Accepted Manuscript

Production and characterization of polyurethane foams from a simple mixture

of castor oil, crude glycerol and untreated lignin as bio-based polyols

Camila S. Carriço, Thaís Fraga, Vânya M.D. Pasa

PII: S0014-3057(16)30411-6
DOI: http://dx.doi.org/10.1016/j.eurpolymj.2016.10.012
Reference: EPJ 7549

To appear in: European Polymer Journal

Received Date: 11 May 2016

Revised Date: 9 August 2016
Accepted Date: 6 October 2016

Please cite this article as: Carriço, C.S., Fraga, T., Pasa, V.M.D., Production and characterization of polyurethane
foams from a simple mixture of castor oil, crude glycerol and untreated lignin as bio-based polyols, European
Polymer Journal (2016), doi: http://dx.doi.org/10.1016/j.eurpolymj.2016.10.012

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 Production and characterization of polyurethane foams from a simple mixture
of castor oil, crude glycerol and untreated lignin as bio-based polyols

Camila S. Carriço1, Thaís Fraga1, Vânya M. D. Pasa1*.

1
Laboratório de Produtos da Biomassa, Departamento de Química, Universidade
Federal de Minas Gerais, Av. Antonio Carlos, 6627, 31270-901, Belo Horizonte,
Minas Gerais - Brazil

* Corresponding author:
e-mail: vmdpasa@terra.com.br
Phone number: + 55 31 3409-7577
Fax: + 55 31 3409-6650

