Elastomers from block copolymers

Block copolymers are useful in many applications where a number of different polymers are connected together to yield a material with hybrid properties. For example, thermoplastic elastomers are block copolymers containing a rubbery matrix (polybutadiene or polyisoprene) containing glassy hard domains (often polystyrene). The block copolymer, a kind of polymer alloy, behaves as a rubber at ambient conditions, but can be molded at high temperatures because of the presence of the glassy domains that act as physical cross-links. In solution, attachment of a water-soluble polymer to an insoluble polymer leads to the formation of micelles in amphiphilic block copolymers. The presence of micelles leads to structural and flow characteristics of the polymer in solution, that differ from either parent polymer. 

We have previously alluded to two major commercial applications of block copolymers the addition of AB diblock copolymers in blends of homopolymers, A and B, to improve the processability and mechanical properties of the mixture, and the use of ABA-type triblock copolymers as thermoplastic elastomers when block A (e.g., PS) is below its glass transition, whereas block B (e.g., polybutadiene) is above its glass transition at ambient temperature. Other products made from block copolymers include pressure-sensitive adhesives, oil additives, and automobile parts. 

Noncrystalline aromatic polycarbonates (qv) and polyesters (polyarylates) and alloys of polycarbonate with other thermoplastics are considered elsewhere, as are aHphatic polyesters derived from natural or biological sources such as poly(3-hydroxybutyrate), poly(glycoHde), or poly(lactide) these, too, are separately covered (see Polymers, environmentally degradable Sutures). Thermoplastic elastomers derived from poly(ester—ether) block copolymers such as PBT/PTMEG-T [82662-36-0] and known by commercial names such as Hytrel and Riteflex are included here in the section on poly(butylene terephthalate). Specific polymers are dealt with largely in order of volume, which puts PET first by virtue of its enormous market volume in bottie resin. 

Thermoplastic copolyester elastomers are generally block copolymers produced from short-chain aUphatic diols, aromatic diacids, and polyalkjlene ether-diols. They are often called polyesterether or polyester elastomers. The most significant commercial product is the copolymer from butane-l,4-diol, dimethyl terephthalate, and polytetramethylene ether glycol [25190-06-1J, which produces a segmented block copolyesterether with the following stmcture. 

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. 

Brown [46] continued the contact mechanics work on elastomers and interfacial chains in his studies on the effect of interfacial chains on friction. In these studies. Brown used a crosslinked PDMS spherical cap in contact with a layer of PDMS-PS block copolymer. The thickness, and hence the area density, of the PDMS-PS layer was varied. The thickness was varied from 1.2 nm (X = 0.007 chains per nm-) to 9.2 nm (X = 0.055 chains per nm-). It was found that the PDMS layer thickness was less than about 2.4 nm, the frictional force between the PDMS network and the flat surface layer was high, and it was also higher than the frictional force between the PDMS network and bare PS. When the PDMS layer thicknesses was 5.6 nm and above, the frictional force decreased dramatically well below the friction between PDMS and PS. Based on these data Brown [46] concluded that ... 

Thermoplastic block copolymers were used for pressure-sensitive and hot-melt rubber adhesives as from the middle sixties. These adhesives found application in packaging, disposable diapers, labels and tapes, among other industrial markets. The formulation of these adhesives generally includes an elastomer (generally containing styrene endblocks and either isoprene, butadiene or ethylene-butylene midblocks) and a tackifier (mainly a rosin derivative or hydrocarbon resin). 

In nonrigid ionomers, such as elastomers in which the Tg is situated below ambient temperature, even greater changes can be produced in tensile properties by increase of ion content. As one example, it has been found that in K-salts of a block copolymer, based on butyl acrylate and sulfonated polystyrene, both the tensile strength and the toughness show a dramatic increase as the ion content is raised to about 6 mol% [10]. Also, in Zn-salts of a butyl acrylate/acrylic acid polymer, the tensile strength as a function of the acrylic acid content was observed to rise from a low value of about 3 MPa for the acid copolymer to a maximum value of about 15 MPa for the ionomer having acrylic acid content of 5 wt% [II]. Other examples of the influence of ion content on mechanical properties of ionomers are cited in a recent review article [7],... 

