Migration resistant glucose esters as bioplasticizers for polylactide

Environmental and sustainability issues have catalyzed efforts to replace traditional polymer additives with biobased alternatives. Glucose pentaacetate (GPA) and sucrose octaacetate (SOA) as model commercial saccharide esters and three synthesized glucose hexanoate esters (GHs) were evaluated as bioplasticizers for polylactide (PLA). For the GHs different reaction times were utilized to reach plasticizers with different number of hexanoate groups to establish how the degree of substitution influences miscibility and migration resistance of the plasticizers. The synthesized GHs, GPA, and SOA all showed good miscibility with PLA. Largest improvements in strain at break were observed for the PLA films containing GH plasticizers. These films also exhibited simultaneous increase in stress at break as compared to plain PLA. The GH plasticizers had low tendency to migrate during aging in water and this migration resistance increased with increasing degree of substitution. The GHs are, thus, promising plasticizer alternatives for bioplastics as they also retain the biodegradable nature of these biobased materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41928.     

Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters

Biodiesel, defined as the mono-alkyl esters of vegetable oils or animal fats, is an “alternative” diesel fuel that is becoming accepted in a steadily growing number of countries around the world. Since the source of biodiesel varies with the location and other sources such as recycled oils are continuously gaining interest, it is important to possess data on how the various fatty acid profiles of the different sources can influence biodiesel fuel properties. The properties of the various individual fatty esters that comprise biodiesel determine the overall fuel properties of the biodiesel fuel. In turn, the properties of the various fatty esters are determined by the structural features of the fatty acid and the alcohol moieties that comprise a fatty ester. Structural features that influence the physical and fuel properties of a fatty ester molecule are chain length, degree of unsaturation, and branching of the chain. Important fuel properties of biodiesel that are influenced by the fatty acid profile and, in turn, by the structural features of the various fatty esters are cetane number and ultimately exhaust emissions, heat of combustion, cold flow, oxidative stability, viscosity, and lubricity.     

Synthesis of alkyl glycoside fatty acid esters in non-aqueous media byCandida sp. lipase

Alkyl glycoside fatty acid esters were successfully synthesized by lipase-catalyzed transesterification of methyl glucoside, methyl glucoside, methyl galactoside and octyl glucoside with methyl oleate. The experiments were carried out in organic media with lipase enzymes fromCandida sp. as biocatalysts. Time course and the effects of temperature, solvent type, substrate concentration, added water and of immobilizedvs. nonimmobilized enzyme were studied. The optimal conditions for the enzymatic synthesis of alkyl glycoside fatty acid esters were: a molar ratio of alkyl glycoside and methyl oleate of 1:4, an immobilized lipase, SP382 fromCandida sp.; benzene/pyridine (2:1, vol/vol) with no added water; temperature, 55°C; reaction time, 48 h; and shaking at 200 rpm. Acceptable levels of oleic acid incorporation (58.6–100 mol%) onto the alkyl glycosides were achieved.     

Combined nonenzymatic-enzymatic method for the synthesis of simple alkyl fatty acid esters from soapstock

