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of Cellular Plastics

Structure and properties of the polyurethane and polyurethane foam

synthesized from castor oil polyols
Uldis Stirna, Brigita Lazdina, Dzintra Vilsone, Maria J Lopez, María del Carmen
Vargas-Garcia, Francisca Suárez-Estrella and Joaquin Moreno
Journal of Cellular Plastics 2012 48: 476
DOI: 10.1177/0021955X12445178

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Article
Journal of Cellular Plastics
48(6) 476–488
Structure and properties ß The Author(s) 2012
Reprints and permissions:
of the polyurethane and sagepub.co.uk/journalsPermissions.nav
DOI: 10.1177/0021955X12445178

polyurethane foam cel.sagepub.com

synthesized from castor

oil polyols
Uldis Stirna1, Brigita Lazdiņa1, Dzintra Vilsone1,
Maria J Lopez2, Marı́a del Carmen Vargas-Garcia2,
Francisca Suárez-Estrella2 and Joaquin Moreno2

Abstract
Polyols were synthesized from castor oil with diethanolamine and triethanolamine at
the molar ratios from 1:1 M to 1:3 M with the total hydroxyl value and amino value in
the range from 291 to 512 mg KOH/g. Bio-based rigid polyurethane foams with good
mechanical properties, a high closed-cell content and the renewable content in the
range from 25.0 to 35.6 wt% were obtained. Polyurethane coatings’ tensile strength
and modulus of elasticity are higher for the samples obtained from castor oil/diethano-
lamine polyols, but the highest elongation at break is for the polyurethane from castor
oil/triethanolamine polyols. In the temperature range from 150 C to 350 C, the poly-
urethanes from castor oil/triethanolamine have lower weight losses than the polyureth-
ane from castor oil/diethanolamine polyols. The presence of polyethylene glycol
enhances the degradability of the bio-based polyurethane foams in the presence of fungi.

Keywords
Castor oil polyols, polyurethane foams, polyurethane coatings, mechanical properties,
biodegradation

Introduction
Since the 1950s, oleochemistry has grown to a major research and technology area in several
institutions and industries. A large variety of products based on fats and oils have been
developed since then for different uses, such as specialities for polymer applications.1,2

1
Polymer Laboratory, Latvian State Institute of Wood Chemistry, Riga, Latvia
2
Department of Applied Biology, University of Almeria, Almeria, Spain
Corresponding author:
Uldis Stirna, Latvian State Institute of Wood Chemistry, 27 Dzerbenes Str., LV-1006, Riga, Latvia.
Email: stirna@edi.lv

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Stirna et al. 477

Many investigations are devoted to the synthesis of polyols from different vege-
table oils such as soybean oil,3–6 rapeseed oil7,8 and palm oil.9,10 For obtaining
polyurethane (PU), vegetable oils have to be functionalized, which is done through
double bond reactions such as epoxidation, hydroformylation and methathesis, or
through ester bond reactions (transesterification, transamidation).1 The use of
vegetable oil polyols in PU foam compositions makes it possible to improve the
properties of some prepared foams, especially their hydrophobicity.1,8 PUs from
vegetable oil polyols have been found to be characterized by higher thermal sta-
bility than those prepared from propylene oxide polyols.11
Castor oil (CO) is a low cost renewable raw material and is attracting research
effort because of its use in coatings, elastomers, sealants, and PU foams. The oil is
obtained from extracting or expressing the seed of a plant which has the botanical
name Ricinus communis of the family Eurphorbiacae.12–16 Leitheiser and Ehrich
have reported that CO can be used to replace the petroleum-based polyol to make
PU foams.17,18 Baser et al.19 have reported the obtaining of rigid PU foams from a
mixture of CO and glycerol and found that glycerol cross-linking gives the foam
sufficient rigidity and reduces shrinking.
CO is already used as a raw material for obtaining PU materials conforming to the
green chemistry requirements. BASF manufactures the Lupranol Balance polyol from
CO, which is used for flexible foam production. Lupranol Balance contains up to
24 wt% of CO.20 CO polyols are used for producing volatile organic compounds free
PU coatings, which are characterized by good mechanical properties and are very
hydrophobic.21 CO based spray foam insulation with a high content of renewable raw
materials is developed. It is an environmentally preferable product and is 100% water
blown.22 To ensure wider possibilities of obtaining PU materials from renewable raw
material resources, studies on the synthesis of new CO polyols as well as the properties
of the PU foams and coatings obtained from these polyols are necessary.
In the present study, results on the synthesis of polyols by way of the amidiza-
tion of CO with DEA, and transesterification with TEA were generalized. Studies
on the mechanical and thermal properties, and biodegradation of the obtained
bio-based PU coatings and PU foams were carried out.

