Aliphatic copolyester with isomorphism in limited composition range

Ye, Hai‐Mu; Tang, Yi-Ren; Song, Yan-Kui; Xu, Jun; Guo, Baohua; Zhou, Qiong

doi:10.1016/j.polymer.2014.09.029

Cited by 22 publications

(25 citation statements)

References 49 publications

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“…Succinic acid is non-toxic, soluble in water and can be easily converted to other bulk chemicals such as 1,4-butanediol, gamma-butyrolactone, tetrahydrofuran, adipic acid, n-methylpyrrolidone or linear aliphatic esters [ 26 , 27 ]. Except for their excellent physicochemical properties, these copolyesters provide biodegradability, biocompatibility and easy compostability, predisposing that their good properties will follow to other succinic acid forms [ 28 , 29 ].…”

Section: Introductionmentioning

confidence: 99%

Thermal Degradation Mechanism and Decomposition Kinetic Studies of Poly(Lactic Acid) and Its Copolymers with Poly(Hexylene Succinate)

2021

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Ιn this work, new block poly(lactic acid)-block-poly(hexylene succinate) (PLA-b-PHSu) copolymers, in different mass ratios of 95/05, 90/10 and 80/20 w/w, are synthesized and their thermal and mechanical behavior are studied. Thermal degradation and thermal stability of the samples were examined by Thermogravimetric Analysis (TGA), while thermal degradation kinetics was applied to better understand this process. The Friedman isoconversional method and the “model fitting method” revealed accurate results for the activation energy and the reaction mechanisms (nth order and autocatalysis). Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS) was used to provide more details of the degradation process with PHSu’s mechanism being the β-hydrogen bond scission, while on PLA the intramolecular trans-esterification processes domains. PLA-b-PHSu copolymers decompose also through the β-hydrogen bond scission. The mechanical properties have also been tested to understand how PHSu affects PLA’s structure and to give more information about this new material. The tensile measurements gave remarkable results as the elongation at break increases as the content of PHSu increases as well. The study of the thermal and mechanical properties is crucial, to examine if the new material fulfills the requirements for further investigation for medical or other possible uses that might come up.

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Section: Introductionmentioning

confidence: 99%

Thermal Degradation Mechanism and Decomposition Kinetic Studies of Poly(Lactic Acid) and Its Copolymers with Poly(Hexylene Succinate)

2021

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“…[13][14][15][16] Recently, 1,6-hexanediol has been successfully produced from biomass-derived raw materials, [17][18][19] which would further stimulate the growth of those polyesters. Furthermore, the even-even copolyesters which are synthesized by 1,6-hexanediol and even diacids have been extensively studied, and specifically poly(hexamethylene succinate-co-butylene succinate), 20 poly(hexamethylene sebacate-co-hexamethylene adipate), 21,22 poly(hexamethylene succinate-co-hexamethylene adipate), 23 poly(hexamethylene sebacate-co-hexamethylene suberate), 24 poly(hexamethylene suberate-co-hexamethylene adipate), 24 poly(hexamethylene adipate-co-butylene adipate) 25 , poly(hexamethylene succinate-co-ethylene succinate) 26 and poly(hexamethylene succinate-cohexamethylene fumarate) 27 are representative examples. Up to date, however, the molecular conformation and polymer chain packing arrangement of even-odd copolyesters are still poorly understood.…”

Section: Introductionmentioning

confidence: 99%

“…A deep comparative study between the isodimorphism and isomorphism behaviors from the point of view of the miscibility extent in different comonomers are needed to be carried out in order to comprehensively understand the mechanism of how does the chemical structures of comonomers regulate the cocrystallization behavior of aliphatic copolyesters. Furthermore, the cocrystallization behavior of even-even poly(alkylene dicarboxylate)s have been extensively studied in past, [21][22][23][24][25]27 however, the exploration for the cocrystallization behavior of even-odd poly(alkylene dicarboxylate)s is not nearly enough. As a critical influencing factor, the even-odd effect can exert remarkable influence on the crystal structure and thermal behavior of aliphatic copolyesters.…”

Section: Introductionmentioning

confidence: 99%

Unique isodimorphism and isomorphism behaviors of even-odd poly(hexamethylene dicarboxylate) aliphatic copolyesters

