Molecular packing and crystalline morphologies of biodegradable poly(alkylene dicarboxylate)s derived from 1,6-hexanediol

Gestí, Sebastià; Almontassir, Ahmed; Casas, María Teresa; Puiggalı́, Jordi

doi:10.1016/j.polymer.2004.10.039

Cited by 29 publications

(36 citation statements)

References 25 publications

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“…Nevertheless, the streaks and the relatively weak reflections observed in some layer lines (see red circles in Figure 9) suggest a cell with greater dimensions as previously reported for some poly(alkylene dicarboxylate)s [26][27][28][29]. Note also that these off meridional reflections can clearly be detected in diffraction patterns recorded from oriented films due to their greater intensity (Figure 10).…”

Section: X-ray Fiber Diffraction Data Ofsupporting

confidence: 77%

“…Electron diffraction patterns of such polyesters indicated that the unit cells projected along the chain axis were rectangular and contained only two molecular segments, the parameters being close to a = 0.500-0.504 nm, and b = 0.73-0.75 nm. However, recent works on some 1,4-butanediol [26] and 1,6-hexanediol [27] derivatives have revealed the existence of unit cells where the b-axis parameter was doubled. These more complex structures were characterized by the fact that neighbouring molecules along the b-axis were only equivalent in chain axis projection.…”

Section: Introductionmentioning

confidence: 99%

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Preferential Incorporation of Azelaic Acid Units into the Crystalline Phase of the Copoly(Alkylene Dicarboxylate) Derived from 1,9-Nonanediol and an Equimolar Mixture of Pimelic and Azelaic Acids

2015

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The crystalline structure of two biodegradable odd-odd polyesters (i.e., poly(nonamethylene pimelate) (PES 9,7) and poly(nonamethylene azelate) (PES 9,9)) was investigated by means of electron and X-ray diffraction of single crystals and oriented fibers, respectively. Truncated rhombic crystals were obtained with an aspect ratio that was strongly depended on the supercooling degree. The crystalline structure of both homopolyesters was defined by an orthorhombic P2 1 ab space group and a large unit cell containing four molecular segments with an all-trans conformation. Nevertheless, the structure in the chain axis projection was equivalent to a simpler cell containing only two segments. Crystalline lamellae were effectively degraded by lipases, starting the enzymatic attack on the lamellar surfaces. The random copolymer constituted by an equimolar amount of pimelate and azelate units (COPES 9,7/9) crystallized according to regular lamellae with a similar molecular arrangement in the chain axis projection. The structure of this copolymer was preferably conditioned by the azelate component as could be deduced from both, diffraction and spectroscopic data. Analysis of small angle X-ray scattering patterns pointed out that less crystalline lamellae with higher amorphous thickness had developed in the copolymer. This feature was interpreted as a consequence of the preferential incorporation of pimelate comonomer units in the folding surface.Polymers 2015, 7 1872

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Section: X-ray Fiber Diffraction Data Ofsupporting

confidence: 77%

Section: Introductionmentioning

confidence: 99%

Preferential Incorporation of Azelaic Acid Units into the Crystalline Phase of the Copoly(Alkylene Dicarboxylate) Derived from 1,9-Nonanediol and an Equimolar Mixture of Pimelic and Azelaic Acids

2015

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“…For the melting point this trend is confirmed by the data in some literature. For example, the 4-8, 4-10, and 4-12 samples have T m equal to 61, 63, and 71 °C respectively [20]; 6-8 and 6-12 melt at 66 and 72 °C, respectively [19], i.e. T m increases with the increment of the number of the -(CH 2 )-groups in the diacid unit.…”

