Carbohydrate Polymer Technologies and Applications 2 (2021) 100099

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Carbohydrate Polymer Technologies and Applications

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carbohydrate-polymer-technologies-and-applications

Wet spinning to prepare filaments from three cellulose carbonated

derivatives: Synthesis, characterization and filament properties
Xin Bao a, b, Chunhong Wang b, *, Zhenyu Zhang a, Qinghua Cao a, Fei Liu a, *, Jing Chen a,
Chuanzhi Zhang a, Haining Na a, *, Jin Zhu a
a
Key Laboratory of Bio-based Polymeric Materials of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo,
Zhejiang 315201, China
b
School of Textile Science and Engineering, Tiangong University, Tianjin 300387, China

A R T I C L E I N F O A B S T R A C T

Keywords: In this article, three kinds of cellulose carbonated derivatives are synthesized by modifying cellulose with alkyl
Cellulose benzyl carbonated derivatives halides (namely bromopropane, benzyl bromide and bromomethyl cyclopropane) in DBU/DMSO/CO2 system.
Cellulose propyl carbonated derivatives The wet spinnability and filament properties of the obtained cellulose carbonated derivatives are investigated.
Cellulose cyclopropyl methyl carbonated
Through rheological analysis, the solutions of various cellulose carbonated derivative in Newtonian fluid state
derivatives
can show good wet spinnability. Filaments with smooth surface and uniform morphology can be obtained from
Cellulosic material filaments
Wet spinnability the solution with viscosity over 0.07Pa•s. The cellulose carbonated derivatives in the filament show similar in
tight orderly rows. Among them, the cellulose propyl carbonated derivative filament exhibits the highest me­
chanical properties and heat resistance. By using of DBU/DMSO/CO2 system, the wet spinning and key control
condition of cellulose carbonated derivatives are combined to achieve for the formation of filament with uniform
morphology.

1. Introduction
As a widely distributed, abundant and degradable natural polymer
material (Jedvert & Heinze, 2017), cellulose is considered as one of the
most promising alternatives to supply even partially replace
petroleum-derived synthetic polymers in future sustainable develop­
ment (Li et al., 2017; Tu, Zhu, Duan & Zhang, 2020; Yuan et al., 2015).
However, due to the recalcitrant molecular structure, cellulose is diffi­
cult to processing (Yamane, Hirase, Miyamoto, Kuwamoto & Yuguchi,
2015; Sayyed, Deshmukh & Pinjari, 2019). This phenomenon becomes
the major inhibition to wide application of cellulose.
In order to achieve the processing and application of cellulose, many
solvent systems have been developed for the dissolving and modifying of
cellulose (e.g. CS2/NaOH (Abramova, Trusova & Rogovin, 1982),
alkali/urea (Cai & Zhang, 2005; Qi, Cai, Zhang & Kuga, 2009) and ionic
liquid (Feng & Chen, 2008; Iguchi, Aida, Watanabe & Smith, 2013; Isik,
Sardon & Mecerreyes, 2014; Protz, Lehmann, Bohrisch, Ganster & Fink,
2021) over the past decade. Among these systems, 1,8-diazabicycloun­
dec-7-ene/dimethylsulfoxide/carbon dioxide (DBU/DMSO/CO2) as a
new solvent system appears at 2013 (Zhang, Oztekin, Barrault, De
Oliveira Vigier & Jérôme, 2013). During the dissolving process of cel­
lulose in this system, with the help of DBU, CO2 reacts with the hydrogen
bond on the molecular chain of cellulose to produce temporary car­
bonate (Onwukamike, Tassaing, Grelier, Grau, Cramail & Meier, 2017).
This process promotes the homogeneous dissolution of cellulose and
enhances the derivatization ability of hydroxyl groups at the same time.
It provided a good precondition and a convenient way to synthesize
cellulose carbonated derivatives, which is also named as cellulose car­
bonate by reference (Elschner & Heinze, 2015). Many researches have
already carried out concerning the dissolving mechanism and the
derivatization method of cellulose in DBU/DMSO/CO2 systems (Chen
et al., 2018; Nanta, Skolpap, Kasemwong & Shimoyama, 2017; Xu et al.,
2017). Worldwide, the role of DBU/DMSO/CO2 systems has been
increasingly acknowledged.
The development of the solvent system can establish a solid foun­
dation for the fabrication of cellulosic material filaments, which refers to
an important way to achieve the processing and application. For
example, For example, original cellulose is reported to dissolve in an
aqueous solution of cuprammonium hydroxide for the spinning into
filaments (Miyamoto, Matsuoka, Matsui, Saito & Okajima, 1996). And