Abstract
Polyurethane foams from bio-based polyols have been studied to produce
sustainable and eco-friendly materials from biomass industrial wastes. Semi-rigid
polyurethane foams were synthesized from physical mixtures of kraft lignin, castor oil
and residual glycerol. The influence of different lignin contents (10, 12.5, 15, 17.5, 20,
25, 30 and 40%) on the foam properties was evaluated. An increase in the density
and a decrease in the thermal stability were observed upon an increasing amount of
lignin. The foam synthesized with 17.5% lignin showed better dimensional and
thermal properties as well as the best cell homogeneity. This formulation was chosen
for further investigation of the effects of the castor oil content, isocyanate/hydroxyl
molar ratio (NCO/OH) and the blowing agent type. Increased foam densities and
compressive strengths were observed with increased castor oil content in the foams.
Similar results were observed upon increasing the NCO/OH molar ratio due to the
higher amount of crosslinking reactions. The evaluation of the blowing agent effect
showed that using cyclopentane and n-pentane, the foams showed higher densities
and lower compressive strengths in comparison to the foams synthesized with the
chemical blowing agent (water). This result can be explained by the faster
volatilization of these organic blowing agents, producing smaller cells in comparison
to the CO2 generated by the reaction of water with isocyanate. Green polyurethane
foams with good properties and industrial interest were produced using a mixture of
residual raw materials (glycerol and lignin) and castor oil as bio-based polyols.
Keywords: polyurethane foams, lignin, crude glycerol, castor oil
1. Introduction
Among all the products derived from polyurethane, foams are versatile
polymeric materials with a broad market that can be classified as flexible, semi-rigid,
or rigid depending on their mechanical performance characteristics and densities.
The main applications of foams are in the furniture industry, including in upholstery,
insulation, and packing, and in automotive applications, including seat cushioning,
bumpers, and sound insulation. This polymer is produced by the reaction of an
isocyanate and a polyol in addition to other additives used to adjust the properties of
the final foam product. However, most of these reagents are derived from
petrochemicals, increasing the dependence on petroleum. Therefore, the
environmental concern and need for sustainable technologies motivate the
production of the polyurethane foams from renewable feedstock [1,2].
Polyurethane foams from bio-based polyols have been studied for the
production of sustainable and eco-friendly materials from industrial waste biomass
such as lignocellulosic [3,4], bio-pitch [5], glycerol [6] and vegetable oils [7]. Among
these raw materials, lignin is a potential candidate for producing bio-based
polyurethane foams due to its abundance and complex chemical structure that allows
its use in a wide range of applications. This polymer exists naturally in plants and
trees, and comprises about 30% of wood. Lignin is an aromatic complex polymer
derived from coniferyl, coumaryl and sinapyl alcohol that contains high
concentrations of phenolic and aliphatic hydroxyl groups. Lignin is obtained in large
quantities from pulp and paper mills or, more recently, as a residue of cellulosic
ethanol production process [2,8].
Recently, many studies were carried out using lignins and other by-products in
polyurethane foam synthesis, as reported by Hatakeyama et al. [9,10], who used
different lignins dissolved in molasses and polyglycols. Another interesting study was
performed by Li and Ragauskas [11,12], who prepared a polyol by reacting lignin with
propylene oxide catalysed by potassium hydroxide. Among other studies, Cinelli et al
[1] liquefied lignin using glycerol and PEG400 as the liquefying agent, and Mahmood
et al. [8] also produced foams using hydrolytically depolymerized Kraft lignin.
These studies indicate that lignin can be used directly or modified chemically
by hydrolysis, epoxidation, hydroxylation, ozonolysis, and hydrogenation. Recently,
many methods were developed for the conversion of biomass into bio-based polyols
via liquefaction [13]. However, in addition to the use of some solvents, most of these
bio-based polyols production methods require the use of some energy source, mainly
heat or microwave, to homogenize the system phases and optimize the physical
properties of the polyols.
The physical mixing of raw materials is desirable for the use of by-products
from bio-fuel production and industrial waste without any type of chemical or physical
pre-treatment and for direct use in polyurethane synthesis. In addition to the physical
mixing being a simple method for the homogenization of miscible materials, the use
of raw materials without pre-treatment is of great interest to industry because it
minimizes the number of steps in production, thereby accelerating the execution of
the overall production process and reducing costs.
The production of polyols from industrial residual sources, such as lignin (from
paper industry and cellulosic ethanol production) and crude glycerol (obtained as by-
product of biodiesel production), add value to these residues, and also contribute to
the economical feasibility of important cellulose industry, biodiesel and bioethanol
commodities. In this study, bio-based polyols were synthesized without pre-treatment
processes using lignin, crude glycerol and castor oil. The polyols mixtures were used
to synthesize different polyurethane foams. The foams’ physical chemical and
mechanical properties were evaluated, and these results appear to be promising for
several industrial applications.

2. Materials and methods

2.1. Materials
Eucalyptus Kraft pulp lignin (Suzano Industry of Paper and Cellulose, Limeira,
São Paulo - Brazil) was obtained from a cellulose pulping process (black liquor) and
is therefore used in its alkaline form. Crude glycerol, obtained as a co-product of
biodiesel production, was kindly supplied by Petrobrás (Usina Darcy Ribeiro-Montes
Claros, Minas Gerais - Brazil). The castor oil was provided by the Polyurethane
Company (Betim, Minas Gerais - Brazil). Desmodur 44 V 20 (Bayer), which is a
mixture of 4,4'-diphenylmethane-diisocyanates, was used as the isocyanate source.
Tegostab 8460 (Evonik), a polyether-modified polysiloxane, was used as the
surfactant. DBTDL (dibutyltin dilaurate), an organometallic catalyst called Kosmos 19
manufactured by Evonik, was used as the catalyst in the syntheses of the
polyurethane foams. Cyclopentane, n-pentane (Sigma Aldrich) and distilled water
were used as the blowing agents.

