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Synthesis and Structure–Property Relationships of Polyesters Containing Rigid Aromatic Structures

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Synthesis and Structure–Property Relationships of Polyesters Containing Rigid Aromatic Structures Synthesis and Structure–Property Relationships of Polyesters Containing Rigid Aromatic Structures Hans Eliot Edling 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, Committee Member Richard D. Gandour, Committee Member Robert B. Moore, Committee Member February 16th, 2018 Blacksburg, VA Keywords: - Copyright 2018 Hans Eliot Edling Synthesis and Structure–Property Relationships of Polyesters Containing Rigid Aromatic Structures Hans Eliot Edling ABSTRACT (Academic) Polyesters are an attractive class of polymer that can be readily modified with a wide range of different comonomers, during polymerization or with melt blending, to achieve a wide variety of physical properties. This research primarily focuses on polyesters that incorporate rigid aromatic structures that have excellent potential to enhance thermal and mechanical properties. Copolyesters were prepared through melt polycondensation of diesters and diols in the presence of an exchange catalyst. Monomer incorporation was verified with nuclear magnetic resonance (NMR) and molecular weights were obtained by measuring inherent viscosity (ηinh). Physical properties were assessed with thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and rheology. Mechanical properties were assessed with tensile and impact testing. Copolyesters of poly(ethylene terephthalate) (PET) were synthesized by substituting dimethyl terephthalate (DMT) with dimethyl 4,4’-biphenyldicarboxylate (4,4’BB) resulting in enhanced glass transition (Tg) temperatures relative to PET while affording melting temperatures (Tm) low enough to allow facile melt processing. Further modification with dimethyl isophthalate (DMI) or dimethyl 3,4’-biphenyldicarboxylate (3,4’BB) slowed crystallization sufficiently to allow biaxial orientation, leading to further studies assessing the permeability of oriented films. Novel amorphous polyesters were synthesized with 3,4’BB or 4,4’BB in combination with neopentyl glycol (NPG), 1,4-cyclohexandimethanol (CHDM) and ethylene glycol (EG). Use of multiple diols produced clear, amorphous copolyesters with Tgs as high at 129 °C. A series of novel high (Tm) copolyesters were synthesized from dimethyl 2,6- naphthalenedicarboxylate (DMN) and 4,4’BB combined with CHDM. Studies were performed with standard DSC and thin film calorimetry to show the convergence of multiples melting endotherms in an effort to determine their origin. Preliminary work was performed on the modification of poly(1,4-cyclohexylenedimethylene terephthalate) (PCT), poly(1,4- cyclohexylenedimethylene 2,6-naphthalate) (PCN) and poly(1,4-cyclohexylenedimethylene 4,4’- bibenzoate) (PCB) with dimethyl p-terphenyl-4,4’’-dicarboxylate. Synthesis and Structure–Property Relationships of Polyesters Containing Rigid Aromatic Structures Hans Eliot Edling ABSTRACT (General Audience) Polyesters have a unique balance of properties that sets them apart from other polymers formed by step growth reactions. The transesterification reaction that forms polyesters occurs continually at reaction temperatures, making it easy to randomly distribute a mixture of different comonomers along the backbone during the polymerization process, or even when blending two different polyesters. Poly(ethylene terephthalate), commonly referred to as PET, is the most important polyester currently in production, and is prized for its transparency, chemical resistance, and recyclability. PET was first made by John Whinfield and James Dickson at Calico Printers’ Association of Mansfield, in 1941 and was eventually licensed to DuPont in the 1970s. It has since become a valuable resource for producing synthetic textiles and replacing heavier materials, such as glass and metal, to produce lightweight containers, especially for food storage. Many of the polyesters, such as PET, that we see on a daily basis are actually copolyesters that contain low levels of additional comonomers that have been added to improve some property of the final polymer or to facilitate processing. In research, modification of polyesters with different comonomers broadens our understanding in how the molecular structure of comonomers affects polyester properties. This makes it possible to tune a copolyester’s physical properties in a way that can enhance its suitability for a wide range of applications. The research described in this dissertation is focused on exploring how rigid monomer structures containing multiple aromatic rings might be used to produce polyesters with improved performance relative to current commercial