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

This content will become publicly available on April 25, 2020

Title: An Ionomeric Renewable Thermoplastic from Lignin-Reinforced Rubber

Abstract

An ionomeric, leathery thermoplastic with high mechanical strength is prepared by a new thermal processing method from a soft, melt-processable rubber. Compositions made by incorporation of equal-mass lignin, a renewable oligomeric feedstock, in an acrylonitrile-butadiene rubber often yield weak rubbers with large lignin domains (1–2 µm). The addition of zinc chloride (ZnCl2) in such a composition based on sinapyl alcohol-rich lignin during a solvent-free synthesis induces a strong interfacial crosslinking between lignin and rubber phases. This compositional modification results in finely interspersed lignin domains (<100 nm) that essentially reinforce the rubbery matrix with a 10–22 °C rise in the glassy-to-rubbery transition temperature. The ion-modified polymer blends also show improved materials properties, like a 100% increase in ultimate tensile strength and an order of magnitude rise in Young's modulus. Coarse-grained molecular dynamics (MD) simulations verify the morphology and dynamics of the ionomeric material. The computed result also confirms that the ionomers have glassy characteristics.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
OSTI Identifier:
1559703
Alternate Identifier(s):
OSTI ID: 1508878
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecular Rapid Communications
Additional Journal Information:
Journal Volume: 40; Journal Issue: 13; Journal ID: ISSN 1022-1336
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ionomeric thermoplastic; lignin; melt‐rheology; molecular dynamics simulation; small‐angle X‐ray scattering

Citation Formats

Barnes, Sietske H., Goswami, Monojoy, Nguyen, Ngoc A., Keum, Jong K., Bowland, Christopher C., Chen, Jihua, and Naskar, Amit K. An Ionomeric Renewable Thermoplastic from Lignin-Reinforced Rubber. United States: N. p., 2019. Web. doi:10.1002/marc.201900059.
Barnes, Sietske H., Goswami, Monojoy, Nguyen, Ngoc A., Keum, Jong K., Bowland, Christopher C., Chen, Jihua, & Naskar, Amit K. An Ionomeric Renewable Thermoplastic from Lignin-Reinforced Rubber. United States. doi:10.1002/marc.201900059.
Barnes, Sietske H., Goswami, Monojoy, Nguyen, Ngoc A., Keum, Jong K., Bowland, Christopher C., Chen, Jihua, and Naskar, Amit K. Thu . "An Ionomeric Renewable Thermoplastic from Lignin-Reinforced Rubber". United States. doi:10.1002/marc.201900059.
@article{osti_1559703,
title = {An Ionomeric Renewable Thermoplastic from Lignin-Reinforced Rubber},
author = {Barnes, Sietske H. and Goswami, Monojoy and Nguyen, Ngoc A. and Keum, Jong K. and Bowland, Christopher C. and Chen, Jihua and Naskar, Amit K.},
abstractNote = {An ionomeric, leathery thermoplastic with high mechanical strength is prepared by a new thermal processing method from a soft, melt-processable rubber. Compositions made by incorporation of equal-mass lignin, a renewable oligomeric feedstock, in an acrylonitrile-butadiene rubber often yield weak rubbers with large lignin domains (1–2 µm). The addition of zinc chloride (ZnCl2) in such a composition based on sinapyl alcohol-rich lignin during a solvent-free synthesis induces a strong interfacial crosslinking between lignin and rubber phases. This compositional modification results in finely interspersed lignin domains (<100 nm) that essentially reinforce the rubbery matrix with a 10–22 °C rise in the glassy-to-rubbery transition temperature. The ion-modified polymer blends also show improved materials properties, like a 100% increase in ultimate tensile strength and an order of magnitude rise in Young's modulus. Coarse-grained molecular dynamics (MD) simulations verify the morphology and dynamics of the ionomeric material. The computed result also confirms that the ionomers have glassy characteristics.},
doi = {10.1002/marc.201900059},
journal = {Macromolecular Rapid Communications},
number = 13,
volume = 40,
place = {United States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on April 25, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

A novel nitrile butadiene rubber/zinc chloride composite: Coordination reaction and miscibility
journal, April 2012


Polymer matrix nanocomposites for automotive structural components
journal, December 2016

  • Naskar, Amit K.; Keum, Jong K.; Boeman, Raymond G.
  • Nature Nanotechnology, Vol. 11, Issue 12
  • DOI: 10.1038/nnano.2016.262

Small-angle x-ray scattering investigations of ionomers with variable-length side chains
journal, November 1991

  • Moore, Robert B.; Bittencourt, Diomar; Gauthier, Mario
  • Macromolecules, Vol. 24, Issue 6
  • DOI: 10.1021/ma00006a024

Computer Simulations of Ionomer Self-Assembly and Dynamics
journal, June 2007

  • Goswami, Monojoy; Kumar, Sanat K.; Bhattacharya, Aniket
  • Macromolecules, Vol. 40, Issue 12
  • DOI: 10.1021/ma070074w

Lignin Structural Variation in Hardwood Species
journal, May 2012

  • Santos, Ricardo B.; Capanema, Ewellyn A.; Balakshin, Mikhail Yu.
  • Journal of Agricultural and Food Chemistry, Vol. 60, Issue 19
  • DOI: 10.1021/jf301276a

