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Article

The Development of a Coconut-Oil-Based Derived Polyol in a Polyurethane Matrix: A Potential Sorbent Material for Marine Oil Spill Applications

by
John Louie L. Tefora
1,2,
Tomas Ralph B. Tomon
1,2,
Joy Ian Dan S. Ungang
1,2,
Roberto M. Malaluan
1,3,
Arnold A. Lubguban
1,3 and
Hernando P. Bacosa
1,2,*
1
Center for Sustainable Polymers, Mindanao State University-Iligan Institute of Technology, Iligan City 9200, Philippines
2
Department of Environmental Science, School of Interdisciplinary Studies, Mindanao State University-Iligan Institute of Technology, Iligan City 9200, Philippines
3
Department of Chemical Engineering and Technology, Mindanao State University-Iligan Institute of Technology, Iligan City 9200, Philippines
*
Author to whom correspondence should be addressed.
J. Mar. Sci. Eng. 2025, 13(6), 1176; https://doi.org/10.3390/jmse13061176
Submission received: 1 May 2025 / Revised: 10 June 2025 / Accepted: 12 June 2025 / Published: 16 June 2025
(This article belongs to the Section Marine Pollution)
Browse Figures
Versions Notes

Abstract

:
Marine oil spills have caused significant environmental problems. Among the array of clean-up methods, the utilization of sorbents emerges as promising for removing and recovering oil from spills. Developing cost-effective, reliable, and eco-friendly material that efficiently and sustainably removes oil from water is increasingly seen as crucial and pressing. In the present study, we report the development of coco-polyurethane (PU) foam (CCF) through the conventional foaming process using varying amounts of coconut-oil-derived polyol (CODP) in a PU matrix. Characterization of the foams showed an increased ester band with the incorporation of COPD into the polyurethane networks and no direct influence of the cell size distribution on the surface morphology. Furthermore, this study highlighted the increasing CODP in every CCF formulation, showing high oil sorption and low water uptake due to its porous structure. The experimental results revealed that CCF is a potential candidate sorbent for the recovery of spilled oil. This signifies a significant leap towards reducing the dependency on petroleum in developing sorbent materials and advancing sustainable responses to oil spills in marine environments.

1. Introduction

Oil spills are among the most common environmental problems, with ecological and health impacts. Smaller spills occur often, with relatively minor consequences compared to those of the major headline-generating spills. Oil enters aquatic environments through natural seepages [1] from reservoirs and anthropogenic activities [2], such as extraction [3], drilling rigs and wells [4], marine transportation [5], and accidental spills [6]. Unlike anthropogenic spills, natural seepage involves the gradual release of oil from geological formations and is not typically classified as a spill [7]. Accidental or intentional discharges of petroleum into nearby aquatic and terrestrial ecosystems can carry hazardous chemicals including polycyclic aromatic hydrocarbons (PAHs); benzene, toluene, ethylbenzene, and xylenes (BTEX); and heavy metals like lead and mercury [8,9,10]. Their effects range from endangerment of the smallest marine organisms to endangerment of human health and stretch to economic decline [11].
Various methods for eliminating and retrieving oil spills in marine waters have been utilized, which include biological, mechanical, and chemical treatment methods [12]. However, multiple methods from these groups suffer several disadvantages, as they lack efficiency and incur high production costs. The usage of specialized equipment such as booms [13,14], skimmers [15,16], and sorbents [17] falls under mechanical methods and is often preferred over chemical and biological methods as it is less detrimental to the environment [1,18,19,20] Among these, sorbents are considered the most ideal method for treating spilled oil because of their capability to collect oil from water and their reusability [21].
Sorbent materials can be natural inorganics such as clay [22], glass wool, and perlite [23]; natural organics like hay, feather, straw, and other carbon-based products; and synthetic materials like foams. An ideal sorbent possesses hydrophobic properties and high uptake capacity, reusability, and retention. According to these requirements, among the many materials that have been developed to absorb oil, polyurethane (PU) foams are effectively considered a promising material. The drawback of traditional polyurethane foam is that it can absorb water and oil. Nonetheless, PU foam has been subjected to surface modification to enhance its oil sorption capacity and reduce its water uptake. Nevertheless, using adsorbents first involves deploying porous materials (e.g., foams, aerogels, or natural fibers) to physically trap and recover the spilled oil; solvents are then often necessary to dissolve the residual oil or regenerate the saturated adsorbents, though this adds costs for the materials, solvent recovery systems, and waste disposal, making mechanical adsorption cheaper for small spills but solvent-assisted methods more viable for large-scale or viscous oil remediation. Thus, the sorbent property of the PU foam can be modified by using different amounts of bio-polyol to replace petrochemical polyol [24,25,26]. Some research in the literature has focused on the bio-polyol tunable structure, partially replacing petroleum-based polyols with bio-polyols [25,27].
These bio-based oils are found to be renewable and more biodegradable than petroleum-based polyols. This can be achieved by using a plant as a polyol source, like soybean oil [28], castor oil [29], palm oil [30], canola oil [31], sunflower oil [32], and rapeseed oil [33], which serve as excellent polyol sources due to their higher unsaturated fatty acid content, which includes ester groups and double bonds in their backbone chains. These functional groups enable convenient chemical modification through various methods. Thus, bio-based oils are found to be renewable and more biodegradable than fossil-based polyols. However, chemical processes like epoxidation, transesterification, and polycondensation must be employed to introduce reactive -OH sites. However, these modifications add steps to the manufacturing process and can constrain the final polymer’s physical and mechanical properties compared to conventional petroleum-derived polyols [34].
Among these sustainable alternative raw materials is coconut oil (CO), a sustainable and natural resource which is being explored for its potential to replace petroleum-based polyols in the production of eco-friendly polyurethane foams [34,35]. Numerous studies have been conducted on the use of coconut oil as a bio-based polyol, particularly aimed at the eco-friendly production of polyurethane foams for various applications [34,36,37,38,39,40]. Moreover, CO contains a significant amount of lauric acid, which can be functionalized through polycondensation [40]. These synthesized CODP compound functions serve as B-side components (polyol mixture) within the polyurethane matrix.
A study by Tomon et al. [41] reported using CO to fabricate novel sorbent materials that utilized the advantageous properties required for effective oil absorption for oil spills. Moreover, polyols profoundly impact the processing and characterization properties of the final polyurethane (PU) foam. Vegetable-oil-based polyols in particular contribute to desirable hydrophobicity and lipophilicity in PU foams [42,43,44]. Hence, utilizing bio-based polyols to prepare bio-based PU foams while simultaneously incorporating bio-based polyols represents a promising research direction. This novel approach combines the advantages of both materials, creating an oil-absorbing PU material. Additionally, using CO as a polyol enhances the PU foam’s overall physical and mechanical properties.
This study focuses on developing and investigating a bio-based polyurethane (PU) foam incorporating the CODP into the polyurethane matrix. Subsequently, as the synthesized CODP replaces a petroleum-based polyol in the synthesis of bio-based polyurethane, varying polyol formulations are simultaneously added during the preparation process, resulting in a coconut polyurethane foam (CCF) material without modifications. This novel biosorbent demonstrates a remarkable oil uptake capacity when absorbing oil from the water’s surface.

