基于芳香亚胺和二硫键聚氨酯的制备及太阳光诱导自修复性能  

Preparation of polyurethane based on aromatic imine and disulfide bonds with sunlight-induced self-healing properties

作　　者：刘文龙 辛翰奇 刘立佳[1,2] 王玉丹 董红星[1] LIU Wenlong;XIN Hanqi;LIU Lijia;WANG Yudan;DONG Hongxing(College of Materials Science and Chemical Engineering,Harbin Engineering University,Harbin 150001,Heilongjiang,China;Yantai Research Institute of Harbin Engineering University,Yantai 264006,Shandong,China)

机构地区：[1]哈尔滨工程大学材料科学与化学工程学院,黑龙江哈尔滨150001 [2]哈尔滨工程大学烟台研究生院,山东烟台264006

出　　处：《精细化工》2025年第3期544-550,691,共8页Fine Chemicals

基　　金：中央高校基本科研业务费项目(3072022QBZ2703);黑龙江省自然科学基金项目(LH2022E045);烟台校地融合发展项目(2022XDRHXMXK08)。

摘　　要：香草醛和对苯二胺经席夫碱反应制备了一种芳香亚胺化合物——4,4'-[1,4-亚苯基双(氮次甲基)]-双(2-甲氧基苯酚)(VPP);以VPP和双(2-氨基苯基)二硫(APD)为扩链剂,向聚氨酯(PU)弹性体中引入芳香亚胺键(Ar—C==N—Ar)和二硫键(S—S)两种动态共价键,制备了具有太阳光诱导自修复能力的PU弹性体材料(PU-VPP-x)(x为VPP物质的量,APD物质的量为8–x,单位为mmol,下同)。通过FTIR、^(1)HNMR、^(13)CNMR、XRD对VPP和PU-VPP-x进行了表征,采用UV-Vis测试了VPP的可见光吸收性能,采用TGA、DSC、电子万能试验机考察了n(VPP)∶n(APD)对PU-VPP-x热性能、力学性能及自修复性能的影响。结果表明,VPP在388 nm的可见光区出现明显的吸收峰,具备可见光吸收能力;PU-VPP-x为无定形材料;由n(VPP)∶n(APD)=1∶3制备的PU-VPP-2的玻璃化转变温度为5.58℃,拉伸强度与断裂伸长率分别为4.80 MPa和582.34%,太阳光照自修复8 h的自修复效率为100.41%。An aromatic imine compound,4,4'-(1,4-phenylenebis(nitrilomethylidyne)-bis(2-methoxyphenol)(VPP),was synthesized from Schiff base reaction of vanillin and p-phenylenediamine.Using VPP and bis(2-aminophenyl)disulfide(APD)as chain extenders,polyurethane(PU)elastomer materials with sunlight-induced self-healing capabilities,denoted as PU-VPP-x[where x represents the amount of substance of VPP(mmol),and the amount of substance of APD is(8–x)mmol,the same below]was prepared by introduction of dynamic covalent bonds including aromatic imine bonds(Ar—C==N—Ar)and disulfide bonds(S—S)into PU elastomer.VPP and PU-VPP-x were characterized by FTIR,^(1)HNMR,^(13)CNMR and XRD,while the visible light absorption performance of VPP was evaluated via UV-Vis.The effects of n(VPP)∶n(APD)on the thermal properties,mechanical properties and self-healing performance of the synthesized PU-VPP-x were analyzed through TGA,DSC and universal testing machine.The results indicated that VPP exhibited a significant absorption peak at 388 nm in the visible light region,confirming its visible light absorption capability.PU-VPP-x showed an amorphous structure.The PU-VPP-2 prepared by n(VPP)∶n(APD)=1∶3 had a glass transition temperature of 5.58℃,a tensile strength of 4.80 MPa,and an elongation at break of 582.34%.The self-healing efficiency of PU-VPP-2 under sunlight irradiation for 8 h was 100.41%.

关 键 词：芳香亚胺键 芳香二硫键 聚氨酯 自修复性能 可见光诱导 功能材料 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]