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Reduction of Epoxidized Vegetable Oils: A Novel Method to Prepare Bio-Based
Polyols for Polyurethanes
Article in Macromolecular Rapid Communications · June 2014
DOI: 10.1002/marc.201400039 · Source: PubMed
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Macromolecular
Rapid Communications Communication
Reduction of Epoxidized Vegetable Oils: A
Novel Method to Prepare Bio-Based Polyols
for Polyurethanes
Chaoqun Zhang, Rui Ding, Michael R. Kessler*
A novel method, epoxidation/reduction of vegetable oils, is developed to prepare bio-based
polyols for the manufacture of polyurethanes (PUs). These polyols are synthesized from castor
oil (CO), epoxidized soybean oil, and epoxidized linseed oil and their molecular structures are
characterized. They are used to prepare a variety of PUs, and their thermomechanical prop-
erties are compared to those of PU made with petroleum-based polyol (P-450). It is shown
that PUs made with polyols from soybean and linseed oil exhibit higher glass transition tem-
peratures, tensile strength, and Young’s modulus and PU made with polyol from CO exhibits
higher elongation at break and toughness than PU made with P-450. However, PU made with
P-450 displays better thermal resistance because of tri-ester structure and terminal functional
groups. The method provides a versatile way to prepare bio-polyols from vegetable oils, and it
is expected to partially or com-
pletely replace petroleum-based
polyols in PUs manufacture.
1. Introduction industrial corporations such as Huntsman, BASF, Cargill,
Atofina, and Oleon have developed more than 20 types of
Vegetable-oil-based polyols enjoy significant interest vegetable- oil-based polyester polyols that are currently
worldwide because they are considered promising can- available on the market.[4,5]
didates for green monomers to synthesize polyurethanes Vegetable oils are triglyceride of fatty acid that usu-
(PUs), which are typically prepared by polyaddition ally contains 12 to 22 carbon atoms and 0 to 3 carbon–
of diisocyanates and polyols that contain at least two carbon double bonds. Except for castor oil (CO), most
hydroxyl groups.[1–3] The exploitation of petrochemical triglyceride oils do not contain the hydroxyl groups nec-
resources increasingly triggers concerns regarding envi- essary in polyols for PU synthesis. The reactive chemical
ronmental pollution, unsustainable depletion, and the sites present in vegetable oils, however, offer several
rising price of petroleum; therefore, there is an increasing routes to introduce hydroxyl groups to the triglyceride
demand for bio-based polyols that can replace petroleum- molecule.
based polyols in PU production in the near future. Recently, Depending on the structure and the reactive sites in
a vegetable oil, specific methods have been developed
to transform an inexpensive, readily available natural
feedstock into a valuable monomer. Epoxidation of
C. Q. Zhang, R. Ding, Prof. M. R. Kessler
carbon–carbon double bonds, followed by ring opening
Department of Materials Science and Engineering,
Iowa State University,Ames, IA 50011, USA
with amines, carboxylic acids/halogenated acids, or alco-
E-mail: michaelr.kessler@wsu.edu hols has been widely investigated for the preparation
Prof. M. R. Kessler of commercial vegetable-based polyols for PUs in recent
School of Mechanical and Materials Engineering years.[6–9] Ozonolysis of vegetable oil into ozonides, fol-
Washington State University, Pullman,WA 99164–2920, USA lowed by reduction to aldehyde and finally to alcohol
Macromol. Rapid Commun. 2014, 35, 1068−1074
1068 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com DOI: 10.1002/marc.201400039
Macromolecular
Reduction of Epoxidized Vegetable Oils: A Novel Method to Prepare Bio-Based Polyols for Polyurethanes Rapid Communications
www.mrc-journal.de
creates polyols that contain primary hydroxyl groups transform infrared spectroscopy (FTIR), and gel permea-
that are far more reactive towards isocyanates than sec- tion chromatography (GPC). PUs produced using these
ondary hydroxyl groups. In addition, the hydroxyl groups polyols were prepared and characterized by dynamic
of polyols prepared using this method are located at the mechanical analysis (DMA), differential scanning calo-
end of the fatty acid chains, which make all the aliphatic rimetry (DSC), thermogravimetric analysis (TGA), and
chains in the macromolecular network resulting in rigid tensile testing. Finally, the thermal and mechanical prop-
PUs.[10] Primary hydroxyl groups can also be introduced erties of PUs from bio-based polyols were compared with
by hydroformylation/reduction with syngas catalyzed by that from petroleum-based polyol.
