Selective atom transfer radical polymerization of 1,2,3,6-tetrahydrobenzyl methacrylate (THBMA) and demonstration of thiol-ene addition reaction in the pendant cycloalkenyl functional group

A tailor-made polymethacrylate bearing reactive pendant cycloalkenyl group was prepared by atom transfer radical polymerization using CuBr as catalyst in combination with N,N,N',N '',N ''-pentamethyldiethylenetriamine (PMDETA) ligand. NMR spectroscopy, matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and gel permeation chromatography (GPC) analyses showed the presence of cycloalkenyl functionality and well-defined molecular weight in the prepared polymer. This reactive cycloalkenyl group was modified by thiol-ene chemistry. The thiol-ene modified polymer showed significantly improved adhesion strength, as determined by lap shear test using a UTM. Nanoindentation experiment showed better surface hardness of the UV-cured thiolated polymer. (C) 2015 Elsevier Ltd. All rights reserved.