Chemical Engineering Journal 370 (2019) 420–431

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Chemical Engineering Journal

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

Depolymerization and characterization of Acacia mangium tannin for the T

preparation of mussel-inspired fast-curing tannin-based phenolic resins
Jiongjiong Lia,b, Wenjie Zhua,b, Shifeng Zhanga,b, Qiang Gaoa,b, Changlei Xiac, Wei Zhanga,b, ,
⁎

Jianzhang Lia,b,
⁎

a
Ministry of Education Key Laboratory of Wood Materials Science and Utilization, Beijing Forestry University, Beijing 100083, China
b
Beijing Key Laboratory of Wood Science and Engineering, Beijing Forestry University, Beijing 100083, China
c
Department of Mechanical and Energy Engineering, University of North Texas, Denton, TX 76203, USA

HIGHLIGHTS GRAPHICAL ABSTRACT

• AMT was depolymerized under acidic

condition using 2-methylfuran to prepare
DAMT.
• DAMT has a similar catechol with
mussel protein and high reactivity.
• DAMT and PEI were used to prepare
phenolic resins with high crosslinking
density and good water resistance.
• The gel time decreased by 67.6% and
the bonding strength increased by
63.6% after the addition of DAMT.
• The developed adhesives exhibited
low formaldehyde emission and high
thermal stability.

ARTICLE INFO ABSTRACT

Keywords: Similar to the 3,4-dihydroxy-L-phenylalanine (DOPA) structures in mussel adhesive proteins (MAPs), tannin
Tannin-based phenolic resins contains abundant similar catechol structures in the flavonoid units, which might be developed into high-per-
Condensed tannin formance adhesives. In this study, Acacia mangium tannin (AMT) was depolymerized under acidic conditions
Depolymerization reactions with 2-methylfuran as a nucleophilic reagent. The depolymerized tannin (DAMT) was combined with poly-
DOPA structures
ethyleneimine (PEI) to prepare tannin-based phenolic resins to mimic the MAP systems. The investigation of the
Adhesion properties
chemical structures of tannin indicated the successful reaction of 2-methylfuran onto the flavonoid units to
increase the chemical reactivity, as evidenced by the MALDI-TOF-MS, GPC, 1H NMR, and FT-IR analyses. The as-
prepared PEI and DAMT-modified phenolic (DTPF-PEI) resin showed a high cross-linking and three-dimensional
network, resulting from the high reactivity of DAMT. Complex reactions were observed during the curing of the
as-prepared resin, including Michael addition and/or Schiff base formation reactions between the amino groups
of PEI and the ortho-quinone of tannins, as well as the condensation reactions between PEI and the phenolic
resins. Compared with tannin-phenol-formaldehyde (TPF) resin, the gel time of the DTPF-PEI resin decreased
from 630 s to 204 s (decreased by 67.6%), the mass loss after hydrolysis decreased by 26.3%, the bonding
strength increased by 63.6% when cured at 135 °C, and the formaldehyde emission decreased by 64.4%. Such
high performance might be contributed by the formation of highly cross-linked networks, as well as the hy-
drogen bonding and pi-cation interactions between the catechol structures and the adhered surfaces. With its

⁎
Corresponding authors at: Ministry of Education Key Laboratory of Wood Materials Science and Utilization, Beijing Forestry University, Beijing 100083, China.
E-mail addresses: zhangwei@bjfu.edu.cn (W. Zhang), lijzh@bjfu.edu.cn (J. Li).

https://doi.org/10.1016/j.cej.2019.03.211
Received 13 December 2018; Received in revised form 22 March 2019; Accepted 23 March 2019
Available online 25 March 2019
1385-8947/ © 2019 Published by Elsevier B.V.
J. Li, et al. Chemical Engineering Journal 370 (2019) 420–431

outstanding performance, including fast curing rate, excellent adhesion properties, low formaldehyde emission,
and high thermal stability, this newly developed adhesive has the potential to be used as an alternative of
conventional phenol-formaldehyde resins.

