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Title: Effect of Microstructure on Chain Flexibility and Glass Transition Temperature of Polybenzofulvene

Abstract

Polybenzofulvene (PBF) is a polydiene with a very high glass transition temperature (Tg), which makes it a potential candidate for use as the hard block for high-temperature thermoplastic elastomer applications. The Tgs of polydienes are known to be related to chain flexibility. However, no studies have been reported that correlate the chain flexibility to the microstructure of PBF. Herein, we present a study of solution properties of linear PBFs with narrow molecular weight dispersity and having 1,2-addition ranging from 23% to 99%. The materials were prepared by living anionic polymerization under different conditions. Specifically, the chain flexibility as defined by the Flory's characteristic ratio, , and dependence of chain flexibility on microstructure by combined measurements of intrinsic viscosity and molecular weight using triple-detector size exclusion chromatography (SEC) is studied. The persistence lengths (lp) and chain diameters (dB) were also estimated using the touched-bead wormlike chain model. To the best of our knowledge, the characteristic ratio of PBF is found to be the highest of all polydienes that have been reported so far.

Authors:
 [1];  [1];  [1];  [2];  [1]; ORCiD logo [3];  [1]
  1. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  2. Aichi Univ. of Education, Kariya (Japan)
  3. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE
OSTI Identifier:
1777762
Alternate Identifier(s):
OSTI ID: 1809444
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Polymer
Additional Journal Information:
Journal Volume: 212; Journal Issue: 1; Journal ID: ISSN 0032-3861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Huiqun, Wang, Weiyu, Lu, Wei, Osa, Masashi, Kang, Nam-goo, Hong, Kunlun, and Mays, Jimmy. Effect of Microstructure on Chain Flexibility and Glass Transition Temperature of Polybenzofulvene. United States: N. p., 2021. Web. doi:10.1016/j.polymer.2020.123276.
Wang, Huiqun, Wang, Weiyu, Lu, Wei, Osa, Masashi, Kang, Nam-goo, Hong, Kunlun, & Mays, Jimmy. Effect of Microstructure on Chain Flexibility and Glass Transition Temperature of Polybenzofulvene. United States. https://doi.org/10.1016/j.polymer.2020.123276
Wang, Huiqun, Wang, Weiyu, Lu, Wei, Osa, Masashi, Kang, Nam-goo, Hong, Kunlun, and Mays, Jimmy. Tue . "Effect of Microstructure on Chain Flexibility and Glass Transition Temperature of Polybenzofulvene". United States. https://doi.org/10.1016/j.polymer.2020.123276.
@article{osti_1777762,
title = {Effect of Microstructure on Chain Flexibility and Glass Transition Temperature of Polybenzofulvene},
author = {Wang, Huiqun and Wang, Weiyu and Lu, Wei and Osa, Masashi and Kang, Nam-goo and Hong, Kunlun and Mays, Jimmy},
abstractNote = {Polybenzofulvene (PBF) is a polydiene with a very high glass transition temperature (Tg), which makes it a potential candidate for use as the hard block for high-temperature thermoplastic elastomer applications. The Tgs of polydienes are known to be related to chain flexibility. However, no studies have been reported that correlate the chain flexibility to the microstructure of PBF. Herein, we present a study of solution properties of linear PBFs with narrow molecular weight dispersity and having 1,2-addition ranging from 23% to 99%. The materials were prepared by living anionic polymerization under different conditions. Specifically, the chain flexibility as defined by the Flory's characteristic ratio, , and dependence of chain flexibility on microstructure by combined measurements of intrinsic viscosity and molecular weight using triple-detector size exclusion chromatography (SEC) is studied. The persistence lengths (lp) and chain diameters (dB) were also estimated using the touched-bead wormlike chain model. To the best of our knowledge, the characteristic ratio of PBF is found to be the highest of all polydienes that have been reported so far.},
doi = {10.1016/j.polymer.2020.123276},
journal = {Polymer},
number = 1,
volume = 212,
place = {United States},
year = {2021},
month = {11}
}

