Lipophilic polymer

Sensors for acidic (HC1, SO2, CO2, acetic acid) or basic gases (NH3, amines) often make use of pH indicator dyes immobilised in polymers. Lipophilic Bromophenol Blue (see section 4.2) dissolved in silicone is... 

Application of a protective overcoat to seal off airborne contaminants was also a popular approach initially. Although many polymers, lipophilic and hydrophilic, have been evaluated as a topcoat, water-soluble poly[ (meth)acryhc acid] is most commonly employed, which can be cast from a water solution without interfacial mixing with the resist layer and can be removed during aqueous base development. However, it has been reported that a poly(acrylic acid) overcoat allows diffusion of water, which reportedly contaminates a chemical amplification resist [211]. Poly(cx-methylstyrene) has been recommended as a good barrier against both airborne base and water [211]. 

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. 

An analysis of partition coefficient data and drug solubilities in PCL and silicone rubber has been used to show how the relative permeabilities in PCL vary with the lipophilicity of the drug (58,59). The permeabilities of copolymers of e-caprolactone and dl-lactic acid have also been measured and found to be relatively invariant for compositions up to 50% lactic acid (67). The permeability then decreases rapidly to that of the homopolymer of dl-lactic acid, which is 10 times smaller than the value of PCL. These results have been discussed in terms of the polymer morphologies. 

Polymers conjugated with 1-adamantyl moieties as lipophilic pendent groups can be utilized to design nanoparticulate dmg delivery systems. Polymer (1) in Fig. 26, which is synthesized by homopolymerization of ethyladamantyl malolactonate, can be employed as highly hydrophobic blocks to construct... 

Surfactants and Colloids in Supercritical Fluids Because very few nonvolatile molecules are soluble in CO2, many types of hydrophilic or lipophilic species may be dispersed in the form of polymer latexes (e.g., polystyrene), microemulsions, macroemulsions, and inorganic suspensions of metals and metal oxides (Shah et al., op. cit.). The environmentally benign, nontoxic, and nonflammable fluids water and CO2 are the two most abundant and inexpensive solvents on earth. Fluorocarbon and hydrocarbon-based surfactants have been used to form reverse micelles, water-in-C02... 

Organic carboxylic acids are commonly found in foods, in the adipate process stream, and as pollutants. Fatty acids are the lipophilic portion of glycerides and a major component of the cell membrane. Phenols are widely used in polymers, as wood preservatives, and as disinfectants. Chloro-phenols such as 4-chlorophenol, two isomeric dichlorophenols, 2,4,6-tri-chlorophenol, three isomeric tetrachlorophenols, and pentachlorophenol were separated on a Dowex (The Dow Chemical Co. Midland, MI) 2-X8 anion exchange resin using an acetic acid-methanol gradient.138... 

Tosylate is displaced by weak oxyanions with little elimination in aprotic solvents, providing alternative routes to polymer-bound esters and aryl ethers. Alkoxides, unfortunately, give significant functional yields of (vinyl)polystyrene under the same conditions. Phosphines and sulfides can also be prepared from the appropriate anions (57), the latter lipophilic enough for phase-transfer catalysis free from poisonning by released tosylate. 

Huber Ch., Werner T., Krause Ch., Wolfbeis O.S., Novel Chloride-Selective Optode Based on Polymer-Stabilized Emulsions Doped with a Lipophilic Fluorescent Polarity-Sensitive Dye. Analyst 1999 124 1617. 

Most indicator chemistry is adapted to aqueous solution (for titration in water). Therefore, the molecules are water-soluble and if dissolved in lipophilic polymers, they are washed out immediately. In order to make dyes, ionophores and ligands soluble in polymers and to avoid leaching of the components into the sample solution, they have to be made lipophilic6. 

Positively or negatively charged indicators can be made lipophilic by ionpairing with surfactants. However, they can also be directly immobilised on the polymer by ion-pairing with ionic polymers (polyelectrolytes) (Table 9). Solutions or suspensions of the polymer are then mixed with aqueous or alcoholic solutions of the dye. 

The recognition process of the analyte by the indicator chemistry can be completely different, dependent on whether a hydrophilic or a lipophilic polymer matrix is used. In the case of lipophilic polymers, analyte ions can... 

