Tailoring of oxidized starch’s adhesion using crosslinker and adhesion

promotor for the recycling of fiberboards

Muhammad Adly Rahandi Lubis, Byung-Dae Park , Min-Kug Hong
Department of Wood and Paper Sciences, Kyungpook National University, Daegu 41566, Republic of Korea
Correspondence to: B.-D. Park (E-mail: byungdae@knu.ac.kr)

ABSTRACT: The growing interest in recycling waste medium density fiberboards (MDFs) is driving the development of new adhesives that
provide sufficient adhesion, and allow disintegration of the waste MDFs. Described in here is the preparation of adhesives based on oxi-
dized starch (OS) in combination with blocked-polymeric 4-4 diphenylmethane diisocyanate (B-pMDI) as a crosslinker and poly(vinyl
alcohol) (PVA) as an adhesion promotor for the recycling of waste MDFs. The COOH groups of OS were reacted with NCO groups
of B-pMDI to form amide linkages, and the CHO groups were reacted with OH groups of PVA through hydrogen bonding. Further,
when applied as an adhesive, the OS formed ester linkages with OH of MDF fibers. As the results, MDF bonded with 1% B-pMDI/15%
PVA/OS adhesive had an internal bonding strength of 0.13 MPa, 0.01 mg L−1 of formaldehyde emission (FE), and 12% of degree of fiber
disintegration. These results demonstrate that the B-pMDI/PVA/OS adhesive is a possible alternative to the current urea–formaldehyde
resins for the recycling of waste MDFs into recycled MDFs without FE. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47966.

KEYWORDS: adhesives; blends; cellulose and other wood products; manufacturing; recycling

Received 18 November 2018; accepted 28 April 2019

DOI: 10.1002/app.47966

INTRODUCTION
As one of the fastest growing wood products, medium density
fiberboards (MDFs) are manufactured by bonding wood fibers
with urea–formaldehyde (UF) resins and are commonly used for
furniture and flooring applications.1 However, UF resins adhesive
emits formaldehyde,2 which is known to cause significant health
risks3,4 In addition, the poor recyclability of waste MDFs is
another important challenge being investigated in the field. It was
reported that the cured UF resins in waste MDFs was difficult to
remove5; hence, the recycling of waste MDFs is challenging. As a
result, waste MDFs are usually sent to boilers or landfill in most
MDFs mills. Although the industry has established flue-gas
cleaning systems, burning is not an environmentally friendly
solution as it releases dioxins, carbon dioxide, methane, and other
pollutants which can harm the environment.6,7 Therefore, the
recycling of waste MDFs is more benign than burning or land-
filling does.8 Growing interest in recycling waste MDFs is driving
the development of new adhesives that provide good adhesion,
and allowing easy disintegration of MDFs. Consequently, it is
necessary to develop alternative adhesives to replace UF resins,
which are suitable for producing high-quality MDF products with
favorable mechanical properties, and more efficient recycling.
Although MDFs have been prepared using renewable adhesives,
such as lignin and chitosan,9,10 starch has good potential as an
adhesive for manufacturing MDFs because it is generally less
expensive than these other renewable adhesives. Starch has been
used for bonding wood since the time of the ancient Egyptians.11
Previous studies have reported that MDFs were fabricated by a
partial substitution of UF resins with starch,12 a mixture of natu-
ral rubber latex and starch,13 and only native starch.14
Starch is a thermoplastic polymer with a linear structure of amy-
lose and branched structure of amylopectin, which has three
hydroxyl groups at C-2, C-3, and C-6 positions in each glucose
unit with the ability to form hydrogen bonds.15,16 The affinity of
starch to water leads to poor water resistance and slow setting of
starch-based adhesives.17 Hence, it is necessary to modify the starch
in order to improve its performance as an adhesive. Several modifi-
cations, such as esterification,18 crosslinking,19 and grafting20 have
been reported to improve the water resistance of starch-based adhe-
sives. However, the viscosity of starch-based adhesives modified
using those methods reaches 10,000 MPa s−1, which limits their
use for MDF production. One way to reduce the viscosity to an
applicable range is to convert starch macromolecules into small
molecules by oxidation processes. The oxidation of starch causes
depolymerization and introduces aldehyde and carboxyl groups,
which minimize the retrogradation of amylose and eventually
improves the stability of the oxidized starch (OS).21 During the oxi-
dation, hydroxyl groups at the C-2, C-3, and C-6 positions of the
starch are first oxidized to aldehyde groups, and further oxidation
converts free hydroxyl or aldehyde groups into carboxyl groups.22

© 2019 Wiley Periodicals, Inc.

