Department of Chemical, Pharmaceutical and Agricultural Sciences, University of Ferrara, via L. Borsari 46, 44124 Ferrara, Italy.
Department of Quality & Environment, DIAB Spa, Longarone, BL, Italy.
Waste Manag. 2022 Nov;153:229-239. doi: 10.1016/j.wasman.2022.09.001. Epub 2022 Sep 18.
Rigid semi-Interpenetrated Polymer Network (semi-IPN) foam based on poly(vinyl chloride) (PVC) and crosslinked polyurea/isocyanurate are complex materials that at present are not recyclable. They are used in many fields, including wind blade cores. In this work we studied the depolymerization of the crosslinked portion of the foam under glycolysis conditions for the separation and reuse of the individual components. Reaction products were characterized by FT-IR, NMR, solvent solubility, DSC, elemental analysis, titration of amine and hydroxyl groups and rheology measurements. Triisocyanurates and urea moieties were synthesized and used as model compounds. Glycolysis conditions were optimized to maximize depolymerization while minimizing PVC degradation. The parameters studied were reaction time (8 min to 3 h), temperature (155 to 200 °C), catalyst (potassium acetate or dibutyl tin dilaurate (DBTL)), glycol (ethylene glycol, 1,4 butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol), as well as the effect of PVC thermal stabilizers such as hindered phenols and organo-phosphites. The results showed that the optimal reaction condition for foam glycolysis is 165-175 °C for 20-30 min, using DBTL as catalyst and including thermal stabilizers. No drastic difference was noticed by the kind of glycol used, except for PEG that led to greater PVC degradation. The greatest part of the crosslinked portion (≥90 %) was depolymerized and the result were mainly hydroxyl- and in minor amount amine- terminated oligomers. The recovered PVC (purity roughly 90 %) had a low degree of degradation and a viscosity suitable for its processing as thermoplastic material, i.e. by injection moulding.
刚性半互穿聚合物网络(半 IPN)泡沫基于聚氯乙烯(PVC)和交联聚脲/异氰脲酸酯,是目前不可回收的复杂材料。它们被广泛应用于多个领域,包括风力叶片芯材。在这项工作中,我们研究了在醇解条件下泡沫交联部分的解聚,以分离和再利用各个组分。通过傅里叶变换红外光谱(FT-IR)、核磁共振(NMR)、溶剂溶解度、差示扫描量热法(DSC)、元素分析、胺基和羟基滴定以及流变学测量对反应产物进行了表征。还合成了三异氰酸酯和脲基部分,并将其用作模型化合物。优化了醇解条件,以最大限度地提高解聚度,同时最小化 PVC 的降解。研究的参数包括反应时间(8 分钟至 3 小时)、温度(155 至 200°C)、催化剂(乙酸钾或二月桂酸二丁基锡(DBTL))、二醇(乙二醇、1,4-丁二醇、二乙二醇、二丙二醇、聚乙二醇),以及 PVC 热稳定剂如受阻酚和有机亚磷酸酯的影响。结果表明,泡沫醇解的最佳反应条件为 165-175°C 反应 20-30 分钟,使用 DBTL 作为催化剂,并包含热稳定剂。所使用的二醇种类没有明显差异,除了 PEG 会导致更大程度的 PVC 降解。交联部分的大部分(≥90%)被解聚,得到的主要是羟基封端和少量胺封端的低聚物。回收的 PVC(纯度约 90%)降解程度低,粘度适合作为热塑性材料进行加工,例如注塑成型。