ABSTRACT In recent years, environmental issues associated with

petrol-based polyurethane foams have prompted the exploration of

biocompatible resources, such as vegetable oils, for their production.
Although many vegetable oils have been used to produce bio-based
polyurethane foams, most of them, such as soybean and palm oil,
threaten the primary sources of human nutrition due to their
interference with the human food chain. Therefore, there is a pressing
need to identify abundant and renewable non-edible primary sources.
In this study, a new biopolyol was synthesized from date seed
(Phoenix dactylifera L.) as a renewable and biocompatible waste
source. The date seed oil (DSO) was extracted using the Soxhlet
method with n-hexane solvent. In the next step, amidation (as a
green method) was used to synthesize the bio-polyol in a one-step,
and solvent-free reaction. The DSO and DSO polyol were evaluated
using FT-IR, 1 H NMR, and 13C NMR spectroscopy. The key parameters
of the DSO polyol, including hydroxyl number, acid value, viscosity,
and thermal stability, were investigated. In the next part of this
research, the DSO polyol was used to produce rigid polyurethane-
polyisocyanurate foams in weight ratios of 0, 30, 50, 70, and 100 %.
The foams modified with DSO polyol were evaluated using various
analyses, including FT-IR, SEM, TGA-DTG, compressive and tensile
strength, water absorption, and aging resistance. The effect of
increasing the percentage of DSO polyol on the properties of the
foams was investigated and discussed. In some analyses, the
modified foams performed better than the reference foam

1. Introduction The characteristics of rigid polyurethane (RPU) foam

include high thermal resistance, strength, adhesion, low density, high
dimensional stability, and resistance to aging. These properties make
RPU foam an essential raw material in various industries, such as
refrigeration, construction, and pipelines (Yang et al., 2015; Alavi
Nikje, 2019). Polyurethane structures are created by reacting between
molecules containing two or more isocyanate groups with compounds
containing two or more hydroxyl or amine groups (Alavi Nikje, 2019;
Paciorek-Sadowska et al., 2020). Polyisocyanurate (PIR) foam is a
specific type of RPU foam formed through the trimerization of three
isocyanate segments, which results in the formation of isocyanurate
functional groups. These isocyanurate groups significantly impact the
properties of the foams, including a high closed-cell content, high
thermal stability, and low thermal conductivity (Makaveckas et al.,
2021). The structure of the isocyanurate functional group is similar to
melamine, making this structure intrinsically flame retardant.
Therefore, foams containing isocyanurate groups will have high
thermal resistance properties (Xu et al., 2018). Studies have
demonstrated that isocyanurate groups exhibit better stability
compared to other functional groups, such as urethane and urea, in

functional groups decompose at 300–350 ℃, whereas the urea

both thermodynamically and thermally contexts. Isocyanurate

functional group decomposes at 250 ℃, the urethane group at 200

℃, the biuret group at 135–140 ℃, and the allophanate group at 106
℃ (Kirpluks et al., 2016). Until now, the most common method of
producing polyurethane foams has been using petrol-based polyols,
specifically aromatic polyether polyol and polyester polyol (APP).
These petrol-based polyols react with polyisocyanates to form rigid
polyurethane-polyisocyanurate foams. However, due to growing
environmental concerns, there has been a focus on finding
biocompatible alternatives to replace these petrol-based raw
materials. As a result, there has been an increase in research on using
biocompatible raw materials such as vegetable oils (VOs), biomass,
and agricultural and industrial waste to reduce the environmental
impact of petrol-based polyurethane foams (Haridevan et al., 2021;
Sarim et al., 2023). Despite these efforts, the use of 100 % bio-based
polyurethane foam is not yet able to compete with petrol-based foam
due to its unfavorable properties. As the percentage of bio-based
polyol increases in the foam matrix, the properties of the foam
become weaker, especially in rigid foams. However, researchers have
successfully incorporated up to 50 % bio-based components into
polyurethane foam without compromising its properties, making it
comparable to petrol-based polyurethanes (Badan and Majka, 2017).
VOs are critical and valuable raw materials for the formulation of bio-
based PU foams. The main component of VOs is triglyceride, which
comprises a glycerol ester with three long fatty acid chains. Some of
the most commonly used edible VOs include soybean, sunflower,
corn, palm, canola, olive, coconut, rice bran, and peanut (Amran et
al., 2021; Magiera et al., 2023; Hipulan et al., 2024). Non-edible oils,
such as castor, jatropha, jojoba, bitter almond, safflower, tall oil, and
tea tree oil, are also commonly used. However, one disadvantage of
using edible VOs in polyurethane formulations is their involvement in
the human food chain. For this reason, the use of non-edible VOs is
preferred (Acuna ˜ et al., 2021; Andersons et al., 2022; Mozaffari et
al., 2022; Paciorek-Sadowska et al., 2020; Prociak et al., 2018; Sahoo
et al., 2018). The most common and widely used production methods
of VO-based polyols in the preparation of PU foams are
hydroformylation/reduction, ozonolysis/hydrogenation,
epoxidation/ring opening, thiol-ene, transesterification, and amidation
(Andersons et al., 2012; Desroches et al., 2012; Kuranska ´ et al.,
2016; Petrovic, 2008; Ramanujam et al., 2019). Amidation can be
performed on VOs using various amines, such as diethanolamine
(DEA) and triethanolamine (TEA), with the assistance of various
catalysts. Scheme 1 shows the overall reaction of date seed oil with
diethanolamine in the presence of a sodium methoxide catalyst. In
this reaction, one mole of triglyceride reacts with three moles of
diethanolamine, resulting in the production of three moles of fatty
amide diol and one mole of glycerol (Andersons et al., 2012). The
solvent-free method of direct amidation is a fast and efficient reaction
that is significant in terms of green chemistry, environmental
considerations, experimental purposes, economic factors, and high
efficiency of amidation. The direct amidation of carboxylic acids and
esters using amines to synthesize amides is highly favorable in terms
of atom economy (Betancourt-Jimenez et al., 2020; Traboni et al.,
2023). Unlike other methods, such as epoxidation/ring opening,
ozonolysis/reduction, and hydroformylation/reduction, the direct
amidation reaction of VOs to produce bio-polyol is a one-step process,
making it more convenient (see SI Scheme S1). Date (Phoenix
dactylifera L.) is a crucial agricultural product in arid and semi-arid
regions worldwide. Over sixty varieties of date fruits have been
reported worldwide. Approximately 10–18 % of the weight of this fruit
is related to its seeds. The highest percentage of fatty acids present
in date seed oil (DSO) is oleic acid, followed by lauric acid, myristic
acid, and palmitic acid, with percentages of 43.23 %, 21.08 %, 13.85
%, and 12.38 %, respectively (Table 1) (Allami et al., 2020). Date
seeds are a waste of the agriculture and food industries that produce
Date-based products. However, these seeds contain valuable
substances such as dietary fiber, oil, carbohydrates, and protein. So
far, DSO has been used in some cosmetic products and
pharmaceutical supplements, as well as in research on bio-diesel
(Allami et al., 2020) and bio-lubricants (Tafti et al., 2017). Although
extensive research has been conducted on the synthesis of bio-polyol
from VOs, the use of DSO for this purpose has not been previously
explored. DSO has the potential to serve as a biocompatible source
for bio-polyol synthesis. Therefore, this study aims to synthesize a
new polyol using DSO and diethanolamine, and to examine the
physical and chemical properties of foams produced from this DSO-
based polyol.

