New supramolecular elastomers were synthesized using vegetable oil materials namely palm acid oil (PAO) and sunflower oil (SFO). The oils were first epoxidized by using formic acid and hydrogen peroxide. The epoxidized oils and adipic acid (AA) were then reacted to make polyacids, mainly triacid. Molar ratio of 1:10 for epoxidized oils and AA led to the formation of higher reactive groups of synthesized polyacid without gelation. Finally, diethylenetriamine (DETA) was added to polyacid to yield oligomers and a polycondensation with urea performed to achieve the desired elastomers. The synthesized materials were characterized by using Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) in order to determine structure and type of bonding. The spectra reveals that the synthesized oligomers are contained amide groups that correctly formed from reaction of amine groups of DETA and acid functionality of polyacids. Moreover, the resulted structures show the formation of multiple hydrogen-bonding in the elastomers

Zeimaran, Ehsan

Universiti Teknologi Malaysia Institutional Repository

SYNTHESIS OF NEW SUPRAMOLECULAR ELASTOMERS FROM SUNFLOWER OIL AND PALM ACID OIL EHSAN ZEIMARAN A thesis submitted in fulfillment of the requirements for the award of the degree of Master of Science (Polymer Technology)  Faculty of Chemical Engineering Universiti Teknologi Malaysia JULY 2011 iiiFor my family, who offered me unconditional love and support throughout the course of this thesis ivACKNOWLEDGEMENT I am heartily thankful to my supervisor, Assoc. Prof. Dr. Hussin Mohd Nor, whose encouragement, guidance and support from the initial to the final level enabled me to develop an understanding of the subject. I am deeply indebted to the technicians and laboratory assistants from Polymer Laboratory especially Mr. Mohd Azri Mohd Amin for their assistance and cooperation in conducting equipments and testing.  Not forgotten thanking to my family for support, encouragement and their advice, which is the most needed for this project. Last but not least, thank you to my friends in developing the project and people who have willingly helped me out with their abilities. vABSTRACT New supramolecular elastomers were synthesized using vegetable oil materials namely palm acid oil (PAO) and sunflower oil (SFO). The oils were first epoxidized by using formic acid and hydrogen peroxide. The epoxidized oils and adipic acid (AA) were then reacted to make polyacids, mainly triacid. Molar ratio of 1:10 for epoxidized oils and AA led to the formation of higher reactive groups of synthesized polyacid without gelation. Finally, diethylenetriamine (DETA) was added to polyacid to yield oligomers and a polycondensation with urea performed to achieve the desired elastomers. The synthesized materials were characterized by using Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) in order to determine structure and type of bonding. The spectra reveals that the synthesized oligomers are contained amide groups that correctly formed from reaction of amine groups of DETA and acid functionality of polyacids. Moreover, the resulted structures show the formation of multiple hydrogen-bonding in the elastomers. viABSTRAK Elastomer supramolekul baru, telah disintesiskan menggunakan bahan-bahan minyak sayuran iaitu asid minyak sawit (PAO) dan minyak bunga matahari (SFO). Pertama sekali, minyak tersebut diepoksikan menggunakan asid formik dan hidrogen peroksida. Minyak terepoksida dan asid adipik (AA) itu  kemudiannya telah ditindakbalaskan menjadi poliasid, terutamanya triasid. Nisbah molar 1:10 untuk minyak terepoksida dan AA telah membawa kepada pembentukan kumpulan-kumpulan dengan kereaktifan yang lebih tinggi, pensintesisan poliasid tanpa gelation. Akhir sekali, dietilenatriamina (DETA) telah ditambahkan kepada poliasid untuk manghasilkan oligomer dan polikondensasi dengan urea dilaksanakan untuk mencapai elastomer yang diingini. Bahan yang telah disintesiskan itu telah dicirikan menggunakan Spektoskopi inframerah (FTIR) dan Resonan magnet nuclear (NMR) untuk menentukan struktur dan jenis ikatan. Spektrum yang terhasil telah mendedahkan oligomer yang telah disintesiskan mengandungi kumpulan amida yang sebetulnya terbentuk daripada tindakbalas kumpulan amina DETA dan kumpulan berfungsi asid, poliasid. Tambahan pula, struktur yang terhasil menunjukkan pembentukan pelbagai ikatan hydrogen dalam elastomer.viiTABLE OF CONTENTS CHAPTER                                TITLE PAGETITLE PAGE DECLARATION iiDEDICATION iiiACKNOWLEDGEMENTS iv ABSTRACT v  ABSTRAK vi  TABLE OF CONTENTS vii  LIST OF TABLES xi  LIST OF FIGURES xii  LIST OF ABBREVIATIONS AND SYMBOLS  xvi    1 INTRODUCTION 1 1.1     Background of research 1          1.1.1     Epoxidation 1          1.1.2     Self-healing elastomer 2 1.2     Problem statement 4 1.3     Objectives of research 5 1.4     Scope of research 62 LITERATURE REVIEW 72.1     Self-healing elastomers 72.2     Thermoplastic elastomers and supramolecular        polymers 102.3     Synthesis of epoxidized vegetable oil 132.4     Hydrolysis of epoxidized oil 17viii3 METHODOLOGY 193.1     Materials 193.2     Preparation of epoxidized oil 193.3     Preparation of polyacid 203.4     Preparation of elastomer 213.5     Iodine value determination 213.6     Acid