European Polymer Journal 160 (2021) 110778

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Biobased 2,5-furandicarboxylic acid (FDCA) and its emerging copolyesters’

properties for packaging applications
Surabhi Pandey a, Marie-Josée Dumont a, *, Valérie Orsat a, Denis Rodrigue b
a
Bioresource Engineering Department, McGill University, 21111 Lakeshore Rd., Ste-Anne-de-Bellevue, QC H9X 3V9, Canada
b
Chemical Engineering Department, Department of Chemical Engineering, Université Laval, 1065 Avenue de la Médecine, Québec City, Québec G1V 0A6, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: The synthesis of 2,5-furandicarboxylic acid (FDCA) based polymers is gaining importance as a replacement for
2,5-furandicarboxylic acid petrochemical polymers due to their excellent thermomechanical and barrier properties. However, the industrial
Food and beverage packaging production of FDCA based homopolyesters is impeded due to several factors including poor optical property, low
Biodegradability
ductility, and slow crystallization rate. In order to tune the properties of FDCA-based homopolyesters, FDCA has
Poly(butylene adipate-co-furandicarboxylate)
Thermomechanical properties
been copolymerized with several aliphatic (adipic acid, succinic acid, lactic acid, sebacic acid, polyglycolic acid,
and polyethylene glycol) and cyclic (caprolactam and isohexides) comonomers. The present review focuses on
the current trends related to the synthesis of FDCA and its copolyesters. The thermomechanical and barrier
properties of copolyesters have been discussed concerning applications in the food and beverage packaging
sectors, with an emphasis on their biodegradability (hydrolytic and enzymatic) and compostability.

1. Introduction sustainable approach to produce polymeric materials [1,2]. These bio-

based polymers can be categorized into three categories namely: (a)
The replacement of fossil fuels with biomass has been regarded as a naturally occurring, (b) chemically synthesized, and (c) polymers

Abbreviations: εb, elongation at break; σb, strength at break; Ƞ, intrinsic viscosity; BDA, 1,4-butanediamine; BIFp, barrier improvement factor; CALB, Candida
antarctica lipase B; CBDO, 2,2,4,4-tetramethyl-1,3-cyclobutanediol; CHDM, 1,4-cyclohexanedimethanol; DBTO, dibutyltin(IV) oxide; DDCA, dodecanedioic acid;
DMFD, dimethyl-2,5-furandicarboxylate; E, Young’s modulus; E′ , storage modulus; FDCA, 2,5-furandicarboxylate; HT, hydrotalcite; ΔHm, melting enthalpy in the
first heating scan; La(acac)3, lanthanum(III) acetylacetonate; Mn, number average molecular weight; Mw, weight average molecular weight; MSP, minimum selling
price; PBA, poly(butylene adipate); PBA-co-PBF, poly(butylene adipate-co-furandicarboxylate); PBA-co-PBT, poly(butylene adipate-co-terephthalate); PBF, poly
(butylene furandicarboxylate); PBF-co-PEG, poly(ethylene glycol-co-butylene furandicarboxylate); PBS, poly(butylene succinate); PBS-co-PBA, poly(butylene suc­
cinate-co-adipate); PBS-co-PBF, poly(butylene succinate-co-furandicarboxylate); PBS-co-PBT, poly(butylene succinate-co-terephthalate); PBSe-co-PBF, poly(butylene
sebacate-co-furandicarboxylate); PCF, poly(1,4-cyclohexanedimethylene furandicarboxylate); PCL, poly(ε-caprolactone); PCL-co-PBF, poly(ε-caprolactone-co-
butylene furandicarboxylate); PCL-co-PHeF, poly(ε-caprolactone-co-hexamethylene furandicarboxylate); PCL-co-PPeF, poly(ε-caprolactone-co-pentylene fur­
andicarboxylate); PDeF, poly(decylene furandicarboxylate); PDG-co-PBF, poly(diglycolate-co-butylene furandicarboxylate); PDI, polymer dispersity index; PDIsF,
poly(decamethylene-co-isosorbide furandicarboxylate); PDoF, poly(dodecylene furandicarboxylate); PE, polyethylene; PEA-co-PEF, poly(ethylene adipate-co-fur­
andicarboxylate); PEBF, poly(2-ethyl-2-butyl-1,3-propylene furandicarboxylate); PEDF, poly(ethylene dodecanedioate-2,5-furandicarboxylate); PEF, poly(ethylene
furandicarboxylate); PESe, poly(ethylene sebacate); PESe-co-PEF, poly(ethylene sebacate-co-furandicarboxylate); PET, poly(ethylene terephthalate); PHA, poly
(hydroxyalkanoates); PHB, poly(hydroxybutyrate); PHeF, poly(hexamethylene furandicarboxylate); PHepF, poly(heptylene furandicarboxylate); PIsBF, poly(iso­
sorbide-co-butylene furandicarboxylate); PIsCBF, poly(isosorbide carbonate-co-butylene furandicarboxylate); PIs(CL)F, poly(ε-caprolactone-co-isosorbide fur­
andicarboxylate); PIsF, poly(isosorbide furandicarboxylate); PLA, poly(lactic acid); PLA-co-PBF, poly(lactic acid-co-butylene furandicarboxylate); PLA-co-PEF, poly
(lactic acid-co-ethylene furandicarboxylate); PNF, poly(nonylene furandicarboxylate); PNgF, poly(neopentyl glycol furandicarboxylate; PNS-co-PNF, poly(neopentyl
glycol succinate-co-furandicarboxylate); POF, poly(octylene furandicarboxylate); PP, polypropylene; PPeF, poly(pentylene furandicarboxylate); PPF, poly(propylene
furandicarboxylate); PPS, poly(propylene succinate); PPS-co-PBA, poly(propylene succinate-co-adipate); PPS-co-PPF, poly(propylene succinate-co-furandicarbox­
ylate); PVP, polyvinylpyrrolidone; ROP, ring opening polymerization; Sb2O3, antimony(III) oxide; SnOct2, stannous octoate; SSP, solid state polymerization; Tc,
crystallization temperature; Td max, maximum decomposition temperature; Tg, glass transition temperature in the second heating scan; Tm, melting temperature in the
first heating scan; TBT, titanium(IV) butoxide; TPA, terephthalic acid; TTIP, titanium(IV) isopropoxide; Zn(Ac)2, zinc acetate.
* Corresponding author.
E-mail address: marie-josee.dumont@mcgill.ca (M.-J. Dumont).

