Molecular Structure, Chain Dimensions, and Linear
Rheology of Poly(4-vinylbiphenyl)
Posted on 2017-11-06 - 21:04
The
linear viscoelasticity and molecular structure of a series
of poly(4-vinylbiphenyl) (PVBP) samples with polydispersities ranging
from 1.08 to 2.75 are investigated using wide-angle X-ray scattering
(WAXS), small-angle neutron scattering (SANS), and rheological measurements.
PVBP chain dimensions, such as statistical segment length, persistence
length, and packing length, are obtained from SANS measurements. Because
of the bulkiness of the biphenyl monomer, PVBP has the lowest chain
flexibility and the largest reptation tube diameter among most common
thermoplastics, including polystyrene and polyvinylcyclohexane.
Nevertheless, PVBP follows the universal power law dependence between
elastic modulus and packing length (GN0 ∝ p–3). X-ray diffraction
of PVBP consist of two main amorphous peaks: one associated with the
interchain (backbone) correlations and a second one arising from phenyl–phenyl
correlations. The latter are due to π–π stacking
of the phenyl rings, mostly arranged in the T-shaped configuration.
Molecular dynamic simulations validate the diffraction peak assignments.
The linear rheology of PVBP samples reveals a thermorheologically
simple response and a very low value of GN0 (0.065 MPa). This is consequence of the low chain flexibility, which
also explains the relatively high entanglement molecular weight value
for PVBP (58.3 kg/mol).
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López-Barrón, Carlos R.; Zhou, Huaxing; Younker, Jarod M.; Mann, Jason A. (2017). Molecular Structure, Chain Dimensions, and Linear
Rheology of Poly(4-vinylbiphenyl). ACS Publications. Collection. https://doi.org/10.1021/acs.macromol.7b01564