Biomass and Bioenergy 105 (2017) 51e58

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Biomass and Bioenergy

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Research paper

Synthesis of sodium carboxymethyl cellulose using bleached crude

cellulose fractionated from cornstalk
Tao Shui a, Shanghuan Feng a, Gang Chen a, An Li c, Zhongshun Yuan a, Hengfu Shui d,
Takashi Kuboki b, *, Chunbao Xu (Charles)a, d, **
a
Department of Chemical and Biochemical Engineering, Western University, London, Ontario N6A 5B9, Canada
b
Department of Mechanical and Materials Engineering, Western University, London, Ontario N6A 5B9, Canada
c
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9, Canada
d
School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan, Anhui 243002, China

a r t i c l e i n f o a b s t r a c t

Article history: In this study, crude cellulose derived from cornstalk, after bleaching, was used as raw material for the
Received 3 October 2016 synthesis of sodium carboxymethyl cellulose (CMC) by reacting with the cellulose with NaOH and
Received in revised form chloroacetic acid at 75
C for 1.5 h. Effects of alkali dosage, concentration of chloroacetic acid on the
6 March 2017
physical and chemical properties of the CMC products were investigated. It was revealed that the re-
Accepted 23 June 2017
Available online 1 July 2017
actants alkali reagent/chloroacetic acid/cellulose at the molar ratio of 4.6:2.8:1and 4:2.5:1, or at the
molar ratio of NaOH/ClCH2COOH z1.6e1.64, resulted in CMC products of relatively high water solubility.
The viscosity-average molecular weight Mv of these two CMC products obtained at molar ratios of
Keywords:
Crude cellulose
4.0:2.5:1 and 4.6:2.8:1 is in the range of 1.94  104e2.48  104 g mol1, and the average DS of the two
Cornstalk products are 0.57 and 0.85, respectively. As the solute concentration is above 2 wt%, the viscosity of the
Alkali reagent CMC-water solution exhibits nonlinear (exponential) increasing with increasing the solute concentration
Etherification (typical of non-Newton fluids).
Sodium carboxymethyl cellulose © 2017 Elsevier Ltd. All rights reserved.
Degree of substitution (DS)

1. Introduction [9,10]. Generally hydroxyl groups in cellulose are replaced by car-

boxymethyl groups in the order of C6 > C3 > C2 [11e13]. In het-
Carboxymethyl cellulose (CMC) is one of the most widely used erogeneous carboxymethylation however the substitution takes
cellulose derivatives in the industry. CMC, a white-cream-colored place in the order C2 z C6 > C3 [7,9,11e13]. For the CMC with the
powder, has wide applications in food, pharmaceutical, de- DS < 0.4, it is swelled but insoluble in water, while for DS of more
tergents and coatings [1,2,3]. CMC can also be utilized for paper or than 0.4, CMC is fully soluble with its hydro-affinity, which in-
textile improvement as fibers [4,5]. It is an anionic linear polymer in creases with the raise of DS [14].
which the original H atom in cellulose hydroxyl group is replaced The continuously increasing demand of instant and defatted
by carboxymethyl substituent (eCH2eCOOe) [6,7]. CMC is food in recent years makes the CMC market grow dramatically [15].
extremely recommended as an additive in many commodity Generally purified cotton (a-cellulose>98.3 wt%) has been widely
products due to its non-toxicity, high water solubility as well as the applied as the feedstock for CMC production [16] while usage of the
outstanding light and thermal stability [8]. Through the reaction of expensive cotton as well as the purification treatment increase the
alkali cellulose in aqueous NaOH with monochloroacetic acid or its cost of the product, which has thus become the limitation for the
sodium salt, CMCs with different degree of substitution (generally growth of CMC production. As such, there is a need for sustainable
in the range 0.5e1.4 for commercial products) can be produced and inexpensive substitutes to cotton cellulose [17].
Cornstalk, containing cellulose (30e35 wt%), lignin (16e20 wt%)
and hemicellulose (25e30 wt%), are very abundant in Canada.
* Corresponding author. Department of Mechanical and Materials Engineering,
Canada produced 10.7 million tons of grain corn in 2011, accom-
Western University, London, Ontario N6A 5B9, Canada. panied with about 15 million tons of cornstalk. In 2015, more than
** Corresponding author. Department of Chemical and Biochemical Engineering, 800,000 ha of grain corn were harvested [18] in Ontario Canada,
Western University, London, Ontario N6A 5B9, Canada. producing approx. 8.8 million tons of grain corn. However,
E-mail addresses: tkuboki@uwo.ca (T. Kuboki), cxu6@uwo.ca (C. Xu).

