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1 POLYAL KYLENE AND POLYARYLENE OXALATES FROM BIORENEWABLE DIOLS VIA ESTER INTERCHANGE By JOHN JAIRO GARCIA OCAMPO 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 2012
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2 2012 John Jairo Garcia Ocampo
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3 To my father and mother
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4 ACKNOWLEDGMENTS I would like to thank the members of my committee : Dr. Wagener, Dr. Smith, and especi ally Dr. Miller for their support and ideas during the development of this project. Of course I also want to thank the University of Florida for the resources, f acilities, professor s and their guidance during the s e years I have to thank the members of th e Butler Polymer Research Laboratory my friends and lab mates of the Miller Lab for the support, and help through this time I cannot forget to thank Dr. Fabio Zuluaga, who encouraged me to join highly grateful with him for encouraging me to look for thi s unique opportunity to be here, as well his guidance along my time here. Finally, I have to thank my parents; their unconditional love and support were key s of who I am
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5 TABLE OF CONTENTS page ACKNOWLEDGMENTS ................................ ................................ ................................ .. 4 LIST OF TABLES ................................ ................................ ................................ ............ 7 LIST OF FIGURE S ................................ ................................ ................................ .......... 8 LIST OF ABBREVIATIONS ................................ ................................ ........................... 14 ABSTRACT ................................ ................................ ................................ ................... 15 CHAPTER 1 MOTIVATION AND TARGETS ................................ ................................ ............... 16 1.1 Polymers: Petroleum Based Commodities ................................ ........................ 16 1.2 Environmental Problematic s ................................ ................................ ............. 16 1.3 Poly mers from Biorenewable Feedstocks ................................ ......................... 16 2 OXALIC ACID ................................ ................................ ................................ ......... 18 2.1 General As pects ................................ ................................ ............................... 18 2.2 Presence in Nature ................................ ................................ ........................... 18 2.3 Synthetic Pathways ................................ ................................ ........................... 19 3 DIOLS ................................ ................................ ................................ ..................... 20 3.1 Aliphatic Diols ................................ ................................ ................................ ... 20 3.2 Aromatic Diols ................................ ................................ ................................ ... 20 4 POLYOXALATES ................................ ................................ ................................ ... 22 4.1 Background ................................ ................................ ................................ ....... 22 4.2 Applicatio ns ................................ ................................ ................................ ...... 22 4.3 Degradability ................................ ................................ ................................ ..... 23 4.4 Polyalkylene Oxalates ................................ ................................ ....................... 23 4.4.1 Synthesis and Characterization ................................ ............................... 24 4.4.2 Effects of Methylene Spacers ................................ ................................ .. 26 4.4.3 Conclusions ................................ ................................ ............................. 28 4.5 Polyarylene and Copoly(Alkylene Arylene) Oxalates ................................ ........ 29 4.5.1 Synthesis and Characterization ................................ ............................... 30 4.5.2 Effect of the Incorporation of Aromatic Units in to the Polymer ................ 31 4.5.3 Degradation ................................ ................................ ............................. 32 4.5.4 New Ideas ................................ ................................ ............................... 33 4.5.4.1 Copolymers with 1,4 butanediol ................................ ..................... 33
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6 4.5.4.2 Polyoxalates based on hydroquinone ................................ ............ 33 4.5.4.3 Vanillin based diols for polyarylene oxalates ................................ .. 34 4.5.5 Conclusions ................................ ................................ ............................. 35 5 EXPERIMENTAL PROCEDURES ................................ ................................ .......... 36 5.1 Molecular Characterization ................................ ................................ ............... 36 5.2 Polymerization Procedures ................................ ................................ ............... 37 5.3 Synthesis of Aromatic Diol ................................ ................................ ................ 42 APPENDIX A PROTON AND CARBON NMR ................................ ................................ .............. 43 B POLYMER DATA ................................ ................................ ................................ .... 65 LIST OF REFERE NCES ................................ ................................ ............................... 94 BIOGRAPHICAL SKETCH ................................ ................................ ............................ 96
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7 LIST OF TABLES Table page 1 1 Presence of oxalic acid in vegetables ................................ ................................ 18 4 1 Polyalkylene oxalates, molecular and thermal properties ................................ ... 25 4 2 Copoly(alkylene arylene) oxalates, macro molecular and thermal properties ..... 30 4 3 Degradation of copoly(alkylene arylene) oxalates ................................ .............. 33
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8 LIST OF FIGURES Figure page 3 1 Resorcinol ................................ ................................ ................................ ........... 21 3 2 Hydroquinone ................................ ................................ ................................ ..... 21 4 1 Degradation study of polyoxalate in aqueous solution ................................ ........ 23 4 2 General reaction of polyoxalates synthesis. ................................ ....................... 24 4 3 General mechanism for Fisher esterification ................................ ...................... 25 4 4 Representation of two chains of polybutylene oxalate ................................ ........ 27 4 5 Melting and glass transition temperatures of polyalkylene oxalates along different number of methylene groups in the backb one ................................ ...... 27 4 6 Representation of two pair s of chains of polypropylene oxalate and polyneopentylene oxalate ................................ ................................ ................... 28 4 7 Resorcinol bis(beta hydroxyethyl)ether ( 4.12 ). ................................ ................... 29 4 8 1 H NMR spectra of polymers 4.9, 4.16 and 4.22 for incorporation calculation .... 31 4 9 Melting temp erature of copoly(alkylene arylene) oxalates. ................................ 31 4 10 Fox equation for random copolymers, where w is weight fraction ...................... 3 2 4 11 Glass transition temperature of copolymers ................................ ....................... 32 4 12 Copolymer using 1,4 butanediol as comonomer. ................................ ............... 33 4 13 Poly resorcinol bis(beta hydroxyethyl)ether oxalate ................................ ........... 34 4 14 Vanillin based unsymmetrical diol ................................ ................................ ....... 34 4 15 Vanillin based symmetrical diols ................................ ................................ ......... 35 5 1 Polymerization device : A hot plate with temperature control, oil bath, flask containing the reagents and connection to a vacuum line through a b ump trap. ................................ ................................ ................................ ................... 37 5 2 Polyprolylene oxalate ( 4.1 ) ................................ ................................ ................. 38 5 3 Polyneopentyl ene oxalate ( 4.2 ) ................................ ................................ .......... 38 5 4 Polybutylene oxalate ( 4.3 ) ................................ ................................ .................. 38
