Bottlebrush (BB) elastomers with water-soluble side chains and tissue-mimetic mechanical properties are promising for biomedical applications like tissue implants and drug depots. This work investigates the microstructure and phase transitions of BB elastomers with crystallizable polyethylene oxide (PEO) side chains by real-time synchrotron X-ray scattering. In the melt, the elastomers exhibit the characteristic BB peak corresponding to the backbone-to-backbone correlation. This peak is a distinct feature of BB systems and is observable in small- or medium-angle X-ray scattering curves. In the systems studied, the position of the BB peak ranges from 3.6 to 4.8 nm in BB elastomers. This variation is associated with the degree of polymerization of the polyethylene oxide (PEO) side chains, which ranges from 19 to 40. Upon crystallization of the side chains, the intensity of the peak decays linearly with crystallinity and eventually vanishes due to BB packing disordering within intercrystalline amorphous gaps. This behavior of the bottlebrush peak differs from an earlier study of BBs with poly(ε-caprolactone) side chains, explained by stronger backbone confinement in the case of PEO, a high-crystallinity polymer. Microstructural models based on 1D SAXS correlation function analysis suggest crystalline lamellae of PEO side chains separated by amorphous gaps of monolayer-like BB backbones.
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Synthesis and characterization of a nematic fully aromatic polyester based on biphenyl 3,4′-dicarboxylic acid
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. 1 H 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.
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- Award ID(s):
- 1809291
- PAR ID:
- 10164202
- Date Published:
- Journal Name:
- Polymer Chemistry
- Volume:
- 10
- Issue:
- 31
- ISSN:
- 1759-9954
- Page Range / eLocation ID:
- 4287 to 4296
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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