2. Materials and Methods

2.1. Materials

The development of the CCF was achieved by integrating a fraction of a bio-based polyol into the polyol blend. The CO used to develop the bio-based constituent of the polyol blend was purchased locally. The petroleum counterpart (Voranol ®4701) of the bio-based polyol, along with the glycerol, the silicone surfactant, and polymeric methylene diphenyl diisocyanate (pMDI, PAPI 135 SH), was provided by Chemrez Technologies, Inc., the Philippines. Catalysts such as Polycat® 8, Polycat® 5, DABCO® 33 LV, dibutyltin dilaurate (DBTDL), and analytical-grade phthalic anhydride (PA) were obtained from Sigma-Aldrich Chemicals, the Philippines. The oils used for testing, such as engine oil, were purchased locally, while the bunker oil was kindly provided by Mabuhay Vinyl Corporation, Iligan City, the Philippines. All chemicals and reagents were used as received and without further modification.

2.2. Preparation of the Coconut-Oil-Derived Polyol

To prepare the coconut polyol used in this study, a methodical process of two steps was performed. Firstly, through the glycerolysis process, the unsaturated fatty acids in the coconut oil were broken down into monoglycerides by reacting them with a certain amount of glycerol, catalyzed by CaO, in a closed Parr reactor with constant stirring and a temperature of 120 °C for 2 h. The resulting monoglycerides were then subjected to polycondensation, following the method developed by Omisol et al. [40]. A pre-determined amount of monoglycerides, glycerol, and PA was weighed and mixed in a 250 mL Erlenmeyer flask, following the standard mass ratio of 16:1:5. The mixture was constantly stirred using a hotplate stirrer at 1000 rpm and 120 °C for 30 min. Then, the temperature was increased to 180 °C for another 3 h. The resulting CODP was then allowed to cool down and stored in a sealed glass container for polyol characterization.

2.3. Characterization of the CODP

Characterization of the CODP and the petroleum-based polyol required the chemical properties to be determined, such as their molecular weight, hydroxyl (OH) values, and functionality [45,46] (Table 1). The hydroxyl number was determined following ASTM D4274 [47], while the molecular weight distribution was characterized through gel permeation chromatography (using a Shimadzu Prominence GPC system). Average functionality, defined as the average number of reactive hydroxyl groups per polyol molecule, is a representative parameter of the crosslinking potential in polyurethane systems [45].