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9 5 5 Polypentylene oxalate ( 4.4 ) ................................ ................................ ................ 39 5 6 Polyhexylene oxalate ( 4.5 ) ................................ ................................ ................. 39 5 7 Polyheptylene oxalate ( 4.6 ) ................................ ................................ ................ 39 5 8 Polyoctylene oxalate ( 4.7 ) ................................ ................................ .................. 39 5 9 Polynonylene oxalate ( 4.8 ) ................................ ................................ ................. 40 5 10 Polydecylene oxalate ( 4.9 ) ................................ ................................ ................. 40 5 11 Polyundecylene oxalate ( 4.10 ) ................................ ................................ ........... 40 5 12 Polydodecylene oxalate ( 4.11 ) ................................ ................................ ........... 41 5 13 Copolymer ( 4.17 ) ................................ ................................ ................................ 41 5 14 Poly resorcinol bis(beta hydroxyethytl)ether oxalate ( 4.22 ) ................................ 41 5 15 Synthesis of Resorcinol bis(beta hydroxyethyl)ether ( 4.12 ) ............................... 42 A 1 1 H NMR of polymer 4.1 ................................ ................................ ....................... 43 A 2 13 C NMR of polymer 4.1 ................................ ................................ ..................... 43 A 3 1 H NMR of polymer 4.2 ................................ ................................ ....................... 44 A 4 13 C NMR of polymer 4.2 ................................ ................................ ..................... 44 A 5 1 H NMR of polymer 4.3 ................................ ................................ ....................... 45 A 6 13 C NMR of polymer 4.3 ................................ ................................ ..................... 45 A 7 1 H NMR of polymer 4.4 ................................ ................................ ....................... 46 A 8 13 C NMR of polymer 4.4 ................................ ................................ ..................... 46 A 9 1 H NMR of polymer 4.5 ................................ ................................ ....................... 47 A 10 13 C NMR of polymer 4.5 ................................ ................................ ..................... 47 A 11 1 H NMR of polymer 4.6 ................................ ................................ ....................... 48 A 12 13 C NMR of polymer 4.6 ................................ ................................ ..................... 48 A 13 1 H NMR of polymer 4.7 ................................ ................................ ....................... 49 A 14 13 C NMR of polymer 4.7 ................................ ................................ ..................... 49
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10 A 15 1 H NMR of polymer 4.8 ................................ ................................ ....................... 50 A 16 13 C NMR of polymer 4.8 ................................ ................................ ..................... 50 A 17 1 H NMR of polymer 4.9 ................................ ................................ ....................... 51 A 18 13 C NMR of polymer 4.9 ................................ ................................ ..................... 51 A 19 1 H NMR of polymer 4.10 ................................ ................................ ..................... 52 A 20 13 C NMR of polymer 4.10 ................................ ................................ ................... 52 A 21 1 H NMR of polymer 4.11 ................................ ................................ ..................... 53 A 22 13 C NMR of polymer 4.11 ................................ ................................ ................... 53 A 23 1 H NMR of compound 4.12 ................................ ................................ ................. 54 A 24 13 C NMR of compound 4.12 ................................ ................................ .................. 54 A 25 1 H NMR of polymer 4.13 ................................ ................................ ..................... 55 A 26 13 C NMR of polymer 4.13 ................................ ................................ ................... 55 A 27 1 H NMR of polymer 4.14 ................................ ................................ ..................... 56 A 28 13 C NMR of polymer 4.14 ................................ ................................ ................... 56 A 29 1 H NMR of polymer 4.15 ................................ ................................ ..................... 57 A 30 13 C NMR of polymer 4.15 ................................ ................................ ................... 57 A 31 1 H NMR of polymer 4.16 ................................ ................................ ..................... 58 A 32 13 C NMR of polymer 4.16 ................................ ................................ ................... 58 A 33 1 H NMR of polymer 4.17 ................................ ................................ ..................... 59 A 34 13 C NMR of polymer 4.17 ................................ ................................ ................... 59 A 35 1 H NMR of polymer 4.18 ................................ ................................ ..................... 60 A 36 13 C NMR of polymer 4.18 ................................ ................................ ................... 60 A 37 1 H NMR of polymer 4.19 ................................ ................................ ..................... 61 A 38 13 C NMR of polymer 4.19 ................................ ................................ ................... 61 A 39 1 H NMR of polymer 4.20 ................................ ................................ ..................... 62
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11 A 40 13 C NMR of polymer 4.20 ................................ ................................ ................... 62 A 41 1 H NMR of polymer 4.21 ................................ ................................ ..................... 63 A 42 13 C NMR of polymer 4.21 ................................ ................................ ................... 63 A 43 1 H NMR of polymer 4.22 ................................ ................................ ..................... 64 A 44 13 C NMR of polymer 4.22 ................................ ................................ ................... 64 B 1 TGA of polypropylene oxalate 4.1 ................................ ................................ ...... 65 B 2 DSC of polypropylene oxalate 4.1 ................................ ................................ ...... 65 B 3 TGA of polyneopentylene oxalate 4.2 ................................ ................................ 66 B 4 DSC of polyneopentylene oxalate 4.2 ................................ ................................ 66 B 5 TGA of polybutylene oxalate 4.3 ................................ ................................ ......... 67 B 6 DSC of polybutylene oxalate 4.3 ................................ ................................ ........ 67 B 7 TGA of polypentylene oxalate 4.4 ................................ ................................ ....... 68 B 8 DSC of polypentylene oxalate 4.4 ................................ ................................ ...... 68 B 9 TGA of polyhexylene oxalate 4.5 ................................ ................................ ........ 69 B 10 DSC of polyhexylene oxalate 4.5 ................................ ................................ ........ 69 B 11 TGA of poly heptylene oxalate 4.6 ................................ ................................ ...... 70 B 12 DSC of polyheptylene oxalate 4.6 ................................ ................................ ...... 70 B 13 TGA of polyoctylene oxalate 4.7 ................................ ................................ ......... 71 B 14 DSC of polyoctylene oxalate 4.7 ................................ ................................ ......... 71 B 15 TGA of polynonylene oxalate 4.8 ................................ ................................ ........ 72 B 16 DSC of polynonylene oxalate 4.8 ................................ ................................ ....... 72 B 17 TGA of polydecylene oxalate 4.9 ................................ ................................ ........ 73 B 18 DSC of polydecylene oxalate 4.9 ................................ ................................ ........ 73 B 19 TGA of polyundecylene oxalate 4.10 ................................ ................................ .. 74 B 20 DSC of polyundecylene oxalate 4.10 ................................ ................................ .. 74
