International Journal of Biological Macromolecules 251 (2023) 126254

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Preparation and characterization of the bonding performance of a

starch-based water resistance adhesive by Schiff base reaction
Jiaxuan Song a, b, Shi Chen b, c, Qianyu Zhang b, c, Xuedong Xi b, c, *, Hong Lei a, **, Guanben Du b, c,
Antonio Pizzi d
a
College of Chemistry and Material Engineering, Zhejiang Agriculture and Forestry University, Hangzhou 311300, China
b
Yunnan Key Laboratory of Wood Adhesives and Glue Products, College of Material Science and Engineering, Southwest Forestry University, 650224 Kunming, China
c
International Joint Research Center for Biomass Materials, Southwest Forestry University, 650224 Kunming, China
d
LERMAB, University of Lorraine, 88051 Epinal, France

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

Keywords: Starch is one of the important raw materials for the preparation of biomass adhesives for its good viscosity and
Natural polymer-based adhesives low-cost properties. However, the drawbacks of poor water resistance and bonding performance seriously restrict
Plywood its application in the wood industry. To resolve those problems, an environment-friendly renewable, and high
Bonding strength
water resistance starch-based adhesive (OSTH) was prepared with oxidized starch and hexanediamine by Schiff
Water resistance
base reaction. In order to optimize the adhesive preparation process, the effect of different oxidation times and
oxidant addition on the mechanical performance of plywood were investigated. In addition, the curing behavior
characteristics, thermomechanical properties, and thermal stability of the OSTH adhesives were analyzed by
differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis
(TG). Fourier-transform infrared (FTIR) spectrometry and Liquid Chromatography-Mass Spectrometry (LC-MS)
were used to explain the reaction mechanisms involved. The results show this adhesive has an excellent bonding
performance at the oxidation time of 12 h with 11 % (w/w, dry starch basis) NaIO4 as an oxidant. The dry shear
strength, 24-hour cold water, and 3-hour hot water (63 ◦ C) soaking shear strength of the plywood bonded with
this resin were respectively 1.87 MPa, 0.96 MPa, and 0.91 MPa, which satisfied the standard requirement of GB/
T 9846-2015 (≥0.7 MPa). Thus, this study provided a potential strategy to prepare starch-based wood adhesives
with good bonding performance and water resistance.

1. Introduction
Starch is widely used in the preparation and synthesis of natural
polymer adhesives due to its wide range of raw materials, renewable and
biodegradable characteristics [1]. However, starch adhesives have poor
bonding strength and water resistance, which greatly limits their
application in the field of wood processing [2]. In order to improve the
performance of starch adhesive, some modification methods of starch
molecules have been considered, such as oxidation, esterification,
etherification, grafting, crosslinking, and so on [3]. Among them, the
oxidative treatment of starch has been widely studied due to its rela­
tively simple process [4–6]. The principle of oxidative modification of
starch is to partially oxidize the hydroxyl groups in starch to aldehyde
and carboxyl groups through oxidants, and then react with other
monomers or compounds [7].
Commonly used starch oxidants are hydrogen peroxide, sodium
hypochlorite, potassium permanganate, sodium periodate, etc. Among
them, sodium periodate oxidation is considered to selectively cleave the
vicinal hydroxyls in carbohydrates to yield aldehyde groups [8]. In
addition, studies have shown that oxidized starch treated with sodium
periodate contains many reactive aldehyde functional groups, so it
presents high stability, good binding, and anti-mildew properties, and
can be used to replace aldehydes in the wood adhesive industry [9].
So far, there have been a large number of studies on the preparation
of wood adhesives from oxidized starch [10–12]. Particularly, the dia­
ldehyde starch-urea adhesive synthesized from dialdehyde starch and

* Corresponding author at: Yunnan Key Laboratory of Wood Adhesives and Glue Products, College of Material Science and Engineering, Southwest Forestry
University, 650224 Kunming, China.
** Corresponding author.
E-mail addresses: xuedong.xi@swfu.edu.cn (X. Xi), leihong@zafu.edu.cn (H. Lei).

