Polystyrene-butadiene triblock copolymer

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

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. 

A polystyrene-poly(ethylene,l-butene)-polystyrene triblock copolymer is produced by the selective hydrogenation of the corresponding triblock copolymer in which the center block consists of random placements of 1,2-poly(1,3-butadiene) and 1,4-poly (1,3-butadiene) units. 

Styrene-1,3-butadiene-styrene (SBS) or styrene-isoprene-styrene (SIS) triblock copolymers are manufactured by a three-stage sequential polymerization. One possible way of the synthesis is to start with the polymerization of styrene. Since all polystyrene chains have an active anionic chain end, adding butadiene to this reaction mixture resumes polymerization, leading to the formation of a polybutadiene block. The third block is formed after the addition of styrene again. The polymer thus produced contains glassy (or crystalline) polystyrene domains dispersed in a matrix of rubbery polybutadiene.120,481,486... 

The supramolecular structure of block co-polymers allows the design of useful materials properties such as polarity leading to potential applications as second-order nonlinear optical materials, as well as piezo-, pyro-, and ferroelectricity. It is possible to prepare polar superlattices by mixing (blending) a 1 1 ratio of a polystyrene)-6-poly(butadiene)-6-poly-(tert-butyl methacrylate) triblock copolymer (SBT) and a poly (styrene)-Apoly (tert-butyl methacrylate) diblock copolymer (st). The result is a polar, lamellar material with a domain spacing of about 60 nm, Figure 14.10. 

Figure 5. Electron micrographs of triblock copolymers of styrene and butadiene. (a) (top left) As cast from THE/methyl ethul ketone (b) (bottom left) cast from the same solvent with 20% polystyrene (Mn — 3,000) (c) (above) cast from the same solvent with 20% polystyrene (Mn = 30,000).

The group of Abetz [77] used polystyrene-fcZocA -poly(l,2-butadiene)-block-polyitert-hutyl methacrylate) triblock copolymers with partially hydrolyzed poly(tert-butyl methacrylate) blocks, together with polystyrene-... 

Fig.5 TEM micrographs of a polystyrene-Z7/oc/c-poly( 1,2-butadiene)-Z7/oc/c-poly(tert-butyl methacrylate) triblock copolymer that is 18% hydrolyzed and polystyrene-Z /oc/c-poly(2-vinylpyridine) diblock copolymer. S denotes polystyrene, V denotes poly(2-vinylpyridine), T/A denotes the partially (18%) hydrolyzed poly(tert-butyl methacrylate), and B denotes poly( 1,2-butadiene). Reprinted with permission from [77]. 2003 American Chemical Society...

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... 

Scalco, Huseby, and Blyler (8), Zosel (9), and Bergen and Morris (10). Prest and Porter (23) applied the same principle to homopolymer blends [poly (2,6-dimethylphenylene oxide)-polystyrene]. Recently some papers were published on triblock copolymers of styrene-butadiene-styrene and on their blends with polybutadiene (24, 25). Triblock copolymers can be considered heterophase material as the different constituent blocks are thermodynamically incompatible with each other, and, consequently, polystyrene domains are enclosed in polybutadiene (continuous matrix). The findings indicate that these systems are in general thermorheologically complex, so that the shift factor ar depends not only on temperature but also on time. These conclusions have been extrapolated to other two-phase systems. 

Studies on the morphology and on the melt rheological, tensile, and impact properties were carried out on ternary blend of iPP with two of the following polymers low and high density polyethylene, styrene-b-ethylene butylene-b-styrene triblock copolymer, polystyrene, and acrylonitrile-butadiene-styrene terpolymer (30-33). The results are interpreted for the effect of each individual component by comparing the ternary blends with the respective iPP-based binary blends as the reference systems. 

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