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使用石英晶体微天平研究聚合物添加剂向水中的排放过程——以有机磷酸酯为例。

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

机构信息

Department of Chemistry, Umeå University, 901 87 Umeå, Sweden.

出版信息

Environ Sci Technol. 2020 Apr 21;54(8):4876-4885. doi: 10.1021/acs.est.9b07607. Epub 2020 Apr 1.

Abstract

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.

摘要

塑料材料含有各种添加剂,这些添加剂在塑料的整个生命周期中都可能释放出来,对环境和人类健康构成威胁。尽管我们了解添加剂从产品中泄漏的情况,但仍缺乏准确和快速的方法来研究排放动力学,特别是缺乏能够深入了解聚合物/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天平(QCM)测量旋涂在石英晶体上的聚合物薄膜向水中释放添加剂的新方法。该方法具有准确性和可重复性,标准误差为±2.4%,适用于一系列具有不同物理化学性质的有机磷酸酯(OPEs)和聚合物。大多数 OPEs 的释放在 10 小时内达到明显的稳态。研究 OPEs 的释放曲线可以用 Weibull 模型拟合,表明释放是一个两阶段过程,初始快速阶段由聚合物薄膜表面附近或表面上易于获得的 OPEs 的分配驱动,较慢阶段由聚合物中的扩散主导。第一排放阶段的动力学主要与 OPEs 的疏水性相关,而扩散阶段与分子大小的相关性较弱。开发的基于 QCM 的方法用于评估和研究有机化学物质从聚合物基质中的释放,非常适合快速筛选添加剂,以确定具有更低排放潜力的更可持续的替代聚合物添加剂。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7bb1/7884016/c5c7af668dab/es9b07607_0001.jpg

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