https://doi.org/10.1016/j.ijbiomac.2023.126254
Received 16 April 2023; Received in revised form 29 July 2023; Accepted 8 August 2023
Available online 9 August 2023
0141-8130/© 2023 Published by Elsevier B.V.
J. Song et al.
urea has been most widely used due to its suitable acidity and non-
pollution to the environment [13,14]. These adhesives exhibit good
dry shear strength and ductility. Nevertheless, there are still some
problems, such as insufficient crosslinking degree, poor water resis­
tance, and harsh reaction conditions, which greatly restrict the devel­
opment and application of starch-based adhesives. The reason for this
problem may be that urea is a carbon amide, and the N atom on the
amide group is affected by the carbon and nitrogen double bond, which
reduces its electron supply capacity. Therefore, the reaction between the
aldehyde group and the amide carbon is difficult to achieve, resulting in
insufficient cross-linking of oxidized starch and urea, thereby affecting
the final bonding strength.
In contrast, primary amines are more reactive than urea, and the
Schiff base reactions between primary amines and aldehyde groups have
been shown to proceed under mild conditions without by-products [15].
Recently, researchers tried to use dialdehyde starch and melamine-
formaldehyde resin (MF) to prepare impregnated decorative paper via
Schiff base reactions [16]. This method improves the toughness of the
material and reduces its formaldehyde emission to around 0.3 mg/L.
However, MF resin was used as the main raw material in this study,
which could not solve the formaldehyde release problem fundamentally.
Liu et al. [17] synthesized a series of self-healing coatings with chitosan
and dialdehyde starch via Schiff base linkage, which showed favorable
self-healing efficiency and bio-adhesion. Yet, this study did not report
the water resistance of the coating.
In our previous studies [18], a sucrose-based adhesive with good
bonding strength and water resistance was successfully prepared by the
oxidation method and Schiff base reaction. Although sucrose can be
obtained at a lower cost, starch is widely available in many plants such
as grains, tubers, roots, fruits, and seeds. Thus, in terms of sources,
starch can be produced at a much lower cost than sucrose. Unfortu­
nately, native starch has drawbacks such as unstable structure and poor
solubility, while wood adhesives are almost always water-soluble. Be­
sides, hexanediamine, as the main raw material for the synthesis of
nylon-66, has become one of the most widely used primary amines.
Hence, inspired by the above, we plan to develop an environmental-
friendly bio-based adhesive named OSTH using oxidized soluble starch
and hexanediamine as the raw materials. Herein, the effects of optimum
oxidation time and the addition of NaIO4 on the physicochemical
properties such as structure, bonding performance, and thermal stability
of starch adhesives were studied.
2. Materials and experiments
2.1. Materials
Poplar veneer (2 mm thick, moisture content of 8–10 %) was pro­
vided by Linyi, Shandong. Soluble starch, sodium periodate, and hex­
anediamine (80 % in water) were bought from Shanghai Macklin
Biochemical Co., Ltd. (Shanghai, China). All chemicals used in the study
were of analytical grade.
2.2. Synthesis of OSTH wood adhesive
Soluble starch was made into a 40 % solution, and 11 % (w/w, based
on dry soluble starch) NaIO4 was thrown in the soluble starch solution,
and the mixture was stirred at 45 ◦ C for 3 h, 6 h, 9 h, 12 h, and 24 h,
respectively, away from light. Then, a certain amount of hexanediamine
was added to continue the reaction for 1 h. A collection of OSTH samples
were obtained, named OSTH-3 h, OSTH-6 h, OSTH-9 h, OSTH-12 h, and
OSTH-24 h, respectively. Furthermore, another set of OSTH samples was
prepared by adjusting the oxidant content when the oxidation time of
soluble starch was 12 h. Samples with oxidant content of 7 %, 9 %, 11 %,
and 13 % (w/w, based on dry soluble starch) were designated as OSTH-
7 %, OSTH-9 %, OSTH-11 %, and OSTH-13 %, respectively.
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International Journal of Biological Macromolecules 251 (2023) 126254
2.3. Fourier transforms infrared (FT-IR) spectroscopy
The lyophilized samples were mixed with dried KBr at a ratio of
1:200 and pressed into tablets. Then, the sample was measured by
infrared spectroscopy using a Varian 1000 FT-IR spectrophotometer
(Varian, America). The spectra were recorded in the wave number range
of 4000 to 500 cm− 1 with a resolution of 4 cm− 1 and 32 scans.
2.4. Liquid chromatography–mass spectrometry (LC–MS) analysis
The LC-MS technique has been conducted to verify the main chem­
ical composition of OSTH resin. The tests were performed in positive ion
mode with a flow syringe pump injection at 3 μL⋅min− 1 and a collision
energy of 20 % for MS2 in the in-source ion trap.
2.5. X-ray photo spectroscopy (XPS) analysis
The chemical composition of the adhesive samples was analyzed by
K-Alpha X-ray photoelectron spectroscopy (XPS, Thermo, USA). The
excitation source was Kα rays (Al: photon energy 1486.6 eV); the flux
energies for full-spectrum and narrow-spectrum scanning were 100 and
50 eV, respectively, and the step size was 1.0 and 0.05 eV. After the
samples to be tested were etched with argon ions for 15 s, all bond en­
ergies were calibrated with the bond energy of surface-contaminated
carbon C1s at 284.8 eV as the standard, and then the collected data
were analyzed with Advantage software.
2.6. Three-layer plywood preparation and testing
The prepared OSTH resin was hand-applied onto the poplar veneer at
a glue spread of 300 g/m2 (double-sided) and further overlapped
together for 5 min. Subsequently, the assembled veneer was sent to a hot
pressing machine for hot pressing at a temperature of 200 ◦ C, a hot
pressing time of 6 min, and a pressure of 1.5 MPa. Next, the three-layer
plywood was divided into specimens with a size of 100 × 25 mm2 after
storing for 1 day at room temperature, and the dimensions are shown in
Fig. 1. Dry strength, 24 h cold water (20 ◦ C) immersion strength, 3 h hot
water (63 ◦ C) immersion strength were tested according to GB/T17657-
2013.
2.7. Residual rate and moisture absorption testing
The cured adhesive samples were dried in an oven at 120 ◦ C to a
constant mass (M). Then, the sample was soaked in hot water (63 ◦ C) for
3 h. Finally, the samples were taken out and dried at 105 ◦ C to constant
weight (m). The residual rate was calculated using the following formula
m/M × 100 %. In addition, the constant weight sample (m0) was ground
into a 120-mesh powder and placed in an environmental chamber (the
temperature and relative humidity were 50 ◦ C and 80 %, respectively).
Next, the constant weight of the sample was recorded (m1) and the
moisture absorption was calculated using the following equation (m1-
m0)/m0 × 100 %.
2.8. Differential scanning calorimetry (DSC) analysis
A differential scanning calorimeter (DCS 204, Netzsch, Germany)
was used to test the curing properties of the adhesives in the temperature
range of 30–300 ◦ C at a rate of 10 K/min under nitrogen protection.
2.9. Dynamic mechanical testing (DMA)
The adhesive was spread on a poplar veneer sample with a size of 50
mm × 10 mm × 2 mm, and then the dynamic thermomechanical test was
carried out by using DMA-242. The temperature range was 30–300 ◦ C,
and the rate was 5 K/min.
J. Song et al. International Journal of Biological Macromolecules 251 (2023) 126254

