In the Laboratory

Formulation, Preparation, and Characterization of

Polyurethane Foams
Moise s L. Pinto
Department of Chemistry and Biochemistry, and CQB, Faculty of Sciences, University of Lisbon, Ed. C8,
Campo Grande, 1749-016 Lisboa, Portugal
moises.pinto@fc.ul.pt

Polymer chemistry, although recognized as an important part
of chemistry, does not find a significant presence in many under-
graduate chemistry curricula. However, polymer chemistry should
be given appropriate attention in undergraduate curricula because
of its importance in the chemical industry and in understanding
chemical principles (1). This article describes a simple and
illustrative laboratory experiment with polyurethane foams that
can be implemented in the undergraduate chemistry curricula.
Polyurethanes are an important class of polymers used to
produce a large number of products. The polyurethane applications
as coatings, foams, fibers, and elastomers demonstrate the flexibility of
urethane chemistry and the creativity of polymer scientists. However,
experiments for producing polyurethanes in the laboratory, especially
as foams, are not easily available. The experiment described here
provides a simple procedure to synthesize polyurethane foams.
This experiment has been used as second-year laboratory project
for a technological chemistry course. The methodology and reagents
are similar to those used in polyurethane industry, which provides
students with the knowledge and skills required to produce poly-
urethanes. The student response to the experiment was positive since
they acknowledged the direct relation of this laboratory experiment
with the production methods used in industry. This aspect increased
their interest and motivation because they recognize that they were
acquiring skills that may be applied in real-world polymer production.
alcohol (OH) groups must be equal. In practice, a small
isocyanate excess is used to compensate for the moisture
(water) usually present in polyols, which also reacts with
isocyanates. The so-called NCO index is a measure of the ratio
between the amount of NCO and OH groups in a given
formulation, that is, (amount of NCO)/(amount of OH). For
example, a formulation with 1.05 NCO index has a 5% excess
(in moles) of NCO groups than needed to completely react with
the OH groups.
To produce foams, a gas must be injected or formed at the
same time that the polymerization occurs. Different methods can
be used for this purpose. The use of low boiling point solvents
that vaporize during polymerization, carbon dioxide injection in
the molds, or adding water to the formulation are common
methods. The use of Freon for this purpose has been banned
because of environmental regulations. When water is used, the
formation of carbon dioxide occurs by reaction with isocyanate:

Formation of Polyurethanes The intermediate carbamic acid decomposes to carbon dioxide

Industrially, polyurethanes are produced by the reaction
between a polyisocyanate and a polyol (also called polyalcohol).
A complete discussion of the chemistry and properties of poly-
urethanes is outside the scope of this article, but can be found in
other publications (2-4). Nevertheless, a small introduction to
the main chemical reactions will be given with a discussion on their
implications for calculating the required reactant amounts. The
polymerization reaction for producing polyurethanes involves the
condensation of a polyisocyanate and a polyol, for example,
To have a complete polymerization of the monomers (polyol and
polyisocyanate molecules), the amount of isocyanate (NCO) and
and an amine. The amine then reacts with another isocyanate to
produce a urea
Thus, each mole of water consumes two isocyanate moles and
generates 22.4 dm3 of carbon dioxide gas (considering standard
pressure and temperature). A surfactant is usually used in the
formulation to help the stabilization of the gas-liquid emulsion
during the initial moments of foam formation; poly-
ether-polysiloxane copolymers are commonly used. An instruc-
tive discussion on foam formation is presented elsewhere (5).
Calculations
To calculate the required amounts of reagents for a poly-
urethane formulation, all of the above reactions must be consid-
ered. The calculations can be used to show students that basic

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10.1021/ed8000599 Published on Web 01/12/2010

