Renewable-based poly((ether)ester)s from 2,5-furandicarboxylic acid

Article abstract of DOI:10.1016/j.polymer.2016.06.015

Polymers based on the renewable monomer 2,5-furandicarboxylic acid (FDCA) have witnessing an incessant growth in recent years, essentially motivated by their unique features and the current concerns about sustainability and environmental issues. However, to date, research has been mainly focused on FDCA-polyesters synthesis, while synthetic routes to afford poly((ether)ester)s remained unexplored until the present study, despite their inherent value. Herein, fully renewable-based poly((ether)ester)s from 2,5-furandicarboxylic acid, poly(ethylene glycol) (PEG) and isosorbide were straightforward synthesised by polycondensation reactions. Interestingly, these materials showed better or comparable thermal properties (e.g. glass transition temperature) than their fossil based counterparts, which can be simply tuned by changing the chain length of PEG segments and also by incorporating (or not) rigid isosorbide moieties. The ensuing products were characterised in detail by means of ATR FTIR, ¹H NMR, TGA and DSC.

Full text of DOI:10.1016/j.polymer.2016.06.015

Polymer 98 (2016) 129e135
Contents lists available at ScienceDirect
Polymer
journal homepage: www.elsevier.com/locate/polymer
Renewable-based poly((ether)ester)s from 2,5-furandicarboxylic acid
, b,
Andreia F. Sousa a *, Jorge F.J. Coelho b, Armando J.D. Silvestre a
a CICECO- Aveiro Institute of Materials and Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
b CEMUC, Department of Chemical Engineering, University of Coimbra, 3030-790 Coimbra, Portugal
a r t i c l e i n f o
a b s t r a c t
Article history:
Polymers based on the renewable monomer 2,5-furandicarboxylic acid (FDCA) have witnessing an
incessant growth in recent years, essentially motivated by their unique features and the current concerns
about sustainability and environmental issues. However, to date, research has been mainly focused on
FDCA-polyesters synthesis, while synthetic routes to afford poly((ether)ester)s remained unexplored
until the present study, despite their inherent value. Herein, fully renewable-based poly((ether)ester)s
from 2,5-furandicarboxylic acid, poly(ethylene glycol) (PEG) and isosorbide were straightforward syn-
thesised by polycondensation reactions. Interestingly, these materials showed better or comparable
thermal properties (e.g. glass transition temperature) than their fossil based counterparts, which can be
simply tuned by changing the chain length of PEG segments and also by incorporating (or not) rigid
isosorbide moieties. The ensuing products were characterised in detail by means of ATR FTIR, 1H NMR,
TGA and DSC.
Received 22 March 2016
Received in revised form
2 June 2016
Accepted 6 June 2016
Available online 7 June 2016
Keywords:
Poly((ether)ester)s
2,5-Furandicarboxylic acid
Polycondensation
Renewable resources
© 2016 Elsevier Ltd. All rights reserved.
1. Introduction
Poly((ether)ester)s (PEE) are an important family of polymers
with unique and remarkable properties, like for example thermal
Sustainability is at the front line of world agenda, in fact
research efforts on the development of sustainable materials,
which are preferably based on renewable resources, have grown
exponentially in the last years [1e3]. In this context, polymers
derived from the renewable-based 2,5-furandicarboxylic acid
(FDCA) [4] also have witnessing an incessant growth [1]. The most
successful member of this family of polymers is definitely poly(-
ethylene 2,5-furandicarboxylate) (PEF), announced as the
renewable-based substitute of the commercially available poly(-
ethylene terephthalate) (PET) [1,4e6]. Although several other
FDCA-polymers have also emerged [1,7e18], to date, emphasis has
essentially been placed on polyesters, nevertheless, synthetic
routes to prepare FDCA-based poly((ether)ester)s (PEE) have been
broadly neglected, despite their high commercial relevance
[19e23]. Indeed, to our knowledge, there is a single work on the
topic of synthesis and characterisation of poly(butylene 2,5-
properties, among others [19e29]. They are currently mainly
composed of hard alkylene terephthalate moieties and soft poly(-
ethylene glycol) (PEG) sequences of different chain length [21,30].
Their properties can be tailored by the relative content of their soft/
hard segments and also by using PEG segments with different
average chain lengths [19e26]. In more specific terms their glass
transition can span from far below to above room temperature
[19,23], and not surprisingly their degradability increases with PEG
content [19,24,31].
