ 51 4 7 Large scale polymerization of DHFA ( 2.27 ) ................................ ........................ 52 4 8 Secondary polymerization of Polyhydroferulic acid ( 2.26 ) ................................ .. 53 4 9 Polymeri zation of DHFA ( 2.5 ) using DBU ................................ ........................... 54 4 10 1 H NMR spectra of Polymer 2.10 with a fed fraction of 50% DHFA .................... 55 4 11 1 H NMR spectra of Poly mer 2.20 with a fed fraction of 50% AFA ....................... 55 4 12 Synthesis of dimethyl 2,5 dihydroxyterephthalate ( 3.1 ) ................................ ...... 56 4 13 Synthesis of 2,5 dihy droxyterephthalic acid ( 3.2 ) ................................ ............... 56 4 14 Synthesis of 2,5 dimethoxyterephthalic acid ( 3.4 ) ................................ .............. 57 4 15 General polymerization procedure for the poly(alkene dimethoxyterephthalate) series ................................ ................................ ........... 58 4 16 Poly(ethylene dimethoxyterephthalate) ( 3.5 ) ................................ ...................... 59 4 17 Poly(propylene dimethoxyt erephthalate) ( 3.6 ) ................................ .................... 59 4 18 Poly(butylene dimethoxyterephthalate) ( 3.7 ) ................................ ...................... 59 4 19 Poly(pentylene dimethoxyterephthalate) ( 3.8 ) ................................ .................... 59 4 20 Poly(hexylene dimethoxyterephthalate) ( 3.9 ) ................................ ..................... 60 4 21 Poly(octylene dimethoxyterephthalate) ( 3.10 ) ................................ .................... 60 4 22 Poly(nonylene dimethoxyterephthalate) ( 3.11 ) ................................ ................... 60 4 23 Poly(decylene dimethoxyterephthalate) ( 3.12 ) ................................ ................... 61 A 1 1 H NMR spectra of polymer ( 2.5 ) ................................ ................................ ........ 62 A 2 13 C NMR spectra of polymer ( 2.5 ) ................................ ................................ ...... 62 A 3 1 H NMR spectra of polymer ( 2.6 ) ................................ ................................ ........ 62 A 4 13 C NMR spectra of polymer ( 2.6 ) ................................ ................................ ...... 63

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10 A 5 1 H NMR spectra of polymer ( 2.7 ) ................................ ................................ ........ 63 A 6 13 C NMR spectra of polymer ( 2.7 ) ................................ ................................ ...... 63 A 7 1 H NMR spectra of polymer ( 2.8 ) ................................ ................................ ........ 64 A 8 13 C NMR spectra of polymer ( 2.8 ) ................................ ................................ ...... 64 A 9 1 H NMR spe ctra of polymer ( 2.9 ) ................................ ................................ ........ 64 A 10 13 C NMR spectra of polymer ( 2.9 ) ................................ ................................ ...... 65 A 11 1 H NMR spectra of polymer ( 2.10 ) ................................ ................................ ...... 65 A 12 13 C NMR spectra of polymer ( 2.10 ) ................................ ................................ .... 65 A 13 1 H NMR spectra of polymer ( 2.11 ) ................................ ................................ ...... 66 A 14 13 C NMR spectra of polymer ( 2.11 ) ................................ ................................ .... 66 A 15 1 H NMR spectra of polymer ( 2.12 ) ................................ ................................ ...... 66 A 16 13 C NMR spectra of polymer ( 2.12 ) ................................ ................................ .... 67 A 17 1 H NMR spectra of polymer ( 2.13 ) ................................ ................................ ...... 67 A 18 13 C NMR spectra of polymer ( 2.13 ) ................................ ................................ .... 67 A 19 1 H NMR spectra of polymer ( 2.14 ) ................................ ................................ ...... 68 A 20 13 C NMR spectra of polymer ( 2.14 ) ................................ ................................ .... 68 A 21 1 H NMR spectra of polymer ( 2.15 ) ................................ ................................ ...... 68 A 22 13 C NMR spectra of polyme r ( 2.15 ) ................................ ................................ .... 69 A 23 1 H NMR spectra of polymer ( 2.16 ) ................................ ................................ ...... 69 A 24 13 C NMR spectra of polymer ( 2.16 ) ................................ ................................ .... 69 A 25 1 H NMR spectra of polymer ( 2.17 ) ................................ ................................ ...... 70 A 26 13 C NMR spectra of polymer ( 2.17 ) ................................ ................................ .... 70 A 27 1 H NMR spectra of polymer ( 2.18 ) ................................ ................................ ...... 70 A 28 13 C NMR spectra of polymer ( 2.18 ) ................................ ................................ .... 71 A 29 1 H NMR spectra of polymer ( 2.19 ) ................................ ................................ ...... 71

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11 A 30 13 C NMR spect ra of polymer ( 2.19 ) ................................ ................................ .... 71 A 31 1 H NMR spectra of polymer ( 2.20 ) ................................ ................................ ...... 72 A 32 13 C NMR spectra of polymer ( 2.20 ) ................................ ................................ .... 72 A 33 1 H NMR spectra of polymer ( 2.21 ) ................................ ................................ ...... 72 A 34 13 C NMR spectra of polymer ( 2.21 ) ................................ ................................ .... 73 A 35 1 H NMR spectra of polymer ( 2.22 ) ................................ ................................ ...... 73 A 36 13 C NMR spectra of polymer ( 2.22 ) ................................ ................................ .... 73 A 37 1 H NMR spectra of polymer ( 2.23 ) ................................ ................................ ...... 74 A 38 1 3 C NMR spectra of polymer ( 2.23 ) ................................ ................................ .... 74 A 39 1 H NMR spectra of polymer ( 2.24 ) ................................ ................................ ...... 74 A 40 13 C NMR spectra of polymer ( 2.24 ) ................................ ................................ .... 75 A 41 1 H NMR spectra of polymer ( 2.25 ) ................................ ................................ ...... 75 A 42 13 C NMR spectra of polymer ( 2.25 ) ................................ ................................ .... 75 A 43 1 H NMR spectra of polymer ( 2.26 ) ................................ ................................ ...... 76 A 44 13 C NMR spectra of polymer ( 2.26 ) ................................ ................................ .... 76 A 45 1 H NMR spectra of polymer ( 2.27 ) ................................ ................................ ...... 76 A 46 13 C NMR spectra of polymer ( 2.27 ) ................................ ................................ .... 77 A 47 1 H NMR spectra of polymer ( 2.28 ) ................................ ................................ ...... 77 A 48 13 C NMR spectra of polymer ( 2.28 ) ................................ ................................ .... 77 A 49 1 H NMR spectra of polymer ( 3.5 ) ................................ ................................ ........ 78 A 50 13 C NMR spectra of polymer ( 3.5 ) ................................ ................................ ...... 78 A 51 1 H NMR spectra of polymer ( 3.6 ) ................................ ................................ ........ 78 A 52 13 C NMR spectra of polymer ( 3.6 ) ................................ ................................ ...... 79 A 53 1 H NMR spectra of polymer ( 3.7 ) ................................ ................................ ........ 79 A 54 13 C NMR spectra of polymer ( 3.7 ) ................................ ................................ ...... 79

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12 A 55 1 H NMR spectra of polymer ( 3.8 ) ................................ ................................ ........ 80 A 56 13 C NMR spectra of polymer ( 3.8 ) ................................ ................................ ...... 80 A 57 1 H NMR spectra of polymer ( 3.9 ) ................................ ................................ ........ 80 A 58 13 C NMR spectra of polymer ( 3.9 ) ................................ ................................ ...... 81 A 59 1 H NMR spec tra of polymer ( 3.10 ) ................................ ................................ ...... 81 A 60 13 C NMR spectra of polymer ( 3.10 ) ................................ ................................ .... 81 A 61 1 H NMR spectra of polymer ( 3.11 ) ................................ ................................ ...... 82 A 62 13 C NMR spectra of polymer ( 3.11 ) ................................ ................................ .... 82 A 63 1 H NMR spectra of polymer ( 3.12 ) ................................ ................................ ...... 82 A 64 13 C NMR spectra of polymer ( 3.12 ) ................................ ................................ .... 83 A 65 1 H NMR spectra of ( 2.1 ) ................................ ................................ ..................... 83 A 66 13 C NMR spectra of ( 2.1 ) ................................ ................................ .................... 83 A 67 1 H NMR spectra of ( 2.2 ) ................................ ................................ ..................... 84 A 68 13 C NMR spectra of ( 2.2 ) ................................ ................................ .................... 84 A 69 1 H NMR spectra of ( 2.4 ) ................................ ................................ ..................... 84 A 70 13 C NMR spectra of ( 2.4 ) ................................ ................................ .................... 85 A 71 1 H NMR spectra of ( 2.5 ) ................................ ................................ ..................... 85 A 72 13 C NMR spectra of ( 2.5 ) ................................ ................................ .................... 85 A 7 3 1 H NMR spectra of ( 3.1 ) ................................ ................................ ..................... 86 A 74 13 C NMR spectra of ( 3.1 ) ................................ ................................ .................... 86 A 75 1 H NMR spectra of ( 3.2 ) ................................ ................................ ..................... 86 A 76 13 C NMR spectra of ( 3.2 ) ................................ ................................ .................... 87 A 77 1 H NMR spectra of ( 3.4 ) ................................ ................................ ..................... 87 A 78 13 C NMR spectra of ( 3.4 ) ................................ ................................ .................... 87 B 1 TGA of polymer ( 2.5 ) ................................ ................................ .......................... 88

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13 B 2 TGA of polymer ( 2.6 ) ................................ ................................ .......................... 88 B 3 TGA of polymer ( 2.7 ) ................................ ................................ .......................... 89 B 4 TGA of polymer ( 2.8 ) ................................ ................................ .......................... 89 B 5 TGA of polymer ( 2.9 ) ................................ ................................ .......................... 90 B 6 TGA of polymer ( 2.10 ) ................................ ................................ ........................ 90 B 7 TGA of polymer ( 2.11 ) ................................ ................................ ........................ 91 B 8 TGA of polymer ( 2.12 ) ................................ ................................ ........................ 91 B 9 TGA of polymer ( 2.13 ) ................................ ................................ ........................ 92 B 1 0 TGA of polymer ( 2.14 ) ................................ ................................ ........................ 92 B 11 TGA of polymer ( 2.15 ) ................................ ................................ ........................ 93 B 12 TGA of polymer ( 2.16 ) ................................ ................................ ........................ 93 B 13 TGA of polymer ( 2.17 ) ................................ ................................ ........................ 94 B 14 TGA of polymer ( 2.18 ) ................................ ................................ ........................ 94 B 15 TGA of polymer ( 2.19 ) ................................ ................................ ........................ 95 B 16 TGA of polymer ( 2.20 ) ................................ ................................ ........................ 95 B 17 TGA of polymer ( 2.21 ) ................................ ................................ ........................ 96 B 18 TGA of polymer ( 2.22 ) ................................ ................................ ........................ 96 B 19 TGA of polymer ( 2.23 ) ................................ ................................ ........................ 97 B 20 TGA of polymer ( 2.24 ) ................................ ................................ ........................ 97 B 21 TGA of polymer ( 2.25 ) ................................ ................................ ........................ 98 B 22 TGA of polymer ( 2.26 ) ................................ ................................ ........................ 98 B 23 TGA of polymer ( 2.27 ) ................................ ................................ ........................ 99 B 24 TGA of polymer ( 3.5 ) ................................ ................................ .......................... 99 B 25 TGA of polymer ( 3.6 ) ................................ ................................ ........................ 100 B 26 TGA of polymer ( 3.7 ) ................................ ................................ ........................ 100