2.2. Foam syntheses

Polyurethane foams were synthesized using the batch process method, also
known as the box process. Initially, the polyols were produced by the physical
mixture method, consisting of mixing two or more compounds to obtain a
homogeneous material. Lignin (L), crude glycerol (G) and castor oil (CO) were mixed
with a mechanical stirrer, Fisatom model 713 D, until the system became completely
homogeneous. The surfactant, catalyst and blowing agent were added to the polyol,
and this mixture was kept under vigorous stirring for 1 min at 500 rpm. Finally, the
isocyanate was added and remained under agitation for 20 sec. The formulation was
poured into a wooden mould with dimensions of 7.0 x 7.0 x 20.0 cm for the growth of
the polymer foam, and the mould was kept closed for 24 hours at room temperature
to perform curing. After curing, the box was opened and the foam was characterized.
For preliminary scanning tests varying the lignin content, 2% of water was
used as the blowing agent and 2% of DBTDL (dibutyltin dilaurate) was used as the
catalyst. The foam formulations for the bio-based polyols are shown in Table 1, and
the isocyanate was added at the NCO/OH ratio of 1.1. The influence of the NCO/OH
molar ratio, catalyst type and content, and blowing agent type and content were
investigated for the foams that showed the best dimensional and thermal stability.

2.4. Characterization
The viscosity of raw materials was measured using a viscometer (Herzog
Ubbelohde Viscometer, model UVH 481) according to the ASTM D 445 standard.
The polyol hydroxyl number values were determined according to the ASTM D4274
standard in an automatic titrator (Kyoto Electronics, AT 500 model). The FTIR
spectra of the raw materials, polyols and foams were collected in a ABB Bomer
spectrometer using 0.1% KBr pellets with a resolution of 4 cm-1, in the 4000 – 400
cm-1 range. Thermal analyses by thermogravimetry (TG) were carried out in a TA
equipment model TA-50 Q at temperatures ranging from 30 to 800°C with a heating
rate of 10° C min-1 under a nitrogen flow of 40 mL min-1 to verify the thermal stability
at different temperatures. The optical microscopy images were obtained using an
Olympus Optical Microscope Model BX41M coupled to a TecVoz camera model DNS
480. Scanning electronic microscopy (SEM) was performed with a JEOL JSM -
6360LV scanning microscope to observe and evaluate the cellular structure of the
foam. The apparent density was measured according to the ASTM D1622 standard,
using 50 × 50 × 25 mm samples in triplicate. Compression tests were carried out
using an Autograph Precision Universal Testing Machine AG-Xplus Series
(Shimadzu) according to the ASTM D1621 standard, with at least five samples tested
to obtain average values, and the specimens’ dimensions were 50 × 50 × 25 mm.

3. Results and Discussion

3.1. Raw material and polyol characterization

The results presented in Table 2 showed that crude glycerol has the highest
reactivity and can be considered as a crosslinking agent due to its low size and high
functionality. Lignin has a hydroxyl number that is 6 times smaller than that of the
crude glycerol, implying a lower reactivity; however, the reactivity of lignin is still
higher than that measured for castor oil. These values are in agreement with the
values reported in the literature [8, 15].
Castor oil showed a viscosity value 10 times higher than that obtained for
crude glycerol, which can be related to its structure. Glycerol possesses only 3
carbons with 3 hydroxyl groups, but the effect on the viscosity of the hydrogen
linkage caused by this polar group was smaller than that of the large chain of the
castor oil, which has 18 carbon atoms.
The infrared spectra of the raw materials used for the preparation of polyols
are shown in Figure 1. The bands at approximately 3400 cm-1 correspond to the
vibration of the hydroxyl groups, and the bands at approximately 2920 and 2870 cm-1
were assigned to CH2 and CH3 stretches of aliphatic chains. The characteristic
stretches of double bonds in the castor oil C=C-H and C=C-C groups were observed
at 3012 and 1621 cm-1, respectively. An average band at 1465 cm-1 was due to the
deformation of alkene CH2 groups, also present in the castor oil structure. The
average intensity of the bands at 1710-1700 cm-1, characteristic of carbonyl and
carboxyl groups, were observed in the spectrum of lignin and most notably in the
castor oil spectrum. The bands at 1600 and 1515 cm-1 correspond to the vibration of
the aromatic rings, and the bands at 1460 to 1420 cm-1, due to the deformation of the
CH on the aromatic ring, were also observed in the lignin spectrum; additionally,
several absorption bands were observed below 1400 cm-1, representing the
contribution of various vibrational modes [8,14,15].
The changes of the hydroxyl number of LGCO polyols upon variation of the
lignin content are shown in Figure 2. As the lignin content increases, the hydroxyl
group value decreased, which can be related to the reduction of the glycerol content,
as shown in Table 2. Glycerol has a higher functionality owing to its high hydroxyl
number, so that result was expected; the lower content of glycerol and the higher
content of lignin reduced the polyol hydroxyl number. The castor oil content was
unaltered for all polyol samples.