Some relevant examples of PEEs include poly((ethylene tere-
phthalate)-co-(poly(ethylene glycol) terephthalate)) (PET-co-PEGT)
and especially poly((butylene terephthalate)-co-(poly(ethylene
glycol) terephthalate)) (PBT-co-PEGT) [21,30], commercialized un-
der the trade name PolyActive® [32], for typical applications such as
films and microspheres [31,33]. More examples include the pol-
y((butylene terephthalate)-co-(poly(tetramethylene glycol) tere-
phthalate)) copolymers [34,35] commercialized under the trade
name Hytrel® (DuPont) [36] or Arnitel® (DSM) [37]. In view of the
present concerns about sustainability and environmental issues,
alternative PEEs entirely based on renewable resources are highly
desirable in the long term. Indeed, a judicious selection of mono-
mers that would include FDCA, as alternative to fossil-based ter-
ephthalic acid, would enhance even further the value of PEE
polymers.
furandicarboxylate)-co-(poly(tetramethylene
glycol)
2,5-
furandicarboxylate) [24], although PEE using FDCA and PEG has
never been investigated before.
* Corresponding author. CICECO- Aveiro Institute of Materials and Department of
Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.
E-mail address: andreiafs@ua.pt (A.F. Sousa).
http://dx.doi.org/10.1016/j.polymer.2016.06.015
0032-3861/© 2016 Elsevier Ltd. All rights reserved.

130
A.F. Sousa et al. / Polymer 98 (2016) 129e135
This study inaugurates, precisely, the development of poly((-
a resolution of 8 cmꢁ1
.
ether)ester)s based on FDCA and incorporating different number-
average molecular weight poly(ethylene glycol) (PEG200, PEG400
or PEG2000). The copolymerisation with renewable-based iso-
sorbide is also an innovation of this study that, to the best of our
knowledge, has never been reported before despite the predictable
thermal properties enhancement of the ensuing PEEs due to iso-
sorbide stiffness. This unique combination of monomers/oligomers
was reacted under conventional solution polycondensation
approach, and the ensuing products were characterised in detail by
means of ATR FTIR, 1H and 13C NMR, DSC and TGA analyses.
2.4.2. Nuclear magnetic resonance (NMR)
1H and 13C NMR spectra of the polymers dissolved in deuterated
chloroform (CDCl3) were recorded using a Bruker AMX 300 spec-
trometer, operating at 300 or 75 MHz, respectively. All chemical
shifts are expressed as parts per million downfield from tetrame-
thylsilane, used as internal standard.
2.4.3. Size-exclusion chromatography (SEC)
SEC analyses of polyesters were performed on a chromatogra-
pher equipped with a PL-EMD 960 light scattering detector, using a
set of two PL HFIP columns (300 mm ꢂ 7.5 mm i.d.) and one PL HFIP
gel guard column (50 mm ꢂ 7.5 mm i.d.), kept at 40 ꢀC and previ-
ously calibrated with polystyrene standards in the range of
1800e30,300 g molꢁ1. A mixture of dichloromethane/chloroform/
1,1,1,3,3,3-hexafluoro-2-propanol (CH2Cl2/CHCl3/HFP) (70/20/10 in
2. Experimental
2.1. Materials
Isosorbide (98%, IS), 1,1,2,2-tetrachloroethane (98%, TCE), anhy-
drous pyridine (99.8%) and deuterated chloroform (99%, CDCl3)
were purchased from Sigma-Aldrich Chemicals Co. Polyethylene
glycol with number-average molecular weight equal to 200
(PEG200) and to 400 (PEG400) were purchased from Merck. 2,5-
Furandicarboxylic acid (98%, FDCA) was purchased from TCI
Europe N.V.. All chemicals were used as received, except for PEGs’
and TCE which were dried prior their use (by vacuum or by using
molecular sieves, respectively).
V/V/V%) was used as the mobile phase with a flow of 1.0 mL minꢁ1
.
All polymers (z3 mg mlꢁ1) were dissolved in CH2Cl2/CHCl3/HFP
mixture (70/20/10 in V/V/V%) and filtered through PTFE mem-
branes before injection.
2.4.4. Thermogravimetric analyses (TGA)
TGA analyses were carried out with a Shimadzu TGA50 analyser
equipped with a platinum cell, using platinum pans to encapsulate
the samples. Typically, samples were heated, at a constant rate of
10 ꢀC minꢁ1, from room temperature up to 800 ꢀC, under a nitrogen
2.2. Synthesis of 2,5-furandicarbonyl dichloride (FDCDCl)
flow of 20 mL minꢁ1
.
Typically, reactions were carried out in solution using FDCA (ca.
5 g) dissolved in dimethylformamide (ca. 50 ml) and an excess of
thionyl chloride (ca. 5 ml). The mixture was refluxed at 80 ꢀC for
15 h, with constant stirring. Subsequently, the excess of SOCl2 and
DMF was removed under vacuum at room temperature and finally
the pure dichloride monomer was isolated by vacuum sublimation,
at approximately 80 ꢀC (isolation yield z 50%).
