Polyurethane (PUR) soft foams release malodorous and potentially toxic compounds when exposed to oxidative conditions. Current chamber test methods cannot distinguish between pre-existing volatiles and those formed during oxidation, nor can they assess the formation rates of oxidation products. We subjected PUR soft foam to oxidative treatment in a continuous air flow at 120 °C. Emissions were convectively transferred from the foam to an exhaust port and analyzed using a thermodesorption–gas chromatography–mass spectrometry (TD-GC-MS) system, with external calibration employed for the quantification of selected analytes. The study identified hydroperoxide formation and degradation as key mechanisms in the breakdown of the polyether soft segments. This process predominantly produces volatiles, such as carboxylic acids, formates, acetates, alpha-hydroxy-ketones, (unsaturated) aldehydes, substituted dioxolanes and dioxanes, glycols, and allyl ethers. Volatiles associated with the degradation of the hard segments include aniline, benzoxazole, 2-methylbenzoxazole, and benzaldehyde. This experimental setup enables reproducible qualitative and quantitative analysis of volatiles formed during the oxidative degradation of PUR soft foams, providing new insights into the segment-dependent chemical pathways of the polymer’s molecular breakdown.
We present a new method for investigating the oxidation and emission behavior of air-permeable materials. Employing this method, a differentiated statement can be made about the extent to which critical volatile organic compounds (VOCs) such as formaldehyde, acetaldehyde, and acrolein are contained in the material as impurities or formed by thermo-oxidative degradation of the polymer matrix in the use phase. The parameters affecting methods of VOC analysis are reviewed and considered for the developed method. The molecular mechanisms of VOC formation are discussed. Toxicological implications of the reaction kinetics are put into context with international guidelines and threshold levels. This new method enables manufacturers of cellular materials not only to determine the oxidative stability of their products but also to optimize them specifically for higher durability. ENVIRONMENTAL IMPLICATION: Cellular materials are ubiquitous in the technosphere. They play a crucial role in various microenvironments such as automotive interiors, building insulation, and cushioning. These materials are susceptible to oxidative breakdown, leading to the release of formaldehyde, acetaldehyde, and acrolein. The ecotoxicological profiles of these compounds necessitate monitoring and regulation. The absence of reproducible and reliable analytical methods restricts research and development aimed at risk assessment and mitigation. This work significantly enhances the toolbox for optimizing the oxidative stability of any open-cell cellular material and evaluating these materials in terms of their temperature-dependent oxidation and emission behavior.
1 April 2022 in American Journal of Infection Control
During shortages of filtering face pieces (FFP) in a pandemic, it is necessary to implement a method for safe reuse or extended use. Our aim was to develop a simple, inexpensive and ecological method for decontamination of disposable FFPs that preserves filtration efficiency and material integrity. Contamination of FFPs (3M Aura 9320+) with SARS-CoV-2 (1.15 × 104 PFUs), Enterococcus faecium (>106 CFUs), and physiological nasopharyngeal flora was performed prior to decontamination by submersion in a solution of 6 % acetic acid and 6 % hydrogen peroxide (6%AA/6%HP solution) over 30 minutes. Material integrity was assessed by testing the filtering efficiency, loss of fit and employing electron microscopy. Decontamination with the 6%AA/6%HP solution resulted in the complete elimination of SARS-CoV-2, E. faecium and physiological nasopharyngeal flora. Material characterization post-treatment showed neither critical material degradation, loss of fit or reduction of filtration efficiency. Electron microscopy revealed no damage to the fibers, and the rubber bands' elasticity was not affected by the decontamination procedure. No concerning residuals of the decontamination procedure were found. The simple application and widespread availability of 6%AA/6%HP solution for decontaminating disposable FFPs make this solution globally viable, including developing and third world countries.
10 October 2024 in Journal of Applied Polymer Science
Styrene substitution is a major area of interest in the unsaturated polyester resins (UPR) industry and research. For most styrene‐free UPRs the unsaturated polyester (UP) formulation was tailored for less toxic reactive diluent monomers (RDM). The main challenge is finding a RDM that can directly substitute styrene in industrial UPR formulations without deterioration of resin and thermoset properties. Therefore, this study concerns vinyl methyl oxazolidinone (VMOX®) as a reactive diluent monomer for industrial high‐temperature UPRs. VMOX® and styrene were compared with dimethyl itaconate (DMI), methyl methacrylate, 2‐hydroxyethyl methacrylate, isobornyl methacrylate, triethylene glycol dimethacrylate and 1,4‐butanediol dimethacrylate. Further, the properties of produced resins and thermosets were investigated. The most striking result was comparable glass transition temperature, crosslink density, and residual monomer content of VMOX®‐ and styrene‐based thermosets. Subsequently, DMI was applied as a reactive co‐diluent for VMOX®‐based resins and thermosets. Significant improvement of VMOX® conversion during resin curing was observed. In conclusion, VMOX® is an excellent candidate for direct styrene substitution in industrial high‐temperature UPRs. Furthermore, the application of DMI as a reactive co‐diluent improves the reactivity of VMOX®‐based resins. The application of VMOX® and reactive co‐diluent monomer certainly creates new possibilities for direct styrene substitution in conventional UPR formulations.
The oxidation of flexible polyurethane (PUR) foams significantly impacts product durability, vehicle indoor air quality, and volatile organic compound (VOC) emissions. This study investigates oxidation kinetics and VOC emissions (65–155 °C) from foams with indices between 70 and 115 (molar ratio of NCO to NCO-reactive groups × 100), where a higher index represents greater hard segment (methylene diphenyl diisocyanate) and lower soft segment (polyether polyol) content. Using a flow-through setup with PTFE chambers and Tenax thermodesorption tubes and dinitrophenylhydrazine (DNPH) cartridges, VOCs from initial analyte loading, hydroperoxide degradation, and autoxidation were distinguished, providing robust kinetic data unaffected by diffusion interference. A higher index accelerated soft segment degradation, increasing oxidation rates and VOC emissions. The activation energy of 1,2-propanediol-1-acetate-2-formate increased from 87 kJ/mol in low-index to 108 kJ/mol in high-index formulations. VOC emissions from high-index foams were tripled for acetaldehyde during long-term aging at 65 °C. While most emissions followed Arrhenius behavior, formaldehyde and acrolein deviated above 100 °C, with higher hard-segment content extending their Arrhenius range. These findings link PUR composition to degradation behavior and emissions, enabling formulation improvements. The results advance methods for evaluating raw material contributions and the performance of antioxidants under realistic aging conditions.