Cellulose nanocrystal-reinforced poly(5-triethoxysilyl-2-norbornene) composites
Abstract
Here, we demonstrate the reinforcement of a previously inaccessible norbornene-silane with a stiff, bio-based nanofiller. Poly(5-triethoxysilyl-2-norbornene) (PTESN), a glassy and thermally stable polymer, was combined with cellulose nanocrystals (CNCs) and solvent cast from toluene to form reinforced materials. Composite films showed excellent translucency and no visible aggregation, which was supported by scanning electron micrographs that showed no signs of CNC aggregation within the polymer matrix. Reinforcement was evident at the moderate loading of 5 wt% CNC, showing a statistically significant enhancement for Young's modulus and even greater reinforcement for 20 wt% CNC loading for Young's modulus (540 MPa vs. 970 MPa) and storage modulus at 25 °C (400 MPa vs. 1200 MPa). We anticipate that there is a strong interaction between the polymer and CNC filler based upon the increase of thermal degradation temperature of the CNCs increasing, for example from 278 °C to 295 °C at 10 wt% CNCs. These interactions were probed via solid-state NMR, which suggests that no covalent bonding occurs between the triethoxylsilyl substituents of the polymer and the CNCs. We therefore hypothesize that hydrogen bonding interactions between PTESN and CNCs are responsible for the increased thermal stability and reinforcement of the polymer material.
- Authors:
-
[1];
[2];
[1]
- Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
- Univ. of Tennessee, Knoxville, TN (United States)
- Publication Date:
- Research Org.:
- Univ. of Tennessee, Knoxville, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1595332
- Alternate Identifier(s):
- OSTI ID: 1566264
- Grant/Contract Number:
- SC0018179
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Polymer Chemistry
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 2; Journal ID: ISSN 1759-9954
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Hendren, Keith D., Higgins, Morgan A., Long, Brian K., and Foster, E. Johan. Cellulose nanocrystal-reinforced poly(5-triethoxysilyl-2-norbornene) composites. United States: N. p., 2019.
Web. doi:10.1039/c9py00963a.
Hendren, Keith D., Higgins, Morgan A., Long, Brian K., & Foster, E. Johan. Cellulose nanocrystal-reinforced poly(5-triethoxysilyl-2-norbornene) composites. United States. https://doi.org/10.1039/c9py00963a
Hendren, Keith D., Higgins, Morgan A., Long, Brian K., and Foster, E. Johan. Wed .
"Cellulose nanocrystal-reinforced poly(5-triethoxysilyl-2-norbornene) composites". United States. https://doi.org/10.1039/c9py00963a. https://www.osti.gov/servlets/purl/1595332.
@article{osti_1595332,
title = {Cellulose nanocrystal-reinforced poly(5-triethoxysilyl-2-norbornene) composites},
author = {Hendren, Keith D. and Higgins, Morgan A. and Long, Brian K. and Foster, E. Johan},
abstractNote = {Here, we demonstrate the reinforcement of a previously inaccessible norbornene-silane with a stiff, bio-based nanofiller. Poly(5-triethoxysilyl-2-norbornene) (PTESN), a glassy and thermally stable polymer, was combined with cellulose nanocrystals (CNCs) and solvent cast from toluene to form reinforced materials. Composite films showed excellent translucency and no visible aggregation, which was supported by scanning electron micrographs that showed no signs of CNC aggregation within the polymer matrix. Reinforcement was evident at the moderate loading of 5 wt% CNC, showing a statistically significant enhancement for Young's modulus and even greater reinforcement for 20 wt% CNC loading for Young's modulus (540 MPa vs. 970 MPa) and storage modulus at 25 °C (400 MPa vs. 1200 MPa). We anticipate that there is a strong interaction between the polymer and CNC filler based upon the increase of thermal degradation temperature of the CNCs increasing, for example from 278 °C to 295 °C at 10 wt% CNCs. These interactions were probed via solid-state NMR, which suggests that no covalent bonding occurs between the triethoxylsilyl substituents of the polymer and the CNCs. We therefore hypothesize that hydrogen bonding interactions between PTESN and CNCs are responsible for the increased thermal stability and reinforcement of the polymer material.},
doi = {10.1039/c9py00963a},
journal = {Polymer Chemistry},
number = 2,
volume = 11,
place = {United States},
year = {Wed Sep 18 00:00:00 EDT 2019},
month = {Wed Sep 18 00:00:00 EDT 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 2 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Polymer Nanocomposites with Cellulose Nanocrystals Featuring Adaptive Surface Groups
journal, January 2017
- Natterodt, Jens C.; Sapkota, Janak; Foster, E. Johan
- Biomacromolecules, Vol. 18, Issue 2
Synthesis and characterization of mechanically flexible and tough cellulose nanocrystals–polyacrylamide nanocomposite hydrogels
journal, February 2013
- Yang, Jun; Han, Chun-Rui; Duan, Jiu-Fang
- Cellulose, Vol. 20, Issue 1
Surface-modified cellulose nanocrystals for biobased epoxy nanocomposites
journal, January 2018
- Yue, Liang; Maiorana, Anthony; Khelifa, Farid
- Polymer, Vol. 134
Mechanical percolation in cellulose whisker nanocomposites
journal, October 1997
- Favier, V.; Cavaille, J. Y.; Canova, G. R.
- Polymer Engineering & Science, Vol. 37, Issue 10
Tensile and thermal properties of nanocellulose-reinforced poly(vinyl alcohol) nanocomposites
journal, January 2011
- Cho, Mi-Jung; Park, Byung-Dae
- Journal of Industrial and Engineering Chemistry, Vol. 17, Issue 1
Dielectric properties of nanocomposites based on cellulose nanocrystals (CNCs) and poly(styrene-co-2-ethyl hexylacrylate) copolymer
journal, September 2017
- Ladhar, A.; Ben Mabrouk, A.; Arous, M.
