Journal of Macromolecular Sciencew, Part B: Physics, 47:392–400, 2008

Copyright # Taylor & Francis Group, LLC

ISSN 0022-2348 print/1525-609X online
DOI: 10.1080/00222340701849509

Effect of Hydroxyethylation on Structure and

Properties of Chitosan Fibers

YONGLE LIU, ZHAOFENG LIU, JUNRONG YU,

AND ZUMING HU
State Key Laboratory for Modification of Chemical Fibers and Polymer
Materials, College of Material Science and Engineering, Donghua University,
Shanghai, People’s Republic of China

Chitosan fibers were modified with epoxyethane in the presence of sodium hydroxide to
enhance the capability of water absorbency. This property offers potential application as
wound dressings with enhanced capability to absorb wound exudates. Four fiber samples
with different degree of substitution (DS) were prepared by changing the mole ratio of
epoxyethane to glucosamine repeat units (GIcN). The resultant fibers were characterized
by FTIR, 13C solid-state NMR, TGA, XRD, and SEM. The FTIR and 13C NMR spectra
indicated that hydroxyethyl groups were mainly attached to C-6 positions. The inter-
and intra-hydrogen bonding were broken while the crystallinity remained unchanged,
indicated by FTIR and XRD results. TGA analysis showed that thermal stability
decreased as DS increased. The modified chitosan fibers with increased hydrophilic
hydroxyethyl groups exhibited lower tensile strength and elongation than initial
chitosan fibers. Hydroxyethylation with lower DS enhanced the water absorbency of
chitosan fibers while maintaining their fibrous structures.

Keywords chitosan fiber, derivatives, hydroxyethylation, structure transition,

absorption

Introduction
Chitosan is readily soluble in aqueous acidic solvents, and chitosan fibers are produced by
wet-spinning chitosan solution into a coagulation bath containing aqueous alkaline.[1]
After many years of research and development, chitosan fibers are now commercially
used in the applications of wound dressings, absorbable sutures, and apparel textiles. In
these applications, chitosan fibers are known for their antimicrobial properties, biocompat-
ibility, nontoxicity, and capability to promote wound healing.[2,3]
Chitosan fibers are known to have reduced tensile strength when they are wet due to
the hydrophilic nature of chitosan.[4] The wet strength can be improved by chemical cross-
linking with epichlorohydrin[5] and dialdehydes[6 – 8] via the amino groups. Previous
studies have demonstrated a significant improvement of wet strength through chemical

Received 28 October 2007; Accepted 28 November 2007.

Address correspondence to Yongle Liu, State Key Laboratory for Modification of Chemical
Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University,
2999 North Renmin Rd., Songjiang District, Shanghai 201620, People’s Republic of China.
E-mail: lyl@mail.dhu.edu.cn or yongle.liu@163.com

392
 Effect of Hydroxyethylation on Chitosan Fibers 393

cross-linking, while dry mechanical properties were improved only slightly or decreased
in some cases. Knaul and coworkers[9] reported on the increase of the mechanical proper-
ties of chitosan fibers treated with buffered solution based on potassium dihydrogen
phosphate and potassium hydrogen phthalate. The chitosan fibers can also be acetylated
with acetic anhydride in methanol, producing regenerated chitin fibers.[10] The acetylated
fibers have an improved thermal stability and tensile strength. Hirano and coworkers[11]
and Choi and colleagues[12] also reported that N-acylated chitosan fibers with longer
hydrocarbon side groups, which were prepared by post-treatment with a series of car-
boxylic anhydrides, showed lower moisture retention and higher tensile strength.
The properties of chitosan fibers can also be modified by attaching functional groups
to the hydroxyl groups or amino groups. Qin and colleagues[13] prepared fibers with
different levels of carboxymethylation by controlling the ratio between the fiber and the
amount of chloroacetic acid applied; the absorption properties for Cu(II) were
improved. Because hydroxyethyl groups have good affinity for water, improved water
absorbency can be obtained by treating the fiber with epoxyethane. When partially hydro-
xyethylated, the fibers can have a high level of swelling while retaining the fibrous
structure. This property has potential application in wound dressings with enhanced absor-
bency of wound exudates.
In this article, hydroxyethylchitosan (HECTS) fibers with different degrees of substi-
tution (DS) were prepared by contacting the fibers with epoxyethane in the presence of
sodium hydroxide. The structures of the modified chitosan fibers were characterized by
FTIR, NMR, XRD, TGA, and SEM. Thermal properties, mechanical properties, and
water absorbency were also examined.

Experimental

Materials
Chitosan fibers used in this study had a degree of deacetylation of 92%, measured by poten-
tiometric titration. Epoxyethane of chemical grade was purchased from Sinopharm Chemical
Reagent Co., Ltd. Other chemicals were of analytic grade without further treatment.

