Poly(butylene 2,5-furan dicarboxylate), a Biobased Alternative to PBT: Synthesis, Physical Properties, and Crystal Structure

Abstract

This paper describes the synthesis, crystal structure, and physicomechanical properties of a biobased polyester prepared from 2,5-furandicarboxylic acid (FDCA) and 1,4-butanediol. Melt-polycondensation experiments were conducted by a two-stage polymerization using titanium tetraisopropoxide (Ti[OiPr] 4 ) as a catalyst. Polymerization conditions (catalyst concentration, reaction time and second stage reaction temperature) were varied to optimize poly(butylene-FDCA), PBF, and molecular weight. A series of PBFs with different M w were characterized by DSC, TGA, DMTA, X-ray diffraction and tensile testing. Influence of molecular weight and melting/ crystallization enthalpy on PBF material tensile properties was explored. Cold-drawing tensile tests at room temperature for PBF with M w 16K to 27K showed a brittle-to-ductile transition. When M w reaches 38K, the Young modulus of PBF remains above 900 MPa, and the elongation at break increases to above 1000%. The mechanical properties, thermal properties and crystal structures of PBF were similar to petroleum derived poly(butylenes-terephthalate), PBT. Fiber diagrams of uniaxially stretched PBF films were collected, indexed, and the unit cell was determined as triclinic (a = 4.78(3) Å, b = 6.03(5) Å, c = 12.3(1) Å, α = 110.1(2)°, β = 121.1(3)°, γ = 100.6(2)°). A crystal structure was derived from this data and final atomic coordinates are reported. We concluded that there is a close similarity of the PBF structure to PBT αand β-forms.

Preparation and properties of aromatic polyester/TiO2 nanocomposites from polyethylene terephthalate

“…The characteristic reflections of TiO 2 (rutile phase) are situated at 27.5 o 2θ (d= 3.24 Å); 36 o 2θ (d= 2.43 Å); 54.3 o 2θ (d= 1.68 Å), in agreement with the commercial TiO 2 used to obtain the nanocomposites and the assignments described in literature 21,22 . The X-ray diffraction pattern of the pure APE sample shows a broad region (15 o -27 o 2θ) characteristic of semicrystalline polyester with one intense reflection at 24.5° 2θ (d= 3.57 Å) and two diffraction peaks (less intense) at 16° 2θ (d= 5.60 Å) and 16.5° 2θ (d= 5.39 Å) are evidenced in agreement with the literature 23 . The X-ray diffraction patterns of APE/TiO 2 nanocomposites obtained with different filler contents show the characteristic peaks of TiO 2 and APE, that evidences the filler/polymer interaction.…”

“…Besides that, the APE was formed by two linear aliphatic segments which could contribute to the formation of different crystalline regions. One single crystallization peak was observed and this behavior has been seen after the cooling process from the melt polymer 23 . Table 2 shows the values of Tm 1 , Tm 2 (melting temperatures of the peak 1 and peak 2, respectively) ΔHm 1 , ΔHm 2 (fusion enthalpies of the peak 1 and peak 2, respectively) and the values of T c (crystallization temperature) and ΔH c (crystallization enthalpy) obtained from the DSC curves (Figure 3) of the pure APE and APE/TiO 2 nanocomposites synthesized.…”

“…It is believed that the interactions between the particles of TiO 2 and the growing polymer chain limited the growth of the APE 24 . In the case of 3 and 5% of TiO 2 , the filler is probably also acting as a catalyst for esterification reaction, since titanium-based compounds are excellent catalysts for esterification and transesterification reactions 23,25 . The polydispersity index (PI) was around 2.0 that is a characteristic value of condensation polymerization.…”

Poly(butylene 2,5-furandicarboxylate-ε-caprolactone): A new bio-based elastomer with high strength and biodegradability

“…PBF material has largely reduced carbon dioxide permeability (19×) and diffusivity (31×) compared to the respective properties of PET [9]. Other polyesters like poly(butylene 2,5-furandicarboxylate) (PBF) [10], poly(butylene adipate-co-butylene 2,5-furandicarboxylate) (PBAF) [11] and poly(butylene succinic-co-butylene 2,5-furandicarboxlylate) (PBSF) [12] with satisfying thermomechanical properties were also successfully prepared. PBF has high tendency to crystallize and allows the continuous fibers to be drawn from melt.…”

“…PBF has high tendency to crystallize and allows the continuous fibers to be drawn from melt. The crystalline structure of PBF is analogous with that of PBT, which contains crystalline states of α-phase (more stable) and β-phase (less stable) [10]. As for furanicaliphatic coplyesters like PBSF and PBAF, the main advantage is that they display enhanced biodegradability compared with neat PBF.…”