3.2. Foam characterization

The composition of polyurethane foams was evaluated by FTIR analysis. The
spectra are presented in Figure 3 and show the characteristic bands for the main
functional groups. The NH stretching and vibrations were observed between 3808
and 3308 cm-1 and 1512 and 1510 cm-1, respectively. The presence of unreacted
isocyanate can be observed in a small band at 2270 cm-1, which can be explained
due to the molar ratio used in these formulations (NCO/OH = 1.1). Other foams were
formulated with lower NCO/OH ratio, but these materials did not show dimensional
stability. The two thin bands at 2900 and 2890 cm-1, corresponding to deformation of
CH2 bonds and other CH bond vibrational modes, are also observed at 1464, 1418,
1364 and 1294 cm-1. The band between 1730 and 1720 cm-1 corresponds to the CO
bond stretch of the free urethane, and at approximately 1700 cm-1, the hydrogen
bond between the carbonyl and hydrogen atoms (from OCONH groups) from the
urethane is also observed. Furthermore, a band related to the stretching of OCONH
asymmetric links at 1380 cm-1 was also revealed [1,16,17]. The band at 1726 cm-1,
related to the carbonyl group, becomes more extended with increasing lignin content
owing to the appearance of the band corresponding to the hydrogen bond with C = O
at 1705 cm-1; this result supports the formation of hydrogen bonds between the polar
groups of the lignin and urethane [18].
The results of the thermal analysis for the various lignin contents in the foams
are shown in Figure 4. The thermal degradation of polyurethanes occurs as a result
of various physical and chemical phenomena that are not dominated by a single
process and depend mainly on the balance between the polymerization and
depolymerization of the functional groups or bonds present in the polymer chains.
Three weight loss regions were observed in the TG curves. A small event observed
in the TG curve at approximately 260°C (approximately 5% weight loss) is probably
due to the loss of some unreacted small molecules. The second event, observed at
approximately 300°C, corresponds to the degradation of the urethane linkage, which
is related to the hard segments of polyurethane structure. This event corresponds to
a weight loss of 35%. The third degradation event is observed at 350°C and is
related to the lignin decomposition. The fourth event at 450°C is associated to the
thermal degradation of the soft segments [1, 5, 17].
The data for the foam densities for samples with different lignin contents are
shown in Figure 5; and these density values are in agreement with the literature data
for foams containing lignin [6, 8, 9, 11]. It was also observed that there is a trend of
increased density with higher lignin content in the foams. This probably occurs
because, in addition to the enhanced system viscosity, the addition of lignin produced
polymer materials with a lower free volume and a higher density; as a consequence,
smaller and denser cells were obtained [19].
Relating the results presented in Figures 2 and 5, it was observed that polyols
with a higher hydroxyl number (lower lignin and higher glycerol amount) yielded
foams with lower densities. While higher densities were expected from higher OH
numbers, due to the increase of crosslinking reactions, an opposite tendency was
observed for our results. This behaviour can be explained by the short size of
glycerol chain, which does not allow crosslinking reactions, causing an increase in
the polymer free volume and consequently a decrease in the density values.
The images obtained by the optical microscopy of the cross-section foams
produced from the polyol LGCO are shown in Figure 6. The cells exhibited an
elongated shape (elliptical), and it was observed that increasing the lignin content
decreases the cell size, confirming the density data (Figure 5). The presence of
smaller particles agglomerated in the foams synthesized with higher lignin content
was also observed. These observations indicate a low homogeneity for the foams
with high concentrations of lignin, especially for those with values higher than 17.5%.
These results are consistent with the apparent density of the foams, suggesting that
the addition of lignin in these formulations increases their density values.
Based on this analysis, it was observed that the foam containing 17.5% of
