ANALYTICAL SCIENCES NOVEMBER 1999, VOL.

15 1083
1999 © The Japan Society for Analytical Chemistry

State Analysis of Water in Polyether-Polyol by High-Frequency

Spectroscopy
Takaya TAKEI*†, Kazuki KAGESHIMA*, Megumi TOMITA*, Yoshinori SUGITANI*,
Kyon Hun MIN** and Kiyoshi MATSUMOTO**

*Kanagawa University, Faculty of Science, Tsuchiya 2946, Hiratsuka, Kanagawa 259–1293, Japan
**Asahi Glass Co. Ltd., Research Center, 1150 Hazawa-cho, Kanagawa-ku, Yokohama,
Kanagawa 221–8755, Japan

Water molecules in polyether-polyol have been analyzed by high-frequency spectroscopy. It has been inferred that there
exist two types of H2O in polyether-polyol. The first type are those which coordinate directly to the OH group at the end
of the polyol chain. The frequency of the maximum absorption peak of these water molecules do not shift with increasing
content of H2O in the high-frequency spectra; these may be referred to as non-freezable water. The second type are those
which bond to the EO chain in the polyol. Excess water molecules which exist near or in the neighborhood of these H2O
should also be included in the second type one. The second type may be referred to as freezable water. These show a fre-
quency shift which reflects the degree of restraint of H2O in the polyol.

Keywords High-frequency spectroscopy, polyether-polyol, water in polyether-polyol

Polyurethane foam is a material which is widely used

for shock absorbers, house walls, and heat containers.
So far, chloro-fluoro-carbons (frons) have been used as
a blowing agent in the manufacturing process of the
polyurethane foam. 1 Nowadays, however, water is
being used as the new blowing agent in place of frons
because of environmental considerations.
Polyether-polyol (hereafter briefly expressed as poly-
ol) is one of the starting materials of the new foam
products.2 Differential scanning calorimetry (DSC)3
has shown that, if polyol is mixed with water, it gives
two types of water: they are referred to as freezable and
non-freezable water depending on the state of restraint
in the polyol.
The nature and/or behavior of water molecules in
macromolecules including polyols have been exten-
sively studied by X-ray diffraction4, NMR 5–7, mass
spectrometry8,9, dielectric measurements10,11, and ther-
modynamic calculations.12,13
In the present study, high-frequency spectroscopy14,15,
which is sensitive to solution structures and/or change
of state of association between molecules, has been
applied to the study of water molecules in the polyol
system. The binding state of water in the polyols has
been analyzed by the high-frequency spectroscopic
method and results were compared with the results of
DSC analysis.
Experimental
Polyol reagent used in this work was commercially
available from Asahi Glass Co. Ltd., having the molec-
ular weight of approximately 3000. Figure 1 shows the
structure. The starting material glycerine is linked with
propylene oxide (PO) chains which were endcapped by
ethylene oxide (EO) chains. The contents of EO were
0, 7, 13, and 20wt.%. The water which was mixed with
polyols was of high purity one, prepared by the Milli-Q
SP system plus Labo-IONPure-12 (Millipore Ltd.).
The mixing ratios of polyol and water were as follows:
In the samples having the weight percent ratio
polyol:EO=100:0, water was added between 0 and
5wt.%. The water added at more than 5wt.% was
found separated from the samples. In the samples hav-
ing the ratio polyol:EO=100:7, water was added
between 0 and 20wt.%. In the samples having the ratio
polyol:EO=100:13, water was added between 0 and

† To whom correspondence should be addressed. Fig. 1 Outline of samples.

1084 ANALYTICAL SCIENCES NOVEMBER 1999, VOL. 15

(a)

Fig. 2 High frequency spectra of polyols.

