Cellulose

https://doi.org/10.1007/s10570-017-1604-3

ORIGINAL PAPER

Bamboo cellulose-derived cellulose acetate for electrospun

nanofibers: synthesis, characterization and kinetics
Jie Cai . Rui Zhou . Tiantian Li . Jingren He . Guozhen Wang .
Haibo Wang . Hanguo Xiong

Received: 9 October 2017 / Accepted: 1 December 2017

Ó Springer Science+Business Media B.V., part of Springer Nature 2017

Abstract Catalysts play a key role in the production Introduction

of cellulose acetate (CA). In this study, CA derived from
bamboo cellulose (BC) was synthesized in a solution Given the current environmental and energy policies,
mixture of acetic acid and acetic anhydride that contains renewable resources have been drawing increasing
catalysts. The catalytic activities of three catalysts (i.e., attention, which has led to focusing on the efficient
sulfuric, methyl benzene sulfonic, and dodecyl benzene utilization of natural cellulosic material for various
sulfonic acids) were investigated in terms of kinetics of applications, such as medicine, automotive, construc-
acetylation, which was established according to the first- tion, and packaging (Olyveira et al. 2013; Rwawiire
order reaction mechanism. Based on this, cellulose- et al. 2015). Cellulose from plants and microorgan-
based nanofibers were further prepared from the acety- isms is abundant and a ubiquitously natural macro-
lated BC solution using an electrospinning technique. molecular material that possesses extremely attractive
Results in this study may be useful for the preparation properties, such as low cost, biodegradability, renewa-
and application of nanomaterials derived from natural bility, high specific strength and modulus, and low
polymeric materials. density (Liu et al. 2014; Tingaut et al. 2010).
Therefore, the demand for new direct and indirect
Keywords Cellulose  Electrospinning  Nanofiber industrial applications for cellulose is evident. Plant
biomass can be effectively and simply converted into
cellulose materials. Among the fibrous plants, bamboo
J. Cai (&)  R. Zhou  T. Li  J. He (&)  G. Wang
can be used as a regenerative natural and environ-
School of Food Science and Engineering, Wuhan
Polytechnic University, Wuhan 430023, China ment friendly resource of cellulose that grows about
e-mail: [email protected]; 1250 species in most tropical countries and regions
[email protected] (e.g., China) (Larik et al. 2015; Scurlock et al. 2000;
J. He Teli and Sheikh 2012). Bamboo is extensively used in
e-mail: [email protected] building various living facilities and tools, as well as in
the agriculture and chemical industries (Hameed et al.
J. Cai  H. Xiong (&)
College of Food Science and Technology, Huazhong 2007; Khan et al. 2010). A limited number of studies
Agricultural University, Wuhan 430070, China has focused on the use of bamboo to generate
e-mail: [email protected] cellulosic materials. Instead, it is traditionally used
as a reinforcing composite material and employed in
H. Wang
School of Chemical and Environmental Engineering, paper making. Converting bamboo pulps into a value-
Wuhan Polytechnic University, Wuhan 430023, China

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added product, such as cellulose fiber, addresses its Experimental