2. Experimental

2.1. Materials

Date seeds (Zahidi variety, Shiraz, Iran), n-hexane (prod. by Neutron,

Iran), DEA (diethanolamine, prod. by Neutron, Iran), NaOCH3 (Sodium
methoxide, prod. by Merck, Germany), NaCl (Sodium chloride, prod.
by Merck, Germany), MgSO4 (Magnesium sulfate, prod. by Merck,
Germany), PMDI (polymeric methylene diphenyldiisocyanat, WANNATE
PM-200, 30.5 wt% NCO, fn = 2.6, prod. by Wanhua, China),
cyclopentane (physical blowing agent, prod. by Persian Chemical Co.,
Iran), DMCHA (N,N’-dimethylcyclohexylamine, prod. by Hejia, China),
deionized water (prod. by Abaneh, Iran), trimerization catalyst
(anhydrous potassium acetate (KAc) 33 % solution in diethylene
glycol (DEG), prod. by Hejia Co., China), TCPP (Tris(2-
chloroisopropyl)phosphate, phosphate-based flame retardant, prod.
by Hejia Co., China), Silicon RZ9887 (Silicon surfactant, prod. by Hejia,
China), polyester polyol (with the same trade name, based on
diethylene glycol and phthalic anhydride, OHval= 240 mg KOH/g, acid
value purification

2.2. Oil extraction

To initiate the oil extraction process, the seeds were first separated
from the fruit and thoroughly washed to ensure that all remaining fruit
on the seeds was removed. The seeds were left to dry completely at
room temperature for one week. Once dried, the seeds were ground
and the resulting powder was passed through a 35-mesh sieve. The
Soxhlet extraction method, using n-hexane as a solvent, was
employed to extract the oil from the powder. The Soxhlet system
involved a round-bottom flask, a Soxhlet extractor, and a condenser
(as shown in SI Fig. S14). To achieve the highest yield, the following
optimal conditions were established: 300 mL of solvent, a solvent to
powder ratio of 6:1 (v/w), an average particle size of powder less than

of 100–110 ℃. After the designated extraction time, the solvent was

500 microns, an extraction time of 6 hours, and a temperature range

removed using a rotary evaporator. The oil extraction yield was

estimated between 14 % and 15 %.

2.3. DSO

polyol synthesis DSO polyol was synthesized using the amidation

method. It is not necessary to use high-functionality polyols to
produce RPU-PIR foams. Therefore, we chose a direct and solvent-free
amidation process for synthesizing the polyol, as it is a convenient
and efficient method. The synthesis of DSO polyol was carried out in a
one-neck flask equipped with an addition funnel, condenser, and
nitrogen inlet (see SI Fig. S14). The starting materials used were DSO

catalyst (0.1729 g, 3.2 mmol). DEA and NaOCH3 were heated at 80 ℃

(7.7805 g, 9.9 mmol), DEA (3.3645 g, 32 mmol), and NaOCH3 as a

for 15 minutes with continuous stirring (750 rpm) under a nitrogen

atmosphere. DSO was then added drop-wise into the glass flask, with
the temperature gradually increasing to 110 ℃. This reaction was
monitored by FT-IR spectroscopy (refer to Supplemental Data 1). The
reaction was allowed to continue for 4 hours at a constant
temperature. After completion, the mixture was cooled and washed
with a NaCl solution (0.1 M) and ethyl acetate (three times) (Patil et
al., 2021). The upper layer containing DSO polyol was separated from
the glycerol layer using a glass separating funnel. It was then dried
over anhydrous MgSO4. Finally, the ethyl acetate solvent was
removed using a rotary evaporator, resulting in pure DSO polyol (refer
to SI Scheme S2 for the mechanism of DSO polyol synthesis).