rhodium or cobalt carbonyl complexes.[1,11,12] Vegetable-
oil-based polyols can also be prepared by transesterifica-
tion of vegetable oils with alcohols or by amidation with 2. Experimental Section
amines.[13,14] Although transesterification and amida-
tion allow for the incorporation of several functionali- 2.1. Materials
ties based on the choice of alcohol or amine, the absence
Polyol 450 (P-450) prepared by reacting propylene oxide with
of hydroxyl groups in the fatty acid chains (unless CO is glycerin, and polymeric diphenylmethane-4,4′-diisocyanate
used) results in long fatty acid chains acting as elastic, (PMDI, NCO content: 31 wt%) were provided by Kumho Petro-
unreactive chains. The recent development of thiol-ene chemical Company. Commercial epoxidized linseed oil (ELO)
click reactions offers promising routes for the preparation and epoxidized soybean oil (ESBO), obtained from Scientific Pol-
of polyols for polyurethane technology.[15] Based on these ymer Inc. (New York, NY), were used to assess the validity of the
routes, several research groups are dedicated to combine epoxidation/reduction method. CO, dibutyltin dilaurate (DBTDL),
the advantages offered by the modification of carbon– lithium aluminum hydride (LiAlH4), magnesium sulfate (MgSO4),
carbon double bonds and those offered by the modifica- methyl ethyl ketone (MEK), hydrogen chloride (HCl), ethyl ace-
tion of esters to develop high functionality polyols. For tate, and tetrahydrofuran (THF, HPLC grade), were purchased
from Sigma-Aldrich (Milwaukee, WI). All materials were used as
example, Kong used 1,3-propanediol for ring-opening of
received without further purification.
epoxidized vegetable oils and transesterification with
the triglycerides.[16] Lligadas developed oligomeric poly-
ether polyols by ring-opening polymerization of epoxi-
2.2. Preparation of Polyols from Vegetable Oils
dized methyl oleate followed by reduction of the ester
groups.[17] 200 mL THF was charged to LiAlH4 (14.72 g for CO, 18.45 g for
In this paper, a novel method will be proposed to pre- ESBO, and 22.23 g for ELO)in a 1000-mL two-neck round bottom
pare high functionality polyols by epoxidation of veg- flask at 0 °C. 100 g vegetable oil (CO, ESBO, and ELO) dissolved in
etable oils, followed by reduction of the epoxy groups 200 mL THF was added drop wise to the LiAlH4 suspension. The
reaction mixture was maintained at 0 °C with vigorous mechan-
and ester. Lithium aluminum hydride, as a conventional
ical stirring overnight. After the reaction was finished, 1 M HCl
strong reducing agent, was chosen to validate this idea.
aqueous solution was added slowly to the reaction mixture and
Recently, several catalytic hydrogenations were devel- cooled by iced water until the solution was clear. Then ethyl ace-
oped and investigated as the replacement of LiAlH4. In tate was added to extract the polyols and the organic layer was
further research, other mild catalytic alternatives will be washed with water at least six times, dried with MgSO4, and fil-
considered and investigated to extend the application of tered. Finally, the polyols derived from reduced castor oil (RCP),
this approach. For example, the reactivity of sodium boro- from reduced epoxidized soybean oil (RSP), and from reduced
hydride can be enhanced for reducing ester and epoxy epoxidized linseed oil (RLP) were obtained after removal of the
group in the presence of certain additives, such as iodine, organic solvent by rotary evaporation and drying in the vacuum
ZnCl2, MeOH.[18,19] Also, other green reductants, such as oven. The trace amounts of Al and Li in the polyols were only
ammonia borane also can be used in neat water as strong present in negligible amounts as shown in Supporting Informa-
tion. The representative preparation routine for RSP is shown in
reducing agent to improve atom efficiency and decrease
Figure 1.
