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Record for a UF thesis. Title & abstract won't display until thesis is accessible after 2012-04-30.

Permanent Link: http://ufdc.ufl.edu/UFE0041414/00001

Material Information

Title: Record for a UF thesis. Title & abstract won't display until thesis is accessible after 2012-04-30.
Physical Description: Book
Language: english
Creator: Mialon, Laurent
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2010

Subjects

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

Notes

Statement of Responsibility: by Laurent Mialon.
Thesis: Thesis (M.S.)--University of Florida, 2010.
Local: Adviser: Miller, Stephen Albert.
Electronic Access: INACCESSIBLE UNTIL 2012-04-30

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2010
System ID: UFE0041414:00001

Permanent Link: http://ufdc.ufl.edu/UFE0041414/00001

Material Information

Title: Record for a UF thesis. Title & abstract won't display until thesis is accessible after 2012-04-30.
Physical Description: Book
Language: english
Creator: Mialon, Laurent
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2010

Subjects

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

Notes

Statement of Responsibility: by Laurent Mialon.
Thesis: Thesis (M.S.)--University of Florida, 2010.
Local: Adviser: Miller, Stephen Albert.
Electronic Access: INACCESSIBLE UNTIL 2012-04-30

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2010
System ID: UFE0041414:00001


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1 SYNTHESIS OF NEW AROMATIC POL YESTERS FROM A BIORENEWABLE FEEDSTOCK: LIGNIN By LAURENT MIALON 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 2010

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2 Laurent Mialon

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3 ACKNOWLEDGMENTS I thank the members of my committee for t heir mentoring and more specifically my adviser Dr. Miller for his ideas and interesting chemistry. I would also like to thank all the members of the Butler Po lymer Laboratories for their help and valuable insight. I acknowledge the Miller group for their encou ragements and ideas through this project. Not forgetting the University of Florida for all the facilities and high quality lectures that I had the chance to attend to. As well as my former institution CPE Lyon in France that gave me the opportunity to co mplete my formation in organic chemist by joining the University of Florida

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4 TABLE OF CONTENTS page ACKNOWLEDG MENTS .................................................................................................. 3 LIST OF TABLES............................................................................................................ 6 LIST OF FIGURES .......................................................................................................... 7 LIST OF ABBR EVIATIONS ........................................................................................... 14 CHA PTER 1 POLYMERS A GENE RAL CONC ERN ................................................................... 17 1.1 Importance of Polymers................................................................................. 17 1.2 Problems of Polymers Massive Producti on ................................................... 18 1.2.1 Feedsto ck Conc erns ............................................................................ 18 1.2.2 Recycli ng Conc erns ............................................................................. 18 2 NEW POLYESTERS FROM A BIORENEWABLE FEEDSTOCK FOR POLYETHYLENE TERE PHTHALATE MIMICS ...................................................... 20 2.1 Polyethylene Terephthal ate, a Uni que Polymer ............................................. 20 2.1.1 Importance of Poly ethylene Tere phthalate .......................................... 20 2.1.2 PETs Prod uction/Sy nthesis ................................................................ 21 2.1.3 PETs Rec ycling Cy cle ........................................................................ 22 2.2 Natural Molecules Giving New Polymers ....................................................... 23 2.2.1 Lignin as a Bi orenewable Feedst ock................................................... 24 2.2.2 Types of M onomers Targeted.............................................................. 25 2.3 Previous Studies ............................................................................................ 27 2.3.1 PET Mimics Based on Furan Derivatives ............................................ 27 2.3.2 Studies on Vanillic Acid / Syringic Acid Derivatives .............................. 28 2.3.2.1 Formation of Bi functional Monomers ...................................... 28 2.3.2.2 Bicoupling of Vanillic Acid ....................................................... 28 2.4 Synthesis and Characterization of Ne w Aromatic Polyesters from Vanillic Acid/S yringic Acid .............................................................................. 29 2.4.1 Effects of the Methoxy Substituent(s) on the Polymer Chain ............... 29 2.4.2 Effects of t he Methylene Spacers ........................................................ 32 2.5 Synthesis of Aromatic Poly esters Starting with Vanillin .................................. 36 2.5.1 Perkin Reaction: Formati on of a Reactive A-B Monomer .................... 36 2.5.2 Previ ous St udies .................................................................................. 37 2.5.3 Synthesis of New Polyesters through a Perk in Reaction ..................... 38 2.5.3.1 Monomer Synt hesis ................................................................ 38 2.5.3.2 Polyme rs Synt heses ............................................................... 39 2. 5.3.3 Activation of the Phenox y Group ............................................ 41 2.6 Conclu sions .................................................................................................... 42

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5 3 COPOLYESTERS OF CAPROLACTONE AND VANILLIC ACID DERIVATIVES.. 43 3.1 Polycaprolactone an Introduc tion ................................................................... 43 3.1.1 Copolymerizations of -Caprolact one by ROP..................................... 43 3.1.2 Copolymerization Between Arom atic Monomers and Caprolactone .... 44 3.2 Synthesis of the Copolye sters ........................................................................ 45 3.3 NMR Study and Type of Copolymer De termi nation........................................ 49 3.3.1 Incorporati on Determi nation ................................................................ 49 3.3.2 Peak Assignment and Ty pe of Copolymer Synthesized ...................... 49 3.4 New Ideas ...................................................................................................... 52 3.4.1 Copolymers with Is osorbide Deri vatives .............................................. 52 3.4.2 Copolymers of PLA .............................................................................. 53 3.5 Conclu sions .................................................................................................... 53 4 EXPERIMENTAL PROCEDURES .......................................................................... 55 4.1 Molecular Char acteriza tions ........................................................................... 55 4.2 Polymerizations Proc edures ........................................................................... 55 4.3 Synthesis Proc edures .................................................................................... 57 APPENDIX A PROTON AND CA RBON NMR .............................................................................. 77 B POLYMER DATA .................................................................................................. 152 LIST OF RE FERENCES ............................................................................................. 174 BIOGRAPHICAL SKETCH .......................................................................................... 179

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6 LIST OF TABLES Table page 1-1 Worldwide polymer consumpti on in 2006estima tion in 2016 ............................ 17 2-1 Thermal and mechanica l properties of PET....................................................... 21 2-2. Study of the methoxy effects, polymer synthesis................................................ 30 2-3 Study of the methoxy e ffects, therma l proper ties................................................ 30 2-4 Polymerization of vani llic acid derivat ives........................................................... 34 2-5 Thermal properties of the van illic acid deriv ative polymers................................ 34 2-6 Poymerization of activa ted dihydrofer ulic acid.................................................... 39 3-1 Series of copolyest ers........................................................................................ 47 3-2 Thermal properties of the copol yesters.............................................................. 47 3-3 Relative intensities of the 1H NMR peaks of Ha and Hb...................................... 51

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7 LIST OF FIGURES Figure page 2-1 Polyethylene te rephthalate formu la.................................................................... 20 2-2 Industrial syn thesis of PET ................................................................................. 22 2-3 Retrosynthes is of TPA ........................................................................................ 22 2-4 Retrosynthesis of ethyl ene glyc ol ....................................................................... 22 2-5 Worldwide post consumer PET utilizat ion in 2005 .............................................. 23 2-6 Chemical structure of the PET ma in chain ......................................................... 24 2-7 From wood, a biorenewable feeds tock, to aromat ic alde hydes .......................... 25 2-8 Formation of PBS by an A-A/BB step-growth pol ymerization ............................ 25 2-9 Unsymmetrical vanillyl alcohol results in a r andom copo lymer ........................... 26 2-10 Formation of polybenzamide by step-growth pol ymerizat ion .............................. 26 2-11 Furan dicarboxylic acid a precurs or fo r PET mimic............................................ 27 2-12 Formation of polyester from vanillic acid a nd syringi c acid ................................. 28 2-13 Bicoupling of vanillic acid for aro matic polyesters............................................... 28 2-14 Polyester syn thesis scheme ............................................................................... 29 2-15 Sketch of a polymer c hain spatia l arrangement.................................................. 31 2-16 Attempt of polymerizat ion of vani llic ester .......................................................... 33 2-17 Phenolic gr oup activation ................................................................................... 33 2-18 Acetyl vanillic ac id oligomer ization ..................................................................... 33 2-19 Synthesis scheme of v anillic acid derivat ives ..................................................... 34 2-20 Synthesis of 2.16 ................................................................................................ 34 2-21 Knoevenagel condensation on an aromatic a dehyde ......................................... 36 2-22 Polymerization limited by the ar o matic hydroxyl group reac tivity........................ 37 2-23 Perkin reaction on v anillin ................................................................................... 37

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8 2-24 Copolymer synthesis with 3-(4-acetox yphenyl )propanoic acid........................... 38 2-25 Homopolymerization of ferulic acetate ................................................................ 38 2-26 Proposed studies on hydrogenat ed acetyl fe rulic acid ........................................ 38 2-27 Monomer synthesis starting with vanil lin ............................................................ 39 2-28 Activation of the phenoxy group for vanillic acid oligomers ................................ 41 2-29 Attempt of polymerization without the activation of the p henoxy group.............. 41 3-1 Polycaprolac tone synt hesis ................................................................................ 43 3-2 Retrosynthesis of -caprolac tone ........................................................................ 43 3-3 Copolymerization of -CL and glycolid e by ROP ................................................ 44 3-4 Tri-block copolymer of polycapr olactone and poly(ethylene succinate)64........... 44 3-5 Key steps in the mechanism for c opolymerizat ion of CL/VA.............................. 46 3-6 Copolymerization of vanillic acid derivative an d caprol actone ............................ 46 3.7 Fox equation for rand om copolymers................................................................. 48 3-8 Evolution of the glass transition with the feed of -caprola ctone ........................ 48 3-9 Determination of VA incorporation (polymer 3. 5) ............................................... 49 3-10 Difference of chemical environment within the polymer chain ............................ 50 3-11 NMR peak from 3-5.9 ppm for different copolymers ........................................... 50 3-12 Peak assignments in the 5-3 ppm range ............................................................ 52 3-13 Proposed Copolymerization Isosorbide Derivatives with -Caprolactone ........... 53 3-14 Proposed copolymer ization of vanillic acid derivatives wit h lactide. ................... 53 4-1 End group analysis for mole cular weight determinat ion ..................................... 57 A-1 1H NMR spectra of compound 2.1 ...................................................................... 78 A-2 13C NMR spectra of compound 2.1 ..................................................................... 79 A-3 1H NMR spectra of compound 2.2 ...................................................................... 80 A-4 13C NMR spectra of compound 2.2 ..................................................................... 81

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9 A-5 1H NMR spectra of compound 2.3 ...................................................................... 82 A-6 13C NMR spectra of compound 2.3 ..................................................................... 83 A-7 1H NMR spectra of compound 2.4 ...................................................................... 84 A-8 13C NMR spectra of compound 2.4 ..................................................................... 85 A-9 1H NMR spectra of compound 2.5 ...................................................................... 86 A-10 13C NMR spectra of compound 2.5 ..................................................................... 87 A-11 1H NMR spectra of compound 2.6 ...................................................................... 88 A-12 13C NMR spectra of compound 2.6 ..................................................................... 89 A-13 1H NMR spectra of compound 2.7 ...................................................................... 90 A-14 13C NMR spectra of compound 2.7 ..................................................................... 91 A-15 1H NMR spectra of compound 2.8 ...................................................................... 92 A-16 13C NMR spectra of compound 2.8 ..................................................................... 93 A-17 1H NMR spectra of compound 2.9 ...................................................................... 94 A-18 13C NMR spectra of compound 2.9 ..................................................................... 95 A-19 1H NMR spectra of compound 2.10 .................................................................... 96 A-20 13C NMR spectra of compound 2.10 ................................................................... 97 A-21 1H NMR spectra of compound 2.11 .................................................................... 98 A-22 13C NMR spectra of compound 2.11 ................................................................... 99 A-23 1H NMR spectra of compound 2.12 .................................................................. 100 A-24 13C NMR spectra of compound 2.12 ................................................................. 101 A-25 1H NMR spectra of compound 2.13 .................................................................. 102 A-26 13C NMR spectra of compound 2.13 ................................................................. 103 A-27 1H NMR spectra of compound 2.14 .................................................................. 104 A-28 13C NMR spectra of compound 2.14 ................................................................. 105 A-29 1H NMR spectra of compound 2.15 .................................................................. 106

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10 A-30 13C NMR spectra of compound 2.15 ................................................................. 107 A-31 1H NMR spectra of compound 2.16 .................................................................. 108 A-32 13C NMR spectra of compound 2.16 ................................................................. 109 A-33 1H NMR spectra of compound 2.18 .................................................................. 110 A-34 13C NMR spectra of compound 2.18 ................................................................. 111 A-35 1H NMR spectra of compound 2.19 .................................................................. 112 A-36 13C NMR spectra of compound 2.19 ................................................................. 113 A-37 1H NMR spectra of compound 2.20 .................................................................. 114 A-38 13C NMR spectra of compound 2.20 ................................................................. 115 A-39 1H NMR spectra of compound 2.21 .................................................................. 116 A-40 13C NMR spectra of compound 2.21 ................................................................. 117 A-41 1H NMR spectra of compound 2.22 .................................................................. 118 A-42 13C NMR spectra of compound 2.22 ................................................................. 119 A-43 1H NMR spectra of compound 2.23 .................................................................. 120 A-44 13C NMR spectra of compound 2.23 ................................................................. 121 A-45 1H NMR spectra of compound 2.24 .................................................................. 122 A-46 13C NMR of compound 2.24 ............................................................................. 123 A-47 1H NMR spectra of compound 2.25 .................................................................. 124 A-48 13C NMR spectra of compound 2.25 ................................................................. 125 A-49 1H NMR spectra of compound 2.26 .................................................................. 126 A-50 13C NMR spectra of compound 2.26 ................................................................. 127 A-51 1H NMR spectra of compound 2.27 .................................................................. 128 A-52 13C NMR spectra of compound 2.27 ................................................................. 129 A-53 1H NMR spectra of compound 2.28 .................................................................. 130 A-54 13C NMR spectra of compound 2.28 ................................................................. 131

