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Synthesis, Properties and Applications of Biobased Polymers

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Green Chemistry".

Deadline for manuscript submissions: closed (15 August 2023) | Viewed by 16841

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Prof. Dr. Dimitrios Bikiaris

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Laboratory of Chemistry and Technology of Polymers and Colors, Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki GR-54124, Greece
Interests: synthesis and characterization of polyesters; development of biobased polymers; biodegradable polymers; polymer composites and nanocomposites; synthesis and characterization of copolymers; polymer blends; recycling of polymers with various techniques; enzymatic hydrolysis studies; modification of natural polymers; polymers for wastewater treatment pollutant removal; polymers for tissue engineering and drug delivery applications; drug–polymer solid dispersions; drug targeting; drug nanoencapsulation and microencapsulation
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Dear Colleagues,

According to the IUPAC definition, a biobased polymer is a polymer derived from biomass or issued from monomers derived from biomass and which, at some stage in its processing into finished products, can be shaped by flow. Biobased polymers have gained a large amount of interest in the last few decades due to the increased need to phase out fossil resources and reduce their impacts on global warming. These pressures have led to the development and growth of a new economy known as the bioeconomy. The first biobased polymers introduced to the markets were poly(hydroxy alkanoate)s produced in the 1980s in bioreactors, and poly(lactic acid) is today the most important synthesized biobased polymer.

Historically, the raw materials used in industry have mostly been renewable, with the utilization of biomass and coal being equal about 100 years ago. In the 1920s, coal tar-based materials took the lead, with their use reaching its zenith around 1930. Thereafter, the rise of fossil gas and oil was irresistible, eliminating coal nearly completely and reducing renewable feedstocks to very modest levels. Since 2000, there has been a great interest again for materials derived from renewable resources, such as biomass, and this demand will certainly increase over the next few years. There are two different strategies for producing bioplastics from biomass. In strategy (i), the biorefining of biomass is employed to produce synthetic crude oil (“renewable oil”), biobased additives and green monomers. In strategy (ii), these monomers are used for effective polymer manufacturing processes.

Innovations in the development of biobased and biodegradable polymers is believed to be one of the best ways for the polymer industry to address environmental issues. For this reason, biodegradable polymers are used in various applications, including biomedicine, drug delivery, additive technologies, agriculture, film, fibers, packaging, the automotive industry, etc. Therefore, it is well known that the future of plastics is going to be green.

This Special Issue aims to collect novel research works and reviews on biobased polymers that have been conducted in the last few years on the synthesis, characterization and application of biobased polymers.

Prof. Dr. Dimitrios Bikiaris
Guest Editor

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Keywords

biobased polymers
biobased monomers
synthetic biobased polymers
biopolymers
eco-friendly polymers
nanocomposites
biodegradability
biopolymer applications

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Published Papers (8 papers)

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Research

24 pages, 5446 KiB

Open AccessArticle

Toughening Effect of 2,5-Furandicaboxylate Polyesters on Polylactide-Based Renewable Fibers

by Giulia Fredi, Edoardo Zonta, Alessandro Dussin, Dimitrios N. Bikiaris, George Z. Papageorgiou, Luca Fambri and Andrea Dorigato

Molecules 2023, 28(12), 4811; https://doi.org/10.3390/molecules28124811 - 16 Jun 2023

Cited by 6 | Viewed by 1477

Abstract

This work presents the successful preparation and characterization of polylactide/poly(propylene 2,5-furandicarboxylate) (PLA/PPF) and polylactide/poly(butylene 2,5-furandicarboxylate) (PLA/PBF) blends in form of bulk and fiber samples and investigates the influence of poly(alkylene furanoate) (PAF) concentration (0 to 20 wt%) and compatibilization on the physical, thermal, and mechanical properties. Both blend types, although immiscible, are successfully compatibilized by Joncryl (J), which improves the interfacial adhesion and reduces the size of PPF and PBF domains. Mechanical tests on bulk samples show that only PBF is able to effectively toughen PLA, as PLA/PBF blends with 5–10 wt% PBF showed a distinct yield point, remarkable necking propagation, and increased strain at break (up to 55%), while PPF did not show significant plasticizing effects. The toughening ability of PBF is attributed to its lower glass transition temperature and greater toughness than PPF. For fiber samples, increasing the PPF and PBF amount improves the elastic modulus and mechanical strength, particularly for PBF-containing fibers collected at higher take-up speeds. Remarkably, in fiber samples, plasticizing effects are observed for both PPF and PBF, with significantly higher strain at break values compared to neat PLA (up to 455%), likely due to a further microstructural homogenization, enhanced compatibility, and load transfer between PLA and PAF phases following the fiber spinning process. SEM analysis confirms the deformation of PPF domains, which is probably due to a “plastic–rubber” transition during tensile testing. The orientation and possible crystallization of PPF and PBF domains contribute to increased tensile strength and elastic modulus. This work showcases the potential of PPF and PBF in tailoring the thermo-mechanical properties of PLA in both bulk and fiber forms, expanding their applications in the packaging and textile industry. Full article

