Structure and dynamics of poly(ethylene-co-1,5-hexadiene) as studied by solid state 13C NMR and quantum chemical calculations

Hiromichi Kurosu, Yuuri Yamamoto, Aki Fujikawa, Emika Kawabata, Masato Sone, Naofumi Naga

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Poly(ethylene-co-1,5-hexadiene) with 1,5-hexadiene (HD) contents of 1.8, 8.1, 9.7 and 20.3% was prepared by copolymerization of ethylene and HD involving intermolecular cyclization. Higher-order structures and dynamics of these samples were studied by solid state NMR and quantum chemistry. The 13C solid state NMR spectra and 13C spin-lattice relaxation time (T1) of the samples were measured. The observed 13C CP/MAS and PST/MAS NMR spectra for all samples were decomposed into six peaks. The cyclopentane units incorporated in the main chain of polyethylene affected not only the crystalline structure but also the noncrystalline structure. This causes a trans-rich conformation in the noncrystalline region. Even in the melt-quenched samples, incorporation of the cyclopentane structure into the polyethylene chain suppresses the increase in the gauche structure in the noncrystalline region. Based on the 13C chemical shift of the methylene carbon, the low cyclopentane content sample assumes an orthorhombic crystal structure, and the high cyclopentane content samples assume a hexagonal-type chain packing. 13C spin-lattice relaxation times show that the crystalline region of the low cyclopentane content sample has two regions with different mobility, although the high cyclopentane content samples have only one region with a high mobility for each peak. Furthermore, quantum chemical calculations for the 13C NMR shieldings were carried out for precise assignment of the peaks.

Original languageEnglish
Pages (from-to)208-214
Number of pages7
JournalJournal of Molecular Structure
Volume921
Issue number1-3
DOIs
Publication statusPublished - 2009 Mar 17

Fingerprint

Cyclopentanes
Nuclear magnetic resonance
Spin-lattice relaxation
Polyethylene
Relaxation time
Crystalline materials
Quantum chemistry
Cyclization
Chemical shift
Shielding
Copolymerization
Conformations
ethylene
1,5-hexadiene
Carbon
Crystal structure

Keywords

  • Dynamics
  • Poly(ethylene-co-1,5-hexadiene)
  • Quantum chemical calculations
  • Solid state NMR
  • Structural analysis

ASJC Scopus subject areas

  • Spectroscopy
  • Analytical Chemistry
  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Structure and dynamics of poly(ethylene-co-1,5-hexadiene) as studied by solid state 13C NMR and quantum chemical calculations. / Kurosu, Hiromichi; Yamamoto, Yuuri; Fujikawa, Aki; Kawabata, Emika; Sone, Masato; Naga, Naofumi.

In: Journal of Molecular Structure, Vol. 921, No. 1-3, 17.03.2009, p. 208-214.

Research output: Contribution to journalArticle

Kurosu, Hiromichi ; Yamamoto, Yuuri ; Fujikawa, Aki ; Kawabata, Emika ; Sone, Masato ; Naga, Naofumi. / Structure and dynamics of poly(ethylene-co-1,5-hexadiene) as studied by solid state 13C NMR and quantum chemical calculations. In: Journal of Molecular Structure. 2009 ; Vol. 921, No. 1-3. pp. 208-214.
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