Poly(L‐lactic acid) with added α‐tocopherol and resveratrol: optical,physical, thermal and mechanical properties

Poly(L ‐lactic acid) (PLLA) films containing various concentrations of two natural antioxidants, α‐tocopherol and resveratrol, were fabricated by a melt compounding and compression molding process. The influence of the antioxidants on the optical properties such as color and UV‐visible light transmission was analyzed. The thermal, mechanical, rheological and physical properties of PLLA films with added antioxidants were assessed. PLLA films with added α‐tocopherol and resveratrol showed a yellowish brown color and the lightness was influenced by the presence of the antioxidants. The glass transition and melting temperatures were significantly reduced with the addition of antioxidants while enhanced thermal stability was observed, which could be a benefit and important for processing and production. PLLA films with added antioxidants were slightly more hydrophobic than neat PLLA. The combination effect of plasticizing and enhancement of the elastic modulus with differing concentrations of two antioxidants played a critical role in the mechanical and thermomechanical properties of PLLA films. The melt viscosity of the PLLA films with added antioxidants was substantially higher than that of neat PLLA. The higher melt viscosity and G′(ω) could be an indication of formation of entanglement between PLLA and the two antioxidants. Copyright © 2012 Society of Chemical Industry     

Migration of α-tocopherol from LDPE films to corn oil and its effect on the oxidative stability

The migration of α-tocopherol (α-T) from low density polyethylene (LDPE) films, added with 20 (film A) and 40 mg g^?1 (film B) to corn oil for 12 weeks at 5, 20 and 30 °C was determined. A LDPE film added with no α-T was used as control (film C). Diffusion coefficient (D) values for the film A system were 1.4 × 10^?11, 7.1 × 10^?11 and 30.3 × 10^?11 cm² s^?1 at 5, 20 and 30 °C, respectively. Meanwhile, D values for the film B system were 1.3 × 10^?11, 9.6 × 10^?11 and 51.1 × 10^?11 cm² s^?1 at the same temperatures. The activation energy (E_a) for the diffusion of α-T was 126.5 (film A) and 105.9 kJ mol^?1 (film B). The effect of the migration of α-T on the oxidative stability of corn oil was evaluated by monitoring hexanal content by solid phase micro-extraction (SPME) and gas chromatography. The hexanal content in the oil showed that both films added with α-T resulted suitable to maintain the oxidative stability of the oil for about 16 weeks at 30 °C, compared to 12 weeks for the oil in contact with the film C.     

Release of butylated hydroxytoluene from an active film packaging to Asadero cheese and its effect on oxidation and odor stability

Antioxidant active packaging consisting of coextruded films made of low density polyethylene (LDPE) added with 0, 8, and 14 mg/g of butylated hydroxytoluene (BHT) and polyamide 6/66 were fabricated. The release of BHT from the films to Asadero cheese was determined. Most of the BHT was diffused from the LDPE layer to the cheese during the first 20 d of storage at 5°C. Diffusion coefficient for the diffusion of BHT from the films 8 and 14 to the cheese was calculated as 6.24E-12 and 6.26E-12 cm²/s, respectively. The release of BHT from the film added with 8 mg/g of the antioxidant in the LDPE layer complied with the legal limit established for food products. However, the film added with 14 mg/g of the antioxidant exceeded that limit. The film added with 8 mg/g of BHT maintained the same levels of oxidized odor from 20 to 100 d of storage.     

Effect of Maleic‐Anhydride Grafting on the Physical and Mechanical Properties of Poly(L‐lactic acid)/Starch Blends

MA is grafted onto both PLLA and starch in an internal mixer in the presence of DCP in a one‐step reactive compatibilization process. The effect of maleation of MA on the physical and mechanical properties and morphology of the blends was assessed. The onset decomposition temperature of the PLLA/starch blends decreased as the starch content increases due to the lower thermal stability of starch and the low effect of the maleation reaction on the thermal stability of the blends. PLLA/starch blends without grafted MA showed higher crystallinity as the starch content increased. Reactive compatibilized blends with less than 20 wt% starch had higher storage modulus, indicating that the compatibility between the two phases was improved.

