Crystallization of poly(butylene-2,6-naphthalate-co-butylene adipate) copolymers: regulating crystal modification of the polymorphic parent homopolymers and biodegradation

Papageorgiou, George Z.; Tsanaktsis, Vasilios; Bikiaris, Dimitrios N.

doi:10.1039/c4ce00651h

Cited by 34 publications

(28 citation statements)

References 68 publications

(72 reference statements)

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“…Similarly, the enthalpy of melting in the bulk (Δ H m ) of the copolymers [Figure (d)] decreases as the PET/PEN component approaches 50/50, and as the reaction period increases. These changes are also associated with the decrease in sequence length, and consistent with the decrease in crystallinity associated with the increase of randomness . For Copolymers 1, 2, and 13, it is expected that Δ H m would be nearly zero in accordance with the Δ H c results above, and indeed these samples did not show a melting peak in the DSC trace.…”

Section: Resultssupporting

confidence: 75%

“…The authors associated this with the soft segment, being rejected from the crystals, modifying the interfacial energy and local chain diffusivity. In the case of PBN/poly(butylene adipate) copolymer system, similar crystalline morphology caused by limited incorporation of the minor comonomer in the crystals was reported . PET/PEI copolymers were reported to show loosely organized crystals with a vague boundary, and in the case of PTT/PEOT, AFM imaging was not possible because of the rejected soft component surrounding the crystals.…”

Section: Resultsmentioning

confidence: 52%

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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: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 52%

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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“…In isodimorphism two crystalline phases and pseudo-eutectic behavior are observed. Isodimorphism has been observed in most cases of random copolymers [47][48][49] .…”

Section: Introductionmentioning

confidence: 99%

Biobased poly(ethylene furanoate-co-ethylene succinate) copolyesters: solid state structure, melting point depression and biodegradability

et al. 2016

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Poly(ethylene furanoate) (PEF) is a fully bio-based polyester with unique gas barrier properties, considered an alternative to poly(ethylene terephthalate) (PET) in food packaging applications. However, it is not biodegradable. For this reason copolymerization with the aliphatic succinic acid monomer, was followed. The respective poly(ethylene furanoate-co-ethylene succinate) (PEFSu) copolymers were prepared via melt polycondensation from 2,5-dimethylfuran-dicarboxylate, succinic acid and ethylene glycol at different ratios.1 HNMR spectroscopy showed the copolymers are random. The crystallization and melting of the copolymers were thoroughly evaluated. Isodimorphic cocrystallization was concluded from both the 2 WAXD patterns and the minimum in the plots of melting temperature versus composition. The pseudo-eutectic melting point corresponded to an ethylene succinate content of about 30 mol%. The enzymatic hydrolysis tests using of Rhizopus delemarand Pseudomonas Cepacia lipase, revealed that the copolymers with up to 50 mol% ES units show measurable weight loss rates. For higher ES content, the copolymers showed fast hydrolysis.

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“…From structure point of view, the partial inclusion of a comonomer in the homopolymer crystal, often provokes lattice distortions, due to the dissimilar molar volumes of the different repetitive units. As a matter of fact, this can result in a comonomer content‐dependent increase or decrease of the interplanar distance with respect to that of the homopolymer . In Figure , the spacings of several crystallographic planes of both α ‐ and β ′‐forms are plotted against the DEN molar content.…”

Section: Resultsmentioning

confidence: 99%

“…As a matter of fact, this can result in a comonomer contentdependent increase or decrease of the interplanar distance with respect to that of the homopolymer. [33] In Figure 8, the spacings of several crystallographic planes of both αand β 0 -forms are plotted against the DEN molar content. No meaningful variations of the interplanar distances with comonomer concentration in the chain are noticed, regardless of the specific plane or polymorph.…”

Section: Although Frommentioning

confidence: 99%

Crystallization of poly(butylene 2,6‐naphthalate) containing diethylene 2,6‐naphthalate constitutional defects

Ding

Soccio

Lotti

et al. 2019

Polymer Crystallization

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The effect of presence of up to 30 mol% diethylene 2,6‐naphthalate (DEN) constitutional defects on the crystallization kinetics and morphology of poly(butylene 2,6‐naphthalate) (PBN) was investigated by differential scanning calorimetry, fast scanning chip calorimetry, polarized‐light optical microscopy, and wide‐angle X‐ray scattering (WAXS). The results indicate that the crystallization behavior of butylene/DEN random copolymers [P(B xDE yN)] is analogous to the PBN homopolymer: at low supercooling direct crystallization from the melt occurs, while at lower crystallization temperature/higher cooling rates, the formation of a liquid crystalline phase precedes the development of the ultimately stable crystal, confirming the validity of Ostwald's rule of stages also for random copolymers. However, the incorporation of DEN counits into the polymer chains retards both crystal and liquid‐crystal formation proportionally to the DEN content. WAXS analysis suggests the exclusion of DEN counits from PBN crystals. Thus, the lower crystallization rate in the copolymers can be associated, with the filtering of crystallizable chain segments at the crystal growth front.

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Crystallization of poly(butylene-2,6-naphthalate-co-butylene adipate) copolymers: regulating crystal modification of the polymorphic parent homopolymers and biodegradation

Abstract: Random PBNAd copolymers were synthesized. They showed isodimorphic cocrystallization. β PBN crystals were formed in copolymers with high BN content.

Cited by 34 publications

References 68 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

Biobased poly(ethylene furanoate-co-ethylene succinate) copolyesters: solid state structure, melting point depression and biodegradability

Crystallization of poly(butylene 2,6‐naphthalate) containing diethylene 2,6‐naphthalate constitutional defects

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