Abe Itsuki, Shibata Mitsuhiro
Department of Applied Chemistry, Faculty of Engineering, Chiba Institute of Technology, 2-17-1, Tsudanuma, Narashino 275-0016, Chiba, Japan.
Molecules. 2024 Oct 12;29(20):4839. doi: 10.3390/molecules29204839.
The condensation reactions of 4,4'-(ethane-1,2-diylbis (oxy)) bis(3-methoxybenzaldehyde) (VV) with cystamine, 1,6-hexamenthylene diamine, and a dimer diamine (Priamine 1075) produced three types of vanillin-derived imine-and disulfide-containing diamines (VC, VH, and VD, respectively). Thermal curing reactions of polyglycerol polyglycidyl ether with VD and mixtures of VC/VD and VH/VD produced bio-based epoxy vitrimers (BEV-VD, BEV-VC/VD, and BEV-VH/VD, respectively). The degree of swelling and gel fraction tests revealed the formation of a network structure, and the crosslinking density increased with a decreasing VD fraction. The glass transition temperature, tensile strength, and tensile modulus of the cured films increased as the VD fraction decreased. In contrast, the thermal degradation temperature of the cured films increased as the VD fraction increased. All the cured films were healed by hot pressing at 120 °C for 2 h under 1 MPa at least three times. The healing efficiencies, based on tensile strength after the first healing treatment, were 75-78%, which gradually decreased as the healing cycle was repeated. When imine-and disulfide-containing BEV-VC/VD and imine-containing BEV-VH/VD with the same VC/VD and VH/VD ratios were used, the former exhibited a slightly higher healing efficiency.
4,4'-(乙烷-1,2-二基双(氧基))双(3-甲氧基苯甲醛)(VV)与胱胺、1,6-己二胺和二聚二胺(Priamine 1075)的缩合反应分别生成了三种类型的含香草醛衍生亚胺和二硫键的二胺(分别为VC、VH和VD)。聚甘油聚缩水甘油醚与VD以及VC/VD和VH/VD混合物的热固化反应分别生成了生物基环氧可修复聚合物(分别为BEV-VD、BEV-VC/VD和BEV-VH/VD)。溶胀度和凝胶分数测试表明形成了网络结构，且交联密度随着VD比例的降低而增加。固化膜的玻璃化转变温度、拉伸强度和拉伸模量随着VD比例的降低而升高。相反，固化膜的热降解温度随着VD比例的增加而升高。所有固化膜在120℃、1MPa下热压2h至少三次后均可愈合。基于第一次愈合处理后的拉伸强度，愈合效率为75 - 78%，随着愈合循环次数的增加逐渐降低。当使用具有相同VC/VD和VH/VD比例的含亚胺和二硫键的BEV-VC/VD和含亚胺的BEV-VH/VD时，前者表现出略高的愈合效率。
