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通过使用邻苯二甲酸二异壬酯基团进行化学改性,将聚氯乙烯废料降解为一种柔性聚合物。

Degradation of PVC waste into a flexible polymer by chemical modification using DINP moieties.

作者信息

Lu Lihui, Kumagai Shogo, Kameda Tomohito, Luo Ligang, Yoshioka Toshiaki

机构信息

Graduate School of Environmental Studies, Tohoku University 6-6-07 Aoba, Aramaki-aza, Aoba-ku Sendai Miyagi 980-8579 Japan

College of Life Science, Shanghai Normal University 100 Guilin Road Shanghai 200234 China

出版信息

RSC Adv. 2019 Sep 13;9(49):28870-28875. doi: 10.1039/c9ra05081g. eCollection 2019 Sep 9.

Abstract

In consideration of the toxicity and high migration capacity of plasticizers, the possibility to obtain flexible PVC chemical modification of PVC was investigated for feedstock recycling. In this work, some Cl atoms of PVC were substituted with fragments of the common plasticizer DINP (diisononyl phthalate) in the presence of KCO (potassium carbonate) or DIEA (,-diisopropylethylamine), and the simultaneous elimination of PVC was suppressed. H NMR (H nuclear magnetic resonance spectroscopy) and H-H COSY (H-H correlation spectroscopy) were used to evaluate the substitution while a novel method of calculating the substitution and elimination ratios was developed using a combination of H NMR and elemental analysis. A maximum substitution rate of 35.7% was achieved using thiophenol as a nucleophile in the presence of DIEA, while the corresponding elimination of HCl was just 4.4%. In addition, the thermal stability of the modified PVCs was very close to that of pure PVC, which suggested that the main characteristics of PVC were preserved. Moreover, the values of all the modified PVCs were less than that of PVC, which means it is feasible to improve the plasticity of PVC substituting some Cl on PVC with DINP moieties. Therefore, an alternative approach for feedstock recycling of PVC by chemical modification was developed in this work.

摘要

考虑到增塑剂的毒性和高迁移能力,为了原料回收,研究了通过聚氯乙烯(PVC)的化学改性来获得软质PVC的可能性。在这项工作中,在碳酸钾(KCO)或二异丙基乙胺(DIEA)存在的情况下,PVC的一些氯原子被常见增塑剂邻苯二甲酸二异壬酯(DINP)的片段取代,同时抑制了PVC的消除。使用氢核磁共振光谱(H NMR)和氢-氢相关光谱(H-H COSY)来评估取代情况,同时开发了一种结合H NMR和元素分析来计算取代和消除率的新方法。在DIEA存在下,使用苯硫酚作为亲核试剂时,最大取代率达到35.7%,而相应的氯化氢消除率仅为4.4%。此外,改性PVC的热稳定性与纯PVC非常接近,这表明PVC的主要特性得以保留。而且,所有改性PVC的 值均小于PVC的 值,这意味着用DINP部分取代PVC上的一些氯来提高PVC的可塑性是可行的。因此,这项工作开发了一种通过化学改性对PVC进行原料回收的替代方法。

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