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Synthesis and Characterization of Amorphous Cycloaliphatic Copolyesters with Novel Structures and Architectures

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Synthesis and Characterization of Amorphous Cycloaliphatic Copolyesters with Novel Structures and Architectures Yanchun Liu Dissertation submitted to the faculty of the Virginia Polytechnic Institute and State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy In Chemistry S. Richard Turner, Committee Chair Timothy E. Long Paul A. Deck Herve Marand Judy S. Riffle March 22, 2012 Blacksburg, Virginia Keywords: amorphous copolyesters, cycloaliphatic monomers, melt-phase polymerization, glass transition temperature, structure-property relationship Copyright @ 2012 by Yanchun Liu Synthesis and Characterization of Amorphous Cycloaliphatic Copolyesters with Novel Structures and Architectures Yanchun Liu ABSTRACT A series of random and amorphous copolyesters containing different cycloaliphatic rings within the polymer chains were prepared by melt polycondensaton of difunctional monomers (diesters and diols) in the presence of a catalyst. These polyesters were characterized by nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), tensile tests and/or dynamic mechanical analysis (DMA). The copolyester based on dimethyl bicyclo[2.2.2]octane-1,4-dicarboxylate (DMCD-2) was observed to have a higher Tg, about 115 ºC, than the other copolyesters with the same compositions in this study. For copolyesters containing different compositions of dimethyl-1,4-cyclohexane dicarboxylate (DMCD) and DMCD-2, the Tg increased linearly with the increase of DMCD-2 mole content. DMA showed that all of the cycloaliphatic copolyesters had secondary relaxations, resulting from conformational transitions of the cyclohexylene rings. The polyester based on DMCD-3 in the hydrolytic tests underwent the fastest hydrolytic degradation among these samples. A new triptycene diol (TD) was synthesized and incorporated into a series of cycloaliphatic copolyester backbones by melt condensation polymerization. Straight chain aliphatic spacers, including ethylene glycol (EG), 1,4-butanediol (BD) and 1,6- hexanediol (HD), were used as co-diols to explore their effects on polyester properties. An analogous series of non-triptycene copolyesters based on various hydroxyethylated bisphenols were also prepared for comparison. The results revealed that the TD-containing polymers had higher thermal stability and higher Tg’s than the corresponding non-TD analogs. For TD-containing copolyesters, the mechanical properties were found to be dependent on the types and compositions of the co-diols. A 1,4-butanediol-based triptycene copolyester was observed to have a significantly increased Tg and modulus while maintaining high elongation at ambient temperature. Furthermore, it was demonstrated that the triptycene polyester exhibited higher Tg and modulus than those containing bisphenol derivatives. However, all of the 1,4-butanediol based copolyesters were brittle and had comparable moduli at low temperatures (-25 oC or -40 oC). Melt polycondensation was also used to prepare a series of all-aliphatic block and random copolyesters including the following aliphatic monomers: trans-DMCD, DMCD- 2, neopentyl glycol (NPG), diethylene glycol (DEG) and dimethyl succinate (DMS). The polymer compositions were determined by 1H NMR, and the molecular weights were determined using SEC. The polyesters were also characterized by TGA, DSC, DMA and tensile tests. Phase separation was not observed in these block copolyesters. However, the block copolyester containing DMCD-2 and NPG was observed to have a higher Tg than the block copolyester based on trans-DMCD and NPG. In addition, these block copolyesters were found to have better mechanical properties than the corresponding random copolyesters. iii Acknowledgements I am immeasurably grateful to my research advisor, Dr. S. Richard Turner, for his diligent and invaluable guidance throughout my graduate work at Virginia Tech. He has given me many useful ideas and suggestions on my research projects. Furthermore, he has encouraged me to try my own ideas. Again, I genuinely thank him for his patience and confidence when I faced challenges in the past five years. In addition, he has also been spending a great deal of time to read and revise this dissertation for me. I would also like to acknowledge my advisory committee members, Dr. Paul Deck, Dr. Judy Riffle, Dr. Herve Marand and Dr. Timothy Long, for their useful advice and help on my research and life. It also took a lot of time for them to give me valuable suggestions on my dissertation. I also thank the Macromolecules and Interfaces Institute (MII) and the department of chemistry for financial assistance. Special thanks to Dr. Garth Wilkes for discussing some of our research results and providing useful suggestions. I would like to express my gratitude to Dr. Timothy Long, Dr. Judy Riffle and Dr. James E. McGrath for allowing me to use many of their instruments. Most of research data reported in this dissertation were measured by their instruments. I am also grateful to some staff members, including Mary Jane Smith, Tammy Jo Hiner, Teresa Dickerson, and Vicki Long, for their help over the years. Moreover, I would like to thank Laurie Good, who edited several chapters of my dissertation. In addition, I would like to take this opportunity to thank the previous and current members of SRT research group—Keiichi Osano, Min Mao, LaShonda Cureton, Bin Zhang, Yi Li, Jenny England, Xu Zhou, Zhengmian Chang, Alice Savage, Sneha S. Kelkar and Kevin iv Barr—for not only providing a wonderful learning environment, but also offering me their great friendship. I wish to thank Shijing Cheng, Renlong Gao, Tianyu Wu, Nancy Zhang, Xingguo Chen and Sha Yang for their insightful discussions and technical support throughout this work. Special thanks to my parents and my husband Liang Chen for their persistent support. My husband Liang Chen also worked in our group for six weeks and synthesized one monomer for me. He, together with my parents-in-law, has given me a lot of help in daily life and has shown me how colorful life can be. Lastly, my baby boy Lucas L. Chen has opened the most wonderful chapter in my life. v Table of Contents Chapter 1: Dissertation Overview ....................................................................................1 Chapter 2: Literature Review on Cycloaliphatic Polyesters .........................................2 2.1 Introduction ...............................................................................................................2 2.1.1 Rationales for polyesters containing cycloaliphatic rings .................................2 2.1.2 Cycloaliphatic monomers for synthesis of polyesters ........................................4 2.1.3 Synthetic methods of cycloaliphatic polyesters .................................................6 2.1.4 Overall structure-property relationship of cycloaliphatic polyesters .................8 2.2 Polyesters based on monocyclic monomers ............................................................13 2.2.1 Monocyclic diol-1,4-cyclohexanedimethanol (1,4-CHDM) .............................13 2.2.2 Monocyclic diol---2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCBD) ...........22 2.2.3 Monocyclic diol---1,3-cyclopentane dimethanol (CPDM) ...............................27 2.2.4 Monocyclic diol---1,4-cyclohexanediol (1,4-CHDO) .......................................29 2.2.5 Monocyclic diacids---1,4-cyclohexanedicarboxylic acid and its derivatives ....31 2.2.6 Monocyclic diacids---1,3-dimethylcyclopentane dicarboxylate (DMCP) ........37 2.3 Polyesters based on bicyclic/multicyclic monomers ................................................38 2.3.1 Bicyclic diol--2,2-bis(4-hydroxycyclohexyl)propane (HBPA) .........................38 2.3.2 Bicyclic diol----isosorbide and its isomers ........................................................40 2.3.3 Bicyclic diols containing bicyclo[2.2.1]heptane (norbornane) rings ................43 2.3.4 Bicyclic diesters containing bicyclo[2.2.1]heptane (norbornane) rings ............45 2.3.5 Bicyclic diols containing bicyclo[2.2.2]octane or bicyclo[3.2.2]nonane rings .46 2.3.6 Bicyclic diacids containing bicyclo[2.2.2]octane or bicyclo[3.2.2]nonane rings ....................................................................................................................................50 2.4 Some specific properties of cycloaliphatic polyesters ............................................58 2.4.1 Thermal properties.............................................................................................58 2.4.2 Mechanical properties .......................................................................................62 2.4.3 Photooxidative stability .....................................................................................66 2.5 Potential applications of cyloaliphatic copolyesters ..............................................70 2.5.1 Cyloaliphatic copolyesters as weatherable materials ........................................70 2.5.2 Certain cyloaliphatic copolyesters as biomaterials ............................................71 vi 2.6 Summary ................................................................................................................72 2.7 References ..............................................................................................................73 Chapter 3: Synthesis and Properties of Cyclic Diester Based Aliphatic Copolyesters ............................................................................................................................................79
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  • Terephthalic Acid & Dimethyl Terephthalate

