Effect of Structure on Properties of Polyols and

Polyurethanes Based on Different Vegetable Oils

ALISA ZLATANIĆ, CHARLENE LAVA, WEI ZHANG, ZORAN S. PETROVIĆ

Kansas Polymer Research Center, Pittsburg State University, 1501 S. Joplin Street, Pittsburg, Kansas 66762

Received 23 April 2002; accepted 15 September 2003

ABSTRACT: We synthesized six polyurethane networks from 4,4⬘-diphenylmethane di-

isocyanate and polyols based on midoleic sunflower, canola, soybean, sunflower, corn,
and linseed oils. The differences in network structures reflected differences in the
composition of fatty acids and number of functional groups in vegetable oils and
resulting polyols. The number average molecular weights of polyols were between 1120
and 1300 and the functionality varied from 3.0 for the midoleic sunflower polyol to 5.2
for the linseed polyol. The functionality of the other four polyols was around 3.5.
Canola, corn, soybean, and sunflower oils gave polyurethane resins of similar crosslink-
ing density and similar glass transitions and mechanical properties despite somewhat
different distribution of fatty acids. Linseed oil– based polyurethane had higher
crosslinking density and higher mechanical properties, whereas midoleic sunflower oil
gave softer polyurethanes characterized by lower Tg and lower strength but higher
elongation at break. It appears that the differences in properties of polyurethane
networks resulted primarily from different crosslinking densities and less from the
position of reactive sites in the fatty acids. © 2004 Wiley Periodicals, Inc. J Polym Sci Part
B: Polym Phys 42: 809 – 819, 2004
Keywords: vegetable oil; polyol; polyurethane; structure