Fig. 1. Photograph of the dimension of specimens for plywood bond performance test.

2.10. Thermogravimetric analysis (TGA)

The thermal stability of the adhesives was tested using a NETZSCH

STA2500 Thermogravimetric Analyzer (TGA). Approximately 5 mg of
the sample was placed in a platinum tray and the sample was heated
from 30 to 800 ◦ C at a heating rate of 10 K/min under nitrogen
protection.

3. Results and discussion

3.1. Analysis of the reaction between oxidized starch and hexanediamine

The FT-IR spectra of soluble starch (ST) and oxidized starch (OST)
are shown in Fig. 2a. In the FT-IR spectrum of ST, the broad absorption
bands around 3400 cm− 1 are the O–H stretching vibration of the
glucose unit, the peaks at 2930 and 2860 cm− 1 are the absorption of the
C–H deformation, and the characteristic peak at 1652 cm− 1 is due to
the water tightly bound to the starch [19]. Besides, the peak at 1368 and
1083 cm− 1 are corresponding to the -CH2 bending vibration and CH2-O-
CH2 stretching vibration, respectively [20]. Compared to OST, in addi­
tion to the characteristic peak mentioned above, a new peak appears at Fig. 3. LC–MS spectrum of the OSTH-12 h adhesive.
1716 cm− 1 corresponding to the C– – O stretching, which indicated that
the hydroxyl groups at C2, C3, and C6 positions of soluble starch are Fig. 3, and their interpretation is in Table 1. Oxidized starch can undergo
successfully oxidized to aldehyde or carboxyl groups [21]. Taking Schiff base reactions with amino-containing substances due to the high
OSTH-12 h adhesive as an example, it can be seen from Fig. 1b that after reactivity of the introduced aldehyde groups, which have been discussed
the addition of hexanediamine, OSTH-12 h showed a new characteristic in previous reports [7]. It is obvious that the species at 254 Da was
peak at 1567 cm− 1, which corresponds not only to the stretching vi­ assigned to the result of two molecules of hexanediamine reacting with
bration of C–– O in the amide I band but also to the stretching vibration one molecule of glyoxal. In addition, the presence of Schiff bases product
– N. Furthermore, the peaks at 1206 and 1090 cm− 1 were assigned
of C– of one and two molecules of hexanediamine reacted with one molecule
to the N–H bending vibration and the C–N stretching vibration peaks, of monomers of oxidized starch is observed at 279 Da and 375 Da. At the
respectively [22]. In summary, it can be tentatively verified that the same time, there is also the product of aldimine condensation at 471 Da,
Schiff base reaction between the aldehyde group on the chain of the 553 Da and 585 Da. Indeed, larger polymers should also have formed,
oxidized starch molecule and the terminal amino group of hexanedi­ but they were not ionized or detected due to the limitations of the testing
amine has occurred. range of this study.
The LC–MS spectrum of the uncured OSTH-12 h adhesive is shown in To further elucidate the reaction mechanism of OSTH adhesives,