Sang

Wei

et al. 2017

Polymer

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Three series of even-odd aliphatic copolyesters, poly(hexamethylene gluarate-co-hexamethylene pimelate) (PHGP), poly(hexamethylene pimelate-co-hexamethylene azelate) (PHPA), and poly(hexamethylene gluarate-co-hexamethylene azelate) (PHGA), were firstly synthesized derived from even diol of 1,6-hexanediol with odd diacids of glutaric acid, pimelic acid or azelaic acid, respectively. Then, their cocrystallization behaviors were systematically investigated by DSC, WAXD, and POM techniques. It is found that both PHGP and PHPA showed isodimorphism with a characteristic eutectic behavior observed from the plot of melting point versus composition, however, PHGA exhibited strict isomorphism in the whole composition range without a eutectic point. WAXD studies also confirmed the unique isodimorphism and isomorphism behaviors for even-odd copolyesters. The only slight change of the methylene number in alkyl unit of comonomers could generate so large difference in crystallization behavior, which exhibits unique physicochemical properties and structure-properties correlations in such even-odd copolyesters. Furthermore, the difference in cocrystallization miscibility effect of comonomers was analyzed by thermodynamics based on the defect Gibbs energy calculated from Wendling-Suter model. For PHGP and PHPA, the comonomer units have better miscibility in the case of the incorporation of shorter unit into the longer unit crystal than the opposite case. By contrast, in the case of PHGA, the HG and HA units are perfectly miscible in a same crystal lattice with only a little difference in crystal cell dimensions due to the identity of chain conformation of HG and HA units during packing into the crystal lattice. Finally, a model of crystal lattice structure of copolyesters was proposed to better understand the difference in cocrystallization miscibility effect of comonomers between isodimorphism and isomorphism.

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“…Isomorphic crystallization refers to two or more comonomers with similar crystalline structure that crystallize together in a single crystal with only one crystalline phase, irrespective of the composition. In this case the melting temperature of the copolymer increases with comonomer content . In contrast, in isodimorphic crystallization the homopolymers have different crystal structures and their copolymers crystallize in either of the crystal lattices depending on the composition, and often both crystals coexist at some intermediate composition.…”

Section: Resultsmentioning

confidence: 98%

Crystallization and photo‐curing kinetics of biodegradable poly(butylene succinate‐co‐butylene fumarate) short‐segmented block copolyester

Sheikholeslami

Rafizadeh

Taromi

et al. 2016

Polymer International

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Short-segmented block copolymers of poly(butylene succinate-co-butylene fumarate) were synthesized and their crystallinity and crosslinking behavior were investigated. 1 H NMR was used to characterize the microstructure and composition of the copolyesters. Molecular weight determination was performed using gel permeation chromatography. Based on the DSC results all copolyesters were crystalline and the degree of crystallinity of the copolymers did not change with butylene fumarate mole fraction due to co-crystallization of the butylene succinate and butylene fumarate groups. Crosslinked copolyesters showed a lower crystallization rate and degree of crystallinity while the crystallization temperature shifted to higher temperatures compared with uncrosslinked copolyesters due to the formation of nucleating agents by crosslinkages. Photo-DSC was used to investigate the crosslinking kinetics for UV-initiated photo-curing. Three kinetics parameters including the rate constant (k) and the orders of the initiation and propagation reactions (m and n, respectively) were determined for the quenched and unquenched copolymers.

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Aliphatic copolyester with isomorphism in limited composition range

Cited by 22 publications

References 49 publications

Thermal Degradation Mechanism and Decomposition Kinetic Studies of Poly(Lactic Acid) and Its Copolymers with Poly(Hexylene Succinate)

Thermal Degradation Mechanism and Decomposition Kinetic Studies of Poly(Lactic Acid) and Its Copolymers with Poly(Hexylene Succinate)

Unique isodimorphism and isomorphism behaviors of even-odd poly(hexamethylene dicarboxylate) aliphatic copolyesters

Crystallization and photo‐curing kinetics of biodegradable poly(butylene succinate‐co‐butylene fumarate) short‐segmented block copolyester

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