Organogels

In polymer chemistry, an organogel is a class of gel composed of an organic liquid phase within a three-dimensional, cross-linked network. Organogel networks can form in two ways. The first is classic gel network formation via polymerization. This mechanism converts a precursor solution of monomers with various reactive sites into polymeric chains that grow into a single covalently-linked network. At a critical concentration (the gel point), the polymeric network becomes large enough so that on the macroscopic scale, the solution starts to exhibit gel-like physical properties: an extensive continuous solid network, no steady-state flow, and solid-like rheological properties.[1] However, organogels that are "low molecular weight gelators" can also be designed to form gels via self-assembly. Secondary forces, such as van der Waals or hydrogen bonding, cause monomers to cluster into a non-covalently bonded network that retains organic solvent, and as the network grows, it exhibits gel-like physical properties.[2] Both gelation mechanisms lead to gels characterized as organogels.

Example of organogelator molecules.

Gelation mechanism greatly influences the typical organogel properties. Since precursors with multiple functional groups polymerize into networks of covalent C-C bonds (on average 85 kcal/mol), networks formed by self-assembly, which relies on secondary forces (generally less than 10 kcal/mol), are less stable.[3],[4] Theorists also have difficulties predicting characteristic gelation parameters, such as gel point and gelation time, with a single and simple equation. Gel point, the transition point from a polymer solution to gel, is a function of the extent of reaction or the fraction of functional groups reacted. Gelation time is the time interval between the onset of reaction– by heating, addition of catalyst into a liquid system, etc.– and gel point. Kinetic and statistical mathematical theories have had moderate success in predicting gelation parameters; a simple, accurate, and widely applicable theory has not yet been developed.

  1. ^ Raghavan, S.R.; Douglas, J.F. Soft Matter. 2012, 8, 8539.
  2. ^ Hirst, A.R.; Coates, I.A.; Boucheteau, T.R.; Miravet, J.F.; Escuder, B.; Castelletto, V.; Hamley, I.W.; Smith, D.K. J. Am. Chem. Soc. 2008, 130, 9113-9121.
  3. ^ Ege, S. N. Organic Chemistry Structure and Reactivity, 5th ed.; Cengage Learning: Mason, Ohio, 2009.
  4. ^ Sinnokrot, M.O.; Sherrill, C.D. J. Phys. Chem. A. 2006, 110, 10656.