1. Introduction structures similar to DOPA. Considering the inherent structure features,

Mussels, as typical promiscuous fouling marine organisms, can
firmly affix themselves to almost any kinds of underwater surfaces via
byssus [1]. The attachment system is composed of several proteins,
commonly referred to as mussel adhesive proteins (MAPs) [2]. Detailed
studies of the MAPs revealed that their key feature is the high content of
the amino acid 3,4-dihydroxy-L-phenylalanine (DOPA, Scheme 1). It
was confirmed that the catecholic functionality of DOPA played a cri-
tical role in the robust adhesion [3]. The catecholic moiety in DOPA has
the capacity of establishing hydrogen bonds and π-π interactions to the
hydrophilic and/or organic surfaces [3]. The phenolic hydroxyl groups
in DOPA can undergo various oxidation reactions at an elevated pH,
resulting in the formation of dopaquinone. The dopaquinone can react
with catechol via reverse dismutation reactions, leading to the forma-
tion of a cross-linked product [4]. In addition, the amino groups in
DOPA structures can also react with the dopaquinone through Michael
addition or Schiff base reactions, resulting in the formation of poly-
dopamine, which is able to affix to various underwater substrates [5].
Inspired by these findings, DOPA has been introduced into many ad-
hesive materials to enhance adhesion properties [1]. However, the re-
latively high cost of DOPA has seriously limited its industrial applica-
tions. Therefore, it is necessary to find an alternative that has similar
catecholic moiety structures but is less expensive.
Condensed tannins (CTs) are cost-efficient, natural environmentally
friendly materials that contain 3 to 8 flavanoid repetition units [7],
which show great potential as a structural mimic of DOPA due to their
catechol-laden structural features (Scheme 1). The most important re-
actions associated with the A-rings in CTs are the polycondensation
reactions with aldehydes, based on which, aldehyde-based adhesives
derived from CTs have been explored [8,9]. The B-rings are generally
composed of pyrogallol rings and catechol rings, which have chemical
CTs might be used as adhesive materials to mimic the adhesive systems
of MAPs.
Phenol-formaldehyde (PF) resins, with excellent mechanical prop-
erties, good moisture and chemical corrosion resistance, have been used
in many fields, including wood-based panel industry, aerospace, mili-
tary industry, electronics, etc. [10]. Condensed tannins containing
abundant phenols have been developed into tannin-based phenolic re-
sins [8,11]. Crude CTs with high molecular weight, great steric hin-
drance, and far apart reactive sites [7], dramatically increase the
viscosity of the synthesized phenolic resins, which reduce the adhesive
performance. Thus, depolymerization of CTs is suggested before being
fabricated into resin [12]. Currently, acid-assisted depolymerization in
the presence of nucleophilic reagents is considered to be a promising
method, in which the A-rings are protonated and the interflavanoid
bonds are cracked, resulting in the formation of terminal flavonoid
units and extension units (carbocation intermediates). The carbocation
intermediates subsequently react with the nucleophilic reagents to form
flavonoid derivatives [13,14]. Two kinds of nucleophilic reagents have
been explored to trap the carbocation intermediates, namely, mercap-
tans [15,16] and activated aromatic compounds [13]. For the mer-
captans, the flavanyl-mercaptyl bonds of the thioetherified flavonoids
are prone to be cleaved when the pH values are higher than 8.5 [17].
Although the CeC bonds between the carbocation intermediates and
the phenolic compounds (phloroglucinol [18] or pyrogallol [19]) are
stable, such nucleophilic reagents are unsuitable for tannin depoly-
merization because they can be used as building blocks themselves.
Recently, an eco-friendly and cost-efficient nucleophile, 2-methylfuran,
has been proved to be capable of depolymerizing CTs [12]. The depo-
lymerized, fully biobased products are stable under alkaline conditions,
which makes them suitable building blocks for the synthesis of tannin-
based adhesives. In addition, the furylated flavonoid derivatives have

Scheme 1. Flavonoid units in condensed tannins and the chemical structure of DOPA (※[6]).

