AbstractPolycarbonate blends with poly(pivalolactone) were found to be completely immiscible based on the glass transitional behavior observed by thermal analysis. Crystallinity of the poly(pivalolactone) was unaffected by blending with polycarbonate. The heat of mixing of low molecular weight analogs of this system, ethyl pivalate and diphenyl carbonate, were found to be endothermic, in contrast to exothermic mixing observed for similar linear esters. Methyl branching adjacent to the ester carbonyl is believed to shield the specific interaction of this unit with the aromatic carbonate structure which leads to exothermic mixing and miscibility of similar unbranched esters with polycarbonate. Blends of poly(2,2‐dimethyl‐1,3‐propylene succinate) were found to be partially miscible with polycarbonate because the shielding is not so great since the methyl groups are further removed from the ester
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