https://doi.org/10.1016/j.eurpolymj.2021.110778
Received 30 July 2021; Received in revised form 17 September 2021; Accepted 19 September 2021
Available online 21 September 2021
0014-3057/© 2021 Elsevier Ltd. All rights reserved.
S. Pandey et al.
fermented by microorganisms [3]. The production routes for biobased
polyesters, such as polylactic acid (PLA), poly(butylene succinate)
(PBS), and poly-(hydroxyalkanoates) (PHA) have already been well
established [4–8]. However, their thermomechanical and barrier prop­
erties are inferior to poly(ethylene terephthalate) (PET), which is
considered the most suitable polymer for beverage packaging. The lack
of aromatic ring structures in the architecture of the current biobased
polymers might be the one reasonable hypothesis for their inferior
properties (summarized in Table 1). Therefore, the exploration of
monomers having rigid aromatic ring structures derived from biomass
has become significant for the development of the next generation of
biobased polymers [9].
Sugar-derived monomers consisting of cyclic structures impart high
glass transition temperatures (Tg), as well as excellent gas and water
vapor barrier properties when polymerized into polyesters. Amongst
them, 2,5-furandicarboxylic acid (FDCA) has been included in the top-
15 list of molecules by the US Department of Energy (DOE) having the
potential to replace petrochemical monomers such as terephthalic acid
(TPA) [10]. Its structural similarity to TPA makes it suitable for the
production of polyesters without a significant decrease in Tg. The FDCA
molecule is composed of a furan ring with two carboxylic acid groups,
which can be converted into succinic acid, 2,5-furandicarbaldehyde,
2,5-dihydroxymethylfuran, among others. The polycondensation reac­
tion of FDCA with ethylene glycol produces poly(ethylene furanoate)
(PEF), which has superior mechanical properties, improved gas barrier
properties, and reduced non-renewable energy consumption as
compared to PET [11–13]. Moreover, FDCA has been copolymerized
with aliphatic and cyclic acid comonomers to improve biodegradability.
These copolyesters have demonstrated outstanding thermomechanical
and gas barrier properties making them suitable candidates for food and
beverage packaging (Table 2).
The most common route for FDCA synthesis is through oxidation of
5-hydroxymethylfurfural (HMF), the latter being produced by carbo­
hydrate dehydration. The production of HMF has been extensively
studied by several authors using feedstocks ranging from simple sugars
to complex carbohydrates [14–21]. However, the direct production of
FDCA from biomass is still limited to fructose, glucose, sucrose, high
fructose corn syrup, jerusalem artichoke, and starch [22–27]. The in­
dustrial production of FDCA has not reached its full potential due to its
low yield and high production cost as the current average for FDCA
synthesis is $2300/kg. To make the process economically viable, FDCA
production cost should be below $1000/ton [28,29]. Motagamwala
et al. (2018) described a process to produce FDCA from fructose where
Table 1
Examples of examples of food and beverage packaging and their limitations.
Polymers Limitations
a
PLA Thermally instable, difficult to heat seal,
brittle, low melt strength, high water vapor
and oxygen permeability making it unsuitable
for oxygen and moisture sensitive beverage
packaging
c
PBAT Comparable properties to LDPE, but is not
biobased as it uses terephthalic acid as a
comonomer
a
PHA and PHB Stiffness, brittleness, thermal instability and
poor impact resistance restricting their
applications in food packaging
a
Starch and Not suitable for hydrophilic foods, low water
b
cellulose based vapor barrier which is responsible for poor
blends processability, brittleness, vulnerability to
degradation, limited long-term stability and
poor mechanical properties
d
PET Highly used for bottle manufacturing and
beverages packaging, but it is not biobased or
biodegradable
a: biodegradable or compostable bioplastics, b: non-biodegradable bioplastics, c:
biodegradable synthetic plastics, and d: non-biodegradable synthetic plastics.
European Polymer Journal 160 (2021) 110778
Table 2
Applications of furanic based homo-/copolyesters for food and beverage
packaging.
Polymers Applications Reference
b
PEF, PBF, Find applications in food and beverage [83,101,161]
and PPF packaging, frozen food trays manufacturing, [156]
and mainly for bottle manufacturing. They
exhibit better barrier properties than
commercially adopted bioplastic such as PET,
PBS, PLA and PBA-co-PBT, but are not
biodegradable
a
PBA-co-PBF Can be used as a biobased replacement for PBA- [73]
co-PBT and is 100% compostable and
enzymatically degradable
a
PIsCBF Potential use in food packaging and [155]
manufacturing of heat resistant containers
a
PPS-co-PPF Exhibit superior barrier properties compared to [72]
PLA and PBA-co-PBT, and offers competitive
ability for food packaging and agricultural films
b
PNF Have been found suitable for low moisture [106]
foods, fatty foods, alcoholic beverages, and
acidic foods
a
PBF-co-DGA Suitable for processed fruits and vegetable [145]
under modified atmospheric packaging
b
P(CHDM)F These are high molecular weight polymers [108]
suitable for beverage packaging
a: biodegradable bioplastics, b: non-biodegradable bioplastics.
the minimum selling price (MSP) was estimated to be around $1490/
ton. They showed that the main processing costs are associated with the
HMF formation stage ($650/ton) and the long residence time (4.3 h) for
HMF oxidation. The group further suggested that the reduction in resi­
dence time (up to 40%) and feedstock cost (by 10%) could drop the MSP
to $1310/ton, which could compete with the current production process
of TPA ($1445/ton) [30]. A techno-economic analysis reported MSP of
HMF as $1715/ton from fructose as feedstock, which was further
reduced to $1446/ton by changing the feedstock to glucose [31].
Replacing simple sugars with food wastes could be a sustainable option
for HMF production from environmental and economic perspectives.
Studies are now emerging where, for instance, starch (bread wastes,
cooked rice, pasta, and noodles) and cellulose-rich food wastes (fruit
peels) have been used to synthesize HMF [14,15,32].
Sustainability has become an integral part of the field of polymer
sciences; therefore, this review focuses on providing condensed infor­
mation related to the synthesis of FDCA using heterogeneous catalysts,
base-free systems, and biomass-derived feedstocks. Herein, the effect of
the addition of aliphatic and cyclic monomers in the FDCA polymeric
chain has been discussed in relation to biodegradability and compost­
ability aspects. Finally, this review presents the effect of copolymeri­
zation on thermomechanical, optical, and gas barrier properties of FDCA
Reference based polymers keeping food and beverage packaging in retrospect.
[157]
2. Industries involved in FDCA production
The downstream processing and catalytic selectivity are major crit­
[158] ical factors for deciding the efficiency of the FDCA production process.
Avantium and BASF, under a joint venture (Synvina), successfully
improved the separation technology and catalyst selectivity to produce
[159]
FDCA with the MSP of $1000/ton. In early 2020, Avantium signed a
memorandum of understanding (MOU) to locate a pilot plant in the
[160] Netherlands with a production goal of 5 kilotons using the "YXY" tech­
nology. This technology involves the dehydration of carbohydrates in an
alcohol medium to form alkoxymethylfurfural or methox­
ymethylfurfural and methyl levulinate, and their subsequent oxidation
[139] to FDCA using acetic acid. This is followed by the polymerization of
FDCA with ethylene glycol to form PEF [29]. Several other companies
including Dupont, Archer Daniels Midland Company, Origin Materials
and Eastman Company, AVA Biochem, and the VTT research center have
2
S. Pandey et al.
also made successive breakthroughs in developing their technologies for
the commercial production of FDCA [33]. A two-step process for the
conversion of sucrose, glucose, and fructose was introduced by Petro­
bras. This process consists of converting sugars into HMF as the first
reaction step over an ion exchange resin, followed by their oxidation to
FDCA [34]. Each technology has its challenges that impede the large-
scale production of FDCA. Most of the microbiological processes yield
a low amount of FDCA for prolonged reaction times. However, the
fermentation pathway is the greenest option compared to the use of
toxic solvents and high temperatures. Using homogenous catalytic sys­
tems such as Co(OAc)2/Mn(OAc)2/HBr and Co(OAc)2/Zn(OAc)2/NaBr
under high pressure and air oxidation of HMF generated approximately
60% FDCA yield. Pure oxygen and t-BuOOH are the commonly used
oxidant during FDCA production [35]. However, the practical applica­
tion of homogeneous catalysts in HMF to FDCA oxidation suffers major
drawbacks including low FDCA yield, byproduct formation, and diffi­
culty in separation and catalyst recovery [36]. Nevertheless, a majority
of companies rely on chemical processes for FDCA production and are
now focusing on developing new techniques using heterogeneous cata­
lysts and green solvent systems [37].
Metal-supported heterogeneous catalysts, for instance, gold (Au),
platinum (Pt), ruthenium (Ru), and palladium (Pd) have been commonly
used for HMF to FDCA oxidation. Pt supported on carbonaceous mate­
rials such as Pt/C and Pt-Pb/C under 1 bar O2 pressure gave 81 and 99%
FDCA yield, respectively [38]. The increase in FDCA yield by Pd doping
led to the development of bimetallic catalysts for HMF oxidation as re­
ported by several authors [39–41]. A range of Pd catalysts have been
synthesized by doping palladium nanoparticles with C, PVP, and metal
oxides as support materials. PVP stabilized Pd nanoparticles (Pd/PVP)
catalyst gave similar yield as obtained with Pt (99% FDCA yield)
[42,43]. The support materials used for metal deposition could also
impact the FDCA yield, for example, Au nanoparticles doped on CeO2
and TiO2 afforded higher FDCA yield (>99%) than Fe2O3 and C [44].
Ru-based catalysts were initially used for HMF oxidation to DFF rather
than FDCA synthesis. The mechanism of HMF to FDCA oxidation over Ru
catalysts and the impact of base materials such as La2O3, MgO, and HT
have been well researched [45,46].
3. Chemistry involved in FDCA production
To understand the reaction pathway for FDCA production, it is
Scheme 1. Reaction pathways for acid-catalyzed dehydration of glucose and fructose [47,48].
3
European Polymer Journal 160 (2021) 110778
imperative to elucidate the initial step of sugars conversion into HMF.
The current industrial production of HMF involves the thermo­
chemical acid-catalyzed dehydration of fructose via the loss of three
water molecules to yield HMF through a cyclic or acyclic route (Scheme
1) [47,48]. Glucose, on the other hand, requires an additional step of
isomerization to fructose before HMF dehydration. According to Antal
et al., the dehydration of HMF from sucrose proceeds via a cyclic route
through the formation of a fructofuranosyl-cation intermediate [48]. An
alternate route was followed by Moreau et al. where 3-deoxyhexosulose
was formed as an intermediate by elimination of 3-hydroxyl group. The
presence of furfural obtained by retro-aldo cleavage suggested that the
acyclic route was prevalent during the HMF synthesis from fructose
[47]. Since the acid-catalyzed carbohydrate is a complex reaction, un­
wanted reactions, such as rehydration, fragmentation, reverse-aldo re­
action, and condensation, occur in parallel. For instance,
dihydroxyacetone and glyceraldehyde appear from reverse-aldo reac­
tion of fructose, formic acid (FA), and levulinic acid (LA) as the rehy­
dration products of HMF, and condensation leads to humin formation
[48]. When complex carbohydrates are present in the feedstock, such as
for food wastes, the formation of HMF undergoes three steps including
the hydrolysis of complex di-/polysaccharides to glucans, their isomer­
ization to fructose, and dehydration to HMF. The dehydration and hy­
drolysis steps are favored by Bronsted acids through the protonation of
the hydroxyl groups of sugars, while the isomerization is catalyzed by
Lewis acids which facilitate the 1,2-hydride shift by accepting electrons
[15].
Oxidation of HMF to FDCA under different catalytic systems
The oxidation of HMF to FDCA can occur through chemical, enzy­
matic, or electrochemical processes. Amongst them, the chemical
transformation seems to be most promising at the industrial level owing
to high yields, product purity, and reaction rate [49]. The chemical
conversion of HMF to FDCA is achieved using high temperature in
presence of additives, (such as base including NaHCO3, Na2CO3, NaOH,
K2CO3) while the biocatalytic transformation occurs at relatively mild
conditions. However, the yield obtained by the latter is not appreciable
[50]. The oxidation route of HMF to FDCA is dependent on the type of
reaction system used and can proceed through two routes (Scheme 2).
The first pathway (Route 1) involves the oxidation of the aldehyde group
to form 5-hydroxymethyl-2-furan carboxylic acid (HFCA); while the
second route follows the alcoholic group oxidation to 2,5-furan dicar­
boxaldehyde (DFF). These intermediate products are then transformed
S. Pandey et al.
Scheme 2. Reaction mechanism for HMF oxidation to FDCA [49].
to formylfurancarboxylic acid (FFCA), which gets oxidized to FDCA
[30].
While homogeneous catalysts, such as [Co/Mn/Br] and [Co/Zn/Br],
provide high FDCA yields during HMF oxidation, the non-recyclability
of these catalysts has limited their use in various reaction systems
[35,51]. Therefore, heterogeneous catalytic systems have gathered
much attention in recent years. Several authors have reported the use of
supported heterogeneous noble metal catalysts, such as Au, Pt, Pd, and
Ru and their alloys, for the conversion of carbohydrates into FDCA under
basic environment [23,25,42,49]. Supported Au nanoparticles (NPs)
have shown excellent performance for the oxidation of HMF to FDCA
under aerobic conditions. For instance, CeO2 supported Au NPs pro­
duced high FDCA yield (99 mol%) from HMF oxidation using highly
concentrated NaOH (4 equivalent of HMF) at 130 ◦ C under 1 MPa air
pressure [52]. TiO2/Au was less efficient, leading to a yield of only 65
mol% FDCA from HMF at a high NaOH to HMF ratio (>20) [53]. A
comparative study on carbon-supported Au, Pt, and Pd NPs reported
that Pt/C and Pd/C were more efficient for HMF oxidation (71–79 mol%
FDCA) than Au/C NPs at a constant HMF to KOH molar ratio of 1:2, 7 bar
O2, 295 K and 7 h of reaction time [40].
Although the basic environment for HMF oxidation generally pro­
vides high FDCA yields, these are characterized by the high base usage
and O2 pressure, which can triggers a parallel reaction for HMF degra­
dation. Other compounds, such as FA, LA, and humins, can be formed,
which depict the instability of HMF under high pH conditions. More­
over, the product formed in a basic environment is FDCA salt, which
cannot be directly used for the synthesis of polymers, thus needs to be
separated using strong mineral acids [54].
Base-free HMF oxidation using heterogeneous catalysts has been
extensively investigated by various researchers [55–58]. Hydrotalcite
supported Au NPs showed 99% FDCA yield from HMF in water at 95 ◦ C
and 7 h under aerobic conditions. The basicity of metallic supports is a
crucial factor to be considered during HMF oxidation to FDCA.
Compared to neutral or acidic supports, such as Au/SiO2 and Au/Al2O3
which yield almost no FDCA, basic supports, such as MgO and hydro­
talcites, achieved full HMF conversion leading to high FDCA yields [55].
However, the instability of hydrotalcites due to high Mg2+ leaching and
MgO dissolution during FDCA formation limits their use and their
recyclability [57]. The incorporation of a second metal with gold using
carbon nanotubes as support (AuPd/CNT) enhanced the basicity of Au-
based catalysts. It was reported that 100% HMF conversion can be
achieved in 12 h using nascent O2 as the oxidant [58]. Another study
investigated the effect of the support material (MgO–MgF2) basicity on
the reaction pathway for HMF to FDCA oxidation [28]. The study
showed that increasing the MgO content enhanced the FDCA production
due to the formation of basic Mg(OH)2 in water. Higher MgO
4
European Polymer Journal 160 (2021) 110778
concentration favored the HFCA route to FDCA formation, with no DFF
detected. When the solute pH dropped below 3.8, FDCA was protonated
which facilitated its direct precipitation. Being the least expensive of all
the noble metals, ruthenium supported on MnCo2O4 gave a 99.1% FDCA
yield from base-free oxidation of HMF in water. The catalyst exhibited
excellent recyclability without the loss of active species [56].
Moreover, the use of ionic liquids (ILs) as solvent is advantageous for
HMF to FDCA oxidation due to the high FDCA solubility. The catalyst
inactivation due to FDCA deposition is minimized by the use of ILs.
Besides, non-noble metal catalysts, such as Fe-Zr-O and Fe-Zr-Ce-O, were
investigated to reduce the cost of HMF oxidation using [BMIM]Cl in a
base free reaction system, yielding 61 and 44 mol% of FDCA yield,
respectively after 24 h [59,60]. The FDCA yield in [BMIM]Cl was
enhanced to 89 mol% by using heteropolyacids at 140 ◦ C, and 1 MPa O2
in 6 h [61]. Furthermore, Motagamwala et al. (2018) used equal parts of
GVL and water to synthesize FDCA (93 mol%) from fructose-derived
HMF using base-free conditions. The high yield obtained was due to
the enhanced solubility of FDCA in the solvent system, which decreased
with decreasing temperature, facilitating FDCA crystallization below
4 ◦ C [30].
Few studies have focused on the synthesis and application of mag­
netic catalysts. Zhang et al. studied the catalytic effect of magnetic
palladium nanocatalyst for efficient conversion of HMF to FDCA (93 mol
%) in water at low K2CO3 concentration (0.5 equivalent mole ratio of
