A thermoanalytical insight into the composition of biodegradable polymers and commercial products by EGA-MS and Py-GC-MS
A thermoanalytical insight into the composition of biodegradable polymers and commercial products by EGA-MS and Py-GC-MS
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DOI：
10.1016/j.jaap.2023.105937
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发表时间：
2023-03
影响因子：
6
通讯作者：
F. De Falco;T. Nacci;Lee J. Durndell;Richard Thompson;I. Degano;F. Modugno
中科院分区：
文献类型：
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作者：
F. De Falco;T. Nacci;Lee J. Durndell;Richard Thompson;I. Degano;F. Modugno
生物可降解聚合物被认为是解决塑料污染相关环境问题的潜在方案。在农业覆盖物和渔具等应用中提出了潜在的惠益，因为在这些应用中，在使用寿命结束时从环境中回收产品可能会有相当大的困难。生物降解是一个复杂的过程，受材料特性和需要生物降解的接收环境的影响。评估降解过程需要通过可靠的分析方法表征可生物降解产品的化学成分（即聚合物和添加剂）。热解与气相色谱和质谱联用（Py-GC-MS）和逸出气体分析与质谱联用（EGA-MS）是新兴的塑料材料分析技术，与更广泛使用的光谱技术（FTIR和拉曼）相比，提供了更高的灵敏度和分辨率。在这项工作中，我们已经应用了一个系统的方法相结合的EGA-MS和多枪Py-GC-MS的热分析调查的5个可生物降解的聚合物和5个生物降解标记的商业产品。我们确定了聚合物PBAT，PBS，PBHV和两种类型的PLA的热降解曲线，主要/区域和热解标记。我们应用所获得的信息，调查4地膜和1渔网的组成。EGA-MS是优化单次或多次热解采集的基础，允许热解产物的最佳Py-GC-MS分离和鉴定。PLA和PBAT被检测到在三个覆盖膜，除了淀粉在膜标记为Mater-Bi和一个未知的组合物。在线硅烷化对于检测含有大麻纤维的复合膜中的多糖是至关重要的。在分析一种新开发的PBSAT树脂制成的渔网时，强调了丁烯、琥珀酸、己二酸和对苯二甲酸单元的存在。最后，Py-GC-MS可有效鉴定添加剂的存在，如1，6-二异氰酸酯基-己烷（扩链剂）和衍生自增塑剂癸二酸二酯的癸二酸二（3-丁烯基）酯。
Biodegradable polymers are proposed as a potential solution to environmental problems related to plastic pollution. Potential benefits have been suggested in applications such as agricultural mulching and fishing gear, where there can be considerable difficulty recovering products from the environment at the end of their service life. Biodegradation is a complex process influenced by both the properties of the material and the receiving environment in which it needs to biodegrade. Assessing the degradation process necessitates the chemical composition (i.e. polymer and additives) of biodegradable products to be characterised by reliable analytical methods. Pyrolysis coupled to Gas Chromatography and Mass Spectrometry (Py-GC-MS) and Evolved Gas Analysis coupled to Mass Spectrometry (EGA-MS) are emerging techniques to characterise plastic materials, providing a greater sensitivity and resolution when compared to more widely used spectroscopic techniques (FTIR and Raman). In this work, we have applied a systematic approach combining EGA-MS and multi-shot Py-GC-MS for the thermoanalytical investigation of 5 biodegradable polymers and 5 biodegradable-labelled commercial products. We identified thermal degradation profiles, mainm/zions and pyrolysis markers for the polymers PBAT, PBS, PBHV and two types of PLA. We applied the obtained information to investigate the composition of 4 mulch films and 1 fishing net. EGA-MS was fundamental to optimise single or multi shot pyrolysis acquisition, allowing an optimal Py-GC-MS separation and identification of the pyrolysis products. PLA and PBAT were detected in three mulch films, with the addition of starch in a film labelled as Mater-Bi and in one of unknown composition. Online silylation was crucial for detecting polysaccharides in a composite film containing hemp fibres. The presence of butylene, succinate, adipate and terephthalate units was highlighted analysing a fishing net made of a newly developed PBSAT resin. Finally, Py-GC-MS was effective in identifying the presence of additives such as 1,6-diisocyanato-hexane (chain extender) and di(3-butenyl) ester of sebacic acid derived from the plasticizer dibutyl sebacate.