2.4.5. Differential scanning calorimetry (DSC)
DSC thermograms were obtained with a TA Instruments Q100
model calorimeter using aluminium pans. Scans were conducted
under nitrogen with a heating rate of 10 ꢀC minꢁ1 in the temper-
ature range of ꢁ80 to 200 ꢀC. Two heating/cooling cycles were
repeated. The second heating scans were done after performing a
cycle in which the samples were heated from 25 to 200 ꢀC and
cooled to ꢁ80 ꢀC to eliminate the thermal history. Glass transition
temperature was determined using the midpoint approach (second
heating trace). Melting temperature was determined as the mini-
mum of the melting endothermic peak during the second heating
cycle, respectively.
2.3. Synthesis of poly((ether)ester)s
Polycondensation reactions were carried out in solution
following an adapted procedure of Gandini et al. [7]. Typically, the
dried diol monomer, either approximately 2.6 mmol of PEG
(PEG200, PEG400 or PEG2000) or an equimolar mixture of
PEG2000 (ca. 1.3 mmol) and IS (ca. 1.3 mmol), dissolved in TCE
(1 ml), was dissolved in pyridine (1.7 ml). Then, this mixture was
allowed to cool down to about 0 ꢀC using an ice bath, and an
equimolar amount of FDCDCl (ca. 2.6 mmol), dissolved in TCE
(1 ml), was added dropwise, under nitrogen flux, and with vigorous
stirring. The reaction was allowed to proceed until room temper-
ature, while its viscosity increased progressively, during approxi-
mately 7 h. The ensuing polymer was precipitated in an excess of
cold ethanol; isolated, either by filtration or by decantation
depending if it was a solid or a viscous liquid, respectively; and
finally dried. Afterwards a film from PEGF2000 was prepared by
depositing a polymer solution in chloroform (ca. 0.1 mg mlꢁ1) onto
a Teflon surface plate, followed by slow evaporation of solvent until
complete dryness, first at room temperature during 1 day and then
at 50 ꢀC for 2 days.
2.4.6. X-ray diffraction (XRD) analyses
XRD diffractograms were acquired using a Philips X’pert MPD
instrument operating with Cu K
a
radiation (
l
¼ 1.5405980 Å) at
40 kV and 50 mA. Samples were scanned in the 2
q
range of 3e50ꢀ,
with a step size of 0.04ꢀ, and time per step of 50 s.
3. Results and discussion
One of the most appealing aspect of this study is concerned with
the fact that for the first time 100% renewable-based poly((ether)
ester)s were straightforward prepared by conventional solution
polycondensation reactions [7] (Scheme 1).
These reactions were carried out by using stoichiometric
amounts of FDCA dichloride and diols (either PEG or an equimolar
mixture of PEG and isosorbide). The ensuing PEGF polymers were
obtained in ca. 65% isolation yield, their number-average molecular
weight ranged from 3300 to 17,300 g molꢁ1 and the poly-
dispersity’s were close to 1.4 as determined by SEC in CH2Cl2/CHCl3/
HFP (Table 1). In addition, here, we demonstrate that these
renewable-based PEEs, in similarity to the fossil-PEE [31], can also
form a film by directly casting a diluted chloroform solution of
PEGISF2000 onto the surface of a Teflon plate.
2.4. Characterisation
2.4.1. Attenuated total reflectance Fourier transform infrared (ATR
FTIR)
Infrared spectra of PEGFs were obtained using a PARAGON 1000
Perkin-Elmer FTIR spectrometer equipped with a single-horizontal
Golden Gate ATR cell. The spectra were recorded after 128 scans, at

A.F. Sousa et al. / Polymer 98 (2016) 129e135
131
Scheme 1. Syntheses of two series of FDCA-based poly((ether)ester)s by polycondensation reaction: I poly((poly(ethylene glycol)) 2,5-furandicarboxylate) (PEGF) and II poly((-
poly(ethylene glycol)) 2,5-furandicarboxylate)-co-poly(isosorbide 2,5-furandicarboxylate) (PEGISF2000).
1465 cmꢁ1 were also detected. In the case of PEGISF2000 these
peaks were overlapped with the typical isosorbide bands. These
attributions were in accordance with literature values for similar
polymers [12,38e40].
Additionally, the success of these polymerisations and the ex-
pected structure of the ensuing polymers were also confirmed by
1H and 13C NMR spectroscopies (Table 2, Fig. 2 and Table S1 of
Supplementary Information). The 1H NMR spectra of PEEs
(Table 2 and Fig. 2) display significant differences compared with
Table 1
Results related to the polycondensations carried out in this study.