(This article belongs to the Special Issue Synthesis, Properties and Applications of Biobased Polymers)

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11 pages, 2285 KiB

Open AccessArticle

Highly Flexible Poly(1,12-dodecylene 5,5′-isopropylidene-bis(ethyl 2-furoate)): A Promising Biobased Polyester Derived from a Renewable Cost-Effective Bisfuranic Precursor and a Long-Chain Aliphatic Spacer

by Sami Zaidi, Abdelkader Bougarech, Majdi Abid, Souhir Abid, Armando J. D. Silvestre and Andreia F. Sousa

Molecules 2023, 28(10), 4124; https://doi.org/10.3390/molecules28104124 - 16 May 2023

Cited by 4 | Viewed by 1702

Abstract

The continuous search for novel biobased polymers with high-performance properties has highlighted the role of monofuranic-based polyesters as some of the most promising for future plastic industry but has neglected the huge potential for the polymers’ innovation, relatively low cost, and synthesis easiness of 5,5′-isopropylidene bis-(ethyl 2-furoate) (DEbF), obtained from the platform chemical, worldwide-produced furfural. In this vein, poly(1,12-dodecylene 5,5′-isopropylidene -bis(ethyl 2-furoate)) (PDDbF) was introduced, for the first time, as a biobased bisfuranic long-chain aliphatic polyester with an extreme flexibility function, competing with fossil-based polyethylene. This new polyester in-depth characterization confirmed its expected structure (FTIR, ¹H, and ¹³C NMR) and relevant thermal features (DSC, TGA, and DMTA), notably, an essentially amorphous character with a glass transition temperature of −6 °C and main maximum decomposition temperature of 340 °C. Furthermore, PDDbF displayed an elongation at break as high as 732%, around five times higher than that of the 2,5-furandicarboxylic acid counterpart, stressing the unique features of the bisfuranic class of polymers compared to monofuranic ones. The enhanced ductility combined with the relevant thermal properties makes PDDbF a highly promising material for flexible packaging. Full article

(This article belongs to the Special Issue Synthesis, Properties and Applications of Biobased Polymers)

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16 pages, 2934 KiB

Open AccessArticle

New Random Aromatic/Aliphatic Copolymers of 2,5-Furandicarboxylic and Camphoric Acids with Tunable Mechanical Properties and Exceptional Gas Barrier Capability for Sustainable Mono-Layered Food Packaging

by Giulia Guidotti, Michelina Soccio, Massimo Gazzano, Valentina Siracusa and Nadia Lotti

Molecules 2023, 28(10), 4056; https://doi.org/10.3390/molecules28104056 - 12 May 2023

Cited by 3 | Viewed by 1645

Abstract

High molecular weight, fully biobased random copolymers of 2,5-furandicarboxylic acid (2,5-FDCA) containing different amounts of (1R, 3S)-(+)-Camphoric Acid (CA) have been successfully synthesized by two-stage melt polycondensation and compression molding in the form of films. The synthesized copolyesters have been first subjected to molecular characterization by nuclear magnetic resonance spectroscopy and gel-permeation chromatography. Afterward, the samples have been characterized from a thermal and structural point of view by means of differential scanning calorimetry, thermogravimetric analysis, and wide-angle X-ray scattering, respectively. Mechanical and barrier properties to oxygen and carbon dioxide were also tested. The results obtained revealed that chemical modification permitted a modulation of the abovementioned properties depending on the amount of camphoric co-units present in the copolymers. The outstanding functional properties promoted by camphor moieties addition could be associated with improved interchain interactions (π-π ring stacking and hydrogen bonds). Full article

(This article belongs to the Special Issue Synthesis, Properties and Applications of Biobased Polymers)

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18 pages, 3483 KiB

Open AccessArticle

Hytrel-like Copolymers Based on Furan Polyester: The Effect of Poly(Butylene Furanoate) Segment on Microstructure and Mechanical/Elastic Performance

by Magdalena Kwiatkowska, Inez Kowalczyk, Zbigniew Rozwadowski, Elżbieta Piesowicz and Anna Szymczyk

Molecules 2023, 28(7), 2962; https://doi.org/10.3390/molecules28072962 - 26 Mar 2023

