Mixing of isotactic and syndiotactic polypropylenes in the melt

The miscibility of polypropylene (PP) melts in which the chains differ only in stereochemical composition has been investigated by two different procedures. One approach used detailed local information from a Monte Carlo simulation of a single chain, and the other approach takes this information from a rotational isomeric state model devised decades ago, for another purpose. The first approach uses PRISM theory to deduce the intermolecular packing in the polymer blend, while the second approach uses a Monte Carlo simulation of a coarse-grained representation of independent chains, expressed on a high-coordination lattice. Both approaches find a positive energy change upon mixing isotactic PP (iPP) and syndiotactic PP (sPP) chains in the melt. This conclusion is qualitatively consistent with observations published recently by Mulhaupt and co-workers. The size of the energy change on mixing is smaller in the MC/PRISM approach than in the RIS/MC simulation, with the smaller energy change being in better agreement with the experiment. The RIS/MC simulation finds no demixing for iPP and atactic polypropylene (aPP) in the melt, consistent with several experimental observations in the literature. The demixing of the iPP/sPP blend may arise from attractive interactions in the sPP melt that are disrupted when the sPP chains are diluted with aPP or iPP chains.