Staff Publications

Staff Publications

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    'Staff publications' is the digital repository of Wageningen University & Research

    'Staff publications' contains references to publications authored by Wageningen University staff from 1976 onward.

    Publications authored by the staff of the Research Institutes are available from 1995 onwards.

    Full text documents are added when available. The database is updated daily and currently holds about 240,000 items, of which 72,000 in open access.

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Record number 429853
Title Structure and Molecular Dynamics in Renewable Polyamides from Dideoxy-Diamino Isohexide
Author(s) Jasinska-Walc, L.; Koning, C.E.; Es, D.S. van; Thiyagarajan, S.
Source Macromolecules 45 (2012)14. - ISSN 0024-9297 - p. 5653 - 5666.
Department(s) FBR Sustainable Chemistry & Technology
Publication type Refereed Article in a scientific journal
Publication year 2012
Keyword(s) folded lamellar crystals - solid-state nmr - infrared temperature - c-13 nmr - nylons 4 - spectroscopy - transition - morphology - resolution - amination
Abstract The chemical structure, the conformation, and the flexibility of the polymer chain fragments present in the polyamides synthesized from 2,5-diamino-2,5-dideoxy-1,4;3,6- dianhydrosorbitol, 1,4-diaminobutane, and either sebacic or brassylic acid have been studied by liquid-state 2D NMR spectroscopy viz. correlation spectra (COSY) and heteronuclear multiple-bond correlation spectra (gHMBC), by 13C cross-polarization/magic-angle spinning (CP/MAS) NMR, by X-ray scattering, and by FT-IR spectroscopy. The presence of 2,5-diamino-2,5-dideoxy-1,4;3,6-dianhydrosorbitol in the crystal phase of the polyamides was probed by wide-angle X-ray diffraction (WAXD), FT-IR, and solid-state 13C NMR. The incorporation of dideoxy-diamino isohexide into the backbone of PA 4.10 or PA 4.13 induces formation of gauche type conformers and gives rise to pseudohexagonal packing of the polymer chains in these semicrystalline copolymers. The experimental determination of the polymer chain structure combined with ab initio calculations revealed the presence of three most abundant diaminoisosorbide (DAIS) conformers. The combination of the 13C chemical shifts of these three conformers could explain all experimental resonances in the region of 50-90 ppm. WAXD and DSC analysis show that the crystallinity, and hence the physical properties of the investigated compositions, can be tailored by the content of the bicyclic diamine in the backbone of the polyamides. ¦ INTRODUCTION The number and types of applications utilizing polyamides (PA) generate new trends in the selection of monomers used in their synthesis. Nowadays, biomass-derived chemicals offer an enormous potential to replace the depleting fossil feedstock and are considered as an environmentally friendly alternative. Despite the obvious benefits offered by renewable resources, bio-based polymers are often believed to be unsuitable for hightemperature industrial chemical processes and applications. However, our recent results1,2 have shown that, based on thorough understanding of the structure-property relationships of different polyamides, it is now possible to prepare fully bio-based polyamides having equally good properties as the ones from petrochemical origin. Widely reported renewable monomers in this field are sebacic acid, brassylic acid, 1,4- diaminobutane, or isohexides.3-13 As pointed out by Fenouillot,3 the use of starch-based 1,4;3,6-dianhydrohexitols (isosorbide, isomannide, and isoidide) or their diamino derivatives with D-manno or L-ido configuration affords entirely bio-based materials with a wide variety of applications.
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