ARTICLE IN PRESS

International Journal of Adhesion & Adhesives 27 (2007) 244–249

www.elsevier.com/locate/ijadhadh

Curing kinetics of polymeric diphenylmethane diisocyanate with

different wood species
Guangbo Hea, Ning Yanb,
a
Wood Composite Group, Forintek Canada Corporation, 2665 East Mall, Vancouver, BC, Canada, V6T 1W5
b
Faculty of Forestry, University of Toronto, 33 Willcocks Street, Toronto, Ont., Canada, M5S 3B3
Accepted 3 April 2006
Available online 28 July 2006

Abstract

The effect of wood species on the curing kinetics of diphenylmethane diioscyanate (pMDI)/wood systems under both oven-dry
and moisture conditions was investigated. The results indicated that wood species did affect the curing kinetics of the pMDI/wood
systems, such as activation energy, reaction rate and reaction enthalpy, under the oven-dry conditions due to the differences in
structure and composition. However, the effect of wood species on the curing kinetics became insignificant when moisture was
introduced into the pMDI/wood systems, suggesting that the reactions between isocyanate and water dominate the curing process. Wood
species seemed not to affect the main reaction mechanism because a similar relationship between the activation energy and the degree of
conversion was obtained for all species. The kinetics were also affected by different pMDI/wood ratios for the oven-dried wood system
but not for the system with moisture, demonstrating that the hydroxyls in wood were restricted as reactant under the oven-dry
conditions.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Thermal analysis; Cure; Wood

1. Introduction [1,3,6,7]. It has been shown that moisture in the wood

Polymeric diphenylmethane diisocyanate (pMDI) resin,
as a wood adhesive, has to react with wood components
and moisture to form the cross-linking network during the
curing [1–6]. Most of the wood components, such as
cellulose, hemi-cellulose, lignin and extractives, contain
hydroxyl groups and can theoretically react with isocya-
nate. These reactions occur to form urethane groups,
providing chemical bonding between the resin and wood.
However, the number of the hydroxyl groups capable of
reacting with isocyanate is small because the mobility of
these groups is low in the solid wood substrate. The
reactions of pMDI with the moisture in wood, therefore,
may dominate the curing process when moisture exists in
the wood substrate [1,6].
Research regarding the effect of moisture on the curing
reactions of pMDI has been reported in the literature
Corresponding author. Tel.: +1 416 946 8070; fax: +1 416 978 3834.
E-mail address: ning.yan@utoronto.ca (N. Yan).
might affect the reaction mechanism, curing products and
curing kinetics. Investigation [3] by nuclear magnetic
resonance spectroscopy showed that the reaction of pMDI
with dried wood resulted primarily in biuret-type struc-
tures. When the moisture content (MC) of the wood was
increased to 4.5% the end products of the curing reaction
were primarily of polyurea-type of structures. Study [7] by
differential scanning calorimetry (DSC) indicated that
the reaction enthalpy and reaction rate were lower for the
oven-dried wood than for the moist wood, while the
activation energy showed more complicated variation. It is
not clear, however, whether wood species may also affect
the curing behavior because pMDI may directly react with
wood hydroxyl groups.
The aim of this study was to investigate the effect
of wood species on the curing behavior of pMDI
resin. DSC was used to characterize the curing process.
The cure kinetics of the pMDI resin were studied using
several wood species under both oven-dry and moist
conditions.

0143-7496/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijadhadh.2006.04.003
 ARTICLE IN PRESS
G. He, N. Yan / International Journal of Adhesion & Adhesives 27 (2007) 244–249 245

