Kinetics studies and characterization of poly(furfuryl alcohol) for use as bio‐based furan novolacs

Abstract

Poly(furfuryl alcohol) (PFA) is an attractive target for the development of bio‐based novolac resins. However, control of the polycondensation reaction is not well understood and side reactions are an important factor for PFA and the development of new resins. The polymerization reactions and kinetics of furfuryl alcohol and 2‐furyl ethanol into polymeric resins are detailed in this work. Nuclear magnetic resonance spectroscopy analysis of reaction kinetics, molecular weight analysis, and rheology analysis confirm that the polymerization reaction rate of 2‐furyl ethanol is much faster than that of furfuryl alcohol because the addition of this methyl group serves to stabilize the carbocation transition state. Side reactions, such as Diels–Alder crosslinking and in particular branching, are quantified and were found to be much more prevalent in the polymerization of PFA. The glass transition temperature was measured to be 376 K for PFA and only 294 K for poly(2‐furyl ethanol). Molecular dynamics simulations showed that the alternative structure that forms in PFA that causes branching results in greater backbone rigidity causing its higher glass transition temperature. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46608.

Tannin-Furanic Foams Formed by Mechanical Agitation: Influence of Surfactant and Ingredient Ratios

“…Combined with a higher intensity of the peak at 1510 cm −1 from the FT-IR analysis, it suggests less ring-opening taking place during formation of the tannin-furfuryl polymer. The reaction conditions do have great influence on the structure and chemical formation of poly(furfuryl alcohol), as shown in the past [ 31 ]. Overall reaction conditions during mechanical foaming are much less severe (in terms of acidity and time) compared to the classical solvent-evaporation approach, that more linear chains of poly(furfuryl alcohol) can be formed between the flavonoid units of tannin.…”

Catalyst-free synthesis of poly(furfuryl alcohol) using deep eutectic solvents

“…This is consistent with the previous report, which considered the initial concentration of the monomer to be constant due to the solvent-free reaction. 49 To estimate the energy of activation (E a ), the Arrhenius equation k = Ae ÀEa/RT was used, where A and R are constants, and T is the reaction temperature. The polymerization reaction was carried out at 60, 70, and 80 1C using the same conditions otherwise.…”

Microstructural and Thermo-Mechanical Characterization of Furfurylated Douglas Fir

“…Results showed that the T g increased with increased FA concentration. It was proposed that the rigid PFA formed both in the cell lumens and within the cell walls and the cross-linking reaction between FA and the cell wall components synergistically contributed to the increase in T g [ 24 , 25 ] since either self-polymerization of FA or cross-linking reaction would result in thermosetting polymers with high rigidity [ 25 ]. A higher concentration of FA led to higher degrees of cross-linking reactions, which reduced the mobility of molecular chain segments of cell walls and finally had a higher T g .…”