Thermoplastic Elastomer - Background

Background

It was not until the 1950s, when thermoplastic polyurethane polymers became available, that TPE became a commercial reality. During the 1960s styrene block copolymer became available, and in the 1970s a wide range of TPEs came on the scene. The worldwide usage of TPEs (680,000 tons/year in 1990) is growing at about 9% per year. The styrene-butadiene materials possess a two-phase microstructure due to incompatibility between the polystyrene and polybutadiene blocks, the former separating into spheres or rods depending on the exact composition. With low polystyrene content, the material is elastomeric with the properties of the polybutadiene predominating. Generally they offer a much wider range of properties than conventional cross-linked rubbers because the composition can vary to suit customer needs.

Block copolymers are interesting because they can "microphase separate" to form periodic nanostructures, as in the styrene-butadiene-styrene block copolymer shown at right. The polymer is known as Kraton and is used for shoe soles and adhesives. Owing to the microfine structure, the transmission electron microscope or TEM was needed to examine the structure. The butadiene matrix was stained with osmium tetroxide to provide contrast in the image. The material was made by living polymerization so that the blocks are almost monodisperse, so helping to create a very regular microstructure. The molecular weight of the polystyrene blocks in the main picture is 102,000; the inset picture has a molecular weight of 91,000, producing slightly smaller domains. The spacing between domains has been confirmed by small-angle X-ray scattering, a technique which gives information about microstructure. Since most polymers are incompatible with one another, forming a block polymer will usually result in phase separation, and the principle has been widely exploited since the introduction of the SBS block polymers, especially where one of the block is highly crystalline. One exception to the rule of incompatibility is the material Noryl, where polystyrene and polyphenylene oxide or PPO form a continuous blend with one another.

Other TPE's have crystalline domains where one kind of block co-crystallizes with other block in adjacent chains, such as in copolyester rubbers, achieving the same effect as in the SBS block polymers. Depending on the block length, the domains are generally more stable than the latter owing to the higher crystal melting point. That point determines the processing temperatures needed to shape the material, as well as the ultimate service use temperatures of the product. Such materials include Hytrel, a polyester-polyether copolymer and Pebax, a nylon or polyamide-polyether copolymer.