HMF) under aerobic conditions [49]. The reaction time and energy
consumption of HMF to FDCA oxidation were substantially reduced
using metal ferrites, MFe2O4 (M = Cu, Mn, Mg, and Co) as catalysts in
presence of tert-butyl hydroperoxide as oxidant and acetonitrile as sol­
vent. The highest FDCA yield was reported as 85 mol% at 100 ◦ C for 5 h
using Mn as the active species [62]. Furthermore, a two-step one-pot
conversion of fructose to FDCA (60 mol%) was achieved using nano-
Fe3O4-CoOx catalyst and tert-butyl hydroperoxide as the oxidant in a
DMSO solvent system [63].
Although FDCA could be produced from HMF with nearly quanti­
tative yields (ranging from 60 to 99 mol%), the cost of HMF is high.
Carbohydrates are much cheaper and more abundant than HMF [44,64].
Therefore, it is more attractive to carry out the oxidative conversion of
carbohydrates into FDCA by one-pot reaction over multiple functional
catalysts combing acidic and metal sites. There have been few studies on
direct carbohydrate conversion into FDCA. For example, Kroger and co-
workers used a biphasic system composed of water/methyl isobutyl
ketone (MIBK) for one-pot conversion of fructose to FDCA using a pol­
ytetrafluorethylene membrane reactor. The fructose was firstly trans­
formed into HMF using Lewatit SPC 108 as the solid acid catalyst, the
HMF was then extracted in the MIBK phase, followed by its oxidation
into FDCA (25%) over metal catalysts. The low FDCA yield and
S. Pandey et al.
cumbersome FDCA separation from the by-products were few draw­
backs in the process [65]. Ribeiro and Schuchardt prepared a bifunc­
tional catalyst by the encapsulation of Co(acac)3 in sol–gel silica,
combining the acidic and redox ability, and studied the one-pot con­
version of fructose to FDCA, obtaining fructose conversion of 72% with a
selectivity of 99%. Compared to the method reported by Kröger and co-
workers, both FDCA yield and selectivity were greatly improved.
However, the reaction was carried out at 165 ◦ C and a pressure of 20 bar,
which are difficult conditions to reach [66].
Another system was reported by Zhang and co-workers where a two-
step method for the conversion of fructose to FDCA was used [67]. The
HMF synthesis from fructose was carried out in isopropanol catalyzed by
HCl. The isopropanol was recollected for the next run by evaporation,
followed by HMF oxidation to FDCA (83%) in water using Au/HT
catalyst. The deposition of humins over the catalyst’s surface led to the
deactivation of the catalyst. Using Jerusalem artichoke tuber (fructose
units being the major component) as the feedstock led to an overall
FDCA yield of 52%. A recent work involved the use of a triphasic reactor
to convert sugars to FDCA in a one-pot process [23]. The triphasic sys­
tem is composed of tetraethylammonium bromide (TEAB) or water
(phase I)–methyl isobutyl ketone (MIBK) (phase II)–water (phase III). In
the designed triphasic setup, sugars (fructose or glucose) were first
dehydrated to HMF in Phase I. HMF was then extracted, purified, and
transferred to Phase III via a bridge (Phase II). Finally, HMF was
oxidized to FDCA over Au/HT catalyst in phase III. Overall, FDCA yields
of 78% and 50% were achieved with fructose and glucose feedstock,
respectively. Phase II plays multiple roles as a bridge for HMF extraction,
transportation, and purification. The same group synthesized Fe3O4@­
SiO2–SO3H acid catalyst which dehydrated fructose to HMF in DMSO as
the solvent system. The HMF was then oxidized to FDCA with t-BuOOH
over nano-Fe3O4–CoOx catalyst. The use of earth-abundant metals and
magnetic catalyst provide more practical approach from recyclability
and economic point of view [63].
In a nutshell, the direct conversion of carbohydrates to FDCA has
come a long way, however the current technologies need significant
improvement for large scale production. Here are some of the challenges
associated with the existing catalytic systems:
1. The feedstocks mainly getting attention for FDCA production are
fructose and glucose, while food and lignocellulosic wastes have not
been well explored yet.
2. The separation of FDCA from the catalytic mixture is also an
important point which still needs to be focused upon. Many of the
current studies use excess of base for HMF to FDCA oxidation which
requires an additional neutralization due to the production of FDCA
salt. This results in a less green and cost intensive process. Therefore,
much more effort is needed to develop more environmentally
friendly catalytic systems that can effectively promote the base-free
oxidation of HMF into FDCA.
3. Preparation of multifunctional catalysts is an important area of
research as they have shown to reduce the amount of side reactions.
The selection of the active sites on the catalyst is essential for the one-
pot conversion of carbohydrates to FDCA.
4. In comparison to catalytic activity of noble metals, the non-noble
metals are much less studied. From the viewpoint of practical
application, transition metal catalysts such as Co, Fe, Mn can be a
more suitable choice in terms of cost, stability, and recyclability, for
the aerobic oxidation of HMF to FDCA.
4. FDCA based homopolyesters and their properties
4.1. Mode of polymerization
4.1.1. Melt polycondensation
The reaction proceeds through direct esterification or trans­
esterification of FDCA or its corresponding ester, with polyhydroxy
5
European Polymer Journal 160 (2021) 110778
alcohol in presence of a catalyst with an excess of diols to obtain olig­
omers, followed by the polycondensation reaction. In general, dimethyl-
2,5-furan dicarboxylate (DMFD), an ester of FDCA, has been used as the
starting material. However, for industrial purposes, direct esterification
is preferred [68,69]. The esterification or transesterification reactions
are generally carried out in a temperature range of 150–180 ◦ C, while
the polycondensation is conducted at a higher temperature range of
180–230 ◦ C. By the end of the esterification step, the mixture becomes
transparent after the Weissenberg effect, which later turns into a molten
product in the polycondensation step. During the polycondensation re­
action, diols are produced as the side product. To evaporate the excess of
diols, the process is carried out under vacuum, thus preventing polymer
oxidation, and facilitating the formation of a high molecular weight
(Mw) polymer [70].
Solid-state polymerization (SSP) is an additional step to further in­
crease the Mw of the melt, by heating the polymer between its glass
transition (Tg) and melting (Tm) temperatures [71]. The most commonly
used organometallic catalyst during melt polymerization is titanium(IV)
butoxide (TBT), which accelerates the polymerization rate of dicar­
boxylic acids [23,63,67]. Other catalysts commonly used during the
polycondensation step are titanium(IV) isopropoxide (TTIP), antimony
(III) oxide (Sb2O3), and zinc acetate (Zn(Ac)2) [75–78].
Several investigations have been reported on the use of combined
catalytic systems to improve the reactivity and polymerization rate. A
white fibrous polymer with the film-forming property was prepared by
melt transesterification of DMFD with 1,6-hexanediol in presence of
calcium acetate and Sb2O3 as the catalyst. The number average molec­
ular weight (Mn) was low (below 10,000 g/mol), while the distribution
was relatively high (polydispersity index = 2.5) [79]. A patent reported
the use of Sn/Ti catalysts to prepare polyesters by reacting FDCA with
different monomers, such as ethylene glycol, 1,3-propanediol, and 1,4-
butanediol monomers in the first step, with subsequent SSP to in­
crease their Mw [70]. Kato & Kasai reported the use of TBT and mag­
nesium acetate during the ester exchange step to produce PEF and PBF,
where PEF was reported to have excellent heat resistance and thermo­
mechanical properties. However, the reaction time was too long (7.5 h)
to achieve high Mw [80]. The combined effect of La(acac)3 and TBT
proved to be more reactive than TBT alone, to catalyze the poly­
condensation of PBF. However, no significant effect on the polymer
thermal stability was observed [81]. During SSP kinetics of PEF, it was
observed that Sn-based catalysts gave higher Mw products than Ti-based
catalysts. Moreover, it was reported that TTIP showed higher reaction
rates, while dibutyltin (IV) oxides (DBTO) enhanced the crystallinity
[82,83].
4.1.2. Ring-opening polymerization
Most of the FDCA-based polyesters have been produced by poly­
condensation using organometallic catalysts. Nevertheless, researchers
have synthesized FDCA copolymers with lactide, isohexides, and
caprolactam as comonomers using entropically driven ring-opening
polymerization (ROP) to obtain high Mw polymers. Being a greener
option, ROP has the advantages of minimum polymer coloration, low
melt viscosity, and shorter reaction time without byproduct formation.
ROP is triggered by the rupture of the aromatic molecule to form a linear
polymer in presence of suitable catalysts. The synthesis involves high
dilution condensation to form cyclic oligomers followed by cyclo­
depolymerization. During the former step, the acid dichloride reacts
with diols under high dilution concentrations (<0.005 M) to form
instant cyclic oligomers in the presence of DABCO as the catalyst. The
crucial step is to remove the linear oligomers formed during the reaction
using flash chromatography. The most commonly used catalyst for ROP
is stannous octoate (SnOct2) [84–86]. The Mw of PEF synthesized using
ROP lied between 50 and 60 kg/mol. However, more research is needed
to explore the polymer properties [87].
S. Pandey et al.
4.1.3. Enzyme assisted polymerization
Apart from chemical catalysis, enzymatic assisted ROP has been re­
ported by various authors for the synthesis of FDCA-based polyesters
[81,84,88–90]. The catalytic activity of these enzymes depends on the
solvent used being more efficient in a hydrophilic environment. Lipases
have been successfully used during ROP. For instance, cyclic (butylene
2,5-furandicarboxylate) oligomers were synthesized and copolymerized
with ε-caprolactone by ROP in presence of Candida antarctica lipase B
(CALB). Since the process avoids the use of both organic solvents and
organometallic catalysts, it is, therefore, a greener option as compared
to other polymerization techniques [84,88]. However, milder conditions
used during ROP prevent the decarboxylation reaction of FDCA leading
to low Mw products in comparison to melt polycondensation. The
copolymer poly(butylene succinate-co-butylene furanoate) PBSF syn­
thesized by ROP using CALB as catalyst had lower Mw (21–47 kg/mol) as
compared to chemical assisted ROP (53–63 kg/mol) [81,84].
4.1.4. Solution and interfacial polycondensation
Polymerization in solution has the merit of being carried out under
mild reaction conditions but has associated shortcomings such as
coloration in the product, low Mw, prolonged reaction time, and the use
of large volumes of solvent. PEF synthesized by solution polymerization
has significantly lower Mw (2500 g/mol) than that produced by trans­
esterification reaction (44500 g/mol) [91]. In terms of Mw and yield of
isolated polymers, the transesterification of monomers gave superior
results than those prepared by solution polycondensation for PEF (as
indicated in Table 3).
4.2. Thermomechanical properties
Amongst all thermal properties, glass transition temperature, Tg is an
important polymeric property to decide the applicability of the respec­
tive polymers in different fields. Compared to PET, PEF is more amor­
phous due to its higher specific and free fractional volume. However,
PEF displays a higher Tg than PET due to its rigid chain structure which
restrains ring flipping. As a result of the suppressed nonlinear axis
rotation, PEF experiences delay in the crystallization process, thus
lacking the presence of cold crystallization temperature and subsequent
melting peak during differential scanning calorimetry analysis [11].
The use of cyclic diols, such as isosorbides, 2,2,4,4-tetramethyl-1,3-
cyclobutanediol (CBDO), and 1,4-cyclohexanedimethanol (CHDM),
when used as monomers during polymerization, further restrict the
chain mobility and increases the polymer’s Tg. For instance, the poly­
merization of rigid CBDO and flexible CHDM with FDCA enhanced the
Tg of copolyesters ranging from 80.3 to 105.7 ◦ C. The Tg varied linearly
with the amount of CBDO units present, while larger amount of CHDM
units enhanced the Mw of the resulting copolyesters [91–93]. Apart from
the concentration of cyclic diol (CHDM), the ratio of cis to trans CHDM
affects the thermal properties of the polyesters formed due to the steric
configuration of the CHDM units [94,95].
Also, increasing the number of C-atoms in linear aliphatic diols is
responsible for Tg lowering as observed for poly(pentylene fur­
andicarboxylate) (PPeF), poly(hexamethylene furandicarboxylate)
(PHeF), poly(heptylene furandicarboxylate) (PHepF), and poly(octylene
furandicarboxylate) (POF). This phenomenon is related to the creation
of more amorphous regions in the polymer [91,96,97].
For copolyesters, the Tg lies between the Tg values of its corre­
sponding homopolyesters and can be described by several mathematical
models namely, Flory-Fox, Gordon-Taylor, Couchman-Karasz, and Kwei
equations. The Flory-Fox equation is relatively simpler but sometimes
fails to represent the experimental values, while other equations take
additional parameters into account, such as heat capacity, hence fitting
the data more accurately than the former equation [97]. The Mw also has
a prominent influence on the thermomechanical properties of the FDCA
polyesters. For instance, a study reported that low Mw species exhibited
reduced Tg, storage modulus (E′ ), and crystallinity for PBF samples
6
European Polymer Journal 160 (2021) 110778
because of the plasticization effect, and a subsequent rise in the melting
enthalpy (ΔHm) with increasing Mw [78]. The tensile properties of PET,
such as Young’s modulus (E), strength at break (σb), and elongation at
break (εb) are respectively 2.2 GPa, 57 MPa, and 200%, while the cor­
responding values for PEF are 3.7 GPa, 72 MPa, and 1%. Even though
PEF has some superior properties to replace PET, the main disadvan­
tages are brittleness, low εb, and slow crystallization rate-limiting its
processability during stretch-blow molding. In particular, a study
demonstrated that the incorporation of CHDM units in PEF led to
comparable E (2.2 GPa) and σb (56 MPa), but superior εb (180%) to that
of PEF, proving its suitability for beverage packaging applications [98].
4.3. Gas barrier properties
The crystallinity level has a major influence on gas permeation rates
as the gas molecules cannot permeate, diffuse, or transport through the
crystalline regions of a polymer. Burgess extensively studied the O2,
CO2, and water vapor transport phenomena in PEF and compared it to
PET, the latter is not suitable for O2 sensitive beverage packaging.
Despite its higher free volume (1.6 times), the O2, CO2, and water vapor
permeability of PEF were significantly lower (11, 19, and 2.1 times,
respectively) than PET. The enhanced barrier properties for PEF were
ascribed to the suppressed ring flipping motion due to the nonlinear axis
and ring polarity of the furan ring as compared to PET’s symmetrical and
non-polar phenyl ring [11,99,100]. Besides the hindered furan ring-
flipping, the gas barrier properties of PEF is also affected by the furan
ring’s polarity [101]. In addition, the inclusion of a cyclic monomer
(CHDM) with a furan ring enhanced the O2 barrier properties of PEF, as
the PECF bottles showed better barrier properties for beverage pack­
aging than commercially available PET [87,102]. The rise in CHDM
units (10 to 98%) improved the O2 and CO2 BIFP of PECF polymers,
resulting in an increase in CO2 and O2 BIFp from 2.4 to 6.8 and 2.3 to 6.7,
respectively [103].
Furthermore, the syn or anti-conformation of FDCA polymeric chains
have a significant effect on the gas and water vapor permeation rate. The
permeability through the polymer is restricted by the formation of
C–H⋯O interactions which occurs when FDCA exists in a syn confor­
mation. The syn or anti conformations are dependent on the number of
odd methylene groups present [104]. Vannini demonstrated that the
permeability of packaging films depends on the presence of an odd
number of methylene groups and the length of the aliphatic chain of
diols. The O2 and water vapor transmission rate of poly(propylene fur­
andicarboxylate) (PPF) is lower than PEF and is further reduced with
aging time due to increasing crystallinity and density. The permeability
loss in aged PPF films is attributed to the highly packed and ordered
polymer crystals with low free volume hindering molecular diffusion
[105].
The gas transmission rate in a film varies with temperature as
described by the Arrhenius equation, i.e. exponential increase with
temperature. At elevated temperatures, the macromolecules’ diffusive
jumps increase the free volume, which subsequently increases the gas
permeation rate in the polymer matrix. Another important factor to
include in permeation phenomena is the activation energy (Ea), which
represents the energy required to initiate the permeation process. A
study has reported that the Ea for CO2 transmission in PPF was 32 kJ/
mol, which is higher than for PEF (23.7 kJ/mol reported by Burgess
et al., 2014) [11,104]. Furthermore, a novel film, poly(neopentyl glycol
furandicarboxylate) (PNF) was tested in contact with food simulants to
evaluate the influence of temperature on gas permeability and food
respiration rate. The presence of branched methylene groups in PNF
reduced the mobility of the carbonyl groups, thus lowering the gas
transmission ratio. The food simulants used to evaluate the gas trans­
mission ratio were ethanol (10, 20, and 50% (v/v)) and acetic acid (3%,
v/v), representing food with a hydrophilic nature, alcoholic beverages,
lipophilic foods, and foods under a pH of 4.5, respectively. The highest
gas transmission ratio was reported for foods with a pH under 4.5.
 Table 3