ADMET is quite possibly the most flexible transition-metal-catalyzed polymerization route known to date. With the introduction of new, functionality-tolerant robust catalysts, the primary limitation of this chemistry involves the synthesis and cost of the diene monomer that is used. ADMET gives the chemist a powerful tool for the synthesis of polymers not easily accessible via other means, and in this chapter, we designate the key elements of ADMET. We detail the synthetic techniques required to perform this reaction and discuss the wide range of properties observed from the variety of polymers that can be synthesized. For example, branched and functionalized polymers produced by this route provide excellent models (after quantitative hydrogenation) for the study of many large-volume commercial copolymers, and the synthesis of reactive carbosilane polymers provides a flexible route to solvent-resistant elastomers with variable properties. Telechelic oligomers can also be made which offer an excellent means for polymer modification or incorporation into block copolymers. All of these examples illustrate the versatility of ADMET. 

FIGURE 5.12 Change in the morphology of an A-B-A block copolymer as a function of composition. (From Walker, M. and Rader, C.P. (eds.). Handbook of Thermoplastic Elastomers, Van Nostrand Reinhold, New York, 1988.)... 

FIGURE 5.13 Complexity diagram for block copolymers. (Adapted from Morton, M., Thermoplastic Elastomer A Comprehensive Review, Legge, N.R., Holden, G., and Schroeder, H.E. (eds.), Hanser, Munich, 1987 and Simon, P.F.W., Ulrich, R., Spiess, H.W., and Wiesner, U., Chem. Mater., 13, 3464, 2001. With permission.)... 

Asathana S., Majoros I., and Kennedy J.P., TPEs Star-block comprising multiple polystyrene-b-PIB arms radiating from a crossUnked polydivinylbengene core. Rubber Chem. TechnoL, 71, 949, 1998. Shim J.S. and Kennedy J.P., Novel thermoplastic elastomers. II. Properties of star-block copolymers of PST-b-PlB arms emanating from cyclosiloxane cores, J. Polym. Set, Part A, Polym. Chem., 37, 815, 1999. 

Cakmak M. and Wang M.D., Structure development in the tubular blown film of PP/EPDM thermoplastic elastomer, Antec 89, 47th Annual Tech. Conference of SPE, New York, May 1, 1989, 1756. Hashimoto T., Todo A., Itoi H., and Kawai H. Domain boundary structure of styrene-isoprene block copolymer films cast from solution. 2. Quantitative estimation of the interfacial thickness of lamellar microphase systems. Macromolecules, 10, 377, 1977. 

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. 

The use of lightly crosslinked polymers did result in hydrophilic surfaces (contact angle 50°, c-PI, 0.2 M PhTD). However, the surfaces displayed severe cracking after 5 days. Although qualitatively they appeared to remain hydrophilic, reliable contact angle measurements on these surfaces were impossible. Also, the use of a styrene-butadiene-styrene triblock copolymer thermoplastic elastomer did not show improved permanence of the hydrophilicity over other polydienes treated with PhTD. The block copolymer film was cast from toluene, and transmission electron microscopy showed that the continuous phase was the polybutadiene portion of the copolymer. Both polystyrene and polybutadiene domains are present at the surface. This would probably limit the maximum hydrophilicity obtainable since the RTD reagents are not expected to modify the polystyrene domains. 

Reversible network structure is the single most important characteristic of a thermoplastic elastomer. This novel property generally arises from the presence of a phase-separated morphology in the bulk material which in turn is dictated by the molecular structure, often of a block copolymer nature. A wide variety of synthetic methods can, in principle, produce endless varieties of thermoplastic elastomers this fact coupled with the advantageous processing characteristics of these materials suggest that the use of thermoplastic elastomers will continue to grow in the 1980 s. 

Block copolymers possess unique and novel properties for industrial applications. During the past 20 years, they have sparked much interest, and several of them have been commercialized and are available on the market. The most common uses of block copolymers are as thermoplastic elastomers, toughened thermoplastic resins, membranes, polymer blends, and surfactants. From a chemist s point of view, the most important advantage of block copolymers is the wide variability of their chemical structure. By choice of the repeating unit and the length and structure of both polymer blocks, a whole range of properties can be adjusted. 

---