Thermoplastic elastomers styrene-diene

Polymers Thermoplastic elastomers Styrene-butadiene-styrene (SBS), styrene-butadiene-rubber (SBR), styrene-isoprene-styrene (SIS), styrene-ethyl-butadiene-styrene (SEBS), ethyl-propyl-dien tetropolymer (EPDM), isobutene-isoprene copolymer (NR), polybutadiene (PBD),natural rubber (l),(2),(3),(4), [8]. [9], [10], [II], [13]... 

ABA triblock copolymers of the styrene-diene type are well known, and owe their unique properties to their heterophase morphology. This arises from the incompatibility between the polystyrene A blocks and the polydiene B blocks, leading to the formation of a dispersion of very small polystyrene domains within the polydiene matrix. This type of elastic network, held together by the polystyrene "junctions", results in thermoplastic elastomer properties. 

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... 

The annual worlwide production of triblock thermoplastic elastomers, clear impact-resistant polystyrene, and other styrene-diene products produced by anionic polymerization exceeds a couple of billion pounds. (Commercial utilization of anionic polymerization also includes the polymerization of 1,3-butadiene alone.)... 

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

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-... 

A variation of the sequential monomer addition technique described in Section 9.2.6(i) is used to make styrene-diene-styrene iriblock thermoplastic rubbers. Styrene is polymerized first, using butyl lithium initiator in a nonpolar solvent. Then, a mixture of styrene and the diene is added to the living polystyryl macroanion. The diene will polymerize first, because styrene anions initiate diene polymerization much faster than the reverse process. After the diene monomer is consumed, polystyrene forms the third block. The combination of Li initiation and a nonpolar solvent produces a high cis-1,4 content in the central polydiene block, as required for thermoplastic elastomer behavior. 

The styrene-diene triblock copolymer consists of individual chains of three blocks, an elastomeric diene block in the center and a thermoplastic styrene block on each end. This polymer is called a thermoplastic elastomer. It exhibits some of the physical properties of elastomers at use temperature and is as pro-cessable as conventional plastics (5). The styrene/diene triblock copolymer has the unique morphology of glassy polystyrene domains in the rubbery diene matrix. Therefore, such an elastomer does not require conventional vulcanization since the glassy polystyrene domains act as physical crosslinks. 

During the past three decades a few groups of materials have been developed that could be considered as being in this category. Designated as thermoplastic elastomers, they include (1) styrene-diene-styrene triblock copolymers (2) thermoplastic polyester elastomers and thermoplastic polyurethane elastomers and (3) thermoplastic polyolefin rubbers (polyolefin blends). 

This interesting behavior of the ABA triblock copolymers is not a unique feature of the styrene-diene stmcture, but can be found in the case of other analogous chemical structures. Thus thermoplastic elastomers have been obtained from other triblock copolymers, where the dienes have been replaced by cyclic sulfides (Morton et al., 1971), cyclic siloxanes (Morton et al., 1974), or alkyl acrylates (Jerome, 2004) poly(alkyl methacrylate) end blocks have also been investigated (Jerome, 2(X)4). 

As stated previously, styrene-diene triblock copolymers are the most important category of thermoplastic elastomers. Unlike most other TPEs, they can be blended with large quantities of additives without a drastic effect on properties. In almost all applications, the actual triblock copolymer content is less than 50%. Oils are used as a processing aid and do not result in a significant loss of properties if the polystyrene domains are not plasticized. For this reason, naphthalenic oils are preferred. The use of inert fillers such as clays or chalks reduces the cost of the final material. Unlike conventional rubbers, inert fillers do not have a substantial effect on the mechanical properties of TPEs. Thermoplastics such as polyethylene or polypropylene are also used to improve the solvent resistance and can increase the upper service temperature. Polystyrene homopolymer is used as a processing aid, which also increases the hard phase weight fraction and causes the material to stiffen. 

EPR is currently replaced by EPDM, a modification with a diene monomer, due to its improved workability. A novel type of elastomer (called a thermoplastic elastomer) exhibits quite revolutionary behavior. Here cross-linking is temporary (at room temperature) while it can flow at higher temperatures, like thermoplastics. The typical one (SBS) is a strictly ordered block copolymer of styrene and butadiene, made by an anionic polymerization. The butadiene chains (at a controlled MW of 70,000) are embedded in a rigid phase of polystyrene spheres (MW of 15,000) thus providing temporary cross-linking at ambient conditions, while being processible at high temperatures like thermoplastics. 

Uses Catalyst in mfg. of rubbers and plastics based on styrol-butadiene, polyisoprene, and polybutadiene initiator in anionic polymerization of styrene and conjugated dienes, thermoplastic elastomers organic synthesis... 

The simplest dependency exists between composition and glass transition temperature Independent from the ratio A/B one finds two values for Tg, one for the block from monomer A and one for the block of B. More complex are the dependencies with the mechanical properties. Here, parameters like the ratio A/B, number of blocks, block length, and alternation of the blocks play a decisive role. This is shown in Examples 3.47 and 3.48 with triblock copolymers of butadiene or isoprene with styrene. If the content of the diene blocks is around 20%, a stiff and elastic, transparent thermoplastic material is obtained. Instead, if the diene content is raised to about 70%, a highly elastic but still rather stiff thermoplastic elastomer is obtained. It has to be stressed that these properties can only be reached, when the polystyrene blocks are the terminal ones. 

The control of chain structure and molecular weight afforded by the organolithium polymerization of dienes, has, of course, been of great technological interest [161,162,209]. Such product developments have been mainly in the form of (1) polybutadiene elastomers of various chain structures [162, 198,209] and functional end groups [210], (2) liquid polybutadienes [211], (3) butadiene-styrene copolymers (solution SBR) [69, 161, 162, 209], and (4) styrene-diene triblock copolymers (thermoplastic elastomers) [212]. 

The ABA triblocks which have been most exploited commercially are of the styrene-diene-styrene type, prepared by sequential polymerization initiated by alkyllithium compounds as shown in Eqs. (99-101) [263, 286]. The behavior of these block copolymers illustrates the special characteristics of block (and graft) copolymers, which are based on the general incompatibility of the different blocks [287]. Thus for a typical thermoplastic elastomer (263), the polystyrene end blocks (-15,000-20,000 MW) aggregate into a separate phase, which forms a microdispersion within the matrix composed of the polydiene chains (50,000-70,000 MW) [288-290]. A schematic representation of this morphology is shown in Fig. 3. This phase separation, which occurs in the melt (or swollen) state, results, at ambient temperatures, in a network of... 

---