Telechelic Polyetherimides with Functionalized End Groups for Enhancement of Mechanical Strength, Flame Retardancy, and Optical Properties

This thesis focuses on understanding the factors that affect the properties of polyetherimide (PEI) and improving the properties. As a high-performance thermoplastic resin, the first challenge in PEI application is its high processing temperature and viscosity. Therefore, two supramolecular strategies were applied to not only solve the problem of high processing temperature or viscosity but also enhance the mechanical and flame retardancy. In addition, the yellow to amber color of PEIs limits its applications in high-tech fields such as microelectronics and optoelectronics. Thus, a fundamental study of how end group and molecular weight affect the optical properties of PEIs provides a better knowledge of the mechanism and an effective strategy for designing PEIs.

To lower the processing viscosity while maintaining or even improving the mechanical properties of PEI, the first strategy was to synthesize PEI oligomers, and incorporate self-complementary quadruple hydrogen bonding ureidopyrimidinone (UPy) units at the chain ends. Surprisingly, the UPy imparted PEI with a Mn as low as 8 kDa (8k-PEI) with great film formability. Excitingly, 8k-PEI-UPy exhibited an outstanding Young's modulus higher than those of state-of-the-art high-molecular-weight (high-MW) commercial PEIs. Therefore, the incorporation of UPy was proved to be an effective method to synthesize low-molecular-weight, high-mechanical-strength PEIs.

Although low-molecular-weight PEI-UPy had high mechanical properties, its limited thermal stability and potentially low flame retardancy, however, restricted its applications in areas such as aerospace and aircrafts. Hence in another strategy, which utilize the phosphonium ionic groups were incorporated into PEI oligomers targeting at achieving high thermal stability, flame retardancy, and mechanical properties simultaneously. Functionalization of dianhydride-terminated PEI by tetraphenylphosphonium bromide afforded the synthesis of phosphonium bromide terminated PEI (PEI-PhPPh3Br), which simultaneously exhibited excellent thermal stability up to ~400°C, outstanding flame retardancy evidenced by high char yield and extremely high limiting oxygen index, and a very high mechanical strength. The study thus provides an efficient strategy to simultaneously enhance the thermal and mechanical properties as well as flame retardancy. Furthermore, the low-molecular-weight PEI-PhPPh3Br had good processability due to its strong shear thinning.

In addition to the thermal and mechanical properties and flame retardancy, the end groups affect the optical properties, especially the yellowness, of PEIs. Understanding how end group and molecular weight affect the yellowness, of PEIs is critical for their applications in fields including optoelectronics and microelectronics. Thereby, PEIs with different Mn and various end groups including electron-withdrawing and electron-donating were prepared and characterized. Electron-withdrawing end groups reduced the yellowness and increased the transparency of PEI, regardless of the Mn. Electron-donating end groups increased the yellowness of PEIs with dependence on the Mn. The Mn affected the yellowness of PEIs by changing end group density and the probability of charge-transfer complex formation. The systematic study reveals the correlations among yellowness, end group, and molecular weight of PEIs.