polymers

Article
Comparative Study on Different Modified Preparation Methods
of Cellulose Nanocrystalline
Xinhui Wang 1 , Na Wang 1 , Baoming Xu 1 , Yili Wang 1 , Jinyan Lang 1 , Junliang Lu 1,2 , Guorong Chen 3
and Heng Zhang 1,2,3, *

1 College of Marine Science and Biological Engineering, Qingdao University of Science & Technology,
Qingdao 266042, China; [email protected] (X.W.); [email protected] (N.W.); [email protected] (B.X.);
[email protected] (Y.W.); [email protected] (J.L.); [email protected] (J.L.)
2 Guangdong Provincial Key Lab of Green Chemical Product Technology, Guangzhou 510640, China
3 Fujian Provincial Key Laboratory of Fire Retardant Materials, Xiamen 361005, China; [email protected]
* Correspondence: [email protected]; Tel.: +86-1595-480-3800

Abstract: Different modification process routes are used to improve the modified cellulose nanocrys-
talline (MCNC) with higher fatty acid by esterification reaction and graft polymerization to obtain
certain hydrophobic properties. Two preparation methods, product structure and surface activity,
are compared and explored. Experimental results show that the modified product is still at the
nanometer level and basically retains the crystal structure of the raw cellulose nanocrystalline (CNC).
The energy consumption of the two preparation methods is low; however, the esterification method
with co-reactant requires short reaction time, and the degree of substitution of the product is high.
The modified product prepared by grafting polymerization method has a high HLB value and
amphiphilicity, which can effectively reduce the surface tension of water. Therefore, it can be used as





 a green and environmentally friendly surface-active substance.
Citation: Wang, X.; Wang, N.; Xu, B.;
Wang, Y.; Lang, J.; Lu, J.; Chen, G.; Keywords: CNC; esterification reaction; graft copolymerization; hydrophobic modification
Zhang, H. Comparative Study on
Different Modified Preparation
Methods of Cellulose Nanocrystalline.
Polymers 2021, 13, 3417. https:// 1. Preface
doi.org/10.3390/polym13193417 Nanocellulose is a degradation product of cellulose, and its basic structural unit is
anhydroglucose. Nanocellulose carries a large number of hydroxyl groups. It not only
Academic Editor: Arn Mignon
inherits some of the cellulose characteristics, such as hydrophilicity, renewability, and
degradability, but also has the characteristics of nanomaterials, such as high specific surface
Received: 12 September 2021
area, hyperfine structure, and high transparency. Therefore, nanocellulose is a new type of
Accepted: 1 October 2021
green environmental protection material with great development prospects [1–3].
Published: 5 October 2021
The hydroxyl group carried by nanocellulose provides excellent modification sites.
Therefore, the physical or chemical modification of nanocellulose can provide new func-
Publisher’s Note: MDPI stays neutral
tions and prepare new nanocellulose functional materials. Most modification techniques of
with regard to jurisdictional claims in
cellulose are also applicable to nanocellulose given that the basic structural units of nanocel-
published maps and institutional affil-
iations.
lulose and cellulose are the same. Among them, physical adsorption is a commonly used
polymer modification scheme. This modification method is convenient to operate, and the
entire production process is simple and can effectively retain the integrity of nanocellulose.
Qing et al. [4] used cetyltrimethylammonium bromide to adsorb on nanocellulose for
hydrophobic drug delivery. The product has been tested, and the result proves that it has
Copyright: © 2021 by the authors.
stable dispersibility and stability in organic solvents, and the raw material nanocellulose
Licensee MDPI, Basel, Switzerland.
has improved in hydrophobicity. Shimizu et al. [5] made 2, 2, 6, 6-tetramethylpiperidine-1-
This article is an open access article
oxy oxidized cellulose nanofibers and quaternary alkylammonium adsorbate by casting
distributed under the terms and
conditions of the Creative Commons
method to produce hydrophobically modified nanocellulose film. The results of hydropho-
Attribution (CC BY) license (https://
bic tests show that the contact angle between the product and water has increased from
creativecommons.org/licenses/by/ the original 50◦ to 100◦ . This method improves the hydrophobicity of the product and can
4.0/). simply and effectively achieve the hydrophobic modification of the product. However,

Polymers 2021, 13, 3417. https://doi.org/10.3390/polym13193417 https://www.mdpi.com/journal/polymers

Polymers 2021, 13, 3417 2 of 14

nanocellulose and the introduced functional groups are combined in the form of van der
Waals forces or hydrogen bonds, which is instability. Because the modified products of
physical modification have weak shear resistance, and the adsorbed substances are easy to
dissociate under a certain external force [6].
The stability of chemically modified nanocellulose is better because the strength of
chemical bonds is higher than van der Waals forces and hydrogen bonds. The commonly
used chemical modification methods include oxidation, silanization, cationization, esterifi-
cation, and graft copolymerization. Among them, TEMPO (2,2,6, 6-tetramethylpiperidine-
1-oxygen radical) oxidation modification can oxidize the hydroxyl methyl on the surface
of nanocellulose to carboxyl group and improve its water solubility. In modified polysac-
charide, only the hydroxymethyl on the surface of the polysaccharide is oxidized without
affecting the hydroxyl groups on the surface [7]. Araki et al. [8] used TEMPO-modified
hydrochloric acid hydrolyzed nanocellulose to prepare homogeneous aqueous suspension.
Silanization is widely used in surface chemical modification of cellulose whiskers, and the
dispersion of the modified nanoparticles in organic solvents is improved; however, the
morphology of the modified nanoparticles slightly changes, and a swelling phenomenon oc-
curs [9]. Grunert et al. [10] modified cellulose nanocrystalline (MCNC) with trimethylsilane
and compounded with cellulose acetate butyrate. The modified nanocellulose can evidently
enhance the energy storage modulus of cellulose acetate butyrate. The hydroxyl groups
of nanocellulose can be cationically modified by derivatization reaction. Zaman et al. [11]
modified the nanocellulose hydrolyzed by sulfuric acid with glycidyl trimethylammonium
chloride and adjusted the surface charge density of the modified product by changing the
water content in the reaction system to be better dispersed in the water system.
Esterification and graft copolymerization are common methods for chemical modifi-
cation of nanocellulose. Esterification is a chemical reaction between nanocellulose and
organic acids or inorganic acids. The reaction is essentially the reaction of hydroxyl and
carboxyl groups to generate ester group, sometimes with acyl halide and anhydride as the
reactants; however, the final result is the generation of ester group. Lakovaara et al. [12]
obtained high strength and sustainable films with increased hydrophobicity and good
mechanical properties by the esterification of cellulose nanofiber and all-cellulose com-
posite films with n-octylsuccinic anhydride. In addition, the experimental method is
relatively mild. Beaumont et al. [13] presented a general concept of wet surface ester-
ification of cellulose using acyl imidazoles, which means acetyl groups are introduced
directly onto never-dried, water-swollen cellulose fibres. This method can obtain cellulose
fibers with higher hydrophobicity in simple and gentle process. Shang et al. [14] pre-
pared super-hydrophobicity/super-oleophilicity with good adsorption capacity through
the freeze-drying process and subsequent esterification. The reaction process of it was
facile and environmental-friendly approach. Spinella et al. [15] prepared functionalized
modified product by direct melt blending of nanocellulose and lactic acid through Fischer
esterification reaction, which improved the dispersion of original nanocellulose in polymer
matrix, increased the contact angle with water, and expanded the application range of this
material. Yuan et al. [16] acetylated nanocellulose by using alkyl succinic anhydride. After
modification, the hydrophobicity of nanoparticles was significantly improved and was
easily dispersed into polar solvents with different dielectric constants. Menezes et al. [17]
reacted the nanocellulose with organic fatty acid chlorides of different hydrocarbon chain
lengths to prepare esterification-modified products with high substitution degree and high
graft density. Berlioz et al. [18] reacted BNC with hexadecyl chloride vapor to obtain the
same esterified product of nanocellulose with high substitution degree. This reaction is a
highly efficient solvent-free esterification reaction, and the crystal structure of the modified
nanocellulose is insignificantly changed. Eyholzer et al. [19] used sulfuric acid as the
catalyst to transfer the reaction of ester group of nanocellulose in hexane–alcohol medium,
and hexyl monomer replaced carboxymethyl through carboxymethylation.
Graft copolymerization can directly react the functional groups of the graft with the
active hydroxyl group of the nanocellulose to form the modified products, or it can initially
Polymers 2021, 13, 3417 3 of 14

