Oil-based Polyol Research Articles

Sustainable Jatropha Oil-Based Membrane with Graphene Oxide for Potential Application in Cu(II) Ion Removal from Aqueous Solution

More recent attention has been focused on the utilization of Jatropha curcas in the field of water treatment. The potential of Jatropha oil in the synthesis of membrane for water filtration had been explored, its performance compared to the addition of graphene oxide (GO) in the polymer matrix. Jatropha oil was modified in a two-step method to produce Jatropha oil-based polyol (JOL) and was blended with hexamethylene diisocyanate (HDI) to produce Jatropha polyurethane membrane (JPU). JPU was synthesized in different conditions to obtain the optimized membrane and was blended with different GO loading to form Jatropha/graphene oxide composite membrane (JPU/GO) for performance improvement. The synthesized pristine JPU and JPU/GO were evaluated and the materials were analyzed using fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), contact angle, water flux, and field emission scanning electron microscopy (FESEM). Results showed that the ratio of HDI to JOL for optimized JPU was obtained at 5:5 (v/v) with the cross-linking temperature at 90 °C and curing temperature at 150 °C. As GO was added into JPU, several changes were observed. The glass transition temperature (Tg) and onset temperature (To) increased from 58 °C to 69 °C and from 170 °C to 202 °C, respectively. The contact angle, however, decreased from 88.8° to 52.1° while the water flux improved from 223.33 L/m2·h to 523.33 L/m2·h, and the pore distribution in JPU/GO became more orderly. Filtration of copper ions using the synthesized membrane was performed to give rejection percentages between 33.51% and 71.60%. The results indicated that GO had a significant impact on JPU. Taken together, these results have suggested that JPU/GO has the potential for use in water filtration.

Waterborne polyurethanes from castor oil-based polyols for next generation of environmentally-friendly hair-styling agents

Commercial hair-styling spray is often formulated with multiple components that contribute to toxicity and environmental pollution. In this work, a series of bio-based waterborne polyurethanes (CWPU) as hair styling agent were prepared from castor oil-based polyols. The resulting polyurethane dispersions exhibit excellent storage stability for at least 24 months. The effects of the castor oil functionality and chain extender structure on the particle size of the polyurethane dispersions were systematically investigated. Hair-styling performance and skin irritation tests on animals were also carefully performed to assess styling performance and safety of these CWPUs. A series of CWPU films was successfully prepared to study the relationship between the structure and performance of the bio-based polymer films. The resulting films show low moisture uptake rate, high transmittance, hydrophilicity and good mechanical properties. When CWPU films exhibit Young’s modulus >50 MPa, elongation at break in the 15–300 % range, and moisture uptake <4 %, these samples exhibit good hair-styling performance, and even better than commercial hair spray product. The skin irritation test is also proved that there is no evidence of skin irritation for these CWPUs which hold great promise for hair styling applications.

Properties of Rigid Polyurethane Foam Modified by Tung Oil-Based Polyol and Flame-Retardant Particles.

Although tung oil is renewable, with an abundant production and low price in China, and it is used to synthesize different polyols for rigid polyurethane foam (RPUF), it remains a challenge to improve the properties of RPUF by redesigning the formula. Therefore, we propose four novel compounds to strengthen the properties of RPUF, such as the catalyst-free synthesis of tung oil-based polyol (PTOK), aluminum phosphate micro-capsule (AM), silica micro-capsule (SiM), and grafted epoxidized monoglyceride of tung oil on the surface of SiO2 (SiE), which were designed and introduced into the RPUF. Because of the PTOK with a catalytic function, the foaming process of some RPUF samples was catalyst-free. The results show that the incorporation of AM, SiM, and SiE, respectively, endow RPUF with a better thermal stability at a high temperature, and the T5%, Tmax1, and Tmax2 of RPUF appeared to be reduced, however, the Tmax3 and residue rate at 800 °C were improved, which may have a positive effect on the extension of the rescue time in case of fire, and the limiting oxygen index (LOI) value was increased to 22.6%. The formula, containing 25% PTOK made the RPUF environment-friendly. The results were obtained by comparing the pore size and mechanical properties of the RPUF—the AM had a better dispersion in the foam, and the foam obtained a better mechanical, thermal, and flame retardancy.