Cited by 5 | Viewed by 2411

Abstract

This paper aims to compare the performance of two Hytrel-like segmented copolymers: “classic” PBT-b-PTMG and fully bio-based PBF-b-PTMG, containing poly(butylene furanoate) as the rigid segment. The idea behind this research is to assess whether the sustainable copolymers can successfully replace those “classic” once at the thermoplastic elastomers’ market. Two series of copolymers were synthesized under the same process parameters, had the same compositions, but differed in aromatic ring structure in terephthalate/furanoate unit. Furthermore, the materials were processed by injection moulding as typical Hytrel products. Then, the samples were subjected to extensive characterisation including NMR, GPC, FTIR, DSC, WAXS, DMTA, TGA techniques and mechanical tests with particular interest in the microstructure formed during processing and its effect on the copolymers’ mechanical and elastic behaviour. The detailed analysis proved that PBF-b-PTMG and PBT-b-PTMG copolymers represent two kinds of materials with similar chemical structure, some features of thermoplastic elastomers, but evident differences in their physical properties. Full article

(This article belongs to the Special Issue Synthesis, Properties and Applications of Biobased Polymers)

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11 pages, 1853 KiB

Open AccessArticle

Thermal and Morphological Analysis of Linear Low-Density Polyethylene Composites Containing d-limonene/β-cyclodextrin for Active Food Packaging

by Monika Dobrzyńska-Mizera, Monika Knitter, Marlena Piss, Cristina Del Barone, Salvatore Mallardo, Gabriella Santagata and Maria Laura Di Lorenzo

Molecules 2023, 28(3), 1220; https://doi.org/10.3390/molecules28031220 - 26 Jan 2023

Cited by 5 | Viewed by 2190

Abstract

Composites made of linear low-density polyethylene (LLDPE) and β-cyclodextrin/d-limonene inclusion complex (CD-lim) were prepared by melt extrusion to develop a novel food packaging material. Scanning electron microscopy evidenced a fairly good dispersion of the filler within the polymeric matrix. Infrared spectroscopy coupled with thermogravimetric analysis confirmed the presence of CD-lim in the composites, proving that the applied technology of including the essential oil within β-CD cages allows for preventing a sizable loss of d-limonene despite a high temperature and shear applied upon extrusion processing. Moreover, the influence of the filler on the thermal properties of PE was assessed. It was found that the cyclodextrin-based inclusion complex significantly fastens the crystallization path of the polyethylene matrix with an improved crystallization rate of the PE/CD-lim composites compared to the neat polymer. Full article

(This article belongs to the Special Issue Synthesis, Properties and Applications of Biobased Polymers)

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16 pages, 4632 KiB

Open AccessArticle

Synthesis and Characterization of Poly(lactic acid) Composites with Organosolv Lignin

by Zoi Terzopoulou, Eleftheria Xanthopoulou, Nikolaos Pardalis, Christina P. Pappa, Stylianos Torofias, Konstantinos S. Triantafyllidis and Dimitrios N. Bikiaris

Molecules 2022, 27(23), 8143; https://doi.org/10.3390/molecules27238143 - 23 Nov 2022

Cited by 12 | Viewed by 2469

Abstract

Lignin, being one of the main structural components of lignocellulosic biomass, is considered the most abundant natural source of phenolics and aromatics. Efforts for its valorisation were recently explored as it is mostly treated as waste from heat/energy production via combustion. Among them, polymer-based lignin composites are a promising approach to both valorise lignin and to fine tune the properties of polymers. In this work, organosolv lignin, from beech wood, was used as fillers in a poly (lactic acid) (PLA) matrix. The PLA/lignin composites were prepared using melt mixing of masterbatches with neat PLA in three different lignin contents: 0.5, 1.0 and 2.5 wt%. Lignin was used as-isolated, via the organosolv biomass pretreatment/fractionation process and after 8 h of ball milling. The composites were characterised with Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy, X-ray Diffraction (XRD), and Differential Scanning Calorimetry (DSC). Additionally, their antioxidant activity was assessed with the 2,2-Diphenyil-1-picrylhydrazyl (DPPH) method, the colour was measured with a colorimeter and the mechanical properties were evaluated with tensile testing. Ball milling, at least under the conditions applied in this study, did not induce a further substantial decrease in the already relatively small organosolv lignin primary particles of ~1 μm. All the produced PLA/lignin composites had a uniform dispersion of lignin. Compression-moulded films were successfully prepared, and they were coloured brown, with ball-milled lignin, giving a slightly lighter colour in comparison with the as-received lignin. Hydrogen bonding was detected between the components of the composites, and crystallization of the PLA was suppressed by both lignin, with the suppression being less pronounced by the ball-milled lignin. All composites showed a significantly improved antioxidant activity, and their mechanical properties were maintained for filler content 1 wt%. Full article

