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回收利用和氟聚合物的使用寿命评估:最新进展、挑战与未来趋势。

Recycling and the end of life assessment of fluoropolymers: recent developments, challenges and future trends.

机构信息

ICGM, University of Montpellier, CNRS, ENSCM, 34095 Montpellier, France.

Kanagawa University, Faculty of Science, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan.

出版信息

Chem Soc Rev. 2023 Jul 3;52(13):4208-4247. doi: 10.1039/d2cs00763k.

Abstract

Herein, we present the state of the art technology on the recycling, reuse, thermal decomposition (by thermolysis, thermal processing, flash pyrolysis, smoldering, open burning, open-air detonation, and incineration), and the life cycle assessment of fluoropolymers (FPs, ranging from poly(tetrafluoroethylene), PTFE, and poly(vinylidene fluoride), PVDF, to various fluorinated copolymers based on VDF and TFE). FPs are niche specialty polymers endowed with exceptional properties and have found many applications in high-tech industries. However, compared to other polymers, the reuse of FPs is still not well-established and is in its infancy. Accordingly, their recycling has attracted increasing interest, even reaching the pilot stage. In addition, recently, several studies have been reported on vitrimers, which are regarded as polymers ranking between thermosets and thermoplastics. In this case, although many articles have reported to date on the thermal degradation of these technical polymers, intensive efforts have been devoted to avoiding the release of low molar mass oligomers and per- and poly-fluoroalkyl substances (PFAS, and especially polymerisation aids such as perfluorooctanoic acid (PFOA) and its alternatives), while various reports demonstrated the complete decomposition of PTFE, leading to the formation of TFE (and hexafluoropropylene or octafluorocyclobutane to a lesser extent). Incineration is one of only a few technologies that can potentially degrade FPs and completely degrade PTFE and other PFAS from 850 °C. Recent studies on the mineralisation of FPs under subcritical water represent an interesting approach to close the loop of the fluorine chemistry cycle. Because of the high molar masses (several million for PTFE) and thermal, chemical, photochemical, and hydrolytic inertness and biological stability of FPs, it has been clearly evidenced that they satisfy the 13 accepted regulatory assessment criteria to be considered as polymers of low concern.

摘要

在此,我们介绍了氟聚合物(从聚四氟乙烯(PTFE)和聚偏二氟乙烯(PVDF)到基于 VDF 和 TFE 的各种氟化共聚物)的回收、再利用、热分解(通过热解、热加工、闪蒸热解、闷烧、露天燃烧、露天爆炸和焚烧)以及生命周期评估的最新技术。氟聚合物是具有特殊性能的利基特种聚合物,已在高科技行业中得到了广泛应用。然而,与其他聚合物相比,氟聚合物的再利用仍未得到很好的建立,仍处于起步阶段。因此,它们的回收已引起越来越多的关注,甚至已进入试点阶段。此外,最近,有几项关于 vitrimers 的研究报告,vitrimers 被认为是介于热固性塑料和热塑性塑料之间的聚合物。在这种情况下,尽管迄今为止已有许多文章报道了这些技术聚合物的热降解,但人们仍致力于避免低摩尔质量低聚物和全氟及多氟烷基物质(PFAS,尤其是聚合助剂如全氟辛酸(PFOA)及其替代品)的释放,同时各种报告表明 PTFE 完全分解,导致 TFE(以及六氟丙烯或八氟环丁烷的形成程度较小)的形成。焚烧是少数几种有可能降解氟聚合物并在 850°C 下完全降解 PTFE 和其他 PFAS 的技术之一。最近在亚临界水中对氟聚合物矿化的研究代表了一种有趣的方法,可以实现氟化学循环的闭环。由于氟聚合物的摩尔质量很高(PTFE 为几百万),并且具有热、化学、光化学和水解惰性以及生物稳定性,因此已经清楚地证明它们满足 13 个公认的监管评估标准,被认为是低关注聚合物。

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