Design and synthesis of functional graphenic and triptycene poli(arylether) materials
Author(s)Goods, John B. (John Benjamin)
Massachusetts Institute of Technology. Department of Chemistry.
Timothy M. Swager.
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This thesis describes the design and development of new methods to functionalize graphitic materials as well as the synthesis and properties of a new triptycene poly(arylether), triptycene- PEEK (Trp-PEEK) and its derivatives. In chapters 1-3, the development of new methods to functionalize graphitic materials with both small molecule functional groups and polymers and their implementation as functional materials is described. Chapter 4 explores the synthesis, postpolymerization functionalization, and applications of a new poly(arylether), Trp-PEEK. Chapter 1: In this chapter, I describe an attempt to covalently functionalize graphene oxide with ketone derivatives via the Carroll rearrangement, a [3,3]-sigmatropic reaction. Graphene oxide was reacted with 5-acyl derivatives of Meldrum's acid to produce p-ketoester functionalized graphene, and these materials were submitted to multiple reaction conditions to induce the Carroll rearrangement. A 13C labeling study the under the explored reaction conditions the revealed that Carroll product is not predominant. However, it was found that the 20% of the installed functionality was not removed by exposure to strong base, suggesting some rearranged product may have been produced. 5-acyl derivatives of Meldrum's acid were ultimately found to be versatile reagents for the functionalization of graphene oxide with various functional groups, allowing for the synthesis of graphenes with controlled intergallery spacings. Chapter 2: Using a modified version of the Arbuzov reaction, graphene oxide is covalently functionalized with phosphonate functionalities. Due to the oxidizing nature of graphene oxide, the reaction produces a large amount of phosphate salts which organize around the covalently installed phosphonate anchor sites. This results in a graphene material which can be extensively decorated with a controllable amount of phosphate material. The ligand properties of this material were explored by synthesizing a number of metal composites. Graphene phosphate was ultimately found to possess outstanding compressive strength properties, which could be tuned according to the reaction conditions. Portions of this chapter contain work which was assisted by Prof. Stefanie A. Sydlik, who aided in the compression strength testing of graphene phosphate and associated analysis. Additionally, Dr. Joseph Walish fabricated the iron molds used to create the graphene phosphate pellets. Chapter 3: The synthesis of a brine-stable graphene is reported. Using AIBN initiated radical polymerization, random co-polymers containing both aniline and imidazole species were synthesized. These polymers were then covalently attached to the graphene basal plane using diazonium chemistry and converted into imidazolium betaine structures. The resulting composite shows indefinite stability in high-temperature brine solutions, which are particularly relevant for the imaging of oil reservoirs. The work reported in this chapter was performed with equal contributions from both John B. Goods and Dr. Carlos Zuniga. Dr. Jason Cox also provided valuable discussions. Chapter 4: A new poly(aryl ether), triptycene poly(ether ether ketone) (Trp-PEEK) was synthesized and its properties investigated. Incorporation of a triptycene into the PEEK backbone results in a significantly elevated glass transition temperature, and its increased solubility allows for high molecular weight polymer to be synthesized without the use of specialty solvents and high temperatures typically required for PEEK. This polymer is derivatized by both sulfonation and nitration. The sulfonated S-Trp-PEEK can be cast into robust transparent membranes, and shows exceptional performance as a proton conductor in this form. It can also stabilize solutions of singlewalled carbon nanotubes in polar solvents, such as water and methanol. From these solutions, conductive films and foams can be cast. The N0 2-Trp-PEEK derivative can be reduced into its amine form and then reacted with isocyanates to form urea and thiourea derivatives of Trp-PEEK. Thio-Trp-PEEK can be used as a selector in the gas-phase sensing of acetone. Its hydrogen bonding properties can also be exploited to form self-healing viscoelastic materials when blended with poly(THF). The work contained in this chapter regarding sulfonated Trp-PEEK and proton conductivity of those polymers was performed with equal contributions from John B. Goods and Lionel Moh. Lionel Moh also assisted with the characterization of the other polymers covered in this chapter.
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2015.Vita. Cataloged from PDF version of thesis.Includes bibliographical references.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
Massachusetts Institute of Technology