Experimental
Materials
Castor oil, lactic acid 85%, "-caprolactone, glycerol, PEG 300 and tin octoate
(catalyst) were supplied from Aldrich. DEA were obtained from Huntsman,
TEA was supplied by BASF. Voratec SD 100 (a polymeric MDI with 2.7 NCO
functionality and 31.2 wt% of NCO) were obtained from Dow Chemical
and Lupranol 3422 (polyether polyol; fn ¼ 5, OHV ¼ 490 mg KOH/g)
from Elastogran. Silicone surfactant L 6912, used as a surfactant, pentamethyl-
diethylenetriamine and bis(2-dimethlaminoethyl)ether, used as a catalyst, were
from Niax. Cyclopentane, used as a blowing agent, was from Solway.

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478 Journal of Cellular Plastics 48(6)

Sample preparation
Polyols of CO were prepared by amidization with DEA or transesterification with
TEA; catalyst zinc acetate (0.15 wt%) was added with stirring.8 The CO amidiza-
tion reaction was carried out at 120–140 C, and transesterification at 140–170 C.
Polycaprolactone (PCL) triols were synthesized by adding "-caprolactone to gly-
cerol at 120 C for 20 h.23 Lactide triol was synthesized by esterifying lactic acid in
the presence of DEA at 130 C. Synthesis time was 30 h.
The PU films from CO polyols were synthesized in a 50% anhydrous toluene
solution at a temperature of 20–25 C. The functional group ratio NCO:OH was
1.1. As the conversion of NCO groups reached 60–70%, the solution was poured
on a fluoroplastic support and left at a temperature of 70 C for 2 h for condition-
ing. The obtained films had a thickness of 150–250 mm.
Rigid PU foams were prepared applying a hand mixing method. The polyol,
catalyst package, surfactant and blowing agent were added by weighing into a
500-mL plastic cup and mixed at 2880 rpm for 10–15 s. Then polymeric MDI
was added, and stirring was continued for 10–15 s. For measuring foaming reactiv-
ity, PU foam core density, and physical and mechanical properties, samples were
foamed into an open box mold with sizes of 200  250 mm2, height 80 mm.
Biodegradable rigid PU foams were prepared from CO/DEA polyol, PCL triol,
lactidtriol and PEG 300, and additives; polymeric MDI was also added. The pro-
cedure for producing biodegradable rigid PU foams was the same as described for
rigid PU foams.

Measurements
Calorimetric measurements were made on a differential scanning calorimeter
Mettler Toledo 823e at the heating rate 10 C/min. The thermogravimetric analysis
(TGA) was carried out with the help of the Mettler Toledo TGA/SDTA 851e in an
inert atmosphere, at the heating rate 10 C/min in the temperature range
20–1000 C. The weight of the sample was in range from 8 to 10 mg. Fourier trans-
form infrared with attenuated reflectance (FTIR-ATR) of PU films was recorded
on a Perkin-Elmer spectrometer ‘Spectrum One FTIR Spectrometer’, resolution
4 cm1. The polyol viscosity measurements were made at 25 C with a Falling Ball
Viscometer KF 100 (Rheo Tec Messtechnik GmbH).
The stress–strain characteristics of PU films were determined by tensile testing 5
to 7 specimens on a Zwick/Roell testing device at the deformation rate 50 mm/min.
Density of the foams and closed-cell content were measured according to the stand-
ards: DIN 53420 and ISO 4590, respectively. Mechanical testing of PU foams was
performed on a testing machine Zwick/Roell 500 N. As a rule, 6 samples on each
experimental point were tested. In the majority of cases, the coefficient of variation
of foams’ characteristics was within 6–15%.
The biodegradability of PU foams was tested by two methods: biodegradation
after exposure to fungi on an agar plate according to a modification of ISO 846,24