INTRODUCTION the number of hydroxyl groups in the polyols,

Oils are an excellent renewable source for chem-
ical industry and particularly for polymer appli-
cations. Because they are relatively unreactive,
they must be functionalized to serve as building
blocks for polymers. Introduction of hydroxyl
groups at the position of double bonds opens the
whole area of applications in polyurethanes. If the
triglyceride structure were preserved, polyols
usually would have functionality greater than
two, giving with diisocyanates thermosetting
polyurethane networks. Network properties
would depend on the crosslinking density, that is,
Correspondence to: Z. Petrovic
pittstate.edu)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 42, 809 – 819 (2004)
© 2004 Wiley Periodicals, Inc.
their distribution in the oil (zero, one, two, three,
or more per fatty acid), and the position in the
fatty acid chain (in the middle or closer to the end
of the chain). Thus, the properties are expected to
depend on the type of vegetable oil. In this work
we studied the effect of structure of six vegetable
oils, canola, midoleic sunflower, soybean, linseed,
sunflower, and corn oil, on properties of polyols
and resulting polyurethane networks. Four oils
(canola, sunflower, soybean, and corn) have sim-
ilar content but different distribution of double
bonds. Linseed oil has the highest and midoleic
sunflower the lowest double bond content of all
oils used in this work.
The transformation of the double bonds of trig-
(E-mail: zpetrovi@ lycerides to hydroxyls and their application in
urethane chemistry have been the subjects of
many studies.1–9 Our group paid special attention
809
810 ZLATANIĆ ET AL.
Figure 1. Reactive sites on different fatty acid
chains.
to the functionalization of soybean oil and the
structure–properties relationship in polyols and
the resulting polyurethanes.10 –16 The structure of
natural oils regarding the type, composition, and
distribution of fatty acid residues in the triglyc-
eride molecules is complex.17 Every oil or fat has
a characteristic fatty acid profile which is unique
to the type of oil. Variability in composition is
expected even in the same type of oil, depending
on the local weather conditions, soil, and plant
characteristics. The principal variation in fatty
acids composition of the oils results from varia-
tions in chain length and the degree of unsatura-
tion. As a consequence, there is variation in the
length of elastically active network chains
(EANC) and dangling chains (DC) in polyure-
thane networks, obtained from oil-based polyols.
Dangling chains are the elastically inactive part
of the polymer structure, which do not support
stress when the sample is under load, but rather
act as a plasticizer. They result from saturated
fatty acids and the portion of fatty acids between
the functional group (usually at the 9th or 10th C
atom) and the chain end. The reactive sites in
polyols with different fatty acids are located on
the 9th or 10th carbon in oleic, linoleic, and lin-
olenic, but the last two have additional OH
groups on 12th or 13th, and linolenic may have an
additional OH group on the 15th or 16th carbon
as depicted in Figure 1.
Thus, to draw conclusions about the effect of
structure on the properties, it is important to
know the exact composition of the oil. Table 1 lists
the fatty acid profiles of the six vegetable oils used
in this study. The polyols were synthesized by a
two-step process: epoxidation followed by ring
opening. The polyols were characterized by mea-
suring the hydroxyl content, molecular weight
and distribution, density, viscosity, and melting
points. Polyurethanes were prepared by reacting
the polyols with 4,4⬘-diphenylmethane diisocya-
nate (MDI). The reactive sites in polyols having
different fatty acids are located on the 9th or 10th
carbon in oleic, linoleic, and linolenic, but the last
two have additional OH groups on the 12th or
13th and linolenic may have an additional OH
group on the 15th or 16th carbon as depicted in
Figure 1.
Crosslinking density of polymer networks was
assessed from swelling in toluene. We used differ-
ential scanning calorimetry (DSC), thermome-
chanical analysis (TMA), dielectric analysis
(DEA), dynamic mechanical analysis (DMA), and
mechanical methods to study the physical, ther-
mal, dielectric, and mechanical properties of poly-
urethanes.
EXPERIMENTAL
Materials
Six vegetable oils of refined, bleached, and de-
odorized grade from canola, soybean, midoleic
sunflower, sunflower, corn, and linseed, together
with fatty acid profiles (Table 1) were supplied by
Archer Daniels Midland. Hydrogen peroxide was
purchased from Sigma as 30% w/w solution. Ion-
exchange resin Amberlite IR-120 in acid form was
supplied from Supelco. Tetrafluoroboric acid (48%
solution in water) was purchased from Aldrich.
Toluene [high-performance liquid chromatogra-
phy (HPLC) grade], methanol (99%), glacial acetic
acid (certified A.C.S. Plus), ethyl acetate (HPLC
grade), methylene chloride (HPLC-GC/MS grade),
anhydrous sodium sulfite, and anhydrous sodium
sulfate were purchased from Fisher Scientific. Ion
exchange resin Lewatite MP-64 was purchased
from Bayer. Mondur M obtained from Bayer is
4,4⬘-diphenylmethane diisocyanate. It was puri-
fied by distillation under reduced pressure.
Methods
We determined iodine value, as the measure of
concentration of double bonds, according to the
Hanus method.18 Epoxy oxygen content determi-
nation was carried out according to the standard
procedure for oils and fats.19 The hydroxyl values
of the polyols were determined according to a
modified ASTM titration method (D 1957-86)
 POLYOLS, POLYURETHANES FROM VEGETABLE OIL 811