chemistry principles are essential in developing polyurethane
formulations. It is helpful to introduce the concept of the
equivalent number of reacting groups, neq, defined as the amount
of reacting groups (OH or NCO) per mass of reagent (usually in
units of mmol g-1). For the case of water, 2 mol of NCO groups
reacts with 18.02 g of water (1 mol), which gives neq(H2O) =
(2 mol)/(18.02 g) = 111.1 mmol g-1. The fundamental idea that
follows is to ensure that the amount of isocyanate groups present in
the reacting mixture is sufficient to react with all the alcohol groups
of the polyol and also with the water. Considering this and also
that, as discussed above, a small excess of polyisocyanate is usually
used, the following equation can be written
misoneq iso mH2 Oneq H2 O mpolyneq polyiNCO
where m(iso), m(H2O), and m(poly) are the masses of poly-
isocyanate, water, and polyol, respectively, neq(iso), neq(H2O), and
neq(poly) are the equivalent numbers of polyisocyanate, water, and
polyol, respectively, and iNCO is the desired NCO index for the
formulation. This equation can be applied to calculate the mass of
polyisocyanate to be used with a given mass of water and polyol to
produce a polyurethane foam. Sometimes difficulties arrive in
knowing the neq(iso) and neq(poly) values for a particular polyol or
polyisocyanate because most suppliers do not characterize their
products with the equivalent number. Polyols are normally
characterized by their OH content in mass equivalent of KOH
per mass of polyol: mg(KOH) g-1. This value can be converted to
neq by simply dividing by the KOH molar mass (56.11 g mol-1).
The percentage of NCO in the polyisocyanate (in mass of NCO
per total mass) is usually used to characterize the polyisocyanates
and this can be converted to neq taking into account the NCO
molar mass (42.02 g mol-1). The number of OH or NCO groups
in the molecule, that is, the functionality of the molecule
(polyisocyanate or polyol), can also be used to obtain the neq
required for the calculations presented above. Additional details
are available in the supporting information.
Experiment
Overview
The experimental details to produce and determine the
apparent bulk densities of foams are given in a later section. They
should be regarded as guidelines to the activities that may be
developed in the laboratory with polyurethane foam synthesis.
Students should be challenged to propose new formulations,
based on known formulations, and make the correspondent
calculations for the quantities of reagents to use. These new
formulations are tested during their work in the laboratory to
support some conclusions about the changes they made. This
approach compels the students to understand the function of
each component in the formulation by observing the effect of
their variation in the reaction and final properties of the foam
materials.
Reagents
The experimental procedure is similar to standard produc-
tion procedures used in industry but at laboratory scale. Usually
the first step is to formulate the polyol by mixing all additives
(catalysts, surfactants, and blowing agents) with the polyol (or
polyols) to obtain a homogeneous mixture called formulated
polyol. The second step is to mix the necessary amount of the
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r 2010 American Chemical Society and Division of Chemical Education, Inc.
In the Laboratory
Table 1. Quantities of MDI and Water in the Formulation of Polyur-
ethane Foams
Foama MDI/g Water/cm3
1 11.5 0.60
2 12.3 0.65
3 13.1 0.70
4 13.9 0.75
5 14.7 0.80
a
Fixed quantities of glycerol propoxylate (20.0 g), DBTL (0.2 g), and
silicone oil (0.4 g) were used.
polyisocyanate with the formulated polyol. Some chemical
companies sell polyols already formulated to be used by mixing
with the polyisocyanate, which are called two-component
systems. Therefore, the procedure that follows gives students a
good idea of what happens in the polyurethane industry, from
the formulation step until its production and use.
Several formulations could be tested, but for clarity, only
one representative series is presented. For the formulated polyol,
glycerol propoxylate (Aldrich, Mn 3600, 41 mg(KOH) g-1) is
used as the triol, dibutyltin dilaurate (DBTL) (Merck, >97%) is
used as the catalyst, and silicone oil (Dow Corning, 193
Surfactant) is used as the foam stabilizer. The polyisocyanate is
diphenylmethane 4,40 -diisocyanate (MDI) (Merck, mixture of
di- and triisocyanates for synthesis). The component quantities
of the formulations are listed in Table 1. The main difference
among the foams is the water content used to obtain foams with
different densities. The polyisocyanate must also be varied
accordingly, as can be seen in Table 1, to compensate for the
additional amount of OH groups in the reaction mixture and to
maintain the NCO index.
Foam Preparation
The required quantities (see Table 1) of polyol, distilled
water, silicone oil, and catalyst are added in a flat-bottom
polyethylene beaker (500 mL). A balance with 0.1 g precision
is used to measure the component quantities; however, the
volume of water is measured with a graduated pipet. The
components are mixed vigorously for 1 min with a mechanical
stirrer to obtain the formulated polyol. The isocyanate is then
added to the same beaker and rigorously stirred for 15 s. The
resulting mixture should be left undisturbed for 1 min, which
allows the formation and growth of the foam. A small increase in
the beaker temperature is noticed, as polymerization reactions
are exothermic. It is not necessary to control the reaction
temperature and the vessel should be opened to the surround-
ings, which allows the generated heat to be released. Under these
conditions, the temperature increase (T) in the vessel walls is
between 30 and 35 C, depending on the reagent's initial
temperature. The initial mixture (about 30 cm3) expands
to produce foams between 250 and 350 cm3 in volume (8 to
12 times its initial volume), depending on the water quantity
used and temperature conditions. It is not required to use a fume
hood during the synthesis if the recommended MDI is used.
However, if another polyisocyanate such as toluene diisocyanate
(TDI) is used, the synthesis of the foam and handling of TDI
must be in a fume hood (see supporting information).
After 1 h, the foams can be removed from the beaker.