Soapstock (SS) is a by-product of the extraction of oilseeds to produce edible oils. Annual U.S. production exceeds one-half million tons. A representative sample of SS consists of 45.1% water, 10.0% free fatty acids, 10.1% triglycerides, 1.8% diglycerides, 3.6% phosphatidylethanolamine, 2.2% phosphatidylinositol, 2.7% phosphatidylcholine, 14.0% solvent-insolubles and 10.5% other material, which was not characterized. A process has been developed that sequentially employs a nonenzymatic and an enzymatic step to convert the lipid-linked and the free fatty acids of SS to the esters of monohydric alcohols. The first step of the process employed alcohol and potassium hydroxide to transesterify the glyceride-and phosphoglyceride-linked fatty acids of the substrate. Because water inhibited the reaction, it was necessary that the SS be dried before use. Nonetheless, even with some batches of SS with water contents below 1% (weight basis), ester hydrolysis accompanied esterification. Each of five examined simple primary alcohols participated effectively in the transesterification reaction, which proceeded rapidly at room temperature and was essentially complete within 1 h. The average ratio of transesterification to hydrolysis in four examined small primary alcohols was 4:1. However, in methanol this value was 99:1 due to the virtual absence of hydrolysis. Significant transesterification by a secondary alcohol (isopropanol) did not occur at room temperature. The minimum effective molar ratio of alcohol to lipid-linked fatty acids was 20:1. The minimum effective concentration of KOH was between 0.10 and 0.15N. The efficiency of the transesterification reaction exceeded 90% of theoretical maximum. The second step of the process involves lipase-mediated esterification of the free fatty acids in the preparation that are not esterified by the alkaline transesterfication. Of four lipase preparations examined (Novo Lipozyme IM 20 and SP435, and Amano PS30 and CE), only SP-435 catalyzed significant esterification of the free fatty acids. The reaction was not catalyzed by heat-denatured enzyme. In the pH range between 6 and 13.5, the enzyme reaction proceeded best at pH 6, although also well at pH 7. The optimal water concentration was 0.70% (vol/vol). At an enzyme dosage of 1.1% (weight basis, relative to the dry weight of SS present) under optimal conditions and at 42°C, 63% of the free fatty acids in a post-alcoholysis mixture were enzymatically esterified. The addition of molecular sieves did not increase esterification, which was probably retarded by the high viscosities of the reactions. Under the optimal conditions identified here, the degree of conversion of the fatty acids in SS to simple alkyl esters by the combined reaction scheme was 81%. Opportunities exist for further optimization of these reactions.     

Metathesis of fatty acid esters

In metathesis reactions, unsaturated compounds are converted into new compounds via an exchange of alkylidene groups: 2 RCH=CHR′⇌RCH=CHR+R′CH=CHR′ Since its discovery in 1964, this catalytic reaction has found several large-scale applications in petrochemistry. One of the most promising synthetic applications of metathesis is to functionalized olefins such as unsaturated esters, ethers, amines, etc., because this allows single-step syntheses of a variety of mono- and difunctional hydrocarbon derivatives. Unfortunately, however, most metathesis catalysts are easily poisoned by polar groups. In 1972 in our institute, the WCl₆-(CH₃)₄Sn system was found to be effective as a catalyst for monogeneous metathesis of fatty acid esters. Thus methyl oleate was converted into 9-octadecene and dimethyl 9-octadecene dioate, starting materials for the synthesis of valuable chemical products. In 1977 we developed a heterogeneous catalyst system: Re₂O₇ on Al₂O₃, activated with a small amout of (CH₃)₄Sn. Systematic research has led to intersting applications of metathesis and cometathesis reactions with these catalysts. An example is the cometathesis of methyl oleate with ethene, to produce shorter-chain compounds with terminal double bonds: CH₃(CH₂)₇CH=CH(CH₂)₇COOCH₃+CH₂=CH₂⇌CH₂=CH(CH₂)₇CH₃+CH₂=CH(CH₂)₇COOCH₃ Cometathesis of olive oil (mainly triolein) with ethene opens the possibility of producing both α-olefins in the C₁₀ range and fatty oils with lower molecular weight (palm oil type). Until now, metathesis of fatty esters has been restricted mainly to synthetic purposes. Large-scale applications depend mainly on the development of more active and cheaper catalyst systems.     

脂肪酸酯的技术与市场发展动向

论述了脂肪酸一元醇酯,多元醇酯的特性、合成及用途,并介绍了由脂肪酸酯开发“绿色”表面活性剂的最新技术动向。     

Kinematic viscosity of biodiesel components (fatty acid alkyl esters) and related compounds at low temperatures