Table 1. Fatty Acid Profilea in Vegetable Oils

Midoleic Soybean Linseed Sunflower

Sample ID Canola Oil Sunflower Oil Oil Oil Oil Corn Oil

Caproic C6:0 0.02

Lauric C12:0 0.02
Myristic C14:0 0.04 0.09 0.05 0.03 0.06
Palmitic C16:0 4.09 4.11 10.88 5.48 5.59 10.81
Palmitoleic C16:1 0.21 0.05 0.07 0.06 0.06 0.11
Heptadecanoic C17:0 0.05 0.04 0.09 0.05 0.05 0.09
Heptadecenoic C17:1 0.09 0.04 0.04 0.04 0.01 0.03
Stearic C18:0 1.86 3.79 4.18 3.52 4.46 1.85
Elaidic C18:1n9t 0.08 0.09 0.05 0.04
Oleic C18:1n9c 56.11 57.15 22.69 18.88 22.18 27.25
C18:1 cis 4.67 1.41 2.21 1.25 0.92 0.95
C18:2 trans 0.02 0.02
C18:2 9c12t 0.16 0.19 0.15 0.06 0.31 0.29
C18:2 12c9t 0.14 0.18 0.13 0.27 0.27
Linoleic C18:2cc 21.01 31.40 52.41 16.10 64.22 56.96
C18:2 cis 0.01 0.05
Arachidic C20:0 0.60 0.25 0.26 0.12 0.24 0.30
C18:3 trans 0.04
C18:3n6t 0.53 0.02 0.17 0.19 0.02 0.04
Eicosenoic C20:1c 1.70 0.21 0.30 0.14 0.19 0.20
Linolenic C18:3n3c 7.89 0.31 6.06 53.73 0.42 0.65
Heneicosanoic C21:0 0.01 0.01 0.02 0.02
Eicosadienoic C20:2cc 0.06 0.02
Behenic C22:0 0.17 0.46 0.14 0.04 0.41 0.03
Eicosatrienoic C20:3n6c 0.05
Erucic C22:1 0.12
Lignoceric C24:0 0.05 0.03 0.06
Nervonic C24:1 0.05
Total trans FAs 0.95 0.50 0.52 0.25 0.65 0.60
Total C18:1 FAs 60.85 58.64 24.95 20.14 23.15 28.19
Total C16:1, C20:1,
C22:1, C24:1 FAs 2.08 0.26 0.37 0.20 0.25 0.31
Total C18:2 FAs 21.33 31.79 52.72 16.21 64.80 57.52
Total C20:2, C22:2 0.06 0.00 0.02 0.00 0.00 0.00
Total C18:3 FAs 8.46 0.33 6.23 53.92 0.44 0.69
Total C20:3 FAs 0.05 0.00 0.00 0.00 0.00 0.00
Total saturated FAs 6.78 8.69 15.60 9.27 10.85 13.10
Totals 99.61 99.71 99.89 99.74 99.49 99.81

*Wt % of fatty acids.

with isopropanol instead of ethanol. The number-
average molecular weights of polyols were deter-
mined with a vapor pressure osmometer (Osmo-
mat 070; UIC, Inc.). Measurements were per-
formed at 60 °C in toluene. Benzil was used as the
calibration standard.
We used a Waters gel permeation chromato-
graph, consisting of a 510 pump, 410 differential
refractometer, and the data collection system, to
determine the molecular weight distribution of
epoxidized vegetable oils and polyols. The flow
rate of the tetrahydrofuran eluent was 1 mL/min
at room temperature. Three Styragel HR columns
from Waters, covering an MW range from 102 to
106, were used. We performed calibration using
nine polystyrene standards with narrow molecu-
lar weight distribution.
The polyol viscosities were measured at 27 °C
with the Rheometric SR-500 Dynamic Stress Rhe-
ometer in the stress-controlled mode, between
parallel plates 25 mm in diameter and with a gap
of 0.20 mm. We measured the densities of polyols
812 ZLATANIĆ ET AL.

excess. The polyol and MDI were preheated sep-

arately at 60 °C, then mixed and poured into the
molds preheated at 100 °C. Curing was carried
out at 100 °C overnight.

Figure 2. Conversion of epoxidized oil to a polyol.