     

Determination of potential migrants present in Nylon 'microwave and roasting bags' and migration into olive oil

Two groups of potential migrants were found in Nylon "microwave and roasting bags' (MRBs): volatile compounds were released at cooking temperatures and non-volatile compounds were extracted with methanol and/or water. A dynamic headspace system at 200 degrees C followed by gas chromatography (GC) coupled to mass spectrometry (MS) was used for determination of volatile compounds. Cyclopentanone (31.7 mg/bag), 2-cyclopentyl cyclopentanone (17.4 mg/bag), hexadecane (2.6 micrograms/bag), heptadecane (3.2 micrograms/bag), octadecane (3.0 micrograms/bag) and epsilon-caprolactam (5.0-35.5 mg/ bag) were the main volatile compounds present in the MRBs. High performance liquid chromatography (HPLC) and mass spectrometry were combined for identification and quantification of non-volatile compounds extracted with methanol (46.0 mg/bag). Nylon 6,6 cyclic monomer and cyclic oligomers up to the tetramer and Nylon 6 monomer and cyclic oligomers up to the octamer were identified and quantified, confirming that the plastic was made of Nylon 6,6 and Nylon 6 polymers. The same non-volatile compounds (except Nylon 6 heptamer and octamer) were found to migrate into olive oil at 175 degrees C for 1 h. A total of 0.916 mg/dm2 (19.2 mg/bag) of non-volatile compounds migrated into olive oil (41.8% of those quantified in the plastic material).     

Release of antioxidants from co-extruded active packaging developed for whole milk powder

Control of oxidation is a basic criterion to maintain the quality of milk and dairy products. Multilayer co-extruded films are often used to limit the diffusion of oxygen from the environment into the package. In this study, multilayer co-extruded films made of high density polyethylene (added with titanium dioxide), ethylene vinyl alcohol and a layer of low density polyethylene containing the antioxidants butylated hydroxyanisole (1.5%), butylated hydroxytoluene (1.5%) and α-tocopherol (4%) were manufactured. The release of the antioxidants from the films to whole milk powder was determined during 30 days at 30 °C. Whole milk powder stability was measured by monitoring vitamin A, hexanal, pentanal and heptanal content. Butylated hydroxytoluene and butylated hydroxyanisole migrated quickly from the films to the milk powder, while α-tocopherol migrated gradually. Multilayer co-extruded films provided an adequate light-barrier for whole milk powder and the film added with α-tocopherol contributed to the protection of vitamin A degradation compared with the other films.     

Migration of α-tocopherol and resveratrol from poly(L-lactic acid)/starch blends films into ethanol

