Stereomodulation of Poly(4-methyl-1-pentene): Adoption of a Neglected and Misunderstood Commercial Polyolefin.

A toolbox of living coordination polymerization methods based on CPAM group 4 metal initiators has been applied for the stereomodulation of poly(4-methyl-1-pentene) (PMP) tacticity to provide new fundamental forms in which thermal phase transitions, T g and T m , can be adjusted over a wide range. Also reported for the first time are the synthesis and properties of authenticated 1,2-regioregular atactic PMP, which serves to correct past errors regarding this fundamental polyolefin.