Increased Performance of Thermoplastic Packaging Materials by Using a Mild Oxidizing Biobased Additive

Green additives such as prodegradants based on natural fatty acids and iron can improve the environmental profile of thermoplastic packaging materials. We present two studies in which this is demonstrated. In the first study, the addition of a green prodegradant to a 5-layer gas barrier laminate during processing provided a laminate with significantly reduced oxygen transmission due to the resulting oxygen-consuming degradation process. The result shows that material reduction and cost efficiency of packaging laminates can be combined, since 5-layer laminates with reduced oxygen barrier layer thickness and retained gas barrier properties are feasible. The products are interesting from an ecological and economic aspect. In the second study, the addition of a green prodegradant to several qualities of polypropylene that are used in packaging applications leads to materials that are readily degraded in accelerated weathering. The molecular weight of the modified polypropylenes after 830 hours of accelerated weathering is reduced from typically 80.000 g/mole to 1.500–2.500 g/mole. At such molecular weight levels, digestion by microorganisms is feasible. The mild prodegradant used in the study does not lead to degradation during processing. Thermoplastics containing such additives are therefore fully recyclable provided that they have not been exposed to a long period of weathering

Thermal oxidation of polyolefins by mild pro-oxidant additives based on iron carboxylates and lipophilic amines: Degradability in the absence of light and effect on the adhesion to paperboard

Marine and inland pollution by non-degradable plastic bags and other plastic articles is a topic of great concern. Natural degradation processes based on oxidation of plastic pollutants could possibly contribute to limit the extent of pollution. Thermal degradation of polyolefins in the absence of light by non-polluting pro-oxidants has not been presented before. In this study, we show that two amines, stearyl amine and [(3-(11-aminoundecanoyl) amino) propane-1-] silsesquioxane (amino-POSS) in combination with ferric stearate (FeSt3) tremendously accelerate the thermal oxidation of polyolefins compared with reference samples. Both amines and FeSt3 are to a large extent based on renewable resources. Polyethylene and polypropylene samples containing less than 100 ppm of iron and 1% of amine were extremely brittle after 10 days in a circulation oven in the absence of light. No significant degradation could be seen with samples containing iron but no amine. In a different application, the initial oxidation of polyethylene can be used in order to increase its adhesion to cardboard. Excellent adhesion between polyethylene and cardboard is important for liquid packaging based on renewable resources. Amino-POSS has been chosen for food packaging applications due to its expected lower leakage from polyethylene (PE) compared with stearyl amine. Film samples of PE/amino-POSS/FeSt3 blends were partly oxidized in a circulation oven. The oxidation was documented by increased carbonyl index (CI) and melt flow index (MFI). The limited extent of oxidation has been proved by unchanged tensile strength and only moderate changes in elongation at break when compared to reference polyethylene films containing no FeSt3 or amino-POSS. The PE/amino-POSS/FeSt3 blends were compression moulded to paperboard. The adhesion of non-aged blends to paperboard decreased with increasing amino-POSS content which is in good compliance with an earlier reported lubricant effect of high amounts of POSS in PE. Thermal ageing of PE/amino-POSS/FeSt3 films prior to coating however led to a significant increase in adhesion. Improved physical interlocking due to increased MFI and interaction between C=O of the blends and OH of paperboard can explain the adhesion improvement. The films were not brittle after thermal ageing, which makes their use in industrial packaging feasible. A mechanism explaining the role of amines during thermal oxidation of polyolefins in the presence of iron is proposed.publishedVersio

Thermal oxidation of polyolefins by mild pro-oxidant additives based on iron carboxylates and lipophilic amines: Degradability in the absence of light and effect on the adhesion to paperboard

