Title
Local Chain Alignment via Nematic Ordering Reduces Chain Entanglement in Conjugated Polymers
Date Issued
26 December 2018
Access level
metadata only access
Resource Type
journal article
Author(s)
Xie R.
Aplan M.P.
Caggiano N.J.
Weisen A.R.
Su T.
Müller C.
Segad M.
Colby R.H.
Pennsylvania State University,
Publisher(s)
American Chemical Society
Abstract
Chain entanglements govern the dynamics of polymers and will therefore affect the processability and kinetics of ordering; it follows that through these parameters chain dynamics can also affect charge transport in conjugated polymers. The effect of nematic coupling on chain entanglements is probed by linear viscoelastic measurements on poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) and poly((9,9-dioctylfluorene-2,7-diyl)-alt-(4,7-di(thiophene-2-yl)-2,1,3-benzothiadiazole)-5′,5″-diyl) (PFTBT) with varying molecular weights. We first verify the existence of nematic phases in both PFTBT and PCDTBT and identify nematic-isotropic transition temperatures, T IN , between 260 and 300 °C through a combination of differential scanning calorimetry, polarized optical microscopy, temperature-dependent X-ray scattering, and rheology. In addition, both PCDTBT and PFTBT show a glass transition temperature (T g ) and T IN , whereas only PFTBT has a melting temperature T m of 260 °C. Comparing the molecular weight dependence of T IN with theoretical predictions of nematic phases in conjugated polymers yields the nematic coupling constant, α = (550 ± 80 K)/T + (2.1 ± 0.1), and the long-chain limit T IN as 350 ± 10 °C for PFTBT. The entanglement molecular weight (M e ) in the isotropic phase is extracted to be 11 ± 1 kg/mol for PFTBT and 22 ± 2 kg/mol for PCDTBT by modeling the linear viscoelastic response. Entanglements are significantly reduced through the isotropic-to-nematic transition, leading to a 10-fold increase in M e for PFTBT and a 15-fold increase for PCDTBT in the nematic phase.
Start page
10271
End page
10284
Volume
51
Issue
24
Language
English
OCDE Knowledge area
Ciencia de los polímeros
Química
Scopus EID
2-s2.0-85059530183
Source
Macromolecules
ISSN of the container
00249297
Sponsor(s)
We acknowledge the financial support of the National Science Foundation DMREF program under grant number DMR-1629006. We thank Anders Mårtensson for the help with GPC measurements and Scott Milner for insightful comments. We also thank Pat Mather for helpful discussions regarding characterization of liquid crystals.
Sources of information:
Directorio de Producción Científica
Scopus