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11 A-55 1H NMR spectra of compound 3.1 .................................................................... 132 A-56 13C NMR spectra of compound 3.1 ................................................................... 133 A-57 1H NMR spectra of compound 3.2 .................................................................... 134 A-58 13C NMR spectra of compound 3.2 ................................................................... 135 A-59 1H NMR spectra of compound 3.3 .................................................................... 136 A-60 13C NMR spectra of compound 3.3 ................................................................... 137 A-61 1H NMR spectra of compound 3.4 .................................................................... 138 A-62 13C NMR spectra of compound 3.4 ................................................................... 139 A-63 1H NMR spectra of compound 3.5 .................................................................... 140 A-64 13C NMR spectra of compound 3.5 ................................................................... 141 A-65 1H NMR spectra of compound 3.6 .................................................................... 142 A-66 13C NMR spectra of compound 3.6 ................................................................... 143 A-67 1H NMR spectra of compound 3.7 .................................................................... 144 A-68 13C NMR spectra of compound 3.7 ................................................................... 145 A-69 1H NMR spectra of compound 3.8 .................................................................... 146 A-70 13C NMR spectra of compound 3.8 ................................................................... 147 A-71 1H NMR spectra of compound 3.9 .................................................................... 148 A-72 13C NMR spectra of compound 3.9 ................................................................... 149 A-73 1H NMR spectra of compound 3.10 .................................................................. 150 A-74 13C NMR spectra of compound 3.10 ................................................................. 151 B-1 DSC of polymer 2.7 .......................................................................................... 153 B-2 TGA of polymer 2.7 .......................................................................................... 153 B-3 DSC of polymer 2.8 .......................................................................................... 154 B-4 TGA of polymer 2.8 .......................................................................................... 154 B-5 DSC of polymer 2.9 .......................................................................................... 155

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12 B-6 TGA of polymer 2.9 .......................................................................................... 155 B-7 DSC of polymer 2.10 ........................................................................................ 156 B-8 DSC of polymer 2.10 ........................................................................................ 156 B-9 DSC of polymer 2.11 ........................................................................................ 157 B-10 TGA of polymer 2.11 ........................................................................................ 157 B-11 DSC of polymer 2.12 ........................................................................................ 158 B-12 TGA of polymer 2.12 ........................................................................................ 158 B-13 DSC of polymer 2.18 ........................................................................................ 159 B-14 TGA of polymer 2.18 ........................................................................................ 159 B-15 DSC of polymer 2.19 ........................................................................................ 160 B-16 TGA of polymer 2.19 ........................................................................................ 160 B-17 DSC of polymer 2.26 ........................................................................................ 161 B-18 TGA of polymer 2.26 ........................................................................................ 161 B-19 GPC analysis of the methanol fraction of 2.29 .................................................. 162 B-20 DSC of polymer 3.1 .......................................................................................... 162 B-21 TGA of polymer 3.1 .......................................................................................... 163 B-22 DSC of polymer 3.1 ( Tg at 30C/min)................................................................ 163 B-23 GPC of polymer 3.1 in THF.............................................................................. 164 B-24 DSC of polymer 3.2 .......................................................................................... 164 B-25 TGA of polymer 3.2 .......................................................................................... 165 B-26 DSC of polymer 3.3 .......................................................................................... 165 B-27 TGA of polymer 3.3 .......................................................................................... 166 B-28 DSC of polymer 3.4 .......................................................................................... 166 B-29 TGA of polymer 3.4 .......................................................................................... 167 B-30 DSC of polymer 3.5 .......................................................................................... 167

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13 B-31 TGA of polymer 3.5 .......................................................................................... 168 B-32 DSC of polymer 3.6 .......................................................................................... 168 B-33 TGA of polymer 3.6 .......................................................................................... 169 B-34 DSC of polymer 3.7 .......................................................................................... 169 B-35 TGA of polymer 3.7 .......................................................................................... 170 B-36 DSC of polymer 3.8 .......................................................................................... 170 B-37 TGA of polymer 3.8 .......................................................................................... 171 B-38 DSC of pol ymer 3.9 .......................................................................................... 171 B-39 TGA of polymer 3.9 .......................................................................................... 172 B-40 DSC of polymer 3.10 ........................................................................................ 172 B-41 TGA of polymer 3.10 ........................................................................................ 173

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14 LIST OF ABBREVIATIONS C concentration (mol/L) Cat catalyst CL -caprolactone DP degree of polymerization DSC differential Scanning Calorimetry g grams GPC gel Permeation Chromatography HDPE high density polyethylene Hz hertz L liter mL milliLiter Mn number average Molecular Weight (Da) Mw weight average Molecular Weight (Da) N2 nitrogen NMR nuclear magnetic resonance [ ] intrinsic viscosity in mL/g [O] oxidation p conversion PBT polybutylene terephthalate PCL polycaprolactone PDI polydispersity Index PE polyethylene PET polyethylene terephthalate PLA polylactic acid

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15 ppm parts per Million PTT polytrimethylene terephthalate PVC poly(vinyl chloride) PS polystyrene ROP ring opening polymerization RU molecular of the repeat unit SN2 bimolecular substitution reaction t time t0 reference time of solvent in viscosity measurements (s) TFA trifluoroacetic acid Tg glass transition temperature (C) TGA thermogravimetric Analysis Tm melting point (C) TPA terephthalic acid Tpeak temperature of TGA for 50% of weight loss under N2 VA vanillic acid VA vanillic acid derivative 2.2 X % of feed

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16 Abstract of Thesis Pres ented to the Graduate School of the University of Florida in Partial Fulf illment of the Requirements for t he Degree of Master of Science SYNTHESIS OF NEW AROMATIC POL YESTERS FROM A BIORENEWABLE FEEDSTOCK: LIGNIN By Laurent Mialon May 2010 Chair: Stephen A. Miller Major: Chemistry Polymer chemistry has taken a very importa nt part in our society. Plastics are everywhere and have diverse applications. The production of polymers is in constant evolution and their feedstock, crude oil, becom es scarcer. Some concerns regarding the recycling of those non biodegrada ble wastes emerged lately. A new biorenewable feedstock lignin is being investigated giving vanillin and syringaldehyde by oxidation. After functionalizations these two molecules could be perfect candidates for new aromatic polyest ers which might be green alternatives to a very common plastic: polyethylene terephthal ate. Several polyesters were synthesized from derivatives of vanillic acid and vanillin by step-growth polymerizations in the bulk. The effects of the chemical structure on the thermal properties were studied. New copolymers between polycaprolactone and aromatic comonomers were also synthesized in order to modify the properties of the aliphatic polyest er. This study could widen the application range of polycaprolac tone, a biocompatible and biodegradable polymer.

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17 CHAPTER 1 POLYMERS A GENERAL CONCERN 1.1 Importance of Polymers Polymers are generally large chain-like molecules that are built up with a repetition of structural units called m onomers. Those macromolecules have been first discovered in 1811 by Henry Braconnot1 who was working on derivatives of cellulose. At first, they were mainly derived from nature. In the early 20th century, Baekeland synthesized the first commercial synthetic thermoset: Bakelite2. The major production of this new material in the US during World War II star ted according to R. Seymour, the polymer age. Since then, a constant effort has been m ade to discovered new macromolecules with various chemical, thermal and ph ysical properties. Today, polymers are everywhere from plastic bags to microproce ssors and represent a major player in the worldwide economy. In 2006, the producti on was about 240 million tons and this number should increase to 400 million tons by 20163. Table 1-1. Worldwide polymer cons umption in 2006estimation in 20163 Consumption 1000 Tons Market Sector 2006 2016 2006-2016 Growth % year Food 42,02571,734 5.5 Textiles 32,17651,630 4.8 Furniture 13,68722,993 5.3 Printing 780 1,220 4.6 Plastics products 43,50078,361 6.1 Fabricated metals 1,519 2,259 4.0 Machinery 2,397 3,658 4.3 Electrical, Electronic 13,81025,499 6.3 Other transportation 9,33016,181 5.7 Vehicles, parts 10,74615,625 3.8 Other equipment 3,852 6,334 5.1 Other manufacturing 21,23833,569 4.7 Construction 45,88672,919 4.7 Total 240,947402,022 5.3

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18 A 1985 U.S. Department of l abor study reported that ab out 60% of the chemical industry workforce was involved in polymers. The production is still in constant progress with the emergence of new industrial powers. 1.2 Problems of Polymers Massive Production 1.2.1 Feedstock Concerns Today, 90% of the polymer production conc erns six major plastics: polyethylene (high and low densities), polypropylene, polyethylene terephthalate, polystyrene, and polyvinyl chloride. Those organic thermoplasti cs are produced in major scale and mainly derived from ethylene. Ethyl ene production is a highly energet ic and expensive process that involves steam cracking of satura ted hydrocarbons associated to several distillations4. This massive production uses huge volumes of crude oil. As a consequence, thermoplastics manufacture is highly dependent on the oil marketa market that has been unstable over the past decades and oil extraction is subject to geopolitical crisis. Petroleum reserves are fi nite and will become scarcer and costly over time5. As the petroleum resources decrease and the plastic demand increases, finding new organic feedstock becomes a necessity6. 1.2.2 Recycling Concerns Since their common use in daily consumption products, plastics recycling has been a major concern. They generate an enormous amount of waste, the result is a socalled trash crisis. In fa ct, polymers packaging is the fa stest growing component of common waste in the U. S. with 12.1% in 20077. Recycling polymers is a challenge mainly be cause, unlike glass or metal, a plastic container is hardly recycled and reused for the same applications. It is generally downcycled. For example, being recycled, a plastic bottle can be used as fibers for

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19 textile but not for food packaging anymore. In 2007, only 6.8% of plastic were recycled7 -meaning that most of them ar e just stored in a landfill, burned or, even worse, thrown away in nature; any of thos e procedures are environmentally unfriendly and ecologically destructive. In addtion, polyolefins have a very slow landfill decomposition process, estimated at 500 to 1000 years8. Even though this time is not very precise and difficult to study, some research on landfill shows that plastics degradation is considerably slower than any other material9. As a polymer chemist, one way to contribut e to this problem would be to find new polymers that should ensure thei r functions but also could ea sily degrade by a chemical process or even better in the env ironment, under mild conditions. In conclusion, in order to have a high ec onomical and ecological impact the new thermoplastics should fulfill the following point s: derive from biomass, be biodegradable under a simple chemical process or in the environment, be resistant enough to ensure its functions, and have a relatively cheap, simple production.

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20 CHAPTER 2 NEW POLYESTERS FROM A BIORENEWABLE FEEDSTOCK FOR POLYETHYLENE TEREPHTHALATE MIMICS 2.1 Polyethylene Terephthalate, a Unique Polymer 2.1.1 Importance of Poly ethylene Terephthalate As presented above, our main concerns about thermoplastics are their nonbiodegrability, their feedstock: crude oil, and of course their complex recycling. One of the most common plastics is polyethylene ter ephthalate (PET), aromatic polyester used for food packaging (plastic bottles) or as a fiber. PET is the third most produced polymer in the world after polyethylene and polyp ropylene. It represents about 18% of the worldwide polymer market. Figure 2-1. Polyethyle ne terephthalate formula The backbone of the polymer chain is made of aromatic units, 80% of the carbons are sp2 hybridized, and those carbons give st iffness to the polymer chain. The two linking sp3 carbons give some flexibility to the main chain, and are responsible for the relatively low glass transiti on temperature. It has excellent mechanical properties such as tensile and impact strength, chemical resistance, clarity when amorphous, and is reasonably thermally stable10, 11. Those specific thermal and mechanical properties coupled with a cheap cost of production make PET the perfect candidate for large scale production and use as a daily consumption product.

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21 Table 2-1. Thermal and mechanical properties of PET10, 12 2.1.2 PETs Production/Synthesis PET is produced in very large scale; t he process has been studied in detail. The macromolecule is obtained by reaction of terephthalic acid (TPA) or its dimethyl ester equivalent dimethylterephthalate (DMT) with ethylene glycol in a step growth polymerization mechanism. The first step of the synthesis is the esterification of terephthalic acid or DMT with ethylene glyc ol into bis(hydroxyethyl) terephthalate (BHET) under high temperat ure and by use of transesterification catalysts13. The BHET diol is then melt-polymer ized under vacuum with an ant imony trioxide catalyst14, 15, 16 to give the polyester with a degr ee of polymerization near 15013. Property Test Method Value (unit) Molecular weight (repeat unit) 192 (g.mol-1) General weight-average MW 30000-80000 (g.mol-1) Density 1.41 Glass transition temperature DSC 69-115(C) Melting temperature DSC 265(C) Heat of fusion DSC 166 (J/g) Breaking strength Tensile 50 (MPa) Tensile strength (Youngs modulus) Tensile 1700 (Mpa) Yield strain Tensile 4% Impact strength ASTM D256-86 90(J.m-1) Linear expansion coefficient 7.10-5(K-1) Water absorption after 24h 0.5% Price 0.5-1.25(.kg-1)/ 0.72($.kg-1)

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22 Figure 2-2. Industrial synthesis of PET Monomer synthesis. Monomers preparation and origin are important, because they will influence the price of the final polym er and also its availability. Terephthalic acid is an aromatic molecule that is industrially produced by oxidation of para -xylene15. The oxidant here is oxygen and the high yiel ding reaction is catalyzed by a manganesecobalt species. Xylene is obtained from a fraction of crude oil: naphtha. Catalytic reforming of octane results in a mi xture of xylenes and ethylbenzene16, p -xylene is extracted from the mixture by low temperature crystallization17. Figure 2-3. Retrosynthesis of TPA The second element needed is ethylene glyco l, this diol can be synthesized by hydrolysis of toxic ethylene oxide, which is derived from ethylene by oxidation over a silver catalyst18. A thermal cracking of ethane, an element of crude oil, gives the desired ethylene19-20. Figure 2-4. Retrosynthesis of ethylene glycol The two main components of PETs synthesis come from crude oil or natural gas. As presented before, this energy sour ce is not desired for economical and environmental reasons. 2.1.3 PETs Recycling Cycle One major drawback of PETs recycling is the waste collection process; even though plastic bottles are one of the most colle cted thermoplastics, 27% of collection in