the amount of inorganic salt residues.[20] For possible
future industrial applications, hydrogen (with ruthenium
hydride complexes as catalyst) offers a promising and 2.3. Preparation of PU from Polyols and PMDI
efficient reductant to be used in mass production.[6,21,22]
2.2 g polyol (P-450, RCP, RSP, and RLP) were dissolved in MEK, and
The current work is devoted to developing a one-pot then PMDI was added at a ratio of OH to NCO of 1:1.05. The pre-
process for preparing PUs from novel polyols possessing cursor solution was allowed to react at 70 °C for 2 h. Then, one
thermomechanical properties comparable to that of drop of DBTDL was added to the reacting solution and stirred
petroleum-based polyols. The structures of these pol- for 5 min. Finally, the solution was poured into a Teflon mold
yols produced from vegetable oils were characterized by to form a 50 × 50 mm (length × width) sheet and post-cured at
proton nuclear magnetic resonance (1H NMR), Fourier 80 °C in an oven overnight. The solvent was removed completely
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Rapid Communications C. Zhang et al.
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Figure 1. 1H NMR spectra and structures for ESBO and RSP.
during the post-cure. The resulting PU films were cut into specific from room temperature to 110 °C at 20 °C min–1 to erase their
dimensions for thermomechanical testing. thermal history. Then the samples were equilibrated at –60 °C,
followed by a second heating cycle to 110 °C at a heating rate
of 20 °C min–1. A TA Instrument Q50 TGA was used to evaluate
2.4. Characterization of Polyols and PUs the thermal stability of the PU films. Samples of approximately
10 mg were heated from room temperature to 700 °C at a heating
The chemical structure of the vegetable oils and their derived
rate of 20 °C min–1 in nitrogen. The tensile properties of the PU
polyols were analyzed by 1H NMR spectroscopy using a Varian
films were measured using an Instron universal testing machine
spectrometer (Palo Alto, CA) at 300 MHz and by FT-IR spectros-
(model 4502) with a cross-head speed of 5 mm min–1. ASTM
copy using a Nicolet 460 FT-IR spectrometer (Madison, WI). The
standard dog-bone samples were used. Average values of at least
OH values of the polyols were titrated according to the Unilever
three replicates of each sample were taken. The toughness of the
method.[23] The acid numbers of the polyols were determined
polymer was obtained from the area under the corresponding
by AOCS Official Method Te 1a-64. The molecular weight of the
tensile stress/strain curves.
vegetable oils and polyol derivatives were determined using a
Thermo Scientific Dionex Ultimate 3000 THF-eluted GPC (Sun-
nyvale, CA) equipped with a Shodex Refractive Index detector.
Thermal and mechanical properties of the resulting PU films 3. Results and Discussion
were characterized using a TA Instruments Q800 DMA with a
film-tension mode of 1 Hz. Rectangular specimens of 0.6 × 10 mm 3.1. Characterization of Polyols
(thickness × width) were used for the analysis. The samples were
cooled and held isothermally for 3 min at –80 °C before the tem- The 1H NMR spectra of vegetable oils and polyols derived
perature was increased to 160 °C at a rate of 3 °C min–1. A TA from them are shown in Figure 1 and 2. The disap-
Instrument Q2000 DSC was used to examine the glass transition pearance of peaks at 2.8–3.2 ppm in RSP indicated the
temperature (Tg). Samples of approximately 5 mg were heated removal of epoxy groups, and the disappearance of
Macromol. Rapid Commun. 2014, 35, 1068−1074
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Macromolecular
Reduction of Epoxidized Vegetable Oils: A Novel Method to Prepare Bio-Based Polyols for Polyurethanes Rapid Communications
www.mrc-journal.de
Figure 2. 1H NMR spectra and structures for epoxidized oils, bio-polyols, and petroleum-derived polyol.
