Copolymers, triblock morphology

FIG. 1, Schematic diagrams of SBS triblock copolymer morphologies, for spherical or cylindrical domains (top two) and lamellar structures (bottom). The interphase is labeled S + B. 

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). 

At r = 0.5 (Fig. 9b), the most interesting and novel morphology can be observed. This morphology can be described as follows. The P4VP cores of the microspheres form a regular structure, and a P4VP bilayer surrounds each microsphere with a honeycomb-like structure, similar to a cell wall, as the number of the microsphere surrounded by the P4VP wall ( T) was 1.08. Similar structures have been observed for ABC triblock copolymers [39]. Our honeycomb-like novel structure, however, is different from that of the ABC triblock co-... 

Chu et al. [24] correlated viscosity-morphology and compatibility of PS-PB blends. The effect of styrene-butadiene triblock copolymer in PS-PB was studied, and it was found that the domain size decreases with an increase of compatibilizer loading. The blending methods influenced the morphology due to the difference in the extent of mixing. 

Morphology of the anionically synthesized triblock copolymers of polyfp-methyl-styrene) and PDMS and their derivatives obtained by the selective chlorination of the hard segments were investigated by TEM 146). Samples with low PDMS content (12%) showed spherical domains of PDMS in a poly(p-methylstyrene) matrix. Samples with nearly equimolar composition showed a continuous lamellar morphology. In both cases the domain structure was very fine, indicating sharp interfaces. Domain sizes were estimated to be of the order of 50-300 A. 

Similar types of lamellar morphologies were observed for triblock copolymers of diphenylsiloxane and dimethylsiloxane having 40 wt% polydiphenylsiloxane, using electron microscopy, 47-148>. The lamellae thickness was approximately equal to the chain length of the rigid polydiphenylsiloxane blocks. These copolymers showed elastomeric properties comparable to those of conventional silica-reinforced, chemically crosslinked silicone rubbers. Tensile tests yielded an initial modulus of 0.5-1 MPa, tensile strength of 6-7 MPa and ultimate elongation between 400 and 800 %. 

Tailoring block copolymers with three or more distinct type of blocks creates more exciting possibilities of exquisite self-assembly. The possible combination of block sequence, composition, and block molecular weight provides an enormous space for the creation of new morphologies. In multiblock copolymer with selective solvents, the dramatic expansion of parameter space poses both experimental and theoretical challenges. However, there has been very limited systematic research on the phase behavior of triblock copolymers and triblock copolymer-containing selective solvents. In the future an important aspect in the fabrication of nanomaterials by bottom-up approach would be to understand, control, and manipulate the self-assembly of phase-segregated system and to know how the selective solvent present affects the phase behavior and structure offered by amphiphilic block copolymers. 

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. 

Hong, B. K. and Jo, W. H. (2000) Effects of molecular weight of SEBS triblock copolymer on the morphology, impact strength, and rheological property of syndiotactic polystyrene/ ethylene-propylene rubber blends. Polymer, 41, 2069-2079. 

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. 

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. 

Hysteresis Behavior. The hysteresis behavior of the HBIB triblock copolymers are given in Figure 13A and of that of the inverted HIBI block copolymer is given in Figure 13B. The difference in the behavior of these two series of block copolymers is tremendous. The origin of these differences are again directly related to the morphology and the architecture of the polymers. 

The morphological behaviour of binary triblock copolymers (ABA) was elucidated in a subsequent work [32]. Including higher harmonics into his computation, Matsen s SCFT is able to bridge the gap between diblock and symmetrically composed triblock copolymers. An asymmetry parameter, r, was introduced which relates the number of segments of the shorter, r N, with that of the longer A block, (1 - x)4>aN (i.e. 0 < r < 1/2 with the limiting... 

The term star-block copolymer is used for a star architecture in which each arm is a diblock. The influence of chain topology on mechanical and morphological properties was investigated for copolymers composed of PS and PB with a constant styrene content of = 0.74 by Michler s group (Fig. 32) [101,102], While hexagonally packed cylinders of PB in a PS matrix were observed in a symmetric PS-fo-PB-fr-PS triblock copolymer, an L phase... 

Since excellent reviews on block copolymer crystallization have been published recently [43,44], we have concentrated in this paper on aspects that have not been previously considered in these references. In particular, previous reviews have focused mostly on AB diblock copolymers with one crystal-lizable block, and particular emphasis has been placed in the phase behavior, crystal structure, morphology and chain orientation within MD structures. In this review, we will concentrate on aspects such as thermal properties and their relationship to the block copolymer morphology. Furthermore, the nucleation, crystallization and morphology of more complex materials like double-crystalline AB diblock copolymers and ABC triblock copolymers with one or two crystallizable blocks will be considered in detail. 

Even though the first report about the synthesis of crystallizable ABC triblock copolymers was published in 1978 for PS-fo-PB-fo-PCL copolymers [114], in that work only a preliminary study of the tensile properties was performed, without considering the crystallizability of the materials. It was only 20 years later, when the preparation of these materials was reconsidered and optimized, that triblock copolymers with relatively narrow molecular weight distributions were obtained [115], a requisite which is indispensable for the generation of well-defined morphologies. To illustrate the complexity and richness of semicrystalline ABC triblock copolymers, PS-fc-PB-fc-PCL triblock copolymers have been chosen. These copolymers have been prepared with a wide composition range (with PCL contents from 11 to 77%) and they have been compared with PS-fc-PCL and PB-fo-PCL diblock copolymers [29,98, 115-118]. 

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