Fig. 2. (a) FT-IR spectra of S and OST. (b) FT-IR spectra of S, OST, and OSTH-12 h adhesive.

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J. Song et al. International Journal of Biological Macromolecules 251 (2023) 126254

Table 1
Possible structures assigned for the selected peaks in the LC–MS spectra of OSTH-12 h adhesive.
M±H Conjecture structures

145 Da

159 Da

175 Da

254 Da

279 Da

310 Da

375 Da

381 Da

441 Da

471 Da
⋅

553 Da

585 Da

603 Da

OSTH-12 h was taken as an example for XPS analysis, which was used as
a supplementary information source along with the FT-IR results dis­
cussed previously, and the results are shown in Fig. 4. In the C1s high-
resolution spectrum of OSTH-12 h (Fig. 4b), peaks at 284.80, 285.82,
286.42, 287.21, 288.29, and 289.09 eV were assigned to C–C, C–N,
C–O, C– – N, C-C=O, C-O-C, and O=C-O [23]. Among them, the presence
of C–N and C– – N reveals the Schiff base reaction between oxidized
starch and hexanediamine. Furthermore, the binding energy of N1s at
~398.94 eV, ~399.92 eV, and ~401.43 eV are considered to belong to
C–– N, N–C, and N–H, respectively (Fig. 4c) [24], which also suggests
that Schiff base and/or Michael addition reactions occur between
oxidized starch and hexanediamine via covalent interactions.

Fig. 4. (a) XPS full survey spectra of OSTH-12 h. (b, c) High-resolution spectra of C 1s and N1s in OSTH-12 h.