lignin, 32.5% of crude glycerol and 50% of castor oil (D formulation) presented the
best dimensional and thermal stability as well as the best cell homogeneity. For this
reason, some variations on this formulation were performed for evaluate the effect of
castor oil content, molar ratio NCO/OH and type of blowing agent.
Table 3 shows the apparent densities of the foams with LGCO polyol; it was
observed that increasing the castor oil content in the foam formulation led to an
increase in the apparent density, suggesting that the polymeric chains were more
packaged with a lower free volume and smaller cells , as also confirmed by the
increased stiffness of these materials. An increase of the density was also observed
with the addition of excess isocyanate (molar ratios NCO/OH = 1.1 to 2.0), which can
be explained by the increase of reactions between the isocyanate with the polyol and
consequently, an increase of crosslinking and a higher content of rigid segments, as
expected.
The examination of the effect of the blowing agent on the density of the foams
showed that the physical blowing agents (cyclopentane and n-pentane) yielded
foams with higher densities than the samples synthesized with a chemical blowing
agent (water); this result can be explained by the rapid volatilization during the highly
exothermic foam growth steps, causing cells with less gas in comparison with the
CO2 produced by the reaction of water with isocyanate. Similar results have been
reported in the literature [20, 21].
The mechanical properties of the foams are proportional to the density, due to
the increase in the cell wall thickness and/or a decrease in the cell size; according to
Euler-Bernoulli beam theory, this gives rise to an increase in the bending moment of
the cell wall [22]. The compressive strength results showed an increase with the
greater castor oil amount in the formulations, indicating that there is a greater content
of crosslinking and rigid segments with higher castor oil content. The increase of
isocyanate content also increases the compressive strength of the foams, except for
the NCO/OH = 1.5 foam, which shows a decrease in this mechanical property,
suggesting a dimensional destabilization of this structure.
The foams produced using physical blowing agents (cyclopentane and n-
pentane) showed lower compressive strength in comparison with those synthesized
with the chemical blowing agent (water), unlike the results reported in the literature.
This behavior can be explained by the low accessibility of the hydroxyl groups from
lignin and short chain of glycerol used in our formulation, which can not react
completely with the isocyanate. As consequence, the unreacted isocyanate,
evidenced in FTIR spectrum (Figure 3), is available to form urea linkages by the
reaction of the isocyanate and water. These urea groups exhibits strong cohesion
and provide more stability and toughness for foams using CO2 as the blowing agent,
differently from the literature data [20, 21].
The green foams obtained in this study, which showed density values of 50-
120 kg m-3 and compressive strength of 10 - 65 kPa, which are similar to those
conventional commercial foams that present densities in the 15 -130 kg m-3 range
and their hardness values are in the 1.3 – 31 kPa range. Based on these results the
foams produced from lignin, crude glycerol and castor oil can potentially be used on
industrial scale in the construction and packaging industry [23].
The foam structure is confirmed by the morphological analysis performed by
SEM as shown in Figures 7-10. It can be observed that increasing lignin content
decreases cell sizes (Figure 7), in accordance with the apparent density and optical
microscopy results. Foams with a lower castor oil content (Figure 8) showed thick
and large cells. An increasing NCO/OH molar ratio was observed to result in a
greater heterogeneity of the cell size and shape, as shown in Figure 9. The SEM
micrographs of the samples obtained with different blowing agents (Figure 10)
showed that physical blowing agents produced foams with smaller cell sizes than the
foams synthesized using water as the blowing agent, as suggested by the density
data. The SEM micrographs also confirmed that the heterogeneity of these
formulations led to a higher standard deviation.