* Corresponding authors.
E-mail addresses: wangchunhong@tiangong.edu.cn (C. Wang), liufei@nimte.ac.cn (F. Liu), nahaining@nimte.ac.cn (H. Na).

https://doi.org/10.1016/j.carpta.2021.100099
Received 15 March 2021; Received in revised form 3 June 2021; Accepted 10 June 2021
Available online 13 June 2021
2666-8939/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
X. Bao et al. Carbohydrate Polymer Technologies and Applications 2 (2021) 100099

Table 1 2.2. Synthesis of cellulose carbonated derivatives

Materials and reagents.
Reagent Abbreviation or Standard Manufacturer In the study, four different contents of cellulose (3wt%, 4wt%, 5wt%,
molecular formula and 6wt%) were respectively dissolved in DBU/DMSO/CO2 system.
Corn cellulose Cellulose DP=1438 Shandong Cellulose was firstly suspended in the mixed solution of DBU and DMSO
Shengquan New in a closed gas reactor. Taking 3wt% as an example, 3wt% (0.338 g)
Material Co., Ltd cellulose, DBU (3 equiv per anhydroglucose unit of cellulose, 0.953 g)
Dimethyl sulfoxide DMSO 99% Aladdin Co., Ltd and 10 g DMSO are stirred at room temperature for several minutes, and
1,8-diazabicyclo[5.4.0] DBU 99% Aladdin Co., Ltd
undec‑7-ene
then transferred to closed gas reactor. Next 0.5 MPa CO2 was charged
Propyl bromide C3H7Br 99% Aladdin Co., Ltd into the reactor and then sealed it. The reactor is heated at 55 ◦ C for 2 h
Benzyl bromide C7H7Br 98% Macklin Co., Ltd until cellulose was completely dissolved.
Cyclopropylmethyl C4H7Br 97% Aladdin Co., Ltd After complete dissolution, the solution of cellulose was cooled down
bromide
to 30 ◦ C. Also taking 3wt% as the example, propyl bromide, benzyl
Carbon dioxide CO2 99% Ningbo Wanli Gas
Co., Ltd bromide and cyclopropylmethyl bromide (5 equiv per anhydroglucose
unit of cellulose, respectively 1.281 g, 1.785 g, and 1.407 g) was added
The equipment used in the experiment and the analysis and testing equipment
separately, and the reaction was allowed to run under 1.2 MPa of CO2 for
are shown in Table 2.
4 h at 30 ◦ C. After that, cellulose propyl carbonated derivatives (CPrC),
cellulose benzyl carbonated derivatives (CBeC), and cellulose cyclo­
Table 2 propyl methyl carbonated derivatives (CCmC) were respectively syn­
Main instruments. thesized. After the reaction, the solution of cellulose carbonated
derivatives was evacuated by vacuum until no bubbles appeared.
Equipment Device model Manufacturers

Magnetic heating and GPSK-500ML Nanjing Zhengxin Instrument 2.3. Wet spinning of the solution of cellulose carbonated derivative
stirring reactor Co., Ltd
Micro push-pull syringe TJ-3A Lange Constant Flow Pump
pump Co., Ltd The above solution (obtained in Section 2.2) of these cellulose
FTIR Nicolet 6700 Thermo-fisher carbonated derivatives was loaded into a plastic syringe with a metallic
NMR AVANCE III Bruker needle with inner diameter of 21 mm at 30 ◦ C. Water was selected as a
400MHz
coagulating solvent for the spinning process at room temperature
Microscope BX51 OLYMPUS
Rotational rheometer Physica MCR-301 Anton Paar GmbH (~25 ◦ C). The spinning solution was injected into the microfluidic
bromide channel and further extruded into the coagulation bath. And injection
SEM Verios G4 UC Thermo scientific flow rate is controlled by a micro push-pull syringe pump at a rate of
XRD D8 ADVANCE BRUKER AXS 0.75 mL/min. During the process of wet spinning, the cellulose
Tensile testing machine Z1.0 Zwick
TGA instrument TGA/DSC1 METTLER TOLEDO
carbonated derivatives were solidified in the coagulation bath to form
DSC DSC214 NETZSCH filaments with diameter 100~200 μm.