2. Experimental where
Z a
da
2.1. Sample preparation F ðaÞ ¼ ,
0 f ðaÞ
pMDI resin was supplied by Huntsman Polyurethanes where a is the degree of conversion, f(a) is the function of a,
(Geismar, LA, USA). Aspen (Populus tremuloides), white F is the heating rate, T is the temperature, Ea is the
birch (Betula popelifolia), maple (Acer saccharum) and apparent activation energy, A is the pre-exponential factor
southern yellow pine (Pinus spp.) were used as wood and R is the gas constant.
reactants in this research. Wood was first ground into flour. Another expression relating the heating rate and
The wood flour was then screened and wood flour of sizes temperature was developed by Kissinger [10] for nth-order
between 35 and 60 mesh was retained for the experiments. reactions
The flour was either conditioned to the target MC of 12%
lnðF=T 2 Þ ¼ E a =RT þ lnðRA=E a Þ. (2)
or dried in an oven at 103 1C for 24 h to obtain oven-dried
wood. The resin/wood mixtures were prepared by mixing For autocatalyzed kinetics, Prime [11] has introduced a
the pMDI resin with the wood flour (including moisture) at modified pre-exponential factor, from which an equation
50/50 or other mass ratios according to the requirements of was derived
the experiments.
lnðF=mT 2 Þ ¼ E a =RT þ lnðRA=E a Þ, (3)

2.2. Differential scanning calorimetry measurements
All DSC measurements and analyses were made with a
Q1000 DSC and the Universal analysis software from TA
instruments. The resin/wood mixtures were subjected to
DSC scanning immediately after made. All samples waiting
for DSC measurement were stored in refrigerator and
measured within 6 h. The amount of resin/wood mixture
loaded into DSC pans was 10–15 mg. High-volume pans
that can withstand vapor pressure up to 3.8 MPa were used
to prevent components of the test samples from evaporat-
ing at higher temperatures up to 250 1C. Dynamic scans
were made at heating rates of 2, 5, and 10 1C/min and the
samples were scanned from 25 to 250 1C. Two replicates
were done for each scan. The maximum error was found to
be 1.0 1C for peak temperature and 5% for reaction
enthalpy.
3. Results and discussion
The activation energy of the curing process was
evaluated from peak temperatures of DSC scans at three
different heating rates. Based on the work of Ozawa [8] and
Flynn and Wall [9], an isoconversional method was
developed to calculate activation energy as follows:
log F ¼ 2:315  0:4567ðE a =RTÞ þ logðAE a =RÞ  log F ðaÞ,
(1)
where m represents 2ap þ 2Bap  3a2p  B, B is the stoichio-
metric ratio of reactants, ap is the degree of conversion at
the peak, and Tp is the peak temperature.
A prediction of the isothermal kinetic parameter can be
made from the non-isothermal DSC data obtained by
the above methods. The time to reach a given degree of
conversion at an arbitrary temperature can be calculated
from an integrated equation [12,13], which is given as
  1 Z T a  
E a;a E a;a
ta ¼ F exp  exp  dT; (4)
RT iso T0 RT
where ta is the reaction time to reach the degree of
conversion, a, at the isothermal temperature (Tiso); Ea,a is
the activation energy at the degree of conversion, a; T0,
and Ta are the scanning temperatures at the degree of
conversion 0 and a, respectively.
3.1. Kinetics of pMDI/wood reactions
It has been shown that moisture in wood has a
significant influence on the curing kinetics [7]. To avoid
confusion of this effect with that difference in wood
species, the pMDI resin was cured with oven-dried wood
and the wood containing a MC of 12%, respectively.
Table 1 shows the activation energy obtained from the
peak temperatures of oven-dried wood. It can be seen that
the activation energies ðE Ki
a Þ calculated by the Kissinger
method were comparable to the results ðE Oza Þ obtained by

Table 1
Peak temperature and activation energy of pMDI/oven-dried wood systems

Samples Tp (1C) E Ki
a (kJ/mol)
R2 E Oz
a (kJ/mol)
R2

2 1C/min 5 1C/min 10 1C/min

Aspen 126.3 146.8 164.5 54.3 0.9998 58.2 0.9999

Birch 132.1 155.9 167.1 59.1 0.9746 62.8 0.9793
Maple 125.1 147.4 165.2 51.2 0.9999 55.3 0.9999
SYP 125.5 143.6 156.7 66.4 0.9987 69.7 0.9988
 ARTICLE IN PRESS
246 G. He, N. Yan / International Journal of Adhesion & Adhesives 27 (2007) 244–249