polyesters. Materials that demonstrate good barrier to gases such as CO2 and O2 are important for packaging that can seal in and preserve food and beverages. In our research, we modified PET with bibenzoate structures to produce films that showed improved gas barrier when stretched in a manner that imitates the stretch blow molding process used to produce bottles. These materials showed good promise for packaging capable of preserving food for longer periods of time. Clear, food safe plastics that do not deform at the boiling temperature of water are important for baby bottles and durable dishwasher safe containers, which are commonly sterilized with boiling water. Until recently, such materials were produced from bisphenol-A polycarbonate (BPA PC), which fell out of favor for food safe applications over concerns that BPA, believed to have endocrine disrupting activity, may leach into food and beverages. Bibenzoate monomers, which increases the application temperature of many polyesters, were combined with different combinations of diol monomers to produce transparent copolyesters that are usable at higher temperatures. These materials demonstrated excellent potential as food safe alternatives to BPA containing materials. Crystalline plastics that resist distorting at high temperatures are important for applications in the electronics and automotive industry. Semicrystalline polyesters provide less expensive alternatives to the costly liquid crystalline polymers commonly used for high temperature applications. We explored the properties of a number of semicrystalline copolyester compositions capable of exceeding the application temperature of semicrystalline polyesters currently on the market. Acknowledgements I am extremely grateful to my research advisor, Dr. S. Richard Turner, for guiding me over the years and urging me to become a better researcher. I continue to be amazed by his enthusiasm for chemistry and his extensive knowledge, which guided me countless times over the years. I would also like to thank my committee members Dr. Richard D. Gandour, Dr. Timothy E. Long and Dr. Robert B. Moore for their invaluable input and guidance on my research projects and presentation skills. This research would not have been possible without the help of Dr. Long’s research group and use of the many instruments they have at their disposal. I especially would like to thank Ryan Mondschein, Katie Valentine, Joseph Dennis, Phillip Scott and Mingtao Chen, all of whom gave up their time to help me with running instruments and performing data analysis. I would like thank Dr. Herve Marand, Dr. Bruce Orler and Matthew Vincent, who provided invaluable help and insights into thermal analysis. I offer special thanks to my collaborators, Dr. David Schiraldi, Dr. Hossein Ghassemi and Dr. Hua Sun, at Case Western Reserve University who provided great help and insightful discussions regarding my research. I would like to thank all the members of the Turner research group who provided a wonderful learning environment and friendship over the years. I would like to thank past members Zhengmian Chang, Haoyu Liu for providing guidance and friendship in my early years as a graduate student and I would like to thank Jing Huang and Sarah Blosch, who stuck it out with me until the end. I would like to thank John Echols, Sam Huff, Haleigh Hutcheson and the many members of the VPI Cave Club who became my family away from home and gave me support over the years. I would also like to thank Steffi Muller, who has been a warm and loving partner during my -vi- last year as a graduate student. Lastly, I would like to thank my family; my parents, Francesca and Geoffrey Edling, for encouraging me over my entire life and my brothers, Ivan and Axel, who have been my role models throughout life. -vii- Attributions Chapter 1: Literature Review on Copolyester Thermoplastics S. Richard Turner, PhD, Department of Chemistry at Virginia Tech is currently a research professor at Virginia Tech. Dr. Turner supplied a portion of the references and contributed with editorial comments Chapter 2: Copolyesters Based on Bibenzoic Acids (published in Polymer) Haoyu Liu, PhD, Department of Chemistry at Virginia Tech, is currently a Senior R&D Scientist/Engineer at Honeywell. Dr. Liu was a co-author on this paper, performed preliminary research on developing melt polymerization, thermal and structural characterization and biaxial orientation. Hua Sun, PhD, Department of Macromolecular Science and Engineering at Case Western Reserve University. Dr. Sun was a co-author on this paper, performed biaxial orientation, performed barrier measurements and contributed with editorial comments. David A. Schiraldi, PhD, Department of Macromolecular Science and Engineering at Case Western
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