Polymer Swelling Hydrophilic polymers

Figure 5.3 Schematic of a swelled hydrophilic polymer matrix.

By plotting the fractional amount of absorbed or desorbed protein, 00, versus time, the difflisivity can be evaluated from the slope of the initial 60% of the total release, with an accuracy of 1 %. This analysis is valid for systems that behave in a Fickian manner, such as an equilibrium swollen hydrogel with evenly dispersed protein. However, non-Fickian transport phenomena are t q)ically observed for swelling hydrophilic polymers initially in the glassy state, as described by Peppas and Lustig (1985). 

Hydrogels. Controlled swelling of hydrophilic polymers, derived from the glossy/mbbery properties of polymers, is used to control the rate of dmg release from matrices. In the mbbery state, accompHshed by lowering the polymer s glass-transition temperature to an appropriate level, the dispersed dmg diffuses as the polymer swells in the presence of water. 

Hydrogels are water-containing polymers, hydrophilic in nature, yet insoluble. In water, these polymers swell to an equiUbrium volume and maintain thek shape. The hydrophilicity of hydrogel is a result of the presence of functional groups such as —NH2, —OH, —COOH, —CONH2, —CONH—, —SO H, etc. The insolubihty and stabiUty of hydrogels are caused by the presence of a three-dimensional network. The scope, preparation, and characterization of hydrogels has been reviewed (107). 

Carbopol is widely used in cosmetic and pharmaceutical practice as a gel-former. Carbopol resins are hydrophilic polymers which swell in water solutions and transform into the gel form at neutralization. At the elaboration of special cosmetic preparations in which carbopol is used, the problem of raw materials compatibility appears. For example, some extracts of aromatic pectin containing materials destroy the gel structure of carbopol. High contents of bivalent metal ions, in particular calcium ions, destructively influence onto the gel-making ability of the system too. 

A. Audibert, J. Lecourtier, L. C. Bailey, and G. Maitland. Use of polymers having hydrophilic and hydrophobic segments for inhibiting the swelling of reactive argillaceous formations (Tutilisation d un... 

When the reaction times for Step 1 are 5 min or longer, the samples severely crack, curl, or dissolve. These results suggest that substantial reaction is occurring in the bulk of the polymer. Significant hydrophilization can occur with reaction times as short as 5 s with RTD concentrations of 0.2-0.5 M. However, 0.002-0.02 M solutions of MeTD or PhTD do not allow sufficient reaction rates for surface hydrophilization at the shorter reaction times. Thus, diffusion of MeTD and PhTD into the polymer must occur readily from the acetonitrile solutions. Acetonitrile was used because it does not swell or dissolve the polymer or RTD-polymer adduct, and the RTDs are soluble and stable in it. This solvent is quite polar (dielectric constant, 38) (25), and this is probably a major factor in the partitioning of the relatively nonpolar RTDs between the polydiene film and the solvent. As noted below, more polar RTDs show less tendency to diffuse into the polymer. 

Hydrophilic polymers (Table 5) provide a matrix which is comparable to an aqueous environment. Ions can diffuse quite freely, but the possible water uptake (10-1000%) can cause significant swelling of the polymer. Swelling of the matrix affects the optical properties of the sensors and, consequently, the signal changes. Immobilization of the indicator chemistry usually is achieved via covalent bonding to the polymer. 

Granular swelling agents. These systems typically consist of cross-linked hydrophilic polymers like e.g. cross-linked poly-(N-vinyl pyrrolidone) or hydrophilic but insoluble polymers, e.g. cellulose that swell to a considerable volume within a few seconds on contact with water. These systems are powerful disintegrants and are used particularly in quick-release detergent tablets put in a dispenser tray. 

Dew condensation sensors are usually made of hydrophilic or swelling organic polymers in which carbon particles are dispersed... 

Soluble matrix systems. The third matrix system is based on hydrophilic polymers that are soluble in water. For these types of matrix systems, water-soluble hydrophilic polymers are mixed with drugs and other excipients and compressed into tablets. On contact with aqueous solutions, water will penetrate toward the inside of the matrix, converting the hydrated polymer from a glassy state (or crystalline phase) to a rubbery state. The hydrated layer will swell and form a gel, and the drug in the gel layer will dissolve and diffuse out of the matrix. At the same time, the polymer matrix also will dissolve by slow disentanglement of the polymer chains. This occurs only for un-cross-linked hydrophilic polymer matrices. In these systems, as shown in Fig. 5.3, three fronts are formed during dissolution9-11 ... 

The same authors developed a process of encapsulation of polymers swelled by halogenated solvents in which ozone is greatly soluble but not monomers to be grafted. After ozonization of polymers swelled in solvents, mixtures of mono unsaturated or di unsaturated monomers are added to the activated polymers. Then, grafting is operated by UV irradiation. Grafting is mainly located at the surface of the starting polymer what prevents the modification of its intrinsic properties. This process permits to produce hydrophilic polysiloxanes used in medical applications (contact lenses, tubes, catheters, etc.). 

Polymer Swelling. Swelling phenomena are generally encountered in both the hydrophilic and hydrophobic polymer matrices during the release of entrapped water soluble drug in an aqueous environment. 

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