Impacts of temperature on the leaching of organotin compounds from poly(vinyl chloride) plastics—A study conducted under simulated landfill conditions

The aim of the study was to investigate whether organotin‐stabilized poly(vinyl chloride) (PVC) products could contribute to the pool of organotins observed in landfill leachates, and if the possible release could be related to different temperatures and landfill degradation phases. Small‐scale anaerobic reactors filled with generic household waste, a mixture of inocula, and different PVC plastics were used in the study and incubated at 20, 37, 55, and 70°C. The reactor units incubated at temperatures of 20–55°C underwent the anaerobic degradation phases that are characteristic for the aging of landfilled waste material. There were, however, differences in the duration of the phases as well as in the total biogas production among the units. Under methanogenic conditions greater losses of organotin compounds were observed as compared to acidogenic conditions. It was shown that the release of organotin stabilizers increases considerably at temperatures above the glass transition of the PVC products. A dealkylation from di‐ into monoalkyltin species was observed, as well as a possible methylation of inorganic tin. However, the main part of the organotins was adsorbed into the solid waste matrix. J. VINYL ADDIT. TECHNOL., 13:176–188, 2007. © 2007 Society of Plastics Engineers     

Syntheses and properties of urethane prepolymers and their corresponding crosslinked films

Trimethylol propane (TMP), polyglycol (PG), and toluene diisocyanate (TDI) were reacted in various molar ratios to produce TMP–TDI–PG–urethane prepolymers and then mixed with equivalent isocyanate generator (Desmodur AP-Stable) in a mixture of m-cresol and naphtha to give polyurethane varnishes which finally became crosslinked films by the casting method. The mechanical properties and viscoelasticities of the PG-modified and PG-free polyurethane crosslinked films and the practicability of magnet wires coated with them were studied in this article. Three different PGs used in this experiment were polyethylene glycol, PEG(#400), polypropylene glycols, PPG(#1000) and PPG(#2000). In the case of adding PEG(#400) for modification, strength at break increased but elongation did not change. Meanwhile, glass transition temperature (T_g) shifted to lower temperature with increasing molar ratio. In the case of adding PPG(#1000) and PPG(#2000) for modification, the samples changed their mechanical properties from hard and brittle to soft and tough. With increasing molar ratios, strength at break initially increased and then decreased gradually, and elongation varied a lot and was consistently contrary to strength at break. T_g occurred at two regions: one at high temperature above 100°C for small molar ratios and the other at low temperature below 100°C for high molar ratios. Besides, for all PG-modified polyurethane crosslinked films, strength at break showed a local maximum at TMP/TDI/PG = 1/1/0.5, which indicated their homogeneous structures. The molar ratios of PG-modified urethane prepolymers, which are suitable for manufacturing practical magnet wires according to testing method JIS-C-3211, are as follows: TMP/TDI/PPG(#100) = 1/1/0.15–0.35 and TMP/TDI/PPG(#2000) = 1/1/0.10. PEG(#400)-modified magnet wires were not accepted on the aging test. The properties of crosslinked films of practical magnet wires are generally as follows: strength at break at 200–700 kg/cm², elongation less than 41%, and T_g at 100–200°C.     

Thermostability and esterification of a polyethylene‐immobilized lipase from Bacillus coagulans BTS‐3

Extracellular lipase from Bacillus coagulans BTS‐3 was immobilized on activated (alkylated, 2.5% glutaraldehyde) and native (nonactivated) polyethylene powder, and its thermostability and esterification efficiency were studied. Immobilization on activated support was found to enhance thermostability as well as esterification efficiency. The optimum time for immobilization on activated (AS) and nonactivated (NS) polyethylene support was found to be 10 min, and the binding of the lipase was markedly higher on AS. Lipase was more efficiently bound to AS (64%) than to NS (30%) at an optimum temperature of 37°C. The pH and temperature optima for AS‐ and NS‐bound lipase were 9.0 and 55°C and 8.5 and 55°C respectively. At 55°C the free lipase, which had a half‐life of 2 h, lost most of its activity at elevated temperatures. In contrast, AS‐bound lipase retained 60%–80% of its original activity at 55°C, 60°C, 65°C, and 70°C for 2 h. Exposure to organic solvents resulted in enhanced lipase activity in n‐hexane (45%) and ethanol (30%). Both AS‐ and NS‐bound biocatalysts were recyclable and retained more than 85% of their initial activity up to the fourth cycle of hydrolysis of p‐nitrophenyl palmitate. The AS‐bound lipase efficiently performed maximum esterification (98%) of ethanol and propionic acid (300 mM each, 1 : 1) in n‐hexane at 55°C. With free or NS‐bound lipase in similar conditions, the conversion of reactants into ester was relatively low (40%). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3986–3993, 2006     