2.4. Preparation of the Coco PU Foam (CCF)

The CCF was synthesized utilizing varying ratios (0–60%) of the CODP and the petroleum-based polyol (Voranol ®4701). Various proportions of the mass of the petroleum-based polyol were substituted with their CODP counterpart. Initially, all of the pre-weighed B-side components, the polyols, the blowing agent, the catalyst, and the surfactant were poured into a plastic cup successively and mixed at 1000 rpm for 60 s.
After this, the required amount of MDI only (A-side) was subsequently added to the polyol blend component and stirred for another 15 s to homogenize the mixture. At the end of the curing reaction, the composite was removed from the mold and cut into small pieces for further experiments. The foaming procedures were carried out using a one-shot method under free-rise conditions [48]. The samples were cut into 25 mm × 25 mm × 25 mm polyurethane (PU) specimens for testing. Each sample was repeated in triplicate to minimize the experimental errors, with a varying ratio of bio-based polyols in the PU foam (Table 2).

2.5. Characterization of the Physical Properties of the CCF (Cell Size, Density Morphology, and Open Cell Content)

The density of the foam samples was determined following ASTM D3574 [49], with the resulting numerical values applied specifically in Equation (1) [50]. The foam’s mass was measured on an analytical balance, while its dimensions were recorded with a caliper. To ensure accuracy, each measurement was replicated three times.
Density = M PU V PU
where MPU and VPU are the mass of PU and volume of PU in length, weight, and height of the coco foam and the petroleum foam.
The volume of each foam was determined using a HumiPyc volumetric analyzer to determine the open cell content. After a maximum of 3 runs for each formulation, the porosity of the foam was measured using a pycnometer and was calculated based on modification of Equation (2) [51].
Porosity ,   % = ( V b − V a V a )   ×   100 % .
where Va is the actual volume, and Vb is the geometric volume.
The foam’s morphological characteristics were visualized and analyzed using scanning electron microscopy (SEM) with a JEOL JSM-6510LA scanning electron microscope (JEOL, Ltd., Tokyo, Japan).

2.6. The Mechanical Properties of the CCF

The compressive test was conducted using a Shimadzu universal testing machine from the Center for Sustainable Polymers (MSU-IIT). The compressive test was based on the guidelines from ASTM D3574-05 [49]. The initial dimensions of the sample were determined before testing. The sample was compressed to 75% of its original thickness at a 2 mm/min speed and then removed. The compressive strength values were reported at 75% strain. Three specimens per sample were tested, with dimensions of 25 mm × 25 mm × 25 mm, and the values are reported as the mean values.

2.7. Fourier Transform Infrared Spectroscopy (FTIR)

Functional groups in the polyurethane foam were identified using a Shimadzu IRTracer-100 FTIR spectrometer with an ATR accessory (Kyoto, Japan). The spectra were recorded in the range of 500–4000 cm−1 at a 4 cm−1 resolution with 40 scans per run.

2.8. The Thermal Decomposition Analysis

The CCF was characterized using a Shimadzu DTG 60H (Shimadzu Corp., Kyoto, Japan) thermogravimetric analyzer to determine the behavior of the samples over a range of temperatures to examine their physical and chemical changes. An average foam sample mass of 5–10 mg was placed in the analyzer, and the heating rate was 10 °C·min−1 under a flow of air at 80 mL·min−1 between 50 °C and 700 °C and a nitrogen flow rate of 40 mL/min.

2.9. Water Contact Angle Measurements

The water contact angle was measured using an optical tensiometer (Biolin Scientific ThetaLite 101, Gothenburg, Sweden) in an ambient-temperature measurement analysis system using a sessile drop standard method. The water contact angles were calculated using deionized water as a probe liquid, with a liquid dispensing volume of 5.0 μg/L. At least three consecutive measurements were taken to determine the water contact angle in a sample.

2.10. Oil and Water Sorption Measurements

The absorption tests were modified from the ASTM F726-99 standard [52] for evaluating adsorbent materials. The method for measuring the amounts of water and oil absorbed was adapted from the ASTM D95-13 standard [53], which is used to determine the water content in petroleum products.
To measure the water sorption of the coco foam, an initially weighed (WPU) triplicate set of 25 mm × 25 mm × 25 mm dry and pristine coco foam samples was placed individually into a 250 mL Erlenmeyer flask consisting of 100 mL of seawater, and another triplicate set of foams was also placed into an Erlenmeyer flask composed of 100 mL of tap water. The Erlenmeyer flask was shaken under mechanical agitation in a water bath shaker (no water in it) with an agitation speed of 100 rpm for 15 min. After the water sorption test, it was removed using a sterilized tweezer to avoid contamination and drained for 30 s and transferred into a pre-weighed container (WPU+abs water). The water sorption capacity was calculated using Equation (3) as
Water   sorption   ( g / g ) = W PU + abs   water − W PU W PU .
where WPU is the initial dry weight of the foam, and WPU+abs water is the weight of the foam with water absorbed.
An initially weighed (WPU) triplicate set of samples of coco foam was placed into a 100 mL beaker half-filled with an oil contaminant for subjection to an oil sorption test. The foam samples were immersed into 50 mL each of engine oil and bunker oil, maintained at room temperature (25 ± 1 °C) for 15 min, and then suspended for 30 s to drain excess oil before they were weighed (WPU+abs oil). The oil sorption capacity was calculated using Equation (4) as
Oil   sorption   ( g / g ) = W PU + absoil   − W PU W PU .
where WPU is the initial dry weight of the foam, and WPU+absoil is the weight of the foam with oil absorbed.