value determination 233.7     Characterization 24          3.7.1     Nuclear Magnetic Resonance 24          3.7.2     Fourier Transform Infrared Spectroscopy 244 RESULTS AND DISCUSSION 254.1     Epoxidation 25          4.1.1     IR analysis 25          4.1.2     NMR analysis 284.2     Acidolysis 32          4.2.1     IR analysis 32          2.2.2     NMR analysis 344.3     Oligomerization 39          4.3.1     IR analysis 39          4.3.2     NMR analysis 414.4     Synthesis of elastomer 44          4.4.1     IR analysis 44          4.4.2     NMR analysis 4.5     Reaction and structure description 45495 CONCLUSIONS AND RECOMMENDATIONS 50 5.1    Conclusion 505.2     Recommendation 51 REFERENCES 52ixLIST OF TABLES TABLE NO. TITLE PAGE2.1 Information about stoicheiometry and condition to synthesize oligomers and rubbers (Monternal et al., 2008)92.2 Molar ratio of reagent for different levels of epoxidation (Gamage et al., 2009)142.3 Characteristic of soy phosphate polyols prepared using different solvent (Guo et al., 2005)184.1 FTIR data of vegetable oils and epoxidized oil 274.2 1H NMR assignment of epoxidized palm acid and epoxidized sunflower oils304.3 13C NMR assignment of epoxidized palm acid and epoxidized sunflower oils304.4 Different molar ratios of epoxidized vegetable oils with related iodine values314.5 FTIR data for polyacids 334.6 1H NMR assignment of polyacids of PAO, SFO 1:5 and SFO 1:10 364.7 13C NMR assignment of polyacids of PAO, SFO 1:5 and SFO 1:10374.8 Acid value of polyacids of EPAO and ESFO 384.9 FTIR data for oligomers 404.10 1H NMR assignment of oligomers and the related structures 424.11 13C NMR assignment of oligomers and the related structures434.12 FTIR data for elastomers 454.13 1H NMR assignment of the supramolecular elastomers 474.14 13C NMR assignment of the supramolecular elastomers 48xLIST OF FIGURES FIGURE NO. TITLE PAGE2.1 Double hydrogen bonding array of two phenylurazole groups (Stadler et al., 1986)72.2 Log-log plot of tear strength versus total microcapsule concentration (Keller et al., 2007)82.3 Self-mending at room temperature when the waiting time is a. less than 5 min b. 6 h c. 18 h (Cordier et al., 2008)102.4 Triple hydrogen bonding array between melamine and three imide groups (Lange and Maijer, 1995)102.5 Quadruple hydrogen bonding dimer of two 2-ureido-4-pyrimidone (UPy) groups ( Sijbesma et al., 1997) 112.6 Structure of bisurea used by Bouteiller et al. (2000) 122.7 Self-association of bisurea units, where R is a phenyl ring in the work of Colombani et al. (2005) and a butylene spacer in the work of Versteegen et al. (2006)122.8 Modification of maleated polyisoprene with 3-amino-1,2,4-triazole (Chino et al., 2001)122.9 Double hydrogen bonding dimer of two imidazolidone groups (Leibler et al., 2005)132.10 Mechanism of epoxidation (Vijayagopalan and Gopalakrishnan, 1971)152.11 Mechanism of synthesizing the polyols in three steps: a) preparation of glycerides from oleic acid and glycerol b) epoxidation of glycerides with formic acid and hydrogen peroxide c) alcoholysis of epoxidized glycerides with polyhydric alcohol (Hoong et al., 2008) 15,16xi4.1 Comparison of FTIR spectra for sunflower oil and palm acid oil 264.2 Comparison of FTIR spectra for epoxidized sunflower oil and palm acid oil 274.3 Comparison of 1H (up) and 13C (down) spectrums of (a) ESFO and (b) EPAO294.4 Proposed structure for epoxidized oleic acid of PAO and SFO314.5 Possible side reactions of during epoxidation (Lee et al., 2009)324.6 FTIR comparison of polyacid attained from PAO and SFO334.7 Comparison of 1H (up) and 13C (down) spectra of polyacid of  (a) SFO 1:10, (b) SFO 1:5 and (c) PAO354.8 Proposed structure of triacid of epoxidized oleic acid from PAO and SFO384.9 FTIR spectrum of oligomers of Empol 1016 and polyacids from PAO and SFO.404.10 1H (up) and 13C (down) NMR spectra of oligomers for (a) SFO 1:10, (b) SFO 1:5 and (c) PAO414.11 Proposed structure of the oligomer from polyacid of PAO and SFO444.12 FTIR spectrA of Elastomers from PAO, SFO 1:5 and SFO 1:10454.13 1H (up) and 13C (bottom) NMR spectra of the supramolecular elastomers derived from (a) SFO 1:10, (b) SFO 1:5 and (c) PAO464.14 Suggested structures of supramolecular elastomer 49xiiLIST OF ABBREVIATIONS AND SYMBOLES AA - Adipic acid AV - Acid value CDCl3 - ChloroformCD3OD - Methanol DETA - DiethylenetriamineEPAO - Epoxidized palm acid oil ESFO - Epoxidized sunflower oil ESO - Epoxidized soybean oil FTIR - Fourier Transform Infrared SpectroscopyGPC - Gel permeation chromatography H2O2 - Hydrogen peroxide HCOOH - Formic acid IV - Iodine valueKBr - Potassium bromide KOH - Sodium hydroxide NMR - Nuclear Magnetic ResonanceOOC - Oxiran oxygen contentPAO - Palm acid oil PDMS - PolydimethylsiloxanePORIM - Palm Oil Research Institute of Malaysia SFO - Sunflower oil TEA - Triethylamine TPE - Thermoplastic elastomersUDETA - 2-aminoethylimidazolidoneUPy - 2-ureido-4-pyrimidoneWijs - Iodine monochloride xiii52REFERENCES Abdulah, B. 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Synthesis of new supramolecular elastomers from sunflower oil and palm acid oil

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Synthesis of new supramolecular elastomers from sunflower oil and palm acid oil

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