Two-Stage Hot-Water Extraction of Galactoglucomannans from Spruce Wood

In order to preserve the polymeric structure and the acetylation degree of extracted galactoglucomannans and, at the same time, achieve high yield, ground spruce wood was subjected to a series of sequential two-stage extractions with an Accelerated Solvent Extraction (ASE) apparatus using plain water at 170°C. The total combined extraction time was one hour in all the extractions. The total yield of the dissolved material after 1 h extraction was almost the same, about 25% of the wood, irrespective of the time ratios between the first and the second extractions. The yield of hemicellulose high polymers with the weight average molar mass of 8–10 kDa during the first extraction had a maximum at 20 min extraction time, amounting to about 7% on dry wood basis, and comprising about half of the total extract. Along with the progress of the extraction, the molar mass of the hemicelluloses decreased and hemicellulose-derived low polymers with the weight average molar mass of 6–2 kDa became dominating. The extracted substances were fractionated, mainly according to their molar mass, by sequential precipitation with ethanol, acetone, and methyl tert-butyl ether (MTBE). The hemicelluloses with some amount of pectins comprised 83–90% of the precipitated polymeric material and the content of galactoglucomannans was about 80%.     

Optimization of the Mass Yield in the Biodiesel Production from Chicken Viscera Oil

This work proposes the conversion of chicken viscera oil into biodiesel through the transesterification reaction using basic catalysis. For this, the properties of the raw material and the interferences of the variables on the mass yield of the chemical procedure were evaluated, such as reaction temperature (50–90 °C), catalyst concentration (0.5–2.5% m/m), oil: alcohol molar ratio (1:3 to 1:15) and reaction time (15–75 min).Through the execution of an experimental design procedure and subsequent application of the response surface methodology it was possible to maximize the yield of the transesterification reaction to 87.41% w/w, using the following experimental conditions: reaction temperature 70 °C, catalyst concentration 1% m/m, molar ratio 1:9, and reaction time 30 min. This result provides a reduction of 200% in the percentage of the catalyst used, 67% in the volume of alcohol, and 700% in the reaction time when compared to works using similar raw material published in the literature. Besides, the quality of the biodiesel produced was verified and is following the standards required by ASTM D6751 and EN 14214.     

The production of ethene/propene/5-ethylidene-2-norbornene terpolymers using metallocene catalysts: Polymerization,characterization and properties of the metallocene EPDM

Metallocene catalysts Et(Ind)₂ZrCl₂/MAO and Et(Ind)₂HfCl₂/MAO were used in ethene/propene copolymerization and in ethene/propene/5-ethylidene-2-norbornene (E/P/ENB) terpolymerization. The copolymerization activity of the Et(Ind)₂ZrCl₂/MAO system was 20 × 10³ kg_polym/mol_Mt *h, the Et(Ind)₂HfCl₂/MAO yielding 5 × 10³ kg_polym/mol_Mt *h. The polymerization activity decreased with diene addition, but this effect was significant only at very large diene feeds. The catalysts incorporated diene readily. Materials with an ethene content of 55 to 70 mol % and an ENB content of 2 to 16 mol % were produced. Et(Ind)₂HfCl₂ produced a considerably higher molar mass material than the Et(Ind)₂ZrCl₂ catalyst. The molar mass distributions were narrow. Copolymers and terpolymers with up to 3 mol % ENB content had some crystallinity. Copolymer T_gs were between −59°C and −55°C. The terpolymer glass transition temperature rose 1.5°C per wt % of ENB in the polymer. Polymer characteristics reported include composition, molar mass distribution, melt flow rate, density, and thermal behavior. The dynamic mechanical and rheological properties of the materials in comparison with commercial E/P/ENB terpolymers are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 35–44, 1997     

Kinetics of transesterification of palm-based methyl esters with trimethylolpropane

