Surface wetting behavior of the poly(styrene-b-isoprene-b-styrene) triblock copolymer with different chemical structures of the polyisoprene block chain

The relationship between the chemical structure of a block copolymer and its surface structure and properties is very important for the careful design of its outer surface layer. For this paper, a series of poly(styrene-b-isoprene-b-styrene) triblock copolymers (SIS), with different chemical structures in the polyisoprene block chain, were synthesized by anionic polymerization and their dynamic wetting behaviors were investigated. The dynamic contact angles of the polyisoprene homopolymer (PI) and the SIS were almost the same when the PI and the corresponding block in the SIS had similar chemical structures. The receding contact angle (θr) of SIS depended on the microstructure of the PI block chain, however, the advancing contact angles (θa) were almost the same regardless of the PI's chemical structures. The receding contact angle (θr) of SIS containing 3,4-PI was far higher than that of SIS with 1,4-PI. Meanwhile, it gradually approached that of SIS with 1,4-PI as the of 3,4-PI content decreased or as the local temperature increased. Contact angle measurement is one of the most sensitive methods for providing information on the outer few angstroms of a polymer's surface. Therefore, by designing SIS with different chemical structures in the PI block, it was confirmed that the properties and structure of the outermost layer of the SIS were controlled primarily by the PI block's chemical structure. This demonstrates the possibility to modulate the surface structure and properties of SIS by adjusting the chemical structure of polyisoprene segment.