S. Pandey et al.
FDCA based homopolyesters and their properties.
Polymer Staring materials Polymerization conditions Catalyst used Polymer properties Ref

PEF Ethylene glycol Esterification: 280 ◦ C, 4 h Sn/Ti Mn = 23000 g/mol; Tm = 170 ◦ C; Tg = 85 ◦ C; Tc = 156 ◦ C; Tdec = [70]
Polycondensation: 280 ◦ C, 6.5 h 332 ◦ C
Solid state condensation: 180 ◦ C
Ethylene glycol Transesterification Sb2O3 Mn = 22400 g/mol; Mw = 44500 g/mol; PDI = 1.99; Tm = 215 ◦ C; [91]
Tg = 80 ◦ C; Tc = 165 ◦ C; Tdec = 398 ◦ C; Y = 79%
DMF + ethylene glycol Transesterification TTIP Y = 93.24%; Mn = 13050 g/mol; Mw = 34000 g/mol; PDI = 2.6 [113]
Ethylene glycol Polytransesterification: 200 ◦ C for about 2 h TBT (0.1 mmol) Mw = 25973 g/mol, ƞ = 0.47 dL/g; Y = 82%; Tm = 201 ◦ C ; Tg = [116]
89 ◦ C ; Tdec = 326 ◦ C ; T50 = 376 ◦ C
2,5-furandicarbonyl chloride + ethylene Solution – Mn = 2000 g/mol; Mw = 2500 g/mol; PDI = 1.25; Tm = 215 ◦ C; Tg [91]
glycol = 80 ◦ C; Tc = 165 ◦ C; Tdec = 398 ◦ C; Y = 23%
Ethylene glycol – – O2 permeability: 2.8 ± 0.7 cm3 STP/(cm3 poly atm) [99]
CO2 permeability: 0.094 cm3 STP/(cm3 poly atm)
Water vapor permeability: 787 ± 110 cm3 STP/(cm3 poly atm)
Ethylene glycol – – O2 permeability: <0.0702 cm3⋅cm/m2⋅day.atm [105]
Ethylene glycol (EG), 1,4-cyclohexanedi­ Esterification: 180 ◦ C at 120 rpm, 150 min TPT (350 ppm) Mn = 27600–32000 g/mol; Mw = 53600–63880 g/mol; PDI = [108]
methanol (CHDM), and dimethyl furan Polycondensation: 230 ◦ C, 170 min 1.91–2, ƞ = 0.6 dL/g; Tm = 211 ◦ C; Tc = 115 ◦ C; Tg = 87 ◦ C; Tmm
dicarboxylate (DM-FDCA) = 170 ◦ C; Tdec = 395 ◦ C; ΔHm = 1 J/g,
PPF 1,3-propanediol Transesterification Sb2O3 Mn = 21600 g/mol; Mw = 27600 g/mol; PDI = 1.28; Tm = 174 ◦ C; [91]
Tg = 50 ◦ C; Tc = 127 ◦ C; Tdec = 390 ◦ C; Y = 76%
1,3-propanediol Esterification: 230 C, 4 h
◦
Sn/Ti Mn = 15000 g/mol; Tm = 150 ◦ C; Tg = 39 ◦ C; Tc = 102 ◦ C; Tdec = [70]
Polycondensation: 230 ◦ C, 6.5 h 335 ◦ C
Solid state condensation: 140 ◦ C
1,3-propanediol – – Mn = 18200 g/mol; Mw = 54600 g/mol; PDI = 3; [105]
O2 permeability: 0.0472 cm3⋅cm/m2⋅day.atm
Water vapor permeability: 0.762 cm3⋅cm/m2⋅day.atm
1,3-propanediol – – O2 permeability: <0.005 cm3⋅cm/m2⋅day.atm [105]
Ageing time (30 min) Water vapor permeability: 0.243 cm3⋅cm/m2⋅day.atm
7

1,3-propanediol Esterification: 180–200 ◦ C, 2–3 h Antimony trioxide Mw = 30000 g/mol; PDI = 2.3; Tm = 169 ◦ C; Tg = 53 ◦ C; Tc = [90]
Polycondensation: 220 ◦ C at 0.1 mbar for 2 h (10.6 mg per gram of 138 ◦ C; Tdec = 335 ◦ C ; ΔHm = 7 J/g; E = 1363 MPa; σb = 31 MPa;
final theoretical εb = 3%; O2 GTR: 0.0224 ± 3x10− 6; CO2 GTR: 0.0288 ± 3 × 10− 6;
polymer) Water vapor GTR: 0.0157 ± 6 × 10− 5
PBF 1,4-butanediol Esterification: 170 ◦ C, 4 h Sn/Ti Mn = 60000 g/mol; Tm = 170 ◦ C; Tg = 31 ◦ C; Tc = 90 ◦ C; Tdec = [65]
Polycondensation: 180 ◦ C, 6.5 h 338 ◦ C
Solid state condensation: 150 ◦ C
DMF + 1,4-butanediol Transesterification TTIP Y = 103.9%; Mn = 13050 g/mol; Mw = 34000 g/mol; PDI = 2.6 [99]
DMF + 1,4-butanediol Transesterification DBTO Y = 103.9%; Mn = 13050 g/mol; Mw = 34000 g/mol; PDI = 2.6 [99]
2,5-furandicarboxylic acid (FDCA), and Esterification:190 to 210 ◦ C for 4 h with N2 TBT (0.5–1 mmol/mol E 875 ± 18 MPa; σmax = 35 ± 2.6 MPa, εmax = 55 ± 10% [80]
1,4-butanediol (BDO)-(diol/diacid molar Polycondensation: 220 to 250 ◦ C for 4 h under a reduced pressure of diacid)
ratio 1.5:1); of 10 Pa
1,4-butylene glycol Polytransesterification: 200 ◦ C for about 2 h TBT (0.1 mmol) Mw = 24364 g/mol, ƞ = 0.45 dL/g; Y = 93%; Tm = 169 ◦ C; Tg = [116]
36 ◦ C; Tdec = 329 ◦ C; T50 = 367 ◦ C
FDCA and 1,4-butanediol Esterification: FA was purified before use, TBT = 1.4 mmol/mol TBT, (La(acac)3⋅H2O Tm = 170 ◦ C; Tc = 115 ◦ C; Tg = 44.8 ◦ C; Tmm = 170 ◦ C; Tdec = [80]

European Polymer Journal 160 (2021) 110778

diacid, diol/diacid = 2.5, 170 ◦ C/1h + 180 ◦ C/2h + 190 ◦ C/1h; 395 ◦ C
Polycondensation: La(acac)3, La/Ti = 1/1 M ratio, 230 ◦ C/4h +
250 ◦ C/1h
2,5-furandicarboxylic acid (FDCA) and 1,4- Esterification: 190 to 210 ◦ C for 4 h with N2 TBT (0.1 mol% diacid); Tm = 167.8 ◦ C; Tc = 95.4 ◦ C; Tg = 35.6 ◦ C; Td max = 416; oC E = [132]
butanediol (BDO)-(diol/diacid molar ratio Polycondensation: 220 to 250 ◦ C for 4 h under a reduced pressure La(acac)3 (0.1 mol% 1860 ± 160 MPa; σmax = 55.6 ± 1.6 MPa; εmax = 256 ± 19%
2:1) of 10 Pa diacid)
PDASF 2,5-furandicarbonyl chloride + D- Solution – Mn = 13750 g/mol; Mw = 23670 g/mol; PDI = 1.72; Tg = 180 ◦ C; [91]
isosorbide Tdec = 450 ◦ C; Y = 91%
PDAIF 2,5-furandicarbonyl chloride + isoidide Solution – Mn = 5670 g/mol; Mw = 7270 g/mol; PDI = 1.28; Tg = 140 ◦ C ; [91]
Tdec = 396 ◦ C; Y = 80%
PBHMF Bis-(2,5-hydroxymethyl)furan Interfacial – Mn = 3880 g/mol; Mw = 5410 g/mol; PDI = 1.39; Tdec = 345 ◦ C, [91]
Y = 60%
PHQF Hydroquinone Interfacial – Tdec = 490 ◦ C; Y = 77% [91]
(continued on next page)
 S. Pandey et al. European Polymer Journal 160 (2021) 110778

However, the stability of PNF was not disturbed during its contact with

[106]
[91] the food simulants. The gas transmission ratio was positively affected by
[75]

[75]

[98]
Ref

relative humidity due to high gas-water interactions [106].

Mn = 22100 g/mol; Mw = 47500 g/mol; PDI = 2.15; Tg = 87 ◦ C ;

0.57–0.66 dL/g; Tm = 239–268 ◦ C; Tc = 115 ◦ C; Tg = 80–84 ◦ C;

MPa; εb = 4%; O2 GTR = 0.0323 cm3⋅cm/m2⋅day.atm; CO2 GTR

4.4. Optical properties

138 ◦ C; Tdec = 335 ◦ C; ΔHm = 30 J/g; E = 1648 MPa; σb = 45

Mw = 50400 g/mol; Mn = 16000 g/mol; ƞ = 0.31 dL/g; Tg =

Mw = 34000 g/mol; PDI = 4; Tm = 197 ◦ C; Tg = 73 ◦ C; Tc =

Tmm = 170 ◦ C; Tdec = 395 ◦ C; ΔHm = 30.6–44.7 J/g; Tcc =
Mn = 33700 g/mol; Mw = 63100 g/mol; PDI = 1.87, ƞ = The commercialization of a polymeric film can also depend on its
transparency. This property is mainly governed by the crystallinity of
150–169 ◦ C; O2 permeability = 0.0036 cc/pkg.day the packaging film since light scattering mainly occurs in the crystalline
region. The commercialization of FDCA based polyesters is also impeded
due to the coloration of the polymeric films, mainly attributed to the
different catalysts or additives used, parallel side reactions occurring at
47.14 ◦ C; T50 = 377 ◦ C; PDI = 3.15

high temperature, presence of sugar-based impurities, and low mono­

= 0.0223 cm3⋅cm/m2⋅day.atm

mer purity [107]. Some purification steps have been adopted during
which the light brown PEF samples turned into white polyester by re-
Tdec = 390 ◦ C; Y = 75%

dissolving in solvents like DMSO or TFA/CHCl3 (1/4 v/v), followed by

Polymer properties

precipitation in methanol [108,109]. It is well-known that the starting

materials used for polymerization have a major influence on the optical
ƞ = 0.34 dL/g

properties of the final polymer. For instance, it was shown that using
DMFD as the starting material for PEF and PBF synthesis generated
fewer colored products than FDCA due to decarboxylation of the latter
under harsh reaction conditions [110,111].
The catalysts generally used for PET synthesis, such as magnesium,
Zn(Ac)2 (0.1%) and TBT

Zn(Ac)2 (0.1%) and TBT

germanium, and cobalt were found to increase the color of FDCA-based

Antimony trioxide

polyesters. The high temperature polycondensation reactions resulted in

TPT (350 ppm)

(0.00075 mol)

darker PEF as compared to the transparent PET. The formation of

Catalyst used

carbonized sugar impurities present in monomers or possible polymer

(0.1%)

(0.1%)

oxidation are two possible reasons for PEF darkening. Since FDCA is a
strong chelating agent, it was proposed that a longer polymerization
–

time might result in the formation of colored furan-metal complexes

[112]. Results have shown that adding a heat stabilizer (tris(non­
ylphenyl)phosphite) reduced the PEF coloration [113]. Another study
used L*a*b color space system to quantify the change in coloration
during PEF synthesis by bulk condensation. The coloration was found to
Esterification: 180–230 ◦ C at 120 rpm, 60–120 min

be dependent on the type of catalysts and the polycondensation time.

Polycondensation: 220 ◦ C at 0.1 mbar for 3 h

For example, titanium-based catalysts imparted higher yellowness

indices for FDCA-based polyesters as compared to zirconium-based
Polycondensation: 280 ◦ C, 80–120 min

catalysts used for polycondensation reactions [108,114]. In addition,

Transesterification: 220 ◦ C for 4 h

Transesterification: 220 ◦ C for 4 h

ROP and solution polymerization yield fewer colored products as

Polycondensation: 200 ◦ C for 5 h

Polycondensation: 200 ◦ C for 5 h

compared to conventional melt polymerization [115].

Note: tetra-isopropyl titanate (TPT), GTR = gas transmission ratio, Y = polymer yield.

Interestingly, the carbon source used for FDCA synthesis also affects
Polymerization conditions

Esterification: 180 ◦ C, 4 h

the optical properties of the PEF film. The PEF films synthesized from
furan-based FDCA via Friedel-Craft reaction and subsequent iodoform
reaction had better transparency than for HMF-based FDCA. The
coloration of the HMF-based PEF films was attributed to the soluble
Solution

humins which coexist with HMF and are difficult to remove even after
their oxidation to FDCA, later affecting the FDCA purity [110].