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J. Li, et al.
phloroglucinolic and/or resorcinolic A-rings, low molecular weight,
high reactivity, decreased steric hindrance, and catecholic moieties,
which mimic the structures of DOPA.
Previous work reported that wood adhesives prepared by mixing
polyethyleneimine (PEI) and demethylated lignin [20] or crude tannins
[21] can be used to mimic the adhesive systems of MAPs. However,
their wet shear strength is limited. The reason may be the high mole-
cular weight and low reactivity of polyphenols, as well as the in-
effective use of the active sites in lignin and the active A-rings in CTs.
The B-rings in depolymerized tannins can be grafted onto the molecular
chains of phenolic resins via reactions between the active A-rings and
formaldehyde to mimic the catechol moiety in DOPA, which should
improve the performance of the synthesized tannin-based phenolic re-
sins. Moreover, the combination of PEI and depolymerized tannin-
based phenolic resins can be used to simulate the adhesive systems of
MAPs; it has great potential for eliminating the disadvantages of using
high-molecule polyphenols, therefore yielding high-performance
tannin-based phenolic resins.
In this study, Acacia mangium tannin (AMT, condensed tannin) was
acid depolymerized in the presence of the nucleophilic reagent 2-me-
thylfuran. Then, the depolymerized AMT (DAMT) and PEI were used to
prepare tannin-based phenolic resins to mimic the MAP adhesive sys-
tems. Matrix-assisted laser desorption/ionization-time-of-flight mass
spectrometry (MALDI-TOF-MS), gel permeation chromatography
(GPC), Fourier transform infrared (FT-IR), thermogravimetric analysis
(TGA), and 1H-nuclear magnetic resonance spectroscopy (1H NMR)
were used to study the depolymerization mechanisms. The synthesized
tannin-based phenolic resins were investigated and evaluated, in terms
of their chemical structures, gelation time, thermal behavior, bonding
strength, and formaldehyde emissions.
2. Materials and methods
2.1. Materials
AMT was purchased from Guangxi Baise Forest Chemicals General
Plant (Guangxi, China). The moisture content of AMT is 10.1%, the
total extract content is 89.9%, the tannin content is 67.1%, the non-
tannin content is 27.3%, the insoluble content is 3.2%, and the pH value
is ca. 5.13. Solid phenol, 37 wt% formaldehyde aqueous solution, so-
dium carbonate, 2-methylfuran, hydrochloric acid (HCl, 37%), absolute
ethyl alcohol, and sodium hydroxide were all analytical grade reagents
provided by Beijing Chemical Reagents Co., Ltd. (China). PEI, a par-
tially branched polyamine with an average molecular weight of 10,
000, was purchased from Aladdin (Shanghai, China). All chemicals
were used as received without any further purification.
2.2. Optimization of the AMT depolymerization reactions
The depolymerization reactions were conducted under acidic con-
ditions in a nitrogen atmosphere. In a typical depolymerization process,
4 g AMT was added into 100 mL 2-methylfuran/absolute ethyl alcohol
solutions (2-methylfuran/absolute ethyl alcohol = 1/3, V/V). Then, 1 g
37% HCl (i.e., 0.1 mol·L-1) was added. The reaction temperature was set
to 50 °C. To investigate the effect of reaction time on the depolymer-
ization of tannins, the depolymerization reactions were conducted for
30 min, 60 min, 90 min, 120 min, 150 min, or 180 min under magnetic
stirring at 400 rpm. To stop the depolymerization reaction, the reaction
solution was cooled to 0 °C in an ice bath, and then 75 mL sodium
carbonate aqueous solution (10.6 g·L-1) was added to neutralize the acid
in the reaction solution. After the addition of sodium carbonate, the pH
of the reaction solution was adjusted to be weakly acidic (pH = ca.
6.5). Ethanol and 2-methylfuran were evaporated under vacuum at
room temperature, resulting in the purification of the obtained pro-
ducts. Finally, the depolymerized products were freeze-dried by placing
them in a vacuum freeze-drier (Sihuan LGJ-25C, Sihuan Co., Ltd,
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Chemical Engineering Journal 370 (2019) 420–431
Beijing, China) for 48 h. The obtained products were denoted as DAMT-
1, DAMT-2, DAMT-3, DAMT-4, DAMT-5, and DAMT-6, respectively.
Prior to the freeze drying, DAMT-2 was dialyzed using dialysis bag (Mw:
3000 Da) for 4 days, and the obtained products was denoted as DAMT-
d.
2.3. Synthesis of neat PF resin and tannin-based phenolic resins
The neat PF resin was synthesized using a molar ratio of 1:2.0 of
phenol to formaldehyde based on our previous work [22,23]. First,
109 g phenol, 62.7 g formaldehyde aqueous solution and 11 g NaOH
solution (40%) were mixed in a flask and heated at 85 °C for 50 min.
Next, 62.7 g formaldehyde aqueous solution and 11 g NaOH solution
(40%) were added to the flask at 85 °C for 60 min. Then, 62.7 g for-
maldehyde aqueous solution and 30 g NaOH solution (40%) were added
to the same flask at 85 °C for 50 min. Finally, the reaction solution was
rapidly cooled to 40 °C to yield the neat PF resin.
For the synthesis of tannin-based phenolic resins, the substitution
rate of phenol by AMT, DAMT-2, or DAMT-d was 40% by weight, which
corresponded to the TPF, DTPF, or DTPF-d resins. The tannin-based
phenolic resins were prepared using a molar ratio of 1:2.0 of phenol
together with tannin to formaldehyde. First, 40 g tannin was added into
100 g distilled water, and the pH value of the mixture was adjusted to
7.0 by using 40% NaOH solution. Next, 60 g phenol, 95 g formaldehyde
aqueous solution, 30 g distilled water, and 10 g 40% NaOH solution
were added to the flask at 90 °C for 10 min. Then, 70 g tannin solution
was added to the flask at 90 °C for 30 min. Subsequently, 70 g tannin
solution, 10 g 40% NaOH solution, and 22.5 g formaldehyde aqueous
solution were added to the flask at 90 °C for 30 min. After that, 20 g
formaldehyde aqueous solution and 30 g 40% NaOH solution were
added to the flask at 90 °C for 30 min. Finally, the reaction mixture was
rapidly cooled to 40 °C to yield the tannin-based phenolic resins.
TPF-PEI and DTPF-PEI resins were synthesized by mixing of PEI and
TPF or DTPF resins using mass ratio of 1:2.0 of PEI to tannins. After
stirring (1000 rpm) at ambient temperature for 30 min, PEI modified
tannin-based phenolic resins were prepared.
2.4. Characterization of tannins and phenolic resins
The MALDI-TOF-MS spectra of tannins were acquired on a MALDI-
TOF instrument (AXIMA Performance, Shimadzu, Japan). A pulsed ni-
trogen laser with a wavelength of 337 nm was used as the irradiation
source. The duration of one laser pulse was 3 ns. The GPC analysis of
tannins was performed on PL-GPC 50 (Varian Inc., Palo Alto, USA). The
1
H NMR spectra of freeze-dried tannins were collected on a JEOL ECS-
400 NMR spectrometer (JEOL, Tokyo, Japan) at a frequency of
300 MHz with an acquisition time of 3.0 s. D2O was used as the solvent.
The FT-IR spectra were performed on a Nicolet 6700 spectrometer
(Nicolet Instrument Corporation, Madison, WI, USA) at a resolution of
4 cm−1. All the spectra were recorded in the frequency range of
500–4000 cm−1 with 32 scans. The TGA spectra were acquired on a
Q50 TGA analyzer (TA Instruments, Newcastle, DE, USA) in a nitrogen
atmosphere (60 mL·min−1) at a heating rate of 10 °C·min−1. The yield
of phenolic resins was calculated according to the weight ratio of the
phenolic resins and the raw materials used during the preparation
process. The gelation time determination of the phenolic resins was
conducted according to the Chinese National Standard (GB/T 14074.3-
2006). For this test, 5.0 g phenolic resins were added into a test tube,
and the time period from the immersion of the test tube into an oil bath
(135 °C) to the start of the gelation of the adhesive was defined as the
gelation time. The mass loss of cured phenolic resins after hydrolysis
was determined according to previous work [24]. The phenolic resin
samples were oven-dried at 120 °C and then ground into 200 mesh
powder. After that, the cured phenolic resins were wrapped using a
qualitative filter paper and immersed in distilled water at 60 °C for 6 h.
Finally, the samples were dried at 105 °C for 3 h and then weighed. The
J. Li, et al. Chemical Engineering Journal 370 (2019) 420–431

weights change before and after hydrolysis was defined as the mass
loss. The accelerated aging test of the cured TPF-PEI resin was per-
formed using a QUV accelerated weathering tester (QUV/Spray, Q-Lab
Co., USA) for a total duration of 72 h, 144 h, and 216 h, respectively.
Each weathering cycle (12 h) consisted of 8 h of UV exposure at 60 °C
and 4 h condensation at 50 °C. The obtained products were denoted as
TPF-PEI-1, TPF-PEI-2, and TPF-PEI-3, respectively. The XPS measure-
ment was performed on a thermo scientific ESCALAB 250 (Thermo
Fisher Scientific, UK) equipped with monochromatic Al Kα radiation.