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23 200521, more than 70% of PET production is not reprocessed at all or left in the environment. The main issue is the generated volumetogether with a slow degradation process. Eventually, some bottles will be burned giving a good amount of thermal energy and less waste volumes but this proc edure is environmentally non-friendly. Due to its massive production, PET has its ow n recycling codenumber oneplaced on the bottom of each bottles. Plastic bottles recycling process is complicated; they need to be suitable for food consumption and therefore follow strict rules and regulations. As a consequence, it is challenging to recycle a used plas tic bottle into another clean one. Depolymerizations processes such as hydrolysis22 and methanolysis23 regenerate monomers/o ligomers that can be purified and polymerized again. These processes are not common at all and it is mu ch cheaper and easier to thermally process the bottles into fibers or flakes used for non-food applications. 70% 2% 5% 1% 9% 8% 1% 4% Fibres 70% Bottles-Non food contact 2% Strapping 5% Polyols/Others 1% Bottles-food contact 9% PET Sheet 8% Moulding/Engineering Resins 1% Chemical Recycling/Other 4% Figure 2-5. Worldwide post consumer PET utilization in 200521 2.2 Natural Molecules Giving New Polymers The properties of the polymer are the most important features for its applications. The targeted new material should have simi lar or better properties than the existing PET. The thermal and mechanical specificit ies of a macromolec ule mainly depend on

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24 the chemical structure and especially on the stiffness of the polymer chain24. Polyethylene terephthalate has 80% of sp2 hybridized carbons and 20% of sp3 hybridized carbons. They provide flexibility to a highly rigid arom atic polymer chain. Figure 2-6. Chemical structure of the PET main chain These aromatic units in the main chain give stiffness to the polymer, which can therefore be used as a food packaging such as plastic bottles without deformation or perforation. This segment also influences t he thermal properties ensuring a fairly high glass transition10 even though the sp3 hybridized carbons tend to give some flexibility to the chain lowering the Tg. The targeted glass transition should be in a range above room temperature to ensure stability at a minimum of 50-60C in or der to avoid thermal deformation during utilization. 2.2.1 Lignin as a Biorenewable Feedstock Vanillin is a potential candidate for the synthesis of aromatic polyesters. It can be obtained from lignin, a biopolymer that c onstitutes about 30% of the carbon in the biosphere25. After cellulose, it is the second most abundant biopolymer on earth. The structure analysis is fairly complex because lignin is a highly branched molecule that is believed to be cross-linked and does not have a simple primary structure26. Industrially, lignin is a side product of the Kraft process in pulping industry, the production is less than 100,000 tons a year27. It is often burned before extr action, and can be a main source of energy to operate pulping factories28.

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25 The extraction process is known29 but not often used; it a ffords the biopolymer that can be oxidized into the expected molecules: vanillin, and syringaldehyde. Those two aromatic molecules have fairly reactive functionalities in para positions. The oxidation process has been studied with various catalysts and the recovery of vanillin is low, about 4-5%30. Some new processes are under investigation, especially a promising ion-exchan ge media that gives the expected aldehydes31. Figure 2-7. From wood, a biorenewabl e feedstock, to aromatic aldehydes 2.2.2 Types of Monomers Targeted The polymerization process generally used fo r polyester formation is a step-growth mechanism. For polycondensations, monomers reacts together forming a polymer releasing small molecules. This reacti on can be performed between two monomers with different functionalities, generally called A-A and B-B or a singl e monomer with both functionalities, called A-B monomer. Figure 2-8. Formation of PBS by an AA/B-B step-growth polymerization32 The monomer used for this type of polymeriz ation should be symmetrical to control the repeat unit of the polymer. Otherwise, a random c opolymer would be synthesized.

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26 For example, vanillyl alcohol will not be used as an A-A monomer because it would certainly encounter difficulty controlli ng the structure of the resulting polymer. Figure 2-9. Unsymmetrical vanillyl alcohol results in a random copolymer It is necessary to perform sufficient modifi cation to the starting materials to have a symmetrical di-acid or diol as A-A or B-B monomers. The second type of reaction involves a so called A-B monomer. The two reactive functionalities are present in a single monomer. Figure 2-10. Formation of polybenzamide by step-growth polymerization33 Those condensation reactions are usually performed in concentrated solutions or under high temperature in the bulk to incr ease the concentration of monomers, and the kinetics of the polymerization. Dynamic va cuum is also applied to remove the side molecules, generally water or alcohols. Thisaccording to LeChatelier principlethermodynamically favors the chemical equilibrium towards the product: here the polymer. Looking at the proposed starti ng materials, it seems th at A-B monomers would be easier to synthesize in few steps. Vanillin is unsymmetrical, this due to its aromatic methoxy functionality. The ot her drawback for the use of an A-A/B-B system is the necessity of an exact equimolar measurement. If any monomer is present in excess, the

PAGE 27

27 formation of high molecular weight polymer will be prevented by the termination of growing chains by the excess functionality34. In summary, a good PET mimic candidate needs to have similar properties, a simple synthesis scheme, and a few simple steps to obtain the A-B monomer. The properties depend on the pr imary structure of the polymer chainhere, the chemical structure of the macromolecule. PET analogues will be synthesized with macromolecules chemically si milar but derived from vanilli n, a biorenewable feedstock. 2.3 Previous Studies 2.3.1 PET Mimics Based on Furan Derivatives Most of the work on PET analogues from biorenewable feedstock is relatively recent and has been done with furan derivatives polymer35. A furan 2,5 dicarboxylic acidone of the 12 priority chemicals for es tablishing a green chemistry industryis reacted with ethylene glycol through an es terification process. The monomer was reacted in the melt under high vacuum in order to remove, ethylene glycol. Figure 2-11. Furan dicarboxylic acid a precursor for PET mimic This moelcule gives thermal properties si milar to PET but does not improve them. The glass transition is fairly similar to t he one of PET but the melting temperature is lower. Furan polymerizations are acid sensitive and degrade under high temperatures leaving brown products36. An alternative to furan chemistr y is the use of vanillic acid as a monomeric precursor.

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28 2.3.2 Studies on Vanillic Acid/ Syringic Acid Derivatives 2.3.2.1 Formation of Bifunctional Monomers A simple oxidation of the aldehyde functi onality of vanillin into a carboxylic acid37 gives vanillic acid. It is a benzoic acid derivative currently used as a flavoring agent. Some studies have been performed on the reac tivity of the hydr oxyl group of the molecule and the formation of bifunctional or A-B type monomers38. This synthesis can also be applied to syringic acid to give a wider range of possible polyester. The thermoplastics synthesizing by a melt step-growth polymerizations show some interest ing thermal and physical properties. Sb2O3 OH O HO O O NaOH OH O O O HO melt O O O O HO H n X X X X=H,OMe X=H Tg=55-60C Tm=254-260C X=OMe Tg=45C Tm=73CH2O Figure 2-12. Formation of polyester from vanillic acid and syringic acid38 2.3.2.2 Bicoupling of Vanillic Acid Another known synthesis is the coupling of two vanillic acid derivatives with a bifunctional reagent giving a dicarboxylic ac id that can be further reacted with a diol38, 39. The resulting polyester has some interest ing properties and has be en pulled into fibers with interesting properties. Figure 2-13. Bicoupling of vanillic acid for aromatic polyesters39

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29 2.4 Synthesis and Characterization of New Aromatic Polyesters from Vanillic Acid/Syringic Acid Vanillic acid has been synthesized into monomers in the past. None of those studies showed the influence of the methoxy group(s) on the polymer backbone and more specifically on the thermal properties of the polymer. A study of the nature of the vanillic acid linker-in other words the nature of the carbon oxygen arrangement between the ester linkages-would be useful to understand the thermal behavior of the macromolecule. 2.4.1 Effects of the Methoxy Substituent(s) on the Polymer Chain Chain-chain interactions and rigidity will have a great influence on the general properties of a polymer chain. We propose a study on the effect of the bulky methoxy group(s) on chain packing and thermal behavior on several polyesters. The work projected here focuses on the synthesis of p -hydroxybenzoic acid, vanillic acid, and syringic acid similar derivatives that will be polymerized and thermally studied. The phenolic alcohol is a reactive functiona lity common to the three molecules. It can be easily deprotonated due to a resonance stabilized conjugated base40 becoming a decent nucleophile for an SN2 reaction. Figure 2-14. Polyester synthesis scheme The thermal stabilities of our polymers under a nitrogen atmosphere were studied using thermogravimetric analysis (TGA) and thermal characteristics that included melting points and glass transition temperatur es were measured by differential scanning calorimetry (DSC).

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30 Table 2-2. Study of the methox y effects, polymer synthesis Entry Monomer X Y Z % yield (%) Polymer a 2.1H H 2 70 2.7 b 2.2OMe H 2 79 2.8 c 2.3OMe OMe 2 71 2.9 d 2.4H H 3 50 2.10 e 2.5OMe H 3 57 2.11 f 2.6OMe OMe 3 82 2.12 Several bimolecular substitution reactions (SN2) give the A-B monomers with 2 or 3 carbon spacers and different substitutions on the aromatic ring. A series of polymers were synthesized in the melt, water was removed by dynamic vacuum. The moderate yields are probably due to the work-up procedure in the sense that the melted polymer was cooled down under nitrogen leaving a hard solid that was dissolved in an appropriate solvent such as trifluoroacetic acid or m -cresol and then crashed out in methanol leaving the low molecular weight material in solution. Table 2-3. Study of the methox y effects, thermal properties Polymer Tg (C) Tm (C) Tpeak (C) Z 2.7 80 203 478 2.8 71 239 433 2.9 66 450 2 2.10 67 179 435 2.11 65 191 435 2.12 51 170 433 3 The thermal properties are directly related to the chemical structure. The spatial disposition and folding of the macromolecul ar chain directly influences the glass

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31 transition for the amorphous part of the chain, the melting point corresponding to the crystalline part of the polymer. Figure 2-15. Sketch of a polym er chain spatial arrangement41 As reported in Table 2-3 it is quite clear that the glass transition decreases by increasing the substituti on on the aromatic group42, 43. The glass transition is directly correlated to the amorphous phase of the poly mer. This phase is not ordered, the space filling is important, and the more space a macromolecule will have to move, in other word the more free volume, the lower the Tg will be. A bulky substitution on the aromatic group gives more free volume to the molecules creating steric hindrance on the chain that can be found on each repeat unit, so along the entire polymer. A double substi tution creates even more space and further lowers the Tg. We can also notice that as the l ength of the methylene spacer increases the difference in glass transitions decreases due to the fact that the aromatic groups are now further apart from one to another. In term of chain packing or crystallinityso the ordered part of the polymer chain shown by the melting point, the double subs titution does not allowed ordering of the chain, polymer 2.9 does not show any melting temperature. The steric hindrance is too high and therefore slows down the crystallization process. This effect is not observed for sample 2.12 since it shows a melting point of 170C. In that specific case it seems the

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32 key is the space between the aromatic groups which is not enough in polymer 2.9 to allow crystallinity. The thermal stability under nitrogen is fair ly consistent for all the polymers. 2.4.2 Effects of the Methylene Spacers Another possible study is to change the number of carbons between the ester bonds and so between the aromat ic rings within the polymer chain. The addition of sp3 carbon spacers should have an effect on the flexib ility of the polymer chain. This implies several changes in the chain-chain intera ctions and crystallization of the polymer. Our study has been focusing on the vanillic ac id derivatives since it comes from a biorenewable feedstock and is r eadily available on a large scale, unlike syringic acid a much more expensive commercial chemical. A synthesis of a series of polymers has been performed. The one step nucleophilic substitution under mild condition presented abov e will be kept as main reaction for the monomer synthesis. The only difference will be for the synthesis of the no carbon spacer molecule. Oligomers of vanillic acid, no carbon spacer. Several studies have been done on the oligomers of p-hydroxybenzoic acid44. But none dealt with the direct polycondensation of vanillic acid. The polycondensation under vacuum has been attempted on vanillic acid without any success. An activation of the carboxylic acid into an ester should give a more volatile bypr oduct and as a consequence should be easier to remove by vacuum. The methanoate ester 2.13 has been synthesized and a melt polymerization with a transesterificaiton catalyst during 24h was a ttempted. An NMR study shows no reaction.

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33 Figure 2-16. Attempt of polymer ization of vanillic ester The phenolic hydroxyl group must be activated to efficiently polymerize vanillic acid45. This activation was accomplished by c onverting the phenolic hydroxyl group to an acetyl group46. OH O O O O OH O HO O O O O N 2.14 Figure 2-17. Phenolic group activation Acetic acid was distilled o ff as a byproduct and collection of this acid allowed the determination of the degree of polymerization (DP) usi ng the Carothers equation47: p DP 1 1 Where p is the conversion of monomer 0 < p < 1 The conversion, p can be calculated from the am ount of acetic acid released during the polymerization. Figure 2-18. Acetyl vanil lic acid oligomerization After a short time, the melt became heter ogeneous and solidified in the flask. The oligomers of vanillic acid have a DP between 5 and 6, as calculat ed using the amount of acetic acid collected during the polymerizat ion. The product was hard and brittle; it could not be melted or dissolved in common solvents. Study of vanillic acid derivatives. Our first study showed the effect of the methoxy pendant group on the polym er chain. Another import ant factor is the type and

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34 the length of spacers between the aromatic groups. A possibilit y is to modify the number of carbon spacers. Figure 2-19. Synthesis scheme of vanillic acid derivatives Table 2-4. Polymerization of vanillic acid derivatives Entry Monomer X Yield % Polymer G 2.14 0 100 2.17 H 2.2 2 79 2.8 I 2.5 3 57 2.11 J 2.15 6 71 2.18 K 2.16 2* 40 2.19 1 pendant methyl group Monomer 2.16 is slightly different since a methyl pendant group was introduced by reacting vanillic acid with a racemic mixture of propylene oxide to give a chiral center on the monomer. Figure 2-20. Synthesis of 2.16 Table 2-5. Thermal properties of t he vanillic acid derivative polymers Polymer Tg (C) Tm (C) Tpeak (C) 2.17 2.8 70 241 433 2.11 65 191 435 2.18 32 445 2.19 71 407 The sp3 hybridized carbons have more degrees of rotational freedom in their conformations than the sp2 aromatic or carbonyl carbons, which are largely locked in a

