Living ring-opening metathesis polymerization of exo-norbornenes bearing both cyano and ester functionalities by a well-defined ruthenium catalyst

Yasushi Nishihara, Yoshiaki Inoue, Akira T. Saito, Yuushou Nakayama, Takeshi Shiono, Kentaro Takagi

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Exo-ethyl 3-cyanobicyclo[2.2.1]hept-5-ene-2-carboxylate (A) and exo- nbutyl 3-cyanobicyclo[2.2.1]hept-5-ene-2-carboxylate (B) bearing both cyano and ester groups were subjected to homopolymerization by ring-opening metathesis polymerization with a well-defined Ru catalyst, (H 2IMes)(3-bromopyridine)2Cl2Ru=CHPh (3) (H 2IMes = M,N′-bis(mesityl)-4,5-dihydroimidazol-2-ylidine) at low temperature. The characterization of the synthesized homopolymers by GPC analyses showed a value of a number-average molecular weight (Mn) as high as 296,000 and a narrow polydispersity index (<1.06). The results imply that the initiator 3 had a compatibility of the polar functional groups and promoted fairly well-defined living polymerization. The glass transition temperatures of the homopolymers obtained from monomer A were significantly higher than those observed for polymers from monomer B obtained under the same reaction conditions. The rates of homopolymerizations of monomer A, B, and the parent norbornene (C) were determined by the monitoring the consumption of the monomers by the 1H NMR spectra. It was revealed that the polymerization rate for the homopolymerization of monomer A was almost same as that of monomer B, but much slower than that of C. On the basis of the successful homopolymerization, the synthesis of block and random copolymers derived from monomers A, B, and C via living polymerization using catalyst 3 was also accomplished.

Original languageEnglish
Pages (from-to)318-329
Number of pages12
JournalPolymer Journal
Volume39
Issue number4
DOIs
Publication statusPublished - 2007

Fingerprint

Bearings (structural)
Living polymerization
Ruthenium
Ring opening polymerization
Homopolymerization
Esters
Monomers
Catalysts
Polydispersity
Functional groups
Polymers
Copolymers
Molecular weight
Polymerization
Nuclear magnetic resonance
Monitoring

Keywords

  • Copolymerization
  • Living polymerization
  • N-heterocyclic carbene ligands
  • Ring-opening metathesis polymerization
  • Ruthenium

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry

Cite this

Living ring-opening metathesis polymerization of exo-norbornenes bearing both cyano and ester functionalities by a well-defined ruthenium catalyst. / Nishihara, Yasushi; Inoue, Yoshiaki; Saito, Akira T.; Nakayama, Yuushou; Shiono, Takeshi; Takagi, Kentaro.

In: Polymer Journal, Vol. 39, No. 4, 2007, p. 318-329.

Research output: Contribution to journalArticle

Nishihara, Yasushi ; Inoue, Yoshiaki ; Saito, Akira T. ; Nakayama, Yuushou ; Shiono, Takeshi ; Takagi, Kentaro. / Living ring-opening metathesis polymerization of exo-norbornenes bearing both cyano and ester functionalities by a well-defined ruthenium catalyst. In: Polymer Journal. 2007 ; Vol. 39, No. 4. pp. 318-329.
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abstract = "Exo-ethyl 3-cyanobicyclo[2.2.1]hept-5-ene-2-carboxylate (A) and exo- nbutyl 3-cyanobicyclo[2.2.1]hept-5-ene-2-carboxylate (B) bearing both cyano and ester groups were subjected to homopolymerization by ring-opening metathesis polymerization with a well-defined Ru catalyst, (H 2IMes)(3-bromopyridine)2Cl2Ru=CHPh (3) (H 2IMes = M,N′-bis(mesityl)-4,5-dihydroimidazol-2-ylidine) at low temperature. The characterization of the synthesized homopolymers by GPC analyses showed a value of a number-average molecular weight (Mn) as high as 296,000 and a narrow polydispersity index (<1.06). The results imply that the initiator 3 had a compatibility of the polar functional groups and promoted fairly well-defined living polymerization. The glass transition temperatures of the homopolymers obtained from monomer A were significantly higher than those observed for polymers from monomer B obtained under the same reaction conditions. The rates of homopolymerizations of monomer A, B, and the parent norbornene (C) were determined by the monitoring the consumption of the monomers by the 1H NMR spectra. It was revealed that the polymerization rate for the homopolymerization of monomer A was almost same as that of monomer B, but much slower than that of C. On the basis of the successful homopolymerization, the synthesis of block and random copolymers derived from monomers A, B, and C via living polymerization using catalyst 3 was also accomplished.",
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AU - Shiono, Takeshi

AU - Takagi, Kentaro

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AB - Exo-ethyl 3-cyanobicyclo[2.2.1]hept-5-ene-2-carboxylate (A) and exo- nbutyl 3-cyanobicyclo[2.2.1]hept-5-ene-2-carboxylate (B) bearing both cyano and ester groups were subjected to homopolymerization by ring-opening metathesis polymerization with a well-defined Ru catalyst, (H 2IMes)(3-bromopyridine)2Cl2Ru=CHPh (3) (H 2IMes = M,N′-bis(mesityl)-4,5-dihydroimidazol-2-ylidine) at low temperature. The characterization of the synthesized homopolymers by GPC analyses showed a value of a number-average molecular weight (Mn) as high as 296,000 and a narrow polydispersity index (<1.06). The results imply that the initiator 3 had a compatibility of the polar functional groups and promoted fairly well-defined living polymerization. The glass transition temperatures of the homopolymers obtained from monomer A were significantly higher than those observed for polymers from monomer B obtained under the same reaction conditions. The rates of homopolymerizations of monomer A, B, and the parent norbornene (C) were determined by the monitoring the consumption of the monomers by the 1H NMR spectra. It was revealed that the polymerization rate for the homopolymerization of monomer A was almost same as that of monomer B, but much slower than that of C. On the basis of the successful homopolymerization, the synthesis of block and random copolymers derived from monomers A, B, and C via living polymerization using catalyst 3 was also accomplished.

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