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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    Semi-Aromatic Polyesters Based on a Carbohydrate-Derived Rigid Diol for Engineering Plastics
    Wu, J. ; Eduard, P. ; Thiyagarajan, S. ; Noordover, B.A.J. ; Es, D.S. van; Koning, C.E. - \ 2015
    ChemSusChem 8 (2015)1. - ISSN 1864-5631 - p. 67 - 72.
    acetalized galactaric acid - poly(butylene terephthalate) - renewable resources - aromatic polyesters - thermal-properties - pet copolyesters - bicyclic diol - d-mannitol - isosorbide - isohexide
    New carbohydrate-based polyesters were prepared from isoidide- 2,5-dimethanol (extended isoidide, XII) through melt polymerization with dimethyl esters of terephthalic acid (TA) and furan-2,5-dicarboxylic acid (FDCA), yielding semi-crystalline prepolymers. Subsequent solid-state post-condensation (SSPC) gave high molecular weight (Mn=30 kgmol 1 for FDCA) materials, the first examples of high Mn, semi-aromatic homopolyesters containing isohexide derivatives obtained via industrially relevant procedures. NMR spectroscopy showed that the stereo-configuration of XII was preserved under the applied conditions. The polyesters are thermally stable up to 3808C. The TA- and FDCA-based polyesters have high Tg (105 8C and 948C, resp.) and Tm (284 8C and 250 8C, resp.) values. Its reactivity, stability, and ability to afford high Tg and Tm polyesters make XII a promising diol for the synthesis of engineering polymers.
    Isohexide hydroxy esters: synthesis and application of a new class of biobased AB-type building blocks
    Thiyagarajan, S. ; Wu, J. ; Knoop, J.R.I. ; Haveren, J. van; Lutz, M. ; Es, D.S. van - \ 2014
    RSC Advances : An international journal to further the chemical sciences 4 (2014)89. - ISSN 2046-2069 - p. 47937 - 47950.
    isosorbide - polyesters - derivatives - acid
    Here we present the synthesis of a new family of sugar derived 1,4: 3,6-dianhydrohexitol based AB-type monomers, containing one methyl ester group and a secondary hydroxyl group in all four possible stereo isomers (RR, RS, SR, SS). Structural characterization of the monomers (5a-d) was established by 1D and 2D NMR analysis, which was further confirmed by single-crystal X-ray structure determination. The application of these monomers in step-growth polymerization afforded fully isohexide based stereo-regular polyesters. Homo polyesters based on the RR and RS monomers were obtained with reasonable molecular weights by melt polymerization (Mn 2400 and 2500 resp.). These materials showed unexpectedly low glass-transition temperatures of 20 degrees C and 15 degrees C respectively. In contrast, the monomers with SR and SS configuration yielded only low molecular weight oligomers. Surprisingly, copolymerization of the RR and SR monomers gave a polyester with higher molecular weight (Mn 4100) and a high T-g of 80 degrees C. These preliminary results show that isohexide hydroxyesters are an intriguing new class of biobased building blocks with many potential applications.
    Fully Isohexide-Based Polyesters: Synthesis, Characterization, and Structure-Properties Relations
    Wu, J. ; Jasinska Walc, L. ; Eduard, P. ; Noordover, B.A.J. ; Es, D.S. van; Koning, C.E. - \ 2013
    Macromolecules 46 (2013)2. - ISSN 0024-9297 - p. 384 - 394.
