Polymer 52 (2011) 2840e2846

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Rigid polyurethane foams from a soybean oil-based Polyol

Suqin Tan a,1, Tim Abraham b, Don Ference b, Christopher W. Macosko a, *
a
Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, MN 55455, USA
b
Cargill Bio-Based Polyurethanes, Plymouth, MN 55416, USA

a r t i c l e i n f o a b s t r a c t

Article history: Polyurethane (PU) rigid foams were synthesized by substituting a polypropylene-based polyol with
Received 3 February 2011 soybean oil-based polyol (SBOP). All the soy-based foams maintained a regular cell structure and had
Received in revised form even smaller average cell size than the control foams. The density of soy-based foams was within 5% of
10 April 2011
the controls, except that the density of foams from 100% SBOP was 17% higher. Soy-based foams also had
Accepted 16 April 2011
Available online 23 April 2011
comparable initial thermal conductivity (k value) and closed cell content, higher Tg and compressive
strength. However, while foams from 50% SBOP showed similar increase in k value to the 0% SBOP foams,
under accelerated aging conditions, the 100% SBOP foams aged faster. Gas permeation tests performed on
Keywords:
Polyurethane foam
PU thin films showed higher N2 permeation for PU thin films made from SBOP which is believed to be the
Soybean oil-based polyol cause of accelerated thermal aging.
Thermal conductivity Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction acids with 20e65% cross-linkers added [4]. By adding a large

Excellent insulation combined with good adhesion, high
strength-to-weight ratio and durability make polyurethane (PU)
rigid foam an indispensable material in the construction industry.
PU rigid foam accounts for about 23% of all PU production.
Like other polymers, PU rigid foams rely on petroleum feed-
stocks. Increasing concern over environmental impact and the
supply of petroleum have motivated the development of PU from
bio-renewable raw materials. According to a lifecycle comparison
conducted by Omni Tech International Ltd., soy-based feedstocks
showed 75% less total environmental impact than petroleum-based
feedstocks due to significant reductions in fossil fuel depletion,
global warming, smog formation, and ecological toxicity [1].
Natural oils have great potential to compete with petroleum in
producing polyols used to make PU. However, except for a few oils
like castor oil and lesquerella oil, most natural oils do not have
hydroxyl groups which are needed to form urethane links with
isocyanate [2,3]. The unsaturated sites in natural oils can be used to
introduce hydroxyl groups, and a number of methods have been
developed to synthesize natural oil-based polyols.
As early as 1974, Lyon prepared PU rigid foams from hydrox-
ymethylated castor oil, safflower oil, and polyol esters of castor
* Corresponding author. Tel.: þ1 612 625 0092; fax: þ1 612 626 1686.
E-mail address: macosko@umn.edu (C.W. Macosko).
1
Present address: HB Fuller, 1200 Willow Lake Blvd., Vadnais Heights, MN 55110,
USA.
amount of cross-linkers, these foams had satisfactory compressive
strength and resistance to shrinkage on humid aging. Rapeseed oil-
and palm oil-based polyols have been used to make PU rigid foams
as well [4,5]. In 1999, Guo and co-workers prepared HCFC- and
pentane-blown PU rigid foams from soy-based polyols made by
epoxidation followed by oxirane ring-opening [6]. However, these
foams were found to have inferior mechanical and thermal insu-
lating properties even with 10e25% glycerol added. Guo et al. [7]
continued to investigate the effect of soy-based polyol structures
on the PU rigid foams. They found that polyols with primary
hydroxyls reacted faster and more completely than polyols which
had secondary hydroxyls. The water-blown PU rigid foams
prepared from soy-based polyols by Narine et al. [8] showed very
low closed cell content. Tu et al. [9] prepared fifty vegetable oil-
based polyols and replaced 50% of the petroleum-based polyols in
water-blown PU rigid foams. However, most of the foams were
inferior to 100% petroleum-based PU rigid foams.
This previous work proved the feasibility and potential of
preparing PU rigid foams from soy-based polyols. However, even
with only partial substitution of petroleum-based polyols with soy-
based polyols, and with a large amount of cross-linkers added, soy-
based PU rigid foams had inferior properties, especially thermal
conductivity (k value) and to a certain extent compressive strength.
Furthermore, previous researchers have not studied the insulation
properties in detail in order to determine the mechanism of k value
aging. In an effort to understand how soy polyols affect foam
properties, we started with a standard formulation used to make
appliance insulation and partially or completely replaced the