(This article belongs to the Special Issue Synthesis, Properties and Applications of Biobased Polymers)

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15 pages, 5057 KiB

Open AccessArticle

Toughening Polyamidoamine Hydrogels through Covalent Grafting of Short Silk Fibers

by Filippo Maggi, Amedea Manfredi, Federico Carosio, Lorenza Maddalena, Jenny Alongi, Paolo Ferruti and Elisabetta Ranucci

Molecules 2022, 27(22), 7808; https://doi.org/10.3390/molecules27227808 - 12 Nov 2022

Cited by 3 | Viewed by 1629

Abstract

Linear amphoteric polyamidoamines (PAAs) are usually water-soluble, biodegradable and biocompatible. Crosslinked PAAs form in water hydrogels, retaining most of the favorable properties of their linear counterparts. The hydrogels prepared by the radical post-polymerization of the oligo-α,ω-bisacrylamido-terminated PAA called AGMA1, obtained by the polyaddition of 4-aminobutylguanidine (agmatine) with 2,2-bis(acrylamido)acetic acid, exhibit excellent cell-adhesion properties both in vitro and in vivo. However, due to their low mechanical strength, AGMA1 hydrogels cannot be sewn to biological tissues and need to be reinforced with fibrous materials. In this work, short silk fibers gave excellent results in this sense, proving capable of establishing covalent bonds with the PAA matrix, thanks to their lysine content, which provided amino groups capable of reacting with the terminal acrylamide groups of the AGMA1 precursor in the final crosslinking phase. Morphological analyses demonstrated that the AGMA1 matrix was intimately interconnected and adherent to the silk fibers, with neither visible holes nor empty volumes. The silk/H-AGMA1 composites were still reversibly swellable in water. In the swollen state, they could be sewn and showed no detachment between fibers and matrix and exhibited significantly improved mechanical properties compared with the plain hydrogels, particularly as regards their Young’s modulus and elongation at break. Full article

(This article belongs to the Special Issue Synthesis, Properties and Applications of Biobased Polymers)

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21 pages, 6120 KiB

Open AccessArticle

Revisiting Non-Conventional Crystallinity-Induced Effects on Molecular Mobility in Sustainable Diblock Copolymers of Poly(propylene adipate) and Polylactide

by Panagiotis A. Klonos, Alexandra Evangelopoulou, Zoi Terzopoulou, Alexandra Zamboulis, Miguel Ángel Valera, Ana Mangas, Apostolos Kyritsis and Dimitrios N. Bikiaris

Molecules 2022, 27(21), 7449; https://doi.org/10.3390/molecules27217449 - 2 Nov 2022

Cited by 7 | Viewed by 2293

Abstract

This work deals with molecular mobility in renewable block copolymers based on polylactide (PLA) and poly(propylene adipate) (PPAd). In particular, we assess non-trivial effects on the mobility arising from the implementation of crystallization. Differential scanning calorimetry, polarized light microscopy and broadband dielectric spectroscopy were employed in combination for this study. The materials were subjected to various thermal treatments aiming at the manipulation of crystallization, namely, fast and slow cooling, isothermal melt- and cold-crystallization. Subsequently, we evaluated the changes recorded in the overall thermal behavior, semicrystalline morphology and molecular mobility (segmental and local). The molecular dynamics map for neat PPAd is presented here for the first time. Unexpectedly, the glass transition temperature, T_g, in the amorphous state drops upon crystallization by 8–50 K. The drop becomes stronger with the increase in the PPAd fraction. Compared to the amorphous state, crystallization leads to significantly faster segmental dynamics with severely suppressed cooperativity. For the PLA/PPAd copolymers, the effects are systematically stronger in the cold- as compared to the melt-crystallization, whereas the opposite happens for neat PLA. The local β_PLA relaxation of PLA was, interestingly, recorded to almost vanish upon crystallization. This suggests that the corresponding molecular groups (carbonyl) are strongly involved and immobilized within the semicrystalline regions. The overall results suggest the involvement of either spatial nanoconfinement imposed on the mobile chains within the inter-crystal amorphous areas and/or a crystallization-driven effect of nanophase separation. The latter phase separation seems to be at the origins of the significant discrepancy recorded between the calorimetric and dielectric recordings on T_g in the copolymers. Once again, compared to more conventional techniques such as calorimetry, dielectric spectroscopy was proved a powerful and quite sensitive tool in recording such effects as well as in providing indirect indications for the polymer chains’ topology. Full article

(This article belongs to the Special Issue Synthesis, Properties and Applications of Biobased Polymers)

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