Towards High Molecular Weight Furan-Based Polyesters: Solid State Polymerization Study of Bio-Based Poly(Propylene Furanoate) and Poly(Butylene Furanoate)

Abstract

In the era of polymers from renewable resources, polyesters derived from 2,5 furan dicarboxylic acid (FDCA) have received increasing attention due to their outstanding features. To commercialize them, it is necessary to synthesize high molecular weight polymers through efficient and simple methods. In this study, two furan-based polyesters, namely poly (propylene furanoate) (PPF) and poly(butylene furanoate) (PBF), were synthesized with the conventional two-step melt polycondensation, followed by solid-state polycondensation (SSP) conducted at different temperatures and reaction times. Molecular weight, structure and thermal properties were measured for all resultant polyesters. As expected, increasing SSP time and temperature results in polymers with increased intrinsic viscosity (IV), increased molecular weight and reduced carboxyl end-group content. Finally, those results were used to generate a simple mathematical model that prognosticates the time evolution of the materials’ IV and end groups concentration during SSP.

Blending PLA with Polyesters Based on 2,5-Furan Dicarboxylic Acid: Evaluation of Physicochemical and Nanomechanical Properties

“…PBAd is a fast-crystallizing polyester with a glass transition T g = −57.3 °C, a double melting peak at 55 and 60 °C, and a melt crystallization T c = 31.4 °C. PBF melts at 170 °C and has T g = 37.7 °C and T cc = 103.4 °C, in agreement with previous reports [ 33 , 34 , 35 , 36 ]. The copolymers PBF-PBAd 75 25 and PBF-PBAd 50 50 show weak cold crystallization and melting during heating after quenching ( Figure S4d ), and PBF-PBAd 25 75 does not crystallize during heating.…”

Molecular mobility and crystallization of renewable poly(ethylene furanoate) in situ filled with carbon nanotubes and graphene nanoparticles

“…Glass transition temperature, T g , heat capacity change during glass transition upon normalization to the amorphous polymer fraction, Δc p,n , cold crystallization temperature, T cc , melting temperature, T m , melt crystallization temperature, T c , mobile amorphous fraction, MAF, rigid amorphous fraction, RAF, and crystalline fraction, CF. Included are values on the average molar mass, M n , as obtained by intrinsic viscosity measurements 76.…”

Synthesis by Melt-Polymerization of a Novel Series of Bio-Based and Biodegradable Thiophene-Containing Copolyesters with Promising Gas Barrier and High Thermomechanical Properties

“…Afterwards, the microorganisms metabolize the water-soluble hydrolysates, in a process known as mineralization, into by-products such as methane, CO 2 , and H 2 O [ 19 , 30 , 70 ]. The enzymatic biodegradation is strongly correlated to properties such as chain composition, molecular weight, and crystallinity of the copolyesters [ 47 , 71 , 72 ]. Herein, the in vitro degradation was evaluated over a period of 30 weeks, with and without the use of porcine pancreatic lipase, at 37 °C in phosphate buffer at pH 7.4.…”

“…Unfortunately, the above polymeric materials possessed some shortcomings, such as low processability and poor mechanical properties, which hindered their widespread applications. Similarly, Papadopoulos and coworkers [ 47 ] investigated a novel poly(hexylene carboxylates) (PHF) blend that seemed to crystallize faster and in more significant amounts than poly(propylene/butylene carboxylates) (PPF/PBF) during cooling below the melting point, but had a lower crystallinity degree and molecular weight due to a lack of aromatics in its structure.…”