4. Conclusions
The properties of the foams produced from polyols obtained by the physical
mixture of lignin, castor oil and crude glycerol may be adjusted according to the
amount of reactants in the formulations. The synthesis process is simple and
inexpensive and does not require biomass pre-treatment. The produced foams with
higher lignin contents showed a decrease in thermal stability and an increase in the
density and compressive strength. Compared to the other tested foams, the foam
with 17.5% lignin in its formulation showed a higher thermal and dimensional stability
as well as a greater cell homogeneity. The effects observed with the increase in the
amount of castor oil and the molar ratio NCO/OH showed that these reagents
promote an increase in the amount of urethane crosslinking, providing greater
stiffness to the foams. The use of volatile blowing agents produce smaller cells with
higher density in comparison with formulations using water as the blowing agent.
However, the use of water produced more rigid foams due the increase of urea
linkages as a by-product of CO2 formation. The use of these polyols from industrial
residual sources in addition to castor oil and water as the blowing agent provides a
high sustainability for these materials and can contribute to the economic feasibility of
the important cellulosic ethanol and biodiesel commodities. Additionally, these
environmentally friendly foams showed good properties and a potential for use on
the industrial scale.

Acknowledgements
The authors would like to acknowledge the financial support of CNPq.

References
[1] Cinelli P, Anguillesi I, Lazzeri A. Green synthesis of flexible polyurethane foams
from liquefied lignin. Eur Polym J 2013; 49 (6): 1174–1184.
[2] Bernardini J, Cinelli P, Anguillesi I, Coltelli MB, Lazzeri A. Flexible polyurethane
foams green production employing lignin or oxypropylated lignin. Eur Polym J 2015;
64: 147–156.
[3] Zhang HR, Pang H, Zhang L, Chen X, Liao B. Biodegradability of Polyurethane
Foam from Liquefied Wood Based Polyols. J Polym Environ 2013 21: 329–334.
[4] Gu R, Sain MM. Effects of Wood Fiber and Microclay on the Performance of Soy
Based Polyurethane Foams. J Polym Environ 2013 21:30–38.
[5] Araújo RCS, Pasa VMD, Melo BN. Effects of biopitch on the properties of flexible
polyurethane. Eur Polym J 2005; 41 (6): 1420–1428.
[6] Luo XL, Hu SJ, Zhang X, Li YB. Thermochemical conversion of crude glycerol to
biopolyols for the production of polyurethane foams. Bioresour Technol 2013; 139:
323-329.
[7] Tu YC., Kiatsimkul P, Suppes G, Hsieh FH. Physical properties of water-blown
rigid polyurethane foams from vegetable oil-based polyols. J Appl Polym Sci 2007;
105: 453–459.
[8] Mahmood N, Yuan Z, Schmidt J, Xu C. Preparation of bio-based rigid
polyurethane foam using hydrolytically depolymerized Kraft lignin via direct
replacement or oxypropylation Eur Polym J 2015; 68: 1–9.
[9] Hatakeyama H, Kosugi R, Hatakeyama T. Thermal properties of lignin- and
molasses-based polyurethane foams. J Therm Anal Calorim 92; (2008): 419-424.
[10] Hatakeyama T, Matsumoto Y, Asano Y, Hatakeyama H. Glass transition of rigid
polyurethane foams derived from sodium lignosulfonate mixed with diethylene,
triethylene and polyethylene glycols Thermochim Acta 416 (2014) 29–33.
[11] Li Y, Ragauskas AJ. Kraft Lignin-Based Rigid Polyurethane Foam. J. Wood
Chem Techno, 32 (2012) 210–224.
[12] Li Y, Ragauskas AJ. Ethanol organosolv lignin-based rigid polyurethane foam
reinforced with cellulose nanowhiskers. RSC Advances 2012; (2): 3347–3351
[13] Karak N. Vegetable Oil-Based Polymers: Properties, Processing and
Applications, Woodhead Publishing 2012.
[14] Pavia D. L., Lampman G. M., Kriz G. S. Introduction to Spectroscopy, 3 rd edition.
Brooks Cole, 2000.
[15] Stirna U, Lazdina B, Vilsone D, Lopez MJ, Vargas-Garcia MC, Suárez-Estrella F,
Moreno J. Structure and properties of the polyurethane and polyurethane foam
synthesized from castor oil polyols. J Cell Plast; 2012; 48: 476
[16] Chen F, Lu Z. Liquefaction of wheat straw and preparation of rigid polyurethane
foam from the liquefaction products. J Appl Polym Sci 2009; 111 (1): 508-516.
[17] Corcuera M A, Rueda L, Fernandez d’Arlas B, Arbelaiz A, Marieta C, Mondragon
I, Eceiza A. Microstructure and properties of polyurethanes derived from castor oil.
Polym. Degrad. Stabil. 2010; 95 (11): 2175-2184.
[18] Luo X., Mohanty A., Misra M. Lignin as a reactive reinforcing filler for water-
blown rigid biofoam composites from soy oil-based polyurethane. Ind Crop Prod
2013; 47: 13-19.
[19] Vilar, W. Química e Tecnologia dos Poliuretanos, Vilar Consultoria, São Paulo,
2002.
[20] Lim , H. , Kim , E. Y., Kim, B. K. Polyurethane foams blown with various types of
environmentally friendly blowing agents. Plast Rubber Compos 39 (2010) 364-369.
[21] Modesti, M., Adriani, V., Simioni, F. Chemical and physical blowing agents in
structural polyurethane foams: Simulation and characterization. Polym Sci Eng 40
(2000) 2046–2057.
[22] H. Jeong, J. Park, S. Kim, J. Lee, N. Ahn. Fiber Polym. 2013, 14, 1301.
[23] Eurofoam, Technical purpose foams. Available in:
<http://www.eurofoam.hu/habtipusok-en/Comfort-purpose-foams/> (accessed June
20, 2006).
 Figure captions

