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

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

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

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
Volume33
Issue number14
DOIs
Publication statusPublished - 2012 Jul 26
Externally publishedYes

Fingerprint

Atom transfer radical polymerization
Polymethyl Methacrylate
Block copolymers
Styrene
Supramolecular chemistry
Metals
Polymerization
Atoms
Phenanthrolines
Free radical polymerization
Macromolecules
Phase separation
Image analysis
Esters
Nuclear magnetic resonance

Keywords

  • 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

Cite this

Catenated PS-PMMA block copolymers via supramolecularly templated ATRP initiator approach. / Bunha, Ajay Kumar; Mangadlao, Joey; Felipe, Mary Jane; Pangilinan, Katrina; Advincula, Rigoberto.

In: Macromolecular Rapid Communications, Vol. 33, No. 14, 26.07.2012, p. 1214-1219.

Research output: Contribution to journalArticle

Bunha, AK, Mangadlao, J, Felipe, MJ, Pangilinan, K & Advincula, R 2012, 'Catenated PS-PMMA block copolymers via supramolecularly templated ATRP initiator approach', Macromolecular Rapid Communications, vol. 33, no. 14, pp. 1214-1219. https://doi.org/10.1002/marc.201200043
Bunha, Ajay Kumar ; Mangadlao, Joey ; Felipe, Mary Jane ; Pangilinan, Katrina ; Advincula, Rigoberto. / Catenated PS-PMMA block copolymers via supramolecularly templated ATRP initiator approach. In: Macromolecular Rapid Communications. 2012 ; Vol. 33, No. 14. pp. 1214-1219.
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