2.11. Foam Regeneration Evaluation

The CCF’s reusability was evaluated after the sorption tests in the water and oil systems. The foams were pressed through a mechanical pressing tool. The foam was weighed after every cycle for 10 cycles. Every cycle, the foam was monitored to evaluate its deformation and sorption capacity.

2.12. Determination of the Hydroxyl Values

Determination of the hydroxyl values was conducted following ASTM D4274-99 [47] Test Method D, where the samples were titrated using standardized 0.5 N NaOH in 25 mL of esterification reagent. An AT-710 automatic potentiometric titrator was used to identify the hydroxyl values of the bio-based and petroleum polyols, expressed in KOH/g.

3. Results and Discussion

3.1. Fourier Transform Infrared Spectroscopy (FT-IR) Analysis

The success of the polyurethane foam reaction was examined using an FTIR analysis, which helped identify the functional groups present in the polyurethane system. FTIR spectra were obtained for the control and the CCF, fabricated using a blend of the CODP and the petro-polyol. It was seen that the band of triglyceride functional groups and the band of free N=C=O at 2267 cm−1 were not found in all varying formulations [54]. This indicated that the -NCO in MDI had fully reacted with the O-H group in the polyol [55,56].
The essential characteristic features of the synthesized foams were observed from the FT-IR spectra for all samples (Figure 1). The presence of bands at 3342 cm−1 is indicative of urethane group stretching (N-H), while a peak number of 1730 cm−1 shows the presence of C=O in the ester bond groups in the polyester bio-based polyol and the urethane group [57]. Additionally, a peak at 1535 cm−1 and C-N bond stretching vibrations show ether bonds forming for petroleum polyols [58], respectively, while the band at 1105 cm−1 signifies the C–O stretching within the urethane group (-NHCOO-). Thus, the formation of a urethane linkage in the polyurethane is confirmed.

3.2. The Thermal Properties of the Foams

A thermogravimetric analysis (TGA) and a derivative thermogravimetric (DTG) analysis were used to characterize each formulation in this study. They were used to determine the behavior of the samples over a range of temperatures to examine their physical and chemical changes. Figure 2 illustrates the TG and DTG curves for the samples. From the thermal decomposition analysis shown above, the foams undergo three stages of percentage mass retention (Table 3). The first stage (T1) refers to the decomposition of the isocyanate groups and the polyol. It shows that an increasing amount of the CODP results in an improvement in the thermal stability.
At this stage of decomposition, formulations with an increasing OH content compared to that in the control PU foam exhibit a greater urethane linkage density due to the increased availability of hydroxyl groups. This higher crosslinking directly enhances the PU foams’ structural integrity and thermal stability.
Furthermore, the second stage (T2) of degradation describes the heat-induced oxidative breakdown of the soft segments, and the last stage (T3) of degradation corresponds to the decomposition of isocyanate. Lastly, upon further heating until 700 °C, in terms of the total mass of the foam samples, with lower thermal decomposition for CCF-60, it experienced a percent weight loss of 13.71%, compared to that in the control, which was degraded with a percentage mass retained of 0.42%. This shows that the thermal stability of the CCF is influenced by an increasing amount of the polyol in the polyurethane matrix and the effect of the OH on each formulation.