Table 2
Peak temperature and activation energy of pMDI/wood (12% MC) systems

Samples Tp (1C) E Ki
a (kJ/mol)
R2 E Oz
a (kJ/mol)
R2

2 1C/min 5 1C/min 10 1C/min

Aspen 100.4 114.3 128.5 65.1 0.9946 68.1 0.9957

Birch 101.5 116.4 131.0 62.2 0.9969 65.3 0.9975
Maple 101.8 116.6 130.3 64.6 0.9983 67.6 0.9987
SYP 95.9 110.4 124.9 61.6 0.9959 64.6 0.9967

R2 is the square of correlation coefficient between heating rate and peak temperature.

the Ozawa method, although the pMDI/wood reactions 180

Oven-dried
were autocatalyzed [7,14]. 160
MC12%
For the oven-dried wood, the activation energies for the 140
various wood species studied were different. SYP had 120

ΔH (J/g)
the highest value while maple had the lowest value. 100
One possible reason is that wood structures affected the 80
diffusion of the reactants, resulting in different contribu- 60
tions to the activation energy. Another possible reason is 40
that the hydroxyls in wood for various species may have
20
different reactivity with isocyanate.
0
The activation energy for the pMDI/wood containing Aspen Birch Maple SYP
12% MC is shown in Table 2. It is evident that the
activation energy increased slightly for all wood species Fig. 1. Reaction enthalpy of curing for pMDI/wood systems.
except SYP, which had the unusual high activation energy
for the oven-dried system. One thing worth noting is that 100
Aspen
the differences in the activation energies among the wood Birch
species became very small after moisture was introduced 85 Maple
into the wood. This is because the reaction between pMDI SYP
Ea,α (kJ/mol)

and water dominated the curing process and masked the

difference resulting from different wood species. 70
The reaction enthalpy also varied among the wood
species, as shown in Fig. 1. For oven-dried wood, birch and 55
maple had higher reaction enthalpies than aspen and SYP.
The reaction enthalpy increased significantly for wood
containing 12% MC. It is also shown that the reaction 40
enthalpies were almost the same for all wood species that 0 20 40 60 80 100
α (%)
contained moisture. This confirmed that the reactions
between isocyanate and water were dominant for all wood Fig. 2. Dependence of the activation energy on the degree of conversion
species. for pMDI/oven-dried wood.
The variation of the activation energy with the degree of
conversion is shown in Figs. 2 and 3. It can be seen that the 100
Aspen
relationship between the activation energy and the degree Birch
of conversion was similar for all wood species under both 85 Maple
oven-dry and moisture-containing conditions. This indi- SYP
Ea,α (kJ/mol)

cated that wood species did not affect the main reaction
mechanism, although the values of activation energies were 70
different among the wood species, especially for the
oven-dried wood. The effect of moisture on the reaction 55
mechanism shown in Figs. 2 and 3 was found to be
consistent with the previous results [7]. When moisture was
introduced into pMDI/wood systems, the activation energy 40
obviously decreased at higher degrees of conversion, 0 20 40 60 80 100
α (%)
implying that the reaction changed from a chemically
controlled regime to a diffusion-controlled regime. This Fig. 3. Dependence of the activation energy on the degree of conversion
trend was not observed for oven-dried systems, probably for pMDI/wood with moisture.
 ARTICLE IN PRESS
G. He, N. Yan / International Journal of Adhesion & Adhesives 27 (2007) 244–249 247

