Application of SSA thermal fractionation and X-ray diffraction to elucidate comonomer inclusion or exclusion from the crystalline phases in poly(butylene succinate-<i>ran</i>-butylene azelate) random copolymers

Arandia, Idoia; Múgica, Agurtzane; Zubitur, Manuela; Iturrospe, Amaia; Arbe, Arantxa; Liu, Guoming; Wang, Dujin; Mincheva, Rosica; Dubois, Philippe; Müller, Alejandro J.

doi:10.1002/polb.24146

Cited by 25 publications

(33 citation statements)

References 52 publications

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“…Other systems lie somewhere between. A study of a poly(butylene succinate‐ ran ‐butylene azelate) showed, by SAXS, an increase in lamellar thickness, as well as an increase in interlamellar amorphous thickness, which they associated with some degree of comonomer inclusion in the crystals, which they could adjust with suitable thermal treatments . This greater lamellar thickness at central compositions (for a given undercooling) might be associated with a smaller free energy change on crystallization than for the homopolymers due to the more random nature of the crystal structure.…”

Section: Resultsmentioning

confidence: 99%

“…A study of a poly(butylene succinate-ran-butylene azelate) showed, by SAXS, an increase in lamellar thickness, as well as an increase in interlamellar amorphous thickness, which they associated with some degree of comonomer inclusion in the crystals, which they could adjust with suitable thermal treatments. 51 This greater lamellar thickness at central compositions (for a given undercooling) might be associated with a smaller free energy change on crystallization than for the homopolymers due to the more random nature of the crystal structure. Rather than a random incorporation of nonmatching monomers into the crystal structure, the PET/PEN system is thought, under suitable crystallization conditions, to cocrystallize by sequence matching with the local rejection of nonmatching sequences, as postulated by Lu and Windle.…”

Section: Crystallization Morphologymentioning

confidence: 99%

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Synthesis of statistical PET/PEN random block copolymers and their crystallizability in the bulk and at the surface

Shinotsuka

Assender

Claridge

2018

J of Applied Polymer Sci

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A series of PET/PEN copolyesters were synthesized by molten transesterification. The degree of randomness and the sequence length of the copolymers were determined by 1H NMR spectroscopy, and the changes in the bulk glass transition temperature (TgB), bulk crystallization temperature (TcB), and bulk melting temperature (TmB) were observed by DSC. A clear relationship was obtained between the observed enthalpy of melting (ΔHm) and degree of randomness (B), and TmB was suppressed for the midcompositions. As with their homopolymer counterparts, there was significant depression in crystallization temperature at the surface (TcS) of the random/block copolymers compared with the bulk, and so surface‐localized crystallization could be induced in spin‐coated thick films (thickness ranging from ca. 400 to 700 nm) by annealing at a temperature in which the surface region is mobile, but the bulk is not. The formation of these clear surface crystals allows the morphology to be directly imaged by AFM, and we observed that the crystallizability and the lamellar morphology of the surface crystals deviated from those of the original homopolymers, depending on the mixing ratio of PET/PEN and degree of randomness. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46515.

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Section: Resultsmentioning

confidence: 99%

Section: Crystallization Morphologymentioning

confidence: 99%

Synthesis of statistical PET/PEN random block copolymers and their crystallizability in the bulk and at the surface

Shinotsuka

Assender

Claridge

2018

J of Applied Polymer Sci

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“… 39 On the other hand, SSA can be exploited also for the characterization of linear polymers, where fractionation occurs only for chain length differences, even if the fractionation is less efficient. 54 Thermal fractionation experiments on pCBT were performed setting as first T s temperature the T s,ideal determined in self-nucleation experiments, i.e., T s = 227 °C. The thermal protocol consisted in seven T s , from 227 °C down to 197 °C.…”

Section: Results and Discussionmentioning

confidence: 99%

Supernucleation and Orientation of Poly(butylene terephthalate) Crystals in Nanocomposites Containing Highly Reduced Graphene Oxide

et al. 2017

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The ring-opening polymerization of cyclic butylene terephthalate into poly(butylene terephthalate) (pCBT) in the presence of reduced graphene oxide (RGO) is an effective method for the preparation of polymer nanocomposites. The inclusion of RGO nanoflakes dramatically affects the crystallization of pCBT, shifting crystallization peak temperature to higher temperatures and, overall, increasing the crystallization rate. This was due to a supernucleating effect caused by RGO, which is maximized by highly reduced graphene oxide. Furthermore, combined analyses by differential scanning calorimetry (DSC) experiments and wide-angle X-ray diffraction (WAXS) showed the formation of a thick α-crystalline form pCBT lamellae with a melting point of ∼250 °C, close to the equilibrium melting temperature of pCBT. WAXS also demonstrated the pair orientation of pCBT crystals with RGO nanoflakes, indicating a strong interfacial interaction between the aromatic rings of pCBT and RGO planes, especially with highly reduced graphene oxide.

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“…particular of random copolymers in which the crystallizable component is frequently interrupted (depending on composition) by the second component (e.g., random isodimorphic copolymers [5] ).…”

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confidence: 99%

“…The SSA fractionated material contains lamellae with a distribution of thickness (and a corresponding distribution of melting points) that is proportional to the defect or comonomer distribution along the crystallizable chains. [5] Such size distribution can be estimated, in some cases, e.g., multiblock copolymers. [6] In the case of polyolefins, in which the SSA technique has been widely used, the SSA has been recently used to perform branching analysis [7,8] and photodegradation studies, [9] among others.…”

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confidence: 99%

SSA fractionation of thermoplastic polyurethanes

Fernández-d’Arlas

Maiz

Pérez-Camargo

et al. 2020

Polymer Crystallization

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The successive self-nucleation and annealing (SSA) thermal fractionation technique has been applied for the first time to thermoplastic polyurethanes (TPUs). The changes in structure and morphology before and after SSA fractionation were monitored by Differential Scanning Calorimetry (DSC), in situ real-time Small and Wide-angle X-ray scattering synchrotron experiments (SAXS/WAXS) and Atomic Force Microscopy (AFM). SSA applies a series of successive cooling and heating runs to a self-nucleated sample that promotes the creation of a series of thermal fractions in the TPUs with a specific lamellar thicknesses and melting point distribution thanks to the multi-block structure of TPUs. The SSA fractionated samples experienced a general increase in lamellar thickness that has been revealed by both AFM and SAXS and a distribution of lamellar thickness estimated by DSC and AFM. The average lamellar thickness of SSA fractionated samples has been estimated by SAXS, AFM, and DSC. The values obtained are in quantitative agreement (within the errors involved in the techniques) when considering that phase segregation in the TPU samples has been promoted by crystallization. The refined crystalline structure obtained after SSA produced a number of clear WAXS reflections, as compared to the unfractionated materials, facilitating the determination of the TPUs crystallinity degree by WAXS.

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Application of SSA thermal fractionation and X-ray diffraction to elucidate comonomer inclusion or exclusion from the crystalline phases in poly(butylene succinate-ran-butylene azelate) random copolymers

Cited by 25 publications

References 52 publications

Synthesis of statistical PET/PEN random block copolymers and their crystallizability in the bulk and at the surface

Synthesis of statistical PET/PEN random block copolymers and their crystallizability in the bulk and at the surface

Supernucleation and Orientation of Poly(butylene terephthalate) Crystals in Nanocomposites Containing Highly Reduced Graphene Oxide

SSA fractionation of thermoplastic polyurethanes

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