Metallocene-mediated synthesis of chain-end functionalized polypropylene and application in PP/clay nanocomposites

This paper summarizes our research in the preparation of chain end functionalized isotactic polypropylene (PP) having a terminal functional group, such as Cl, OH, and NH2. The chemistry involves metallocene-mediated propylene polymerization using rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2/MAO complex in the presence of styrene derivatives (St-f) and hydrogen, which serve as the chain transfer agents. The molecular weight of the resulting PP polymers with a terminal Cl, OH and NH2 group (i.e., PP-t-Cl, PP-t-OH and PP-t-NH2) are inversely proportional to the molar ratio of [St-f]/[propylene]. Despite the extremely low concentration of functional group, the high molecular weight chain end functionalized PP-t-OH and PP-t-NH3+ exhibit a distinctive advantage over other functional PP polymers containing side chain functional groups or long functional blocks. The terminal hydrophilic OH and NH3+ cations, with good mobility and reactivity, effectively hydrogen bond and ion-exchange the cations (Li+, Na+, etc.) located between the clay interlayers, respectively. Such interactions anchor the PP chain to the clay surfaces. On the other hand, the remaining rest of the unperturbed end-tethered high molecular weight PP tail exfoliates the clay layers. This exfoliated structure is maintained even after further mixing of the PP-bearing platelets with pure neat PP polymers.

Chain end functionalized polypropylene polymers having a terminal functional group, such as Cl, OH, and NH2, have been prepared by a combination of metallocene catalyst and functional chain transfer agents in the presence of hydrogen. Despite the extremely low concentration of functional group, the chain end functionalized PP polymers show excellent surface activity in forming exfoliated PP/clay nanocomposites.Figure optionsDownload as PowerPoint slide