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14 B 27 TGA of polymer ( 3.8 ) ................................ ................................ ........................ 101 B 28 TGA of polymer ( 3.9 ) ................................ ................................ ........................ 101 B 29 TGA of polymer ( 3.10 ) ................................ ................................ ...................... 102 B 30 TGA of polymer ( 3.11 ) ................................ ................................ ...................... 102 B 31 TGA of polymer ( 3.12 ) ................................ ................................ ...................... 103 B 32 DSC of polymer ( 2.5 ) ................................ ................................ ........................ 103 B 33 DSC of polymer ( 2.6 ) ................................ ................................ ........................ 10 4 B 34 DSC of polymer ( 2.7 ) ................................ ................................ ........................ 104 B 35 DSC of polymer ( 2.8 ) ................................ ................................ ........................ 105 B 3 6 DSC of polymer ( 2.9 ) ................................ ................................ ........................ 105 B 37 DSC of polymer ( 2.10 ) ................................ ................................ ...................... 106 B 38 DSC of polymer ( 2.11 ) ................................ ................................ ...................... 106 B 39 DSC of polymer ( 2.12 ) ................................ ................................ ...................... 107 B 40 DSC of polymer ( 2.13 ) ................................ ................................ ...................... 107 B 41 DSC of polymer ( 2.14 ) ................................ ................................ ...................... 108 B 42 DSC of polymer ( 2.15 ) ................................ ................................ ...................... 108 B 43 DSC of polymer ( 2.16 ) ................................ ................................ ...................... 109 B 44 DSC of polymer ( 2.17 ) ................................ ................................ ...................... 109 B 45 DSC of polymer ( 2.18 ) ................................ ................................ ...................... 110 B 46 DSC of polymer ( 2.19 ) ................................ ................................ ...................... 110 B 47 DSC of polymer ( 2.20 ) ................................ ................................ ...................... 111 B 48 DSC of polymer ( 2.21 ) ................................ ................................ ...................... 111 B 49 DSC of polymer ( 2.22 ) ................................ ................................ ...................... 112 B 50 DSC of polymer ( 2.23 ) ................................ ................................ ...................... 112 B 51 DSC of polymer ( 2.24 ) ................................ ................................ ...................... 113

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15 B 52 DSC of polymer ( 2.25 ) ................................ ................................ ...................... 113 B 53 DSC of polymer ( 2.26 ) ................................ ................................ ...................... 114 B 54 DSC of polymer ( 2.27 ) ................................ ................................ ...................... 114 B 55 DSC of polymer ( 3.5 ) ................................ ................................ ........................ 115 B 56 DSC of polymer ( 3.6 ) ................................ ................................ ........................ 115 B 57 DSC of polymer ( 3.7 ) ................................ ................................ ........................ 116 B 58 DSC of polymer ( 3.8 ) ................................ ................................ ........................ 116 B 59 DSC of polymer ( 3.9 ) ................................ ................................ ........................ 117 B 60 DSC of polymer ( 3.10 ) ................................ ................................ ...................... 117 B 61 DSC of polymer ( 3.11 ) ................................ ................................ ...................... 118 B 62 DSC of polymer ( 3.12 ) ................................ ................................ ...................... 118 B 63 GPC of polymer ( 2.5 ) ................................ ................................ ........................ 119 B 64 GPC of polymer ( 2.6 ) ................................ ................................ ........................ 119 B 65 GPC of polymer ( 2.7 ) ................................ ................................ ........................ 120 B 66 GPC of polymer ( 2.8 ) ................................ ................................ ........................ 120 B 67 GPC of polymer ( 2.9 ) ................................ ................................ ........................ 121 B 68 GPC of polymer ( 2.10 ) ................................ ................................ ...................... 121 B 69 GPC of polymer ( 2.11 ) ................................ ................................ ...................... 122 B 70 GPC of polymer ( 2.12 ) ................................ ................................ ...................... 122 B 71 GPC of polymer ( 2.13 ) ................................ ................................ ...................... 123 B 72 GPC of polymer ( 2.14 ) ................................ ................................ ...................... 123 B 73 GPC of polymer ( 2.15 ) ................................ ................................ ...................... 124 B 74 GPC of polymer ( 2.16 ) ................................ ................................ ...................... 124 B 75 GPC of pol ymer ( 2.17 ) ................................ ................................ ...................... 125 B 76 GPC of polymer ( 2.18 ) ................................ ................................ ...................... 125

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16 B 77 GPC of polymer ( 2.19 ) ................................ ................................ ...................... 126 B 78 GPC of polymer ( 2.20 ) ................................ ................................ ...................... 126 B 79 GPC of polymer ( 2.21 ) ................................ ................................ ...................... 127 B 80 GPC of polymer ( 2.22 ) ................................ ................................ ...................... 127 B 81 GP C of polymer ( 2.23 ) ................................ ................................ ...................... 128 B 82 GPC of polymer ( 2.24 ) ................................ ................................ ...................... 128 B 83 GPC of polymer ( 2.25 ) ................................ ................................ ...................... 129 B 84 GPC of polymer ( 2.26 ) ................................ ................................ ...................... 129 B 85 GPC of polymer ( 3.5 ) ................................ ................................ ........................ 130 B 86 GPC of polymer ( 3.6 ) ................................ ................................ ........................ 130 B 87 GPC of polymer ( 3.7 ) ................................ ................................ ........................ 131 B 88 GPC of polymer ( 3.8 ) ................................ ................................ ........................ 131 B 89 GPC of polymer ( 3.9 ) ................................ ................................ ........................ 132 B 90 GPC of polymer ( 3.10 ) ................................ ................................ ...................... 132 B 91 GPC of polymer ( 3.11 ) ................................ ................................ ...................... 133 B 92 GPC of polymer ( 3.12 ) ................................ ................................ ...................... 133 B 93 Tensile strength testing of polymer ( 2.26 ) ................................ ........................ 134

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17 LIST OF ABBREVIATIONS ACA AFA C CA Cat. DBU DHCA HDFA DHSS DHTA DMDHT DMDMT DMF DMSO DMSS DMTA DSC FA g GPC Hz J mg MHz Acetyl coumaric Acid Acetyl ferulic Acid Celsius Coumaric Acid Catalyst 1,8 diazabicyclo[5.4.0]undec 7 ene Acetyl dihydrocoumaric Acid Acetyl dihydroferulic Acid 2,5 dihydroxysuccinylsuccinate 2,5 dihydroxyterephthalic Aci d Dimethyl 2,5 dihydroxyterephthalate Dimethyl 2,5 dimethoxyterephthalate Dimethylformamide Dimethyl sulfoxide Di methylsuccinylsuccinate Dimethoxyterephthalic Acid Differential Scanning Calorimetry Ferulic Acid Grams Gel Permeation Chromatography Hertz Jo ules Milligram Mega hertz

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18 mL mol mol% MS M W NMR N 2 PDI DE DET PP PS PVC ppm SA T g TGA THF T m Milliliter Moles Mole percent Methyl Succinate Weight average molecular weight Nuclear magnetic resonance Nitrogen gas Polydispersity index Polyethylene Poly(ethylene terephthalate) Polypropylene Polystyrene Poly(vinyl chloride) P arts per million Succinic Acid Glass transition temperature Thermal gravimetric analysis Tetrahydrofuran Melting temperature

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19 Abstract of Thesis Presented to the Graduate School of the University of Florida in Partial Fulfillment of t he Requirements for the Degree of Master in Science POLY(ETHYLENE TEREPHTHALATE) MIMICS FROM BIORENEWABLE FEEDSTOCK S By Gabriel Short August 2016 Chair: Stephen A. Miller Major: Chemistry Worldwide, an estimated 311 millions tons of plastics is produc ed annually and when disposed of, accumulate in landfills and waterways 1 3 To lessen environmental impact, biorenewable and degradable polymer s that mimic commodity plastics are needed 4 Herein, two series of poly(ethylene terephthalate) mimics are repor ted. Copolymers derived from fe rulic acid and coumaric acid utilize four monomers: acetyl ferulic acid and acetyl coumaric acid, as well as their hydrogenated forms While the number average molecular weight ( M n ) is low, i nitial thermal and physical data show that the copolymers are suitable mimics for a number of commercial polymers with glass transition temperatures ( T g ) ranging from 60 177 C. While succinic acid (SA) is normally derived from petrochemicals, companies have recently synthesized bio suc cinic acid through the fermentation of non food biomass, industrial waste, and corn glucose. 5,6 To form a PET mimic, SA is dimerized yielding dimethylsuccinylsuccinate (DMSS) and after three steps, 2,5 dimethoxyterephthalic acid (DMTA) is produced. 7,8 Reacting DMTA with a number of alkyl diols, fro m n= 2 10, a series of PET mimics was formed with M w above 10,000 g/mol and T g ranging from 7 74 C

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20 CHAPTER 1 MOTIVATION FOR BIORENEWABLE POLYMERS 1.1 What is the Problem w ith Current Polymers? S ince the commercialization of polymers in the early 190 0s, polymers have played an important role in everyday life. The depth and breadth of polymer usage in society as well as its affect on the world is impressive ; po lymeric materials have found applications as varied as vulcanized rubber, water bottles, an d drug release s ystems. However, problems arise from irresponsible polymer usage , the industry uses 26% of the total amount of polymers annually produced. Th is portion has a value of roughly $100 billion dollars, yet most of this is disposed of after the first use impacting the environment and the economy. 2 H istorically monomers have been produced from no n renewable synthetic sources, and even today commodity plastics are synt hesized utilizing materials derived from finite resources includ ing petroleum and natural gas. Availability of t hese resources is in sharp decline with some estimates predicting that oil reserves will last for only the next 53 years. 9 As pol ymer use continues to increase annually an important question arises 4 This question is two fold: one, what should be done with the existing polymers that are filling up waterways and landfills; and two, what should be done in order to safeguard the future of our planet? 1.2 Biorenewable Polymer s Place in The World Two important areas of research arise from the aforementioned dilemma: finding a monomer source other than petroleum and find ing a way to lessen the impact of

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21 consumer polym er wastes. Attempts to lessen the impact of consumer waste have been made though the ins tallation of recycling programs; however the United adherence to recycling programs has been notoriously poor 10 While some discarded polymers can be recycled, studies done by the Environmental Protection Agency in 2012 show that the United State s produced 10% of the annual 311 million tons of global plastic waste, with only 9% of those pla stics actually being recycled. This equates to 28 million tons of plastics per year entering landfills and waterways in the U.S. alone. Figure 1 1. Annual production of m ajor commodity polymers 11 Commodity plastics are separated into five major groups: polyethylene (PE), polypropylene (PP), poly(vinyl chloride) (PVC), poly(ethylene terephthalate) (PET), and polystyrene (PS) as shown in Figure 1 1 In order to replace commodity plastics, b iorenewable polymers must be able to mimic the ir thermal and physica l properties 1.3 Biorenewable Starting Materials Research presented herein is focused on synthesizing from biorenewable feedstocks. The i in all fields of chemistry is a growing trend due to realization that modern habits are causing a dangerously high level of pollutants 12 reference to minimization of waste produced, maximiza tion of atom economy, reduction

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22 of the use of hazardous compound s during synthesis, and utilization o f biorenewable sources where practical. 13 When defining what a b iorenewable feedstock is, answers encompass a broad range of sources all of which come from industrial/agricultura l wastes or dedicated energy crops. 14 The key component is that biorenewable starting materials are naturally produced each year and ideally are sustainably produced. 1.3 .1 Ferulic and Coumaric Acid Both p coumaric acid (CA) ( 2 ) and ferulic acid (FA) ( 2.3 ) are naturally occurring hydroxycinnamic acids Hydroxycinnamic acids encompass a number of compounds that contain an aromatic ring with a C3 chain As the most abundant hydroxycinnamic acid available from plant cells, ferulic acid is available from a wide variety of bi orenewable sources including maize bran, sugar beet pulp, wheat bran, and rice bran. 15 18 Quantifiable amounts of ferulic acid have been extracted from a number of different sources as listed in Table 1 1. 19 21 Table 1 1 Concentration of ferulic acid from different sources Ferulic Acid Source Concentration (mg/ 0.1 kg) Sugar cane bagasse 1300 Sugar beet pulp 800 Popcorn 313 Bamboo shoots 244 Brown rice 24 Coffee 14.3 Peanut 8.7 Spinach 7.4 Extracted in roughly the same concentrations as ferulic acid, coumaric acid is readily available and can be obtained from a number of plant sources including berries, grains flowers, and many of the same monocot sources as feru lic acid. 22 24 Ferulic and coumaric acid act as crosslinkers between lignin and hemicellulose in plants.

