Research Article

pubs.acs.org/journal/ascecg

Green One-Pot Synthesis of Surface Hydrophobized Cellulose

Nanocrystals in Aqueous Medium
Youngman Yoo and Jeffrey P. Youngblood*
School of Materials Engineering, Purdue University, West Lafayette, Indiana 47907, United States
*
S Supporting Information

ABSTRACT: The surface hydrophobization of cellulose

nanocrystals (CNCs) by fatty acids (FAs), biodiesel, or plant
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oils was conducted via a green process using an organic solvent

less one-pot method. In the process, an aqueous lactic acid
syrup served as a reactive solvent to provide a stable and well-
dispersed water suspension of CNC and participate in esteri-
fication reactions, producing an intermediate product of
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polylactic acid (PLA) oligomer grafted CNCs (CNC-g-PLA).

This reactive solvent and intermediate product system allows
for an in situ solvent exchange from water to lactic acid
without prior drying of the CNC and a subsequent efficient
esterification reaction of CNC with carboxylic acids or esters
having a long hydrocarbon chain (FAs). Another advantage of the proposed process is the possibility to reuse the reagents in the
subsequent reaction in order to reduce the production cost. The grafting efficiency of the CNC-g-PLA-FA samples covalently
grafted with PLA and FAs were characterized by Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), and
13
C nuclear magnetic resonance spectroscopy (ss-NMR). The change of dimensions and degree of crystallinity of the modified
CNC was evaluated by dynamic light scattering (DLS) and X-ray diffraction (XRD). Different organic solvents were used here to
investigate the relative hydrophobicity of the modified CNCs comparing the transmittance of their suspensions in the ultraviolet
and visible (UV−vis) spectrometer, and evaluating their hydrodynamic radius by dynamic light scattering (DLS) techniques.
Grafting of renewable materials on the surface of CNCs was developed by polyesterification that is capable of being
environmentally friendly and mass-produced without any organic solvents or toxic reagents.
KEYWORDS: Cellulose nanocrystals, Hydrophobicity, Surface modification, Dispersibility, Teas plot, Esterification

■ INTRODUCTION
Cellulose is the most abundant biobased material on earth (more
than 50% of the biomass). This cellulose occurs naturally in, for
example, trees, cotton, bacteria, and algae. The cellulose fibers in
wood are composed of amorphous and crystalline regions. These
crystalline regions are rod-shaped, nanosized particles remaining
after the acid hydrolysis of amorphous regions of cellulose fibers.
During the past decade, there has been great interest in cellulose
nanocrystals (CNCs) due to their unique characteristics; they
have a high aspect ratio, low coefficient of thermal expansion,
high thermal conductivity, are 100% renewable, very strong, stiff,
and resilient. Therefore, the intriguing ability of CNCs to
reinforce host materials and form a dense network leads to highly
versatile, sustainable, and environmentally friendly polymer com-
posites capable of enhancing mechanical, thermal, and physical
properties.1−7
However, there are limitations and drawbacks, which are
linked to their intrinsic physical properties including high
moisture absorption of CNC based materials, agglomeration of
nanoparticles, difficulty in redispersing agglomerated particles,
and incompatibility with hydrophobic polymers in nanocom-
posite applications. The last of these limits the use of CNCs as
reinforcing agents for thermoplastic composite applications due
to the low compatibility of CNCs in organic media (both
solvents and polymer matrices). Moreover, even if relatively
compatible, it is not easy to redisperse the agglomerated CNCs
caused by the strong hydrogen bonding of the crystals into a
solution or polymer matrix.8,9 However, the most optimal
solution to this issue is surface hydrophobization of CNCs which
is achieved by the use of direct chemical modification, as cellulose
has an enormous amount of hydroxyl groups in its structure.10
When carbodiimide, isocyanates, epoxides, acid anhydrides, acid
halides, and alkyl halides are used as a covalent attachment of
molecules, they react with the surface hydroxyl groups of cellu-
lose to yield hydrophobic surfaces bearing hydrocarbon moieties
that promote an excellent dispersion of CNCs in organic
media.8,11−15 Moisture sensitivity and corresponding dimen-
sional changes can be considerably avoided if the CNC is fairly
modified by hydrophobic attachments and there are strong
interactions between the modified CNC and polymer matrix.
Functionalization of CNCs has already been much reported in
the literature using (1) physical adsorption of some types of
Received: April 15, 2016
Revised: May 23, 2016
Published: May 23, 2016

© 2016 American Chemical Society 3927 DOI: 10.1021/acssuschemeng.6b00781

ACS Sustainable Chem. Eng. 2016, 4, 3927−3938
ACS Sustainable Chemistry & Engineering
surfactants,16−20 (2) covalent attachment of molecules,21−32 and
(3) grafting polymers at the surface of the CNCs.32−42
Nonetheless, most of these techniques require the use of
hazardous solvents and reactants that are toxic to human health
and the environment. These solvents and reactants are also too
expensive to be utilized in large-scale industrial applications.
It is difficult for CNCs to react with organic reagents directly
due to their poor solubility in the organic phase. CNCs in a water
suspension typically need a solvent exchange with dimethyl
sulfoxide (DMSO), dimethylformamide (DMF), or other com-
patible solvent. They also need special reagents such as acid
chloride, acid anhydride, isocyanate or carbodiimide, which can
be difficult to handle and are expensive. Furthermore, process
lines exposed to organic solvents that release high levels of
volatile organic compounds (VOCs) as chemical gases can
pollute the air and have a harmful effect on human health.
Nowadays, regulators and consumers are increasingly demand-
ing products that emit lower levels of VOCs. Therefore, there has
been a great effort from both academia and industry in the
development of green technologies capable of changing the use
of toxic organic solvents to safer alternatives such as solvent-free
reactions or aqueous media reactions.43 All the research projects
related to this issue aim to reduce solvent-derived environmental
harm. Therefore, the development of safer, more economically
feasible, and more ecofriendly methods, accompanied by higher
grafting yields is needed.
