Dynamically Vulcanized Thermoplastic Elastomers

Abstract

Abstract Thermoplastic elastomers (TPEs) exhibit the functional properties of conventional thermoset rubber, yet can be processed on thermoplastic fabrication equipment. The great majority of TPEs have hetero-phase morphology, whether the TPE is derived from block copolymers, rubber-plastic compositions or ionomers. Generally speaking, the hard domains (or the ionic clusters) undergo dissociation at elevated temperatures, thus allowing the material to flow. When cooled, the hard domains again solidify and provide tensile strength at normal use temperatures. The soft domains give the material its elastomeric characteristics. In this review article, the focus is on rubber-plastic polymer compositions as a group of TPEs which have achieved significant growth in the marketplace in the last two decades. The growth has been primarily in the nonpolar (olefinic) elastomer/polyolefin thermoplastic materials because of the wide range of products generated, their performance and their significant acceptance by the automotive sector in applications requiring elastic recovery. The field of TPEs based on polyolefin rubber-plastic compositions has grown along two distinctly different product lines or classes: one class consists of a simple blend and classically meets the definition of a thermoplastic elastomeric olefin (TEO), commonly called a thermoplastic polyolefin (TPO) in earlier literature. In the other class, the rubber phase is dynamically vulcanized, giving rise to thermoplastic vulcanizates (TPVs), named elastomeric alloys (EAs) in some previous literature. Both the simple blends and the dynamically vulcanized TPEs have found wide industrial application. It is the dynamically vulcanized TPE that has the performance characteristics required for true thermoset rubber replacement applications. The first TPE introduced to the market based on a crosslinked rubber-plastic composition (1972) was derived from W. K. Fisher's discovery of partially crosslinking the EPDM phase of EPDM/polypropylene (PP). Fisher controlled the degree of vulcanization by limiting the amount of peroxide, to maintain the thermoplastic processability of the blend. Crosslinking was performed while mixing, a process known as dynamic vulcanization. It is worth noting, however, that the dynamic vulcanization process and the first crosslinked EPDM/PP composition were discovered independently by Gessler and Haslett and by Holzer, Taurus and Mehnert in 1958 and 1961, respectively. Significant improvement in the properties of these blends was achieved in 1975 by Coran, Das and Patel by fully vulcanizing the rubber phase under dynamic shear while maintaining the thermoplasticity of the blend. These blends were further improved by Abdou-Sabet and Fath in 1977 by the use of phenolic curatives to improve the rubber-like properties and the flow (processing) characteristics.