because the reactions for the oven-dried systems were
conducted within the diffusion-controlled regime in the
whole process, or because the increase in the activation
energy induced by the decomposition of biuret masked this
trend.
The curing rate for the wood species studied was
different as illustrated in Figs. 4 and 5. The curing rate
was fastest for SYP, followed by aspen and maple, and
slowest for birch under oven-dry conditions. The curing
rate became much faster for all wood species when
moisture was added into the wood. It is obvious that the
effect of wood species on the curing rate was small
compared to the effect of moisture on the curing rate,
because the hydroxyls in wood have a lower mobility and
react with isocyanate much more slowly than water.
3.2. pMDI/wood ratio and autocatalyzed kinetics
The reactions of pMDI resins with wood and moisture
are autocatalyzed as illustrated in the previous research
[7,14]. It was interpreted that the hydroxyls in oven-dried
wood were restricted in their rate of reaction with
isocyanate because of the low mobility of the hydroxyl
groups [7]. In this study, different pMDI/wood ratios were
100
80
60
α (%)
used to confirm this phenomenon. Fig. 6 shows the
reaction enthalpy for the different pMDI/wood ratios.
It is obvious that the reaction enthalpy based on the
amount of the pMDI resin increased for the oven-dried
wood when the pMDI/wood ratio was decreased from
50/50 to 25/75. This increase in the reaction enthalpy
indicated that the percentage of reacted isocyanate
increased in the curing system when the pMDI/wood ratio
was decreased. In comparison, the reaction enthalpy
remained almost unchanged for wood with a 12% MC,
even when the pMDI/wood ratio was decreased, because
most isocyanate in the curing system has reacted for both
ratios.
Further analysis found that the activation energy was
also affected by pMDI/wood ratios as shown in Table 3.
The activation energy ðE Ki a Þ calculated by Kissinger
method and (Ea) by autocatalysis evidently increased for
the oven-dried wood, but remained almost unchanged for
the wood with the 12% MC when the pMDI/wood ratio
was decreased. It can be seen that the increase in the
activation energy for the oven-dried wood resulted from
the increase in stoichiometric ratio (B) because a higher
percentage of pMDI has reacted when the pMDI/wood
ratio was decreased.
To calculate the kinetics of the autocatalyzed reaction,
the stoichiometric ratio should be known. Unfortunately, it
is impossible to get this information for the curing
reactions of pMDI/wood systems, because the effective
hydroxyl concentration was unknown due to the hetero-
geneous nature of the system. It is necessary, therefore, to
assume a series of B values and calculate the corresponding

Aspen
40
Birch
350
20 Maple Oven-dried
SYP 300 MC12%
0
250
ΔH (J/gpMDI)

0 50 100 150 200

t (min)
200
Fig. 4. Conversion advancement with reaction time for the pMDI/oven-
dried wood systems. 150

100
100
50
80 R/W=50/50 R/W=25/75

Fig. 6. Effect of pMDI/wood ratio on the reaction enthalpy.

60
α (%)

Aspen Table 3
40 Activation energy of pMDI/aspen under different conditions
Birch

20 Maple pMDI/aspen MC (%) E Ki

a (kJ/mol)
Ea (kJ/mol) B
SYP (mass ratioa)

0 50/50 0 54.3 55.4 0.5

0 2 4 6 8 10 12 65.1 63.3 1
t (min) 25/75 0 63.8 61.7 0.8
12 67.3 64.2 1
Fig. 5. Conversion advancement with reaction time for the pMDI/wood
systems with moisture. a
The mass ratio includes the moisture weight.
 ARTICLE IN PRESS
248 G. He, N. Yan / International Journal of Adhesion & Adhesives 27 (2007) 244–249

activation energy values. An appropriate B and corre- 70

sponding activation energy value can then be chosen by 60
comparison with the activation energy calculated by means
of other methods. 50