Recycling of bio-polyurethane foam using high power ultrasound

Three different types of waste bio-polyurethane foams (bio-PUFs) made of castor oil-based polyol, castor oil-based polyol with isosorbide-based isocyanate, and soybean oil-based polyol were ultrasonically decrosslinked, and blended with a traditional PUF formula for fabrication of automotive seat cushions. The seating comfort of recrosslinked PUFs was quantified by calculating the hardness, hysteresis loss, and sag factor as derived from the indentation force deflection test, and found to exhibit improved seating comfort. In this regard, the ultrasonically decrosslinked bio-PUFs were examined by gel fraction, crosslink density, FT-IR spectroscopy, and thermal property, and the improvement of comfort was attempted to explain by analyzing the morphological changes of recrosslinked PUFs using SEM.

Unsaturated canola oil-based polyol as effective nucleating agent for polyurethane hard segments

The polyurethane (PU) phase separation could significantly affect its properties. Many factors influence PU phase separation, including soft and hard segments type, their content, and presence of external components such as nanoparticles. The aim of this research was to control the PU phase separation behavior by an internal component which was chemically bonded in PU backbone. For this purpose, a low molecular weight polyester was synthesized and used as a co-soft segment for PU synthesis. The polyester was synthesized by hydroxylation and esterification reaction of unsaturated bonds of raw Canola oil. The PUs were synthesized by two-step polymerization method of poly tetramethyleneglycol (PTMG) and synthesized polyester as soft segments, hexamethylene diisocyanate (HDI), and 1,4 butanediol in 1:3:2 M ratio. In order to study the chemical structure of synthesized materials, specifying the nucleating ability of the synthesized polyol for hard segments, as well as studying its effects on PU properties, different analysis including Fourier Transform Infrared Spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction analysis (XRD), Dynamic Mechanical Thermal Analysis (DMTA) and gas permeability were used. Results showed that the presence of the synthesized polyester in the PU structure significantly affects its properties and caused appearance of a new domain for hard segments. These results suggested that polyester polyol can change the PU micro-phase separation by changing hard segments crystalline order.

Experimental and finite element approach for finding sound absorption coefficient of bio-based foam

The enormous consumption of Polyurethane foam leads to severe environmental pollution and health hazards, so it is necessary to overcome this problem. This paper presents alternative and less hazardous foam that differs from traditional foams. A bio-based foam was developed either by using castor oil-based polyol or natural fibers as fillers. In the present study, rigid foam is synthesized by both castor polyol and luffa fiber, whereas for flexible foam, only luffa fiber is incorporated. Luffa fillers enhance the porosity of Polyurethane foam, which is the dominating factor influencing the value of the sound absorption coefficient. Both rigid and flexible foams were developed with 5, 10 and 15 percentages of filler loaded. The samples are tested experimentally using the two-microphone impedance tube method and the measured result was compared with the numerical result, which is predicted from COMSOL Multiphysics. The experimental results of flexible foam demonstrate good agreement with numerical results. The results indicate that the addition of Luffa fibers enhances the sound absorption performance of flexible foam and deterioration in the rigid foam because of the high viscosity of castor oil polyol.

Influence of Chemical Structure of Petrochemical Polyol on Properties of Bio-polyurethane Foams

In this study, the influence of the chemical structures of petrochemical polyols on the foaming process of polyurethane compositions as well as on selected properties of the foams obtained has been investigated. Two types of petrochemical polyols were used—polyester and polyether polyols as well as their blends with a rapeseed oil-based polyol. Dielectric polarization, temperature and expansion velocity were determined during the foaming process of the polyurethane systems with different polyol components. The results show the highest reactivity of the polyester polyol and a decrease of the polyurethane system’s reactivity as a result of a partial replacement of the petrochemical polyol with the bio-based polyol. The content of the closed cells in the materials obtained strongly depends on the petrochemical polyol used. The results indicate that the chemical structure of the petrochemical polyol had a significant effect on the cellular structure as well as the physical–mechanical properties of the final products. A significant worsening of the foams’ mechanical properties was observed as an effect of a partial replacement of the polyester polyol with the rapeseed oil-based polyol. In contrast, a partial replacement of the polyether polyol caused an improvement of the cell structure keeping the mechanical properties of the modified foams at the same level.

