Cellulose nanocrystal-reinforced poly(5-triethoxysilyl-2-norbornene) composites

Hendren, Keith D.; Higgins, Morgan A.; Long, Brian K.; Foster, E. Johan

doi:10.1039/c9py00963a

Cellulose nanocrystal-reinforced poly(5-triethoxysilyl-2-norbornene) composites

Journal Article · Wed Sep 18 00:00:00 EDT 2019 · Polymer Chemistry

DOI:https://doi.org/10.1039/c9py00963a· OSTI ID:1595332

^[1]; Higgins, Morgan A. ^[2]; ^[2]; ^[3]

Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Univ. of Tennessee
Univ. of Tennessee, Knoxville, TN (United States)
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Tennessee, Knoxville, TN (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0018179

OSTI ID:: 1595332

Alternate ID(s):: OSTI ID: 1566264

Journal Information:: Polymer Chemistry, Journal Name: Polymer Chemistry Journal Issue: 2 Vol. 11; ISSN PCOHC2; ISSN 1759-9954

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (28)

Preparation of poly(styrene- co -hexylacrylate)/cellulose whiskers nanocomposites via miniemulsion polymerization Elmabrouk, Aymen Ben; Wim, Thielemans; Dufresne, Alain Journal of Applied Polymer Science, Vol. 114, Issue 5 https://doi.org/10.1002/app.30886	journal	December 2009
Fabrication and Properties of Polyethylene/Cellulose Nanocrystal Composites Sapkota, Janak; Natterodt, Jens C.; Shirole, Anuja Macromolecular Materials and Engineering, Vol. 302, Issue 1 https://doi.org/10.1002/mame.201600300	journal	August 2016
Reinforcing Poly(ethylene) with Cellulose Nanocrystals Sapkota, Janak; Jorfi, Mehdi; Weder, Christoph Macromolecular Rapid Communications, Vol. 35, Issue 20 https://doi.org/10.1002/marc.201400382	journal	September 2014
Studies of interactions between silane coupling agents and cellulose fibers with liquid and solid-state NMR Salon, Marie-Christine B.; Gerbaud, Guillaume; Abdelmouleh, M. Magnetic Resonance in Chemistry, Vol. 45, Issue 6 https://doi.org/10.1002/mrc.1994	journal	June 2007
Mechanical percolation in cellulose whisker nanocomposites Favier, V.; Cavaille, J. Y.; Canova, G. R. Polymer Engineering & Science, Vol. 37, Issue 10 https://doi.org/10.1002/pen.11821	journal	October 1997
Synthesis and characterization of mechanically flexible and tough cellulose nanocrystals–polyacrylamide nanocomposite hydrogels Yang, Jun; Han, Chun-Rui; Duan, Jiu-Fang Cellulose, Vol. 20, Issue 1 https://doi.org/10.1007/s10570-012-9841-y	journal	February 2013
A comparative guide to controlled hydrophobization of cellulose nanocrystals via surface esterification Peng, Shane X.; Chang, Huibin; Kumar, Satish Cellulose, Vol. 23, Issue 3 https://doi.org/10.1007/s10570-016-0912-3	journal	March 2016
Cellulose-based nanocomposites prepared via mini-emulsion polymerization: Understanding the chemistry of the nanocellulose/matrix interface Mabrouk, A. Ben; Salon, M. C. Brochier; Magnin, A. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 448 https://doi.org/10.1016/j.colsurfa.2014.01.077	journal	April 2014
Investigation on the effect of cellulosic nanoparticles’ morphology on the properties of natural rubber based nanocomposites Bendahou, Abdelkader; Kaddami, Hamid; Dufresne, Alain European Polymer Journal, Vol. 46, Issue 4 https://doi.org/10.1016/j.eurpolymj.2009.12.025	journal	April 2010
A detailed investigation into the gas permeation properties of addition-type poly(5-triethoxysilyl-2-norbornene) Belov, Nikolay; Nikiforov, Roman; Starannikova, Ludmila European Polymer Journal, Vol. 93 https://doi.org/10.1016/j.eurpolymj.2017.06.030	journal	August 2017
Tensile and thermal properties of nanocellulose-reinforced poly(vinyl alcohol) nanocomposites Cho, Mi-Jung; Park, Byung-Dae Journal of Industrial and Engineering Chemistry, Vol. 17, Issue 1 https://doi.org/10.1016/j.jiec.2010.10.006	journal	January 2011