Kinetics of transesterification of palm-based methyl esters (POME) with trimethylolpropane (TMP) to polyol esters was investigated. A kinetic model of reaction was obtained by assuming a series of irreversible elementary reactions at various temperatures. The reaction rate constants were determined under limited conditions. The optimal ratios for k ₂/k ₁ and k ₃/k ₁ were 0.70–0.80 and 0.21–0.25, respectively. Both palm oil methyl esters (PPOME) and palm-kernel oil methyl esters (PKOME) were reacted with TMP by using sodium methoxide as catalyst. The POME-to-TMP molar ratio and catalyst weight percentage were held constant at 10∶1 and 0.4%, respectively. The effects of temperature (70–110°C) and raw materials (PKOME and PPOME) were investigated and found to have a significant impact on the reaction kinetics. When using a large excess of POME and continual withdrawal of methanol via vacuum, the reaction reached completion in less than 20 min at 80°C. After removal of unreacted POME, the final product contained apprximately 98 wt% triesters.     

Synthesis of Ascorbyl Palmitate with Immobilized Lipase from Pseudomonas stutzeri

Synthesis of ascorbyl palmitate by enzymatic esterification of palmitic acid and ascorbic acid was conducted in an organic medium with Pseudomonas stutzeri lipase TL immobilized in different supports and its performance was compared with commercial Novozym 435 lipase used as a reference. The enzyme was immobilized in different supports and the best catalyst was selected in terms of immobilization yield and mass specific activity to perform the reactions of synthesis. Synthesis of ascorbyl palmitate was optimized considering temperature, substrate molar ratio and enzyme to limiting substrate mass ratio as variables, and substrate conversion and specific productivity as evaluation parameters. The best reaction conditions for immobilized lipase TL were 55 °C, 1:5 ascorbic to palmitic acid molar ratio, and 1:10 lipase to ascorbic acid mass ratio, obtaining 57 % substrate conversion and a specific productivity of 0.013 [g ascorbic acid/(g enzyme × min)]; the best conditions for Novozym 435 were 70 °C, ascorbic to palmitic acid molar ratio 1:10, and 1:10 lipase to ascorbic acid mass ratio, obtaining 51 % substrate conversion and a specific productivity of 0.016 [g ascorbic acid/(g enzyme × min)].     

Cyano-substituted polyester,polyurethanes, and epoxy resin derived from 2,6-bis(4-hydroxybenzylidene)-1-dicyanomethylene–cyclohexane

The condensation of cyclohexanone with 4-hydroxybenzaldehyde utilizing dry HCI as the catalyst afforded 2,6-bis(4-hydroxybenzylidene)cyclohexanone. The latter was condensed with malononitrile to yield 2,6-bis(4-hydroxybenzylidene)-1-dicyanomethylene–cyclohexane, which was used as the starting material for the preparation of a novel class of polyesters, polyurethanes, and epoxy resins. In addition, a model diester and diurethane were synthesized and their spectroscopic data were correlated with those of the corresponding polymers. It was shown that the introduction of the dicyanomethylene groups in the polymer backbone remarkably improved the polymer solubility as well as its thermal stability. The crosslinked polymers obtained upon curing the polyester and polyurethanes at 300°C for 40 h were stable up to 365–407°C in N₂ or air and afforded anaerobic char yields of 64–70% at 800°C. © 1994 John Wiley & Sons, Inc.     

Mechanical,hygroscopic, and thermal properties of metal particle and metal evaporated tapes and their individual layers

Mechanical and thermal properties of magnetic tapes and their individual layers strongly affect the tribology of magnetic head–tape interface and reliability of tape drives. Dynamic mechanical analysis, longitudinal creep, lateral creep, Poisson's ratio, the coefficient of hygroscopic expansion (CHE), and the coefficient of thermal expansion (CTE) tests were performed on magnetic tapes, tapes with front coat or back coat removed, substrates (with front and back coats removed), and never‐coated virgin films of the substrates. Storage modulus and loss tangent values were obtained at a frequency range from 0.016 to 28 Hz, and at a temperature range from ?50 to 150 or 210°C. Longitudinal creep tests were performed at 25°C/50% RH, 40°C/25% RH, and 55°C/10% RH for 50 h. The Poisson's ratio and lateral creep were measured at 25°C/50% RH. CHE was measured at 25°C/15–80% RH. CTE values of various samples were measured at a temperature range from 30 to 70°C. The tapes used in this research included two magnetic particle (MP) tapes and two metal evaporated (ME) tapes that were based on poly(ethylene terephthalate) and poly(ethylene naphthalate) substrates. The master curves of storage modulus and creep compliance for these samples were generated for a frequency range from 10^?20 to 10¹⁵ Hz. The effect of tape manufacturing process on the various mechanical properties of substrates was analyzed by comparing the data for the substrates (with front and back coats removed) and the never‐coated virgin films. A model based on the rule of mixtures was developed to determine the storage modulus, complex modulus, creep compliance, and CTE for the front coat and back coat of MP and ME tapes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1319–1345, 2004     

