硫代杯[4]芳烃对Mn或Cu催化天然橡胶热氧老化的影响研究  

Effect of Sulfothiacalix[4]arene on Mn or Cu Catalyzed Thermo-oxidative Aging of Natural Rubber

作　　者：陈念 于人同[1] 廖建和[1] CHEN Nian;YU Rentong;LIAO Jianhe(School of Materials Science and Engineering,Hainan University,Haikou,Hainan 570228,China)

机构地区：[1]海南大学材料科学与工程学院,海南海口570228

出　　处：《热带作物学报》2024年第10期2192-2200,共9页Chinese Journal of Tropical Crops

基　　金：国家重点研发计划项目(No.2022YFD230120201);海南大学热带高效农业产业技术体系专项资金(No.THAITS-3)。

摘　　要：杯[4]芳烃作为一类主体化合物,由于其独特的分子结构,可以通过氢键、静电力或范德华作用力等与客体分子结合形成主-客体化合物。在杯[4]芳烃桥接结构上引入硫原子后可以使其空腔尺寸变大,同时硫原子特有的识别作用,与天然橡胶中微量的过渡金属铜(Ⅱ)或锰(Ⅱ)有很强的配位能力,形成结构稳定的磺化硫代杯[4]芳烃-金属配合物后可抑制过渡金属在天然橡胶热氧老化中的催化作用,达到改善天然橡胶热氧老化性能的目的。在本研究中,我们合成了磺化硫代杯[4]芳烃并通过FTIR、DSC和TGA等分析探究磺化硫代杯[4]芳烃在过渡金属离子铜(Ⅱ)或锰(Ⅱ)催化天然橡胶热氧老化中的防护效果。与未添加磺化硫代杯[4]芳烃组样品相比,添加组样品的FTIR谱图中O-H、C=O和C=C的信号均有减弱,DSC曲线上的氧化诱导温度分别提升约18.87℃和29.90℃,TGA中的外延起始热分解温度分别提升11.82℃和15.03℃。这表明磺化硫代杯[4]芳烃在过渡金属离子铜(Ⅱ)或锰(Ⅱ)在催化天然橡胶热氧老化过程中可以作为一种有效的抗热氧老化剂。Calix[4]arene,a class of host compounds,is capable of forming host-guest compounds with guest molecules through hydrogen bonding,electrostatic forces,or van der Waals forces.With the incorporation of sulfur atoms into the molecular structure of calix[4]arene,the cavity size of calix[4]arene would increase.At the same time,sulfur atoms offer strong coordination abilities to trace amounts of variable metallic ions(Mn2+,Cu2+)presented in natural rubber.The complexes prepared by sulfothiacalix[4]arene salt and metal ions can mitigate catalytic effects of variable metallic ions on the aging reactions of natural rubber,thus improving the thermal oxidative aging performance of natural rubber.Sulfothiacalix[4]arene was synthesized and the protective effect of sulfothiacalix[4]arene on the thermo-oxidative aging behavior of natural rubber was investigated by means of FTIR,DSC,TGA and so on.After the experiment,compared with the samples without the addition of sulfothiacalix[4]arene,it was found that the signals of O-H,C=O and C=C in the FTIR spectra of the samples with the addition group were weakened,the thermo-oxidative aging temperatures on the DSC curve were increased by about 18.87℃and 29.90℃,and the epitaxial initial thermal decomposition temperatures in TGA were increased by 11.82℃and 15.03℃,respectively.It is concluded that sulfothiacalix[4]arene could be used as a highly effective anti-aging agent in the thermo-oxidative aging of natural rubber.

关 键 词：芳烃 过渡金属配合物 天然橡胶 热氧老化 

分 类 号：TQ332[化学工程—橡胶工业]