Polymer
diol(s) (%)a
Mw/g molꢁ1 b Ðc Isolation yield (%)d
PEGF200
PEGF400
PEGF2000
0.5 PEG200
0.5 PEG400
0.5 PEG2000
3300
7400
1.8 57.6
1.4 56.8
1.3 76.0
1.2 68.7
17 300
PEGISF2000 0.25 PEG2000 þ 0.25 IS 13,200
a
Molar percentage of diol added. PEG200, PEG400 and PEG2000 stands for PEG
with number-average molecular weight equal to 200, 400 and 1,200, respectively;
and IS for isosorbide.
their precursors, viz.: two resonances at ca.
d 4.49 and 3.82 ppm,
b
Weight-average molecular weight of PEEs determined by SEC in CH2Cl2/CHCl3/
attributed to the methylene protons of OCH2 and OCH2CH2 groups
of PEG (Ha, Hb), owing to the neighbouring carbonyl group of furan
moiety, respectively. Additionally, in the particular case of
PEGISF2000 the 1H NMR spectra also show several resonances
HFP.
c
Polydispersity index of PEEs determined by SEC in CH2Cl2/CHCl3/HFP.
Weight isolation yields of precipitated polymers in ethanol.
d
associated with isosorbide moieties at ca.
d 5.46e5.41, 5.06, 4.69
and 4.05e4.11 ppm arising from H20 and H50, H30, H40 and H10 and
H60 protons, near the carbonyl group of furan moiety, respectively
[41e43].
3.1. Structural characterisation
These novel PEEs were extensively characterised by means of
ATR FTIR spectroscopy, as illustrated in Fig. 1 for PEGF2000 and
PEGISF2000 polymers, and their PEG2000 counterpart precursor.
Their main characteristic FTIR spectroscopic features were
(Fig. 1): two new bands, one near 1720 cmꢁ1, attributed to the C]O
These spectra also display the typical furan resonances associ-
ated with H3 and H4 protons at
the near isosorbide or PEG moieties, respectively; and a singlet at
z 3.65 ppm, arising from Hc and Hd protons of OCH2 group of PEG
block.
Moreover, a deeper inspection of PEGISF2000 1H NMR results
d z 7.26 and/or at 7.23 ppm due to
d
stretching mode (yC]O) of an ester moiety and the other band at
1273 cmꢁ1 attributed to CeOeC stretching mode (yCeOeC), also
from an ester group. Additionally the absence of a detectable band
of OeH stretching mode (yOH) near 3415 cmꢁ1 corroborated, thus,
that these polymers reached a reasonable molecular weight.
Additionally, both the characteristic bands of furan moieties
allowed assessing the real molar ratios of IS and PEG units in the
polymer, calculated using the integration areas of H3 and H4 furanic
proton resonances near IS or PEG moieties at
d z 7.26 and at
7.23 ppm (ratiozAH3;H4;FꢁIS=AH3;H4;FꢁPEG), respectively. Results
have shown that isosorbide moieties were incorporated in rela-
tively higher quantities rather than PEG ones (around 3 times
more), despite the starting feed ratio used (equimolar amounts of IS
and PEG) (Table 2). This observation could be due to the lower
reactivity of PEG oligomers under the polycondensation reaction
conditions used. Nevertheless, the incorporated PEG had an impact
on PEGISF2000 properties as discussed below.
were detected. Indeed, their spectra show near 3160 and 3113 cmꢁ1
,
two weak bands arising from ¼ CeH stretching mode ( ¼CeH)
y
associated with furan moiety; and several bands at 1580, 959, 840
and 766 cmꢁ1 typical of 2,5-disubstituted furan heterocycle.
The signals associated with PEG moiety at 2879 cmꢁ1, arising
from the antisymmetric and symmetric stretching of CeH bond of
CH2 groups (yCeH
sym) and the CeH bending vibration near
asym,

132
A.F. Sousa et al. / Polymer 98 (2016) 129e135
Fig. 1. ATR FTIR spectra of PEG2000 macromonomer and related polyesters PEGF2000 and PEGISF2000.
Table 2
Main 1H NMR resonances of PEGFs.
d
/ppm
Multa
Assignment
Integration area
PEGF200
PEGF400
PEGF2000
PEGISF2000
7.26
7.23
5.46e5.41
5.06
4.69
4.49
4.05e4.11
3.82
s
s
s, q
t
d
t
m
t
s
H3, H4, F-IS
H3, H4, F-PEG
H20, H50, F-IS
H30, F-IS
e
e
e
1.0
0.3
1.0
0.5
0.5
1.5
2.1
1.7
64.8
1.0
e
1.0
e
1.0
e
e
e
e
H40, F-IS
e
e
e
Ha, F-PEG
H10, H60, F-IS
Hb, F-PEG
2.1
e
2.0
e
2.1
e
2.1
4.9
2.1
13.8
2.3
83.9
3.65
Hc, Hd, PEG-PEG
a
Mult stands for multiplicity
The 1H NMR spectrum of PEGISF2000 provided another
important piece of information related with how F, IS, and PEG
were preferentially linked, viz., F-IS or F-PEG. Hence, the related
these polymers confirmed, precisely, that the thermal stability can
be tailored by changing the monomers used. Indeed, they were
typically thermally stable up to z248e352 ꢀC, in the following
increasing temperature order: PEGF200 z PEGF400 < PEGF2000 ≪
PEGISF2000. The highest thermal stability temperature (ca. 352 ꢀC)
was achieved for the polymer incorporating isosorbide, i.e.
