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

Title: Design, synthesis, and characterization of lightly sulfonated multigraft acrylate-based copolymer superelastomers

Abstract

Multigraft copolymer superelastomers consisting of a poly(n-butyl acrylate) backbone and polystyrene side chains were synthesized and the viscoelastic properties of the non-sulfonated and sulfonated final materials were investigated using extensional rheology (SER3). The non-linear viscoelastic experiments revealed significantly increased true stresses (up to 10 times higher) after sulfonating only 2–3% of the copolymer while the materials maintained high elongation (<700%). The linear viscoelastic experiments showed that the storage and loss modulus are increased by sulfonation and that the copolymers can be readily tuned and further improved by increasing the number of branching points and the molecular weight of the backbone. Here, in this way, we show that by tuning not only the molecular characteristics of the multigraft copolymers but also their architecture and chemical interaction, we can acquire thermoplastic superelastomer materials with desired viscoelastic properties.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [2];  [4]; ORCiD logo [1];  [1]; ORCiD logo [3]
  1. Department of Chemistry, University of Tennessee, Knoxville, USA, Chemical Sciences Division
  2. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, USA
  3. Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, USA
  4. Department of Chemistry, University of Tennessee, Knoxville, USA
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1418384
Alternate Identifier(s):
OSTI ID: 1423075
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Published Article
Journal Name:
RSC Advances
Additional Journal Information:
Journal Name: RSC Advances Journal Volume: 8 Journal Issue: 10; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Misichronis, Konstantinos, Wang, Weiyu, Cheng, Shiwang, Wang, Yangyang, Shrestha, Umesh, Dadmun, Mark, Mays, Jimmy W., and Saito, Tomonori. Design, synthesis, and characterization of lightly sulfonated multigraft acrylate-based copolymer superelastomers. United Kingdom: N. p., 2018. Web. doi:10.1039/C7RA08641E.
Misichronis, Konstantinos, Wang, Weiyu, Cheng, Shiwang, Wang, Yangyang, Shrestha, Umesh, Dadmun, Mark, Mays, Jimmy W., & Saito, Tomonori. Design, synthesis, and characterization of lightly sulfonated multigraft acrylate-based copolymer superelastomers. United Kingdom. doi:10.1039/C7RA08641E.
Misichronis, Konstantinos, Wang, Weiyu, Cheng, Shiwang, Wang, Yangyang, Shrestha, Umesh, Dadmun, Mark, Mays, Jimmy W., and Saito, Tomonori. Mon . "Design, synthesis, and characterization of lightly sulfonated multigraft acrylate-based copolymer superelastomers". United Kingdom. doi:10.1039/C7RA08641E.
@article{osti_1418384,
title = {Design, synthesis, and characterization of lightly sulfonated multigraft acrylate-based copolymer superelastomers},
author = {Misichronis, Konstantinos and Wang, Weiyu and Cheng, Shiwang and Wang, Yangyang and Shrestha, Umesh and Dadmun, Mark and Mays, Jimmy W. and Saito, Tomonori},
abstractNote = {Multigraft copolymer superelastomers consisting of a poly(n-butyl acrylate) backbone and polystyrene side chains were synthesized and the viscoelastic properties of the non-sulfonated and sulfonated final materials were investigated using extensional rheology (SER3). The non-linear viscoelastic experiments revealed significantly increased true stresses (up to 10 times higher) after sulfonating only 2–3% of the copolymer while the materials maintained high elongation (<700%). The linear viscoelastic experiments showed that the storage and loss modulus are increased by sulfonation and that the copolymers can be readily tuned and further improved by increasing the number of branching points and the molecular weight of the backbone. Here, in this way, we show that by tuning not only the molecular characteristics of the multigraft copolymers but also their architecture and chemical interaction, we can acquire thermoplastic superelastomer materials with desired viscoelastic properties.},
doi = {10.1039/C7RA08641E},
journal = {RSC Advances},
number = 10,
volume = 8,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C7RA08641E

Figures / Tables:

Scheme 1 Scheme 1: (a) Synthesis of the PS macromonomer and (b) synthetic route and post-polymerization sulfonation of the multigraft copolymers.

Save / Share:

Works referenced in this record:

Morphological studies of a triblock copolymer ionomer by small-angle x-ray scattering
journal, November 1993

  • Lu, Xinya; Steckle, W. P.; Weiss, R. A.
  • Macromolecules, Vol. 26, Issue 24
  • DOI: 10.1021/ma00076a033

Investigations on mechanical properties of PI–PS multigraft copolymers
journal, October 2009


Thermoplastic Elastomers—Three Decades of Progress
journal, July 1989

  • Legge, N. R.
  • Rubber Chemistry and Technology, Vol. 62, Issue 3
  • DOI: 10.5254/1.3536257

Characterization and thermal properties of poly(n-butyl acrylate-g-styrene) graft copolymers
journal, January 2001


Synthesis and characterization of brush-like multigraft copolymers P n BA- g -PMMA by a combination of emulsion AGET ATRP and emulsion polymerization
journal, September 2015


Selective modification of block copolymers as proton exchange membranes
journal, November 2004


Influence of Site-Specific Sulfonation on Acrylic Graft Copolymer Morphology
journal, May 2008

  • Saito, Tomonori; Mather, Brian D.; Costanzo, Philip J.
  • Macromolecules, Vol. 41, Issue 10
  • DOI: 10.1021/ma800178d

