Many industrial polymers which find application in contemporary materials are copolymers. Copolymers feature multiple distributions, that govern their physical properties, including the sequence distribution. Styrene-acrylate copolymers are an important class of polymers, their monomer sequence is typically determined by ¹³C NMR which suffers from low sensitivity and spectral resolution. A series of studies have shown that Py-GC can be applied to determine the sequence length of copolymers. The accuracy of the trimer assignments and the appropriate calibration approaches yielding reliable data have however not yet been validated. In the present study we propose a comprehensive workflow to ensure the accuracy of the sequence determination by Py-GC, next to NMR. In-depth analysis of the trimers observed in the Py-GC pyrograms of model styrene-acrylate copolymers was performed and specific MS fragments relating to the trimer sequence were assigned. A comparison of a series of copolymers yielded reliable assignments for the trimer signals. The obtained sequence lengths were in agreement with those calibrated with the benchmark method, ¹³C NMR. Py-GC was found to consistently underestimate the acrylate sequence length. Py-GC calibration with ¹³C NMR was thus found to be indispensable for the accurate absolute quantification of the sequence length by Py-GC. The calculated randomness did not vary significantly after NMR calibration, indicating that NMR calibration might not be required in all cases to obtain (relative) information on the sequence of a copolymer.

许多在现代材料中得到应用的工业聚合物都是共聚物。共聚物具有多重分布，这决定了它们的物理性质，包括序列分布。苯乙烯-丙烯酸酯共聚物是一类重要的聚合物，其单体序列通常由¹³C NMR 具有低灵敏度和光谱分辨率。一系列研究表明，Py-GC 可用于确定共聚物的序列长度。然而，尚未验证三聚体分配的准确性和产生可靠数据的适当校准方法。在本研究中，我们提出了一个全面的工作流程，以确保 Py-GC 的序列测定准确性，仅次于 NMR。对模型苯乙烯-丙烯酸酯共聚物的 Py-GC 热解图中观察到的三聚体进行了深入分析，并指定了与三聚体序列相关的特定 MS 片段。一系列共聚物的比较产生了三聚体信号的可靠分配。获得的序列长度与用基准方法校准的序列长度一致，¹³C核磁共振。发现 Py-GC 始终低估丙烯酸酯序列长度。^{因此，发现使用13} C NMR 进行Py-GC 校准对于通过 Py-GC 对序列长度进行准确的绝对定量是必不可少的。计算出的随机性在 NMR 校准后没有显着变化，表明可能并非在所有情况下都需要 NMR 校准来获得有关共聚物序列的（相对）信息。