4.5. Impact of types of diol and their reactivity on polymer characteristics

Ethylene glycol (EG), 1,4-cyclohexanedi­
methanol (CHDM), and dimethyl furan
carboxylic acid) and 1,3-propanediol

The optical properties of furanic homopolyesters can be improved

5,5-(propane-2,2-diyl)-bis(furan-2-
Bis-(1,4-hydroxymethyl)benzene

using copolymerization by adjusting the ratio of the diol units. The main
issue with this process is the variation of diols’ reactivity with FDCA
FDCA and 1,3-propanediol

dicarboxylate (DM-FDCA)

which affects the polymerization rates and ultimately influences the

properties of the homopolymers, or copolymers formed. A kinetic study
showed that the reactivity of diols depends upon the electronic effect of
Staring materials

Neopentyl glycol

–OH groups and increases with the length of the carbon chain. This
explains why 1,4-butylene glycol is more reactive towards FDCA than
ethylene glycol [116].
The presence of nonvolatile cyclic diols (such as isosorbide, isoidide,
Table 3 (continued )

and hydroquinone) have positive effects on the stiffness of polymeric

chains as compared to aliphatic diols (such as ethylene glycol) [91].
PECF(25–100)

Various authors have reported novel polyesters developed using long-

chain aliphatic diols, mostly consisting of odd methylene groups
Polymer

PHMBF

PPF1

PPF2

[96,106,117]. As expected, longer chain diols (1,5-pentanediol, 1,7-hep­

PNF

tanediol, and 1,9-nonanediol) should have exhibited higher Tm for their

8
S. Pandey et al.
corresponding polyesters. However, the results were surprising as PPeF
displayed higher Tm than PHeF and PNF. Unfortunately, the study did
not investigate the diol’s reactivity towards polymerization with FDCA
[96]. Later, Xie et al. applied the Mayo-Lewis equation for free radical
copolymerization and deduced the apparent reactivity ratio for ethylene
glycol (0.75), 1,5-pentanediol (3.78), and 1,6-hexanediol (4.6), which
supported the long-chain theory suggested by Ma et al. (2012) [125].
The lower reactivity of ethylene glycol was attributed to its higher
volatility [97,117].
Enzyme assisted polymerization reaction was carried out for a series
of linear aliphatic diols (having 4–12 C-atoms) and their corresponding
diacid ethyl esters with DMFD to test the specificity of these substrates to
CALB. Based on the results, diols seem to be better substrates than the
corresponding diacid ester as they produced a higher polymerization
degree. Besides, monomers having higher steric hindrance have an
electronic advantage towards their reactivity during polymerization
[90]. The novel monomer formed by this new rigid difuranic C11 diol
monomers showed excellent reactivity towards FDCA, due to the pres­
ence of pendant group allowing easier condensation reactions leading to
higher Mw polyesters [118].
5. Biodegradability induced FDCA based copolyesters
5.1. Biodegradability
Biodegradability is the property by which a polymer completely
decomposes into CO2, CH4, H2O, inorganic compounds, or biomass
under the action of microorganisms, light, or chemicals. However, if the
decomposition of the polymers takes place at a compost site with known
microorganisms under controlled conditions, it is called compostable. As
per the European Bioplastics Association, all food and beverage pack­
aging materials should be either biodegradable or compostable to fulfill
the criteria of being carbon neutral and environment friendly [119,120].
Although most of the oil-based plastics, such as polyethylene (PE),
polypropylene (PP), and poly(ethylene terephthalate) (PET), are cate­
gorized as non-biodegradable; some of them, like poly(e-caprolactone)
(PCL) and poly(butylene adipate-co-terephthalate) (PBA-co-PBT), are
biodegradable in nature. Similarly, it is a misconception that all bio­
based plastics are biodegradable in nature. For instance, cellulose ace­
tate, which is a natural derivative of polysaccharide cellulose, does not
degrade into nature and loses its biodegradability due to chemical
modifications [121]. Thus, the biodegradability of a polymer is
controlled by the material’s properties rather than its origin. The poly­
mer degradation rate depends on intrinsic factors, such as types of
functional groups, wettability, crystallinity, Mw distribution, and reac­
tivity with catalysts; as well as extrinsic factors including temperature,
relative humidity, and type of microbes present [122,123]. The biode­
gradability and compostability of bioplastics can be determined using
various standardized tests such as a) anaerobic biodegradability (ASTM
D5511 and ASTM D5526), b) aerobic biodegradability (ASTM D5338
and ASTM D5209), and c) compostability (ASTM D6400 and EN 13432)
[124].
Currently, PLA (trade name: Bio-flex, Biophan, Ecoloju, Lacea), PHA
(trade name: Nodax, Biopol), PBS, and starch-based blends (trade name:
Ecostar, Bioplast, Novon) are commercially available biodegradable
bioplastics for food and beverage packaging. Other aliphatic polyesters,
such as poly(butylene adipate) (PBA), poly(propylene succinate), poly
(butylene succinate-co-adipate), and poly(propylene succinate-co-
adipate), are gaining importance due to their renewable nature and
biodegradability. Unfortunately, these aliphatic polyesters are charac­
terized by poor thermomechanical and barrier properties restricting
their application as food and beverage packaging [125,126]. As a so­
lution, aromatic segments (terephthalic acid) have been introduced in
the aliphatic backbone to obtain copolymers with desirable properties
and high biodegradability. Aliphatic-aromatic copolyesters, such as poly
(butylene succinate-co-terephthalate) (PBS-co-PBT) and poly(butylene
9
European Polymer Journal 160 (2021) 110778
adipate-co-terephthalate) (PBA-co-PBT), exhibit superior thermo­
mechanical properties over PLA; and have been shown to biodegrade
under 50% aromatic content [127–129]. The latter has been commer­
cialized under the trade name Ecoflex (BASF) and Easter-bio (Eastman
Chemical) [130]. However, the non-renewable nature of terephthalic
acid has opened opportunities for the search for new biobased mono­
mers for its replacement. Avantium estimated that PET bottles take
approximately 300–500 years to decompose, while full PEF biodegra­
dation can be achieved in 250–400 days under an industrial composting
environment (58 ◦ C in soil) [29]. The incorporation of biobased FDCA
instead of nonrenewable terephthalic acid helped the biodegradability
of the polymer which was comparable to well-known copolyesters like
PBS-co-PBT and poly(butylene adipate-co-terephthalate) (PBA-co-PBT)
[131]. Thus, the forthcoming sections discuss the thermomechanical
properties and biodegradability of FDCA-based copolyesters which are
summarized in Tables 3 and 4. Table 3 enlists the polymerization
techniques and the homopolyesters properties while Table 4 compares
the copolymerization conditions and the properties of the copolyesters
produced.Table 5 summarizes the conditons for the hydrolytic or
enzymatic degrdation and compostability of FDCA-based copolyesters.
5.2. Copolymerization with aliphatic monomers
5.2.1. FDCA and adipic acid copolyesters
Biobased copolyesters of adipic acid and FDCA with different diols
(ethylene glycol, 1,3 propanediol, and 1,4-butanediol) have been syn­
thesized using melt polycondensation and SSP in presence of different
catalysts [68,71,75,132]. The addition of biobased aromatic moiety
(FDCA) in the aliphatic backbone improved the chain rigidity, thermal
stability, and biodegradability of commercially available adipic acid
polymers, such as PBA and poly(butylene adipate-co-terephthalate)
(PBA-co-PBT) [71]. For instance, poly(butylene adipate-co-
furandicarboxylate) (PBA-co-PBF) can be an alternative to PBA-co-PBT
(also known as Ecoflex). However, the poor optical properties of the
former restrict its use in beverage packaging. The color of PBA-co-PBF
varies with the FDCA content displaying yellowish, claret red, and
chestnut brown polymers at 0–10, 20–60, and 70–100 mol% FDCA
content, respectively. Several purification steps have been carried out to
obtain FDCA copolyesters of high purity and to reduce the side reactions
which are the origin of unwanted coloration [132].
The thermomechanical properties, crystallinity, and biodegradation
rate of PBA-co-PBF range between the adipic acid and FDCA homo­
polyesters and can be controlled by tuning the amount of FDCA in the
feed. According to Zhou et al., the addition of FDCA from 0 to 50 mol%
decreased the crystallinity and Tm of PBA-co-PBF due to increased
randomization in the polymers. However, further addition of FDCA (75
to 100 mol%) enhanced those properties due to the crystallization of the
butylene furanoate units. Nearly amorphous copolyesters, owing to low
Tg (− 44 to − 19 ◦ C) and high elongation (1000%), were obtained for low
FDCA content (20–50 mol%). Conversely, the copolyesters obtained
were semi-crystalline with high Tg (7–36 ◦ C), good tensile modulus, and
better tensile strength at higher FDCA content (75–100 mol%) [73].
Moreover, PBA-co-PBF has excellent tensile properties (E = 18 to 160
MPa, σb = 9 to 17 MPa, and εb = 370 to 910%) making them suitable for
a wide range of applications from biodegradable elastomers to ther­
moplastics [132].
The main factors affecting the biodegradability of a polymer include
chain mobility, Tm, Mw, and crystallinity. In general, poly(ethylene
adipate-co-furandicarboxylate) (PEA-co-PEF) and PBA-co-PBF, having
10% aromatic content, show better lipase-assisted enzymatic hydrolysis
(100% mass loss) than their respective aliphatic homopolyesters. This is
due to a reduction in Tm and crystallinity for PEA-co-PEF and PBA-co-
PBF. Further increase in FDCA content (>10 mol%) can decrease the
biodegradation rate as the aromatic ester bonds are more resistant to
enzymatic hydrolysis than the aliphatic ones [68,73]. The hydrolytic
degradation depends on the chemical structure, crystallinity, and
 Table 4

S. Pandey et al.
Mechanical, thermal, and molecular characteristics of FDCA based aliphatic-aromatic copolyesters.
Copolyesters (FDCA Copolyester synthesis Catalysts Mw Mn PDI Ƞ Tg Tm Td max Tc ΔHm E σb εb [Ref]
mol%) (g/mol) (g/mol) (-) (dL/g) (oC) (oC) (oC) (oC) (J/g) (MPa) (MPA) (%)

FDCA and adipic acid copolyesters

PBAF (10–75) Direct esterification: TBT 54100–76800 26400–41300 1.72–2.23 – – – – – – 0.14–110 2.6–30 425–1850 [73]
190–210 ◦ C for 4 h under N2 (0.5–1
Polycondensation: mmol/mol
220–250 ◦ C at 10 Pa for 4 h diacid)

PBAF (10–90) Direct esterification: TBT (0.1 65000–103000 30000–57000 1.79–2.25 – − 53.2–23.3 27.4–155.7 417–430 – 6.4–38.6 17.7–122 9.8–42 307–748 [132]
200–230 ◦ C for 4–6 h mol%
Polycondensation: 240 ◦ C at diacid); La
200–400 Pa for 2.5–6 h (acac)3
Drying: Vacuum (60 ◦ C for (0.1 mol%
12 h) diacid)
PPAF Esterification: 200 ◦ C for 5 h Zn(Ac)2 39,300 13,400 2.93 0.21 − 14.2 79.26 400 – 5.92 – – – [75]
under N2 (0.1 mol
Polycondensation: 220 ◦ C for %) and
4 h under vacuum TBT (0.1
mol%)
PEAF (5–95) Transesterification:150 to TBT (400 – – Ng 0.36–0.47 − 32 to 75 44.8–190.3 393.7–406.7 – – – – – [68]
170 ◦ C for 5 h under Ar ppm)
Polycondensation: 170 ◦ C at
5 Pa for 30 min; 220 to
240 ◦ C for 5 h at 720 rpm (for
oligomers)
Melt polycondensation:
220–240 ◦ C for 1–4 h at 5 Pa,
10

400 rpm (for copolyesters)

P(BDA)AF (10–30) Solution precipitation: 1 h – 4470–13560 – 3.9–5.3 0.19–0.51 54–73 262–293 358–365 – 57–73 – – – [71]
stirring and vacuum drying
at 50 ◦ C for 48 h
Polycondensation: 170 ◦ C for
1 h, 220 ◦ C for 6 h under 0.3
MPa
SSP: 220 ◦ C for 12 h, gas flow
rate of 2000 mL/min
PBAF (40–60) Direct esterification: TBT (0.1 99000–167200 – 1.87–2.18 1.12–1.8 – 53.6–112 – – 13–34.2 – – – [69]
200–220 ◦ C for 3–4 h under mol% of
N2 diacid)
Polycondensation: 230 ◦ C at
50–300 Pa for 1 h and 240 ◦ C
for 2–5 h
Drying: Vacuum (40 ◦ C for

European Polymer Journal 160 (2021) 110778

24 h)

FDCA and succinic acid copolyesters

PBSF (10–50) Direct esterification: 190 ◦ C TBT (1.4 35000–65000 18500–29000 1.7–2.7 – − 25-(− 3.5) 75.5–105 396–400 25.2–53.1 19.9–79.5 – – – [81]
for 2 h, 200 ◦ C for 2 h mmol/mol
Polycondensation: 230 ◦ C for diacid)
1 h, 250 ◦ C for 4 h under
vacuum
PBSF (60–90) Direct esterification: 170 ◦ C TBT (1.4 38600–89100 15700–40800 2.38–2.45 – 6.5–30.5 111–159 394–398 76.3–88.2 14.7–37.9 – – – [81]
for 1 h, 180 ◦ C for 2 h, 190 ◦ C mmol/mol
for 1 h diacid), La
Polycondensation: 230 ◦ C for (acac)3
(continued on next page)
 Table 4 (continued )

S. Pandey et al.
Copolyesters (FDCA Copolyester synthesis Catalysts Mw Mn PDI Ƞ Tg Tm Td max Tc ΔHm E σb εb [Ref]
mol%) (g/mol) (g/mol) (-) (dL/g) (oC) (oC) (oC) (oC) (J/g) (MPa) (MPA) (%)

