Dihydroxystearic Acid Research Articles

Sustainable approach for catalytic epoxidation of oleic acid followed by in situ ring-opening hydrolysis with applied ion exchange resin

Abstract Vegetable oils are rich in unsaturated bonds that can be converted to epoxidized oleic acid. They are considered sustainable, renewable, and also environmentally friendly. To date, there is a paucity of studies on production of dihydroxystearic acid (DHSA) using an eco-friendly ion exchange resin as it is not fully utilised. As a result, the aim of this study is to elucidate the mechanism of ring-opening by hydrolysis for the production of DHSA using amberlite IR-120H as a catalyst. The process of epoxidizing oleic acid involved the in situ generation of performic acid, which was then used to convert oleic acid into epoxidized oleic acid. This performic acid was created by combining formic acid, serving as the oxygen carrier, with hydrogen peroxide, acting as the oxygen donor. Under optimal conditions, the maximum relative conversion of oleic acid to oxirane was attained, with up to 85 %. Overall, DHSA with a high hydroxyl value (182 mg KOH/g), was successfully produced from oleic acid using in situ hydrolysis of epoxidized oleic acid.

Recent advances of ring opening of epoxidation of palm oil derived from oleic acid via in situ hydrolysis under moderate temperature

AbstractEpoxidized oleic acid was considered a more sustainable alternative to traditional plasticizers such as phthalates, which have been linked to potential health and environmental hazards. This study aims to synthesize and characterize the formation of dihydroxystearic acid (DHSA) from the ring opening of epoxidized oleic acid. The optimal reaction parameters to produce DHSA were found using sulfuric acid as catalyst in which the maximum relative conversion was reached up to 86%. The detection of hydroxyl group was using Fourier Transform Infrared Spectroscopy. Then, a mathematical model was developed using MATLAB software, and as a result the kinetic model provided a good description of the reaction process, and it could be used to predict the behavior of the reaction under different conditions. Overall, the optimal reaction conditions and the maximum relative conversion of palm oleic acid to oxirane, are important contributions to the field of green chemistry.

Investigating the potential of dihydroxystearic acid as feedstock for rigid polyurethane foam

Rigid polyurethane (PU) foam has been widely used for a multitude of applications, primarily as thermal insulation materials. With the exhortation of “green chemistry” and sustainable development, bio-based polyols are being introduced to replace the conventional petrochemical-based polyols. Hence, the use of 9, 10-dihydroxystearic acid (DHSA), derived from palm oil-based oleic acid, as a feedstock for rigid PU foam production was explored. In this study, the effects of the weight ratio percentage of DHSA on the characteristics of the resulting PU foams were investigated. The DHSA was utilized as a co-polyol to synthesize rigid PU foams by reacting with the diisocyanate compound, blowing agent and additives. In general, the effects of DHSA in the formulations on the quality of the foams were relatively similar to PU formulation without the addition of DHSA, particularly in terms of density, compressive strength, thermal conductivity, cell structure and dimensional stability. The remarkable effect of DHSA addition in the PU formulations was observed through the open PU cell content using a pycnometer and scanning electron microscopy (SEM). The addition of DHSA has the ability to open the cell structure of the resulting rigid PU foams. The open cell content increased notably from 6.83% to 90.99% when the DHSA content was increased from 0% to 50%. The ability of DHSA to produce open-cell rigid PU foam widens up the potential applications of rigid PU foams as sound absorption materials.

Ultraperformance liquid chromatography-based metabolite profiling and cytotoxic activity of the ethyl acetate extract of two endophytic Penicillium sp.