0032-3861/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2011.04.040
 S. Tan et al. / Polymer 52 (2011) 2840e2846 2841

petroleum-based polyol with a soybean oil-based polyol (SBOP). Table 1

The density, cell morphology, compressive strength and k value Polyol properties comparison.

were compared. The loss of k value with aging was further inves- Polyol Control SBOP
tigated, the first study of long term insulation performance of soy- JeffolÒ FX31-240 X-0210
based PU rigid foams. OH number (mg KOH/g) 240 235
Molecular Weight (g/mol) 700 1100
Functionality 3.0 4.4
2. Experimental Viscosity (mPa s) 250 8900
Acid Value (mg KOH/g) e 1.7
2.1. Materials Water content (ppm) e 3000
Manufacture/Resource Huntsman Cargill

A commercially available petroleum-derived polypropylene-

based polyol, JeffolÒ FX31-240 (Huntsman International), was
chosen as the control polyol. A commercial soybean oil-based
polyol X-0210 (Cargill) was selected as the SBOP. Fig. 1 shows the
structure of the control polyol and the general structure of X-0210.
The properties of the two polyols are listed in Table 1. Note that the
viscosity and water content of the SBOP are significantly higher
than the control polyol.
The isocyanate was polymeric methylenediphenyl diisocyanate,
PMDI (Rubinate Ò M, Huntsman). Diethylene glycol (Huntsman
International) was used as a chain extender to avoid foam
shrinkage. N,N-Dimethylcyclohexylamine (PolycatÒ8, AirProducts,
CAS 98-94-2) was used as the gelation catalyst. Pentam-
ethyldiethylenetriamine (PolycatÒ5, AirProducts) was used as the
blowing catalyst. Polyether-modified polysiloxane (TEGOSTAB
B-8404, Goldschmidt Chemical Corporation) was the surfactant and
denoted as surfactant A. TEGOSTAB B-8404 is a general-purpose
silicone surfactant used in PU rigid foam formulations. It was
found to work satisfactorily for the SBOP system compared to other
surfactants [6]. In order to study the effect of surfactant hydro-
phobicity, BYK-LPX 7105 (BYK USA Inc.) which is much more
hydrophobic than TEGOSTAB B-8404 was also used. This surfactant
is denoted as surfactant B. The relative hydrophobicity was deter-
mined by a cloud point test of surfactant solutions. The physical
blowing agent is n-pentane (Anhydrous, 99%, AldrichÒ). Distilled
water was obtained in our laboratory. Water amount used was
adjusted according to the water content in the polyols. All the
chemicals were used as received.
2.2. Foam synthesis
A low isocyanate index formulation which is similar to those
typically used in appliance insulation for free rise foams was
selected. Table 2 lists the formulation details. The amount of each
ingredient was based on 100 parts by weight of total polyol.
Polyol, surfactant, distilled water, n-pentane, and catalysts were
weighed and placed in an 800 mL polypropylene cup. The mixture
was homogenized using a 10-mm drill (Delta VSR Drill, D21008)
equipped with a 2.8-in diameter mixing blade for 40e50 s, at
a speed of 2500 rpm. The pre-weighed PMDI was then added to the
mixture, and mixing was continued for another 10 s. The foam was
then allowed to rise freely at room temperature. The foams were
cut one week later and the properties of the foams measured,
including density, cell morphology, k value and its aging, and
dynamic mechanical properties.
2.3. Characterization
2.3.1. Foam reaction kinetics
In order to understand the effect of adding SBOP, foam kinetics
was studied. Adiabatic temperature rise is a simple and quick
method [10,11]. Since PU rigid foams are good insulating materials,
any container with a diameter over 5e10 cm is sufficient to maintain
adiabatic conditions in the center of the reacting mixture [11]. Given
the adiabatic conditions, isocyanate conversion can be calculated
from the temperature profile using Equations (1) and (2) [10].
r DTm
pðNCOÞ ¼ (1)
DTrxn
mw m
DHr;u þ DHr;r OH fn
Q Mw MOH
DTrxn ¼ ¼ (2)
Cp mT Cp m T
In the above equations, p is the isocyanate conversion; r is the
stoichiometric ratio of functional groups (kept to 1 in all our
experiments); ΔTm is the temperature rise during foaming; ΔTrxn is
the maximum temperature rise; Q is the total amount of heat
generated during foaming; Cp is the specific heat capacity of foam,
which is taken as 1.5 J/(g∙ K) based on DSC measurements of the
final foams; m is the reactant mass; ΔHr is the heat of reaction; M is
the molecular weight of reactant; fn is the functionality of the
polyol, subscripts u, r, w, T and OH represent urea, urethane, water,
total and polyol respectively. ΔHr,u and ΔHr,r were taken as
125.5 kJ/mol and 93.9 kJ/mol [12,13].
An insulated plastic cup with a diameter of about 10 cm was
used as the reaction vessel. The reaction mixture based on a total
weight of about 25g was prepared using the same foam synthesis
procedure as in section 2.2. Temperature profiles during foaming
were monitored using a type J thermo-couple with a 0.25 mm dia-
meter (OmegaÒ), which was connected to a digital-thermometer.
An adapter was used to connect the digital-thermometer to
a computer and the temperature was recorded. The physical

