Analytical pyrolysis coupled to gas chromatography and mass spectrometry (Py-GC–MS) can provide both qualitative and quantitative data on polymer mixtures, but no standardized protocols are available yet for the application of this technique in the field of environmental microplastics analysis. In this paper, we describe the preparation of a mixture of eleven common polymers, that could be used as reference sample for microplastics analysis in environmental samples by Py-GC–MS. The mixture is obtained combining two solutions with a total of nine polymers, and a solid mixture of two polymers with an inorganic diluent. First, a set of characteristic pyrolysis products and m/z signals is proposed as markers to perform semi-quantitative calculations. Then, changes in the pyrolytic yields of characteristic products due to secondary reactions in the pyrolytic environment are systematically evaluated. The characteristic pyrolysis product of polyurethane (PU), 4,4’-diphenylmethane diisocyanate (MDI), was found to be highly susceptible to hydrolysis by the inorganic diluent, except when deactivated silica was used. Finally, the performance of the reference mixture using the silica diluent is evaluated in terms of reproducibility and linearity of response. Relative standard deviations lower than 10% and good linearity of the integrated areas (r² > 0.96) were obtained for all polymers except PU and polyethylene terephthalate. The results show that the proposed mixture could be used in Py-GC–MS analyses of microplastics as a reliable reference material for at least nine of the eleven investigated polymers.

分析热解与气相色谱和质谱联用（Py-GC-MS）可以提供聚合物混合物的定性和定量数据，但尚无标准化方案可用于该技术在环境微塑料分析领域的应用。在本文中，我们描述了11种常见聚合物的混合物的制备方法，该混合物可用作通过Py-GC-MS分析环境样品中的微塑性的参考样品。得到的混合物是将两种溶液与总共九种聚合物混合，以及两种聚合物与无机稀释剂的固体混合物的混合物。首先，一组典型的热解产物和m / z信号被建议用作执行半定量计算的标记。然后，系统地评估了由于热解环境中的二次反应导致的特征产物的热解产率的变化。发现聚氨酯（PU）的特征热解产物4,4'-二苯基甲烷二异氰酸酯（MDI）对无机稀释剂极易水解，除非使用了失活的二氧化硅。最后，根据可再现性和响应线性评估了使用二氧化硅稀释剂的参考混合物的性能。相对标准偏差低于10％，并且积分区域具有良好的线性度（r ²对于除聚氨酯和聚对苯二甲酸乙二酯以外的所有聚合物，均获得了> 0.96）。结果表明，建议的混合物可用于微塑料的Py-GC-MS分析，作为至少11种研究聚合物中9种的可靠参考材料。