Influence of Chemical Structures on Isodimorphic Behavior of Three Different Copolycarbonate Random Copolymer Series

Arandia, Idoia; Meabe, Leire; Aranburu, Nora; Sardón, Haritz; Mecerreyes, David; Müller, Alejandro J.

doi:10.1021/acs.macromol.9b02078

Cited by 18 publications

(32 citation statements)

References 39 publications

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“…In the case of PBA, the reaction was heated at 190ºC during 3 hours, then at 210ºC during 3 hours and finally at 230ºC during 3-4 hours under vacuum as reported in literature. The characterization was consistent with literature data 23,27 .…”

Section: Methodssupporting

confidence: 90%

Chemical Structure Drives Memory Effects in the Crystallization of Homopolymers

Sangroniz

Meabe

et al. 2020

Macromolecules

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Although the study of melt memory has attracted much interest, the effect of polymer chemical structure on its origin has not been fully elucidated. In this work, we study melt memory effects by Differential Scanning Calorimetry employing a selfnucleation protocol. We use homologous series of homopolymers containing different polar groups and different number of methylene groups in their repeating units: polycarbonate, polyesters, polyethers and polyamides. We show that melt memory in homopolymers is generally controlled by the strength of the intermolecular interactions. The incorporation of methylene groups reduces melt memory effects by decreasing the strength of segmental chain interactions, which is reflected by the decrease in dipolar moments and solubility parameters. This work presents for the first time a unified view of the melt memory effects in different homopolymers.

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Section: Methodssupporting

confidence: 90%

Chemical Structure Drives Memory Effects in the Crystallization of Homopolymers

Sangroniz

Meabe

et al. 2020

Macromolecules

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“…The β-form is only found upon heating, and more details can be found in ref 13. In the case of PCs with higher n CH 2 (e.g., n CH 2 = 10 and 12), it has been considered that the unit cell resembles the orthorhombic unit cell of linear PE, with a = 0.740 nm, b = 0.493 nm, and c (fiber axis) = 0.2534 nm, and the very strong and strong reflections correspond to the (110) and (200) planes, respectively. 45 For instance, Liu et al 46 assigned the reflections of the PC10 and PC12 samples to the orthorhombic PE unit cell, as well as Arandia et al 20 in the case of the PC12 sample.…”

Section: Resultsmentioning

confidence: 99%

“…16,17 Among organocatalysts, 4-dimethylaminopyridine (DMAP) shows the best catalytic performance 18,19 and allows obtaining different PCs 12,18 and copolycarbonates. 20 Despite the production of different PCs (i.e., with different contents of methylene groups, n CH 2 , in the polymer repeating units), previous studies have been focused on the degradation properties 6 and applications 12 and only a few works on the structure [e.g., "Brill transition" in poly (octamethylene carbonate) 13 and the memory effect. 21 However, the crystallization behavior has not been explored in detail, leaving interesting phenomena, such as the even−odd effect, pending of investigation.…”

Section: Introductionmentioning

confidence: 99%

Even–Odd Effect in Aliphatic Polycarbonates with Different Chain Lengths: from Poly (Hexamethylene Carbonate) to Poly (Dodecamethylene Carbonate)

et al. 2020

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We have characterized a series of aliphatic polycarbonates synthesized by organocatalysis containing a variable number of methylene groups (n CH2 ) in their repeating units ranging from n CH2 = 6 to 12. The melting and crystallization behavior, and crystalline structures were studied by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), and wide-angle X-ray scattering (WAXS). We found a clear even–odd effect in terms of thermal properties and crystalline structure, for n CH2 = 6 to 9, and a saturation of the even–odd effect, for n CH2 = 10 to 12. These results were independent of the crystallization conditions employed: nonisothermal, isothermal, and successive self-nucleation and annealing. The even–odd region showed that the even samples had higher melting temperatures than the odd ones and a monoclinic unit cell. On the other hand, the odd samples showed an orthorhombic unit cell. Both even and odd samples exhibited a trans-conformation, with a dilution of the impact of the carbonyl group as evidenced by the weakening of the crystalline memory effect as n CH2 increases, independent of the even or odd nature of the samples. In the saturation region, methylene, instead of the carbonyl groups, dominated the behavior, resulting in thermal properties that changed almost linearly with n CH2 . The unit cells were all orthorhombic, and the strength of the memory effect was similar, as n CH2 increased. Accordingly, the samples showed a shift of the FT-IR bands toward a PE-like dominated conformation.

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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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Influence of Chemical Structures on Isodimorphic Behavior of Three Different Copolycarbonate Random Copolymer Series

Cited by 18 publications

References 39 publications

Chemical Structure Drives Memory Effects in the Crystallization of Homopolymers

Chemical Structure Drives Memory Effects in the Crystallization of Homopolymers

Even–Odd Effect in Aliphatic Polycarbonates with Different Chain Lengths: from Poly (Hexamethylene Carbonate) to Poly (Dodecamethylene Carbonate)

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

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