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35 planar fashion. So increasing the amount of carbon spacers gi ves much more flexibility and mobility to the polymer chain. This can be seen with 2.17 and 2.18, the two extremes polymers where 2.17 is poly(vanillic acid) without any carbon spacers and where 2.18 has 6 carbon spacers. 2.17 is a very stiff infusibl e and insoluble oligomer without any glass transition and 2.18 has a low glass transition and appears to be much more flexible. This general trend is confirmed with 2.8 and 2.11 as the glass transition tends to decrease with the increment of carb on spacers. The thermal stability is still reasonable under nitrogen. Polymer 2.19 is a special case in our study si nce it has a chiral center. As mentioned earlier, monomer 2.16 is a racemic mixture, the propylene oxide used for the synthesis was optically inactive. The polym erization is longer t han any other ones and gives lower yield as well. DSC shows without any surprise that 2.19 is an amorphous polymer. The polymer has stereocenters and is atactic. As a consequence the chain packing into crystals is very unlikely. Such behavior can be seen for several kind of atactic polymers such as polystyrene48. The glass transition is similar to 2.8 The chain movement seems to be more difficult with an extra methyl group but it al so gives more free vo lume to the polymer chain in the amorphous phase. The amorphous phase has more free volume in that case and more energy is necessary to have chain motion due to chain-methyl interactions. Doing a comparison with the t hermal properties of polyethylene( Tg = -130C)49 and polypropylene ( Tg = -10C)50 an increase of glass transition was expected from 2.8 and 2.19 but our structure is different the methyl group is not, in terms of atomic mass, very

PAGE 36

36 important in the repeat unit, so the effect on the interaction is not as important as the one seen in polypropylene. 2.5 Synthesis of Aromatic Po lyesters Starting with Vanillin Vanillin and syringaldehyde are two molecule s of choice for that study since they have an aromatic unit and two reactive functionalities: a phenolic alcohol and an aldehyde. The phenolic part of the molecule has been studied previously. Another option is to functionalize these two molecules into A-B monomers by reaction on the aldehyde group. 2.5.1 Perkin Reaction: Formati on of a Reactive A-B Monomer An aldehyde functional group is fairly reactive; and hence several reactions are possible. Our goal is to obtain an A-B monom er in order so an acid functionality needs to be synthesized to give a polyester. Our study focuses on a few step syntheses with relatively good yield and atom economy. T hese factors have been taken into account during the research for aldehyde reaction. Condensations are a good way to obtain unsaturated acid groups. A Wittig reaction is an option51 but is quite complicated and wasteful for our synthesis. A much simpler way is to do a Knoevenagel reaction52; these condensation reactions are generally a fairly simple, high yielding and fast53. Figure 2-21. Knoevenagel condens ation with an aromatic adehyde54 This reaction would give us an A-B monom er that could be hydrogenated and then polymerized in the bulk.

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37 Figure 2-22. Polymerization limited by the aromatic hydroxyl group reactivity According to our previous study on vanil lic acid, the phenolic hydroxyl group is not particularly reactive even under harsh polym erization conditions. Activation of the alcohol functionality could make it react wit h the acid and give the desired polyester. For poly(hydroxybenzoic acid) the reaction does not occur with the simple alcohol, an activation with an acetyl group is necessary for the polymer formation45. Functionalization of the alcohol group is an option55 but would increase our synthesis by an extra step. Further research led us to the Perkin reaction56. Acetic anhydride reacts with an aromatic aldehyde, condensati on of the aldehyde as well as the functionalization of the hydroxyl group are obtained in a one step high yielding reaction. Figure 2-23. Perkin reaction on vanillin57 The Perkin reaction is relatively fast and conditions are mild. The work up as well is fairly easy and does not involve any complicated purification step; a simple recrystallization gives the pure yellow solid. 2.5.2 Previous Studies The Perkin reaction has been mainly used in natural product syntheses57. Biodegradable liquid crystals have been a ttempted by copolymerizing 3-(4acetoxyphenyl) propanoic acid and 4-acetoxybenzoic acid58.

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38 Figure 2-24. Copolymer syn thesis with 3-(4-aceto xyphenyl)propanoic acid The resulting molecule is a random c opolyester, a liquid cr ystal that shows nematic behavior above 220C and biodegrades in vitro. Polymerization of acetyl ferulic acid has been patented59; the polymerization is done in the bulk and under 5-6 hours of va cuum to remove acetic acid. Figure 2-25. Homopolymerizat ion of ferulic acetate 2.5.3 Synthesis of New Polyesters through a Perkin Reaction Polycondensations have been attempted on the ferulic acid derivatives and most of the polymers reported are colored and will not be good substitutes for polyethylene terephthalate (PET). Ferulic acid is an unsaturated carboxylic acid, the alkene double bond can be hydrogenated to give an AB monomer that is polymerizable under the same set of conditions. This hydrogenati on gives more flexibility to the polymer chain leading to other the rmal and mechanical properties than those patented for the ferulic polyester. Figure 2-26. Proposed studies on hy drogenated acetyl ferulic acid 2.5.3.1 Monomer Synthesis The monomer was obtained after a 2 st ep synthesis composed of the Perkin reaction followed by the saturation of the alkene bond by reaction of hydrogen gas over

PAGE 39

39 palladium on charcoal 10%. Compound 2.20 is a colored compound (brownish yellow) but the hydrogenation gives a beige monomer much more suitable for our study. Figure 2-27. Monomer synthes is starting with vanillin This 2 step synthesis is relatively fast with fairly good yield. The work up for each reaction involves a simple recrystallization, no purification by column chromatography is necessary. 2.5.3.2 Polymers Syntheses Table 2-6. Poymerization of ac tivated dihydroferulic acid Entry Polymer Temperature (C) Catalysta Melt time (h)/stirring stops(h) Vacuum time (min) yield % Intr. Viscob (mL/g) Mvc DPd Mn a 2.22 200-220 2/1.5 120 83 31 12940 27 4811 b 2.23 200-220 Sb2O3 2/0.5 120 67 29 11950 23 4099 c 2.24 200-220 Zn(OAc)2 2/0.5 120 82 27 10980 38 6772 d 2.25 200-220 Zn(OAc)2 2/0.5 360 91 36 15500 50 8910 e 2.26 220-250 Zn(OAc)2 2/0.5 360 68 35 14800 100 17820 f 2.27 200-220 Zn(OAc)2 2h/10 43 17 6330 17 3029 a) Catalyst loading at 1mol% b) Intrinsic viscosity measured with an Ubbelhode in a mixture phenol/1,1,2,2tetrachloroethane (1/2) at 35C c) Calculated with [ ]= 1.09-2 Mv0.84 with [ ] in mL/g d) Measured by end group analysis First step of the polymerization was a melt under nitrogen to form oligomers. This was done in order to avoid sublimation of the unreacted monomers. Once vacuum was applied the polymerizations were surprisingly fast, and we can clearly see the distillation of acetic acid.

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40 After a few minutes, the me lt became more viscous until stirring was not possible anymore giving a brown viscous melt at the end of the polymerizat ion. The polymers were obtained by dissolution of the melt in a 1-to-5 mixture of trif luoroacetic acid and dichloromethane. The solution was then cras hed out with methanol-a solvent in which the monomer is soluble-leaving a beige powder that was f iltered and dried in vacuo. Different conditions were tested and grouped in Table 2-6. The effect of the catalyst is not tremendous, although to our knowledge the reactions seemed to be faster in presence of either antimony trio xide and zinc diacetate dihydrate since the acetic acid removal appeared to be more ef ficient when vacuum is applied and the stirring stops sooner than with the other ca talysts. The end group analysis also shows that the zinc catalyst gives better polym erization degree under similar conditions. The intrinsic viscosities, measured wit h an Ubbelhode viscometer, give more information about the molecular weight of those polymers. Polymers 2.22 2.28 have similar chain structure and can be compared in term of chain length with their intrinsic viscosities. The intrinsic viscosities increase slight ly with increasing vacuum time. For polymers 2.26 and 2.27where the vacuum was 6hthe viscosity was slightly higher than for the 2 hour vacuum pol ymers. More acetic acid was removed and the reaction was toward the polymer formation and chain length increase. For polymer 2.27 the reaction was stopped during the pol ymerization and we can clearly see the difference in intrinsic viscosity the yield was still fairly good so even lower molecular weight polymers are insoluble in methanol. The intrinsic viscosity [ ] allows us to estimate t he molecular weight of our polymers by comparing them with PET, this will give a relative value, the actual

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41 molecular will be compared to a PET standard. Polyethylene terephthalate has a similar structure to our aromatic polyester. The values obtained with the Mark-Houwink parameters give us an estimation of the molecular weight of our polymers. By comparison with the end group analyses, which are absolute values, we can see that the values are in the same or der of magnitude but slightly off. It seems that the MarkHouwink parameters are more va lid for high molecular weight materials, as we can see for polymer 2.26 A DSC measurement has been performed for 2.26 -the highest molecular weight material-showing a Tg of 66C and a melt of 205-210C. Those values are in the range of PETs thermal properties. 5.3.3 Activation of the Phenoxy Group As presented previously for the oligomerization of vanillic acid, the activation of the phenoxy group is a necessity for the reaction to occur. O HO O O O O O OH H n Figure 2-28. Activation of the phenoxy group for vanillic acid oligomers In our case, the acid group is slightly di fferent since it is bonded to the aromatic unit by 2 sp3 hybridized carbons that makes it mo re accessible. A simple study would be to attempt polymerization after removal of the acetoxy group. Figure 2-29. Attempt of polymerization without the activation of the phenoxy group

PAGE 42

42 The polymerization was left for a long time (5-6h) under vacuum and neither distillation of acetic acid or viscosity c hanges were apparent. The reaction was finally stopped after 6h, and only to give 5% of inso luble polymer in methanol. The methanol fraction was collected and solvent removed under vacuum leaving a brown solid in the flask. A GPC analysis of the methanol fraction 2.29soluble in THFshowed low molecular weight material. 2.6 Conclusions Polyethylene terephthalate is an important thermoplasti c that comes from crude oil. A possible greener feedstock for PET mimi cs is lignin. Lignin is a biopolymer that can be oxidized into a variety of possi ble monomers that include syringaldehyde and vanillin. Monomers of vanillic acid and syringic acid derivatives were synthesized and polymerized in the melt giving information about the effect of t he aromatic methoxy substituent(s) on the thermal properties. The carbon spacing is also an important structural component that influences the t hermal properties. Functionalization of the aldehyde group of vanillin through a Perkin reaction gives a polyester with thermal properties similar to PET in a very fast polymerization reaction.

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43 CHAPTER 3 COPOLYESTERS OF CAPROLACTONE AND VANILLIC ACID DERIVATIVES 3.1 Polycaprolactone an Introduction Polycaprolactone is an aliphatic polyester that can be obtained from a lactone: -caprolactone by Ring Opening Polymerization (ROP). This reaction gives a polyester with a flexible sp3 hybridized carbon chain. O O O O n ROP Cat. Tg=-60C Tm=60C Figure 3-1. Polycaprolactone synthesis -Caprolactone is synthesized with t he Baeyer-Villiger oxidation of cyclohexanone60 that can be obtained by oxidation of cyclohexane61. Figure 3-2. Retrosynthesis of -caprolactone Polycaprolactone has a fairly low glass transition and melting point62 giving a limited range of applications to the polye ster. It is a semicrystalline polymer biodegradable and biocompatible. Its principal applications ar e in biomedical research for implants or even drug delivery systems63. Some copolymerizations have been studied in order to improve those properties and widen its range of applications. 3.1.1 Copolymerizations of -Caprolactone by ROP Polycaprolactone is a biocompatible pol ymer that has many applications in biomedical devices. As a result its been copolymerized with other biocompatible monomers: lactide64 and glycolide65.

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44 Figure 3-3. Copolymerization of -CL and glycolide by ROP The ring opening reaction is one way to obtain long chain of polycaprolactone. Some copolymers can be synthesized by polycondensation but in general only block copolymers are achieved by formation of a block of prepolymer that can be used as an initiator for the fast ROP reaction66. Figure 3-4. Tri-block copolymer of polycaprolactone and poly(et hylene succinate)64 Thermal and mechanical properties can be tuned by adjusting the ratio of the comonomers in order to sele ctively modify the properti es of the macromolecule67.The biodegradation of polycaprol actone could also be changed by copolymerization68. 3.1.2 Copolymerizations between Ar omatic Monomers and Caprolactone A copolymerization between caprolact one and an aromatic monomer could drastically change the lifetime of the chain with a higher resistivity to hydrolysis. Biodegradation is highly depende nt on crystallinity and type of copolymers (random or block) as well as ratios of aromatic/aliphatic chains69. By incorporation of an aromatic repeat uni t into the polycaprolactone chain, we could be able to tune the thermal and mechanical properties as well as the biodegradation. In term of synthesis, this polymerization is kind of unusual as it is based on a ring opening polymerization mechanism for the -caprolactone coupled with a step-growth polymerization for the aromatic unit. These copolymerizations are usually performed in

PAGE 45

45 the melt with a good transesterification catalyst to have good incorporation of both monomers. Some studies have been reported on the polymerization of -caprolactone and terephthalic acid70 and with a derivative of poly(hydroxybenzoic acid)71. A good comonomer for that reaction would be 4-(2-hydroxyethoxy)-3methoxybenzoic acid, monomer 2.2 Not only is monomer 2.2 is fairly easy to synthesize in the lab on a decent scale, it also has the most interesting thermal properties since its homopolymer has a relati vely high glass transition and melting point. This should give interesting copolymers with -caprolactone due to the different structures of bot h homopolymers. 3.2 Synthesis of the Copolyesters The polymerization is going to be a co mbination of ring opening polymerization and step-growth polymerization-both reactions catalyzed by the good transesterification catalyst: titanium isopropoxide72. Titanium catalysts have been extensively studied for PET polymerization and the mechanism shows the incorporation of random repeat units within the polymer chain73. The catalyst is a Lewis acid and a transesterifi cation catalyst that allows the formation of oligomers of VA by polycond ensation reaction and the ring opening polymerization of CL. Then a 4 centered mechanism with the ester and a coordinated oxygen allows transesterification to occur. This impor tant step happens with c aprolactone or the vanillic acid oligomers giving randomness to the chain. Moreover, chains can be randomly transesterified in any repeat unit; th is gives even more disorganized chains. The catalyst can be released by ligand exchange.

