M. Kobayashi et al.

: Synthesis and Properties of Liquefied Wood/Epoxy Resins 93

Holzforschung
54 (2000) 93–97

Application of Liquefied Wood to a New Resin System-

Synthesis and Properties of Liquefied Wood/Epoxy Resins
By Masahiko Kobayashi, Kyoko Tukamoto and Bunichiro Tomita
Institute of Agricultural and Forest Engineering, University of Tsukuba, Tsukuba, Ibaraki, Japan

Keywords Summary
Liquefied wood A new resin system was developed by reacting liquefied wood with various epoxy compounds. Exami-
Diglycidyl ether of ethylene nation of the optimum conditions for the synthesis of the resins, and the behavior of liquefied wood in
glycol oligomers the cured resins were undertaken. Generally, the compatibility and film forming performance of lique-
Diglycidyl ether of fied wood/epoxy resins became better as the wood content increased. The presence of only one broad
bisphenol A dispersion peak, due to the glass transition, was observed during dynamic mechanical measurement of
Liquefied wood / epoxy resins resin films suggesting that the different components of the resin were compatible. The glass transition
Film temperature of the cured resins could be modified by changing the kinds of epoxy compounds and the
Compatibility wood contents of liquefied wood. The presence of rubber elasticity at higher temperatures suggests that
Viscoelastic property the resin systems consisted of cross-linking polymer networks.
Glass transition temperature

Introduction ty by selecting different epoxy compounds and changing the

In recent years, considerable effort has been devoted to uti-
lizing wood as a new source of raw materials for chemicals
and resins. New technologies and products have been devel-
oped including liquefaction of wood and chemically modi-
fied wood (Shiraishi et al. 1985; Yao et al. 1993, 1994). Shi-
raishi and coworkers have investigated wood solubilization
for more than ten years. In a series of studies, they have
developed two major methods for the liquefaction of wood;
one is liquefaction with phenols, and the other with poly-
hydric alcohols. The former has been developed to synthe-
size phenolic like formaldehyde based resins (Lin et al.
1995). The use of liquefied wood obtained using polyhydric
alcohols such as ethylene glycol oligomers is mainly limit-
ed to polyurethane-like foams obtained by reacting lique-
fied wood with polyisocyanate (Yao et al. 1996). New resin
systems have also been developed by reacting different
kinds of lignins with poly-functional epoxy compounds
(Tomita et al. 1989; Nonaka et al. 1997).
This paper outlines a new resin system obtained by react-
ing liquefied wood, produced using polyhydric alcohols,
with various epoxy compounds. Examination of the opti-
mum conditions for the synthesis of the resins, and the
behavior of liquefied wood in the cured resins were under-
taken in three experiments. The first involved an evaluation
of the compatibility and film forming performance of the
cured resins. The second the determination of the N,N-
dimethylformamide (DMF) soluble components of the
cured films. The third is the measurement of the tempera-
ture dependency of dynamic viscoelastic properties of the
cured resins.
The technological and scientific importance of this work
is to synthesize new resins with various mechanical proper-
quantity of wood. The cured resins may possibly be applied
to some kind of adhesive and rubber-like materials.
Experimental
Preparation of liquefied wood
The heartwood meal of Japanese cedar (Cryptomeria japonica D.
Don) was used as wood raw material. The wood meal was dried at
105 °C for one day before it was used. The dried wood meal was
placed in a separable two-necked flask equipped with condenser
and mechanical stirrer after it was mixed with chemicals, that is,
polyethylene glycol (average molecular weight 400), glycerol and
sulfuric acid. The weight percentage of glycerol in polyhydric
alcohols was 20 %. The amount of sulfuric acid used as a catalyst
was 3 % of the whole polyhydric alcohols. Liquefied wood with a
wood to polyhydric alcohol ratio (W/P ratio) of 1/2.5 was placed
in the separable glass flask, submerged in an oil bath preheated at
170 °C, and reacted for 90 min with mechanical stirring. A differ-
ent reaction procedure was used when the W/P ratio was 1/1. The
first step involved mixing two-fifths of the total amount of wood
with the prescribed amount of polyhydric alcohol. Then the mixture
was heated in an oil bath at 150 °C in order to suppress the reaction
velocity. Subsequently one-fifth of the total amount wood meal was
added three times every 30 min reacted with stirring for 60 min.
Synthesis of liquefied wood/epoxy resins
The chemical structures of epoxy compounds and curing reagent
are shown in Figure 1. Liquefied wood was thoroughly mixed in
an earthenware mortar with the following epoxy compounds, three
kinds of water-soluble diglycidyl ether of ethylene glycol
oligomers (DGEEG, Nagase Chemicals Co. Ltd., Japan) ; ethylene
glycol diglycidyl ether (EGDGE), diethylene glycol diglycidyl
ether (DEGDGE) and tetraethylene glycol diglycidyl ether
(TEGDGE), as well as an oily diglycidyl ether of bisphenol A
(DGEBA , Shell Chemical Co. Ltd., Japan). Many kinds of resins
were synthesized by changing the type of epoxy compound and the

