Copolymers Obtained by ε-Caprolactam and Methyl Methacrylate Polymerization in the Presence of Polyimides

Abstract

New copolymers have been synthesized by anionic or radical photopolymerization of ε-caprolactam or methyl methacrylate (MMA) in the presence of dissolved polyimides bearing hexafluoroisopropylidene, fluorene or other groups. Using diimides as models it was shown that the kinetics of anionic polymerization of ε-caprolactam depends on the nature of spacer between the imide cycles. The mechanical and tribological properties of copolymers, their water absorbance and the microstructure of copolymer films were studied. It was found that upon the selection of polyimide activator it was possible to gain the desirable control over the polymer properties, namely, the gel fraction content, phase composition, compression modulus, notched Izod impact strength, friction coefficient and temperature of frictional contact. The kinetics of radical polymerization of MMA in the presence of polyimide and model diimide has been studied by differential scanning photocalorimetry and infrared spectroscopy. From the results of the reaction kinetics and the study of polymer structures by Fourier transform infrared spectroscopy, nuclear magnetic resonance, size-exclusion chromatography and thermogravimetric analysis it has been established that radical photopolymerization of MMA in the presence of polyimide leads to the formation of copolymers owing to chain transfer reactions and/or chain termination by the relevant condensation polymer. It has been established that the imide cycles play a significant role in the formation of both copolymers with ε-caprolactam and MMA, respectively.