47966 (1 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47966

ARTICLE WILEYONLINELIBRARY.COM/APP
OS has been used in film formation,23 coatings,24 binders,25 ther-
moplastic composites,26 flame retardants,27 and wood adhesives28;
hence, it is expected to be a potential adhesive for MDF.
The hydrophilicity of starch should make the OS adhesive easy to
recycle. In addition, no formaldehyde is emitted from the OS-
bonded panel. However, to date, very limited studies have investi-
gated the use of OS on the manufacture of MDFs for their
recycling. Therefore, it is necessary to develop an OS adhesive
that provides an appropriate balance between good adhesion and
easy disintegration of MDFs for recycling. Moreover, the OS
adhesive should have low viscosity to allow it to be sprayed onto
wood fibers for bonding.11 Available literature reports that the
modification of OS with a crosslinker can promote chemical
crosslinking by forming ester linkages.29 Blocked-polymeric 4-4
diphenylmethane diisocyanate (B-pMDI) can be used as a
crosslinker which releases NCO groups after deblocking, and pro-
motes reactions with aldehyde and carboxyl groups of OS.30 In
addition, poly(vinyl alcohol) (PVA) can be used as a promotor to
improve the adhesion of OS through the formation of hydrogen
bonds between OS and PVA.19
Hence, the present work aims to prepare a novel MDF adhesive
based on OS synthesized via oxidation using hydrogen peroxide.
OS’s adhesion performance was tuned by mixing OS with B-
pMDI as a crosslinker and PVA as an adhesion promoting agent.
The functional groups and thermal properties of neat OS, B-
pMDI/OS, and B-pMDI/PVA/OS adhesives were investigated
using Fourier transform infrared (FTIR) spectroscopy and differ-
ential scanning calorimetry (DSC) analysis. This article, for the
first time, reports a method of tailoring the adhesion of OS adhe-
sives by combining with crosslinker and adhesion promoter for
the recycling of MDFs. It is expected that the control of levels of
B-pMDI and PVA in the OS adhesives could provide a good bal-
ance between adhesion and easy disintegration with MDFs for
their recycling.
EXPERIMENTAL
Materials
Corn starch (28.5% amylose, 18% moisture content), hydrogen per-
oxide (30 wt %), copper sulfate (99 wt %), sodium dedocyl sulfate
(98 wt %), ammonium persulfate (99 wt %), and PVA (molecular
weight of 22,000 g mol−1) were used to prepare the OS. Liquid pMDI
(31% NCO, Lupranate M20S, BASF, Ludwigshafen, Germany),
sodium bisulfate (58.5 wt %), and acetone (99.8 wt %) were used to
prepare the B-pMDI. Urea granules (99 wt %), formalin (37 wt %),
formic acid (20 wt %), sodium hydroxide (20 wt %), and ammonium
chloride (20 wt %) were used to synthesize UF resin. These chemicals
were purchased from Duksan or Daejung Chemical, Seoul, Korea.
Virgin wood fibers made of Red pine (Pinus densiflora Siebold &
Zucc., 3% moisture content) were supplied from a commercial MDF
mill (Hansol Home Deco, Iksan, Korea).
Oxidation of Starch
OS was prepared according to previously published methods with
some modifications.28,29 A starch solution was prepared by mixing
200 g corn starch and 250 mL of distilled water. The solution was
sonicated for 30 min at 25  C and 20 kHz. The solution then was
gelatinized at 80  C for 1 h under continuous stirring at 100 rpm.
47966 (2 of 10)
The temperature was adjusted to 50  C, and subsequently, 0.5%
copper sulfate, 0.5% ammonium persulfate, and 0.25% sodium
dedocyl sulfate based on the weight of starch were added to the
gelatinized starch. Subsequently, 127.5 mL H2O2 was added to
obtain OS with a H2O2/starch mole ratio of 1.0. The oxidation reac-
tion was performed by maintaining the temperature at 50  C and
pH at 3 for 5 h under continuous stirring at 500 rpm, and the reac-
tion was completed when the pH was stable at 3.
Preparation of OS Adhesives
Two series of OS adhesives were prepared for MDF manufacture
and recycling. The first one was prepared by mixing OS with
B-pMDI levels of 0, 1, 3, and 5% based on the OS solids content.
Approximately 0.7, 2.2, an© 2019 Wiley Periodicals, Inc.d 3.6 g of
B-pMDI were added into 200 g of OS to prepared 1, 3, and 5% B-
pMDI/OS, respectively. The mixture was stirred at 80  C and
300 rpm for 30 min. The B-pMDI with a HSO3/NCO mole ratio of
1.5 had a deblocking temperature of 78.3  C was prepared
according to the published method.31 The second series of adhe-
sives was prepared by adding different PVA contents (5, 10, and
15% based on the OS solids content) into the OS. Around 3.6, 7.2,
and 10.8 g of PVA were added into 200 g of OS to prepared 5, 10,
and 15% PVA/OS, respectively. The mixture was stirred at 80  C
and 500 rpm for 2 h. Furthermore, around 0.7 g of B-pMDI (1%
based on the OS solids content) was added to the PVA/OS and
stirred for 30 min. This optimum level was obtained by comparing
the mean values of density, internal bonding (IB) strength, modulus
of rupture (MOR), modulus of elasticity (MOE), thickness swelling
(TS), water absorption (WA), and formaldehyde emission (FE); the
B-pMDI/OS-bonded MDF using statistical analysis. As a control,
UF resins with formaldehyde/urea mole ratio of 1.0 were synthe-
sized using an alkaline–acid two-step reaction, as reported in the
literature.32,33
MDF Manufacture
Laboratory MDFs were manufactured using three types of adhe-
sives: UF resins, B-pMDI/OS, and B-pMDI/PVA/OS. As a control,
two MDFs with 700 kg m−3 density were manufactured with UF
resin according to a published method.34 Briefly, a mixture of 12%
UF resins and 1% emulsion wax (based on the dried fiber mass)
was mixed with 3% ammonium chloride (based on the UF resins
solids content). The adhesives were sprayed onto the fibers in a
drum-type mechanical blender using an atomization nozzle with
1 mm diameter. The blended fibers were then used to prepare the
fiber mat using a centrifugal air blower. The fiber mat was pre-
pressed for 30 s and then hot-pressed at 180  C using a single-phase
pressing schedule of 2.45 MPa for 4 min to produce MDFs
(300 × 400 × 15 mm3). For the evaluation of the OS adhesives,
eight MDFs with 700 kg m−3 density were prepared using
B-pMDI/OS adhesives with various B-pMDI contents. Approxi-
mately 12% of B-pMDI/OS based on the fiber dry mass was sprayed
onto the fibers using the same conditions as UF resins-bonded
MDF. The fibers sprayed with OS adhesives were then used to pre-
pare the fiber mat using a centrifugal air blower. The fiber mats
