Elastomer segmentation

Block copolymers with stmctures such as A—B or B—A—B ate not thermoplastic elastomers, because for a continuous network to exist both ends of the elastomer segment must be immobilized in the hard domains. Instead, they are much weaker materials resembling conventional unvulcanized synthetic mbbers (4). 

All these elastomers, especially poly(ethylene- (9-butylene) and poly(ethylene- (9-propylene), are nonpolar. The corresponding block copolymers can thus be compounded with hydrocarbon-based extending oils, but do not have much oil resistance. Conversely, block copolymers with polar polyester or polyether elastomer segments have Htde affinity for such hydrocarbon oils and so have better oil resistance. 

Among the polyurethane, polyester, and polyamide thermoplastic elastomers, those with polyether-based elastomer segments have better hydrolytic stabihty and low temperature flexibiUty, whereas polyester-based analogues are tougher and have the best oil resistance (43). Polycaprolactones and aUphatic polycarbonates, two special types of polyesters, are used to produce premium-grade polyurethanes (12). 

Commercially, anionic polymerization is limited to three monomers styrene, butadiene, and isoprene [78-79-5], therefore only two useful A—B—A block copolymers, S—B—S and S—I—S, can be produced direcdy. In both cases, the elastomer segments contain double bonds which are reactive and limit the stabhity of the product. To improve stabhity, the polybutadiene mid-segment can be polymerized as a random mixture of two stmctural forms, the 1,4 and 1,2 isomers, by addition of an inert polar material to the polymerization solvent ethers and amines have been suggested for this purpose (46). Upon hydrogenation, these isomers give a copolymer of ethylene and butylene. 

Trade name Manufacturer Type Elastomer segment Notes... 

Adhesives, Coatings, and Sealants. Eor these appHcations, styrenic block copolymers must be compounded with resins and oils (Table 10) to obtain the desired properties (56—58). Materials compatible with the elastomer segments soften the final product and give tack, whereas materials compatible with the polystyrene segments impart hardness. The latter are usually styrenic resins with relatively high softening points. Materials with low softening points are to be avoided, as are aromatic oils, since they plasticize the polystyrene domains and reduce the upper service temperature of the final products. 

Such an example has been recently worked out, combining a very hard block i.e. polypivalolactone (PPVL), with a thermostable elastomer segment i.e. polydimethyl-siloxane (PDMS), using the reactions sequence described in scheme 3. (One should note that the starting PDMS has been obtained through a previously described procedure (14), avoiding any unstable Si-O-C bond in the final produc t). 

Elastomer segment -of TPE [ELASTOMERS SYNTHETIC - THERMOPLASTIC ELASTOMERS] (Vol 9)... 

Medical PUs are another subset of PU elastomers. Segmented PUs were first suggested for use in a biomedical application in 1967. ° Early work with PU elastomers showed that these materials could be used for implants without causing a large, unwanted inflammatory response. The first medical devices made of PUs, however, were found to be susceptible to hydrolysis and degraded faster than desired. ° From that time, new biostable materials have been developed for use as pacemaker leads, catheters, vascular grafts. 

Obviously, elastomer desorption occurs gradually, because of the very broad interaggregate distance distribution that induces an also broad distribution of bridging elastomer segments. This explains the smooth decrease of G for mixes and its step shape for shorter molecules such as oUs. 

Progressively, desorption induces a homogenization of bridging elastomer segment lengths. This homogenization and the stabilization of the modulus will be discussed in detail in the next section. 

To generalize, when the elastomer segment is small with respect to the glassy segment, uniform spheres a few hundred angstroms in diameter pervade the polystyrene matrix. As the length of the elastomer segment is... 

In the case of polysiloxane elastomers, segmental orientation has been of interest for both elongation - and compression. ... 

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