Tailoring the isothermal crystallization kinetics of isodimorphic poly (butylene succinate-ran-butylene azelate) random copolymers by changing composition

Arandia, Idoia; Zaldua, Nerea; Maiz, Jon; Pérez-Camargo, Ricardo A.; Múgica, Agurtzane; Zubitur, Manuela; Mincheva, Rosica; Dubois, Philippe; Müller, Alejandro J.

doi:10.1016/j.polymer.2019.121863

Cited by 32 publications

(34 citation statements)

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“…In this work, the values of T 0 m (listed in Table SI-1 and plotted in Figure 1) were obtained by isothermal crystallization DSC experiments followed by Hoffman-Weeks extrapolations (see Figure SI-3). ∆H v is the volumetric melting enthalpy (J/m 3 ) and it was estimated by ∆H V = ∆H 0 m × ρ, so that ρ = 1.26 g/cm 3 and ∆H 0 m = 213 J/g for neat PBS [25] and ρ = 1.14 g/cm 3 and ∆H 0 m = 139.5 J/g for neat PCL [26].…”

Section: Nucleation Kinetics Studied By Plommentioning

confidence: 99%

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Controlling the Isothermal Crystallization of Isodimorphic PBS-ran-PCL Random Copolymers by Varying Composition and Supercooling

et al. 2019

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In this work, we study for the first time, the isothermal crystallization behavior of isodimorphic random poly(butylene succinate)-ran-poly(ε-caprolactone) copolyesters, PBS-ran-PCL, previously synthesized by us. We perform nucleation and spherulitic growth kinetics by polarized light optical microscopy (PLOM) and overall isothermal crystallization kinetics by differential scanning calorimetry (DSC). Selected samples were also studied by real-time wide angle X-ray diffraction (WAXS). Under isothermal conditions, only the PBS-rich phase or the PCL-rich phase could crystallize as long as the composition was away from the pseudo-eutectic point. In comparison with the parent homopolymers, as comonomer content increased, both PBS-rich and PCL-rich phases nucleated much faster, but their spherulitic growth rates were much slower. Therefore, the overall crystallization kinetics was a strong function of composition and supercooling. The only copolymer with the eutectic composition exhibited a remarkable behavior. By tuning the crystallization temperature, this copolyester could form either a single crystalline phase or both phases, with remarkably different thermal properties.

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Section: Nucleation Kinetics Studied By Plommentioning

confidence: 99%

“…In this work, we employed the value of ∆H 0 m = 213 J/g for neat PBS and PBS-rich phase composition that has been recently obtained by some of us [25]. This value was determined employing a combined DSC and X-ray diffraction method using isothermal crystallization data.…”

Section: Nucleation Kinetics Studied By Plommentioning

confidence: 99%

Controlling the Isothermal Crystallization of Isodimorphic PBS-ran-PCL Random Copolymers by Varying Composition and Supercooling

et al. 2019

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“…Moreover, the changes in the unit cell parameters of both crystal phases with composition evidence comonomer inclusion. Our group has recently studied isodimorphism in several random copolymer systems [19][20][21][22][23][24][25][26][27][28][29]. Isodimorphic crystallization has recently been found in different types of random copolymers such as poly (decamethylene succinate-ran-decamethylene fumarate), poly (butylene succinate-co-cis-butene succinate) and poly (hexamethylene carbonate)-co-poly (hexamethylene urethane) [30][31][32][33][34][35].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, Crystallization and Mechanical Properties of Isodimorphic PBS-ran-PCL Copolyesters

et al. 2021

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Isodimorphic behavior is determined by partial inclusion of comonomer segments within the crystalline structure and arises from the comparatively similar repeating chain units of the parental homopolymers. Isodimorphic random copolymers are able to crystallize irrespective of their composition and exhibit a pseudo-eutectic behavior when their melting point values are plotted as a function of comonomer content. At the pseudo-eutectic point or region, two crystalline phases can coexist. On the right-hand and the left-hand side of the pseudo-eutectic point or region, only one single crystalline phase can form which is very similar to the crystalline structures of the parent homopolymers. This article aims to study the synthesis method, structure, crystallization behavior and mechanical properties of isodimorphic random PBS-ran-PCL copolyesters. Moreover, this study provides a comprehensive analysis of our main recent results on PBS-ran-PCL random copolyesters with three different molecular weights. The results show that the comonomer composition and crystallization conditions are the major factors responsible for the crystalline morphology, crystallization kinetics and mechanical performance of isodimorphic random copolyesters. Our studies demonstrate that in the pseudo-eutectic region, where both crystalline phases can coexist, the crystallization conditions determine the crystalline phase or phases of the copolymer. The relationships between the comonomer composition and mechanical properties are also addressed in this work.

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“…Various methods have been carried out to overcome the drawbacks. Copolymerization by introducing comonomeric units can decrease the spherulite size of PBS by raising the randomness of the polymer chains [8]. However, the thermal properties including melting point and enthalpy are highly degraded at the same time [9,10].…”

Section: Introductionmentioning

confidence: 99%

Dependence of Crystallization Behavior of Interacting Telechelic Poly(butylene succinate) Oligomer on Molecular Weight

Chen

Zhang

2021

Crystals

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A large spherulite structure deteriorates the mechanical properties of crystalline polymers, and therefore various methods have been explored to increase primary nucleation density. Recently, chain-end modification has been proposed as an effective approach for regulating polymer crystal nucleation. However, the relevant nucleation mechanism still requires investigation. Therefore, in this work, 2-ureido-4[1H]-pyrimidinone (UPy) units, which can form stacks via quadruple hydrogen bonds with each other, are introduced as end groups for the preparation of interacting telechelic poly(butylene succinate) (PBS-UPy) oligomers with different molecular weights (Mns). The crystallization, especially the nucleation behavior of PBS-UPy, is studied in detail by comparing with the corresponding pre-polymer, the hydroxyl-terminal PBS (PBS-OH). The thermal properties of PBS-UPy exhibit similar Mn-dependent tendency to those of PBS-OH, but with weaker total crystallization rate. The spherulite growth rate is significantly reduced, whereas the primary nucleation density is highly promoted, after introducing UPy groups. Further investigation reveals that the mechanism of UPy stacks’ influence on nucleation ability changes from inhibition to promotion with respect to Mn. Even under an inhibition of nucleation ability, the final nucleation density is obviously increased because of a significant decline of the growth rate. In addition, the change in the impact of UPy stacks on nucleation ability is speculated to originate from the memory expression feasibility of ordered conformation in the melt during crystallization.

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Tailoring the isothermal crystallization kinetics of isodimorphic poly (butylene succinate-ran-butylene azelate) random copolymers by changing composition

Cited by 32 publications

References 35 publications

Controlling the Isothermal Crystallization of Isodimorphic PBS-ran-PCL Random Copolymers by Varying Composition and Supercooling

Controlling the Isothermal Crystallization of Isodimorphic PBS-ran-PCL Random Copolymers by Varying Composition and Supercooling

Synthesis, Structure, Crystallization and Mechanical Properties of Isodimorphic PBS-ran-PCL Copolyesters

Dependence of Crystallization Behavior of Interacting Telechelic Poly(butylene succinate) Oligomer on Molecular Weight

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