- Polymer, Vol. 125
CP/MAS 13 C NMR Study of Cellulose and Cellulose Derivatives. 1. Complete Assignment of the CP/MAS 13 C NMR Spectrum of the Native Cellulose
journal, June 2002
- Kono, Hiroyuki; Yunoki, Shunji; Shikano, Tamio
- Journal of the American Chemical Society, Vol. 124, Issue 25
Molecular dynamics of poly(styrene-co-2-ethyl hexylacrylate) copolymer/cellulose nanocrystals nanocomposites investigated by dielectric relaxation spectroscopy: Effect of the silane content
journal, December 2016
- Ladhar, A.; Arous, M.; Boufi, S.
- Journal of Molecular Liquids, Vol. 224
Cellulose-based nanocomposites prepared via mini-emulsion polymerization: Understanding the chemistry of the nanocellulose/matrix interface
journal, April 2014
- Mabrouk, A. Ben; Salon, M. C. Brochier; Magnin, A.
- Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 448
Accessing Siloxane Functionalized Polynorbornenes via Vinyl-Addition Polymerization for CO 2 Separation Membranes
journal, June 2016
- Gmernicki, Kevin R.; Hong, Eunice; Maroon, Christopher R.
- ACS Macro Letters, Vol. 5, Issue 7
Fabrication and Properties of Polyethylene/Cellulose Nanocrystal Composites
journal, August 2016
- Sapkota, Janak; Natterodt, Jens C.; Shirole, Anuja
- Macromolecular Materials and Engineering, Vol. 302, Issue 1
A detailed investigation into the gas permeation properties of addition-type poly(5-triethoxysilyl-2-norbornene)
journal, August 2017
- Belov, Nikolay; Nikiforov, Roman; Starannikova, Ludmila
- European Polymer Journal, Vol. 93
Light-Healable Supramolecular Nanocomposites Based on Modified Cellulose Nanocrystals
journal, February 2013
- Biyani, Mahesh V.; Foster, E. Johan; Weder, Christoph
- ACS Macro Letters, Vol. 2, Issue 3
Investigation on the effect of cellulosic nanoparticles’ morphology on the properties of natural rubber based nanocomposites
journal, April 2010
- Bendahou, Abdelkader; Kaddami, Hamid; Dufresne, Alain
- European Polymer Journal, Vol. 46, Issue 4
Alkoxysilyl functionalized polynorbornenes with enhanced selectivity for heavy hydrocarbon separations
journal, January 2016
- Sundell, Benjamin J.; Lawrence III, John A.; Harrigan, Daniel J.
- RSC Advances, Vol. 6, Issue 57
Biobased Nanocomposites Prepared by In Situ Polymerization of Furfuryl Alcohol with Cellulose Whiskers or Montmorillonite Clay
journal, November 2008
- Pranger, Lawrence; Tannenbaum, Rina
- Macromolecules, Vol. 41, Issue 22
A comparative guide to controlled hydrophobization of cellulose nanocrystals via surface esterification
journal, March 2016
- Peng, Shane X.; Chang, Huibin; Kumar, Satish
- Cellulose, Vol. 23, Issue 3
Cellulose nanocrystal: A promising toughening agent for unsaturated polyester nanocomposite
journal, January 2015
- Kargarzadeh, Hanieh; M. Sheltami, Rasha; Ahmad, Ishak
- Polymer, Vol. 56
Glassy Polynorbornenes with Si–O–Si Containing Side Groups. Novel Materials for Hydrocarbon Membrane Separation
journal, November 2013
- Bermeshev, Maxim V.; Syromolotov, Alexandr V.; Starannikova, Ludmila E.
- Macromolecules, Vol. 46, Issue 22
Recent Advances in Nanocellulose Composites with Polymers: A Guide for Choosing Partners and How to Incorporate Them
journal, May 2018
- Chakrabarty, Arindam; Teramoto, Yoshikuni
- Polymers, Vol. 10, Issue 5
Studies of interactions between silane coupling agents and cellulose fibers with liquid and solid-state NMR
journal, June 2007
- Salon, Marie-Christine B.; Gerbaud, Guillaume; Abdelmouleh, M.
- Magnetic Resonance in Chemistry, Vol. 45, Issue 6
Current characterization methods for cellulose nanomaterials
journal, January 2018
- Foster, E. Johan; Moon, Robert J.; Agarwal, Umesh P.
- Chemical Society Reviews, Vol. 47, Issue 8
Preparation of poly(styrene- co -hexylacrylate)/cellulose whiskers nanocomposites via miniemulsion polymerization
journal, December 2009
- Elmabrouk, Aymen Ben; Wim, Thielemans; Dufresne, Alain
- Journal of Applied Polymer Science, Vol. 114, Issue 5
Studies on the properties and formation mechanism of flexible nanocomposite hydrogels from cellulose nanocrystals and poly(acrylic acid)
journal, January 2012
- Yang, Jun; Han, Chun-Rui; Duan, Jiu-Fang
- Journal of Materials Chemistry, Vol. 22, Issue 42
Reinforcing Poly(ethylene) with Cellulose Nanocrystals
journal, September 2014
- Sapkota, Janak; Jorfi, Mehdi; Weder, Christoph
- Macromolecular Rapid Communications, Vol. 35, Issue 20
Nonflocculating and Chiral-Nematic Self-ordering of Cellulose Microcrystals Suspensions in Nonpolar Solvents
journal, October 2000
- Heux, L.; Chauve, G.; Bonini, C.
- Langmuir, Vol. 16, Issue 21