N-methylmorpholine-oxide system is used to dissolve non-derivatized
cellulose for the preparation of high-performance lyocell filament
(Gavillon & Budtova, 2007). In terms of cellulose derivatization spin­
ning, only cellulose acetate filament is currently available. However, the
cellulose acetate filament is wet-spinned by searching the soluble sol­
vent (acetone) after finishing the cellulose pulp and acetic anhydride. As
to the latest DBU/DMSO/CO2 system (DMSO and DBU can dissolve
cellulose under a certain pressure of CO2), due to its particular dis­
solving mechanism to dissolve cellulose, non-derivatized cellulose is not
only achieved to spin in this system, but also cellulose derivatives are
easily obtained to be expected to spin into uniform filaments. Further­
more, the spinning of cellulose derivatives is rarely reported until today.
In order to achieve the wet spinning of cellulose derivative with the
utilization the DBU/DMSO/CO2 system, three halogenated substances
(bromopropane, benzyl bromide and bromine methylcyclopropane) are
used to modify cellulose. The obtained cellulose carbonated derivatives
are continuously tried in wet spinning to prepare filament. Rheological
analysis is used to investigate the wet spinnability of cellulose carbon­
ated derivatives. Mechanical property and heat resistance of the cellu­
lose carbonated derivative filaments are also researched.
2. Materials and methods
2.1. Materials and equipment
A list of the materials and reagents used is provided (see Table 1).
Among them, the cellulose was milled with a vertical ball mill equipped
with a 40-mesh screen size (Thomas scientific) for 1 h and then dried at
110 ◦ C for 24 h to completely remove moisture before further use. All
the reagents were used without any further purification.
2.4. Characterization
The spun cellulose carbonated derivative filaments are cut into
powder. Fourier transform infrared spectroscopy (FTIR) was used for the
characterization of the synthesis of them. The scanning wave number
range was 400–4000 cm− 1, and the scanning frequency was 32 times. In
order to determine the structure of cellulose carbonate derivatives, NMR
tests were carried out. 1H NMR spectra were recorded using Bruker
operating at 400 MHz at 80 ◦ C with 1000 scans. All products were dis­
solved in DMSO‑d6 with concentrations of 5–10 mg/mL. Data were re­
ported in ppm relative to DMSO‑d6 at 2.5 ppm.
The wet spinnability of CPrC, CBeC and CCmC solutions with
different concentrations and the obtained filaments was recorded with a
digital camera. Rheological tests were used to show the formation
condition of filaments. Take 15 mL of the synthetic cellulose carbonate
derivative spinning solution and put it into the rheometer tester. Flow
behavior was conducted at a shear rate of 0.1–1000s− 1 to investigate the
solution of different cellulose carbonated derivatives at 30 ◦ C. Dynamic
rheological behavior was obtained from frequency sweeps over the
range of 0.1–1000 rad/s using an amplitude oscillatory rheological
measurement.
Microscopic morphology of cellulose carbonated derivative fila­
ments were observed with a Thermo Scientific Verios G4 UC scanning
electron microscope. Prior to SEM observation, the samples were sput­
tered with platinum. FTIR spectroscopy was used to determine the
chemical structure of the filaments of cellulose carbonated derivatives.
Put the prepared filament on a glass slide, and then measure the diam­
eter of the filament with a microscope BX51.Crystal structure and
crystallinity (Cr) of cellulose carbonated derivative filaments was
characterized with a D8 ADVANCE X-ray Diffractometer. The diffracted
intensity was tested with Cu Kα radiation at 40 kV and 40 mA in a 2θ

