Polystyrene end-labeled with 2,7-dibromofluorene synthesized using an adaptation of reverse atom transfer radical polymerization

Bellamarie Ludwig, Eric S. Tillman

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Polystyrene with high amounts of end-labeling was synthesized using iniuating systems comprised of conventional radical initiators and 2,7-dibromofluorene or other fluorene derivatives in an adaptatioo of reverse atom transfer radical polymerization (RATRP). Benzoyl peroxide (BPO) or 2,2′-azoisobutyronitrile (AIBN) were decomposed and allowed to react with 2,7-dibromofluorene, 2-bromofluorene, or fluorene in the presence of ligand-bound CuX2 allowing for abstraction of the 9-H from the flouorenyl species and the establishment of an equilibrium between the subsequent active radical and the dormant alkyl halide. Gel permeation chromatography (GPC) traces indicated CuCl2-catalyzed reactions produced polymers possessing narrow polydispersity index (PDI) values <1.3 with AIBN and 2,7-dibromofluorene systems, while analogous reactions catalyzed using CuBr2 were less controlled (PDI > 1.7). Analysis of the polymers using UV-vis spectroscopy and UV-GPC demonstrated competition between initiation from both the conventional radical initiator and fluorenyl species generating polymers end-labeled with both the 2,7-dibromofluorene and isobutyronitrile groups. Fluorene or 2-bromofluorene as co-initiators led to lowered amounts of end-labeling, but the polymers generally possessed lower PDI values compared to 2,7-dibromofluorene systems.

Original languageEnglish (US)
Pages (from-to)2143-2152
Number of pages10
JournalMacromolecular Chemistry and Physics
Volume206
Issue number21
DOIs
StatePublished - Nov 1 2005

Fingerprint

Atom transfer radical polymerization
Polystyrenes
polystyrene
Polymers
initiators
polymerization
gel chromatography
polymers
Gel permeation chromatography
Polydispersity
Labeling
marking
atoms
Benzoyl Peroxide
Benzoyl peroxide
peroxides
Ultraviolet spectroscopy
halides
Ligands
Derivatives

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

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abstract = "Polystyrene with high amounts of end-labeling was synthesized using iniuating systems comprised of conventional radical initiators and 2,7-dibromofluorene or other fluorene derivatives in an adaptatioo of reverse atom transfer radical polymerization (RATRP). Benzoyl peroxide (BPO) or 2,2′-azoisobutyronitrile (AIBN) were decomposed and allowed to react with 2,7-dibromofluorene, 2-bromofluorene, or fluorene in the presence of ligand-bound CuX2 allowing for abstraction of the 9-H from the flouorenyl species and the establishment of an equilibrium between the subsequent active radical and the dormant alkyl halide. Gel permeation chromatography (GPC) traces indicated CuCl2-catalyzed reactions produced polymers possessing narrow polydispersity index (PDI) values <1.3 with AIBN and 2,7-dibromofluorene systems, while analogous reactions catalyzed using CuBr2 were less controlled (PDI > 1.7). Analysis of the polymers using UV-vis spectroscopy and UV-GPC demonstrated competition between initiation from both the conventional radical initiator and fluorenyl species generating polymers end-labeled with both the 2,7-dibromofluorene and isobutyronitrile groups. Fluorene or 2-bromofluorene as co-initiators led to lowered amounts of end-labeling, but the polymers generally possessed lower PDI values compared to 2,7-dibromofluorene systems.",
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Polystyrene end-labeled with 2,7-dibromofluorene synthesized using an adaptation of reverse atom transfer radical polymerization. / Ludwig, Bellamarie; Tillman, Eric S.

In: Macromolecular Chemistry and Physics, Vol. 206, No. 21, 01.11.2005, p. 2143-2152.

Research output: Contribution to journalArticle

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