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Studies of Emission Processes of Polymer Additives into Water Using Quartz Crystal Microbalance-A Case Study on Organophosphate Esters

机译:石英晶体微天平研究高分子添加剂向水中的排放过程-以有机磷酸酯为例

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Plastic materials contain various additives, which can be released during the entire lifespan of plastics and pose a threat to the environment and human health. Despite our knowledge on leakage of additives from products, accurate and rapid approaches to study emission kinetics are largely lacking, in particular, methodologies that can provide in-depth understanding of polymer/additive interactions. Here, we report on a novel approach using quartz crystal microbalance (QCM) to measure emissions of additives to water from polymer films spin-coated on quartz crystals. The methodology, being accurate and reproducible with a standard error of ±2.4%, was applied to a range of organophosphate esters (OPEs) and polymers with varying physicochemical properties. The release of most OPEs reached an apparent steady-state within 10 h. The release curves for the studied OPEs could be fitted using a Weibull model, which shows that the release is a two-phase process with an initial fast phase driven by partitioning of OPEs readily available at or close to the polymer film surface, and a slower phase dominated by diffusion in the polymer. The kinetics of the first emission phase was mainly correlated with the hydrophobicity of the OPEs, whereas the diffusion phase was weakly correlated with molecular size. The developed QCM- based method for assessing and studying release of organic chemicals from a polymeric matrix is well suited for rapid screening of additives in efforts to identify more sustainable replacement polymer additives with lower emission potential.
机译:塑料材料包含各种添加剂,这些添加剂可能会在塑料的整个使用寿命中释放出来,并威胁到环境和人类健康。尽管我们了解添加剂从产品中泄漏的知识,但仍缺乏准确,快速的研究排放动力学的方法,尤其是无法深入理解聚合物/添加剂相互作用的方法。在这里,我们报告了一种使用石英晶体微量天平(QCM)来测量旋涂在石英晶体上的聚合物薄膜向水中排放添加剂的新颖方法。该方法准确,可重复,标准误差为±2.4%,适用于一系列具有不同理化性质的有机磷酸酯(OPE)和聚合物。大多数OPE的释放在10小时内达到了明显的稳态。所研究的OPE的释放曲线可以使用Weibull模型拟合,这表明释放是一个两相过程,其初始快相由在聚合物膜表面或附近容易获得的OPE的分配驱动,而速度较慢相以在聚合物中的扩散为主。第一发射相的动力学主要与OPE的疏水性相关,而扩散相与分子大小的相关性较弱。评估和研究有机化学物质从聚合物基体中释放出来的基于QCM的开发方法非常适合快速筛选添加剂,以努力确定具有较低排放潜力的更可持续的替代聚合物添加剂。

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