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94 M. Kobayashi et al.: Synthesis and Properties of Liquefied Wood/Epoxy Resins
Fig. 1. Chemical structures of epoxy compounds and curing agent.
ratios of liquefied wood to epoxy compounds, represented as L/E
ratio. Triethylene tetramine (TETA) was used as a curing reagent.
The amounts of curing reagent was varied and 48 % sodium
hydroxide was used to adjust the acidity of the reaction mixes dur-
ing curing. Epoxy compounds on their own, without the addition
of liquefied wood were also mixed with the curing reagent stoi-
chiometrically. Cured films were obtained by casting the mixtures
onto teflon sheets after the addition of curing reagent. Films were
cured at room temperature for one day, and then heating them at
150 °C in an oven for 3 hours.
Solvent extraction of cured films
Cured films were extracted with DMF at 80 °C for 2 hours after
allowing them to stand at room temperature for one day. After
extraction, the insoluble parts were filtered off, dried at 105 °C for
more than one day, weighed, and percentage weight losses calcu-
lated. Gel permeation chromatography (GPC) of DMF-soluble
components was performed by using a Waters 600E Multisolvent
Delivery System with a Shodex KD-2002 column heated at 50 °C,
using DMF containing 0.01M lithium bromide as an eluent. Detec-
tion involved the use of Waters 410 Differential Refractometer and
Hewlett Packard HP-1100 Series Diode Array Detector .
Dynamic mechanical measurement
Samples were prepared by casting the viscous resin mixture into
a teflon mold whose size was 40 mm (length) 12 mm (width)
0.80 mm (thickness), and by curing using the same conditions as
mentioned previously. The dynamic viscoelastic-spectra were
measured with an Advanced Rheometric Expansion System (Reo-
metric Scientific Co. Ltd.) at a frequency of 1 Hz and a tempera-
ture-programmed speed of 3 °C/min.
Results and Discussion
Solvent extraction, compatibility and filming performance
of cured resin
Table 1 shows the percentage weight decrease after DMF
extraction of the cured resins synthesized from three kinds
of water-soluble epoxy compounds and liquefied wood with
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a W/P ratio of 1/2.5. These results suggest that films con-
taining EGDGE were superior to those containing
TEGDGE and DEGDGE because they were less soluble in
DMF. Compatibility and film forming performance of these
resins were also evaluated visually. In the case of TEGDGE,
the components of the cured resins seemed to be quite com-
patible because the resin films were fairly transparent.
However, such films were fragile and quite weak. In the
case of DEGDGE, the film forming performance was fairly
good when the L/E ratio was 1/3, but it became worse as the
L/E ratio increased to 1/2 or 1/1. In the case of EGDGE,
both compatibility and film forming performance were
comparatively good even when the L/E ratio was increased
to more than 1/1.
The effect of acidity during curing on the DMF solubil-
ity of films was investigated for resins containing EGDGE
with an L/E ratio of 1/0.5. It was noted that the solubility of
films in DMF was largely unaffected by pH during curing
and therefore acidic conditions for liquefied wood were
adopted as a general curing condition.
Table 2 shows the DMF solubility of the cured resins
synthesized from EGDGE and liquefied wood when the
W/P ratio was 1/1. The ratio of L/E was changed from 1/0.5
to 1/0.25. These results indicate that, when the L/E ratio was
more than 1/0.4, solubility in DMF increased. It was also
observed that the compatibility of the resin components
became slightly worse when the L/E ratio was greater than
1/0.4. The film forming performance became worse, when
the L/E ratio was more than 1/0.3. Generally, a W/P ratio of
1/1 resulted in better film forming performance than that
obtained at a ratio of 1/2.5, at room temperature.
Table 3 shows the DMF solubility of the cured resins
synthesized using DGEBA which as mentioned above, is an
oily compound. It was surprising that this oily epoxy com-
pound was solubilized into liquefied wood, just as for
water-soluble epoxy compounds. Films containing DGEBA
with an L/E ratio of 1/1 were less soluble in DMF than those
with an L/E ratio of 1/0.5. This suggests that when the for-
mer ratio is employed the resin forms a highly cross-linked
polymer network. The cured resin with an L/E ratio of 1/1
was hard networks, but that with an L/E ratio of 1/0.5 had
better elasticity at room temperature. The cured resins syn-
thesized with DGEBA generally had better film forming
performance than those synthesized with water-soluble
epoxy compounds. All solvent extractions in our experi-
ments were done using DMF. Since DMF is one of the high-
est polar solvents, its ability to solubilize the resins synthe-
sized here was high.
GPC measurement of DMF-soluble parts of cured films
GPC measurement was carried out to analyze the compo-
nents of the resins removed by DMF. Initially, GPC chro-
matograms were recorded by a differential refractometric
detector. The DMF-soluble parts of liquefied wood itself
whose W/P ratio was 1/1 are shown in Figure 2a. Figure 2b
shows a chromatogram of DMF-soluble components of a
cured resin synthesized using liquefied wood with a W/P
ratio 1/1 and an L/E (EGDGE) ratio 1/0.5. Figure 2c shows
M. Kobayashi et al.: Synthesis and Properties of Liquefied Wood/Epoxy Resins 95