PEGISF2000, in accordance with reported studies about isosorbide-
based polyesters [7,42,44]. Thereafter, these polymers decomposed
with a major decomposition step at ca. 371e423 ꢀC; followed by a
broader second step at approximately 500 ꢀC (only for PEGF200
and PEGF400), which left ca. 5% residue at this temperature.
The DSC thermograms of the PEGF series of polymers (Table 3
and Fig. 3) display a single glass transition (Tg), below room tem-
perature, ascribed to the soft PEG segments. The Tg values
decreased with the increasing chain length of these segments,
associated with a decreasing polymer backbone stiffness. There-
fore, PEGF200 has the highest Tg, followed by PEGF400, and
PEGF2000 (Tg z ꢁ6.5, ꢁ29.0, ꢁ35.1 ꢀC, respectively). As expected,
these Tg values are substantially higher than those of their PEG
precursors (with similar molecular-weights) [45], due to the
molar
ratios
A
H3;H4;FꢁIS=ðAH3;H4;FꢁPEG þ AH3;H4;FꢁIS
Þ
and
AH3;H4;FꢁPEG=ðAH3;H4;FꢁPEG þ AH3;H4;FꢁISÞ were calculated and esti-
mated to be approximately equal to 0.76 and 0.23, respectively. F-IS
linkage, thus, prevailed, which is consistent with the formation of a
copolymer with isosorbide-furandicarboxylate blocks and incor-
porating PEG segments.
3.2. Thermal and XRD properties
An important aspect of these furan-based poly((ether)ester)s
are their tailor-made properties, especially in terms of thermal
behaviour, simply achieved by using different number-average
molecular weight PEGs (i.e. 200, 400 and 2000 g molꢁ1) or by
incorporating rigid isosorbide units (Scheme 1) providing thus, to
the ensuing polymers, soft hydrophilic moieties of different length
(PEGFs’ series) or rigid structures (PEISF2000), respectively. The
TGA values (Table 3 and Fig. S2 of Supplementary Information) of

A.F. Sousa et al. / Polymer 98 (2016) 129e135
133
Fig. 2. 1H NMR spectra of PEGF2000 and PEGISF2000.
room temperature (ca. ꢁ26 ꢀC), associated with PEG soft segments
amorphous domains; one Tm around 40 ꢀC also associated with
PEG2000; and an additional Tg, at 168 ꢀC, ascribed to a second
Table 3
Characteristic glass transition (Tg), melting (Tm), decomposition at 5% weight loss
(Td,5%) and at maximum decomposition (Td,max) temperatures of all PEGFs studied.
Polymer
Tg/oC
Tm/oC
Td,5%/oC
Td,max/oC
amorphous
phase
enriched
in
the
stiff
isosorbide-
furandicarboxylate segments. Noteworthy, the Tg value of poly(-
isosorbide 2,5-furandicarboxylate) homopolyester reported in the
literature (ca. 180 ꢀC [7]) is in accordance with this quite high value
(ca. 168 ꢀC), although slightly higher. Another aspect is that a
substantial increase in this Tg value was achieved compared with
those reported in the literature for their fossil counterpart (which
typically vary between ca. 26e58 ꢀC) [19], enlarging thus the ser-
vice temperature range of typical PEEs.
The existence of several distinct thermal events is indicative of
microphase separation promoted by the existence of two different
blocks, one corresponding to the hydrophilic soft segments of
PEG2000 and the other typical of hard isosorbide-
furandicarboxylate segments as also pointed out by 1H NMR
analysis.
PEGF200
PEGF400
PEGF2000
PEGISF2000
ꢁ6.5
e
253.5
248.2
318.3
352.2
371.4, 493.9
372.9, 523.6
377.3
ꢁ29.0
e
ꢁ35.1
49.1
40.9
ꢁ26.4; 168.1a
422.6
a
Tg values obtained from the second heating scan at 20 ꢀC minꢁ1, after quenching.
presence of the stiff furan moieties, but are in accordance with their
fossil counterparts [19,46,47]. Also, in the case of PEGF2000 a Tm
around 49 ꢀC was detected, probably due to the fact that only the
longest soft PEG segments has enough chain mobility to form
crystalline domains [46]. However, comparing the Tm of PEGF2000
with that of its PEG2000 precursor a depression of about 5 ꢀC is
noted.