ineffective use.
The development of cellulose nanofiber has Materials
attracted considerable attention over the last few
decades because of its abundance and low cost while All reagents, which include bleaching bamboo pulps,
possessing unique characteristics, such as large speci- acetone, N,N-Dimethylacetamide (DMAc), sulfuric
fic surface area and high mechanical performance, acid, methyl benzene sulfonic acid, dodecyl benzene
thereby extending its application field (Chen et al. sulfonic acid, and sodium hydroxide were purchased
2011; Kalia et al. 2011). The production of nanofibers commercially and used as received, without further
can be easily realized through a facile fiber spinning purification treatment. Distilled deionized water was
process, namely, electrospinning, which utilizes a used in all our experiments.
high-DC electric field to charge the polymer solution
and overcome surface tension, such that every Synthesis of cellulose acetate from bamboo
nanoscale fiber is drawn from the nozzle (Dan-
wanichakul and Danwanichakul 2014; Deng et al. A purification method of plant cellulose was per-
2013; Huang et al. 2017; Li et al. 2015). Direct formed using a NaOH aqueous solution treatment to
electrospinning of cellulose into nanofiber is not ideal obtain BC. Subsequently, CA derived from BC was
because of its poor solubility in the most common synthesized in a mixture solution of acetic acid and
solvents (Kuzmenko et al. 2014; Lu and Hsieh 2010). acetic anhydride that contains catalysts. The catalytic
The modification of cellulose materials has been activities of three catalysts, namely, sulfuric acid
proposed to obtain soluble cellulose derivatives for the (H2SO4), methyl benzene sulfonic acid (PTSA), and
preparation of nanofibers (Cai et al. 2016a, b, 2017b). dodecyl benzene sulfonic acid (DBSA), were inves-
Cellulose acetate (CA) is one of the most significant tigated in terms of the kinetics of the acetylation (Du
cellulose derivatives commercially and is a promising 2006), which was established according to the first-
alternative in synthesizing cellulose materials for order reaction mechanism. After the reaction, a
electrospinning to produce nanofiber. The idea of mixture of sulfuric and acetic acids was added to
using bamboo to produce cellulose-based nanofibers obtain the corresponding degree of substitution (DS).
emerges in this context. Bamboo cellulose acetate (B-CA) was precipitated out
Although numerous studies on the synthesis of CA by further adding the distilled water, which was
have been conducted, limited reports on the use of separated by using vacuum filtration, followed by
bamboo pulp fiber and its application to nanomaterials vacuum drying (Cai et al. 2016b). DS was measured
are available. Therefore, the preparation of CA from using the strand method based on ASTM D 871-63
bamboo pulp-derived cellulose for electrospinning (Chen et al. 2013).
was investigated in the present study to produce
cellulose-based nanofibre effectively for improved Electrospinning
bamboo cellulose (BC) solubility. The kinetic data of
the synthesis of CA studies were processed to optimize A custom-built electrospinning setup in the laboratory
the acetylation reaction. The chemical composition, was utilized into prepare the nanofibers (Cai et al.
morphology, and thermal property of the products 2017a). A homogeneous solution with different B-CA
were characterized and compared in detail through concentrations in acetone/DMAc (2/1, m/m) was
chemical analysis, nuclear magnetic resonance obtained at room temperature under constant stirring.
(NMR), scanning electron microscopy (SEM), and The electrospinning conditions of fabricating B-CA
Fourier transform infrared spectroscopy (FTIR). nanofibers with relatively uniform structure and fewer
Based on this, cellulose-based nanofibers were then beads were optimized.
further prepared through electrospinning.
Characterization

The morphology of the samples was observed through

SEM (Joel Neoscope and Supra 55VP). FTIR spectra

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Cellulose

were observed on a Nexus-470 spectrometer using region, as shown as follows (He et al. 2008; Sun et al.
KBr disc method. Cross polarization/magic angle 2008):
spinning (CP/MAS) 13C solid-state NMR measure- S1
ments were performed on a Bruker AV400 Xc ¼  100%
S1 þ S2
spectrometer.
where Xc is the crystallinity; and S1 and S2 are the
integrated areas of the crystalline and amorphous
Results and discussion phases, respectively.
The Xc values for the purified sample calculated
Bamboo pulp was treated with NaOH aqueous solu- using 13C NMR spectra were larger than those of the
tion to obtain BC fibers (Fig. 1a). The 13C-CP/MAS original sample. After treatment, the BC fiber
NMR spectra of the bamboo pulp and purified increased by * 10.3% due to the separate removal
products are shown in Fig. 1b, where the main of hemicelluloses and lignin and the destruction of the
resonance region ranges from 60 to 150 ppm. All amorphous phase in BC after purification by NaOH
samples showed high resolved spectra caused by the solution.
predominant crystalline fibrils in the cellulose matrix. Catalysts play a valuable role in the production of
The cellulose crystallinities in the samples can be cellulose acetate. The catalytic activities of the three
computed from the percentage of the integrals of the catalysts (i.e., H2SO4, PTSA, and DBSA) were
C4 signals centered at 86–95 ppm and 80–86 ppm, investigated in terms of the kinetics of the acetylation.
representing the crystalline and amorphous phasess, The kinetic study of the synthesis of B-CA derived
respectively, based on the fitting result of the C4 from BC was made as a function of reaction time in the
presence of different catalysts.