Synthesis of well-defined multigraft copolymers
journal, January 2011


Rheological properties and crystallization behavior of comb-like graft poly( l -lactide): influences of graft length and graft density
journal, January 2016

  • Leng, Xuefei; Wei, Zhiyong; Bian, Yufei
  • RSC Advances, Vol. 6, Issue 36
  • DOI: 10.1039/C6RA02697D

Prediction of the Glass Transition Temperature of Multicyclic and Bulky Substituted Acrylate and Methacrylate Polymers Using the Energy, Volume, Mass (EVM) QSPR Model
journal, January 1996

  • Cypcar, Christopher C.; Camelio, Philippe; Lazzeri, Veronique
  • Macromolecules, Vol. 29, Issue 27
  • DOI: 10.1021/ma961170s

Theory of Microphase Separation in Block Copolymers
journal, November 1980


Interpretation of hysteresis behaviour of PI–PS multigraft copolymers by adapting to the dynamic flocculation model
journal, November 2008


Effect of Molecular Architecture on Dynamics of Multigraft Copolymers:  Combs, Centipedes, and Barbwires
journal, October 2003

  • Mijović, Jovan; Sun, Mingyun; Pejanović, Srdjan
  • Macromolecules, Vol. 36, Issue 20
  • DOI: 10.1021/ma034881g

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

Novel Synthetic Strategy for the Sulfonation of Polybutadiene and Styrene–Butadiene Copolymers
journal, January 2013

  • Buonerba, Antonio; Speranza, Vito; Grassi, Alfonso
  • Macromolecules, Vol. 46, Issue 3
  • DOI: 10.1021/ma301972m

Multigraft copolymer superelastomers: Synthesis morphology, and properties
journal, April 2011


Transport Properties of Sulfonated Poly(styrene- b -isobutylene- b -styrene) Triblock Copolymers at High Ion-Exchange Capacities
journal, January 2006

  • Elabd, Yossef A.; Napadensky, Eugene; Walker, Charles W.
  • Macromolecules, Vol. 39, Issue 1
  • DOI: 10.1021/ma051958n

Toughening elastomers using mussel-inspired iron-catechol complexes
journal, October 2017

  • Filippidi, Emmanouela; Cristiani, Thomas R.; Eisenbach, Claus D.
  • Science, Vol. 358, Issue 6362
  • DOI: 10.1126/science.aao0350

Thermoplastic elastomers: fundamentals and applications
journal, November 2000


Morphology and Tensile Properties of Multigraft Copolymers with Regularly Spaced Tri-, Tetra-, and Hexafunctional Junction Points
journal, June 2006

  • Zhu, Yuqing; Burgaz, Engin; Gido, Samuel P.
  • Macromolecules, Vol. 39, Issue 13
  • DOI: 10.1021/ma060067s

Synthesis and Characterization of Graft Copolymers Poly(isoprene- g -styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization
journal, January 2015

  • Wang, Wenwen; Wang, Weiyu; Li, Hui
  • Industrial & Engineering Chemistry Research, Vol. 54, Issue 4
  • DOI: 10.1021/ie504457e

Block copolymer ionomers: 1. Synthesis and physical properties of sulphonated poly(styrene-ethylene/butylene-styrene)
journal, January 1991


Structural characterization and surface modification of sulfonated polystyrene–(ethylene–butylene)–styrene triblock proton exchange membranes
journal, April 2003


All-Acrylic Multigraft Copolymers: Effect of Side Chain Molecular Weight and Volume Fraction on Mechanical Behavior
journal, September 2015

  • Goodwin, Andrew; Wang, Weiyu; Kang, Nam-Goo
  • Industrial & Engineering Chemistry Research, Vol. 54, Issue 39
  • DOI: 10.1021/acs.iecr.5b02560

Triblock copolymer ionomer membranes
journal, March 2004

  • Elabd, Yossef A.; Walker, Charles W.; Beyer, Frederick L.
  • Journal of Membrane Science, Vol. 231, Issue 1-2
  • DOI: 10.1016/j.memsci.2003.11.019

A new multiplet-cluster model for the morphology of random ionomers
journal, September 1990

  • Eisenberg, A.; Hird, B.; Moore, R. B.
  • Macromolecules, Vol. 23, Issue 18
  • DOI: 10.1021/ma00220a012

Effect of Molecular Architecture on Phase Behavior of Graft Copolymers
journal, August 2008

  • Zhang, Liangshun; Lin, Jiaping; Lin, Shaoliang
  • The Journal of Physical Chemistry B, Vol. 112, Issue 32
  • DOI: 10.1021/jp802770z

High-Strain-Induced Deformation Mechanisms in Block–Graft and Multigraft Copolymers
journal, December 2011

  • Schlegel, R.; Duan, Y. X.; Weidisch, R.
  • Macromolecules, Vol. 44, Issue 23
  • DOI: 10.1021/ma201353w

Polymers with Complex Architecture by Living Anionic Polymerization
journal, December 2001

  • Hadjichristidis, Nikos; Pitsikalis, Marinos; Pispas, Stergios
  • Chemical Reviews, Vol. 101, Issue 12
  • DOI: 10.1021/cr9901337

Stress softening of multigraft copolymers
journal, December 2009


Triblock copolymer ionomer membranes
journal, June 2003


Morphology and transport properties of protons and methanol through partially sulfonated block copolymers
journal, March 2005


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.