Poly hydrophilic functions

Many researchers have tried to prepare poly[n] catenane. However, all attempts have so far been unsuccessful. The first proposal for the preparation of poly[n]catenane was illustrated in the early 1970s [262-265]. Hydrocarbon terminated by hydrophilic functional groups was spread on the organic solvent-water interface. It was claimed that connection of the resulting U-shaped molecules by appropriate cyclic compounds followed by ring-closure afforded poly[n] catenane. However, no direct evidence for the poly[n] catenane structure was reported. A more sophisticated proposal based on the... 

SPSs), sulfonated polyimides (SPIs), sulfonated polyfphenylene) s (SPPs), sulfonated poly(arylene)-type polymers (SPAs), and sulfonated poly(phosphazene)s (SPPtis). " They contain hydro-phobic blocks (hydrocarbon backbone) and hydrophilic blocks (containing sulfonic acid groups). Sulfonic acid groups, which are commonly employed as hydrophilic functional groups, form well-defined nanosized channels for proton conduction. 

Materials that typify thermoresponsive behavior are polyethylene—poly (ethylene glycol) copolymers that are used to functionalize the surfaces of polyethylene films (smart surfaces) (20). When the copolymer is immersed in water, the poly(ethylene glycol) functionaUties at the surfaces have solvation behavior similar to poly(ethylene glycol) itself. The abiUty to design a smart surface in these cases is based on the observed behavior of inverse temperature-dependent solubiUty of poly(alkene oxide)s in water. The behavior is used to produce surface-modified polymers that reversibly change their hydrophilicity and solvation with changes in temperatures. Similar behaviors have been observed as a function of changes in pH (21—24). 

The selectivity of pervaporation membranes varies considerably and has a critical effect on the overall separation obtained. The range of results that can be obtained for the same solutions and different membranes is illustrated in Figure 41 for the separation of acetone from water using two types of membrane (89). The figure shows the concentration of acetone in the permeate as a function of the concentration in the feed. The two membranes shown have dramatically different properties. The siUcone mbber membrane removes acetone selectively, whereas the cross-linked poly(vinyl alcohol) (PVA) membrane removes water selectively. This difference occurs because siUcone mbber is hydrophobic and mbbery, thus permeates the acetone preferentially. PVA, on the other hand, is hydrophilic and glassy, thus permeates the small hydrophilic water molecules preferentially. 

In most cases, these active defoaming components are insoluble in the defoamer formulation as weU as in the foaming media, but there are cases which function by the inverted cloud-point mechanism (3). These products are soluble at low temperature and precipitate when the temperature is raised. When precipitated, these defoamer—surfactants function as defoamers when dissolved, they may act as foam stabilizers. Examples of this type are the block polymers of poly(ethylene oxide) and poly(propylene oxide) and other low HLB (hydrophilic—lipophilic balance) nonionic surfactants. 

A related technique involves incorporation of monofunctional poly(etliylene oxide) chains as nonionic, internal emulsifier groups. Even PMDI can be dispersed in water using this nonionic method (Scheme 4.24). High-molecular-weight (ca. 2000 g/m) monols are usually used which act as chain terminators and long, hydrophilic tails which function as an emulsifying agent. 

Matsusaki M, Hiwatari K, Higashi M et al (2004) Stably-dispersed and surface-functional bionanoparticles prepared by self-assembling amphipathic polymers of hydrophilic poly (y-glutamic acid) bearing hydrophobic amino acids. Chem Lett 33 398-399... 

Various commercial suppliers now offer fullerene derivatives with functionalities available for bioconjugation, including carboxylic and poly-hydroxylic derivatives, which are very hydrophilic and water-soluble (BuckyUSA, NanoLab, NanoNB, Nano-C, and Aldrich). 

TiCU readily functionalizes hydrophilic polymers such as poly(vinyl alcohol), m-ciesol novolac and methacrylic acid copolymers as well as moderately hydrophobic polymers such as poly(methyl methacrylate), poly(vinyl acetate), poly(benzyl methacrylate) and fully acetylated m-cresol novolac. HCI4 did not react with poly(styrene) to form etch resistant films indicating that very hydrophobic films follow a different reaction pathway. RBS analysis revealed that Ti is present only on the surface of hydrophilic and moderately hydrophobic polymer films, whereas it was found diffused through the entire thickness of the poly(styrene) films. The reaction pathways of hydrophilic and hydrophobic polymers with HCI4 are different because TiCl is hydrolysed by the surface water at the hydrophilic polymer surfaces to form an etch resistant T1O2 layer. Lack of such surface water in hydrophobic polymers explains the absence of a surface TiC>2 layer and the poor etching selectivities. 

A photooxidative scheme has been developed to pattern sub half-micron images in single layer resist schemes by photochemical generation of hydrophilic sites in hydrophobic polymers such as poly(styrene) and chlorinated poly(styrene) and by selective functionalization of these hydrophilic sites with TiCU followed by O2 RIE development. Sub half-micron features were resolved in 1-2 pm thick chlorinated poly(styrene) films with exposures at 248 nm on a KrF excimer laser stepper. The polymers are much more sensitive to 193 nm (sensitivity 3-32 mJ/cm2) than to 248 nm radiation (sensitivity -200 mJ/cm2) because of then-intense absorption at 193 nm. 

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