4
J. Song et al.
In summary, FT-IR, LC-MS and XPS analysis verified that the reaction
between oxidized starch and hexanediamine was a Schiff base reaction,
and a possible reaction process could be deduced, as shown in Scheme 1.
3.2. Effect of oxidation times on the mechanical performance of OSTH
adhesives
3.2.1. XPS analysis
It has been shown that XPS analysis can be used in the quantitative
analysis of adhesives to determine changes in elemental content and
thus to evaluate and analyze certain performance indicators of adhesives
[25]. Therefore, XPS was used to indirectly determine the aldehyde
group content of oxidized starch in this study. The XPS analysis results of
OSTH adhesives prepared under different oxidation times are shown in
Fig. 5 and Table 2. It can be seen from the results the relative C1s C (C-
C=O) content of oxidized starch increases continuously with the
oxidation time in a certain range (3 h–12 h). However, the C1s C content
decreased from 28.11 % to 14.59 % when the oxidation time extend to
24 h, which was due to the concentration of aldehyde groups on the
oxidized starch being too high to easy to form hemiacetal structures with
the adjacent hydroxyl groups [26], resulting in a decrease in the content
of aldehyde groups. In addition, the C1s B rows represent the relative
concentration of C-OH binding energy in OST. Before the oxidation time
of 12 h, a large number of hydroxyl groups in the starch were oxidized to
form aldehyde groups, so this relative concentration showed a
decreasing trend. However, the aldehyde groups on the oxidized starch
may be further oxidized to carboxyl groups as the oxidation reaction
continues, which also contain C-OH in their structure. Even though there
is an oxidant that is continuously depleting the hydroxyl group content,
the newly added carboxyl groups are also continuously providing hy­
droxyl groups, so in the OST-24 h the relative concentration of C1s B
showed an increasing trend. What’s more, the C1s D row indicates the
relative concentration of O=C-O (carboxyl groups) binding energy in
OST, and its increasing concentration in OST-24 h indicates an increase
in the content of carboxyl groups, which also provides a basis for an
increase in the content of C-OH. In summary, an oxidation time of 12 h
for starch is the preferred choice and its aldehyde group content was
highest in the experimental range.
3.2.2. Bonding performance
Shear strength has an important impact on the physical and me­
chanical properties of the plywood, it can test the quality of the gluing of
plywood, but also measure the durability of plywood [27]. Fig. 6a dis­
plays the mechanical strength of the bonded samples under different
oxidation times of the OSTH adhesive. It can be seen that the dry shear
strength of all OSTH adhesives is >0.7 MPa (Fig. 6a), which meets the
requirements of GB/T 9846-2015. In fact, the shear strength of plywood
Scheme 1. Inferred reaction mechanism for synthesize of OSTH adhesive.
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International Journal of Biological Macromolecules 251 (2023) 126254
far exceeded this measured value, which was verified in the case of the
wood failure rate of over 40 % (Fig. 6b). For wet shear strength, it is
positively correlated with the oxidation time within a certain range,
which can be ascribed to the fact that more aldehyde groups were
generated on the oxidized starch as the oxidation time increased,
resulting in a more sufficient crosslink between it and hexanediamine
thus improving the water resistance of the adhesive. However, a
decreased trend was observed as the oxidation time increased to 24 h.
This phenomenon is due to the high concentration of aldehyde groups on
the oxidized starch when the oxidation time reaches 24 h. It was very
easy to form hemiacetal structures with the adjacent hydroxyl groups,
which prevented the reaction of the aldehyde group on the oxidized
starch with the amino group on the hexanediamine, leading to insuffi­
cient cross-linking (coincides with the result in Section 3.2.1). There­
fore, an optimal oxidation time is set to 12 h in the following
experiments.
In addition, the literature points out that water resistance is a key
parameter in determining whether an adhesive is suitable for a practical
application and it can be reflected by the wet shear strength of the
plywood, but it is not absolute [28]. Therefore, a moisture absorption
test was also carried out in this study as supporting information for
judging the water resistance of the adhesive, and the consequence is
shown in Fig. 6c. As can be seen in the results, the value of the residual
rate slowly increases with the increase in oxidation time when the
oxidation time is in the range of 3 h to 12 h. When the oxidation time
reached 12 h, that is, OSTH-12 h adhesive, the residual rate increased by
6.8 % compared with OSTH-3 h (85.3 %), reaching 91.1 %. The increase
in residual rate may be due to the large number of aldehyde groups in
the oxidized starch forming a compact and homogeneous structure with
the amino group of hexanediamine through covalent bonding, which
increases the crosslinking degree of the OSTH adhesive and reduces the
number of hydrophilic groups, thereby prevents water intrusion. Be­
sides, further evidence of the best water resistance of OSTH-12 h ad­
hesives is the moisture uptake value. As we all know, moisture uptake
refers to the property of being able to absorb water from a gaseous
environment. Briefly, most of the substances with good moisture uptake
have a large comparative area in general or have an affinity for water.
Therefore, moisture uptake also can be considered as indirect evidence
to determine the hydrophilicity of an adhesive. As can be seen from the
moisture uptake value given in Fig. 6c, OSTH-12 h adhesive shows the
lowest moisture uptake values compared to other resins, indicating its
good water resistance, which coincides with the plywood test results.
Last but not least, the OSTH adhesive prepared in this study (OSTH-
12 h as an example) not only has superior wet shear strength (63 ◦ C)
than conventional adhesives such as UF [29] MUF [30], and SPI-
modified MUF resin [31] (Fig. 6d) but also without formaldehyde
emission, which can be considered as an eco-friendly material with great
J. Song et al. International Journal of Biological Macromolecules 251 (2023) 126254

Fig. 5. High-resolution spectra of C1s of OSTH adhesive with different oxidation times.