The optical sensors are composed of ion-selective carriers (ionophores), pH indicator dyes (chromoionophores), and lipophilic ionic additives dissolved in thin layers of plasticized PVC. Ionophores extract the analyte from the sample solution into the polymer membrane. The extraction process is combined with co-extraction or exchange of a proton in order to maintain electroneutrality within the unpolar polymer membrane. This is optically transduced by a pH indicator dye (chromoionophore)10. 

In the case of co-extraction, a selective anion-carrier (ionophore) extracts the analyte anion into the lipophilic sensor membrane. In order to maintain electroneutrality, a proton is co-extracted into the membrane where it protonates a pH indicator dye contained in the polymer membrane. Due to protonation, the dye undergoes a change in either absorption or fluorescence. (Figure 6 and Tables 13 and 14). 

The sensor layer consists of a selective ionophore (e.g. valinomycin for potassium), a lipophilic anionic site (borate) and the cationic PSD. Before interaction with potassium, a lipophilic ion pair between the cationic PSD and borate anion is formed in the polymer layer. When valinomycin (also contained in the layer) selectively extracts potassium into the layer, then the positively charged valinomycin-potassium complex forms an ion pair with... 

Macromolecules have also been specifically designed and synthesized for use as emulsifiers for lipophilic materials and as stabilizers in the colloidal dispersion of lipophilic, hydrocarbon polymers in C02. We have demonstrated the amphiphilicity of fluorinated acrylate homopolymers, such as PFOA, which contain a lipophilic, acrylate like backbone and C02-philic, fluorinated side chains (see Fig. 3) [103]. It has been demonstrated that a homopolymer which physically adsorbs to the surface of a polymer colloid prevents agglomeration by the presence of loops and tails (see Fig. 4) [113]. The synthesis of this type of... 

In 1994, we reported the dispersion polymerization of MM A in supercritical C02 [103]. This work represents the first successful dispersion polymerization of a lipophilic monomer in a supercritical fluid continuous phase. In these experiments, we took advantage of the amphiphilic nature of the homopolymer PFOA to effect the polymerization of MMA to high conversions (>90%) and high degrees of polymerization (> 3000) in supercritical C02. These polymerizations were conducted in C02 at 65 °C and 207 bar, and AIBN or a fluorinated derivative of AIBN were employed as the initiators. The results from the AIBN initiated polymerizations are shown in Table 3. The spherical polymer particles which resulted from these dispersion polymerizations were isolated by simply venting the C02 from the reaction mixture. Scanning electron microscopy showed that the product consisted of spheres in the pm size range with a narrow particle size distribution (see Fig. 7). In contrast, reactions which were performed in the absence of PFOA resulted in relatively low conversion and molar masses. Moreover, the polymer which resulted from these precipitation... 

Solvent polymeric membranes, conventionally prepared from a polymer that is highly plasticized with lipophilic organic esters or ethers, are the scope of the present chapter. Such membranes commonly contain various constituents such as an ionophore (or ion carrier), a highly selective complexing agent, and ionic additives (ion exchangers and lipophilic salts). The variety and chemical versatility of the available membrane components allow one to tune the membrane properties, ensuring the desired analytical characteristics. 

The main classes of plasticizers for polymeric ISEs are defined by now and comprise lipophilic esters and ethers [90], The regular plasticizer content in polymeric membranes is up to 66% and its influence on the membrane properties cannot be neglected. Compatibility with the membrane polymer is an obvious prerequisite, but other plasticizer parameters must be taken into account, with polarity and lipophilicity as the most important ones. The nature of the plasticizer influences sensor selectivity and detection limits, but often the reasons are not straightforward. The specific solvation of ions by the plasticizer may influence the apparent ion-ionophore complex formation constants, as these may vary in different matrices. Ion-pair formation constants also depend on the solvent polarity, but in polymeric membranes such correlations are rather qualitative. Insufficient plasticizer lipophilicity may cause its leaching, which is especially undesired for in-vivo measurements, for microelectrodes and sensors working under flow conditions. Extension of plasticizer alkyl chains in order to enhance lipophilicity is only a partial problem solution, as it may lead to membrane component incompatibility. The concept of plasticizer-free membranes with active compounds, covalently attached to the polymer, has been intensively studied in recent years [91]. 

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