Biomass‐derived furanic polycarbonates: Mild synthesis and control of the glass transition temperature

Abstract

Bis(hydroxymethyl)furan (BHMF) is a promising biomass‐derived polymer platform, but it is incompatible with traditional methods used for synthesizing polycarbonates (PCs) owing to its thermal instability. In this study, BHMF‐based furanic (FR) PCs were prepared successfully at a relatively low temperature through the mediation of carbonyldiimidazole. The low Tg of aliphatic FR‐PCs was controlled elaborately, exploiting the reactivity of furan in the Diels–Alder reactions and the molecular rigidity of the resulting oxabicycles. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1796–1800

Self-Healable and Recyclable Biomass-Derived Polyurethane Networks through Carbon Dioxide Immobilization

“…As shown in Figure 2b, the T d5% s were in the range of 190 • C-222 • C, and the pattern of weight loss appeared to be very similar for all the PCUs. We attributed the initial weight loss of 15%-20% at approximately 200 • C to the decomposition of the bis(oxymethyl)furan moiety, which had the lowest thermal stability [51]. Next, the second loss at nearly 230 • C means the carbamate and carbonate decompositions.…”

“…In this study, we prepared biomass-derived urethane-based network polymers using a FCD, a new platform derived from the direct immobilization of CO 2 into BHMF [2,[51][52][53]. The synthesized PCU network polymers were fabricated into films (Figure 1) and their thermal and thermomechanical properties were thoroughly characterized.…”

2,5-Furandicarboxylic Acid: An Intriguing Precursor for Monomer and Polymer Synthesis

“…In addition to lower reactivity than phosgene, these materials require the separation of by-products at high temperatures to maintain reaction kinetics. This presents the same issue as FDCA-based polymer production: if BHMF is to be used as a diol, these high temperatures will result in thermo-oxidative degradation due to the low thermal stability of BHMF [47]. Some research groups have proposed fluoridetriggered carbonylation to produce PCs via carbonyldiimidazole (CDI).…”

“…The application of BHMF, in this case, presents an opportunity to improve these polymers, as the furanic moiety will increase chain rigidity and hence T g , which is highly dependent on polymer chain torsional freedom. Choi et al have developed a method using the Diels-Alder reaction between BHMF and a dienophile to produce a rigid bicycle that can decrease the torsional freedom of PC polymer chains and increase T g [47]. Their two-step CDI-mediated method was accomplished under mild conditions (required for BHMF thermal instability) due to the high polymerization reactivity of CDI.…”

Effective Biobased Phosphorus Flame Retardants from Starch-Derived bis-2,5-(Hydroxymethyl)Furan

“…Glucose, and other carbohydrates, may also serve as a source of bis-2,5-(hydroxymethyl)furan (BHMF). This difunctional alcohol has been used for the production of poly(ester)s [53][54][55][56] and plasticizers [57]. In this case, it was converted to the corresponding diacrylate.…”