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23 1.3 .2 Succinic Acid Until recently, succinic acid had only been synthetically obtained from petro leum throug h methods such as carbonylation of acrylic acid, hydrogenation of maleic acid, and electrolytic reduction of maleic acid. 25 27 Companies such as Myriant and Bioamber have synthesized a bio succinic acid from the fe rmentation of non food biomass, industrial waste, and corn glucose. 5,6 There are a variety of synthetic methods of accessing succinic acid which avoid the use of petrochemicals, such as th rough the met abolic pathways of genetically engineered E. coli and other bacterial strains. 28 1.3 .3 Aliphatic Diols Aliphatic diols used in this body of work can all be obtained from renewable sources. Both short diols, with carbon spacers of 2 4, and long diols such as 1,10 decanediol can be obtained from plant oils castor beans, triglycerides, and fatty acids like linoleic acid 29,30 Other diols can be derived from naturally occurring acids through h ydrogenation : 1,5 pentanediol from glutaric acid, 1,6 hexanediol from adipic acid, 1,8 octanediol from suberic acid, and 1,9 nonanediol from azelaic acid. 31

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24 CHAPTER 2 FERULIC ACID AND COUMARIC ACID BASED COPOLYMERS 2 .1 Background and Introduction Various routes have been developed for the synthesis of biorenewable polymer s ; Hillmyer et al used terpenes as monomers to form susta inable thermoplastic elastomers and Allais et al used fully biorenewable monomers based on ferulic acid and succinic acid to synthesize polyesters with tunable thermal properties. 32,33 L ignin, commonly collected as a byproduct of paper manufacturing, has even been utilized in the synthesis of green composite polymers. 34 Ideally green polymers should be easily degradable under environmental condition s while simultaneously origi nating from a renewable source. However, this is not always the case. Poly(lactic acid) (PLA) is the most abundant consumer polyester derived from a biorenewable source. While its synthesis can be biorenewable, special industri al conditions such as specific pH and temperature are necessary for degradation. 35 Re cent attempts have been made to improve the thermal properties along with the degradability of PLA by blending it with clays, sta rch es and even the introduction of comonomers in small percentages 36 Conversely, Poly ( caprolactone) (PCL) is derived from synthetic sources and can degrade in mild environmental conditions. 37 Thus, not every polymer synthesized from biorenewable sources is degradable, nor is every synthetic polymer non degradable. Green polymers start to become truly beneficial as commo dity plastic replacements when they can be synthesized from f ully renewable sources and are environmentally degradable such as those investigated by Allais 33 The primary issue with many bior enewable polymers is a deficiency in thermal and physical properties. To utilize a biorenewable polymer as a commodity plastic, it

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25 must display thermal and physical properties similar to those of the commodity plastic it is meant to mimic. Many green polymers lack the phys ical properties necessary to replace commodity plastics with hig her glass transition temperatures. For example, PLA blended w ith starch is degradable but is also brittle and has an even lower T g than PLA alone. 36 The biorenewable PLA has a T g of 50 62 C but shows improved th ermal properties over PCL ( T g of 62 C). Yet, the application of PLA limited due the T g To be useful, a green polymer must mimic the common commodi properties. Two high volume plastics, Polystyrene ( T g of 100 C) and Poly(ethylene terephthalate) ( T g of 68 C), have improved thermal properties in a region suitable for wide spread application. 38 Overcoming the di screpancy between biorenewability and is where our research has significant importance 2.2 Copolymer Series F A ( 2.3 ) and CA ( 2 ) are used in this body of work as monomer precursors In particular, we are inte rested in polymerizations utilizing acetyl dihydrocoumaric acid (DHCA) ( 2.2 ) and acetyl dihydroferulic acid (D HFA ) ( 2.5 ) as co monomers. p hydroxyl a cetylation of FA and CA result in acetylferulic acid (AFA) ( 2.4 ) and acetylcoumaric (ACA) ( 2. 1 ), respective ly. Following h ydrogen ation of the unsaturated carboxylic acid DHCA and DHFA are obtained The rationale behind acetylation is to produce AB type monomers capable of undergo ing transesterification.

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26 Figure 2 1. Synthesis of biorenewable monomers from FA ( 2.3 ) and CA ( 2 ) Previous tes ting in our lab has shown that when working with FA ( 2.3 ) and CA ( 2 ) traditional Fisher esterif ication yield poor results, affording oligomeric products at best Hydrogenation of AFA ( 2.4 ) and ACA ( 2.1 ) yields a more conformationally flexible structure and affords the possibility of lowering or increasing the T g via partial or complete hydrogenation to impart tunable thermal properties. Two copolymers with different feed ratios were synthesized a nd characterized: DHCA co DHFA and DHCA co AFA. The feed rat ios were investigated from 0 100% for each monomer. In addition, l arge scale reactions were attempted using DHFA in order to obtain mechanical testing. Replacements for commodity plastics must match or excel the ir thermal and physical properties in order t o be successful. Synthesizing polymers from renewable sources is an important and necessary transition from dependence on finite resources. 39 The main problem with renewable polymers is insufficient thermal and physical prope rties. Pol y(lactic acid) (PLA) is the most industria lly employed bio based polyester however, it suffers from a low glass transition temperature (~60 C) which inhibits wider application. Copolymers synthesized from CA and FA derivatives may posses higher T g which w ou ld allow for wide spread application.

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27 2.2.1 Synthesis and Characterization Figure 2 2. The m onomer AFA ( 2.4 ), DHCA ( 2.2 ), and DHFA ( 2.5 ) The synthesis of two copolymers utilized three monomers: AFA ( 2.4 ) DHFA ( 2.5 ) and DHCA ( 2.2 ) shown in Figure 2 2 Acetylation of the hydroxycinnamic acids was carried out in a single pot utilizing conditions previously reported by our lab. 40 These two compounds, ACA ( 2.1 ) and AFA ( 2.4 ), were used as monomers for copolymerizations. These purified compo unds were subsequently hydr ogenated to yield DHFA and DHCA, resulting in four monomers. Figure 2 3. Monomer synthesis starting with FA ( 2.3 ) and CA ( 2 ), acetylation to form AFA ( 2.4 ) and ACA ( 2. 1 ) and hydrogenation to form DHFA ( 2. 5 ) and DHCA ( 2. 2 ) Two co polymer series were synthesized utilizing three of the four monomers: Poly(hydrocoumaric co ferulic) acid and Poly(hydrocoumaric co hydroferulic) acid. Reactions were carried out in the melt with 1.2 mol % Zn(OAc) 2 2 O catalyst, under inert atmospheric conditions and covered with foil to ensure that light did not initiate radical reactions. 41 The polymerizations were heated for 4 hours w ith a temperature ramp from 150 230 C. After reaching 230 C, the reaction was placed under dynamic vacuum for 3 hours. As vacuum was applied to remove the acetic acid byproduct the

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28 mixture reaction solidified. Solidification of the reaction was indicative of high conversion. Work up of the reactions consisted of dissolving the crude product in a mixture of dichloromethane and trifluoroacetic acid, followed by precipitation into cold methanol. Yields for the two series ranged from 70 94% with the c opolymers containing above 60% feed ratios of AFA ( 2.4 ) having lower yields. Figure 2 4. Copolymerizations utilizing DHCA ( 2.2 ) DHFA ( 2.5 ) and AFA ( 2.4 ) 2.2.2 Effects of Internal Alkene As seen in Table 2 1 and Table 2 2, c hanging the monome r feed ratio resulted in varied thermal ( i.e. T g and T m ) and physical properties for the copolymer series. Addition of AFA ( 2.4 ) increased the T g incrementally, due to limited bond mobility of the conformationally locked trans double bond. Hydrogenation of the trans double bond to form DHFA ( 2.5 ) results in an increase in the degrees of freed om and a decrease in the rotational energy barrier; in turn these molecular changes cause a lower T g (73 C) as compared to polyferulic acid

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29 Table 2 1. Thermal and physical data obtained from copolymerization of the DHCA ( 2.2 ) and DHFA ( 2.5 ) Entry DHC A: DHFA DHCA:D HFA c M n b (g/mol) PDI b T g a (C) T m a (C) T 50 (C) Feed Ratio NMR Ratio 2.5 100 0 100 0 1600 1.9 57 415 2.6 90 10 90.7 9.3 1000 4.7 53 225 409 2.7 80 20 91.5 8.5 56 232 408 2.8 70 30 85.3 14.7 1300 6.7 57 221 389 2.9 60 40 59.5 40.5 3800 3.4 47 170 371 2.10 50 50 48.7 51.3 3500 2.4 53 168 407 2.11 40 60 36.2 63.8 2200 4.9 53 187 404 2.12 30 70 23.2 76.8 3100 4.4 51 201 420 2.13 20 80 2.5 97.5 1700 4.8 53 240 414 2.14 10 90 6.7 93.3 1400 4.6 57 238 414 2.15 0 100 0 100 4400 3.9 60 243 413 a Determined by DSC. b Values calculated using GPC in hexafluoroisopropanol (HFIP) with poly(methyl methacrylate) standards. c Integration calculations shown in experimental. The Poly(hydroferulic co hydrocoumaric) acid series (Table 2 1 ) displayed similar thermal properties despite feed ratio changes. Slight variance s in glass transit ion temperat ure were observed ranging from 47 60 C. The addition of a methoxy group between the co monomers should change the T m as it would hinder the c rystallinity of the copolymers. This series showed an increase in T m a s the polymer reached 100% feed of either monomer. Some of the polymers had minimal solubility in hexafluoroisopropanol, in a mixture of trifluoroacetic acid and methylene chloride (used to precipitate the polymers), or in chloroform d with six drops of trifluoroacetic acid (used as NMR solvent). It may be due to this partial intractability that NMR ratios do not match the feed ratios accurately. Molecular weight did not show a trend corr elating with

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30 amounts of comonomer consumed ; instead they proved to be sporadically alternating between oligomers and polymers of M n up to 4400 g/mol. Such inconsistencies could be resolved if the polymerizations were stirred at higher temperatures this iss ue will be discussed further on. Table 2 2. Thermal and physical data obtained from copolymerization of the DHCA ( 2.2 ) and AFA ( 2.4 ) Entry DHCA:AFA DHCA:AFA c M n b (g/mol) PDI b T g a (C) T m a (C) T 50 (C) Feed Ratio NMR Ratio 2.5 100 0 100 0 1600 1 .9 57 415 2.16 90 10 94.1 5.9 2000 2.9 449 2.17 80 20 86.6 13.4 1200 2.6 28 431 2.18 70 30 73.2 26.8 1700 2.5 54 218 434 2.19 60 40 66.8 33.2 1800 2.5 68 455 2.20 50 50 51.3 48.7 1900 2.7 57 469 2.21 40 60 40.9 59.1 1200 2.5 83 488 2 .22 30 70 34.8 65.2 1200 2.4 109 423 2.23 20 80 19.5 80.5 1200 2.4 96 286 431 2.24 10 90 8 92 1100 3.5 98 440 2.25 0 100 0 100 1400 2.5 114 427 a Determined by DSC. b Values calculated using GPC in hexafluoroisopropanol (HFIP) with poly(methyl me thacrylate) standards. c Integration calculations shown in experimental. The p oly(hydrocoumaric co ferulic) acid series (Table 2 2) exhibited glass transition temperatures which increased with the amount of AFA ( 2.4 ) comonomer used. A substantial increas e in T g was observed with inco rporation of more than 30% the more conformationally locked monomer. This trend is caused by the addition of a trans double bond in the polymer backbone that limits degree of rotational freedom,

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31 thus im proving thermal properties. AFA containing polymers are difficult to dissolve and surp risingly only two had a discerni ble T m A possible explanation for this lack of a T m could be a large PDI causing a broad peak that could not be seen on the thermograph, i.e. th e plasticization of the long polymer chains by the smaller ones. Differential scanning calorimetry ( DSC ) can be used with temperatures up to the 5% wei ght loss temperature, which was between 220 310 C and it is possible that the T m for these polymers is closer to the degradation temperature than to the 5% weight loss These polymers all had one similar problem : stirring. After vacuum is applied to the reaction mixture, it promptly solidifies. This inability to stir results in lower molecular weight pol ymers. Reported in Table 1 and Table 2 is the number average molecular weight of the polymers in the series which is influenced by the number of chains at certain lengths than the mass of individual chains. None of the polymer series achieved a M n over 10 000 g/mol, which was the goal for this polymer. This mass was set as the goal as polymer characteristi cs are not significantly influenced over this molecular weight 42 Attempts at changing the polymerization conditions in hopes of i ncreasing molecular weight have been attempted. Lower polymeriz ation temperatures resulted in no polymeriz ation or oligomerization while higher polymerization temperatures resulted in formation of a black charred polymer of low molecular weight. Figure 2 5 Secondary polymerization of polyhydroferulic acid.

