4.7 Article

Kinetics and mechanism of nonisothermal crystallization of biobased poly (hexamethylene 2,5-furan dicarboxylate)

Journal

POLYMER
Volume 285, Issue -, Pages -

Publisher

ELSEVIER SCI LTD
DOI: 10.1016/j.polymer.2023.126366

Keywords

Crystallization kinetics; Biobased polyester; 2,5-furandicarboxylic acid; Isoconversional methods; Sbirrazzuoli crystallization method

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Biobased poly(hexamethylene 2,5-furan dicarboxylate) (PHF) was successfully synthesized by a two-stage melt polycondensation method. The nonisothermal crystallization from the melt and glass states was studied using various thermal analysis techniques. The research reveals the changes in the crystallization mechanism and proposes a method for accurately simulating the crystallization rate curve.
Biobased poly(hexamethylene 2,5-furan dicarboxylate) (PHF) was synthesized by the two-stage melt poly condensation method (transesterification and polycondensation) in a glass batch reactor. The nonisothermal crystallization from the melt and from the glass was studied by means of Differential Scanning Calorimetry, Fast Scanning Calorimetry and advanced kinetic analysis. It is shown that changes in the crystallization regime occurs at certain temperatures and that the end of the crystallization presents some deviation from what is predicted by the Hoffman-Lauritzen's theory of growth rate. A method is presented that allows the determination of the equilibrium melting temperature, the infinite glass transition temperature, the temperature at maximum of the growth rate, and accurate simulation of crystallization rate curves. An equation is proposed for modelling the crystallization process using a methodology that avoid the problem of local minima occurring when too many parameters must be determined simultaneously.

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