In this paper, we focus on the surface hydrophobization of
cellulose nanocrystals in aqueous conditions. The main strategies
of this research are to replace toxic solvents and reagents
(nonbiodegradable) with greener alternatives, which pose no
health risk to workers, are less volatile, and have low VOCs, but
are easily biodegradable, and to change the approaches to a
grafting method that does not require organic solvents. This
study also suggests that the reactants, which are presented in this
paper, can be recycled after reaction in order to reduce the envi-
ronmental footprint of the product as well as enhance economic
feasibility. To achieve this, we suggest using aqueous DL-lactic
acid syrup, which can be oligomerized by water distillation. The
byproduct, polylactic acid (PLA) oligomers, and unreacted lactic
acid act as a solvent for the CNCs instead of water, yielding an
intermediate product of a short chain PLA grafted CNC in the
first step. Then, the PLA oligomer grafted CNC (CNC-g-PLA)
can be more hydrophobically modified via an esterification of
fatty acids (or plant oils containing several different kinds of fatty
acids) in the PLA oligomers medium having increased wettability
in the organic phase. The reason the reaction can be conducted in
“One-Pot” is the in situ solvent exchange through the esteri-
fication reaction of the lactic acid driven by water evaporation
without prior drying of the CNC. It is also possible to retain a
high content of CNC in the final product since a polyester-
ification reaction of the lactic acid reaches equilibrium when
having a short chain length of PLA (repeating unit 2 to 10) unlike
the typical ring opening polymerization (ROP) of a DL-lactide
monomer.36 The use of sustainable, bioderived lactic acid and
fatty acids for the esterification of CNCs not only allows higher
grafting efficiency of CNC, but also leads to an environmentally
friendly production process, sustainability, low TVOC emission
level, ease of use, and high safety. Wood-derived CNCs were
modified with different lengths of fatty acids using this single pot,
aqueous surface hydrophobization reaction. The grafting density
and efficiency of the CNC was examined with infrared spectros-
copy (FT-IR), solid-state 13C NMR (ss-NMR), and elemental
analysis (EA). The crystallinity of a core of unmodified cellulose
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was measured with X-ray diffraction (XRD) and ss-NMR.
Different organic solvents were used here to define relative
hydrophobicity of the modified CNCs comparing transmittance
of their suspensions in the ultraviolet and visible (UV−vis)
spectrometer, and evaluating their hydrodynamic radius by
dynamic light scattering (DLS) techniques.
■ EXPERIMENTAL SECTION
Materials. Zinc acetate dihydrate at 98%, dibutyltin dilaurate at 95%,
DL-lactic acid (LA) at 85% syrup, hexanoic acid at 99.5%, dodecanoic
acid at 98%, oleic acid at 90%, methyl palmitate at 97% technical grade,
Tung oil at 80% ester of eleostearic acid, linseed oil, toluene at 99.8%,
hexane (anhydrous 95%), acrylonitrile at 99%, 1-methoxy-2-propanol at
99%, 2-butanone at 99%, and chloroform at 99.5% were purchased from
Sigma-Aldrich, St. Louis, MO, USA. Ethanol (200 proof) was purchased
from VWR, West Chester, PA, USA. All reagents were used as received
without further purification. 11.9 wt % never-dried CNC suspension in
water, which is in sulfate half-ester form with 1 wt % sulfur and has
sodium as counterion, was manufactured by USDA Forest Service-
Forest Products Laboratory (FPL), Madison, WI, USA and distributed
by University of Maine, Orono, ME, USA.44
Chemical Modification of Cellulose Nanocrystals. A scheme of
the single pot, aqueous surface hydrophobization method is shown in
Figure 1. There are two esterification routes used in grafting seven
different side groups onto the surface of CNCs. In step 1 (route 1), the
aqueous CNC suspension at 11.9% (w/w) was diluted into deionized
(DI) water to give a final suspension concentration of 5 wt %. An excess
of 85% (w/w) DL-lactic acid syrup (the equivalent COOH of the lactic
acid:OH of the dried CNC ratio = 10) was added to the aqueous CNC
suspension and ultrasonicated for 1 min. The mixture was added to a
500 mL 3-necked flask provided with a stirrer and a condenser. Then,
150 ppm of a zinc acetate dihydrate catalyst according to the DL-lactic
acid (LA) syrup weight was further added thereto, and polyesterification
reaction was performed by heating at 180 °C. In step 2 (route 1), after 70
to 99% of the water byproduct was removed by distillation, an excess of
fatty acid reactant (the equivalent COOH of the fatty acid:OH of the
dried CNC ratio = 2.8) and 200 ppm of a dibutyltin dilaurate (DBTDL)
catalyst according to the fatty acid weight were introduced to the
intermediate products that are composed of PLA oligomer grafted CNC
(CNC-g-PLA) and PLA homopolymer. The reaction temperature was
increased to 190 °C, reaction pressure was decreased to 100 mmHg for
30 min, and then an excess amount of lactic acid was discharged while
running the reaction under low vacuum. Subsequently, reaction pressure
was slowly decreased to 10 mmHg and was maintained until the
distillation column top temperature dropped below 35 °C, thereby
preparing a fatty acid and PLA grafted CNC (CNC-g-PLA-FA). Then,
the viscous and syrupy product was collected into a ceramic bowl and
cooled.
After complete reaction, the resulting nanoscale particles were
separated from the unreacted fatty acid and homo-PLA oligomers by
dispersion-centrifugation (6,000 rpm at 25 °C for 30 min.) several times
with an excess of ethanol. Finally, the prepared nanoscale particles were
dried at 50 °C for 24 h in a vacuum system and then were collected.