The present study evaluated the mycochemical abundance, and the cytotoxic and hemolytic activities of ethyl acetate extract (EAE) of endophytic Penicillium camponotum (PC) and Penicillium fuscoglaucum (PF). Higher yield was noted in EAE-PF with total phenols (26.59 ± 1.52 mg of GAE/g DW) and flavonoids (3.12 ± 1.83 mg of QE/g DW). The EAE-PF inhibited the proliferation of two breast cancer cells (BT-474 and MDA-MB-231) with the half-maximal inhibitory concentration (IC50) of 0.112 and 0.120 mg/mL, respectively, while the IC50 values against HEK-293 and NIH3T3 cells were not found up to 1 mg/mL dose of EAE-PF. Moreover, EAE-PF (1 mg/mL) demonstrated its trivial toxicity in erythrocytes with ∼4.6% of hemolysis. The metabolic profiling of EAE-PF revealed the presence of mycochemicals including penicitide B (C18H34O5), p-hydroxyphenethyl anisate (C16H16O4), and dihydroxystearic acid (C18H36O4). Furthermore, these compounds exhibited substantial interactions with human cancer-related proteins such as epidermal growth factor receptor (EGFR), N-myristoyltransferase isoform 2 (NMT-2), cyclin-dependent kinase 2 (CDK-2), and c-mesenchymal epithelial transition factor kinase (c-Met K) evidenced by in-silico molecular docking analysis. Overall, this report suggests further studies on the isolation and purification of novel anti-cancer compounds from endophytic PF.

Catalytic Epoxidation of Oleic Acid and Subsequent Ring-Opening by In Situ Hydrolysis for Production Dihydroxystearic Acid

Catalytic Epoxidation of Oleic Acid and Subsequent Ring-Opening by In Situ Hydrolysis for Production Dihydroxystearic Acid

Single step synthesis of Dihydroxystearic Acid (DHSA) from Epoxidized Palm Oil

Single step synthesis of Dihydroxystearic Acid (DHSA) from Epoxidized Palm Oil

Selective epoxidation of the unsaturated fatty acids

Nowadays, epoxidized vegetable oils are of major significance since they are derived from renewable and sustainable natural resources and are eco-friendly. Epoxide is a crucial chemical precursor to produce alcohols, glycols, and polymers such as polyester and epoxy resin. Oleic acid’s long alkyl chain including an unsaturated double bond (C=C) makes it an appealing fatty acid for producing eco-friendly epoxide. The epoxidation of unsaturated fatty acid was accomplished by generating performic acid in situ to yield epoxidized oleic acid. The result of this reaction will be dihydroxystearic acid (DHSA). DHSA is one of the chemical precursors used to manufacture cosmetics. The optimal level of epoxidized unsaturated oleic acid was 82%.

PH-Responsive Liquid Marbles Based on Dihydroxystearic Acid.

Herein, we report pH-responsive liquid marbles stabilized by 9,10-dihydroxystearic acid (DHSA). The particle morphology and the pH-responsive behavior of the liquid marbles were investigated. The rolling time during the preparation of liquid marbles has a great influence on the thickness of powder adsorption and the stability of the marbles. Compared with the liquid marbles stabilized by other fatty acids (e.g., stearic acid and docosoic acid), the liquid marbles prepared by DHSA have a much higher mechanical robustness. The increase in the number of hydroxyl groups on the carbon chain of fatty acids improves the mechanical robustness of the liquid marbles. Such liquid marbles immediately disintegrated on the surface of an alkaline solution or after exposure to NH3 gas, which extends their applications in the NH3 sensor and chemical reactions.

Highly production of dihydroxystrearic acid from catalytic epoxidation process by in situ peracid mechanism

AbstractEpoxidized vegetable oils are great concern as they are obtained from sustainable, and renewable natural resources. The epoxidation of palm oil‐derived oleic acid was carried out by using in situ generated performic acid to produce epoxidized palm oil‐derived oleic acid. The maximum conversion of palm oil‐derived oleic acid into oxirane was 86% by applying the in situ peracid mechanism. Based on the Fourier‐transform infrared spectrum, the hydroxyl group was observed within a wavenumber range of 1210–1320 cm−1. Last, a mathematical model was developed using Runge–Kutta method and after 100 iterations, the reaction rate parameters were obtained as follows:= 0.046 mol·L−1·min−1,= 39.058 mol·L−1·min−1,= 2.789 mol·L−1·min−1, and= 0.0235 mol·L−1·min−1for of dihydroxystearic acid production.