Fig. 1. Polyol structure: (left) control polyol, (right) major component in SBOP.
2842 S. Tan et al. / Polymer 52 (2011) 2840e2846

Table 2 120  C and held for 10 min, and finally heated at 10  C/min to 220  C.
Foam and film formulation. The value of the heat capacity at room temperature was determined on
Chemical Foam Film the second heating cycle [16]. The specific heat capacity of foam was
Weight (pbw)
DEG added Glycerol added
used to calculate thermal conductivity (k value) [17].
Polyol (petro/soy) 100 100 100
Diethylene glycol (DEG) 6.0 6.0 0 2.3.7. Thermal conductivity, k, measurement
Glycerol 0 0 16 Thermal conductivity or k value is the most important property
Water 2.6 0 0 for PU rigid foam [18e20]. A typical k value measurement is based
PolycatÒ 8 4.0 Vary Vary
on the rate of steady state heat transfer across a foam with known
PolycatÒ 5 1.0 0 0
Surfactanta 2.0 0 0
thickness, which is induced by two different known temperatures
n-pentane 8.0 0 0 between two opposite surfaces of the foam [18,20]. However, the
Acetone 0 125 125 current steady state method requires a large sample size, typically
Isocyanate 130 109.8 123.8 30.5 cm  30.5 cm  5 cm. This method is not suitable for lab scale
Isocyanate index 125 105 105
samples. Recently, Harikrishnan et. al. have reported a simple and
a
Surfactant A is TEGOSTAB B-8404 (Goldschmidt Chemical Corporation) and rapid technique based on a transient measurement using a needle
surfactant B: BYK-LPX 7105 (BYK USA Inc.)
probe [17]. This method is rapid with accuracy within 5%. It is
widely used in the measurement of k value and thermal diffusivity
blowing agent n-pentane was not used and the isocyanate index of liquids and solids [17].
was kept at 100 to make the reaction stoichiometrically balanced To evaluate the long term insulating performance of PU rigid
and thus isocyanate conversion depends only on the gelling and foams, an accelerated k value aging test was done. Foam cubes with
blowing reactions. An excess of isocyanate could lead to other 12 cm on a side were cut from the top of the cup foam. They were
reactions such as isocyanate trimerization and further reaction placed in an oven at 70  C and the k value measured periodically. It
between isocyanate and urethane. has been determined that the air ingress is 6e12 times faster at
70  C compared to room temperature [18].
2.3.2. Foam density
Foams from the core of the caps of the foam at the top of the cup 2.3.8. Dynamic mechanical analysis (DMA)
were cut into 2.5 cm cubes and weighed to determine density. A disk (8 mm diameter  8 mm thickness) was cut from the
Three to four pieces were cut from three different foam batches and foam and tested in sinusoidal oscillation between two 8-mm
the average density was reported. diameter serrated parallel plates (ARES, TA Instruments). Contact
was maintained by loading the sample at the plate temperature of
2.3.3. Scanning electron microscopy (SEM) 160  C and applying a constant normal force of 16  8 g throughout
Foams were cut with a razor blade into rectangular slices: the experiment. Strain sweep test was performed first to determine
7  10  3 mm. Each sample slice was sputter coated with a layer of the linear viscoelastic region of the sample. Storage modulus (G0 )
50 Å platinum. A JEOL 6500 field emission scanning electron and loss modulus (G00 ) were recorded at 1 Hz and 0.1% strain over
microscope was used to examine the cell morphology [14]. The a temperature range from 0 to 220  C at a temperature ramp rate of
sample was then attached to the stub using conductive carbon tape. 3  C/min.
The sample was imaged under an accelerating voltage of 10 kV and
37 magnification. The cellular structure of the foam was observed 3. Results and discussion
parallel to the free-rising direction. An average of 5 images was
collected on each foam. 3.1. Foam kinetics
In this study, apparent long axis, which is the maximum chord
length of a cell [15], was measured using ImageJ. The average cell In Fig. 2 the isocyanate conversion profile showed that foaming
size and its standard deviation were based on 100e150 cells. of 0% and 100% SBOP had the same isocyanate conversion in the

2.3.4. Closed cell content

Closed cell content was measured by gas displacement
following the standard procedures described in ASTM D-6226 using
Micromeritics AccuPyc 1340.