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46 Figure 3-5. Key steps in the mechanism for copolymerization of CL/VA The polymerization will be performed in the melt to favor the step-growth polymerization of the vanillic acid deriv ative and under vacuum for water removal. Distillation of the -caprolactone must be avoided in order conserve consistent incorporation in comonomer. The melt will be held under nitrogen for 1h in order to have formation of oligomers and avoid lost of the liquid caprolactone. Higher molecular weight polymer is obtained by applying vacuum and removing water as a byproduct. The reaction is considered complete when the magnetic stirring is not effective which may be anywhere between 28h depending on the feed. Figure 3-6. Copolymerization of vanillic acid derivative and -caprolactone The copolymerizations are reproducible and give in relatively high yield macromolecules with diverse repeat units. T he NMR shows that the resulting chain is randomly distributed with divers e integration peaks due to several possibilities in the

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47 repeat unit arrangement. We could have imagi ned that the ring opening polymerization would have been faster but it seems that the transesterification catalyst does not favor the addition mechanism. Table 3-1. Series of copolyesters Entry Polymer Feed CL x % NMR in CL % Weight % in CL % Yield k 3.1 100 100 100 79 l 3.2 90 89.3 83 80 m 3.3 80 79 69 67 n 3.4 70 63.1 50 68 o 3.5 60 53.4 40 65 p 3.6 50 38 27 67 q 3.7 40 34 23 82 r 3.8 30 29.8 20 77 s 3.9 20 16.7 11 69 t 3.10 10 9.2 6 76 As shown in the table 3-1 the vanillic acid derivative 2.2 insertion is close to its feed. Thermal analyses by DSC have conduct ed to determine the glass transitions and melting point of each polymer sample. Table 3-2. Thermal properties of the copolyesters. Polymer Feed CL/VA NMR in CL % Weight % in CL Tg (C) Tm (C) Tg Fox (C) 3.1 100 100 100-6453 -60.0 3.2 90 89.3 83-40.941.5 -45.4 3.3 80 79 69-26.8112 -31.6 3.4 70 63.1 50-4.6139.5 -10.4 3.5 60 53.4 406.2172.4 2.4 3.6 50 38 2729.7198.3 22.5 3.7 40 34 2341.4222.7 27.7 3.8 30 29.8 2046.3204.3 33.1 3.9 20 16.7 1159.8206.7 49.9 3.10 10 9.2 666.2231.1 59.4 The Tg is related to the primary structure of the c hain; the more flexible units in the chain such as sp3 hybridized carbons the mo re flexible and lower the Tg will be. For high

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48 feed in -caprolactone a low Tg is observed. This can be easily seen in figure 3-8 the Tg decreases almost linearly with increase in the flexible repeat unit. The melting point values do not follow a regular trend but we can confirm that, generally, the melting point decreases when the feed of -caprolactone increases. According to the Fox equation74 for an A-B copolymer: b a a aTg w Tg w Tg )1( 1 Figure 3-7. Fox equation for random copolymers So knowing the composition of the copolymer by NMR and the Tg of both homopolymers we can predict and compare the measured glass transition to a calculated value. Thermal analyses are so mewhat dependent on the molecular weight of the polymers but are pretty comparable to the one calculated with the Fox equation. Figure 3-8. Evolution of the glass transition with the feed of -caprolactone The glass transition values are close to the calculated values given by the Fox equation.

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49 3.3 NMR Study and Type of Copolymer Determination An NMR study of the copolyesters c an give us more information about the structure of the macromolecules. A first look at the spectra for diverse feed shows us extra peaks compared to the homopolymers spectrum. 3.3.1 Incorporation Determination The incorporationof vanillic acid has been the main concern in those polymerizations. Since ring opening polymerizations are supposed to be faster than stepgrowth polymerization mechanisms. By NMR VA shows peaks between 7.5-8ppm corresponding to 2 aromatic hydrogens. Polycaprolactone has a specific peak in the 2-2.5ppm region that matches the 2 -hydrogens to the carbonyl. Both peaks are supposed to have-in the case of homopolymersan integration val ue of 2. By measuring the intensity of both peaks and calculating a ratio, we get the incorporation in VA. Figure 3-9. Determination of VA incorporation (polymer 3.5) 3.3.2 Peak Assignment and Type of Copolymer Synthesized The NMR of all the copolymers shows so me extra peaks in the 3-6ppm region compared to what would be expected acco rding to the homopolymers spectra.

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50 In a copolymerization 3 cases are possible: Random copolymer showing randomly incorporation of both monomers VAVACLCLCLCLCLCLVACLCLVA Alternating Copolymer : regular alternation of both repeat units VACL VACL VACL VACL VACL Copolymer block: 2 blocks of polymers with the same repeat unit o VAVAVAVAVA VAVACLCLCLCLCLCLCLCL A first look at the spec tra for diverse feed shows us extra peaks than the homopolymers. A first assumption is that the chemical envir onment is not the same for the hydrogen of a similar repeat unit but with other neighboring molecules. Figure 3-10. Difference of chemical environment within the polymer chain A study of the integr ation of the NMR peak can give us more information about the peak assignment. Figure 3-11. NMR peak from 3-5.9 ppm for different copolymers 4.76pp m 4.34pp m

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51 This NMR study shows the difference in the NMR spectra with the increment of VA in the melt. We can see a peak at 4.8 ppm appearing and some extra peaks in the 4-4.8 ppm range compari ng to the homopolymers Table 3-3. Relative intensities of the 1H NMR peaks of Ha and Hb Polymer %CL Intensity I1 4.76ppm Intensity I2 4.34ppm Intensity 4.1ppm ratio I2/I1 3.2 90 0.35 2.49 12.1 7.1 3.3 80 0.48 2.09 4.82 4.4 3.4 70 0.77 2.13 2.67 2.8 3.5 60 0.9 1.72 1.34 1.9 3.6 50 1.04 1.31 0.65 1.3 3.7 40 1.28 1.2 0.53 0.9 3.8 30 1.35 1 0.37 0.7 3.9 20 1.42 0.57 0.74 0.4 3.10 10 1.49 0.4 0.3 0.3 Peaks at 4.76 ppm and 4.34 ppm are both respectively coupled with another adjacent peak but are the clearest on the NM R spectra. The reference peak will be at 7.0 ppm it correspond to 2 ar omatic hydrogens of VA. This study is more qualitative and helps to assign the peaks in our spectra. According to table 3-3 the intensity of peak I1 increases with the feed in VA and peak and inverse for I2. In that copolymer the ratio of I2/I1 is inconsistent so no alter nating copolymer has been formed. A block copolymer would show very little in tensity in one of the peak since only one of VA-CL repeat unit would be possible. Here the variation with the feed is for both intensities. We can conclude that the copolymer fo rmed in the bulk is a random copolymer. According to intensities I1 and I2, the peaks can be assigned in the following NMR spectra.

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52 Figure 3-12. Peak assignm ents in the 3-5 ppm range An NMR study shows the randomness of th e polymer chain. Notably in the 3-6 ppm region where peaks for t he VA/CL repeat unit appears in addition to the known peak of the 2 homopolymers. A study of t he ratio gives the composition of the copolyesters that is fairly clos e to the feed in each monomer. 3.4 New Ideas 3.4.1 Copolymers with Isosorbide Derivatives Another set of copolymers could be st udied starting with a different natural molecule: isosorbide. Isosorbide is a heterocyclic compound derived from glucose75, 76. It is a diol that has been used in the past as an initiator for ring opening polymerization of -caprolactone77. A functionalization of isosorbide in to an A-B monomer, alcohol/ acid type could give an interesting comonomer for -caprolactone. CL/VA 70/30

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53 Figure 3-13. Proposed copolymerizat ion isosorbide derivatives with -caprolactone 3.4.2 Copolymers of PLA Poly(lactic acid) has been one of the most developed and studied organic green polymer. It is a biodegradable aliphatic polyester that c an be obtained from ring opening polymerization of lactide78. Lactide that can be obtained by transformation of lactic acid, extracted from sugar cane or corn starch79. PLA is also biocompatible and has been used extensively for biomedical applications80. Figure 3-14. Proposed copolymeriz ation of vanillic acid derivatives with lactide. Similar to polycaprolactone the biodegradat ion could be tuned by insertion of aromatic repeat units in the aliphatic polyester backbone81. The properties and biodegradation could be selected and adapt ed, depending on the applications, with the feed in vanillic acid derivative into the polymer. It should be noted that the thermal properties of PLA, specifically the Tg,could not be changed much since the glass transitions of both polymers are similar. The Tg of PLA is around 60C82 and the homopolymer of vanillic acid derivatives is about 70C, so no big change is expected in the glass transition for a random copolymer. 3.5 Conclusions Polycaprolactone is an aliphatic polymer that is biocompatib le and biodegradable. Unfortunately its applications are limited by it s thermal properties. Copolymers of vanillic

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54 acid derivatives and caprolactone have been successfully synthesized by a stepgrowth/chain-growth copolymerization givi ng good incorporation of vanillic acid derivatives into the chain. The glass trans ition increased with the feed in vanillic acid derivatives and was compared to the calc ulated values obtained from the Flory equation. An NMR study show ed that the monomers inse rtion was random and gave incorporation ratios similar to the feed ratios. Finally some new ideas emerged from those results with notably the use of isosorbide and lactide for new biodegradable copolymers.

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55 CHAPTER 4 EXPERIMENTAL PROCEDURES 4.1 Molecular Characterizations Nuclear magnetic resonance (NMR) spec tra were recorded using a Varian Mercury 300 MHz spectrometer. Chemical sh ift is reported in parts per million (ppm) downfield relative to tetramethylsilane (T MS, 0.0 ppm) or specified solvent. Coupling constants ( J) are reported in Hertz (Hz). Multipli cities are reported using the following abbreviations: s, singlet; d, doubl et; t, triplet; q, quartet; quin, quintuplet; m, multiplet; br, broad. Differential scanning chromatographies were measured with DSC Q1000 from TA instruments. About 5-10 mg of samples were weighed in a sealed pan that went through a heat/cool/heat cycle at 10C/min. The te mperature range depends on the experiment but was limited to 300C by the instrument. Thermogravimetric analyses were measured with TGA Q5000 from TA Instruments. 5-10 mg of sample were heated at 50 C/min from 25-600C. Gel permeation chromatographies were meas ured at 40C in THF with a flow rate of 1 mL/min with Polystyrene standar d in a GPCV 2000 from WATERS. Viscosity measurements were done at 35C in a 1:2 mixture of phenol: 1,1,2,2 tetrachloroethane with a CANNONUbbelohde type 150. 4.2 Polymerizations Procedures Syntheses. All the polymerizations were carried out in a closed flask connected to the Schlenk line with a 180 glass connecto r. The flaskloaded with monomer and the catalystwas purged with nitrogen and evac uated 3 times before melting the solid monomer with a heati ng mantel. The temperature wa s regulated with a variac transformer. Agitation was effected with a m agnetic stir bar. The melt was kept under

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56 nitrogen to allow the formation of oligomers and limit the sublimation during vacuum is applied. Dynamic vacuum was applied on the mo lten polymer to remove water or acetic acid. At the end of the polymerization t he product was cooled under nitrogen leaving a solid that was dissolved in a mixture of trifluoroacetic acid and dichloromethane and then crashed in cold methanol. The solid polyme r was obtained by filtration and dried on the Schlenk line overnight. For the polymerization with the air sensitive titanium catalyst, the vanillic acid derivatives were weighed in the flask; capr olactone and the catalyst were added in the box and the flask was sealed before being opened under nitrogen on the Schlenk line. Caprolactone was distilled over calcium hydride and stored in the glove box. Viscosity measurements Intrinsic viscosity measurements were performed with a Ubbelohde viscometer. 15 mL of clean 1: 2 mixture of phenol: 1, 1, 2, 2tetrachloroethane were poured in the viscometer and allowed to thermally equilibrate for 2h. Exactly 1 mL of about 8 g/L solution of polymer was added for each measurement until the final volume is 20 mL in the viscome ter giving a final concentration of about 2 g/L. 0 lim][sp c to tot with csp )(spcf c By doing the Kramer plot, and extrapolating to infinitely dilute solution (c->0) we obtain the intrinsic viscosity. The value is then related to the Mark-Houwink constant for PET in the same solvent and temperature83. 84.0 21009.1][vM

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57 End group analysis. End group analysis is one way to determine molecular weight of a polymer by NM R study. The chemical envir onment for the end group is different than the one for a repeat unit in the middle of the polymer chain. For example, in a polyester all the ester linkage have t he same chemical environment and the end group will be an acid so a different type of st ructural bond. This implies a difference in chemical shift by NMR and can be noticed for relatively low polymerization degree polymers. For polymers 2.22 2.27 the end group will be an acid and the acetyl groupgroup that as a specific chemical shift at about 2.4 ppm. Figure 4-1. End group analysis for molecular weight determination. Knowing the integration of the methyl group Iend by NMR and the 4 hydrogens we can get the number of repeat unit in the polymer chai n with the following equation. DPRUMand I I DPn end n 4 3 4.3 Synthesis Procedures 2.1 4-(2-hydroxyethoxy)benzoic acid 20.0 g (0.145 mol) of p -Hydroxybenzoic acid were dissolved in a mixture of 17.1 g (0.428 mol) of sodium hydrox ide and 5.3 g (0.035 mol) of s odium iodide in 80 mL of water. The mixture was refluxed and 17.1 g (0. 212 mol) of 2-chloroethanol were slowly