using a Paar DMA5000 density meter at 23 °C. RESULTS AND DISCUSSION

The densities of polyurethane networks were
measured by immersion in water according to Composition of Vegetable Oils
ASTM 792. We used the Thermal Analyst system
Table 1 displays the composition of selected veg-
from TA Instruments, consisting of the Controller
etable oils, obtained from GC-MS analysis. The
3100 with a DSC 2910 module, TMA 2940 mod-
dominant constituents (over 80%) of all the oils
ule, TGA 2050 module and dielectric analyzer
are C18 fatty acids. The differences between the
DEA 2070, to study the thermal transitions and
oils arise mainly from the distribution of the C18
stability and dielectric properties of the vegetable
acids containing different numbers of double
oil– based polyols and polyurethanes. Dynamic
bonds: stearic, C18:0, oleic, C18:1, linoleic, C18:2
mechanical analysis of polyurethanes was carried
and linolenic, C18:3. Therefore, six oils could be
out on a DMA 2980 Dynamic Mechanical Ana-
divided into three groups. Canola and midoleic
lyzer from TA Instruments. The storage (E⬘) and
sunflower oil contain about 60% of oleic acid and
loss (E⬙) moduli and tan ␦ were recorded from ⫺80
lower iodine numbers (Table 2). The dominant
°C to 100 °C, at the heating rate of 5 °C/min and
fatty acid in soybean, sunflower, and corn oils is
frequency of 10 Hz.
linoleic, whereas highly unsaturated linseed oil
We employed a Q-Test 2 tensile machine from
contains more than 50% linolenic.
MTS to determine tensile strength and elongation
Using the composition of oils, we calculated
at break. The sample length was 50 mm and the
some of the parameters of oils and derivatives and
extension rate 50 mm/min. Flexural moduli were
compared them with the experimental results
obtained on the same tensile machine using 70-
(Table 2). Molecular weights of the oils differ very
mm-long, 25-mm-wide, and 2-mm-thick speci-
little because the C18 fraction is similar in all the
mens. Notched Izod impact strength was deter-
oils. Table 2 also gives molecular weights and
mined on a Resil Impactor from CEAST, Model
hydroxyl numbers of the polyols derived from
P/N 6957.000.
these oils. Theoretical MW and OH numbers are
based on assumption that no dimers and trimers
Preparation of Polyols are formed and that one hydroxyl group is formed
The polyols were synthesized by epoxidation of per double bond. Iodine values as a measure of
oils and subsequent ring opening of the epoxy the double bond content of oils, calculated from
groups to hydroxyls. The epoxidation of vegetable the oils’ composition, are in good agreement with
oils was carried out in toluene, with peracetic acid the experimentally determined ones.
formed in situ as described elswhere.16,20 Epoxy
yield was fairly uniform for all the oils (91–94%)
as determined by measuring epoxy oxygen con- Characterization of Polyols
tent. The polyols were synthesized from epoxi-
The conversion of the double bonds to epoxy
dized oils by oxirane ring opening with boiling
groups during the epoxidation reaction was rela-
methanol in the presence of a tetrafluoroboric
tively high for all the oils, varying from 91% to
acid catalyst.12,13 Total conversion of double
94%. Although canola oil is closer in unsaturation
bonds to hydroxyls varied from 75.5% to 83.7%, as
to midoleic sunflower oil, owing to more efficient
displayed later in Table 3.
conversion of double bonds to hydroxyls, canola
Figure 2 illustrates the epoxy ring opening in
polyol became closer in hydroxyl numbers to soy-
the presence of an acid catalyst and methanol.
bean, sunflower, and corn polyols. From iodine
values before and after epoxidation we found that
Synthesis of Polyurethanes double bonds reacted quantitatively. This also in-
Polyurethanes were obtained by reacting the dicated that 5– 8% of epoxy groups were lost in
polyols with MDI. MDI was used in 2% molar side reactions. Gel permeation chromatography
 POLYOLS, POLYURETHANES FROM VEGETABLE OIL 813

Table 2. Calculated and Experimentally Determined Properties of Vegetable Oils and Oil-Based Polyols

Midoleic
Property Canola Sunflower Soybean Linseed Sunflower Corn

Oil MW 879 879 872 871 873 871

Functionality 3.94 3.71 4.49 6.44 4.63 4.37
(Iodine value, mg I2/100 g) calc 113.8 107.0 130.5 187.6 134.6 127.3
(Iodine value, mg I2/100 g) exp 114.1 107.6 126.6 182 133.3 125.2
Epox. oil MW 942 938 944 974 947 941
(Epoxy oxygen content, %) calc 6.69 6.32 7.60 10.58 7.82 7.43
(Epoxy oxygen content, %) exp 6.29 5.87 6.95 9.5 7.07 6.72
Polyol MW 1068 1057 1088 1180 1096 1081
(Polyol MW) exp 1123 1191 1249 1274 1302 1180
(OH#, mg KOH/g) calc 207.0 196.7 231.4 306.2 237.1 226.8
(OH#, mg KOH/g) exp 173.6 163.5 179.3 247.8 177.8 179.0