2.5. Preparation and characterization of plywood

Three-layer plywood with the dimension of 400 mm × 400 mm

× 4.5 mm was prepared using poplar veneers. First, each side of the
middle veneer was coated with (125–150) g·m−2 phenolic resins. The
glued plywood was then hot-pressed at 135 °C or 115 °C under 1.0 MPa
for 5 min. Finally, the prepared plywood was stored at room tempera-
ture for 2 days prior to use.
The shear strength of plywood (100 mm × 25 mm × 4.5 mm) was
measured as per ASTM D906-98 A. The emission of formaldehyde from
plywood was measured by the method of acetylacetone according to
previous work [25]. First, a glass dish containing 300 mL distilled water
was placed in the bottom of a 10-L desiccator. Ten plywood samples
(15 cm × 5 cm) were then placed in the same desiccator, which was
kept at 20 °C for 24 h. Finally, the formaldehyde concentration in the
distilled water was determined using an ultraviolet spectroscope (UV)
at a wavelength of 412 nm.
3. Results and discussion
3.1. Depolymerization and characterization of tannins
3.1.1. Molecular mass measurements of tannins
The MALDI-TOF-MS spectra of AMT are shown in Fig. 1. The re-
petitive pattern of peaks observed in the MALDI-TOF-MS spectra was
used to identify a specific oligomer series in AMT, including three types
of flavonoid units, namely, fisetinidin (A, 274.3 Da), catechin and ro-
binetinidin (B, 289.3 Da), and delphinidin (C, 304.3 Da) (Fig. 2). A
series of peaks at 903.1 Da, 1174.7 Da, 1446.3 Da, 2070.1 Da,
2342.3 Da, and 2614.6 Da, which are separated by ca. 273 Da, indicated
the presence of A-type flavonoid units [26]. The low intensity of these
peaks suggested that small quantities of profisetinidin repeating units
were present in the AMT. The peaks at 903.1 Da, 1190.8 Da, 1478.5 Da,
1766.1 Da, 2054.4 Da, 2342.3 Da, and 2629.9 Da, which were clearly
separated by ca. 289 Da mass, indicated the presence of B-type
Fig. 2. Typical polymer structures of flavonoid repeating units in AMT: (A)
fisetinidin, (B) catechin and robinetinidin, and (C) delphinidin.
flavonoid unit [26]. These peaks revealed that catechin and robineti-
nidin are the dominant repeating units in the ATM, as evidenced by
their high intensity. A series of peaks at 1174.7 Da, 1478.5 Da,
1782.2 Da, and 2070.1 Da separated by ca. 304 Da were related to the
occurrence of C-type flavonoid units [26]. The mass increment of ca.
16 Da between adjacent peaks could be explained by different numbers
of hydroxyl groups attached to the flavonoid unit [27].
The number of repeating units present in the oligomers can be
calculated using the following expression: M = 274.3A + 289.3B
+ 304.3C + 2.0 (endgroups, 2 × H), where A, B and C represent the
relevant flavonoid monomers. For instance, the peak at 1190.8 Da is a
flavonoid tetramer according to two possible combinations of repeating
units such as (I) one A-type unit and three C-type units plus 2H end-
groups; (II) two B-type units and two C-type units plus 2H endgroups.
The possible combinations of the three repeating flavonoid units and
the polymerization degrees are shown in Table S1. Analysis of the AMT
revealed that these tannins have oligomers of up to 9 repeating flavo-
noid units. These abundant aromatic building blocks can be used to
prepare phenolic resins. Owing to the presence of fisetinidin and ca-
techin repeating units that contain catechol structures, AMTs have
promising potentials to mimic the DOPA structures.
The MALDI-TOF-MS spectra of the depolymerized tannins are shown
in Fig. 3. Most of the peaks present in the spectra of DAMT differ from
those in the spectra of AMT (Fig. 1). After depolymerization reactions, the
dominate peaks decreased and many low molecular weight peaks
emerged. These observations indicated successful depolymerization of the
AMTs, which could also be confirmed by GPC and TGA measurements

Fig. 1. MALDI-TOF-MS spectra of AMT. (a) 500 Da – 1750 Da and (b) 1750 Da – 2800 Da.

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J. Li, et al. Chemical Engineering Journal 370 (2019) 420–431

Fig. 3. MALDI-TOF-MS spectra of DAMT: (a) DAMT-1, DAMT-2, and DAMT-3 in the range of 500 Da – 2800 Da; (b) DAMT-4, DAMT-5, and DAMT-6 in the range of
500 Da – 2800 Da; (c) DAMT-1, DAMT-2, and DAMT-3 in the range of 250 Da – 600 Da; (d) DAMT-4, DAMT-5, and DAMT-6 in the range of 250 Da – 600 Da.

(Fig. S1–S2 and Table S2). As shown in Fig. 3a and Fig. 3b, a series of
peaks with a repeating interval of ca. 81 Da were noted, which may be
related to a 2-methylfuran unit (82.1 Da − 1H = 81.1 Da). It was con-
firmed that 2-methylfuran reacted with the carbocation intermediates to
form the nucleophile adducts. Peaks at 272.3 Da – 275.4 Da corresponded
to the occurrence of A-type flavonoid monomer units (fisetinidin), peaks at
282.1 Da – 285.1 Da were related to the B-type flavonoid monomer units
(catechin and robinetinidin), and peaks at 311.8 Da – 312.5 Da indicated
the presence of the C-type flavonoid monomer units (delphinidin). The
series peaks at 354.1 Da – 356.0 Da, 363.6 Da – 364.3 Da, and 394.0 Da –
394.3 Da could be associated with the furylated A-type, furylated B-type,
and furylated C-type flavonoid monomer units, respectively. The in-
tegrated intensity of peaks associated with the flavonoid monomers and
the furylated flavonoid monomers initially increased and then deceased as
the reaction time increased. Series of peaks in the spectrum of DAMT-2
exhibited the highest integrated intensity of the depolymerized tannins,
indicating that more flavonoid monomer units were obtained after reac-
tion for 1.0 h.

Fig. 4. (a) FT-IR spectra of AMT and DAMT-2, (b) 1H NMR spectra of AMT and DAMT-2.