Polyurethane-coated urea using fully vegetable oil-based polyols: Design, nutrient release and degradation

Fully vegetable oil-based polyols with a low hydroxyl value and viscosity were designed and prepared using epoxidized soybean oil (ESO) and oleic acid as raw materials, which were also used to prepare polyurethane films 1-5 with different isocyanate indices. Their structures were characterized by FTIR and 1H NMR. The GPC data indicated that the number-average molecular weight (Mn) of the polyols was 3331 and the distribution index was 1.578. The effects of the isocyanate index on the morphology, DMA, mechanical properties, water absorption, water contact angle, TGA and soil degradation of PU films were investigated. When the isocyanate index increased from 1.13 to 2.65, the glass transition temperature (Tg) and crosslinking density (νe) of polyurethane increased from −4.5 °C to 74.7 °C and from 630 mol/m3 to 2000 mol/m3, respectively. By 180 days, the degradation percentages of the five PU films (1-5) were 10.23%, 20.01%, 21.85%, 26.78% and 29.63%, respectively. Two coated ureas (Oil-PCUs) were successfully prepared containing 70% vegetable oil. The 80% cumulative release of Oil-PCUs-6% (isocyanate index: 1.58) took more than 70 days, indicating that the prepared Oil-PCUs have great potential for use in agriculture, forestry and grasslands.

The effect of rapeseed oil-based polyols on the thermal and mechanical properties of ureaurethane elastomers

Two types of rapeseed oil-based polyols in the content of 20 wt% and 50 wt% were used for synthesis of ureaurethane elastomers (EPUU) with isocyanate index 1.07. The bio-polyols were synthesized by epoxidation and opening of oxirane rings using isopropanol (RO) and diethylene glycol (MK). The aim of this work was to evaluate the impact of bio-polyols on the thermal and mechanical properties of the manufactured EPUUs, produced with poly(ethylene adipate) (PEA). Differences in the structure of used bio-polyols caused changes in the number of hydrogen bonds and degree of phase separation in EPUUs. As the content of bio-polyols increases, the number of hydrogen bonds connecting the rigid segments of these materials is reduced. The consequence of these changes is variation in the thermal characteristics of these materials. Cross-linking density calculated from dynamical mechanical thermal analysis increases for materials with 20% of both types of rapeseed oil-based polyols and is the highest for material 80PEA/20MK. An introduction of the MK polyol also resulted in an increase in the elongation at break of the modified elastomers.

Characterisation of ureaurethane elastomers with rapeseed oil-based polyol

The purpose of this study was to evaluate the effect of rapeseed oil-based (RO) polyol on the thermal and mechanical properties of the tested ureaurethane elastomers (EPUUs) produced with poly(ethylene adipate) (PEA). The bio-polyol was synthesized by epoxidation and opening of oxirane rings using diethylene glycol (DG). The use of RO polyol in the amount 40 wt.% in polyol premixes changed the chemical structure of EPUUs with different hard segments (HS) content, what in a consequence indicates the change in quantity of the number of hydrogen bonds and degree of phase separation (DPS). The consequence of these changes are variation in the thermal characteristics of these materials. The DSC analysis showed that an addition of the RO polyol causes the increase in the glass transition temperature of the soft phase with an increase of HS content in EPUUs. An introduction of the RO polyol also resulted in an decrease in the elongation at break with an increase of HS content in the modified elastomers.

Waterborne polyurethane-silica nanocomposite adhesives based on castor oil-recycled polyols: Effects of (3-aminopropyl)triethoxysilane (APTES) content on properties