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58 added to the reaction flask under nitrogen. A fter 24h, the reaction flask was cooled down, and acidified with dilute hydrochloric acid solution until the product crashed out. The white crystals were filtered and recr ystallized twice from a 5/1 solution of ethanol/water. 15.1 g of white product were obtained in a 57% yield. 1H NMR (CDCl3, 300 MHz): (ppm) = 12.61 (br. s, 1H, COOH), 7.87 (d, J = 8.9 Hz, 2H, Ar-H), 7.01 (d, J = 8.9 Hz, 2H, Ar-H), 4.91 (t, J = 4.9 Hz, 1H, OH), 4.05 (t, J = 4.5 Hz, 2H, OCH2), 3.72 (q, J = 4.9 Hz, 2H, C H2OH). 13C NMR (DMSO, 75 MHz): (ppm) = 167.0, 162.3, 1 31.4(2), 122.9, 114.3(2) 69.8, 59.4. 2.2 4-(2-hydroxyethoxy)-3-methoxybenzoic acid To a solution of 80.0 g (0.48 mol) of v anillic acid, 80.9 g (2.0 mol) of sodium hydroxide and 14.9 g (0.10 mol) of sodium iodide in 100 mL of water. 59.2 g of 2chloroethanol (0.74 mol) were added dropw ise at 100C under nitrogen diluted in 200 mL of ethanol. After 24h of reflux, the mixture was c ooled at room temperature, concentrated under vacuo, and the remaining solid dissolved in water and washed with diethyl ether. The aqueous solution was acidif ied with hydrochloric acid (3M) and gave a beige solid that after recrysta llization in ethanol was whit e. Filtration gave 72.9 g of 2.2 in 72% yield. 1H NMR (CDCl3, 300 MHz): (ppm) = 12.5 (br. s, 1H, COOH), 7.48 (dd, J = 8.4 Hz, 1.9 Hz, 1H, Ar-H), 7.39 (d, J = 1.9 Hz, 1H, Ar-H ), 6.99 (d, J = 8.5 Hz, 1H, Ar-H),

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59 4.84 (t, J = 5.0 Hz, 1H, OH), 3.99 (t, J = 5.0 Hz, 2H, OCH2), 3.75 (s, 3H, OCH3), 3.68 (q, J = 5.0 Hz, 2H, C H2OH). 13C NMR (DMSO, 75 MHz): (ppm) = 167.4, 152.4, 148. 7, 123.5, 123.2, 112.3, 112.2, 70.5, 59.7, 55.7. 2.3 4-(2-hydroxyethoxy)-3,5-dimethoxybenzoic acid 7.1 g (0.036 mol) of syringic acid, 3.3 g (0.083 mol) of sodium hydroxide and 0.9 g (0.006 mol) of sodium iodide were dissolved in 75 mL of water. 4.2 g (0.052 mol) of 2chloroethanol were added dropwise to the hot mixture. A fter 24h, of reaction under reflux, the aqueous solution was acidified with hydrochloric acid an d extracted with ethyl acetate. The organic solvent was removed and 5.4 g of crude product were left, it was recrystallized in a mixture of ethanol and wate r leaving 3.5 g of white pure powder in a 41% yield. 1H NMR (CD3CO, 300 MHz): (ppm) = 12.84 (br. s, 1H COOH), 7.23 (s, 2H, ArH), 4.61 (t, J = 5.7 Hz, 1H, OH), 3.94 (t, J = 5.6Hz, 2H, OCH2), 3.82 (s, 6H), 3.62 (q, J = 5.6Hz, 2H, CH2OH). 13C NMR (DMSO, 75 MHz): (ppm) = 170.7, 153.0(2), 140.9, 125.0, 107.3(2), 75.4, 61.4, 56.2(2). 2.4 4-(3-hydroxypropoxy)benzoic acid

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60 20.0 g (0.145 mol) of vanil lic acid, 17.6 g (0.314 mol) of potassium hydroxide and 2.7 g (0.018 mol) were dissolved in 100 mL of water. 16.5 g (0.175 mol) of 3chloropropan-1-ol were added to the hot mi xture slowly. After 24h of reaction, the aqueous solution was acidified with chlorhydric acid and a white solid crashed out. The crude product was recrystallized in a mix of et hanol and water to give 13.4 g of white powder in a 48% yield. 1H NMR (CDCl3, 300 MHz): (ppm) = 12.58 (br. s, 1H, COOH), 7.86 (d, J = 8.8 Hz, 2H, Ar-H), 6.99 (d, J = 8.8Hz, 2H, Ar-H), 4.56 (t, J = 5.0 Hz, 1H, OH), 4.09 (t, J = 6.4 Hz, 2H, OCH2), 3.54 (m, 2H, C H2OH), 1.86 (quin, J = 6.2 Hz, 2H, CH2C H2CH2). 13C NMR (DMSO, 75 MHz): (ppm) = 167.0, 162.3, 131. 4(2), 122.8, 114.2(2), 64.9, 67.2, 32.0. 2.5 4-(3-hydroxypropoxy)-3-methoxybenzoic acid Same procedure as 2.4 46% yield. 1H NMR (CDCl3, 300 MHz): (ppm)= 12.63 (br. s, 1H, COOH), 7.54 (dd, J = 8.0 Hz, 2.0 Hz, 1H, Ar-H), 7.43 (d, J = 2.0 Hz, 1H, Ar-H ), 7.04 (d, J = 8.5 Hz, 1H, Ar-H), 4.56 (t, J = 5.3Hz, 1H, OH), 4.09 (t, J = 6.4 Hz, 2H, OCH2), 3.8 (s, 3H, OCH3), 3.55 (q, J = 5.3 Hz, 2H, CH2OH), 1.88 (quin, J = 6.4 Hz, 2H, CH2C H2CH2) 13C NMR (DMSO, 75 MHz): (ppm) = 167.1, 152.0, 148. 4, 123.2, 122.8, 112.0, 111.7, 65.3, 57.2, 55.5, 32.0. 2.6 4-(3-hydroxypropoxy)-3,5-dimethoxybenzoic acid

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61 OH O O HO O O 2.6 10.0 g (0.05 mol) of syringic acid, 4.6 g (0 .12 mol) of sodium hydroxide and 0.95 g (0.0063 mol) of sodium iodide were dissolved in 80 mL of water. 5.1 g (0.054 mol) of 3chloropropan-1-ol were added dropwise to the hot mixture. After 48h, the reaction was cooled to room temperature and acidified with hydrochloric acid. 8.0 g of crude product crashed out of solution. The product was di ssolved in ethyl acetate and crashed with excess of hexanes giving 6.7 g of pure product in a 52% yield. 1H NMR (CD3CO, 300 MHz): (ppm) = 7.29 (s, 2H, Ar-H), 4.1 (t, J = 6.1 Hz, 2H, OCH2), 3.86 (s, 6H, OCH3), 3.73 (t, J = 6.1Hz, 2H, CH2OH), 1.86 (quin, J = 6.1 Hz, 2H, CH2C H2CH2). 13C NMR (CDCl3, 75 MHz): (ppm) = 170.7, 152.8(2), 141.5, 124.7, 107.2(2), 72.4, 61.3, 56.2(2), 32.1. 2.7 poly(4-(2-hydroxyethoxy)benzoic acid) 1.5 g (8.2 mmol) of 2.1 and 0.018 g (0.062 mmol) of ant imony trioxide were heated at 200-250C under nitrogen for 1h. Vacuum was applied for 16h until no more stirring was possible. The procedure des cribed above gave 0.95 g of 2.7 in a 70% yield 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 8.03 (d, J = 8.5 Hz, 2H, Ar-H), 7.01 (d, J = 8.5Hz, 2H, Ar-H), 4.75 (br s, 2H, COOC H2), 4.42 (br. s, 2H, OCH2). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 169.5, 163.4, 132.5(2), 121.6, 114.8(2), 66.2, 64.4.

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62 2.8 poly(4-(2-hydroxyethoxy)-3-methoxybenzoic acid) 1.5 g (7.2 mmol) of 2.2 and 0.02 g (0.069 mmol) of antimony trioxide were melted at 200-250C under nitrogen for 1h. Vacuum wa s applied for 6h until no more stirring was possible. After work up, 1.1 g of beige powder were obtained in 79% yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 7.71 (d, J = 8.5Hz, 1H, Ar-H), 7.5 (d, J = 1.7Hz, 1H, A r-H), 6.98 (d, J = 8.8Hz, 1H, Ar. H), 4.74 (m, 2H, COOCH2), 4.46 (br. s, 2H, OCH2), 3.92 (s, 3H, OCH3) 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 168.4, 152.1, 148.6, 125.0, 122.3, 112.7, 112.4, 67.2, 63.9, 56.3. 2.9 poly (4-(2-hydroxyethoxy)-3,5-dimethoxybenzoic acid) 2.0 g (8.13 mmol) of 2.3 and 0.02 g (0.069 mmol) of antim ony trioxide were melted under nitrogen at 150-200C for 1h. Vacuum was applied for 30h. Work up gave 1.3 g of powder in 71% yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 7.37 (s, 2H, Ar-H), 4.68 (br, 2H, COOCH2), 4.54 (br., 2H, OCH2), 3.84 (s, 6H, OCH3). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 168.4, 152. 7(2), 140.2, 125.2, 107.5(2), 71.3, 65.2, 56.3(2). 2.10 poly (4-(3-hydroxypropoxy)benzoic acid)

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63 OH O O O n H 2.10 1.5 g (7.85 mmol) of 2.4 and 0.022 g (0.075 mmol) of antimony trioxide were melted under nitrogen at 150-200 C for 1h. Vacuum was applied for 5h. Work up gave 0.7 g of powder in 50% yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 8.05 (d, J = 8.5 Hz, 2H, Ar-H), 7.03 (d, J = 8.5 Hz, 2H, Ar-H), 4. 59 (br. s, 2H, COOCH2), 4.25 (br. s, 2H, OCH2), 2.34 (m, 2H, CH2C H2CH2). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 170.2, 163.7, 132.4(2), 121.5, 114.8(2), 113.3, 64.9, 63.3. 2.11 poly(4-(3-hydroxypropoxy)-3 -methoxybenzoic acid) 2.1 g (9.3 mmol) of 2.5 and 0.036 g (0.12 mmol) of antim ony trioxide were melted under nitrogen at 200-250C for 1h. Vacuum was applied for 5h. Work up gave 1.1 g of powder in 57% yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 7.71 (br s, 1H, Ar-H), 7.57 (m, 1H, Ar. H), 6.96 (d, J = 8.5Hz, 1H, Ar-H), 4.56 (t, J = 6.1 Hz, 2H, COOCH2), 4.27 (t, J = 6.1 Hz, 2H, OCH2), 3.94 (s, 3H, OCH3), 2.34 (m, 2H, CH2C H2CH2). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 168.6, 152.6, 148.2, 124.8, 121.9, 112.5, 111.7, 65.6 62.8, 56.2, 28.2. 2.12 poly(4-(3-hydroxypropoxy)-3,5-dimethoxybenzoic acid

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64 1.7 g (6.63 mmol) of 2.6 and 0.017 g (0.058 mmol) of antimony trioxide were melted under nitrogen at 200-250 C for 1h. Vacuum was applied for 5h before the magnetic stirring stops. Work up gave 1.3 g of powder in 82% yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 7.35 (s, 2H, Ar-H), 4.63 (t, J = 6.4 Hz, 2H, COOCH2), 4.33 (t, J = 5.9 Hz, 2H, OCH2), 3.89 (s, 3H), 2.26 (quin, J = 6.2 Hz, 2H, CH2C H2CH2). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 169.5, 153. 1(2), 140.7, 125.7, 107.9(2), 71.1, 64.2, 56.4(2), 29.0. 2.13 methyl 4-hydroxy-3-methoxybenzoate 30.0 g (0.18 mol) of vanillic acid were dissolved in 150 mL of hot methanol. 6 mL of sulfuric acid were added as a catalyst and the reaction mixture is left for 48h at reflux under nitrogen. The solvent was removed and t he solid was dissolved in ethyl acetate and then washed with sodium bicarbonate. The organic layer was washed with brine and magnesium sulfate before bei ng removed under vacuum giving 25.0 g of product in 80% yield. 1H NMR (CDCl3, 300 MHz): (ppm) = 7.63 (dd, J = 8.2 Hz, 2.0 Hz, 1H, Ar-H), 7.54 (d, J = 2.0 Hz, 1H, Ar-H), 6.93 (d, J = 8.2 Hz, 1H, Ar-H), 6.12 (br. s, OH), 3.92 (s, 3H, OCH3), 3.88 (s, 3H, OCH3).

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65 13C NMR (CDCl3, 75 MHz): (ppm) = 167.3, 150.4, 146. 6, 124.6, 122.6, 114.5, 112.2, 56.5, 52.4. 2.14 4-acetoxy-3-methoxybenzoic acid OH O O O O 2.14 20.6 g (0.12 mol) of vanillic acid were di ssolved in 50 mL of acetic anhydride (0.53 mol) and 50 mL (0.62 mol) of pyridine. The mixture was stirred at room temperature overnight poured on 500 mL of water and acid ified with hydrochloric acid. The aqueous solution was extracted with et hyl acetate and rotovaped. A re crystallization from ethyl acetate gave 17.3 g of a beige powder in 67% yield. 1H NMR (CDCl3, 300 MHz): (ppm) = 7.73 (dd, J = 8.2 Hz, 1.7 Hz, 1H, Ar-H), 7.68(d, J = 1.7 Hz, 1H, Ar-H), 7.11(d, J = 8.2 Hz, 1H, Ar-H), 3.88 (s, 3H, OCH3), 2.32 (s, 3H, CH3). 13C NMR (CDCl3, 75 MHz): (ppm) = 171.1, 168.5, 151. 1, 144.2, 123.4, 122.9, 113.8(2), 56.0, 20.6. 2.15 4-(6-hydroxyhexyloxy)-3-methoxybenzoic acid To a solution of 15.0 g (0.089 mol) of van illic acid, 15.5 g (0.26 mol) of potassium hydroxide, 2.14 g (0.014 mol) of sodium iodide in a mixture of 30 mL of water, and 100 mL of ethanol. 6-chlorohexanol was added dr opwise to the hot solution under nitrogen. After 24h of reflux, the mixture was cooled at room temperatur e, concentrated under

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66 vacuo and the remaining solid dissolved in water. The aqueous solution was acidified with hydrochloric acid (3M) and gave a beige solid that after recrystallization in ethanol/water mixture was white. Filtration gave 18.3 g of 2.14 in 76% yield. 1H NMR (DMSO, 300 MHz): (ppm) = 12.65 (br. s, 1H, COOH), 7.54 (dd, J = 8.4 Hz, 2.0 Hz, 1H, Ar-H), 7.44 (d, J = 2.0 Hz, 1H, Ar-H ), 7.03 (d, J = 8.4 Hz, 1H, Ar-H), 4.36 (t, J = 5.4 Hz, 1H, OH), 4.02 (t, J = 6.7 Hz, 2H, OCH2), 3.8 (s, 3H, OCH3), 3.36 (br. s, 2H, CH2OH), 1.72 (quin, J = 6.7 Hz, 2H, CH2), 1.42 (m, 6H, OCH2(C H2)3CH2OH). 13C NMR (DMSO, 75 MHz): (ppm) = 167.2, 152.1, 148. 4, 123.2, 122.8, 112.1, 111.8, 68.2, 60.7, 55.5, 32.5, 28.7, 25.4, 25.3. 2.16 4-(2-hydroxypropoxy)-3-methoxybenzoic acid OH O O O HO 2.16 15.0 g (0.089 mol) of vanillic acid and 10.6 g of potassium hydroxide were dissolved in 50 mL of water. 10.4 g of pr opylene oxide were added to the solution at room temperature. The mixture was left to stir at room temperature for 72h, then acidified and extracted with ethyl acetate. The organic layer was washed over brine and magnesium sulfate before being removed u nder vacuum leaving a beige-yellow solid. The solid was dissolved in acetone and crashed with cold hexane leav ing 9.5 g of beige powder in 57% yield. 1H NMR (DMSO, 300 MHz): (ppm) = 12.66 (br. s, 1H, COOH), 7.54 (dd, J = 8.4 Hz, 1.8 Hz, 1H, Ar-H), 7.44 (d, J = 1.8 Hz, 1H, Ar. H ), 7.04 (d, J = 8.4 Hz, 1H, Ar-H), 4.89 (d, J = 4.4 Hz, 1H, OH), 3.94 (m, 3H, CH and CH2), 3.81 (s, 3H, OCH3), 1.16 (d, J = 6.1 Hz, 3H, CH3).