(GPC) analysis of epoxidized products did not
show the presence of oligomers.
The number-average molecular weight of poly-
ols, determined by vapor pressure osmometry,
was higher than that calculated from the compo-
sition of oils, presumably owing to the presence of
oligomers in polyols. This was especially notice-
able in the case of the polyol from sunflower oil,
which had the highest content of oligomers (25%
compared with 15–18% for other samples) and the
lowest double bond to hydroxyl conversion (Table
3). The extent of side reactions during formation
of polyols depends on several factors such as the
catalyst concentration, temperature, time, and
methanol– epoxy molar ratio. The side reaction in
the hydroxylation stage is mainly polymerization,
that is, formation of dimers and trimers through
the epoxy ring opening by newly formed OH
groups. The degree of intermolecular reactions
can be estimated from the GPC chromatograms of
polyols (Fig. 3). The percentage of high-molecular-
weight species significantly affects the viscosity of
polyols. In the case of the linseed oil-based polyol,
however, a high OH content was primarily re-
sponsible for the high viscosity value.
We used the group contribution method,21
based on the additivity of molar volumes of chem-
ical groups present in the compound, to calculate
polyol densities. We used the values of the group
contribution to molar volume reported by Fedors.
Theoretical polyol functionality was included in
the calculation. Experimental densities of polyols
were 6.4 – 8.2% lower than calculated, as seen in
Table 3.
All polyols from the vegetable oils exhibited
similar thermal behavior. Two to three weak
melting peaks between ⫺40 and 0 °C (Table 3)
were ascribed to different crystalline structures
present in the polyols. DSC thermograms of the
polyols are displayed in Figure 4.
Functionality of Polyols from Vegetable Oils
Number-average functionalities of polyols ob-
tained from vegetable oils were calculated from
the hydroxyl number and theoretical molecular
weight:
Mn䡠OH#
fn⫽
56110
The functionality of the polyols is lower than
the number of double bonds per molecule of the
starting oils because a part of the functional
groups was lost in the side reactions during the
preparation of the polyols. The true functionality
of the polyols is increased when oligomers are
present. Functionality of dimers and trimers is
almost twice and three times that of monomeric
species.
Characterization of Polyurethanes
Swelling of Networks and Sol Fraction
Swelling degree of the vegetable oil– based poly-
urethanes in toluene at room temperature varied
from 40% for the highly crosslinked linseed oil–
based polyurethane network to 96% for the mido-
leic sunflower oil– based one (Table 4).
Crosslinking density can be extracted from
swelling data. The Flory-Rehner theory allows
calculation of the concentration of EANCs, ␯ e, or
molecular weight of network chains, Mc, but the
 814
ZLATANIĆ ET AL.

Table 3. Properties of Polyols Based on Vegetable Oils

OH#, Wt % of Viscosity Calc. Exp. Tm

mg Conversion Mn Mn Oligomers at 27 °C, Density Density,b (DSC),
Starting Oil KOH/g % (VPO) Calc.a Functionality from GPC Pa 䡠 s g/cm3 g/cm3 °C

