POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. 2008; 19: 17291734

Published online 19 August 2008 in Wiley InterScience (www.interscience.wiley.com) DOI: 10.1002/pat.1188

Effects of the hydroxyl value of polyol in rigid

polyurethane foams
Ho Lim2, Sung Hee Kim1 and Byung Kyu Kim1*
1
2

Department of Polymer Science and Engineering, Pusan National University, Busan 609-735, Korea
Korea Polyol Co., Ulsan, 680-090, Korea

Received 12 December 2007; Revised 8 April 2008; Accepted 17 April 2008

Rigid polyurethane foams (RPUFs) have been fabricated from crude MDI (CMDI) and polypropylene
glycols (PPGs) of various hydroxyl values (OHVs) of 300600 with an environmentally friendly
blowing agent (HFC 365mfc). The closed cell content, compression strength, and dimensional
stability of the foam increased with increase in the OHV due to the increased crosslink density,
which was evidenced from the increased glass transition temperature (Tg). The cream time, gel time,
tack-free time, and density of the foam showed a minimum at 500OHV. The decrease and increase
around the minimum were, respectively, interpreted in terms of increased mixture mobility and
extensive allophanate crosslinks, which retard gelling as well as foaming reactions. The thermal
conductivity also showed a small minimum at 500OHV. Copyright # 2008 John Wiley & Sons, Ltd.
KEYWORDS: rigid polyurethane foam; hydroxyl value; cell structure; dimensional stability; thermal conductivity

INTRODUCTION
Polyurethanes (PUs) are used as coatings, adhesives,
sealants, elastomers (CASE), and fibers as well as flexible,
semi-rigid, and rigid foams.13 Rigid polyurethane foams
(RPUFs) have closed cell structure with low thermal
conductivity, high compression strength, low density, high
strength-to-weight ratio, and low moisture permeability.24
Consequently, RPUFs find such applications as insulation of
refrigerators, freezers, piping, tanks, ship building, and
liquefied natural gas (LNG) cargoes.57
The foaming can be done using a one-shot or two-shot
method. In one-shot method, all materials are put into a
mixing cup and mixed homogeneously before they are
poured into a mold. In two-shot method, all materials except
the isocyanate are mixed before the isocynate is added. The
foaming can be carried out with a physical blowing agent,
chemical blowing agent, or mixture of the two.5 In physical
blowing, reactions between isocyanate and polyol produce
polyurethane linkages with the emission of heat of reaction.
Then, the blowing agent vaporizes and the gas is trapped in
the closed cells of the foam. Typically, thermal conductivity
of the blown gas is very low. This, together with small closed
cell structure, gives extremely low thermal conductivity of
the RPUF. In chemical blowing, water (most widely used
blowing agent) reacts with isocyanate to form unstable
carbamic acid, which immediately decomposes into an
amine and carbon dioxide.2,8
The conventional blowing agents such as monofluorotrichloromethane (R11) and difluorodichloromethane (R12)
*Correspondence to: B. K. Kim, Department of Polymer Science
and Engineering, Pusan National University, Busan 609-735,
Korea.
E-mail: bkkim@pnu.edu

have been suggested to contribute to the depletion of the

stratospheric ozone layer and their use has been regulated in
many countries. So, the use of environment friendly blowing
agents has become an important and urgent issue in the
synthesis of polyurethane foam.911 Water can, in part,
replace such environmentally hazardous blowing agents.
However, the excessive use of water causes a negative
pressure gradient due to the rapid diffusion of CO2 through
the cell wall, causing cell deformation.2,3,12
The reaction kinetics of RPUF formation mainly depends
on the rates of blowing and gelling reactions, which on the
other hand are governed by an amine and a tin catalyst,
respectively.4,6 On the other hand, the properties of the foam
mainly depend on the characteristics of polyol such as
functionality and hydroxyl value (OHV), and type and
amount of surfactant, and blowing agent. To reinforce the
foam, composites formation with particle, clay, and fiber are
being considered.1317
We synthesized various types of RPUF from crude
methylene diphenyl diisocyanate (CMDI) and polypropylene glycols (PPG) with an environmentally friendly physical
blowing agent, viz. HFC 365mfc (CF3CH2CF2CH3). The
effects of OHV on the performance of foams have been
extensively analyzed in terms of forming kinetics, cell
morphology (cell size, closed cell content), compression
strength, dimensional stability, dynamic mechanical, and
thermal properties of the foams.