424
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As for the spectral range of 500 Da – 2800 Da (Fig. 3c and d), the
intense peaks of the DAMT were clearly different, and they were dif-
ferent from those of the AMTs, which may be explained by the con-
densation and rearrangement of molecular fragments during the de-
polymerization process [28]. The spectra clearly showed dominant
fragment peaks at 533.6 Da – 595.9 Da, and exhibited oligomer series
with a polymerization degree of up to 3 – 4 repeating units. The
polymerization degree decreased initially and then increased as the
reaction time increased. Through the spectral analysis, the reaction
time of 1.0 h seems to be the most effective reaction condition for AMT
depolymerization, as evidenced by their low polymerization degree and
high integrated intensity of dominant fragment peaks at 533.6 Da –
595.9 Da.
Based on the abovementioned results, it can be concluded that the
flavonoid monomer units, oligomers, and corresponding flavonoid de-
rivatives coexisted in the depolymerized tannins. The as-prepared
DAMTs with low molecular weight, low steric hindrance, and catechol
structures might be fabricated into a high-performance phenolic resin.
3.1.2. FT-IR and 1H NMR measurements of tannins
Motivated by the above results, the optimum reaction conditions for
efficient depolymerization of AMT into flavonoid monomers and/or
oligomers were the use of 2-methylfuran in 0.1 mol·L-1 HCl solution at
50 °C for 60 min. The chemical structures of AMT and DAMT-2 were
analyzed by FT-IR (Fig. 4a) and 1H NMR (Fig. 4b). As seen in Fig. 4a,
the broad peak at approximately 3303 cm−1 was related to the eOH
stretching vibrations. The absorption band at 2939 cm−1 was asso-
ciated with the CeH stretching vibration of the eCH and eCH2 groups
of the aliphatic hydrocarbon [29]. The absorption bands at 1616 cm−1,
1512 cm−1, and 1453 cm−1 were the characteristic bands of aromatic
ring stretching vibration. The high integrated intensity of the band at
1616 cm−1 associated with the CeC stretching vibrations revealed that
the C4eC8 bond was the dominated interflavonoid linkage in AMT
[30]. The single absorption band at 1512 cm−1 indicated that the AMT
was mainly composed of procyanidin, which was consistent with the
MALDI-TOF-MS data [31]. The peaks in the region of 1204–1030 cm−1
indicated the CeOeC linkages, including aromatic CeO and aliphatic
CeO present in the AMT [28]. The absorption bands in the range of
841–616 cm−1 were related to the CeH of benzene rings and the OeH
of alcohol vibration [32].
After the depolymerization reactions, some apparent differences were
observed. As seen in the spectrum of DAMT-2, the bands associated with
the eOH stretching vibrations became broader and shifted from
3303 cm−1 to 3372 cm−1, suggesting an increased hydrogen bonding in-
teractions and an increase in the content of hydroxyl groups. This
Scheme 2. The depolymerization mechanism of AMT using 2-methylfuran as a nucleophilic reagent under acidic conditions.
425
Chemical Engineering Journal 370 (2019) 420–431
phenomenon can be explained by the successful depolymerization of AMT.
It can be clearly observed that the integrated intensity of band at ap-
proximately 2925 cm−1 increased after the depolymerization reactions. A
new peak at 1382 cm−1 associated with the methyl groups was present in
the spectrum of DAMT-2, but absent in the spectrum of AMT. In addition,
the absorption bands in the range of 1204–1030 cm−1 due to the CeOeC
linkages became stronger. These observations confirmed that 2-methyl-
furan has been successfully added to the flavonoid units, indicating a
positive effect of the nucleophilic reagent on the depolymerization of AMT.
The 1H NMR spectra of AMT and DAMT-2 are shown in Fig. 4b. As
seen in the spectrum of AMT, the protons linked to the C3 position and
protons in the residual carbohydrates can be observed between
3.45 ppm and 3.92 ppm. The protons at the C4 position when R1 = eH
can be observed at 3.99 ppm [33]. The proton signals at 4.95 ppm in-
dicated the presence of protons at the C4 position when R1 = another
flavonoid unit [33]. The proton signals between 4.25 ppm and
4.35 ppm were attributed to the protons at the C2 position. The protons
at the C6 position resonated at 5.82 ppm, and the proton signals at
5.99 ppm were attributed to the protons at the C8 position [34]. The
proton signals in the range of 6.25–6.82 ppm were assigned to the
aromatic protons in the flavonoid units. The protons in the hydroxyl
groups can be observed at 8.31 ppm [33,34].
Compared with the AMT, some clear differences were observed after
depolymerization. For instance, the intensity of the proton signal at
8.31 ppm increased in the DAMT-2, indicating an increased content of
hydroxyl groups. The intensity of the proton signal at 4.95 ppm de-
creased after the depolymerization reactions, and the DAMT-2 showed
higher intensity of the proton signal at 3.99 ppm than the AMT. These
results indicated that the interflavanoid bonds connecting the flavonoid
units are cleaved, resulting in the formation of flavonoid monomer
units and oligomers. It can be clearly observed that new proton signals
associated with protons in the methyl groups and at the C3′' positions
are present in the spectrum of the DAMT-2. These results confirmed
that the 2-methylfuran units have been successfully added to the fla-
vonoid units of tannins, which is consistent with the above results. The
depolymerization mechanism is illustrated in Scheme 2. Under acidic
conditions, the interflavonoid bonds between the subunits are cleaved
through a heterolytic process, resulting from the protonation of A-rings.
The terminal flavonoid and extension subunits are released as neutral
monomeric flavan-3-ols and carbocation intermediates, respectively.
Subsequently, the carbocations are trapped by 2-methylfuran, resulting
in the formation of flavonoid derivatives.
Based on the abovementioned results, it can be concluded that
DAMT-2 had low molecular weight, low steric hindrance, high re-
activity, and good thermal stability (Fig. S2), and it can be used as
J. Li, et al.
promising building block to prepare low-cost tannin-based phenolic
