Qiannan Zheng,Dengfeng Wang,Xiujin Gong,Lin Liu,Han Wu,Zihan Li,Haojie Hong,Juming Yao
The development of high-performance biodegradable polylactic acid (PLA) materials integrating high strength, malleability and toughness is desired but an ongoing challenge. In this work, a novel full-biobased block copolymer was designed and synthesized by grafting L (+)-lactide (L-LA) and ε -caprolactone ( ε -CL) onto lignin via ring-opening polymerization. The obtained lignin-PLA-PCL block copolymer was composed of rigid lignin and poly (LA-CL) rubber segment, could self-assemble into uniform nano-micelles with average diameters of 80–100 nm regulated by simply altering copolymer content. The incorporation of lignin-PLA-PCL copolymers into PLA matrix induced the formation of many cavities, promoted free volume between PLA matrix and copolymer to accelerate chain mobility, achieving excellent ductility and stretchability with maximum stretching deformation of 64.8 %. The resultant PLA composites with the copolymer content as low as 5 wt% displayed simultaneously improved strength (41.84 MPa) and toughness (8.1 MJ/m 3 ), 6.7 % and 1520 % increment than those of neat PLA, respectively. The reinforcing and toughening mechanisms were explored and verified that the combination of cavity growth and fibrillation, followed by extensive shear yielding of matrix, causing substantial plastic deformation. This study extended the design strategy and the foundation for simultaneous reinforcing and toughening PLA plastics using lignin-derived rubbery micelles.
Yan Zhang,Jiaoman Li,Xinxing Wu,Dongyue Wang,Shengnan Zhou,Shuaibo Han,Hui Wang,Fangli Sun
To improve the compatibility and reactivity of lignosulfonate (LS) with epoxy oligomers, the LS was firstly functionalized with anhydride via the carboxylation reaction . The carboxylated lignosulfonate (CLS) reinforced epoxy resin with excellent mechanical and shape memory performance was prepared facilely via distributing the CLS into the combined epoxy monomers of DGEBA and PEGDGE with the aid of water, rather than using the normal organic solvents . The incorporated CLS promoted the curing reaction of epoxy resin. A typical sea-island structure was formed in the cured sample at the CLS content of 5 phr, exhibiting the highest increases in tensile strength , modulus, elongation at break and toughness by 23.8 %, 18.2 %, 217 % and 113 %, respectively, relative to neat epoxy. Interestingly, the incorporation of CLS at a proper amount led to the simultaneous strengthening and toughing effects on cured epoxy resin, which could be attributed to the rigid structure of CLS covalently introduced in the epoxy resin network and the heterogeneous structure formed in the epoxy matrix. The rigid CLS component also restrained the movement of chain segments, consequently, the mechanical stability was enhanced and the fast shape recovery rate of epoxy resin network was slowed down to some extent.