Spherical and vesicular ionic aggregates in Zn-neutralized sulfonated polystyrene ionomers
journal, January 2001


Sustainable Elastomers from Renewable Biomass
journal, June 2017


A path for lignin valorization via additive manufacturing of high-performance sustainable composites with enhanced 3D printability
journal, December 2018

  • Nguyen, Ngoc A.; Barnes, Sietske H.; Bowland, Christopher C.
  • Science Advances, Vol. 4, Issue 12
  • DOI: 10.1126/sciadv.aat4967

Responsive lignin for shape memory applications
journal, January 2019


Lignin-Based Triple Shape Memory Polymers
journal, August 2015


An approach towards tailoring interfacial structures and properties of multiphase renewable thermoplastics from lignin–nitrile rubber
journal, January 2016

  • Bova, Tony; Tran, Chau D.; Balakshin, Mikhail Y.
  • Green Chemistry, Vol. 18, Issue 20
  • DOI: 10.1039/C6GC01067A

Nanoscale Morphology in Precisely Sequenced Poly(ethylene- co -acrylic acid) Zinc Ionomers
journal, June 2010

  • Seitz, Michelle E.; Chan, Christopher D.; Opper, Kathleen L.
  • Journal of the American Chemical Society, Vol. 132, Issue 23
  • DOI: 10.1021/ja101991d

Counterion Effect on the Rheology and Morphology of Tailored Poly(dimethylsiloxane) Ionomers
journal, February 2006

  • Batra, Ashish; Cohen, Claude; Kim, Hansoo
  • Macromolecules, Vol. 39, Issue 4
  • DOI: 10.1021/ma052275a

Lignin: a nature-inspired sun blocker for broad-spectrum sunscreens
journal, January 2015

  • Qian, Yong; Qiu, Xueqing; Zhu, Shiping
  • Green Chemistry, Vol. 17, Issue 1
  • DOI: 10.1039/C4GC01333F

Polymers from Renewable Resources: A Perspective for a Special Issue of Polymer Reviews
journal, January 2008


Effect of Polymer Architecture and Ionic Aggregation on the Scattering Peak in Model Ionomers
journal, March 2011


Investigation on crosslinking behaviors of NBR/PVC filled with anhydrous copper sulfate particles by dynamic mechanical analysis
journal, January 2006

  • Shen, Fei; Yuan, Xiaofang; Wu, Chifei
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 45, Issue 1
  • DOI: 10.1002/polb.20977

Molecular Origins of the Thermal Transitions and Dynamic Mechanical Relaxations in Perfluorosulfonate Ionomers
journal, July 2005

  • Page, Kirt A.; Cable, Kevin M.; Moore, Robert B.
  • Macromolecules, Vol. 38, Issue 15
  • DOI: 10.1021/ma0503559

An Acrylonitrile–Butadiene–Lignin Renewable Skin with Programmable and Switchable Electrical Conductivity for Stress/Strain-Sensing Applications
journal, December 2017


Self-assembled highly ordered acid layers in precisely sulfonated polyethylene produce efficient proton transport
journal, May 2018


Ionic Aggregate Structure in Ionomer Melts: Effect of Molecular Architecture on Aggregates and the Ionomer Peak
journal, December 2011

  • Hall, Lisa M.; Seitz, Michelle E.; Winey, Karen I.
  • Journal of the American Chemical Society, Vol. 134, Issue 1
  • DOI: 10.1021/ja209142b

Unexpected variation in lignin
journal, April 1999


A New Class of Renewable Thermoplastics with Extraordinary Performance from Nanostructured Lignin-Elastomers
journal, March 2016

  • Tran, Chau D.; Chen, Jihua; Keum, Jong K.
  • Advanced Functional Materials, Vol. 26, Issue 16, p. 2677-2685
  • DOI: 10.1002/adfm.201504990

Composites from renewable and sustainable resources: Challenges and innovations
journal, November 2018

  • Mohanty, Amar K.; Vivekanandhan, Singaravelu; Pin, Jean-Mathieu
  • Science, Vol. 362, Issue 6414
  • DOI: 10.1126/science.aat9072

Analysis of small-angle x-ray scattering data for model polyurethane ionomers: evaluation of hard-sphere models
journal, April 1991

  • Visser, Susan A.; Cooper, Stuart L.
  • Macromolecules, Vol. 24, Issue 9
  • DOI: 10.1021/ma00009a068

Acid-Catalyzed Cross-Linking Reactions at Benzylic Sites in Fluorene Monomers, Polymers, and Lignin 1
journal, September 1999

  • Hagaman, Edward W.; Lee, S. K.
  • Energy & Fuels, Vol. 13, Issue 5
  • DOI: 10.1021/ef980269s

Dynamics of entangled linear polymer melts:  A molecular‐dynamics simulation
journal, April 1990

  • Kremer, Kurt; Grest, Gary S.
  • The Journal of Chemical Physics, Vol. 92, Issue 8
  • DOI: 10.1063/1.458541

Morphologies of block copolymers composed of charged and neutral blocks
journal, January 2012

  • Wang, Xiaojun; Goswami, Monojoy; Kumar, Rajeev
  • Soft Matter, Vol. 8, Issue 11
  • DOI: 10.1039/c2sm07223h