Waterborne castor oil-recycled polyol based polyurethane-silica nanocomposite adhesives (WPU) with polymer matrix and silica nanoparticles chemically bonded have been successfully prepared through a sol-gel process. A series of waterborne polyurethane adhesives with hard segment contents from 71.3 to 74.5 wt%, were synthesized using an isophorone diisocyanate, 2-bis(hydroxymethyl) propionic acid, recycled castor oil-based as soft segments and (3-aminopropyl)triethoxysilane (APTES) as chain extender. The depolymerized oligoester obtained from glycolysis of poly(ethylene terephthalate) (PET) waste using triethylene glycol (TEG), was transesterified with castor oil (CO) which resulted in the formation of hydroxyl-functional polyester polyol, with hydroxyl value of 414 mgKOH g−1. The molecular structures and mass of glycolyzed PET oligoesters, castor oil-based polyol and castor oil-based polyurethane-silica nanocomposite adhesives were estimated by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The structure and properties of the resulting films were investigated by FTIR, wide angle X-ray diffraction measurement (XRD), thermogravimetry (TG) and differential scanning calorimetry (DSC). TG analysis indicated that APTES can improve the thermal stability of WPU. XRD showed that the crystallinity of WPU decreased with the increase alkoxysilane content. The extent of crosslinking was investigated to show a dependence on silica concentration, which increased the glass transition temperature and particle size of polyurethane nanocomposites with increasing alkoxysilane content due to the condensation of the alkoxysilane groups. The hardness, adhesion and gloss quality of the polyurethane films were also determined considering the effect of APTES content, so this paper confirmed the suitability of using these castor oil-based waterborne polyurethane-silica nanocomposites as new adhesive materials with high performance coatings materials. The experimental results reveal that the APTES and the hard segment content play a key role in controlling the structure and properties of the PU cast films based on castor oil-recycled polyols.

Synthesis and Characterization of Novel Castor Oil-Based Polyol for Potential Applications in Coatings

In this study, three sorts of polyols were successfully synthesized from castor oil using a Dean-Stark quick, eco-friendly and high-efficiency method. For this purpose, castor oil was epoxidized in the presence of two types of catalysts including γ-alumina and formic acid, named as ECOAl and ECOF, respectively. Epoxidized castor oils were then characterized by use of hydrogen nuclear magnetic resonance (H-NMR) and oxirane oxygen content analysis. The relative percentages of conversion double bond to oxirane were obtained 96% and 74% for ECOAl and ECOF, respectively. Ring opening reaction of ECOAl was performed by two types of saponified castor oil as well as castor oil in a system equipped with Dean–Stark apparatus. The synthesized polyols were characterized by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), viscometer and OH number evaluation. The material obtained in this research is a candidate to be intended in synthesis of polyurethane for coating applications.

Effects of Tung Oil-Based Polyols on the Thermal Stability, Flame Retardancy, and Mechanical Properties of Rigid Polyurethane Foam.

A phosphorus-containing tung oil-based polyol (PTOP) and a silicon-containing tung oil-based polyol (PTOSi) were each efficiently prepared by attaching 9,10-dihydro-9-oxa-10-phosphaphenanthrene (DOPO) and dihydroxydiphenylsilane (DPSD) directly, respectively, to the epoxidized monoglyceride of tung oil (EGTO) through a ring-opening reaction. The two new polyols were used in the formation of rigid polyurethane foam (RPUF), which displayed great thermal stability and excellent flame retardancy performance. The limiting oxygen index (LOI) value of RPUF containing 80 wt % PTOP and 80 wt % PTOSi was 24.0% and 23.4%, respectively. Fourier transfer infrared (FTIR), Nuclear Magnetic Resonance (NMR) and thermogravimetric (TG) analysis revealed that DOPO and DPSD are linked to EGTO by a covalent bond. Interestingly, PTOP and PTOSi had opposite effects on Tg and the compressive strength of RPUF, where, with the appropriate loading, the compressive strengths were 0.82 MPa and 0.25 MPa, respectively. At a higher loading of PTOP and PTOSi, the thermal conductivity of RPUF increased while the RPUF density decreased. The scanning electron microscope (SEM) micrographs showed that the size and closed areas of the RPUF cells were regular. SEM micrographs of the char after combustion showed that the char layer was compact and dense. The enhanced flame retardancy of RPUF resulted from the barrier effect of the char layer, which was covered with incombustible substance.

Effect of Evening Primrose Oil-Based Polyol on the Properties of Rigid Polyurethane⁻Polyisocyanurate Foams for Thermal Insulation.