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67 13C NMR (DMSO, 75 MHz): (ppm) = 167.0, 152.0, 148. 4, 123.1, 122.9, 112.1, 112.0, 73.8, 64.4, 55.5, 20.3. 2.18 Poly (4-(6-hydroxyhexyloxy)-3-methoxybenzoic acid) 3.0 g (11.3 mmol) of 2.14 and 0.027 g (0.093 mmol) of antimony trioxide were melted under nitrogen at 200-250 C for 1h. Vacuum was applied for 4h before the magnetic stirring stops. Work up gave 1.95 g of product in 71% yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 7.73 (dd, J = 8.8 Hz, 2.0 Hz, 1H, Ar-H), 7.58 (d, J = 2.0 Hz, 1H, Ar-H ), 6.94 (d, J = 8.8 Hz, 1H, Ar-H), 4.38 (t, J = 6.7 Hz, 2H, COOCH2), 4.13 (t, J = 6.7 Hz, 2H, OCH2), 3.97 (s, 3H, OCH3), 1.85 (m, 4H, COOCH2C H2 and OCH2C H2 ), 1.53 (m, 4H, COOCH2CH2C H2 and OCH2CH2C H2). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 170.1, 153. 5, 148.3, 125.9, 122.2, 113.6, 112.2, 69.8, 67.2, 56.7, 29.1, 28.8, 26.1, 26.0. 2.19 Poly (4-(2-hydroxypropoxy)-3-methoxybenzoic acid) 2.0 g (8.7 mmol) of 2.15 and 0.024 g (0.082 mmol) of antimony trioxide were melted under nitrogen at 150-200C for 4h. Vacuum was applied for 5h before the magnetic stirring stopped. Work up gave 0.72 g of product in 40% yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 7.70 (d, J = 8.5 Hz, 1H, Ar-H), 7.56 (d, J = 2.0 Hz, 1H, Ar-H), 6.98 (d, J = 8.5 Hz, 1H, Ar-H), 5.56 (m, 1H, CH), 4.29 (m, 2H, CH2), 3.87 (s, 3H, OCH3), 1.5 (d, J = 6.5 Hz, 3H, CH3).

PAGE 68

68 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) =168.7, 152.8, 148.3, 125.5, 122.6, 114.1, 112.7, 71.3, 71.1, 56.5, 16.2. 2.20 3-(4-acetoxy-3-methoxyphenyl)acrylic acid 30.0 g of vanillin (0.197 mol) and 26.0 g of sodium acetate (0.317 mol) were dissolved in 200 mL of acetic anhydride (2. 12 mol). About 1 mL of pyridine was added to the flask and the mixture wa s heating up until reflux. A fter 24h, the brown solution was poured over about 500 g of crushed ice and the solution was st irred until apparition of a yellow-brown solid. The flask was left overnight in the freezer and the dark yellow solid filter. The crude solid was recrystallized in a mix of acetic acid and water to give 32.3 g of yellow beige solid in a 69% yield. 1H NMR (DMSO, 300 MHz): (ppm) = 12.35 (br. s, 1H, COOH), 7.56 (d, J = 15.9 Hz, 1H, Ar-CH) 7.46 (d, J = 1.7 Hz, 1H, Ar -H ), 7.24 (dd, J = 8.2 Hz, 1.7 Hz, 1H, Ar-H), 7.09 (d, J = 8.2 Hz, 1H, Ar-H), 6.56 (d, J = 15.9 Hz, 1H, C H COOH), 3.8 (s, 3H, OCH3), 2.24 (s, 3H, CH3). 13C NMR (DMSO, 300MHz): (ppm) = 168.4, 167.6, 151. 1, 143.4, 140.8, 138.3, 123.2, 121.3, 119.5, 1 11.8, 56.0, 20.4. 2.21 3-(4-acetoxy-3-metho xyphenyl)propanoic acid 15.0 g (0.064 mol) of 2.20 were dissolved in a mixture of 150: 80 mL of tetrahydrofuran: methanol. The solution was placed in a Parr pressure reactor and 1.5 g

PAGE 69

69 of palladium over charcoal 10% was added. The reaction was stirred under room temperature and under 60 psi of hydrogen for 5h. The bl ack solution was filtered through Celite545 to remove the palladium. The re sulting clear brown solution was dried over magnenisum sulfat e and condensed under vacuo. It was then dissolved in tetrahydrofuran and crashed with hexanes giving 12.8 g of beige product in 85% yield. 1H NMR (DMSO, 300 MHz): (ppm) = 12.15 (br. s, 1H COOH), 6.98 (s, 1H, ArH), 6.93 (d, J = 7.9Hz, 1H, ArH), 6.76(d, J = 7.9 Hz, 1H, Ar-H), 3.72 (s, 3H, OCH3), 2.79 (t, J = 8.0 Hz, 2H, Ar-CH2), 2.53 (t, J = 8.0 Hz, 2H, C H2COOH), 2.20 (s, 3H, CH3). 13C NMR (DMSO, 300MHz): (ppm) = 174.1, 168.9, 150. 8, 140.1, 137.8, 122.7, 120.3, 113.1, 55.9, 35.5, 30.5, 20.7. 2.22 poly(3-(4-hydroxy-3-methoxyphenyl)propanoic acid) 1.6 g (6.8 mmol) of 2.21 were melted under nitrogen for 2h and vacuum was applied for 2h leaving a brown solid that was dissolved in a mixture of trifluoroacetic acid and dichloromethane and crashed in me thanol. 1.0 g of beige product was obtained by filtration in 83% yield. 1H NMR (CDCl3/CF3COOD, 300 MHz): (ppm) = 6.92 (m, 3H, Ar-H), 3.84 (s, 3H, OCH3), 3.11 (m, 2H, CH2), 3.0 (m, 2H, CH2). 13C NMR (DMSO, 300MHz): (ppm) = 176.1, 150.9, 140. 6, 138.3, 123.2, 121.8, 113.9, 56.6, 36.2, 31.2. 2.23 poly(3-(4-hydroxy-3-met hoxyphenyl)propanoic acid)

PAGE 70

70 O O OH O n O 2.23 1.6 g (6.8 mmol) of 2.21 and 0.021 g (0.072 mmol) of antimony trioxide were melted under nitrogen for 2h and 2h of vacuum was applied for 2h leaving a brown solid that was dissolved in a mixtur e of trifluoroacetic acid and dichloromethane and crashed with methanol. 0.8 g of beige product was obtained by filtration in 67%yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 6.88 (m, 3H, Ar-H), 3.80 (s, 3H, OCH3), 3.07 (m, 2H, CH2), 2.96 (m, 2H, CH2). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 175.5, 150.4, 140.1, 137.8, 122.6, 120.0, 113.4, 56.1, 35.8, 30.7. 2.24 poly(3-(4-hydroxy-3-methoxyphenyl)propanoic acid) 1.6 g (6.8 mmol) of 2.21 and 0.018 g (0.082 mmol) of zinc diacetate dihydrate were melted under nitrogen for 2h and vacuum was applied for 2h leaving a brown solid that was dissolved in a mixtur e of trifluoroacetic acid and dichloromethane and crashed with methanol. 1.0 g of beige product was obtained by filtration in 82%yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 6.92 (m, 3H, Ar-H), 3.84 (s, 3H, OCH3), 3.11 (m, 2H, CH2), 3.00 (m, 2H, CH2). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 175.4, 150.4, 140.0, 137.8, 122.6, 121.7, 113.3, 56.0, 35.7, 30.7. 2.25 poly(3-(4-hydroxy-3-methoxyphenyl)propanoic acid)

PAGE 71

71 1.6 g (6.8 mmol) of 2.21 and 0.018 g (0.082 mmol) of zinc diacetate dihydrate were melted under nitrogen for 2h and vacuum was applied for 6h leaving a brown solid that was dissolved in a mixtur e of trifluoroacetic acid and dichloromethane and crashed with methanol. 1.1 g of beige product was obtained by filtration in 91%yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 6.9 (m, 3H, Ar-H), 3.83 (s, 3H, OCH3), 3.10 (m, 2H, CH2), 2.99 (m, 2H, CH2). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 175.5, 150.4, 140.0, 137.7, 122.6, 121.1, 113.3, 56.0, 35.7, 30.7. 2.26 poly(3-(4-hydroxy-3-methoxyphenyl)propanoic acid) 1.6 g (6.8 mmol) of 2.21 and 0.017 g (0.077 mmol) of zinc diacetate dihydrate were melted under nitrogen at 220-250C for 2h and vacuum was applied for 6h leaving a brown solid that was dissolved in a mixture of trifluoroacetic ac id and dichloromethane and crashed with methanol. 0.82 g of beige product was obtained by filtration in 68%yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 6.88 (m, 3H, Ar-H), 3.8 (s, 3H, OCH3), 3.07 (m, 2H, CH2), 2.96 (m, 2H, CH2). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 175.0, 150.4, 139.8, 137.7, 122.5, 121.0, 113.1, 56.0, 35.7, 30.7. 2.27 poly(3-(4-hydroxy-3-methoxyphenyl)propanoic acid)

PAGE 72

72 1.6 g (6.8 mmol) of 2.21 and 0.017 g (0.077 mmol) of zinc diacetate dihydrate were melted under nitrogen for 2h and vacuum was applied for 10min leaving a brown solid that was dissolved in a mixture of trifluoroacetic acid and dichloromethane and crashed with methanol. 0.9 g of beige product was obtained by filtration in 75%yield. 1H NMR (CF3COOD/CDCl3, 300 MHz): (ppm) = 6.88 (m, 3H, Ar-H), 3.8 (s, 3H, OCH3), 3.07 (m, 2H, CH2), 2.96 (m, 2H, CH2). 13C NMR (CF3COOD/CDCl3, 75 MHz): (ppm) = 176.0, 150.5, 140.4, 138.0, 122.8, 121.6, 113.7, 56.2, 35.9, 30.9. 2.28 3-(4-hydroxy-3-methoxy phenyl)propanoic acid 8.0 g (0.034 mol) of 3.5 and 4.7 g (0.118 mol) of sodium hydroxide were dissolved in 100 mL of water. The soluti on was refluxed for 5h. After cooling to room temperature the aqueous solution was acid ified with hydrochloric acid and extracted with dichloromethane. The organic layer was wa shed with brine and dried over magnesium sulfate. The evaporation of the solvent left a yellow crude product that was dissolved in dichloromethane and crashed with excess of hexanes. The work up gave 5.5 g of a beige powder in 83% yield. 1H NMR (CDCl3, 300 MHz): (ppm) = 6.97 (d, J = 8.0 Hz, 1H, Ar-H), 6.73 (br. s, 1H, Ar. H ), 6.71 (d, J = 1.9 Hz, 1H, Ar-H ), 3.88 (s, 3H, OCH3), 2.90 (t, J = 7.8 Hz, 2H, Ar-CH2), 2.70 (t, J = 7.8 Hz, 2H, CH2COOH).

PAGE 73

73 13C NMR (CDCl3, 75MHz): (ppm) = 179.2, 146.4, 144. 1, 132.0, 120.8, 114.4, 110.9, 55.8, 36.0, 30.3. 2.29 Poly(3-(4-hydroxy-3-methoxyphenyl)propanoic acid) 1.6 g (8.2 mmol) and 0.0195g (0.067 mmol) of antimony trioxide were heated under nitrogen for 5h and vacuum was applied for 6h. At the end of the 6h the product was still a brown melt in the flask. The product was dissolved in dichloromethane and trifluoroacetic acid and only 0.07 g of product crashed out of methanol in a 5% yield. The methanol was rotovaped leaving 1.5 g of brown solid that was analyzed by GPC showing low molecular weight material. 3.1 polycaprolactone 3.0 g (26 mmol) of caprolactone a nd 0.083 g (0.29 mmol) of Ti(OiPr)4 were heated at 80C for 1h under nitrogen and then the temperature was sl owly raised to 150C. The reaction was left 18h until stirring stopped. The orange solid was dissolved in chloroform and crashed in methanol giving 2.2 g, yield of 79%. 1H NMR (300MHz, CDCl3) in ppm: (ppm) = 4.05 (t, J = 6.7Hz, 2H, COOCH2), 2.3 (t, J = 7.5 Hz, 2H, CH2COO), 1.64 (m, 4H, COOCH2C H2, C H2CH2COO), 1.38 (m, 2H, C H2CH2CH2O). 13C NMR (CDCl3, 75 MHz): (ppm) = 173.5, 64.1, 34. 1, 28.3, 25.5, 24.5.