2.3.5. Compressive strength

Compressive strength was measured using ASTM D-1621 on
foam samples with dimensions of 5.0 cm  5.0 cm  2.5 cm. The
samples were placed between two parallel plates with a larger area
than the specimen and the force required to compress the foam at
the rate of 0.25 cm/min was measured. The compressive strength
was the value of the maximum applied force divided by the initial
sample surface area when the maximum applied force occurred
before the strain reached 10%. Otherwise, the compression applied
force was taken when the strain was 10%.

2.3.6. Differential scanning calorimetry (DSC)

DSC (Q1000, TA Instruments) was used to measure the heat capacity
of the foams. About 7e10 mg of compressed foam sample was loaded
into an aluminum standard inverted pan and sealed. The sample was Fig. 2. Isocyanate conversion from adiabatic temperature rise during foam formation
first heated at 10  C/min e 150  C and equilibrated for 2 min, cooled to for 0% and 100% SBOP.
 S. Tan et al. / Polymer 52 (2011) 2840e2846
first 20 s. After the initial 20 s, SBOP reacted slightly slower than
that of control, and reached a slightly higher plateau value of
isocyanate conversion. The isocyanate can react with water,
diethylene glycol and polyol. Based on their relative reactivity, the
first 20 s was mainly due to the reactions of isocyanate with water
and diethylene glycol. The slower reactivity afterward was mainly
due to the lower reactivity of the secondary OH groups in SBOP. For
the control, the reactions reached a plateau value by about 50 s,
while for SBOP it reached a plateau only after about 100 s. The
higher isocyanate conversion is probably due to the higher degree
of phase mixing in the soy-based foaming system.
3.2. Foam density, cellular morphology and compressive strength
The resulting foam properties are summarized in Table 3. The foam
density increased with increasing SBOP substitution but only signif-
icantly at 100% substitution. With the same SBOP substitution, foam
density did not change significantly between the two surfactants.
Good insulating performance of PU rigid foam requires high
closed cell content. All the soy-based PU foams had closed cell
contents comparable to the control foam (see Table 3). SEM images
(Fig. 3) showed that all the foams consisted of well-defined closed
cells regardless of the polyol type. Foams with 0% SBOP had the
largest average cell size. With SBOP substitution, PU rigid foams
had a smaller average cell size. We suggest that the higher viscosity
of SBOP (see Table 1) helped to reduce cell drainage by gravity at the
initial foaming stage which led to a smaller average cell size.
Using the more hydrophobic surfactant B, the average cell size
became even smaller. This suggested that it acted more strongly in
stabilizing cell structure. We don’t believe that this is due to the
different compatibilities of B-side (polyol, diethylene glycol, cata-
lyst, water, n-pentane and surfactant) with different surfactant
hydrophobicities. Our compatibility test [21] has shown that there
is no significant difference by using these two surfactants. Overall,
the SEM study suggested that cell morphology was not significantly
altered by substituting SBOP for the petroleum-based polyol in the
foam formulation.
Compressive strength also increased with soy substitution
(Fig. 4) possibly due to the decrease in cell size.
3.3. Dynamic mechanical properties
In Fig. 5, both G0 and tan (d) data were plotted for the foams from
0%, 25%, 50%, 75% and 100% SBOP. In the glassy state, all samples
had comparable plateau G0 values of about 2  106 Pa. The higher G0
for the 100% SBOP sample was due to the higher foam density. As
the SBOP substitution increased, glassy to rubbery transition shif-
ted gradually to higher temperatures. In the rubbery state, all foams
had comparable G0 of about 2  104 Pa. Tg was determined from the
peak in tan (d) and increased from 98  C to 142  C with increasing
SBOP substitution. With increasing SBOP substitution, the tan (d)
peak broadened possibly due to the SBOP being more heteroge-
neous in structure compared to the petroleum-based polyol.
Table 3
Foam properties comparison.
% SBOP 0 25 50
substitution
Density (kg/m3) 39.5  0.8 39.7  0.9 39.8
Tg ( C) 98 107 123
K value (mW/(m K)) 23.4  0.6 e 24.0
Closed cell content (%) 89.09  1.07 e 88.76
Cell size (mm) 431  91 392  84 390
a
Samples made with surfactant B, others with surfactant A.
2843
3.4. Thermal conductivity
Thermal conductivity is the key property that governs insulation