resins. The highly reactive phloroglucinolic and resorcinolic A-rings can
react with formaldehyde. Hence, the catechol units (B-rings) in DAMT-2
can be grafted onto the molecular chains of the phenolic resin, and the
high content of catechol rings can be used to mimic the DOPA struc-
tures. To increase their similarity to the MAP adhesive systems, poly-
amines can be added to the tannin-based phenolic resins. The catechol
units are readily oxidized to form ortho-quinone structures under al-
kaline conditions [35]. Subsequently, the ortho-quinone structures can
react with polyamine via Michael addition and/or Schiff base formation
reactions [36]. These reactions can result in the formation of a cross-
linked and three-dimensional network, which are believed to enhance
the properties of the synthesized phenolic resins. These reaction me-
chanisms are depicted in Scheme 3.
3.2. Chemical structure measurement of the tannin-based phenolic resins
The AMT and DAMT-2 were used to prepare tannin-based phenolic
resins, and the obtained resins were denoted as TPF and DTPF, re-
spectively. To mimic the MAP adhesive systems, PEI, a polyamine, was
added to the synthesized tannin-based phenolic resins. In addition, the
DAMT-d was also used to prepare tannin-based phenolic resin, and the
obtained resin was denoted as DTPF-d. The FT-IR spectra of the cured
phenolic resins and PEI are shown in Fig. 5. As shown in Fig. 5a, all the
tannin-based phenolic resins exhibited similar FT-IR absorption profiles
compared to the PF resin, because of their similar chemical structures.
In addition, DTPF and DTPF-d resins had similar chemical structures
based on the FT-IR analysis. The absorption bands in the range of
3700–3300 cm−1 and 2950–2800 cm−1 were related to the hydroxyl
groups and the CeH stretching vibrations in the eCH2 groups, re-
spectively. All the phenolic resins exhibited typical aromatic rings in
the region 1700–1400 cm−1, phenolic CeO stretching at 1208 cm−1,
and CeO stretching at 1010 cm−1 [37]. The presence of aromatic CeH
was observed at 878 cm−1, 775 cm−1, and 708 cm−1 [38]. Compared
with the spectrum of PF resins, the integral intensity of bands at
1464 cm−1, 1438 cm−1, and 1208 cm−1 became weaker in the spectra
of TPF, DTPF, and DTPF-d resins. These observations were accounted
for the high content of nontannin materials in the tannin samples.
As shown in Fig. 5b, spectrum of PEI showed typical NeH bands
Scheme 3. Reaction mechanisms of the depolymerized tannins.
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Chemical Engineering Journal 370 (2019) 420–431
between 3346 cm−1 and 3278 cm−1, CeH stretching vibrations in
eCH2 groups between 2935 cm−1 and 2814 cm−1, NeH bending vi-
brations in eNH2 groups at 1595 cm−1, CeN stretching vibration at
1457 cm−1, and NeH bending vibrations in eNH groups at 1119 cm−1
[39]. Amino groups of PEI impart the ability to react with ortho-qui-
none structures via Michael addition and Schiff base formation reac-
tions, which have been used to prepare wood adhesives by combining
with poly (N-acryloyldopamine) [40] or demethylated lignins [20]. In
addition, the combination of PEI and Douglas-fir condensed tannins to
manufacture wood adhesives were also explored [21]. In this approach,
the depolymerized AMT was used to prepare tannin-based phenolic
resins, and the combination of PEI and such phenolic resins was used to
increase their similarity to the MAP adhesive systems and enhance
adhesion properties. After the addition of PEI, the amino groups in PEI
reacted with the ortho-quinone in the tannin framework, resulting in
the formation of C]N and/or CeN groups, as shown in Scheme 3. The
amino groups can also react with the methylol groups in the phenolic
resins, leading to the formation of CeN groups [41]. However, no ab-
sorption bands associated with such groups were observed in the
spectra of TPF-PEI and DTPF-PEI resins, expect for the enhanced peak
at 2830 cm−1. The reason may be the overlaps of bands between the
C]N (ca. 1665 cm−1), CeN (ca. 1460) and the aromatic rings
(1700–1400 cm−1) in the phenolic resins [42,43]. The absorption
bands related to eNH2 groups (3346–3278 cm−1) in the FT-IR spectrum
of PEI were sharp, and the TPF-PEI and DTPF-PEI resins exhibited wide
and flat absorption bands in the range of 3700–3300 cm−1, which may
be because there were no or very little unreacted PEI in the phenolic
resin systems.
3.3. Thermal properties of the tannin-based phenolic resins
The TGA and DTG curves of the phenolic resins are shown in Fig. 6. For
the PF, TPF, DTPF, and DTPF-d resins, three main mass loss events, i.e.,
below 250 °C, (250–450) °C, and (450–600) °C were observed. The con-
densation reaction between methylol groups caused the mass loss in the
first thermal event [44]. The condensation reactions of methylol and
phenolic hydrogen, as well as between two hydroxyl functional groups
resulted in the mass loss in the second thermal event [44]. Degradation of
methylene groups led to the mass loss in the third thermal event [23].
J. Li, et al.
Fig. 5. (a) FT-IR spectra of phenolic resins and (b) FT-IR spectrum of PEI.
Compared with the PF resin, the T10% increased from 193.5 °C to
239.5 °C for the TPF resin, to 227.1 °C for the DTPF resin, and to
228.0 °C for the DTPF-d resin; the weight residual at 600 °C increased
from 67.2% to 68.4% for the TPF resin, to 68.7% for the DTPF resin,
and to 69.0% for the DTPF-d resin. DTPF and DTPF-d resins had similar
thermal stability based on the TGA analysis. The T10% of the TPF-PEI
and DTPF-PEI resins was 214.6 °C and 258.6 °C, respectively. The PEI-
modified phenolic resins exhibited inferior thermal stability in the
second thermal event, which may be caused by the degradation of the
PEI framework [45]. The residual weight of the DTPF-PEI resin at
600 °C was higher than that of the TPF-PEI resin. These results led us to
the conclusions that the DTPF and DTPF-d resins had good thermal
stability, as evidenced by the high residual weight at 600 °C. The DTPF-
PEI resin exhibited the best thermal stability in the first thermal event,
as evidenced by the high T10%. The high thermal stability of the DTPF-
