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The catalytic behavior of cobalt (II) phthalocyanine (CoPc) immobilized on bentonite clay, with different complex loadings ranging between 0.2 and 2.2 wt%, in the presence of n-butyl amine solvent, was investigated in bulk polymerization of methyl methacrylate without using an activator or cocatalyst. The interaction of CoPc molecules with a bentonite surface, encouraged by the amine, involved the inclined stacking model, i.e., interaction between N-atoms of the macro-ring system and OH's of the support. Two different mechanistic pathway regions could be suggested, depending on complex loadings. The first was in the range, 0.2À1.0 wt% CoPc, behaving in ionic fashion as the bare bentonite. Isolated oriented molecules probably activated bentonite through the exposure of new internal acid sites during intercalation. The second, in the range of 1.4À2.2 wt% CoPc, proceeded via combined mechanisms, ionic functioned by bentonite support and free radical functioned by complex packed oriented stacks, staggered in clay galleries to cover a fraction of internal active acid sites. The number of polymer chains formed per one CoPc center (reaction turnovers) was >2-$10 with diluted catalyst samples. With higher loadings, one chain was formed per active site. Such behaviors, without a detectable effect on polymer characteristics or enchainment sequence, were studied in light of intercalation, orientation and accessibility models.

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