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32 In order t o increase the molecular weight, chain extension of polyhydroferulic acid (PHFA) ( 2.15 ) was attempted. In itially, direct re polymerization resulted in charred polymers of lower molecular we ight than the initial trial as the M n decreased from 5300 g/mol to 34 00 g/mol. To solve this problem, the polymer was acetylated and polymerized in one pot. Following acetylation, excess acetic anhydride and acetic acid were distilled off during the polyme rization under vacuum. A n a cetylation was performed to insure end groups were properly functionalized for transesterification This process increased the molecular weight slightly to 6500 g/mol (PDI of 4.0). The thermal properties of polydihydroferulic aci d ( 2.26 ) proved similar to those of the large batch of polydihydroferulic acid ( 2.27 ) The T g stayed within the range of polyhydroferulic acid (69 C) and a T m of 194 C was visible ; however a crystallization peak (~150 C) during its heating cycle was exp ressed. This peak has not been previously noted on DSC thermograms of PHFA and no parameters have been changed. In order to test if this can be reproduced in other samples, they can be annealed below their T m on the DSC. Figure 2 6. Large scale p olymer ization of DHFA ( 2.5 ) forming polymer ( 2.27 ) Another way to solve the problem of low molecular weight and processing difficulties was to attempt large scale reactions using a custom reaction vessel. The reaction vessel used was an airtight metal canister a ble to be heated temperatures above 250 C while being mechanically stirred. For these reactions, heating time was increased in order to ensure homogeneous heating of the monomers. An optimized reaction (Figure 2 6 ) utilized 40 g of DHFA ( 2.5 ) loaded into the reaction vessel and

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33 dried for 5 hours. Once dried and deoxygenated, the reaction mixture was heated for 4 hours and vacuum was pulled for a subsequent 8 hours. Utilizing this reactor with pure DHFA yielded no change in thermal properties ( T g = 70 C, T m = 207 C) but increas ed the molecular weight up to a M n of 7000g/mol. Tensile strength was obtained via mechanical testing on the polyhydroferulic acid ( 2.27 ) and w hen compared to PLA (28 50 MPa) and PET (1.7 GPa), the tensile strength of ( 2.27 ) at 11.6 MPa is low. 38 The low strength is partially due to low molecular we ight, charring due to difficulties during polymerization and processi ng problems stemming from solubility issues. 2.2.3 Glass Transition Temperature Comparison A total of six different copolymers can be syn thesized from the four monomers as depicted in Figure 2 7. Poly(ferulic co coumaric) acid (f) was attempted, however, n o polymer was formed and further polymerizations using AFA ( 2.4 ) and ACA ( 2.1 ) together were ceased. One possible reason is due to the high melting temperature caused by the trans double bond rigidity in both monomers Figure 2 7. Six different polymers available from the four monomers Poly(hydroferulic co hydrocoumaric) acid (a) poly(hydroferulic co coumaric) acid (b) poly(hydroferulic co ferulic) acid (c) poly(hydrocoumaric co coumaric) acid (d) poly(hydrocoumaric co ferulic) acid (e) and poly(feru lic co coumaric) acid (f) Ha Thi Hoang Nguyen, a fellow graduate student in the lab, synthesized three copolymer series: poly(hydroferulic co coumaric) acid (b) poly(hydroferulic co ferulic)

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34 acid (c) and poly(hydrocoumaric co coumaric) acid (d) The M n of these series were all under the ideal 10 000 g/mol. Thermal data collected from all fi ve series is shown in Figure 2 8 where the glass transition temperatures of each series are plotted with the values of the most common commodity plastics. Depending o n the composition of the polymer, thermal properties of any commodity plastic can be mimicked. As seen in the AHCA co ACA copolymer, the T g is visibly higher than that of polycarbonate. However, due to high ACA ( 2.1 ) content the series has a problem with p rocessability. Figure 2 8 T g of five copolymer series compaired to several commodity plastics With the exception of the DHCA co DHFA copolymer series, all showed T g values properti es above those of PET, p oly(vinyl chloride), and even polystyre ne. A poly(hydrocoumaric) acid ( 2. 1 5 ) recently synthesized had a lower T g than that made by PC PS PV PET PLA

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35 Ms. Nguyen, 57 C as compared to 74 C This was primarily due to molecular weight of ( 2.15 ), 1600 g/mol while the synthesized polymer had a M n of 6600 g/mol. Many of the DHCA co DHFA and DHCA co AFA series had low molecular weight, which directly affects the glass transition temperature. Even at lower molecular weights, many of the copolymers match the thermal properties of commodity plastics. The poor physical pro perties of the PHFA sample that was tested could be attributed to the same molecular weight problem. Once a polymer of high molecular weight can be consistently synthesized, physical properties will be re tested and it is expected that improvements will be seen. 2.2.4 New Ideas and Conclusion The unsaturated carboxylic acid in ferulic and coumaric acid is exploited by our group for little more than hydrogenation yet it is a facile reactive handle. The use of create di or tri blocks is a field that has been explored recently and may have substantial application in the area of green polymers. 43 Utilizing the trans double bond, thiol ene click reactions photo cyclization and Diels Alder reactions can be undertaken. In this vein of thought, e xploration into incorporating amide functionality through the internal double bond has begun. One route is through the reaction of amine alcohol s, such as ethanolami ne, with ferulic acid An aza Michael addition at the unsaturated ketone would yield monomers capable of forming polyamides ; however this reaction has yet to yield reproducible results 44 To overcome this, DHFA ( 2.5 ) can be used in the place of ferulic acid. While yielding two different monomers, both would incorporate amine functionality into the monomers.

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36 The r eadily available and renewable monomer precursors ferulic and coumaric acids were used to synthesize a number of monomers. These monomers were then co polymerized to form several series that display thermal properties mimicking those of traditionally used plastics. This study showed that renewable feed stocks could be used to reach glass transition temper atures of heavily used commercial plastics. The benefit of polymers formed from CA and FA derivat ives is that when degraded, they break down to oligomer and eventually to the biorenewable monomers Even oligomers released into the environment can further d egrade via natural processes. Future goals for these projects will begin with degradation studies to ensure degradability in environmental conditions for the two series of copolymers.

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37 CHAPTER 3 SUCCINIC ACID BASED POLY(ETHYLENE TEREPHTHALATE ) MIMIC 3.1 Ba ckground and Introduction Poly(ethylene terephthalate) (PET) has many commodity applications, the most prevalent being its use in disposable water bottles manufacturing. Each year, 8% of plastic prod uction, roughly 25 million tons, consists of PET 11 PET is synthesized through the esterification of terephthalic acid with ethylene glycol Ethylene glycol can come from renewable sources; however terephthalic aci d is a product of petrochemical based synthesis whi ch places stress on the limited petroleum reserves 45 Figure 3 1. Structure of poly(ethylene terephthalate) Coupled with the large amount of PET produced, its irresponsible disposal has caused environmental accumulation 2 In marine conditions, it takes 15 years for the surface of PET plastic to begin to be altered. 46 A slight change in surface morphology is not necessarily degradation, as t he environment tends to break down larger pieces into microplastics. 3 Early this year, researchers found two unique bacteria that are able to break down PET 47 The mutated bacteria are rare but could help with the existing PET pollution problem. However, the problems of future production, as petroleum reserves are finite, and waste build up remain prevalent Researchers have made attempts to produce PET mimics from renewable sources with mixed success. Mu oz Gue rra et al. synthesized biorenewable diol and diacid monomers from a protected tartaric acid. 48 As renewable monomers they are

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38 interesting but have insufficient thermal properties to be a PET mimic Replacing the terephthalic acid with their tartaric acid based mimic, the glass transition temperature drops substantially (from T g = 75 C to T g = 7 C ). Our lab has synthesized polyhydroferulic acid as a PET mimic with T g matching or excee ding that of PET (68 C ) and Chapter 2 outlines these c opolymers 40 One problem with these polymers is their low molecular weight, and their processing could prove to be problematic due to limited solubility Other labs have contributed to the field of bio renewable PET mimics beginning at a number of substantially different points. A few examples of these renewable PET mimics include composites synthesized from recycled waste PET, limonene converted into terephthalic acid then polymerized and even Diels Alder reaction between bio derived 2,5 dimethylfuran and acrolein to form p xylene which when oxidized forms terephthalic acid. 49 51 In the hopes of finding another route to form bio renewable PET m imics, our group began to search for a new monomer source. What was found was a method of forming PET mimi cs from biorenewable succinic acid. Figure 3 2. Synthesis of 2,5 dimethoxyterephthalic acid ( 3.4 ), starting from succinic acid and progressing throu gh dimethylsuccinylsuccinate ( 3 ) Succinic acid (SA) is normally produced though syntheses beginning with petroleum products, but recently companies, for example BioAmber and Myriant, have begun producing bio succinic acid. This bio based succinic acid come s from the fermentation of sugars collected from sustainable sources. These sources include

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39 industrial waste and corn glucose from non food harvests. Interestingly, dimerization and subsequent aromatization forms a diacid similar to terephthalic acid, as s een in Figure 3 2. After the esterification of SA, dimerization of methyl succinate yields dimethylsuccinylsuccinate (DMSS ) ( 3 ) T his procedure has been reported in a number of patents. 7,52,53 After three steps 2,5 dimethoxyterephthalic acid (DMTA) ( 3.4 ) is synthesized as the target molecule. This monomer, along with its derivatives can be used as terephthalic acid replacements to generate a number of PET mimics. 3.2 D imethyl 2,5 d imethoxyterephthalate and Derivatives In order to synthesize a terephthalic acid mimic, succinic acid must be esterified and then dimerized. Figure 3 3 shows the proposed synthetic pathway An excess of sodium methoxide is required in order to afford the reactive intermediate. The dimerization synthesis has been initiated, but DM SS has not yet been formed. Investigations into the synthesis of DMSS from SA are ongoing. However, in order to expedite the monomer synthesis, DMSS was acquired commercially. Figure 3 3. Proposed synthesis of DMSS ( 3 ) from SA The first step from DMSS ( 3 ) to dimethyl 2,5 dihydroxyterephthalate (DMDHT) ( 3.1 ) is an aromatization utilizing N chlorosuccinimide in acetic acid. This reac tion was refluxed for one hour and cooled to room temperature. The product was recovered by

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40 vacuum filtration and subsequentl y washed with acetic acid, water, and finally ethyl ether The product was purified by recrystall ization from acetic acid. The resulting yellow crystals were used in the synthesis of two different monomers: DMTA ( 3.4 ) and 2,5 dihydroxyterephthalatic acid ( DHTA) ( 3.2 ) Synthesis of DHTA ( 3.2 ) required the saponification of DMDHT ( 3.1 ). After 12 hours of reflux under basic conditions, the solvent was evaporated off and the resulting solid was dissolved in water and acidified. Once acid was added to the soluti on, product precipitate d Upon filtering, a yellow green powder was collected DMTA had an addition al methylation prior to saponification. Potassium carbonate and methyl iodide were added to DMTA in acetone and refluxed for 24 hours. After acetone was remo ved, the resulting dimethyl 2,5 dimethoxy terephthalate (DMDMT) ( 3.3 ) was dissolved in water and saponified using the same procedure as previously stated. Figure 3 4. Possible b iorenewable terephthalic acid mimics synthesized from DMSS ( 3 ) 3.3 Polyester Copolymers From Diols and Succinic Acid Based Monomers The p olymerization of DHTA ( 3.2 ) was initially attempted with ethylene glycol, however an intractable solid was produced and the molecular weight was un controlled Thus, a full series of polymerizatio ns were performed using DMTA ( 3.4 ). T he t hermal data from the two polymers formed from DHTA will be discussed in section 3.3.2.