2.4. Characterization of DSO and DSO polyol

The functional groups in DSO and DSO polyol were analyzed using FT-
IR on a Bruker TENSOR-27 spectrometer. Spectroscopy was performed
at room temperature, using KBr pellets. In addition, 1 H and 13C NMR
spectroscopy were performed on a Bruker-DRX-300. The samples
were dissolved in deuterated chloroform at 1 %w/v. Other properties
were evaluated, including pH, hydroxyl number (HN), acid value (AV)

and viscosity. The viscosity was determined at 25 ℃ using a digital

according to ASTM D4662–08, density according to ASTM D4669–07,

rheometer (Anton Paar, Austria). Gel permeation chromatography

(GPC) was performed using a WATERS-1515, USA. Relative analyzed
using the polystyrene standard. TGA/DSC analysis was performed
under a nitrogen flow using (DSC-Q300/TA and Perkin-Elmer Pyris

℃ to 400 ℃ at a heating rate of 10 ℃/min. The functionality of DSO

Diamond, USA). The sample weighing 15–17 mg was heated from 30

polyol was obtained from Eq. (1) (Szycher, 1999):

2.5. Preparation of RPU-PIR foam samples

Modified low-density polyurethane-polyisocyanurate rigid foams were

formulated using DSO polyol. Foam samples were produced by
replacing DSO polyol with petrol-based polyol in varying mass
equivalents, ranging from 0 to 1. The total equivalent mass of
synthetic and petrol-based polyol was set at 1. In the formulation of
foams, aromatic polyester polyol was utilized as a petrol-based polyol
to prepare foam samples. The excellent flammability performance of
RPU-PIR foams is partly attributed to the presence of polyisocyanurate
functional groups, as well as the numerous aromatic moieties found in
their hard segments. Due to the presence of aromatic moieties in
their structure, aromatic polyester polyols have a higher resistance to
burning compared to polyether polyols. Additionally, the higher
thermal stability of polyester polyols, in contrast to polyether polyols,
can be attributed to easier thermal-oxidative decomposition of the
polyether structure. Therefore, the use of aromatic polyester polyol in
the preparation of RPU-PIR foams plays a significant role in increasing
the thermal resistance of these foams (Haridevan et al., 2021; Xu et
al., 2018). The amount of PMDI required to achieve an isocyanate
index (II) of 1.7 was calculated, taking into account the reaction of
isocyanate with water and the effect of increasing the percentage of
bio-polyol in the polyol premixes. This calculation was based on the
method proposed by Dworakowska et al. (2022) and Ivdre et al.
(2020), and the corresponding weight was determined (see SI pages
16–18 for further details). Five types of foam were produced, including
S1 foam, which served as the reference without DSO polyol, and four
types (S2-S5) containing increasing amounts of DSO polyol, ranging
from 0.3 to 1 mass equivalent. The production formulation of foam
samples modified with DSO polyol is provided in Table 2. The foam
samples were produced in a laboratory setting using the open mold
and one-step method. First, the polyol mixture, which included DSO
polyol replaced with petrol-based polyol in different ratios (0, 30, 50,
70, and 100 %), was thoroughly mixed with blowing agent, surfactant,
catalysts, and flame retardant. Then, a specific amount of PMDI was
suddenly added to the cup of polyol. The mixture was stirred using a
mechanical stirrer at 2000 rpm for 10 seconds. The mold was then
kept stationary, and the reaction time and foam growth were recorded
using an electronic chronometer. The creaming, gelling, and tack-free
time were recorded according to the ASTM D7487 standard. The first
moment of color change was noted as the creaming time, the
moment of polymer network formation as the gelation time, and the
point at which the foam surface was not sticky, as the tack-free time
was reported. After the foam growth was completed, the sample was
left at 38 ◦C for 24 hours to allow the foam to fully cure before
conducting any analysis.

2.6. Characterization of foam samples

The apparent density of foam samples (core density) was evaluated.

Five samples from each type of the foam were used to determine the
apparent density of foam. The foam volume was not less than 125
cm3 and was measured using a caliper. The weight of each cube was
measured using a digital scale with an accuracy of 0.0001 g. To
evaluate the thermal stability of the samples, a thermogravimetric

flow. The foam sample (3–6 mg) was heated to 800 ℃ at a heating
(TG) analyzer (Perkin-Elmer Pyris Diamond, USA) was used with N2

rate of 20 ℃/min. The foam morphology was observed using scanning

electron microscopy (SEM) VEGA3 images. After fracturing, the
samples were prepared in dimensions of 10 x 10 x 10 mm in the
direction of foam growth. They were then dried and coated with a thin
layer of gold. The measurements were taken at a voltage of 20
kilovolts and various magnifications (15, 50, and 150 X), with a
working distance of 15–16 mm. The microstructural characterization
of the foam samples was analyzed using Image J software (Schneider
et al., 2012).

Where: num. - number of cells in the SEM image, M - the

magnification of the SEM image, and area - image area. The
compressive and tensile strength of the foam samples were evaluated
using a universal mechanical tester (Zwick/Roell, Germany). For the
compressive strength test, the samples with an area of 2.7 mm x 2.7
mm x 2.7 mm were prepared and tested at room temperature with a
compression rate of 2 mm/min, parallel to the foam rise, according to
the ASTM D1621. For the tensile strength test, samples with
dimensions of 12 mm x 12 mm x 100 mm, were prepared and tested
at a stretching speed of 8 mm/min, according to the ASTM D1623. The
resistance to aging of the reference foam and DSO polyol-based foam

with dimensions of 50 mm, for 48 hours at 120 ℃ according to ISO

samples was investigated using a thermostat process for samples

1923:1981. The investigation focused on the changes in volume (ΔV)

and mass (Δm) after the aging resistance test (Paciorek-Sadowska et
al., 2018a). All length measurements and volume calculations were
done with a caliper, and weight was measured using a digital scale
with an accuracy of 0.0001 g. To investigate the resistance of the
foam samples to water absorption (WA), the foams were immersed in
distilled water for 96 hours, according to the ASTM D2842 standard.
The foam samples were prepared with dimensions of 27 mm x 27 mm
x 27 mm. The percentage of WA was determined by calculating the
ratio of the weight of the sample after the test to its initial weight.

