Furandicarboxylate Polyesters: A Comprehensive ADMET Study of a Novel Class of Furan‐Based α,ω‐Diene Monomers

Abstract

The present research article delves into the preparation of a new class of bio‐based polyesters from α,ω‐diene furandicarboxylate monomers. In particular, it exploits the use of acyclic diene metathesis polymerisation (ADMET) on 2,5‐furandicarboxylic acid (FDCA)‐derived compounds. First, a library of furan‐based α,ω‐diene monomers was prepared via acid‐ or base‐catalyzed transesterification of 2,5‐furandicarboxylic acid dimethyl ester (FDME) with commercially available alcohols incorporating terminal olefins, i. e., allyl alcohol, but‐3‐en‐1‐ol, hex‐5‐en‐1‐ol and dec‐9‐en‐1‐ol. Then, the novel monomers were subjected to ADMET polymerisation employing different catalysts and reaction conditions. Interestingly, first‐generation Grubbs catalyst was found to be the best promoter for ADMET polymerisation. This catalyst allowed the preparation of a new family of bio‐based polyesters with molecular weights up to 26.4 kDa, with good thermal stability, and adaptable cis‐trans conformations. Results also revealed that the monomer structure had a direct impact on the polymerisation efficiency and the resulting thermal properties. The effect of green bio‐based solvents such as Cyrene™, dimethyl isosorbide (DMI) and γ‐valerolactone (GVL) on the polymerisation process was also studied. Data collected showed that the solvent concentration influenced both the yield and length of polymers formed. Furthermore, some co‐polymerisation experiments were conducted; the successful integration of different monomers in the resulting copolymer was shown to affect the glass transition temperature (Tg) of the resulting materials.

Anti-Ultraviolet Biobased Polyesters Synthesized by Acyclic Diene Metathesis Polymerization

“…To obtain high-molecular-weight polymers, the byproduct ethylene was removed under a continuous vacuum. It has been demonstrated that the carbon chain length of monomers had an impact on ADMET polymerization, which reflected as the longer alkyl length between olefins and functional groups improved polymerization efficiency. ,, HF and UF with multiple methylene groups (4 and 9) between olefin and ester groups were synthesized for ADMET polymerization (entries 1 and 2, Table ), and the corresponding homopolymers PHF and PUF were obtained with the number-average molecular weights ( M n ) of 14.6 and 15.1 kDa (Figure S9), respectively. The presence of heteroatoms such as oxygen atoms in the ether group and carbonyl group can cause the poisoning of metal in the catalyst to some extent and thus alter the activity of the catalyst itself .…”

From Vanillin to Concrete Plasticizers: An Innovative Path through ADMET Polymerization

“…Shifting our attention to environmentally friendly polymerization methods, ADMET (acyclic diene metathesis) polymerization emerges as an intriguing option due to its catalytic nature and the generally moderate temperatures required for polymerization. − Moreover, its characteristic of not necessitating solvents further enhances its appeal. Simultaneously, the development of biobased phenolic monomers derived from lignin has already been a focal point of research during the past decade. , Numerous studies have investigated the synthesis of new olefinic monomers from lignin-derived molecules, such as ferulic acid or vanillin (Table S1, Supporting Information, SI).…”