Canola 173.6 83.7 1123 1068 3.30 17.04 2.94 1.0608 0.9968 ⫺36
⫺16
Midoleic
sunflower 163.5 82.7 1191 1057 3.08 16.69 1.85 1.0532 0.9885 ⫺38
⫺18
0
Soybean 179.3 79.4 1249 1088 3.47 18.56 3.35 1.0779 1.0066 ⫺32
⫺15
3.6
Linseed 247.8 82.7 1274 1180 5.21 14.85 18.2 1.1375 1.0513 ⫺24
⫺8
Sunflower 177.8 75.5 1302 1096 3.47 25.08 4.08 1.0823 1.0090 ⫺34
⫺15
2.5
Corn 179.0 80 1180 1081 3.44 15.7 2.71 1.0741 1.0032 ⫺35
⫺16
⫺0.3
a
Assuming complete double bonds to hydroxyls conversion and no formation of oligomers.
b
At 23 °C.
 POLYOLS, POLYURETHANES FROM VEGETABLE OIL
Figure 3. GPC chromatograms of polyols from vege-
table oils.
result would depend on the adopted model of rub-
ber elasticity:
[⫺V1 共A␾21/3 ⫺ 2B␾2/f兲]
1/ ␯ e ⫽ Mc/␳2 ⫽
关ln(1 ⫺ ␾2) ⫹ ␾2 ⫹ ␹12⌽22]
Here, ␳2 is the density of the dry polymer, V1 is
the molar volume of the solvent, ⌽2 is the volume
fraction of the polymer in the swollen sample, f is
the functionality of the network branch points,
and ␹12 is the polymer–solvent interaction param-
eter. Factors A and B within the Junction Fluc-
tuation theory of Flory (JFF theory) have the
following limits: A ⫽ (f ⫺ 2)/f, B ⫽ 0 (phantom
network); A⫽1, B⫽1 (affine network).
Application of this equation for determining ␯e
and Mc requires knowledge of the interaction pa-
rameter from independent measurements. The
polymer–solvent interaction parameter ␹12 was
estimated from the solubility parameters for the
solvent, ␦1, and the polymer network, ␦2:
共 ␦ 1 ⫺ ␦ 2兲 2V1
␹ 12 ⫽
RT
The solubility parameter for toluene was taken to
be 18.3 J ⁄2/cm ⁄2. The solubility parameters of
1 3
the polyurethane networks were calculated using
the group contribution method21 to the molar at-
traction constant, F (Hoy), and the solvent molar
volume, V1. Table 4 presents the ␦2 and ␹12 values
for polymer networks, as well as corresponding
molecular weights of the network chains. These
values are approximate at best, but the calculated
crosslinking densities give a basis for comparison
of different samples. However, the calculated ␹12
for the linseed-based polyurethane network was
very high owing to the higher content of MDI in
815
its structure, giving meaningless values for Mc
and ␯e. The absolute values for Mc are underesti-
mated compared with ideal values being about
930 for networks from trifunctional and about 780
for four functional polyols and MDI, but they give
the sense of the order of magnitude.
The sol fraction was determined after multiple
extractions with toluene. We calculated the con-
tent of the soluble part (Ws) from the difference in
the weight of the dry sample before (w1) and after
(w2) multiple extractions:
W s ⫽ (w1 ⫺ w2 )/w1
The presence of the sol indicates imperfect
crosslinking in polyurethanes. The sol content in
polyurethanes from canola and midoleic sun-
flower oil was approximately two times lower
than that in the networks from soybean, sun-
flower, and corn oil. The concentration of EANCs
is sensitive to network imperfections.22 In the
model network based on triolein, for example, the
presence of only 0.5% of sol translates to the de-
crease of the crosslinking density of 40 –50% of its
maximum value.23 Lower crosslinking density
may be caused by incomplete chemical reaction or
cyclization reactions during crosslinking. It has
been shown24 that the probability of the forma-
tion of elastically inactive network structures
during formation of the polyurethanes increases
with increasing functionality of the polyols. Table
4 presents the swelling characteristics of polymer
networks from the vegetable oils, as well as cor-
responding molecular weights of the network
chains.
Figure 4. DSC thermograms of polyols from different
vegetable oils.
816 ZLATANIĆ ET AL.

Table 4. Swelling Properties of Polyurethanes from Vegetable Oils in Toluene

Solubility Affine Model

Swelling Sol Parameter Polymer–Solvent
Density, Degree,a Fraction, ␦2, J1/21 Interaction ␯e, 103, Mc, g
g cm⫺3 % % cm⫺3/2 Parameter ␹12 mol cm⫺3 mol⫺1

Canola 1.087 80.98 1.11 21.42 0.422 1.764 616

Midoleic sunflower 1.078 96.49 1.47 21.19 0.361 1.573 685
Soybean 1.094 80.45 2.66 21.58 0.466 1.542 710
Linseed 1.144 40.40 0.68 23.08 0.987
Sunflower 1.101 80.16 2.52 21.58 0.466 1.534 718
Corn 1.092 85.56 2.84 21.56 0.461 1.408 776
a
Based on the weight of the swollen and original (dry) sample.