3.3. The Influence of the CODP Replacement on the Morphology and Physico-Mechanical Characteristics of the Foams

The synthesized material was characterized using SEM to investigate the surface morphology. The varying amount of the CODP in each polyurethane mixture influenced the foam cell morphology through its reactivity and surface tension. SEM images of the controlled PU and the CCF are shown in Figure 3. The morphology analysis using SEM showed that the control PU showed a mixture of elongated and spherical-shaped open pores. The morphologies of the foams containing varying fractions of the coconut-oil-based derived PU (CCF-20 to CCF-50) showed increased porosity, composed of homogenous pores. Thus, CCF-60’s pores slightly increased as the petroleum content decreased. Moreover, the comparatively low molecular weight of the CODP results in a higher proportion of hard segments derived from isocyanate components within the polymer chains, despite the abundance of CODP segments.
The incorporation of the CODP into the polyurethane foam matrix did not significantly affect the cell diameter, cell shape, or pore uniformity in the 3D structure, as evidenced by the SEM analysis in Figure 3a,c,e,g,i, during polymerization [59]. This observation is further supported by the consistent cell size distributions (Figure 4). Although the cell size distributions of the control foams were similar, the same conclusion could not be drawn for the CCFs, which were found to be down-shifted. It can be observed from Figure 4 that PU foam is made with increasing homogeneity in the hydroxyl values, resulting in a more uniform cell distribution.
The cell size distribution within the foam is uniform, predominantly measuring within a range of 107.65 μm to 161.80 μm, with minimal variance between the cells (Figure 4). The cell size observed in this study’s flexible polyurethane foam closely aligns with the 163.8 μm reported in Wang et al. [60] Uniformity in cell size, with a predominance of open cells, is considered advantageous for the quality of flexible polyurethane foams and their application to oil spill applications Hebda et al. [61].
The average cell size varied with the bio-petrol polyol ratio, showing differences in size and homogeneity. Figure 3 shows the average cell size volume with the influence on the porosity. The average cell size in each polyurethane foam is essential to its initial oil sorption. Small cell sizes in the PU foam are important to the sorption capability because the capillary effects create a force of liquid sorption, facilitating the oil’s retention.
The synthesized control foams and CCFs exhibited homogeneous cell size distributions, in contrast to heterogeneous structures, which typically influence the sorption capacity. The CCFs showed slightly increased porosity, with an increased pore concentration. These results are correlated with the SEM images (Figure 4), in which it is possible to note the differences among the pores for each sample. All of the synthesized foams that contained the CODP showed a higher porosity and were suitable for oil spill clean-up applications.

3.4. The Influence of the Hydroxyl Values on the Density and Compressive Strength of the Synthesized Foams

Density serves as an important parameter for characterizing synthesized foams. A foam’s density is directly affected by the molecular weight and the hydroxyl value of the polyol used. Polyurethane foams, as classified by Artavia et al. [62], ranging from 10 to 120 kg·m−3 are flexible. These foams are produced through a reaction with polyols, specifically triols with a molecular weight of 3000–4000 g/mol and a hydroxyl number of 40–56 mg KOH/g. A comparative analysis of the densities of the polyurethane foams, prepared using different CODP formulations in contrast to petroleum-based polyols, is depicted in Figure 5a.
This comparison is pivotal in understanding the material properties and performance of the resultant foam. It shows that the higher the content of the CODP (up to 60%) in the polyol system, the lower the foam’s density (Figure 6a). A study by Chan et al. [63] shows that they have a low molecular weight due to higher hydroxyl values tending to produce higher-density foam. Interestingly, the density of the synthesized CCFs decreases with an increasing CODP content, which we attribute to the water content present in the polyol. The presence of residual water reacts with an excess of isocyanate, resulting in the formation of CO2 particles and triggering an additional foaming reaction. The same was seen in the results of Olszewski et al. [64], where the density of foams made of a biomass liquefaction polyol was decreased.
The mechanical properties of foam, such as its mechanical strength, are intrinsically linked to its density. This indicates that a lower-density foam may exhibit greater flexibility and less mechanical resilience. Conversely, a higher compressive strength is indicative of a foam’s durability. The compressive strength of the PU foams was correlated with their CODP content (Figure 5b). Quantitatively, the compressive strength values exhibited a significant increase with the hydroxyl values, increasing from 1.98 kPA for the control sample to 15.84 kPA for the foam with a 60% content of the bio-replacement polyol [65]. In addition, the increase in the compressive strength is attributed to the reaction between water and isocyanate, which occurs concurrently with an increased amount in every formulation of the bio-replacement. As the bio-polyols increase, more isocyanate is involved in the reaction, which results in a higher crosslinking density [66].

3.5. Wettability and Hydrophobicity of the Synthesized Foams

A foam’s capacity to repel water is a crucial factor when addressing oil contamination, ensuring it selectively absorbs oil while being unable to absorb water through its surface [67,68]. One of the applications in this study of bio-based polyurethane (PU) foam is developing a hydrophobic foam suitable for oil spill applications. This effect can be evaluated by measuring the contact angle of the PU foams before and after modifying the CODP/petroleum-based polyol ratio. Wettability and hydrophobicity are characteristics determined by the angle formed when water comes into contact with a material’s surface. The water contact angle (θ) on a flat surface, which is less than 90° for hydrophilic materials and greater than 90° for hydrophobic materials, serves as the initial test for classifying a material’s wettability and hydrophobicity [69,70]. A comparative study of the hydrophilic and hydrophobic properties of the synthesized foam is shown in Table 4. The control PU foam, CCF-20, CCF-40, CCF-50, and CCF-60 are classified as hydrophobic, with values > 90°. The increasing hydrophobicity of the foams originates from the increased cell surface roughness due to the increasing polyester CODP content but also the presence of hydrophobic functional groups on the surface of the PU cells. Furthermore, it should be noted that the isocyanate functional groups from pMDI may react with the remaining hydroxyl functional groups from the coconut-oil-derived polyol.