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41 3.3.1 Poly(alkyl ene dimethoxyterephthal a tes) Synthesis and Characterization The poly(alkyl ene dimethoxyterephthal a te ) series wa s synthesized utilizing 2,5 dimethoxyterephthalic acid ( 3.4 ) and diols with carbon spacers ranging from 2 10. Reactions were carried out in the melt with 1.2 mol% Sb 2 O 3 the most prevalent catalyst for industrial synthesis of polyesters. 54,55 As seen in Figure 3 5, the polymerization began with heating the round bottom flask which was charged with with DMTA ( 3.4 ) and a diol, using a temperature ramp from 190 210 C over 18 hours. This heating ramp under vacuum helped to minimize the loss of monomer s du e to vacuum. Increasing the temperature helped to melt the polymer and increase stirring. After this heating period, vacuum was applied to the reaction for an additional 8 hours to remove water and to further increase conversion. The temperature was incre ased from 210 240 C under vacuum to insure maximum conversion. Due to the l ack of a mechanical stirrer, these reactions began to solidify at 210 C under vacuum. While this represents an increase in molecular weight as the polymerization becomes more v iscous, it also rendered the magnetic stir bar useless. F igure 3 5. General polymerization procedure for poly(alk yl ene dimethoxyterephthalate) series Polymerizations were carried out between DMTA ( 3.4 ) and eight different diols. The thermal and physical characterizations of these eight polymers are displayed in Table 3 1. As with the previous series of polymerizations, the intended molecular weight

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42 was over 10,000 g/mol. The polymerizations were all obtained with a molecular weight above 19,000 g/mol wit h the exception of DMTA and ethylene glycol. Table 3 1. Thermal and physical data obtained from polymerizations of DMTA and diols Entry Diol M n b (g/mol) PDI b T g a (C) T m a (C) T 50 a (C) 3.5 Ethylene Glycol 5,900 3.3 74 163 c 361 3.6 1,3 Propanediol 21, 900 3.7 63 371 3.7 1,4 Butanediol 19,500 4.6 45 149 358 3.8 1,5 Pentanediol 31,700 2.4 33 369 3.9 1,6 Hexanediol 21,000 2.7 27 114 c 364 3.10 1,8 Octanediol 23,000 2.5 15 113 362 3.11 1,9 Nonanediol 29,000 2.2 10 380 3.12 1,10 Decanediol 36,200 2.5 7 80 c 377 a Determined by DSC. b Values calculated using GPC in hexafluoroisopropanol (HFIP) with poly(methyl methacrylate) standards. c Values for T m were only found after isotherming the polymers. The other polymers expressed high molecular weights and had acceptable polydispersity values for condensation polymerizations, with the exception of diols with carbon spacers of 2 4. These three polymers showed wider gel permeation chromatography (GPC) peaks representing a l arge r disparity in chain lengt hs within the samples A possible reason for this is that these diols are liquids with lower boiling points: ethylene glycol boils around 195 C 1,3 propanediol boils at 211 C and 1,4 butanediol boils at 235 C A s the polymerization is c arried out at h igh temperatures, some of these diols are boiled off during the reactions, leading to an excess of DMTA ( 3.4 ) and a broadening of the molecular weight range. The liquid diols are added in a molar ratio of 1:1.03 taking into consideration the fact that some monomer will be boiled off. Although 1,5 pentanediol is a liquid, its boiling point is over 240 C and therefore volatility is not an issue. The thermal properties for this series followed predictions, yet demonstrated interesting peculiarities Glass t ransiti on temperatures decrease from 74 C for poly(ethylene dimethoxyterephthalate) to 7 C for poly(decylene

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43 dimeth carbon chain length increases, the T g decreses This trend is expected as longer chain lengths increase th e degrees of freedom for each repeat unit and this lowers the temperature needed to cause long range segmental motion. The graphical representation depicted in Figure 3 6 shows how the data follows the predicted trend. An interesting observation about thes e polymers is t hat o nly the diols with even carbon chain lengths displayed a T m and only when annealed with the exception of polymer ( 3.10 ) It is possible that the odd numbered diol containing polymers have melting points, but the ir crystallization times are longer than what the DSC allows Figure 3 6 Comparison of T g and T m for poly(alkylene dimethoxyterephthalate) series Poly(ethylene dimethoxyterephthalate) is a structural mimic of PET with an aromatic diacid linked together by ethylene glycol and has a slightly higher T g of 74 C compared to T g of 68 C While the T m is lower than that of PET ( 163 C as compared to 250 C ) it is an entirely biorenewable mimic. Interestingly, the most difficult polymerization was the polymerization of DMT A and ethylene glycol. This T g T m

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44 polymerization yielded polymers of lower molecular weight when compared to those synthesized from with other diols. One issue was the boiling off of the short chain diol and to counteract this issue, the ratio of ethylene glycol to DMTA was varied (Table 3 2). Reactions were attempted with a 1:1 ratio but resulted in charred monomer. The highest molecular weight obtained was just over 10,000 g/mol ; however the PDI was very broad which had a noticeable influence on the T g loweri ng it by about 15 C Only one of the poly(ethylene dimethoxyterephthalate) polymers synthesized displayed a melting te mperature. It is not coincidental that the same polymer also had the narrowest PDI, as a more uniform molecular weight dispersion allows for faster crystallization. 56 Table 3 2. Optimization of polymerization between DMTA and ethylene glycol a Determined by DSC. b Values calculated using GPC in hexafluoroisopropanol (HFIP) with poly(methyl methacrylate) standards. 3.3.2 Comparison of Po ly(alkyl ene dimethoxyterephthal a tes) with Poly(alkyl ene dihydroxyterephthalates) Two polymers were synthesized from 2,5 dihydroxyterephthalic acid: poly(ethylene dihydroxyterephthalate) and poly(decylene dihydroxyterephthalate). Polymerizations were carri ed out under the same conditions as for the series of 2,5 dimethoxyterephthalic acid. These polymers behaved similarly during the polymerization but have drastically different thermal properties.

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45 Table 3 3. Thermal property comparison between polymers wit h three different diacids a Determined by DSC. As seen in Table 3 3, polymers containing DHTA ( 3.2 ) have significantly higher T g than the polymer series containing DMTA ( 3.4 ) as well as higher T g than PET. While poly(ethylene dimethoxyterephthalate) and PET have the same T g both are 100 C less than that of p oly(ethylene dihydroxyterephthalate) Even poly(dec ylene dihydroxyterephthalate) a C 10 diol which should have a low T g displayed increased thermal properties. The T g and T m are significantly highe r as compared to poly(decylene dimeth oxyterephthalate) One possibility for this drastic increase in thermal properties could be intermolecular hydrogen bonding. While this increases thermal properties, it also increases the difficulty of polymer processin g The lack of a melting point for p oly(ethylene dihydroxyterephthalate) could be due to the T m proximity to its degradation temperature or due to low M n and broad PDI. GPC data was unable to be obtai ned due to a lack of polymer solubility. 3.4 New Ideas a nd Conclusion Future projects for this body of wo rk start with the synthesis of DMSS ( 3 ) from succinic acid. The two polymers containing DHTA ( 3.2 ) as a monomer have shown promise with improved thermal properties when compared to PET As such, future work will include the synthesis of an entire series of polymers utilizing DHTA In addition to this series, polymerizations with hydrolyzed DMSS have begun and are currently in the optimization phase. After the reaction is optimized, a series of polymers matchi ng the

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46 series with DMTA will be run in parallel with those using DHTA as a monomer. After these have been synthesized, a degradation study of all three polymer series will be undertaken to test if they are able to undergo a quicker degradation than PET Th is study shows that polymers based on succinic acid derived monomers are a viable mimic for poly(ethylene terephthalate). The series resulting from the polymerizations of DMTA ( 3.4 ) with diols of carbon lengths n=2 10 have a T g range from 7 74 C Long er diols decrease the thermal properties while poly(ethylene dimethoxyterephthalate) has properties matching those of PET. Two polymers containing DHTA have exhibited thermal properties higher than that of the DMTA series and PET. Molecular weight is consi stently higher than 10,000 g/mol with the exception of poly(ethylene dimethoxyterephthalate).

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47 CHAPTER 4 EXPERIMENTAL 4 .1 Molecular Characterization Nuclear magnetic resonance was performed on an Inova 500 MHz spectrometer for both proton ( 1 H NMR) and carbon ( 13 C NMR) experiments. For 1 H NMR, coupling constants ( J ) will be reported in Hertz (Hz) and all chemical shifts will be reported using parts per million (ppm) downfield relative to residual proton peaks from specified solvent or tetramethylsilane ( TMS, 0.0 ppm). Multiplicities will be denoted utilizing abbreviations: singlet (s); doublet (d); triplet (t); quartet (q); multiplet (m). Thermal characterization was carried out using differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA) DSC thermograms were obtained utilizing a DSC Q1000 from TA Instruments ( New Castle, DE). Each run used 3 5 mg of sample, in a hermetically sealed aluminum pan. This sample was then subjected to thr ee cycles of heat/cool/heat at 10 C/min from 60 C to its 5% weight loss obtained by TGA. TGA analyses were obtained on a Q5000 from TA Instruments. Samples, ranging from 5 1 0 mg, were heated at 20 C/m in from room temperature to 600 C under N 2 Molecular weight was determined using gel permeation chro matography. The Agilent Technologies (Santa Clara, CA) 1260 Infinity Series liquid chromatography system was used with an internal differential refractive index detector, a PL HFIP gel column (7.5 mm i.d., 300 mm length), and a mobile phase of 0.1% potass ium triflate (K(OTf)) in HPLC grade hexafluoroisopropanol (HFIP) at a flow rate of 0.3 mL/min. Calibration was performed using polymethyl methacrylate (PMMA) standards with narrow polydispersity.