Table 1. The effects of type of epoxy compound and blend ratio on the DMF solubility of various liquefied wood/epoxy resins

Epoxy compound Wood/Polyhydric Curing condition Liquefied wood/ TETA (g) Degree of
alcohol ratio Epoxy ratio weight reduction
( W/P ratio ) ( L/E ratio ) (%)

TEGDGE 1/2.5 Acid 1/1 0.125 53.41

1/2 0.251 30.54
1/3 0.375 28.35
DEGDGE 1/2.5 Acid 1/1 0.201 39.46
1/2 0.402 22.18
1/3 0.603 18.78
EGDGE 1/2.5 Acid 1/1 0.217 30.00
1/2 0.434 18.80
1/3 0.651 13.24

Table 2. The effect of the amount of TETA and blend ratio on the DMF solubility of various liquefied wood/epoxy (EGDGE) resins

Epoxy compound Wood/Polyhydric Curing condition Liquefied wood/ TETA (g) Degree of
alcohol ratio Epoxy ratio weight reduction
( W/P ratio ) ( L/E ratio )

EGDGE 1/1 Acid 1/0.5 0.05 32.04

0.10 30.48
0.15 28.86
0.20 28.76
0.25 26.02
0.30 32.06
EGDGE 1/1 Acid 1/0.4 0.15 29.59
0.20 30.01
EGDGE 1/1 Acid 1/0.3 0.15 32.36
0.20 30.24
EGDGE 1/1 Acid 1/0.25 0.15 36.05
0.20 40.47

Table 3. The effect of the amount of TETA and blend ratio on the DMF solubility of various liquefied wood/epoxy ( DGEBA ) resins

Epoxy compound Wood/Polyhydric Curing condition Liquefied wood/ TETA (g) Degree of
alcohol ratio Epoxy ratio weight reduction
( W/P ratio ) ( L/E ratio )