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Works referenced in this record:

The Effect of Rate of Shear on the Viscosity of Dilute Solutions of Polyisobutylene 1
journal, May 1951

  • Fox, T. G.; Fox, J. C.; Flory, P. J.
  • Journal of the American Chemical Society, Vol. 73, Issue 5
  • DOI: 10.1021/ja01149a001

Temperature coefficients of unperturbed dimensions for atactic polypropylene and alternating poly(ethylene-propylene)
journal, February 1989


Solution properties and characteristic ratio of near-monodisperse poly(tert-butyl methacrylate)
journal, August 1990

  • Karandinos, Anthony; Mays, Jimmy W.; Hadjichristidis, Nikos
  • Polymer Bulletin, Vol. 24, Issue 2
  • DOI: 10.1007/BF00297326

Temperature dependence of the unperturbed dimensions of alternating poly(ethylene-propylene)
journal, March 1992

  • Zirkel, A.; Richter, D.; Pyckhout-Hintzen, W.
  • Macromolecules, Vol. 25, Issue 2
  • DOI: 10.1021/ma00028a069

Anionic polymerization: High vacuum techniques
journal, January 2000


Solution Properties of 1,3-Cyclohexadiene Polymers by Laser Light Scattering and Small-Angle Neutron Scattering
journal, January 2006

  • Yun, Seok I.; Terao, Ken; Hong, Kunlun
  • Macromolecules, Vol. 39, Issue 2
  • DOI: 10.1021/ma052022h

Connection between Polymer Molecular Weight, Density, Chain Dimensions, and Melt Viscoelastic Properties
journal, August 1994

  • Fetters, L. J.; Lohse, D. J.; Richter, D.
  • Macromolecules, Vol. 27, Issue 17
  • DOI: 10.1021/ma00095a001

Ultrahigh molecular weight polymers in dilute solutions
journal, June 1999


Configurational Statistics of 1,4-Polybutadiene Chains
journal, March 1971


Effects of chain microstructure on the viscoelastic properties of linear polymer melts: polybutadienes and hydrogenated polybutadienes
journal, December 1984

  • Carella, Jose M.; Graessley, William W.; Fetters, Lewis J.
  • Macromolecules, Vol. 17, Issue 12
  • DOI: 10.1021/ma00142a059

Microscopic and macroscopic evaluation of fundamental facets of the entanglement concept
journal, April 1991


Excluded-Volume Effects in Dilute Polymer Solutions. XIII. Effects of Chain Stiffness
journal, February 1982


On the Configurational Statistics of Ethylene‐Propylene Copolymers
journal, September 1972

  • Mark, J. E.
  • The Journal of Chemical Physics, Vol. 57, Issue 6
  • DOI: 10.1063/1.1678622

Further Test of the Two-Parameter Theory of Dilute Polymer Solutions: Poly(p-bromostyrene)
journal, March 1971

  • Takashima, Koichi; Tanaka, Genzo; Yamakawa, Hiromi
  • Polymer Journal, Vol. 2, Issue 2
  • DOI: 10.1295/polymj.2.245

Conformational Energies of n-Alkanes and the Random Configuration of Higher Homologs Including Polymethylene
journal, February 1966

  • Abe, A.; Jernigan, R. L.; Flory, P. J.
  • Journal of the American Chemical Society, Vol. 88, Issue 4
  • DOI: 10.1021/ja00956a001

Dilute solution properties of randomly branched poly(methyl methacrylate)
journal, January 1996


Experimental techniques in high-vacuum anionic polymerization
journal, January 2005

  • Uhrig, David; Mays, Jimmy W.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 43, Issue 24
  • DOI: 10.1002/pola.21016