http://dx.doi.org/10.1016/j.biombioe.2017.06.016
0961-9534/© 2017 Elsevier Ltd. All rights reserved.
52 T. Shui et al. / Biomass and Bioenergy 105 (2017) 51e58

cornstalk and other agricultural lignocellulosic biomass have been Table 1. The contents of three major components in the cornstalk
paid little attention due to their limited applications mainly as feedstock, i.e., Klason lignin (acid insoluble), a-cellulose and
organic fertilizer, silage for livestock and source for heat and elec- hemicellulose were determined in accordance with NREL/TP-510-
tricity. Therefore, there is growing interest worldwide in trans- 42618 [28]. Briefly, the extractive content (EC) of oven dried raw
forming cornstalk or other crop residues into value-added bio- cornstalk sample was first determined by soxhlet extraction in
products, such as CMC. toluene/ethanol (2:1, v/v) for 24 h. The lignin content of the oven
Effort have been made since 1980 in searching for less expensive dried cornstalk sample was then determined by a sequential acid
alternatives to expensive cotton, such as various lignocellulosic hydrolysis of the extracted cornstalk first with 72 wt% sulfuric acid
biomasses (rich in cellulose), for production of CMC. According to at 30
C for 120 min and then with 4 wt% diluted sulfuric acid at
the study of Mario et al. [19], banana pseudo stem, known as a 121
C for 60 min. The holocellulose content of oven-dried corn-
potential cellulose source, was utilized for CMC synthesis. CMC stalk was determined using a modified Chlorination method using
product with DS, viscosity, purity and crystallinity of 0.75, the extracted cornstalk sample in water-acetic acid-sodium chlorite
4033 mPas, 98.23 wt% and 38.33 wt% respectively, was achieved mixed solvent at 50e70
C for more than 24 h to remove lignin.
through alkalization using 15 wt% NaOH followed by etherification Based on the resulted solid residue, the holocellulose content (HC)
using sodium monochloracetate (MCA). Furthermore, sugar beet was determined. Furthermore, the content of a-cellulose was
pulp was applied for production of CMC (with 0.667 DS) by reacting determined by treating the obtained holocellulose sample with 17.5
beet pulp with 30 wt% NaOH solution and sodium mono- wt% NaOH solution at room temperature to remove hemicellulose,
chloracetate in isobutyl alcohol as the solvent [20]. Cellulose iso- while the content of hemicellulose was finally determined by dif-
lated from Lantana camara was converted to CMC (DS 1.22) by ference. More detailed procedure to determine the contents of
reacting with aqueous NaOH and MCA for 3.5 h at 55
C in isopropyl lignin, cellulose and hemicellulose was provided in the previous
alcohol solvent [21]. Moreover, cellulose derived from a variety of article [27].
lignocellulosic biomasses, such as orange mesocarp, water hya- The chemicals used in this study, such as sodium hydroxide (50
cinth, sugarcane straw, corncob and cornstalk, etc. was utilized for wt% solution), chloracetic acid (solid, 99 wt%), ethanol (95 vol%),
the synthesis of CMC and other cellulose derivatives [22e26]. hydrochloric acid (36.5e38 wt%), etc. were all purchased from
In our previous work published recently [27], a highly efficient Caledon Laboratory Chemicals, and were used as received.
organosolv fractionation approach was developed to fractionate
cornstalk into cellulose and lignin using a mixed solvent of acetic 2.2. Methods
acid/formic acid/water (3:6:1, v/v/v). The obtained crude cellulose
can be a source of glucose for fuel ethanol production, but a more 2.2.1. Cornstalk fractionation
valuable application of the cornstalk-derived crude cellulose is as Fractionation of cornstalk was carried out in a 100 cm3 autoclave
an inexpensive feedstock for bio-based materials. This work aimed reactor (Parr 4590), following the procedure detailed in our pre-
to utilize the cornstalk-derived crude cellulose, after bleaching vious article [27]. In a typical run, briefly, 5.0 g air-dried cornstalk,
pretreatment, as a feedstock for the synthesis of CMC. This study 25 cm3 mixed solvent of acetic acid/formic acid/water (3:6:1, v/v/v)
centered on determination of best molar ratio of the reaction re- was added into the reactor. The reactor was then sealed, evacuated
agents (alkali reagent/etherifying reagent/cellulose) for the syn- and pressurized to 1.0 MPa with N2. The reactor was heated at the
thesis of CMC using cornstalk-derived cellulose. The chemical rate of approximately 10
C min1 to 90
C under approximately
structure, water solubility, average DS as well as other physical 300 rpm stirring for 180 min. After reaction, the reactor was cooled
properties such as viscosity of the CMC product were measured. to room temperature. The gas in the reactor was vented and the
reactor was opened. The slurry in the reactor was poured into a
2. Materials and methods 250 cm3 glass beaker, and the reactor was rinsed with ethyl acetate.
The spent ethyl acetate was also transferred to the 250 cm3 glass
2.1. Materials beaker. After 15 min, mixture in the beaker was filtered, while the
filter cake was further rinsed with ethyl acetate till the filtrate
Cornstalk used in this work was supplied by Ontario Federation became colorless. The solid residue present in the filtration cake
of Agriculture (OFA), collected from a local farm in South Ontario. was then rinsed with distilled water, dried at 105
C in an oven, and
However, the chain of custody of the biomass feedstock is not designated as crude cellulose.
available, hence it should be noted that the limited information
may impose a reasonable degree of uncertainty on the reproduc- 2.2.2. Crude cellulose bleaching
ibility and repeatability of the study. The cornstalk was air-dried at Sodium chlorite was used for crude cellulose bleaching. Briefly,
room temperature to a moisture content of <10 wt%, and then 2.5 g crude cellulose, 80 cm3 hot distilled water (50
C), 0.5 cm3
ground into particles to pass 20 mesh sieve. Elemental composition acetic acid and 1.0 g sodium chlorite were added into a 250 cm3
and chemical components of oven-dried cornstalk are presented in Erlenmeyer flask. The mixture was then heated under stirring

