Synthesis of bottlebrush polystyrenes with uniform, alternating, and gradient distributions of brushes via living anionic polymerization and hydrosilylation

Macromol Rapid Commun. 2015 Apr;36(8):726-32. doi: 10.1002/marc.201400660. Epub 2015 Feb 16.

Abstract

By combining living anionic polymerization and hydrosilylation, densely grafted bottlebrush polymers with controlled spacing of branch points are prepared. Dimethyl(4-vinylphenyl)silane and dimethyl(4-(1-phenylvinyl)phenyl)silane are anionically (co)polymerized to synthesize uniform, alternating, and gradient in-chain silyl-hydride (Si-H) functionalized backbones. The spacing of branch points is controlled effectively by regulating the distribution of Si-H groups along the backbones. Three backbones with a similar number of Si-H groups but variable distributions are used to synthesize corresponding bottlebrush polymers via hydrosilylation between the backbones and chain-end vinyl functionalized polystyrene. The uniformly grafted bottlebrush exhibits the highest hydrodynamic radius (Rh ) of 5.6 nm and the lowest Tg of 79 °C which may be attributed to its compact grafted structure. This methodology exhibits high efficiency and convenience for the construction of bottlebrushes with controlled distribution of brushes.

Keywords: bottlebrush polymers; controlled branching; hydrosilylation; living anionic polymerization.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anions / chemistry
  • Polymerization*
  • Polymers / chemical synthesis*
  • Polymers / chemistry
  • Polystyrenes / chemical synthesis*
  • Polystyrenes / chemistry*
  • Silanes / chemical synthesis*
  • Silanes / chemistry
  • Surface Properties

Substances

  • Anions
  • Polymers
  • Polystyrenes
  • Silanes