The Oxidative Cleavage of 9,10‐Dihydroxystearic Triglyceride with Oxygen and Cu Oxide‐based Heterogeneous Catalysts

This paper deals with a new heterogeneous catalyst for the second step in the two‐step oxidative cleavage of unsaturated fatty acids triglycerides derived from vegetable oil, a reaction aimed at the synthesis of azelaic and pelargonic acids. The former compound is a bio‐monomer for the synthesis of polyesters; the latter, after esterification, is used in cosmetics and agrochemicals. The reaction studied offers an alternative to the currently used ozonization process, which has severe drawbacks in terms of safety and energy consumption. The cleavage was carried out with oxygen, starting from the glycol (dihydroxystearic acid triglyceride), the latter obtained by the dihydroxylation of oleic acid triglyceride. The catalysts used were based on Cu2+, in the form of either an alumina‐supported oxide or a mixed, spinel‐type oxide. The CuO/Al2O3 catalyst could be recovered, regenerated, and recycled, yielding promising results for further industrial exploitation.

High Yield Dihydroxystearic Acid (DHSA) Based on Kinetic Model from Epoxidized Palm Oil

In recent years, studies related to the epoxidation of fatty acids have garnered much interest due to the rising demand for eco-friendly epoxides derived from vegetable oils. From the epoxidation reaction, there is a side reaction involving epoxide and water. This reaction produces a by-product – dihydroxystearic acid (C<sub>18</sub>H<sub>36</sub>O<sub>4</sub>, DHSA). DHSA is one of the chemical precursors in the production of cosmetic products. Therefore, a kinetic model was developed to determine the optimised epoxidation process and concentration of DHSA, where each of the reactions was identified. The kinetic rate, <i>k</i> parameters obtained were: <i>k</i><sub>11</sub> = 6.6442, <i>k</i><sub>12</sub> = 11.0185, <i>k</i><sub>21</sub> = 0.1026 for epoxidation palm oleic acid, and <i>k</i><sub>41</sub> = 0.0021, <i>k</i><sub>51</sub> = 0.0142 in degradation process. The minimum error of the simulation was 0.0937. In addition, DHSA yield optimisation was done through Taguchi method, and the optimum conditions obtained were H<sub>2</sub>O<sub>2</sub>/oleic acid – OA unsaturation molar ratio 1 : 1 (level 2), formic acid – FA/OA unsaturation molar ratio 0.5 : 1 (level 1), temperature 35 °C (level 1), and agitation speed 100 rpm (level 1). A high yield of DHSA can be achieved under these conditions.

Formation of Dihydroxystearic Acid (DHSA) from Epoxidized Palm Oleic Acid by Peracid Mechanism and Their Kinetic Study

Dihydroxystearic acid (DHSA) is a product derived from a chemical modification of palm oleic acid. Application of these valuable fatty acids can be found in cosmetics, as a thickening agent and as a coating agent for pigments due to its unique structure. This study investigates the effect of a catalyst on epoxidation and the formation of DHSA by peracid mechanism. The epoxidation yield calculated by relative conversion to oxirane (RCO%) with a high yield of 95% achieved. Thereafter, the epoxidized oleic acid was hydrolyzed to produce DHSA. The formation of DHSA was verified by analysed the physicochemical properties using Fourier Transform Infra-red (FTIR). The kinetic model was being conducted to determine reaction rate using Particle Swarm (PS). The result showed that PS obtained a minimum error of 0.2005 and a correlation coefficient, r of 0.9999.

Performance of palm oil‐based dihydroxystearic acid as ionizable molecule in waterborne polyurethane dispersions

