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Polymers
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Biobased Polymers and Their Structure-Property Relationships
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Biobased Polymers and Their Structure-Property Relationships

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Biobased and Biodegradable Polymers".

Deadline for manuscript submissions: closed (15 July 2025) | Viewed by 3451

Special Issue Editors

Dr. Alessandra Longo

E-Mail Website
Guest Editor
Institute for Polymers, Composites and Biomaterials–National Research Council (IPCB-CNR), 700185 Rome, Italy
Interests: crystallization mechanisms of polymers; polylactide; the influence of crystals and chain aggregates on foaming; foam morphology; material thermal properties by simply vary processing conditions
Dr. Maria Laura Di Lorenzo

E-Mail Website
Guest Editor
National Research Council (CNR)—Institute of Polymers, Composites and Biomaterials (IPCB), Via Campi Flegrei, 34, 80078 Pozzuoli, NA, Italy
Interests: advanced thermal analysis; polymer crystallization; melting; glass transition; structure-property relationships: the three-phase structure of semicrystalline polymers; biodegradable polymers; polymer blends
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Plastic pollution and the reduction in the use of oil-derived plastics has become a daily theme in social and scientific debate, leading to advancements in the development of biobased polymers. These materials, produced from annually renewable resources, are promising candidates to be eco-friendly substitutes for oil-based plastics, contributing to the global effort to create a circular economy and minimize the environmental footprint.

Huge research efforts have focused on improving biobased polymer properties to achieve the versatility and advantageous characteristics that typify widely used diffused oil-based plastics. This Special Issue considers this context, delving into the relationship between the structures of biobased polymers based on processing and their properties, which determine their applications across various industrial fields.

Here, we present an overview of recent developments in biobased polymer research to shed light on the links between polymers’ architectures and their mechanical, chemical and physical properties.

Research articles, reviews, and short communications focused on the various aspects of structure–property relationships of biobased polymers are welcome, with our aim being to push the boundaries of the sustainability of polymer science.

Dr. Alessandra Longo
Dr. Maria Laura Di Lorenzo
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 250 words) can be sent to the Editorial Office for assessment.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • biobased polymers
  • thermal properties
  • mechanical performance
  • barrier properties
  • structure–processing–properties triangle

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Published Papers (3 papers)

