Styrenic Thermoplastic Elastomer - Chapter

Closely related to these but thermoplastic rather than rubber-like in character are the K-resins developed hy Phillips. These resins comprise star-shaped butadiene-styrene block copolymers containing about 75% styrene and, like SBS thermoplastic elastomers, are produced by sequential anionic polymerisation (see Chapter 2). 

In Chapters 3 and 11 reference was made to thermoplastic elastomers of the triblock type. The most well known consist of a block of butadiene units joined at each end to a block of styrene units. At room temperature the styrene blocks congregate into glassy domains which act effectively to link the butadiene segments into a rubbery network. Above the Tg of the polystyrene these domains disappear and the polymer begins to flow like a thermoplastic. Because of the relatively low Tg of the short polystyrene blocks such rubbers have very limited heat resistance. Whilst in principle it may be possible to use end-blocks with a higher Tg an alternative approach is to use a block copolymer in which one of the blocks is capable of crystallisation and with a well above room temperature. Using what may be considered to be an extension of the chemical technology of poly(ethylene terephthalate) this approach has led to the availability of thermoplastic polyester elastomers (Hytrel—Du Pont Amitel—Akzo). 

It is important to appreciate that polymer produced by an anionic chain-growth mechanism can have drastically different properties from one made by a normal free radical reaction. Block copolymers can be synthesized in which each block has different properties. We mentioned in Chapter 4 that Michael Szwdrc of Syracuse University developed this chemistry in the 1950s. Since that time, block copolymers produced by anionic polymerization have been commercialized, such as styrene-isoprene-styrene and styrene-butadiene-styrene triblock copolymers (e.g., Kraton from Shell Chemical Company). They find use as thermoplastic elastomers (TPE), polymers that act as elastomers at normal temperatures but which can be molded like thermoplastics when heated. We will discuss TPEs further in Chapter 7. 

Considerable efforts have been directed, primarily in Kennedy s group [3], to synthesize a series of block copolymers of isobutene with isoprene [90,91], styrene derivatives [92-104], and vinyl ethers [105-107]. Figure 7 lists the monomers that have been used for the block copolymerizations with isobutene. The reported examples include not only AB- but also ABA- and triarmed block copolymers, depending on the functionality of the initiators (see Chapter 4, Section V.B, Table 3). Obviously, the copolymers with styrene derivatives, particularly ABA versions, are mostly intended to combine the rubbery polyisobutene-centered segments with glassy styrenic side segments in attempts to prepare novel thermoplastic elastomers. These styrene monomers are styrene, p-methylstyrene, p-chlorostyrene, a-methylstyrene, and indene. 

The properties of block copolymers differ from those of a blend of the correponding homopolymers or a random copolymer (Chapter 7) with the same overall composition. An important practical example is the ABA-type styrene/butadiene/styrene triblock copolymer. These behave as thermoplastic elastomers. Ordinary elastomers are cross-linked by covalent bonds, e.g., vulcanization (see Chapter 2) to impart elastic recovery property, as without this there will be permanent deformation. Such cross-linked rubbers are therraosets and so cannot be softened and reshaped by molding. However, solid thermoplastic styrene/butadiene/styrene triblock elastomers can be resoftened and remolded. This can be explained as follows. At room temperature, the triblock elastomers consist of glassy, rigid, polystyrene domains... 

Styrene-based thermoplastic elastomers (see Chapter 4) are sensitive to oxidation since they contain unsaturated soft segments. These elastomers are manufactured by solution polymerization process in aliphatic hydrocarbons. In order to prevent autoxidation during the finishing steps (stripping, drying), which manifests itself by a rise in melt flow index and discoloration of the raw polymer, antioxidant is added to the polymer solution before finishing. Hence the antioxidant has to be soluble in the polymerization solvent. 

The convenience of this technique has led to the development of many commercial products, including thermoplastic elastomers based on triblocks of styrene, butadiene, and isoprene. The initiator used in these systems is based on hydrocarbon-soluble organolithium initiators. In some cases, a hydrocarbon-soluble dilithio initiator has been employed in the preparation of multiblock copolymers. Several techniques are used to prepare thermoplastic elastomers of the ABA type. All these are discussed in detail in Chapter 2. A short summary of these techniques is given here. 

Use of a chemically saturated rubber such as chlorobutyl, together with styrene as the monomer, with the rubber the predominant component by weight, results in a material similar in behavior to the thermoplastic elastomers (see Chapter 4). In all cases two glass transitions and other evidence suggested phase separation. 

Paul, D.R. (1987) Compatibilization of polymer blends by styrene/hydrogenated butadiene block copolymers, in Thermoplastic Elastomers a Comprehensive Review (eds N.R. Legge, G. Holden, and H.E. Schroeder), Hanser, Munich, Chapter 12, Section 6. 

Azodicarbonamide (AZC) is by far the most widely used CBA. It can foam PVC, including plasticised PVC, as well as the polyolefins, the styrenics, polyamides, PPO and some thermoplastic elastomers. AZC decomposes exothermically at around 210 °C to give nitrogen gas, along with other degradation products such as mea, cyanuric acid and cyamelide as solid by-products. Another possible residue is semicarbazide, traces of which have been found in foamed gaskets made of PVC blown with azodicarbonamide (see Chapter 7). 

This chapter has provided a general summary of fatigue concepts, measurement techniques or methods, data presentation, and theory. It was meant to be introductory only and additional details should be obtained from the literature cited in this chapter [24-26], Chapters Styrenic Plastics, Polyether Plastics, Polyester Plastics, Polyimide Plastics, Polyamide Plastics (Nylons), Polyolefins and Acrylics, Thermoplastic Elastomers, Fluoropolymers, High-Temperature Polymers contain hundreds of plots of fatigue-related data on hundreds of different plastics. 

In the case of sPS, the problem of its brittleness can be even more acute since it has to compete with engineering plastics which possess an inherent toughness superior to that of sPS. For this reason, a good impact modification of this product is of paramount importance and may even be essential for its survival as a commercial thermoplastic. For this reason a chapter of this book has been dedicated to the impact modification of sPS using elastomers. Since rubber modification plays such an important role for styrene polymers, whether atactic or sydiotactic, we will first look at the methods of energy dissipation in these homopolymers on impact. 

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