3. Results and discussion

3.1. Spectroscopy test results of DSO and DSO polyol

The obtained spectra are shown in Fig. 1 and Fig. 2. DSO: FT-IR (cm−
1 , KBr pellets): shows peaks at 3446 (OH stretching), 2923 and 2853
(asymmetrical and symmetrical stretching of C–H of long fatty acid
chain), 1746 (–C––O stretching (ester)), 1627 (–CH2–), 1465 (–C–H
(CH2)), 1377 (–CH3 bend), 1161 (C–O), 1115 (C–O stretching (ester)),
722 (-HC––CH- (cis)) (Amigh and Taghian Dinani, 2020) (Fig. 1). 1 H
NMR (300 MHz, CDCl3) (δ, ppm): shows peaks at 5.32 (–CH=CH–),
5.29 (glycerin methylene protons), 4.41 and 4.06 (–CH2–O–), 2.76 (–
CH2–COOR), 2.30 (–CH2–C––C), 1.93 (–CH2–CH2–COOR), 1.60 and
1.27 (–CH2– of fatty acid chain), 0.87 (–CH3) (Fig. 2A). 13C NMR (75
MHz, CDCl3) (δ, ppm): shows peaks at 174.22 and 172.15 (–C––O,
ester), 130.57 and 127.44 (–CH=CH–), 69.45 and 62.28 (–CH2–O–),
35.65–21.27 (–CH2– of fatty acid chain), 14.49 (–CH3) (Fig. 2B). DSO
polyol: FT-IR (cm− 1 , KBr pellets): shows peaks at 3385 (OH
stretching), 2923 and 2853 (asymmetrical and symmetrical stretching
of C–H of long fatty amide chain), 1623 (–C––O stretching (amide)),
1466 (–C–H (CH2)), 1365 (–CH3 bend), 1170 (C–N stretching), 1052 (–
C–O), 721 (-HC––CH- (cis)) (Fig. 1). 1 H NMR (300 MHz, CDCl3) (δ,
ppm): shows peaks at 5.32 (–CH=CH–), 3.90 and 3.39 (N–(CH2)2–OH),
2.74 (–CH2–CONR), 2.19 (–CH2–C––C), 2.01 (–CH2–CH2–CONR), 1.58
and 1.25 (–CH2–), 0.72 (–CH3) (Fig. 2A). 13C NMR (75 MHz, CDCl3) (δ,
ppm): shows peaks at 175.84 (–N–CO–CH2–, (amide group)), 130.23–
127.60 (–CH=CH–) (Acuna ˜ et al., 2021), 61.46–60.81 and 52.33–
50.60 (N–(CH2)2–OH), Due to the weak C-N bond, rotation around this
bond is slow during resonance. As a result, groups attached to N (R2–
N-C=O) may exhibit peaks at two distinct points during the
spectroscopy test, despite their similarities (Pavia et al., 2008). 33.65–
25.62 (–CH2– of the long fatty amide chain), 14.64 (–CH3) (Fig. 2B).

3.2. Analytical and physicochemical test results of DSO and DSO

polyol

The results related to the physical, chemical, and thermal properties

of DSO and DSO polyol are listed in Table 3. The AV of the synthetic
polyol decreased from 1.8 mg KOH/g (oil) to 0.2 mg KOH/g (DSO
polyol). This decrease in AV indicates a reduction of free fatty acids in
the oil and the progression of the amidation reaction. The yield of
amidation (% conversion) can be estimated from the AV of the DSO
and DSO polyol obtained through titration. The % conversion was
determined through titration using the following Eq. (3) (Tarigan et al.,
2023): %conversion = AVDSO− AVDSO polyol AVDSO × 100 (3)
Where, AVDSO polyol _ represents the acid value of the DSO polyol,
and AVoil _ represents the acid value of the DSO. The % conversion
was calculated to be 89 %. The synthesized DSO polyol had a HN of
306 mg KOH/g and a pH of 7.4. The synthesized DSO polyol had a
light orange color. In a study conducted by Acuna ˜ et al. (2021), bio-
polyol was synthesized using castor oil amidation. Comparing the
results of polyol synthesis from castor oil with the results related to
polyol synthesized from date seed oil shows that the reported HN of
the bio-polyol obtained from castor oil is higher than that of the polyol
synthesized from date seed oil. This difference can be attributed to
the presence of secondary hydroxyl groups in the fatty acid chain of
castor oil. Kirpluks et al. (2017) also synthesized a polyol from
rapeseed oil using the amidation method. The rapeseed oil-based
polyol had a HN of 471 mg KOH/g and an AV of less than 2. Similarly,
Patil et al. (2021) synthesized a polyol from algae oil using the
amidation reaction. The product obtained through the reaction of
algae oil with diethanolamine had a HN of 196 mg KOH/g. In order to
produce RPU-PIR foams, synthetic polyols should have a hydroxyl
number above 250 mg KOH/g. A comparison of the results from this
research with previous research indicates that the unique properties
of various oils, particularly their fatty acid profiles, are effective in the
properties of the synthesized oil-based polyol. The synthesized DSO
polyol has a higher viscosity than the DSO. One reasons for the
increased viscosity of polyols is the formation of intermolecular
hydrogen bonds within them (Jiang et al., 2018). The presence of
terminal alcohol groups in DSO polyol enables the formation of
intermolecular hydrogen bonds. The thermal stability of bio-polyol is
one of the basic parameters evaluated in this research. Small changes