DGEBA 1/1 Acid 1/1 0.10 21.31

1/1 0.15 19.50
1/1 0.20 20.40
DGEBA 1/1 Acid 1/0.5 0.10 33.67
1/0.5 0.15 30.61
1/0.5 0.20 33.50

a chromatogram of DMF-soluble components of a cured
resin synthesized using liquefied wood with a W/P ratio 1/1
and an L/E (DGEBA) ratio 1/0.5. Figure 2a indicates that
the liquefied wood contains a large proportion of high
molecular-weight constituents. On the other hand, high
molecular-weight constituents were not be observed in Fig-
ure 2b and Figure 2c. It can therefore be concluded that the
high molecular-weight constituents of liquefied wood react-
ed with epoxide to form cross-linked polymer networks.
Comparing Figure 2b with Figure 2c, the molecular weight
distribution of the DMF-soluble part of the cured resin syn-
thesized with water-soluble epoxy compound was almost
the same as that obtained with oily epoxy compound, but
the former resin contained more low molecular-weight con-
stituents than the latter resin. GPC measurement of raw
materials used to synthesize resins, i.e., the solvent used
for liquefaction (PEG 400, glycerol, and sulfuric acid) and
two kinds of epoxy compounds, revealed peaks; the sol-
vent used for liquefaction/50.75 min; EGDGE/60.56 min;
DGEBA/57.26 min. The lower-molecular weight con-
stituents which were not incorporated in cross-linked poly-
mer networks were extracted by DMF and can be consid-
ered to be linear polymers or unreacted constituents includ-
ing the solvent used for liquefaction.
Figures 3a, b and c are the chromatograms for the same
samples analysed in Figure 2a, b and c, respectively, but
they were recorded by a UV detector at 280 nm. Such a
detection method is capable of revealing the presence of