PEI resin can be explained by the highly cross-linked resin network,
which can be confirmed by FT-IR measurement.
3.4. Physical properties of the tannin-based phenolic resins
The yield of the phenolic resins is shown in Fig. 7a. As seen, the
yield of the PF, TPF, DTPF, and DTPF-d resins was 99.43%, 99.31%,
99.35%, and 99.33%, respectively. During the resin preparation pro-
cess, phenols, formaldehyde, and catalysts were added to a flask
equipped with a condenser, and there were almost no raw materials
volatilized from the flask. Therefore, the yield of the phenolic resins
Fig. 6. (a) TGA and (b) DTG curves of the phenolic resins.
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Chemical Engineering Journal 370 (2019) 420–431
was close to 100%. The mass loss after hydrolysis of the cured phenolic
resins is shown in Fig. 7b. The mass loss of the PF resin was 21.87%,
while the mass losses of the TPF and DTPF resins were 27.20% and
25.67%, respectively. The increased mass loss of the TPF and DTPF
resins may be caused by the presence of soluble carbohydrates in
condensed tannins [28]. Compared with the TPF resin, the decreased
mass loss of the DTPF resin may be explained by the reduced molecular
weight and enhanced reactivity of the DAMT. The mass loss of the
DTPF-d resin was 25.08%, which was similar to that of the DTPF resin.
After the incorporation of PEI, the mass loss of TPF-PEI and DTPF-PEI
resins decreased to 24.66% and 20.05%, respectively. This is because
PEI cross-linked with the molecular chains of the phenolic resin, in-
creased the cross-linking density and reduced the content of small so-
luble molecules (e.g., free formaldehyde) of the phenolic resins. In
addition, the enhanced cross-linking density can improve water re-
sistance of the phenolic resins and limit the dissolution of small mole-
cules from the resins.
Fig. 8a shows the gel time and the viscosity of the tannin-based
phenolic resins. The viscosity of the TPF resin was higher than that of
the PF resin, possibly due to the higher molecular weight of the AMT
than phenol [28]. The DTPF resin exhibited lower viscosity than the
TPF resin, caused by the decreased molecular weight of the DAMT. The
viscosity of the DTPF-d resin was approximately 166 mPa·s, which was
similar to that of the DTPF resin (ca. 173 mPa·s). With the addition of
PEI, the viscosity of the tannin-based phenolic resins significantly in-
creased. This might result from the increased hydrogen bonding
J. Li, et al.
Fig. 7. (a) The yield of phenolic resins; (b) The mass loss after hydrolysis of the cured phenolic resins.
interactions between the amino groups of PEI and the hydroxyl groups
of the phenolic resins, because the depolymerization of tannins resulted
in an increased content of hydroxyl groups as confirmed by FTIR and 1H
NMR measurements (Fig. 4). Therefore, higher viscosity was de-
termined for the DTPF-PEI resin, compared with the TPF-PEI resin
(Fig. 8a). As a consequence, the gel time of the TPF resin decreased due
to the high viscosity of the TPF resin and the high molecular weight of
the AMT. The gel time of the DTPF and DTPF-d resins were 552 s and
560 s, respectively, which were shorter than that of the TPF resin, al-
though the DTPF and DTPF-d resins had low viscosities. These ob-
servations may be explained by the high reactivity of the depolymer-
ized tannins, which benefits from the depolymerization reaction. The
PEI-modified phenolic resins exhibited shorter gel time than the other
phenolic resins, due to their high viscosity and the reactions between
the PEI and the tannin-based phenolic resins [20]. Notably, compared
with the PF resin, the gel time of the DTPF-PEI resin decreased from ca.
702 s to ca. 204 s. These results led us to the conclusion that the ad-
hesives synthesized by this approach can promote the preparation of
fast-curing tannin-based phenolic resins.
The bonding strength and formaldehyde emission of the phenolic
resins are shown in Fig. 8b. After being cured at 135 °C, the bonding
strength of phenolic resins was higher than the requirement for ex-
terior-grade plywood (0.70 MPa) according to the Chinese National
Standard (GB/T 14732-2017), and the formaldehyde emissions were all
below 0.50 mg/L, meeting the E0 grade [25]. The bonding strength and
formaldehyde emission of TPF resin were 0.88 MPa and 0.45 mg/L, and
those of the DTPF resin were 1.07 MPa and 0.32 mg/L, respectively.
The enhanced properties of the DTPF resin were caused by the high
Fig. 8. (a) Gel time and viscosity of the phenolic resins; (b) Bonding strength and formaldehyde emission of the phenolic resins.
428
Chemical Engineering Journal 370 (2019) 420–431
reactivity of the DAMT and the fast curing rate of the DTPF resin. The
bonding strength and formaldehyde emission of the DTPF-d resin were
1.06 MPa and 0.35 mg/L, respectively, which were similar to those of
the DTPF resin. The bonding strength of the tannin-based phenolic re-
sins increased with the addition of PEI, achieving ca. 1.17 MPa and ca.
1.44 MPa for the TPF-PEI and DTPF-PEI resins, respectively. The for-
maldehyde emission of the TPF-PEI and DTPF-PEI resins decreased after
the addition of PEI, which can be explained by the reactions between
amino groups and the phenolic resins [41]. It is worth noting, the DTPF-
PEI resin had higher bonding strength and lower formaldehyde emis-
sion than the neat PF resin.
Due to the low curing temperature of the MAP adhesives, the in-
troduction of the simulated DOPA structures and polyamine was sup-
posed to decrease the curing temperature of the phenolic resins. To
evaluate whether the synthesized tannin-based phenolic resins can be
cured at low temperature, the bonding strength of plywood prepared by
hot pressing at 115 °C was investigated. As shown in Fig. 8b, the
bonding strength of TPF, DTPF, and DTPF-d resins were 0.54 MPa,
0.62 MPa, and 0.61 MPa, respectively, all below 0.70 MPa. After the
addition of PEI, the bonding strengths of TPF-PEI and DTPF-PEI resins
increased to 0.82 MPa and 1.14 MPa, respectively. It is worth noting
that, the DTPF-PEI resin exhibited higher bonding strength than the