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12 B 21 TGA of polydodecylene oxalate 4.11 ................................ ................................ .. 75 B 22 DSC of polydodecylene oxalate 4.11 ................................ ................................ .. 75 B 23 TGA of copolymer 4.13 ................................ ................................ ....................... 76 B 24 DSC of copolymer 4.13 ................................ ................................ ...................... 76 B 25 TGA of copolymer 4.14 ................................ ................................ ....................... 77 B 26 DSC of copolymer 4.14 ................................ ................................ ...................... 77 B 27 TGA of copolymer 4.15 ................................ ................................ ....................... 78 B 28 DSC of copolymer 4.15 ................................ ................................ ...................... 78 B 29 TGA of copolymer 4.16 ................................ ................................ ....................... 79 B 30 DSC of copolymer 4.16 ................................ ................................ ...................... 79 B 31 TGA of copolymer 4.17 ................................ ................................ ....................... 80 B 32 DSC of copolymer 4.17 ................................ ................................ ...................... 80 B 33 TGA of copolymer 4.18 ................................ ................................ ....................... 81 B 34 DSC of copolymer 4.18 ................................ ................................ ...................... 81 B 35 TGA of copolymer 4.19 ................................ ................................ ....................... 82 B 36 DSC of copolymer 4.19 ................................ ................................ ...................... 82 B 37 TGA of copolymer 4.20 ................................ ................................ ....................... 83 B 38 DSC of copolymer 4.20 ................................ ................................ ...................... 83 B 39 TGA of copolymer 4.21 ................................ ................................ ....................... 84 B 40 DSC of copolymer 4.21 ................................ ................................ ...................... 84 B 41 TGA of copolymer 4.22 ................................ ................................ ....................... 85 B 42 DSC of copolymer 4.22 ................................ ................................ ...................... 85 B 43 GPC of polyneopentylene oxalate 4.2 ................................ ................................ 86 B 44 GPC of polypentylene oxalate 4.4 ................................ ................................ ...... 86 B 45 GPC of polyhexylene oxalate 4.5 ................................ ................................ ....... 87
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13 B 46 GPC of polyheptylene oxalate 4.6 ................................ ................................ ...... 87 B 47 GPC of polyoctylene oxalate 4.7 ................................ ................................ ........ 88 B 48 GPC of polynonylene oxalate 4.8 ................................ ................................ ....... 88 B 49 GPC of polydecylene oxalate 4.9 ................................ ................................ ....... 89 B 50 GPC of polyundecylene oxalate 4.10 ................................ ................................ 89 B 51 GPC of polydodecylene oxalate 4.11 ................................ ................................ 90 B 52 GPC of copolymer 4.13 ................................ ................................ ...................... 90 B 53 GPC of copolymer 4.14 ................................ ................................ ...................... 91 B 54 GPC of copolymer 4.15 ................................ ................................ ...................... 91 B 55 GPC of copolymer 4.16 ................................ ................................ ...................... 92 B 56 GPC of copolymer 4.17 ................................ ................................ ...................... 92 B 57 GPC of copolymer 4.18 ................................ ................................ ...................... 93 B 58 GPC of copolymer 4.19 ................................ ................................ ...................... 93
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14 LIST OF ABBREVIATION S C Celsius Cat. Catalyst Da Dalton DMSO Dimethyl sulfoxide DSC Differential Scanning Calorimetry g Gram s GPC Gel Permeation Chromatography Hz Hertz J Joule s mg Milligram MHz Mega hertz mL Milliliter mol Moles mol% Mole percent M w Weight average molecular weight NMR Nuclear magnetic resonance N 2 Nitrogen gas PDI Polydispersity index ppm Parts per million T g Glass transition temperature TGA Thermal gravimetric anal ysis THF Tetrahydrofuran T m Melting temperature
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15 Abstract of Thesis Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master in Science POLYALKYLENE AND POLYARYLENE OXALATES FROM BIORENEWABLE DIOLS VIA ESTER INTERCHANGE By John Jairo Garcia Ocampo December 2012 Chair: Stephen A. Miller Major: Chemistry It is difficult to think about a modern world without polymers ; they are part of our l ives and serve different purposes making our life somehow easier. However, polymers are mainly products from petroleum, which is a non renewable resource T he price tends to be high and variable, and degradation of many of those polymers is s low in environmental conditions. Regar ding this situation the re is an increasing interest in finding biorenewable resources that could lead to cheaper and more abundant starting materials for synthesis of these polymers, as well as developing novel biodegradable polymers to reduce the impact o f their disposal in land fi l ls. Although occurrence of oxalates is wide in nature, few studies have been done with polymers containing this functional group. Some of these studies have been related with degradation of polyoxalates indicating the potential biodegradability of these compounds. In the present work a methodology to synthesize poly oxalates in melt and acid catalyzed was developed. The thermal properties of different polyalkylene and polyarylene oxalates were studied, with special focus in the decanediol and resorcinol bis(beta hydroxyethyl)ether as potential biorenewable diols that can provide higher melting temperature ( T m ) and glass transition temperature ( T g ) to the polymer
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16 CHAPTER 1 MOTIVATION AND TARGETS 1.1 Polymers: Petroleum Based Commodit ies P olymer synthesis and applications are some of the hottest topics in scientific research over the last century, with hundreds of thousands of publications per year in this area. Their versatility and t he relative easiness to synthesize and process them led to a massive production of consumer goods around the world. The petrochemical industry is the mai n source of raw material s of synthetic polymers nowadays. However, this convenient source implies a problem: petroleum is not a renewable resource, which means eventually in the future humanity will r un out of it A mong other causes, this uncertainty leads to its unstable price and it is believed that is going to be higher in the next decades increasing the prices of these polymers. 1.2 Environmental Problematic s Another concern about most of petroleu m based polymers is the environmental impact in the biosphere. These polymers might take hundreds or thousands of years to decompose in lands rivers or oceans, causing contamination and harming the life of many species including ourselves. Considering this, our group is focused on polymers with high degradability (either chemical or biological) and/or synthesized from biorenewable resources to diminish the impact in the environment of the production of plastics in the world. 1.3 Polymers f ro m Bio r enewable Feedstock s There is an increasing interest in finding novel polymers from biorenewable feedstock s to replac e petroleum as raw material as well as finding potential biodegradable plastics which decompose faster under environmental conditions P oly
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17 lactic acid (PLA) is one of the polymers being used; lactic acid is produced by fermentation of sugars