Biodiesel, defined as the mono-alkyl esters of vegetable oils and animal fats is, has undergone rapid development and acceptance as an alternative diesel fuel. Kinematic viscosity is one of the fuel properties specified in biodiesel standards, with 40 °C being the temperature at which this property is to be determined and ranges of acceptable kinematic viscosity given. While data on kinematic viscosity of biodiesel and related materials at higher temperatures are available in the literature, this work reports on the kinematic viscosity of biodiesel and a variety of fatty acid alkyl esters at temperatures from 40 °C down to −10 °C in increments of 5 °C using the appropriately modified standard reference method ASTM D445. Investigating the low-temperature properties of biodiesel, including viscosity, of biodiesel and its components is important because of the problems associated with the use of biodiesel under these conditions. Such data may aid in developing biodiesel fuels optimized for fatty ester composition. An index termed here the low-temperature viscosity ratio (LTVR) using data at 0 °C and 40 °C (divide viscosity value at 0 °C by viscosity value at 40 °C) was used to evaluate individual compounds but also mixtures by their low-temperature viscosity behavior. Compounds tested included a variety of saturated, monounsaturated, diunsaturated and triunsaturated fatty esters, methyl ricinoleate, in which the OH group leads to a significant increase in viscosity as well as triolein, as well as some fatty alcohols and alkanes. Esters of oleic acid have the highest viscosity of all biodiesel components that are liquids at low temperatures. The behavior of blends of biodiesel and some fatty esters with a low-sulfur diesel fuel was also investigated.     

Vesicles from sucrose fatty acid esters

It has been confirmed, from observations with an electron microscope after staining negatively with aqueous uranyl acetate solutions and using a flourescent microscope, that sucrose fatty acid esters form closed vesicles. The range of particle size of the vesicle, consisting of chromatographically fractionated sucrose dilaurate, was apparently 70–700 nm in the longer diameter of individual vesicles based on the transmission electron microscopic (TEM) observation. The weight-average particle size was 424 nm as shown by means of the photon-correlation method. The amounts of 6-carboxyfluorescein trapped in the vesicles of sucrose fatty acid esters were determined, and it was ascertained that the volumes of the central water phase depended upon the acyl chain lengths of fatty acid residues. Further, the effect of the additives [cholesterol and dicetyl phosphate (DCP) was examined. As an example, the vesicle of sucrose stearate had a central water phase of 1.7 one water/mol ester, and showed a slow release of 6-carboxyfluorescein from the central water phase after preparation of the vesicle.     

Rapid synthesis of fatty acid esters for use as potential food flavors

Lipase-catalyzed esterification has been performed in hexane to generate novel mixtures of fatty acid esters from specially chosen combinations of fatty acids and alcohols. By varying the alcohol and enzyme compositions in the enzymatic reactions, different ester mixtures were produced, which were further purified and analyzed for ester composition by gas chromatography-mass spectrometry. Depending on the combination of alcohols and enzymes used, the final ester mixture exhibited significant compositional variation. These mixtures could be manipulated at the synthesis step, thereby enabling a high degree of product control. Such manipulation over enzyme-catalyzed ester synthesis in mixtures may be useful in the preparation of ester flavors for use in the food industry.     

Rapid synthesis of fatty acid esters for use as potential food flavors

Lipase-catalyzed esterification has been performed in hexane to generate novel mixtures of fatty acid esters from specially chosen combinations of fatty acids and alcohols. By varying the alcohol and enzyme compositions in the enzymatic reactions, different ester mixtures were produced, which were further purified and analyzed for ester composition by gas chromatography-mass spectrometry. Depending on the combination of alcohols and enzymes used, the final ester mixture exhibited significant compositional variation. These mixtures could be manipulated at the synthesis step, thereby enabling a high degree of product control. Such manipulation over enzyme-catalyzed ester synthesis in mixtures may be useful in the preparation of ester flavors for use in the food industry.     

Performance of sulfoxylated fatty acid methyl esters

Sulfoxidation of fatty acid methyl esters with SO₂, O₂, and ultraviolet light of appropriate wavelength has led to the synthesis of methyl esters sulfonates or sulfoxylates known as Φ-MES because of the possible random position of SO₃ group in the alkyl chain. This work describes experimental measurements of physical properties such as solubility and viscosity of sodium Φ-MES water solutions. Amphipathic properties such as surface tension, critical micelle concentration, wetting and foaming powers were measured as well and compared to linear alkylbenzene sodium sulfonate (LAS). Finally, stability to water hardness, dishwashing test, and detergency performance were evaluated. Expectedly, these products may be used as LAS partners either in heavy-duty powders or in hand dishwashing liquids. Experimental results on Φ-MES of varying carbon number indicate that C₁₆ is the optimal carbon chain length.     