Ea (kJ/mol)
Fig. 7 shows the variation in calculated activation 40
energies for different values of B. Even though the kinetics
30
of the autocatalysed reaction may not be suitable for the Aspen
oven-dried wood/pMDI system, there was a linear relation- 20 Birch
ship between the calculated activation energy and the Maple
10 SYP
stoichiometric ratio, B. One possible reason could be that
even in the case of oven-dry condition there may still be a 0
trace of moisture within the system. It should be noted that 0 0.2 0.4 0.6 0.8 1 1.2
B
the variation in activation energies was not sensitive to
stoichiometric ratios for most wood species. This made it Fig. 8. Relationship between the calculated activation energies and the
difficult to get an accurate value of the stoichiometric assumed stoichiometric ratios for pMDI/wood systems with moisture.
ratio, because the activation energy used for choosing a
stoichiometric ratio generally has a deviation up to 10%.
The chosen stoichiometric ratio and the corresponding Table 5
Peak conversion and activation energy by autocatalyzed kinetics for
activation energy based on Fig. 7 for the pMDI/oven-dried pMDI/wood (MC ¼ 12%, B ¼ 1) systems
wood system are listed in Table 4. The stoichiometric ratio
for aspen seemed to be higher than for the other three Samples ap (%) Ea (kJ/mol) E Oz
a (kJ/mol)
species. This semi-quantitative result also showed that the
2 1C/min 5 1C/min 10 1C/min
stoichiometric ratios for the pMDI/oven-dried wood
system were much lower than 1, indicating that the number Aspen 73.5 70.3 65.1 63.3 68.1
of hydroxyls was limited in reacting with isocyanate. To Birch 72.3 69.3 64.8 61.0 65.3
Maple 74.2 70.2 66.3 62.3 67.6
illustrate the error in stoichiometric ratio associated with
SYP 70.8 67.0 63.1 61.4 64.6
the use of above method, we chose the stiochiometric ratio

of 0.5 for all oven-dried wood systems and calculated the

75 corresponding activation energy (the values shown in the
70
parenthesis, Table 4). The result suggested that the chosen
stoichiometric ratio could be increased to 0.5 and the
65 corresponding activation energy values calculated would
Ea (kJ/mol)

60 still be similar.
Fig. 8 shows the variation in calculated activation energy
55
with different stoichiometric ratios for the pMDI/wood
50 Aspen system with a 12% MC. It was clear that the activation
Birch energies for all species were close to one another when the
45 Maple
SYP stoichiometric ratio approached 1. This value was chosen
40 for all species, and reasonable activation energies (the
0 0.2 0.4 0.6 0.8 1 1.2 maximum error was less than 10% compared to the
B
corresponding E Oza values) were calculated (Table 5). This
Fig. 7. Relationship between the calculated activation energies and the result also indicated that the effect of wood species on the
assumed stoichiometric ratios for pMDI/oven-dried wood systems. kinetics was masked by moisture. The moisture increased
the stoichiometric ratio by reacting with most amount of
the isocyanate remaining in the system.
Table 4
Peak conversion and activation energy by autocatalyzed kinetics for
pMDI/oven-dried wood
4. Conclusions

Samples ap (1C) B Ea (kJ/mol) E Oz

a (kJ/mol) Wood species affected the kinetics of curing for the
pMDI/wood system in terms of activation energy, reaction
2 1C/min 5 1C/min 10 1C/min
enthalpy and reaction rate, probably due to different
Aspen 48.0 51.5 55.3 0.4 57.7 (55.4a) 58.2 structures and compositions. This influence, however, was
Birch 50.2 55.2 51.0 0.1 62.4 (59.5) 62.8 masked by the moisture present in the wood, because water
Maple 46.2 51.2 50.4 0.1 55.0 (50.7) 55.3 is much easier to react with isocyanate than are the
SYP 53.3 53.7 54.7 0.1 69.6 (67.0) 69.7
hydroxyls in wood. The trends in the activation energy with
a
The values in the parenthesis were calculated from B ¼ 0.5. the degree of conversion were similar for all species,
 ARTICLE IN PRESS
G. He, N. Yan / International Journal of Adhesion & Adhesives 27 (2007) 244–249
indicating that wood species did not affect the main
reaction mechanism. The difference in the activation
energy values among the wood species for oven-dried
systems indicated that wood structures affected the
diffusion of reactants and the hydroxyls in wood for
various species may have different reactivity with isocya-
nate. The kinetics were also affected by the pMDI/wood
ratios for the oven-dried wood systems, but not for the
systems with moisture, confirming that the hydroxyls in
wood were restricted as reactants under the oven-dry
conditions.
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