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For the free radical polymerization of polar monomers which are soluble in ionic liquids (ILs) an extraordinary strong solvent effect can be observed. The solvent influence of the ILs leads to a strong enhancement of the polymerization rate and extremely high, mostly broadly distributed molecular weights. The experimentally determined very high propagation rate coefficient kp and the reduction of the activation energy of propagation EA can be explained by H‐bonds between both the monomer molecules and the growing radical chains and the cations and anions of the ILs. The high viscosity of the ILs themselves as well as the increase of the viscosity during the polymerization process are responsible for the high molecular weights and the mostly high polydispersities. The systematic variation of the rate constants of propagation kp and termination kt using microwave reactor, IL/conventional organic solvent mixtures and increased reaction temperatures is studied.

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Summary: Microwave irradiation is supposed to disturb the polar interactions between the ionic liquid and the monomer molecules or the polymer radicals which probably leads to a decrease in k p compared to conventional heating. This work deals with the comparison of the influence of microwave heating and conventional heating on polymerizations in the ionic liquids

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