The article presents the results of research on the synthesis of a new biopolyol based on evening primrose oil, and its use in the production of rigid polyurethane–polyisocyanurate foams intended for thermal insulation. The obtained biopolyol was subjected to analytical, physicochemical, and spectroscopic tests (Fourier transform infrared (FTIR), 1H NMR, 13C NMR) to confirm its suitability for the synthesis of polyurethane materials. Then, it was used for the partial replacement of the petrochemical polyol in the polyurethane formulation. Obtained rigid polyurethane–polyisocyanurate foams are characterized by a lower apparent density, brittleness, water absorption, and thermal conductivity coefficient λ. In addition, foams modified by biopolyols had a higher content of closed cells and higher aging resistance. The results of the conducted research showed that the use of the biopolyol based on evening primrose oil may be an alternative to petrochemical polyols. The research presented herein is perfectly consistent with the trends of sustainable development and the philosophy of green chemistry.

Colloidal stability and rheology of jatropha oil-based waterborne polyurethane (JPU) dispersion

Jatropha oil-based waterborne polyurethane (JPU) dispersions were produced by polymerising the jatropha oil-based polyols (JOLs) with isophrene diisocyanate (IPDI) and dimethylol propionic acid (DMPA). The colloidal stability of the resulting JPU dispersions were studied by particle size analysis and rheology measurements. Inclusion of up to 5.4 wt.% of DMPA as an internal emulsifier produced a wide range of particle sizes from 84 nm to 825 nm. The dispersions have a solid content of 24.2–26.9 wt.% with a relatively low viscosity in the range 6.2–60.2 mPa s. The JPU dispersions exhibited the typical flow behaviour of the commercial polyurethane dispersions, ranging from almost Newtonian to a shear thinning fluid, and the experimental data correlated well with the Cross model. The samples were stable after 18 months of storage under room conditions.

Effect of Aluminium Filler Content on the Mechanical Properties of Polyurethane Foam

Start In this work, the effects of Aluminium (Al) filler content in Polyurethane (PU) foam with different weight percentages (0.5 wt.% to 3.0 wt.%) were evaluated on morphology, density and compressive strength. The pure PU and PU/Al foam composites were produced from palm oil-based polyol (POP) and methylene diphenyl diisocyanate (MDI) with a ratio of 1:1. Scanning Electron Microscope (SEM) morphology showed that the cell structure of PU/Al foam composites is less homogeneous as compared to the pure PU. The PU/Al foam composites displayed a higher number of cells with a smaller cell size as the amount of Al content was increased. The addition of 1.5 wt.% Al on the PU foam showed the highest density and compressive strength in 0.073 g/cm3 and 0.56 MPa, respectively. Meanwhile, the further addition of Al on PU foam has decreased the density and compressive strength value. The experimental compressive strength results have compared to the theoretical results that tested by using ANSYS MULTIPHYSICS (15.0) software.

Mechanical Properties of Palm Oil Polyol based Polyurethane Foam Reinforced Wollastonite Clay

The palm oil polyol based polyurethane (PU) foam reinforced wollastonite clay was prepared to study the effects of wollastonite clay addition towards the mechanical properties of PU foam. The palm oil polyol based PU foam with NCO: OH ratio of 1:1.22 was synthesized by mixing palm oil-based polyol, p-MDI, DMCHA, PMDETA, distilled water and incorporation of different amount of wollastonite clay powder (1, 3, 5 and 7 wt%). The FTIR analysis showed the absence of NCO peak at 2280 cm−1 suggesting the complete conversion of isocyanates into urethane during the mixing process. Based on FESEM/EDX, it was found that the wollastonite clay were fitted into the PU matrix, whereby SEM showed an open cell structure of PU foam reinforced wollastonite clay. The density of PU foam reinforced wollastonite clay is increased as the amount of clay reinforcement is increased. This is due to the high viscosity of the mixture which hinder the foam from rising and hence produced a denser foam, thus reduced the pore sizes. Hence, the compressive strength increased as the density and wollastonite weight percentage in the foam is increased.