Figure 1. Spectra of raw materials for polyol production.

Figure 2. Hydroxyl number versus lignin content of the polyols used to produce
containing a mixture of lignin, crude glycerol and castor oil (LGCO polyol).

Figure 3. FTIR spectra of foams produced with different lignin content (A) 10%, (B)
12.5%, (C) 15%, (D) 17.5%, (E) 20%, (F) 25%, (G) 30% and (H) 40% of lignin.

Figure 4. TG (a) and DTG (b) curves of foams with LGCO polyol containing different
amounts of lignin (A) 10%, (B) 12.5%, (C) 15%, (D) 17.5%, (E) 20%, (F) 25%, (G)
30% and (H) 40% of lignin.

Figure 5. Variation of foams density with the lignin content.

Figure 6. Images of LGCO foams with different contents of lignin: (a) A, (b) B, (c) C,
(d) D, (e) E, (f) F, (g) G and (h) H (magnification of 50x).

Figure 7. SEM micrographs of LGCO foams varying lignin content. (a) A, (b) B, (c) C,
(d) D, (e) E, (f) F, (g) G and (h) H.

Figure 8. SEM micrographs of LGCO foams varying castor oil content in D

formulation. (a) 25, (b) 50 and (c) 75% of castor oil.

Figure 9. SEM micrographs of LGCO foams varying NCO/OH molar ratio in D

formulation. (a) NCO/OH = 1.1, (b) NCO/OH = 1.5 and (c) NCO/OH = 2.0.