(b)

100wt.%. Finally in the samples having the ratio poly-

ol:EO=100:20, water was added between 0 and
100wt.%. These materials were mixed by a mechanical
mixer, and the mixed materials were left overnight to
remove bubbles which were produced during the mix-
ing.
Measurement of the high-frequency spectra was con-
ducted using the measuring system previously
reported14, in the frequency range 0 – 2000 MHz at room
temperature. Thermal measurements were conducted
using a machine (DSC3200) made by MAC Science.
The temperature curve of each sample specimen was
recorded in the procedure, where the temperature of the
specimen, 10 mg for each run, was cooled down to
–120˚C at the rate of –5 deg/min, and then heated up to
100˚C at the rate of 10 deg/min. Fig. 3 Spectra of polyol samples with the addition of water:
EO content 0wt.% (a), and EO content 20wt.% (b).

Results and Discussion

Figure 2 shows the high-frequency spectra of polyols
which contain 0, 7, 13, and 20wt.% of EO without
water. Each spectrum shows the maximum peak at
1650 MHz with different intensities. The intensities are
approximately proportional to the EO content, suggest-
ing a certain kind of relation to some hydrophilic part
of EO. Details for this are not yet elucidated and are
now being examined.
Figure 3 shows the spectra of polyol samples which
contain water molecules in various ratios. Figure 3(a)
shows the spectra of the samples having the composition
polyol:EO=100:0, with the water added at 0 – 5wt.%
with respect to the polyol. Figure 3(b) shows the spectra
of the samples having the composition polyol:
EO=100:20, with the water added at 0 – 100wt.% with
respect to the polyol. In the spectra of the polyol with
0wt.% EO (Fig. 3(a)), the maximum peak at 1650 MHz
does not show any shift for the water contents between
0 – 5wt.%, but shows a gradual increase of intensity
with further increase of water added. The only
hydrophilic part of the polyol which has 0wt.% of EO
seems to be the OH group at the end of the PO chain.
To an OH group in the PO chain, three water molecules
are spatially able to coordinate by hydrogen bonding.
In the sample having the weight composition
polyol:water=100:5, the atomic ratio between OH and
H 2 O molecule corresponds approximately to 1:3.
Consequently, all of the water molecules added within
0 – 5wt.% seem to coordinate to the OH group, settling
into a bounded state in the polyols. These water mole-
cules are characterized as “non-freezable by cooling”,
because they are strongly bound to the spices of a tetra-
hedron and the interaction between water molecules is
not strong enough to freeze. On the contrary, the sam-
ples having the weight composition polyol:EO=100:20,
show the drastic shift of the maximum peak towards
low frequency with the addition of 0 – 100wt.% water.
It should be noted that the polyol which was added
20wt.% of water shows an additional strong peak at
ANALYTICAL SCIENCES NOVEMBER 1999, VOL. 15
(a)
(b)
Fig. 4 Plots of frequency of the maximum frequency absorp-
tion versus the amount of water added: 0 – 100wt.% (a), and
detailed representation in 0 – 20wt.% (b).
1250 MHz, resulting in a superposed spectra of two
strong peaks. Further, with the increase of water up to
100wt.% with respect to polyol, the strong peak
observed at 1500 MHz shows a rapid decrease of inten-
sity, while the peak at 1250 MHz shows a gradual shift
down to 600 MHz. These experimental results suggest
that when water is added to polyol, there exist two
types of water:
(a) The first one is that which coordinates to the OH
group at the end of the polyol chain. This is not rele-
vant to the shift of the maximum absorption frequency.
(b) The second one is that which bonds to the EO chain
in the polyol. This shows a frequency shift.
In Fig. 4, plots of maximum absorption frequencies of
polyols with the EO contents 7, 13, and 20wt.% are
shown. Figure 4(a) shows the overall range of the
water added between 0 and 100wt.% with respect to
polyol, while Fig. 4(b) shows only the portion of the
range between 0 and 20wt.% for the added water. As
seen in Fig. 4(a), the observed main two peaks show
1085
different behavior of shift with the change of the water
content: one peak is observed for polyols with the
water content at 0 – 20wt.% and shows a frequency
shift from 1650 MHz to 1500 MHz, where the peak
disappears, while the other peak is observed for the