were prepressed for 30 s and then hot-pressed at 180  C using a
single-phase pressing schedule of 2.45 MPa for 10 min to fabricate
MDFs. Using the same method as for the B-pMDI/OS samples, six
MDFs were prepared using B-pMDI/PVA/OS adhesives with
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47966
ARTICLE WILEYONLINELIBRARY.COM/APP
different PVA contents. All MDFs were conditioned for 2 days at
28  2  C prior to cutting and testing.
Characterization of OS Adhesives
Some basic properties of OS adhesives, such as nonvolatile solids
content, viscosity, and gelation time were determined. The nonvola-
tile solids content of OS adhesives for various B-pMDI and PVA
contents was obtained by drying 2 g of the sample in an oven at
105  C for 3 h and dividing the oven-dried weight by the initial
weight. The viscosity of OS adhesives was determined using a cone-
plate viscometer (DV-II+, Brookfield, Middleboro, MA) with
spindle no. 2 at 27  2  C and 60 rpm. The gelation time of OS
adhesives was measured using a gel time meter at 100  C (Davis
Inotek Instruments). All experiments were replicated three times.
FTIR spectroscopy (Frontier; PerkinElmer) was performed to quali-
tatively investigate the functional groups of the OS adhesives with
different B-pMDI and PVA contents. The powdered adhesives were
pressed into pellets with KBr as a reference, and were scanned from
400 to 4000 cm−1 with a resolution of 4 cm−1 and 32 scans per
sample. Semiquantitative analysis was done by normalizing the each
spectrum using the min–max normalization method. It was done
by subtracting each spectrum with its minimum value and divided
with its range value (maximum value subtracts minimum value).35
The change in normalized intensity of functional groups was
observed as a function of B-pMDI and PVA. A DSC system
(Discovery 25; TA Instruments) was used to investigate the exother-
mic peak temperature of B-pMDI/PVA/OS adhesives at different
levels of B-pMDI and PVA. Approximately 5 mg of liquid
B-pMDI/PVA/OS mixed was sealed in a high-pressure capsule pan
and then heated from 30 to 300  C at 2.5, 5, and 10  C min−1 of
heating rate, and under a nitrogen flow of 50 mL min−1.
Physical and Mechanical Properties of MDF
Some physical and mechanical properties of MDFs were deter-
mined using a standard procedure.36 Around 10 samples
(50 × 50 × 15 mm3) were prepared to determine IB strength, and
four samples (200 × 50 × 15 mm3) were prepared for MOR and
MOE. IB strength, MOE, and MOR were determined using a uni-
versal testing machine (H50KS; Tinius Olsen Ltd., Redhill, UK) at
loading speeds of 2, 10, and 10 mm min−1, respectively. Further,
10 samples for TS and WA tests were soaked for 24 h in water,
and then the thickness and weight were measured after removing
surface water. FE was determined by placing 10 MDF specimens
in a desiccator at 20  2  C for 24 h. Further, approximately
25-mL aliquot solutions were pipetted into 100-mL flasks, and
25 mL acetyl acetone–acetic acid ammonium solutions were sub-
sequently added to the flask. The solutions were then heated for
10 min at 65  2  C in a water bath. Finally, the solutions were
cooled to room temperature (25  2  C) before further analysis.
FE was analyzed using ultraviolet–visible spectrophotometry
(Optizen 3220 UV; Mecasys, Korea) at a wavelength of 412 nm to
determine the FE values.
Hydrolysis of MDF
MDF panels were cut into cube specimens (20 × 20 × 15 mm3). A
total of 30 MDF cubes were prepared from five different MDF sam-
ples: UF resin, 1% B-pMDI/OS, and 1% B-pMDI/PVA/OS at three
different PVA contents (5, 10, and 15% based on the OS solids con-
tent). The MDF cubes were hydrolyzed under two conditions
47966 (3 of 10)
Figure 1. Typical FTIR spectra of native starch and OS. [Color figure can
be viewed at wileyonlinelibrary.com]
(25  C for 6 h and 80  C for 1 h) as the previously reported proce-
dures with three replications for each sample.5,37 The mass loss, the
degree of fiber disintegration, pH of the extract solution, and func-
tional groups of the MDFs after hydrolysis were determined to
compare the recyclability of the MDF. The mass loss was deter-
mined by measuring the weight of MDF cubes before and after
hydrolysis, while the pH was determined using a digital pH meter.5
Furthermore, the degree of fiber disintegration was calculated by
dividing the dry weight of MDF cubes, in the panel form, after
hydrolysis with the dry weight of MDF cubes before hydrolysis.
Statistical Analysis
Multivariate analysis was conducted to compare the mean values
of MDF properties, while Duncan multiple range test at α = 0.05
was used to determine the optimum B-pMDI and PVA content
in the OS adhesive. Statistical analysis was undertaken using the
SPPS 17 software (SPSS Inc.).
RESULTS AND DISCUSSION
Adhesive Properties
FTIR spectra showed the formation of C O bonds (1715 cm−1)
in the aldehyde and carboxyl groups in the OS (Figure 1), indi-
cating that starch was successfully oxidized by converting the
OH groups on the C-2, C-3, and C-6 positions of the glucose
unit to aldehyde and carboxyl groups using hydrogen peroxide.22
In addition, the peak at 1630 cm−1 in both native starch and OS
was attributed to intramolecular O H bonds.23
After the addition of B-pMDI into OS, there were several new peaks
detected, such as C H of pMDI at 2723 cm−1, C O of amide link-
age at 1586 cm−1, and C N of amide at 1348 cm−1 [Figure 2(a)].
In addition, the peak at 3300 cm−1, which belonged to O H in OS,
was replaced with the N H of pMDI at 3258 cm−1. No significant
changes were observed for other functional groups of B-pMDI/OS
as the B-pMDI content increased. Furthermore, FTIR spectroscopy
was also conducted to evaluate whether additional chemical reac-
tions occurred in 1% B-pMDI/PVA/OS with different PVA con-
tents [Figure 2(b)]. The peak at 3300 cm−1 was assigned to O H of
OS and intermolecular hydrogen bonds in PVA/OS. This peak did
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47966
ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 2. FTIR spectra of (a) B-pMDI/OS with different B-pMDI contents, (b) 1% B-pMDI/PVA/OS with different PVA contents, (c) normalized intensity
of B-pMDI/OS with different B-pMDI contents, (d) normalized intensity of 1% B-pMDI/PVA/OS with different PVA contents (e) normalized intensity of
specific functional groups in B-pMDI/OS, and (f) normalized intensity of specific functional groups in 1% B-pMDI/PVA/OS. [Color figure can be viewed at
wileyonlinelibrary.com]

