端氨基丁苯液体橡胶的制备及性能研究

Preparation and Properties of Amine-terminated Styrene-butadiene Liquid Rubber

以溶聚丁苯橡胶(SSBR)为原料,通过反应控制相转移催化法对其进行环氧化,进一步对环氧基团进行裂解反应制得端醛基丁苯液体橡胶(ATBS),然后采用端基转化法改变端基基团,制得端肟基(OTBS)和端氨基丁苯液体橡胶(AmTBS).采用核磁共振氢谱和碳谱以及红外光谱,对原料、中间产物以及端氨基丁苯液体橡胶的组成与结构进行了表征与分析;根据化学滴定法测定了端氨基丁苯橡胶的胺值,并计算了氨基官能度;通过热重分析、示差量热扫描法对产物的热性能进行了测试与分析.端氨基丁苯橡胶的流变性能测试结果表明,其符合牛顿流体的特征,本体黏度在一定范围内对温度变化较为敏感.降解法制备的端氨基丁苯液体橡胶可进一步拓宽丁苯液体橡胶的应用领域.

Liquid rubber is a class of viscous oligomers with low molecular weight,fluidity at room temperature and good processing properties.Telechelic liquid rubber with one functional group at each terminal end could undergo crosslinking,chain extension and other reactions with other monomers or polymers,further expanding the application fields of liquid rubber.Liquid styrene-butadiene rubber(LSBR)is a low molecular-weight copolymer of butadiene and styrene,which has good compatibility with many rubbers.One of commonly used functionalized butadiene styrene liquid rubber is hydroxyl-terminated butadiene styrene rubber(HTBS),which is usually produced via free radical polymerization or anionic polymerization.In this study,taking solution-polymerized styrene-butadiene rubber(SSBR)as a starting material,aldehyde-terminated styrene-butadiene rubber(ATBS)was obtained by the reaction-controlled phase-transfer catalytic epoxidation and oxidative cleavage of epoxy groups.Then,the oxime-and amino-terminated butadiene-styrene rubbers(OTBS and AmTBS)were further obtained by the conversion of terminal groups.The composition and structure of materials,intermediate products and AmTBS were characterized and analyzed by proton and carbon nuclear magnetic resonance(1H and 13CNMR),and Fourier transform infrared(FTIR)spectroscopies.The results showed that AmTBS was successfully synthesized.The amine value of AmTBS was determined according to the chemical titration and the amino functionality was calculated to be approximately 2.0.The thermal properties of products were analyzed by thermogravimetric analysis(TGA)and differential scanning calorimetry(DSC).The results of rheological properties of AmTBS indicated that they matched the characteristics of Newtonian fluids and their intrinsic viscosities were sensitive to the temperature in a certain range.The AmTBS prepared by the degradation method possessed superior properties and could further broaden the application fields of LSBR.