Marine and inland pollution by non-degradable plastic bags and other plastic articles is a topic of great concern. Natural degradation processes based on oxidation of plastic pollutants could possibly contribute to limit the extent of pollution. Thermal degradation of polyolefins in the absence of light by non-polluting pro-oxidants has not been presented before. In this study, we show that two amines, stearyl amine and [(3-(11-aminoundecanoyl) amino) propane-1-] silsesquioxane (amino-POSS) in combination with ferric stearate (FeSt3) tremendously accelerate the thermal oxidation of polyolefins compared with reference samples. Both amines and FeSt3 are to a large extent based on renewable resources. Polyethylene and polypropylene samples containing less than 100 ppm of iron and 1% of amine were extremely brittle after 10 days in a circulation oven in the absence of light. No significant degradation could be seen with samples containing iron but no amine. In a different application, the initial oxidation of polyethylene can be used in order to increase its adhesion to cardboard. Excellent adhesion between polyethylene and cardboard is important for liquid packaging based on renewable resources. Amino-POSS has been chosen for food packaging applications due to its expected lower leakage from polyethylene (PE) compared with stearyl amine. Film samples of PE/amino-POSS/FeSt3 blends were partly oxidized in a circulation oven. The oxidation was documented by increased carbonyl index (CI) and melt flow index (MFI). The limited extent of oxidation has been proved by unchanged tensile strength and only moderate changes in elongation at break when compared to reference polyethylene films containing no FeSt3 or amino-POSS. The PE/amino-POSS/FeSt3 blends were compression moulded to paperboard. The adhesion of non-aged blends to paperboard decreased with increasing amino-POSS content which is in good compliance with an earlier reported lubricant effect of high amounts of POSS in PE. Thermal ageing of PE/amino-POSS/FeSt3 films prior to coating however led to a significant increase in adhesion. Improved physical interlocking due to increased MFI and interaction between C=O of the blends and OH of paperboard can explain the adhesion improvement. The films were not brittle after thermal ageing, which makes their use in industrial packaging feasible. A mechanism explaining the role of amines during thermal oxidation of polyolefins in the presence of iron is proposed

Toolbox of the assessment of clinical skills

Microfibrillated cellulose (MFC), TEMPO-pretreated MFC, and hybrid polymer/MFC mix were used for the production of layered films with interesting properties for application in food packaging. The series of samples were prepared from MFC (base layers) using a dispersion-casting method. The same procedure as well as a bar coating technique was applied to form top layers of different basis weights. The barrier properties and formation of the layered films were investigated in relationship to the preparation procedures, combination of layers, and areal weight (basis weight). Characterization was done with respect to oxygen transmission rates (OTR), water vapor transmission rates (WVTR), tensile properties, and contact angles (CA) with water. The produced layered films yielded OTR values of 4 mL m-2 day-1 and fulfilled oxygen barrier requirements for a modified atmosphere packaging (MAP). Hornification of the MFC films, however, occurred during drying, which may result in a loss of the film’s beneficial properties

The formation and characterization of sustainable layered films incorporating Microfibrillated Cellulose (MFC)

Microfibrillated cellulose (MFC), TEMPO-pretreated MFC, and hybrid polymer/MFC mix were used for the production of layered films with interesting properties for application in food packaging. The series of samples were prepared from MFC (base layers) using a dispersion-casting method. The same procedure as well as a bar coating technique was applied to form top layers of different basis weights. The barrier properties and formation of the layered films were investigated in relationship to the preparation procedures, combination of layers, and areal weight (basis weight). Characterization was done with respect to oxygen transmission rates (OTR), water vapor transmission rates (WVTR), tensile properties, and contact angles (CA) with water. The produced layered films yielded OTR values of 4 mL m-2 day-1 and fulfilled oxygen barrier requirements for a modified atmosphere packaging (MAP). Hornification of the MFC films, however, occurred during drying, which may result in a loss of the film’s beneficial properties.publishedVersio

Double Proton Tautomerism via Intra- or Intermolecular Pathways? The Case of Tetramethyl Reductic Acid Studied by Dynamic NMR: Hydrogen Bond Association, Solvent and Kinetic H/D Isotope Effects

Using dynamic liquid-state NMR spectroscopy a degenerate double proton tautomerism was detected in tetramethyl reductic acid (TMRA) dissolved in toluene-d8 and in CD2Cl2. Similar to vitamin C, TMRA belongs to the class of reductones of biologically important compounds. The tautomerism involves an intramolecular HH transfer that interconverts the peripheric and the central positions of the two OH groups. It is slow in the NMR time scale around 200 K and fast at room temperature. Pseudo-first-order rate constants of the HH transfer and of the HD transfer after suitable deuteration were obtained by line shape analyses. Interestingly, the chemical shifts were found to be temperature dependent carrying information about an equilibrium between a hydrogen bonded dimer and a monomer forming two weak intramolecular hydrogen bonds. The structures of the monomer and the dimer are discussed. The latter may consist of several rapidly interconverting hydrogen-bonded associates. A way was found to obtain the enthalpies and entropies of dissociation, which allowed us to convert the pseudo-first-order rate constants of the reaction mixture into first-order rate constants of the tautomerization of the monomer. Surprisingly, these intrinsic rate constants were the same for toluene-d8 and CD2Cl2, but in the latter solvent more monomer is formed. This finding is attributed to the dipole moment of the TMRA monomer, compensated in the dimer, and to the larger dielectric constant of CD2Cl2. Within the margin of error, the kinetic HH/HD isotope effects were found to be of the order of 3 but independent of temperature. That finding indicates a stepwise HH transfer involving a tunnel mechanism along a double barrier pathway. The Arrhenius curves were described in terms of the Bell–Limbach tunneling model

The Stability of Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes in Water

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