In the particular case of PEGISF2000, the corresponding ther-
mogram displays three different thermal events: one Tg below
Fig. 3. DSC thermograms of a) all PEGFs and PEGISF2000 (heating rate of 10 ꢀC minꢁ1) and b) of PEGISF2000 displaying the high glass transition (taken at a faster heating rate of
20 ꢀC minꢁ1).

134
A.F. Sousa et al. / Polymer 98 (2016) 129e135
[2] G. Walther, High-performance polymers from nature: catalytic routes and
processes for industry, ChemSusChem 7 (2014) 2081e2088.
[3] A. Gandini, The irruption of polymers from renewable resources on the scene
of macromolecular science and technology, Green Chem. 13 (2011)
1061e1083.
[4] J.J. Bozell, G.R. Petersen, Technology development for the production of bio-
based products from biorefinery carbohydratesdthe US Department of
Energy’s “Top 10” revisited, Green Chem. 12 (2010) 539e554.
[5] A. Gandini, A.J.D. Silvestre, C.P. Neto, A.F. Sousa, M. Gomes, The furan coun-
terpart of poly(ethylene terephthalate): an alternative material based on
renewable resources, J. Polym. Sci. Polym. Chem. 47 (2009) 295e298.
[6] E. de Jong, M.A. Dam, L. Sipos, G.-J.M. Gruter, Furandicarboxylic acid (FDCA), a
versatile building block for a very interesting class of polyesters, in: P.B. Smith,
R.A. Gross (Eds.), Biobased Monomers, Polym. Mater., 1105, American
Chemical Society, , Washington, 2012, pp. 1e13.
[7] M. Gomes, A. Gandini, A.J.D. Silvestre, B. Reis, Synthesis and characterization of
poly(2,5-furan dicarboxylate)s based on a variety of diols, J. Polym. Sci. Polym.
Chem. 49 (2011) 3759e3768.
[8] M. Jiang, Q. Liu, Q. Zhang, C. Ye, G. Zhou, A series of furan-aromatic polyesters
synthesized via direct esterification method based on renewable resources,
J. Polym. Sci. Polym. Chem. 50 (2012) 1026e1036.
[9] G.Z. Papageorgiou, V. Tsanaktsis, D.G. Papageorgiou, K. Chrissafis,
S. Exarhopoulos, D.N. Bikiaris, Furan-based polyesters from renewable re-
sources: crystallization and thermal degradation behavior of poly(hexa-
methylene 2,5-furan-dicarboxylate), Eur. Polym. J. 67 (2015) 383e396.
[10] J. Ma, Y. Pang, M. Wang, J. Xu, H. Ma, X. Nie, The copolymerization reactivity of
diols with 2,5-furandicarboxylic acid for furan-based copolyester materials,
J. Mater Chem. 22 (2012) 3457e3461.
[11] V. Tsanaktsis, G.Z. Papageorgiou, D.N. Bikiaris, A facile method to synthesize
high molecular weight biobased polyesters from 2,5-furandicarboxylic acid
and long chain diols, J. Polym. Sci. Polym. Chem. 53 (2015) 2616e2632.
[12] M. Matos, A.F. Sousa, A.C. Fonseca, C.S.R. Freire, J.F.J. Coelho, A.J.D. Silvestre,
Fig. 4. XRD patterns of PEGF2000, PEGISF2000 and PEG2000 precursor.
The semi-crystalline character of PEGF2000 and PEGISF2000
polymers was corroborated by the presence of two sharp signals in
their X-ray diffractograms (Fig. 4), at 2
q
z 19 and 23ꢀ, i.e., a pattern
similar to that of PEG2000. Additionally, an amorphous halo cen-
tred at ca. 20ꢀ is also observed in the case of PEGF2000 and
PEGISF2000, albeit not present in their more crystalline PEG
precursor.
A
new generation of furanic copolyesters with enhanced degradability:
poly(ethylene 2,5-furandicarboxylate)-co-poly(lactic acid) copolyesters,
Macromol. Chem. Phys. 215 (2014) 2175e2184.
[13] Z. Yu, J. Zhou, F. Cao, B. Wen, X. Zhu, P. Wei, Chemosynthesis and character-
ization of fully biomass-based copolymers of ethylene glycol, 2,5-
furandicarboxylic acid, and succinic acid, J. Appl. Polym. Sci. 130 (2013)
1415e1420.
[14] N. Jacquel, R. Saint-Loup, J.-P. Pascault, A. Rousseau, F. Fenouillot, Bio-based
alternatives in the synthesis of aliphatic-aromatic polyesters dedicated to
biodegradable film applications, Polymer 59 (2015) 234e242.
