Thermoplastic elastomers styrene block copolymers

Styrene-Diene. These ( styrenic ) thermoplastic elastomers are block copolymers of styrene with butadiene (SBS) or isoprene (SIS) in about 30/70 monomer ratio. 

Besides the thermoplastic elastomers based on poly(styrene-6-elastomer- -styrene) block copolymers, five others are of commercial importance polyurethane/elastomer block copolymers, polyester/elastomer block copolymers, polyamide/elastomer block copolymers, polyolefin block copolymers, and polyetherimide/polysiloxane block copolymers. All five have the multiblock A-B-A-B. structure. The morphology of the polyurethane, polyester,... 

Proportion of Hard Segments. As expected, the modulus of styrenic block copolymers increases with the proportion of the hard polystyrene segments. The tensile behavior of otherwise similar block copolymers with a wide range of polystyrene contents shows a family of stress—strain curves (4,7,8). As the styrene content is increased, the products change from very weak, soft, mbbedike materials to strong elastomers, then to leathery materials, and finally to hard glassy thermoplastics. The latter have been commercialized as clear, high impact polystyrenes under the trade name K-Resin (39) (Phillips Petroleum Co.). Other types of thermoplastic elastomers show similar behavior that is, as the ratio of the hard to soft phase is increased, the product in turn becomes harder. 

Global consumption of thermoplastic mbbers of all types is estimated at about 600,000 t/yr (51). Of this, 42% was estimated to be consumed in the United States, 39% in Western Europe, and 19% in Japan. At present, the woddwide market is estimated to be divided as follows styrenic block copolymers, 48% hard polymer/elastomer combinations, 26% thermoplastic polyurethanes, 12% thermoplastic polyesters, 4% and others, 9%. The three largest end uses were transportation, 23% footwear, 18% and adhesives, coatings, etc, 16%. The ranges of the hardness values, prices, and specific gravities of commercially available materials are given in Table 4. 

Trade names and suppHers of commercial thermoplastic elastomers of all types are given in Tables 5—7. Table 5. Trade Names of Thermoplastic Elastomers Based on Styrenic Block Copolymers ... 

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). 

Currently, important TPE s include blends of semicrystalline thermoplastic polyolefins such as propylene copolymers, with ethylene-propylene terepolymer elastomer. Block copolymers of styrene with other monomers such as butadiene, isoprene, and ethylene or ethylene/propy-lene are the most widely used TPE s. Styrene-butadiene-styrene (SBS) accounted for 70% of global styrene block copolymers (SBC). Currently, global capacity of SBC is approximately 1.1 million tons. Polyurethane thermoplastic elastomers are relatively more expensive then other TPE s. However, they are noted for their flexibility, strength, toughness, and abrasion and chemical resistance. Blends of polyvinyl chloride with elastomers such as butyl are widely used in Japan. ... 

Puskas, J.E., Pattern, W.E., Wetmore, P.M., and Krukonis, A. Multiarm-star polyisobutylene-polystyrene thermoplastic elastomers from a novel multifunctional initiator, Polym. Mater. Set Eng., 82,42 3, 1999. Brister, L.B., Puskas, J.E., and Tzaras, E. Star-branched PIB/poly(p-t-bu-Styrene) block copolymers from a novel epoxide initiator, Polym. Prepr., 40, 141-142, 1999. 

Another important class of copolymers synthesized by chain polymerisation are block (or sequenced) copolymers diblock and triblock copolymers being the most important ones. They are very useful as compatibilisers (emulsifiers) in immiscible polymer blends. Another major use is as thermoplastic elastomers. Both uses are best explained through the example of butadiene-styrene block copolymers. 

An interesting observation arose with the thermoplastic elastomer styrene/ butadiene (S/B) tri-block copolymer (Kraton ). These are made by anionic... 

Abbreviation for styrene-butadiene-styrene block copolymer, a thermoplastic elastomer. 

Styrene-butadiene-styrene block copolymers 1965 Thermoplastic elastomers ... 

TPEE or COPE ThermoPlastic Ester Elastomer or CO-PolyEster SBC Styrenic Block Copolymer... 

In addition to the triblock thermoplastic elastomers, other useful copolymers of styrene with a diene are produced commerically by living anionic polymerization. These include di-and multiblock copolymers, random copolymers, and tapered block copolymers. A tapered (gradient) copolymer has a variation in composition along the polymer chain. For example, S-S/D-D is a tapered block polymer that tapers from a polystyrene block to a styrene-diene random copolymer to polydiene block. (Tapered polymers need not have pure blocks at their ends. One can have a continuously tapered composition from styrene to diene by... 

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Table 5. Trade Names of Thermoplastic Elastomers Based on Styrenic Block Copolymers...

Thermoplastic elastomers (TPE s) are characterized by the exceptional property that, without vulcanization, they behave as cross-linked rubbers. They are block-copolymers, in which blocks of the same nature assemble in hard domains, acting as cross-links between the rubbery parts of the chain. These hard domains lose their function when they reach their softening temperature, so that the material can then be processed as a thermoplast. One of the oldest member of the family of TPE s is SBS (styrene-butadiene-styrene block copolymer), but several other TPE s have been developed, i.a. on the basis of polyesters, polyurethanes and polyolefins. In their properties these polymers cover a broad range between conventional rubbers and soft thermoplastics. 

Although styrene-diene diblock copolymers are used in some applications, particularly in the area of viscosity index improvement (VII) additives for motor oil, styrenic block copolymers are most often used as thermoplastic elastomers. In these applications the styrene blocks phase separate, crosslinking the rubber blocks in a thermally reversible fashion. The simplest structure capable of exhibiting this behavior is a linear styrene-diene-styrene triblock. The most obvious way to produce such a molecule is by sequential polymeriza-... 

The acrylic site has the same reactivity as in an alkyl acrylate and it is possible to synthesize butadiene-acrylate or butadiene-styrene block copolymers. Thermoplastic elastomers synthesized using this process have intermediate properties between those of elastomers and thermoplastics. 

This is an example of the preparation of ABA-type thermoplastic elastomer. Styrene is polymerized first since styryl initiation of isoprene is faster than the reverse reaction. The reaction is carried out in a nonpolar solvent with Li" " as the counterion to enable predominantly cis-l,4-polyisoprene to be formed in the second growth stage. The living polystyrene-6/ocfc-polyisoprene AB di-block copolymer resulting from the second stage is then coupled by a double nucleophilic displacement of Cl ions from a stoichiometric equivalent of dichloromethane to give a polystyrene-61ock-polyisoprene-/)/ock-polystyrene triblock copolymer. 

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