not change to that for N H (3258 cm−1) due to the higher portion
of PVA than B-pMDI. The intensity of this peak increased with
increasing PVA content in the OS. Other peaks at 2925, 1715, 1630,
and 1348 cm−1 were similar to those observed in the B-pMDI/OS
spectra.
Semiquantitative analysis showed that the normalized intensity of
C O of carboxyl groups at 1715 cm−1 decreased from 0.21 to an
average 0.13 after the addition of B-pMDI, meaning that the car-
boxyl groups reacted with the NCO group of B-pMDI to form
amide linkages, as indicated by the peak at 1586 and 1348 cm−1
[Figure 2(c,d)].38 In case of 1% B-pMDI/PVA/OS adhesives, it
was also found that peak of carboxyl groups at 1715 decreased in
normalized intensity, and new peak was detected at 1600 cm−1,
which was attributed to the C O stretching vibration of acid
hydrolyzed PVA [Figure 2(e,f)].39
DSC analysis was performed to evaluated thermal behavior of OS
adhesives. As expected, the Tp values of OS adhesives increased as a
function of heating rate [Figure 3(a)], and the Tp values decreased
as the PVA content increased [Figure 3(b)]. Further, DSC thermo-
grams depicted two exothermic peaks (Tp) in B-pMDI/OS and B-
pMDI/PVA/OS adhesives. The first peak, Tp1, (dot) at 134–155  C
only appeared when B-pMDI was added, while no peak was
observed in pure OS, meaning that the Tp1 was attributed to the for-
mation of amide linkages from the reaction of carboxyl groups of

47966 (4 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47966

ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 3. Typical DSC thermogram of (a) 1% B-pMDI/OS at different heating rates, and (b) 1% B-pMDI/PVA/OS with different levels of PVA at
2.5  C min−1. [Color figure can be viewed at wileyonlinelibrary.com]

OS and NCO groups of B-pMDI. It was possible that the NCO of
B-pMDI could have reacted with COOH of OS to form amide
(R NCO R) linkages.38 Second peak, Tp2, (asterisk) around
210  C could be due to the degradation of OS adhesives, which also
happened at exothermic.40 This peak decreased with increasing in
PVA level in B-pMDI/PVA/OS adhesive.
The nonvolatile solids content, viscosity, and gelation time of the
OS adhesives are summarized in Table I. Pure OS had quite low
solids content, low viscosity, and long gelation time, which was in
agreement with the previous study.29,30 No significant changes
were observed after the addition of B-pMDI. However, the solids
content and viscosity of OS increased gradually with the addition
of B-pMDI and PVA together. The gelation time of the OS was
reduced by 12% with the addition of 1% B-pMDI and 15% PVA,
indicating that B-pMDI/PVA/OS had higher reactivity than the
pure OS. This was probably due to the chemical crosslinking in the
OS adhesives, which was supported by the FTIR spectra (Figure 2)
and DSC of OS adhesives (Figure 3). FTIR spectra and DSC ther-
mograms showed the formation of amide linkage (1586 and
1348 cm−1) for crosslinking the OS adhesives at 134  C when 1%
B-pMDI and 15% PVA were added into the OS. However, no peak
was observed in pure OS. In addition, an increase in viscosity after
addition of 15% PVA probably resulted in more close-packed OS
molecules, which could reduce the gelation time. However, mate-
rials with such a long gelation time would require longer hot-
pressing time to manufacture the MDF panels.