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18 CHAPTER 2 OXALIC ACID 2.1 General Aspects Also known as ethanedioic acid, oxalic acid is the simplest dicarboxylic acid, having a formula of C 2 H 2 O 4 Its molecular weight is 90.04 g/mol Anhydrous oxalic acid can be crystallized from glacial acetic acid, is orthorhombic and the crystals can be pyramidal or elongated octahedral. It is hygroscopic and the melting point is at 189.5 C Oxalic acid s ublimes at 157 C ; meanwhile at higher temperatures it may decompose into CO CO 2 formic acid and water. 1 2.2 Presence i n Nature Oxalic acid is present in many vegetables, especially in the cell sap of plants belonging to the Oxalis and Rumex families as the potassium or calcium salt. Also species of Penicillium and Aspergillus convert sugar into calcium oxalate with 90% yields under optimal conditions. 1 Oxalic acid is also present in different quantities in some vegetables as shown in Table 1 1. 2 Table 1 1. Presence of oxalic acid in vegetables Vegetable Concentration (%) Amaranth 1.09 Beans, snap 0.36 Beet leaves 0.61 Brussels sprouts 0.36 Carrot 0.50 Cassava 1.26 Chives 1.48 Collards 0.45 Garlic 0.36 Lettuce 0.33 Pepper 0 .04 Potato 0 .05 Purslane 1.31 Radish 0 .48 Sweet potato 0 .24 Tomato 0.05
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19 2.3 Synthetic Pathways Oxalic acid can be obtained b y fusio n of cellulose matter with NaOH, by oxidation with HNO 3 and also by passing carbon monoxide through concentrated NaOH or Na 2 CO 3 1 In 1926 Walter Wallace patented a procedure when oxalic acid is produced by absorption of carbon monoxide in alkali or alkaline solution under heat and pressure to form sodium formate solution, which was evaporated and heated to form sodium oxalate, then t reated with calcium hydroxide and water to precipitate calcium oxalate, which was at the end t reated with sulfuric acid to obtain finally the oxalic acid. 3 Oxidation of glucose or other carbohydrates can also be done using NaOH and HNO 3 or air in presence of vanadium pentoxide. 4 In the literature there are several papers reporting o xalic esters that can be produced by the carbonylation of alcohols using Pd (II) complexes 5 8
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20 CHAPTER 3 DIOLS 3.1 Aliphatic Diols Aliphatic diols have been used widely to syn thesize polyesters, ethyleneglycol being one of the most popular to produce polyethyleneterephth alate (PET). 1,3 propanediol can be polymerized with terephthalic acid or dimethyl terephthalate to produce polytrimethylene terephthalate (PTT) and it has been obtained from hydroformy lation of ethylene oxide to afford 3 hydroxypropionaldehyde and then hydrogenation of the aldehyde to alcohol. Currently DuPont has developed a synthetic way starting with corn syrup and using a genetically modified strain of E.Coli 9 Another way to produce it is by conversion of glycerol using C lostridium diolis bacteria and Enterobacteriaceae 10 1,4 butanediol is also used to produce elastic fibers and polyurethanes. It has been processed indus trially by reacting acetylene with formaldehyde to form 1,4 butynediol, which is finally hydrogenated. Genomatica a company in San Diego CA had genetically modified E. Coli to metabolize sugar in to 1,4 butanediol. 1 1 ,12 1,10 decanediol is a potential gr een diol that can be obtained from castor oil, a mixture of fatty acids that contains mostly ricinoleic acid (up to 90%) present in the castor beans 1 3 ,1 4 3.2 Aromatic Diols Aromatic diols play an important role in the synthesis of polyesters due the presence of sp 2 hybridized aromatic carbons which provide more rigidity to the polymer backbone 1 5
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21 Resorcinol is an aromatic diol (benzene 1,3 diol) which is currently obtained from the petroch emical industry, although it c ould be obtained from distillation of Brazilwood extract as well In 1994 the production of resorcinol was estimated to be 30 000 to 35 000 tons. It is used primarily in the rubber industry for tires reinforced rubber and hig h quality wood adhesives. It is also used in the pharmaceutical industry, in the preparation of dyes, cosmetics and as a cross linking agent for neoprene. 1 6 Figure 3 1. Resorcinol Hydroquinone (benzene 1,4 diol) is another interesting aromatic diol and is an isomer of resorcinol It has been synthesized through the cumene process and hydroxylation of phenol. Frost and coworkers found a benzene free synthetic pathway to obtain this diol by oxidation of glucose which is promising in order to obtain biorenewable aromatic diols. 17 Figure 3 2. Hydroquinone
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22 CHAPTER 4 POLY OXALATES 4.1 Background Polyoxalates have been studied for many years Carothers and coworkers publ ished in 1930 a work involving the synthesis of polyethylene, polypropylene, polyhexylene and polydecylene oxalate In the case of polyethylene oxalate, they mentioned the existence of three forms: a monomer ( T m = 144 C) with a molecular weight between 118 and 126 Da a soluble polymer ( T m = 159 C) with a molecular weight about 2400 Da and an insoluble polymer ( T m = 172 C) with an unknown but probably higher molecular weight Carothers and coworkers also found some fractions with intermediate melting points which they claimed could be a mixture of these forms although the s e fractions were unstable at standard conditions. Polypropylene oxalate was synthesized from 1,3 propanediol and diethyl oxalate showing a melting temperature of 86 C, meanwhile poly hexylene and poly d ecylene oxalate had melting temperatures of 66 and 79 C respectively. 18 Recently other research groups have been studying some properties and possible applications of polyoxalates, including copolymemerization with other components like azelaic acid 19 ur ethanes 20 and terephthalates 21 4.2 Applications Because of their degradability, one of the most important applications of polyox alates has been in the medicine In 1977 Coquard et al. obtained a patent for implantable surgical articles based on polyesters of succinic and oxalic acid and relatively short diols between 2 and 6 carbon atoms 22 In 1978 and 1980 Shalaby et al. obtained two patent s for absorbable coating for sutures u sing polyalkylene oxalates
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23 specifically mixtures of butylene, hexylene, octylene and dodecylene oxalate 2 3 ,2 4 Starting in the 19 80 s some studies of novel drug delivery systems for medical purposes have been focusing on polyoxalates for this purpose as we ll 2 5 2 7 4.3 Degradability Being degradab le is one of the most remark able properties of polyoxalates. C uriously there are no t many accessible publications about this important characteristic. Probably some of the most interesting results about their degra dability w ere obtained by Park and coworkers who conducted research in polyoxalates as potential drug delivery systems as it was mentioned above. They placed the polyoxalates in form of fine powders in phosphate buffer solution (pH 7.4, 100 mM) at 37 C. After mixing the solution gently, hydrolyzed polymers were collected at specific times, and their molecular weight s were measured as using GPC. They found that the molecular weight went from 100% to about 25% in 50 hours as shown in Figure 4 1. 27 Figure 4 1. Degradation study of polyoxalate in aqueous solution 4.4 Polya lkylene Oxalates A methodology was developed to obtain polyoxalates in a greener way, as part of the goals of this research. Oxalyl chloride has been widely used to synthesize
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24 polyoxalates showing interesting results 26,27 but this would yield HCl as byproduct in this synthesis which is not very ecofriendly; desirable. Using o xalic acid is also a possibility yielding water as byproduct w hich is envi ronmentally favored. However, using esters of oxalic acid such as dimethyl and diethyl oxalate offer a considerable advantage over oxalic acid which is the lower boiling point of the eventual byproducts in the polymerization: methanol and ethanol respecti vely. This lower boiling point can be used in order to eliminate this byproduct easier by heat and/or vacuum ; therefore the polymerization will be favored. Figure 4 2 General reaction of polyoxalates synthesis. Another issue considered in order to have a greener pathway to obtain polym ers was the absence of solvents; t his could be not only friendly to the environment and avoid potential hazardous chemicals but also could be interesting in an economic point of view due fewer expenses in the process. 4.4 .1 Synthesis and Characterization In a fi rst stage of the research, poly oxalates were synthesized increasing one by one the number of methylene spacers between the oxalate units. To do that different terminal aliphatic diols starting from 1,3 prop anediol u ntil 1,12 dodecanediol were employed Polyprop ylene oxalate and polybutylene oxalate were not soluble in THF therefore the molecular weight could not be obtained by GPC as the other polymers.
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25 Figure 4 3. General mechanis m for Fisher esterification 28 Table 4 1. Poly alkylene oxalates, molecular and thermal properties Entry Polymer M w (kDa) PDI Yield (%) T g ( C) T m ( C) H m (J g 1 ) H C (J g 1 ) 4.1 N.A. N.A. 44.8 2 78 a 53 a -4.2 19.3 1.73 62.9 7 103 a 57 a -4.3 N.A. N.A. 72.2 -98 64 64 4.4 41.4 1.90 79.1 34 56 a 56 a -4.5 40.7 1.68 77.7 -76 65 62 4.6 29.5 1.80 61.9 48 35 a 19 a -4.7 62.4 1.69 85.1 -76 55 64 4.8 71.3 1.76 76.7 47 40 a 5 2 a 51 4.9 67.6 1.85 83.2 -79 57 65 4.10 33.3 2.14 73.4 29 55 71 71 4.11 69.3 1.76 84.7 -80 76 73 a Data obtained from the first heating cycle.