ABSTRACTWaterborne polyurethane dispersions (WPUDs) containing a renewable palm oil‐based 9,10‐dihydroxystearic acid (DHSA) as an isocyanate‐reactive compound bearing ionizable carboxylic group to incorporate hydrophilic groups into the polymer chain have been successfully prepared. The WPUDs were prepared by using polyether and polyester polyols of 2000 molecular weight, DHSA and its traditional petroleum‐based counterpart 2,2‐bis(hydroxymethyl)‐propionic acid (DMPA), and an aliphatic diisocyanate (isophorone diisocyanate, IPDI). A comparison was made between the properties of WPUDs obtained using blends of DHSA and DMPA at different molar ratios and a reference WPUD based on DMPA. The particle size of polyester type WPUDs containing DHSA was reduced at a 0.5 to 0.5 molar ratio of DMPA to DHSA. A lower initial temperature was used in the preparation of NCO‐prepolymers with DHSA as compared to DMPA and this eased the preparation of WPUDs. The effect of molar ratio of DMPA to DHSA on the properties of films and coatings prepared with WPUDs was evaluated. The best properties were obtained with WPUDs prepared with a 0.5 to 0.5 molar ratio of DMPA to DHSA. The incorporation of renewable palm oil‐based DHSA into WPUDs improved water resistance (lower water uptake) and exhibited good combination of properties including hardness, adhesion strength, tensile strength, and elasticity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43614.

Application of Taguchi Optimization Method in Improving the Selectivity of Dihydroxystearic Acid

Dihydroxystearic acid (DHSA) is perceived to be of significant value to various types of industries, especially the oleochemical industry. It is produced by reacting palm-based crude oleic acid (OA) with formic acid and hydrogen peroxide through thein situepoxidation-dihydroxylation, a multistep reaction process. Optimization of the reaction’s operating conditions with respect to the selectivity of DHSA was conducted via the Taguchi method of optimization. The selectivity of DHSA was determined based on gas chromatography (GC) analysis. The signal-to-noise (S/N) ratio analysis procedure in Taguchi method revealed that the optimum operating conditions for the production of crude DHSA with respect to its selectivity were found to be: catalyst (sulphuric acid) loading at 0.5 gm, formic acid-to-oleic acid unsaturation mole ratio of 1:1, hydrogen peroxide-to-oleic acid unsaturation mole ratio of 0.75:1 and reaction temperature: 85°C. ANOVA tested at 90% confidence level revealed that reaction temperature and catalyst loading highly affect the selectivity of DHSA. The selectivity of DHSA was improved to 97.2% by applying the optimum operating conditions as obtained by Taguchi method.

Effects of temperature and solvent concentration on the solvent crystallization of palm-based dihydroxystearic acid with isopropyl alcohol

Palm-based dihydroxystearic acid of 69.55% purity was produced in a 500-kg-per-batch operation pilot plant and purified through solvent crystallization in a custom fabricated simultaneous batch crystallizer unit. The effects of temperature and solvent concentration on yield, particle size distribution and purity were studied. The purity was higher, while the yield and particle size were lower and smaller, respectively, at higher temperature and solvent concentration. The solvent crystallization process efficiency was rated at 66–69% when carried out with 70–80% isopropyl alcohol at 20°C.

Screening of the Entire USDA Castor Germplasm Collection for Oil Content and Fatty Acid Composition for Optimum Biodiesel Production

Castor has tremendous potential as a feedstock for biodiesel production. The oil content and fatty acid composition in castor seed are important factors determining the price for production and affecting the key fuel properties of biodiesel. There are 1033 available castor accessions collected or donated from 48 countries worldwide in the USDA germplasm collection. The entire castor collection was screened for oil content and fatty acid composition by nuclear magnetic resonance (NMR) and gas chromatography (GC), respectively. Castor seeds on the average contain 48.2% oil with significant variability ranging from 37.2 to 60.6%. Methyl esters were prepared from castor seed by alkaline transmethylation. GC analysis of methyl esters confirmed that castor oil was composed primarily of eight fatty acids: 1.48% palmitic (C16:0), 1.58% stearic (C18:0), 4.41% oleic (C18:1), 6.42% linoleic (C18:2), 0.68% linolenic (C18:3), 0.45% gadoleic (C20:1), 84.51% ricinoleic (C18:1-1OH), and 0.47% dihydroxystearic (C18:0-2OH) acids. Significant variability in fatty acid composition was detected among castor accessions. Ricinoleic acid (RA) was positively correlated with dihydroxystearic acid (DHSA) but highly negatively correlated with the five other fatty acids except linolenic acid. The results for oil content and fatty acid composition obtained from this study will be useful for end-users to explore castor germplasm for biodiesel production.

