122-32-7Relevant articles and documents
Propylsulfonic acid functionalized mesoporous silica catalysts for esterification of fatty acids
Jeenpadiphat, Sirima,Bj?rk, Emma M.,Odén, Magnus,Tungasmita, Duangamol Nuntasri
, p. 253 - 259 (2015)
The catalytic properties of 3 types of mesoporous silica SBA-15 (rope, rod and fiber), with 9.2 nm or 12.1 nm large mesopores, were examined with respect to their morphology and pore size. Commercially available Amberlyst-15 and the small pore sized MCM-41 were used for comparison. The catalysts were prepared by functionalization of the silica supports with propylsulfonic acid (Pr-SO3H) using post-synthesis grafting with 3-mercaptopropyltrimethoxysilane as a propyl-thiol precursor. All materials remained in a well-ordered hexagonal mesoporous structure after Pr-SO3H functionalization. The performance of the Pr-SO3H-functionalized mesoporous silicas was evaluated in terms of their catalytic activity in the esterification of oleic acid with short (methanol) and long (glycerol) chain alcohols, i.e., to test the effect of the pore size on the substrate conversion and product yield. The synthesized catalysts were highly active and the product composition could be tuned by selective choice of the mesopore size. The Pr-SO3H-functionalized rope-shaped SBA-15 gave the highest catalytic activity (in terms of the highest methyl oleate and triglyceride yields and oleic acid conversion level), which was higher than that obtained with the commercial Amberlyst-15 catalyst. A high acid amount, large specific surface area and a suitable pore size are the likely reasons for the high yield gained by Pr-SO3H-functionalized rope-shaped SBA-15 silica.
Synthesis of the structured lipid 1,3-dioleoyl-2-palmitoylglycerol from palm oil
Chen, Ming-Lung,Vali, Shaik Ramjan,Lin, Jih-Yao,Ju, Yi-Hsu
, p. 525 - 532 (2004)
Human milk fat contains 20-25% palmitic acid (16:0) and 30-35% oleic acid (18:1). More than 60% of the palmitic acid occurs at the sn-2 position of the glycerol backbone. Palm oil is a rich source of both palmitic and oleic acids. The structured lipid 1,3-dioleoyl-2-palmitoylglycerol (OPO) is an important ingredient in infant formula. OPO was synthesized from palm oil by a three-step method. In the first step, low-temperature fractionation was applied to palm oil FA, yielding a palmitic acid-rich fraction (87.8%) and an oleic acid-rich fraction (96%). The palmitic acid content was further increased to 98.3% by transforming palmitic acid into ethyl palmitate. In the second step, esterificalion of ethyl palmitate and glycerol catalyzed by lipase Novozym 435 under vacuum (40 mm Hg) was employed for the synthesis of tripalmitin. Finally, OPO was obtained by the reaction of tripalmitin with oleic acid catalyzed by Lipase IM 60. In this final step, the TAG content in the product acylglycerol mixture was 97%, and 66.1 % oleic acid was incorporated into TAG. Analysis of the FA composition at the sn-2 position of TAG showed 90.7 mol% of palmitic acid and 9.3 mol% of oleic acid. OPO content in the product TAG was ca. 74 mol%. Thus, an efficient method was developed for the synthesis of OPO from palm oil.
RP-HPLC/MS-APCI analysis of branched chain TAG prepared by precursor-directed biosynthesis with rhodococcus erythropolis
Schreiberová, Olga,Krulikovská, Tereza,Sigler, Karel,?ejková, Alena,?ezanka, Tomá?