The procedure of route 2 was performed as previously described in
route 1, with the exception that the same amounts of an FA and a
DBTDL catalyst as in route 1 were directly introduced to the aqueous
LA and CNC suspension at the initial step of polyesterification of LA.
The interfacial esterification reaction of route 2 inevitably caused a 100%
increase in reaction time compared to the rate of route 1.
Recycling fatty acids dissolved in the washing ethanol was conducted
by distillation of the solvent via rotary-evaporation for 1 h. The pro-
cedure for the use of the recycled reagents was performed as previously
described in route 1, with the exception that the polyesterification of
CNC with carboxylic acids was performed with half of the recycled
reagents.
Characterization of Cellulose Nanocrystals. Fourier Transform
Infrared Spectroscopy (FT-IR). Qualitative analyses of pristine CNC
and modified CNCs were conducted by FT-IR transmission spectra
using KBr pellets. (FTIR Spectrum 100, PerkinElmer, Waltham, MA,
DOI: 10.1021/acssuschemeng.6b00781
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ACS Sustainable Chemistry & Engineering
Figure 1. Esterification reaction scheme, using one-pot, (a) two step (route 1) and (b) one step (route 2), for hydrophobization of cellulose nanocrystals
with fatty acid or its ester derivative: hexanoic acid, dodecanoic acid, palmitic acid (from biodiesel), oleic acid, linoleic acid, α-linolenic acid (from
Linseed oil), or α-eleostearic acid (from Tung oil).
USA). All spectra were collected per sample vary from 450 to 4000 cm−1
with a resolution of 4 cm−1 and 10 scans.
13
C CP/MAS Solid-State NMR Spectroscopy. 13C CP/MAS spectra
were performed on a Chemagnetics CMX-400 NMR instruments
equipped with a multicnclear MAS probe. The pulse sequence used was
the “cp_toss_pm” sequence from the spectrometer’s pulse program
library, which included the TOSS (Dixon et al. 1982) and TPPM
methods. Acquisition parameters contained 1H and 13C RF field
strengths of 50 kHz, a cross-polarization time of 2 ms, a TPPM decou-
pling pulse of 7.1 μs, a relaxation delay of 6 s, a data acquisition time of
32 ms with a specimen spinning rate of 5.6 kHz and a sweep width of
32 kHz. Commonly, 1024−2048 scans were obtained (103−206 min)
and the data were handled with exponential multiplication (line-
broadening of 35 Hz) and zero-filled twice prior to Fourier transfor-
mation.
Elemental Analysis (EA). Element analysis of the C, H, O, and N
elements in the CNC and modified CNCs samples were performed by
Galbraith Laboratories, Inc., Knoxville, TN, USA. The measured data
have provided the degree of substitution (DS), which corresponds to the
number of grafted hydroxyl groups per anhydrous glucose unit (AGU)
according to the following equation:
6 × MC−AGU − %C × MAGU
DS =
Mester × %C − MC−ester (1)
where %C is the measured carbon content in the sample and MC‑AGU,
MAGU, Mester, and MC‑ester are linked to the carbon molar mass of an
anhydrous glucose unit, the molar mass of an anhydrous glucose unit,
the mass of the grafted ester and the carbon mass of the grafted moieties,
respectively. The analyses were conducted two times and the average
was utilized. They have been adjusted supposing unmodified samples
as pristine cellulose and samples produced during the same analysis
series.
Dispersibility Test. Pure CNC and modified CNCs were dispersed in
solvents with different Hansen’s solubility parameters (HSP) to evaluate
their dispersibility. HSP is a typical tool utilized to check the dissolution
ability of polymers in solvent and solvent mixtures.45 HSPs have three
parameters: dispersion (δd), polarity (δp), and hydrogen bonding (δh).
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The total solubility parameter (δt) can be estimated using eq 2, which
takes interaction energy embodied by all three components into account.45
δt 2 = δd 2 + δ h 2 + δp2 (2)
For study of dispersion of modified CNCs that were kept “wet” in their
flushing solvent (methanol or ethanol), the weight percentage of modified
CNCs in the “wet” dispersions was first fixed gravimetrically.
A suitable amount of “wet” sample was used to collect 50 mg of modified
CNC. A certain amount of each solvent was added so that the final
concentration of modified CNC was kept at 10 mg/mL. The “wet” sample
was sonicated at 25% amplitude for 0.5 min and dispersed in its respective
solvent. All suspensions were left remaining for 24 h to permit possible
settling before they were examined.
X-ray Diffraction Analysis (XRD). Pristine CNC and modified CNC
powder were molded into thin film and attached on transparent tapes.
They were performed in a Bruker GADDS 2D X-ray diffractometer
(2D-XRD) using a 546 nm Cu Kα source at 30 mA, 10 kV for 360 s and a
beam size of 500 μm at 6.13 cm from detector in transmission mode.
The intensity was plotted against the 2θ angles from the diffraction
pattern. The profile fitting of individual X-ray diffraction peaks of pure
CNC and modified CNCs were performed using the PROFIT software.
The XRD deconvolution was completed by using peak assignments
based on standard powder diffraction patterns of cellulose I and II and
fitting peak profiles with pseudo-Voight functions. The precision for the
peak-position determination conducted by PROFIT was calculated to
be in the range 0.001−0.003° 2θ. The CNC crystallinity index (CI, %)
was evaluated using eq 3:46
⎛ Ac ⎞
CI (%) = ⎜ ⎟ × 100
⎝ A a + Ac ⎠ (3)
where Ac represents the total crystalline area of deconvoluted XRD
patterns, whereas Aa represents the total amorphous area of a hump-like
peak with widespread area from 5° to 30° (2θ) and full width at half
maxima (fwhm) from 8 to 13° (2θ). An example of deconvoluted XRD
patterns can be seen in Figure S3 of the Supporting Information.