Table I. Properties of the Adhesives

1% B-pMDI/5% 1% B-pMDI/10% 1% B-pMDI/15%

Property UF resin OS B-pMDI PVA/OS PVA/OS PVA/OS
Solids content (%) 62.1 36.3 100 37.7 42.7 48.3
−1 a
Viscosity (MPa s ) 272 124.0 151.6 171.3 191.7
a
Gelation time (s) 187 625 597 563 549
a
The values are not available in the solid form.

Table II. Properties of MDFs Bonded with B-pMDI/OS Adhesives at Different B-pMDI Contents

B-pMDI content (wt %) Density (kg m−3) IB strength (MPa) MOR (MPa) MOE (MPa) TS (%) WA (%) FE (mg L−1)
Controla 728 0.13 7.8 2661.4 54.1 78.1 0.89
(8.93)b (0.01) (0.50) (169.0) (5.07) (10.55) (0.02)
0 731 0.06 4.5 1530.1 150.8 431.9 0.01
(18.47) (0.01) (0.53) (177.0) (19.35) (15.44) (0.00)
1 736 0.08 5.1 1835.4 60.3 123.9 0.01
(16.03) (0.01) (0.62) (208.0) (10.39) (17.90) (0.00)
3 735 0.07 4.8 1493.5 85.3 178.3 0.01
(18.56) (0.01) (0.95) (317.0) (14.77) (19.58) (0.00)
5 730 0.03 3.9 1292.6 100.6 261.6 0.01
(22.59) (0.01) (0.71) (239.0) (10.54) (29.11) (0.00)
a
The control is MDFs bonded with UF resins.
b
The values in parentheses are the standard deviation.

47966 (5 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47966

ARTICLE WILEYONLINELIBRARY.COM/APP

Table III. Duncan Multiple Range Test Results for the Properties of MDFs panel density and FE values. IB strength, MOR, and MOE values
Bonded with OS Adhesive with Different B-pMDI Contents of MDFs bonded with B-pMDI/OS showed similar trends, show-
ing that the values increased up to 1% B-pMDI addition and
B-pMDI then decreased after 3 and 5% B-pMDI addition. It was expected
content that higher B-pMDI content would improve the performance of
(wt %) Density IB strength MOR MOE TS WA FE MDF; however, it was not the case. This may have been due to
0 a* b a b c d a the B-pMDI agglomerating at high concentration in the OS,
resulting in dark spots on the MDF surface.41
1 a a b a a a a
3 a ab bc ab a b a The B-pMDI/OS-bonded MDFs had an average of 0.01 mg L−1
5 a c c ab b c a
of FE while the UF-bonded MDFs emitted nearly 90 times of this
level (0.89 mg L−1). It was clear that the FE of OS adhesives was
*The different letters are significantly different at p value of 0.05. in the range of a detection limit. However, the adhesion perfor-
mance of B-pMDI/OS was not comparable to that of the UF
Properties of MDF resins. This is probably because the OS adhesives had lower solids
The properties of MDFs bonded with OS at different B-pMDI content, lower viscosity, and longer gelation time than those of
contents are shown in Table II. The B-pMDI/OS bonded MDF the UF resins (Table I), resulted in lower reactivity and lower
panel generally had poorer physical and mechanical properties crosslinking density than that of UF resins.42 The TS and WA
than those of MDFs bonded with neat UF resins, except the values of MDFs bonded with OS adhesives were six times higher

Figure 4. Properties of MDFs bonded with 1% B-pMDI/PVA/OS with different PVA contents: (a) IB strength; (b) FE; (c) MOR; (d) MOE; (e) TS; and (f) WA.

