Special Issue "Biodegradable and Biobased Polyesters"

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

Deadline for manuscript submissions: closed (26 October 2018).

Special Issue Editor

Prof. Dimitrios Bikiaris
E-Mail Website
Guest Editor
Laboratory of Polymer Chemistry and Technology, Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki, Macedonia, 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; modification of natural polymers; polymer 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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Special Issue Information

Dear Colleagues,

In recent years, the potential replacement of fossil fuels, for the production of appropriate monomers using inexpensive and renewable starting materials, such as cellulose, starch, lignin, proteins, and vegetable oils, is increasingly being explored, with the aim of developing a more sustainable bio-based economy. The production of polymers from renewable resources is an old practice, and the first approach involved the modification of natural polymers. However, this practice is limited today, and most efforts are focused on the preparation of biobased monomers for polymer synthesis. These bio-based polymers constitute one of the fastest growing markets and current producers estimate that their production capacity will reach nearly 12 million tons by 2020.

Biobased polyesters is one of the most important classes, and there are many monomers available on the market for their synthesis, including acids (levulinic acid, succinic acid, sebacic acid, adipic acid, aspartic acid, terephthalic acid, 2,5-furandicarboxylic acid, vanillic acid, Itaconic acid, lactic acid, hydroxybutyric acid, 3-hydroxypropionic acid, etc.) and glycols (ethylene glycol, 1,3-propanediol, 1,4-butanediol, isosorbide, xylitol, sorbitol, glycerol, etc.). Some biomass-derived polyesters, such as poly(lactic acid), poly(butylene succinate), poly(butylene adipate), poly(butylene succinate adipate), etc., and non-degradable alipharomatic polyesters, such as poly(ethylene terephthalate), poly(butylene teraphtahlate), poly(ethylene furan dicarboxylate) (PEF), poly(propylene furan dicarboxylate), poly(butylene furan dicarboxylate) (PBF), and several of their copolymers, are currently among the most promising biobased polyesters.

The aim of this Special Issue is to highlight the progress and fundamental aspects for the synthesis, characterization, properties, and application of biobased polyesters, as well as their copolymers, composites, and nanocomposites.

Prof. Dimitrios Bikiaris
Guest Editor

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Keywords

  • Biobased polyesters

  • Monomers from renewable sources

  • Biodegradable polyesters

  • Aliphatic polyesters

  • Alipharomatic polyesters

  • Copolyesters

  • Thermal properties

  • Mechanical properties

Published Papers (25 papers)

