Ethylene vinyl acetate (EVA) copolymers with different amounts of vinyl ace
tate were melt-functionalized with maleic anhydride. The effect of benzoyl
peroxide, t-butyl perbenzoate, and dicumyl peroxide (DCP) as free-radical i
nitiators on the functionalization performance was studied. The crosslinkin
g reactions occur to a larger extent than in polyethylene, indicating that
the vinyl acetate groups favor the formation of free radicals. From all the
experiments performed in this study, the recommended initiation system to
achieve the best values of the functionalization degree and the lower gel c
ontent involves the use of DCP in a concentration of about 0.3 wt % and a m
aleic anhydride concentration around 5.0 wt %. From FTIR and TGA analyses,
it is suggested that the hydrogen abstraction in the EVA copolymers occurs
both in the methyl group of the acetate moiety and in the tertiary C-H. The
free radicals generated in the tertiary C-H react with maleic anhydride in
a higher proportion. (C) 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72:
1799-1806, 1999.