3.6. The Oil Sorption Capacity, Oil/Water Selectivity, and Reusability of the Synthesized Foam

The efficacy of hydrophobization is based on a lower amount of water being absorbed by the material. In this way, a lower water uptake signifies a more effective foam for oil spill applications. The control PU and the CCF network structure led to homogeneous cell sizes and higher porosity in the material; thus, the sorption ability for water and oil was then investigated to determine the optimum for oil spill applications. The experimental data revealed significant variance in the water absorption capacity of the CCF 20, CCF 40 and CCF 60 foams, as evidenced in Figure 6a. The performance differences between CCF 20, 40, and 60 are clearly demonstrated through three trends in the physical properties: (1) CCF 60’s greater density compared to that of CCF40 and CCF 20 directly enhances its oil absorption capacity; (2) its more uniform pore structure improves its oil selectivity; and (3) hydrophobicity is attributed to an increased coconut-oil-derived polyol (CODP) content. These measurable characteristics fully account for the performance variations observed. Conversely, the control foam shows a higher uptake both of tap water and seawater. CCF-20, CCF-40, CF-50, and CCF-60 show less uptake of distilled water and seawater due to the effect of the higher content of rigid segments, where CCF 50 and CCF 60 have sorption capacities of 0.89 ± 0.27 g/g and 0.59 ± 0.38 g/g; see Figure 6a.
In the oil system, the foams exhibited varying oil sorption capacities (OACs) compared to that of the control PU, as depicted in Figure 7 While the varying proportions of the bio-based polyol replaced in the foams were significant, the oil’s viscosity emerged as a more critical factor in influencing the sorption capacity of the PU foam [71]. Engine oil was selected as a light organic contaminant. The oil sorption capacity increased with the amount of CODP replacement, measuring at 8.58 ± 0.25 g/g (control), 9.73 ± 0.26 g/g (CCF 20), 11.29 ± 0.23 g/g (CCF 40), 14.05 ± 0.37 g/g (CCF 50), and 12.67 ± 0.31 g/g (CCF 60). In contrast, bunker oil served as a viscous heavy contaminant, with foam sorption capacities of 10.65 ± 0.37 g/g (control), 11.73 ± 0.24 g/g (CCF 20), 12.59 ± 0.23 g/g (CCF 40), 15.65 ± 0.37 g/g (CCF 50), and 13.47 ± 0.35 g/g (CCF 60). The oil sorption capacity shows a correlation with the foam density on increasing the CODP from 20 to 60 wt% (Figure 6a). This dependence is observed from the increasing mass-to-volume ratio of the denser foams, which show a greater surface area for interaction with oil (Figure 6b). Furthermore, foams with a lower density (CCF-50 and CCF-60) demonstrated an increased oil uptake capacity for both the light and heavy oil contaminants. This showed that CCF-50 is suitable for oil spills with less water uptake and has a better oil sorption capacity performance for light to heavy oil contaminants. As confirmed by the contact angle and SEM analyses, the driving force of oil sorption for the CCFs may have stemmed from the improved hydrophobicity and open cell structures with an increasing CODP content. The sorption capacity of the CCF is greater than that of the 100% petroleum-based polyol.
CCF-50, with its optimal surface morphology and hydrophobicity, proves to be an effective material for extracting oil contaminants from bodies of water. This was demonstrated in an absorption test by immersing the CCF-50 foam in water with highly viscous bunker fuel (Supplementary Figure S1).
The foam rapidly absorbed the floating bunker oil, showcasing its superior efficiency in oil–water separation. Remarkably, the CCF50 PU foam remained afloat even after the oil absorption clean-up, leaving the water’s surface clean and oil-free.
In general, CCF-50 showed the best results in the sorption tests, especially in the water and oil lone systems, where the foam was responsible for the highest proportional oil sorption among the different systems studied. Therefore, a reuse test was applied to this foam (Figure 7). CCF-50 was subjected to 10 cycles of sorption/desorption in a multi-component system of seawater and engine and bunker oil. There were no signs of compaction or surface or structural characteristics changes after these cycles. The amounts of seawater and bunker oil showed minor variations between cycles (15.87 ± 0.60 g/g of oil sorbed in cycle 1 and 17.78 ± 0.51 g/g in cycle 10). In addition, the findings show that CCF-50 offers the potential to be recycled, which is cost-friendly [72].

3.7. The Oil Sorption Capacities of Common Sorbents

The oil sorption capacity of the synthesized CCFs was evaluated further through a comparative analysis with sorbent materials commonly used for oil spill remediation (Table 5). When compared to the existing literature, the CODP-incorporated CCFs exhibited comparable oil sorption capacities to those of conventional sorbents. While the alternative sorbent materials displayed varying oil sorption performances, the CODP-based polymer matrix formed multiple pores, enhancing both the physical and mechanical properties.
The facile synthesis of the CCFs, combined with the abundance of coconut-based products, positions these materials as a sustainable alternative to petroleum-based polyurethanes for oil spill mitigation. With their exceptional oil sorption capability, environmental compatibility, and scalable production, CCFs present a promising and transformative solution for effective clean-ups of marine oil spills.

