Polymer-based miscible systems

The polymer-based miscible systems can be either intermolecular mixtures, for instance polymer solutions and blends, or intramolecular mixtures, such as block copolymers, star-shape multi-arm copolymers, grafted copolymers, random copolymers, and gradient copolymers with a composition gradient from one chain end to the other. Polymer-based miscible systems can phase separate into segregated phases with stable interfaces, or crystallize into crystalline ordered phases. In other words, there are two types of phase transitions, phase separation and crystallization. Under proper thermodynamic conditions, two phase transitions may occur simultaneously. The interplay of these two transitions will dictate the final morphology of the system. In the following, we will choose polymer solutions as typical examples to introduce the polymer-based miscible systems. 

It is known that, in a polymer blend, thermodynamic incompatibility between polymers usually causes demixing of polymers. If the polymer is equilibrated in air, the polymer with the lowest surface energy (hydrophobic polymer) will concentrate at the air interface and reduce the system s interfacial tension as a consequence. The preferential adsorption of a polymer of lower surface tension at the surface was confirmed by a number of researchers for a miscible blend of two different polymers. Based on this concept, surface modifying macromolecules (SMMs) as surface-active additives were synthesized and blended into polymer solutions of polyethersulfone (PES). Depending on the hydro-phobic or hydrophilic nature of the SMM, the membrane surface becomes either more hydrophobic or more hydrophilic than the base polymeric material. ... 

Polymer-based multi-component systems can be classified into two categories one is a miscible system, in which polymers are homogeneously mixed with other molecules the other one is a composite system, in which polymers are not mixed with other molecules, except at interfaces. 

PBI is one of the most highly studied high temperature polymers in miscible blends. The fundamental reason for the observation of miscibility in PBl-based systems is the presence of the N-H functional group that can interact with the functional groups which are present on the backbone of other polymers. Thus, miscibility in these type of systems is an example of a specific interaction that leads to a negative enthalpy of mixing, a requirement for forming miscible mixtures. 

This section describes the horseradish peroxidase-catalyzed synthesis of both homo- and copolymers of aromatic polymers based on phenols, naphthols, aniline, and their derivatives. Syntheses of novel optically active polymers are studied by changing the environment in which the enzyme functions, along with the organization of the monomers in the reaction mixture. To this objective, enzyme-catalyzed polymer syntheses are carried out in bulk monophasic conditions in which the solvent is miscible with water, biphasic solvent systems in which the solvents used for the syntheses are not miscible with water, and oil-in-water system in the presence of a detergent called reverse micelles. These experimental approaches are shown schematically in Fig. 4. 

In the preceding chapter we have, based on the Flory-Huggins theory, discussed the basis for the phase behavior of polymer blends. Miscible polymer blends and polymer solutions have, even in the mixed one-phase system, spatial variations in the polymer concentration. These concentration fluctuations reflect the thermodynamic parameters of the free energy, as described in the Flory-Huggins model. 

After a temptative structure-based classification of different kinds of polymorphism, a description of possible crystallization and interconversion conditions is presented. The influence on the polymorphic behavior of comonomeric units and of a second polymeric component in miscible blends is described for some polymer systems. It is also shown that other characterization techniques, besides diffraction techniques, can be useful in the study of polymorphism in polymers. Finally, some effects of polymorphism on the properties of polymeric materials are discussed. 

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