Heterotactic-specific radical polymerization of N-isopropylacrylamide and phase transition behavior of aqueous solution of heterotactic poly(N-isopropylacrylamide)

Tomohiro Hirano, Takahiro Kamikubo, Yuya Okumura, Yoichi Bando, Ryosuke Yamaoka, Takeshi Mori, Koichi Ute

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Radical polymerization of N-isopropylacrylamide (NIPAAm) in toluene at low temperatures, in the presence of fluorinated-alcohols, produced heterotactic polymer comprising an alternating sequence of meso and racemo dyads. The heterotactic- ity reached 70% in triads when polymerization was carried out at -40 °C using non- afluoro-tert-butanol as the added alcohol. NMR analysis revealed that formation of a 1:1 complex of NIPAAm and fluorinated-alcohol through C=O-H-O hydrogen bonding induces the heterotactic specificity. A mechanism for the heterotactic-specific polymerization is proposed. Examination of the phase transition behavior of aqueous solutions of heterotactic poly(NIPAAm) revealed that the hysteresis of the phase transition between the heating and cooling cycles depended on the average length of meso dyads in poly(NIPAAm).

Original languageEnglish
Pages (from-to)2539-2550
Number of pages12
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume47
Issue number10
DOIs
Publication statusPublished - May 15 2009

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Free radical polymerization
Alcohols
Phase transitions
Polymerization
tert-Butyl Alcohol
Toluene
Butenes
Hysteresis
Hydrogen bonds
Polymers
Nuclear magnetic resonance
Cooling
Heating
N-isopropylacrylamide
poly-N-isopropylacrylamide
Temperature

All Science Journal Classification (ASJC) codes

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

Heterotactic-specific radical polymerization of N-isopropylacrylamide and phase transition behavior of aqueous solution of heterotactic poly(N-isopropylacrylamide). / Hirano, Tomohiro; Kamikubo, Takahiro; Okumura, Yuya; Bando, Yoichi; Yamaoka, Ryosuke; Mori, Takeshi; Ute, Koichi.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 47, No. 10, 15.05.2009, p. 2539-2550.

Research output: Contribution to journalArticle

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AU - Hirano, Tomohiro

AU - Kamikubo, Takahiro

AU - Okumura, Yuya

AU - Bando, Yoichi

AU - Yamaoka, Ryosuke

AU - Mori, Takeshi

AU - Ute, Koichi

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AB - Radical polymerization of N-isopropylacrylamide (NIPAAm) in toluene at low temperatures, in the presence of fluorinated-alcohols, produced heterotactic polymer comprising an alternating sequence of meso and racemo dyads. The heterotactic- ity reached 70% in triads when polymerization was carried out at -40 °C using non- afluoro-tert-butanol as the added alcohol. NMR analysis revealed that formation of a 1:1 complex of NIPAAm and fluorinated-alcohol through C=O-H-O hydrogen bonding induces the heterotactic specificity. A mechanism for the heterotactic-specific polymerization is proposed. Examination of the phase transition behavior of aqueous solutions of heterotactic poly(NIPAAm) revealed that the hysteresis of the phase transition between the heating and cooling cycles depended on the average length of meso dyads in poly(NIPAAm).

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