Functionalized polymers with diblock copolymers

The microphase separation of amphiphilic block copolymers can be utilized as a secondary self-assembly step in the formation of SPs. For example, the complexation of two mono-functional polymers with complementary, noncovalent end groups can lead to AB diblock copolymers that then phase separate into a micelle (Figure 38(b)). 

When dealing with polymer blends or blockcopolymers, surface enrichment or microstructures may be observed as already discussed in Sect. 3.1. Quite similar effects may be expected for buried interfaces e.g. between polymer and substrate where one component may be preferentially enriched. In a system of PS, PVP and diblock copolymer PS-6-PVP it has been shown by FRS that the copolymer enrichment is strongly concentration dependent [158]. In a mixed film of PS(D) and end-functionalized PS on a silicon wafer the end-functionalized chains will be attached to the silicon interface and can be detected by NR [159],... 

The formation of nanopattemed functional surfaces is a recent topic in nanotechnology. As is widely known, diblock copolymers, which consist of two different types of polymer chains cormected by a chemical bond, have a wide variety of microphase separation structures, such as spheres, cylinders, and lamellae, on the nanoscale, and are expected to be new functional materials with nanostructures. Further modification of the nanostructures is also useful for obtaining new functional materials. In addition, utilization of nanopartides of an organic dye is also a topic of interest in nanotechnology. 

Further modification of the above nanostructures is useful for obtaining new functional materials. Thirdly, we apply the dopant-induced laser ablation technique to site-selectively doped thin diblock copolymer films with spheres (sea-island), cylinders (hole-network), and wormlike structures on the nanoscale [19, 20]. When the dye-doped component parts are ablated away by laser light, the films are modified selectively. Concerning the laser ablation of diblock copolymer films, Lengl et al. carried out the excimer laser ablation of diblock copolymer monolayer films, forming spherical micelles loaded with an Au salt to obtain metallic Au nanodots [21]. They used the laser ablation to remove the polymer matrix. In our experiment, however, the laser ablation is used to remove one component of block copolymers. Thereby, we can expect to obtain new functional materials with novel nanostmctures. 

Fig. 67. Experimental variations of the interdiffusion coefficient Qi(Q)/Q2 as a function of Q at the total polymer concentration c = 0.34 g/cm3 for the two investigated sytems ( ) diblock copolymer PSD-PSH 561/ben-zene + d-benzene ( ) mixture of homopolymers PSH155/PSD425/d-benzene. The solid lines are visual aids. (Reprinted with permission from [171]. Copyright 1989 American Chemical Society, Washington)...

In the case of heterogeneous polymers the experimental methods need to be refined. In order to analyze those polymers it is necessary to determine a set of functions / (M), which describe the distribution for each kind of heterogeneity i This could be the mass distributions of the blocks in a diblock copolymer. The standard SEC methods fail here and one needs to refine the method, e.g., by performing liquid chromatography at the critical point of adsorption [59] or combine SEC with methods, which are, for instance, sensitive to the chemical structure, e.g., high-pressure liquid chromatography (HPLC), infrared (IR), or nuclear magnetic resonance spectroscopy (NMR) [57],... 

A carbazole-functionalized norbornene derivative, 5-CN-carbazoyl methy-lene)-2-norbornene, CbzNB, was polymerized via ROMP using the ruthenium catalyst Cl2Ru(CHPh)[P(C6Hii)3]2 [100]. The polymerization was conducted in CH2C12 at room temperature, to afford products with polydispersity indices close to 1.3. Subsequent addition of 5-[(trimethylsiloxy)methylene]-2-norbornene showed a clear shift of the SEC trace of the initial polymer, indicating that a diblock copolymer was efficiently prepared in high yield. 

A system of n AB diblock copolymers each with a degree of polymerization N and A-monomer fraction, /, is considered. The A and B monomers occupy a fixed volume, l/g0, and the system is incompressible with a total volume, V, equal to hN/qq. A variable s is used as a parameter than increases continuously along the length of a polymer. At the A monomer end, s = 0, at the junction point, s = f, and at the other end, s = 1. The functions r (s) define the space curve occupied by the copolymer a (Matsen and Schick 1994). 

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... 

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