Synthesis and characterization of a nematic fully aromatic polyester based on biphenyl 3,4′-dicarboxylic acid

Katherine V. Heifferon; Glenn A. Spiering; Samantha J. Talley; Maruti Hegde; Robert B. Moore; S. Richard Turner; Timothy E. Long

doi:10.1039/c9py00683d

Synthesis and characterization of a nematic fully aromatic polyester based on biphenyl 3,4′-dicarboxylic acid

Katherine V. Heifferon, Glenn A. Spiering, Samantha J. Talley, Maruti Hegde, Robert B. Moore, S. Richard Turner, Timothy E. Long

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

Melt acidolysis polymerization of hydroquinone with a kinked monomer, biphenyl 3,4′-bibenzoate, afforded a novel liquid crystalline polymer (LCP), poly(p-phenylene 3,4′-bibenzoate) (poly(HQ-3,4′BB)). Selection of hydroquinone diacetate (HQ_a) or hydroquinone dipivilate (HQ_p) facilitated either a tan or white final polymer, respectively. ¹H NMR spectroscopy confirmed consistent polymer backbone structure for polymers synthesized with either derivative of hydroquinone. Poly(HQ-3,4′BB) exhibited the onset of weight loss at about 480 °C, similar to commercially available Vectra® LCP. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) revealed a glass transition temperature (T_g) of 190 °C and an isotropic temperature (T_i) near 330 °C. The observation of a melting temperature (T_m) depended upon the thermal history of the polymer. Wide-angle X-ray scattering (WAXS) and polarized optical microscopy (POM) confirmed the formation of a nematic glass morphology after quench-cooling from the isotropic state. Subsequent annealing at 280 °C or mechanical deformation induced crystallization of the polymer. Rheological studies demonstrated similar shear thinning behavior for poly(HQ-3,4′BB) and Vectra® RD501 in the power law region at 340 °C. Zero-shear viscosity measurements indicated that HQ_a afforded higher melt viscosities after identical polymerization conditions relative to HQ_p, suggesting higher molecular weights.

Original language	English (US)
Pages (from-to)	4287-4296
Number of pages	10
Journal	Polymer Chemistry
Volume	10
Issue number	31
DOIs	https://doi.org/10.1039/c9py00683d
State	Published - Aug 21 2019
Externally published	Yes

ASJC Scopus subject areas

Bioengineering
Biochemistry
Polymers and Plastics
Organic Chemistry

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@article{dd890d33f5754ddab93ea1d15e810d0d,

title = "Synthesis and characterization of a nematic fully aromatic polyester based on biphenyl 3,4′-dicarboxylic acid",

abstract = "Melt acidolysis polymerization of hydroquinone with a kinked monomer, biphenyl 3,4′-bibenzoate, afforded a novel liquid crystalline polymer (LCP), poly(p-phenylene 3,4′-bibenzoate) (poly(HQ-3,4′BB)). Selection of hydroquinone diacetate (HQa) or hydroquinone dipivilate (HQp) facilitated either a tan or white final polymer, respectively. 1H NMR spectroscopy confirmed consistent polymer backbone structure for polymers synthesized with either derivative of hydroquinone. Poly(HQ-3,4′BB) exhibited the onset of weight loss at about 480 °C, similar to commercially available Vectra{\textregistered} LCP. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) revealed a glass transition temperature (Tg) of 190 °C and an isotropic temperature (Ti) near 330 °C. The observation of a melting temperature (Tm) depended upon the thermal history of the polymer. Wide-angle X-ray scattering (WAXS) and polarized optical microscopy (POM) confirmed the formation of a nematic glass morphology after quench-cooling from the isotropic state. Subsequent annealing at 280 °C or mechanical deformation induced crystallization of the polymer. Rheological studies demonstrated similar shear thinning behavior for poly(HQ-3,4′BB) and Vectra{\textregistered} RD501 in the power law region at 340 °C. Zero-shear viscosity measurements indicated that HQa afforded higher melt viscosities after identical polymerization conditions relative to HQp, suggesting higher molecular weights.",

author = "Heifferon, {Katherine V.} and Spiering, {Glenn A.} and Talley, {Samantha J.} and Maruti Hegde and Moore, {Robert B.} and Turner, {S. Richard} and Long, {Timothy E.}",

note = "Funding Information: This work is sponsored by ExxonMobil Chemical Company. Funding Information: The authors thank Dr. Ryan Mondschein and Dr. Eliot Edling for insightful discussions throughout the project. The morphological characterization is supported by National Science Foundation under Grant No. DMR-1809291. Publisher Copyright: {\textcopyright} 2019 The Royal Society of Chemistry.",

year = "2019",

month = aug,

day = "21",

doi = "10.1039/c9py00683d",

language = "English (US)",

volume = "10",

pages = "4287--4296",

journal = "Polymer Chemistry",

issn = "1759-9954",

publisher = "Royal Society of Chemistry",

number = "31",

}

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T1 - Synthesis and characterization of a nematic fully aromatic polyester based on biphenyl 3,4′-dicarboxylic acid