Chromatographic analysis of sorbitan fatty acid esters

A procedure is described for the separation, identification and quantitative estimation of mono-, di- and tri-fatty acid esters of sorbitol and of its anhydrides. Stearic, palmitic and oleic acid esters of sorbitol, 1,4-sorbitan and isosorbide were synthesized in the laboratory. Lipid classes were separated by liquid partition column chromatography and TLC. The individual mono-and di-fatty acid esters and the polyols were analyzed by GLC as trimethylsilyl ethers. Recoveries of known compounds in mixtures were in a range of 92% to 100%. Presented at the AOCS-AACC Joint Meeting, Washington, D.C., April 1968.     

Chlorophyll-sensitized peroxidation of saturated fatty acid esters

Chlorophyll-sensitized peroxidation of methyl laurate and methyl stearate was carried out at 30–40 C under intermittent exposure to light from a 500 w tungsten bulb. Hydroperoxides were isolated by solvent partition, reduced to hydroxy esters and purified by silicic acid column chromatography and preparative thin layer chromatography (TLC). Gas liquid chromatography, TLC, IR spectrophotometry, NMR and mass spectroscopy of the hydroxy esters showed that the oxygen attack was exclusively on the α-methylenic carbon atom. One of 28 papers presented at the Symposium, “Metal-Catalyzed Lipid Oxidation,” ISF-AOCS World Congress, Chicago, September 1970.     

Chemo-enzymatic synthesis of disaccharide fatty acid esters

A novel enzymatic method for the synthesis of disaccharide fatty acid esters was developed with immobilizedMucor miehei lipase (Lipozyme IM-60; Novo Nordisk, Bagsvaerd, Denmark) as a catalyst. A range of lactose and maltose monoesters was prepared in overall yields of 48–77% from the corresponding sugar acetals and fatty acids.     

Dilatometric investigations of fatty acid methyl esters

Summary The coefficients of expansion and melting dilations were measured for methyl palmitate, methyl stearate, methyl arachidate, methyl behenate, and methyl oleate. The dilatometric curve for the heating cycle of methyl palmitate and methyl stearate in the solid state was composed of a linear section to 49 degrees below the melting point, followed by a curvilinear section to the melting point. The heating and cooling cycle curves for methyl palmitate show the same volume change from −38°C. to 29°C., but the shape of the curves is different. The same relation holds for methyl stearate from −38°C. to 37.5°C. “After-contractions” were found in volume measurements within a few degrees of the melting point of both esters. Equilibrated points were found within 0.5 degrees of the final melting temperature of methyl stearate. A striking similarity exists between curves for variation of the dielectric constant with temperature for long chain linear molecules and the dilatometric data. Presented at the fall meeting, American Oil Chemists' Society, Mnneapolis, Minn., October 11, 1954. Issued as Paper No. 196 on the “Uses of Plant Products” and as N.R.C. No. 3671.     

α-sulfonated fatty acid esters: II. Solution behavior of α-sulfonated fatty acid polyethylene glycol esters

Sodium α-sulfonated, fatty acid polyethylene glycol monoesters [C _m H_2m+1CH(SO₃Na)COO(C₂H₄O) _n H] and diesters [C _m H_2m+1CH(SO₃Na)COO(C₂H₄O) _n COCH(SO₃Na)C _m H_2m+1], wherem=10–16 andn=1–35, were prepared by esterification of α-sulfonated, fatty acids with polyethylene glycols, followed by neutralization with NaOH. Crude products were purified by reversed-phase column chromatography on an octadecyl-modified silica gel. Characteristic solution behavior of these α-sulfonated fatty acid esters was, examined, and the following features were observed. All monoesters prepared in this work had Krafft points below 0°C and also possessed good calcium stabilities. Critical micelle concentrations of the monoesters increased monotonously, as a rule, with an increase in the number of oxyethylene units. These results suggest that the polyethylene glycol residue of the monoester behaves as a hydrophile. On the other hand, diesters possessed high water solubility, low foamability, and critical micelle concentrations that were lower by a factor of ten compared to those of the monoesters.     