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26 In general it can be seen the heat s of melt for polyalkylene oxalates were very similar as well as the PDIs. 4.4.2 Effect s of M ethylene S pacers Table 4 1 show s the different yields for each polymerization. Starting from some poor quantities like 45% for polypropylene oxalate to better ones higher than 80% for polyoctylene, polydecylene and polydodecylene oxalate, which also showed larger molecular weights. Differential scanning calorimetry (DSC) showed for polyoxal ates with an odd number of methylene groups a first cycle with an evident T m peak for that polymer, but during the cooling stage the polymer was n o t able to crystalize, leading to a second cycle that showed only a T g for those polymers and an absence of T m suggesting an amorphous character of those polymers O n the other hand, first and second heating cooling DSC cycles for polyoxalates with even number of methylene spacers were very similar showing a typical T m The T g of the poly alkylene oxalates in general was relatively low. Among the polyoxalates with an odd number of methylene groups, polypropylene oxalate ha s the highest T g and T m probably due to the space between the oxalic units which match better with the oxalic units in the other chains decreasing the free volume in the polymers and thus exhibit better packing A s imilar case occurs with polybutylene oxalate, for which the length of the aliphatic region match e s with the length of the oxalic units favoring a good packing between polymer ch ains as shown in F igure 4. 4
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27 Figure 4 4 Representation of two chains of polybutylene oxalate In the particular case of the polynonylene oxalate (nine methylene groups between oxalic units) the behavior was more like the polymers with even number suggesting that after a certain length between the oxalic units the effect o f the odd even spacers is less relevant. In F igure 4 5 it can be obs erved the interesting odd/even tendency of the melting temperatures along the methylene spacers in the polymer. Figure 4 5 Melting and glass transition temperatures of polyalkylene oxalates along different number of methylene groups in the backbone
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28 Alth ough the polyneopentylene oxalate was not included in the graphic because of its side groups, it is interesting to compare th e effect of those with the poly propylene oxalate. Both have the same length between each oxalic unit along the polymer backbone, bu t polyneopentylene oxalate has a higher T g and T m This behavior suggest s that the extra methyl groups of the polyneopentylene oxalate occupy the free volume t hat might be be tween the polypropylene oxalate, reducing the free volume between polymer chains. Figure 4 6 Representation of two pair s of chains of polypropylene oxalate and polyneopentylene oxalate 4.4.3 Conclusions Polyalkylene oxalates were successfully synthesized using a different methodology in melt and removal of methanol by vacuum under high temperatures, leading to a greener process. Analyzing the different polymers obtained varying the number of methylene spacers it was found that polyoxalates with an odd number of methylene groups between the oxalic units tended to be h ighly amorphous ; meanwhile
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29 polyoxalates with an even number of methylene groups were semicrystalline. Yields for polymerization in general tend to increase with bigger diols as well as the molecular weights, but PDIs were similar. Heat of melt for polymer s w as very similar for most of the polymers. 4.5 Polyarylene and Copoly( A lky lene A rylene ) Oxalates In order to provide more rigidity to the polymer backbone and obtain higher melting and glass transition temperatures, aromatic diols were incorporated to the polymer in different ratios in relation to an alkylene diol. The 1,10 decanediol was chosen not only because it provided interesting properties to the polyoxalates such as good solubility, good yield, relatively high crystallinity mel ting point, but also because it is potential ly biorenewable 17 Resorcinol bis(beta hydroxyethyl)ether is a diol derivative from resorcinol, an aromatic diol which was extended not only to provide some flexibility to the polymer chain but also to make c ap able o f polymeriz ation with dimethyl oxalate Figure 4 7 Resorcinol bis( beta hydroxyethyl)ether ( 4.12 ) Indeed, polymerization with resorcinol itself was attempted without success under our conditions as it could be expected considering the low reactivity of phenols in a typical acid catalyzed Fisher esterification 28 T hus the functionalization of the phenol ic groups to primary alcohols would make the incorporation of this compound feasible.
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30 4. 5 1 Synthesis and Characterization Feed of aliphatic and aromatic diols changed in amounts of 10 mol%. T he actual incorporation was confirmed by 1 H NMR. B oth diols were effectively incorporated in the backbone of the polymer in ratios close to the feed Table 4 2 Copoly ( alkylene arylene ) oxalates, macro molecular and thermal properties Entry Feed percentage Inc. of 1 H NMR (%) M w (kDa) PDI Yield (%) T g ( C) T m ( C) H m (J / g) Aliphatic (%) Aromatic (%) 4.9 100 0 0 67.6 1.85 83.2 -79 57 4.13 90 10 11 64.9 1.80 76.2 24 70 52 4.14 80 20 22 71.3 1.79 80.0 20 66 46 4.15 70 30 26 59.8 1.84 83.4 15 64 51 4.16 60 40 38 62.3 1.95 70.5 18 58 7 4.17 50 50 48 63.7 2.12 75.8 5 95 25 4.18 40 60 57 57.5 2.07 61.1 4 103 41 4.19 30 70 68 43.7 1.95 72.6 14 122 20 4.20 a 20 80 77 N.A. N.A. 73.2 25 133 35 4.21 a 10 90 84 N.A. N.A. 46.4 29 138 41 4.22 a 0 100 100 N.A. N.A. 56.4 34 156 50 a Polymers not soluble in THF To determine incorporation of the diols, polymers 4.9 and 4.22 were compared and peaks were identified respectively. It was found that the quintuplet at 1.73 ppm which corresponds to four of the protons in the aliphatic region did not overlap with any other peak from the aromatic diol Furthermore, the multiplet at 6.51 ppm corresponding to three of the aromatic protons did n o t overlap with any signal of the aliphatic diol. Conside ring this and comparing areas of these peaks led us to confirm that both aliphatic and aromatic diols were fully incorporated in to the polymer. Figure 4 8 shows a typical comparison of the different spectra in order to calculate the incorporation.
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31 Figure 4 8 1 H NMR spectra of polymers 4.9, 4.16 and 4.22 for incorporation calculation 4.5.2 Effect of the Incorporation of Aromatic Units in to the Polymer The increase of the aromatic diol feed in the polymer at the beginning showed a dec rease in the T m of the co polymer from 79 C ( T m of the polydecylene oxalate) to a minimum of 58 C at a ratio of 40:60, after this point the tendency was rever s ed and the T m was increased t o 156 C as shown in the F igure 4 9 Figure 4 9 Melting temperature of co poly( alkylene arylene) oxalates
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32 O n the other hand, T g showed a line ar increasing behavior along the incorporation of the aromatic diol in the copolymer T his behavior was expected according to the Fox equation which predicts the T g of a copolymer or a polymer blend based on the individual T g of each homopolymer 29 Figure 4 1 1 shows this behavior. Figure 4 10 Fox equation for random copolymers where w is weight fraction Figure 4 1 1 Glass transition temperature of co poly mers 4.5.3 Degradation The samples obtained were stor ed in vials inside a cabinet away from light under a regular atmosphere and about a year later the molecular weight s were obtained via GPC in the same conditions they we re obtained before as shown in T able 4 3. It seems that the presence of moisture in the headspace of the vial was enough to hydrolyze the polymer chains allowing this decrease in molecular weight.
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33 Table 4 3 Degradation of c opoly( alkylene arylene ) oxalates Entry Sept 2011 Feed percentage m (%) Feed percentage n (%) M w ( kDa) PDI M w ( kDa) 4.9 100 0 67.6 1.85 4.13 90 10 64.9 1.80 4.14 80 20 71.3 1.79 4.15 70 30 59.8 1.84 4.16 60 40 62.3 1.95 4.17 50 50 63.7 2.12 4.18 40 60 57.5 2.07 4.19 30 70 43.7 1.95 4.5.4 New Ideas 4.5.4.1 Copolymers with 1,4 butanediol 1,4 butanediol is a potential ly biorenewable dio l 11,12 and copolymerizations with this compound could yield a new series of co poly(alkylene arylene) oxalates with presumably higher polymer melting temperatures. Figure 4 1 2 Copolymer using 1,4 butanediol as comonomer. 4.5.4.2 Polyoxalates b ased on h ydroquinone Another potential biorenewable diol is hydroquinone 17 an isomer of resorcinol. Using similar methodology it can be reacted as resorcinol to obtain an extended diol more reactive with oxalates. Because of the linearity of this diol, more crystalline polymers would be expec ted from this monomer, as well as copolymers with aliphatic diols.
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34 Figure 4 1 3 Poly resorcinol bis(beta hydroxyethyl)ether oxalate 4.5.4.3 Vanillin b ased d iols for p olyarylene o xalates Vanillin is an aromatic compound present in lignin together with cellulose a component of plants and very abundant in nature ; it is the second main constituent of wood and one of the top polymer s in abundance on earth along with cellulose 30,31 Because o f the presence of a phenolic group, an extension of this alcohol would be desirable in order to have a successful polymerization, as well as the reduction of the aldehyde group to obtain the diol. Unfortu nately this would lead to a n un symmetric al diol ; the refore the polymer could be very amorphous due to random regiochemistry, but the presence of aromatic sp 2 carbons in the backbone c ould provide high T g Figure 4 1 4 Vanillin based unsymmetrical diol Another approach can be used in order to obtain vanillin based symmetrical diols, which is the coupling of two molecules of vanilli finally re ducing the aldehyde groups. Varying the number of methylene groups between the co upled aromatic rings the properties of the eventual polyoxalates could be tuned.