Synthesis of alkenyl succinic anhydrides from methyl esters of high oleic sunflower oil

Alkenyl succinic anhydrides (ASA) have been prepared by ene‐reaction of high‐oleic sunflower oil methyl esters with maleic anhydride in a 50% xylene medium. Response surface methodology (RSM) was used to investigate the influence of two factors: reaction temperature and molar ratio between maleic anhydride (MA) and methyl esters (SME). The studied parameters in 8‐h reactions were the methyl oleate conversion, the distillation yield in ASA, and responses allowing the indirect estimation of side reaction products: clarity index and dynamic viscosity. The highest yield in ASA (>70%; clarity index ≈10) was reached for a temperature of 240–250 °C with a molar ratio of 1.5–1.7. But for an industrial application requiring minimized side products (clarity index >40), the optimal synthesis conditions were: temperature between 220 and 235 °C and molar ratio of 1.2–1.35 (yield ≈55%). Such conditions did not provide a medium free of side products, even if xylene decreased their formation. Compared to solvent‐free synthesis, conversion was lower with xylene. With solvent, higher temperatures were needed to reach the same yields. Supplementary heating compensated the reagent dissolution effect that slows down the kinetics of the ene‐reaction. The influence of reaction time at 220 °C with a MA/SME ratio of 1.2 in a 50% xylene medium was studied. A reaction time of 8–10 h provided a good compromise between ASA yield and side products.     

Synthesis of monoterpene esters by alcoholysis reaction with Mucor miehei lipase in a solvent-free system

The syntheses of geranyl acetate and citronellyl acetate by alcoholysis reaction catalyzed by immobilized lipase from Mucor miehei was studied for the first time in a solvent-free system. Reactions were carried out at a terpene alcohol/acyl donor molar ratio of 1:5 with Lipozyme at 10% of the total weight of the reactants in a solvent-free system. Incubations were carried out at 55 to 60°C for ethyl and butyl acetates as acyl donors, whereas for methyl acetate the incubation temperature was 40 to 45°C. Excess concentration of acyl donor increases the percentage of geranyl acetate and citronellyl acetate, while excess of terpene alcohol concentration decreases the same. Yields from 75 to 77% molar conversion (90 to 98% conversion, w/w) were obtained after 8 to 28 h of reaction time.     

Nonlinear viscoelastic behavior of butadiene–acrylonitrile copolymers filled with carbon black

Various viscoelastic measurements including dynamic mechanical measurements in tension at 110 Hz from ?60° to 160°C, tensile stress relaxation measurements with 100% elongation at 25°, 54°, and 98°C, capillary flow measurements at 70°, 100°, and 125°C, and high-speed tensile stress–strain measurements carried to break at 25°, 56°, and 98°C were performed on four samples of carbon black-filled butadiene–acrylonitrile copolymers. All the data were treated with the same equation for time–temperature conversion. The capillary viscosity–shear rate curves were significantly lower than the complex viscosity–angular frequency curves, indicating “strain softening” with extrusion. The viscosity was estimated from the stress–strain relationship at the yield point. The viscosity as a function of the strain rate is significantly higher than the complex viscosity as a function of angular frequency, indicating “strain hardening” with extension. The strain softening and strain hardening are attributable to the structural changes upon deformation of the carbon black-filled elastomers. With the unfilled elastomers, neither strain softening nor strain hardening were observed in similar measurements.     

Production of liquid fuels from waste plastics

Exploratory work was carried out to develop a process for conversion of mixed plastic wastes into liquid transportation fuels or petrochemicals. The concept used is based on thermal depolymerization of the polymers in a suitable solvent followed by catalytic conversion of the resulting polymeric fragments into hydrocarbons with boiling points below 525°C. The process is carried out batch-wise over a zeolite catalyst at temperatures from 350°C to 450°C and at atmospheric pressure. No hydrogen is used and volatile products formed are continuously removed from the reactor. Tests were carried out on polyethylene and polypropylene alone, and on mixtures of the two. Finally, a synthetic mixture of four different plastics was tested. From 90% to 98% of the plastic was converted to gases or distillable hydrocarbons. Of this yield, from 20% to 55% was gas, primarily propylenes and butylenes, and from 32% to 70% was a light hydrocarbon oil. Very little non-distillable coke or residue was formed. The use of mixtures did not affect the high conversions obtained, but the results could only be approximately predicted based on a pro-rating of results for the individual components.     