However, the foams should cure for at least 1 week before
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 In the Laboratory
making the density measurements. The polyethylene beaker is
the best choice for performing the foam synthesis because it is
easy to detach the foam from this type of material. In addition,
some pressure must be applied to the foam and the beaker to
remove the foam, and the risk of beaker breakage is avoided if it is
made from polyethylene or another thermoplastic.
An interesting alternative to the described synthesis procedure
is to use molds with different shapes (preferably made of some
thermoplastic). To do this, simply pour the final liquid mixture into
the mold and remove the foam after 1 h. This can be used to
pedagogically illustrate the industrial benefits of the polyurethane
foam technologies, that is, obtaining foam objects with different
shapes. In fact, molding is commonly used in the polyurethane
industry to obtain a range of products. For example, in the
automotive industry, the polyurethane foam molding is used to
produce steering wheels, car seats, and car consoles, among others.
The soles of many sport shoes are also produced in an analogous way.
Density Measurement
During the synthesis of foams, students can evaluate the
effect of the quantity of water on the foam rise inside the flasks.
The students can easily observe that the foams with more water
tend to expand and raise more. Differences among samples can
also be observed in the cellular structure of the foams because
foams produced with more water quantities have larger cells.
This can be explained by the quantity of CO2 generated, which is
proportional to the water content in the formulation. Usually
the water content is expressed as a percentage of polyol mass, that
is, mass of water per mass of polyol. These differences are
reflected in the apparent bulk density of the foams and can be
quantified by a simple procedure. The apparent bulk density
reflects the density of the cellular material including the cells (6).
In fact, the cells are small holes in the polymeric material and,
thus, when their volume is considered, the apparent density
becomes much lower than the effective density of the polymer,
which constitutes only the cell walls.
The apparent bulk density of the synthesized foams is
measured in this experiment by determining the mass and
geometric volume of foam samples. From the synthesized foam
samples, students cut small cubes of known size (about 1 to 2 cm
per side) using a sharp knife. The sizes of the samples are
determined using a ruler or a Vernier caliper. In principle, one
cube per foam type is sufficient, but more may be made to obtain
replicate measurements. If a cork borer is available, it can be used
instead to cut foam cylinders of known size. The geometrical
shape of the samples should be as perfect as possible since the
volume will be estimated using the mathematical definition for
the chosen geometrical shape. The foam cubes are weighed using
an analytical balance with at least 1 mg precision. The apparent
bulk density, dapp, can then be calculated by,
m from the main trend of the data. This is caused by a foam collapse
dapp
V
where m is the mass and V is the geometrical volume.
Alternatively, the volume of the samples can be determined
by submerging the foam samples in a half-full measuring cylinder
and record the rise in the water level. A small thin wire or spatula
can be used to pull down the foam piece inside the water.
However, if this approach is followed, the sample weighing
should be made before the volume measurement, to avoid errors
in the mass determination due to excessive moisture in samples.
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214 Journal of Chemical Education Vol. 87 No. 2 February 2010
Figure 1. Apparent bulk density of foam produced using the formula-
tions listed in Table 1. The bars represent the typical standard deviation of
measurements ((2.5 kg m-3).
Hazards
MDI is irritating to eyes, respiratory system, and skin.
Polymeric MDI is the least hazardous of the commonly available
polyisocyanates as it has low vapor pressure (7). This reduces its
hazards during handling compared to the other common poly-
isocyanates (TDI, HDI), but, similar to the other polyisocya-
nates, is an allergen and sensitizer (7, 8). MDI reacts with
hydrogen donors, in some cases violently, and the reaction with
water produces carbon dioxide, which can burst containers if
water is allowed to enter. Dibutyltin dilaurate is toxic if
swallowed and is irritating to eyes and skin. It is also toxic to
aquatic organisms, causing long-term adverse effects in the
aquatic environment. Glycerol propoxylate and silicone oil are
slightly hazardous in case of skin contact (irritant), of eye contact
(irritant), and of ingestion.
Care should be taken when handling the mechanical stirrer.
The sharp instrument used to cut the specimens must be handled
with care.
Results
It is expected that the apparent bulk density decreases with
increasing water content in the formulation. Quite often, the
masses of the formulation components are expressed as mass
percentage of the polyol to indicate their content in the formula-
tion. The results obtained for some foam samples are plotted in
Figure 1. The error bars represent the typical standard deviation of
replicate measurements ((2.5 kg m-3). The apparent bulk density
decreases with the water content and varies from 54 to 33 kg m-3.
The foam at the highest water content (4%, foam 5) shows an
increase relative to previous foam (at 3.75%, foam 4) and deviates
during the foam rise, allowing some CO2 to escape without
expanding the polymer. This happens when too much gas is
produced and the surfactant used (silicone oil) cannot sufficiently
stabilize the emulsion. The water content at which this behavior
will start to occur depends on the type and quantity of surfactant
used.
The students use the data collected from their experiments
to plot a graph similar to that shown in Figure 1. Students should
realize that the results obtained are apparent density values, and
for this, it may be helpful to compare the obtained values with the
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pubs.acs.org/jchemeduc r 2010 American Chemical Society and Division of Chemical Education, Inc.