react with the active hydroxyl group of the nanocellulose by the small molecular monomer,
and then perform chemical modification by the polymerization of the small molecular
monomer grafted on the nanocellulose, namely, chain growth. Goffin et al. [20] grafted
PLA on the surface of cellulose nanocrystalline through ring-opening polymerization.
The length of grafting chain in the modified products is short due to the crystallization
of PLA on the surface of nanocellulose. Westlund et al. [21] prepared graft products
with special functions by modifying nanocellulose with tris-[2-(dimethylamino) ethyl]
amine as ligand and 11-(40 -cyanophenyl-400 -phenoxy) undecyl acrylonitrile and methyl
acrylate as monomers. Lee et al. [22] grafted acrylamide onto the surface of nanocellulose
by ultraviolet light initiation by using benzophenone as initiator. The grafting ratio of
modified products increased with the increase in initiator concentration. The introduction
of acrylamide chain improved the dispersion ability of nanocellulose. Morandi et al. [23]
grafted polyphenylene onto the surface of nanocellulose by using ethyl bromoisobutyrate
as initiator. The modified products showed chiral nematic structure in thermotropic and
lyotropic liquid crystal and had strong adsorption for 1,2, 4-trichlorobenzene.
Among nanocellulose modification methods, esterification and graft copolymerization
have more mature reaction routes and do not require harsh reaction conditions; thus,
they have the most industrial application prospects. In our previous studies, we investi-
gated the graft copolymerization method of nanocellulose, grafting high fatty acids with
FeSO4 /H2 O2 system or 2(NH4 )2 SO4 ·Ce(SO4 )2 ·4H2 O as initiator. Under the same reaction
conditions, the initiation efficiency of FeSO4 /H2 O2 was better than that of tetravalent
cerium ion in ammonium cerium sulfate, and the degree of substitution (DS) of the ob-
tained product was relatively high [24–26]. However, only a few studies compared the
esterification method with that using co-reactant. The esterification reaction modified
cellulose nanocrystalline has the characteristics of facile and eco-friendly. Therefore, low
reaction temperature and green reagent were used in this experiment. Nanocellulose and
higher fatty acids were used as raw materials to graft alkanes onto nanocellulose by intro-
ducing co-reactants and initiators, respectively. The performance of reaction products was
evaluated by comparing the degree of difficulty of the two reaction types. The differences
in surface activity of the products were analyzed on the basis of the reaction mechanism,
thereby providing a feasible process route for the modification of nanocellulose.

2. Preparation and Characterization of Cellulose Nanocrystalline (CNC) and

Modified Products
2.1. Chemicals and Materials
Trifluoroacetic anhydride was purchased from Shanghai Aladdin Biochemical Technol-
ogy Co., Ltd. Ferrous sulfate was obtained from China Shanghai Pierce Chemical Reagent
Co., Ltd. Hydrogen peroxide at 30% (w/w) was purchased from Tianjin Dingshengxin
Chemical Co., Ltd. Chloroform, sodium hydroxide, and absolute ethanol were purchased
from Sinopharm Chemical Reagent Co., Ltd. Lauric acid was obtained from Tianjin BASF
Chemical Co., Ltd. Palmitic acid was obtained from Tianjin Bodi Chemical Co., Ltd. Stearic
acid was purchased from Tianjin Beichen Fangzheng Reagent Factory. Concentrated sulfu-
ric acid, hydrochloric acid, was purchased from Yantai Sanhe Chemical Reagent Co., Ltd.
These chemicals are all analytical pure. Pharmaceutical grade microcrystalline cellulose
was purchased from Chengdu Kelong Chemical Reagent Factory. The MD3500 dialysis
bag was purchased from an American company, Viskase.

2.2. Preparation of CNC

Concentrated sulfuric acid aqueous solution at 60% (w/w) was prepared and naturally
cooled. It was directly added to a flask containing microcrystalline cellulose (MCC) when
its temperature dropped to approximately 45 ◦ C. The magnetic heater was heated to 45 ◦ C,
and the speed was adjusted to 500 rpm. Timing after the mixture is evenly stirred, the
whole reaction is protected by nitrogen. After 2.5 h, heating was stopped, the mixed
solution was transferred to a beaker, and a large amount of deionized water was added
 2.2. Preparation of CNC
Concentrated sulfuric acid aqueous solution at 60% (w/w) was prepared and natu-
rally cooled. It was directly added to a flask containing microcrystalline cellulose (MCC)
when its temperature dropped to approximately 45 °C. The magnetic heater was heated
Polymers 2021, 13, 3417 to 45 °C, and the speed was adjusted to 500 rpm. Timing after the mixture is evenly stirred, 4 of 14
the whole reaction is protected by nitrogen. After 2.5 h, heating was stopped, the mixed
solution was transferred to a beaker, and a large amount of deionized water was added
tototerminate
terminatethe theacid-catalyzed
acid-catalyzedhydrolysis
hydrolysisreaction.
reaction.Finally,
Finally,the
themilky
milkywhite
whiteproduct
product
mixed
mixed with microcrystalline cellulose and CNC obtained after adding deionizedwater
with microcrystalline cellulose and CNC obtained after adding deionized water
was
wastransferred
transferredtotoa a5050mLmLcentrifuge
centrifugetube.tube.The
Theturbid
turbidliquid
liquidwas
wascentrifuged
centrifugedatatthe
thespeed
speed
ofof5000
5000rpm
rpmtotoseparate
separatethe theupper
upperlayerlayerofofacid-containing
acid-containingwastewasteliquid,
liquid,and
anddeionized
deionized
water
waterwaswasadded
addedtotocontinuously
continuouslydilute
dilutethetheconcentration
concentrationofofthethesulfuric
sulfuricacid
acidaqueous
aqueous
solution.
solution. This process is repeated until the supernatant liquid became turbid, and thenthe
This process is repeated until the supernatant liquid became turbid, and then the
supernatant
supernatantliquid
liquidcontaining
containingthe thedesired
desiredCNCCNCwas wascollected.
collected.
TheThecollected
collectedupper
upperlayer
layerofofCNC
CNCcolloid
colloidwas
wasconcentrated
concentratedbybyvacuum
vacuumdistillation,
distillation,
and
and then transferred to the dialysis bag (molecular weight 3500) under3030°C
then transferred to the dialysis bag (molecular weight 3500) under ◦ Cdeionized
deionized
water
waterenvironment
environmentwith withmagnetic
magneticstirring;
stirring;dialysis
dialysiswas
wasrepeated
repeateduntil
untilthe
thepHpHbecame
became
neutral.
neutral.Finally,
Finally,a atransparent
transparentandandlight
lightblue
blueglowing
glowingCNCCNCcolloid
colloidwas
wasobtained.
obtained.