47966 (6 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47966

ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 5. Typical FTIR spectra of MDFs bonded with 1% B-pMDI/PVA/OS
adhesives with different PVA contents. [Color figure can be viewed at
wileyonlinelibrary.com]
than those of UF-bonded MDFs. However, introducing B-pMDI
into the OS could improve the water resistance of MDFs, where
1% B-pMDI/OS showed 60.3% TS and 123.9% WA values, while
the UF-bonded MDFs showed 54.1% TS and 78.1% WA. The sta-
tistical analysis suggested that the addition of 1% B-pMDI in the
OS was an optimum level to obtain the best MDF properties
(Table III).
To obtain OS adhesives with acceptable physical and mechanical
properties of MDF, as well as good recyclability, PVA was added
into the OS prior to the addition of 1% B-pMDI. Physical proper-
ties, mechanical properties, and FE values of MDFs bonded with
1% B-pMDI/PVA/OS as a function of PVA content are shown in
Figure 4. The IB strength of MDFs bonded with 1%
B-pMDI/PVA/OS increased gradually with increasing the PVA
content. The addition of 15% PVA in the OS resulted in an IB
strength of 0.13 MPa, which was comparable to that of UF resins-
bonded MDFs [Figure 4(a)]. This could be due to the presence of
ester linkages in MDFs bonded with 1% B-pMDI/PVA/OS. The
carboxyl groups of OS adhesives can react with OH groups of
the wood, forming C O groups as ester linkage, as shown by the
FTIR peak at 1730 cm−1 in Figure 5. The addition of PVA greatly
increased the solids content and viscosity, and decreased the gela-
tion time of the B-pMDI/PVA/OS adhesives via hydrogen bonding
between OS and PVA (Table I). Similar to B-pMDI/OS-bonded
MDFs, the FE values of MDFs bonded with 1% B-pMDI/PVA/OS
were 0.01 mg L−1, while UF-bonded MDFs showed a value of
0.89 mg L−1 [Figure 4(b)]. Since formaldehyde was not used in the
Table IV. Statistical Analysis of the Properties of MDFs Bonded with 1%
B-pMDI/OS Adhesives at Different PVA Contents
Concentration
of PVA (wt %) IB strength MOR MOE TS WA
0 c* b b c d
5 b ab ab b c
10 a ab ab ab b a
15 a a a a a a
*The different letters are significantly different at p value of 0.05.
47966 (7 of 10)
preparation of OS adhesives, the FE values were close to a detec-
tion limit. However, the small amount of formaldehyde from
MDFs bonded with OS adhesives was originated from the alde-
hyde groups of OS, or from biogenic formaldehyde.43
Both MOR and MOE values showed a similar trends to the IB
strength, which increased with increasing PVA content. The sam-
ple with 15% PVA in B-pMDI/OS showed comparable values to
the UF resins-bonded MDFs [Figure 4(c,d)]. MDFs bonded with
1% B-pMDI/15% PVA/OS had smooth, and dense surfaces due
to the longer hot-pressing time, resulting in similar MOR and
MOE values to those of the UF resins-bonded MDFs. The TS
and WA values of MDFs bonded with 1% B-pMDI/PVA/OS were
comparable to those of the UF-bonded MDFs [Figure 4(e,f)]. The
presence of ester linkages at 1730 cm−1 and hydrogen bonds in
MDFs bonded with 1% B-pMDI/PVA/OS (Figure 5) could have
enhanced both adhesion and water resistance of the MDFs. The
statistical analysis showed that MDFs with good mechanical
properties, proper dimensional stability, and almost zero formal-
dehyde emission can be produced by adding 15% PVA to the 1%
B-pMDI/OS adhesives (Table IV).
Recyclability of MDFs
Developing OS adhesives with good adhesion performance and
high recyclability is necessary for developing recyclable MDFs.
Herein, the recyclability of MDFs bonded with 1% B-
pMDI/PVA/OS with various PVA contents was investigated at dif-
ferent hydrolysis conditions. Figure 6 shows pictures of MDFs
bonded with UF resin and 1% B-pMDI/15% PVA/OS after hydro-
lysis at 25  C for 6 h. It can be seen that the UF-bonded MDF
solution did not change color after hydrolysis for 6 h [Figure 6(a)].
In contrast, the solution of MDFs bonded with 1% B-pMDI/15%
PVA/OS started to change from a clear solution to light brown
after 2 h of hydrolysis, and became dark brown after 6 h [Figure 6
(b)]. The brown color is thought to be due to the dissolution of
OS adhesives and wood extractives in the solvent. In the case of
MDFs bonded with 1% B-pMDI/15% PVA/OS, the OS adhesives
were much easier to be removed than the UF resins did. As shown
in Figure 7, the solution of both 1% B-pMDI/15% PVA/OS- and
UF resins-bonded MDFs hydrolysis at 80  C for 1 h changed to
light brown after 10 and 20 min. A similar observation was
reported for the removal of cured UF resin from MDFs.5,37
The mass loss of MDFs after hydrolysis is shown in Figure 8(a).
Regardless of the type of adhesive, hydrolysis at 80  C for 1 h
resulted in higher mass loss than those of the hydrolysis at 25  C
for 6 h. This mass loss was responsible for the removal of OS
adhesives and wood extractives, and was reduced by adding 15%
PVA, but still maintained at higher value than that of UF resins.
This indicated that 1% B-pMDI/15% PVA/OS could be used to
manufacture MDFs with a proper adhesion performance and high
FE recyclability compared to UF resins-bonded MDFs. The degree of
a fiber disintegration was also investigated to evaluate the recyclabil-
a ity of MDFs [Figure 8(b)]. More fibers were disintegrated after
hydrolysis at 80  C for 1 h compared to treatment at 25  C for
6 h. Similar to the mass loss, the addition of 15% PVA to the 1%
B-pMDI/OS decreased the degree of fiber disintegration, while the
value was still higher than that of UF resins.
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47966
ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 6. Photographs of the hydrolysis of MDFs bonded with (a) UF resins and (b) 1% B-MDI/15% PVA/OS at 25  C for 6 h. [Color figure can be viewed
at wileyonlinelibrary.com]

Figure 7. Photographs of the hydrolysis of MDFs bonded with (a) UF resins and (b) 1% B-pMDI/15% PVA/OS at 80  C for 1 h. [Color figure can be viewed
at wileyonlinelibrary.com]

Measurements of the pH of the extract solutions after the hydrolysis 3. Figure 9(a) shows the pH of MDF extract solutions after hydroly-
of MDF cubes were performed to verify whether the OS was sis at 25  C for 6 h. The pH of all samples decreased gradually as a
extracted by this process. The original pH of the OS adhesives was function of hydrolysis time. The pH of the extract solutions of UF

Figure 8. (a) Mass loss and (b) fiber disintegration of MDFs bonded with 1% B-pMDI/OS adhesives with different PVA contents after hydrolysis under dif-
ferent conditions.