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■ RESULTS
Aqueous One-Pot, Chemical Modification of Cellulose
Nanocrystals. The esterification of cellulose nanocrystal
(CNC) by fatty acids, biodiesel, or plant oils was conducted
via a reactive solvent method (scheme in Figure 1). This method
coincides with the following criteria of an ecofriendly produc-
tion process: the use of an aqueous suspension and renewably
sourced lactic acid/fatty acids for grafting, low environmental
foot-print of the product, low VOC emissions, and the possibility
to reuse excess reactant derivatives by purification. The key
factor of the green process is the use of lactic acid as a reactive
solvent for the esterification of CNC with fatty acids, biodiesel,
or plant oils having a long hydrocarbon chain. The aqueous
lactic acid syrup and its oligomers can provide a stable and
well-dispersed water suspension of CNC and participate in
esterification reactions, producing the intermediate product of
PLA oligomer grafted CNC (CNC-g-PLA). This reactive solvent
and intermediate product system allows for efficient esterifica-
tion of CNC with fatty acids due to an in situ solvent exchange
from water to lactic acid and its derivatives without prior
drying of the CNC and the improved compatibility/wettability
between CNC-g-PLA and fatty acid and of both in the exchanged
solvent.
The reaction methods are presented in Figure 1. In route 1, the
CNC-g-PLA was directly prepared by in situ reaction of CNC
with lactic acid in aqueous media in the presence of zinc acetate
dihydrate [Zn(O2CCH3)2(H2O)2]. Then, a water distillation
accompanied by the polyesterification of lactic acid leads to an
in situ solvent exchange from water to the lactic acid oligomers.
After a fatty acid is added in step 2, the excellent wetting behavior
of reagents by the lactic acid oligomers allows for the esteri-
fication of a fatty acid with the CNC-g-PLA in the presence
of dibutyltin dilaurate (DBTDL). In route 2, all components
can form an oil-in-water emulsion, wherein a fatty acid is the
dispersed oil phase and aqueous lactic acid suspension of
CNC is the external phase. A direct condensation of lactic acid
monomers happens through water distillation. Water removal
by azeotropic distillation is crucial to favor the esterification
condensation reaction. Catalysts such as zinc acetate, manganese
Figure 2. 1H NMR data of recycled reagents of CNC-g-PLA-C12.
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acetate, and alkali metal alcoholates may be applied if desired to
increase reaction yield.
The CNC-g-PLA was produced by the mixture of lactic acid
derivatives utilized for the esterification of a CNC as a solvent
and reagent. Then, as a reagent for the esterification of a CNC-g-
PLA, hexanoic acid, dodecanoic acid, methyl palmitate, oleic acid,
tung oil, and linseed oil were utilized. Grafting agents with dif-
ferent hydrocarbon lengths and acid/ester (or glyceride) func-
tions were compared to examine the role of reagent types on
modification and hydrophobization of CNCs. A constant molar
ratio between the reagents and the CNC hydroxyl group was
applied to provide a fair comparison between fatty acids (or fatty
acid esters) with different lengths of hydrocarbon chains.
Recycling of Carboxylic Acids. This single-pot, aqueous
surface hydrophobization procedure uses the reactant, lactic acid,
and its oligomers as the solvent. These lactic acid derivatives
(monomer or oligomers) and fatty acid used can be recycled in
order not only to enhance economic feasibility but also to decrease
the environmental footprint of the product. To evaluate these
byproducts can be recycled and reused as reactants in subsequent
reactions, we examined the exact composition of byproducts of
the PLA/dodecanoic acid reaction through 1H NMR analysis as
shown in Figure 2 and conducted a grafting reaction using half of
the recycled reagents. Byproducts were composed mainly of PLA
oligomer dodecanoic acid esters (including traces of free PLA
oligomers and dodecanoic acid). There was no reactive site loss of
the reagents even at high temperature (above 150 °C) and low pH
(below 5).
Qualitative Characterization of the Grafting Efficiency.
Figure 3 shows the FTIR spectra of the pristine CNC, lactic acid,
lauric acid, CNC-g-PLA, and CNC-g-PLA-FAs. Compared with
the spectrum of CNC, a new peak appeared at 1750 cm−1, which
was not shown in unmodified CNCs. This new peak may be
attributed to either the emerging carbonyl groups of the ester
bond in polylactic acid or in the fatty acid ester, demonstrat-
ing esterification success of the CNC. No band at 1730 and
1700 cm−1 related to lactic acid and fatty acid reagents was ob-
served for modified CNCs indicating purity and efficiency of the
washing step during workup. At the same time, the relative height
change of other peaks in the fingerprint region after modification
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was observed at 1060 cm−1. Nevertheless, both peak heights at
1750 and 1060 cm−1 could provide a rough comparison among
Figure 3. FT-IR spectra of (a) pristine CNC, (b) lactic acid, (c) lauric
acid, (d) PLA grafted CNC (CNC-g-PLA), and CNC-g-PLAs modified
with (e) dodecanoic acid (CNC-g-PLA-C12), and (f) oleic acid (CNC-
g-PLA-C18).
Figure 4. 13C NMR spectra of a) pristine CNC, b) PLA grafted CNC (CNC-g-PLA), and CNC-g-PLAs modified with c) hexanoic acid (CNC-g-PLA-C6),
d) dodecanoic acid (CNC-g-PLA-C12−1, 2, and 3), e) methyl palmitate (CNC-g-PLA-C16−1 and 2), f) oleic acid (CNC-g-PLA-C18−1 and 2), g) linseed
oil (CNC-g-PLA-Lin), and h) tung oil (CNC-g-PLA-Tung).