EXPERIMENTAL
Raw materials
Four types of PPG having OHV (mg KOH g
1 of sample) of
300, 400, 500, and 600 (GSF4-300, GSF4-400, GSF4-500,
Copyright # 2008 John Wiley & Sons, Ltd.

1730 H. Lim, S. H. Kim and B. K. Kim

Table 1. Formulations to synthesize RPUFs

Polyol (g)
Samples
OH3
OH4
OH5
OH6

GSF4-300

GSF4-400

GSF4-500

GSF4-600

HFC 365mfc (g)

8404 (g)

PC 8 (g)

CMDI (g)

52.63

45.78

40.49

35.95

4.41

0.81

0.41

41.73
48.59
53.88
58.42

GSF4-n is PPG of hydroxyl number of n.

GSF4-600, functionality 4) were provided by Korea Polyol

Co. (Korea). CMDI was provided by Huntsman (Suprasec-5005), HFC 365mfc by Solvay Chemicals (Belgium),
whereas Polycat-8 (PC 8) as foaming catalyst by Air
Products. Silicon surfactant (B 8404) was provided by
Goldschmidt. Polyols were dehydrated before use at 908C
for 24 hr in a vacuum oven. Other chemicals were used as
received.

based on the original thickness has been taken as the

compression strength of the foam. Dimensional stability was
measured at 80 and
308C for the duration of 24 hr following
ASTM D 2126.

RESULTS AND DISCUSSION

Kinetics of foaming process

Preparation of samples
The rigid foams were synthesized by one-shot method. All
raw materials were first put into a mixing vessel (UtraTurrox T-50, Ika-Werke) and mixed for 30 sec at 7000 rpm.
Then the mixtures were discharged to an open mold
(200 mm  200 mm  200 mm) and the foam cake was cured
for 1 week at room temperature. The NCO index (100
isocyanate equivalents/polyol equivalents) was fixed at 110.
The basic formulations are given in Table 1.

Characterizations
Density of the foam was measured according to ASTM D
1622 with a sample size of 30 mm  30 mm  30 mm
(width  length  thickness), and an average of at least five
measurements was taken to report. The closed cell content
was determined by an air pycnometer following ASTM D
2850 with specimen dimension, 50 mm  50 mm  25 mm.
Thermal conductivity was measured using HC-074 (Laser
Comp) according to ASTM C 518. The cell morphology was
observed under a scanning electron microscope (SEM,
HITACHI S3500N). Samples were cryogenically fractured
in liquid nitrogen and gold sputtered before they were
scanned in the free rising direction. Dynamic mechanical
tests were performed with a dynamic mechanical thermal
analyzer (DMTA, Rheometrics MK-IV) from 30 to 2508C
at 10 Hz and 2% strain using compression mode. Mechanical
properties at room temperature were measured using a
Universal Testing (Ametek, Lloyd). Compression strength
was determined by ASTM D 1621 at a crosshead speed of
3.0 mm min
1 with the sample dimension of 30 mm 
30 mm  30 mm.11 The force required for at 10% deformation

Kinetics of the foam formation are typically followed by the

cream time, gel time, and tack-free time.4,6 The cream time
corresponds to the start of bubble rise and, hence, color of
the mixture becomes cream-like from dark brown due to the
formation of bubbles. Gel time is the starting point of stable
network formation by intensive allophanate crosslinkings
as well as urethane and urea linkages. At the tack-free time,
the outer surface of the foam loses its stickiness and the foam
can be removed from the mold. Table 2 shows that cream
time, gel time and tack-free time decrease with increasing
OHV showing a minimum at 500OHV, beyond which they
increase. For example, the tack-free time is 314 sec for OH3,
245 sec for OH5, and 260 sec for OH6. The increased kinetic
rate is primarily due to the increased mobility by the
decreased molecular weight (Mn) of the PPG. On the other
hand, the decreased kinetic rate with 600OHV implies that
excessive allophanate crosslinkings between the urethane
linkages and free isocyanate groups provide the mixture

Table 2. Reactivity and foam properties

OH3

OH4

OH5

OH6

Cream time (s)

95
92
90
91
Gel time (s)
259
240
228
230
Tack-free time (s)
314
281
245
260
Density distribution (%)
3.48
2.06
1.83
0.43
Compression strength (MPa)
0.98
1.12
1.15
1.25
Compression strength anisotropy (%)
1.36
1.59
1.69
1.87
Copyright # 2008 John Wiley & Sons, Ltd.