Enzymatic synthesis of wax esters from rapeseed fatty acid methyl esters and a fatty alcohol

Wax esters were transesterified from fatty acid methyl esters of rapeseed and a fatty alcohol (1-hexadecanol, 16:0). The amounts of both the substrates were fixed to 0.1 mmol and an immobilized enzyme, Lipozyme, was used as catalyst. The experiment was performed following a statistic central composite design with five variables. The enzyme/lipid ratio was varied between 0.3–0.9 of the substrate weight and the enzyme was equilibrated to different water activities varying from 0.11 to 0.44. A temperature range of 50–80°C was investigated and the reaction time lasted up to 40 min. A solvent, isooctane, constituted 0–30% of the substrate weight. The first experimental series was performed in small closed test tubes. In the second series the caps of the test tubes were off to evaporate the methanol produced during the reaction. The highest initial reaction rate was 9.6 g_{wax esters}/g_enzyme · h. It appeared when: the enzyme/lipid ratio was low, 0.3, the temperature was high, 80°C; no isooctane was present; and the water activity was below 0.11. The initial reaction rate was independent of the caps on the test tubes. With the large amount of enzyme the yield of wax esters was above 70% after 10 min in both experimental series. In the reaction with caps, the reaction reached equilibrium at 83% after 20 min at 80°C. However, without caps the continuous evaporation of methanol increased the equilibrium constantly, and after 40 min at 80°C a yield of 90% was reached.     

Methyl esters in the fatty acid industry

Methyl esters, derived from natural fats or oils, can be used as alternatives to fatty acids in the production of a number of derivatives. The derivatives that can be made from methyl esters include fatty alkanolamides, fatty alcohols, isopropyl esters, and sucrose polyesters. By using methyl esters as the raw materials, several benefits may be realized, such as, the ability to make higher purity finished products, the use of milder conditions during syntheses, and the need for less expensive materials of construction. In addition to the applications mentioned, methyl esters are being used increasingly in fractional distillations because they have lower boiling points and are less corrosive than fatty acids.     

Paper chromatography of unsaturated fatty acid esters as their mercuric acetate addition compounds

Summary A method is described by which unsaturated fatty acid esters can be separated and identified by reversed-phase paper chromatography. The procedure is based upon the formation of the mercuric acetate addition compounds of the esters and the detection of the compounds on the chromatograms, using the sensitive color reaction with diphenylcarbazone. The application of this technique to the analysis of the component unsaturated acids of natural fats has been examined, and tetradecenoic acid in olive oil and hexadecenoic acid in linseed oil both formerly unidentified have been detected as the minor component acids by means of the method. The preliminary investigation on the absorption spectra of diphenylcarbazone complexes derived from the addition compounds has been made to bring the method into quantitative use.     

Preparation of fatty acid esters of polyol glucosides

Starch is readily converted into glucosides by heating with a polyol, such as propylene glycol or glycerol, for a short time at 125 C in the presence of a catalytic amount of sulfuric acid. The product resulting from the reaction of 3 or more moles of polyol per anhydroglucose unit consists mostly of polyol monoglucosides, which are quite resistant to degradation under alkaline interesterification conditions. Attempts to interesterify the glucosides under the usual conditions employed with fats and oils (methyl esters, 0.1% sodium hydroxide, and temperatures up to 200 C) produced no glucoside esters. However, interesterification proceeded readily at temperatures between 160 and 200 C when 5 to 10% soaps and hydrophilic esters (mixtures containing mono- and diglycerides or an ester of diethylene glycol monomethyl ether) were employed. Under pressures low enough to rapidly distill off the freed polyol or alcohol, most reactions could be completed in less than an hour. Good yields of glucoside esters were obtained with starch, glycerol, and fat when the required operations were conducted in sequence in one vessel without intermediate purifications.