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Thermal decomposition characteristics of poly(propylene carbonate) using TG/IR and Py-GC/MS techniques

机译:TG / IR和Py-GC / MS技术分析聚碳酸亚丙酯的热分解特性

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摘要

The thermal decomposition behaviour of poly(propylene carbonate)s (PPC)s synthesized with varying molecular weights was studied at various pyrolysis temperatures by the combination of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and thermogravimetric analysis/infrared spectrometry (TG/IR) techniques. The pyrolysis products of PPCs with lower molecular weight of 26,900 and higher molecular weight of 144,600 at different pyrolysis temperatures were identified using Py-GC/MS. The dynamic decomposition was also explored with the TG/IR technique. The results showed that chain scission occurs at relatively lower temperature than for the unzipping reaction, and an increase in molecular weight can reduce the amount of the active terminal groups and restrict unzipping reaction to some extent. It was also observed that the backbone structure plays a great role in thermal decomposition behaviour of PPC. The same perfectly alternating structure leads to the same decomposition mechanism whereas unzipping needs a high activation energy and takes place at high decomposition temperature. The final pyrolysates are cyclic propylene carbonate, and 1,2 propanediol. Low molecular weight PPC undergoes a one-stage pyrolysis and high molecular weight PPC pyrolysis obeys two-step pyrolysis mechanism, viz. main chain random scission and unzipping. The thermal decomposition behaviour of PPC in the absence and presence of a metal complex catalyst was studied by TG/IR. It was further observed that the metal complex catalyst has little effect on the thermal decomposition of the PPC. The catalyst only slightly reduced the activation energy leading to the accelerated depolymerization reaction. (C) 2003 Elsevier Science Ltd. All rights reserved. [References: 30]
机译:通过热解-气相色谱/质谱(Py-GC / MS)和热重分析/红外光谱的结合,研究了在不同的热解温度下,不同分子量的聚碳酸亚丙酯(PPC)的热分解行为。 (TG / IR)技术。使用Py-GC / MS鉴定了在不同热解温度下分子量分别为26,900和分子量较高的144,600的PPC的热解产物。还使用TG / IR技术探索了动态分解。结果表明,在比解链反应低的温度下发生断链,并且分子量的增加可以减少活性末端基团的量并在一定程度上限制解链反应。还观察到主链结构在PPC的热分解行为中起重要作用。相同的完全交替的结构导致相同的分解机理,而拉开拉链则需要很高的活化能并在很高的分解温度下发生。最终的热解产物是环状碳酸亚丙酯和1,2-丙二醇。低分子量PPC经历一级热解,而高分子量PPC则遵循两步热解机理,即。主链随机断裂和拉开。通过TG / IR研究了在不存在和存在金属络合物催化剂的情况下PPC的热分解行为。进一步观察到金属络合物催化剂对PPC的热分解影响很小。催化剂仅稍微降低了活化能,导致加速的解聚反应。 (C)2003 Elsevier ScienceLtd。保留所有权利。 [参考:30]

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