4. Conclusions
In conclusion, novel FDCA-poly((ether)ester)s entirely based on
renewable monomers (i.e. FDCA, PEG and isosorbide) were suc-
cessfully synthesised. Moreover, their general properties can
compete with terephthalic acid-based polymers or at least they are
comparable, which indicates that FDCA-based poly((ether)ester)s
are a viable alternative to their highly successful commercially-
available counterparts derived from petrochemicals [32]. Indeed,
these new PEEs present film-forming ability and the properties can
be fine-tuned, by the simple adjustment of the chain length of PEG
segments and also by incorporating (or not) rigid isosorbide moi-
eties. An attractive challenge is the development of FDCA-based
PEEs porous specimens (including composite ones) and to assess
their properties including the mechanical performance.
[15] B. Wu, Y. Xu, Z. Bu, L. Wu, B.-G. Li, P. Dubois, Biobased poly(butylene 2,5-
furandicarboxylate)
and
poly(butylene
adipate-co-butylene
2,5-
furandicarboxylate)s: from synthesis using highly purified 2,5-
furandicarboxylic acid to thermo-mechanical properties, Polymer 55 (2014)
3648e3655.
[16] C.H.R.M. Wilsens, J.M.G.A. Verhoeven, B.A.J. Noordover, M.R. Hansen, D. Auhl,
S. Rastogi, Thermotropic polyesters from 2,5-Furandicarboxylic acid and
vanillic acid: synthesis, thermal properties, melt behavior, and mechanical
performance, Macromolecules 47 (2014) 3306e3316.
[17] C.H.R.M. Wilsens, B.A.J. Noordover, S. Rastogi, Aromatic thermotropic poly-
esters based on 2,5-furandicarboxylic acid and vanillic acid, Polymer 55
(2014) 2432e2439.
[18] J. Deng, X. Liu, C. Li, Y. Jiang, J. Zhu, Synthesis and properties of a bio-based
epoxy resin from 2,5-furandicarboxylic acid (FDCA), RSC Adv.
5 (2015)
15930e15939.
[19] A.A. Deschamps, D.W. Grijpma, J. Feijen, Poly(ethylene oxide)/poly(butylene
terephthalate) segmented block copolymers: the effect of copolymer
composition on physical properties and degradation behavior, Polymer 42
(2001) 9335e9345.
Acknowledgments
[20] M. Niaounakis, Biopolymers: Processing and products, Elsevier Science,
Amsterdam, Netherlands, 2014.
[21] D. Coleman, Block copolymers: copolymerization of ethylene terephthalate
and polyoxyethylene glycols, J. Polym. Sci. 14 (1954) 15e28.
[22] A.M. Reed, D.K. Gilding, J. Wilson, Biodegradable elastomeric bio-
materialsepolyethylene oxide/polyethylene terephthalate copolymers, Trans.
Am. Soc. Artif. Intern Organs 23 (1977) 109e115.
[23] T. Kiyotsukuri, T. Masuda, N. Tsutsumi, W. Sakai, M. Nagata, Poly(ethylene
terephthalate) copolymers with a smaller amount of poly(ethylene glycol)s
and poly(butylene glycol)s, Polymer 36 (1995) 2629e2635.
~
^
AFS wish to thank FCT (Fundaçao para a Ciencia e Tecnologia)
and POPH/FSE for a postdoctoral grant (SFRH/BPD/73383/2010).
This work was developed within the scope of the project CICECO-
Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013),
financed by national funds through the FCT/MEC and when
appropriate co-financed by FEDER under the PT2020 Partnership
Agreement.
[24] Z. Qian, S. Li, Y. He, X. Liu, Synthesis and in vitro degradation study of
poly(ethylene terephthalate)/poly(ethylene glycol) (PET/PEG) multiblock
copolymer, Polym. Degrad. Stab. 83 (2004) 93e100.
Appendix A. Supplementary data
[25] J. Hu, H. Yu, Y. Chen, M. Zhu, Study on phase-change characteristics of PET-
PEG copolymers, J. Macromol. Sci. Part B Phys. 45 (2006) 615e621.
[26] D. Qiu, P. Zhang, S. Zhang, J. Sun, J. Wang, L. Dai, Synthesis and non-isothermal
crystallization kinetics of poly(ethylene terephthalate)- co -poly(propylene
glycol) copolymers, Polym. Adv. Technol. 26 (2015) 1130e1140.
[27] Q. Xu, J. Chen, W. Huang, T. Qu, X. Li, Y. Li, et al., One pot, one feeding step,
two-stage polymerization synthesis and characterization of (PTT-b-PTMO-b-
PTT), Macromolecules 46 (2013) 7274e7281.
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.polymer.2016.06.015.
References
[28] W. Huang, Y. Wan, J. Chen, Q. Xu, X. Li, X. Yang, et al., One pot synthesis and
characterization of novel poly(ether ester) multiblock copolymers containing
poly(tetramethylene oxide) and poly(ethylene terephthalate), Polym. Chem. 5
[1] A.F. Sousa, C. Vilela, A.C. Fonseca, M. Matos, C.S.R. Freire, G.-J.M. Gruter, et al.,
Biobased polyesters and other polymers from 2,5-furandicarboxylic acid: a
tribute to furan excellency, Polym. Chem. 6 (2015) 5961e5983.

