Kilogram-Scale Production of Sustainable PCF Copolyesters Based on Novel Cyclic Diol THFDM Derived from 5-Hydroxymethylfurfural: Trade-Off between the THFDM Structure and Various Properties of Copolyesters

Abstract

By a novel kilogram-scale production method, copolyesters of poly(1,4-cyclohexyldimethylene-co-hydroxymethyl tetrahydrofuran 2,5-furandicarboxylate) (PCTF) with the entire composition range were synthesized using a 5 L steel reactor. The composition and microstructure of copolyesters were investigated by NMR spectra, which confirmed the random distribution of segments. The 2,5-hydroxymethyl tetrahydrofuran (THFDM) content in copolyesters was lower than that of the initial feeding ratio, which was attributed to the lower reaction reactivity (giving 1.35 × 10 −2 and 1.06 × 10 −2 min −1 for the FDCA reaction with CHDM and THFDM, respectively) and the lower boiling point of THFDM compared with that of 1,4-cyclohexanedimethanol (CHDM). It is worth mentioning that the cyclic structure and ether groups in THFDM attained a balance between their opposing influence on the T g of the copolyesters, resulting in only a slight change in the T g (ranging from 89.3 to 76.2 °C). With the incorporation of THFDM, the crystallization ability of copolyesters decreased and the d-spacing increased, as confirmed by wide-angle X-ray diffraction (WAXD) and isothermal crystallization kinetics analysis. The inclusion−exclusion model proposed by the Wendling−Suter theory provided an explanation for the crystallization behavior. For the mechanical properties, the mechanical behavior could be adjusted to realize the brittle-to-ductile transition, which was significantly influenced by the crystallization degree. The investigation of the secondary relaxations caused by the transition of conformation of CHDM and THFDM rings proved the switching of the mechanical behavior. Notably, large-scale production of THFDM has been realized, making it possible to synthesize this promising material for practical usage.

Scale Synthesis of Poly(butylene carbonate-co-terephthalate) and Its Depolymerization–Repolymerization Recycling Process

“…As shown in Scheme , PBCT copolyesters with different aromatic molar ratios were synthesized by the melt polycondensation procedure, which involved esterification and polycondensation processes. To guarantee the stability and credibility of the final products, a 5 L steel reactor was used to prepare the kilogram-scale PBCTs . First, predetermined amounts of DMT, DMC, and BDO (molar ratio of ester/diol = 1:1.8) and the catalyst of TBT (0.2 wt % based on the weight of ester, which was actually reacted with the diol) were added into the 5 L steel reactor.…”

“…To guarantee the stability and credibility of the final products, a 5 L steel reactor was used to prepare the kilogram-scale PBCTs. 24 First, predetermined amounts of DMT, DMC, and BDO (molar ratio of ester/diol = 1:1.8) and the catalyst of TBT (0.2 wt % based on the weight of ester, which was actually reacted with the diol) were added into the 5 L steel reactor. It is essential to point out that the predetermined amounts of DMC were composed of two parts: actual participated response and consumption of azeotrope.…”

Biodegradable Poly(butylene succinate) Copolyesters Modified by Bioresoured 2,5-Tetrahydrofurandimethanol

“…2,5-Tetrahydrofurandimethanol (THFDM) could realize high efficiency conversion from biobased 5-hydroxymethylfurfural (HMF) and large-scale production. More recently, it was successfully introduced into PET and PCF polyesters, as reported by our group, 29,30 resulting in the optimization of properties. Moreover, the copolymerization of THFDM can achieve the aim of introduction of ether groups without sacrificing strength and T g , while the biodegradability of THFDM-based copolyesters still needs further investigation.…”

Synthesis of Poly(Ester-Ether) Polymers via Hydroesterificative Polymerization of α,ω-Enol Ethers

“…Based on these observations, we envisioned that modification of 10-undecenol through etherification would inhibit aldehyde formation, while also opening up this polymerization strategy to more structurally diverse monomers (Figure B). Further, introduction of ether linkages into a polymer can increase the biodegradability and decrease the crystallinity of the resulting polyester. , Herein, we report the hydroesterificative polymerization of undecenol-derived α,ϖ-enol-ethers. This strategy expands the range of the thermal properties of hydroesterification-derived polyesters and includes attractive bioderived building blocks such as isosorbide and cyclohexanedimethanol.…”

“…Further, introduction of ether linkages into a polymer can increase the biodegradability and decrease the crystallinity of the resulting polyester. 17,18 Herein, we report the hydroesterificative polymerization of undecenol-derived α,ϖ-enolethers. This strategy expands the range of the thermal properties of hydroesterification-derived polyesters and includes attractive bioderived building blocks such as isosorbide and cyclohexanedimethanol.…”