Catenated PS-PMMA block copolymers via supramolecularly templated ATRP initiator approach

Ajay Kumar Bunha, Joey Mangadlao, Mary Jane Felipe, Katrina Pangilinan, Rigoberto Advincula*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)


A novel route to synthesize catenated macrocyclic PS-PMMA block copolymers is demonstrated via combination of supramolecular chemistry and controlled radical polymerization (CRP). Polymerization of styrene with bromopropionate ester initiator coupled with phenanthroline Cu(I) complex affords a four arm PS macroinitiator, which upon further chain extension by polymerization of MMA generates a four arm PS-PMMA block copolymer. Intramolecular coupling of PS-PMMA-Br arms via low temperature styrene-assisted atom transfer radical coupling (ATRC) leads to the formation of PS-PMMA catenand, which generates the metal-free catenated macrocyclic PS-PMMA block copolymer after removal of Cu metal. The interlocked structures of catenated block copolymers are confirmed by GPC, NMR, and AFM image analysis. Macromolecular nano-objects and knotted macromolecules are a challenge due to difficulty in enabling end-group ring closure reactions or multi-arm connectivity. Of specific interest is the ability to adapt the method to block copolymer synthesis, which can lead to interesting phase-separation properties. We describe a novel route using supramolecularly templated macroinitiators capable of block copolymer synthesis by ATRP followed by ring closure ATRC.

Original languageEnglish
Pages (from-to)1214-1219
Number of pages6
JournalMacromolecular Rapid Communications
Issue number14
Publication statusPublished - 2012 Jul 26
Externally publishedYes


  • atom transfer radical coupling
  • atom transfer radical polymerization
  • catenated block copolymers
  • metal ligand template
  • poly(styrene-b-methyl methacrylate)

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry


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