A.F. Sousa et al. / Polymer 98 (2016) 129e135
2575e2579.
135
(2014) 945e954.
[29] J.W. Zhang, F. Liu, J.G. Wang, H.N. Na, J. Zhu, Synthesis of poly(butylene
terephthalate)-poly(tetramethylene glycol) copolymers using terephthalic
acid as starting material: a comparation between two synthetic strategies,
Chin. J. Polym. Sci. 33 (2015) 1283e1293.
[39] A.F. Sousa, M. Matos, C.S.R.R. Freire, A.J.D.D. Silvestre, J.F.J.J. Coelho, New
copolyesters derived from terephthalic and 2,5-furandicarboxylic acids: a step
forward in the development of biobased polyesters, Polymer 54 (2013)
513e519.
[30] Hoeschele GK. Segmented thermoplastic copolyester elastomers. (E I du pont
nemours company), US3954689, 1976.
[31] A. Zhang, Z. Feng, Z. Xie, Long-term investigation on hydrolytic degradation
and morphology of poly(ethylene glycol terephthalate)-b- poly(butylene
terephthalate) copolymer films, J. Appl. Polym. Sci. 111 (2009) 1462e1470.
[40] O. Goerz, H. Ritter, N-Alkylated dinitrones from isosorbide as cross-linkers for
unsaturated bio-based polyesters, Beilstein J. Org. Chem. 10 (2014) 902e909.
[41] J.M. Koo, S.Y. Hwang, W.J. Yoon, Y.G. Lee, S.H. Kim, S.S. Im, Structural and
thermal properties of poly(1,4-cyclohexane dimethylene terephthalate) con-
taining isosorbide, Polym. Chem. 6 (2015) 6973e6986.
[32] PolyActive® Microspheres
-
OctoPlus, January 2016. PolyActive®-Micro-
[42] S. Chatti, S.M. Weidner, A. Fildier, H.R. Kricheldorf, Copolyesters of isosorbide,
spheres, Accessed, http://www.octoplus.nl/nl/Expertise/.
[33] A. El-Ghalbzouri, E.N. Lamme, C. van Blitterswijk, J. Koopman, M. Ponec, The
use of PEGT/PBT as a dermal scaffold for skin tissue engineering, Biomaterials
25 (2004) 2987e2996.
[34] R.W. Seymour, J.R. Overton, L.S. Corley, Morphological characterization of
polyester-based elastoplastics, Macromolecules 8 (1975) 331e335.
[35] A. Stroeks, K. Dijkstra, Modelling the moisture vapour transmission rate
through segmented block Co-poly(ethereester) based breathable films,
Polymer 42 (2001) 117e127.
succinic acid, and isophthalic acid: biodegradable, high T g engineering
plastics, J. Polym. Sci. Polym. Chem. 51 (2013) 2464e2471.
[43] Z. Wei, C. Zhou, Y. Yu, Y. Li, Biobased copolyesters from renewable resources:
synthesis and crystallization behavior of poly(decamethylene sebacate-co-
isosorbide sebacate), RSC Adv. 5 (2015) 42777e42788.
[44] W.C. Shearouse, L.M. Lillie, T.M. Reineke, W.B. Tolman, Sustainable polyesters
derived from glucose and castor oil: building block structure impacts prop-
erties, ACS Macro Lett. 4 (2015) 284e288.
[45] F.E. Bailey, J.V. Koleske, Properties of Poly(Ethylene Oxide). Poly (Ethylene
Oxide), Academic Press, , New York, 1976, pp. 105e149.
[46] S. Fakirov, T. Gogeva, Poly(ether/ester)s based on poly(butylene tere-
phthalate) and poly(ethylene glycol), 2. Effect of polyether segment length,
Makromol. Chem. 191 (1990) 615e624.
[36] Hytrel® TPC-ET Thermoplastic Polyester Elastomer | DuPont USA, May 2016.
Accessed, http://www.dupont.com/products-and-Services/plastics-Polymers-
Resins/thermoplastics/brands/hytrel-Thermoplastic-Elastomer.html.
[37] The Age of Arnitel®
- DSM, May 2016. Accessed, http://www.dsm.com/
products/arnitel/en_US/home.html.
[38] D.L. Snavely, J. Dubsky, Near-IR spectra of polyethylene, polyethylene glycol,
[47] S. Fakirov, T. Gogeva, Poly(ether/ester)s based on poly(buty1ene tere-
phthalate) and poly(ethy1ene glycol), 1. Poly (ether/ester)s with various
polyether: polyester ratios, Makromol. Chem. 191 (1990) 603e614.
and polyvinylethyl ether, J. Polym. Sci. Part
A Polym. Chem. 34 (1996)