Melt Chain Dimensions of Polylactide
journal, March 2004

  • Anderson, Kelly S.; Hillmyer, Marc A.
  • Macromolecules, Vol. 37, Issue 5
  • DOI: 10.1021/ma0357523

On the estimation of unperturbed dimensions from intrinsic viscositiesxcin
journal, January 1963

  • Stockmayer, W. H.; Fixman, Marshall
  • Journal of Polymer Science Part C: Polymer Symposia, Vol. 1, Issue 1
  • DOI: 10.1002/polc.5070010109

Statistical Mechanics of Dilute Polymer Solutions. II
journal, August 1950

  • Flory, P. J.; Krigbaum, W. R.
  • The Journal of Chemical Physics, Vol. 18, Issue 8
  • DOI: 10.1063/1.1747866

Intrinsic viscosity of oligo- and polystyrenes
journal, August 1989

  • Einaga, Yoshiyuki; Koyama, Hitoshi; Konishi, Toshiki
  • Macromolecules, Vol. 22, Issue 8
  • DOI: 10.1021/ma00198a037

Rheological Investigation of Polybutadienes Having Different Microstructures over a Large Temperature Range
journal, December 1995

  • Zorn, Reiner; McKenna, Gregory B.; Willner, Lutz
  • Macromolecules, Vol. 28, Issue 25
  • DOI: 10.1021/ma00129a014

Molecular characterization of poly(2-methyl-1,3-pentadiene) and its hydrogenated derivative, atactic polypropylene
journal, December 1985

  • Xu, Zhongde; Mays, Jimmy; Chen, Xuexin
  • Macromolecules, Vol. 18, Issue 12
  • DOI: 10.1021/ma00154a034

Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties
journal, December 2016


Characteristic ratios of atactic poly(vinylethylene) and poly(ethylethylene)
journal, June 1983

  • Xu, Zhongde; Hadjichristidis, Nikos; Carella, Jose M.
  • Macromolecules, Vol. 16, Issue 6
  • DOI: 10.1021/ma00240a019

High Anionic Polymerizability of Benzofulvene: New Exo-Methylene Hydrocarbon Monomer
journal, June 2015


Transport coefficients of helical wormlike chains. 4. Intrinsic viscosity of the touched-bead model
journal, January 1988

  • Yoshizaki, Takenao; Nitta, Itaru; Yamakawa, Hiromi
  • Macromolecules, Vol. 21, Issue 1
  • DOI: 10.1021/ma00179a033

Characteristic ratios of model polydienes and polyolefins
journal, December 1984

  • Mays, Jimmy; Hadjichristidis, Nikos; Fetters, Lewis J.
  • Macromolecules, Vol. 17, Issue 12
  • DOI: 10.1021/ma00142a048

Random-Coil Configurations of cis-1,4-Polybutadiene and cis-1,4-Polyisoprene. Theoretical Interpretation
journal, October 1966

  • Mark, J. E.
  • Journal of the American Chemical Society, Vol. 88, Issue 19
  • DOI: 10.1021/ja00971a009

Conformational characteristics of some model polydienes and polyolefins
journal, November 1991

  • Hattam, Paul; Gauntlett, Stephen; Mays, Jimmy W.
  • Macromolecules, Vol. 24, Issue 23
  • DOI: 10.1021/ma00023a022

High Temperature Thermoplastic Elastomers Synthesized by Living Anionic Polymerization in Hydrocarbon Solvent at Room Temperature
journal, March 2016


The characteristic ratios of stereoirregular polybutadiene and polyisoprene
journal, April 1982

  • Hadjichristidis, Nikos; Zhongde, Xu; Fetters, L. J.
  • Journal of Polymer Science: Polymer Physics Edition, Vol. 20, Issue 4
  • DOI: 10.1002/pol.1982.180200415

Chain Conformation of Poly( d -lactide) in Tetrahydrofuran by Static Light Scattering, Small-Angle X-ray Scattering, and Intrinsic Viscosity
journal, February 2020