Polymeric surfactants system copolymers

Exploiting ATRP as an enabling technology, we have recently synthesised a wide range of new, controlled-structure copolymers. These include (1) branched analogues of Pluronic non-ionic surfactants (2) schizophrenic polymeric surfactants which can form two types of micelles in aqueous solution (3) novel sulfate-based copolymers for use as crystal habit modifiers (4) zwitterionic diblock copolymers, which may prove to be interesting pigment dispersants. Each of these systems is discussed in turn below. 

Emulsion polymerization has become an important process for the production of a large number of industrial polymers in the form of polymer colloids or latexes. They are the base of adhesives, paints and especially of waterborne coatings. An interest has been developed in recent years in emulsion polymerization systems in which the classical low molecular weight surfactaints are replaced by polymeric surfactants, either hydrophilic-hydrophobic block and graft copolymers (1-4) or functionalized oligomers (5). 

Polymerization of the alkoxyallene with macromonomers having a poly (ethyleneglycol) group by [(7r-allyl)Ni(OCOCF3)]2/PPh3 produces a graft copolymer with narrow molecular weight distribution [129]. The products serve as polymeric surfactants in the polymer blend system of polystyrene and poly(methyl methacrylate). 

These are stable micelles that are formed with polymeric surfactants. Amphiphilic block copolymers such as the pluronics (polyoxyethylene-polyoxypropylene block copolymers) are able to self-assemble into polymeric micelles and hydrophobic drugs may be solubilized within the core of the micelle or, alternatively, conjugated to the micelle-forming polymer. Although micelles are rather dynamic systems that continuously exchange units between the micelle structure and the free units in solution, those composed of polyoxyethylene - poly(aspartic acid) have been found sufficiently... 

As discussed above, the incorporation of an oil-soluble polymeric surfactant that adsorbs strongly at the O/W interface would be expected to cause a reduction in the Ostwald ripening rate. To test this hypothesis, an A-B-A block copolymer of poly(hydroxystearic acid) (PHS, the A chains) and PEO (the B chain) PHS-PEO-PHS (Arlacel P135) was incorporated in the oil phase at low concentrations (the ratio of surfactant to Arlacel was varied between 99 1 and 92 8). For the hexadecane system, the Ostwald ripening rate showed a decrease with the addition of Arlacel PI 35 surfactant at ratios lower than 94 6. Although similar results were... 

Elemental analysis (EA) is a convenient method for determination of copolymer and blend composition if one homopolymer contains an element not present in the second one. For example, EA can be properly used to quantify nitrogen in copolymers containing acrylonitrile units and oxygen in polymeric surfactants such as poly(oxy-alkylene). Therefore, for a binary system, every element can be balanced according to the following equation ... 

Gd + complexes is synthetically one of the easiest ways to create nanosize systems. MiceUe-like structures can also be obtained from block copolymers which consist of a nonionic hydrophilic polar part (the Gd chelate) and a hydrophobic part (for instance, methylene groups) which behave as typical nonionic polymeric surfactants. ... 

One particular asset of structured self-assemblies is their ability to create nano- to microsized domains, snch as cavities, that could be exploited for chemical synthesis and catalysis. Many kinds of organized self-assemblies have been proved to act as efficient nanoreactors, and several chapters of this book discnss some of them such as small discrete supramolecular vessels (Chapter Reactivity In Nanoscale Vessels, Supramolecular Reactivity), dendrimers (Chapter Supramolecular Dendrlmer Chemistry, Soft Matter), or protein cages and virus capsids (Chapter Viruses as Self-Assembled Templates, Self-Processes). In this chapter, we focus on larger and softer self-assembled structures such as micelles, vesicles, liquid crystals (LCs), or gels, which are made of surfactants, block copolymers, or amphiphilic peptides. In addition, only the systems that present a high kinetic lability (i.e., dynamic) of their aggregated building blocks are considered more static objects such as most of polymersomes and molecularly imprinted polymers are discussed elsewhere (Chapters Assembly of Block Copolymers and Molecularly Imprinted Polymers, Soft Matter, respectively). Finally, for each of these dynamic systems, we describe their functional properties with respect to their potential for the promotion and catalysis of molecular and biomolecu-lar transformations, polymerization, self-replication, metal colloid formation, and mineralization processes. 

In Chapter 1, Murgia, Palazzo, and coworkers investigated the physicochemical behaviors of a binary IL bmimBF and water, and the ternary NaAOT, water and bmimBF mixtures essentially through the evaluation of the self-diffusion coefficients of the various chemical species in solution by PGSTE-NMR experiments. The diffusion of water molecules and bmimBF ions were found to be within different domains, which suggested that the systems were nanostructured with formation of micelles having positive curvature and a bicontinuous micellar solution for the former and the later systems, respectively. The remarkable differences between the two systems are attributed to the specific counterion effect between the aforementioned ILs and the anionic surfactant. In Chapter 2, Bermudez and coworkers focused on the characterization of small (conventional surfactants) and polymeric amphiphiles (block copolymers) in different types of ILs (imidazolium, ammonium. 

Polymeric surfactants of the block (A-B or A-B-A) or graft (BA ) type are essential materials for the preparation of many systems, e.g., dyestuffs, paper coatings, inks, agrochemicals, pharmaceuticals, personal care products, ceramics, and detergents. A block copolymer is a linear arrangement of blocks of varying composition [5] ... 

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