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different efficiencies of grafting for fatty acid ester side chains due
to the existence of the PLA side chain.
To evaluate the grafting efficiency of LA and FAs, 13C solid-
state NMR spectroscopy data were performed, and spectra are
shown in Figure 4. There are peaks assigned to the C1−C6
carbons’ signals of the AGU that extend from 57 to 108 ppm. Not
fully hydrolyzed cellulose chains split C4 and C6 peaks into their
amorphous parts at high frequencies and their crystalline parts at
low frequencies. The peaks at 60 to 70 ppm corresponding to the
hydroxymethyl C6 carbons split into two peaks; one at 62 ppm,
associated with the disordered chains mainly at the surface, and a
second peak at 65 ppm, arising from the crystalline core.47 There
are C2, C3, and C5 peaks between 70 and 75 ppm and the C1
peak is placed at lower frequencies (105 ppm). Upon grafting of
PLA, there are peaks from PLA modification as a carbonyl carbon
(C7), a α-carbon (C8), and a methyl carbon (C9). The carbons
in the lactic acid-substituted hydroxyl groups of the cellulose and
end-repeating group of the PLA chain are classified differently
from those in the center by adding a prime symbol (′). C6′ peak
at around 64 ppm was overlapped by the peak at 65 ppm arising
from the crystalline core of the C6 peak.48 This result caused the
peak at 65 ppm to rise along with the O-lactyl carbonyl carbon
content in the C6 position. C7 and C7′ are assigned to the broad
signals between 170 to 175 ppm. C8 and C8′ are definitely
overlapped by the CNC signals. Lastly, C9 and C9′ are assigned
to the two signals at 17 and 21 ppm, respectively. 13C solid-state
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NMR spectroscopy data can be utilized to determine the degree Table 1. Degree of Polymerization of the Grafted PLA and
of polymerization (DPavg) of the PLA on the CNC. This data Degree of Substitution of the Modified CNCs
could be calculated by using the ratio of the two C9 and C9′
PLA fatty acid
signal areas and using eq 4:36
sample DPavg DS DSsurf DS DSsurf
∑ intergral (C9 + C9′)
DPavg = × 100% CNC-g-PLA 6.0 0.03 0.24
integral (C9′) (4) CNC-g-PLA-C6-1a 2.1 0.04 0.31 0.01 0.06
CNC-g-PLA-C6-2b 3.0 0.04 0.30 0.01 0.05
then, upon grafting of FA on the CNC-g-PLA, there are new
CNC-g-PLA-C12-1a 2.6 0.06 0.45 0.02 0.14
peaks in the grafted CNC spectra. Thus, peaks between 15
CNC-g-PLA-C12-2b 2.7 0.04 0.28 0.02 0.14
and 40 ppm correspond to the grafted aliphatic carbons of FA CNC-g-PLA-C12-3c 3.0 0.03 0.25 0.02 0.13
(terminal carbon at 14 ppm) and peaks between 170 and CNC-g-PLA-C16-1a 8.0 0.04 0.29 0.01 0.06
175 ppm correspond to the carbonyl carbons of LA and FA. The CNC-g-PLA-C16-2b 2.7 0.03 0.24 0.01 0.12
comparison of degree of substitution (DS) between the poly- CNC-g-PLA-C18-1a 2.9 0.03 0.24 0.02 0.19
esterifications using different reagents were quantitatively per- CNC-g-PLA-C18-2b 2.3 0.04 0.30 0.02 0.12
formed. The calculation of the ratio (Rc) of the chains exposed on CNC-g-PLA-Linb 8.2 0.04 0.31 0.01 0.04
the surface of the nanocrystals was conducted by Habibi et al. CNC-g-PLA-Tungb 3.1 0.06 0.47 0.01 0.11
using eq 5:49 a
m-CNCs as produced via route 1 (Figure 1). bm-CNCs as produced
⎛ d(1 1̅ 0) d(110) ⎞ via route 2 (Figure 1). cCNC-g-PLA-C12 as produced by using the
R c = 2⎜ + ⎟ recycled reagents.
⎝ L1 L2 ⎠ (5)
the height L1 (6.7 nm), width L2 (6.7 nm), and length L3 (64 nm) route 2. Furthermore, biodiesel modified CNC (CNC-g-PLA-
of the crystal were taken from a morphology data of TEM C16-2) produced via route 2 showed higher grafting efficiency
analysis. Considering the only cellulose Iβ structure, three lattice than CNC-g-PLA-C16-1 produced via route 1. These results
planes of a cellulose nanocrystal have faces composed of the suggest that a hydrolysis of ester type reagents is required prior to
(200), (110), and (11̅0) planes within the crystal structure, their esterification with alcohol type reagents. The reason for less
having approximate d-spacings of 0.39, 0.53, and 0.61 nm, grafting efficiency may be less wettability of the fatty acid methyl
respectively.2 ester or triglyceride substances in the lactic acid derivatives
Equation 6 can be used to calculate the number of moles of medium. Moreover, the higher boiling temperature of glycerol
hydroxyl groups per gram on the surface of cellulose nanocrystals derived from the plant oils might be unfavorable thermodynami-
(NOH in mol g−1), which was introduced by Eyley et al.12 cally in accordance with the Le Chatelier principle. On the other
hand, adjusting the pH to below 5 with fatty acids promotes their
n1 + n2 ⎛ L1 + L 2 L + L1 ⎞ esterification reaction with CNC dispersed in lactic acid syrup.