, p. 743 - 756 (2010)
Reversed phase liquid chromatography-atmo-spheric pressure chemical ionization mass spectrometry (RP-HPLC/MS-APCI) was used to analyze both synthetic triacylglycerols (TAG) having 1-3 branched fatty acids (FA) in the molecule, and natural TAG prepared by precursor directed biosynthesis from valine, leucine and iso-leucine and the corresponding branched short-chain acids in cultivations of Rhodococcus erythropolis. The technique made it possible to identify and quantify TAG differing in a single branched-chain FA. Altogether 11 TAG were synthesized, out of which 8 were synthesized stereospecifi-cally. Branched-and straight-chain-TAG were separated and identified while TAG differing only in iso or anteiso FA could not be separated. The APCI mass spectra of iso-, anteiso-and straight-chain TAG were completely identical. The natural material was found to contain 19 TAG having at least one branched FA. Cultivation on six different substrates showed, apart from the presumed and common incorporation of precursors to iso-even, iso-odd and anteiso FA, also some unusual features such as an increase in the content of odd-FA after the addition of Val (attributed to catabolism of Val to propionate) or the appearance of branched monounsaturated FA. The two-sample paired t test, when applied to the TAG, showed that only the pair Val and isobutyrate differ in incorporation into FA-see, e.g. proportions of M/M/O and brM/brM/O (1.2:1.2 and 1.9:1.2, respectively). Also, incorporation of Val (isobu-tyrate) yielded only TAG having two branched FA in the molecule, whereas Leu and Ile (isovalerate and 2-methyl-butyrate) gave only TAG with a single branched FA in the molecule. AOCS 2010.
Optimization of Candida sp. 99-125 lipase catalyzed esterification for synthesis of monoglyceride and diglyceride in solvent-free system
Zhao, Yanjun,Liu, Junfeng,Deng, Li,Wang, Fang,Tan, Tianwei
, p. 157 - 162 (2011)
Esterification of glycerol and oleic acid catalyzed by lipase Candida sp. 99-125 was carried out to synthesize monoglyceride (MAG) and diglyceride (DAG) in solvent-free system. Beta-cyclodextrin as an assistant was mixed with the lipase powder. Six reaction variables, initial water content (0-14 wt% of the substrate mass), the glycerol/oleic acid molar ratio (1:1-6:1), catalyst load (3-15 wt% of the substrate mass), reaction temperature (30-60 °C), agitator speed (130-250 r/min) and beta-cyclodextrin/lipase mass ratio (0-2) were optimized. The optimal conditions to the synthesis of MAG and DAG were different: the optimal glycerol/oleic acid molar ratio, beta-cyclodextrin/lipase mass ratio, catalyst load and reaction temperature were 6:1, 0, 5%, 50 °C for MAG, and 5:1, 1.5, 10%, 40 °C for DAG, respectively. The optimal water content and agitator speed for both MAG and DAG were 10% and 190 r/min, respectively. Under the optimal conditions, 49.6% MAG and 54.3% DAG were obtained after 8 h and 4 h, respectively, and the maximum of 81.4% MAG plus DAG (28.1% MAG and 53.3% DAG) was obtained after 2 h under the DAG optimal condition. Above 90% purity of MAG and DAG can be obtained by silica column separation.
Model studies and the ADMET polymerization of soybean oil
Tian, Qingping,Larock, Richard C.
, p. 479 - 488 (2002)
Grubbs' ruthenium catalyst 2 has been employed in model studies of the acyclic diene metathesis (ADMET) polymerization of soybean oil. In the presence of 0.1 mol% of catalyst 2, the ADMET polymerization of ethylene glycol dioleate afforded the isomerized (E)-dioleate (27%), dimer (18%), trimer (13%), tetramer (7%), pentamer (5%), hexamer (4%), heptamer (4%), and 9-octadecene (21%). Only a trace of any intramolecular cyclized product was formed. Under the same conditions, glyceryl trioleate underwent ADMET polymerization to produce dimer, trimer, tetramer, pentamer, and monocyclic oligomers, with monocyclic oligomers predominating. The high number of repeat units in the monocyclic oligomers (n ? 6, 10, and 21) indicates that cross-linking occurs readily in this process. Based on our model system studies, we have examined the ADMET polymerization of soybean oil and succeeded in producing polymeric materials ranging from sticky oils to rubbers.
FUNCTIONALISED MATERIALS, PROCESS FOR THE PRODUCTION AND USES THEREOF
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Paragraph 0041; 0055, (2015/04/22)
The invention relates both to processes for the production of functionalised materials containing alkyl sulfonic acids groups and their use as heterogeneous catalysts. The invention also relates to precursors of these new products and new organopolysiloxane sulfonic acids.