Table 1
Elemental composition and chemical components of oven-dried cornstalk.

Elemental composition (wt%) Chemical components (wt%)

a b
C H O N Ash Extractivesc Lignind Cellulosed Hemi-Cellulosee
f
45.01 (0.24) 5.67 (0.18) 45.38 (0.23) 1.50 (0.27) 2.44 (0.00) 1.34 (0.12) 18.57 (1.13) 35.31 (0.65) 32.58 (2.22)
a
By difference assuming negligible sulfur content.
b
Ashed at 575
C.
c
Soxhlet extraction in toluene/ethanol (2:1, v/v) for 24 h
d
Determined in accordance with NREL/TP-510-42618 [28].
e
By difference.
f
values in parenthesis are relative errors from 2 to 3 measurements.
 T. Shui et al. / Biomass and Bioenergy 105 (2017) 51e58 53

(150 rpm) in a water bath at 70
C for 60 min, then additional reactions: Alkalization and Etherification. In alkalization, cellulose
0.5 cm3 acetic acid and 1.0 g sodium chlorite were added. After each is modified by sodium hydroxide to produce sodium cellulosate, as
succeeding 60 min, a fresh portion of 0.5 cm3 acetic acid and 1.0 g shown in Eq. (1) below. In etherification, firstly, chloroacetic acid
sodium chlorite were added. After 7e8 h of bleaching under stir- dissolve in the sodium hydroxide to form sodium chloroacetate, as
ring, the mixture was left in the water bath for 24 h. The mixture shown in Eq. (2). Then, the chlorine in sodium chloroacetate
was then cooled to room temperature and filtered, and the reacted with the sodium cellulosate to generate CMC, as given
collected residue was further rinsed with distilled water during below in Eq. (3). Since this system is under alkaline condition, there
filtration. Then the obtained bleached cellulose (residue after are some by-products generated, such as glycolic acid, sodium
filtration) was vacuum dried at 65
C for 24 h, weighed (for glycolate, water, and sodium chloride, as shown in Eqs. (4) and (5)
bleached crude cellulose yield calculation), and then ground into [26]. It shall be noted, during the process, hemicellulose can also be
particles to pass 20 mesh sieve, subject to CMC synthesis. etherified.
It should be noted that bleaching using sodium chlorite is not    
desirable for industrial application due to the environmental and C6 H7 O2 ðOHÞ3 n
þ n NaOH/ C6 H7 O2 ðOHÞ2 ONa n þ n H2 O
health concerns. The reason we bleached the crude cellulose using (1)
the acid chlorite method is to demonstrate the usability of the
crude cellulose isolated from cornstalk for CMC production. In ClCH2 COOH þ NaOH/ClCH2 COONa þ H2 O (2)
future studies, in particular for pilot-/large-scale demonstration of
this process, other bleaching methods (e.g., H2O2) will be adopted.  
C6 H7 O2 ðOHÞ2 ONa n þ n ClCH2 COONa
  (3)
/ C6 H7 O2 ðOHÞ2 OCH2 COONa n þ n NaCl
2.2.3. CMC synthesis
Taking into account the <100 wt% purity for the bleached
cornstalk-derived cellulose and its poorer reactivity than pure ClCH2 COONa þ H2 O/HOCH2 COOH þ NaCl (4)
cellulose, molar ratio of the etherification agent to CMC was set at
2.0e3.0, higher than the conventional molar ratio (0.5e1.5) when ClCH2 COONa þ NaOH/HOCH2 COONa þ NaCl (5)
pure cellulose is used. The CMC synthesis procedure can be
described by a block flow diagram, as shown in Fig. 1. Briefly, take
the molar ratio of 4:2:1 (sodium hydroxide/chloroacetic acid/cel-
lulose) as an example, 1.00 g bleached cellulose was weighed in a 2.3. Characterizations
50 cm3 glass beaker, treated with 0.99 g 50 wt% NaOH solution and
10 cm3 distilled water for alkalization. The beaker was then covered 2.3.1. Characterizations of crude cellulose
