Imidization reactions onto PMMA copolymers were performed in the presence of primary amines. This study allowed establishing a correlation between the functional group of the primary amine and the reactivity of the primary amine toward ester groups of PMMA. This correlation was allowed by using model PMMA/PMAA copolymers, i.e., obtained using a chain transfer agent by radical polymerization. According to the suggested mechanism of PMMA imidization, methylamine afforded higher content of glutarimide groups, hence leading to high Tg values of about 160°C. The use of bulky groups for the primary amine instead, i.e., cyclohexyl, decreased the content of glutarimide function. Thermogravimetric analysis revealed a high thermostability of imidized PMMA with a starting degradation temperature of about 400°C, also dependant of the amine functional group. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
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