skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Chain conformation of polymer melts with associating groups

Abstract

Molecular association has profound influences on the viscoelastic properties of polymers with associating side groups. The conventional wisdom is that interchain association dominates in the melt state, and the dynamics of the associative polymer network therefore might be understood by extending the classical molecular approaches such as the Rouse and reptation models for linear chains. Using small-angle neutron scattering and molecular dynamics simulation, here we show that while interchain association is important, intrachain association can not be neglected in determining the static structures of associating polymers in the melt state. Analyses of the radius of gyration, static structure factor, and intrachain mean-square distance of polymers with associating side groups have revealed a substantial deviation from the random walk structure at even moderate association strength and degree of functionality. This finding emphasizes the important role of intrachain loops in associative polymer networks.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Tsinghua University, Beijing (China)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1498183
Alternate Identifier(s):
OSTI ID: 1502550
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Published Article
Journal Name:
Journal of Physics Communications
Additional Journal Information:
Journal Volume: 3; Journal Issue: 3; Journal ID: ISSN 2399-6528
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Carrillo, Jan-Michael Y., Chen, Wei-Ren, Wang, Zhe, Sumpter, Bobby G., and Wang, Yangyang. Chain conformation of polymer melts with associating groups. United States: N. p., 2019. Web. doi:10.1088/2399-6528/ab09bb.
Carrillo, Jan-Michael Y., Chen, Wei-Ren, Wang, Zhe, Sumpter, Bobby G., & Wang, Yangyang. Chain conformation of polymer melts with associating groups. United States. doi:10.1088/2399-6528/ab09bb.
Carrillo, Jan-Michael Y., Chen, Wei-Ren, Wang, Zhe, Sumpter, Bobby G., and Wang, Yangyang. Fri . "Chain conformation of polymer melts with associating groups". United States. doi:10.1088/2399-6528/ab09bb.
@article{osti_1498183,
title = {Chain conformation of polymer melts with associating groups},
author = {Carrillo, Jan-Michael Y. and Chen, Wei-Ren and Wang, Zhe and Sumpter, Bobby G. and Wang, Yangyang},
abstractNote = {Molecular association has profound influences on the viscoelastic properties of polymers with associating side groups. The conventional wisdom is that interchain association dominates in the melt state, and the dynamics of the associative polymer network therefore might be understood by extending the classical molecular approaches such as the Rouse and reptation models for linear chains. Using small-angle neutron scattering and molecular dynamics simulation, here we show that while interchain association is important, intrachain association can not be neglected in determining the static structures of associating polymers in the melt state. Analyses of the radius of gyration, static structure factor, and intrachain mean-square distance of polymers with associating side groups have revealed a substantial deviation from the random walk structure at even moderate association strength and degree of functionality. This finding emphasizes the important role of intrachain loops in associative polymer networks.},
doi = {10.1088/2399-6528/ab09bb},
journal = {Journal of Physics Communications},
number = 3,
volume = 3,
place = {United States},
year = {2019},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1088/2399-6528/ab09bb

Save / Share:

Works referenced in this record:

Chain conformation and solubility of associating polymers
journal, May 1986


Swollen conformations of associating polymer chains
journal, August 1993


Multicanonical Monte Carlo Simulation of a Polymer with Stickers
journal, August 1996

  • Urakami, Naohito; Takasu, Masako
  • Journal of the Physical Society of Japan, Vol. 65, Issue 8
  • DOI: 10.1143/JPSJ.65.2694

Thermodynamics of Reversibly Associating Polymer Solutions
journal, June 1999


Phase Diagram of Solutions of Associative Polymers
journal, May 2004


Thermodynamics of reversibly associating ideal chains
journal, January 2005

  • Loverde, Sharon M.; Ermoshkin, Alexander V.; De La Cruz, Monica Olvera
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 43, Issue 7
  • DOI: 10.1002/polb.20372

Equilibrium Structure and Dynamics of Self-Associating Single Polymers
journal, September 2011

  • Sing, Charles E.; Alexander-Katz, Alfredo
  • Macromolecules, Vol. 44, Issue 17
  • DOI: 10.1021/ma200830t

Dynamics of Entangled Solutions of Associating Polymers
journal, February 2001

  • Rubinstein, Michael; Semenov, Alexander N.
  • Macromolecules, Vol. 34, Issue 4
  • DOI: 10.1021/ma0013049

Dynamics of reversibly crosslinked chains
journal, July 1989


Effect of segment-segment association on chain dimensions
journal, July 1982


Thermoplastic elastomers by hydrogen bonding 1. Rheological properties of modified polybutadiene
journal, September 1986

  • Stadler, R.; de Lucca Freitas, L.
  • Colloid and Polymer Science, Vol. 264, Issue 9
  • DOI: 10.1007/BF01500752

Thermoplastic elastomers by hydrogen bonding: 5. Thermorheologically complex behaviour by hydrogen bond clustering
journal, May 1987

  • Freltas, LianedeLucca; Burgert, Josef; Stadler, Reimund
  • Polymer Bulletin, Vol. 17, Issue 5
  • DOI: 10.1007/BF00255615