with aluminum foil and left in the 35
C water bath for 1 h with Bleached crude cellulose were characterized by Fourier trans-
150 rpm agitation. After that, another isometric of 0.99 g 50 wt% form infrared spectroscopy (FT-IR, Perkin Elmer) at the wavelength
NaOH solution was pre-mixed with 1.17 g chloroacetic acid. The of 4000e500 cm1 with a resolution of 4 cm1, to qualitatively
mixture was diluted with 35 cm3 95 vol% ethanol and added into determine the functional structure.
the beaker. The reactor was then heated in 75
C water bath for In addition, the contents of a-cellulose and hemicellulose in the
1.5 h with 200 rpm agitation for cellulose etherification. After bleached crude cellulose were measured. Briefly, 2.0 g dried
cooling down to room temperature, all the mixture was neutralized bleached crude cellulose (also called hollocellulose) obtained pre-
with hydrochloric acid and filtered, rinsed with 95 vol% ethanol 3 viously was fed into a 100 cm3 three-neck flask, followed by the
times. The residues were then dried in an oven at 105
C for 3 h, and addition of 10 cm3 17.5 wt% NaOH solution. The mixture was stirred
the dried residues were collected as the CMC products. It shall be for 5 min at room temperature, extra 5 cm3 of 17.5 wt% NaOH was
noted that the reaction time for cellulose etherification reaction then added and the mixture was further stirred for 40 min 33 cm3
(fixed at 1.5 h in this study as mentioned above) was determined distilled water was added and the mixture was left at room tem-
based on a series of preliminary tests at a varying research time perature for 60 min. The mixture was filtered, and the filtration
(1 h, 1.5 h, 2 h, 3 h), where the results of preliminary tests revealed residue was transferred to a 250 cm3 beaker, stirred and rinsed with
that the properties of the CMC did not change significantly after 100 cm3 8.3 wt% NaOH solution at room temperature. The mixture
1.5 h under the current reaction conditions (temperature, molar was filtered. The filtration residue was rinsed with distilled water
ratios). followed by filtration. Such rinsing and filtration operations were
In the process of CMC synthesis, there are two main chemical repeated three times. 15 cm3 10 vol% acetic acid was added into the
filtration residue. After 5 min, the acid was removed through vac-
uum filtration. Residual acetic acid in the solid residue was
removed by water rinsing followed by vacuum filtration. The water
rinsing-filtering operations were repeated till the acetic acid was
completely removed from the sample (determined with pH mea-
surement). The residue was finally rinsed with approx. 250 cm3
distilled water, then dried at 105
C for 24 h, weighed and desig-
nated as a-cellulose. The a-cellulose content was then calculated
based on the wt% mass of the a-cellulose in the bleached crude
cellulose. The content of hemicellulose in the bleached crude cel-
lulose was calculated simply by difference.

2.3.2. Characterizations of CMC products

The functional structure of the CMC products obtained from the
Fig. 1. Block diagrams of experimental procedure for experimental procedure for synthesis at different reactant ratios was characterized by FT-IR
synthesis of CMC with bleached cornstalk-derived cellulose. (Perkin Elmer) at the wavelength of 4000e500 cm1 with a
54 T. Shui et al. / Biomass and Bioenergy 105 (2017) 51e58

