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文物收藏中的塑料:聚氯乙烯的降解与特性研究。

Plastics in heritage collections: poly(vinyl chloride) degradation and characterization.

出版信息

Acta Chim Slov. 2020 Dec;67(4):993-1013.

Abstract

Museums and galleries house increasingly large collections of objects and contemporary art made of plastic materials, many of which undergo rapid material change. The main degradation processes of poly(vinyl chloride) (PVC) are elimination of HCl and plasticizer migration or leaching. This results in visible discolouration, stickiness and cracking. Degradation is known to be a multi-stage process that includes HCl elimination, formation of conjugated polyenes and cross-linking. Elimination of HCl begins due to structural irregularities (allylic and tertiary chlorides) and results in the formation of polyenes. When at least 7 conjugated double bonds are present, discolouration of PVC becomes visible. Non-invasive techniques, such as IR and Raman spectroscopy are used for polymer identification and plasticizer quantification. Plasticizer degradation and particularly the late stages of PVC degradation can be investigated using SEC, GC-MS, TGA and DSC. Studies in heritage collections have revealed that, apart from HCl, PVC objects emit 2-ethylhexanol and other volatile degradation products, however, there is currently no indication that HCl is emitted at usual indoor conditions. There seems to be a general lack of systematic research into PVC degradation at the conditions of storage and display, which could result in the development of dose-response functions and in the development of preventive conservation guidelines for the management of PVC collections.

摘要

博物馆和美术馆收藏了越来越多的塑料材料制成的文物和当代艺术品,其中许多材料都在迅速发生物质变化。聚氯乙烯(PVC)的主要降解过程是消除 HCl 和增塑剂的迁移或浸出。这会导致明显的变色、粘性和开裂。降解被认为是一个多阶段的过程,包括 HCl 的消除、共轭聚烯烃的形成和交联。HCl 的消除始于结构不规则性(烯丙基和叔氯),并导致聚烯烃的形成。当存在至少 7 个共轭双键时,PVC 的变色变得可见。IR 和拉曼光谱等非侵入性技术用于聚合物识别和增塑剂定量。使用 SEC、GC-MS、TGA 和 DSC 可以研究增塑剂降解,特别是 PVC 的后期降解。对文物藏品的研究表明,除了 HCl,PVC 制品还会释放 2-乙基己醇和其他挥发性降解产物,但目前没有迹象表明在通常的室内条件下会释放 HCl。似乎缺乏对存储和展示条件下 PVC 降解的系统研究,这可能导致剂量反应函数的发展,并为 PVC 藏品的管理制定预防性保护指南。

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