Styrenic triblock copolymers

Figure 3.8. Schematic representation of the polystyrene domain structure in styrene-butadiene-styrene triblock copolymers. (After Holden, Bishop and Legge )...

Block copolymers can contain crystalline or amorphous hard blocks. Examples of crystalline block copolymers are polyurethanes (e.g. B.F. Goodrich s Estane line), polyether esters (e.g. Dupont s Hytrel polymers), polyether amides (e.g. Atofina s Pebax grades). Polyurethanes have enjoyed limited utility due to their relatively low thermal stability use temperatures must be kept below 275°F, due to the reversibility of the urethane linkage. Recently, polyurethanes with stability at 350°F for nearly 100 h have been claimed [2]. Polyether esters and polyether amides have been explored for PSA applications where their heat and plasticizer resistance is a benefit [3]. However, the high price of these materials and their multiblock architecture have limited their use. All of these crystalline block copolymers consist of multiblocks with relatively short, amorphous, polyether or polyester mid-blocks. Consequently they can not be diluted as extensively with tackifiers and diluents as styrenic triblock copolymers. Thereby it is more difficult to obtain strong, yet soft adhesives — the primary goals of adding rubber to hot melts. 

Ban H.T., Kase T., Kawabe M., Miyazawa A., Ishihara T., Hagihara H., Tsunogae Y., Murata M. and Shiono T.A. New approach to styrenic thermoplastic elastomers S3Tithesis and characterization of crystalline styrene-butadiene-styrene triblock copolymers. Macromolecules, 39, 171, 2006. 

Pakula T., Saijo K., Kawai H., and Hashimoto T. Deformation behaviour of styrene butadiene styrene triblock copolymer with cyhndrical morphology, Macromo/ecu/er, 18, 1294, 1985. 

Magonov, S.N., Elings, V., Cleveland, J., Denley, D., and Whangbo, M.-H., Tapping-mode atomic force microscopy study of the near-surface composition of a styrene-butadiene-styrene triblock copolymer film, Surf. Sci., 389, 201, 1997. 

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. 

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 elastomeric behavior requires that the block copolymer develop a microheterogeneous two-phase network morphology. Theory predicts that microphase separation will occur at shorter block lengths as the polarity difference between the A and B blocks increases. This prediction is borne out as the block lengths required for the polyether-polyurethane, polyester-polyurethane, and polyether-polyester multiblock copolymers to exhibit thermoplastic elastomeric behavior are considerably shorter than for the styrene-diene-styrene triblock copolymers. 

Table 19.3 Typical reaction conditions for the hydrogenation of polybutadiene (PB), styrene-butadiene diblock copolymer (SB), styrene-butadiene-styrene triblock copolymer (SBS) and nitrile butadiene rubber (NBR).

Elabd, Y. A. and Napadensky E. 2004. Sulfonation and characterization of poly(styrene-isobutylene-styrene) triblock copolymers at high ion-exchange capacities. Polymer 45 3037-3043. 

Since their commercial introduction by Shell in 1965, the poly(styrene-b-(buta-diene or isoprene)-b-styrene) triblock copolymers (SBS or SIS) have attracted a... 

A second route is termed sequential anionic polymerization. More recently, also controlled radical techniques can be applied successfully for the sequential preparation of block copolymers but still with a less narrow molar mass distribution of the segments and the final product. In both cases, one starts with the polymerization of monomer A. After it is finished, monomer B is added and after this monomer is polymerized completely again monomer A is fed into the reaction mixture. This procedure is applied for the production of styrene/buta-diene/styrene and styrene/isoprene/styrene triblock copolymers on industrial scale. It can also be used for the preparation of multiblock copolymers. 

HEMA-Styrene Triblock Copolymers and Polyether-Segmented Polyamide... 

Figure 9. of a styrene-isoprene styrene triblock copolymer... 

SEBS Poly(styrene-ethylene-co-butylene-styrene) triblock copolymer... 

Figure 12.4 Chromatograms of a styrene-isoprene-styrene triblock copolymer sample (a) microcolumn SEC trace (b) capillary GC trace of the introduced section x . Peak identification is as follows 1, ionol 2, not identified 3, Irganox 565. Reprinted with permission from Ref. (12).

Diblock copolymers, especially those containing a block chemically identical to one of the blend components, are more effective than triblocks or graft copolymers. Thermodynamic calculations indicate that efficient compat-ibilisation can be achieved with multiblock copolymers [47], potentially for heterogeneous mixed blends. Miscibility of particular segments of the copolymer in one of the phases of the bend is required. Compatibilisers for blends consisting of mixtures of polyolefins are of major interest for recyclates. Random poly(ethylene-co-propylene) is an effective compatibiliser for LDPE-PP, HDPE-PP or LLDPE-PP blends. The impact performance of PE-PP was improved by the addition of very low density PE or elastomeric poly(styrene-block-(ethylene-co-butylene-l)-block styrene) triblock copolymers (SEBS) [52]. 

Chiu, H.-T. Chiu, W.-M. The toughening behavior in propylene-ethylene block copolymer filled with carbon black and styrene-ethylene butylene-styrene triblock copolymer. Mater. Chem. Phys. 56, 108-115 (1998). 

It is important to appreciate that polymer produced by an anionic chain-growth mechanism can have drastically different properties from one made by a normal free radical reaction. Block copolymers can be synthesized in which each block has different properties. We mentioned in Chapter 4 that Michael Szwdrc of Syracuse University developed this chemistry in the 1950s. Since that time, block copolymers produced by anionic polymerization have been commercialized, such as styrene-isoprene-styrene and styrene-butadiene-styrene triblock copolymers (e.g., Kraton from Shell Chemical Company). They find use as thermoplastic elastomers (TPE), polymers that act as elastomers at normal temperatures but which can be molded like thermoplastics when heated. We will discuss TPEs further in Chapter 7. 

Since A and B are constants for a given copolymer and the possible temperature interval is relatively limited, a transition is predicted at an approximately constant shear stress. Melt transitions have in fact been reported at approximately constant shear stresses for styrene-butadiene-styrene triblock copolymers (4). However, this behavior was certainly not observed for the styrene methylmethacrylate diblock copolymer,... 

Block copolymers -A-A-A-A-A-A-B-B-B-B- Styrene-butadiene diblock copolymers Styrene-butad iene-styrene triblock copolymers Polyurethane multiblock copolymers (elastomeric yams)... 

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