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48 Tensile strength was tested by Dr. Megan Robertson at the University of Houston Department of Chemical and Biomolecular Engineering, using an Instron (Norwood, MA) tensile tester. NMR solvents deuterated dimethyl sulfoxide (DMSO d 6 ) and deuterated chloroform (CDCl 3 ) were purchased from Cambridge Isotope Laborator ies. Trifluoroacetic acid succinic acid, dimethylsuccinylsuccinate, propane diol, butane diol, and nonane diol were obtained from Sigma Aldrich. Ethylene glycol, pentanediol, hexanediol, octanediol, and decanediol were obtained from Acros Organics. Coum aric acid and ferulic a cid were purchased from Alibaba. All other chemicals, unless otherwise stated, were used as received without further purification. Unless otherwise stat ed, all polymer NMR samples were prepared in CDCl 3 with 4 6 drops of trifluoroac etic acid to aid in solubility 4 .2 Synthesis of Ferulic and Coumaric Acid Based Polymers 4 .2.1 Monomer Synthesis The first step in monomer synthesis is an acetylation 200 g of either f erulic acid (1.03 mol) or coumaric acid (1.22 mol) was added to a 1 L beaker. A 1:1 molar ratio of acetic anhydride was added and stirred using an overhead mechanical stirrer until thoroughly mixed. A 1:1 molar ratio of pyridine was added to the mixture and stirred, resulting in a yellow liquid. White solid forme d after 5 mi nutes of stirring. After cooling to room temperature, the solid was split into two separate 1 L E rlenmeyer flasks and 1 L of water was added to each one. This solution was then stirred for 16 hours The reaction mixture was then gravity filtered and rinsed three times with water. Once dry, the white solid was ground using a mortar and pestle, then added to a round bottom flask. Tetrahydrofuran (THF) added to the AFA in a 3 mL: 1 g (product) ratio and to the ACA

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49 in a 1.5 mL : 1 g (product) ratio and triturat ed. The product was vacuum filtered after 24 hours of trituration. Acetyl ferulic acid was obtained as a white power in 90% yie ld (219 g). Acetyl coumaric acid was obtained as a white powder in 80% yield (201 g). Figure 4 1. Synth esis of acetyl ferulic acid ( 2.4 ) 1 H NMR (DMSO d 6 J =16.1 Hz, 1 H), 7.12 (d, J =8.1 HZ, 1 H), 7.26 (d J =7.8 Hz, 1 H), 7.40 (s, 1 H), 7.58 (d, J =15.9 Hz, 1 H), 12.09 (s, 1 H). 13 C NMR (DMSO d 6 143. 8, 151.6, 168.1, 168.9. Figure 4 2. Synthesis of acetyl coumaric acid ( 2.1 ) 1 H NMR (DMSO d 6 J =16.1 Hz 1 H), 7.17 (d, J =8.5 Hz, 2 H), 7.59 (d, J =16. 1, 1 H), 7.73 (d, J =8.5 Hz, 2 H), 12.40 (s, 1 H). 13 C NMR (DMSO d 6 ppm 21.3, 119.8, 122.8, 129.9, 132.4, 143.4, 152.3, 168.0, 169.5. The second step of monomer synthesis was hydrogenation of AFA ( 2.4 ) and ACA ( 2.1 ) Hydrogenations were carried out in a 1 .5 L high pressure flask. 80 g of either acetyl ferulic acid (0.339 mol) or acetyl coumaric acid (0.388 mol) and 5% by weight Pd/C catalyst were added to the flask followed by 780 mL of a 1.87:1 mL THF to methanol mixture. Once the solution was stirring, the reaction was purged and placed

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50 under hydrogen gas at 60 psi. The reaction continued under H 2 for 19 hours. Initially a grey suspension of starting material and Pd/C completion of the reaction is denoted by change to a black suspension of Pd/C. Upon completion, the reaction was filtered through celite. The f iltrate was subsequently evaporated under reduced pressure until the volume reached 30 mL at which point the product was left to crystallize overnight. Crystals were gravity filtered and washed with cold hexanes. Acetyl dihydroferulic acid (DHFA) was obtained as whi te crystal s in 96% yield (77.4 g). Acetyl dihydrocoumaric acid (DHCA) was obtained as a colorless crystal with a yield of 96% (76.5 g). Figure 4 3. Synthesis of acetyl dihydroferulic acid ( 2.5 ) 1 H NMR (DMSO d 6 J =7.7 Hz, 2 H), 2.83 (t, J =7.6 Hz, 2 H), 3.75 (s, 3 H), 6.79 (d, J =8.0 Hz, 1 H), 6.96 (d, J =8.0 Hz, 1 H), 7.00 (s, 1 H), 12.16 (s, 1 H). 13 C NMR (DMSO d 6 140.3, 151.0, 169.1, 174.2. Figure 4 4. Synthesis of acetyl dihydrocoumaric acid ( 2.2 ) 1 H NMR (DMSO d 6 J =7.6 Hz, 2 H), 2.81 (t, J =7.6 Hz, 2 H), 7.01 (d, J =8.3 Hz, 2 H), 7.25 (d, J =8.3 Hz, 2 H). 13 C NMR (DMSO d 6 174.2.

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51 4 .2.2 Polymer Synthesis Figure 4 5. Polymerization set up. An oil bath holding a round bottom flask with stirrer connected to a bump trap is set on a hot plate with temperature control. The apparatus is attached to a Schlenk line. Figure 4 6 Synthesis of copolymers utilizing AFA ( 2.4 ), DHFA ( 2.5 ), and DHCA ( 2.2 ) Polymerizations for the copolymer series containing DHF A ( 2.5 ) DHCA ( 2.2 ) AFA ( 2.4 ) or ACA ( 2.1 ) were carried out in the set up shown in Figure 4 5. Copolymers

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52 were made adding tw o monomers (DHFA, DHCA, AFA, or ACA) to an oven dried 50mL round bottom flask. 1.2 mol% of zinc acetate dihydrate was subsequently added. The m onomer ratio was altered ranging from 0 100% for co polymerizations. The mixture was melted under nitrogen with a temperature ramp of 150 230 C for 4 hours Th e system was placed under dynamic vacuum for an additional 3 hours before being cooled and purified. Purification of the polymers was carried out by dissolving the polymers in 4:1 mL dichloromethane: triflu oroacetic acid solution, stirring for approximately 1 hour. Isolation of the polymer was achieved by precipitating the dissolved polymer into 150 mL of cold methanol. The solution was filtered and the polymer was washed with methanol, then left to dry over night under vacuum. Figure 4 7 Larg e scale polymerization of DHFA ( 2.27 ) Large scale polymerizations of polyhydroferulic a cid were carried out in a metal reactor with a heating mantle and overhead mechanical stir rod. The reactor was filled with 40 g ( 0.17 mol) of acetyldihydroferulic acid and 1.2 mol% (442 mg) of zinc acetate dihydrate; it was subsequently deoxygenated under dynamic vacuum for 5 hours. Under an inert atmosphere, the mixture was melted over an increasing temp erature gradient from 130 200 C for a period of 3 hours. The system was then placed under dynamic vacuum with an increasing temp erature gradient from 200 250 C. This removed the volatile condensation product (acetic acid) in order to increase molecular weight. Vacuum was pulled for 7.5 hours before cooling. Once cool, the resulting solid was

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53 disso lved in a mixture of 150 mL DCM / 50 mL CHCL 3 / 30 mL TFA before being precipitated into 800 mL of cold methanol. Following gravity filtration, a li ght brown product was obtained and drie d under vacuum on a Schlenk line. Yield for this procedure varied ranging from 75 90%. 1 H NMR (CDCl 3 3.09 (m, 4 H), 3.81(s, 3 H), 6.91 (m, 3 H). 13 C NMR (CDCl 3 150.5, 173.7. Figure 4 8 Secondary polymerization of Polyhydroferulic acid ( 2.26 ) 1 g (0.18 mmol) of p olyhydroferulic a cid (5300 g/mol) was added to a round bottom flask along with 3 mL (10.8 mmol) aceti c anhydride and 20.6 mg (0.09 m mol) zinc acetate dihydrate. The r eaction was stirred at room temperature for 1 hour under nitrogen Temperatu re was increased from 150 250 C over 2 hours then dy namic vacuum was pulled at 250 C for 2 hours. The p olymer was dissolved in a 4:1 mL dichloromethane: TFA solution, stirring for approximately 1 hour. Isolation of the polymer was achieved by precipitating the dissolved polymer into 150 mL of cold methanol. The solution was filtered and the po lymer was washed with methanol. After drying overnight under vacuum, an 85% yield was obtained 1 H NMR (CDCl 3 H) 3.80 (s, 3 H), 6.85 6.94 (m, 3 H), 13 C NMR (CD Cl 3 7, 122.5, 137.8, 139.6, 150.6, 173.5.

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54 Figure 4 9 Polymerization of DHFA ( 2.5 ) using DBU Polymerization of DHFA ( 2.5 ) u sing 1,8 diazabicyclo[5.4.0]undec 7 ene (DBU) was carried out in an oven dried 50mL round bottom flask. 1.0 g (4.2 mmol) DHFA ( 2.5 ) and 1.2mol % of DBU were added before the reaction was placed under inert atmosphere. T emperature was varied from 70 220 C over the course of 3.5 hours. Dynamic va cuum was held at 220 C for 3 hours prior to cooling. Product was obtained as a d ark brown powder in 60% yield (442 mg ). 1 H NMR (CDCl 3 13 C NMR (CDCl 3 150.5, 173.7. 4.2.3 Incorporation Ratio for Polymer Series From on AFA, DHFA, and DHCA. Incorporation of the sec ond monomer into the two different copolymer series was calculated using NMR analysis. For the poly(hydrocoumaric co hydroferulic) acid polymer series, the incorporation ratio was calculated comparing the methylene peaks to the methoxy group on dihydrofer ulic acid. For the Poly(hydrocoumaric co ferulic) acid series, the incorporation was calculated comparing either normalized methylene or methoxy group (normalized group from monomer with greater feed ratio) to the other. Figure 4 10 shows poly(hydrocoumari c co hydroferulic ) acid with a monomer feed raio of 50:50. ([ ]/3)*4 = (x/8) *100 = DHFA% incorporation and 100 DHFA% = DHCA% incorporation The actual incorporation is calculated as: ([3.08/3]*4) = (4.10/8)*100 = 51.3% DHFA and 100 51.3 = 48.7% DHCA.

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55 Figure 4 10. 1 H NMR spectra of Polymer 2.10 with a fed fraction of 50 % DHFA Figure 4 20 shows poly(hydrocoumaric co ferulic) acid with a monomer feed ratio of 50:50. Here the methylene peaks have been normalized, thus calculations for incorporation utilize the methoxy peak. ([ ]/3)*.5 = x*100 = AFA% incorporation and 100 AFA% = DHCA% incorporation. The actual incorporation is calculated as: ([2.65/3])*.5 = 0.442*100 = 44.2% AFA and 100 44.2 = 55.8% DHCA. Figure 4 11. 1 H NMR spectra of Polym er 2.20 with a fed fraction of 50% AFA

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56 4.3 Succinic Acid Based Poly(ethylene terephthalate) Mimic Synthesis 4.3.1 2,5 d imethoxyterephthalic Acid Synthesis Figure 4 12 Synthesis of dimethyl 2,5 dihydroxyterephthalate ( 3.1 ) Dimethylsuccinylsuccinate ( 3 ) ( 100 g, 438 mmol, 1 eq.) was added to acetic acid (AcOH) (310 mL). Under nitrogen at 80C, N chlorosuccinimide (62.2 g, 452 mmol, 1.03 eq.) was added slowly in portions and then stirred at 80C for 1 hour The p recipitate was collected by vacuum filtration and washed with acetic acid, three aliquots of water, and two aliquots of diethyl ether. It was then dried under vacuum. Any precipitate in the mother liquor was filtered and washed accordingly. Dimethyl 2,5 dihydroxyterepht h alate ( 3.1 ) was r ecrystallized in acetic acid yielding yellow crystals in 90% yield. 1 H NMR (CDCl 3 3.98 (s, 6 H) 7.46 (s, 2 H), 10.05 (s, 2 H) 13 C NMR (CDCl 3 52.8, 117.7, 118.3, 152.9, 169. 5 Figure 4 13 Synthesis of 2,5 dihydroxyterepht h alic acid ( 3.2 ) Dimethyl 2,5 dihydroxyterepht h alate ( 3.1 ) (10 g, 44.2 mmol, 1 eq.) was added to a round bottom flask equipped with a magnetic stirrer and reflux condenser. NaOH (7.1 g, 176.8 mmol, 4 eq.) and methanol (120 mL) were added to form a suspension that was refluxed for 12 h ours. The s olvent was evaporated under reduced pressure and the