resolution of 4 cm1. Furthermore, the CMC products dissolved in The DS of the CMC product was then determined by the amount of
D2O were characterized by proton nuclear magnetic resonance (1H- NaOH consumed determined by titration. In this work, CMC
NMR). The 1H-NMR spectra for the CMC products were acquired at products with a DS up to 0.85 were obtained with the bleached
25
C using a Varian Inova 600 NMR spectrometer equipped with a crude cellulose (derived from cornstalk).
Varian 5 mm triple-resonance indirect-detection HCX probe. A total
of 16e32 scans were accumulated using a 2 s recycle delay and 3.6 s 3. Results and discussion
acquisition time. Furthermore, the micro-structure of the CMC
products was observed by Scanning Electron Microscope (SEM) on 3.1. Characterizations of bleached crude cellulose
a Hitachi's Tabletop Electron Microscope TM3030Plus.
The yield and composition of oven-dried bleached crude cellu-
2.3.3. Water solubility of the CMC products lose are shown in Table 2.
Water solubility of the CMC products was measured by quan- On one hand, bleached crude cellulose with 81.3 wt% a-cellulose
tifying residual solids in 1 wt% CMC-water solution. Specifically, content was used as the cellulosic material for CMC synthesis. On
0.50 g CMC sample was weighed to mix with 50.0 g water at room the other hand, after alkalization and etherification process, 18.6 wt
temperature (25
C) in a 100 cm3 glass beaker. The beaker was then % hemicellulose is expected to be modified into short chain car-
left in the ultrasonic oscillator for 5 min followed by shaking at boxymethyl substituendum which has lower viscosity as well as
160 rpm for 24 h. The residue was collected by vacuum filtration. good water solubility compared with the commercial CMC prod-
The residue was dried at 105
C for 3 h and weighed. The dry weight ucts. Thus the viscosity of CMC-water solution would be decreased.
of the residue was then used for calculation of water solubility of However, abundant xylan generated by the hydrolysis of hemicel-
the CMC product. lulose would adhere to and mask the molecules of cellulose tightly.
A part of the cellulose molecules masked by xylan have limited
2.3.4. Viscosity and molecular weight of the CMC products access to the alkalization or etherification reactants, which would
The viscosity of the CMC-water solution and the viscosity-based result in a lower reaction efficiency and DS [26]. Taking into
average molecular weight (MV) was measured on a Rheometer AR- consideration the poor reactivity of the bleached crude cellulose
G2 at ambient conditions with a shear rate of 100s1 and an due to the masking effects of xylan, a high molar ratio (2e3:1) of
Ubbelohde Viscometer, respectively, at 25
C and 101 kPa, using the etherification agent-to- the bleached crude cellulose was
distilled water as a reference (mwater ¼ 0:8937 mPas at 25
C). For employed in this study.
measurement of MV, the time ti, taken by a solution of a certain
concentration to flow from the start point to the end set in the
3.2. Effects of the reactants molar ratio on water solubility of the
Ubbelohde Viscometer, was recorded. The intrinsic viscosity [h]
CMC products
(cm3 g1) can be calculated by two linear regression of y-x in-
tercepts, where x is the concentration wt% of the solution, while y
Water solubility of the CMC products, depending on their degree
can be calculated by:
of substitution (DS), is a key property for many applications. Thus,
  effects of the reaction conditions, in particular the reactants molar
ti
y1 ¼ 1 ci ; i ¼ 1; 2; 3; 4; 5 ; ratio, on water solubility of the CMC products (measured by the
t6
residues content in water) were examined in this work. To this end,
  two series of the tests were performed to explore (1) effects of the
ti alkali agent (NaOH), (2) effects of the etherification agent
y2 ¼ ln ci ; i ¼ 1; 2; 3; 4; 5:
t6 (ClCH2COOH) and the best molar ratio of NaOH:ClCH2COOH:Cel-
lulose among the test conditions.
t6 in the equations above is the time cost by reference solution In series (1) tests, the molar ratios of NaOH/ClCH2COOH/cellu-
during the measurement. Theoretically, the intercepts of y1 and y2 lose were in the range of 4e5:2:1, where the ClCH2COOH: Cellulose
should be the same value and must be > 0. [h] can be then calcu- molar ratio was fixed at 2:1 in all tests for this series. The variations
lated by multiplying one of the intercepts by 1000. Viscosity-based of water solubility of the CMC products (represented by their res-
average molecular weight MV (g mol1) can be reached by: idue contents in water) with varying the amount of NaOH in the
  reaction feed are shown in Fig. 2.
½h ¼ KMVa ¼ 5:37  102 MV0:73 From Fig. 2, it can be observed that effects of the alkali agent
(NaOH) on water solubility of the CMC products are minimal. While
where the constant K ¼ 5.37  102 cm3 g1, a ¼ 0.73 for CMC- increasing the molar ratio of NaOH/ClCH2COOH/cellulose from
water solution at room temperature [29]. 4.0:2:1 to 4.8:2:1, there was almost no significant change in the
water solubility of the CMC products, with over 70 wt% residue
2.3.5. Average degree of substitution for the CMC products content in water suggesting relatively poor etherification efficiency.
The average DS for the CMC products was determined by stan- Although the water solubility of the sample obtained at the molar
dard method of ASTM D 1439 [30], as briefly described below: 4.0 g ratio of 5.0:2:1 greatly improved, the obtained CMC products at
CMC was weighed, stirred with 75 cm3 95 vol% ethanol and 5 cm3 such high alkali dosage shows yellow caking appearance,
HNO3 to convert the water soluble CMC to solid particles. The slurry
was then heated and boiled for 5 min and then agitated by stirring Table 2
for 15 min. The slurry was precipitated with 80 vol% ethanol until Yield and composition of oven-dried bleached crude cellulose.
all of the acid has been removed (using diphenylamine). The res-
Yielda/wt% Components/wt%
idue was washed with a small amount of the anhydrous methanol
Celluloseb Hemicellulose
and dried. 1.0e1.5 g solid sample was weighed, mixed with 100 cm3
water and 25 cm3 0.3e0.5 mol L1 NaOH, stirred and heated to 42.56 (±1.64) 81.3 (±4.65) 18.6 (±4.83)
boiling for 15e30 min. While the solution is hot, excess NaOH was a
Yield based on the weight of the air-dried cornstalk.
titrated with 0.3e0.5 mol dm3 HCl to a phenolphthalein end point. b
a-cellulose.
 T. Shui et al. / Biomass and Bioenergy 105 (2017) 51e58 55