2.3.Preparation
2.3. PreparationofofMCNC
MCNC
2.3.1. Preparation ofofMCNC
2.3.1. Preparation MCNCbybyEsterification
EsterificationReaction
Reaction
Trifluoroaceticanhydride
Trifluoroacetic anhydridewas wasused
usedasasthe
theco-reactant
co-reactanttotoactivate
activatethree
threehigher
higherfatty
fatty
acids in situ to produce a mixed acid anhydride intermediate. Then, the
acids in situ to produce a mixed acid anhydride intermediate. Then, the dried CNC pow-dried CNC powder
was
der added
was addedto ato
four-necked flaskflask
a four-necked containing mixedmixed
containing acid anhydride intermediate
acid anhydride to generate
intermediate to
MCNC at different temperatures and reaction times. The system should
generate MCNC at different temperatures and reaction times. The system should be an- be anhydrous
and ethanol-free
hydrous becausebecause
and ethanol-free trifluoroacetic anhydride
trifluoroacetic is chemically
anhydride active and
is chemically can react
active with
and can
water and absolute ethanol. Through preliminary experiments and exploration,
react with water and absolute ethanol. Through preliminary experiments and exploration, chloroform
was selected
chloroform wasasselected
the liquid
as phase system
the liquid of the
phase reaction.
system of theThe entire reaction
reaction. process
The entire was
reaction
under nitrogen protection. When the reaction was over, the mixture was cooled to room
process was under nitrogen protection. When the reaction was over, the mixture was
temperature, and the substances that did not participate in the reaction were removed
cooled to room temperature, and the substances that did not participate in the reaction
by alternate washing with absolute ethanol and water, and the resulting product was
were removed by alternate washing with absolute ethanol and water, and the resulting
separated. Then, ethanol was used as the solvent to extract the product using a Soxhlet
product was separated. Then, ethanol was used as the solvent to extract the product using
extractor. Finally, the product was vacuum dried at 40 ◦ C. The reaction mechanism is
a Soxhlet extractor. Finally, the product was vacuum dried at 40 °C. The reaction mecha-
shown in Equation (1).
nism is shown in Equation (1).
O O

F3C C F3C C
O + CH3(CH2)nCOOH O + CF3COOH
F3C C CH3(CH2)n C

O O O

F3C C HO (1)
(1)
OH RO
O + O OR
O +
CH3(CH2)n C O CF3COOH
O
HO n RO
O n

R=CH3(CH2)nCO, H

2.3.2.Preparation
2.3.2. PreparationofofMCNC
MCNCbybyGraft
GraftCopolymerization
Copolymerization
An An appropriateamount
appropriate amountofofself-made
self-madeCNC
CNCcolloidal
colloidalsolution
solutionwas
wasobtained
obtainedand
andmixed
mixed
with an ethanol solution mixed with dissolved fatty acids. The reaction was carried out in
with an ethanol solution mixed with dissolved fatty acids. The reaction was carried out in a
flask, stirring and mixing continuously for 0.5 h in the water bath environment at 50 ◦ C to
a flask, stirring and mixing continuously for 0.5 h in the water bath environment at 50 °C
toobtain
obtain even mixture.
even Then,
mixture. a quantitative
Then, initiator
a quantitative was added,
initiator was and the reaction
added, and thetemperature
reaction
and time were changed to carry out the chemical modification reaction of CNC. The entire
reaction process was under nitrogen protection. After the reaction, a mixed suspension
of MCNC was obtained, and the suspension was separated and washed alternately with
alcohol and water. Finally, the product was vacuum dried at a temperature of 40 ◦ C.
In the process of MCNC preparation with FeSO4 /H2 O2 as the initiator, Fe2+ and H2 O2
undergo a redox reaction, thereby triggering H2 O2 to generate active free radicals. The free
radicals cause fatty acids and CNC to form two active free radicals. Finally, these active
 temperature and time were changed to carry out the chemical modification reaction of
CNC. The entire reaction process was under nitrogen protection. After the reaction, a
mixed suspension of MCNC was obtained, and the suspension was separated and washed
alternately with alcohol and water. Finally, the product was vacuum dried at a tempera-
Polymers 2021, 13, 3417 ture of 40 °C. 5 of 14
In the process of MCNC preparation with FeSO4/H2O2 as the initiator, Fe2+ and
H2O2 undergo a redox reaction, thereby triggering H2O2 to generate active free radicals.
The free radicals cause fatty acids and CNC to form two active free radicals. Finally, these
free radicals react with each other to complete the chemical modification of CNC [27–29].
active free radicals react with each other to complete the chemical modification of CNC
The reaction mechanism of this process is shown in Equation (2).
[27–29]. The reaction mechanism of this process is shown in Equation (2).
Fe2+ + H+ + H2O2 Fe3+ + H 2O + OH

O O

n*
OH + OH O + H 2O
n*

HO HO
OH OH
O + OH O
O + H2 O
O
HO n CH 2O (2)
(2)
n

O HO HO
OH OH
H+ + O + O O
n* + H 2O
O O
CH 2O O
n n
C
O n*

2.4.Test
2.4. TestMethod
Method
2.4.1. Determination andCalculation
2.4.1. Determination and Calculationof
ofDS
DSof
ofMCNC
MCNC
Thesynthesized
The synthesizedMCNC
MCNCwas wasrepeatedly
repeatedlywashed
washedwith
withethanol
ethanoland
anddeionized
deionizedwater,
water,
filtered, and dried to obtain the product, and the DS was determined by the saponification
filtered, and dried to obtain the product, and the DS was determined by the saponification
method [30,31].
method [30,31].
2.4.2. X-ray Diffraction
2.4.2. X-ray Diffraction
CNC and MCNC powder samples were obtained for X-ray diffraction measurement.
CNC temperature,
At room and MCNC powder samplessubstance
the measured were obtained
was for X-ray
tested diffraction
with measurement.
a DX-2700 XRD tester
At
(Bruker Corporation, Ettlingen, Germany) at a scanning rate of 0.02 /min. TheXRD
room temperature, the measured substance was tested with a◦ DX-2700 tester
diffraction
(Bruker Corporation, Ettlingen, Germany) at a scanning rate of 0.02°/min. The diffraction
setting parameters are as follows: Cu target, 40 kV, and 30 mA; the diffraction angle 2θ
setting
range isparameters are◦ .as follows: Cu target, 40 kV, and 30 mA; the diffraction angle 2θ
set to 10◦ –60
rangeTheis set to 10°–60°.
crystallinity index CrI value can be calculated by Segal equation (Equation (3)) [32],
The crystallinity index CrI value can be calculated by Segal equation (Equation (3))
as follows:
[32], as follows: I002 −Iam
CrI = × 100% (3)
I002
I002 − Iam
CrII=
(CrI: relative crystallinity index; 002 : maximum ×100%
intensity of 002 lattice diffraction; I(3)
am :
diffraction intensity of the same unit at 2θ = I002
18◦ )

