Synthesis and Characterization of Amorphous Bibenzoate (Co)polyesters: Permeability and Rheological Performance

Ryan J. Mondschein, Joseph M. Dennis, Haoyu Liu, Ramesh K. Ramakrishnan, Sergei Nazarenko, S. Richard Turner, Timothy Edward Long*

*この研究の対応する著者

研究成果: Article査読

18 被引用数 (Scopus)

抄録

Melt polycondensation of bibenzoate dimethyl esters with ethylene glycol enabled the synthesis of polyesters containing linear (4,4′-bibenzoate (4,4′BB)) and kinked (3,4′-bibenzoate (3,4′BB)) repeating units. Novel 3,4′BB:4,4′BB (co)polyesters with ethylene glycol (EG) showed an onset of weight loss (Td,5%) above 350 °C. 1H NMR spectroscopy confirmed 4,4′BB:3,4′BB incorporation, and size exclusion chromatography (SEC) revealed high molecular weights. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) revealed glass transition temperatures (Tg) approaching 121 °C, crystallization and melting transition temperatures (Tc and Tm), and sub-Tg β-relaxations. 4,4′BB incorporation below ∼45 mol % afforded an amorphous morphology, while 4,4′BB incorporation above 45 mol % induced crystallinity. Melt rheology elucidated the effect of structure on flow behavior, and time-temperature superposition (TTS) revealed distinct flow transitions. TTS analysis also provided insight into the structural influence of regioisomers on fractional free volume (fg) and flow activation energies (Ea). Incorporation of the symmetrical 4,4′BB monomer negligibly affected the fg but imparted a stiffer overall chain, resulting in higher Ea. Positron annihilation lifetime spectroscopy (PALS) of the (co)polyesters confirmed a lack of change in free volume through measuring the average free volume of a spherical hole. Determination of oxygen permeability offered fundamental understanding of the relationship of monomer symmetry with gas permeability and free volume in unoriented films; kinked 3,4′BB monomer afforded higher overall barrier in amorphous films. Finally, tensile testing elucidated Young's moduli and yield strengths, confirming (co)polyesters' mechanical similarity to BPA-polycarbonate. Moduli ≤2.7 GPa and yield strengths up to 74 MPa confirmed BB-based (co)polyesters enhanced properties compared to other high-Tg polyesters.

本文言語English
ページ(範囲)7603-7610
ページ数8
ジャーナルMacromolecules
50
19
DOI
出版ステータスPublished - 2017 10月 10
外部発表はい

ASJC Scopus subject areas

  • 有機化学
  • ポリマーおよびプラスチック
  • 無機化学
  • 材料化学

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