Upcycling of polyethylene waste to biodegradable adhesive and coating via Baeyer-Villiger reaction: A new view on oxidation-fracture mechanism and structure-function relationship

• Published in: Polymer (Guilford) 2024-11, Vol.313, p.127689, Article 127689
• Main Authors: Shen, Chengfeng, Zhang, Qiang, Wei, Xiangyue, Ye, Pengbo, Liu, Xuehui, Xu, Shimei, Wang, Yu-Zhong
• Format: Article
• Language: English
• Subjects: Adhesive; Baeyer-villiger oxidation; Coating; Interfacial forces; Polyethylene
• ISSN: 0032-3861
• DOI: 10.1016/j.polymer.2024.127689

Non-biodegradable polyethylene waste accumulates in large quantities in the environment posing a serious threat to the survival of creatures. Meanwhile, polyethylene suffers from inherent polarity limitations that curtails its application scope. Oxidation is an efficient approach of upcycling waste polyethylene through introduction of hydrophilic functional groups (such as –COOH, –OH), yet often at the expense of their original hydrophobicity. Herein, the hydrophobic ester groups, were introduced via Baeyer-Villiger oxidation to ingeniously balance the contradiction among hydrophobicity, interfacial forces and sustainability of polyethylene oxidation products. A tandem conversion mechanism among the oxidative groups was proposed while the decrease in molecular weight and branching degree was clarified to be a result of β-scissions occurring the branches during the oxidation. Meanwhile, the effect of oxidation degree and molecular weight on interfacial forces was revealed. The excellent hydrophobicity and corrosion resistance of the oxidized polyethylene coating can be attributed to the low content of carboxyl/hydroxyl groups, rich hydrophobic ester groups and the retained long carbon chain structure. Besides, the introduced ester groups and lower molecular weight also provided the oxidation products with potential biodegradability. This work provided a new insight on the Baeyer-Villiger oxidation of polyethylene and the potential for upcycling of polyethylene waste into sustainable materials. [Display omitted] •The ester groups introduced by B–V oxidation of LDPE improved interfacial forces.•Oxidized PE shows good adhesion, coating and corrosion resistance.•-OH/-CO groups convert into ester groups tandemly and drop to stable low level.•It is β-scissions at branches not ester break caused decrease in molecular weight.