polyol. Weight loss at temperatures below 100 ℃ is related to the

in the DSC thermogram indicate the thermal stability of the DSO

substances. The decomposition of DSO polyol starts at 150 ℃. This

evaporation of water and the decomposition of low-boiling point

decomposition behavior is similar to the study conducted by Paciorek-

Sadowska et al. (2018b). In the DSC thermogram, only two

℃ and 187 ℃. The TGA results show that the temperature

temperature degradation peaks (Td 1 and Td 2) were observed at 155

degradation at T5 % of the DSO polyol is 186 ℃ (see Supplemental

data 3 and SI Fig. S7, S8). The summary of the thermal test results
indicates that the DSO polyol has acceptable thermal stability.

3.3. Foaming process and reactivity of DSO polyol

The reactivity and characteristics of the prepared modified foams are

given in Table 4. One advantage of polyols with low functionality is
their lower viscosity, which impacts foam formation and its curing
process. The chemical structure of polyurethane-polyisocyanurate
consists of blocks connected by covalent bonds. These blocks are
arranged in an alternating pattern. Hard segments, which have high
polarity, are related to the isocyanate and isocyanurate structures,
while soft segments, which have low polarity, are related to the polyol
structures (Prociak et al., 2023; Septevani et al., 2015). During the
mixing process of polyol and polyisocyanate, the reaction of water
with polyisocyanate results in the formation of urea and biuret bonds.
It was observed that increasing the amount of bio-polyol leads to a
faster creaming time (the initial rate of nuclei formation) and a faster
gelling time (the rate of polymerization). For a detailed overview of
the primary reactions involved in the synthesis of RPU-PIR foams,
refer to SI Scheme S3. This high rate and higher reactivity in the DSO
polyol-based foams can be attributed to amide groups in the
synthesized DSO polyol, which act as catalysts and accelerate the
reaction. Placing primary alcoholic hydroxyl groups at the beginning
of the synthesized DSO polyol provides better reactivity with the –
NCO group, leading to a higher cross-linking density (Fan et al., 2012;
Haridevan et al., 2021). However, the tack-free time was increased in
samples containing DSO polyol, possibly due to dangling fatty acid
chains in the DSO polyol. These chains may prevent cross-linking and
decrease reactivity. However, there are likely other factors that
contribute to changes in reactivity. Furthermore, the adhesion of DSO
polyol-based foams to the mold was found to increase. On the other
hand, the synthesized DSO polyol improved the miscibility of the
polyol mixture with cyclopentane and significantly reduced the overall
viscosity of the polyol mixture. This decrease in viscosity effectively
increases the reaction rate of the isocyanate and polyol mixture. As
viscosity decreases, molecular mobility increases, leading to higher
reactivity (Ryszkowska et al., 2018; Chuayjuljit et al., 2010). The
synthesized DSO polyol has a lower viscosity (860 mPa•s) compared
to petrol-based polyol (4250–4750 mPa•s). As a result, increasing the
percentage of DSO polyol results in a lower final viscosity of the polyol
mixture. Compared to the reference foam, the samples containing
DSO polyol displayed a significant increase in foam height. This
increase in foam height is attributed to the lower viscosity of the
polyol mixture, which allows for faster diffusion of the blowing agent.
This leads to larger cell diameter and increased foam height
(Kuranska ´ et al., 2020).

3.4. FT-IR spectral analysis of RPU-PIR foams

The FT-IR spectra of polyurethane-polyisocyanurate foam samples,

along with their prominent peaks, are shown in Fig. 3. The presence of
bonds characteristic of isocyanurate functional groups at 1680–1710
and 1405–1415 cm− 1 , as well as urethane bonds at 1700–1740 cm−
1 , can be observed. The remaining free –NCO is also visible at 2280–
2270 cm− 1 . However, in samples S2 and S4, this peak is no longer
present. Removing the peak in the 2280–2270 cm− 1 region indicates
that the reaction is complete and that no unreacted isocyanate
remains in the foam matrix. The bending and stretching peaks of N-H
bond are visible at 1515 cm− 1 and 3358 cm− 1 (Chuayjuljit et al.,
2010). The absence of hydroxyl group peak in the range of 3400–3500
cm− 1 further confirms that the reaction between polyol and
isocyanate is complete, indicating that the amount of isocyanate used
was sufficient for the polymerization reaction. In addition, the peak
corresponding to carbodiimide (a side product in the trimerization
reaction), which appears at 2136 cm− 1 , confirms the participation of
-NCO groups in the trimerization reaction and the formation of
isocyanurate rings during foam formation

3.5. Thermal degradation of bio-based foams

The thermal degradation process of PU foams involves several

stages, including isocyanate, hydroxyl, and amine (Szycher, 1999).
The results of the thermogravimetric analysis and relevant data are
specified in Table 5 and Fig. 4. The data in Table 5 indicate that the T5
% for samples containing DSO polyol occurred at lower temperatures
than S1. However, the T25 % and T50 % of S3 and S4 samples were
higher than S1. The weight loss percentage at T25 % and T50 % in
sample S5 was lower than that of S1. On the other hand, the weight
loss percentage at Tmax2 in samples containing DSO polyol was
significantly lower than in the S1 sample. This trend of decreasing
weight loss was also observed at Tmax4. The TG curve of the foam

