A facile pathway to furan derivatives from lignocellulosic biomass via 5-acetoxymethylfurfural (AMF) was developed. AMF possesses advantageous properties due to its less-hydrophilic acetoxymethyl group relative to the hydroxymethyl group of 5-hydroxymethylfurfural (HMF). The hydrophobicity and chemical stability of AMF allowed practical isolation and purification to afford a highly pure product of up to 99.9 %. AMF was produced in good to excellent yields under mild conditions from 5-chloromethylfurfural (CMF) and alkylammonium acetates, both of which could be obtained directly from lignocellulosic biomass. Heterogeneous reactions with polymer-supported alkylammonium acetates were also established; this showed the feasibility of a continuous process for this pathway. AMF could be transformed into various promising furanic compounds, such as 2,5-furandicarboxylic acid (FDCA), 2,5-furandimethanol (FDM), and 5-hydroxymethyl-2-furanoic acid (HFA), in high yields.
The isothermal crystallization kinetics of maleic anhydride grafted polypropylene (mPP) in hybrids with unmodified or organically modified montmorillonite (MMT), which have been prepared by melt intercalation in a mixer, has been investigated by using time-resolved wideangle X-ray scattering (WAXS) and differential scanning calorimetry (DSC). WAXS and transmission electron microscopy (TEM) showed that the mPP/unmodified MMT hybrids formed macrophase-separated mixtures rather than intercalated nanocomposites, while mPP/organically layered silicate (OLS) hybrids formed exfoliated nanocomposites. The crystallization rate of mPP/ unmodified silicate hybrids became faster with the MMT addition because agglomerated silicates in the mPP matrix act as nucleating agents. On the other hand, the crystallization rate of the mPP/OLS hybrids was slowed with the OLS addition. This retardation of the mPP crystallization is probably due to the presence of well-dispersed exfoliated silicates as diffusion or displacement barriers for crystallization. Interestingly, these well-dispersed exfoliated silicates change the crystal orientation as well as the crystallization kinetics of mPP in mPP/OLS nanocomposites, showing larger (040) peak than (110) peak for the R form crystal in WAXS profiles.
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