2.4.3.(CrI: relative crystallinity

Determination index;
of Particle Size I002: maximum intensity of 002 lattice diffraction; Iam:
diffraction intensity of the same unit at 2θ = 18°)
CNC colloid and MCNC suspension are diluted and ultrasonically dispersed for
testing. Malvern Zetasizer Nano-ZS90-type Malvern laser particle size analyzer (Malvern
2.4.3. Determination of Particle Size
(China) instrument Co. Ltd., Shanghai, China) is used. The particle refractive index is set
CNCwater
to 1.470, colloidisand
usedMCNC
as thesuspension
dispersant,arethediluted and ultrasonically
temperature dispersed
of the test system is 25for test-
◦ C, the
ing. Malvern Zetasizer Nano-ZS90-type Malvern
count rate is 349.8 kcps, and the time is set to 60 s. laser particle size analyzer (Malvern
(China) instrument Co. Ltd., Shanghai, China) is used. The particle refractive index is set
to 1.470,
2.4.4. water is used
Calculation of theasHLB
the dispersant,
Value of MCNC the temperature of the test system is 25 °C, the
countEquation
rate is 349.8 kcps, and the time is set
(4) is used to calculate the HLB to 60value
s. of the MCNC.

Hydrophilic group quality

HLB = Surfactant quality × 100
5
The quality of the hydrophilic group 100
= Lipophilic base quality+Hydrophilic group quality × 5
(4)
= (B−A −DS × 100
1)× DS+ A 5
Polymers 2021, 13, 3417 6 of 14

(A: relative molecular mass of glucoside unit; B: relative molecular mass of fatty acid
groups (C12 H23 O, C16 H33 O, C18 H37 O) connected to CNC in the form of ester bonds; DS:
degree of substitution of MCNC).

2.4.5. Determination of Surface Tension

The CNC and MCNC test liquids with different contents are configured, and the sur-
face tension of the QBZY-2 automatic surface tension meter (Shanghai Fangrui Instrument
Co., Ltd., Shanghai, China) was used to determine the surface tension.

3. Results and Discussion

3.1. Factors Affecting the DS of MCNC
The saponification method was used to determine the DS to explore the influence of
different reaction conditions on the DS of the modified product. The co-reactant or initiator,
three higher fatty acids, and CNC are combined, and the corresponding temperature
change interval and time change interval are selected to prepare MCNC under different
reaction conditions.

3.1.1. Effect of Co-Reactant Content on the DS of MCNC

Trifluoroacetic anhydride acts as a co-reactant to react with three types of higher
fatty acids to generate active intermediates, namely, mixed acid anhydrides. MCNC was
prepared by the reaction of mixed anhydride and CNC. The amount of fatty acid was the
same as that of the co-reactant according to the esterification reaction mechanism. When
lauric acid was used as the grafting substance, the temperature should be controlled at
50 ◦ C, and the reaction time should be 5 h. When palmitic acid and stearic acid were used
as grafting substances, the reaction temperature was controlled at 55 ◦ C and the reaction
time was 6 h. The test results are as follows.
Figure 1 shows that the DS of MCNC is related to the feed ratio of the substances
participating in the reaction and the hydrocarbon chain length of the hydrophobic groups
of MCNC. As the adding ratio of anhydroglucose unit (AGU), co-reactant and fatty acid
increases, the DS of MCNC gradually increases. When the feeding ratio reaches 1:3:3, the
curve tends to be flat. On the basis of the esterification reaction mechanism, the increase
in the feed ratio increases the concentration of the mixed acid anhydride in the reaction
system, thereby increasing the probability of reacting with the CNC hydroxyl group. Thus,
the degree of product substitution increases. However, when the feeding ratio is excessive,
although the concentration of the mixed acid anhydride still increases on a macro scale,
the contact concentration of the mixed acid anhydride with the hydroxyl group gradually
becomes saturated; thus, the DS does not change evidently. The DS of MCNC-C12 is higher
than that of MCNC-C16 and MCNC-C18; it is determined by the steric hindrance of higher
saturated fatty acids. With the continuous increase in fatty acid hydrocarbon chain length,
its steric hindrance effect gradually becomes evident, inhibiting the increase in substitution
degree. Therefore, the DS of the three MCNC from high to low is MCNC-C12, MCNC-C16,
and MCNC-C18, under the same conditions.

3.1.2. Effect of Initiator and Content on the DS of MCNC

FeSO4 /H2 O2 was selected as the initiator, the content of the added initiator was
changed at a specific reaction temperature and time, and lauric acid, palmitic acid, and
stearic acid were used to react with the CNC. CNC reacted with lauric acid in the 50 ◦ C
water bath environment for 8 h, CNC and palmitic acid reacted in the 55 ◦ C water bath en-
vironment for 20 h, and CNC reacted with stearic acid in the 60 ◦ C water bath environment
for 24 h. Different initiator types were added, and the addition amount was changed to
prepare MCNC with different DS under these reaction conditions. The DS is measured,
and the results are shown in the figure.
 0.35

0.30 MCNC-C12

Degree of Substitution
0.25 MCNC-C16
MCNC-C18
Polymers
Polymers 13,13,
2021,
2021, 3417
3417 0.20 7 of7 of
15 14
0.15

0.10

0.40
0.05

0.35
0.00
1：1：1 1：2：2 1：3：3 1：4：4 1：5：5 1：6：6
0.30 MCNC-C12
Ratio of AGU to Co-reaction Reagent

Degree of Substitution
0.25 MCNC-C16
Figure 1. Effect of the ratio of co-reaction reagent on substitution degree of MCNC. (MCNC-C12:
MCNC-C18
MCNC
0.20 grafted with lauric acid; MCNC-C16: MCNC grafted with palmitic acid; MCNC-C18:
MCNC grafted with stearic acid.)
0.15