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35 Figure 4 1 5 Vanillin based symmetrical diols 4.5. 5 Conclusions Copolymerizations of aliphatic and aromatic diols with dimethyl oxalate were successfully achieved Incorporation of the aromatic diol was proved using 1 H NMR with incorporation results very close to the feed ratios. It was prove n that the addition of aromatic fuctionality provided higher T g with their incorporation in the polymer backbone exhibiting a linear increase according to the Fox equation ; meanwhile T m decreased to a minimum at 40:60 incorporation, to finally reach a maximum when the polymer had a 100% of the aromatic based monomer
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36 CHAPTER 5 EXPERIMENTAL PROCEDU RE S 5.1 Molecular Characterization Proton and carbon nuclear magnetic resonance ( 1 H and 13 C NMR) spectra were recorded using a Varian Inova 500 MHz spectrometer and /or Mercury 300 MHz Chemical shifts are reported in parts per million (ppm) downfield relative to tetramethylsilane (TMS, 0.0 ppm) or residual proton in the specified solvent. Coupling constants ( J ) are reported in Hertz (Hz). Multiplicities are reported using the following abbreviations: s, singlet; d, doublet; t, triplet; q, quartet; quin, quintupl et; m, multiplet; br, broad. Differential scanning calorimetry thermograms were obtained with a DSC Q1000 from TA instruments. About 3 mg of each sample were massed and added to a sealed pan that passed through a heat/cool/heat cycle at 10 C/min. The te mperature ranged from 100 to 200 C. Thermogravimetric analyses were measured under nitrogen with a TGA Q5000 from TA Instruments. About 5 10 mg of each sample were heated at 10 C/min from room temperature to 600 C. Gel permeation chromatography (GPC) was performed at 40 C using a Waters Associates GPCV2000 liquid chromatography system with an internal differential refractive index detector and two Waters Styragel HR i.d., 300 mm length) using HPLC grade tetrahydrofuran (T HF) as the mobile phase at a flow rate of 1.0 mL/min. Calibration was performed with narrow polydispersity polystyrene standards.
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37 5.2 Polymerization Procedures The polymerizations were typically conducted in a round bottom flask, connected to a rotary eva poration bump trap t h a t was connected to a vacuum line. With this apparatus molecules of condensation could be collected and visualized in the bump trap, followed by removal of all volatiles without changing the initial glassware configuration. In the first step, dimethyl oxalate was added to the flask with one mole equivalent of the corresponding diol(s) and about 2 mol% of para toluenesulfonic acid ( p TSA) and stirred under nitrogen atmosphere for one hour. Later the temperature was raised to 130 C and stirred for two more hours. The n ext step consisted of pulling vacuum for an hour and finally increas ing the temperature of the system to 220 C for three hours. Figure 5 1 Polymerization device : A hot plate with temperature control, oil bath, flask containing the reagents and connection to a vacuum line through a b ump trap.
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38 For the polymer workup the product was allowed to cool at room temperature and dissolved in about 30 40 mL of methylene chloride for e ntries 4.1 to 4.1 1 and 4.13 to 4.1 9 or dimethyl sulfoxide (D MSO) for e ntries 4. 20 to 4.2 2 The polymer was precipitated by the addition of the solution in about 100 mL of cold methanol. The system was filtered and the polymer was dried under vacuum Figure 5 2. Polyprolylen e oxalate ( 4.1 ) 1 H NMR (299MHz CHLOROFORM d) = 4.42 (t, J = 6.1 Hz, 4 H), 2.20 (quin, J = 6.1 Hz, 2 H) 13 C NMR (126MHz CHLOROFORM d) = 157.4, 63.5, 27.3 Figure 5 3. Polyneopentyl ene oxalate ( 4.2 ) 1 H NMR (500MHz, CHLOROFORM d) = 4.12 (s, 4 H), 1.07 (s, 6 H) 13 C NMR (126MHz, CHLOROFORM d) = 157.1, 70.9, 35.0, 21.5 Figure 5 4. Polybutylene oxalate ( 4.3 ) 1 H NMR (500MHz, CHLOROFORM d) = 4.38 4.31 (m, 4 H), 1.92 1.84 (m, 4 H) 13 C NMR (126MHz CHLOROFORM d) = 157.6, 66.3, 24.8
PAGE 39
39 Figure 5 5. Polypentylene oxalate ( 4.4 ) 1 H NMR (500MHz CHLOROFORM d) = 4.30 (t, J = 6.6 Hz, 4 H), 1.80 (quin, J = 7.2 Hz, 4 H), 1.51 (quin, J = 7.5 Hz, 2 H) 13 C NMR (126MHz CHLOROFORM d) = 157.8, 66.7, 27.8, 22.1 Figure 5 6. Polyhexylene oxalate ( 4.5 ) 1 H NMR (500MHz CHLOROFORM d) = 4.29 (t, J = 6.6 Hz, 4 H), 1.76 (quin, J = 7.0 Hz, 4 H), 1.49 1.40 (m, 4 H) 13 C NMR (126MHz, CHLOROFORM d) = 157.9, 110.0, 66.8, 28.1, 25.3 Figure 5 7. Polyheptylene oxalate ( 4.6 ) 1 H NMR (300MHz, CHLOROFORM d) = 4.28 (t, J = 6.9 Hz, 4 H), 1.83 1.66 (m, 4 H), 1.49 1.32 (m, 6 H) 13 C NMR (75MHz, CHLOROFORM d) = 157.9, 67.0, 28.6, 28.1, 25.5 Figure 5 8. Polyoctylene oxalate ( 4.7 )
PAGE 40
40 1 H NMR (500MHz, CHLOROFORM d) = 4.28 (t, J = 6.6 Hz, 4 H), 1.74 (quin, J = 7.1 Hz, 4 H), 1.44 1.30 (m, 8 H) 13 C NMR (126MHz, CHLOROFORM d) = 158.0, 67.0, 28.9, 28.2, 25.6 Figure 5 9. Polynonylene oxalate ( 4.8 ) 1 H NMR (500MHz CHLOROFORM d) = 4.28 (t, J = 6.8 Hz, 4 H), 1.73 (quin, J = 6.8 Hz, 4 H), 1.44 1.27 (m, 10 H) 13 C NMR (126MHz, CHLOROFORM d) = 158.0, 67.1, 29.2, 29.0, 28.2, 25.6 Figure 5 10. Polydecylene oxalate ( 4.9 ) 1 H NMR (299MHz, CHLOROFORM d) = 4.28 (t, J = 6.8 Hz, 4 H), 1.73 (qui n, J = 6.9 Hz, 4 H), 1.47 1.19 (m, 12 H) 13 C NMR (126MHz CHLOROFORM d) = 158.1, 67.1, 29.3, 29.1, 28.3, 25.7 Figure 5 11. Polyundecylene oxalate ( 4.10 ) 1 H NMR (500MHz CHLOROFORM d) = 4.28 (t, J = 6.8 Hz, 4 H), 1.73 (quin, J = 7.0 Hz, 4 H), 1.43 1.23 (m, 14 H) 13 C NMR (126MHz CHLOROFORM d) = 158.0, 67.1, 29.4, 29.1, 28.2, 25.7
