Influence of Bibenzoate Regioisomers on Cyclohexanedimethanol-Based (Co)polyester Structure-Property Relationships

Ryan J. Mondschein, Joseph M. Dennis, Haoyu Liu, Ramesh K. Ramakrishnan, Justin M. Sirrine, Tobin Weiseman, Ralph H. Colby, Sergei Nazarenko, S. Richard Turner, Timothy Edward Long

    Research output: Contribution to journalArticle

    Abstract

    Melt polymerization enabled the synthesis of semi-aromatic (co)polyesters containing 1,4-cyclohexanedimethanol (CHDM), 4,4′-bibenzoate (4,4′BB), and 3,4′-bibenzoate (3,4′BB). Proton nuclear magnetic resonance ( 1 H NMR) spectroscopy confirmed monomer incorporation, and size exclusion chromatography (SEC) revealed molecular weights and polydispersity indices (PDIs) consistent with high conversion melt phase synthesized polyesters. All bibenzoate-based polyesters exhibited a high onset of 5 wt % loss temperature according to thermogravimetric analysis (TGA) (>350 °C), and differential scanning calorimetry (DSC) provided compositionally dependent glass transition temperatures (T g s) approaching 135 °C and crystalline melting temperatures where applicable. Dynamic mechanical analysis (DMA) probed sub-T g β-relaxations with minimal changes in intensity, suggesting that cyclohexyl ring relaxations dominated the low temperature energy absorption for all (co)polyester compositions. Time-temperature superposition (TTS) analysis from melt rheology revealed increasing characteristic relaxation times with increasing 4,4′BB content, which was attributed to the linear 4,4′BB stiffening the polymer chain. Increased kinked 3,4′BB content promoted chain entanglement, resulting in a lower entanglement molecular weight and a higher number of entanglements per chain (N/N e ). Similarly, increases in 3,4′BB content improved tensile yield strength and Young's modulus due to a higher polymer density and potentially due to an increase in entanglement density. Finally, scanning electron microscopy (SEM) suggested mostly brittle failure after necking and strain hardening in tensile specimens. As a result, structure-property relationships afforded insight into regioisomer impacts on thermal, rheological, and mechanical performance for bibenzoate-based (co)polyester regioisomers.

    Original languageEnglish
    Pages (from-to)835-843
    Number of pages9
    JournalMacromolecules
    Volume52
    Issue number3
    DOIs
    Publication statusPublished - 2019 Feb 12

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    Polyesters
    Polymers
    Molecular weight
    Nuclear magnetic resonance
    Size exclusion chromatography
    Energy absorption
    Polydispersity
    Dynamic mechanical analysis
    Rheology
    Strain hardening
    Relaxation time
    Temperature
    Nuclear magnetic resonance spectroscopy
    Yield stress
    Melting point
    Thermogravimetric analysis
    Differential scanning calorimetry
    Monomers
    Elastic moduli
    Polymerization

    ASJC Scopus subject areas

    • Organic Chemistry
    • Polymers and Plastics
    • Inorganic Chemistry
    • Materials Chemistry

    Cite this

    Mondschein, R. J., Dennis, J. M., Liu, H., Ramakrishnan, R. K., Sirrine, J. M., Weiseman, T., ... Long, T. E. (2019). Influence of Bibenzoate Regioisomers on Cyclohexanedimethanol-Based (Co)polyester Structure-Property Relationships. Macromolecules, 52(3), 835-843. https://doi.org/10.1021/acs.macromol.8b02411

    Influence of Bibenzoate Regioisomers on Cyclohexanedimethanol-Based (Co)polyester Structure-Property Relationships. / Mondschein, Ryan J.; Dennis, Joseph M.; Liu, Haoyu; Ramakrishnan, Ramesh K.; Sirrine, Justin M.; Weiseman, Tobin; Colby, Ralph H.; Nazarenko, Sergei; Turner, S. Richard; Long, Timothy Edward.

    In: Macromolecules, Vol. 52, No. 3, 12.02.2019, p. 835-843.

    Research output: Contribution to journalArticle

    Mondschein, RJ, Dennis, JM, Liu, H, Ramakrishnan, RK, Sirrine, JM, Weiseman, T, Colby, RH, Nazarenko, S, Turner, SR & Long, TE 2019, 'Influence of Bibenzoate Regioisomers on Cyclohexanedimethanol-Based (Co)polyester Structure-Property Relationships', Macromolecules, vol. 52, no. 3, pp. 835-843. https://doi.org/10.1021/acs.macromol.8b02411
    Mondschein, Ryan J. ; Dennis, Joseph M. ; Liu, Haoyu ; Ramakrishnan, Ramesh K. ; Sirrine, Justin M. ; Weiseman, Tobin ; Colby, Ralph H. ; Nazarenko, Sergei ; Turner, S. Richard ; Long, Timothy Edward. / Influence of Bibenzoate Regioisomers on Cyclohexanedimethanol-Based (Co)polyester Structure-Property Relationships. In: Macromolecules. 2019 ; Vol. 52, No. 3. pp. 835-843.
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    abstract = "Melt polymerization enabled the synthesis of semi-aromatic (co)polyesters containing 1,4-cyclohexanedimethanol (CHDM), 4,4′-bibenzoate (4,4′BB), and 3,4′-bibenzoate (3,4′BB). Proton nuclear magnetic resonance ( 1 H NMR) spectroscopy confirmed monomer incorporation, and size exclusion chromatography (SEC) revealed molecular weights and polydispersity indices (PDIs) consistent with high conversion melt phase synthesized polyesters. All bibenzoate-based polyesters exhibited a high onset of 5 wt {\%} loss temperature according to thermogravimetric analysis (TGA) (>350 °C), and differential scanning calorimetry (DSC) provided compositionally dependent glass transition temperatures (T g s) approaching 135 °C and crystalline melting temperatures where applicable. Dynamic mechanical analysis (DMA) probed sub-T g β-relaxations with minimal changes in intensity, suggesting that cyclohexyl ring relaxations dominated the low temperature energy absorption for all (co)polyester compositions. Time-temperature superposition (TTS) analysis from melt rheology revealed increasing characteristic relaxation times with increasing 4,4′BB content, which was attributed to the linear 4,4′BB stiffening the polymer chain. Increased kinked 3,4′BB content promoted chain entanglement, resulting in a lower entanglement molecular weight and a higher number of entanglements per chain (N/N e ). Similarly, increases in 3,4′BB content improved tensile yield strength and Young's modulus due to a higher polymer density and potentially due to an increase in entanglement density. Finally, scanning electron microscopy (SEM) suggested mostly brittle failure after necking and strain hardening in tensile specimens. As a result, structure-property relationships afforded insight into regioisomer impacts on thermal, rheological, and mechanical performance for bibenzoate-based (co)polyester regioisomers.",
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    AU - Sirrine, Justin M.

    AU - Weiseman, Tobin

    AU - Colby, Ralph H.

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