    chiral building-blocks - renewable resources - poly(butylene terephthalate) - coating applications - melting behavior - succinic acid - polymers - isosorbide - crystallization - crystallinity
    Here we present a novel series of biobased polyesters solely based on renewable isohexide building blocks, synthesized via melt polymerization. The recently developed isoidide dicarboxylic acid (IIDCA) was polymerized with rigid renewable diols such as isosorbide (IS), isomannide (IM), isoidide (II), and the novel 2,5-methylene-extended isoidide dimethanol (IIDML). Both IIDCA and IIDML were developed to increase the reactivity of the isohexide building block, while retaining rigidity and hence the beneficial effects on Tg. Compared to the parent isohexides, IIDML showed a markedly higher reactivity, resulting in three to four times higher weight-average molecular weight (Mw) values of the synthesized polyesters. The molecular structure of the novel polyesters was analyzed by 1H, 13C and 2D-COSY NMR techniques, confirming that the stereoconfigurations of the isohexide moieties were preserved under the applied polymerization conditions. The II/IS-based polyesters have high Tg values noted of 70 and 85 °C, respectively, while the IIDML-based polyester has a lower Tg of approximately 45 °C, yet with an higher degree of crystallinity than the parent isohexide-based polyesters. A systematic study on structure-thermal properties relations comparing these novel polyesters with, e.g., aliphatic polyesters reveals that, when incorporated into polyesters, both IIDCA and IIDML are able to increase the Tg by approximately 70 °C, which is comparable to the parent isohexides. Given the enhanced reactivity, high thermal stability and the retained ability to increase the Tg, IIDML is a promising renewable building block for performance polymers.
    An Investigation of Polyamides Based on Isoidide-2,5-dimethyleneamine as a Green Rigid Building Block with Enhanced Reactivity
    Wu, J. ; Jasinska-Walc, L. ; Dudenko, D. ; Rozanski, A. ; Hansen, M.R. ; Es, D.S. van; Koning, C.E. - \ 2012
    Macromolecules 45 (2012)23. - ISSN 0024-9297 - p. 9333 - 9346.
    solid-state-nmr - infrared temperature - renewable resources - brill transition - isosorbide - isohexide - polymers - mas - spectroscopy - crystals
    Novel, semicrystalline polyamides and copolyamides were synthesized from a new carbohydrate-based diamine, namely isoidide-2,5-dimethyleneamine (IIDMA). In combination with 1,6-hexamethylene diamine (1,6-HDA) as well as the biobased sebacic acid (SA) or brassylic acid (BrA), the desired copolyamides were obtained via melt polymerization of the nylon salts followed by a solid-state polycondensation (SSPC) process. Depending on the chemical compositions, the number average molecular weights (Mn) of the polyamides were in the range of 4000–49000 g/mol. With increasing IIDMA content in the synthesized copolyamides, their corresponding glass transition temperatures (Tg) increased from 50 °C to approximately 60–67 °C while the melting temperatures (Tm) decreased from 220 to 160 °C. The chemical structures of the polyamides were analyzed by NMR and FT-IR spectroscopy. Both differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analyses revealed the semicrystalline character of these novel copolyamides. Variable-temperature (VT) 13C{1H} cross-polarization/magic-angle spinning (CP/MAS) NMR and FT-IR techniques were employed to study the crystal structures as well as the distribution of IIDMA moieties over the crystalline and amorphous phases of the copolyamides. The performed ab initio calculations reveal that the stability of the IIDMA moieties is due to a pronounced “boat” conformation of the bicyclic rings. The incorporation of methylene segments in between the isohexide group and the amide groups enables the hydrogen bonds formation and organization of the polymer chain fragments. Given the sufficiently high Tm values (200 °C) of the copolyamides containing less than 50% of IIDMA, these biobased semicrystalline copolyamides can be useful for engineering plastic applica
    Semicrystalline Polyesters Based on a Novel Renewable Building Block
    Wu, J. ; Koning, C.E. ; Es, D.S. van; Thiyagarajan, S. ; Haveren, J. van - \ 2012
    Macromolecules 45 (2012)12. - ISSN 0024-9297 - p. 5069 - 5080.