neat PF resin (0.98 MPa), which was similar to the trend observed when
cured at 135 °C. This means that the DTPF-PEI resin has high adhesion
strength and can be cured at low temperature, which has great potential
in industrial applications.
The properties of the DTPF resin were similar to that of the DTPF-d
resin according to the above-mentioned results. Therefore, the dialysis
J. Li, et al.
of the depolymerized tannin had little effect on the properties of the
prepared tannin-based phenolic resins.
The adhesive mechanisms of the DTPF-PEI resins are summarized in
Scheme 4. Compared with the TPF resin, the increased adhesion
properties of the DTPF-PEI resin can be explained by three main rea-
sons. First, the depolymerization of AMT decreased the molecular
weight and increased the content of reactive functional groups. The
increased reactive sites promoted the methylolation and polymerization
reactions between tannins and formaldehyde, resulting in the formation
of a network structure with high cross-linking density. Second, the
amino groups in PEI can react with the ortho-quinone in tannins
through Michael addition and/or Schiff base formation reactions, in
addition to the condensation reactions with the methylol groups in the
phenolic resins [21]. All these reactions can increase the cross-linking
density and enhance the physical and/or chemical crosslinking between
the tannin-based phenolic resins and the adhered surfaces. Third, the
catechol structures in the cross-linked networks can interact with the
adhered surfaces via hydrogen bonding and pi-cation interactions [1],
which can further enhance the adhesion properties of the phenolic re-
sins.
3.5. Accelerated aging test of the tannin-based phenolic resin
The FT-IR spectra of the accelerated aged TPF-PEI resins are shown
in Fig. 9a. After the accelerated aging test, the accelerated aged TPF-PEI
resins exhibited decreased content of hydroxyl groups (approximately
at 3191 cm−1) and methylol groups (approximately at 1010 cm−1)
[37]. In addition, absorption bands related to the CeO stretching vi-
brations gradually disappeared as the increase of accelerated aging
time. The intensity of peaks associated with the aromatic rings gradu-
ally decreased and new peaks related to the C]O groups generated in
the spectra of the accelerated aged TPF-PEI resins [38]. These ob-
servations indicated that TPF-PEI resins were gradually degraded
during the accelerated aging test.
Fig. 9b shows the XPS spectra of the accelerated aged TPF-PEI re-
sins. As seen, the relative content of carbon atom increased first and
then decreased and the relative content of oxygen atom decreased first
and then increased as the aging time increased. These observations
indicated the TPF-PEI resins were gradually decomposed as the increase
Scheme 4. Adhesion mechanisms of the DTPF-PEI resins.
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Chemical Engineering Journal 370 (2019) 420–431
of aging time, which was consistent with the FT-IR measurement. It is
noteworthy that the content of nitrogen atom increased as the increase
of aging time. This observation may be because the PEI molecular
chains did not release from the TPF-PEI resin systems during the ac-
celerated aging test. In this approach, the dosage of PEI in the tannin-
based phenolic resins was low, PEI can react with the phenolic resin
systems through Michael addition, Schiff base formation, and con-
densation reactions, the amino groups in PEI can form strong H-
bonding with the hydroxyl groups in the phenolic resin systems, and the
branched chain of PEI can entangle with the molecular chains of phe-
nolic resins. In addition, after curing of the phenolic resins, the liquid
adhesives were converted to a stable, three-dimensional network.
Therefore, it is not easy for the PEI molecular chains to release from the
phenolic resin systems during the accelerated aging test.
4. Conclusions
Tannin-based phenolic resins have been successfully fabricated by
using depolymerized natural AMT. PEI was subsequently added to the
synthesized phenolic resins to mimic the MAP adhesive systems. The
MALDI-TOF-MS measurement revealed that the flavonoid repeating
units forming the AMT were (A) fisetinidin, (B) catechin and robineti-
nidin, and (C) delphinidin. The AMT was successfully depolymerized
and the 2-methylfuran was added to the flavonoid units in DAMT. The
enhanced reactivity of DAMT, the Michael addition and/or Schiff base
formation reactions between PEI and tannins, and the condensation
reactions between the amino groups and the methylol groups facilitated
the formation of cross-linked, three-dimensional phenolic resin network
structures with high cross-linking density. Compared with the PF resin,
the gel times of the TPF-PEI and DTPF-PEI resins decreased from 702 s
to 322 s (decreased by 54.1%) and 204 s (decreased by 70.9%), re-
spectively. Compared with the TPF resin, the mass loss after hydrolysis
of the DTPF-PEI resin decreased from 27.20% to 20.05% (decreased by
26.3%), the bonding strength increased from 0.88 MPa to 1.44 MPa
(increased by 63.6%), and the formaldehyde emission decreased from
0.45 mg/L to 0.16 mg/L (decreased by 64.4%), which were close to
those of the neat PF resin. When cured at 115 °C, the bonding strength
of the DTPF-PEI resin was 1.14 MPa, which was higher than that of the
neat PF resin (0.98 MPa) and the TPF resin (0.54 MPa). The strong
J. Li, et al.
Fig. 9. (a) FT-IR spectra and (b) XPS spectra of the accelerated aged TPF-PEI resins.
bonding strength resulted from the highly cross-linked network and the
hydrogen bonding and pi-cation interactions between the catechol
structures and the adhered surfaces. The tannin-based adhesives syn-
thesized in this work exhibited a fast curing rate, good adhesion
properties, low formaldehyde emission, and high thermal stability,
which have great potential for industrial applications.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China [Project 31700491], and the Fundamental
Research Funds for the Central Universities [No. 2016ZCQ01].
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.03.211.
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