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41 Figure 5 1 2. Polydodecylene oxalate ( 4.11 ) 1 H NMR (500MHz CHLOROFORM d) = 4.30 (t, J = 7.1 Hz, 4 H), 1.76 (quin, J = 7.0 Hz, 4 H), 1.44 1.25 (m, 16 H) 13 C NMR (126MHz, CHLOROFORM d) = 158.0, 67.2, 29.5, 29.4, 29.1, 28.3, 25.7 Figure 5 1 3 Cop olymer ( 4.1 7 ) 1 H NMR (300MHz, CHLOROFORM d) = 7.22 7.10 (m, 1 H), 6.60 6.43 (m, 3 H), 4.61 (br. s., 4 H), 4.33 4.17 (m, 8 H), 1.81 1.65 (m, 4 H), 1.29 (br. s., 12 H) 13 C NMR (126MHz CHLOROFORM d) = 159.4, 158.0, 157.8, 157.5, 157.3, 130.1, 107.5, 101.9, 67.3, 67.1, 65.2, 64.9, 29.3, 29. 1, 28.2, 25.6 Figure 5 14. Poly resorcinol bis(beta hydroxyethyl)ether oxalate ( 4.22 ) 1 H NMR (299MHz, DMSO d 6 ) = 7.31 7.03 (m, 1 H), 6.68 6.40 (m, 3 H), 4.53 (d, J = 2.8 Hz, 4 H), 4.33 4.12 (m, 4 H) 13 C NMR (126MHz, DMSO d 6 ) = 159.7, 157.5, 130.6, 130.5, 110.0, 107.8, 107.2, 101.7, 70.0, 65.8, 65.5, 60.0
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42 5.3 Synthesis of Aromatic Diol Figure 5 1 5 S ynthesis of Resorcinol b is(beta hydroxyethyl)ether ( 4.12 ) Resorcinol and ethylene carbonate were added with a catalytic amount of triphenylphosphine (PPh 3 ) melted at 150 C and stirred under nitrogen atmosphere overnight T hen 200 mL of methanol were added to the reaction in ice bath, filtered and washed with co ld methanol to finally dry under vacuum. The compound was confirmed by NMR. 1 H NMR (500MHz, DMSO d 6 ) = 7.16 (t, J = 8.3 Hz, 1 H), 6.52 6.47 (m, 3 H), 4.84 (t, J = 5.4 Hz, 2 H), 3.95 (t, J = 5.2 Hz, 4 H), 3.70 (q, J = 5.2 Hz, 4 H) 13 C NMR (126MHz, DMSO d 6 ) = 159.9, 129.9, 106.7, 101.2, 69.5, 59.6
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43 APPENDIX A PROTON AND CARBON NM R Figure A 1. 1 H NMR of polymer 4.1 Figure A 2. 1 3 C NMR of polymer 4.1
PAGE 44
44 Figure A 3. 1 H NMR of polymer 4.2 Figure A 4. 1 3 C NMR of polymer 4.2
PAGE 45
45 Figure A 5. 1 H NMR of polymer 4.3 Figure A 6. 1 3 C NMR of polymer 4.3
PAGE 46
4 6 Figure A 7. 1 H NMR of polymer 4.4 Figure A 8. 1 3 C NMR of polymer 4.4
PAGE 47
47 Figure A 9. 1 H NMR of polymer 4.5 Figure A 10. 1 3 C NMR of polymer 4.5
PAGE 48
48 Figure A 11. 1 H NMR of polymer 4.6 Figure A 12. 1 3 C NMR of polymer 4.6
PAGE 49
49 Figure A 13. 1 H NMR of polymer 4.7 Figure A 14. 1 3 C NMR of polymer 4.7
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50 Figure A 15. 1 H NMR of polymer 4.8 Figure A 16. 1 3 C NMR of polymer 4.8
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51 Figure A 17. 1 H NMR of polymer 4.9 Figure A 18. 1 3 C NMR of polymer 4.9
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52 Figure A 19. 1 H NMR of polymer 4.10 Figure A 20. 1 3 C NMR of polymer 4.10
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53 Figure A 21. 1 H NMR of polymer 4.1 1 Figure A 22. 1 3 C NMR of polymer 4.1 1
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54 Figure A 23. 1 H NMR of compound 4.1 2 Figure A 24 1 3 C NMR of compound 4.1 2
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55 Figure A 25. 1 H NMR of polymer 4.1 3 Figure A 26. 1 3 C NMR of polymer 4.1 3
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56 Figure A 27. 1 H NMR of polymer 4.1 4 Figure A 28. 1 3 C NMR of polymer 4.1 4
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57 Figure A 29. 1 H NMR of polymer 4.1 5 Figure A 30. 1 3 C NMR of polymer 4.1 5
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58 Figure A 31. 1 H NMR of polymer 4.1 6 Figure A 32. 1 3 C NMR of polymer 4.1 6
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59 Figure A 33. 1 H NMR of polymer 4.1 7 Figure A 34. 1 3 C NMR of polymer 4.1 7
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60 Figure A 35. 1 H NMR of polymer 4.1 8 Figure A 36. 1 3 C NMR of polymer 4.1 8
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61 Figure A 37. 1 H NMR of polymer 4.1 9 Figure A 38. 1 3 C NMR of polymer 4.1 9
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62 Figure A 39. 1 H NMR of polymer 4. 20 Figure A 40. 1 3 C NMR of polymer 4. 20
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63 Figure A 41. 1 H NMR of polymer 4. 21 Figure A 42. 1 3 C NMR of polymer 4. 2 1
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64 Figure A 43. 1 H NMR of polymer 4. 22 Figure A 44. 1 3 C NMR of polymer 4. 22
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65 APPENDIX B POLYMER DATA Figure B 1 TGA of poly propylene oxalate 4.1 Figure B 2 DSC of poly propylene oxalate 4.1
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66 Figure B 3 TGA of poly neopentylene oxalate 4. 2 Figure B 4 DSC of poly neopentylene oxalate 4. 2
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67 Figure B 5 TGA of poly butylene oxalate 4. 3 Figure B 6 DSC of poly butylene oxalate 4. 3
PAGE 68
68 Figure B 7 TGA of poly pentylene oxalate 4. 4 Figure B 8 DSC of poly pentylene oxalate 4. 4
PAGE 69
69 Figure B 9 TGA of poly hexylene oxalate 4. 5 Figure B 10 DSC of poly hexylene oxalate 4. 5
PAGE 70
70 Figure B 11 TGA of poly heptylene oxalate 4. 6 Figure B 12 DSC of poly heptylene oxalate 4. 6
PAGE 71
71 Figure B 13 TGA of poly octylene oxalate 4. 7 Figure B 14 DSC of polyoctylene oxalate 4. 7
PAGE 72
72 Figure B 15 TGA of poly nonylene oxalate 4. 8 Figure B 16 DSC of poly nonylene oxalate 4. 8
PAGE 73
73 Figure B 17 TGA of poly decylene oxalate 4. 9 Figure B 18 DSC of poly decylene oxalate 4. 9
PAGE 74
74 Figure B 19 TGA of poly undecylene oxalate 4. 10 Figure B 20. DSC of polyundecylene oxalate 4. 10
PAGE 75
75 Figure B 21 TGA of poly dodecylene oxalate 4. 11 Figure B 22 DSC of poly dodecylene oxalate 4. 11
PAGE 76
76 Figure B 23 TGA of co polymer 4. 13 Figure B 24 DSC of co polymer 4. 13
PAGE 77
77 Figure B 25 TGA of co polymer 4. 14 Figure B 26 DSC of co polymer 4. 14
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78 Figure B 27 TGA of co polymer 4. 15 Figure B 28 DSC of co polymer 4. 15
PAGE 79
79 Figure B 29 TGA of co polymer 4. 16 Figure B 30 DSC of co polymer 4. 16
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80 Figure B 31 TGA of co polymer 4. 17 Figure B 32 DSC of co polymer 4. 17
PAGE 81
81 Figure B 33 TGA of co polymer 4. 18 Figure B 34 DSC of co polymer 4. 18
