Syndiotactic Poly(4-methyl-1-pentene)-Based Stereoregular Diblock Copolymers: Synthesis and Self-Assembly Studies

Syndiotactic poly(4-methyl-1-pentene) (sP4M1P)-based stereoregular diblock copolymers, namely sP4M1P-b-polystyrene and sP4M1P-b-polymethylmethacrylate, were prepared from an alpha-bromoester-capped sP4M1P macroinitiator, which was chain extended with styrene and methyl methacrylate, respectively, via the atom transfer radical polymerization reaction. The alpha-bromoester-capped sP4M1P was generated by the esterification of hydroxyl-capped sP4M1P with alpha-bromoisobutyryl bromide. The hydroxyl-capped sP4M1P was synthesized by inducing a selective chain transfer reaction to aluminum during the syndiospecific polymerization of 4-methyl-1-pentene in the presence of a syndiospecific metallocene catalyst. As stereoregular diblock copolymers are difficult to prepare using existing methods, the current study offers an effective process for the preparation of sP4M1P-based stereoregular diblock copolymers. These copolymers were found to have well-defined architectures and they can undergo molecular self-assembly into ordered nanostructures, as evidenced by small-angle X-ray scattering analyses.

Automated summary

In this study, sP4M1P-based stereoregular diblock copolymers were prepared by atom transfer radical polymerization reaction, starting from alpha-bromoester-capped sP4M1P macroinitiator and chain extending with styrene and methyl methacrylate. This method offers an effective process for the preparation of stereoregular diblock copolymers, which have well-defined architectures and can undergo molecular self-assembly into ordered nanostructures.