Polymer-aggregate incompatibility

It is speculated that the effect of temperature on the critical electrolyte concentration is similarly related to the effect of temperature on the structure of aqueous solutions. An increase in temperature has been shown to extend the range of micellar solutions to a higher salinity in anionic surfactant systems (31). Hence, polymer-aggregate incompatibility would be less when the temperature is increased. However, addition of alcohol or change in temperature... 

Qutubuddin, S. "Polymer-Aggregate Incompatibility, Phase Behavior and Electrophoretic Laser Light-Scattering Investigations of Microemulsions with Ultralow Interfacial Tensions", Ph.D. Thesis, Carnegie-Mellon University,... 

There also exists a need to avoid surfactant aggregate structures such as lamellar liquid crystals which exhibit high viscosity (29-32). System parameters should be such that mixing between the fluids in the surfactant, oil and polymer slugs does not occur. A dispersion of surfactant and oil would form an undesired emulsion, while a dispersion of surfactant and polymer, if incompatible, could lead to phase separation, which would decrease the effectiveness of the process. Other points to take into account are (i) the mass transfer of surfactant to the oil bank can change the interfacial tension, and (ii) surfactant-polymer incompatibility leads to a phase separation, which would reduce the efficiency of the process (30, 31). 

In general, the synthesis of relatively nonpolar sequences (cf. 18-19 in Fig. 17), proceeds efficiently on the nonpolar polymer matrix, polystyrene, but the assembly of strongly polar sequences (cf 20-21 in Fig. 17) is particularly difficult on this polymer [70a]. This arises because the hydrophilic grafts (20-21) are not compatible with the nonpolar polymer backbone. As a result, the polymer-bound peptide chains interact within themselves, and become inaccessible as a result of intra-resin H-bonding [71]. Interestingly, an opposite problem of polymer-peptide incompatibility is observed in the case of the polar polymer, dimethylacrylamide. In this case, peptide synthesis proceeds favorably for polar sequences (cf 20-21), but the synthesis of strongly hydrophobic sequences (e.g. 18-19, in Fig. 17) is not practicable because of intra-resin hydrophobic aggregation [70b]. For a recent study of peptide-peptide and peptide-polymer interactions and solvation in solid phase synthesis see Ref [72]. 

In general, block copolymers are heterogeneous (multiphase) polymer systems, because the different blocks from which they are built are incompatible with each other, as for example, in diene/styrene-block copolymers. This incompatibility, however, does not lead to a complete phase separation because the polystyrene segments can aggregate with each other to form hard domains that hold the polydiene segments together. As a result, block copolymers often combine the properties of the relevant homopolymers. This holds in particular for block copolymers of two monomers A and B. 

The steric stabilization, which is imparted by polymer molecules grafted onto the colloidal particles, is extensively employed.3 Amphiphilic block copolymers are widely used as steric stabilizers. The solvent-incompatible moieties of the block copolymer provide anchors for the polymer molecules that are adsorbed onto the surface of the colloidal particles, and the solvent-compatible (buoy) moieties extend into the solvent phase. When two particles with block copolymers on their surface approach each other, a steric repulsion is generated bet ween the two particles as soon as the tips of the buoy moieties begin to contact, and this repulsion increases the stability of the colloidal system.4-6 Polymers can also induce aggregation due to either depletion 7-11 or bridging interactions.12 15... 

It was concluded that definition of asphaltenes based only on solubility is not a satisfactory criterion and that the behavior of asphaltenes in chromatographic separations is incompatible with such structures where the polymer units are interconnected predominantly by a-bonds. The asphaltenes are a complex state of aggregation best represented by the stacked cluster structure (micelle), which, however, cannot explain some of the GPC behavior of very dilute asphaltene solutions. 

The intention of this brief survey has been to demonstrate that besides the "classical" aspects of isotropic polymer solutions and the amorphous or partially crystalline state of polymers, a broad variety of anisotropic structures exist, which can be induced by definable primary structures of the macromolecules. Rigid rod-like macromolecules give rise to nematic or smectic organization, while amphiphilic monomer units or amphiphilic and incompatible chain segments cause ordered micellar-like aggregation in solution or bulk. The outstanding features of these systems are determined by their super-molecular structure rather than by the chemistry of the macromolecules. The anisotropic phase structures or ordered incompatible microphases offer new properties and aspects for application. 

Since the ions in ionic polymers are held by chemical bonds within a low dielectric medium consisting of a covalent polymer backbone material with which they are incompatible, the polymer backbone is forced into conformations that allow the ions to associate with each other. Because these ionic associations involve ions from different chains they behave as crosslinks, but because they are thermally labile they reversibly break down on heating. lonomers therefore behave as cross-Unked, yet melt-processable, thermoplastic materials, or if the backbone is elastomeric, as thermoplastic rubbers. It should be noted that it is with the slightly ionic polymers, the ionomers, where the effect of ion aggregation is exploited to produce meltprocessable, specialist thermoplastic materials. With highly ionic polymers, the polyelectrolytes, the ionic cross-linking is so extreme that the polymers decompose on melting or are too viscous for use as thermoplastics. 

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