Figure 1. Densities of RPUFs versus OHV. This figure

is available in colour online at www.interscience.wiley.com/
journal/pat
Polym. Adv. Technol. 2008; 19: 17291734
DOI: 10.1002/pat

Rigid polyurethane foams

1731

Figure 2. SEM morphologies of the RPUFs versus OHV.

with high viscosity which retards gelling and urethane
foaming reactions.

Foam density and density distribution

Foam density (Fig. 1) decreases with increasing OHV
showing a minimum at 500OHV, beyond which it increases.
Density decrease is an indication of increased blowing
efficiency which is due to the increased mixture mobility as
the Mn decreases.18,19 On the other hand, increase beyond the
minimum is most likely due to the intensive formations of
allophanate crosslinks which retard foaming reactions due to
the increased mixture viscosity. The allophanate crosslinks
are likely to increase with decreasing Mn of polyol due to the
increased number of isocyanate group added to the
formulation (Table 1) and urethane linkages to be formed.
Regarding the density distribution (Table 2), density
decreases along the bubble rising direction, i.e. from bottom
to top, and the effect is less pronounced with increasing
OHV. The vertical distribution is mainly due to the gravity
effect giving rise to great compression at bottom. On the
other hand, high OHV provides cell walls with great
elasticity by great crosslink density, and the walls are less
vulnerable to deformation. Table 2 shows that the density
distribution monotonically decreases with increasing the
OHV, and it is 3.48 for OH3 and 0.43% for OH6, implying that
more or less uniform distribution is obtained with high cell
wall elasticity.

shapes and the size decreases as the OHV increases. The

closed cell content asymptotically increases from about 88 to
94% while the cell size decreases from about 350 to 160 nm as
the OHV increases from 300 to 600.
Regarding the formation of cells, exothermic heat of
reaction causes the supersaturation of the reaction mixture,
leading to phase separation into gas followed by diffusion
into the nuclei, which are small air bubbles entrapped during
the mixing of raw materials.20 Then, the nuclei grow into
bubbles and spherical cells by adopting more gases or by
coalescing with neighboring ones. As the blow ratio
increases, the spherical bubbles are eventually separated
by the cell membrane and become polyhedral. Obviously, the
bubble coalescence becomes difficult as the elasticity of the
cell wall increases. That is, with the increase in OHV or

Cell morphology foam diameter

Fig. 2 shows the SEM morphology of the cell as a function of
OHV, with the average size and closed cell content in Fig. 3. It
is seen that the foams consist of spherical and polyhedral
Copyright # 2008 John Wiley & Sons, Ltd.

Figure 3. Cell sizes and closed cell contents of the RPUFs

versus OHV.
Polym. Adv. Technol. 2008; 19: 17291734
DOI: 10.1002/pat

1732 H. Lim, S. H. Kim and B. K. Kim

decrease of Mn, crosslink density increases due to the

increased allophanate reactions and the elasticity of the cell
wall increases. This gives small cells.

Compression strength
The compression strength is closely related to the dimensional stability of closed cell foams. As the temperature goes
up, gas pressure inside the cell increases, and the pressure
difference relative to the atmospheric pressure becomes
great. If the foam is to be dimensionally stable under these
conditions, the compression strength must be greater than
the pressure rise.2 A minimum compression strength of
0.1 MPa is generally recommended for closed cell foam.3 The
compression strength of our foam is greater than 0.97 MPa,
and it monotonically increases with OHV from 0.98 (OHV3)
to 1.25 MPa (OHV6), together with its anisotropy (strength
ratio of parallel to perpendicular direction) (Table 2) due to
the increased cell elasticity. The elasticity of crosslinked
polymer is given by21
GN

rRT
Mc

temperature, and molecular weight between crosslinks,

respectively. Since OHV is inversely proportional to the
Mn of polyol for given equivalent weight, large OHV
corresponds to the small Mc since the urethane linkages are
the sites for allophanate crosslinks. This will be seen by the
increased glass transition temperature (Tg) with increasing
OHV from the dynamic mechanical measurements to follow.

