Synthesis and characterization of poly (styrene‐b‐[(butadiene)1−x‐(ethylene‐co‐butylene)x] ‐b‐styrene) star‐like molecular polymers produced by partial hydrogenation of SBS

This article reports the synthesis and characterization of four arm star‐shaped poly(styrene‐ b ‐[(butadiene) 1−x ‐(ethylene‐ co ‐butylene) x ]‐ b ‐styrene) (SBEBS) copolymers. A series of SBEBS copolymers with different compositions of the elastomeric block were produced by hydrogenating a given poly(styrene‐ b ‐butadiene‐ b ‐styrene) (SBS) copolymer using a catalyst prepared from bis( η 5 ‐cyclopentadienyl)titanium(IV) dichloride and n ‐butyllithium. The characterization was accomplished by proton nuclear magnetic resonance spectroscopy ( 1 H NMR), infrared spectroscopy (FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The results indicate that there is a selective saturation of the polybutadiene block over the polystyrene block; this selectivity was determined by the Ti/Li molar ratio and the concentration of Ti. It was observed that the saturation rate of the 1,2‐vinyl was higher than that of the 1,4‐ trans and 1,4‐ cis poly(butadiene)‐ b isomers. The DSC and DMA results indicate that the degree of hydrogenation had a profound effect on the polymer's relaxation behavior. All samples exhibited a biphasic system behavior with two distinct transitions corresponding to the elastomeric and polystyrene blocks. SBEBS copolymers with higher saturation levels (>33%) exhibited a crystalline character. The TGA results indicated a characteristic weight loss temperature in all samples, with slightly higher thermal degradation stabilities in the materials with higher degrees of saturation. POLYM. ENG. SCI., 54:2332–2344, 2014. © 2013 Society of Plastics Engineers