700 ℃ also increased for S2, S3, and S4. The DTG curve shows more
samples is displayed in Fig. 4A. The residue (ash) at temperature of

specific results than the TGA curve. The DTG curve (Fig. 4B) shows

range of 119–226 ℃, observed only in samples containing DSO

that the first stage of degradation (Tmax1) occurred at a temperature

polyol. Tmax1 is associated with the thermal decomposition of amide,

urethane, and urea groups, as well as the separation of alcohol and

range of 317–374 ℃, is related to the destruction of polymer chains,

isocyanate segments. The second stage (Tmax2), at a temperature

breaking of urethane bonds, decomposition of the carbodiimide

group, and isocyanurate ring segments. The third and fourth stages of
degradation can be attributed to the destruction of the soft segments
of the polymer and cross-linking. In some cases, the third stage of
degradation (Tmax3) may be attributed to the decomposition of
unreacted isocyanate and hydroxyl groups (Amran et al., 2019). We
only observed this stage in S5. This finding is supported by the FT-IR
spectrum results. The peak in the 2280–2270 cm− 1 range,
corresponding to unreacted -NCO, shows a higher absorption in
sample S5 compared to the other samples. As the percentage of bio-
polyol increases, the number of degradation steps also increases.
Foam samples containing bio-polyol showed significantly reduced
weight loss at Tmax 2 and 4. Moreover, the comparison of the 2D
contour plots related to the burning process of the foam samples
indicates that sample S3 experienced the least amount of weight loss.
In contrast, sample S5 experienced the greatest amount of weight
loss during the thermal resistance test. Furthermore, the high thermal
temperatures above 700 ℃ (see SI Fig. S15).
resistance of samples S2 and S3 is evident for over 40 minutes and at

3.6. Morphology of bio-based RPU-PIR foam samples

The pore structure of foam samples is an important factor that

significantly impacts their mechanical behaviors. The morphology of
foams is determined during the foaming process, which is influenced
by various factors such as the separation of different phases, the
viscosity of the mixture, and the surface tension. These factors play
an essential role in determining the final shape and structure of the
foam. Surfactants play a crucial role in determining the shape, size,
and uniformity of cells in foams by reducing the surface tension,
which results in smaller cell size and a higher percentage of closed
cells. However, increasing the blowing agents in the foam formulation
can lead to larger cell size. To ensure accurate research results and
eliminate the influence of other factors, the amount of blowing agent,
surfactant, catalysts, and other additives in the foam formulation was
kept constant throughout the study. This was done to avoid the
potential effects of the ingredients in the polyol mixture. The use of
bio-polyol in foam formulation improves miscibility with blowing
agent. A shorter gelling time during the foaming process can result in
larger average cell size in the foam. On the other hand, reducing the
viscosity of the polyol mixture can result in less uniform cell size and
shape in the foam. High viscosity can prevent the rapid growth and
enlargement of cell size by hindering the reactivity and release of
gases in the polyol mixture, ultimately affecting the homogeneity of
cells (Chuayjuljit et al., 2010; Peyrton and Av´erous, 2021). In the
photographic images, there is no significant change in the
appearance of the foam up to a ratio of 70 %. However, in the S5, the
cells were slightly enlarged (Fig. 6A and see SI Fig. S16). Micrographs
of foam samples with the lowest and highest contribution of bio-polyol
are shown in Fig. 5. Examination of SEM images of foam samples does
not show any collapse, breakage, or cell collisions in the S1 foam and
the S2 foam. The morphology of the produced foams is typically a
closed-cell structure with a polygonal shape. Increasing the
percentage of DSO polyol did not cause the cells to open. However, in
the S5 sample, the cross-linking density decreased, causing the cells
to rupture and coalesce into larger cells. As a result, the sample
lacked sufficient mechanical strength (Jiang et al., 2018).
Furthermore, in S5, the shape of the cells was irregular, and some cell
walls were ruptured. This could be due to insufficient time for the
walls to stabilize during cell growth, leading to structural defects and
rupture (Hipulan et al., 2024). In other words, these ruptures may be
attributed to the reaction speed and high gas pressure, which can
cause weak walls to rupture. The results of the study on foam
morphology are presented in Table 6. All morphological evaluations
were based on an average of 50 cells. The results show that the cell
size (diameter) increased with a higher percentage of DSO polyol (see
SI Fig. S17). This phenomenon can be attributed to the poor reactivity
of DSO polyol and the presence of dangling fatty acid chains, which
negatively impact the cross-linking process and the chemical reaction
with isocyanate. These dangling fatty acid chains do not fully bind to
other molecules (Paciorek-Sadowska et al., 2018a). The cell density
has an inverse relationship with cell diameter. A lower average cell
diameter results in a higher cell density. Additionally, a more uniform
distribution of cell diameters leads to a higher cell density. This
uniformity in the celular structure is crucial for the effectiveness of
thermal insulation foams (Borowicz et al., 2020). The thickness of the
cell walls is a crucial factor in determining foam properties. The
measurements showed minimal differences in cell wall thickness
between the reference foam and the foams containing bio-polyol.
However, the samples containing DSO polyol exhibited a slight
increase in wall thickness. The strut thickness has significantly
increased in S4 and S5. By increasing the cell size, thickening the
walls, and enhancing the strut thickness (specifically in the plateau
region of cell edges), the apparent density of foam decreased
significantly. The results of investigating the morphology of bio-based
foams in this research can be compared with previous studies. For
instance, the cell size in the samples containing 0.3, 0.5, and 0.7 Eq
DSO polyol (S2, S3, and S4) were found to be smaller than those in
the sample containing 0.3 Eq of synthetic polyol from Oenothera
biennis seed oil, which measured at 408 ± 31 µm. Furthermore, the
wall thickness of the DSO polyol-based foam samples was observed to
be less than that of the foam samples based on Oenothera biennis
seed oil, measuring at 21 ± 3 μm (Paciorek-Sadowska et al., 2018b).
Additionally, a comparison between the foam containing 70 % DSO
polyol (S4) and the foam containing 70 % rapeseed oil-based polyol
revealed that the DSO polyol-based foam had smaller cells, and some
areas showed cell-like wrinkles. In contrast, the foam sample
containing rapeseed oil-based polyol had cells with a larger diameter
(Prociak et al., 2018). Another study by Acuna ˜ et al. (2021) used a
polyol based on castor oil to produce rigid foams. A comparison of the
foam morphology of samples containing 100 % DSO polyol (S5) and
100 % castor oil-based polyol showed slightly different results. The
foam produced from castor oil had a cell size of 812 µm, with a porous
and non-homogeneous cell shape and evident wall ruptures. In
contrast, the foam containing DSO had a smaller average cell size of
550.61 µm.