Properties of poly(styrene)-“grafted” silk fibers and molecular weight of poly(styrene)

Poly(styrene) was grafted onto silk fibers in an aqueous medium, using ammonium persulphate initiator. Add-ons of up to 100% were achieved. The add-on increased linearly with the monomer concentration of the grafting system, all other factors remaining constant. The yield of the reaction attained about 80% and the extent of homopolymerization was negligible. The equilibrium moisture regain decreased noticeably with increasing add-on. Breaking load showed a tendency to increase in the 0–55% range of poly(St) content, while elongation at break and work of rupture decreased. The DSC endothermal peak at 315°C slightly shifted towards higher temperature by graft—copolymerization, and a new endothermal transition appeared beyond 400°C. TG measurements showed an increase of weight retention beyond 300°C for poly(St)-“grafted” silk fibers. The dynamic mechanical behavior was characterized by a shift to lower temperature of the loss modulus peak. The transverse dimension of the fibers increased with increasing add-on. The polymeric residue remaining after alkaline dissolution of silk fibroin showed a porous texture with a sponge-like morphology. The molecular weight of poly(St) removed from silk increased up to 120 kDa in the 0–55% add on range and then remained constant. The “Poly(St)/Silk” molar ratio increased linearly over the add-on range examined. © 1996 John Wiley & Sons, Inc.     

Characterization of Anacardium occidentale exudate polysaccharide

The composition, structure and molar mass distribution of Anacardium occidentale exudate polysaccharide of Brazilian origin was investigated. The composition from gas–liquid chromatography (GLC) and ¹³C NMR was 72% β-D -galactopyranose, 14% α-D -glucopyranose, 4·6% α-L -arabinofuranose, 3·2% α-L -rhamnopyranose and 4·5% β-D -glucuronic acid. A thorough analysis of high resolution ¹³C NMR spectra from intact, partially hydrolysed and Smith-degraded polysaccharide enabled reliable chemical shift assignments to be made, and indicated the presence of three types of unit within the branched galactan core: linked at C-1 and C-3, at C-1 and C-6, and at C-1, C-3 and C-6. The polysaccharide was fractionated with respect to molar mass using water/ethanol as a solvent/non-solvent system. The polysaccharide and fractions were characterized by gel permeation chromatography (GPC), intensity light scattering, dilute solution viscometry and sedimentation velocity. The intrinsic viscosity in 0·1M aqueous NaCl at 25°C was found to depend on molar mass according to: [η]/(cm³g^-1)=0·052M^0·42. The molar mass distribution for the whole polysaccharide, determined by GPC using a universal calibration, exhibited two main peaks at 28000 and 67000gmol^-1, together with traces of much higher molar mass material. © 1998 SCI.     

Ethanolysis of Refined Soybean Oil Assisted by Sodium and Potassium Hydroxides

The ethanolysis of refined soybean oil was investigated through a 2³ experimental design that was carried out under the following levels: ethanol:oil molar ratios (MR) of 6:1 and 12:1, NaOH concentrations of 0.3 and 1.0 wt% in relation to the oil mass, and reaction temperatures of 30 and 70 °C. The ethanol:oil MR and the alkali concentration had an almost equivalent influence on the reaction yield, whereas the influence of increased reaction temperatures was very limited and higher catalyst concentrations led to greater yield losses due to the formation of soap. Ethyl ester yields of 97.2% were obtained at 70 °C, MR of 12:1 and 0.3 wt% NaOH. Replacement of 0.3 wt% NaOH by 1.0 wt% KOH under the same reaction conditions led to lower ester yields. Likewise the former, KOH provided the maximum ester yield (95.6%) at the highest molar ratio (12:1), with the reaction temperature having little influence on the catalyst performance. Ester yields beyond 98% were only achieved when a second ethanolysis stage was included in the process. In this regard, the application of 2 wt% Magnesol^® after the first ethanolysis stage eliminated the need for water washing prior to the second ethanolysis stage and helped to generate a final product with less contaminating unreacted glycerides.     