alkali compound, reducing the alkalization of cellulose and thus

reducing the nucleophilic replacement of the chlorine in chloro-
acetic acid, leading to a lower etherification efficiency. From
Fig. 3(a) and (b), it is clearly shown that the molar ratios of 4:2.5:1
and 4.6:2.8:1 seem to be best feed compositions during the test
conditions, resulting in very low residue contents in water (<5e12
wt%), namely > 88e95 wt% water solubility. Coincidently, the two
outstanding molar ratios of 4:2.5:1 and 4.6:2.8:1 give the similar
ratio of NaOH/ClCH2COOH, being 1.6e1.64.

3.3. FT-IR analysis of the CMC products

Functional compositions of the obtained CMC products were

analyzed by FT-IR, and the spectra of some typical samples are
Fig. 2. Effects of the alkali agent (NaOH) on water solubility of the CMC products
obtained at various molar ratios of NaOH/ClCH2COOH/cellulose in the range of (4e5):
shown in Fig. 4, where all spectra were normalized with respect to
2: 1. the peak intensity of -CH- group at around 2750 cm1 that was
believed to be unchanged in CMC and cellulose. Normalization of
the FTIR spectra makes it easy for the comparison of other char-
suggesting serious degradation at an excessive dosage of NaOH. acteristic peaks.
Thus a too high dosage of alkali agent is not recommended. The peak detected at 1030 cm1 refers to the C-O bond of ether
In series (2) tests, two alkali dosages, NaOH/cellulose ¼ 4:1 and (C-O-C) and alcohol in glucose units in both cellulose and CMC. The
4.6:1, i.e., a lower and a medium high molar ratio, were selected, characteristic peak at 1700 cm1 refers to the C¼O in the substit-
while the molar ratio of ClCH2COOH-to-cellulose was increased uent group of the CMC products or some C¼O group containing by-
from 2:1 to 3:1. The variations of water solubility of the CMC products. Due to the negligible mass of by-products, the C¼O peak
products (represented by their residue contents in water) with can be employed as a characteristic IR absorption peak for the ester
varying the amount of ClCH2COOH in the reaction feed are shown group of the CMC products. The intensity of this C¼O peak can thus
in Fig. 3. Generally, an increased dosage of the etherification agent be used to evaluate the etherification extent for the cellulose
in the reaction feed enhanced the water solubility of the resulted sample. Meanwhile, the peak observed at around 3400 cm1 is
CMC products, as expected due to the increased extent of ether- attributed to the hydroxyl group (-OH) that is substituted during
ification reactions. However, there appears to be an excellent the etherification reaction. Thus, from the comparisons of C¼O and
dosage the etherification agent, at which the product solubility eOH peaks intensities, the extent of substitution can be estimated.
attains maximum values. As shown in Fig. 3(a), a too high dosage of From Fig. 4(a), the characteristic C¼O peak at 1700 cm1 is
ClCH2COOH led to reduced solubility of the CMC product, likely present in all CMC products obtained at various molar ratios of
because the presence of excessive acid would neutralize OH of NaOH/ClCH2COOH/cellulose in the range of (4e5): 2: 1. The strong
C¼O peak for the CMC product at 5:2:1 (molar ratio) implies large
extent of etherification at such high dosage of NaOH in the CMC
synthesis. However, as mentioned previously, the obtained CMC
product at 5:2:1 (molar ratio) shows yellow caking appearance,
suggesting serious degradation at an excessive dosage of NaOH.
Fig. 4(b) and (c) presents effects of the etherification agent, i.e.,
chloracetic acid on the functional compositions of CMC products.
Commonly, with an increase in the dosage of chloracetic acid, the
C¼O peak in the resulted CMC product becomes stronger, indi-
cating greater etherification extent for the cellulose sample at a
larger excess dosage of the etherification agent. However, for CMC
product obtained at 4:3:1 (molar ratio), although it exhibits a
strong C¼O peak, there is an obvious increase in the C-O peak
probably due to production of a mass of glucose produced by hy-
drolysis of the un-reacted cellulose and CMC. As such, an extremely
large excess of chloracetic acid should be for CMC production.
From Fig. 4(b) and (c), CMC products obtained at molar ratios of
4:2.5:1 and 4.6:2.8:1 exhibit prominent strength of C¼O peak and
lower -OH peak, suggesting a relatively high content of the car-
boxymethyl groups in the CMC products. Thus, the best NaOH/
ClCH2COOH/cellulose molar ratios during the project for CMC
synthesis from the cornstalk-derived bleached cellulose appears to
be at 4:2.5:1 or 4.6:2.8:1, i.e., NaOH/ClCH2COOH z1.6e1.64 (mol
mol1). The greater etherification extent for the cellulose in the
CMC products at the best molar ratio explains their better water
solubility as discussed in the previous section (Fig. 3).