applications for PU rigid foams. k value is closely related to foam
density and cell morphology. Total k value consists of four parts:
lgas, lradiation, lsolid and lconvection [20]. Foams with a high density
have lower lradiation, but a higher non cellular PU portion leads to
higher lsolid. Though the PU solid only accounts for a small
percentage of the whole foam, it has a much higher k value
(220 mW/(m$K)) than the physical blowing agent gas n-pentane
(13.7 mW/(m$K)) and CO2 (15.3 mW/(m$K)). At a fixed foam
density, lradiation will decrease with decreasing cell diameter. It has
been reported that the k value increases substantially, nearly 50%,
as cell size increases from 0.25 mm to 0.6 mm [22]. The level of
closed cell content should also be kept as high as possible. Open
cells allow more convection, and even air to enter the foam, which
has much higher k value (24.9 mW/(m$K)) than that of n-pentane
and CO2 [18]. Thus, a low k value results from a low foam density,
a small average cell size and a high closed cell content.
Thermal conductivity or k value measurement was done on
samples from 0%, 50% and 100% SBOP. With surfactant A which was
more hydrophilic, foams from 50% SBOP had comparable density
and about a 10% smaller cell size, though 100% SBOP foams had
much higher density and an even smaller cell size, which led to
foam k value as low as control foams. The two surfactants of
different hydrophobicities gave foams with thermal insulating
properties comparable to the control foams.
3.5. Foam aging
Since PU rigid foams are largely used in building and appliance
insulation, the change in k value with time is also important. Long
term insulating performance was investigated by an accelerated
foam aging test. Fig. 6 showed the foam aging results for 0%, 50%
and 100% SBOP for both surfactants. All these curves showed an
initial rapid k value increase, followed by a more gradual increase
after 50 days. Foams from 50% SBOP with both surfactants had very
similar k value aging as the 0% SBOP foams; k value had only
increased from 23 to 24 mW/(m$K) to about 26.5e27 mW/(m$K)
after 150 days of aging. However, the foams from 100% SBOP aged
faster. The k value increased from about 24 mW/(m$K) to as high as
28.5 mW/(m$K). With the more hydrophobic surfactant B, foams
from 100% SBOP aged even faster, with the k value increasing to
about 30.5 mW/(m$K). The foam aging tests for both surfactants
revealed that soy-based foams from 100% SBOP had faster k value
aging compared to control foams and soy-based foams from 50%
SBOP.
3.6. PU film gas permeability study
Over time, PU rigid foams will undergo k value changes due to
the change in gas composition. For freshly made PU rigid foam, the
gas trapped inside the cell is a mixture of mostly physical blowing
75 100 50a 100a
 1.1 41.3  1.3 46.4  2.0 40.0  1.0 49.0  1.8
134 142 110 143
 0.6 e 24.2  0.6 23.3  0.2 24.9  0.7
 0.44 e 90.68  0.44 e e
 102 375  128 386  102 360  94 349  103
2844 S. Tan et al. / Polymer 52 (2011) 2840e2846
Fig. 3. Foam SEM images: (a) 0%; (b) 50%; (c) 75% and (d) 100% SBOP, surfactant A.
agent (n-pentane in this study), some CO2, and a small amount of
air. Driven by the partial pressure difference between foam cells
and the atmosphere, air will gradually diffuse into the cells. Simi-
larly, CO2 and pentane will diffuse out of the cells. Generally, CO2
diffuses out much faster than other gases [23]. The process of air
diffusion is slower than CO2, but it’s concentration inside the cells
will gradually increase with N2 building up faster than O2. For
physical blowing agents like CFC and HFC, and pentane, the
permeability is very low [23]. Since both N2 and O2 have higher k
values than CO2 and n-pentane, the change in gas composition
leads to the increase in k value over time.
In order to determine whether the faster k aging was due to
higher gas permeability with SBOP substitution, gas permeation
Fig. 4. Compressive strength of PU rigid foams.
through a PU thin film, which can represent the polymer in the PU
rigid foam, was measured. This method eliminates the influence of
foam cell morphology but requires high quality film samples. The
film formulation is listed in Table 2.
3.6.1. Film preparation
Since isocyanate can easily react with water and moisture in the
air, the most difficult part was to avoid producing bubbles during
the preparation procedure. Water was not added because urea
linkages in the polymers only slightly affect the gas permeation
[24]. Polyols were dried under high vacuum, high temperature