Dynamic mechanical analysis

The dynamic mechanical properties of the foams are shown
in Fig. 4 where the rubbery plateau modulus and tand peak
temperature of the foam increase as the OHV increases.22 The
increase in plateau modulus is an indication of increased
crosslink density (Eqn (1)). This states that more of the
allophanate crosslinks are formed with the increase in OHV.
The tand peak temperature corresponds to the Tg of the foam.
Based on this, the Tg of the foams are about 100 (OH3),
133 (OH4), 179 (OH5), and 2058C (OH6), respectively. As the
crosslink density increases, the glass-rubber transition
becomes less pronounced.

(1)

Here, GN , r, R, T, and Mc are is the rubbery plateau

modulus, density, gas constant (8.314 m3Pa mol
1 K
1),

Dimensional stability
Closed cell foams shrink at low temperature and expand at
high temperature. Typically, less than 1% of volume change

Figure 4. Storage modulus (a) and tand peaks (b) of the RPUFs versus OHV.
Copyright # 2008 John Wiley & Sons, Ltd.

Polym. Adv. Technol. 2008; 19: 17291734

DOI: 10.1002/pat

Rigid polyurethane foams

1733

Figure 5. Volume changes of the RPUFs for the duration of 24 hr versus OHV.

is desired for sufficient strength. Fig. 5 shows that the volume

change asymptotically decreases with increasing OHV, and
the largest volume change is less than 1%. The shrinkage at

308C is smaller than the expansion at 808C. The smaller
volume change viz. the greater dimensional stability with
greater OHV is due to the increased elasticity of cell wall
introduced by the allophanate crosslinks.

Thermal conductivity of the foam

Heat conduction through the closed cell foams can be
approximated by a series model which is composed of
polymer walls and gas cells in series.23 Conductive heat flux
(q) through the composite wall is given by
DT
(2)
R
where DT is the temperature drop across the foam and R is
the conduction resistance given by the following equation:

n

X
XW;i XG;i
R
(3)

kW
kG
i1
q

Here, XW,i and XG,i are the wall thickness and cell
dimension, and n is the number of walls, respectively. For
uniform cells, wall thickness (XW,i) and cell dimension (XG,i)
are constant to give



XW XG
Rn
(4)

kW
kG

more or less at the same value with 600OHV (Fig. 6). The
decrease is mainly due to the decreased cell size giving a
large number of n as analyzed above. With 600OHV, it seems
that decreased cell size is more or less balanced with
increased foam density giving rise to small change in thermal
conductivity.

CONCLUSIONS
The RPUFs have been fabricated from CMDI and PPGs of
various OHVs with an environmentally friendly blowing
agent (HFC 365mfc) and the following conclusions have been
derived.
The compression strength and dimensional stability of
the foam increased with increasing OHV due primarily to the
increased crosslink density, which is accompanied by the
decreased cell size and increased closed cell content. Direct
evidence of the increased crosslink density was seen from the
increased Tg as well as the increased rubbery plateau
modulus.
The cream time, gel time, tack-free time, and density of the
foam showed a minimum at 500OHV. The decrease up to the
minimum is due to the increased mixture mobility, whereas

In a typical closed cell foam, the polymer walls occupy

36 vol% of the foam.3 In addition, the conductivity of the
polymer is much greater than that of the blowing gas. So, the
first term, viz. polymer wall resistance can be neglected to
give


XG
Rn
(5)
kG
The above simple analysis shows that the thermal
insulation of closed cell foam increases linearly with the
number of closed cells, i.e. effect of insulation increases as the
cell size decreases.24
The thermal conductivity of our foam decreases from
0.0242 (OH3) to 0.0222 (kcal mhr
1 8C) (OH5) and it stays
Copyright # 2008 John Wiley & Sons, Ltd.

Figure 6. Thermal conductivities of the RPUFs versus OHV.

Polym. Adv. Technol. 2008; 19: 17291734
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1734 H. Lim, S. H. Kim and B. K. Kim

the increase beyond the minimum by the extensive

allophanate crosslinks which retard foaming reactions.
Thermal conductivity of the foam decreased with increasing OHV up to 500OHV, beyond which it stayed almost
constant. The decrease is mainly due to the decreased cell
size coupled with the decreased density. On the other hand,
decreased cell size is more or less balanced, with increased
foam density with 600OHV giving rise to no change in
thermal conductivity.

Acknowledgments
This research was financially supported by the Ministry of
Education, Science Technology (MEST), and Korea Industrial
Technology Foundation (KOTEF) through the Human
Resource Training Project for Regional Innovation. BKK is
also indebted to the NCRC organized at PNU.

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Polym. Adv. Technol. 2008; 19: 17291734

DOI: 10.1002/pat