Hydroxyethylation of Chitosan Fibers

To prepare HECTS fibers with epoxyethane, 5 g of chitosan fibers were soaked in 25 wt.%
NaOH aqueous solution at 08C for 4 h, and then the excessive alkali solution was removed
by centrifugation. The fibers were then put into a reaction container under vacuum. A
desirable amount of epoxyethane was added into the system and reacted at 408C for
1.5 h. The fibers were suspended in 80 vol% aqueous ethanol solution, and diluted HCl
was added to neutralize the excessive NaOH. The fibers were separated from the mixture
and washed with 80 vol% ethanol solution twice and then dehydrated by anhydrous
ethanol and air-dried. By changing the mole ratios of epoxyethane to the glucosamine
repeat units, four samples with different DS were obtained; these are listed in Table 1.

Measurements
Chemical functional groups of the chitosan and HECTS fibers were characterized by FTIR
spectra (Nicolet, Nexus-670) and 13C solid-state NMR (Bruker, Avance 5000). DS was
determined by elemental analysis (Vario ELIII, Elementar). The crystal structure of the
394 Y. Liu et al.

Table 1
Mole ratios of epoxyethane to glucosamine units and DS of HECTS fibers

Samples Mole ratio C, % N, % H, % DS Efficiency, (%)

CTS — 37.38 6.91 7.12 — —

HECTS1 0.73 36.64 6.36 6.96 0.04 5.0
HECTS2 1.46 40.43 6.69 7.39 0.20 13
HECTS3 2.20 41.44 6.15 7.54 0.58 26
HECTS4 3.66 41.60 5.53 7.54 1.02 28

chitosan and HECTS fibers were characterized by XRD (D/max-2550 PC diffractometer,

40 kV, 300 mA).
The thermal properties were measured by thermogravimetric analysis (TGA;
TG209F1, NETZSCH) at a heating rate of 108C/min in N2 atmosphere from 30 to
6008C. The tensile properties of the mono-fibers were measured on a XQ-1 tensile
tester (Donghua University). The gauge length was 10 mm and the extension rate was
10 mm/min. The test was performed at 208C, 65% R.H. The water absorbency was
evaluated by comparing the fiber diameters before and after absorption through micro-
scopic pictures. The surface morphologies of the chitosan and HECTS fibers were
observed using a scanning electron microscope (SEM; JSM-6300, JEOL).

Results and Discussion

Characteristics of HECTS Fibers

Some typical FTIR spectra of HECTS fibers are shown in Fig. 1. The FTIR spectra of
HECTS2 and HECTS4 are similar to that of chitosan fibers, but the intensity of the C-H
stretching vibration of the methylene group in the region of 2850–2920 cm – 1 increased

Figure 1. FTIR spectra of chitosan fibers and HECTS fibers.

 Effect of Hydroxyethylation on Chitosan Fibers 395

as DS increased. The broad bands at 3432 cm – 1 were multi-absorption due to overlapping of

O-H and N-H stretching vibration. The breadth of the band indicated the existence of inter-
and intra-hydrogen bonding between -OH and -NH2 groups. After being partially hydro-
xyethylated, the breadth decreased, indicating that hydrogen bonding was weakened. The
intensity of the amide I band at 1599 cm – 1 was decreased as DS increased, and even disap-
peared in the FTIR spectrum of HECTS4, leaving only a shoulder. This result suggests that
the substitution in HECTS occurred at the C-6 position on the chitosan unit.[14]
Figure 2 represents the 13C solid-state NMR spectra of chitosan and HECTS fibers.
The intensity of the signal of C-6 at 60.36 ppm increased as DS increased and the d
chemical displacement moved to 60.97 ppm, indicating that the hydroxyethyl groups
were attached to the chitosan molecular chain.

X-ray Diffraction
The XRD patterns of chitosan fibers and HECTS fibers are illustrated in Fig. 3. The XRD
of initial chitosan fibers shows a sharp intense diffraction at the (110) plane near

13
Figure 2. C solid-state NMR spectra of chitosan fibers and HECTS fibers.
396 Y. Liu et al.

Figure 3. X-ray powder diffractions of chitosan fibers and HECTS fibers.

2u ¼ 20.18 and a less intense diffraction at the (020) plane near 2u ¼ 10.18.[15 – 17]
However, as DS of hydroxyethylation increased, the diffraction peaks near 2u ¼ 108
were comparatively sharpened and moved to lower 2u values. By peak fitting of the
diffraction profiles in Fig. 3, the accurate d-spacing and relative intensity were calculated,
as shown in Table 2. The crystallinity of HECTS fibers was not changed or slightly higher
than that of chitosan fibers. The d-spacing of the (020) planes increased from 8.83 Å for
chitosan to 10.3 Å for HECTS2 and 11.8 Å for HECTS4, and the relative intensity of this
diffraction decreased slightly.