NOH = ⎜⎜ + 1 ⎟⎟
ρNAL1L 2c ⎝ d(110) d(1 1̅ 0) ⎠ In the case of hexanoic acid, there were less 13C NMR peaks
corresponding to grafting of CNC. Because of its lower boiling
+ 2(ρNAL3d(110)d(1 1̅ 0))−1 (6) temperature, a severe loss of hexanoic acid was caused by
application of a vacuum during the polyesterification reaction of
where n1 and n2 are the number of primary hydroxyl groups CNC-g-PLA-C6. 13C NMR data shows that the surface modi-
(0.4843) and the number of secondary hydroxyl groups fication rate of the CNC-g-PLA-C12, CNC-g-PLA-C16, CNC-g-
(1.0066), respectively, facing (110) (or (11̅0)) in the unit cell; PLA-18, and CNC-g-PLA-Tung are more than 0.10 (Table 1).
ρ is the density of crystalline cellulose Iβ (1.605 g cm−3); NA is Unlike Tung oil composed of nearly aliphatic carboxylic acids,
Avogadro’s number, and c is the unit cell dimension (1.038 nm).12 not triglyceride, the poor reactivity of Linseed oil reaction
Equation 7 connects NOH to surface degree of substitution demonstrated the significance of appropriate plant oil selection
(DSsurf). 1.5 is the number of accessible hydroxyl groups per for the application of the esterification method. All CNC-g-PLA-
AGU on the surface; Nmod is the number of moles of modification C12-1, -2, and -3 samples produced by using three different
per gram of product; and Xcel is the mass fraction of cellulose in methods: route 1, route 2, and the recycling method exhibited
the product. DSsurf can be easily linked with bulk DS via the chain similar grafting efficiencies, although double reaction times of
ratio (Rc) using eq 8:12 route 2 and the reagents-recycled process were needed due to
1.5Nmod their interfacial reactions. Likewise, CNC-g-PLA-C6-1 and -2
DSsurf = have similar grafting efficiencies. However, in the case of a long
XcelNOH (7) chain oleic acid, there was a considerable difference between
DS = R c DSsurf (8)
grafting efficiencies of CNC-g-PLA-C18-1 and -2. In conclusion,
in order to successfully graft on the cellulose surface, the fatty
Half of the total hydroxyl groups in the AGU could be utilized as acid should be free long-chain fatty acids rather than triglycerides
viable grafting sites; thus, half the integral of the total CNC or fatty acid esters in route 1 and high-boiling substances (boiling
corresponds to an integral of all viable sites according to eq 7. points higher than 200 °C at 100 mmHg) in both route 1 and 2.
Overall, the 13C NMR results demonstrate the degree of substi- To analyze further the modification efficiency of LA and FAs
tution (DS and DSsurf) and the DPavg of the grafted LA oligomers onto the CNC, elemental analysis was used to evaluate the degree
and are presented in Table 1. In route 1, acid reagents show of substitution (DS). Table S1 in the Supporting Information
higher grafting efficiencies than ester reagents. The reverse is true summarizes the weight fractions of C, H, O, and N elements for
of route 2. For example, in the case of linseed oil and tung oil, pristine CNC and modified CNCs. A change in the % C of
there was no 13C NMR peak corresponding to grafting of CNC. modified CNC and the ratio O/C change from 1.11 for pristine
Thus, plant oil modified CNCs were inevitably created through CNC to 0.92 for CNC-g-PLA-C12, 0.79 for CNC-g-PLA-C18,
3932 DOI: 10.1021/acssuschemeng.6b00781
ACS Sustainable Chem. Eng. 2016, 4, 3927−3938
ACS Sustainable Chemistry & Engineering
Figure 5. DLS data of pristine CNC and modified CNC suspensions.
Figure 6. Dispersion of pristine CNC and modified CNCs in solvents. The concentration of CNC suspensions was kept at 10 mg/mL.
3933
Research Article
and 0.98 for CNC-g-PLA-Tung were consistent with NMR and
confirmed the successful grafting of fatty acids onto the CNC.
Morphology and Crystallinity of Pristine CNC and
Modified CNCs. The grafting reaction needs to conserve the
morphology and crystallinity of CNC in order to be a practicable
grafting method. Figure S1 in the Supporting Information shows the
dimensions of length (L) of 64 ± 5 nm and width (d) of 7 ± 1 nm of
CNC obtained by TEM analysis coupled with ImageJ treatment.
The contrast in TEM analysis is typically enhanced by longer
exposure with low illumination, but organic materials can be
easily damaged by the electron beam. Additional contrast of the
TEM image can be obtained by negatively staining the particles
with uranyl acetate, which is not soluble in organic solvents.
Similarly to as found by others, compared to pure CNC samples,
negatively stained images of hydrophobized CNCs could not be
gained due to agglomeration in an aqueous solution and being
incapable of staining with a uranyl aqueous acetate solution.15,50
Accordingly, DLS was a more practical approach to a quick
comparison of samples, although TEM must be conducted to
accurately measure the particle sizes. DLS of the pristine CNC
DOI: 10.1021/acssuschemeng.6b00781
ACS Sustainable Chem. Eng. 2016, 4, 3927−3938
ACS Sustainable Chemistry & Engineering Research Article

in water and CNC-g-PLA-C18 in acetone presented apparent

particle sizes of 124 nm (61 nm after sonication for 30s) and
285 nm, respectively, having a unimodal particle size distribution
and exhibiting no aggregation in the samples (Figure 5). Because
the Stokes−Einstein equation in the DLS technique was derived
under the assumptions of the hydrodynamic diameter of a
spherical particle, the particle sizes obtained were the approximate
values and did not indicate the actual dimensions of the rod-like
nanoparticles. Nanoscale characterization of pristine CNC and
modified CNC suspensions by TEM and DLS shows that the
surface modification did change the size a little, but it did not
change either morphology or degree of aggregation of the pristine
CNC in various solvents arranged according to Hildebrand solu-
bility parameter.