2
X. Bao et al.
Fig. 1. Schematic of the synthesis of cellulose carbonated derivatives in DBU/DMSO/CO2 system (a), FTIR spectra (b) and 1H NMR in DMSO (d6) (c) of synthesized
cellulose carbonated derivatives.
range between 5◦ and 40◦ The degree of crystallinity (Cr) was calculated
according to the Eq. (1),
Fc
Cr = × 100% (1)
Fc + Fa
Where Fc and Fa are the areas of crystal and amorphous region,
respectively. Furthermore, the decomposition temperatures of different
cellulose carbonated derivative filaments were recorded by TGA. The
test temperature range was 25–600 ◦ C, and the heating rate was 10 ◦ C/
min.
As for the cellulose carbonate filament, the diameter was first tested
under a microscope. And the appearance of the filament was observed in
detail under the SEM electron microscope. In terms of mechanical
property, the spun filaments (about 50 cm length) is taken to be fixed on
both ends of the tensile machine. 1 kN sensor was selected to measure
the tensile strength and elongation of the fibrous filaments as well as the
gel state fibers according to GB/T 3916–2013. The stretching velocity
was 250 mm/min. 10 independent specimens with a gauge length of
400 mm were used in the test to calculate average value. In terms of
chemical structure, about 5 mg of the prepared filament is dried at
110 ◦ C for 24 h. After cutting it with scissors, it was mixed with potas­
sium bromide, pressed into a tablet, and scanned 32 times under the
FTIR test. In terms of crystallinity, put the cut fibers into a copper Kα
radiation table. The diffracted intensity was tested with Cu Kα radiation
at 40 kV and 40 mA in a 2θ range between 5◦ and 40◦ In terms of heat,
about 10 mg of the prepared filament is dried at 110 ◦ C for 48 h. After
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Carbohydrate Polymer Technologies and Applications 2 (2021) 100099
cutting it into small pieces, put it into the crucible. Temperature range of
TGA test is 25–600 ◦ C, and the heating rate is 10 ◦ C/min. Temperature
range of DSC test is 40–200 ◦ C, and the heating rate is 20 ◦ C/min.
3. Results and discussion
3.1. Synthesis and wet spinnability of cellulose carbonated derivatives
Cellulose is dissolved in DBU/DMSO/CO2 system to form cellulose
carbonate and then respectively reacted with three different haloge­
nated substances (known as propyl bromide, cyclopropyl methyl bro­
mide and benzyl bromide, see Fig. 1(a)) via nucleophilic substitution as
similar as the process shown in the previous reference (Onwukamike
et al., 2017). The obtained cellulose carbonated derivatives are detected
by FTIR spectroscopy (as show in Fig. 1(b)). Distinct peaks at 1750cm− 1
and 1255cm− 1 are found on the FTIR curves of various cellulose
carbonated derivatives, which can be attributed to the C = O stretching
vibration band and C - O stretching vibration band. In addition, there are
exhibited multiple C - H stretching vibration band at 2850 to 3000cm− 1
of halogenated substituents. It is the C-H vibration peak of the newly
synthesized substituent, except for the peak 2895cm− 1 belonging to
AGU. From the results of FTIR, it can be understood that cellulose
carbonated derivatives are successfully synthesized.
In addition, the chemical structures of the synthersized cellulose
carbonated derivatives were tested by 1H NMR (see Fig. 1(c). From the
NMR curve of CPrC, newly introduced propyl peaks are shown at the
X. Bao et al.
Fig. 2. Digital photos of CPrC, CBeC and CCmC filaments formed by wet-spinning.
chemical shift of 0.84 ppm and 1.25 ppm. An obvious broad chemical
shift at 7.38 ppm concerning benzyl group is exhibited of CBeC. The
peaks at 0.15 ppm, 0.4 ppm and 1.02 ppm verified the introduction of
cyclopropylmethyl in CPrC. Accordingly, the degree of substitution (DS)
of CPrC, CBeC, and CPrC are calculated from NMR curves at 0.56, 0.52
and 0.50, respectively.
Cellulose carbonated derivatives prepared from the cellulose solu­
tions with the concentration from 3 to 6% are wet-spun into filaments.
As shown in Fig. 2, 3% CPrC can only form uneven filament. After
increasing the concentration to 4 to 6%, smooth and uniform filaments
of CPrC can be produced. As to the wet spinning of 3 and 4% CBeC, it can
be seen that almost no uniform filament is appeared. However, during
the wet spinning of 5,6% CBeC, it can easily produce the filaments with
uniform morphology. Further using CCmC for wet spinning, only 6%
CCmC can achieve wet spinning to form uniform filament.
Rheological behavior of the solution of cellulose carbonated de­
rivatives at different concentration is analyzed by rotational rheometer.
It can be seen from Fig. 3 that the viscosity of the solution of 3,4% CPrC
remains almost constant at ~0.035Pa•s and 0.071Pa•s within the shear
rate is 0.1 to 1000s− 1, respectively. Its fluid state inclines to be Newton
fluid. When the concentration is increased to 5,6%, the viscosity shows a
decrease with the increase of shear rate with the value over 0.27Pa•s. It
exhibits the character of pseudoplastic fluid. By considering the for­
mation of filament (see Fig. 2), the CPrC solution existed in Newtonian
fluid state will achieve wet spinning to form uniform filament when its
viscosity is higher than 0.07. As to the solutions of 3,4% CBeC, they also