3.1.2.
0.10Effect of Initiator and Content on the DS of MCNC

FeSO4/H2O2 was selected as the initiator, the content of the added initiator was
0.05
changed at a specific reaction temperature and time, and lauric acid, palmitic acid, and
0.00
stearic acid
1：1：1 were used to
1：2：2 react 1：4：4
1：3：3 with the1：5：5
CNC. 1：6：6 CNC reacted with lauric acid in the 50 °C
Ratio of AGU to Co-reaction Reagent
water bath environment for 8 h, CNC and palmitic acid reacted in the 55 °C water bath
environment
Figure
Figure 1. Effect
1. Effect
forof20
of the the h,ratio
ratio
and CNC
of reacted
co-reaction
of co-reaction
with
reagent
reagent
stearic acid in
on substitution
on substitution
the 60
degree
degree
°Cofwater
of MCNC.MCNC. bath environ-
(MCNC-C12:
(MCNC-C12:
ment
MCNC
MCNC for 24
grafted h.
grafted Different
with
withlauric
lauric initiator
acid;
acid; types
MCNC-C16: were
MCNC-C16:MCNC added,
MCNCgrafted and
graftedwiththe addition
withpalmitic
palmiticacid;amount was
acid;MCNC-C18:
MCNC-C18: changed
MCNC
to
MCNC prepare
grafted
grafted MCNC with
with stearic
with stearic different
acid.)acid.) DS under these reaction conditions. The DS is measured,
and the results are shown in the figure.
Figure
Figure
3.1.2. Effect of22Initiator
shows
showsthat andunder
that under
Content the
theFeSO
onFeSO
the4DS/H
4 /H2Oof22O redox
2 redox
MCNC initiation
initiationsystem,
system,as the amount
as the amount of
of initiator
initiator increases,
increases, the theDS DSof of lauric
lauric acid,
acid, palmitic
palmitic acid,
acid,
FeSO4/H2O2 was selected as the initiator, the content of the added initiator was and
and stearic
stearic acid
acid esterified
esterified CNC
CNC
initiallyatincreases,
initially
changed a specificandand then
thengradually
reaction gradually
temperaturetends
tends to to
and be flat.flat.
be
time, When
and Whenthe the
lauric amount
acid, of initiator
amount
palmiticof acid, isand
0.8%,
initiator is
lauric
0.8%, acid
lauric as
acidtheasgraft
the can
graft obtain
can the
obtain best
the DS
best of
DS 0.24
of under
0.24
stearic acid were used to react with the CNC. CNC reacted with lauric acid in the 50 °C this
under preparation
this preparation method.
method. In
addition,
In addition, thetheamount
amount of initiator continues to increase,
of 8initiator andandthe the
DS tends to betostable. The
water bath environment for h, CNCcontinues
and palmitic to increase,
acid reacted DS 55
in the tends
°C water be stable.
bath
substitution
The substitution effect of palmitic acid and stearic acid is the same as that of lauric acid. The
environment for 20effect
h, and ofCNC
palmitic acidwith
reacted and stearic
stearic acidacidin is the
the 60same as thatbath
°C water of lauric
environ-acid.
bestbest
The DS is DSobtained
is obtained when the the
when dosage
dosageof the
of initiator
the initiatoris 1.2%.
is The
1.2%. substitution
The substitution degrees
degrees of
ment for 24 h. Different initiator types were added, and the addition amount was changed
palmitic acid and stearic acid areare
0.16 and 0.12, respectively.
toofprepare
palmitic acid
MCNC and
withstearic
differentacid 0.16
DS under and
these 0.12, respectively.
reaction conditions. The DS is measured,
and the results are shown in the figure.
FeSO /H O 4 2 2
Figure 2 shows that under the
0.25 L: MCNC-C12 L FeSO L 4/H2OL2 redox initiation system, as the amount of
P: MCNC-C16
initiator S:
increases,
MCNC-C18 the DS of lauric acid, palmitic acid, and stearic acid esterified CNC
initially
0.20
increases, and then gradually tends to be flat. When the amount of initiator is
Degree of Substitution

0.8%, lauric acid as the graft can obtain the best DS of 0.24 under this preparation method.
L P P
In addition, the amount of initiator continues to increase, and the DS tends to be stable.
0.15 P
The substitution effect of palmiticPacid and stearic S
acid S
is the same as that of lauric acid.
The best DS is obtained when the dosage of the initiator is 1.2%. The substitution degrees
L S
0.10
of palmitic acid
L
and stearic Pacid are S0.16 and 0.12, respectively.
P
S
S
0.05 FeSO4/HP S
2O2

0.25 L: MCNC-C12 L L L
P: MCNC-C16
S: MCNC-C18
0.00
0.20 0 0.3 0.5 0.7 0.8 0.9 1.2 1.5
Degree of Substitution

Initiator addition/%
L P P
Figure
Figure
0.15 Effectof
2.Effect
2. ofinitiator
initiatortype
typeand
and dosage
dosage
P onon substitution
substitution degree
degree of
of MCNC.
MCNC. (MCNC-C12:
(MCNC-C12: MCNC
MCNC grafted with lauric acid; P
MCNC-C16: MCNC S S
grafted with palmitic
grafted with lauric acid; MCNC-C16: MCNC grafted with palmitic acid; MCNC-C18: acid; MCNC-C18:
MCNC grafted
MCNC
with grafted
stearic with
acid.)
L
stearic acid.) S
0.10 P
L P S
The main reason S forSthis phenomenon is the steric hindrance of the system on the
0.05 P S
glucoside unit. When the amount of initiator is not optimal, the initiation efficiency of the
reaction system gradually increases as the content of initiator increases, the concentration
0.00
of initiated active free radicals increases, and the degree of reaction substitution increases.
0 0.3 0.5 0.7 0.8 0.9 1.2 1.5
In addition, the FeSO4 /H 2 O2 system
Initiator
generates free radicals on the primary hydroxyl group
addition/%
at the C6 position of the glucoside unit. When the amount of initiator is higher than the
Figure 2. Effect
optimal of initiator
amount, the DS type andproduct
of the dosage on substitution
tends degreeAtofthis
to be stable. MCNC.
time,(MCNC-C12:
although increasing
MCNC grafted with lauric acid; MCNC-C16: MCNC grafted with palmitic acid; MCNC-C18:
the amount of initiator can still increase the concentration of free radicals, the space steric
MCNC grafted with stearic acid.)
hindrance effect of higher fatty acids greatly affects the esterification efficiency between free
Polymers 2021, 13, 3417 8 of 14

radicals, and the steric hindrance effect increases with the increase in the length of the fatty
acid hydrocarbon chain, thereby limiting the continued increase in the DS of the product.
Therefore, the steric hindrance effect of higher fatty acid becomes an important factor
affecting the DS when the free radical content reaches a certain concentration. Under
the FeSO4 /H2 O2 system, the DS of lauric acid, palmitic acid, and stearic acid MCNC
also decreases.