AU - Heifferon, Katherine V.

AU - Spiering, Glenn A.

AU - Talley, Samantha J.

AU - Hegde, Maruti

AU - Moore, Robert B.

AU - Turner, S. Richard

AU - Long, Timothy E.

N1 - Funding Information: This work is sponsored by ExxonMobil Chemical Company. Funding Information: The authors thank Dr. Ryan Mondschein and Dr. Eliot Edling for insightful discussions throughout the project. The morphological characterization is supported by National Science Foundation under Grant No. DMR-1809291. Publisher Copyright: © 2019 The Royal Society of Chemistry.

PY - 2019/8/21

Y1 - 2019/8/21

N2 - Melt acidolysis polymerization of hydroquinone with a kinked monomer, biphenyl 3,4′-bibenzoate, afforded a novel liquid crystalline polymer (LCP), poly(p-phenylene 3,4′-bibenzoate) (poly(HQ-3,4′BB)). Selection of hydroquinone diacetate (HQa) or hydroquinone dipivilate (HQp) facilitated either a tan or white final polymer, respectively. 1H NMR spectroscopy confirmed consistent polymer backbone structure for polymers synthesized with either derivative of hydroquinone. Poly(HQ-3,4′BB) exhibited the onset of weight loss at about 480 °C, similar to commercially available Vectra® LCP. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) revealed a glass transition temperature (Tg) of 190 °C and an isotropic temperature (Ti) near 330 °C. The observation of a melting temperature (Tm) depended upon the thermal history of the polymer. Wide-angle X-ray scattering (WAXS) and polarized optical microscopy (POM) confirmed the formation of a nematic glass morphology after quench-cooling from the isotropic state. Subsequent annealing at 280 °C or mechanical deformation induced crystallization of the polymer. Rheological studies demonstrated similar shear thinning behavior for poly(HQ-3,4′BB) and Vectra® RD501 in the power law region at 340 °C. Zero-shear viscosity measurements indicated that HQa afforded higher melt viscosities after identical polymerization conditions relative to HQp, suggesting higher molecular weights.

AB - Melt acidolysis polymerization of hydroquinone with a kinked monomer, biphenyl 3,4′-bibenzoate, afforded a novel liquid crystalline polymer (LCP), poly(p-phenylene 3,4′-bibenzoate) (poly(HQ-3,4′BB)). Selection of hydroquinone diacetate (HQa) or hydroquinone dipivilate (HQp) facilitated either a tan or white final polymer, respectively. 1H NMR spectroscopy confirmed consistent polymer backbone structure for polymers synthesized with either derivative of hydroquinone. Poly(HQ-3,4′BB) exhibited the onset of weight loss at about 480 °C, similar to commercially available Vectra® LCP. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) revealed a glass transition temperature (Tg) of 190 °C and an isotropic temperature (Ti) near 330 °C. The observation of a melting temperature (Tm) depended upon the thermal history of the polymer. Wide-angle X-ray scattering (WAXS) and polarized optical microscopy (POM) confirmed the formation of a nematic glass morphology after quench-cooling from the isotropic state. Subsequent annealing at 280 °C or mechanical deformation induced crystallization of the polymer. Rheological studies demonstrated similar shear thinning behavior for poly(HQ-3,4′BB) and Vectra® RD501 in the power law region at 340 °C. Zero-shear viscosity measurements indicated that HQa afforded higher melt viscosities after identical polymerization conditions relative to HQp, suggesting higher molecular weights.

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DO - 10.1039/c9py00683d

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VL - 10

SP - 4287

EP - 4296

JO - Polymer Chemistry

JF - Polymer Chemistry

IS - 31

ER -

Synthesis and characterization of a nematic fully aromatic polyester based on biphenyl 3,4′-dicarboxylic acid

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