Tuning the Thermal Properties and Morphology of Isodimorphic Poly[(butylene succinate)-<i>ran</i>-(ε-caprolactone)] Copolyesters by Changing Composition, Molecular Weight, and Thermal History

Safari, Maryam; Ilarduya, Antxon Martı́nez de; Múgica, Agurtzane; Zubitur, Manuela; Muñoz‐Guerra, Sebastián; Müller, Alejandro J.

doi:10.1021/acs.macromol.8b01742

Cited by 35 publications

(85 citation statements)

References 43 publications

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“…The pseudo-eutectic sample, MM W -BS 45 CL 55 , exhibits a very particular phase behavior, one or both phases can be formed depending on the crystallization conditions (via nonisothermal or isothermal crystallization) [ 37 , 38 ].…”

Section: Resultsmentioning

confidence: 99%

“…Figure 6 shows the phase diagram of HM W -BS x CL y copolyesters. This series of random high-molecular-weight copolymers display similar calorimetric properties to medium-molecular-weight BS x CL y [ 37 ]. They show a single-phase melt and a single glass transition temperature and, upon cooling from the melt, the materials crystallize over the entire composition range as confirmed by X -ray diffraction studies.…”

Section: Resultsmentioning

confidence: 99%

“…As the molecular weight of copolyesters produced by enzymatic ROP is strongly affected by polymerization conditions, such as the presence of small traces of water molecules and low reaction temperatures, the second series of copolyesters were synthesized by a metal-catalyzed melt-polymerization in the presence of titanium tetraisopropoxide (TTP) as the catalyst in order to increase the molecular weight [ 37 , 38 ]. In summary, the transesterification-ROP reactions of ε-caprolactone (CL), 1,4-butanediol (BD) and dimethyl succinate (DMS) were carried out at 160 °C for 4 h, and then the polymerizations were completed by polycondensation at reduced pressure and 190 °C for 3 h. We named this series of copolyesters MM W -BS x CL y (i.e., medium molecular weights series).…”

Section: Methodsmentioning

confidence: 99%

“…These copolyesters were studied in detail in our previous research works (see refs. [ 37 , 38 ]). The weight-average molecular weights of MMw-BS x CL y copolyesters were between 17k−30k g/mol.…”

Section: Methodsmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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

et al. 2021

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“…PBS and PCL are semicrystalline polymers whose thermal properties (melting temperature ( T m ) or glass transition temperature ( T g )) can be tuned by copolymerization. In fact, it has been found that poly(butylene succinate- co -ε-caprolactone) copolyester is crystalline for all compositions and crystallized isodimorphically for intermediate compositions [ 10 ].…”

Section: Introductionmentioning

confidence: 99%

A Biodegradable Copolyester, Poly(butylene succinate-co-ε-caprolactone), as a High Efficiency Matrix Former for Controlled Release of Drugs

et al. 2021

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A biodegradable copolyester, poly(butylene succinate-co-ε-caprolactone) (PBS_CL), was used for first time as an excipient for pharmaceutical dosage forms using direct compression and hot processing techniques (ultrasound-assisted compression (USAC) and hot melt extrusion (HME)). Robust binary systems were achieved with hot processing techniques, allowing a controlled release of the drug. With only 12% v/v of PBS_CL, controlled release forms were obtained using USAC whereas in HME over 34% v/v of excipient is necessary. Amounts over 23% v/v allowed a long-extended release for more than 72 h following diffusional kinetic. Thanks to the high melting point of theophylline and the physicochemical properties of PBS_CL selected and synthesized, the structure of the excipient inside the USAC tablets and HME filaments corresponds to a continuum medium. A percolation threshold around 23% v/v was estimated, which agrees with a continuum percolation model. The polymer shows a high excipient efficiency value using HME and USAC. A nanostructured matrix with wall thicknesses lower than 0.1 µm was obtained. This leads to a very effective coating of the drug particles by the excipient, providing a slow and reproducible release. The present study therefore supports the use of PBS_CL, for the preparation of controlled release dosage forms using hot processing techniques.

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Effect of hydrogen bonds on phase structure and crystallization behavior of UPy‐functionalized polyurethane

Chen

et al. 2022

J of Applied Polymer Sci

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Hydrogen bonding has been reported to be crucial to crystallization behavior and phase structure and consequently the properties of polyurethane (PU). However, the relationship between hydrogen bonds, crystallization, and phase structure still remains a hot topic of researches because it determines the final performance of materials. Herein, a 5‐(2‐hydroxyethyl)‐6‐methyl‐2‐aminouracil (UPy) group capable of forming multiple hydrogen bonds is incorporated into polyurethanes (PUUPys) to ascertain the effect of hydrogen bonds on the structure and properties of PU. It is found that the content of hydrogen bonds increases with UPy amount, which induces obvious changes in crystallization behavior of soft and hard segments. The varied crystallization further promotes microphase separation, and makes phase structure transform from two‐phase (crystalline soft domains and amorphous domains) with lower UPy amount into three‐phase (crystalline soft domains, crystalline hard domains, and amorphous domains) with higher UPy content. The adjustable hydrogen bonding and phase structure endow PUUPy with tunable mechanical properties, which, in combination with the inherent self‐healing characteristics of UPy groups, indicate great potentials of PUUPys in smart materials. This work demonstrates the principle of changing hydrogen bonding to obtain best performance in structural design of polyurethanes.

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Tuning the Thermal Properties and Morphology of Isodimorphic Poly[(butylene succinate)-ran-(ε-caprolactone)] Copolyesters by Changing Composition, Molecular Weight, and Thermal History

Abstract: Tuning the thermal properties and morphology of isodimorphic poly[(butylene succinate)-ran-(ɛ-caprolactone)] copolyesters by changing composition, molecular weight and thermal history

Cited by 35 publications

References 43 publications

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

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

A Biodegradable Copolyester, Poly(butylene succinate-co-ε-caprolactone), as a High Efficiency Matrix Former for Controlled Release of Drugs

Effect of hydrogen bonds on phase structure and crystallization behavior of UPy‐functionalized polyurethane

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