illustrate the similar wet spinning behavior. The value of viscosity is too
low at 0.018Pa•s and 0.044Pa•s to achieve good wet spinnability.
However, the solutions of 5,6% CBeC exhibit character of pseudoplastic
fluid, and the viscosity of them reach to over 0.099Pa•s and 0.157Pa•s.
Under this condition, filament with smooth surface and uniform
morphology can be prepared from wet spinning. Fig. 3(c) gives the
rheological curves of the solution of 3–6% CCmC. All the solutions show
the character of Newtonian fluid with the viscosity at 0.01–0.07Pa•s.
Only 6% CCmC solution with the highest viscosity at 0.07Pa•s can
achieve wet spinning to prepare filament with uniform morphology. All
the results show that some solutions of cellulose carbonated derivatives
have good wet spinnability even in Newtonian fluid state. The key factor
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Carbohydrate Polymer Technologies and Applications 2 (2021) 100099
to ensure the formation of filament with uniform morphology is the
value of viscosity over 0.07Pa•s.
Dynamic shear viscosities of the solutions of cellulose carbonated
derivatives are also measured in the experiment. As exhibited in Fig. 4,
storage modulus (G’) and loss modulus (G’’) of the solutions of all the
cellulose carbonated derivatives didn’t show gel point in the dynamic
viscosity test from 0.1 to 1000s− 1. These results of steady shear viscosity
and dynamic shear viscosities show the molecular entanglement is not
the necessary condition for the wet spinnability of cellulose carbonated
derivatives to form uniform filament.
3.2. Morphology and properties of cellulose carbonated derivative
filaments
SEM images (250X and 1000X) of CPrC, CBeC and CCmC filaments
are shown in Fig. 5. Filaments prepared by the solution of 4–6% CPrC,
5,6% CBeC and 6% CCmC are all shown smooth surface and uniform
morphology. And average diameters of the filaments are summarized in
Fig. 6, which is obtained by randomly measuring 20 points of each
filament. The average diameters of 4%, 5%, and 6% CPrC filaments are
140±21 μm, 166±16 μm, and 188±11 μm, respectively. Higher con­
centration of the CPrC solution induces larger diameter of the filaments.
As to the filaments obtained from the solution of 5,6% CBeC, the di­
ameters of the filaments are 167±15 and 169±10 μm. And the diameter
of 6% CCmC filament is 145±16 μm. The change of filament diameters is
in accord with the change of the viscosity of cellulose carbonated de­
rivative solution.
The mechanical properties of the filaments prepared by the 6% CPrC,
6% CBeC and 6% CCmC are also listed in Fig. 6. The tensile strength and
elongation of CPrC filament is 0.315cN/dtex and 35.37%. The me­
chanical properties of CBeC filament is a little lower. Its tensile strength
is 0.167cN/dtex and the elongation is 12.12%. CCmC filament shows the
lowest tensile strength at 0.061cN/dtex. The elongation is only 8.39%.
FTIR spectra of cellulose carbonated derivative filaments are shown
in Fig. 7(a). The characteristic peaks of the 1255cm− 1C-O bond, the
1750cm− 1C=O bond, and C-H stretch vibration bands at 2850 to
3000cm− 1 can be clearly found on the curves. These absorption bands
are in accord with the FTIR spectra (Fig. 1(b)) of the synthesized
X. Bao et al.
Fig. 3. Steady shear viscosity of the solution of CPrC, CBeC and CCmC with
different concentrations at 30 ◦ C, respectively.
cellulose carbonated derivatives before wet spinning. This result reflects
that the chemical structure of cellulose carbonated derivatives keep
unchanged during wet spinning.
XRD patterns of cellulose carbonated derivative filaments are illus­
trated in Fig. 7(b). All the filaments show a main diffraction peak at
~20.8◦ on XRD curves, which represents the conformation of the mo­
lecular chain of cellulose carbonate derivatives. Compared with cellu­
lose, the molecular arrangement has undergone a conformational
change. There is no obvious difference existed between various cellulose
carbonated derivative filaments.
TGA is used further to discuss the heat resistances o the cellulose
carbonated derivative filaments. As shown in Fig. 8(a), CPrC filament
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Carbohydrate Polymer Technologies and Applications 2 (2021) 100099
Fig. 4. Dynamic shear viscosity of CPrC, CBeC and CCmC solutions of different
concentrations at different angular frequency, respectively.
shows the highest decomposition temperature at 268 ◦ C and the largest
residual mass of 11.02%. The decomposition temperatures of CBeC and
CCmC filaments are basically the same, which are 244 and 247 ◦ C
respectively. And DSC measurements of the cellulose carbonated de­
rivative filaments were performed, and the results are shown in Fig. 8
(b). There is no obvious glass transition platform exhibited in the DSC
spectrum. The relative high decomposition temperatures of cellulose
carbonated derivative filaments further prove that the chemical struc­
ture of the obtained cellulose carbonated derivatives remains stable
during wet spinning at room temperature.
4. Conclusions
In this research, three kinds of cellulose carbonated derivatives
(namely CPrC, CBeC, CCmC) are successfully synthesized by use of DBU/
X. Bao et al. Carbohydrate Polymer Technologies and Applications 2 (2021) 100099

