Acrylic Monomers Useful for Post-Polymerization Modifications

Post-polymerization modifications enable the synthesis of polymers with architectures that are difficult to obtain directly by polymerization and are therefore expected to be applied to the development of functional polymers. For instance, N-succinimidyl acrylate (1) and N-succinimidyl methacrylate (2), bearing a succinimide group, react with primary amines to form amide bonds. Therefore, these monomers have been used for the synthesis of polymers capable of immobilizing biomolecules such as enzymes.¹⁾
Polymers derived from N-phthalimidyl acrylate (3) and N-phthalimidyl methacrylate (4), which contain a phthalimide group, can generate carbon radicals on the polymer backbone.^2,3) Subsequent transformations via these radical intermediates, such as hydrogenation,^2,3) alkene addition,⁴⁾ and phosphonylation,⁵⁾ have been reported. In the case of hydrogenation, the polymer units derived from 3 and 4 are converted into ethylene or propylene units, respectively.
Furthermore, saccharin methacrylamide (5) has been reported to yield alternating copolymers with styrene or conjugated dienes.^6,7) The saccharin units in the copolymers are converted into alkyl methacrylate units through alcoholysis.

References

• 1) Enzyme stability in polymer hydrogel–enzyme hybrid nanocarrier containing phosphorylcholine group
  • X. Huang, J. Li, Y. Araki, T. Wada, Y. Xu, M. Takai, RSC Adv. 2024, 14, 18807.
• 2) Ethylene-Free Synthesis of Polyethylene Copolymers and Block Copolymers
  • S. Frech, E. Molle, A. J. Butzelaar, P. Theato, Macromolecules 2021, 54, 9937.
• 3) Photoinduced SET to access olefin-acrylate copolymers
  • J. B. Garrison, R. W. Hughes, J. B. Young, B. S. Sumerlin, Polym. Chem. 2022, 13, 982.
• 4) Decarboxylation of Poly[N-(acryloyloxy)phthalimide] as a Versatile Tool for Postpolymerization Modification
  • S. Frech, E. Molle, C. Hub, P. Theato, Macromol. Rapid Commun. 2022, 43, 2200068.
• 5) Organophotoredox-Catalyzed Postfunctionalization of Poly(methacrylate) Derivatives via Radical–Polar Crossover Phosphonylation
  • T. Tamano, K. Sato, H. Ohmiya, S. Inagi, Angew. Chem. Int. Ed. 2025, 64, e202507572.
• 6) One-Pot Preparation of Methacrylate/Styrene Alternating Copolymers via Radical Copolymerization and Alcoholysis Modification: Sequence Impacts on Glass Transition Temperature
  • Y. Kametani, M. Ouchi, ACS Polym. Au 2021, 1, 10.
• 7) Copolymerizations of Saccharin Methacrylamide with Dienes toward Softer Alternating Copolymers and Advanced Sequence Control
  • Y. Kametani, M. Ouchi, Macromol. Chem. Phys. 2022, 223, 2100249.

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