    succinic acid - poly(butylene terephthalate) - coating applications - melting behavior - polymers - resources - isosorbide - chemistry - 1,4/3,6-dianhydrohexitols - crystallization
    Isohexides, like e.g. isosorbide, are well-known carbohydrate-based rigid diols which are capable of dramatically increasing the glass transition temperature of polyesters. However, their relatively low reactivity has thus far hampered large-scale industrial applications in the polymer field. Recently, with the aim to increase reactivity while at the same time retain rigidity, we have developed a new isoidide dicarboxylic acid (IIDCA) by transforming the secondary hydroxyls into carboxylate functionalities. Here we report the first polymers based on IIDCA and linear a,¿-diols. The novel polyesters were obtained via melt polymerization and exhibited weight-average molecular weights in the range of 13¿000–34¿000 g/mol and polydispersities close to 2.0. NMR analyses showed that the exo–exo configuration of the isoidide dicarboxylate units was preserved during synthesis. Both differential scanning calorimetry and wide-angle X-ray diffraction analyses showed that the IIDCA polyesters are semicrystalline materials. A systematic study on structure–thermal properties relations among relevant series of polyesters, such as isomeric polymers based on isoidide, revealed several interesting differences in melting and glass transition temperatures, which are thought to be related to variations in chain packing and free volume.
    Biocatalytic synthesis of polyesters from sugar-based building blocks using immobilized Candida antarctica lipase B
    Habeych Narvaez, D.I. ; Juhl, P.B. ; Pleiss, J. ; Vanegas, D.M. ; Eggink, G. ; Boeriu, C.G. - \ 2011
    Journal of Molecular Catalysis. B, Enzymatic 71 (2011)1-2. - ISSN 1381-1177 - p. 1 - 9.
    ring-opening polymerization - dynamic kinetic resolution - secondary alcohols - organic medium - isosorbide - 3(s)-isopropylmorpholine-2,5-dione - esterification - isomannide - oligomers - isoidide
    The synthesis of linear ester oligomers (LEOs) and cyclic ester oligomers (CEOs) from non-activated succinic acid (A) in combination with di-anhydro hexitols (B, DAH) in a toluene based medium using immobilized Candida antarctica lipase B (CAL B), was studied. The conversion is highest for isomannide and decreases in the order isomannide > isosorbide isoidide. These experimental results were corroborated by substrate-imprinted docking indicating that the hydroxyl group oriented inwards the “V”-shaped plane of the DAHs (endo-hydroxyl) is preferred over the outwards oriented hydroxyl group (exo-hydroxyl) by CAL B. The maximum conversions under optimized conditions were 88.2% and 93.7% for succinic acid and isomannide, respectively. MALDI-TOF detected products at 24 h were a mixture of cyclic (35.1%) and linear ester oligomers (64.9%). Cyclic ester oliogomers were the most abundant products during the first 8 h of reaction (32.5–48.7%), where the first cyclic of the series (CEO1) was the most predominant cyclic product (23–40%).
    Isohexide Derivatives from Renewable Resources as Chiral Building Blocks
    Wu, J. ; Eduard, P. ; Thiyagarajan, S. ; Haveren, J. van; Es, D.S. van; Koning, C.E. ; Lutz, M. ; Fonesca Guerra, C. - \ 2011
    ChemSusChem 4 (2011)5. - ISSN 1864-5631 - p. 599 - 603.
    asymmetric transfer hydrogenation - molecular structure - terephthalic acid - crystal-structure - isosorbide - chemistry - polymers - ligands - polyurethanes - isomannide
    A new family of C2/C5 carbon-extended isohexide derivatives is synthesized in a stereo-controlled manner with high purity and good yield. These chiral and rigid biobased building blocks can be widely applied: in pharmaceuticals, cholesteric liquid crystals, and as building blocks for high-performance polymers. The isoidide-based diacid is a potential renewable alternative to terephthalic acid.
    Chiral building blocks from biomass : 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol
    Thiyagarajan, S. ; Gootjes, L. ; Vogelzang, W. ; Wu, J. ; Haveren, J. van; Es, D.S. van - \ 2011
    Tetrahedron 67 (2011)2. - ISSN 0040-4020 - p. 383 - 389.
    derivatives - isosorbide
    An efficient route towards the synthesis of 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol 4 has been developed resulting in significant improvements in both isolated yields and purity when compared to literature procedures. As a consequence, resin-grade 2,5-diamino-2,5-dideoxy-1,4-3,6-dianhydroiditol 4 has become available for laboratory scale step-growth polymer synthesis. Additionally, an interesting renewable chiral 2-amino-2-deoxy-1,4-3,6-dianhydroiditol 10, has been isolated.
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