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Research

17 pages, 6012 KB  
Article
Relaxation of Shear-Induced Orientation and Textures in Semi-Dilute DNA Solutions
by Scarlett Elizabeth López-Alvarez, François Caton, Denis C. D. Roux, Félix Armando Soltero Martínez, Florian Scholkopf, Frédéric Nallet, Guillermo Toriz, Arnaud Saint-Jalmes, Marguerite Rinaudo and Lourdes Mónica Bravo-Anaya
Polymers 2025, 17(18), 2452; https://doi.org/10.3390/polym17182452 - 10 Sep 2025
Viewed by 881
Abstract
Recent studies on semi-dilute Calf-Thymus DNA (CT-DNA) solutions have revealed the presence of birefringence and small-scale textures influenced by shear and ionic strength. In this study, we investigate these phenomena on the same solutions to elucidate the underlying shear-induced supramolecular organization and relaxation [...] Read more.
Recent studies on semi-dilute Calf-Thymus DNA (CT-DNA) solutions have revealed the presence of birefringence and small-scale textures influenced by shear and ionic strength. In this study, we investigate these phenomena on the same solutions to elucidate the underlying shear-induced supramolecular organization and relaxation dynamics using rheo-birefringence, rheology, and rheo-SAXS (small-angle X-ray scattering). Static SAXS confirmed concentration-dependent inter-chain correlations in the 15–25 nm range, while rheology revealed a slipping yield-stress behavior. Oscillatory strain sweep and steady state rheo-birefringence experiments correlated the appearance of textures with the onset of flow and a stress plateau observed over a shear rate range from approximately 1 to 1000 s−1. Transient rheo-birefringence and rheo-SAXS revealed two distinct relaxation mechanisms on well-separated time scales: a fast process lasting a few seconds, inversely proportional to the shear rate, consistent with the orientational relaxation of DNA segments on a ~20 nm scale; and a slower relaxation over tens of seconds, independent of the shear rate, associated with the disappearance of textures, and attributed to a diffusive process. These findings provide significant insights into the mechanisms governing DNA organization and dynamics in semi-dilute solutions under flow and highlight the need for temporally resolved start-up rheo-SAXS and rheo-birefringence measurements, as well as theoretical models describing these processes across various spatial and temporal scales. Full article
(This article belongs to the Special Issue Biobased Polymers and Their Structure-Property Relationships)
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14 pages, 2390 KB  
Article
Synthesis, Thermal Behavior and Mechanical Property of Fully Biobased Poly(hexamethylene Furandicarboxylate-co-hexamethylene Thiophenedicarboxylate) Copolyesters
by Haidong Yang, Shiwei Feng and Zhaobin Qiu
Polymers 2025, 17(14), 1997; https://doi.org/10.3390/polym17141997 - 21 Jul 2025
Viewed by 808
Abstract
In order to increase the toughness of poly(hexamethylene furandicarboxylate) (PHF) without severely compromising its strength at break, novel biobased poly(hexamethylene furandicarboxylate-co-hexamethylene thiophenedicarboxylate) (PHFTh) copolyesters and their parent homopolyesters, PHF and poly(hexamethylene thiophenedicarboxylate), were successfully synthesized through melt polycondensation in this research. [...] Read more.
In order to increase the toughness of poly(hexamethylene furandicarboxylate) (PHF) without severely compromising its strength at break, novel biobased poly(hexamethylene furandicarboxylate-co-hexamethylene thiophenedicarboxylate) (PHFTh) copolyesters and their parent homopolyesters, PHF and poly(hexamethylene thiophenedicarboxylate), were successfully synthesized through melt polycondensation in this research. Despite the variation in their compositions, all the PHFTh copolyesters exhibited excellent thermal stability. The PHFTh copolyesters were semicrystalline in nature, showing the lowest eutectic melting points and isodimorphism behaviors over the whole composition range. As the hexamethylene thiophenedicarboxylate (HTh) unit content increased, the glass transition temperature of the copolyesters gradually decreased, while the chain mobility was accordingly enhanced. Therefore, the introduction of the HTh unit significantly increased the elongation at break of the PHFTh, achieving a balance between strength and toughness. The biobased PHFTh copolyesters showed tunable thermal behaviors and excellent mechanical properties and may find potential end uses from a practical application viewpoint. Full article
(This article belongs to the Special Issue Biobased Polymers and Their Structure-Property Relationships)
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17 pages, 4188 KB  
Article
Novel Biobased Double Crystalline Poly(butylene succinate)-b-poly(butylene 2,5-thiophenedicarboxylate) Multiblock Copolymers with Excellent Thermal and Mechanical Properties and Enhanced Crystallization Behavior
by Haidong Yang, Shiwei Feng and Zhaobin Qiu
Polymers 2025, 17(4), 450; https://doi.org/10.3390/polym17040450 - 8 Feb 2025
Cited by 3 | Viewed by 1179
Abstract
Novel biobased double crystalline poly(butylene succinate)-b-poly(butylene 2,5-thiophenedicarboxylate) (PBS-b-PBTh) multiblock copolyesters with excellent thermal and mechanical properties were prepared from two hydroxyl-terminated PBS-diol and PBTh-diol prepolymers via a chain extension reaction. Both PBS and PBTh segments were semicrystalline, with the [...] Read more.
Novel biobased double crystalline poly(butylene succinate)-b-poly(butylene 2,5-thiophenedicarboxylate) (PBS-b-PBTh) multiblock copolyesters with excellent thermal and mechanical properties were prepared from two hydroxyl-terminated PBS-diol and PBTh-diol prepolymers via a chain extension reaction. Both PBS and PBTh segments were semicrystalline, with the aliphatic PBS segment being the soft segment while the aromatic PBTh segment was the hard segment. In the case of PBS-b-PBTh, the two segments were partially miscible in the amorphous region; moreover, the melting temperature of each segment still remained very high compared with that of each homopolyester PBS and PBTh. The melt crystallization behavior of both segments was enhanced in the case of PBS-b-PBTh, which was attributed to different mechanisms. The crystal structure study revealed that both segments crystallized separately and showed the characteristic diffraction peaks, respectively. Compared with that of PBS, PBS-b-PBTh displayed a significant increase in the elongation at break while still maintaining a relatively high break strength. This research provides some new insights to synthesize biobased polyesters with excellent thermal and mechanical properties, which should be interesting from a sustainable viewpoint. Full article
(This article belongs to the Special Issue Biobased Polymers and Their Structure-Property Relationships)
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