Glass Transition Temperature of Polyurethanes
from Vegetable Oils
We used four different methods to determine Tg to
cross-check each other, because both DSC and
TMA do not show always a clear transition. Tg
values from DMA and DEA are frequency depen-
dent and temperature control is not as good as in
DSC, but reading the position of maxima is un-
mistakable. TMA gives values close to those of
DSC. Figure 5 shows the DSC curves of the poly-
urethanes. The Tg, taken as a temperature of
inflection on DSC curves, was around 30 °C for
networks from soybean, corn, sunflower, and
canola oil, whereas midoleic sunflower oil– based
polymer displayed a Tg at 24 °C. Highly
crosslinked polyurethane from linseed oil had a
Tg at 77 °C.
Thermomechanical analysis of polyurethanes
showed unusually high thermal expansion of
Figure 5. DSC curves of polyurethanes from vegeta-
ble oils.
these polyurethanes. For all of the polymers, Tg
values taken from the change of slope on thermo-
mechanical curves were slightly lower than those
determined by DSC (Table 5). The linear coeffi-
cients of thermal expansion (LCTE) in the rub-
bery state (measured at 50 °C above Tg) were
around 400 ⫻ 10⫺6 K⫺1 for all samples except for
the linseed oil–polyurethane (320 ⫻ 10⫺6 K⫺1),
pointing to a higher crosslinking density of the
latter. High LCTE values indicating high free
volume in these samples may be related to the
plasticizing effect of dangling chains. LCTE below
Tg was 85 ⫻ 10⫺6 K⫺1 for the linseed oil– based
PU and 100 –110 ⫻ 10⫺6 K⫺1 for other polyure-
thanes, which exceeds the LCTE of most linear
glassy thermoplastic polymers (50 –90 ⫻ 107mi-
⫺1
nus;6 K ), indicating higher free volume in the
glassy state as well, which may relax with time
and cause physical aging and increasing density.
Glass transition temperatures, determined by
DMA from the maxima on G⬙ vs T are listed in
Table 5. DMAs generally give higher values of Tg
compared with the DSC and TMA method, but
the trend was the same: the lowest Tg was re-
corded in the polyurethane from midoleic sun-
flower oil and the highest was seen in the linseed
oil– based polymer.
Figure 6 displays tan ␦ peaks for different poly-
urethanes. The width at the half height of the
dumping factor peak, as a measure of crosslinking
density, is relatively similar for all the samples
except that from linseed oil. The shape and posi-
tion of tan ␦ peak are known to be affected by
many factors such as crosslinking density and
distribution of crosslinking densities in inhomo-
geneously crosslinked materials, content of plas-
ticizer or filler, and orientation of molecular struc-
ture. Polymer networks based on triglycerides
 POLYOLS, POLYURETHANES FROM VEGETABLE OIL 817

Table 5. Thermal, Dielectric, and Mechanical Properties of Polyurethanes from Vegetable Oils

Tg, °C
Tensile Elongation Flexural Impact
DMA DEA at E aa Strength, at Break, Modulus, Resistance,
DSC TMA G⬙ max 10 Hz kJ/mol MPa % MPa J/m

Canola 32 30 40 64 187 22.9 131 353 180

Midoleic sunflower 24 21 33 47 172 14.8 168 10 408
Soybean 31 30 35 67 181 20.2 108 312 178
Linseed 77 74 77 209 56.3 8 2015 21
Sunflower 32 29 38 69 193 21.7 107 443 198
Corn 30 29 38 64 192 17.7 122 309 221
a
Activation energy of the glass transition.

