Crystallization of isomorphic poly(butylene succinate-co butylene fumarate) biopolyester: Single crystals and ring-banded spherulites

Yong, Zheng; Liu, Xiao; Liu, Fengquan; Xue, Jinxin; Zhou, Jianjun; Huo, Hong

doi:10.1016/j.polymertesting.2018.04.035

Cited by 10 publications

(9 citation statements)

References 45 publications

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“…Similar phenomena were observed in random copolymers. 20,26 The lamellar thickening effect in PBSFA10 was more remarkable, which would reflect the more sensitive response on the accommodation of BS unit into the crystal structure, that is, BS units were less favorable in PBFA10 lattices in comparison with PBF lattices. Such a phenomenon was in line with the higher ϵ value in PBSFA10 series than in PBSF series.…”

Section: Investigation On Co-crystallizationmentioning

confidence: 99%

“…Further, introduction of a third crystallizable unit could be an effective way. On the basis of isodimorphism in both poly(butylene succinate- ran -butylene adipate) (PBSA) , and poly(butylene fumarate- ran -butylene adipate)(PBFA) and isomorphism in PBSF, , a complicated ternary co-crystallization system of poly(butylene succinate- ran -butylene fumarate- ran -butylene adipate) (PBSFA) has been proposed . Thus, in this study, butylene adipate (BA) is employed as the third crystallizable unit to manipulate the isomorphism of PBSF.…”

Section: Introductionmentioning

confidence: 99%

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Manipulating the Co-crystallization Behavior in Isomorphic Copolymers by Introducing a Third Monomeric Unit

Liu

Wei

et al. 2023

Macromolecules

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Isomorphism is a distinctive kind of co-crystallization behavior of random copolymers and provides opportunities to regulate the crystalline structure and performance without the loss of crystallinity. Though the intrinsic structural differentiation would induce variation of accommodation capacity in the co-crystal lattice for different co-monomeric units, subtle manipulation of isomorphism has not been realized yet. In this study, butylene adipate (BA) as the crystallizable unit is incorporated into an isomorphism system model of poly(butylene succinate-ran-butylene fumarate) (PBSF) to form the terpolymers of PBSFA, and the crystallization features are investigated. It is confirmed that part of BA (i.e., ≤20 mol %) does not hinder the isomorphism formation in the terpolymers of PBSFA but influences the accommodation capacities of the isomorphic counterparts of butylene succinate (BS) and butylene fumarate (BF). When BA with 10 mol % is copolymerized, the adoption of BS unit in isomorphism becomes less favorable in comparison to the biopolymers of PBSF, showing an increase of the defect Gibbs free energy for the co-crystal and a decrease of the accommodation ratio of BS. However, with a further lifting of the BA content to 20 mol %, the accommodation preference of BS and BF in the isomorphism lattice reverses, and BS turns into a favorable unit instead of BF. Such a transition of accommodation capacity might be due to the deterioration of intersegmental interaction caused by the third co-crystallizable unit of BA. This work directly reveals the differentiation of co-monomeric units in the isomorphic lattice and sheds light on the manipulation of isomorphism.

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Section: Investigation On Co-crystallizationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Manipulating the Co-crystallization Behavior in Isomorphic Copolymers by Introducing a Third Monomeric Unit

Liu

Wei

et al. 2023

Macromolecules

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“…Among these polymers, poly(butylene fumarate) is a fully biobased polyester that achieved amazing popularity due to its semicrystalline nature, high melting temperature of ∼130 °C, and high tensile strength. Furthermore, copolymerization is the most commonly used method to render FA-based polymers with tailored properties. − Nevertheless, the compounds copolymerized with FA were almost saturated aliphatic diacids or lactones containing single carbon–carbon bonds, leading to a decrease in the amount of available unsaturated sites within the polymer backbone. As a result, polymers with saturated bonds substituting for fumarate lose the outstanding physicochemical performances provided by unsaturated bonds.…”

Section: Introductionmentioning

confidence: 99%

High Molecular Weight Unsaturated Copolyesters Derived from Fully Biobased trans-β-Hydromuconic Acid and Fumaric Acid with 1,4-Butanediol: Synthesis and Thermomechanical Properties

Xiong

Xiao

et al. 2019

ACS Sustainable Chem. Eng.

