Activation volume selected polymerization reactions

Considerable gains have recently been made in the research of polymer catalysis which has emerged from the interaction of the fields of macromolecular, coordination and catalytic chemistry. Using synthetic macromolecules one can create polymeric catalysts which function like enzymes and almost simulate their activity and selectivity. Consequently, polymer catalysis could enable the high-yield manufacture of industrially important products at low-reaction volumes involving minimal energy consumption. 

Here is the Boltzmann constant, T is (absolute) temperature, r is the hydrodynamic radius of monomer, and rj is the viscosity of the reaction mixture. For polymerization systems, rj should be understood as the microviscosity (or solvent viscosity), because it is well known that termination rate coefficients do not vary according to bulk viscosity (see above). From the above considerations one expects that A t(l,l) (ri7/) The additional expectation is that EA(kt(l,l))xEA(t] ), where Ea denotes activation energy. Table 1.8 gives activation energies and activation volumes (AV = —RT dln k/dp)j.) for selected acrylate and methacrylate termination rate coefficients. 

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