contain dangling chains arising from the polyol.
Although dangling chains are uniform in length
in the triolein-based networks,25 there is a distri-
bution of lengths of dangling chains in networks
from natural oils as a consequence of the hetero-
geneity of their composition
Figure 7 shows the change of permittivity and
loss factor for soybean-based polyurethane. The
activation energy of the glass transition, Ea, was
calculated from the loss factor–temperature
curves and the shift of temperature of the max-
ima, T, with frequency, f:
lnf ⫽ lnf0 ⫺ Ea/RT
R is the gas constant. The activation energy in-
creased linearly with crosslinking density, from
172 kJ/mol for the polyurethane from mid– oleic
sunflower oil to 210 kJ/mol for the sample from
linseed oil. Activation energy of the glass transi-
tion reflects the mobility of the chains, which is
higher for samples with lower Ea. As would be
expected, the highest mobility was found in the
midoleic oil– based polyurethanes and the lowest
in the linseed oil– based ones. A linear relation-
ship between activation energy and crosslinking
density was found in similar systems.26
Mechanical Properties of Polyurethane Networks
Tensile strengths of all the polyurethane samples
fell in the range of 15–23 MPa except for the
polyurethane based on linseed oil, which dis-
played about three times higher strength. Two
factors affected tensile strength: the crosslinking
density of samples and the physical state of the
material at the test temperature. Because the Tg
of all samples except the linseed-based one was in
the vicinity of the testing temperature, they were
tested in the leathery state (transient from glassy
to rubbery), which resulted in somewhat lower
strengths and moduli and high elongations at

Figure 6. Tan ␦ vs temperature of polyurethanes Figure 7. Permittivity and loss factor vs temperature
from different vegetable oils. for polyurethane from soybean polyol and MDI.
818 ZLATANIĆ ET AL.
Figure 8. Effect of the polyol OH number on theoret-
ical ␯e and Mc of polyurethane networks, calculated
under the assumption of complete conversion.
break. The linseed oil– based sample exhibited
brittle fracture and very low elongation at break
compared with other polyurethanes, but tensile
strength and modulus were comparable with
those of strong plastic materials.
Dependence of Properties on Crosslinking Density
The hydroxyl number of the polyols is a linear
function of the crosslinking density of the poly-
urethanes, expressed as the number of elastically
active network chains per unit volume, and in-
versely proportional to the average molecular
weight between crosslinks, Mc, at complete con-
version (Fig. 8) Thus, it is useful to examine the
dependence of properties of the polyurethanes on
the OH number of corresponding polyols. Figure 9
shows linear relationships between Tg, deter-
mined by DSC, and OH numbers. A nearly linear
Figure 9. Dependence of DSC Tg of polyurethanes on
the OH number of polyols.
Figure 10. Effect of OH number of polyols on tensile
strength and elongation at break of polyurethanes.
relationship was observed in tensile strength and
flexural modulus vs the OH number, but elonga-
tion at break and impact strength displayed ex-
ponential decay (Figs. 10 and 11). In our case, one
sample (from midoleic sunflower oil) was in the
rubbery state and all others in either the leathery
or glassy state at the testing temperature. Elon-
gation at break and impact resistance are usually
much higher in the rubbery state.
CONCLUSIONS
We converted six vegetable oils to polyols and
used them to prepare polyurethanes. The oils
Figure 11. Effect of OH number of polyols on flexural
modulus and Notched Izod impact strength of polyure-
thanes.
 POLYOLS, POLYURETHANES FROM VEGETABLE OIL
were divided into three groups: low unsaturated
midoleic sunflower and canola, highly unsatur-
ated linseed, and three oils with intermediate
unsaturation. The polyol functionality and
crosslinking density of polyurethanes were re-
lated to the double bond content in oils, except
that canola polyol migrated to the group of inter-
mediate functionality. Functionality of the poly-
ols resulting from oils with intermediate unsat-
uration was close to 3.5, that from linseed oil was
5.2, and midoleic sunflower had functionality
around 3.0. Canola, corn, soybean, and sunflower
oils gave polyurethane resins of similar crosslink-
ing density, and thus similar Tg values and me-
chanical properties despite somewhat different
distributions of fatty acids. Linseed oil– based
polyurethanes had higher crosslinking density
and thus higher mechanical properties, whereas
midoleic oil gave softer polyurethanes character-
ized by lower Tg and lower level of strength but
higher elongation at break. The differences in
properties arose primarily from different
crosslinking densities of polyurethane networks
and less from the position of functional groups in
the fatty acids in polyols. Mobility of chains in the
networks was inversely proportional to the
crosslinking density.
This material is based on work supported by the Coop-
erative State Research, Education and Extension Ser-
vice, U.S. Department of Agriculture, under Agreement
99-35504-7873.
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