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Stirna et al. 479

and capability to serve as a sole carbon source for several fungi.25 In both tests, the
following fungi were used: Coniophora puteana CECT 20145, Gloeophyllum trabeum
CECT 20146, Aspergillus niger CECT 2700, Aspergillus flavus CECT 2949,
Phanerochaete chrysosporium CECT 2779, Phanerochaete flavido-alba FPL 106507
and Trichoderma reesei CECT 2414. The fungi used in the studies of biodegradation
were those indicated in the international standard ISO 846 and other selected
because of their biodegradative capabilities. The main goal was to determine
whether the fungi that can be found in most environments are able to degrade the
materials either by altering their properties or by using them as a sole carbon source.
Each sample was soaked in a suspension of a fungus and placed into Petri-dishes
containing malt extract agar (2% malt extract, 2% dextrose, 2% agar).
Colonization and weight loss (%) for three replicates of the samples exposed to
each fungus during 8 weeks at 30 C were tested.
The analysis of PU foams as a sole carbon source for fungal growth was per-
formed by using agar plate media composed of a mineral salt solution, with 0.5%
(w/v) of powdered PU foams added. PU foams powder (particle size <1 mm)
was obtained by using a MF 10 basic grinder (IKA Werke). One plug (1 cm2) of a
7-day-old culture of each fungus on potato dextrose agar was inoculated on plates.
Cultures were incubated for 3 weeks at 30 C and fungal growth was evaluated.

Results and discussion

Castor oil polyol synthesis and properties
Castor oil is triacylglycerol, in which approximately 90% of fatty acid chains are
ricinoleic acid. CO has the following structure (Figure 1).
Ricinoleic acid, a monounsaturated, 18-carbon fatty acid, is unusual in that it
has a hydroxyl functional group on the 12th carbon. Idealized CO average Mn is
930 g/mol and OHV is 165 mg KOH/g.
In comparison with other vegetable oils, CO has a higher solubility parameter
(). Thus, soybean oil , which is determined by the inverse gas chromatography
method, is 8.37 cal1/2/cm3/2,26 but CO  ¼ 9.00 cal1/2/cm3/2.27 Hence, CO, in com-
parison with other vegetable oils, has a higher , and this facilitates its transester-
ification with glycerol or TEA, or also the amidization with DEA, because the
synthesis process proceeds in a homogeneous state already from the outset.
Because CO has low OHV, and its structure has low-activity secondary
OH-groups, it is not especially suitable for obtaining rigid PU foams. One of the
solutions how to expand the applicability of CO for obtaining rigid PU foams is to
chemically introduce primary hydroxyl groups onto CO triacylglycerols. That can
be done by amidization of CO with DEA, or also by the transesterification of CO
with TEA. The results of the systematic studies on the obtaining and properties of
PU coatings or PU foams from such polyols are not described.
CO polyols with DEA and TEA were synthesized with increasing molar ratio
from 1 : 1 M to 1 : 3 M.

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480 Journal of Cellular Plastics 48(6)

O OH

H2C O O OH

HC O O OH

H2C O

Figure 1. Idealized structure of castor oil.

Figure 2. Dependence of the conversion degree of NH groups, synthesizing polyols

at the molar ratio CO/DEA ¼ 1/2. Temperature is 140 C. CO amidization in the
presence of 0.15% zinc acetate (1); non-catalytic CO amidization (2).
CO: castor oil; DEA: diethanolamine.