Section: Nonisothermal Analysis: Crystallization and Melting Processesmentioning

confidence: 99%

The effect of aliphatic chain length on thermal properties of poly(alkylene dicarboxylate)s

et al. 2007

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Some poly(alkylene dicarboxylate)s, derived from ethanediol or 1,4-butanediol and different diacids, have been synthesized and analyzed by DSC to determine the correlations existing between the thermal properties and the length of the aliphatic chain. The polymers show crystallization and melting temperatures and enthalpies which increase as the polymethylene segments lengthen, due to the formation of more stable crystals. The samples derived from ethanediol are peculiar; they show reorganization processes during the melting and the melting temperatures are notably higher with respect to those of the other polyesters. This behavior is discussed. Isothermal analysis highlights that poly(alkylene dicarboxylate)s are fast crystallizing polymers. The Avrami analysis suggests a crystallization mechanism characterized by heterogeneous nucleation and three dimensional growth; secondary crystallizations is present only in the samples characterized by short -(CH 2 )-sequences, due to the reorganization of less perfect crystalline forms. A comparative study between the crystallization rates as a function of the undercooling is reported.

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“…The SAXS long period peak is clearly seen at a value of the scattering vector, q = 2sin [21][22][23][24]. The intensity of the indicated reflections increased sharply at the beginning of crystallization and slowly after a short time interval.…”

Section: Samples By Time-resolved Saxs/waxd Experimentsmentioning

confidence: 97%

“…Poly(alkylene dicarboxylate)s, a specific group within polyesters, are gaining increasing attention because the marketing of polybutylene succinate, which is supplied by Showa High Polymers as Bionolle TM and is characterized by a relatively low production cost, easy processability and good thermal and mechanical properties [12,14]. Several works in the literature deal with the structure and crystallization process of poly(alkylene dicarboxylate)s [15][16][17][18][19][20][21][22][23][24][25]. It was demonstrated that their molecular conformation and packing arrangement depend on the length of the polyalkylene segment and the parity of chemical units involved (i.e.…”

Section: Introductionmentioning

confidence: 99%

Study on the crystallization of poly(alkylene dicarboxylate)s derived from 1,9-nonanediol and mixtures with different ratios of azelaic acid and pimelic acid units

2015

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Polyalkylene dicarboxylates derived from 1,9-nonanediol and mixtures with different ratios of pimelic acid and azelaic acid were synthesized by thermal polycondensation.All samples had a high degree of crystallinity although it was found to decrease with the comonomer content.Crystallization kinetics of the two homopolymers and the copolymer with the eutectic composition was studied by calorimetric and optical microscopy techniques. Similar Avrami parameters were determined for the three samples and a spherulitic growth with heterogeneous nucleation was deduced. Spherulites showed negative birefringence and a fibrillar or ringed texture depending on the sample. Furthermore, clear differences were found in the primary nucleation density, the spherulitic growth rate and even in the secondary nucleation constant deduced from the Lauritzen-Hoffman treatment.The three studied samples had a similar arrangement of molecular chains, and consequently their WAXD patterns showed the same strong reflections related to the molecular packing. SAXS data revealed that a lamellar insertion mechanism was characteristic for non-isothermal crystallization from the melt. In addition, significant differences were found between the crystal lamellar thicknesses of the homopolymer and copolymer samples. Diffraction and spectroscopic data suggested that the lamellar crystals of the eutectic copolymer were mainly constituted by azelate units whereas the pimelate units were preferentially located in the amorphous regions including the interlamellar amorphous layer associated with the chain folds.

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Molecular packing and crystalline morphologies of biodegradable poly(alkylene dicarboxylate)s derived from 1,6-hexanediol

Cited by 29 publications

References 25 publications

Preferential Incorporation of Azelaic Acid Units into the Crystalline Phase of the Copoly(Alkylene Dicarboxylate) Derived from 1,9-Nonanediol and an Equimolar Mixture of Pimelic and Azelaic Acids

Preferential Incorporation of Azelaic Acid Units into the Crystalline Phase of the Copoly(Alkylene Dicarboxylate) Derived from 1,9-Nonanediol and an Equimolar Mixture of Pimelic and Azelaic Acids

The effect of aliphatic chain length on thermal properties of poly(alkylene dicarboxylate)s

Study on the crystallization of poly(alkylene dicarboxylate)s derived from 1,9-nonanediol and mixtures with different ratios of azelaic acid and pimelic acid units

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