47966 (8 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47966

ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 9. pH values of the extract solutions from MDFs bonded with 1% B-pMDI/OS adhesives with different PVA contents after hydrolysis at (a) 25  C
for 6 h and (b) 80  C for 1 h. [Color figure can be viewed at wileyonlinelibrary.com]
resins-bonded MDFs was in the range of 4.9–5.1, while those of
MDFs bonded with pure OS were in the range 3.8–4.4. The pH of
virgin Red pine fiber was reported to be around 4.8–5.5.44–47 There-
fore, it was clear that most of the OS adhesive was extracted after
hydrolysis of OS-bonded MDFs at 25  C for 6 h, while only wood
extractives were extracted from UF resins-bonded MDFs. However,
it should be noted that the addition of B-pMDI and PVA to the OS
increased the pH of extract solutions from 3.8 to 4.8, indicating the
presence of ester linkages and hydrogen bonds (Figure 5) changed
the pH of pure OS. By contrast, the hydrolysis of MDFs bonded
with OS adhesives at 80  C for 1 h had the same pH values as in
the case of hydrolysis at 25  C for 6 h [Figure 9(b)]. Hence, high
temperature hydrolysis extracted a similar amount of OS adhesive
compared to the low-temperature treatment, but in a shorter time.
In particular, the pH of the extract solution from UF resins-bonded
MDFs increased with increasing hydrolysis time, which was clearly
due to the formation of free ammonia from the degradation of UF
resins at high temperature.48,49
CONCLUSIONS
OS adhesives were successfully prepared by mixing OS with vari-
ous B-pMDI and PVA contents, which were then used to pro-
duce MDFs. MDFs bonded with pure OS had low IB strength
and very poor water resistance. Introducing B-pMDI into the OS
greatly enhanced the physical and mechanical properties of
MDFs panel, but the properties were still inferior to those of UF
resins-bonded MDFs. However, the MDF properties could be
improved by adding PVA to 1% B-pMDI/OS, which had physical
and mechanical properties comparable to those of the UF resins
system. The mass loss and degree of fiber disintegration after
hydrolysis of MDFs bonded with OS adhesives were higher than
those of UF resins-bonded MDFs, indicating enhanced recyclabil-
ity. In addition, the pH of the extract solutions after hydrolysis of
MDFs bonded with OS adhesives was more acidic than those of
UF resins-bonded MDFs, showing that the OS adhesives were
much easier to extract. We proposed that the OS adhesive with a
composition of 1% B-pMDI and 15% PVA was found as a proper
combination for manufacturing MDFs panel with balanced adhe-
sion and disintegration properties to produce high-quality MDF
panels that can be easily recycled.
47966 (9 of 10)
ACKNOWLEDGMENTS
This study was conducted with the support from the Korea Forest
Science Technology (Project grant no. 2015077B10-1718-AA01)
provided by the Korea Forest Service (Korea Forestry Promotion
Institute).
REFERENCES
1. Mantanis, G. I.; Athanassiadou, E. T.; Barbu, M. C.;
Wijnendaele, K. Wood Mater. Sci. Eng. 2018, 13, 104.
2. Abdullah, Z. A.; Park, B. D. J. Appl. Polym. Sci. 2009, 114,
1011.
3. Hauptmann, M.; Jay, H.; Lubin, P. A.; Stewart, R. B.;
Hayes; Aaron, B. J. Natl. Cancer Inst. 2003, 95, 1615.
4. Cogliano, V.; Yann, G.; Robert, B.; Kurt, S.; Béatrice, S.;
Fatiha, E. G. Lancet Onco. 2004, 5, 528.
5. Lubis, M. A. R.; Hong, M. K.; Park, B. D. J. Wood Chem.
Technol. 2018, 38, 1.
6. Karazipour, A.; Kües, U. Wood Production, Wood Tech-
nology, and Biotechnological Impacts; Universitätsverlag:
Göttingen, Germany, 2007. p. 509.
7. Tatàno, F.; Barbadoro, L.; Mangani, G.; Pretelli, S.;
Tombari, L.; Mangani, F. Waste Manag. 2009, 29, 2656.
8. Morris, J. J. Ind. Ecol. 2017, 21, 844.
9. Tupciasukas, R.; Gravitis, J.; Abolins, J.; Veveris, A.;