4. Conclusions and Recommendations

This study synthesized PU foams using varying amounts of two types of polyols (a petroleum-based polyol and a coconut-oil-based derived polyol). Successful synthesis of polyurethane foam was achieved by employing a polyol blend. The incorporation of the CODP markedly influenced the foam’s physical and mechanical characteristics, increasing the reactivity between the polyol systems and isocyanates due to the increase in ester bonds (C=O) seen in FTIR with an increase in the bio-replacement. The morphological analysis showed that the PU foams, including the CODP, showed no significant difference in their cell size distribution and open porosity compared to those in the control foam. The results also showed higher hydrophobicity with an increased proportion of the CODP. The sorption tests showed that the sorption capability increased in CCF-50 with the content of CODP, showing improved oil sorption and less water uptake.
After at least 10 cycles of sorption/desorption, CCF-50 maintained a stable sorption capacity, demonstrating its potential as a bio-sorbent material. Further studies should broaden the experimental scope to include oil products with different viscosities and densities, such as crude oil, fuel oil, and kerosene.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/jmse13061176/s1. Figure S1: Actual images of CCF-50’s absorption of bunker oil from the water’s surface.

Author Contributions

Writing—original draft: J.L.L.T.; conceptualization: J.L.L.T., T.R.B.T., J.I.D.S.U., R.M.M., A.A.L. and H.P.B.; methodology: J.L.L.T., T.R.B.T. and A.A.L.; investigation: J.L.L.T., T.R.B.T. and J.I.D.S.U.; formal analysis: J.L.L.T., T.R.B.T. and J.I.D.S.U.; writing—review and editing: J.L.L.T. and H.P.B.; supervision: T.R.B.T., R.M.M., A.A.L. and H.P.B. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

The datasets utilized and/or analyzed during the current study are available from the corresponding author upon reasonable request.

Acknowledgments

The first author would like to acknowledge the support from the Department of Science and Technology (DOST) through the Accelerated Science and Technology Human Resource Development Program (ASTHRDP) scholarship program and the Center for Sustainable Polymers, Mindanao State University-Iligan Institute of Technology, for permitting the use of the laboratory for experimentation and the equipment for the analysis.

Conflicts of Interest

The authors declare no conflicts of interest.

Abbreviations

The following abbreviations are used in this manuscript:
ASTMAmerican Society for Testing Materials

