Phase behavior copolymers

Fig. 5. Phase behavior of blends of a styrene—acrylonitrile copolymer containing 19 wt % of acrylonitrile with other SAN copolymers of varying AN content and as a function of the molecular weight of the two copolymers (° ) one-phase mixture ( ) two-phase mixtures as judged by optical clarity. Curve...

In a somewhat wider sense, one can define amphiphiles as molecules in which chemically very different units are linked together. For example, the structures formed by A B block copolymers in demixed A and/or B homopolymer melts and their phase behavior are very similar to those of classical amphiphiles in water and/or oil [13,14]. Copolymers are used not only to disperse immiscible homopolymer phases in one another, but also to create new, mesoscopically structured materials with unusual and interesting properties [15]. 

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. 

Minich E.A., Nowak A.P., Deming T.J., and Pochan, D.J. Rod-rod and rod-coil self-assembly and phase behavior of pol3fpeptide diblock copolymers. Polymer, 45, 1951, 2004. 

LeiblerL., Theory of microphase separation in block copolymers. Macromolecules, 13, 1602, 1980. Eoerster S., Khandpur A.K., Zhao J., Bates E.S., Hamley I.W., Ryan A.J., and Bras W. Complex phase behavior of polyisoprene-polystyrene diblock copolymers near the order-disorder transition. Macromolecules, 21, 6922, 1994. 

Linse, P, Phase Behavior of Poly(ethylene oxide)-Poly(propylene oxide) Block Copolymers in Aqueous Solutions, Journal of Physical Chemistry 97, 13896, 1993. 

The topic is split into two volumes and is organized as follows. In the first chapter the progress in different synthetic routes to controlled block copolymers of various architectures will be presented, the second chapter tries to give an overview of the phase behavior of block copolymers in the bulk state and in concentrated solution. The interplay between crystallization on... 

Phase behavior in complex fluids such as polymer blends and block copolymers has been a rich area of the chemical sciences. Near-critical and other transitional phenomena are frequently prominent. Since molecular movement in viscous systems such as these is comparatively slow, phase transitions can be studied more easily in time, and manipulated by quenching and other external influences. Processes for controlled growth of ordered materials are often readily influenced by diffusion, a variety of external fields, and the influence of interacting boundaries, or flow. 

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. 

Molecular architecture modifies the phase behavior of block copolymers. In block copolymers, macrophase separation is prevented by the connectivity of the polymer chains. The transition from a homogeneous melt to a heteroge-... 

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... 

The benefits of utihzing combinatorial methods for investigating polymer properties have been outlined recently [19,166,167]. Polymer gradient brush assemblies are expected to play an active role in further combinatorial material effort. Possible areas of interest include (but are not hmited to) study of phase behavior (stability) in hquid [168] and polymer blend [169] systems, morphological transitions in block copolymers [170,171], cell culturing [58,172], and others. 

Schwahn, D. Willner, L. Phase Behavior and Flory-Huggins Interaction Parameter of Binary Polybutadiene Copolymer Mixtures with Different Vinyl Content and Molar Volume. Macromolecules 2002,35, 239-247. 

The morphology of this supramolecular diblock copolymer library has been investigated by means of atomic force microscopy (AFM) measurements. As illustrated in Fig. 21, at first glance different morphologies were obtained for different compositions. However, interpreting the phase behavior of supramolecular block copolymers is not straightforward. There are several important parameters that play a role in the phase behavior. For instance, the amorphous phase of PEG, the crystalline phase of PEG, the metal complex, and the amorphous PSt contribute to... 

Therefore, polyrotaxanes can be simply defined as polymeric materials containing rotaxane units. They are different from conventional linear homopolymers because they always consist of two components, a cyclic species mechanically attached to a linear species. They also differ from polymer blends as the individual species are interlocked together and from block copolymers since the two components are noncovalendy connected. Thus new phase behavior, mechanical properties, molecular shapes and sizes, and different solution properties are expected for polyrotaxanes. Their ultimate properties depend on the chemical compositions of the two components, their interaction and compatibility. This review is designed to summarize the syntheses of these novel polymers and their properties. 

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