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57 solid was dissolved in water then acidified with HCl The precipitate was filtered and recrysta llized in ethanol/water (95/5) yielding a yellow green powder in 57% yield. 1 H NMR ( DMSO d 6 ) 7.30 (s, 2 H), 12.98 (s, 2 H) 13 C NMR (DMSO d 6 ) 117.8, 119.8, 152.5 170. 8. Figure 4 14 Synthesis of 2,5 d imethoxyterephthalic acid ( 3.4 ) This two step synthesis was carried out in a two neck round bottom flask equipped with a magnetic s tirrer and reflux condenser. Dimethyl 2,5 dihydroxyterephtalate (DMDHT) (10 g, 44.2 mmol, 1 eq.) and K 2 CO 3 (27.8 g, 201.3 mmol, 4.6 eq.) were dissolved in acetone (350 mL). Methyl iodide (6.6 mL, 106.2 mmol, 2.4 eq.) was added and then the mixture was heat ed to 85 C for 24 h ours while stirring. Afterwards, the solvent was evaporated under reduced pressure and the residue dissolved in water (200 mL) with NaOH (4.0 g, 100.5 mmol, 2.3 eq.), then refluxed for 20 h ours After cooling to room temperature the sol ution was filtered and HCl was added until precipitate formed The precipitate was filtered then reflux ed in ethanol (80 mL) for 2 hours. Filtration obtained a beige powder in 90% yield. 1 H NMR (DMSO d 6 ) 3.79 (s, 3 H), 7.30 (s, 2 H), 12.98 (s, 1 H ). 13 C NMR (DMSO d 6 ) 56.8, 114.9, 125.4, 151.5, 167.2

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58 4.3.2 Polymer Synthesis Figure 4 15 General polymerization procedure for the poly(alkene dimethoxyterephthalate) series The polymerizations for polymers containing 2,5 dimethoxyterephthalic acid (DMTA) were carried out in a polymerization setup shown in Figure 4 5. These polymerizations were done in the melt by adding DMTA to the round bottom flask followed by antimony oxide (Sb 2 O 3 ) and then the aliphatic diol. Diols n= 2,3,4 were viscous li quids and were added by volume with a molar ratio of DMTA: diol of 1:1.03 or 1:1.2 for ethylene glycol all solid diols were added in a 1:1 molar ratio of DMTA: diol. Vacuum was then pulled for 1 hour to remove any residual solvent. The reaction was placed under a nitrogen atmosphere and stirred at 190 C for 14 hours. After, the temperature was increased to 210 C for 4 hours. At this time, the reactions were highly viscous and many could not stir. Dynamic vacuum was then applied to the reaction at 210 C f or 4 hours. The temperature was then increased to 240 C and held for 4 hours. After 8 hours of vacuum was applied the stir bar was no longer stirring in the reactions. Due to the intractable nature of these polymers, they were collected from the round bo ttom flask using heat with no further purification.

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59 Figure 4 16 Poly(ethylene dimethoxyterephthalate) ( 3.5 ) 1 H NMR (CDCl 3 3.77 (s, 6 H), 4.70 (s, 4 H), 7.42 (s, 2 H) 13 C NMR (CDCl 3 56.2, 63.2, 115.6, 123.0, 152.7, 166.1 Figure 4 17 P oly(propylene dimethoxyterephthalate) ( 3. 6 ) 1 H NMR (CDCl 3 2.32 (s, 2 H), 3.87 (s, 6 H), 4.57 (s, 4 H), 7.27 7.46 (m, 2 H), 10.33 (s, 2 H) 13 C NMR (CDCl 3 22.5, 56.3 62.9 113.1, 115.3, 152.6, 160.9 Figure 4 18 Poly(butylene dimethoxytere phthalate) ( 3. 7 ) 1 H NMR (CDCl 3 1.96 (s, 4 H), 3.87 (s, 6 H), 4.43 (s, 4 H), 7.38 (s, 2 H) 13 C NMR (CDCl 3 25.4, 56.6, 65.1, 115.4, 124.1, 152.4, 166.0 Figure 4 19 Poly(pentylene dimethoxyterephthalate) ( 3. 8 ) 1 H NMR (CDCl 3 1.63 (d, J =7.1 Hz, 2 H), 1.82 1.94 (m, 4 H), 3.87 (s, 6 H), 4.39 (tm J =6.6 Hz, 4 H), 7.39 (s, 2 H)

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60 13 C NMR (CDCl 3 22.5, 28.2, 56.6, 65.6, 115.4, 124.0, 152.4, 166.2 Figure 4 20 Poly(hexylene dimethoxyterephthalate) ( 3. 9 ) 1 H NMR (CDCl 3 1.54 ( s, 4 H) 1.82 (d, J =6.0 Hz, 4 H) 3.88 (s, 6 H) 4.36 (t, J=6.6 Hz, 24 H) 7.39 (s, 2 H) 13 C NMR (CDCl 3 25.6, 28.5, 56.7, 65.62, 115.4, 124.1, 152.4, 166.2 Figure 4 21 Poly(octylene dimethoxyterephthalate) ( 3. 10 ) 1 H NMR (CDCl 3 1.32 1.63 (m, 8 H) 1.68 1.92 (m, 4 H) 3.89 (s, 6 H) 4.34 (t, J =6.6 Hz ,4 H) 7.39 (s, 2 H) 13 C NMR (CDCl 3 25.9, 28.6, 29.2, 56.68, 65.8, 115.4, 124.2, 152.4, 166.1 Figure 4 22 Poly(nonylene dimethoxyterephthalate) ( 3. 11 ) 1 H NMR (CDCl 3 1.23 1.52 (m 10 H) 1.71 1.91 (m, 4 H) 3.89 (s, 6 H) 4.35 (t, J =6.6 Hz, 4 H) 7.40 (s, 2 H)

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61 13 C NMR (CDCl 3 2 5.9, 28.6, 29.2, 29.5, 56.7 65.9 115.4, 124.1, 152.4, 166. 2. Figure 4 23 Poly(decylene dimethoxyterephthalate) ( 3. 12 ) 1 H NMR (CDCl 3 1.30 1.50 (m, 12 H) 1.73 1.83 (m, 4 H) 3.89 (s, 6 H) 4.34 (t, J =6.6 Hz, 4 H) 7.39 (s, 2 H) 13 C NMR (CDCl 3 25.9 2 8.6, 29.2, 29.5, 56.7, 65.9, 115.4, 124.5, 152.4, 166.2

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62 APPENDIX A PROTON AND CARBON NMR Figure A 1. 1 H NMR spectra of polymer ( 2.5 ) Figure A 2. 13 C NMR spectra of polymer ( 2.5 ) Figure A 3. 1 H NMR spectra of polymer ( 2.6 )

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63 Figure A 4. 13 C NMR spectra of polymer ( 2.6 ) Figure A 5. 1 H NMR spectra of polymer ( 2.7 ) Figure A 6. 13 C NMR spectra of polymer ( 2.7 )

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64 Figure A 7. 1 H N MR spectra of polymer ( 2.8 ) Figure A 8. 13 C NMR spectra of polymer ( 2.8 ) Figure A 9. 1 H NMR spectra of polymer ( 2.9 )

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65 Figure A 10. 13 C NMR spectra of polymer ( 2.9 ) Figure A 11. 1 H NMR spectra of polymer ( 2.10 ) Figure A 12. 13 C NMR spectra of poly mer ( 2.10 )

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66 Figure A 13. 1 H NMR spectra of polymer ( 2.11 ) Figure A 14. 13 C NMR spectra of polymer ( 2.11 ) Figure A 15. 1 H NMR spectra of polymer ( 2.12 )

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67 Figure A 16. 13 C NMR spectra of polymer ( 2.12 ) Figure A 17. 1 H NMR spectra of polymer ( 2.13 ) F igure A 18. 13 C NMR spectra of polymer ( 2.13 )

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68 Figure A 19. 1 H NMR spectra of polymer ( 2.14 ) Figure A 20. 13 C NMR spectra of polymer ( 2.14 ) Figure A 21. 1 H NMR spectra of polymer ( 2.15 )

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69 Figure A 22. 13 C NMR spectra of polymer ( 2.15 ) Figure A 23. 1 H NMR spectra of polymer ( 2.16 ) Figure A 24. 13 C NMR spectra of polymer ( 2.16 )

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70 Figure A 25. 1 H NMR spectra of polymer ( 2.17 ) Figure A 26. 13 C NMR spectra of polymer ( 2.17 ) Figure A 27. 1 H NMR spectra of polymer ( 2.18 )

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71 Figure A 28. 13 C NMR spectra of polymer ( 2.18 ) Figure A 29. 1 H NMR spectra of polymer ( 2.19 ) Figure A 30. 13 C NMR spectra of polymer ( 2.19 )

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72 Figure A 31. 1 H NMR spectra of polymer ( 2.20 ) Figure A 32. 13 C NMR spectra of polymer ( 2.20 ) Figure A 33. 1 H NMR spectra of polymer ( 2 .21 )

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73 Figure A 34. 13 C NMR spectra of polymer ( 2.21 ) Figure A 35. 1 H NMR spectra of polymer ( 2.22 ) Figure A 36. 13 C NMR spectra of polymer ( 2.22 )

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74 Figure A 37. 1 H NMR spectra of polymer ( 2.23 ) Figure A 38. 13 C NMR spectra of polymer ( 2.23 ) Figure A 39. 1 H NMR spectra of polymer ( 2.24 )

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75 Figure A 40. 13 C NMR spectra of polymer ( 2.24 ) Figure A 41. 1 H NMR spectra of polymer ( 2.25 ) Figure A 42. 13 C NMR spectra of polymer ( 2.25 )

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76 Figure A 43. 1 H NMR spectra of polymer ( 2.26 ) Figure A 44. 13 C NMR spectra of polymer ( 2.26 ) Figure A 45. 1 H NMR spectra of polymer ( 2.27 )

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77 Figure A 46. 13 C NMR spectra of polymer ( 2.27 ) Figure A 47 1 H NMR spectra of polymer ( 2.28 ) Figure A 48 13 C NMR spectra of polymer ( 2.28 )

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78 Figure A 49 1 H NMR spectra of po lymer ( 3.5 ) Figure A 50 13 C NMR spectra of polymer ( 3.5 ) Figure A 51 1 H NMR spectra of polymer ( 3.6 )

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79 Figure A 52 13 C NMR spectra of polymer ( 3.6 ) Figure A 53 1 H NMR spectra of polymer ( 3.7 ) Figure A 54 13 C NMR spectra of polymer ( 3.7 )

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80 Figu re A 55 1 H NMR spectra of polymer ( 3.8 ) Figure A 56 13 C NMR spectra of polymer ( 3.8 ) Figure A 57 1 H NMR spectra of polymer ( 3.9 )

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81 Figure A 58 13 C NMR spectra of polymer ( 3.9 ) Figure A 59 1 H NMR spectra of polymer ( 3.10 ) Figure A 60 13 C NMR s pectra of polymer ( 3.10 )

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82 Figure A 61 1 H NMR spectra of polymer ( 3.11 ) Figure A 62 13 C NMR spectra of polymer ( 3.11 ) Figure A 63 1 H NMR spectra of polymer ( 3.12 )

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83 Figure A 64 13 C NMR spectra of polymer ( 3.12 ) Figure A 65 1 H NMR spectra of ( 2.1 ) Figure A 66 13 C NMR spectra of ( 2.1 )

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84 Figure A 67 1 H NMR spectra of ( 2.2 ) Figure A 68 13 C NMR spectra of ( 2.2 ) Figure A 69 1 H NMR spectra of ( 2.4 )

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85 Figure A 70 13 C NMR spectra of ( 2.4 ) Figure A 71 1 H NMR spectra of ( 2.5 ) Figure A 72 13 C NMR spectra of ( 2.5 )

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86 Figure A 73 1 H NMR spectra of ( 3.1 ) Figure A 74 13 C NMR spectra of ( 3.1 ) Figu re A 75 1 H NMR spectra of ( 3.2 )