PAGE 74

74 HO O O O O O H nmO 3.2-3.9 p 3.2 Copoly [caprolactone-4-(2-hydroxyet hoxy)-3-methoxybenzoic acid] 90/10 To 0.62 g (2.9 mmol) of 4-(2-hydroxy ethoxy)-3-methoxybenzoic acid were added 3.02g (26 mmol) of caprolactone and 0.08 g(0.28 mmol) of Ti(OiPr)4. The mixture was melted at about 150C under nitrogen and left to stir for 1h. Vacuum was applied for 2h until stirring stopped. The solid/gel was dissolved in chloroform and crashed out with methanol giving 2.7 g of polymer in 80% yield. 3.3 Copoly[caprolactone-4-(2-hydroxyet hoxy)-3-methoxybenzoic acid] 80/20 To 1.0 g (4.8 mmol) of 4-(2-hydroxyet hoxy)-3-methoxybenzoic acid were added 2.18 g (19 mmol) of caprolactone and 0.08 g (0.28 mmol) of Ti(OiPr)4. The mixture was melted at about 150C under nitrogen and left to stir for 1h. Vacuum was applied for 6h until stirring stopped. The solid/gel was di ssolved in chloroform and was crashed with methanol giving 2.1 g of polymer in 67% yield. 3.4 Copoly[caprolactone-4-(2-hydroxyet hoxy)-3-methoxybenzoic acid] 70/30 To 1.5 g (7.1 mmol) of 4-(2-hydroxyet hoxy)-3-methoxybenzoic acid were added 1.9 g (16.7 mmol) of caprolactone and 0.07 g (0.24 mmol) of Ti(OiPr)4. The mixture was melted at about 150C under nitrogen and left to stir for 1h. Vacuum was applied for 6h until stirring stopped. The solid/gel was dissolved in chloroform and crashed out with methanol giving 2.2 g of powder in 68% yield. 3.5 Copoly[caprolactone-4-(2-hydroxyet hoxy)-3-methoxybenzoic acid] 60/40 To 1.5 g (7.1 mmol) of 4-(2-hydroxyet hoxy)-3-methoxybenzoic acid were added 1.2 g (10.5 mmol) of caprolactone and 0.05 g (0.18 mmol) of Ti(OiPr)4. The mixture was

PAGE 75

75 melted at about 150C under nitrogen and left to stir for 1h. Vacuum was applied for 6h until stirring stopped. The solid/gel was dissolved in chloroform and crashed out with methanol giving 1.74 g of powder in 67% yield. 3.6 Copoly[caprolactone-4-(2-hydroxyet hoxy)-3-methoxybenzoic acid] 40/60 To 1.5 g (7.1 mmol) of 4-(2-hydroxyet hoxy)-3-methoxybenzoic acid were added 0.81 g (7.1 mmol) of caprolactone and 0.05 g (0.18 mmol) of Ti(OiPr)4. The mixture was melted at about 150C under nitrogen and left to stir for 1h. Temper ature was raised to 200C and Vacuum was applied for 3h until stirring stopped. The solid/gel was dissolved in a mixture of chloroform and trifluoroacetic acid and crashed out with methanol giving 1.54 g of powder in 67% yield. 3.7 Copoly[caprolactone-4-(2-hydroxyet hoxy)-3-methoxybenzoic acid] 30/70 To 2.5 g (11.8 mmol) of 4-(2-hydroxy ethoxy)-3-methoxybenzoic acid were added 0.59 g (5.2 mmol) of caprolactone and 0.05 g (0.18 mmol) of Ti(OiPr)4. The mixture was melted at about 150C under nitrogen and left to stir for 1h. Temper ature was raised to 200C and vacuum was applied for 3h until sti rring stopped. The solid/gel was dissolved in a mixture of chloroform and trifluoroacet ic acid and crashed out with methanol giving 2.2 g of powder in 77% yield. 3.8 Copoly[caprolactone-4-(2-hydroxyet hoxy)-3-methoxybenzoic acid] 20/80 To 3.0 g (14.2 mmol) of 4-(2-hydroxy ethoxy)-3-methoxybenzoic acid were added 0.45 g (3.9 mmol) of caprolactone and 0.064 g (0.23 mmol) of Ti(OiPr)4. The mixture was melted at about 200C under nitrogen and le ft to stir for 1h. Temperature was raised to 250C and vacuum was applied for 3h until stirring stopped. The solid/gel was dissolved in a mixture of chloroform and trifluoroacetic acid and crashed out with methanol giving 2.2 g of bei ge powder in 69% yield.

PAGE 76

76 3.9 Copoly[caprolactone-4-(2-hydroxyet hoxy)-3-methoxybenzoic acid] 10/90 To 2.5 g (11.8 mmol) of 4-(2-hydroxy ethoxy)-3-methoxybenzoic acid were added 0.16 g (1.4 mmol) of caprolactone and 0.05 g (0.18 mmol) of Ti(OiPr)4. The mixture was melted at about 200C under nitrogen and left to stir for 1h. Temperat ure was raised to 250C and vacuum was applied for 2h until sti rring stopped. The solid/gel was dissolved in a mixture of chloroform and trifluoroacetic acid and crashed out with methanol giving 1.85 g of beige powder in 76% yield.

PAGE 77

77 APPENDIX A PROTON AND CARBON NMR

PAGE 78

78 Figure A-1. 1H NMR spectra of compound 2.1

PAGE 79

79 Figure A-2. 13C NMR spectra of compound 2.1

PAGE 80

80 Figure A-3. 1H NMR spectra of compound 2.2

PAGE 81

81 Figure A-4. 13C NMR spectra of compound 2.2

PAGE 82

82 Figure A-5. 1H NMR spectra of compound 2.3

PAGE 83

83 Figure A-6. 13C NMR spectra of compound 2.3

PAGE 84

84 Figure A-7. 1H NMR spectra of compound 2.4

PAGE 85

85 Figure A-8. 13C NMR spectra of compound 2.4

PAGE 86

86 Figure A-9. 1H NMR spectra of compound 2.5

PAGE 87

87 Figure A-10. 13C NMR spectra of compound 2.5

PAGE 88

88 Figure A-11. 1H NMR spectra of compound 2.6

PAGE 89

89 Figure A-12. 13C NMR spectra of compound 2.6

PAGE 90

90 Figure A-13. 1H NMR spectra of compound 2.7

PAGE 91

91 Figure A-14. 13C NMR spectra of compound 2.7

PAGE 92

92 Figure A-15. 1H NMR spectra of compound 2.8

PAGE 93

93 Figure A-16. 13C NMR spectra of compound 2.8

PAGE 94

94 Figure A-17. 1H NMR spectra of compound 2.9

PAGE 95

95 Figure A-18. 13C NMR spectra of compound 2.9

PAGE 96

96 Figure A-19. 1H NMR spectra of compound 2.10

PAGE 97

97 Figure A-20. 13C NMR spectra of compound 2.10

PAGE 98

98 Figure A-21. 1H NMR spectra of compound 2.11

PAGE 99

99 Figure A-22. 13C NMR spectra of compound 2.11

PAGE 100

100 Figure A-23. 1H NMR spectra of compound 2.12

PAGE 101

101 Figure A-24. 13C NMR spectra of compound 2.12

PAGE 102

102 Figure A-25.1H NMR spectra of compound 2.13

PAGE 103

103 Figure A-26. 13C NMR spectra of compound 2.13

PAGE 104

104 Figure A-27.1H NMR spectra of compound 2.14

PAGE 105

105 Figure A-28. 13C NMR spectra of compound 2.14

PAGE 106

106 Figure A-29. 1H NMR spectra of compound 2.15

PAGE 107

107 Figure A-30. 13C NMR spectra of compound 2.15

PAGE 108

108 Figure A-31. 1H NMR spectra of compound 2.16

PAGE 109

109 Figure A-32. 13C NMR spectra of compound 2.16

PAGE 110

110 Figure A-33. 1H NMR spectra of compound 2.18

PAGE 111

111 Figure A-34. 13C NMR spectra of compound 2.18

PAGE 112

112 Figure A-35. 1H NMR spectra of compound 2.19

PAGE 113

113 Figure A-36. 13C NMR spectra of compound 2.19

PAGE 114

114 Figure A-37. 1H NMR spectra of compound 2.20

PAGE 115

115 Figure A-38. 13C NMR spectra of compound 2.20

PAGE 116

116 Figure A-39. 1H NMR spectra of compound 2.21

PAGE 117

117 Figure A-40. 13C NMR spectra of compound 2.21

PAGE 118

118 Figure A-41. 1H NMR spectra of compound 2.22

PAGE 119

119 Figure A-42. 13C NMR spectra of compound 2.22

PAGE 120

120 Figure A-43. 1H NMR spectra of compound 2.23

PAGE 121

121 Figure A-44. 13C NMR spectra of compound 2.23

PAGE 122

122 Figure A-45. 1H NMR spectra of compound 2.24

PAGE 123

123 Figure A-46. 13C NMR of compound 2.24

PAGE 124

124 Figure A-47. 1H NMR spectra of compound 2.25

PAGE 125

125 Figure A-48. 13C NMR spectra of compound 2.25

PAGE 126

126 Figure A-49. 1H NMR spectra of compound 2.26

PAGE 127

127 Figure A-50. 13C NMR spectra of compound 2.26

PAGE 128

128 Figure A-51. 1H NMR spectra of compound 2.27

PAGE 129

129 Figure A-52. 13C NMR spectra of compound 2.27

PAGE 130

130 Figure A-53. 1H NMR spectra of compound 2.28

PAGE 131

131 Figure A-54. 13C NMR spectra of compound 2.28

PAGE 132

132 Figure A-55. 1H NMR spectra of compound 3.1

PAGE 133

133 Figure A-56. 13C NMR spectra of compound 3.1

PAGE 134

134 Figure A-57. 1H NMR spectra of compound 3.2

PAGE 135

135 Figure A-58. 13C NMR spectra of compound 3.2

PAGE 136

136 Figure A-59. 1H NMR spectra of compound 3.3

PAGE 137

137 Figure A-60. 13C NMR spectra of compound 3.3

PAGE 138

138 Figure A-61. 1H NMR spectra of compound 3.4

PAGE 139

139 Figure A-62. 13C NMR spectra of compound 3.4

PAGE 140

140 Figure A-63. 1H NMR spectra of compound 3.5

PAGE 141

141 Figure A-64. 13C NMR spectra of compound 3.5

PAGE 142

142 Figure A-65. 1H NMR spectra of compound 3.6

PAGE 143

143 Figure A-66. 13C NMR spectra of compound 3.6

PAGE 144

144 Figure A-67. 1H NMR spectra of compound 3.7

PAGE 145

145 Figure A-68. 13C NMR spectra of compound 3.7

PAGE 146

146 Figure A-69. 1H NMR spectra of compound 3.8

PAGE 147

147 Figure A-70. 13C NMR spectra of compound 3.8

PAGE 148

148 Figure A-71. 1H NMR spectra of compound 3.9

PAGE 149

149 Figure A-72. 13C NMR spectra of compound 3.9

PAGE 150

150 Figure A-73. 1H NMR spectra of compound 3.10

PAGE 151

151 Figure A-74. 13C NMR spectra of compound 3.10

PAGE 152

152 APPENDIX B POLYMER DATA

PAGE 153

153 Figure B-1. DSC of polymer 2.7 Figure B-2. TGA of polymer 2.7

PAGE 154

154 Figure B-3. DSC of polymer 2.8 Figure B-4. TGA of polymer 2.8

PAGE 155

155 Figure B-5. DSC of polymer 2.9 Figure B-6. TGA of polymer 2.9

PAGE 156

156 Figure B-7. DSC of polymer 2.10 Figure B-8. DSC of polymer 2.10

PAGE 157

157 Figure B-9. DSC of polymer 2.11 Figure B-10. TGA of polymer 2.11

PAGE 158

158 Figure B-11. DSC of polymer 2.12 Figure B-12. TGA of polymer 2.12

PAGE 159

159 Figure B-13. DSC of polymer 2.18 Figure B-14. TGA of polymer 2.18

PAGE 160

160 Figure B-15. DSC of polymer 2.19 Figure B-16. TGA of polymer 2.19

PAGE 161

161 Figure B-17. DSC of polymer 2.26 Figure B-18. TGA of polymer 2.26

PAGE 162

162 Figure B-19. GPC analysis of the methanol fraction of 2.29 Figure B-20. DSC of polymer 3.1 a b

PAGE 163

163 Figure B-21. TGA of polymer 3.1 Figure B-22. DSC of polymer 3.1 ( Tg at 30C/min)

PAGE 164

164 Figure B-23. GPC of polymer 3.1 in THF Figure B-24. DSC of polymer 3.2 a b

PAGE 165

165 Figure B-25. TGA of polymer 3.2 Figure B-26. DSC of polymer 3.3

PAGE 166

166 Figure B-27. TGA of polymer 3.3 Figure B-28. DSC of polymer 3.4

PAGE 167

167 Figure B-29. TGA of polymer 3.4 Figure B-30. DSC of polymer 3.5

PAGE 168

168 Figure B-31. TGA of polymer 3.5 Figure B-32. DSC of polymer 3.6

PAGE 169

169 Figure B-33. TGA of polymer 3.6 Figure B-34. DSC of polymer 3.7

PAGE 170

170 Figure B-35. TGA of polymer 3.7 Figure B-36. DSC of polymer 3.8

PAGE 171

171 Figure B-37. TGA of polymer 3.8 Figure B-38. DSC of polymer 3.9

PAGE 172

172 Figure B-39. TGA of polymer 3.9 Figure B-40. DSC of polymer 3.10

PAGE 173

173 Figure B-41. TGA of polymer 3.10

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179 BIOGRAPHICAL SKETCH Laurent Mialon was born in 1984 in Franc e. He attended the lyce polyvalent de St-Romain en Gal and obtained the scientif ic Baccalaurat with honors in 2002. Growing a general interest for science, he entered in fall 2002, the preparatory classes to CPE Lyon with a specialization in physics and chemistry. He was admitted to the engineering school Chimie Physique Electron ic Lyon (CPE Lyon) in 2005, obtaining his diplme dingnieur in spring 2009. After 2 years of engineering school he enrolled the chemistry department at the University of Florida, specializing in organic chemistry and polymer science. His research on biorenewab le polymers was directed by Dr. Stephen A. Miller. He started working as a polymer chemist in R&D for AkzoNobel in February 2010 in Newcastle, UK.