Fig. 1 a Photograph of BC fibers derived from bamboo pulp, b 13C NMR spectra of the bamboo pulp before and after purification, and
c, d result of the the C4 region fitting of a 13C NMR spectrum from bamboo pulp before (c) and after (d) purification

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Acetylation refers to the reaction that introduces an Moreover, the initial mass of cellulose, volume of
acetyl functional group into a chemical compound, acetic acid, and initial concentration of acetic anhy-
which is known as the equilibrium limited chemical dride were defined as m, V, and [A]o, respectively. So,
reactions. The following model was assumed to
govern the CA reaction system:
162 V
DS ¼ ½Ao ½Ao ekt ð6Þ
m
K1
A þ B
C þ D Changing Eq. (6) into a function yields:
K1  
K2 m
C þ E ! F þ A ln 1  DS  ¼ kt ð7Þ
162 V½Ao
On the basis of the scheme (*), the following
According to Eq. (7), the catalystic effect on the
equation is obtained:
acetylation reaction is shown in Fig. 2.
1 ½A½B The rate contacts of acetylation reaction in different
¼ ð1Þ
kc ½C½D catalysts were calculated and are presented in Table 1.
Using H2SO4 as a catalyst showed a high rate,
where [] is the concentration of the reactants and
indicating that H2SO4 has good catalytic activity in
products. The concentration modification rate of
the acetylation reaction for BC. Therefore, H2SO4 can
intermediate can be expressed as follows:
be used as a catalyst to further produce B-CA for the
d ½C application to electrospun nanofibers in further
 ¼ k2 ½C½E  k1 ½C½D  k1 ½A½B experiments.
dt ð2Þ
d ½C Acetylation is the process of transformation from a
¼ k1 ½A½B  ðk1 ½D þ k2 ½EÞ½C
dt heterogeneous medium to a homogeneous one. In the
The reaction rate equation for acetylation may be reaction system, the solvent is initially diffused at the
written according to Eqs. (1) and (2): exterior of the cellulose matrix. Then, the solvents
enter towards the center, which breaks the hydrogen
d ½A  bonding of intra- and intermolecular with the appear-
 ¼ k1 ½A½B  ðk1 ½D þ k2 ½EÞ½C
dt ance of the active and accessible hydroxyl groups
d ½A  kc ½A½B
 ¼ k1 ½A½B  ðk1 ½D þ k2 ½EÞ ð3Þ (Obataya and Minato 2007; Yang et al. 2008).
dt  ½D
 Moreover, the acetylation reaction destructed the
d ½A k2 kc ½E½B
 ¼ k1 ½B  k1 kc ½B  ½A crystalline of cellulose, which started from the amor-
dt ½D phous region into the crystallites as an erosion
To simplify the computation, the following mechanism. The increase in the degree of acetyl
assumptions were made: (a) equation equilibrium substitution of the resulted products may be caused by
could be easily obtained (1) within a temperature, and the fibriform destruction and polymerisation. B-CA
(b) catalyst and acetic acid concentrations remain was precipitated after the reaction process (see
unchanged during the reaction process. Therefore, Fig. 3c).
½E½B
k1 ½B  k1 kc ½B  k2 kcD can be regarded as a con- The morphologies of BC and B-CA were detected
½  using SEM. Cellulose fibers showed obvious differ-
stant defined as k. Equation (3) is written as follow: ence from acetylated samples in their microstructure.
d ½A  SEM images (Fig. 3a, b) show that the BC fiber is
 ¼ k½A ð4Þ circular with a diameter ranging from 10 to 15 lm,
dt
whereas, the B-CA structure is randomly and loosely
The equation above follows a pseudo-first-order aligned rather than in fibriform structure. Many pores
reaction. By integrating it, Eq. (4) was changed to: were distributed on the surface of the B-CA particle.
½A ¼ ½Ao ekt ð5Þ These significant morphology differences between BC
and B-CA were caused by the substantial acetylation
reaction.