more complete curing than the other four adhesives under the same
Table 2
curing condition [34]. It is in keeping with the DSC test results.
C element binding mode and relative concentration of OSTH adhesives with
Furthermore, further confirmation that the curing temperature of OSTH-
different oxidation times.
24 h adhesive is lower than that of the other four adhesives is the in­
Name Peak Be Group a (at. b (at. c (at. d (at. e (at.
crease in the slope of storage modulus curve. The OSTH-24 h adhesive
(eV) %) %) %) %) %)
had the greatest slope, which means it was the most reactive of the five
C1s A 284.8 C-C 15.68 16.42 15.40 17.31 26.81 resins. Subsequently, E′ increases rapidly with the deepening of curing
C1s B 286.5 C-OH 60.72 61.30 64.43 50.84 54.22
and crosslinking degree, and the maximum value is observed at a spe­
C1s C 287.7 C- 11.56 15.84 16.78 28.11 14.59
C=O cific temperature. As can be seen in Fig. 7b, the OSTH-12 h adhesive
C1s D 288.9 O=C- 12.04 6.44 3.39 3.74 4.38 showed a higher E′max (4662 MPa) than the other four adhesives,
O demonstrating that it could provide a better bonding strength, which is
also in accord with the results of the shear strength of plywood. Last, the
E′ of the five OSTH adhesives decreases rapidly as the temperature
development prospects for the preparation of high-performance
continues to rise, which may be caused by the molecular chain breakage
plywood.
of the cured adhesive and the charring of the wood at superfluous
temperatures [35].
3.2.3. Thermal properties
TGA was used to study the thermal stability and decomposition
The thermal performance of the OSTH adhesive was evaluated by
behavior of OSTH adhesives with different oxidation times, and the
DSC, DMA, and TG tests. The DSC thermograms of different cured ad­
results were given in Fig. 7c. From the TGA and DTG curves, it is not
hesives are shown in Fig. 7a. Here, all OSTH have an obvious endo­
difficult to see that the trend of OSTH adhesives with different oxidation
thermic peak around 114–120 ◦ C, corresponding to the melting
times is roughly the same, and they all present three stages of weight loss
endothermic peak caused by the destruction of the crystal structure after
thermogravimetric curve. The mass loss of the first stage (35–230 ◦ C) is
oxidation [32]. Furthermore, an exothermic peak caused by the curing
about 10 %, which may be caused by the evaporation of residual
of the OSTH adhesive can be observed around 180 ◦ C, which justifies the
moisture [36]. The second stage (230–500 ◦ C) is the foremost stage of
hot-pressing temperature of 200 ◦ C.
thermal decomposition, which contains two phases of mass loss. The
Dynamic thermomechanical analysis (DMA) test results for five
first is at 230–350 ◦ C, which is caused by the breakage of hydrogen and
OSTH adhesives are shown in Fig. 7b. First, the storage modulus (E′) of
covalent bonds between the starch molecular chains. The second at
OSTH adhesives with different oxidation times decreased around
350–500 ◦ C, which is caused by the destruction of the adhesive cross­
30–100 ◦ C. This may be due to the fact that the fluidity of the adhesive
linking network [37]. The third stage (500–800 ◦ C) had less chemical
becomes better and the wood thermally softens as the temperature in­
reaction and the mass loss rate decreased gradually. Apparently, the
creases. Next, the initial curing temperature of the adhesive can be
residual mass of OSTH-12 h (22.54 %) is higher than that of other ad­
identified by the temperature at which the E′ begins to increase in the
hesives, indicating that the OSTH adhesive prepared under this condi­
DMA test [33]. Obviously, the temperatures at which the E′ of OSTH-3 h,
tion had prominent thermal stability, confirming the strengthening of its
OSTH-6 h, OSTH-9 h, OSTH-12 h, and OSTH-24 h adhesives started to
molecular structure and supporting the results of improved bonding
increase sharply were 106, 93, 101, 92, and 89 ◦ C respectively. This
strength and water resistance.
shows that the curing temperature of OSTH-24 h adhesive has a lower
curing temperature, which also means that OSTH-24 h resin can achieve