4 h, 250 ◦ C for 1 h under (Ti: La =

vacuum 1: 1)
PBSF (5–60) Esterification: 60–80 ◦ C Zr(OBu)4 – 1250–61700 1.8–6.5 0.022–0.191 c31 –( 54–111 – 50–63 31–57 75–84 18–23 952–1400 [135]
under N2 (Zr/diacid 17)
Polycondensation: = 0.0018)
230–270 ◦ C at 0.7 mbar
PESF (5–95) Esterification: 190 ◦ C under TBT: – – – 0.34–0.41 – – – – – – – – [137]
Ar, 500 rpm diacid-
Polycondensation: 230 ◦ C for 0.0003
60 min under vacuum (5 Pa),
720 rpm
PBSF (40–60) Direct esterification: TBT (0.1 162100–167200 – 1.95–2.07 1.12–1.53 – 55.5–112 – – 18.4–34.2 – – – [69]
200–220 ◦ C for 3–4 h under mol% of
N2 diacid)
Polycondensation: 230 ◦ C at
50–300 Pa for 1 h and 240 ◦ C
for 2–5 h
Drying: Vacuum (40 ◦ C for
24 h)
PBSF (10–90) Cyclic oligomers of FDCA CALB 21000–47000 – 1.3–1.7 0.25–0.55 − 25–20 72–140 396–400 – 4–55 – – – [84]
and SA vacuum dried for 24 (40% w/
h w)
Ring opening
polymerization: 120–150 ◦ C
for 24 h
PBSF (10–90) Cyclic oligomers of FDCA Sn(Oct)2 53000–63000 – 1.75–1.95 0.54–0.74 –23–28 60–166 395–401 – 6–71 – – – [84]
and SA vacuum dried for 24 (0.5 mol
11

h %)
Ring opening
polymerization: 180–230 ◦ C
for 12 h
PPSF (10–90) Transesterification: 170 ◦ C TBT (0.15 – 48900–81600 1.7–2 1.03–1.6 − 24.6–47.7 – 410–416 – ng 1–2374 0.2–87.3 6–1730 [72]
(before annealing) for 1 h, 180 ◦ C for 3–5 h mol%
Polycondensation: diacid)
230–240 ◦ C at 10–30 Pa
PPSF (10–90) Transesterification: 170 ◦ C TBT (0.15 – 48900–81600 1.7–2 1.03–1.6 − 24.6–47.7 80.3–151.2 410–416 – 12.5–33.2 45–3077 9.2–95.8 5–725 [72]
(after annealing) for 1 h, 180 ◦ C for 3–5 h mol%
Polycondensation: diacid)
230–240 ◦ C at 10–30 Pa
14
CO2 permeability coefficient: 0.06–0.6 Barrer, O2 permeability coefficient: 0.0072–0.04 Barrer, and water vapor transmission rate: 3.52–9.37 × 10− g⋅cm/ cm2⋅s⋅Pa
PNSF (30–90) Transesterification: 180 ◦ C Zn(Ac)2 – 118000–718000 1.6–2.0 0.9–1.67 – 165–186.3 – – 0.4–15.6 3.1–2527 1.9–88 5.8–2109 [136]
(before annealing) for 3–5 h and Sb2O3

European Polymer Journal 160 (2021) 110778

Polycondensation: 240 ◦ C for
4 h at < 50 Pa
14
CO2 permeability coefficient: 0.03–0.053 Barrer, O2 permeability coefficient: 0.022–0.042 Barrer, and water vapor transmission rate: 3.47–4.83 × 10− g⋅cm/ cm2⋅s⋅Pa
Transesterification: 180 ◦ C Zn(Ac)2 – 118000–718000 1.6–2.0 0.9–1.67 13.5–61.9 66.7–186 441–460 – 9.9–29.2 52–3560 8.9–102 3.5–454 [72]
PNSF (30–90) for 3–5 h and Sb2O3
(after annealing) Polycondensation: 240 ◦ C for
4 h, at < 50 Pa
14
CO2 permeability coefficient: 0.027–0.051 Barrer, O2 permeability coefficient: 0.022–0.04 Barrer, and water vapor transmission rate: 2.98–4.79 × 10− g⋅cm/ cm2⋅s⋅Pa

FDCA and lactic acid copolyesters

PELF (7–73) Solubilization: 80–210 ◦ C for Sb2O3 (1 6900–9000 – – – 25–76.4 119.6 289.3–570.5 84.3 – – – – [140]
5 h, kept for 2 h under wt%) or
vacuum (0.001 mbar) and SnCl2 . p-
constant stirring TSA
(continued on next page)
 Table 4 (continued )

S. Pandey et al.
Copolyesters (FDCA Copolyester synthesis Catalysts Mw Mn PDI Ƞ Tg Tm Td max Tc ΔHm E σb εb [Ref]
mol%) (g/mol) (g/mol) (-) (dL/g) (oC) (oC) (oC) (oC) (J/g) (MPa) (MPA) (%)

Precipitation: Dissolved in
TFA, and precipitated by
adding excess of ethanol
PBLF (5–20) (after Transesterification: 180 ◦ C TBT (0.5 – – – – 60 168 360–368 120.5 30.2–36.4 2661–3200 64.1–74.8 183.5–223 [139]
annealing) for 4 h, under N2 mmol)
Polycondensation:
230–245 ◦ C for 2 h, kept at
60 Pa for 0.5 h, Vacuum
drying at 80 ◦ C for 6 h,
Extrusion at 185 ◦ C and 30
rpm, Injection molding:
injection at 185 ◦ C, injection
pressure 60 MPa, back
pressure 100 MPa, mold at
35 ◦ C
PBLF (10–40) Solubilization and TBT (0.15 73500–96500 – 2–2.3 1.1–1.3 37–38.7 90–162.2 402–404 100.9 19.5–25.7 1044–1220 39.8–52.7 6.2–7.8 [86]
precipitation: 150 ◦ C for > 5 mmol),
h, dissolved in CHCl3, Sb2O3
precipitated using CH3OH (0.15 wt
Transesterification: 180 ◦ C %), SnOct2
for 4–6 h, under N2 (0.1 wt%)
Polycondensation: 210 ◦ C for
6 h, under 300 Pa
14
CO2 permeability coefficient: 0.057–0.1 Barrer, O2 permeability coefficient: 0.015–0.033 Barrer, and water vapor transmission rate: 2.4–3.7 × 10− g⋅cm/ cm2⋅s⋅Pa

FDCA and caprolactam copolyesters

High dilution condensation: CALB (10 22000–50000 – 1.25–2 – − 37–19 52–148 382–392 27–136 12–35 – – – [88]
12

PB(CL)F (10–80) 130–150 ◦ C under N2 wt%) or

Transesterification by ROP: TBT (1
200 ◦ C for 24 h mol%)
PB(CL)F (10–90) Transesterification: TBT (0.15 10500–97900 – 1.5–1.8 1.1–1.65 − 34.5–28.4 41–159.5 – − 15.4–100.4 4.7–34.6 11–902 3–68 720–1270 [74]
170–200 ◦ C for 4–6 h, mol% of
Polycondensation: 220 ◦ C at the
15 Pa for 5 h DMFD),
Purification: dissolved in Sb2O3
CHCl3 and stirred at room (0.15 wt
temperature, then %)
precipitated using CH3OH,
dried at 50 ◦ C for 72 h
PPe(CL)F (50–90) Transesterification: TTIP, – – – 0.34–0.42 − 16.1–12.1 40.9–41.3 403.2–408.9 – – – – – [78]
160–190 ◦ C for 4.5 h, under SnOct2
N2, (0.1 mol%
Polycondensation: CL)

European Polymer Journal 160 (2021) 110778

220–230 ◦ C at 5 Pa for 2 h,
ROP: 190 ◦ C for 1.5 h under
N2, 20 min under 5 Pa
PHe(CL)F (50–90) Transesterification: TTIP, – – – 0.24–0.36 − 31.7- 76.3–134.1 400.8–405.9 28.1–89.9 18.1–52.1 – – – [86]
160–190 ◦ C for 4.5 h, under SnOct2 (− 0.1)
N2, (0.1 mol%
Polycondensation: CL)
220–230 ◦ C at 5 Pa for 2 h,
ROP: 190 ◦ C for 1.5 h under
N2, 20 min under 5 Pa
PI(CL)F (10–50) Esterification: 210 ◦ C for 3 h TBT (0.2 33300–1260001 13800–54300 2.32–2.59 0.91–2.14 − 9.9–132.1 – 303.3–369.4 – – 858–1649 44–73 23–480 [152]
at 150 rpm, under N2, mol% of

(continued on next page)

 Table 4 (continued )

S. Pandey et al.
Copolyesters (FDCA Copolyester synthesis Catalysts Mw Mn PDI Ƞ Tg Tm Td max Tc ΔHm E σb εb [Ref]
mol%) (g/mol) (g/mol) (-) (dL/g) (oC) (oC) (oC) (oC) (J/g) (MPa) (MPA) (%)

ROP: 220 ◦ C for 3 h at 150 FDCA),

rpm, under N2, (0.2 mol%
Polycondensation: 250 ◦ C for of CL)
3 h at 200 rpm, under 100 Pa
FDCA and isosorbide copolyesters
PDIsF Transesterification: TTIP (400 55300–84500 11500–25400 – – − 1.2–20.6 64.3–110.9 439.2–443.8 39–57.4 30.1–37.9 88.5–284.5 0.75–20.53 191.7–274.5 [77]
160–190 ◦ C for 4.5 h, under ppm)
N2,
Polyesterification:
160–190 ◦ C for 4.5 h, under
N2,
Polycondensation:
220–250 ◦ C for 2 h, under
vacuum
PBImF High dilution condensation: DABCO 39000–63000 – 1.5–2.0 – 45–97 160–169 388–403 146 12–30 – – – [87]
In FDCA-Cl2 and Im (5 (12.5
mmol), THF was added, mmol), Sn
filtered ad then washed with (Oct)2
HCl (0.1 M) (0.5 mol
ROP: 220 ◦ C for 6 h, under %)
N2
PICBFS (10–80) Transesterification: – 57500–67800 – 1.6–1.81 0.77–0.82 74.8–102.3 – 402–403 – – 1242–1330 69–71.5 7–23 [155]
100–180 ◦ C at 1 atm,
160–180 ◦ C at 1 atm
Melt polymerization:
200–240 ◦ C, at 10 Pa
CO2 permeability coefficient: 0.19–1.55 Barrer and O2 permeability coefficient: 0.2–1.67 Barrer
13

PBIF Transesterification: 200 ◦ C DBTO 18400–37400 9300–19100 1.94–2.04 0.45–0.88 55.3–150.6 – 405–416.9 – – 1464–1900 53–140 15–435 [76]
for 2 h at 150 rpm, 210 ◦ C for (0.15 mol
1 h Polycondensation: % of
250 ◦ C for 6 h at 200 rpm DMFD)
under 100 Pa

FDCA and sebacic acid copolyesters

PBScF (5–20) Direct esterification: 200 ◦ C TBT (1 71000–103000 35600–46200 2–2.25 – 6.39–28.26 144.73–166.17 387–393 – 24.57–36.61 – 33.6–50.8 100–780 [144]
for 3 h, at 170 rpm mmol/mol
Polycondensation: 230 ◦ C for diacid)
5 h at 90 rpm under vacuum

FDCA and polyglycolic acid copolyesters

PBF-DGA Direct esterification: 180 ◦ C TBT, TTIP – – – 0.521–0.572 6–26 106–151 380–388 82 14–36 130–688 13–29 241–419 [145]
for 4 h, (150 ppm)
Polycondensation: 220 ◦ C at

European Polymer Journal 160 (2021) 110778

0.1 mbar, 235 ◦ C for 5 min
CO2 GTR: 198–456 (cm3/m2.day.bar), O2 GTR: 113–193 (cm3/m2.day.bar), N2 GTR: 96–189 (cm3/m2.day.bar), and C2H4 GTR: 112–185 (cm3/m2.day.bar)
PBFGA (10–60)- Esterification (OGA): 160 ◦ C Zn(Ac)2 68500–89500 – 1.8–1.9 1–1.15 36.3–38.2 85–156 395–402 – 2.7–33.2 524–1262 15.5–44 223–332 [146]
annealed for 4–6 h under N2, (0.5 wt%),
Transesterification (OBF): TBT,
170 ◦ C for 4–6 h under N2, Sb2O3
Polycondensation:
190–195 ◦ C for 4–5 h at 30
Pa
CO2 permeability coefficient: 0.05–0.11Barrer, O2 permeability coefficient: 0.02–0.05 Barrer, and water vapor transmission rate: 2.65–5.61 × 10− 14 g⋅cm/ cm2⋅s⋅Pa

FDCA and PEG copolyesters

PEF-PEG (20–80) 80500–126000 34000–49000 2.34–2.61 – 78.5–84.9 26–58.4 351.5–360.1 – 10.03–29.85 – 8–27 4–61 [148]
(continued on next page)
 S. Pandey et al. European Polymer Journal 160 (2021) 110778

hydrophilicity of the polymer, which is favored by the nucleophilic

[150]

[147]

[149]
substitution of the ester groups by water molecules [75]. This also de­
[Ref]

pends on the pH of the medium, which subsequently controls the mass

loss of the polymeric chains. Under neutral conditions, the carboxylic

565–1087

403–1091
groups of the oligomers and copolyesters autocatalyze the hydrolytic

52.4
degradation process. However, this process is accelerated under alkaline
(%)
εb

conditions. For instance, mass loss of 52% was observed for PBA-co-PBF

22.6–56.2
(having 40–60 mol% butylene furanoate units) compared to 1% in
16.1–66
(MPA)

neutral and acidic conditions within 22 weeks. The PBA-co-PBF with

σb

higher FDCA units (60 mol%) is 100% compostable (ISO 14855-1:2005

–
and GB/T 19277.2-2013) and degrades faster than its terephthalic acid
29–476

34–655
counterparts (45 mol%) after 180 days. The oxygen-containing furan
(MPa)

ring of FDCA is more hydrophilic than the benzene ring, which explains
E

100.93–164.9 24.42–32.36 –
why PBA-co-PBF is more prone to being attacked by the enzymes
secreted by microorganisms [69]. Furthermore, the copolymerization of
3.1–28.2

8.4–16.9

dodecanedioic acid (DDCA), FDCA and ethylene glycol resulted in series

(J/g)
ΔHm

of fully bio-based poly(ethylene dodecanedioate-2,5-

furandicarboxylate) (PEDF) copolyesters. The weight loss in the PEDF
26.7–107

copolyesters increased linearly with the molar content of the aliphatic

41–115

units [133].
(oC)
Tc

5.2.2. FDCA and succinic acid copolyesters

406–430

430–438

392–401

Another attractive biobased monomer to yield semi-crystalline

Td max

aliphatic polyester is succinic acid, which has been integrated with

(oC)

FDCA during polymerization to synthesize a plethora of novel bio­

polymers [73,134]. In comparison to PBS (E = 680 MPa, σb = 30 MPa,
− 34.3–35.5 121.9–167.6

108.5–168.7

and εb = 130%), PBF has higher E (1.8 GPa) and σb (35 MPa), but lower
20.93–62.19 185–213

εb (2.5%) with reduced biodegradability. Thus, to enhance these prop­

(oC)
Tm

erties, Wu et al. developed poly(butylene succinate-co-

furandicarboxylate) (PBS-co-PBF) having tunable properties ranging
from amorphous polymers with low Tg and very high εb (~600%), to
crystalline polymers with high E (360–1800 MPa) and σb (20–35 MPa).
(oC)
Tg

The higher furanic content (>60%) induced darker pigmentation in the

polymer which might be due to impurities in the FDCA monomer or a
0.62–0.99
1.39–1.9
1–1.42

coloration effect of TBT. The purification using acetic acid significantly

(dL/g)

lightened the color of the PBS-co-PBF [81].