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Jmse 13 01176 g001
Figure 1. The FT-IR spectra of the coconut-oil-derived polyol (CCF) prepared using varying fractions of bio-based and petroleum-based polyol blend loading.
Figure 1. The FT-IR spectra of the coconut-oil-derived polyol (CCF) prepared using varying fractions of bio-based and petroleum-based polyol blend loading.
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Jmse 13 01176 g002
Figure 2. TGA and DTG curves for the CCF prepared using varying fractions of CODP and petroleum-based polyol blend loading.
Figure 2. TGA and DTG curves for the CCF prepared using varying fractions of CODP and petroleum-based polyol blend loading.
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Jmse 13 01176 g003
Figure 3. The morphology of the foam specimens (scanning electron microscopy), cross-sectional visual images, and cell size distribution in varying bio-based and petroleum polyol blends: (a–d) control, (e–h) CCF-20, (i–l) CCF-40, (m–p) CCF-50, and (q–t) CCF-60.
Figure 3. The morphology of the foam specimens (scanning electron microscopy), cross-sectional visual images, and cell size distribution in varying bio-based and petroleum polyol blends: (a–d) control, (e–h) CCF-20, (i–l) CCF-40, (m–p) CCF-50, and (q–t) CCF-60.
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Jmse 13 01176 g004
Figure 4. Variations in the physical properties influenced by varying bio-based/petroleum-based polyol ratios, featuring the porosity and the average cell diameter of the foams.
Figure 4. Variations in the physical properties influenced by varying bio-based/petroleum-based polyol ratios, featuring the porosity and the average cell diameter of the foams.
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Figure 5. The influence of hydroxyl values on the (a) density and (b) compressive strength of varying ratios of bio-based polyols in polyurethane foam (CCF) and the petroleum-based polyol control foam.
Figure 5. The influence of hydroxyl values on the (a) density and (b) compressive strength of varying ratios of bio-based polyols in polyurethane foam (CCF) and the petroleum-based polyol control foam.
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Figure 6. The (a) water and (b) oil sorption capacity of varying ratios of CODP polyurethane foam (CCF) and petroleum-based polyol control foam.
Figure 6. The (a) water and (b) oil sorption capacity of varying ratios of CODP polyurethane foam (CCF) and petroleum-based polyol control foam.
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Figure 7. Seawater, engine oil, and bunker oil sorption behavior throughout the 10 cycles of sorption/desorption using CCF-50.
Figure 7. Seawater, engine oil, and bunker oil sorption behavior throughout the 10 cycles of sorption/desorption using CCF-50.
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Table 1. Properties of coconut-oil-based (CODP) and petroleum-based polyol (Voranol ®4701).
Table 1. Properties of coconut-oil-based (CODP) and petroleum-based polyol (Voranol ®4701).
PolyolsVoranol ®4701CODP
OH Value33–36122
Molecular Weight (Mw) g/mol7282519
Average Functionality (fav)3.00480
SourceFossil FuelCoconut Oil
Table 2. Formulation details for fabrication of PU foams with different CODP/petro-polyol ratios.
Table 2. Formulation details for fabrication of PU foams with different CODP/petro-polyol ratios.
Foam FormulationComponentsControlCCF-20CCF-40CCF-50CCF-60
PolyolVoranol ®470110080605040
CODP020405060
Table 3. Thermal degradation temperatures and percentage mass remaining of the CCF and the petroleum-based control foam.
Table 3. Thermal degradation temperatures and percentage mass remaining of the CCF and the petroleum-based control foam.
Foam
Samples		 Tmax, °C Mass Remaining, %
T1T2T3m1m2m3
Control376.65419.58661.8773.1620.480.42
CCF-20374.53421.80659.6672.4725.245.17
CCF-40374.12425.54664.6172.0429.7910.73
CCF-50363.9422.46664.4172.0331.3211.73
CCF-60361.37427.1663.2472.7935.5913.71
Table 4. Water contact angle measurements of PU foams and cross-sectional images of a single water droplet on the surface of the different formulations.
Table 4. Water contact angle measurements of PU foams and cross-sectional images of a single water droplet on the surface of the different formulations.
Foam FormulationCross-Sectional Image of Single Water DropletAverage Contact Angle (θ)
ControlJmse 13 01176 i001104.54 ± 2.58
CCF-20Jmse 13 01176 i002107.89 ± 2.47
CCF-40Jmse 13 01176 i003112.47 ± 3.76
CCF-50Jmse 13 01176 i004115.67 ± 2.07
CCF-60Jmse 13 01176 i005118.69 ± 2.14
Table 5. Comparison of oil sorption capacities of synthesized CCFs and other commonly used sorbent materials.
Table 5. Comparison of oil sorption capacities of synthesized CCFs and other commonly used sorbent materials.
Sorbent MaterialMaterial TypePreparation MethodPollutantsOil Sorption Capacity (g/g)References
Non-Woven Polypropylene BlanketsPolypropyleneMelt-spinningCrude Oil 8–12[73]
Rice HusksBiomass-based sorbentPyrolysisCrude Oil, Diesel Oil2.98–6.22[74]
Organo-ClayModified clay mineral sorbentSurface modificationDiesel Oil, Engine Oil2.1–7.2[22]
PU Foam with 25% Rice Straw (3 mm in Size)Bio-based PU Incorporation of filler into the polyurethane matrixDiesel Oil4.1–6.1[75]
Synthesized CCFs with 50% CODPBio-based PUOne-shot foaming methodBunker Oil, Engine Oil14.0–16.0This Study
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MDPI and ACS Style

Tefora, J.L.L.; Tomon, T.R.B.; Ungang, J.I.D.S.; Malaluan, R.M.; Lubguban, A.A.; Bacosa, H.P. The Development of a Coconut-Oil-Based Derived Polyol in a Polyurethane Matrix: A Potential Sorbent Material for Marine Oil Spill Applications. J. Mar. Sci. Eng. 2025, 13, 1176. https://doi.org/10.3390/jmse13061176

AMA Style

Tefora JLL, Tomon TRB, Ungang JIDS, Malaluan RM, Lubguban AA, Bacosa HP. The Development of a Coconut-Oil-Based Derived Polyol in a Polyurethane Matrix: A Potential Sorbent Material for Marine Oil Spill Applications. Journal of Marine Science and Engineering. 2025; 13(6):1176. https://doi.org/10.3390/jmse13061176

Chicago/Turabian Style

Tefora, John Louie L., Tomas Ralph B. Tomon, Joy Ian Dan S. Ungang, Roberto M. Malaluan, Arnold A. Lubguban, and Hernando P. Bacosa. 2025. "The Development of a Coconut-Oil-Based Derived Polyol in a Polyurethane Matrix: A Potential Sorbent Material for Marine Oil Spill Applications" Journal of Marine Science and Engineering 13, no. 6: 1176. https://doi.org/10.3390/jmse13061176

APA Style

Tefora, J. L. L., Tomon, T. R. B., Ungang, J. I. D. S., Malaluan, R. M., Lubguban, A. A., & Bacosa, H. P. (2025). The Development of a Coconut-Oil-Based Derived Polyol in a Polyurethane Matrix: A Potential Sorbent Material for Marine Oil Spill Applications. Journal of Marine Science and Engineering, 13(6), 1176. https://doi.org/10.3390/jmse13061176

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