Poly(ethylene furanoate-co-ethylene terephthalate) biobased copolymers: Synthesis, thermal properties and cocrystallization behavior Maria Konstantopoulou 1 , Zoe Terzopoulou 2 , Maria Nerantzaki 2 , John Tsagkalias 2 , Dimitris S. Achilias 2 , Dimitrios N. Bikiaris 2 *, Stylianos Exarhopoulos 1,3 , Dimitrios G. Papageorgiou 4 , George Z. Papageorgiou 3 * 1 Department of Food Technology, Technological Educational Institute of Thessaloniki, PO Box 141, GR-57400 Thessaloniki, Greece 2 Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24, Thessaloniki, Macedonia, Greece 3 Chemistry Department, University of Ioannina, P.O. Box 1186, GR-45110 Ioannina, Greece 4 School of Materials and National Graphene Institute, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom Abstract A series of poly(ethylene furanoate-co-terephthalate) (PEFT) copolymers, with compositions ranging from neat poly(ethylene furanoate) (PEF) to poly(ethylene terephthalate) (PET), was synthesized by melt and solid state polycondensation (SSP). 1 HNMR spectra revealed that the copolymers were random, while the WAXD patterns of the copolyesters indicated isodimorphic cocrystallization. A minimum was observed in the plot of
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Synthesis, thermal properties and cocrystallization behavior
Maria Konstantopoulou1, Zoe Terzopoulou2, Maria Nerantzaki2, John Tsagkalias2,
Dimitris S. Achilias2, Dimitrios N. Bikiaris2*, Stylianos Exarhopoulos1,3, Dimitrios G.
Papageorgiou4, George Z. Papageorgiou3*
1Department of Food Technology, Technological Educational Institute of
Thessaloniki, PO Box 141, GR-57400 Thessaloniki, Greece2Laboratory of Polymer Chemistry and Technology, Department of Chemistry,
Aristotle University of Thessaloniki, GR-541 24, Thessaloniki, Macedonia, Greece3Chemistry Department, University of Ioannina, P.O. Box 1186, GR-45110 Ioannina,
Greece4School of Materials and National Graphene Institute, The University of Manchester,
Oxford Road, Manchester, M13 9PL, United Kingdom
Abstract
A series of poly(ethylene furanoate-co-terephthalate) (PEFT) copolymers, with
compositions ranging from neat poly(ethylene furanoate) (PEF) to poly(ethylene
terephthalate) (PET), was synthesized by melt and solid state polycondensation (SSP). 1HNMR spectra revealed that the copolymers were random, while the WAXD
patterns of the copolyesters indicated isodimorphic cocrystallization. A minimum was
observed in the plot of the melting temperature (Tm) vs composition while the glass
transition temperatures (Tg) varied almost linearly with increasing ET units. The
crystallization rates and degree of crystallinity decreased with comonomer content.
Several thermodynamic models were applied for the analysis of the melting point
depression. A small portion of the comonomer units was found to be introduced into
the homopolymer crystals. It was also realized that it is easier to incorporate the EF
units into the PET crystal than the opposite. PLM was used to observe the spherulitic
morphologies formed during isothermal melt crystallization. Thermogravimetric
analysis (TGA) indicated that the thermal stability of PEFTs decreases slightly with
increasing furanoate content. Finally, the mechanism of decomposition was evaluated
via Py-GC/MS, which consisted of mostly heterolytic scission and less of homolytic
scission reactions.
Keywords: Poly(ethylene furanoate); poly(ethylene terephthalate); random
copolymers; cocrystallization.
Corresponding author: Dimitrios N. Bikiaris, email: [email protected]; George Z.
99 %), ethylene glycol (EG) and tetrabutyl titanate (TBT) catalyst of analytical grade
were purchased from Aldrich Co. 2,5-dimethylfuran-dicarboxylate (DMFD) was
synthesized from 2,5-FDCA and methanol as described in our previous work.[36] All
other materials and solvents used were of analytical grade.
2.2. Copolymer synthesis
Neat PEF and PET polyesters were prepared by the two-stage melt polycondensation
method (esterification and polycondensation) in a glass batch reactor as described in
previous works [36, 62]. Bis(hydroxyl ethyl-furanoate) (BHEF) was synthesized by
transesterification from DMFD and EG in a molar ratio of diester/diol=1/2.2. Both
reagents were charged into the reaction tube of the polyesterification apparatus with
400 ppm of TBT. The reaction mixture was heated at 150 °C under argon flow for 2h,
at 160 °C for additional 2h and finally at 170oC for 1h. CH3OH byproduct was
removed from the reaction mixture by distillation and at the end of this step
temperature was increased at 200oC and vacuum was applied for 20 min in order to
remove the EG excess, producing BHEF. Bis(hydroxyl ethyl-terephthalate) (BHET)
was synthesized from DMT and EG using a similar procedure as described previously
for BHEF production. The PEFT copolymers were then synthesized by melt
polycondensation using different BHEF/BHET feeding ratios (Table 1). The mixture
was heated at 220 oC for 2h at stirring speed 720 rpm and vacuum application, at 230 oC for 2h and at 240 oC for additional 1h. Time was remained stable in all copolymers
while used temperatures were gradually increased by 5oC increasing BHET amount
by 15%. After the polycondensation reaction was completed, the polyesters were
easily removed, milled and washed with methanol. Solid state polycondensation was
applied to increase the molecular weight of the samples at temperatures 20oC lower
than melting point of each copolymer for 4h under vacuum application.
2.3. Polyester characterization
2.3.1. Intrinsic viscosity measurement.
Intrinsic viscosity [η] measurements were performed using an Ubbelohde viscometer
at 30 oC in a mixture of phenol/1,1,2,2-tetrachloroethane (60/40, w/w).
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