Solvent crystallization of palm based dihydroxystearic acid with isopropyl alcohol: Effects of solvent quantity and concentration on particle size distribution, crystal habit and morphology, and resultant crystal purity

Crude dihydroxystearic acid was prepared from palm based oleic acid and was then solvent purified with isopropyl alcohol in a custom fabricated simultaneous batch crystallizer unit. The crystallized dihydroxystearic acid was a functional ingredient that acted as multipurpose intermediate for synthesis of various fine chemicals, cosmetics and personal care products. The effects of solvent quantity and concentration on particle size distribution, crystal habit and morphology, and resultant crystal purity were studied. The crystals were purer but smaller and the span of the distribution curve was wider at higher solvent quantity and concentration. Through scanning electron microscopy and X-ray diffraction, it was observed that the crystals agglomerated into plate-like (flaky) habit with triclinic crystal structure. Solvent crystallization with 80% IPA at 20 °C and solute:solvent ratio of 1.0:1.0 was the most optimized and efficient, producing β-DHSA crystals that has high resistance against fat exudation during vacuum filtration process.

Development, Characterization and Commercial Application of Palm Based Dihydroxystearic Acid and Its Derivatives: an Overview

Hydroxyl fatty acids and their derivatives are of high value due to their wide range of industrial application, including cosmetic, food, personal care and pharmaceutical products. Realizing the importance of hydroxyl fatty acids, and yet due to the absence of the conventional starting raw materials, Malaysia has developed 9,10-dihydroxystearic acid (9,10-DHSA) and its derivatives from locally abundant palm based oils. The aim of this article is to provide a general description of the works that have thus far being done on palm based 9,10-DHSA: starting from its conception and production from commercial grade palm based crude oleic acid via epoxidation and hydrolysis, purification through solvent crystallization and characterization through wet and analytical chemistry, moving on to developmental works done on producing its derivatives through blending, esterification, amidation and polymerization, and completing with applications of 9,10-DHSA and its derivatives, e.g. DHSA-stearates and DHSA-estolides, in commercial products such as soaps, deodorant sticks and shampoos. This article incorporates some of the patent filed technological knowhow on 9,10-DHSA and its derivatives, and will also point out some of the shortcomings in previously published documents and provide some recommendations for future research works in mitigating these shortcomings.

Effect of Solvent Concentration and Cooling Modes on Morphology, Particle Size Distribution, and Yield of Dihydroxystearic Acid (DHSA) Crystals

Palm-based dihydroxystearic acid was purified by employing solvent crystallization using ethanol and ethanol/water mixture as solvents. Two different cooling modes, rapid and natural cooling, were employed for the crystallization process. In this study, the cooling effects on morphology, habit, particle size distribution, and yield of dihydroxystearic acid crystals were investigated. The dihydroxystearic acid crystals appeared to agglomerate into sphere-like and plate-like structures, depending on the cooling modes and the presence of water. By manipulating the solvent and cooling modes, the crystal yield ranged from 0.8% to 42.1%, while the crystal purity ranged from 73.3% to 91.4%. Solvent crystallization using ethanol was best achieved through natural cooling with the dihydroxystearic acid to ethanol ratio of 1.0:1.0, which produced the narrowest particle size distribution curve with the largest average particle size.

Habit and morphology study on the palm-based 9,10-dihydroxystearic acid (DHSA) crystals

Dihydroxystearic acid (DHSA) and its derivatives are hydroxyl fatty acids suitable to be used as multipurpose intermediates in the synthesis of personal care products and decorative cosmetics. In Malaysia, DHSA has been successfully produced from palm-based oleic acid, via epoxidation with per-formic acid followed with hydrolysis of the epoxide. The objective of this paper is to study the crystals of DHSA produced under different crystallization conditions. The crystal habit and morphology were observed in terms of scanning electron microscopy (SEM) and X-ray diffraction (XRD). Results show that solvent type, solvent concentration and cooling mode affect the crystal habit but not the morphology. The DHSA crystals agglomerated into either sphere-like or plate-like habit structure while always maintaining the triclinic crystal system.