polyols with the water content over 20wt.% and shows
a frequency shift from 1250 MHz to 600 MHz with the
increase of the water content. The former is considered
to be due to the water restrained in the polyol chain.
The latter peak, on the other hand, is considered as the
water which is converging to the approximate frequen-
cy of 500 MHz, which is characteristic of the bulk
water.
In Fig. 4(b), the shifts of maximum absorption fre-
quencies are shown by two or three straight lines for
each sample. In other words, the frequency change for
the polyol of each EO content can be divided into two
or three regions of water content. The turning points
for each polyol containing 7, 13, and 20wt.% of EO
were 8, 14, and 20wt.% of water, respectively.
In the range of added water 0 – 5wt.%, the degrees of
the frequency shift towards low frequency direction are
in the order of the amount of the EO added, that is, in
the order 20>13>7>0(wt.%). This must be closely
related to the degree of the hydrophilicity of polyol.
Further, as described before, the shift of the maximum
absorption peak is considered to be due to the water
molecules which coordinate to the oxygen atom of
ether group in the EO chain. This is supported by the
fact that the polyol having higher EO content is able to
contain a larger amount of water which is interacting
with the EO chain. This leads to showing the larger
shift of the maximum absorption frequency. These
water molecules behave like the non-freezable water
because they are much more strongly bound, by cool-
ing, to the oxygen atoms in EO chain.
The water content where the rate of the change of the
shift turns to a larger slope may indicate the instant
when the water molecule can no longer be attached
directly to the polyol chain, but begin to interact with
the water molecules which are bound to the polyol
chain. In other words, this is the instant when the addi-
tional water molecules begin to form clusters by them-
selves. Excess water molecules after this, are regarded
as free water. This kind of water will freeze by cooling
because the interactions between water molecules
strongly increase by cooling. Consequently, in the
region before the turning point of the slope, only the
non-freezable water exists, while after the turning
point, two types of water, freezable and non-freezable
water, co-exist.
In Fig. 5, the amount of non-freezable water obtained
by DSC analysis is compared with the results obtained
by the present high-frequency analysis. DSC data were
obtained as follows: the melting energy of the frozen
water was calculated from the area of the melting peak
observed near 0˚C in the temperature curve. It was
assumed that the melting energy of the frozen water in
polyol was the same as that of the free water, which has
1086
Fig. 5 Plots of the amount of non-freeezable water as
obtained by DSC study and by high-frequency spectroscopy.
the value 79.9 cal/g at 273.2 K. The change of the
melting energy due to the change of melting tempera-
ture was corrected by the specific heat data of water
and ice. Plots of the amount of the freezable water ver-
sus water content of frozen water in polyol give a linear
relationship between the two parameters. Extrapolation
of the obtained straight line to the zero point of abscissa
gives the initial content of nonfreezable water. Results
of the two methods agreed at a satisfactory level. Data
obtained by high-frequency analysis give a somewhat
smaller value of content of the non-freezable water than
those obtained by DSC study. This may reflect the
binding state of water, since the high-frequency mea-
surements were conducted at a higher temperature
(room temperature) than the temperature for DSC mea-
surements. This is also supported by the fact that, with
the increase of temperature, the mixed sample solution
approaches to a clouding point and begins to separate
in two phases, showing the reduction of the binding
force of water.
The change of the bound state of water in the polyol
can be detected by high-frequency spectroscopic meth-
ANALYTICAL SCIENCES NOVEMBER 1999, VOL. 15
ods. The method is more advantageous than the DSC
method in the sense that it gives the same kind of infor-
mation without changing the temperature of the sample
as in the DSC study.
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(Received May 1, 1999)
(Accepted July 23, 1999)