3.1.3. Effect of Reaction Time on Substitution Degree of MCNC

Lauric acid was used as raw material, and trifluoroacetic anhydride was used as
co-reaction agent; they are mixed in a molar ratio of 1:1. The mixture was prepared at
4 h, 5 h, 6 h, 7 h, and 8 h, by changing the reaction time in a water bath at 50 ◦ C with the
molar ratio of 3:1 to CNC. The preparation method of palmitic acid and stearic acid as
raw materials was similar to that of lauric acid, but the reaction temperature was raised to
55 ◦ C. After the reaction, an appropriate amount of stearic acid MCNC was obtained, and
the DS was tested by saponification method.
With 0.8% FeSO4 /H2 O2 as the initiator, lauric acid was reacted with CNC in a water
bath at 50 ◦ C to prepare MCNC-C12. The reaction time was set at 6 h, 7 h, 8 h, 9 h, and 10 h,
according to the same experimental method to prepare MCNC-C16 and MCNC-C18. The
reaction temperature was set to 55 ◦ C, and 1.2% FeSO4 /H2 O2 was selected as the initiator.
The reaction times of 16 h, 18 h, 20 h, 22 h, and 24 h were set for the graft copolymerization
of CNC with palmitic acid as the raw material. The reaction temperature was set to 55 ◦ C,
and 1.2% FeSO4 /H2 O2 was selected as the initiator. The reaction times of 16 h, 18 h, 20 h,
22 h, 24 h, and 25 h were set for the graft copolymerization of CNC with stearic acid as
the raw material. After the reaction, an appropriate amount of stearic acid MCNC was
obtained, and the DS was tested by saponification method. The test results are as follows.
Figure 3 shows that under the same conditions, the DS of lauric acid was higher
than that of palmitic acid, whereas that of stearic acid was the lowest. The esterification
produced the mixture of anhydrides with higher activity than fatty acids in the first place;
thus, its substitution degree is higher than the graft copolymerization under the same
conditions. Moreover, the time interval for the preparation of three fatty acid esterified
CNC by this method is more concentrated. However, in the graft copolymerization, the
reaction time was longer because the steric hindrance caused by the over-long hydrocarbon
chains of palmitic acid and stearic acid was much higher than that of lauric acid. In addition,
their reaction activity was lower than that of anhydride. In general, the reaction time of the
modified products of lauric acid was lower than that of the modified products of the two
other acids. In summary, in the system with trifluoroacetic anhydride as co-reactive agent,
Polymers 2021, 13, 3417
the optimal reaction time with lauric acid as the raw material is 5 h, palmitic acid as the
9 of 15
raw material is 6 h, and stearic acid as the raw material is 6 h. However, in the initiator
system, the optimal reaction time of the three fatty acids was 8 h, 20 h, and 24 h.
0.40
esterification reaction
0.35 grafting copolymerization
C12
Degree of Substitution

0.30
C16
0.25
C12

0.20
C16
C18
0.15

0.10 C18

0.05

5 10 15 20 25
Time/h

Figure 3. Effect of reaction time on substitution degree

degree of
of MCNC.
MCNC.

3.1.4. Effect of Temperature on the DS of MCNC

Trifluoroacetic anhydride was considered the co-reactant, and CNC was mixed at a
molar ratio of 3:1. The amounts of fatty acids involved in the reaction were the same as
Polymers 2021, 13, 3417 9 of 14

3.1.4. Effect of Temperature on the DS of MCNC

Trifluoroacetic anhydride was considered the co-reactant, and CNC was mixed at a
molar ratio of 3:1. The amounts of fatty acids involved in the reaction were the same as
that of the co-reactant. When lauric acid was used, the reaction time was controlled at 5 h,
and the reaction temperatures were set at 40 ◦ C, 45 ◦ C, 50 ◦ C, 55 ◦ C, and 60 ◦ C. When soft
fatty acid was used, the reaction time was controlled at 6 h, and the reaction temperatures
were set at 40 ◦ C, 45 ◦ C, 50 ◦ C, 55 ◦ C, and 60 ◦ C. When stearic acid was used, the reaction
time was controlled at 6 h, and the reaction temperatures were set at 40 ◦ C, 45 ◦ C, 50 ◦ C,
55 ◦ C, and 60 ◦ C; when stearic acid was used, the reaction time was controlled at 6 h, and
the reaction temperatures were set at 40 ◦ C, 45 ◦ C, 50 ◦ C, 55 ◦ C, and 60 ◦ C.
At 8 h reaction time, CNC was graft-modified with lauric acid by adding 0.8%
FeSO4 /H2 O2 at 35 ◦ C, 40 ◦ C, 45 ◦ C, 50 ◦ C, 55 ◦ C, 60 ◦ C, and 65 ◦ C. At 20 h reaction
time, CNC was graft-modified with soft stearic acid by adding 1.2% FeSO4 /H2 O2 at 35 ◦ C,
40 ◦ C, 45 ◦ C, 50 ◦ C, 55 ◦ C, 60 ◦ C, and 65 ◦ C. At 24 h reaction time, CNC was graft modified
with stearic acid by adding 1.2% FeSO4 /H2 O2 at 35 ◦ C, 40 ◦ C, 45 ◦ C, 50 ◦ C, 55 ◦ C, 60 ◦ C,
and 65 ◦ C. Appropriate amounts of the prepared fatty acid modification products were
Polymers 2021, 13, 3417 taken and tested for their DS by saponification method. 10 of 15
Figure 4 reflects the effect of reaction temperature on the degree of product substitution
when grafting CNC by both preparation methods. The trend of the curves in the figure is
the same as that of the effect of reaction time on the DS of the modified products. Lauric
20 h at 55 °C with 1.2% initiator and 0.12 for 24 h at 60 °C with 1.20% initiator for MCNC-
acid has a higher DS than soft and stearic acid under the same conditions due to the steric
C18. The differences
hindrance inpolymer.
effect of the the DS between
Relatively thehigh
two DS
methods were dueatto
were obtained 50the
◦ C different princi-
to 60 ◦ C for both
ples of modifying
preparations, but CNC with co-reactants
the reaction temperature and initiators.
was Thehigher
relatively naturefor
of stearic
the modified prod-
acid because
uct by introducing
as the hydrocarbon a co-reactant
chains of the is the reaction
fatty between the
acids involved mixed
in the anhydride
reaction grow,andtheirthesteric
hy-
droxyl groups of the CNC, which are at the C6, C2, and C3 positions. On the contrary, the
hindrance becomes progressively greater. When the molecular weight of the fatty acid
use of an18
reaches initiator
carbons,forthethesteric
preparation
hindrance of the modified
becomes product involves
an important factor in thethe
initiation
DS of theof
the hydroxyl group at the C 6 position, and the number of reaction sites is different between
modified reaction, and the reaction system requires a higher temperature to better activate
the
thetwo methods; hence a difference is found in the DS.
reactants.
0.40
esterification reaction
0.35
grafting copolymerization
Degree of Substitution

0.30

C12
0.25
C12
C16
0.20
C18
C16
0.15
C18
0.10

0.05

0.00
30 40 50 60 70
Temperature/℃

Effectof
Figure4.4.Effect
Figure ofreaction
reactiontemperature
temperatureon
onsubstitution
substitution degree
degree of
of MCNC.
MCNC.

In summary,
3.2. X-ray when
Diffraction using
Analysis of trifluoroacetic
MCNC anhydride as the co-reactant, the optimum
◦
reaction conditions for MCNC-C12 were 50 C, 5 h, and 1:3 feeding ratio, and the degree
X-ray diffraction analysis of CNC and MCNC prepared by different methods. The
of product substitution was 0.32. The optimum reaction conditions for MCNC-C16 were
test◦results are shown in the following figure 5:
55 C, 6 h, and 1:3 feeding ratios; the DS was 0.27. The optimum reaction conditions for
MCNC-C18 were 55 ◦ C, 6 h, and 1:3 feeding ratio, and the degree of product substitution
was 0.23. In the FeSO4 /H2 O2 redox system, the highest DS of 0.24 was achieved by adding
0.8% initiator at a reaction temperature of 50 ◦ C for 8 h. The highest DS of 0.24 was achieved
by adding 1.2% initiator at a reaction temperature of 55 ◦ C for MCNC-C16
MCNC-C18 for 20 h. In the
Intensity count

FeSO4 /H2 O2 redox system, the highest DS of 0.24 was achieved by adding 0.8% initiator
Intensity count