densities of common substances (liquids or solids), for example,
water as a density of about 1000 kg m-3 (1 g cm-3), which is
about 20 times more than the highest value in Figure 1. However,
the polyurethane polymer density of the sample series is on
average 1700 kg m-3 (determined with a gas pycnometer), which
means that if nonfoamed polyurethane were produced it would
not float in water, contrary to the foam samples. A nonfoamed
polyurethane sample may be produced simply by not using water
in the formulation (and adjusting the MDI quantity to 2 g), but
some difficulties may occur to remove the produced sample and
also to obtain a true nonfoamed material, since small quantities
of water are often present in the polyols.
Each student group (3 to 4 students per group) writes a lab
report due the session after the experimental work is complete
(usually two sessions are needed for the experimental work).
Student groups are allowed to share data with other groups,
especially the data obtained with the unique formulation deve-
loped by each group. The student groups must answer questions,
which directs them to conclusions about polyurethane foams
and formulations. (The questions are available in the supporting
information.) Before starting the experiment, students are
instructed to read the questions so they can plan additional
experiments that allows them to obtain results to support their
answers.
Additional Activities
The polymer samples produced using this experimental
procedure can be tested in the laboratory to determine other
important properties besides the apparent bulk density. The
given formulation produces polyurethane foams with elasto-
meric properties; thus, the tensile and mechanical properties can
be determined in samples using relatively simple procedures
(9, 10). Some small changes can be made in the formulation
by adding a short chain polyol, such as glycerol, to increase the
foam stiffness (see the supporting information).
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r 2010 American Chemical Society and Division of Chemical Education, Inc.
In the Laboratory
The rubber (elastic) properties of the polyurethanes may
also be useful in the introduction to more theoretical aspects of
chemistry. In fact, the rubber-like properties have been proposed
by several authors to introduce basic concepts in physical
chemistry and thermodynamics to students (11-14).
Literature Cited
1. Stenzel, M. H.; Barner-Kowollik, C. J. Chem. Educ. 2006, 83,
15211530.
2. Seymour, R. B.; Kauffman, G. B. J. Chem. Educ. 1992, 69, 909910.
3. Bailey, M. E. J. Chem. Educ. 1971, 48, 809813.
4. Woods, G. The ICI Polyurethanes Book, 1st ed.; John Wiley and
Sons: New York, 1987.
5. Hansen, L. D.; McCarlie, V. W. J. Chem. Educ. 2004, 81, 1581
1584.
6. D1622-98, Standard Test Method for Apparent Density of Rigid
Cellular Plastics; American Society for Testing and Materials:
West Conshohocken, PA, 1998.
7. NIOSH Safety and Health Topic: Isocyanates. http://www.cdc.
gov/niosh/topics/isocyanates/ (accessed Nov 2009).
8. Hocking, M. B.; Canham, G. W. R. J. Chem. Educ. 1974, 51,
A580A581.
9. Gilmer, T. C.; Williams, M. J. Chem. Educ. 1996, 73, 10621065.
10. Stevens, E. S.; Baumstein, K.; Leahy, J. M.; Doetschman, D. C.
J. Chem. Educ. 2006, 83, 15311533.
11. Mark, J. E. J. Chem. Educ. 2002, 79, 14371443.
12. Pellicer, J.; Manzanares, J. A.; Zuniga, J.; Utrillas, P.; Fernandez, J.
J. Chem. Educ. 2001, 78, 263267.
13. Smith, B. J. Chem. Educ. 2002, 79, 14441452.
14. Smith, B. J. Chem. Educ. 2002, 79, 14531461.
Supporting Information Available
Supplemental material and instructor notes on calculations, poly-
ols, isocyanates, CAS numbers, and alternative formulations. This
material is available via the Internet at http://pubs.acs.org.
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