Molecular dynamics of poly(styrene-co-2-ethyl hexylacrylate) copolymer/cellulose nanocrystals nanocomposites investigated by dielectric relaxation spectroscopy: Effect of the silane content Ladhar, A.; Arous, M.; Boufi, S. Journal of Molecular Liquids, Vol. 224 https://doi.org/10.1016/j.molliq.2016.10.031	journal	December 2016
Cellulose nanocrystal: A promising toughening agent for unsaturated polyester nanocomposite Kargarzadeh, Hanieh; M. Sheltami, Rasha; Ahmad, Ishak Polymer, Vol. 56 https://doi.org/10.1016/j.polymer.2014.11.054	journal	January 2015
Dielectric properties of nanocomposites based on cellulose nanocrystals (CNCs) and poly(styrene-co-2-ethyl hexylacrylate) copolymer Ladhar, A.; Ben Mabrouk, A.; Arous, M. Polymer, Vol. 125 https://doi.org/10.1016/j.polymer.2017.07.090	journal	September 2017
Surface-modified cellulose nanocrystals for biobased epoxy nanocomposites Yue, Liang; Maiorana, Anthony; Khelifa, Farid Polymer, Vol. 134 https://doi.org/10.1016/j.polymer.2017.11.051	journal	January 2018
Polymer Nanocomposites with Cellulose Nanocrystals Featuring Adaptive Surface Groups Natterodt, Jens C.; Sapkota, Janak; Foster, E. Johan Biomacromolecules, Vol. 18, Issue 2 https://doi.org/10.1021/acs.biomac.6b01639	journal	January 2017
Accessing Siloxane Functionalized Polynorbornenes via Vinyl-Addition Polymerization for CO ₂ Separation Membranes Gmernicki, Kevin R.; Hong, Eunice; Maroon, Christopher R. ACS Macro Letters, Vol. 5, Issue 7 https://doi.org/10.1021/acsmacrolett.6b00435	journal	June 2016
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 Kono, Hiroyuki; Yunoki, Shunji; Shikano, Tamio Journal of the American Chemical Society, Vol. 124, Issue 25 https://doi.org/10.1021/ja010704o	journal	June 2002
Nonflocculating and Chiral-Nematic Self-ordering of Cellulose Microcrystals Suspensions in Nonpolar Solvents Heux, L.; Chauve, G.; Bonini, C. Langmuir, Vol. 16, Issue 21 https://doi.org/10.1021/la9913957	journal	October 2000
Glassy Polynorbornenes with Si–O–Si Containing Side Groups. Novel Materials for Hydrocarbon Membrane Separation Bermeshev, Maxim V.; Syromolotov, Alexandr V.; Starannikova, Ludmila E. Macromolecules, Vol. 46, Issue 22 https://doi.org/10.1021/ma4021278	journal	November 2013
Biobased Nanocomposites Prepared by In Situ Polymerization of Furfuryl Alcohol with Cellulose Whiskers or Montmorillonite Clay Pranger, Lawrence; Tannenbaum, Rina Macromolecules, Vol. 41, Issue 22 https://doi.org/10.1021/ma8020213	journal	November 2008
Light-Healable Supramolecular Nanocomposites Based on Modified Cellulose Nanocrystals Biyani, Mahesh V.; Foster, E. Johan; Weder, Christoph ACS Macro Letters, Vol. 2, Issue 3 https://doi.org/10.1021/mz400059w	journal	February 2013
Current characterization methods for cellulose nanomaterials Foster, E. Johan; Moon, Robert J.; Agarwal, Umesh P. Chemical Society Reviews, Vol. 47, Issue 8 https://doi.org/10.1039/C6CS00895J	journal	January 2018
Alkoxysilyl functionalized polynorbornenes with enhanced selectivity for heavy hydrocarbon separations Sundell, Benjamin J.; Lawrence III, John A.; Harrigan, Daniel J. RSC Advances, Vol. 6, Issue 57 https://doi.org/10.1039/C6RA10383A	journal	January 2016
Cellulose nanomaterials review: structure, properties and nanocomposites Moon, Robert J.; Martini, Ashlie; Nairn, John Chemical Society Reviews, Vol. 40, Issue 7 https://doi.org/10.1039/c0cs00108b	journal	January 2011
Studies on the properties and formation mechanism of flexible nanocomposite hydrogels from cellulose nanocrystals and poly(acrylic acid) Yang, Jun; Han, Chun-Rui; Duan, Jiu-Fang Journal of Materials Chemistry, Vol. 22, Issue 42 https://doi.org/10.1039/c2jm35498e	journal	January 2012
Nanocellulose Dufresne, Alain https://doi.org/10.1515/9783110480412	book	November 2017
Recent Advances in Nanocellulose Composites with Polymers: A Guide for Choosing Partners and How to Incorporate Them Chakrabarty, Arindam; Teramoto, Yoshikuni Polymers, Vol. 10, Issue 5 https://doi.org/10.3390/polym10050517	journal	May 2018

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