The analysis of the X-ray diffraction patterns for pristine
CNC and modified CNCs were performed to check a change in
the crystalline structure of CNC in Figures S2 and S3 of the
Supporting Information. There was only a slight increase (less
than 10%) in crystalline index (CI) after grafting (Table S2 in the
Supporting Information). This slight increase in crystallinity is
most probably caused by the hydrolysis or crystallization of
the amorphous component of CNC under acid conditions and
high temperatures used to promote the esterification.21,35 An
additional method, developed by Newman et al.,51 examined the
separation area ratio of C4 carbon peak in 13C NMR spectra to
calculate the CI of pristine CNC and modified CNCs (Figure S4
in the Supporting Information). The CI of both pristine CNC
and modified CNCs was measured by using this method (Table
S2 in the Supporting Information). The result suggests that there
was little change in the CI after grafting.
Dispersion of Modified CNCs in Organic Solvents. The
main purpose of hydrophobization of CNCs is to improve their
dispersibility in an organic solvent or polymer matrix. Figure 6
illustrates pristine CNC and modified CNCs dispersed in
solvents (water, ethanol, acetonitrile, acetone, 1-methoxy-2-
propanol, tetrahydrofuran, chloroform, and toluene). Modified
CNCs were kept in their washing solvent (ethanol) after Figure 7. UV/vis absorbance plot of modified CNCs suspension in
centrifugation as a concentrated gel-like form in order to enhance various organic solvents with respect to their surface degree of substi-
their dispersibility.15 These “wet” samples were then redispersed tution (DS) and grafted molecule length.
in organic solvents by a sonication for at least 30 s. The sus-
pensions were left undisturbed overnight to equilibrate and allow narrow dispersibility window. They have higher dispersibility
for the visual observation of precipitation behavior. The presence overall in solvents but do not make any transparent suspension
of residual washing solvent can bring about a change in the HSP indicating relatively large aggregates dispersing. CNC-g-PLA-
value of the final solvent in the suspension. However, because of C12, CNC-g-PLA-16, and CNC-g-PLA-18 are dispersible in all
the infinitesimal presence of residual washing solvent, the overall solvents except hexane and water and thus have a broad dis-
HSP value of the solvent mixture did not alter drastically.45 persibility window. CNC-g-PLA-C12 and CNC-g-PLA-16
The compatibility of the pristine CNC with hydrophobic displayed a similar dispersibility in different organic solvents.
systems is very low because of the hydrophilic nature of the CNC This is because of the enhanced dispersibility of CNC-g-PLA-16
surface. The improvement of the CNC dispersion in an organic as length of the aliphatic chain became longer even at a lower DS
solvent after surface grafting was achieved as shown in Figure 6. value. CNC-g-PLA-C6 has a higher DS value than CNC-g-PLA-
The modified CNCs were homogeneously dispersed in various Lin. Nevertheless, the longer aliphatic chain grafted CNC (CNC-
organic solvents, whereas pristine CNC aggregated and precipi- g-PLA-Lin) exhibited better dispersibility compared to the
tated to the bottom. shorter aliphatic chain grafted CNC (CNC-g-PLA-C6) even
Figure 7 shows that dispersibility of pristine CNC and grafted having a higher DS value. CNC-g-PLA-C12, CNC-g-PLA-C16,
CNCs (CNC-g-PLA-C6-1, -C12-1, -C16-2, -C18-1, -Lin, and and CNC-g-PLA-C18 suspensions in various solvents displayed
-Tung) in various solvents arranged according to Hildebrand excellent transparency, due to the smaller size of their aggregates,
solubility parameters (water 23.5, ethanol 12.92, acetonitrile which demonstrated better dispersion of the less aggregated
11.9, acetone 9.77, tetrahydrofuran 9.52, 1-methoxy-2-propanol particles. This means that their grafted alkyl chain length and DS
9.5, chloroform 9.21, and toluene 8.91 cal1/2 cm−3/2) can be of modified CNCs (CNC-g-PLA-C12, -C16, and -C18) affects
determined by both DS and the length of the aliphatic chain used. their dispersibility. Linseed oil modified CNC (CNC-g-PLA-
For the different lengths of grafted CNCs, highly grafted CNCs Lin) did not show good dispersibility; whereas Tung oil modified
had a lower absorbance (high transparency) than less grafted CNC (CNC-g-PLA-Tung) has better dispersibility in nonpolar
ones. Accordingly, CNC-g-PLA and CNC-g-PLA-C6 have a solvents: chloroform and toluene. Overall, the dispersibility of
3934 DOI: 10.1021/acssuschemeng.6b00781
ACS Sustainable Chem. Eng. 2016, 4, 3927−3938
ACS Sustainable Chemistry & Engineering
Figure 8. Teas charts of pristine CNC and modified CNCs in solvents.
the modified CNC in organic medium increased with increases in
their DS and grafted molecule length, and the hydrophobicity of
solvent used.
The DLS data (Figure 5) shows that, for the different lengths
of grafted CNCs, highly grafted CNCs had a slightly lower
hydrodynamic radius (highly dispersible) than less grafted ones
3935
Research Article
in their suspensions. The dispersibility of the modified CNC in
organic medium was retained up to a certain point (at least
by Hildebrand solubility parameters 10 cal1/2 cm−3/2) and then
sharply reduced with increases in the hydrophobicity of solvent
used. Likewise, the DLS data is in accordance with the trends
observed for the UV/vis absorbance data (Figure 7) of modified
DOI: 10.1021/acssuschemeng.6b00781
ACS Sustainable Chem. Eng. 2016, 4, 3927−3938
ACS Sustainable Chemistry & Engineering
CNC suspensions in different solvents except toluene. The con-
flict between the two results in toluene was caused by misleading
optic data from scattering in a forward direction.52,53 Agglomera-
tion of CNCs in the toluene increases particle size, which
increases the forward scattering, contributing to the enhanced
clarity and reduced haze of the CNC suspension. On the basis of
the combined analysis from both absorbance and DLS data,
dispersibility windows of grafted CNCs were estimated by
outlining around ACN, acetone, THF, 1-methoxy-2-propanol,
and chloroform.