Biodiesel from canola oil using a 1 : 1 molar mixture of methanol and ethanol

Canola oil was transesterified using a 1 : 1 molar mixture of methanol and ethanol (M/E) with potassium hydroxide (KOH) catalyst. The effects of catalyst concentration (0.5–1.5 wt‐%), molar ratio of M/E to canola oil (3 : 1 to 20 : 1) and reaction temperature (25–75 °C) on the percentage yield measured after 2.5 and 5.0 min were optimized using a central composite design. A maximum percentage yield of 98% was obtained for a catalyst concentration of 1.1 wt‐% and an M/E to canola oil molar ratio of 20 : 1 at 25 °C at 2.5 min, whereas a maximum percentage yield of 99% was obtained for a catalyst concentration of 1.15 wt‐% and all molar ratios of reactants at 25 °C at 5 min. Statistical analysis demonstrated that increasing catalyst concentration and molar ratio of reactants resulted in curvilinear and linear trends in percentage yield, both at 2.5 and 5 min. However, reaction temperature, which affected the percentage yield at 2.5 min linearly, was insignificant at 5 min. The resultant mixed methyl/ethyl canola esters exhibited enhanced low‐temperature performance and lubricity properties in comparison to neat canola oil methyl esters and also satisfied ASTM D6751 and EN 14214 standards with respect to oxidation stability, kinematic viscosity, and acid value.     

Mechanical,hygroscopic, and thermal properties of ultrathin polymeric substrates for magnetic tapes

Mechanical, hygroscopic, and thermal properties of improved ultrathin polymeric films for magnetic tapes are presented. These films include poly(ethylene terephthalate) (PET), poly(ethylene naphthalate) (PEN), and aromatic polyamide (ARAMID). PET films are currently the most commonly used polymeric substrate material for magnetic tapes, followed by PEN and ARAMID. The thickness of the films ranges from 6.2 to 4.8 μm. Tensile tests were run to obtain the Young's modulus, F5 value, strain at yield, breaking strength, and strain at break. The storage modulus, E′, and the loss tangent, tan δ, were measured using a dynamic mechanical analyzer (DMA) at temperature ranges of ?50 to 150°C (for PET) and ?50 to 210°C (for PEN and ARAMID) and at a frequency range of 0.016–28 Hz. Frequency–temperature superposition was used to predict the dynamic mechanical behavior of the films over a 28‐decade frequency range. Short‐term longitudinal creep behavior of the films during 10, 30, 60, and 300 s, 7 MPa, were measured at 25 and 55°C. Long‐term longitudinal creep measurements were performed at 25, 40, and 55°C for 100 h. The Poisson's ratio and 50‐h long‐term lateral creep were measured at 25°C/15% RH, 25°C/50% RH, 25°C/80% RH, and 40°C/50% RH. The in‐plane coefficient of hygroscopic expansion (CHE) at 25°C/20–80% RH and the coefficient of thermal expansion (CTE) at 30–70°C were measured for all the samples. The properties for all films are summarized. The relationship between the polymeric structure and the mechanical and physical properties are discussed, based on the molecular structure, crystallinity, and molecular orientation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3052–3080, 2003     

Enzymatic Production of Monoacylglycerols (MAG) and Diacylglycerols (DAG) from Fish Oil in a Solvent-Free System

Mono- (MAG) and diacylglycerols (DAG) are of nutritional interest. MAG and DAG containing eicosapentaenoic (EPA) and docosahexaenoic (DHA) acids were produced in a solvent-free system via glycerolysis of menhaden oil catalyzed by Novozym 435. The effect of the molar ratio of glycerol to oil, enzyme concentration, and reaction temperature on MAG and DAG production was assessed. The optimal temperature was in the range of 55–70 °C for production of both acylglycerols. The increase in the substrates molar ratio led to a decrease in MAG and DAG content. The enzyme concentration was fixed at the lowest level evaluated (5%, by weight of substrates). High content of MAG (25% by weight) and DAG (41% by weight) containing, respectively, 12.46% EPA and 11.16% DHA, and 14.57% EPA and 13.70% DHA, were produced after 24 h at 70 °C, with 5% of lipase (by weight of substrate) and a glycerol-to-oil molar ratio of 1:1. For this reaction, a molar triacylglycerol (TAG) conversion of about 60% was achieved at equilibrium (10 h).