Figure 10. SEM micrographs of LGCO foams varying the blowing agent in D
formulation. (a) water, (b) n-pentane, (c) cyclopentane and (d) a mixture of water and
cyclopentane.
 Tables
Table 1. Foam formulations for bio-based polyols.

Formulation A B C D E F G H
Reagents Parts by weight
Lignin 10 12.5 15 17.5 20 25 30 40
Glycerol 40 37.5 35 32.5 30 25 20 10
Castor oil 50 50 50 50 50 50 50 50
Catalyst 2 2 2 2 2 2 2 2
Surfactant 2 2 2 2 2 2 2 2
Blowing agent 2 2 2 2 2 2 2 2

Table 2. Physical chemical properties of the raw materials.

Hydroxyl number Viscosity

Raw materials -1
(mg KOH.g ) (mPa.s-1 at 30°C)
Lignin 305.6 -
Crude glycerol 1827.6 111.7
Castor oil 163.0 1101.7

Table 3. Apparent densities and mechanical properties of foams produced with

LGCO polyol (D formulation).

Compressive Compressive
Sample Density (kg.m-3)
strenght (kPa) modulus (kPa)
25% CO 52.7 ± 1.7 14.4 ± 5.1 9.8 ± 3.5
50% CO 54.9 ± 4.0 35.0 ± 4.3 10.2 ± 2.5
75% CO 108.7 ± 2.2 48.0 ± 1.3 32.1 ± 13.6
NCO/OH=1.1 54.9 ± 4.0 35.0 ± 4.3 10.2 ± 2.5
NCO/OH=1.5 77.1 ± 9.8 24.4 ± 5.0 26.3 ± 4.7
NCO/OH=2.0 130.2 ± 7.0 64.9 ± 8.9 56.7 ± 15.3
H2O 54,9 ± 4.0 35.0 ± 4.3 10.2 ± 2.5
NP 71.1± 0.5 28.1 ± 14.3 34.4 ± 17.0
 CP 81.3 ± 13,9 24.7 ± 4.0 39.6 ± 9.8
H2O/CP 71.4 ± 6.9 22.6 ± 10.1 32.1 ± 13.6
NP = n-pentane and CP= cyclopentane
Figure 1

LGCO polyol
250

Lignin
200
Transmitance (%)

150
Castor oil

100
Crude glycerol

50

0
4000 3500 3000 2500 2000 1500 1000
-1
Wavenumber (cm )
Figure 2

1100

1000
Hydroxyl number (mg KOH/g)

900

800

700

600

500

400

300

200

10 15 20 25 30 35 40

Lignin content (%)

Figure 3

150 A

B
125

C
Transmitance (%)

100 D

75 E

F
50

G
25
H

0
4000 3500 3000 2500 2000 1500 1000
-1
Wavenumber (cm )
Figure 4

100 0,000
A
90
B
-0,002
80
C
70
-0,004
D
Weight (%)

60

50
A
D E
-0,006
40 B
F
30 F -0,008
C G
20

10 -0,010 H
H E
G
0
100 200 300 400 500 600 700 200 250 300 350 400 450 500 550 600

Temperature (°C) Temperature (°C)

(a) (b)
Figure 5

120

110

100
Density (kg.m -3)

90

80

70

60

50
10 15 20 25 30 35 40
Lignin content (%)
Figure 6

(a) (b) (c) (d)

(e) (f) (g) (h)

Figure 7

(a) (b) (c) (d)

(e) (f) (g) (h)

Figure 8

(a) (b) (c)

Figure 9

(a) (b) (c)

Figure 10

(a) (b)

(c) (d)
 Highlights

 Residual biopolyols were used to synthesize semi-rigid polyurethane foams

 Different content of lignin, castor oil and glycerol were reacted with MDI
 The foams with 17.5% lignin presented the best dimensional and thermal properties
 The castor oil content, NCO/OH ratio and blowing agent type were studied
 This simple process yielded foams with good properties for industrial application
Graphical abstract