Andzs, M.; Liitia, T.; Tamminen, T. Holzforschung. 2017,
71, 555.
10. Ji, X.; Dong, Y.; Yu, R.; Du, W.; Gu, X.; Guo, M.
Holzforschung. 2018, 72, 275.
11. Onusseit, H. Ind. Crop Prod. 1993, 1, 141.
12. Jarusombuti, S.; Bauchongkol, P.; Hiziroglu, S.;
Fueangvivat, V. Forest Prod. J. 2012, 62, 58.
13. Akbari, S.; Gupta, A.; Khan, T. A.; Jamari, S. S.;
Ani, N. B. C.; Poddar, P. J. Indian Acad. Wood Sci. 2014,
11, 109.
14. Abbott, A. P.; Conde, J. P.; Davis, S. J.; Wise, W. R. Green
Chem. 2012, 14, 3067.
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47966
ARTICLE WILEYONLINELIBRARY.COM/APP
15. Buléon, A.; Colonna, P.; Planchot, V.; Ball, S. Int. J. Biol.
Macromol. 1998, 23, 85.
16. Tester, R. F.; Karkalas, J.; Qi, X. J. Cereal Sci. 2004, 39, 151.
17. Hemmilä, V.; Adamopoulos, S.; Karlsson, C.; Kumar, A.
RSC Adv. 2017, 7, 38604.
18. Din, Z. U.; Xiong, H.; Wang, Z.; Fei, P.; Ullah, I.;
Javaid, A. B.; Wang, Y.; Jin, W.; Chen, L. Int. J. Biol.
Macromol. 2017, 104, 846.
19. Sridach, W.; Jonjankiat, S.; Wittaya, T. J. Adhes. Sci.
Technol. 2013, 27, 1727.
20. Wang, Z.; Gu, Z.; Hong, Y.; Cheng, L.; Li, Z. Carbohydr.
Polym. 2011, 86, 72.
21. Rutenberg, M. W.; Solarek, D. In Starch: Chemistry and
Technology, 2nd Ed.; Whistler, R. L., Bemiller, J. N.,
Paschall, E. F., Eds.; Academic Press: Atlanta, GA, USA,
1984, p. 311.
22. Patel, K. F.; Mehta, H. U.; Srivastava, H. C. J. Appl. Polym.
Sci. 1974, 18, 389.
23. Xu, H.; Canisag, H.; Mu, B.; Yang, Y. ACS Sustain. Chem.
Eng. 2015, 3, 2631.
24. Caźon, P.; Velazquez, G.; Ramírez, J. A.; Vázquez, M. Food
Hydrocoll. 2017, 68, 136.
25. Bie, Y.; Yang, J.; Nuli, Y.; Wang, J. RSC Adv. 2016, 6, 97084.
26. Wu, H.; Liu, C.; Chen, J.; Chen, Y.; Anderson, D. P.;
Chang, P. R. J. Appl. Polym. Sci. 2010, 118, 3082.
27. Zhang, S.; Liu, F.; Peng, H.; Peng, X.; Jiang, S.; Wang, J.
Ind. Eng. Chem. Res. 2015, 54, 11944.
28. Zhang, Y.; Ding, L.; Gu, J.; Tan, H.; Zhu, L. Carbohydr.
Polym. 2015, 115, 32.
29. Lubis, M. A. R.; Park, B. D. J. Adhes. Sci. Technol. 2018, 32,
2667.
30. Wicks, D. A.; Wicks, Z. W. Prog. Org. Coat. 2001, 41, 1.
31. Lubis, M. A. R.; Park, B. D.; Lee, S. M. Int. J. Adhes. Adhes.
2017, 73, 118.
47966 (10 of 10)
32. Park, B. D.; Jeong, H. W.; Lee, S. M. J. Appl. Polym. Sci.
2011, 120, 1475.
33. Lubis, M. A. R.; Park, B. D. Holzforschung. 2018, 72, 759.
34. Hong, M. K.; Lubis, M. A. R.; Park, B. D. J. Korean Wood
Sci. Technol. 2017, 45, 444.
35. Korean Standard F 3200: Fiberboards, Korean Standard
Association, Seoul, 2006.
36. Wilkox, K. R. Thesis, University of Manchester, 2014.
37. Grigsby, W. J.; Carpenter, J. E. P.; Sargent, R. J. Wood
Chem. Technol. 2014, 34, 225.
38. Blagbrough, I. S.; Mackenzie, N. E.; Ortiz, C.; Scott, A. I.
Tetrahedron Lett. 1986, 27, 1251.
39. Mansur, H.; Sadahira, C. M.; Souza, A. N.;
Mansur, A. A. P. Mater. Sci. Eng. C. 2008, 28, 539.
40. Soliman, A. A. A.; El-Shinnawy, N. A.; Mobarak, F.
Thermochim. Acta. 1997, 296, 149.
41. Cooper, M. D. Thesis, University of Canterbury, 1992.
42. Park, B. D.; Kim, J. W. J. Appl. Polym. Sci. 2008, 108, 2045.
43. Tasooji, M.; Wan, G.; Lewis, G.; Wise, H.; Frazier, C. E.
ACS Sustain. Chem. Eng. 2017, 5, 4243.
44. Xing, C.; Zhang, S. Y.; Deng, J. Holzforschung. 2004, 58, 408.
45. Xing, C.; Zhang, S. Y.; Deng, J.; Riedl, B.; Cloutier, A. Wood
Sci. Technol. 2006, 40, 637.
46. Lubis, M. A. R.; Hong, M. K.; Park, B. D.; Lee, S. M. Eur.
J. Wood Wood Prod. 2018, 76, 1515.
47. Hong, M. K.; Lubis, M. A. R.; Park, B. D.; Sohn, C. H.;
Roh, J. K. Wood Mater. Sci. Eng. 2018, 1. https://doi.org/
10.1080/17480272.2018.1528479.
48. Roffael, E.; Hüster, H. G. Eur. J. Wood Wood Prod. 2012,
70, 401.
49. Wan, H.; Wang, X. M.; Barry, A.; Shen, J. BioResources.
2014, 9, 7554.
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47966