Poly(L-lactic acid) (PLLA)/starch blends with various concentrations of two natural antioxidants, α-tocopherol (α-TOC) and resveratrol, were fabricated by a melt blending and compression molding processes. The effects of the two antioxidants on the optical (color), thermal and mechanical properties of PLLA/starch blends with antioxidants were assessed. PLLA/starch blend films with α-TOC and resveratrol showed a yellowish color influenced by the combined effect of white starch and the brown color of the antioxidants. The glass transition and melting temperatures were significantly reduced with the addition of antioxidants while enhanced thermal stability was observed, which could be a benefit and important for processing and production. The enhanced mechanical properties could be attributed to not only a compatibilization effect based on the chemical linkage between PLLA and starch chains, but also restriction of the chain mobility by antioxidants. The release of resveratrol from PLLA and PLLA/starch blend films into ethanol followed Fickian behavior. The D values of α-TOC were in the range of 0.47–3.95 × 10⁻¹¹ cm² s⁻¹ for PLLA films and 0.70–6.83 × 10⁻¹¹ cm² s⁻¹ for PLLA/starch blend films at 13 °C, 5.67–13.0 × 10⁻¹¹ cm² s⁻¹ for PLLA films and 4.10–24.2 × 10⁻¹¹ cm² s⁻¹ for PLLA/starch blend films at 23 °C, and 89.0–118.0 × 10⁻¹¹ cm² s⁻¹ for PLLA films and 123–282 × 10⁻¹¹ cm² s⁻¹ for PLLA/starch blend films at 43 °C. The D values of resveratrol were in the range of 0.073–0.54 × 10⁻¹⁰ cm² s⁻¹ for PLLA films and 1.42–6.93 × 10⁻¹⁰ cm² s⁻¹ for PLLA/starch blend films at 13 °C, 0.90–3.44 × 10⁻¹⁰ cm² s⁻¹ for PLLA films and 4.16–22.3 × 10⁻¹⁰ cm² s⁻¹ for PLLA/starch blend films at 23 °C, and 24.8–74.1 × 10⁻¹⁰ cm² s⁻¹ for PLLA films and 40.1–309 × 10⁻¹⁰ cm² s⁻¹ for PLLA/starch blend films at 43 °C.     

Migration of α-tocopherol from an active multilayer film into whole milk powder

Antioxidant active packaging is a promising technology for whole milk powder (WMP) protection. In this study, the migration of α-tocopherol from a multilayer active packaging (made of high density polyethylene, ethylene vinyl alcohol and a layer of low density polyethylene containing the antioxidant) to WMP was studied. A model based on the Fick’s diffusion equation was used to calculate the diffusion coefficients (D) of α-tocopherol as 2.34 × 10⁻¹¹, 3.06 × 10⁻¹¹, and 3.14 × 10⁻¹¹ cm² s⁻¹ at 20, 30 and 40 °C, respectively. The D at 20 °C was different from those at 30 and 40 °C (P < 0.05); but it was similar at 30 and 40 °C. This low influence of temperature on the migration of α-tocopherol from 20 to 40 °C assures the release at real storage and commercialization conditions in regions with warm/hot climate. The antioxidant delivering system delayed the lipid oxidation of WMP and it was more effective at 30 and 40 °C since the rate of oxidative reactions was higher at these temperatures than at 20 °C.     

Migration of bisphenol A (BPA) from can coatings into a fatty-food simulant and tuna fish.

The effect of heat processing, storage time and temperature on the migration of bisphenol A (BPA) from organosol and epoxy can coatings to a fatty-food simulant and tuna was determined. Analyses of BPA were performed by RP-HPLC with fluorescence detection. Four migration experiments, performed between 2000 and 2003, using cans with organosol, epoxy and a combination of both types of coatings were performed under different processing conditions and storage times. Migration levels as high as 646.5 microg kg(-1) BPA from an organosol coating of tuna fish cans were found using a fatty-food simulant following the heat processing of the simulant-filled cans. Levels ranging from 11.3 to 138.4 microg kg(-1) BPA from tuna cans coated with an epoxy resin migrated to the fatty-food simulant during 1 year at 25 degrees C. Levels of BPA migration into a fatty-food simulant from thermally processed and stored tuna cans coated with a combination of organosol and epoxy resins and from vegetable cans coated with an epoxy resin were below the limit of quantitation of 10.0 microg kg(-1). Migration of BPA to tuna ranged from <7.1 to 105.4 microg kg(-1) during long-term storage at 25 degrees C. BPA levels in tuna cans purchased from three local supermarkets ranged from <7.1 to 102.7 microg kg(-1). The highest migration levels were found following heat processing at temperatures as high as 121 degrees C and at times as long as 90 min. Coatings from different can batches can give different levels of BPA migration. The migration levels of BPA found in this work are below the present European Union migration limit, except the 646.5 microg kg(-1) found after the commercial heating process was applied to the simulant-filled cans coated with the organosol resin.