Chow Cheuk-Fai, Lam Chow-Shing, Lau Kai-Chung, Gong Cheng-Bin
Department of Science and Environmental Studies, The Education University of Hong Kong, 10 Lo Ping Road, Tai Po, Hong Kong, China.
Department of Chemistry, City University of Hong Kong, Kowloon Tong, Hong Kong, China.
Polymers (Basel). 2021 Oct 25;13(21):3672. doi: 10.3390/polym13213672.
A new mechanochemical method was developed to convert polymer wastes, polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PVC), to fuel gases (H, CH, and CO) under ball-milling with KMnO at room temperature. By using various solid-state characterizations (XPS, SEM, EDS, FTIR, and NMR), and density functional theory calculations, it was found that the activation followed the hydrogen atom transfer (HAT) mechanism. Two metal oxidant molecules were found to abstract two separate hydrogen atoms from the α-CH and β-CH units of substrates, [-CH-CH(R)-], where R = H in PE, R = CH in PP, and R = Cl in PVC, resulting in a di-radical, [-CH-C(R)-]. Subsequently, the two unpaired electrons of the di-radical were recombined into an alkene intermediate, [-CH = C(R)-], which underwent further oxidation to produce H, CH, and CO gases.
开发了一种新的机械化学方法,在室温下用高锰酸钾球磨,将聚合物废料聚乙烯(PE)、聚丙烯(PP)和聚氯乙烯(PVC)转化为燃料气体(H、CH和CO)。通过各种固态表征(XPS、SEM、EDS、FTIR和NMR)以及密度泛函理论计算,发现活化遵循氢原子转移(HAT)机制。发现两个金属氧化剂分子从底物[-CH-CH(R)-]的α-CH和β-CH单元中提取两个单独的氢原子,其中PE中R = H,PP中R = CH,PVC中R = Cl,生成双自由基[-CH-C(R)-]。随后,双自由基的两个未成对电子重新组合成烯烃中间体[-CH = C(R)-],该中间体进一步氧化生成H、CH和CO气体。