peaks at 5.2–5.3 ppm ( CH2CHCH2 ) and 4.1–4.4 ppm hydroxyl groups and the removal of epoxy groups, respec-
( CH2 CHCH2 ) in RSP demonstrated the removal of ester tively. The molecular weights of the polyols are summa-
groups. The appearance of peaks in RSP at 3.5–3.8 ppm rized in Table 1. After the reduction of ester and epoxy
indicated the formation of OH functional groups. These groups into hydroxyl groups, the molecular weights of
results confirmed that the epoxy and ester groups were the resulting polyols was approximate 1/3 the molecular
successfully reduced into hydroxyl groups. Using the area weight of vegetable oils (The number average molecular
for peaks at 0.8–0.9 ppm (the terminal-CH3) of RSP for nor- weight of ESBO by GPC is 1420.[24]
malization (with an integrated value of 3), the functionali-
ties of the polyol can be determined (see Table 1). Similar
3.2. Characterization of PUs
results were found for the reduction process of CO and ELO
into corresponding polyols, as shown in Figure 2. The thermomechanical properties of the PUs derived from
The reduction from epoxy and ester to hydroxyl func- P-450, RCP, RSP, and RLP were investigated using DMA
tionality was also confirmed by the FTIR spectra shown within a temperature range of −80 °C to 150 °C. As shown
in Figure 3. The disappearance of the peak at 1746 cm−1 in Figure 4, it was observed that in bio-polyols an increase
for bio-polyols compared to that of corresponding epoxi- in OH number resulted in respective PUs an amplitude
dized vegetable oils, indicating the removal of ester decrease of the tan δ peak and a shift to higher tempera-
groups. In addition, the absorbance increase at 3380 cm−1 tures. The corresponding storage modulus measured in the
and decrease at 821 cm−1 indicated the formation of new rubbery state increased from PU–RCP to PU-RSP to PU-RLP,
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Table 1. The properties of bio-derived and petroleum-derived polyols.
Functionality OH number Acid number Number average PDIa State at room
[mg KOH g−1] [mg KOH g−1] molecular weight by GPC temperature
P-450 3 355 – 702 1.05 Liquid
RCP 2 353.1 ± 0.8 0.8 498 1.02 Liquid
RSP 2.4 377.0 ± 0.6 0.6 533 1.05 Wax
RLP 3.1 434.0 ± 0.8 0.8 562 1.04 Wax
a)
Polydispersity index.
indicating an increase in the degree of cross-linking caused summarized in Table 2. The DSC results confirmed the
by an increase in hard segments. The Tg was determined Tg determined by DMA in dependence of the structures
by the peak maximum of tan δ (see Table 2). Although the of polyols. PU-RLP exhibited the highest Tg, while PU-RCP
OH number of P-450 was similar to that of RCP, PU-450 exhibited the lowest Tg.
