Block copolymers ordered state

At present, there is no comprehensive theory that can enable one to predict the rheological behavior of a block copolymer, ordered or disordered, in terms of its molecular parameters. It can easily be surmised that prediction of the rheological properties of a block copolymer in the ordered state would be a difficult task, because the type of microdomain structure (spheres, cylinders, gyroids, or lamellae) must be incorporated into the development of a molecular theory. It should be pointed out that spherical... 

Besides its effects on morphology, comonomer sequence distribution also affects copolymer crystallization kinetics. In statistical copolymers, due to the broad distribution of crystaUizable sequence lengths, bimodal melting endotherms are typically observed. In block copolymers, the dynamics of crystallization have features characteristic of both homopolymer crystallization and microphase separation in amorphous block copolymers. In addition, the presence of order in the melt, even if the segregation strength is weak, hinders the development of the equihbrium spacing in the block copolymer solid-state structure. 

It is well known that block copolymers and graft copolymers composed of incompatible sequences form the self-assemblies (the microphase separations). These morphologies of the microphase separation are governed by Molau s law [1] in the solid state. Nowadays, not only the three basic morphologies but also novel morphologies, such as ordered bicontinuous double diamond structure, are reported [2-6]. The applications of the microphase separation are also investigated [7-12]. As one of the applications of the microphase separation of AB diblock copolymers, it is possible to synthesize coreshell type polymer microspheres upon crosslinking the spherical microdomains [13-16]. 

Polyarylate (PAR)-b-PSt and PAR-b-PMMA for compatibiiizers are described 135,39,40). The addition of PAR-b-PSt (1-10 parts) to 100 parts of a blend of PAR-PSt (7w-3w) resulted in improvement of the tensile and flexural modulus (Fig. 4), and PSt dispersed particles were diminished from 1-5 microns to an order that is undetectable by SEM, indicating the excellent, compatibilizing effect of the block copolymer. The alloy thus formed exert the characteristic of PAR, an engineering plastic, as well as easy processability of PSt. Addition of PAR-b-PMMA (3 or 8 parts) to 100 parts of a blend of PAR-polyvinylidenefluoride (PVDF) (7w-3w) resulted in improved microdispersed state of PVDF due to compatibility of PMMA with PVDF, while segregation of PVDF onto the surface was controlled. 

Microdomain stmcture is a consequence of microphase separation. It is associated with processability and performance of block copolymer as TPE, pressure sensitive adhesive, etc. The size of the domain decreases as temperature increases [184,185]. At processing temperature they are in a disordered state, melt viscosity becomes low with great advantage in processability. At service temperamre, they are in ordered state and the dispersed domain of plastic blocks acts as reinforcing filler for the matrix polymer [186]. This transition is a thermodynamic transition and is controlled by counterbalanced physical factors, e.g., energetics and entropy. 

Ordered body-centered cubic structures were observed by shearing aqueous gels made from anionic PtBS-PMANa block copolymer micelles [163]. The emergence of the ordered gel state could be accounted for similar building up of a polyelectrolyte-based fibrillar network that can be oriented under shear. 

In addition to the previously mentioned driving forces that determine the bulk state phase behavior of block copolymers, two additional factors play a role in block copolymer thin films the surface/interface energies as well as the interplay between the film thickness t and the natural period, Lo, of the bulk microphase-separated structures [14,41,42], Due to these two additional factors, a very sophisticated picture has emerged from the various theoretical and experimental efforts that have been made in order to describe... 

Table 1 Summary of block copolymers studied in order to control microdomain orienta-tions in thin film states ...

Fig. 9 Schematic representation of three approaches to generate nanoporous and meso-porous materials with block copolymers, a Block copolymer micelle templating for mesoporous inorganic materials. Block copolymer micelles form a hexagonal array. Silicate species then occupy the spaces between the cylinders. The final removal of micelle template leaves hollow cylinders, b Block copolymer matrix for nanoporous materials. Block copolymers form hexagonal cylinder phase in bulk or thin film state. Subsequent crosslinking fixes the matrix hollow channels are generated by removing the minor phase, c Rod-coil block copolymer for microporous materials. Solution-cast micellar films consisted of multilayers of hexagonally ordered arrays of spherical holes. (Adapted from [33])...

The examples discussed above illustrate the importance of block copolymer chain segment incompatibilities for the phase separation of bulk materials, combined with the ability to perform chemistry within specific nanoscale domains to impose permanence upon those self-assembled nanostructured morphologies. Each is limited, however, to crosslinking of internal domains within the solid-state assemblies in order to create discrete nanoscale objects. To advance the level of control over regioselective crosslinking and offer methodologies that allow for the production of additional unique nanostructured materials, the pre-assembled structures can be produced in solution (Figure 6.4), as isolated islands with reactivity allowed either internally or on the external... 

Stepanek, P. and Lodge, T. P. (1996). Light scattering by block copolymer liquids in the disordered and ordered state. In Light scattering. Principles and development, (ed. W. Brown). Oxford University Press, Oxford. 

Block copolymers containing crystallizable blocks have been studied not only as alternative TPEs with improved properties but also as novel nanos-tructured materials with much more intricate architectures compared to those produced by the simple amorphous blocks. Since the interplay of crystallization and microphase segregation of crystalline/amorphous block copolymers greatly influences the final equilibrium ordered states, and results in a diverse morphological complexity, there has been a continued high level of interest in the synthesis and characterization of these materials. 

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