6
J. Song et al.
Fig. 6. Effect of oxidation time of starch on the mechanical performance of OSTH adhesives: (a) shear strength; (b) the wood failure of the plywood specimens in the
dry strength test; (c) residual rate and moisture uptake value of different cured adhesives after hydrolysis; (d) performance comparison of OSTH adhesives
with analogs.
3.3. Effect of oxidant content on the mechanical performance of OSTH
adhesives
3.3.1. XPS analysis
As we all know, oxidants play a vital role in starch modification, and
the level of oxidant content will directly affect the degree of starch
oxidation and the corresponding properties of the related products [38].
The content of aldehyde groups in OSTH adhesives under different
oxidant content is shown in Fig. 8. It can be seen that the relative C1s C
(C-C=O) contents of oxidized starch increased with the increasing NaIO4
concentration when the NaIO4 addition amount was 7–11 %. Whereas,
the relative C1s C (C-C=O) contents of oxidized starch will gradually
decrease when the NaIO4 addition is >11 % (i.e. 13 %). Similar to OST
samples prepared at different oxidized times, the relative C1s B (C-OH)
content showed a downward trend until the oxidant addition of 11 %,
which indicated the hydroxyl groups in the starch were oxidized to
aldehyde groups. However, as the oxidation reaction proceeded, the
aldehyde group was transformed into the carboxyl group due to the
excessive oxidation, as evidenced by an increasing trend in the relative
concentrations of C1s B and C1s D when the oxidant addition was
increased to 13 %. Thus, it was determined that the highest concentra­
tion of the aldehyde group was achieved at 11 % oxidant addition
(Table 3).
3.3.2. Bonding performance
The effect of oxidant content on the shear strength of OSTH adhesive
was shown in Fig. 9a. From the results of dry and wet shear strength,
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International Journal of Biological Macromolecules 251 (2023) 126254
with the increased addition of NaIO4, the value of shear strength first
increased and then decreased. Fig. 9a shows that when the amount of
NaIO4 increases from 7 to 11 %, the hot water (63 ◦ C) strength of the
OSTH adhesive increases from 0.40 MPa to 0.96 MPa, an increase of 140
%. This may be attributed to the fact that with the increase of oxidant
content, the molecular chains of starch were gradually broken, and the
hydroxyl groups in the molecular structure were transformed into the
more reactive aldehyde groups and carboxyl groups, which react with
hexanediamine to form sturdy chemical bonds, thus improving the
water resistance [39]. When the amount of NaIO4 increased to 13 %, the
hot water (63 ◦ C) strength decreased to 0.61 MPa, which was mainly due
to the serious degradation of starch molecules and weakening of inter­
molecular hydrogen bonds with further increase of oxidant content,
thereby affecting the water resistance. Hence, the optimum content of
oxidant for the preparation of OSTH adhesives was 11 % (w/w, dry
starch basis).
The residual rates of OSTH adhesives with different oxidant contents
were also investigated, and the results were illustrated in Fig. 9b.
Likewise, the OSTH adhesive shows more wonderful water resistance
with the increase of the amount of oxidant. The residual rate and
moisture uptake value of OSTH-7 % were 88.5 % and 9.6 %, respec­
tively. When the NaIO4 additive reached 11 %, the residual rate of the
adhesive increased by 2.9 % to 91.1 % and the moisture uptake value
decreased to 7.5 %. As mentioned in 3.2.2, a high residual rate meant
few samples were dissolved, which meant favorable water resistance.
Similarly, a low moisture uptake value means poor hydrophilicity of the
sample, which also means good water resistance. To sum up, it is
J. Song et al.
Fig. 7. Thermal properties of OSTH adhesive prepared with different oxidation times: (a) DSC curves; (b) DMA curves; (c) TGA and DTG curves.
revealed that the OSTH-11 % adhesive exhibit the optimal water resis­
tance, again in line with the shear strength results.
3.3.3. Thermal properties
Fig. 10a exhibits the DSC results of the OSTH adhesive with different
additions of oxidants. It can be seen that the initial temperatures (Ti/◦ C:
191.9, 187.4, 183.9, 180.9), peak temperature (Tp/◦ C: 195.1, 189.9,
186.9, 183.3), and the conclusion temperature (Tc/◦ C: 201.2, 195.2,
192.9, 188.5) obviously decreased with the increase of the oxidizer
content. It could be explained that the structure of oxidized starch
molecules was damaged severely during the process of oxidation, and
the degree of cracking increased in the oxidized starch molecular so that
the cure can be achieved at lower temperatures [40].
The DMA curves of the OSTH adhesives synthesis with different
amounts of NaIO4 added are shown in Fig. 10b. The E′ gradually
increased when the addition of NaIO4 was increased from 7 % to 11 %
and reached a maximum at 11 % of NaIO4 addition. This suggests that
OSTH adhesives possess the best bonding performance when NaIO4 is
added at 11 %, which coincides with the results of shear strength tests on
plywood. Nevertheless, the excessive addition of oxidant, >11 %,
adversely affects bonding properties as the structure of starch is seri­
ously damaged and decomposed into short chains. At this time, the
polymerization of small molecular substances occurs in the system, and
8
International Journal of Biological Macromolecules 251 (2023) 126254
a three-dimensional network structure is not formed, which is not
enough to provide strong strength support [41].
The TG and DTG curves for the OSTH adhesives with different ad­
ditions of oxidant was given in Fig. 10c. The weight loss in the region I
(30–230 ◦ C) was relatively low, about 10 %, which should be caused by
the elimination/evaporation of small molecules and the water adsorbed
on the surface of the solid resin powder [42]. Region II (230–500 ◦ C) is
the stage with the most dramatic mass loss and contains both the
disruption of the intermolecular forces of the starch (230–350 ◦ C) and
the disruption of the resin crosslinking network (350–500 ◦ C) [43]. In
this stage, the OSTH-7 % adhesive had an onset decomposition tem­
perature (T0) at 255.6 ◦ C. With the increase of the oxidant content, T0
slightly shifted to low temperature, that is, the T0 of OSTH-13 % adhe­
sive was 239.7 ◦ C. This may be due to the fact that the excess oxidant
disrupts the ordered structure of the starch molecules and generates a
large number of aldehyde groups, leading to weaker bonding between
the chains of adhesive molecules and a lower initial temperature for
thermal decomposition [36]. Last, the decomposition of degradable
substances basically completed in the range of 500–800 ◦ C, so the
weight loss process is relatively slow and the TG curve tends to be stable.
By examining the bond performance of the OSTH adhesives, the
optimal preparation conditions were determined as follows: the oxida­
tion time was 12 h, and the amount of oxidant added was 11 %. It must
J. Song et al. International Journal of Biological Macromolecules 251 (2023) 126254