Fig. 5. SEM images (Inside the rectangle is the 250X magnified image, and inside the ellipse is 1000X) of CPrC, CBeC and CCmC filament formed by wet-spinning.

Fig. 6. Average diameter and tensile properties of CPrC, CBeC and CCmC filaments obtained by the solution of (a) 4% CPrC, (b) 5% CPrC, (c) 6% CPrC, (d) 5% CBeC,
(e) 6% CBeC, and (f) 6% CCmC.

DMSO/CO2 system. Continuously, wet spinnabilities of the obtained spinnability in Newtonian fluid state. When viscosity of the solution is
cellulose carbonated derivatives are detected. Results show that the over 0.07Pa•s, cellulose carbonated derivative filaments with smooth
solution of cellulose carbonated derivative will exhibit good wet surface and uniform morphology can be obtained. Although the

6
X. Bao et al.
Fig. 7. FTIR spectra (a) and X-ray diffraction (b) of CPrC, CBeC and CCmC filaments.
Fig. 8. TGA (a) and DSC (b) curves of CPrC, CBeC and CCmC filaments.
diameters of cellulose carbonated derivative filaments changes with the
concentration of spinning solution, it found that all the cellulose
carbonated derivative filaments has similar crystal structure. The CPrC
filament, among of cellulose carbonated derivative filaments, exhibits
the highest mechanical properties and heat resistance. The conditions to
synthesize cellulose carbonated derivatives and to prepare filaments are
decided, which expands the potential future application of cellulose as
fibrous filaments.
Declaration of Competing Interest
The authors declare no competing financial interest.
Acknowledgments
We are grateful for the National Natural Science Foundation of China
(21978310 & 51773217), the financial support by the Key Research and
Development Program of Shandong Province (2019JZZY020217),
Youth Innovation Promotion Association CAS (2017339), Science and
Technology Service Network Plan (KFJ-STS-QYZD-2021-16-002).
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