MCNC-C18
at a reaction temperature of 50 ◦ C for MCNC-C12. The maximum DS was 0.16 for 20 h at
MCNC-C16
MCNC-C16

MCNC-C12
MCNC-C12

CNC
 0.40
esterification reaction
0.35
grafting copolymerization

Degree of Substitution
0.30
Polymers 2021, 13, 3417 C12 10 of 14
0.25
C12
C16
0.20
C18
C16
55 ◦0.15
1.2% initiator and 0.12 for 24 h at 60 ◦ C with 1.20% initiator for MCNC-C18.
C with
differences in the DS between theC18two methods were due to the different principles of
The0.10
modifying CNC with co-reactants and initiators. The nature of the modified product by
0.05
introducing a co-reactant is the reaction between the mixed anhydride and the hydroxyl
groups
0.00 of the CNC, which are at the C6 , C2 , and C3 positions. On the contrary, the use
30 40 50 60 70
of an initiator forTemperature/℃
the preparation of the modified product involves the initiation of the
hydroxyl group at the C6 position, and the number of reaction sites is different between
Figure
the two 4. methods;
Effect of reaction
hence temperature
a differenceon
is substitution
found in thedegree
DS. of MCNC.

3.2.
3.2. X-ray
X-ray Diffraction
Diffraction Analysis
Analysis of
of MCNC
MCNC
X-ray diffraction analysis
X-ray diffraction analysisofofCNC
CNCand
and MCNC
MCNC prepared
prepared by by different
different methods.
methods. The The
test
results are shown in the following Figure 5:
test results are shown in the following figure 5:

MCNC-C18
Intensity count

Intensity count
MCNC-C18
MCNC-C16
MCNC-C16

MCNC-C12
MCNC-C12

CNC
CNC

10 20 30 40 50 60 10 20 30 40 50 60
Scattering angle(degrees of 2θ) Scattering angle(degrees of 2θ)
A B

Figure 5. X-ray diffraction pattern of

of fatty
fatty acid
acid MCNC.
MCNC.((A): diffractioncurve
(A: diffraction curveof
of MCNC
MCNC crystal
crystal prepared
prepared by esterification
method, and (B):
B: diffraction
diffractioncurve
curveofofMCNC
MCNCcrystal
crystalprepared
preparedbybygraft
graftcopolymerization
copolymerizationmethod).
method).

Regardless of
Regardless of whether
whether the esterification substance with CNC is lauric acid, palmitic
acid, or stearic acid, the essence of the grafted CNC is the same. The difference in steric
acid, or stearic acid,
hindrance caused
hindrance caused by by the chain length causes different crystallinity. Therefore, the XRD
diffraction peak
diffraction peak value
valueof ofvarious
variousproducts
productsprepared
prepared under
under thethesame
same system
system is different, but
is different,
the peak
but position
the peak is approximately
position the same.
is approximately The results
the same. show that
The results show thethat
diffraction peak of
the diffraction
the MCNC
peak of the is weakened
MCNC at the intensity
is weakened of I002 , and
at the intensity of the
I002,crystallinity of the modified
and the crystallinity products
of the modified
decreases. However, the products of the grafted MCNC with three
products decreases. However, the products of the grafted MCNC with three types of ad- types of advanced
fatty acids
vanced still
fatty have
acids diffraction
still peaks at
have diffraction the intensity
peaks of I002 , of
at the intensity IamI002
, and
, Iam,I004
and, indicating that
I004, indicating
the products still maintain the basic crystal structure of CNC. The new diffraction peak
generated by MCNC and the decrease in the area of the diffraction peak at the intensity of
I002 also prove the chemical modification of CNC.

3.3. MCNC Particle Size Test

MCNC was prepared under the optimal reaction conditions to detect the particle
size of CNC and three types of MCNC, using trifluoroacetic anhydride as co-reactant and
FeSO4 /H2 O2 as initiator. The test results are as follows:
Figure 6 shows that the average particle size of CNC modified by fatty acids ex-
ceeds the average particle size of the original CNC (168 nm), which is in the range of
240–260 nm. However, the specific surface area is lower than the value of unmodified
CNC (19,260 m2 /kg), which is in the range of 17,400–17,500. In general, regardless of
the advanced fatty acid and method selected to prepare MCNC, the difference between
the particle size, particle size distribution coefficient, and specific surface area is very
small, and can even be approximately considered the same. However, because the long
chain of carbon and hydrogen replaced the original hydrogen atoms after esterification of
fatty acids and CNC, the molecular weight increased to varying degrees, and the spatial
 nm. However, the specific surface area is lower than the value of unmodified CNC (19,260
m2/kg), which is in the range of 17,400–17,500. In general, regardless of the advanced fatty
acid and method selected to prepare MCNC, the difference between the particle size, par-
ticle size distribution coefficient, and specific surface area is very small, and can even be
Polymers 2021, 13, 3417 approximately considered the same. However, because the long chain of carbon and hy-
11 of 14
drogen replaced the original hydrogen atoms after esterification of fatty acids and CNC,
the molecular weight increased to varying degrees, and the spatial scale of molecular
structure increased. Thus, the particle size of the modified products still increased slightly;
scale of molecular structure increased. Thus, the particle size of the modified products
it was higher than that of the unmodified CNC. Nevertheless, the esterified cellulose par-
still increased slightly; it was higher than that of the unmodified CNC. Nevertheless, the
ticles are still nanometer in size. The figure shows that the grafting of long-chain fatty
esterified cellulose particles are still nanometer in size. The figure shows that the grafting
acids did not significantly increase the original nanometer particle size, but only increased
of long-chain fatty acids did not significantly increase the original nanometer particle
the particle size in a small range. In addition, modified products with wider particle size
size, but only increased the particle size in a small range. In addition, modified products
distribution are greater than the original CNC size distribution coefficient. This finding
with wider particle size distribution are greater than the original CNC size distribution
shows that during the esterification reaction of CNC, a certain degree of flocculation has
coefficient. This finding shows that during the esterification reaction of CNC, a certain
occurred. The reduction of the specific surface area of the MCNC causes the original CNC
degree of flocculation has occurred. The reduction of the specific surface area of the MCNC
to be grafted
causes with long
the original CNC hydrocarbon chains,
to be grafted withweakening their reactivity
long hydrocarbon chains,toweakening
a certain extent.
their
Therefore, CNC is still at the nanoscale level and has large specific surface
reactivity to a certain extent. Therefore, CNC is still at the nanoscale level and areahas
after es-
large
terification and grafting of carbon and hydrogen long chains. This condition lays
specific surface area after esterification and grafting of carbon and hydrogen long chains. a good
foundation
This conditionfor their
lays asubsequent functional
good foundation applications.
for their subsequent functional applications.

I: grafting copolymerization
CNC II: esterification reaction

MCNC-C12-I

MCNC-C16-I
12.8
MCNC-C18-I
Intensity/%

MCNC-C12-II
9.6
MCNC-C16-II
6.4

3.2 MNCC-C18-II

0.0
200 400 600 800
Size/nm

Figure 6.
Figure Particle size
6. Particle size distribution
distribution of
of MCNC.
MCNC.