Fig. 8. High-resolution spectra of C1s of OSTH adhesive with different oxidant content.

be noted that the oxidation time and oxidant addition play a decisive
Table 3
role in the oxidative modification of starch and thus affect the bonding
C element binding mode and relative concentration of OSTH adhesives with
performance of the adhesive. Therefore, the measurement and precise
different oxidant content.
control of oxidation degree are of great importance and significance,
Name Peak Be (eV) Group a (at.%) b (at.%) c (at.%) d (at.%)
which will be investigated and optimized in future studies to fully un­
C1s A 284.8 C-C 15.90 19.08 17.31 16.21 derstand the effect of synthesis conditions on the polymer structure and
C1s B 286.5 C-OH 64.43 54.15 50.84 62.72 properties.
C1s C 287.7 C-C=O 15.98 17.70 28.11 14.40
C1s D 288.9 O=C-O 3.69 9.07 3.74 6.67

Fig. 9. Effect of oxidant content of starch on the mechanical performance of OSTH adhesives: (a) shear strength; (b) residual rate and moisture uptake value of
different cured adhesives after hydrolysis.

9
J. Song et al.
Fig. 10. Thermal properties of OSTH adhesive prepared with different oxidant content: (a) DSC curves; (b) DMA curves; (c) TGA and DTG curves.
4. Conclusions
In this study, a renewable and eco-friendly oxidized starch-
hexanediamine adhesive with good bonding performance was ob­
tained from the Schiff base reaction between oxidized starch and hex­
anediamine. The OSTH adhesive prepared in this study exhibited well
bonding strength and water resistance at an oxidation time of 12 h and
NaIO4 content of 11 % (w/w, dry starch basis). The dry strength, 24 h
cold water strength, and hot water (63 ◦ C) strength of the plywood
bonded with it are 1.87 MPa, 0.91 MPa, and 0.96 MPa, respectively.
These values meet the requirement of the China national standard GB/T
9846–2015 (≥0.7 MPa) and are highly competitive as a substitute for
existing industrial formaldehyde-based adhesives. Meanwhile, the re­
sults of DMA analysis verified that the OSTH adhesive prepared with an
oxidation time of 12 h and NaIO4 addition of 11 % display the best
storage modulus, which is consistent with the results of the shear
strength of plywood. FTIR and XPS analysis also confirmed that the
amino groups in hexanediamine react with the aldehydes group in
oxidized starch to form a cross-linked system, thereby ensuring the
bonding effect.
CRediT authorship contribution statement
Jiaxuan Song: Conceptualization, Writing - original draft, Writing -
review & editing. Shi Chen: Methodology, Implementation, Data cura­
tion. Qianyu Zhang: Validation, Formal analysis. Hong Lei: Resources,
Funding acquisition, Supervision. Xuedong Xi: Project administration,
10
International Journal of Biological Macromolecules 251 (2023) 126254
Supervision, Writing - review & editing. Guanben Du: Project admin­
istration, Supervision. Antonio Pizzi: Supervision, Writing - review &
editing.
Declaration of competing interest
The authors declare that we have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors gratefully acknowledged the financial assistance from
the National Natural Science Foundation of China (32160346), the
Yunnan Provincial Natural Science Foundation (202201AU070222,
202101BD070001-074), and the Scientific Research fund project of
Yunnan Provincial Department of Education (2022J0490).
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