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82 Figure B 35 TGA of co polymer 4. 19 Figure B 36 DSC of co polymer 4. 19
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83 Figure B 37 TGA of co polymer 4. 20 Figure B 38 DSC of co polymer 4. 20
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84 Figure B 39 TGA of co polymer 4. 21 Figure B 40 DSC of co polymer 4. 21
PAGE 85
85 Figure B 41 TGA of co polymer 4. 22 Figure B 42 DSC of co polymer 4. 22
PAGE 86
86 Figure B 4 3 GPC of poly neopentylene oxalate 4. 2 Figure B 4 4 GPC of poly pentylene oxalate 4. 4
PAGE 87
87 Figure B 4 5 GPC of poly hexylene oxalate 4. 5 Figure B 4 6 GPC of poly heptylene oxalate 4. 6
PAGE 88
88 Figure B 4 7 GPC of poly octylene oxalate 4. 7 Figure B 48 GPC of poly nonylene oxalate 4. 8
PAGE 89
89 Figure B 49 GPC of poly decylene oxalate 4. 9 Figure B 5 0 GPC of poly undecylene oxalate 4. 10
PAGE 90
90 Figure B 5 1 GPC of poly dodecylene oxalate 4.1 1 Figure B 5 2 GPC of co polymer 4.1 3
PAGE 91
91 Figure B 5 3 GPC of co polymer 4.1 4 Figure B 5 4 GPC of co polymer 4.1 5
PAGE 92
92 Figure B 5 5 GPC of co polymer 4.1 6 Figure B 5 6 GPC of co polymer 4.1 7
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93 Figure B 5 7 GPC of co polymer 4.1 8 Figure B 58 GPC of co polymer 4.1 9
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94 LIST OF REFERENCES (1) Windhol z, M. ; Budavari, S. ; Blumetti, R. F. ; Otterbein, E. S. ; Ed s In The Merk Index an encyclopedia of chemicals, drugs and biological Tenth edition; Merck & Co., Inc.: Rahway, N.J., 1983, p 991 (2) United States Department of Agriculture. National Agricultural Library. http://www.nal.usda.gov/fnic/foodcomp/Data/Other/oxalic.html (accessed November 4, 2012) (3) Wallace, W. Manufacture of Oxalates and Oxalic Acid. U.S. Pat ent 1 602 802 Oct 12, 1926. (4) Ei ichi, Y.; Tomiya, I.; Tsuyoshi, S.; Yukio, Y. Process for the production of oxalic acid. U.S. Patent 3,678,107 July 18, 1972. (5) Rivetti, F.; Romano, U. J. Organomet Chem 1979 174 221 226 (6) Amadio, E. Oxidative Carbonylation of Alkanols Catalyzed by Pd(II) Phosphine (7) Morris, J. E.; Oakley, D.; Pippard, D. A.; Smith, D. J. H. J. Chem. Soc. Chem. Commun 1987 410 411. (8) Gaffney, A M. ; Sofranko, J. A. Preparation of Dialkyl Oxalates By The Oxidative Carbonylation of Alcohols with a Heterogeneous Pd V P Ti Containing Catalyst System. U.S. Pat ent 4 447 638 May 8, 1984. (9) http://www.chem.uu.nl/brew/BREWsymposiumWiesbaden11mei2005/WEBSITEBr ewPresentations51105.PDF (accessed November 4, 2012) (10) Biebl H. ; K. Menzel K.; Ze ng, A.; Deckwer W Appl. Microbiol. Biotechnol. 1999 52 ( 3 ) 289 297. (11) Genomatica. Sustainable Chemicals. http://www.genomatica.com/products/bdo/ (accessed November 4 2012) (12) Burk, M. J. Int. Sugar J. 2 010 112 30 35. (13) Mutly, H.; Meier, M. Eur. J. Lipid Sci. Technol. 2010 112 10 30 (14) Chemistry 2006 (15) Stevens, M. P.; Chemical Structure and Polymer Morphology. Polymer Chemistry Third Edition; Oxford University Press: New York, 1999; p 71. (16) IARC Monographs. http://monographs.iarc.fr/ENG/Monographs/vol71/mono71 52.pdf (accessed Nov 4 2012)
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95 (17) Ran, N .; Knop, D. R.; Draths, K. M.; Frost, J. W J. Am. Chem. Soc 2001 123 10927 10934. (18) Carothers W. ; Arvin, J. ; Dorough, G. J. Am. Chem. Soc 1930 52 3292 3300. (19) Finelli, L., Lotti, N.; Murani, A. Eur. Polym. J 2002 38 1987 1993. (20) Tanak a, H.; Adachi F.; Kunimura, M.; Kurachi, K. Polym. Eng. Sci 2005 45 163 173. (21) Shin, J.; Yeh, K. J. Appl. Polym. Sci 1999 74 921 936. (22) Coquard, J.; Sedivy, P.; Ruaud, M.; Verrier, J. Bioresorbable Surgical Articles. U.S. Patent 4,032,933, July 5, 1977. (23) Shalaby, S. ; Jamiolkowski, D. Poly(Alkylene Oxalate) Absorbable Coating for Sutures. U.S. Patent 4,105,034, August 8, 1978. (24) Shalaby, S.; Jamiolkowski, D. Synthetic Absorbable Surgical Devices of Poly(Alkylene Oxalates). U.S. Patent 4,205,399, June 3, 1980. (25) Holland, S ; Tighe, B.; Gould, P. J. Controlled Release 1986 4 155 180. (26) Kim, S.; Seong, K.; Kim, O.; Kim, S.; Seo, H. ; Lee, M. ; Khang, G. ; Lee, D. Biomacromolecules 2010 11 555 560. (27) Park, H.; Kim, S. ; Kim, S. ; Song, Y. ; Seung, K. ; Hong, D. ; Khang, G.; Lee, D. Biomacromolecules, 2010 11 2103 2108. (28) Brown W.; Foote, C. ; Iverson, B.; Anslyn, E. Organic Chemistry Fifth Edition; Brooks/Cole Cengage Learning: Belmont, CA, 2009; p 635. (29) Painter P.; Coleman, M. Essentials of Polymer Science and Engineering ; DEStech Publications, Inc.: Lancaster, PA., 2009; p. 328. (30) Boerjan, W.; Ralph, J.; Baucher, M. Annu. Rev. Plant Biol. 2003 54 519. (31) Davin, B .; Lewis, N. Current Opinion in Biotechnology 2005 16 407.
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96 BIOGRAPHICAL SKETCH John Jairo Garcia O campo was born in 1982 in Cali, Colombia. After he attended high school he made his studies in chemistry at Universidad del Valle in Cali where he obtained his bachelor degree in chemistry in December 2006 During his last s years of bachelor he developed his thesis at t he sugarcane research center (CENICANA) in Florida, Valle del Cauca, Colombia developing research with cellulosic material, and after the culmination of this work he started working at the laboratory of q uality c ontrol in Bayer Cali. After his graduation he moved to Lloreda S.A. in Yumbo, Valle del Cauca, when he worked also in the laboratory of quality control for a couple of years before moving finally to Gainesville in the U.S. to join the Organic Division of the Chemistry Departmen t at the University of Florida in August 2009, focusing his research in the synthesis of potential biorenewable and biodegradable polymers under the dir ection of Dr. Stephen A. Miller obtaining his Master of Science degree in December 2012.
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