Amphiphilic block co-polymers

Finally, it should be mentioned that a combination of COSMO-RS with tools such as MESODYN [127] or DPD [128] (dissipative particle dynamics) may lead to further progress in the area of the mesoscale modeling of inhomogeneous systems. Such tools are used in academia and industry in order to explore the complexity of the phase behavior of surfactant systems and amphiphilic block-co-polymers. In their coarse-grained 3D description of the long-chain molecules the tools require a thermodynamic kernel... 

Figure 18.10 Nanoparticulate drug delivery systems formed by amphiphilic block co-polymers and their characteristics [55]. 

Gbltner C.G., Berton B., Kramer E., Antonietti M. Nanoporous silicas by casting the aggregates of amphiphilic block co-polymers the transition from cylinders to lamellae and vesicles. Adv. Mater. 1999 11 395-398... 

An important group of surface-active nonionic synthetic polymers (nonionic emulsifiers) are ethylene oxide (block) (co)polymers. They have been widely researched and some interesting results on their behavior in water have been obtained [33]. Amphiphilic PEO copolymers are currently of interest in such applications as polymer emulsifiers, rheology modifiers, drug carriers, polymer blend compatibilizers, and phase transfer catalysts. Examples are block copolymers of EO and styrene, graft or block copolymers with PEO branches anchored to a hydrophilic backbone, and star-shaped macromolecules with PEO arms attached to a hydrophobic core. One of the most interesting findings is that some block micelle systems in fact exists in two populations, i.e., a bimodal size distribution. 

Block co-polymers Self-assembled mask Parallel, fast, small size, no resist, solvents, etc. Material constraints, no long-range order, cleanliness New amphiphilic, diblock copolymers, multifunctional structures... 

Using amphiphilic poly(2-oxazoline) derived block co-polymer backbones, immobilized palladium and rhodium carbene NHC complexes have been prepared for use in C-C couplings and hydroformylation, respectively. For the synthesis of the supported rhodium complex, the NHC ligand was attached to prefabricated support This was... 

Zhang, G., Ma, J., Li, Y., and Wang, Y. (2003) Synthesis and characterization of poly (L-alanine)-block-poly (ethylene glycol) monomethyl ether as amphiphilic biodegradable co-polymers. Journal of Biomaterials Science, Polymer Edition, 14,1389-1400. 

Many kinds of nonbiodegradable vinyl-type hydrophilic polymers were also used in combination with aliphatic polyesters to prepare amphiphilic block copolymers. Two typical examples of the vinyl-polymers used are poly(/V-isopropylacrylamide) (PNIPAAm) [149-152] and poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) [153]. PNIPAAm is well known as a temperature-responsive polymer and has been used in biomedicine to provide smart materials. Temperature-responsive nanoparticles or polymer micelles could be prepared using PNIPAAm-6-PLA block copolymers [149-152]. PMPC is also a well-known biocompatible polymer that suppresses protein adsorption and platelet adhesion, and has been used as the hydrophilic outer shell of polymer micelles consisting of a block copolymer of PMPC -co-PLA [153]. Many other vinyl-type polymers used for PLA-based amphiphilic block copolymers were also introduced in a recent review [16]. 

By covalent linkage of different types of molecules it is possible to obtain materials with novel properties that are different from those of the parent compounds. Examples of such materials are block-copolymers, soaps, or lipids which can self-assemble into periodic geometries with long-range order. Due to their amphiphilic character, these molecules tend to micellize and to phase-separate on the nanometer scale. By this self-assembly process the fabrication of new na-noscopic devices is possible, such as the micellization of diblock-co-polymers for the organization of nanometer-sized particles of metals or semiconductors [72 - 74]. The micelle formation is a dynamic process, which depends on a number of factors like solvent, temperature, and concentration. Synthesis of micelles which are independent of all of these factors via appropriately functionalized dendrimers which form unimolecular micelles is a straightforward strategy. In... 

The interfacial properties of an amphiphilic block copolymer have also attracted much attention for potential functions as polymer compatibilizers, adhesives, colloid stabilizers, and so on. However, only a few studies have dealt with the monolayers o well - defined amphiphilic block copolymers formed at the air - water interface. Ikada et al. [124] have studied monolayers of poly(vinyl alcohol)- polystyrene graft and block copolymers at the air - water interface. Bringuier et al. [125] have studied a block copolymer of poly (methyl methacrylate) and poly (vinyl-4-pyridinium bromide) in order to demonstrate the charge effect on the surface monolayer- forming properties. Niwa et al. [126] and Yoshikawa et al. [127] have reported that the poly (styrene-co-oxyethylene) diblock copolymer forms a monolayer at the air - water... 

The multifunctional initiators may be di- and tri-, azo- or peroxy-compounds of defined structure (c.g. 20 ) or they may be polymeric azo- or peroxy-compouiids where the radical generating functions may be present as side chains or as part of the polymer backbone." Thus, amphiphilic block copolymers were synthesized using the polymeric initiator 21 formed from the reaction between an a,co-diol and AIBN (Scheme 7.22)." Some further examples of multifunctional initiators were mentioned in Section 3.3.3.2. It is also possible to produce less well-defined multifunctional initiators containing peroxide functionality from a polymer substrate by autoxidalion or by ozonolysis." ... 

Another pyrrolidone-based phosphine has been incorporated into amphiphilic, water-soluble diblock co-polymers based on 2-oxazalone derivatives (Scheme 61). The synthesis involved the initial preparation of a diblock co-polymer precursor with ester functionalities in the side chain. This was achieved by sequential polymerization of 2-methyl-2-oxazoline to form the hydrophilic block that provides water solubility, and subsequently a mixture of ester-functionalized oxazoline 147 and 2-nonyl-2-oxazoline, the latter increasing the hydrophobicity of the second polymer block. Having made the backbone, the ester functionalities were converted into carboxylic acids giving polymer 148, which was then reacted with the phosphine ligand to give the desired supported material, 149. This was used in asymmetric hydrogenation reactions with success. 

Finally we note that, apart from double-tailed surfactant molecules, vesicular aggregates can also be formed from a number of other building blocks, including nonionic amphiphiles to form niosomes, single-tailed surfactants and complex (co)polymers, polypeptides, and dendrimers. In this chapter we restrict our discussion to encapsulation processes by vesicles formed from synthetic surfactants and phospholipids. 

Methyl methacrylate (MMA) and sodium styrene sulfonate (SSNa) are water-soluble. These polymers behave like a low MW surfactant as they form micelles in aqueous solution in which the hydrophobic part is directed towards the centre and the hydrophilic part is situated on the periphery of the micelle. Owing to such features, amphiphilic block copolymers have wide-ranging applications in drugs, pharmaceuticals, coatings, cosmetics and paints. They also exhibit very high antibacterial activities. Oikonomou and co-workers used ATRP to prepare amphiphilic block copolymers, consisting of polymethyl methacrylate (PMMA) and poly (sodium styrene sulfonate) (PSSNa) blocks [18]. The synthesis methods are described below. 

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