3.4. SEM micrographs of the CMC products

Fig. 3. Effects of etherifying agent (ClCH2COOH) on water solubility of the CMC
products obtained at various molar ratios of NaOH/ClCH2COOH/cellulose in the range Fig. 5 illustrates SEM micrographs of the CMC products obtained
of 4: (2.0e3.0): 1 (a) or 4.6: (2.0e2.8): 1 (b). at two outstanding molar ratios, i.e., 4.0:2.5:1(b) and 4.6:2.8:1(a),
56 T. Shui et al. / Biomass and Bioenergy 105 (2017) 51e58

structure. Thus, it is clear that etherification of cellulose does not

change the fibrous particles structure of cellulose.

1
3.5. H-NMR spectra of the CMC products

Fig. 6 illustrates 1H-NMR spectra the CMC products in D2O ob-

tained at molar ratios of 4.0:2.5:1 and 4.6:2.8:1 as well as the
molecular structure of sodium CMC at DS ¼ 1.
Characteristic 1H chemical shifts of the protons substitution at
the position of C6, C2 (a), C2 (b) and C3 (given in Fig. 6(c)),
respectively are in the range of 4.3e3.7 mHz/Hz [31], also shown in
zoomed pictures, where the 4 characteristic peaks are designated
as B, C, D and E. Unsubstituted hydroxyl groups are shown at
around 1 mHz/Hz. The range of 4.3e3.7 mHz/Hz refers to the protons
connected to substituted or unsubstituted C2 (3.7e3.9 mHz/Hz), C3
(4.2e4.0 mHz/Hz), C6 (4.3e4.2 mHz/Hz) [32]. Therefore, the 1HNMR
spectra confirms the successful etherification of the cornstalk-
derived cellulose. Comparing the area integration of B, C, D, E
with that of the unsubstituted hydroxyl group peaks in Fig. 6, the
relative values of DS may be obtained. Comparing Fig. 6(a) and (b),
one may conclude that the CMC product obtained at the molar ratio
of 4.6:2.8:1 appears to have a relatively higher DS than that of the
CMC product obtained at the molar ratio of 4:2.5:1.

