Unique Isodimorphism of Poly(decamethylene succinate-<i>ran</i>-decamethylene fumarate): Large Pseudoeutectic Region and Fantastic Crystallization/Melting Behavior

Ye, Hai‐Mu; Wang, Jing; Wang, Cai-Shui; Li, Hongfang

doi:10.1021/acs.macromol.8b01848

Cited by 22 publications

(25 citation statements)

References 26 publications

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“…These results indicate the existence of weak interaction among AD units, similar to the observation of hydrogenbonding interaction in polymer melt [43,44]. The slight shift of band 1623 cm −1 also confirms the existence of weak interaction [45]. The C≡C groups in AD units plausibly prefer to stack together or aggregate, which could reduce the electron-donating effect and induce the blue-shift of the specific C=O absorption band at 1623 cm −1 .…”

Section: In Situ Ftir Investigationsupporting

confidence: 81%

Poly(butylene succinate-co-butylene acetylenedicarboxylate): Copolyester with Novel Nucleation Behavior

Huang

Chen

et al. 2021

Polymers

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Big spherulite structure and high crystallinity are the two main drawbacks of poly(butylene succinate) (PBS) and hinder its application. In this work, a new type of copolyester poly(butylene succinate-co-butylene acetylenedicarboxylate) (PBSAD) is synthesized. With the incorporation of acetylenedicarboxylate (AD) units into PBS chains, the crystallization temperature and crystallinity are depressed by excluding AD units to the amorphous region. In contrast, the primary nucleation capability is significantly strengthened, without changing the crystal modification or crystallization kinetics, leading to the recovery of total crystallization rate of PBSAD under the same supercooling condition. The existence of specific interaction among AD units is found to be crucial. Although it is too weak to contribute to the melt memory effect at elevated temperature, the interaction continuously strengthens as the temperature falls down, and the heterogeneous aggregation of AD units keeps growing. When the aggregating process reaches a certain extent, it will induce the formation of a significant amount of crystal nuclei. The unveiled nucleation mechanism helps to design PBS copolymer with good performance.

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Section: In Situ Ftir Investigationsupporting

confidence: 81%

Poly(butylene succinate-co-butylene acetylenedicarboxylate): Copolyester with Novel Nucleation Behavior

Huang

Chen

et al. 2021

Polymers

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“…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%

“…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]. (3) Total exclusion behavior: When the repeating units of two homopolymers are dissimilar, the minor comonomer would be completely kept out from the crystalline structure of the main component.…”

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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“…In a strict isomorphic system, the melting point and enthalpy of fusion should change linearly with crystal composition [34][35][36], but our PEO/urea/thiourea IC system does not follow this law. There are two possible reasons: (1) The two types of host small molecules do not distribute homogeneously at the molecular level in the IC crystals, but exhibit the homogeneous mixing for the XRD characterization;…”

Section: Thermodynamic Stability Of the Peo/urea/thiourea Ternary Incmentioning

confidence: 91%

Critical Size of Secondary Nuclei Determined via Nucleation Theorem Reveals Selective Nucleation in Three-Component Co-Crystals

Gao

Guo

2019

Entropy

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The critical size of the secondary nuclei plays an important role in determining the crystal growth rate. In the past, the Nucleation Theorem has been applied to determine the number of molecules in the critical nuclei of a single-component crystal via variation of the crystal growth rate with dilution by the non-crystallizable component. In this work, we extend the method to the three-component co-crystal poly (ethylene oxide)/urea/thiourea inclusion compound. The theoretical crystal growth kinetics were deduced and the dependence of the radial growth rate of the inclusion compound spherulites on the mass fraction of urea in urea/thiourea was measured. The results reveal that the secondary nuclei of the poly (ethylene oxide)/urea/thiourea inclusion compound consist mainly of ethylene oxide repeating units and urea molecules. We propose that only urea molecules and ethylene oxide repeating units are selected to form the secondary nuclei while co-crystallization of the three components happens at the lateral spreading stage. As a result, the composition of the critical secondary nuclei is different from that of the bulk inclusion compound crystals. The work is expected to deepen our understanding of the nucleation of multi-component co-crystals.Entropy 2019, 21, 1032 2 of 12 compound (IC) during its crystal growth process [17]. The PEO/urea ICs consist of guest PEO chains residing in the cavities formed by the host urea molecules [18][19][20][21][22][23][24][25][26]. By replacing a small amount of urea with N,N -dimethyl urea with the PEO concentration unchanged, we could change the rate of secondary nucleation and determine the critical size of the secondary nuclei of the PEO/urea IC β crystal. Here, dimethylurea acted as a dilute agent, which was completely precluded from the crystal lattice. In the PEO/urea IC β crystal, the fixed stoichiometric ratio of 3/2 exists between ethylene oxide (EO) repeating units and urea molecules [22][23][24]27]; the crystallization unit is an entity containing 1 urea and 1.5 EO repeating units. Taking an entity as a unit of crystallization, the inclusion compound can be simplified as one-component crystal. A power-law relationship between the radial growth rate G and the mass fraction x of urea in the total mass of urea and the diluent was observed, and the exponent gave the critical size of the secondary nucleus. Our results revealed that a critical secondary nucleus of the PEO/urea IC β crystal consisted of 4 to 9 entities in the studied temperature range [17].In this work, we attempt to extend the Nucleation Theorem to determine the critical size of the secondary nuclei in a three-component co-crystal system poly (ethylene oxide)/urea/thiourea inclusion compound. Thiourea is an analogue molecule of urea, and as a result, the three components co-crystallize. PEO/urea/thiourea IC prepared by electrospinning was reported by Ye et al. [28], but the crystal growth kinetics were not examined. Here we find that the spherulites of PEO/urea/thiourea IC can form by isothermal crystalliz...

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Unique Isodimorphism of Poly(decamethylene succinate-ran-decamethylene fumarate): Large Pseudoeutectic Region and Fantastic Crystallization/Melting Behavior

Cited by 22 publications

References 26 publications

Poly(butylene succinate-co-butylene acetylenedicarboxylate): Copolyester with Novel Nucleation Behavior

Poly(butylene succinate-co-butylene acetylenedicarboxylate): Copolyester with Novel Nucleation Behavior

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

Critical Size of Secondary Nuclei Determined via Nucleation Theorem Reveals Selective Nucleation in Three-Component Co-Crystals

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