Ƞ

The presence of furanic units (butylene furanoate) showed an overall

increase in Tg, while a negative effect on crystallinity and Tm was
PDI

observed in butylene succinate rich copolyesters. The poor crystalliza­

(-)

tion rate of furanoate segments arises due to asymmetric furan ring and
30600–46900

45600–66800

odd C-atom in the diol groups. Yet, the low melt strength and poor
crystallization rate of PBS-co-PBF (≥60 mol% FDCA) limited the film-
(g/mol)

forming ability via extrusion-blowing [135]. It has been observed that

Mn

the spherulite morphology contributing to the crystalline structure in

–

homopolyesters is destroyed during copolymerization. However, it can

be restored by annealing (post-treatment). For instance, thermal
annealing of poly(propylene succinate-co-furandicarboxylate) (PPS-co-
(g/mol)

PPF) and poly(neopentyl glycol succinate-co-furandicarboxylate) (PNS-

Mw

co-PNF) enhanced their crystallinity. Moreover, the E and σb values of

TBT (300
Catalysts

Sb2(EG)3
TBT (0.2

TBT (0.2

these copolyesters exceeded the commercial biodegradable packaging

mol% of

mol% of

(0.15%/
DMFD),
Zn(Ac)2
µL/mol

DMFD)

DMFD)

DMFD)
(0.2%/
diacid)

materials, while εb decreased after the treatment. The CO2, O2, and H2O
mol

mol

barrier properties for these novel copolymers were superior to

Polycondensation: 230 ◦ C for

Polycondensation: 220 ◦ C for

Polycondensation: 220 ◦ C for

Polycondensation: 235 ◦ C for

170–200 ◦ C for 3–5 h under

170–200 ◦ C for 3–5 h under

Direct esterification: 190 ◦ C

commercially available bioplastics like PLA and PBA-co-PBT. The

Transesterification: 190 ◦ C

cm3⋅cm/cm2⋅s⋅cmHg.

excellent barrier properties are related to higher steric hindrance from

for 1 h, then heated to
Copolyesters (FDCA Copolyester synthesis

for 3–4 h at 480 rpm

the additional methyl groups decreasing the gas and water vapor
Transesterification:

Transesterification:
5 h under vacuum

adsorption, as well as diffusion and desorption through the polymeric

3–5 h at 5 Pa

3–5 h at 5 Pa

film [72,136].
Since the catalysts used during polymerization reactions have a
210 ◦ C,

direct influence on the optical properties of the polymers, the replace­

4h
N2

N2

10

ment of Ti with Zr-based catalyst by Jacquel et al. caused much less

Note: 1 Barrer = 10−
Table 4 (continued )

coloration in the product during the melt polycondensation of PBS-co-

PBF-PEG (10–60)

PEF-PEG (10–60)

PBF than reported by Wu et al. [81,135]. Another strategy applied for

PBS-co-PBF synthesis was ROP under a milder condition (120–150 ◦ C)
PBF-PEG

than melt polycondensation (180–230 ◦ C). On the downside, the lipase-

mol%)

catalyzed ROP exhibited lower yield (88–93%) and Mw (15–45 kg/mol)

for PBS-co-PBF than what was obtained by a chemocatalytic process

14
S. Pandey et al.
(50–65 kg/mol, 65–91%) [84].
Furthermore, several studies have shown that increasing the succinic
acid content improved the enzymatic and hydrolytic biodegradability of
copolyesters because of the dissimilarities generated in the crystal lat­
tices [72,136,137]. During lipase action, poly(ethylene succinate-co-
furandicarboxylate) (PES-co-PEF) (with 17% ethylene furanoate units)
was reported to have 15% weight loss within a month. The higher fur­
anic content negatively affected the weight loss of the polyester due to
high rigidity, hydrophobicity, Tg, Tm, and limited chain mobility hin­
dering the enzymatic attack on the ester groups [137]. The enzymatic
biodegradability of PPS-co-PPF was predicted using number average
sequence length of aromatic units as the indicator, where they reported
that a value less than 3 indicated weight loss of around 15% [72].
Moreover, it has been suggested that lipase-assisted hydrolytic degra­
dation results in better biodegradation of copolymeric chains. For PBS-
co-PBF, the enzyme-assisted hydrolytic degradation rate in neutral pH
(7.4) was triggered in the presence of lipase and the weight loss was
reported as 20% in 22 weeks [84]. For PNS-co-PNF, the enzymatic and
hydrolytic degradation was limited in the range of 3 to 13% owing to the
high steric hindrance, crystallinity, and Mw that restricted the water
diffusion in the polymeric chain [136]. Compared to adipic acid, suc­
cinic acid as a comonomer imparts higher crystallinity in the copo­
lyesters. This is why only 14% weight loss was observed for PPS-co-PPF
compared to 52% for PBA-co-PBF in alkaline medium. On the other
hand, PBS-co-PBF samples (15 mol%) have been found to be compost­
able, while according to EN 13432 [135], the time required to reach
90% biodegradation increased from 71 to 106 days with the addition of
butylene furanoate units (>45 mol%) [69].
5.2.3. FDCA and lactic acid copolyesters
The majority of compostable plastics are composed of PLA having
lactic acid as the monomer being produced by bacterial fermentation of
carbohydrates. The industrial production of PLA is carried through
polycondensation of lactic acid. However, the ROP of lactic acid dimers
(lactides) is gaining attention due to its solvent-free synthesis process
[138]. Attempts have been made to copolymerize PLA with PEF and PBF
homopolyesters to improve brittleness, crystallization, Tg and, barrier
properties. The incorporation of PBF units in PLA backbone improved its
tensile and gas barrier properties. The εb, CO2, O2, and water vapor
transmission rates of poly(lactic acid-co-butylene furandicarboxylate)
(PLA-co-PBF) increased by 25, 7.4, 6.3, and 2 times respectively,
compared to that of PLA homopolyesters [139]. However, the Tm and
crystallization rate decreased with respect to the homopolyesters, after
the addition of lactide units. The copolymerization of PLA and PEF led to
the disruption of the original poly-(L-lactic acid) structure yielding
random polymer structures with low Mw ranging from 6900 to 9000 g/
mol. Inevitably, the loss of crystallinity and hydrophilicity of lactide
units during copolymerization improved the water absorption and hy­
drolytic degradation rate of poly(lactic acid-co-ethylene fur­
andicarboxylate) PLA-co-PEF (60% in 12 weeks) [140]. Compared to
ethylene furanoate analogues, weight loss of PLA-co-PBF was limited to
35%, while Tg increased due to intermolecular forces provided by the
furan rings [86]. Moreover, the optical properties of PBF-co-PLA formed
by hot pressing, injection molding, or 3D printing were superior to that
of neat PLA or PBF [141].
5.2.4. Sebacic acid
Sebacic acid is a naturally occurring long chain dicarboxylic acid that
has been incorporated with other polyesters to improve their crystal
quality, Tg, and structural morphology [142]. The tensile property of
poly(ethylene sebacate) (PESe) was comparable to that of PE, having
values of E = 110 MPa, σb = 20 MPa, and εb = 510%. Meanwhile, poly
(ethylene sebacate-co-furandicarboxylate) (PESe-co-PEF) was shown to
have similar properties to well-known copolyesters like PBS-co-PBT.
Increasing the amount of FDCA produced imperfect crystals which
later caused more difficult PESe-co-PEF crystallization. The copolyesters
15
European Polymer Journal 160 (2021) 110778
obtained were in a rubbery state at low FDCA(40–60%) which then
transformed into fully amorphous structure at higher FDCA content
(60–90%) [143].
It should be noted that the introduction of sebacic units in PBF
reduced the crystallization rate and caused instability in the crystal
lattice of poly(butylene sebacate-co-furandicarboxylate) (PBSe-co-PBF)
because of additional flexibility due to long chain. Increasing the sebacic
acid content (5 to 20%) reduced the σb from 51 to 33 MPa, while the εb
increased from 8.1 to 780%. The decomposition temperature shifted to a
higher value with sebacic units addition, as the former is more resistant
to heat than furan rings [144]. Until now, no study has been conducted
to investigate the biodegradability of sebacic acid series polymers with
FDCA units.
5.2.5. Polyglycolic acid
Polyglycolic acid (PGA) has a similar structure to lactic acid but
without the methyl group which can successfully induce biodegrad­
ability when copolymerized with PBF [145,146]. This flexible como­
nomer can impart structural mobility due to its amorphous nature by
conversion of a rigid plastic into a soft elastomer, thus decreasing the Tg
and crystallinity of the copolymer formed. Compared to PCL and PLA,
PGA-based polyesters have superior barrier properties and are more
susceptible to hydrolytic degradation. For instance, enzymatic hydro­
lysis was responsible for a 60% loss in weight for poly(ethylene glycol-
co-butylene furandicarboxylate) (PGA-co-PBF). The same copolyester
can also replace PBA-co-PBT owing to its excellent rigidity and barrier
properties. The copolymer has lower CO2 (53–118 times), O2 (15 times),
and water vapor (6 times) permeability than Ecoflex [146]. The use of
diglycolic acid instead of glycolic acid for copolymerization with PBF
increased the hydrophilic and compostable nature of the polyester
formed. Moreover, the copolyester poly(diglycolate-co-butylene fur­
andicarboxylate) (PDG-co-PBF) has a high CO2 gas transmission rate
relative to O2, which makes it an interesting candidate for food pack­
aging applications under modified atmosphere packaging (MAP) [145].
5.2.6. Polyethylene glycol
Polyethylene glycol (PEG) is the base for the most common class of
linear polymer with a wide variation in Mw ranging from 600 to 20000
g/mol. The low Mw PEG (1000–6000 g/mol), when copolymerized with
PBF, decreases the E and σb of the poly(ethylene glycol-co-butylene
furandicarboxylate) (PEG-co-PBF) copolyester with a significant in­
crease in εb. On the other hand, larger moieties (10 and 20 kg/mol),
reduce the εb and increase the E because of their high crystallinity [147].
As in the case of random copolymers, the presence of the rigid furan ring
severely inhibits or disrupts the crystallization of the PEG block. The
study conducted by Wang et al. (2017a) showed that increasing the PEG
chain length could facilitate the copolyesters to more easily crystallize,
while the enthalpy of melting of the PEG block and the crystallization of
the copolymers also significantly increased [148]. For isothermal crys­
tallization, the introduction of PEG significantly enhanced the crystal­
lization rates as expected, which can be determined from the
crystallization half-times. Depending on their Mw and molar content,
PEG moiety can induce biodegradability in PEF [149] and PBF
[147,150]. The hydrophilicity of the furanic homopolyesters increases
with the addition of PEG moiety, thus making the polymer more sus­
ceptible to hydrolytic and soil degradation.
5.3. Copolymerization of FDCA and cyclic monomers
5.3.1. FDCA and caprolactam copolyesters
Poly(ε-caprolactone) (PCL) is a semi-crystalline polymer produced
by ROP of ε-caprolactone. It has exceptional biodegradability but is not
used as a beverage packaging material due to its low Tm (~65 ◦ C), Tg
(~− 60 ◦ C), and poor elasticity [151]. To improve these thermo­
mechanical properties, functional copolyesters like poly(ε-caprolactone-
co-butylene furandicarboxylate) (PCL-co-PBF) were synthesized using
S. Pandey et al. European Polymer Journal 160 (2021) 110778

Table 5
Summary of FDCA-based biodegradable or compostable copolyesters.
Copolymer Degradation medium pH Temperature Specimen Time Weight loss (%) Reference
(◦ C)