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87 Figure A 76 13 C NMR spectra of ( 3.2 ) Figure A 77 1 H NMR spectra of ( 3.4 ) Figure A 78 13 C NMR spectra of ( 3 .4 )

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88 APPENDIX B POLYMER CHARACTERIZATION DATA Figure B 1. TGA of polymer ( 2.5 ) Figure B 2. TGA of polymer ( 2.6 )

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89 Figure B 3. TGA of polymer ( 2.7 ) Figure B 4. TGA of polymer ( 2.8 )

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90 Figure B 5. TGA of polymer ( 2.9 ) Figure B 6. TGA of polymer ( 2.10 )

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91 Figure B 7. TGA of polymer ( 2.11 ) Figure B 8. TGA of polymer ( 2.12 )

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92 Figure B 9. TGA of polymer ( 2.13 ) Figure B 10. TGA of polymer ( 2.14 )

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93 Figure B 11. TGA of polymer ( 2.15 ) Figure B 12. TGA of polymer ( 2.16 )

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94 Figure B 13. TGA of polymer ( 2.17 ) Figure B 14. TGA of polymer ( 2.18 )

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95 Figure B 15. TGA of polymer ( 2.19 ) Figure B 16. TGA of polymer ( 2.20 )

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96 Figure B 17. TGA of polymer ( 2.21 ) Figure B 18. TGA of polymer ( 2.22 )

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97 Figure B 19 TGA of polymer ( 2.23 ) Figure B 20 TGA of polymer ( 2. 24 )

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98 Figure B 21 TGA of polymer ( 2.25 ) Figure B 22 TGA of polymer ( 2.26 )

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99 Figure B 23 TGA of polymer ( 2.27 ) Figure B 24 TGA of polymer ( 3.5 )

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100 Figure B 25. TGA of polymer ( 3.6 ) Figure B 26. TGA of polymer ( 3.7 )

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101 Figure B 27. TGA of polymer ( 3. 8 ) Figure B 28. TGA of polymer ( 3.9 )

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102 Figure B 29. TGA of polymer ( 3.10 ) Figure B 30. TGA of polymer ( 3.11 )

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103 Figure B 31. TGA of polymer ( 3.12 ) Figure B 32. DSC of polymer ( 2.5 )

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104 Figure B 33. DSC of polymer ( 2.6 ) Figure B 34. DSC of polymer ( 2.7 )

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105 Figure B 35. DSC of polymer ( 2.8 ) Figure B 36. DSC of polymer ( 2.9 )

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106 Figure B 37. DSC of polymer ( 2.10 ) Figure B 38. DSC of polymer ( 2.11 )

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107 Figure B 39. DSC of polymer ( 2.12 ) Figure B 40. DSC of polymer ( 2.13 )

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108 Figure B 41. DSC of polymer ( 2.1 4 ) Figure B 42. DSC of polymer ( 2.15 )

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109 Figure B 43. DSC of polymer ( 2.16 ) Figure B 44. DSC of polymer ( 2.17 )

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110 Figure B 45. DSC of polymer ( 2.18 ) Figure B 46. DSC of polymer ( 2.19 )

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111 Figure B 47. DSC of polymer ( 2.20 ) Figure B 48. DSC of polymer ( 2.21 )

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112 Figure B 49. DSC of polymer ( 2.22 ) Figure B 50. DSC of polymer ( 2.23 )

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113 Figure B 51. DSC of polymer ( 2.24 ) Figure B 52. DSC of polymer ( 2.25 )

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114 Figure B 53. DSC of polymer ( 2.26 ) Figure B 54. DSC of polymer ( 2.27 )

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115 Figure B 55. DSC of polyme r ( 3.5 ) Figure B 56. DSC of polymer ( 3.6 )

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116 Figure B 57. DSC of polymer ( 3.7 ) Figure B 58. DSC of polymer ( 3.8 )

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117 Figure B 59. DSC of polymer ( 3.9 ) Figure B 60. DSC of polymer ( 3.10 )

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118 Figure B 61. DSC of polymer ( 3.11 ) Figure B 62. DSC of polymer ( 3.12 )

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119 Peaks M p M n M w M z M z+1 M v PDI Peak 1 827 923 2344 5975 11242 5319 2.5 Figure B 63 GPC of polymer ( 2.5 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 1544 1467 5417 15148 26180 13604 3.7 Figure B 64 GPC of polymer ( 2.6 )

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120 Peaks M p M n M w M z M z+1 M v PDI Peak 1 4330 1309 8733 26396 47684 23600 6.7 Figure B 65 GPC of polymer ( 2.7 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 5734 3826 13012 33616 57034 30386 3.4 Figure B 66 GPC of polymer ( 2.8 )

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121 Peaks M p M n M w M z M z+1 M v PDI Peak 1 4330 1309 8733 26396 47684 23600 6.7 Figure B 67 GPC of polymer ( 2.9 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 5765 3463 8392 16737 26230 15438 2.4 Figure B 68 GPC of polymer ( 2.10 )

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122 Peaks M p M n M w M z M z+1 M v PDI Peak 1 7671 2897 12038 29444 48702 26799 4.2 Fig ure B 69 GPC of polymer ( 2.11 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 8476 3784 15081 38482 64152 34890 4 .0 Figure B 70 GPC of polymer ( 2.12 )

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123 Peaks M p M n M w M z M z+1 M v PDI Peak 1 5128 2240 9037 25650 44346 23022 4 .0 Figure B 71 GPC of polymer ( 2 .13 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 1974 1824 6992 20229 36493 18047 3.8 Figure B 72 GPC of polymer ( 2.14 )

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124 Peaks M p M n M w M z M z+1 M v PDI Peak 1 6784 4419 17380 48755 79694 44105 3.9 Figure B 73 GPC of polymer ( 2.15 ) Peaks M p M n M w M z M z +1 M v PDI Peak 1 1389 1966 5700 15440 27621 13798 2.9 Figure B 74 GPC of polymer ( 2.16 )

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125 Peaks M p M n M w M z M z+1 M v PDI Peak 1 890 1210 3101 8027 14238 7184 2.6 Figure B 75 GPC of polymer ( 2.17 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 1951 1690 417 3 9636 15793 8761 2.5 Figure B 76 GPC of polymer ( 2.18 )

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126 Peaks M p M n M w M z M z+1 M v PDI Peak 1 2023 1772 4465 10581 18021 9570 2.5 Figure B 77 GPC of polymer ( 2.19 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 887 931 3590 12792 21890 11347 3.9 Figure B 78 GPC of polymer ( 2.20 )

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127 Peaks M p M n M w M z M z+1 M v PDI Peak 1 1004 1237 3061 7482 12861 6744 2.5 Figure B 79 GPC of polymer ( 2.21 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 815 1201 2859 7054 12256 6341 2.4 Figure B 80 GPC of polymer ( 2.22 )

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128 Pea ks M p M n M w M z M z+1 M v PDI Peak 1 742 1155 2738 7048 12560 6297 2.4 Figure B 81 GPC of polymer ( 2.23 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 67 80 201 1182 2334 993 2.5 Figure B 82 GPC of polymer ( 2.24 )

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129 Peaks M p M n M w M z M z+1 M v PDI Peak 1 67 68 70 74 82 74 1 Figure B 83 GPC of polymer ( 2.25 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 15070 8495 30128 80352 145890 71909 3.5 Figure B 84 GPC of polymer ( 2.26 )

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13 0 Peaks M p M n M w M z M z+1 M v PDI Peak 1 10425 5935 19622 46804 76033 42664 3.3 Figure B 85 GPC of polymer ( 3.5 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 33781 21869 81852 245153 490656 215059 3.7 Figure B 86 GPC of polymer ( 3.6 )

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131 Peaks M p M n M w M z M z+1 M v PDI Peak 1 32677 19531 89261 368408 1019622 304848 4.6 Figure B 87 GPC of pol ymer ( 3.7 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 49971 31699 75290 158882 291373 143375 2.4 Figure B 88 GPC of polymer ( 3.8 )

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132 Peaks M p M n M w M z M z+1 M v PDI Peak 1 33484 21026 57082 135108 256597 120638 2.7 Figure B 89 GPC of polymer ( 3.9 ) Peaks M p M n M w M z M z+1 M v PDI Peak 1 37191 23358 58344 130645 254316 116827 2.5 Figur e B 90 GPC of polymer ( 3.10 )

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133 Peaks M p M n M w M z M z+1 M v PDI Peak 1 46041 29200 65632 124646 217551 114031 2.2 Figure B 91 GPC of polymer ( 3.11 ) Peaks M p M n M w M z M z+ 1 M v PDI Peak 1 59092 36159 91096 211083 433489 186965 2.5 Figure B 92 GPC of polymer ( 3.12 )

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134 Figure B 93 Tensile strength testing of polymer ( 2.26 )

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135 LIST OF REFERENCES (1) US Environmental Protection Age ncy. Wastes Resource Conservation: Common Wastes & Materials. http://www.epa.gov/ wastes/conserve/materials/plastics.htm (accessed April 21, 2015) (2) Neufeld, L.; Stassen, F.; S heppard, R.; Gilman, T.; Eds., The New Plastics Economy: Rethinking the Future of Plastics (World Economic Forum, 2016) www3.weforum.org/docs/WEF_The_New_Plastics_Economy.pdf (3) Erik sen, M.; Lebreton, L. C. M.; Carson, H. S.; Thiel, M.; Moore, C. J.; Borerro, J. C.; Galgani, F.; Ryan, P. G.; Reisser, J. PLoS ONE 2014 9 e111913. (4) Statista: Production of Plastics Worldwide from 1950 to 2013. http://www.statista.com/ statistics/ 282732/global production of plastics since 1950/ (accessed April 21, 2015) (5) Myriant anuary 2016. http://www.myriant.com/products/bio succinic acid.cfm (6) 2016. http://w ww.bio amber.com/bioamber/en/products (7) Odian, G. G. Principles of polymerization ; 4th ed.; Wiley Interscience: Hoboken, N.J., 2004. pp 29 32. (8) Rolf, M. L.; Schutze, D .; Neeff, R .' Runzheimer, H; Bayer Aktiengesellschaft (Leverkusen, DE): Process for the Preparation of Dimethyl Succinylosuccinate, the Disodium Salt thereof, Dianilinodihydroterephthalic Acids, the Dimethyl Esters and Salts thereof, and Dianilinoterephthalic Acids, and the Dimethyl Esters and Salts thereof. U S Patent 4,435,589 March 06 1984. (9) DiLallo, M. USA Today. http://www.usatoday.com/story/money/business/ 2014/06/28/ the world was 533 years of oil left/11528999 / (accessed September 20, 2015) (10) US Environmental Protection Agency. Municipal Solid Waste http://www.epa.gov/wastes/nonhaz/municipa l/index.htm (accessed September 8, 2015) (11) Moolji,S. Proceedings from the Petrochemical Conclave, Goa, India, January 6 7 2012 (12) Cheng, H. N.; Richard, A. G.; Patrick, B. S. In Green Polymer Chemistry: Biobased Materials and Biocatalysis ; American Chemical Society: 2015; Vol. 1192, p 1.

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139 BIOGRAPHICAL SKETCH Gabriel Nicholas Shor t was born in Phoenix, Arizona in 1990. After high school, he attended the University of San Diego San Diego, California. Here, he obtained his Bachelor of Arts in Chemistry. During his time at the University of San Diego Gabriel worked as an undergradua te researcher focused on polycarbamates functionalized with startch side chains. Immediately after graduation, he joined the Organic Division of the Chemistry Department at the University of Florida i n Gainesville, Florida fall 2013 His research under the guidence of Dr. Stephen A. Miller has focused on the synthesis of degradible polyersters from biorenewable feekstocks towards mimicing commodity plastics, particularly poly(ethylene terephthalate) Finally, obtaining his Master of Science degree in August 2016.