Copolyesters developed from bio‐based 2,5‐furandicarboxylic acid: Synthesis, sequence distribution, mechanical, and barrier properties of poly(propylene‐co‐1,4‐cyclohexanedimethylene 2,5‐furandicarboxylate)s

Abstract

A series of poly(propylene‐co‐1,4‐cyclohexanedimethylene 2,5‐furandicarboxylate)s (PPCFs) with different compositions were synthesized from bio‐based aromatic monomer 2,5‐furandicarboxylic acid and 1,3‐propanediol (PDO), along with 1,4‐cyclohexanedimethylene (CHDM). The chemical structure, composition, and sequence distribution of PPCFs were determined by nuclear magnetic resonance (1H NMR and 13C NMR). Results showed that the compositions of copolyesters depended on the feed molar ratio of PDO and CHDM, and all the obtained PPCFs copolyesters had triad component in a random sequential structure. With the addition of CHDM, the gas barrier properties of poly(propylene 2,5‐furandicarboxylate) (PPF) deteriorated. However, when the content of CHDM reached 79%, PPCF79 still showed the CO2 and O2 barrier improvement factor of 4.5 and 3.25, respectively, which were better than those of poly(ethylene naphthalate), a well‐known polymer with barrier property. Besides, PPCF79 showed good performance on tensile modulus, tensile strength, elongation at break, and the crystallization enthalpy was improved from 3.2 J g−1 for PPF to 30.7 J g−1 for PPCF79. It has the potential to serve as a promising bio‐based polymer with excellent comprehensive performance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47291.

Tuning the Properties of Furandicarboxylic Acid-Based Polyesters with Copolymerization: A Review

“…Titanium(IV) isopropoxide is regularly used, solely or in combination with TBT [ 28 , 29 , 60 , 68 , 77 , 93 , 97 , 100 ]. Zinc(II) acetate is also often used for the first step (Sb 2 O 3 is generally added for the polycondensation step) [ 30 , 31 , 34 , 35 , 36 , 48 , 58 , 59 , 102 ]. Dubois et al have synthesized a home-made titanium-silica complex that exhibited high catalytic activity [ 37 , 45 , 56 ].…”

“…On the other hand, when two diols are used to prepare copolymers from 2,5-FDCA, two main strategies can be singled out. The use of cyclic diols such as isosorbide [ 68 , 97 , 99 , 100 ], CHDM [ 59 , 65 ], and CBDO [ 34 ] leads to increased T g , since the chain mobility of the end products is severely hindered. At the same time, increasing the length of aliphatic diols used always leads to higher chain mobility and thus to lower T g values.…”

“…Cyclic diols that have been copolymerized with FDCA polyesters include CHDM, Is, and CBDO. CHDM was found to improve the thermal stability of PPF [ 59 ], PBF [ 59 ], and PIsF [ 99 ] as the starting decomposition temperature increased with increasing CHDM content. For the first two series of copolymers, the temperature at which degradation occurs with the fastest rate ( T d.max ) was also higher, which is in accordance with the CHDM content.…”

“…The high barrier properties were maintained in temperatures > T g . PPF-PCHDMF has smaller CO 2 and O 2 permeability than PET and PEN, but slightly larger than PPF [ 59 ]. The same effect was observed in PPF- co -PPS copolymers, with the permeability increasing while increasing the propylene succinate content [ 62 ].…”

“…PPF- co -PCHDMF 20/80 synthesized with DMFD had acceptable optical properties that were similar of those of PET with a little higher haze [ 59 ]. PEF- co -PCBDOF copolymers ( Figure 22 e) were colorless and transparent before annealing, and after annealing, only the one with 10 mol% CDBO content remained transparent [ 35 ].…”