Thermal Properties
TG, differential thermogravimetry (DTG), and DSC curves of pyrolysis in the temperature
range of 25 – 5008C for chitosan fibers and HECTS fibers are shown in Fig. 4. A wide
endothermic DSC peak appeared, being coupled with weight loss at about 608C. This
thermal event was related to the evaporation of water present in the samples. The

Table 2
Variation of d-spacing of main diffractions in XRD patterns of chitosan fibers and HECTS
fibers with different DS
(020) (110)

Crystallinity Relative Relative

Samples (%) 2u d(Å) intensity 2u d(Å) intensity

Initial 28.1 10.1 8.83 19.5 20.1 4.41 25.2

HECTS2 31.8 8.6 10.3 16.9 20.2 4.40 31.5
HECTS4 31.6 7.5 11.8 13.9 20.3 4.36 24.5
 Effect of Hydroxyethylation on Chitosan Fibers 397

Figure 4. TG (a), DTG (b), and DSA (c) curves of chitosan fibers and HECTS fibers.

weight loss was 10 – 11% of the initial weight for all the samples, while the endothermic
areas increased as DS increased. This suggests that the affinity of chitosan fibers to water
was enhanced. Thermal decomposition occurred in the temperature range of 240 –3008C.
The initial chitosan fibers showed a maximum rate of decomposition at 2848C, while the
partially hydroxyethylated samples showed the equivalent DTG peak at 2578C for
HECTS2 and 2398C for HECTS4. As DS increased, thermal stability of HECTS
decreased.

Mechanical Properties
The tensile measurements of chitosan fibers and hydroxyethylated chitosan fibers are
shown in Fig. 5. The modified chitosan fibers with increased hydrophilic hydroxyethyl
groups exhibited lower dry tensile strength and elongation than the initial chitosan
fibers, possibly due to the destruction of hydrogen bonding by hydroxyethylation. The
wet breaking strength was too weak to be measured, especially when DS was higher
than 0.4.

Water Absorbency
As shown in the FTIR spectra and X-ray diffraction patterns, hydroxyethyl groups
destroyed hydrogen bonding and expanded the spacing of the 020 plants in the chitosan
fibers. These transitions enhanced the water affinity of chitosan fibers. The partially
398 Y. Liu et al.

Figure 5. Tensile strength and elongation vs. DS of HECTS fibers.

hydroxyethylated fibers showed higher water swelling ratio than chitosan fibers, as shown
in Fig. 6. The swelling ratio tended to increase as DS increased. When the DS reached
0.58, the modified fibers were highly absorbent and became weak and difficult to
handle when it was wet, as shown in Fig. 7. HECTS with DS in excess of 0.60 were
water soluble and lost their fibrous structure when they were submerged in water. The
result indicates that HECTS fibers show higher water absorbency and swelling capability,
which is useful for absorbing and retaining wound exudates when these fibers are used as
wound dressings.

Figure 6. Water absorption capability vs. DS of HECTS fibers.

 Effect of Hydroxyethylation on Chitosan Fibers 399

Figure 7. Photomicrographs (400) of chitosan fibers and wet HECTS fibers: (a) dry chitosan fiber,
(b) wet chitosan fiber, (c) HECTS1, (d) HECTS2, (e) HECTS3.

Surface Morphology
Figure 8 shows SEM photographs of chitosan fibers and HECTS fibers. The surface patterns
of all these sample were smooth, and no significant differences were observed. The result
indicates that the process of hydroxyethyl treatment did not affect surface morphology.

Figure 8. SEM photographs of chitosan fibers and HECTS fibers: (a) chitosan, (b) HECTS2,
(c) HECTS4.
400 Y. Liu et al.

Conclusions
The chemical and solid structures of chitosan fibers were modified by hydroxyethylation.
The hydroxyl groups were attached to the molecular chains of chitosan and broke the inter-
and intra-hydrogen bonding. The crystallinity remained unchanged, while the 020 spacing
expanded as DS increased. The existence of hydrophilic hydroxyl groups and the struc-
tural changes enhanced the water absorbency of chitosan fibers while maintaining their
fibrous structures. The modified chitosan fibers with increased hydrophilic hydroxyethyl
groups exhibited lower tensile strength and elongation than the initial chitosan fibers.
The partially hydroxyethylated chitosan fibers are more hydrophilic, which allows the
fibers to absorb and maintain wound exudates in wound dressings.

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