(110  C), and high speed stirring for 2e3 h before use. Acetone was
used to dilute the reaction mixture. This not only helped to make
a thin and homogeneous film, but also helped to avoid trapping
bubbles. The amount of catalyst was also adjusted to balance the
rate of the gelling reaction and acetone evaporation. The gelling
reaction should be fast enough to avoid the reaction between
isocyanate and moisture as much as possible, but should be slow
enough for most of the acetone to evaporate.
PU thin films of 300e500 mm thickness were prepared in an
open-faced film casting mold [21]. The mold was made from
a 35.6 cm  35.6 cm high density polyethylene (HDPE) sheet with
an aluminum picture frame with a height of 2.5 cm. Prior to casting
the films, the mold was carefully leveled in order to obtain
a uniform film thickness.
Polyol, DEG, catalyst and isocyanate were blended with acetone
in a 200 ml polypropylene plastic cup. The mixture was stirred
gently until a homogeneous solution was formed. The solution was
then poured into the mold carefully to avoid air entrainment.
Another HDPE sheet was placed over the aluminum frame about
1 cm above the film to allow bubbles to escape and prevent direct
contact with moist air. The film was kept at room temperature for
24 h, during which the solution gradually solidified and most of the
acetone had evaporated. The film was removed from the HDPE
 S. Tan et al. / Polymer 52 (2011) 2840e2846
Fig. 5. (a) Dynamic elastic modulus, G0 and (b) tan (d) vs. temperature.
sheet and cut into disks having a diameter of 4.2 cm. The disks were
placed between MylarÒ sheets for further curing at room temper-
ature for 120 h. A heavy piece of steel was placed on top to ensure
film flatness. The disks were then placed in a vacuum oven for
a final cure for 48 h.
Fig. 6. Thermal conductivity increase with time at 70  C.
2845
Fig. 7. N2 permeation of PU thin films. (- SBOP with DEG, , SBOP without DEG;
B SBOP with glycerol) (Barrer ¼ 3.348  1019 kmol m/(m2 s Pa)).
3.6.2. Gas permeation measurement
Gas permeation tests based on a constant volume-variable
pressure method [25,26] were performed on a home-built appa-
ratus [26]. The film was fit and sealed into the gas transmission cell to
form a semi-barrier between the two chambers. The apparatus was
evacuated overnight. N2 flow was fed to one side of the chamber and
the pressure change in the opposite chamber which had been
evacuated was monitored as a function of time. Gas permeation
constants were obtained from the pressure change normalized with
the pressure gradient across the sample, film area and thickness [27].
Fig. 7 illustrates the N2 permeation results of PU thin films from
0%, 50% and 100% SBOP. It was found that by substituting 50% SBOP,
N2 permeation did not change significantly. However, films from
100% SBOP had a much higher N2 permeation, almost as twice that
of the control films. The N2 permeation results showed good
agreement with the foam k value aging results. The much higher N2
permeation of the 100% SBOP PU thin film led to faster k value aging
than the control or 50% SBOP PU thin film.
Another study was done to investigate the effect of a chain
extender and a cross linker on N2 permeation of soy-based PU thin
films. PU thin films were made from pure SBOP (i.e. without dieth-
ylene glycol), as well as SBOP with glycerol instead of diethylene
glycol. Samples from pure SBOP had higher N2 permeation than the
samples from SBOP with diethylene glycol. However, by adding
glycerol instead of diethylene glycol, N2 permeation dramatically
decreased. The gas permeation test has shown that the addition of
a chain extender or a cross linker can decrease N2 permeation.
4. Conclusions
PU rigid foams were prepared from a soy-based polyol, SBOP. The
experimental results demonstrated that by replacing a typical
petroleum-based polyol with SBOP, Tg increased and foams had
comparable foaming kinetics, density, cellular morphology, and
initial thermal conductivity (k value). Compressive strength of the
soy-based PU rigid foams were superior to those of petroleum-based
foams possibly due to smaller cell size. However, while foams from
50% SBOP showed similar k value aging to control foams, foams from
100% SBOP aged much faster. The mechanism behind foam k value
aging was studied by measuring the N2 permeation of PU thin films.
It was found that PU thin films with 50% SBOP substitution had
2846 S. Tan et al. / Polymer 52 (2011) 2840e2846

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