Controlled Hydroxyl Functionality of Soybean Oil-Based Polyols for Polyurethane Coatings with Improved Anticorrosion Properties

One of the major challenges in current polymer industry is to develop renewable and sustainable alternatives to petroleum-based raw materials. In this study, soybean oil (SO) was adopted as a renewable resource to afford polyols (MSO) with predetermined primary hydroxyl values (OHVs). The MSOs were prepared through a simple thiol-ene click reaction between the SO and 2-mercaptoethanol. The OHVs of the MSOs were adjusted simply by controlling the conversion of carbon-carbon double bonds of SO to OH groups. To explore their potential applications, series of polyurethane (PU) coatings were prepared from the MSOs. The MSOs with increased OHVs afforded PU coatings with higher glass transition temperature and improved adhesion strength values. Notably, increased OHVs of MSOs afforded PU coatings with improved anticorrosion properties in 3.5 wt% NaCl corrosive medium, which was attributed to the strong adhesion and blocking characteristics of the PU coatings. This study demonstrated that the number of hydroxyl functionality of the bio-based polyols played a crucial role in controlling the characteristics of the PU coatings.

Effect of the silica nanofiller on the properties of castor oil-based waterborne polyurethane hybrid dispersions based on recycled PET waste

The paper describes the chemical depolymerization of the polyethylene terephthalate (PET) waste from postconsumer soft drink bottles and a search for the way to use this product. The depolymerized oligoester obtained from glycolysis of PET waste using tiethylene glycol was transesterified with castor oil which resulted in the formation of hydroxyl-functional polyester polyol, with hydroxyl value of 391 mg KOH g−1. In the presented paper, series of castor oil-based waterborne polyurethane (CPU)/silica hybrid dispersions were prepared using dimethylolpropionic acid as an ionic center. The polyurethane prepolymers with pendent castor oil groups were prepared first, and then different concentrations of hydrophilic fumed silicas (0, 0.5, 0.75, 1.0 and 2.0 wt%) were added. For waterborne polyurethane dispersions of hydrophilic fumed silica with the surface area (50 ± 15 m2/g) and a primary particle size of 40 nm in the polymer matrix, ultrasound waves were used. The hybrid dispersions were prepared by adding the required amount of triethylamine and water. The molecular structures and mass of glycolyzed PET oligoesters, castor oil-based polyol and castor oil-based polyurethane–silica hybrid dispersions were estimated by FTIR method and gel permeation chromatography.The incorporation effect of SiO2 nanoparticles into the PU matrix on the thermal and mechanical properties of resulting polyurethane films has been examined by Fourier transform infrared spectroscopy (FTIR), thermogravimetry analysis, differential scanning calorimetry (DSC), SEM microscope, and measurement of the coatings properties. The DSC data results suggest that hard segment glass temperature decreases, but mixed-phase glass transition temperature increases with increasing SiO2 content. The FTIR deconvolution result of the degree of phase separation between oxide nanoparticles and hard segment supports to the DSC analysis. The addition of silica oxide caused the increase in the thermal stability. The T10% and T50% of CPU films (the temperatures where 10 and 50% weight loss occurred) increased with increasing the SiO2 content. UV–Vis spectrophotometry showed that introduction of nanosilica particles into polyurethane enhanced the shielding property of obtained films for UV light. The hardness, adhesion, and gloss quality of the polyurethane films were also determined considering the effect of the phase separation and the SiO2 content, so this paper confirmed the suitability of using these castor oil-based waterborne polyurethane/silica hybrid dispersions as new materials with high-performance coatings materials.

A Study of Rapeseed Oil-Based Polyol Substitution with Bio-based Products to Obtain Dimensionally and Structurally Stable Rigid Polyurethane Foam

Water-blown polyurethane foams from low functionality polyols are characterized by intensive shrinkage, high density, post blowing, and longer demold time. These drawbacks can be partially, or fully, eliminated by varying chemical parameters of the main components. Therefore, an aliphatic polyester rapeseed oil-based polyol was modified with bio-based glycerin (RGL) and propylene glycol (RPG). The impact of the molecular weight and hydroxyl value of the blends were evaluated by testing obtained bio-based polyurethane foams. Compared to RGL-based foams, RPG-modified foams had the strictest standard (EN 13165) requirements regarding dimensional stability. These foams demonstrated a reduced apparent density from 12.6 to 20.8%, a faster foam curing capability by 47%, and the shortest demold time due to the open cell structure. The RGL modified foams had better cross-linking capability, slower ageing of thermal conductivity, and an increased compressive strength of 82.7% compared to the non-modified foam.