PROCESS FOR PREPARING BIODEGRADABLE LUBRICANT BASE OILS
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Paragraph 0074; 0091, (2015/06/03)
The invention discloses an improved process for preparing fatty acid esters with 100 mol % selectivity suitable as biodegradable lubricant base oils, comprising contacting a fatty compound with an alcohol in presence of a solid, phosphonate catalyst having molecular formula: M(X)2-nYn.mH2O where X refers to phenyl phosphonate, Y refers to HPO42? or HPO32?, M refers to a metal or metalloid ion preferably taken from the group consisting of Zr, Zn, Cd, Al, Sn, La and Ce, the value of n varies from 0.2 to 1.8 and the value of m varies from 0 to 5, wherein the fatty compound is a fatty acid or fatty acid methyl or ethyl ester or vegetable oil or animal fat or their mixture thereof and alcohol is a monohydric alcohol with 6 to 22 carbon atoms or a polyol with at least two hydroxyl groups.
Synthesis of monoglycerides by esterification of oleic acid with glycerol in heterogeneous catalytic process using tin-organic framework catalyst
Wee, Lik H.,Lescouet, Tristan,Fritsch, Julia,Bonino, Francesca,Rose, Marcus,Sui, Zhijun,Garrier, Eva,Packet, Dirk,Bordiga, Silvia,Kaskel, Stefan,Herskowitz, Moti,Farrusseng, David,Martens, Johan A.
, p. 356 - 363 (2013/05/21)
Selective synthesis of monoglycerides by esterification of glycerol with fatty acids is a difficult reaction because of immiscibility of reagents and the formation of di- and tri-glyceride by-products. In this work a heterogeneous catalytic process was conceived in which the reactant mixture was homogenized using tert-butanol solvent. Candidate catalysts were screened in the reaction of oleic acid with glycerol. While under such reaction conditions zeolites were rather inactive, metal-organic frameworks and, especially, tin-organic frameworks were found promising. A tin-organic framework (Sn-EOF) was most active and achieved ≥98 % monoglyceride selectivity at 40 % conversion in catalyzing esterification of oleic acid with glycerol at a low reaction temperature of 150 C. Leaching of tin from Sn-EOF catalyst was suppressed by limiting the amount of oleic acid in the starting mixture. Characterization of the acid sites of Sn-EOF by pyridine-chemisorption and FTIR revealed Lewis acidity to be responsible for the catalytic activity.
PALM OIL ENRICHED IN UNSATURATED FATTY ACIDS
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Paragraph 0067; 0068, (2013/06/06)
A process for producing a food oil containing at least 50% monounsaturated fatty acids from palm oil is disclosed. Fatty acids are released from palm oil glycerides, such as by fat-splitting. The free fatty acids (FFA) are separated to obtain a fraction enriched in unsaturated palm fatty acid. This fraction is subject to a condensation reaction with glycerol to form an oil comprising mainly triglycerides (triacylglycerols). The condensation reaction is catalyzed by an enzyme.
Zirconium phenyl phosphonate phosphite as a highly active, reusable, solid acid catalyst for producing fatty acid polyol esters
Varhadi, Poonam,Kotwal, Mehejabeen,Srinivas
, p. 129 - 136 (2013/07/26)
The application of zirconium phenyl phosphonate phosphite (ZrPP) as a solid acid catalyst for producing polyol esters by esterification of glycerol or trimethylolpropane with a fatty acid (C8-C18.1) is reported for the first time. ZrPP exhibits high catalytic activity and in particular, (di + tri) esters selectivity (92.3 mol%). These esters of polyols are known for their application as biolubricants. The catalyst prepared using phosphorous acid to phenyl phosphonic acid molar ratio of 3:1 was found superior. The influence of process parameters on activity and selectivity of the catalyst was investigated. ZrPP was reusable in at least three recycling experiments. Hydrophobicity due to exposed phenyl groups on the surface is the possible cause for superior esterification activity of this novel, solid catalyst.