    Terephthalic Acid & Dimethyl Terephthalate

    Report No. 9-A TEREPHTHALICACID AND DIMETHYLTEREPHTHALATE SUPPLEMENT A by LLOYD M. ELKIN m . contributions by SHIGEYOSHI TAKAOKA January 1967 A private report by the l PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I CONTENTS I INTRODUCTION. ........................ 1 II SUMMARY ........................... 3 III INDUSTRY STATUS . 9 IV CHEMISTRY . 15 Ammoxidation of p-Xylene . 15 Terephthalic Acid by Bromine-Promoted Catalytic Air Oxidation ofp-Xylene......................... 17 Terephthalic Acid by Catalytic Oxidation of p-Xylene in the Presence of Methyl Ethyl Ketone (MEK) Activator , . 18 Terephthalic Acid by Nitric Acid Oxidation of p-Xylene . 19 Terephthalic Acid from Phthalic Anhydride . 19 Dimethyl Terephthalate from p-Xylene by Successive Oxidations and Esterifications . 20 V BIS(B-HYDROXYETHYL) TEREPHTHALATE FROM TEREPHTHALONITRILE MADE BY AMMOXIDATION OF P-XYLENE ................. 23 Review of Processes ..................... 23 Crude Terephthalonitrile Production and Purification .... 23 Ammonia Recovery ...................... 27 Bis(2-hydroxyethyl) terephthalate Production and Purification ....................... 27 Process Description ..................... 29 Process Discussion ..... ; ................ 51 Crude Terephthalonitrile Production ............ 51 Ammonia Recovery ...................... 52 Terephthalonitrile Purification .............. 52 Bis(2-hydroxyethyl) terephthalate Production ........ 52 Bis(2-hydroxyethyl) terephthalate Purification ....... 53 Ethylene Glycol Recovery .................