FDCA and adipic acid copolyesters

PEAF Rhizopus oryzae lipase (0.09 mg/mL) and 7.2 37 Films (5 cm2 × 0.4 mm) 22 100 [68]
Pseudomonas cepacia lipase (0.01 mg/mL) days
PBAF Lipase from porcine pancreas (0.1 mg/mL) 7.2 37 Films (10 cm2 × 0.3 28 9–100 [73]
mm) days
PBAF NaH2PO4 (0.2 M)/acetic acid 4 25 Films (15 × 6) 22 1 [73]
weeks
PBAF Sodium acetate/NaOH (0.2 M/0.2 M) 12 25 Films (15 × 6) 22 52 [73]
weeks
PBAF Neutral 7 25 Films (15 × 6) 22 1.4–1.8 [73]
weeks
PBAF Compost (ISO 14855–1:2005 and GB/T ng 58 Films (20 mm × 20 110 >90 [73]
19277.2–2013) mm), 0.0015 g days
PPAF Acidic aqueous solution 4.35 37 – 28 0.69 [75]
days

FDCA and succinic acid copolyesters

PBSF Compost (ISO 14855–1:2005 and EN 13432) – 58 – – – [135]
PESF Rhizopus delemar lipase (0.1 mg/mL) and 7.2 50 Film (5 cm2 × 2 mm) 30 2.5–15 [137]
Pseudomonas cepacia lipase (0.01 mg/mL) days
PBSF NaH2PO4 (0.2 M)/ acetic acid 4 25 Films (15 × 6) 22 1 [69]
weeks
PBSF Sodium acetate/NaOH (0.2 M/0.2 M) 12 25 Films (15 × 6) 22 14 [69]
weeks
PBSF Neutral 7 25 Films (15 × 6) 22 1.4–1.8 [69]
weeks
PBSF Compost (ISO 14855-1:2005 and GB/T 19277.2- – 58 Films (20 mm × 20 110 90 [69]
2013) mm), 0.0015 g days
PBSF Citric acid buffer 2 37 Disks (10 mm dia), 30 10 [84]
20–30 mg days
PBSF Sodium phosphate buffer 7.4 37 Disks (10 mm dia), 30 5 [84]
20–30 mg days
PBSF Sodium phosphate buffer/Lipase porcine pancreas 7.4 37 Disks (10 mm dia), 30 15–20 [84]
(10 mg) 20–30 mg days
PPSF Phosphate buffer solution/Lipase porcine pancreas 7.4 37 Film (2 cm2 × 0.3 mm) 28 5.7–14.8 [72]
(0.1 mg/mL) days
PNSF PBS/CALB (0.1 mg/mL) 7.4 37 Film (0.3 mm thick) 70 3–13 [136]
days
PNSF PBS 7.4 37 Film (0.5 mm thick) 70 <10 [136]
days

FDCA and lactic acid copolyesters

PELF Phosphate buffer solution 6.9 37 Square samples (12–50 12 22–60 [140]
mg) weeks
PBFL Phosphate buffer solution 7 50 – 80 3–35 [86]
days

FDCA and caprolactum copolyesters

PB(CL)F Sodium phosphate buffer 7.4 25 Disk (10 mm dia, 200 40 2 [88]
µm thick, 20–30 mg) days
PB(CL)F Sodium phosphate buffer/Lipase porcine pancreas 7.4 25 Disk (10 mm dia, 200 40 40 [88]
(10 mg) µm thick, 20–30 mg) days
PB(CL)F Phosphate buffer solution 7.4 37 Film (2 × 2 × 0.03 cm3) 8 ~10 [74]
weeks
3
PB(CL)F Phosphate buffer solution/Lipase porcine pancreas 7.4 37 Film (2 × 2 × 0.03 cm ) 8 ~24 [74]
(0.1 mol/L) weeks
3
PB(CL)F Phosphate buffer solution/ CLAB (0.1 mol/L) 7.4 37 Film (2 × 2 × 0.03 cm ) 8 ~34 [74]
weeks
PPe(CL)F Phosphate buffer solution/Pseudomonas cepacia 7.4 37 Square shaped film (5 25 15 [85]
lipase (0.01 mg/mL) & Rhizopus oryzae lipase (0.09 cm2 × 0.4 mm) days
mg/mL)
PHe(CL)F Phosphate buffer solution/Pseudomonas cepacia 7.4 37 Square shaped film (5 25 32 [85]
lipase (0.01 mg/mL) & Rhizopus oryzae lipase (0.09 cm2 × 0.4 mm) days
mg/mL)

FDCA and isosorbide copolyesters

PDIsF Garden soil 6.5 25 Film (20 mm × 10 mm 23 15–16 [77]
× 0.1 mm) weeks
PBImF Sodium phosphate buffer 7.4 37 Disks (10 mm dia, 200 30 20 [87]
µm thick, 20–30 mg) days
PBImF Sodium phosphate buffer/Lipase porcine pancreas 7.4 37 Disks (10 mm dia, 200 30 50 [87]
(10 mg) µm thick, 20–30 mg) days
PICBF(S) Phosphate buffer solution/Lipase porcine pancreas 7.4 – Film (-) 29 13.2 [155]
(0.1 mol/L) days

FDCA and PGA copolyesters

(continued on next page)

16
S. Pandey et al. European Polymer Journal 160 (2021) 110778

Table 5 (continued )
Copolymer Degradation medium pH Temperature Specimen Time Weight loss (%) Reference
(◦ C)

PBF-DGA Compost – 60 Film (20 × 40 mm, 0.2 62 40 [145]

mm thick) days
PBFGA Phosphate buffered saline 7.4 37 Film (0.3 mm thick) 35 <1.5 [146]
days
PBFGA Phosphate buffered saline/Lipase porcine pancreas 7.4 37 Film (0.3 mm thick) 70 35–6- [146]
(0.1 mg/mL) days

FDCA and PEF copolyesters

PBF-PEG PBS solution 7.4 37 – 5 44 [150]
weeks
PBF-PEG NaOH solution (0.01 mol/L) – 37 – 5 64.6 [150]
weeks
PBF-PEG Pure water 7 37 – 49 < 7 for low Mw, [147]
days 11–22 for low Mw
PBF-PEG Phosphate buffer saline 7.2–7.4 37 – 49 18 for low Mw [147]
days
PBF-PEG NaOH solution (0.0001 mol/L) 10 37 – 49 40 for high Mw [147]
days
PBF-PEG NaOH solution (0.01 mol/L) 12 37 – 24 h 100 [147]
PEF-PEG Phosphate buffered solution 7.2 37 Film: 1 cm × 3 cm × 100 15.3 [149]
(0.1–0.3) mm days

cyclic oligomers of FDCA and ε-caprolactone by enzyme and chemical
assisted ROP. The Tg of PCL-co-PBF increased with the addition of rigid
butylene furanoate units due to a reduction in chain mobility. Compared
to PBF homopolyesters, PCL undergoes faster crystallization during
thermal processing. Therefore, copolymerization resulted in a slow
crystallization rate for PCL-co-PBF, which further deteriorated with
increasing butylene furanoate units. Regardless of the insensitivity of
these copolyesters to hydrolytic degradation under neutral conditions,
they degrade well in presence of enzymes and higher caprolactam units
[88]. The slow degradation for PCL-co-PBF occurred due to the hydro­
phobicity of the copolyesters limiting hydrolysis under ambient condi­
tions. Moreover, the protein structure of the enzyme has a significant
impact when it comes to breaking ester bonds. A study revealed that
Candida antarctica lipase B (CALB) is more suitable for enzymatic hy­
drolysis than lipase from porcine pancreas, as it has the appropriate
protein structure needed for the ester bond breakage [74].
Furthermore, two novel thermally improved copolyesters, poly
(ε-caprolactone-co-pentylene furandicarboxylate) (PCL-co-PPeF) and
poly(ε-caprolactone-co-hexamethylene furandicarboxylate) (PCL-co-
PHeF) consisting of higher boiling point diols (1,5-pentanediol and 1,6-
hexanediol) as comonomers, were synthesized by ROP using stannous
octoate as the catalyst. Both the copolymers exhibited low Mw because
of the competitive side reaction and thermal degradation during harsh
conditions of melt polycondensation. The increase in caprolactam units
negatively affected the thermal stability of the polymeric chain, thus
yielding low Tm, Tg, and ΔHm for these copolyesters. The enzymatic
weight loss of PCL-co-PHeF was faster than PCL-co-PPeF, achieving a
maximum of 32% vs. 15% respectively, within 25 days. This enzyme
facilitated weight loss was associated with the lower Tm, Tg, and crys­
tallinity of the copolyester. However, the lower Mw played a key role in
disintegration during hydrolysis [85]. Furthermore, the brittleness of
the poly(isosorbide 2,5-furandicarboxylate) (PIsF) homopolyesters was
modified by copolymerization with caprolactam leading to increased
mobility of the chain resulting in amorphous poly(isosorbide 2,5-fur­
andicarboxylate-co-ε-caprolactone) (PIs(CL)F) copolyesters. Increasing
the number of caprolactam units improved the εb of PIs(CL)F copo­
lyesters from 23 to 480% [152].
5.3.2. FDCA and isohexides copolyesters
Isohexides constitute a group of renewable bicyclic rigid diols pro­
duced by dehydration of sugar alcohols, thus yielding three isomers
namely Isosorbide (Is), Isomannide (Im), and Isoidide (Id). They impart
excellent structural rigidity and thermal stability to the polymeric chain.
Incorporation of Is in PBF improved the Tg of the homopolyester yielding
high Mn copolymers poly(isosorbide-co-butylene furandicarboxylate)
(PIsBF) ranging from 18400 to 37499 g/mol [76]. Due to these prop­
erties, isohexides have been proposed as the most suitable candidate to
replace toxic bisphenol-A as the hardening agent in food and beverage
packaging. Despite these advantages, the insertion of isohexides in the
polymeric chain often results in chain irregularity and disrupts the
crystalline structure, thus restricting their application at the industrial
scale [153]. A relevant example is presented by Gomes et al. where they
synthesized fully amorphous homopolyesters by solution polymeriza­
tion of FDCA with Is and Id [91].
The presence of linear aliphatic diols with numerous methylene
groups in the furanic chain has also been shown to control the crystal­
lization ability with a Tm suitable for thermoplastic processing. FDCA-
based homopolyesters comprising of diols with 8, 9, 10, and 12 meth­
ylene groups were reported to display a significant degree of crystal­
linity [154]. In order to address the issue of poor crystallinity, Is and
1,10-decanediol were used as comonomers to produce a novel copo­
lyester: poly(decamethylene-co-isosorbide furandicarboxylate) (PDIsF).
The presence of Is units effectively increased the Tg and delayed the
onset of decomposition. The asymmetric secondary hydroxyl groups in Is
imposed large steric hindrance for soil microorganisms to act on the
ester linkages resulting in delayed biodegradation. As a consequence,
the Is units negatively affected the weight loss in PDIsF chains [77].
Moreover, the stability of the secondary hydroxyl groups present in
isohexides leads to low reactivity during polymerization reactions and
hinders industrial-scale production of such FDCA-based copolyesters.
Ouyang et al. described a semi-continuous method for large-scale pro­
duction of poly(ester carbonates) having FDCA and Is as the co­
monomers, where the oligomers of Is and dimethyl carbonate were
reacted with DMFD and 1,4-butanediol to obtain poly(isosorbide
carbonate-co-butylene furandicarboxylate) (PIsCBF). These PIsCBF
copolyesters were characterized by high Mw and Tg, but the process did
not improve the crystallinity of the polyesters. This was coupled with
poor O2 and CO2 barrier properties of the PIsCBF copolyesters due to
their amorphous structure [155]. Another study compared the behavior
of three isohexides (Is, Im, and Id) produced through cyclic oligomeri­
zation. It was reported that cyclic oligomers of Im were more stable than
those of Is and Id. The higher reactivity of Is and Id was attributed to the
instability in spatial orientation of the secondary hydroxyl groups at the
endo and exo positions. The addition of Im units had a positive effect on
Tg, as well as the hydrolytic degradation of PBF (20% in 30 days), which
further accelerated up to 50% in presence of lipase [87].

17
S. Pandey et al.
6. Conclusion
Although significant progress has been made on the preparation of
HMF and biomass-derived FDCA, there are still several challenges that
must be addressed to reach its sustainable production at a reasonable
cost. Firstly, the catalyst selectivity and recovery during HMF oxidation
is a critical factor that should be considered. While noble metal catalysts
have exhibited excellent catalytic performance in FDCA production, the
development of efficient, low-cost, and multi-functional green catalysts
in a base-free environment still needs further investigation. In addition,
the feedstocks used for FDCA synthesis have a major impact on the cost
of FDCA production. Therefore, the use of food and lignocellulosic
wastes as potential low-cost substrates should be further exploited for
the development of such processes. To achieve large-scale FDCA pro­
duction, the design should be based on all the technical, economical, and
sustainable challenges. Moreover, copolymerization could be used as a
way to create FDCA-based polymers for food and beverage packaging
with the required physicochemical properties. Simultaneously, prob­
lems related to coloration, high cost, and poor biodegradability can be
solved using copolymerization. It is important not to overlook the
method of bioplastics disposal, their impact on microplastic formation in
the environment and marine life. Therefore, the life cycle assessment
studies of these polymeric materials are important before bringing them
into the industrial chain.
7. Funding Sources
This study was financially supported by the Ministère de l’Economie
et de l’Innovation (MEI), through “Transform Action, programme
d’appui au développement des secteurs stratégiques et des créneaux
d’excellence en Montérégie”, Agriculture and Agri-Food Canada,
through “Growing Forward 2′′ , the Ministère de l’Agriculture, des
Pêcheries, et de l’Alimentation du Québec (MAPAQ) through the Con­
sortium de Recherche Innovation Transformation Alimentaire (RITA)
and also by Québec food industries through the Conseil de la Trans­
formation Alimentaire du Québec (CTAQ).
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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