3.7. Mechanical behavior of foam samples

One of the main differences between petrol-based foam structures

and modified foams using DSO polyol is the low functionality and
presence of dangling fatty acid chains in DSO polyol. This feature
leads to a lower cross-linking density in the foam samples containing
synthesized polyol, ultimately reducing their mechanical strength. In
addition, dangling fatty acid chain in synthetic polyol can cause
plasticization and weaken mechanical properties. The foam
morphology is an essential factor in determining mechanical
properties. A smaller cell diameter, a homogeneous cell structure with
high cell density, and minimal wall rupturing are essential for
improved mechanical properties (Hipulan et al., 2024). After
conducting compressive strength testing of foam samples, the ability
to recover the original shape is a crucial factor in investigating the
pneumatic performance of foams. High-density foams may pulverize
or take longer to return to their original shape after being compressed
and deflated. In contrast, low-density foams return to their original
shape after the compressive strength test and have a shorter
recovery time. Also, one of the influential factors in the recovery
behavior of foams is the higher cross-linking of their components
(Gama et al., 2015; Prociak et al., 2024). Fig. 6A shows the recovery
behavior of the foams after the compressive strength test. The
observations indicated from this test show that the foam samples
have largely recovered their original shape, as expected from low-
density foams. Fig. 6B shows the compressive stress-strain curve of
foam samples. Evaluating compressive strength in rigid polyurethane
foams is critical, especially in applications where the thermal
insulation foam is subjected to continuous pressure. Significant
changes can be observed during the compressive strength test,
especially when the test is performed above or below room
temperature. In this study, the mechanical properties were
investigated at room temperature. When the compressive strength
exceeds 0.1 MPa, it indicates that the pressure difference between
atmospheric pressure and air pressure inside the foam cells will not
affect the shape of the foam (Borowicz et al., 2020). The compressive
strength test was applied to the samples with up to 50 % strain. The
results showed that the stress remained relatively constant from 10 %
to 50 % strain. Investigations showed that the compressive strength
decreases with an increasing percentage of DSO polyol in the foam
formulation. This decrease in compressive strength was particularly
evident in samples S4 and S5. It is important to note that changes in
the apparent density of foam can lead to variations in its mechanical
properties. In this study, the density of rigid foams ranged from 30.72
to 34.68 kg/m3 (1.92–2.17 lbs/ft3 ). The results related to the
compressive strength of the foam samples are summarized in Table 7.
The compressive strength was measured at a 10 % strain range
(elasticity stage). It was observed that decreasing the density of
foams containing DSO polyol resulted in a decrease in their
compressive strength. While the compressive strength of S1 (0.22
MPa) and S2 (0.19 MPa) did not differ significantly, there was a sharp
decrease in the compressive strength of the foams from 0.22 MPa
(S1) to 0.05 MPa (S5). A significant decrease in compressive strength
observed in S4 and S5 can be attributed to a reduction in density, a
decrease in cross-links within the polymer, an increase in cell size,
and a weakening of the cell walls (Guan and Hanna, 2004).
Additionally, there was a slight difference in the modulus of elasticity
between S1 and S2. The effect of reducing the density of foam
samples containing biopolyol on the reduction of compressive
strength has also been reported in previous studies. In a study by
Paciorek-Sadowska et al. (2018b), it was found that increasing the
amount of polyol based on Oenothera biennis seed oil resulted in a
decrease in compressive strength. For example, in the sample
containing 0.3 Eq of polyol based on Oenothera biennis seed oil, the
compressive strength decreased from 0.201 MPa to 0.183 MPa
compared to the reference foam. Similarly, in a study by Borowicz et
al. (2020) on RPU-PIR foams based on mustard oil, the density of the
foams decreased from 45 kg/m3 (reference foam) to 40 kg/m3 in the
sample containing 0.3 Eq of mustard oil-based polyol. This decrease
in density effectively decreased the compressive strength, from 0.38
MPa (reference foam) to 0.3 MPa in the sample containing 0.3 Eq of
bio-polyol. As the percentage of bio-polyol increased, the decrease in
compressive strength became more evident and intense. For instance,
in the sample containing 0.6 Eq of mustard oil-based polyol, the
compressive strength decreased to 0.2–0.25 MPa. Fig. 6C shows the
tensile strength curve of the RPU-PIR foam samples. The presence of
minor defects in the foam structure, an increase in cell size, and the
weakening of cell walls can significantly reduce the tensile strength of
the foams (Uram et al., 2021). This is because during the tensile
strength test, the cell walls experience vertical deformation, and the
applied pressure affects the edges of the cells. If the applied force
exceeds the resistance of the struts, cracks and tears will form. In
simpler terms, the thickness of the struts directly affects the tensile
strength of foam samples (Marșavina and Linul, 2020). Table 7
displays the results of the tensile strength test of foam samples.
Examining the results of this test shows that by increasing the
percentage of DSO polyol in the formulation of the samples from 0 %
to 100 %, the tensile strength has decreased from 0.41 MPa (S1) to
0.31 MPa (S5). However, this decrease was not linear, as a slight
increase was observed in S4 and S5 compared to S3. The young’s
modulus (E) also increased from 6.22 MPa (S1) to 14.55 MPa (S5). An
increase in E indicates a higher resistance to elongation and fracture,
evident in samples S2, S4, and S5. In addition, increasing the
percentage of DSO polyol led to a decrease in elongation at break. It
was observed that this reduction followed a linear trend, with the
elongation at break decreasing from 77.28 % (S1) to 25.06 % (S5).