3.6. Physical and chemical properties of the CMC products

As displayed in Table 3, both CMC products obtained at molar

ratios of 4.0:2.5:1 and 4.6:2.8:1, or at the molar ratio of NaOH/
ClCH2COOH z1.6e1.64, are white powders, and their water solu-
tions (2 wt%) have high viscosity, i.e., 9e16 mPas (or cP) likely due
to the excellent water solubility of these two CMC products.
Although the residual hemicellulose might contribute to the water
solubility, the outstanding solubility of the CMC products shall
mainly be attributed to the cellulose modification.
As shown in Table 4, the viscosity-average molecular weight MV
of these two CMC products obtained at molar ratios of 4.0:2.5:1 and
4.6:2.8:1 is in the range of 1.94  104e2.48  104 g mol1, and the
average DS of the two products are 0.57 and 0.85, respectively. The
measured DS values are smaller than the targeted DS (DS ¼ 2),
which was likely resulted from the formation of by-products during
the synthesis, e.g., HOCH3COONa, xylan, NaCl and modified hemi-
cellulose present in the cellulose feedstock (bleaching crude cel-
lulose from cornstalk). These impurities in the final CMC products
would hence decrease the average DS and viscosity dramatically,
while showing less effects on the appearance and water solubility
of the CMC products. It shall be noted that these CMC products can
be purified in the industrial operations by removing impurities by
some work-up processes such as methanol rinse and H2SO4
acidification.
Fig. 7 shows variations of viscosity of the CMC-water solution
with the CMC concentration (wt%). With both CMC products (ob-
tained at molar ratios of 4.0:2.5:1 and 4.6:2.8:1), commonly while
increasing the CMC concentration in the solution, the viscosity of
CMC e water solution increases slightly and linearly until the CMC
concentration is 2 wt%. Such viscosity-substrate concentration
relationship, i.e., the viscosity of the solution increases linearly with
the concentration of solute, is typical of Newton fluids. As also in
Fig. 7, when the solute concentration is above 2 wt%, the viscosity of
the CMC-water solution exhibits nonlinear (exponential)
Fig. 4. FT-IR spectra of the CMC products obtained at various molar ratios of NaOH/ increasing with increasing of the solute concentration (typical of
ClCH2COOH/cellulose in the range of (4e5): 2: 1 (a), 4: (2.0e3.0): 1 (b) and 4.6:
non-Newton fluids), caused mainly by the inter-enwinding of CMC
(2.0e2.8): 1 (c).
molecular chains [26]. Furthermore, the viscosity of the water so-
lution of CMC product obtained at the molar ratio of 4.0:2.5:1
compared with that of the bleached crude cellulose. The micro- exhibited a faster increase, more dramatically than and surpassing
graphs of all samples are similar, containing fibrous particles that of the water solution of the other CMC product (4.6:2.8:1 M
 T. Shui et al. / Biomass and Bioenergy 105 (2017) 51e58 57

Fig. 5. SEM micrographs of CMC products, as well as the bleached crude cellulose (c).

ratio) at the solute concentration above 2 wt%. This is possibly

caused by outstanding swelling behavior of the CMC molecule with
a lower DS [33]. In this case, the high viscosity of two samples at 2
wt% can be explained by the modification happened on the crude
cellulose.

3.7. Study summary

Sodium carboxymethyl cellulose (CMC) materials were suc-

cessfully synthesized using bleached crude cellulose derived from
cornstalk after alkalization and etherification processes.

(1) The CMC products synthesized at molar ratio (NaOH/

ClCH2COOH/cellulose) of 4.0:2.5:1 and 4.6:2.8:1, or at the
molar ratio of NaOH/ClCH2COOH z 1.6e1.64, are white
powders with excellent water solubility, and their water
solutions (2 wt%) have a viscosity of 9e16 mPas.
(2) The viscosity-average molecular weight MV of these two
CMC products obtained at molar ratios of 4.0:2.5:1 and
4.6:2.8:1 is in the range of 1.94  104e2.48  105 g mol1,
and the average DS of the two products are 0.57 and 0.85,
respectively.
(3) As the solute concentration is above 2 wt%, the viscosity of
the CMC-water solution exhibits nonlinear (exponential)
increasing with increasing of the solute concentration
(typical of non-Newton fluids). Hence the obtained CMC
products can be utilized as surfactants or thickeners in
coatings and detergents or other industrial applications.

4. Conclusions

Crude cellulose fractionated from cornstalk, after leaching, can

Fig. 6. 1H-NMR spectra the CMC products in D2O obtained at molar ratios of 4.0:2.5:1 be used as the raw material for the synthesis of sodium carbox-
(a) and 4.6:2.8:1 (b) and the molecular structure of sodium CMC at DS ¼ 1 (c). ymethyl cellulose (CMC) by reacting with the cellulose with NaOH

Table 3
Appearance and viscosity of the CMC products.

The molar ratio of the reactant (Alkali/ether/ The molar ratio of alkali/ Appearance Viscosity of CMC-water solution (2 wt%, Shear rate during viscosity
feedstock) etherifying agent 25
C)/(mPas) measurement/s1

4.0: 2.5: 1 1.60 White 8.65 100

powders
4.6: 2.8: 1 1.64 White 16.24 100
powders
58 T. Shui et al. / Biomass and Bioenergy 105 (2017) 51e58

Table 4
Molecular weight, pH and DS of the CMC.

Molar ratio of the reactant (Alkali/ether/feedstock) Viscosity-average molecular weight MV/(gmol1) Intrinsic viscosity [h]/(cm3g1) Water solubility (wt%) DS

4.0: 2.5: 1 1.94  104 72.43 88.6 0.57 (±0.2%)

4.6: 2.8: 1 2.48  104 86.63 95.6 0.85 (±0.4%)

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