The CO amidization kinetics studies have shown that, in parallel to amidization,

also the transesterification process occurs.
CO amidization at the initial stage of the reaction occurs much slower than in
the presence of a catalyst – zinc acetate, although the rates of the amidization
process at the final stage of the reaction are of equal value in both cases
(Figure 2). At the end of the CO amidization reaction, the NH groups’ conversion
degree in the cases of both catalytic and non-catalytic reactions reaches 86 wt%,
while 14 wt% of the product consists of fatty acid amino esters. These results
indicate that, in the synthesized CO polyol, there are both ricinoleic acid dietha-
nolamides and ricinoleic acid amino esters. According to Kroll et al.,28 fatty acid
diethanolamides and amino esters are in equilibrium (Figure 3).
Transesterifying CO with TEA at the molecular ratio 1 : 3, ricinoleic acid esters
with the following structure are mainly formed (Figure 4).
Table 1 summarizes the characterization of the synthesized CO polyols.
The data summarized in Table 1 show that, with increasing molar ratio
CO/DEA and CO/TEA, the OHV þ NHV of the synthesized polyols increase.
The synthesized polyols have relatively low viscosity, although it is the highest
for CO DEA polyols. With increasing molar excess of DEA over CO from 1 to
3, the content of ricinoleic acid diethanolamide and glycerol grows in the obtained
polyol. Similarly, polyol structure changes occur also when transesterifying CO

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Stirna et al. 481

R CH2 CH2 OH CH2 CH2 OH

C N NH

O CH2 CH2 OH CH2 CH2 O

C R

Figure 3. Structure of CO/DEA fatty acid diethanolamide and amino esters and their
equilibrium. R ¼ saturated and unsaturated C15–C18 fatty acid radicals.
CO: castor oil; DEA: diethanolamine.

CH2 CH2 OH

O CH2 CH2 N

R C CH2 CH2 OH

O
OH

(CH2)7 CH CH CH3

R= CH CH2 (CH2)5

Figure 4. Structure of CO/TEA ester.

CO: castor oil; TEA: triethanolamine.

Table 1. Characteristics of the synthesized CO polyols

Molar ratio
Castor oil CO/DEA or OHV þ NHV CO content Viscosity
polyols CO/TEA (mg KOH/g) in polyol (wt%) (mPas at 25 C)

CO/DEA 1:1 318 86.9 750

CO/DEA 1:2 420 81.6 815
CO/DEA 1:3 512 74.7 2340
CO/TEA 1:1 291 86.2 740
CO/TEA 1:2 404 75.7 713
CO/TEA 1:3 472 67.5 750

with TEA. CO/TEA esters are catalytically active polyols. As can be seen from
Table 1, the synthesized polyols have high content of renewable raw materials.
The course of the vegetable oil amidization and transesterification processes can
be judged also from calorimetric measurements. DSC experiments were carried out
with CO and DEA, as well as CO and TEA blends at their molar ratio 1:3 M at
140 C. It is calculated from DSC curves that the process of CO amidization with
DEA at 140 C occurs with the enthalpy 29.74 cal/g, but the CO transesterification

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482 Journal of Cellular Plastics 48(6)

Table 2. Properties of PU films obtained from CO/DEA and CO/TEA polyols

Polyol used Mc (g/mol)  t (MPa) E (MPa) " (%) Tg (oC)

CO/DEA 1:1 505 45.1 1558 5.0 65.0

CO/DEA 1:2 460 57.4 1765 7.2 84.5
CO/DEA 1:3 420 53.8 1684 6.0 75.0
CO/TEA 1:1 529 19.8 749 37.8 44.5
CO/TEA 1:2 480 25.3 1023 24.2 52.3
CO/TEA 1:3 465 39.8 1540 25.2 54.0
Castor oil 880 14.1 54.9 126 18.6

with TEA occurs at the enthalpy 28.60 cal/g. These DSC data indirectly indicate
that not only the amidization process, but also the transesterification one can occur
as CO reacts with DEA.

