Solvents gelation

For comparison, the a-ethyl-a-butyl monomer was also polymerized under the same conditions in N-methylpyrrolidone, NMP, as the reaction solvent. Gelation did not occur in this solvent, although the polymer precipitated almost immediately after initiation. 

Fig.18 Bola-type i-Val (114-116) andr-Ile (117,118) organic solvent gelators and doubly charged hydrogelators 119-121...

A gd consists of gelator(s) and solvent(s) and is defined as a substantially dilute cross-Unked system which exhibits no flow in the steady state [1]. Its soHd-Hke appearance is caused by the inunobiHzation of solvent molecules in a three-dimensional network created by either physical or chemical forces. At molecular level, solvent molecules are mobile within the three-dimensional network, but their movements are limited by capillary forces and solvent-gelator interactions. 

Besides pH, other preparative variables that can affect the microstructure of a gel, and consequendy, the properties of the dried and heat-treated product iaclude water content, solvent, precursor type and concentration, and temperature (9). Of these, water content has been studied most extensively because of its large effect on gelation and its relative ease of use as a preparative variable. In general, too Httie water (less than one mole per mole of metal alkoxide) prevents gelation and too much (more than the stoichiometric amount) leads to precipitation (3,9). Other than the amount of water used, the rate at which it is added offers another level of control over gel characteristics. 

Fibers spun by this method may be isotropic or asymmetric, with dense or porous walls, depending on the dope composition. An isotropic porous membrane results from spinning solutions at the point of incipient gelation. The dope mixture comprises a polymer, a solvent, and a nonsolvent, which are spun into an evaporative column. Because of the rapid evaporation of the solvent component, the spinning dope solidifies almost immediately upon emergence from the spinneret in contact with the gas phase. The amount of time between the solution s exit from the spinneret and its entrance into the coagulation bath has been found to be a critical variable. Asymmetric fibers result from an inherently more compatible solvent/nonsolvent composition, ie, a composition containing lower nonsolvent concentrations. The nature of the exterior skin (dense or porous) of the fiber is also controlled by the dope composition. 

Sol—Gel Technology. The sol—gel process involves conversion of a metal alkoxide or mixture of metal alkoxides, dissolved in an organic solvent (generally the patent alcohol) into a hydroxooxyalkoxide sol, followed by gelation and sintering to give the desired ceramic material. 

Polyelectrolyte complex membranes are phase-inversion membranes where polymeric anions and cations react during the gelation. The reaction is suppressed before gelation by incorporating low molecular weight electrolytes or counterions in the solvent system. Both neutral and charged membranes are formed in this manner (14,15). These membranes have not been exploited commercially because of then lack of resistance to chemicals. 

MethylceUulose with a methyl DS less than about 0.6 is alkali-soluble. Erom about 1.6 to 2.4, it is water-soluble (most commercial grades) above 2.4, it is soluble in a wide variety of organic solvents. MethylceUulose solutions in water start to gel at 55° C, independent of molecular weight. The gelation is a function of the DS, rate of heating, and type and amounts of additives such as salts. As the temperature increases, the viscosity initially decreases (typical behavior). When the gelling temperature is reached, the viscosity sharply rises until the flocculation temperature is reached. Above this temperature, the viscosity coUapses. This process is reversible with temperature (75). 

The chlorosilanes are dissolved in a suitable solvent system and then blended with the water which may contain additives to control the reaction. In the case of methylsilicone resin the overall reaction is highly exothermic and care must be taken to avoid overheating which can lead to gelation. When substantial quantities of chlorophenylsilanes are present, however, it is often necessary to raise the temperature to 70-75°C to effect a satisfactory degree of hydrolysis. 

One of the simplest ways to prepare a chitin gel is to treat chitosan acetate salt solution with carbodiimide to restore acetamido groups. Thermally not reversible gels are obtained by AT-acylation of chitosans N-acetyl-, N-propionyl- and N-butyryl-chitosan gels are prepared using 10% aqueous acefic, propionic and bufyric acid as solvents for treatment with appropriate acyl anhydride. Both N- and 0-acylation are found, but the gelation also occurs by selective AT-acylation in the presence of organic solvents. 

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