3.8. Dimensional stability of bio-based foam samples

Thermal testing is commonly used to assess the aging resistance of

foam samples by exposing them to high temperatures for 24–72
hours. This process is crucial as it allows the measurement of
dimensional and weight changes, which are critical factors in
applications such as thermal insulation. Even minor changes, such as
less than 1 % in dimension and 3 % in volume, can have a significant
impact (Paciorek-Sadowska et al., 2019). In addition to other
measured parameters, mass changes at high temperatures were also
investigated. These changes can be attributed to physical factors,
such as loss of water or release of gases, or chemical changes, such
as decomposition of foam constituents (Berardi, 2019). The
relationship between the equivalent amount of DSO polyol and
dimensional and mass stability is shown in Fig. 7A. No visual
distortions were observed in the foams, indicating that the
dimensional stability of the foam samples falls within the
commercially acceptable range. At high temperatures, the foam
samples experienced weight and volume loss due to the release of
trapped gases within the cells. The weight loss was found to be more
significant than the volume loss. Samples S2 and S4 showed better
dimensional stability compared to the reference foam. Regarding
weight changes, S4 exhibited specific weight stability, while S5
showed worsening weight stability. Previous studies have also
reported good dimensional stability in foam samples containing VO-
based polyol. For instance, in a study conducted by Kuranska ´ et al.
(2013), it was discovered that rapeseed oil-based polyol in foam
samples leads to good dimensional stability. This finding was further
confirmed by a study by Borowicz et al. (2020), which demonstrated
that foams containing mustard oil-based polyol also showed good
dimensional stability. The use of bio-polyol has a positive effect on the
thermal and dimensional stability of foam samples.

3.9. Water absorption (WA) of foam samples

The Water absorption (WA) capacity is an important factor in

determining the quality of foam, as its porous structure allow for
water absorption. The WA capacity of foam is primarily influenced by
its morphology. A uniform cell structure, higher cell density, and
closed cell percentage all contribute to reducing WA. However, larger
cells can increase the WA capacity of foam samples (Bondaug et al.,
2024). Adding bio-polyol, which contains long hydrophobic aliphatic
chains, is important in increasing surface roughness and reducing
surface energy. This feature ultimately leads to a decrease in the WA
of foam samples (Członka et al., 2018). After immersing the foam
samples in water for 96 hours, they were removed, and their water
absorption was examined. The relationship between the percentage
of bio-polyol (renewable material percentage in the foam) and water
absorption capacity is shown in Fig. 7B. As the percentage of DSO
polyol increases, the WA ability of the foam samples decreases. The
hydrophobic fatty acid chains of DSO polyol have been effective in
reducing WA. This feature prevents water from penetrating the foam,
making it suitable for thermal insulation in high-humidity
environments and antibacterial applications. This decrease in water
absorption is evident in samples S2 and S4. However, samples S3 and
S5 show an increase in WA, which can be attributed to their larger cell
size and ruptured walls, especially in S5. These observations are
consistent with the results of the morphological characteristics of the
foam samples. Defects in foam morphology allow more water to
penetrate and remain in the pores. A similar trend has been reported
in mustard oil-based foam samples, where the sample containing 0.4
equivalents of mustard oil-based polyol had the lowest water
absorption. However, at higher ratios (0.5 Eq and 0.6 Eq), the water
absorption of bio-based foam samples increased (Borowicz et al.,
2020).

4. Conclusions

A new polyol was synthesized from DSO using the amidation method,
which is a solvent-free, one-step process. During the amidation
reaction, crude glycerol is produced as a by-product. This crude
glycerol can be utilized as a bio-polyol for the preparation of RPU
foams. RPUPIR foam samples were successfully prepared by reacting
isocyanate with a mixture of DSO polyol and petrol-based polyol. The
DSO polyol gradually replaced the petrol-based polyol in different
ratios from 0 to 1 mass equivalent. The produced foams had an
apparent density in the range of 1.92–2.17 lbs/ft3 . The results
showed that the apparent density of the foam decreased with the
increase of DSO polyol content. The foam sample containing 30 %
DSO polyol (S2) showed slight differences from the reference foam in
several tests, including dimensional stability and water absorption,
but overall showed improved properties. The mechanical and thermal
property tests for this sample were within an acceptable range. It was
also observed that the chemical structure of the synthesized DSO
polyol significantly affected the foaming process, heat resistance,
aging, water absorption, and overall improvement of properties in
foams. These results suggest that DSO polyol can be used as a
substitute for petrol-based polyols. However, in foams containing 50
% or more DSO polyol in some tests, including compressive strength,
indicated a reduction in foam strength. Therefore, it is recommended
to use DSO polyol at levels below 50 % to preserve the desired
properties of rigid foams. In addition, the cost of the final product
should also be considered. Using a renewable waste source for polyol
synthesis, such as DSO, can significantly reduce foam production
costs. Furthermore, it is affordable to use foams with lower density in
industries