Polyurethane coatings
In contrast to CO, the synthesized castor oil polyols have higher OHV and high con-
tent of primary OH groups (50–66% from total OH group content), and this circum-
stance makes them an attractive raw material for obtaining both rigid PU foams and
PU coats. Table 2 summarizes the data on the mechanical properties of the PU,
obtained from the synthesized CO polyols. As can be seen from the data listed in
Table 2, the PU from CO/DEA have higher tensile strength ( t), modulus of elasticity
(E) and glass transition temperature (Tg) than the PU films from CO/TEA polyols.
This is explained by the fact that the PUs from the CO/DEA polyols in the main
chain’s structure has tertamide groups, which are characterized by high cohesion
energy. In turn, the PUs from CO/TEA esters have higher elongation at break (").
The mechanical properties and glass transition temperature of the PU obtained
from CO and polymeric MDI are close to those reported by other authors.1
The obtained results make it possible to purposefully form formulations from
CO/DEA and CO/TEA type polyols for obtaining rigid PU foams or coats.
The structure of the PU obtained from CO/DEA 1 : 3 M has mainly ricinoleic
acid diethanolamide groups. In turn, the structure of the PU from CO/TEA 1 : 3 M
has mainly ricinoleic acid amino ester groups.
The structure of the obtained PUs is determined from FTIR-ATR spectroscopy
data (Figure 5).
FTIR, cm1: 3410-3450 (NH non-bonded); 3300 (H-bonded NH); 2853 (CH2
symmetrical); 2926 (CH2 asymmetrical); 3007 (CH ¼ CH unsaturation); 2278
(NCO groups); 1739 (C ¼ O ester); 1710 (C ¼ O urethane); 1640 (C ¼ O amide).
The obtained PUs from CO/DEA, in contrast to the PU from CO/TEA, have a
peak at 1640 cm1, typical for C ¼ O amide.
The PU synthesized from CO polyols can be characterized as polymers with
a cross-linking structure, which contains the short side chains –(CH2)5CH3.

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Stirna et al. 483

Figure 5. FTIR spectra of PUs obtained from CO/TEA 1:2 polyol (1) and CO/DEA 1:2
polyol (2). FTIR: Fourier transform infrared; CO: castor oil; TEA: triethanolamine;
DEA: diethanolamine.

%
4
100 5
1 6
7

80 2

3
60

40

20

0
100 200 300 400 500 600 700 800 900 °C
: METTLER STARe SW9.30

Figure 6. TGA thermograms in nitrogen of PU made from different castor oil polyols.
CO/DEA 1:3 (1); CO/DEA 1:2 (2); CO/DEA 1:1 (3); CO/TEA 1:1 (4); CO/TEA 1:2 (5);
CO/TEA 1:3 (6) and CO (7).
TGA: thermogravimetric analysis; CO: castor oil; DEA: diethanolamine; TEA: triethanolamine.

Such side chains enhance the hydrophobic properties of PU. The solubility param-
eter for the side chain (CH2)5CH3, which is calculated according to Fedors,29 is
equal to 7.85 cal1/2/cm3/2, but the van der Waals volume (Vw), calculated according
to Askadskii,30 is 65.6 cm3/mol.
Decomposition of PU films obtained from different CO polyols with polymeric
MDI was tested. Thermal stability, as measured by TGA in nitrogen, was the
highest in the PU from CO/TEA polyols and lowest in that from CO/DEA polyols,
as can be seen from Figure 6.
The thermal stability of PU at the initial stage of decomposition was estimated
using a temperature at which polymers lose 5 wt%. The results as follows: PU from

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484 Journal of Cellular Plastics 48(6)

Table 3. Formulations of rigid PU foam from different CO polyols

PU foam formulations, pbw BIO 16 BIO 17 BIO 18 BIO 19 BIO 20 BIO 21

Polyol CO/DEA 1:1 95 – – – – –

Polyol CO/DEA 1:2 – 100 – – – –
Polyol CO/DEA 1:3 – – 100 – – –
Polyol CO/TEA 1:1 – – – 93 – –
Polyol CO/TEA 1:2 – – – – 100 –
Polyol CO/TEA 1:3 – – – – – 100
Glycerol 5 – – 7 – –
Water 2.5 – – 2.5 2.5 2.5
Cyclopentane – 12 12 – – –
Pentamethyldiethylenetriamine 0.4 0.4 0.4 – – –
Bis(2-dimethlaminoethyl) ether 1.0 1.0 1.0 1.0 0.5 1.0
Surfactant L 6915 1.5 1.5 1.5 1.5 1.5 1.5
Polymeric MDI 147 154 151 152 150 150
Isocyanate index 110 130 123 110 110 110

CO/DEA 1:1 – 226 C, CO/DEA 1:2 196 C, CO/DEA 1:3 184 C, CO/TEA 1:1
280 C, CO/TEA 1:2 264 C, CO/TEA1:3 – 233 C. With increasing molar excess
of DEA or TEA over CO from 1 to 3 M, the thermal stability of the PU obtained
from CO/DEA and CO/TEA polyols decreases in temperature range 150–350 C.
Rapid decomposition of PU takes place till temperature reaches 500 C, at this
temperature weight residue is 10 to 27 wt%.