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96 M. Kobayashi et al.: Synthesis and Properties of Liquefied Wood/Epoxy Resins
Fig. 2. Gel permeation chromatogram of DMF-soluble parts of
liquefied wood and liquefied wood/epoxy resins.
Note: Detector : Waters 410 Differential Refractometer.
Legend: a) DMF-soluble part of liquefied wood, W/P ratio = 1/ 1.,
b) DMF-soluble part of liquefied wood/epoxy resin, W/P
ratio = 1/1,L/E (EGDGE) = 1/0.5., c) DMF-soluble part of
liquefied wood/epoxy resin, W/P ratio = 1/1, L/E (DGEBA)
= 1/0.5.
lignin components. Figure 3b and Figure 3c indicate that
each of the DMF-soluble part of the cured resins reveals a
large peak between 40min and 50min, but Figure 3a does
not show such a peak. Therefore it seems that lignin com-
ponents of liquefied wood are apt to react with epoxide to
form cross-linked polymer networks.
Temperature dependency of viscoelastic property of lique-
fied wood/water-soluble epoxy resin
Figure 4a shows the temperature dependency of the vis-
coelastic property of the cured resin synthesized from liq-
uefied wood at a W/P ratio of 1/1 and an L/E (EGDGE) ratio
of 1/1. G’ and G“ indicate storage modulus and loss modu-
lus, respectively. From this Figure, it can be seen that the
cured resin had only one dispersion peak of loss modulus at
its glass transition temperature, and rubber elasticity can be
observed at higher temperatures. The presence of only one
dispersion peak suggests that many hydroxyl groups, which
are present in liquefied wood, reacted with the epxide, and
that compatible resin networks were constructed. The same
tendency is observed in Figure 4b for a cured resin synthe-
sized with a W/P ratio 1/1 and an L/E ratio 1/0.5. From
these figures, it can be seen that as the wood content in the
cured resins increased, the dispersion peak due to the glass
transition broadened and shifted to higher temperature. The
broadening of the peak can be explained by a decrease of
molecular mobility owing to the steric hindance effect
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Fig. 3. Gel permeation chromatogram of DMF-soluble parts of liq-
uefied wood and liquefied wood/epoxy resins.
Note: Detector: Hewlett Packard HP - 1100 Series Diode Array
Detector.
Legend: a) DMF-soluble part of liquefied wood, W/P ratio = 1/1.,
b) DMF-soluble part of liquefied wood/epoxy resin, W/P ratio
= 1/1, L/E (EGDGE) = 1/0.5., c) DMF-soluble part of liquefied
wood/epoxy resin, W/P ratio = 1/1,L/E (DGEBA) = 1/0.5.
caused by the addition of liquefied wood (Nonaka et al.
1997). These figures can be compared with Figure 4c which
shows the property of the cured epoxy resin itself. The
cured resin which did not contain liquefied wood showed
the highest glass transition temperature of all kinds of
resins. The fact that the glass transition temperature shifted
to lower temperature when liquefied wood was added may
be due to plasticization of the resins by polyhydric alcohol
and low molecular-weight components.
Temperature dependency of viscoelastic property of lique-
fied wood/oily epoxy resin
Figure 5a shows the temperature dependency of the vis-
coelastic property of the cured resin synthesized from
liquefied wood and DGEBA when the W/P ratio was 1/1
and the L/E ratio was 1/1. Figure 5b is that for resin
synthesized with a W/P ratio of 1/1 and an L/E ratio of
1/0.5. From these figures, it can also be seen that the cured
resin had only one dispersion peak of loss modulus at glass
transition temperature, and that the dispersion peak broad-
ened noticeably as the wood content in the cured resins
increased. However, as the wood content increased, the
glass transition temperature became lower, which will be
due to plasticization of resins by low molecular-weight
components present in the liquefied wood. These figures
may be compared with Figure 5c which shows the property
of the cured epoxy resin itself. The cured resin which did
M. Kobayashi et al.: Synthesis and Properties of Liquefied Wood/Epoxy Resins
Fig. 4. Temperature dependence of visco-elastic property of cured
water-soluble epoxy resin and two kinds of liquefied wood/water-
soluble epoxy resins.
Note: a (쏔, 쐽): liquefied wood/EGDGE resin, W/P ratio = 1/1,
L/E ratio = 1/1., b (왖, 왕) : liquefied wood/EGDGE epoxy resin,
W/P ratio = 1/1, L/E ratio = 1/0.5., c (쎲, 쑗): EGDGE epoxy
resin.
not contain liquefied wood had a dispersion peak at the
highest temperature.
The properties of the resins containing water-soluble
epoxy compounds were considerably affected by the L/E
ratio. On the other hand, resins containing the oily epoxy
compound were only slightly affected by the L/E ratio.
Generally, the effects of addition of liquefied wood were on
resin properties remarkable in the case of the resin synthe-
sized with oily epoxy compound because it had a broader
dispersion peak of loss modulus. All the results of the tem-
perature dependency of viscoelastic property of the cured
resins suggest good compatibility and characteristics of
their components.
Conclusion
A new method of reacting liquefied wood with various
epoxy compounds has been developed. New resins could be
made using this system, although they contained compo-
nents that were soluble in DMF. The high molecular-weight
constituents of liquefied wood were incorporated into the
resin possibly in the form of cross-linked polymer net-
works. Dynamic mechanical measurements showed that
cured resins had a good compatibility. It was also found that
the glass transition temperature of cured resins could be
modified over a wide range by selecting different epoxy
compounds and changing the quantity of wood. The forma-
tion of cross-linked networks was suggested by the presence
of rubber elasticity at higher temperatures. It is significant
from a practical point of view that the resinification of liq-
uefied wood can be performed by a simple method using a
high content of wood. These are the advantages of this
resin-system over that developed previously. The issue
hereafter is to enhance the reaction ratio of the whole com-
ponents by identifying low-molecular weight components
of DMF-soluble part or selecting more suitable curing
reagents.
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97
Fig. 5. Temperature dependence of visco-elastic property of cured
oily epoxy resin and two kinds of liquefied wood/water-soluble
epoxy resins.
Note: a (쏔, 쐽): liquefied wood/DGEBA resin, W/P ratio = 1/1,
L/E ratio = 1/1., b (왖, 왕) : liquefied wood/DGEBA epoxy resin,
W/P ratio = 1/1, L/E ratio = 1/0.5., c (쎲, 쑗): DGEBA epoxy
resin.
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Received November 2nd 1998
M. Kobayashi
K. Tsukamoto
Prof. Dr. B. Tomita
Institute of Agricultural and Forestry Engineering
Faculty of Agriculture
University of Tsukuba
Tsukuba-shi
Ibaraki-ken
305-8572
Japan
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