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This work describes the synthesis, structure, and physical and thermomechanical properties of fully biobased unsaturated copolyesters via melt-polycondensation of renewable monomers trans-β-hydromuconic acid and fumaric acid with 1,4-butanediol conducted by a two-step polymerization employing stannous octoate as a catalyst and 4-methoxyphenol as a radical inhibitor. The polymerization conditions, including catalyst amount, second-stage reaction temperature, and time, were optimized to prepare high molecular mass unsaturated copolyesters without isomerization and saturation reaction in the unsaturated double bonds. Consequently, a series of poly(butylene hydromuconoate-co-butylene fumarate) (PBHBF) samples with weight-average molecular weight over 80 kg/mol were obtained. The chemical structures identified by 1H and 13C NMR indicated that the notorious side reactions of isomerization and saturation of CC bonds in unsaturated polyesters were eliminated in the obtained PBHBF copolyesters. From the physical property analyses by wide-angle X-ray diffraction (WAXD), polarized optical microscopy (POM), and differential scanning calorimetry (DSC), semicrystalline nature was evidenced for all the samples; furthermore, isodimorphic behavior was observed in this copolyester system. The crystallinity degree and thermal properties including glass transition, melting, and crystallization temperatures could be effectively adjusted by controlling the comonomer composition. The resulting copolyesters exhibited excellent tensile properties, which were comparable or even superior to those of polyethylene and most well-known saturated aliphatic polyesters. Overall, these biobased unsaturated polyesters with superior thermomechanical properties and potential biodegradation appear to be the promising materials for practical applications.

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“…39 This behavior is different in isomorphic copolymers, such as PBSF, where identical T s can be used for preparing single crystals independent of the composition. 27 Similar situations were encountered in branched polyethylene and poly(ethylene-ran-carbon monoxide) (PE-ran-CO) copolymers, 40 but in those copolymer systems characterized by total comonomer exclusion, less than 10% comonomer content could greatly decrease the T s . 29,41 Similar to the behavior of PBS, the copolymer seeds are also sensitive to temperature.…”

Section: Resultsmentioning

confidence: 99%

Comonomer Inclusion in Single Crystals of Isodimorphic Random Copolymers of Butylene Succinate and ε-Caprolactone

Safari

Zhou

et al. 2023

Macromolecules

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Random copolymers exhibit diverse crystallization behavior depending on whether comonomers are excluded or included in the crystalline phase. To understand the crystallization behavior of crystallizable isodimorphic random copolymer, in this work, we selected poly[(butylene succinate)-ran-(ε-caprolactone)], BS x CL y , copolyesters and studied their single crystal structure and morphology. The single crystals of PBS homopolymer and BS-rich copolymers were prepared by the self-seeding method in o-dichlorobenzene. The prepared single crystals were characterized by atomic force microscopy (AFM) and transmission electron microscopy. The suitable seeding temperature and the dissolution temperature of the copolymers decreased with the comonomer content. The morphological features, including size, shape, layer number, and thickness, of the single crystals depend on the seeding temperature, crystallization temperature, and, most interestingly, the composition. The size of the single crystals increased with the seeding temperature, while the aspect ratio increased with the crystallization temperature. Higher CL content in the copolymers contributed to multilayered crystals and curved edges. These characteristics were explained by the difference in growth rate and the number of dislocations, both of which are expected to be influenced by the comonomers. As revealed by AFM, the thickness of the single crystals increased with CL contents, which is the opposite of what has been reported for copolymers with high degree of comonomer exclusion. Electron diffraction of the single crystals showed smaller lattice expansion as compared to melt crystallized samples, indicating a lower degree of comonomer inclusion of CL units.

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Crystallization of isomorphic poly(butylene succinate-co butylene fumarate) biopolyester: Single crystals and ring-banded spherulites

Cited by 10 publications

References 45 publications

Manipulating the Co-crystallization Behavior in Isomorphic Copolymers by Introducing a Third Monomeric Unit

Manipulating the Co-crystallization Behavior in Isomorphic Copolymers by Introducing a Third Monomeric Unit

High Molecular Weight Unsaturated Copolyesters Derived from Fully Biobased trans-β-Hydromuconic Acid and Fumaric Acid with 1,4-Butanediol: Synthesis and Thermomechanical Properties

Comonomer Inclusion in Single Crystals of Isodimorphic Random Copolymers of Butylene Succinate and ε-Caprolactone

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