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Fig. 2 Effect of catalyst on

acetylation reaction: a1, a2
PTSA; b1, b2 DBSA; c1, c2
H2SO4

Table 1 Constants of acetylation reaction rate for different absorption band increased with the stretching of the
catalysts carbon–oxygen (C–O) of the acetyl group
Catalyst S* k** (1043–1243 cm -1). (3) Finally, a decreasing intensity
of absorption peaks was sited at around
PTSA - 0.008 0.008 3200–3500 cm -1, which was assigned to the hydro-
DBSA - 0.028 0.028 xyl (O–H) stretching region. This decrease occurred as
H2SO4 - 0.051 0.051 the hydroxyl groups were replaced by acetyl groups in
*Slope, **rate constant the reaction (Barud et al. 2008; Li et al. 2008).
Cellulose has poor solubility in most solvents
because of the strong inter- and intra-molecular
The acetylation on BC was further confirmed by the interactions (Cai et al. 2016b; Minnick et al. 2016).
FTIR spectra, as shown in Fig. 3d. The formation of Thus, constructing nanofibrous assemblies via direct
acetylated products could be monitored by three major electrospinning is difficult. Alternatively, utilizing CA
differences between the chemical structures of the as a soluble cellulose derivative may enhance its
original BC and B-CA, as follows. (1) An absorption electrospinning capability to prepare nanofibers with
band appeared at 1731–l759 cm-1, corresponding to controlled morphology and alignment. On the basis of
the carbonyl (C=O) stretching region. (2) An this possibility, nanofiber biomaterials were prepared

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Fig. 3 SEM images of BC

fibers before (a) and after
b acetylation, c photographs
of acetylated products,
d FTIR spectra of BC and
B-CA, e schematic
illustration of
electrospinning, and f SEM
images of B-CA nanofibers

from the B-CA derived from BC using an electro- Conclusion

spinning technique under optimal conditions (electro-
spinning voltage of 22 kV, flow rate of 1 mL/h, and In this work, cellulose acetate (CA) derived from
distance of 15 cm) (see Fig. 3e, f). bamboo cellulose (BC) was produced in a solution
mixture of acetic acid and acetic anhydride that
contains catalysts. The catalytic activities of the three

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catalysts used were investigated in terms of the kinetic Deng L, Young RJ, Kinloch IA et al (2013) Carbon nanofibres
of the acetylation, which were processed to optimize produced from electrospun cellulose nanofibres. Carbon
58:66–75
the acetylation reaction. Consequently, nanofibers Du J (2006) Catalysts for esterification of cellulose and its
were prepared from the acetylated BC solution via application (Master’s Dagree Dissertation). Donghua
an electrospinning technique. The results may be used University, Shanghai (in Chinese)
into develop nanomaterials derived from natural Hameed BH, Din AT, Ahmad AL (2007) Adsorption of
methylene blue onto bamboo-based activated carbon:
polymeric materials. kinetics and equilibrium studies. J Hazard Mater
141:819–825
Acknowledgments This work has been supported by the He J, Cui S, Wang S (2008) Preparation and crystalline analysis
Natural Science Foundation of Hubei Province of China (No. of high-grade bamboo dissolving pulp for cellulose acetate.
2017CFB198), the Science and Technology Research Project of J Appl Polym Sci 107:1029–1038
Hubei Provincial Department of Education (No. Q20161701), Huang W, Zhan Y, Shi X et al (2017) Controllable immobi-
the Talent Introduction Foundation of Wuhan Polytechnic lization of naringinase on electrospun cellulose acetate
University (China) (No. 2016RZ22), and Huazhong nanofibers and their application to juice debittering. Int J
Agricultural University Scientific & Technological Biol Macromol 98:630–636
Selfinnovation Foundation (No. 2012SC21). Jie Cai also Kalia S, Dufresne A, Cherian BM et al (2011) Cellulose-based
thanks the Chutian Scholar Program of Hubei Provincial bio- and nanocomposites: a review. Int J Polym Sci
Government, China. 2011:2341–2348
Khan RA, Khan MA, Zaman HU et al (2010) Comparative
Compliance with ethical standards studies of mechanical and interfacial properties between
jute and E-glass fiber-reinforced polypropylene compos-
Conflict of interest The authors declare that they have no ites. J Reinf Plast Compos 29:1078–1088
conflict of interests. Kuzmenko V, Naboka O, Gatenholm P, Enoksson P (2014)
Ammonium chloride promoted synthesis of carbon nano-
fibers from electrospun cellulose acetate. Carbon
67:694–703
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