Kinetic studies on the imine base/isocyanate‐induced radical polymerization of vinyl monomers

Specific imine bases (IB) in conjunction with various isocyanates (IC) mediate the radical polymerization of radically polymerizable monomers such as methyl methacrylate (MMA). Advantageously, the 2‐(methylmercapto)‐2‐thiazoline MMT/IC combination as initiator works even at room temperature for polymerization of MMA. The coefficients a, b, and c of the basic rate law of monomer consumption dM]/dt = k_p·IC]^a·IB]^b·M]^c were determined. The order a has been determined to 0.5 showing the root law of radical polymerization with respect to the IC component as initiator. Moreover, b and c amount 1. The initiator combination MMT/ IC was applied to determine the influence of the molecular structure of the IC on the rate of monomer conversion. For aromatic isocyantes, the gross rate constant of monomer consumption correlates with the Hammet constant of aromatic substituents. The activation energies of the gross polymerization rate constant of several initiator mixtures were determined whereby the value of E_A,Br was found to be between typical values of radical polymerization initiated by photochemical reactions (～20 kJ/mol) and commonly used thermal decomposing initiators (～80 kJ/mol). Presumptions on the initiating and terminating step of the IB/IC mediated polymerization were done by means of electrospray ionization mass spectrometry, NMR spectroscopy, and the elemental composition of the head and end group of the resulting polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012