exhibited a higher Tg and storage modulus than PU-RCP TGA weight loss curves in nitrogen for PU films are
at both high and low temperatures, which was attributed shown in Figure 6 and the corresponding data are sum-
to the tri-ether groups in P-450. These glycerin-propylene marized in Table 2. The decomposition of the PUs
oxide-based polyether groups allow for pre-cross-linking occurred in three stages: dissociation of the unstable
of the polyol. On the other hand, the hydroxyl groups in urethane bond between 150 and 330 °C, decomposition
P-450 are terminal, making the whole polyether chain part of the soft polyol segments between 330 and 400 °C, and
of the network. In contrast, the hydroxyl groups in RCP are the further degradation of fragments produced after the
positioned in the middle of the fatty acid chains. A portion second stage.[26] The OH numbers increased from RCP to
of the chains was therefore not included in the network RSP to RLP, resulting in an increase in urethane bond for-
and left acting as plasticizers. In addition, the tan δ curve mation; therefore, the thermal stability of the respective
of PU-RLP exhibited multiple transitions surrounding the PUs decreased in the first stage. The thermal stability of
Tg region, showing behavior similar to PUs from soybean PU-P-450 and PU-RCP were similar during the first stage
phosphate ester polyol and PMDI reported by Mohanty.[25] because of their similar OH numbers. In the second stage,
This phenomenon may be the result of the complicated the described cross-linking structure caused by tri-esters
composition of the polyols, including mono-ol, diol, and in P-450 resulted in a thermal stability of PU-P-450 that
triol derived from oleic, linoleic and linolenic fatty acid. was higher than the stabilities of the bio-PUs. PU–RCP
DSC scans of the PUs are shown in Figure 5. The Tg exhibited the lowest thermal stability, as reported by
values were determined by the midpoint temperature others,[27] which may be the result of degradation induced
between the slope of the heat capacity change and are by carbon–carbon double bonds in CO fatty acids.
Figure 4. Storage modulus and tan δ of PUs derived from P-450,
Figure 3. FTIR spectra of epoxidized vegetable oils and polyols. RCP, RSP, and RLP.
Macromol. Rapid Commun. 2014, 35, 1068−1074
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Reduction of Epoxidized Vegetable Oils: A Novel Method to Prepare Bio-Based Polyols for Polyurethanes Rapid Communications
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Table 2. Thermal and mechanical properties of PUs based on P-450, RCP, RSP, and RLP.
DMA Tg DSC Tg TGA in nitrogen Tensile strength Young’s modulus Elongation Toughness
[°C] [°C] [°C] [MPa] [GPa]a at break [MPa]
[%]
T10 T50
PU-P-450 69.8 26.6 318 366 19.7 ± 1.7 0.36 ± 0.04 69.3 ± 1.3 8.8
PU-RCP 55.6 23.7 315 347 20.1 ± 0.7 0.42 ± 0.05 90.4 ± 6.7 13.8
PU-RSP 79.7 45.5 313 355 26.1 ± 0.1 0.55 ± 0.08 9.5 ± 2.1 1.64
PU-RLP 97.0 52.3 305 350 35.1 ± 5.9 1.19 ± 0.25 11.9 ± 3.8 4.1
a)Modulus calculated from the initial slope of the stress–strain curve.
The stress–strain curves of PUs from P-450, RCP, RSP,
and RLP are shown in Figure 7. Young’s modulus, tensile
strength, elongation at break, and toughness of PU films
are summarized in Table 2. The glass transition tempera-
tures for PUs derived from P-450 and RCP determined by
DSC indicated that these PUs were in an elastomeric state
at tensile testing condition of room temperature, dis-
playing large elongation at break, while PUs derived from
RSP and RLP exhibited brittle behavior in the glassy state
indicated by their higher Tgs. As the hydroxyl numbers
of RCP, RSP, and RLP increased, the tensile strength of the
corresponding PUs increased because of their increasing
cross-linking density, as discussed in the section on ther-
momechanical properties. The tensile strength of PUs
derived from P-450 and RCP was almost identical because
of the similar OH number of their respective polyols. The
latter exhibited higher elongation at break because of the
flexible chains in RCP, leading to higher toughness of the Figure 6. TGA weight loss curves in nitrogen for PUs derived from
PU derived from RCP. P-450, RCP, RSP, and RLP.
Figure 5. DSC scans of PUs (20 °C min–1) derived from P-450, RCP, Figure 7. Stress–strain curves of PUs derived from P-450, RCP, RSP,
RSP, and RLP. and RLP.
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