SynopsisThe work reported here concerns the peroxide crosslinking of ethylene-vinyl acetate rubber. Calculated values for scission-to-crosslinking ratios are higher for EVA than for low-density polyethylene. In the temperature range from 150 to 200OC at a constant peroxide content, a rise in temperature results in a decrease in the obtained gel content. Some tensile and modulus-temperature results on crosslinked EVA samples are also reported on.
INTRODUCTIONEthylene-vinyl acetate (EVA) copolymers are used as modifiers for wax and other systems and in hot melt adhesives.' EVA copolymers have a lower softening point than polyethylene, a phenomenon which has been attributed by Nielsen2 to the formation of shorter sequences of polyethylene, thus lowering the melting point of the crystalline zones. EVA copolymers with low VA content (below 20% by weight) can be used directly, while the high VA-content copolymers are often used as modifiers for other systems. Contrary to the melting or softening point decrease, the glass transition temperature increases as the VA content in the copolymer is increa~ed.~ For the homopolymers, the Tg of poly-(vinyl acetate) is about 3OoC, as compared to about -85OC for polyethylene.EVA copolymers containing about 45% weight vinyl acetate are completely amorphous rubbers.Technical information on EVA is available mainly from the manufacturers who also claim that it can be readily c r o s~l i n k e d .~~ EVA rubbers are cured with either dicumyl peroxide or Varox peroxide (2,5-bis (tert-butylperoxy)-2,5-dimethylhexane). The Mooney rheometers and Monsanto capillary extrusion rheometerg have been used to study the peroxide crosslinking of EVA rubbers. EVA rubber vulcanizates can be obtained by compression and injection molding. EVA rubbers are also curable in open steam. Oven curing, however, at atmospheric pressure is inappropriate. Loanlo explains that the crosslinking mechanism of EVA is somewhat more complicated as compared to polyethylene due to the presence of two active sites in addition to the methylene groups in the polymer chain (tertiary and methyl hydrogens). Kuckro et a1.I' were mainly interested in the insulating properties of the copolymer and studied the effects Pollac et a1.12 have studied the thermoelastic properties of crosslinked EVA. Mittelhauser and Graessley13 were able to crosslink branched poly(viny1 acetate) by gamma irradiation with a cobalt-60 source. The work reported herein describes the chemical crosslinking of EVA copolymer characterized by a high content of VA.
EXPERIMENTALLevapren 452, EVA copolymer (45% VA content, Bayer, Germany) was crosslinked with different concentrations of dicumyl peroxide 40C (Dicup, 40% active). The copolymer was thoroughly mixed with the peroxide at 110°C in the mixing head of a Brabender Plastograph. Crosslinking was initiated by raising the temperature of the mixing head while recording torque-time and temperature-curves. The point at which the torque started to rise was chosen as representing the onset of crosslinking. Crosslinked...