Teas plots for each type of grafted CNC are shown in Figure 8,
using Hansen’s solubility parameters for solvents used in the
solubility test. To determine the dispersibility of modified CNC
suspensions, their optical transparency at 500 nm wavelength of
visible light was compared via UV/vis spectrometer (10 mg/mL),
splitting them into five levels according to their transparency based
on absorbance data. Therefore, these results demonstrate that
their dispersibility is proportional to their DS and the length of
the aliphatic chain used. Clear suspensions with an absorbance
range of 0 to 0.3 at 500 nm, which indicates a higher dispersion
of small aggregates of modified CNC, were marked as level 5.
Well-dispersed, slightly turbid samples with the absorbance
range of 0.31 to 0.7 and 0.71 to 1.2 were marked as level 4 and
level 3, respectively. Less-dispersed, heavily turbid samples with
the absorbance range of 1.21 to 2.0 and more than 2.0 were
marked as level 2 and level 1, respectively. Samples with sedi-
mentation height were marked as level 0. The “dispersibility
windows” of grafted CNCs are specified by outlining around
level 2 or level 3 in the teas chart. The highly grafted CNCs
typically displayed a wide dispersibility window, which shifted
toward the lower right corner, compared to the pristine CNC and
CNC-g-PLA (Figure 8). Dispersion characteristics of grafted
CNCs into polymer can also be specified by the Teas plot,
showing similar dispersibility windows.
On the whole, major factors must be considered to determine
the most workable reagents to hybridize CNCs. The hydro-
phobicity of the grafted CNCs, which is determined by the
chemical structure of the side chain aliphatic groups of reagents,
is governed by their practical application. In this system, easy-to-
use and commercially available reagents, fatty acids or their
ester derivatives, can be utilized. Not only that, but untreated
raw materials, biodiesel or high free fatty acid types of plant oils,
can be used. This esterification method is not limited by a water
immiscibility of a fatty acid. The use of various kinds of inexpensive
commercial carboxylic acids is allowed by a lactic acid reactive
solvent system that is a solvent-free one-pot synthesis in aqueous
medium. For surface modifications of CNCs, grafting with longer
chain fatty acids is more recommended than with shorter acids.
The strong interaction of a polymer matrix with the dispersed
hydrophobized CNC particles, primarily via hydrogen bonding or
bond network, can be reduced with the presence of long aliphatic
chain groups in a polymeric nanocomposite. However, more than
50% hydroxyl groups are still remained unmodified on the surface
of the hydrophobized CNCs; thus, strong intermolecular
interactions between the modified CNC particle and a polymeric
matrix are expected to occur. Furthermore, for nanocomposites
based on C12−C18 fatty acid-grafted CNCs, the storage modulus
might be expected to increase with the filler content, since their
long side chain moiety enables nanoparticles to have a good
nanofiller−matrix interfacial interaction and load transfer.21,54,55
Therefore, the simple, ecofriendly, and industrially friendly
technology of this green process meets the feasibility of scaling
up a surface modification process of CNCs.
3936
Research Article
■ CONCLUSION
Surface modification treatments for CNCs were conducted by
grafting fatty acids (FAs), biodiesel, or plant oils in order to
improve the dispersion of nanoparticles in organic solvents. The
key factor of this one-pot synthesis process is the use of the lactic
acid as a reactive solvent for the esterification of CNC with acids
or esters having a long hydrocarbon chain. Furthermore, the
lactic acid derivatives can be reused in order not only to decrease
the environmental footprint of the product but also to enhance
economic feasibility. It was shown that approximately one-third
of all the available OH groups on the surface were modified with
polylactic acid oligomer and fatty acid side chains. This level
was enough to improve dispersibility in various organic solvents
without damaging structural morphology and crystallinity of the
grafted CNCs. Surface hydrophobization methods of CNCs
through one-step and two-step esterification reaction were com-
pared according to fatty acids and their esters as a reagent. Fatty
acid reagents had better grafting efficiency than other reagents
for two-step reaction. The reverse was true of fatty acid ester
reagents due to their low wettability in lactic acid derivatives
medium. For the determination of a grafted moiety, utilizing a
long chain aliphatic carboxylic acid (a high-boiling substance)
was more viable approach due to higher grafting efficiency and
more dispersibility of grafted CNCs in various organic solvents
such as acetonitrile, acetone, tetrahydrofuran, 1-methoxy-2-
propanol, and chloroform. Therefore, the simple, ecofriendly,
and industrially friendly technology of this one-pot reaction
process meets the feasibility standards for scaling up a surface
modification process of CNCs.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the ACS
Publications website at DOI: 10.1021/acssuschemeng.6b00781.
TEM image of pristine CNC, EA analysis and crystallinity
Index (CI%) of pristine CNC and modified CNCs, and
UV/vis absorption data of pristine CNC and modified
CNCs in solvents used in this study (PDF).
■ AUTHOR INFORMATION
Corresponding Author
*J. P. Youngblood. Email: jpyoungb@purdue.edu. Phone:
+1 765-496-2294. Fax: +1 765 494-1204.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank Debby Sherman from DSimaging, LLC for
obtaining the TEM images and John Harwood from Purdue
Interdepartmental NMR Facility for obtaining the 13C solid-state
NMR spectra. The authors acknowledge for financial support the
National Science Foundation Scalable Nanomanufacturing program
under award CMMI-1449358, the Forest Products Laboratory under
awards 11-JV-11111129-118 and 11-CR-11111129-109.
■
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3938 DOI: 10.1021/acssuschemeng.6b00781

ACS Sustainable Chem. Eng. 2016, 4, 3927−3938