Thermoplastic elastomers by hydrogen bonding. 3. Interrelations between molecular parameters and rheological properties
journal, October 1987

  • De Lucca Freitas, Liane Lucy; Stadler, Reimund
  • Macromolecules, Vol. 20, Issue 10
  • DOI: 10.1021/ma00176a027

Thermoplastic elastomers by hydrogen bonding 4. Influence of hydrogen bonding on the temperature dependence of the viscoelastic properties
journal, December 1988

  • de Lucca Freitas, L.; Stadler, R.
  • Colloid and Polymer Science, Vol. 266, Issue 12
  • DOI: 10.1007/BF01414399

Relaxation Dynamics of Bidisperse Temporary Networks
journal, April 1994

  • Seidel, Ulf; Stadler, Reimund; Fuller, Gerald G.
  • Macromolecules, Vol. 27, Issue 8
  • DOI: 10.1021/ma00086a014

The molecular dynamics of thermoreversible networks as studied by broadband dielectric spectroscopy
journal, January 1995

  • M�ller, M.; Fischer, E. W.; Kremer, F.
  • Colloid & Polymer Science, Vol. 273, Issue 1
  • DOI: 10.1007/BF00655672

On the Motional Coupling between Chain and Junction Dynamics in Thermoreversible Networks
journal, September 1995

  • Mueller, M.; Stadler, R.; Kremer, F.
  • Macromolecules, Vol. 28, Issue 20
  • DOI: 10.1021/ma00124a034

Dilute solution properties of polybutadiene modified by 4-phenyl-1,2,4-triazoline-3,5-dione
journal, October 1996

  • Bica, Clara I. D.; Burchard, Walther; Stadler, Reimund
  • Macromolecular Chemistry and Physics, Vol. 197, Issue 10
  • DOI: 10.1002/macp.1996.021971027

Behaviour of modified and unmodified polybutadienes in the semidilute regime
journal, October 1997


Small-angle neutron scattering from sulfonate ionomer solutions. 1. Associating polymer behavior
journal, September 1988

  • Lantman, C. W.; MacKnight, W. J.; Higgins, J. S.
  • Macromolecules, Vol. 21, Issue 5
  • DOI: 10.1021/ma00183a026

Small-angle neutron scattering from sulfonate ionomer solutions. 2. Polyelectrolyte effects in polar solvents
journal, September 1988

  • Lantman, C. W.; MacKnight, W. J.; Sinha, S. K.
  • Macromolecules, Vol. 21, Issue 5
  • DOI: 10.1021/ma00183a027

Thermoreversible Gelation in Solutions of Associative Polymers. 1. Statics
journal, February 1998

  • Semenov, Alexander N.; Rubinstein, Michael
  • Macromolecules, Vol. 31, Issue 4
  • DOI: 10.1021/ma970616h

Molecular origin of supramolecular self-assembling in statistical copolymers
journal, April 1992

  • Hilger, Christopher; Draeger, Martin; Stadler, Reimund
  • Macromolecules, Vol. 25, Issue 9
  • DOI: 10.1021/ma00035a031

Dynamics of reversible networks
journal, August 1991

  • Leibler, Ludwik; Rubinstein, Michael; Colby, Ralph H.
  • Macromolecules, Vol. 24, Issue 16
  • DOI: 10.1021/ma00016a034

Triazolinedione Modified Polydienes
journal, December 1980

  • Butler, George B.
  • Industrial & Engineering Chemistry Product Research and Development, Vol. 19, Issue 4
  • DOI: 10.1021/i360076a008

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Implementing molecular dynamics on hybrid high performance computers – short range forces
journal, April 2011

  • Brown, W. Michael; Wang, Peng; Plimpton, Steven J.
  • Computer Physics Communications, Vol. 182, Issue 4
  • DOI: 10.1016/j.cpc.2010.12.021

Structure and dynamics of confined flexible and unentangled polymer melts in highly adsorbing cylindrical pores
journal, August 2014

  • Carrillo, Jan-Michael Y.; Sumpter, Bobby G.
  • The Journal of Chemical Physics, Vol. 141, Issue 7
  • DOI: 10.1063/1.4893055

Small-angle neutron scattering from sulfonate ionomers
journal, January 1981

  • Earnest, T. R.; Higgins, J. S.; Handlin, D. L.
  • Macromolecules, Vol. 14, Issue 1
  • DOI: 10.1021/ma50002a040

Structure factors for regular polymer gels and networks
journal, December 1993

  • Hammouda, Boualem
  • The Journal of Chemical Physics, Vol. 99, Issue 11
  • DOI: 10.1063/1.465533

Some statistical properties of flexible ring polymers
journal, February 1965


Scattering Function of Wormlike Rings
journal, February 2014

  • Tsubouchi, Ryutaro; Ida, Daichi; Yoshizaki, Takenao
  • Macromolecules, Vol. 47, Issue 4
  • DOI: 10.1021/ma402572k

Equilibration of long chain polymer melts in computer simulations
journal, December 2003

  • Auhl, Rolf; Everaers, Ralf; Grest, Gary S.
  • The Journal of Chemical Physics, Vol. 119, Issue 24
  • DOI: 10.1063/1.1628670