Zinc xanthates polymerize propylene oxide into high polymer (PPO) with coordination mechanism. In order to identify structure and stereoisomerisms of this polymer, PPO was subjected to thermal and column fractionation. Obtained fractions were characterized by end-group analysis, cryoscopy, viscometry, IR and 13C-NMR spectroscopy, melting temperature. PPO is composed of a high molecular weight, stereoregular, crystallizable polymer (K-polymer) with low molecular weight (=500 g/mol) D-polymer. Presence of double bonds and hydroxyl terminals was interpreted as the product of an anionic mechanism. K-Polymers can be thermally fractionated on the basis of their melting temperature (Tm) rather than molecular weight (Mwt). It&amp / #8217 / s found that higher Tm fractions have lower Mwt, but they precipitate at higher temperatures than higher Mwt but lower Tm fractions. In column fractionation, K-polymers were deposited on glass beads from isooctane solution in a narrow temperature interval. Then the precipitated samples were split into a number of fractions by using again isooctane but at a higher temperature than the precipitation temperature by increasing residence time from 5 minutes to several hours. It&amp / #8217 / s found that rate of solubility is not controlled by molecular weight, but controlled by percentage crystallinity and Tm. Highest Tm polymers, with relatively higher Mwt showed faster rate of solution than that of lower Tm, lower Mwt but higher percent crystalline fractions. This discrepancy was accounted by suggesting a stereo-block structure where tactic blocks are bound each other with non-crystallizable atactic blocks. The mechanism of polymerization was also discussed in some detail.

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