Polyurethane foam
PU foam formulations were composed according to the data on polyols, listed in
Table 1. Their characteristics are summarized in Table 3.
The properties of the PU foams listed in Table 3 are summarized in Table 4.
The foams obtained from CO/DEA and CO/TEA polyols are characterized by
good compressive and tensile strength and high closed-cell content. Similarly to PU
films, also PU foams from CO/TEA polyols have a higher elongation at break than
the PU foams from CO/DEA polyols. Table 5 demonstrates that PU foams with a
high renewable content can be obtained from the synthesized CO polyols.
To assess the possibilities of obtaining biodegradable PU foams, PU foam for-
mulations were formed, which incorporated a CO/DEA polyol, biodegradable
polycaprolactone (PCL) triols, lactide triol and PEG 300. For producing PU
foams, cyclopentane and water were used. The composition of these formulations
is listed in Table 5.
The polymeric matrix of the obtained PU foams is characterized by the mole-
cular weight per branching unit (Mc), and the bio-content and biodegradable

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Stirna et al. 485

Table 4. Properties of rigid PU foams from CO/DEA and CO/TEA polyols

Properties of PU foams BIO 16 BIO 17 BIO 18 BIO 19 BIO 20 BIO 21

Core density (kg/m3) 41 46 41 50 40 49

Compressive strength, // (MPa) 0.22 0.28 0.24 0.31 0.21 0.32
Compressive strength, o (MPa) 0.16 0.21 0.14 0.21 0.12 0.17
Modulus in compression, // (MPa) 5.28 5.07 6.10 6.22 4.20 6.18
Modulus in compression, o (MPa) 3.07 3.34 2.10 3.69 2.15 3.45
Tensile strength, o (MPa) 0.23 0.22 0.20 0.39 0.30 0.33
Modulus in tension (MPa) 5.75 4.20 4.00 6.42 4.21 5.95
Elongation at break (%) 6.3 6.0 5.7 9.8 11.0 6.6
Closed-cell content (%) 96.2 95.2 82.6 94.9 90.7 91.0
Polymer matrix parameters
Mca (g/mol) 501 480 430 525 505 482
Renewable content (%) 35.6 31.7 29.4 33.3 29.9 25.0
a
Molecular weight per branching unit.

Table 5. Biodegradable rigid PU foam formulation

PU foam formulations (pbw) BIO-8 BIO-11 BIO-13 BIO-15

CO/DEA molar ratio 1:2 60 80 50 100

PCL triol M ¼ 1000 40 – – –
Lactidtriol M ¼ 650 – – 30 –
PEG M ¼ 300 – 20 20 –
Water 2.5 2.0 2.0 2.5
Cyclopentane 2.0 3.0 – 3.0
Catalyst package 1.4 1.2 4.0 1.2
Surfactant L 6915 2.0 1.5 1.5 1.5
Polymeric MDI 128 148 130 152
Polymer matrix parameters
Mc (g/mol) 545 540 727 493
Biocontent/biodegradable (wt%) 21.3/38.7 25.9/25.9 30.1/30.1 31.8/31.8

unit content. PU foams’ core density was in a range of 30–39 kg/m3, but the closed-
cell content was from 75% to 90%.
The weight loss of the PU foams after exposure to seven selected fungi is plotted
in Figure 7.
The composition of the PU foams had a dramatic effect on the in vitro biodeg-
radation rate. The material prepared with the highest CO content without PEG 300
(BIO-15) exhibited low (e.g.<2%) degradation by all tested fungi. However, in
comparison, the material prepared with a high CO content (80%), but with PEG
300 (BIO-11) added, showed enhanced biodegradation levels.

