Elastomers, thermoplastics triblock type

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). 

Tong J.D. and Jerome R., Dependence of the ultimate tensile strength of thermoplastic elastomers of the triblock type on the molecular weight between chain entanglements of the central block. Macromolecules, 33, 1479, 2000. 

Sequential addition of different monomer charges to a living anionic polymerization system is useful for producing well-defined block copolymers. Thermoplastic elastomers of the triblock type are the most important commercial application. For example, a styrene-isoprene-styrene triblock copolymer is synthesized by the sequence... 

Thermoplastic Elastomers. These represent a whole class of synthetic elastomers, developed siace the 1960s, that ate permanently and reversibly thermoplastic, but behave as cross-linked networks at ambient temperature. One of the first was the triblock copolymer of the polystyrene—polybutadiene—polystyrene type (SheU s Kraton) prepared by anionic polymerization with organoHthium initiator. The stmcture and morphology is shown schematically in Figure 3. The incompatibiHty of the polystyrene and polybutadiene blocks leads to a dispersion of the spherical polystyrene domains (ca 20—30 nm) in the mbbery matrix of polybutadiene. Since each polybutadiene chain is anchored at both ends to a polystyrene domain, a network results. However, at elevated temperatures where the polystyrene softens, the elastomer can be molded like any thermoplastic, yet behaves much like a vulcanized mbber on cooling (see Elastomers, synthetic-thermoplastic elastomers). 

With these polymers hard blocks with T s well above normal ambient temperature are separated by soft bloeks which in the mass are rubbery in nature. This is very reminiscent of the SBS triblock elastomers discussed in Chapter 11 and even more closely related to the polyether-ester thermoplastic elastomers of the Hytrel type deseribed in Chapter 25. 

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. 

Solvent Resistance. One of the distinct advantages of a crystalline thermoplastic elastomer over an amorphous one should be its superior solvent resistance, since the latter types are generally soluble. Table III shows the swelling behavior of the H2-BIB triblocks in toluene at 25°C. It can be seen that the maximum swelling obtained was in the case of the H2-BIB-34, which had the lowest end-block content. Furthermore, the equilibrium swelling ratio of 3-26 obtained for this polymer is considerably less than the value of 5 or 6 generally exhibited by a well-vulcanized natural rubber. 

Since soluble multifunctional initiators are more readily available in cationic polymerization than in the anionic counterpart, ABA type linear triblock copolymers have been almost exclusively prepared using difunctional initiation followed by sequential monomer addition. The preparation and properties of ABA type block copolymer thermoplastic elastomers (TPEs), where the middle segment is PIB, have been reviewed recently [47]. 

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... 

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. 

SB block copolymers are made anionically. These copolymers can be dlblocks, triblocks, and radial block copolymers with different degrees of tapering. Kraton was introduced in the mid-1960s by Shell. Another major manufacturer is Phillips with Solprene and K-Resins. These products can be used as thermoplastic elastomers or as impact modifiers. One of the most interesting aspects of these resins is the different types of morphologies that can be obtained as shown in Figure 6 (12-15). 

There are two important types of polymer in which an elastomeric and a glassy or non-crystalline rigid component are copolymerised. The simpler thermoplastic elastomers are usually triblock ABA copolymers with B as the elastomeric component and A as the glassy component, whereas the segmented polyurethane elastomers are multiblock copolymers in which alternate blocks are hard , i.e. relatively inflexible, and soft , i.e. relatively flexible. 

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. 

The flow behavior of block copolymers differs from that of the parent homopolymers. Let us first examine the temperature dependence of the viscosity rj for the thermoplastic elastomers. Below the glass transition temperature of polystyrene (about 110 C) the triblock material has a viscosity intermediate between that of the parent homopolymers, as shown in Figure 4.22. This is normal and expected. However, at a temperature where flow is well developed in the polystyrene, 140 C, an inversion occurs, the block copolymer assuming the higher viscosity (Holden et a/., 1969b). The reason for this inversion lies in the difficulty of pulling styrene blocks out of their normal phase and into and through the polybutadiene phase, and vice versa. Motions of this type are required for viscous flow, and... 

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... 

Block copolymers made from ethylene and propylene are valuable industrial materials. They can be used as thermoplastic elastomers and as compatibOizing agents for homopolymer blends. The properties of this type of copolymer depend on the microstructure of the blocks, the relative lengths of the blocks, and the overall molecular v eight. An ABA triblock copolymer structure containing crystalline A blocks and an amorphous B block can exhibit elastomeric behavior. The crystalline "hard" blocks can consist of isotactic or syndiotactic polypropylene (iPP or sPP) units or linear polyethylene (PE). The amorphous "soft" blocks can consist of atactic polypropylene (aPP) or ethylene-propylene copolymer (ethylene-propylene rubber, EPR). 

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