3.4. Calculation of HLB Value of MCNC

3.4. Calculation of HLB Value of MCNC
In accordance with the HLB value equation (Equation (4)), the HLB values of MCNC
under Invarious
accordance withreaction
optimal the HLBconditions
value equation (Equation (4)),
were calculated and the HLBinvalues
shown of MCNC
Table 1.
under various optimal reaction conditions were calculated and shown in Table 1.
Table 1. HLB value of fatty acid graft MCNC.

HLB Value
MCNC
Esterification Grafting Copolymerization
MCNC-C12 14.68 15.73
MCNC-C16 14.29 16.17
MCNC-C18 14.49 16.69

By comparison, the HLB values of MCNC prepared by grafting copolymerization

are slightly higher than that of MCNC prepared by esterification. The HLB values of
MCNC are affected by the DS and the length of the grafted hydrocarbon chain. With the
increase in DS, the HLB values show a decreasing trend. The increase in DS increases the
number of hydrophobic groups, and the modified products become more lipophilic. Thus,
the MCNC gradually tend to be hydrophobic, and the HLB values decreases. However,
due to the different molecular weights of the grafted fatty acids, the calculation results
of HLB value would be affected to some extent. In addition, the phenomenon indicates
that the HLB value of low-DS MCNC is higher than that of low-DS MCNC. In general, all
modified products are hydrophilic and lipophilic. The raw CNC contains a large number
of unsubstituted hydroxyl groups due to the low DS of MCNC. Thus, modified products
tend to be hydrophilic. Therefore, the amphiphilicity of MCNC is determined by the DS
and the length of the grafted hydrocarbon chain.
Polymers 2021, 13, 3417 12 of 14

3.5. Influence of MCNC Concentration on Surface Tension of Water

CNC and MCNC were configured into different concentrations of suspension to be
tested. During the test, the suspension was pretreated with ultrasound, and the surface
tension of suspension was measured at 25 ◦ C. The following results were obtained.
Figure 7 shows that CNC and their modified products can effectively reduce the
surface tension of water, and the modified products have a more evident reduction effect
on the surface tension. With the gradual increase in the concentration of various substances
in water, the decreasing trend of surface tension changes from rapid to smooth. When a
certain concentration is reached, continuously increasing its concentration does not cause a
significant change in the surface tension of the water. The concentration value at this point
is called the critical micelle concentration (CMC). In Figure 7, the CMC of the CNC and the
MCNC appear near 12.5 mg/L, and the surface tension reduction intensity increases as the
length of the hydrocarbon chain grafted on the CNC increases. Thus, MCNC-C18 has the
best effect on reducing the surface tension of water, followed by MCNC-C16 and MCNC-
C12. The figure shows that the carbon chain length slightly affects the critical micelle
concentration because the main molecular chain skeleton of CNC is a macromolecular
structure. At the same concentration of the same modified products, the esterification
method has better surface tension reduction effect than the grafting copolymerization
method. Its essence is due to the higher DS of the products prepared by the esterification,
Polymers 2021, 13, 3417 and the change in the carbon chain length slightly affects the overall structure. In addition,
13 of 15
the structure analysis indicates that the MCNC cannot ionize in water; thus, MCNC belongs
to the non-ionic surfactant.

I: grafting copolymerization CNC

75 II: esterification reaction MCNC-C12-I
MCNC-C12-II
Surface tension (mN/m)

MCNC-C16-I
70
MCNC-C16-II
MCNC-C18-I

65 MCNC-C18-II

60

55

50
0 5 10 15 20 25
Concentration of NCC, MNCC (mg/L)

Figure
Figure 7.
7. Effect
Effect of
of MCNC
MCNC concentration
concentration on
on surface
surface tension
tension of
of MCNC
MCNC suspension.
suspension.

4. Conclusions
4. Conclusions
The MCNC
The MCNC prepared
prepared by by esterification
esterification and
and grafting
grafting copolymerization
copolymerization isis compared.
compared.
Both methods can complete the reaction with low energy consumption, but
Both methods can complete the reaction with low energy consumption, but the prepara- the preparation
timetime
tion of the esterification
of the method
esterification methodis shorter
is shorterand
andthe
theDS
DSofofMCNC
MCNCisishigher.
higher. The X-ray
The X-ray
diffraction and particle size analysis of the modified products show that the
diffraction and particle size analysis of the modified products show that the products pre- products
prepared
pared by two
by the the two methods
methods maintain
maintain the crystal
the crystal structure
structure of theof theCNC,
raw raw CNC, andare
and they they
at
are nanometer
the at the nanometer level.
level. The The measurement
measurement results results
of HLBofvalue
HLB and
value and surface
surface tensiontension
prove
prove
that that
the the modified
modified products
products have have hydrophilic
hydrophilic and lipophilic
and lipophilic properties,
properties, andandthe the effect
effect of
of reducing the surface tension of water is better than that of raw CNC. Because of good
reducing the surface tension of water is better than that of raw CNC. Because of good
biodegradability, the modified product can be used as a new type of green surface-active
biodegradability, the modified product can be used as a new type of green surface-active
substance, which are endowed with emulsion, dispersion, wetting, washing, sterilization,
substance, which are endowed with emulsion, dispersion, wetting, washing, sterilization,
water resistant, antistatic, solubilization and stable features. Further, it will be widely
water resistant, antistatic, solubilization and stable features. Further, it will be widely con-
concerned in food, chemical, agriculture, construction and other fields, to achieve high
cerned in food, chemical, agriculture, construction and other fields, to achieve high value
value utilization of biomass resources.
utilization of biomass resources.

Author Contributions: Methodology, J.L. (Jinyan Lang); software, J.L. (Junliang Lu); validation,
N.W. and X.W.; data curation, Y.W.; writing—original draft preparation, J.L. (Jinyan Lang); writ-
ing—review and editing, N.W. and X.W.; visualization, B.X. and G.C.; supervision, H.Z.; project
administration, H.Z.; funding acquisition, H.Z. All authors have read and agreed to the published
version of the manuscript.
Polymers 2021, 13, 3417 13 of 14

Author Contributions: Methodology, J.L. (Jinyan Lang); software, J.L. (Junliang Lu); validation, N.W.
and X.W.; data curation, Y.W.; writing—original draft preparation, J.L. (Jinyan Lang); writing—review
and editing, N.W. and X.W.; visualization, B.X. and G.C.; supervision, H.Z.; project administration,
H.Z.; funding acquisition, H.Z. All authors have read and agreed to the published version of
the manuscript.
Funding: This work was supported by the Shandong Provincial Key Research and Development
Program (SPKR&DP) (Grant No. 2019GGX102029), the Research Fund Program of Guangdong
Provincial Key Lab of Green Chemical Product Technology (Grant No. GC202112) and open fund of
the Key Laboratory of Fire-Retardant Materials of Fujian Province (Grant No. FH202101).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: This work was supported by the Shandong Provincial Key Research and De-
velopment Program (SPKR&DP) (Grant No. 2019GGX102029), the Research Fund Program of
Guangdong Provincial Key Lab of Green Chemical Product Technology (Grant No. GC202112)
and open fund of the Key Laboratory of Fire-Retardant Materials of Fujian Province (Grant No.
FH202101). Thanks to Shuyin Tan, Mengdi Ru, Xun Zhu, Jufang Zhang and Jingxue Yang, for their
participation in the translation of this manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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