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486 Journal of Cellular Plastics 48(6)

Figure 7. Weight loss (%) for tested PU foams after 8 weeks of exposure to Aspergillus flavus
(Af), Aspergillus niger (An), Coniophora puteana (Cp), Gloeophyllum trabeum (Gt), Phanerochaete
chrysosporium (Pch), Phanerochaete flavido-alba (Pfa) and Trichoderma reesei (Tr). PU: polyurethane.

Table 6. Fungal colonization (EN ISO 846:1997) for samples exposed to

fungi during 8 weeks

Fungi BIO-8 BIO-11 BIO-13 BIO-15

Aspergillus flavus 2 1 1 0
Aspergillus niger 2 2 2 2
Coniophora puteana 1 2 2 1
Gloeophyllum trabeum 1 1 1 1
Phanerochaete chrysosporium 0 1 0 1
Phanerochaete flavido-alba 2 1 2 1
T richoderma reesei 2 1 2 1

As can be seen from Figure 6, the materials showing the highest biodegradation
rates were BIO-8 and BIO-13, both containing similar amounts of CO and poly-
meric MDI but lower ones than the other material tested. Increased amounts of CO
are known to decrease biodegradability because of the hydrophobic nature of the
long aliphatic hydrocarbon chains of the fatty acid part of CO.
The colonization rating scheme is based on the visual assessment by ISO 846: (0)
non-apparent growth even under the microscope (the material is not a nutritive
medium for the microorganism); (1) invisible growth or hardly visible to the naked
eye but clearly visible under the microscope (the material contains nutritive sub-
stances); (2) slight growth covering less than 25% of the surface (the material is not
resistant to fungal attack); (3) growth covering more than 25% of the specimen
surface (the material is not resistant to fungal attack).
The materials BIO-8, BIO-11 and BIO-13 were more easily colonized by nearly
all fungi than BIO-15 (Table 6).
The growth of fungi on media with PU foams as the sole source of carbon was
performed to determine whether the polymers were completely solubilized by extra-
cellular fungal enzymes. This is usually tested by measuring the radius of a clear halo
surrounding the microorganism colony.25 This was not possible for the materials
tested because they form aggregates in the agar medium rather than turbid agar.

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Stirna et al. 487

Hence, we only tested the presence or absence of the growth of microorganisms

on the mentioned media because it indicates whether the microorganism may use
the material as a nutritive source and, consequently, could biodegrade it at high
rates. A. niger was the only microorganism able to grow from all materials tested.
P. flavido-alba grew in BIO-8, BIO-11 and BIO-13, but not in BIO-15. None of
the other fungi tested were able to use the materials as the sole carbon source.
Consequently, the reported microorganisms may serve to test the biodegradability
of this type of materials under harsh conditions or to develop a suitable process for
the controlled biodegradation process after disposal.

Conclusions
Water and cyclopentane blown bio-based rigid PU foams obtained from CO dietha-
nolamide and CO triethanolamine polyols have good compressive and tensile strength
properties. PU foams from CO triethanolamine polyols show higher elongation at
break than PU obtained from CO diethanolamide polyols. PU foams have high
closed-cell content, and the renewable content in the range from 25.0 to 35.6 wt%.
The bio-based PU coatings from CO triethanolamine polyols have higher elong-
ation at break but lower tensile strength and modulus of elasticity than PU coatings
from CO diethanolamide polyols. With increasing molar ratio CO/DEA and
CO/TEA from 1 to 3, the thermal stability of the PUs obtained from these polyols
decreases in the temperature range from 150 C to 350 C. The PUs from CO
triethanolamine polyols have lower weight losses than the PUs from CO dietha-
nolamide polyols. PUs from CO diethanolamide polyols have higher glass transi-
tion temperature than PUs from CO triethanolamine polyols.
Biodegradation of CO-based PU foams by fungi shows that the degradation of the
polymer is different depending mainly on the CO and PEG 300 content. The presence
of PEG 300 enhances the degradability of the PU foams in the presence of fungi,
while the increased CO content decreases biodegradability. The fungi A. niger and
P. flavido-alba are able to use these materials as the sole carbon source.

Funding
The work has been funded by the European Regional Development Fund, contract No.
2DP/2.1.1.1.0/10/APIA/VIAA/054.

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