平衡溶胀法研究谷氨酸二硫代氨基甲酸镧对SBR/SiO_2复合材料界面作用的影响  

STUDIES ON THE INFLUENCE OF LANTHANUM GLUTAMIC DITHIOCARBAMATE ON THE INTERFACIAL REINFORNCEMENT OF SBR/SiO_2 COMPOSITES BY SWELLING EQUILIBRIUM TEST

作　　者：杨树颜[1] 刘岚[1] 贾志欣[1] 贾德民[1] 罗远芳[1] 刘亚蓝[1] 

机构地区：[1]华南理工大学材料科学与工程学院,广州510640

出　　处：《高分子学报》2011年第7期709-717,共9页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号50608034and50873036);华南理工大学中央高校基本科研业务费专项资金(基金号2009ZM0306);广东省大学生创新性实验计划项目(项目号S1010561042)资助

摘　　要：通过合成一种含有二硫代羧基,羧基和镧离子的新型稀土促进剂——谷氨酸二硫代氨基甲酸镧(简称La-GDTC),并利用平衡溶胀法研究了La-GDTC对丁苯橡胶(SBR)/SiO2复合材料界面作用的影响.交联密度测试表明,SiO2的加入能够有效提高SBR/La-GDTC/SiO2复合材料的交联密度;而SBR/La-GDTC/SiO2复合材料的溶胀Gibbs自由能ΔG下降,熵减ΔS上升,表明了复合材料的硫化网络非均匀性提高,SiO2的界面化学环境发生改变;Kraus曲线得到的聚合物-填料相互作用参数证实了La-GDTC能够提高SBR与SiO2的界面黏结.应力-应变曲线表明La-GDTC对SBR/SiO2复合材料的增强作用明显优于二乙基二硫代氨基甲酸锌(ZDC)体系.通过扫描电镜照片分析,证实了La-GDTC能够促进SiO2在SBR基体中的分散和提高橡胶基体与SiO2的界面黏结作用;而ZDC则不具备这些功能.A new rubber functional agent with dithiocarbamate group,carboxyl groups and lanthanum ion,called lanthanum glutamic dithiocarbamate（La-GDTC）,was synthesized and its chemical structure was characterized by FTIR and element analysis.The interfacial interactions of SBR/La-GDTC/SiO2composites were measured by toluene swelling-equilibrium test under room temperature.The crosslinking density data of SBR/La-GDTC/SiO2 composites turned out,with the increasing loading of silica content,that the crosslinking density evolved to a high extent considerably,without respect to the obstructed effect of the silica particles on sulfur crosslink reaction.The swollen Gibbs free energy parameters of the composites ΔG decreased dramatically and ΔS increased obviously,both of which interpreted that the chemistry environment of the silica particles in the rubber hybrid composites changed to some extent,leading to a more heterogeneous network existed in the composites and a different chemical bonding structure between the rubber matrix and inorganic particles.Also,the interphase interaction parameter C,obtained from Kraus equations,was the value of 2.02 and verified the reinforcement between SBR and silica particles via the hydrogen bonds and chemical bonds between the La-GDTC and silica particles.The tensile strength,elongation at break and tear strength all pointed out that the mechanical properties of the La-GDTC system were much higher than those of the ZDC system.Also,in the SEM photographs,well-dispersed silica fine particles and more fluctuated surface of the La-GDTC-4 were attained,however,the silica clusters aggregation and smooth surface of the fracture were observed in the ZDC-4,implying that the interface interaction between the SBR/silica particles of the La-GDTC system was much stronger than that of the ZDC system.Based on the fore-mentioned experimental observation,an interphase structure between the rubber matrix and the inorganic particles was discussed.

关 键 词：丁苯橡胶 二氧化硅 稀土促进剂 界面 平衡溶胀 

分 类 号：TB332[一般工业技术—材料科学与工程]