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Research

Open AccessArticle
Solid-State Polymerization of Poly(Ethylene Furanoate) Biobased Polyester, III: Extended Study on Effect of Catalyst Type on Molecular Weight Increase
Polymers 2019, 11(3), 438; https://doi.org/10.3390/polym11030438 - 06 Mar 2019
Cited by 2
Abstract
In this study, the synthesis of poly(ethylene furanoate) (PEF), catalyzed by five different catalysts—antimony acetate (III) (Sb Ac), zirconium (IV) isopropoxide isopropanal (Zr Is Ip), antimony (III) oxide (Sb Ox), zirconium (IV) 2,4-pentanedionate (Zr Pe) and germanium (IV) oxide (Ge Ox)—via an industrially [...] Read more.
In this study, the synthesis of poly(ethylene furanoate) (PEF), catalyzed by five different catalysts—antimony acetate (III) (Sb Ac), zirconium (IV) isopropoxide isopropanal (Zr Is Ip), antimony (III) oxide (Sb Ox), zirconium (IV) 2,4-pentanedionate (Zr Pe) and germanium (IV) oxide (Ge Ox)—via an industrially common combination of melt polymerization and subsequent solid-state polymerization (SSP) is presented. In all reactions, proper amounts of 2,5-dimethylfuran-dicarboxylate (DMFD) and ethylene glycol (EG) in a molar ratio of DMFD/EG= 1/2 and 400 ppm of catalyst were used. Polyester samples were subjected to SSP procedure, under vacuum application, at different reaction times (1, 2, 3.5, and 5 h) and temperatures of 190, 200, and 205 °C. Carboxyl end-groups concentration (–COOH), intrinsic viscosity (IV), and thermal properties, via differential scanning calorimetry (DSC), were measured for all resultant polymers to study the effect of the used catalysts on the molecular weight increase of PEF during SSP process. As was expected, it was found that with increasing the SSP time and temperature, the intrinsic viscosity and the average molecular weight of PEF steadily increased. In contrast, the number of carboxyl end-groups content showed the opposite trend as intrinsic viscosity, that is, gradually decreasing during SSP time and temperature increase. It is worthy to note that thanks to the SSP process an obvious and continuous enhancement in the thermal properties of the prepared PEF samples was attained, in which their melting temperatures (Tm) and degree of crystallinity (Xc) increase progressively with increasing of reaction time and temperature. To predict the time evolution of polymers IV, as well as the hydroxyl and carboxyl content of PEF polyesters during the SSP, a simple kinetic model was developed. From both the theoretical simulation results and the experimental measurements, it was demonstrated that surely the Zr Is Ip catalyst shows the best catalytic characteristics compared to all other used catalysts herein, that is, leading in reducing—in a spectacular way—the activation energy of the involved both transesterification and esterification reactions during SSP. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Preparation and Characterization of Hydrophobically Grafted Starches by In Situ Solid Phase Polymerization
Polymers 2019, 11(1), 72; https://doi.org/10.3390/polym11010072 - 05 Jan 2019
Cited by 3
Abstract
Three kinds of hydrophobic groups grafted starches of maleic anhydride grafted starch (MAH-g-starch), lactic acid grafted starch (LA-g-starch), and methyl acrylate grafted starch (MA-g-starch) were prepared by in situ solid phase polymerization. The results of Fourier transform [...] Read more.
Three kinds of hydrophobic groups grafted starches of maleic anhydride grafted starch (MAH-g-starch), lactic acid grafted starch (LA-g-starch), and methyl acrylate grafted starch (MA-g-starch) were prepared by in situ solid phase polymerization. The results of Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) confirmed successful grafting. The grafting ratios of MAH-g-starch, LA-g-starch, and MA-g-starch were 6.50%, 12.45%, and 0.57%, respectively. Influenced by the grafting ratio, LA-g-starch had the best relative hydrophobicity and the largest molecular weight, and those for MA-g-starch were the worst. The surfaces of grafted starches were covered with graft polymer, with obvious surface roughness and bond degree of MAH-g-starch and LA-g-starch. The crystalline structure of grafted starches showed some damage, with LA-g-starch exhibiting the greatest decrease in crystallinity, and less of a change for MA-g-starch. Overall, the grafting reaction improved thermoplasticity, with LA-g-starch the most improved, followed by MAH-g-starch, and then MA-g-starch. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Bulk Modification of Poly(lactide) (PLA) via Copolymerization with Poly(propylene glycol) Diglycidylether (PPGDGE)
Polymers 2018, 10(11), 1184; https://doi.org/10.3390/polym10111184 - 24 Oct 2018
Cited by 1
Abstract
Copolymers of l-lactide and poly(propylene glycol) diglycidyl ether (PPGDGE380) were synthesized by ring opening polymerization (ROP). Stannous octoate was used as the catalyst and 1-dodecanol as the initiator. The effect of the variables on the thermal properties of the copolymers [...] Read more.
Copolymers of l-lactide and poly(propylene glycol) diglycidyl ether (PPGDGE380) were synthesized by ring opening polymerization (ROP). Stannous octoate was used as the catalyst and 1-dodecanol as the initiator. The effect of the variables on the thermal properties of the copolymers was investigated by differential scanning calorimetry (DSC). Contact angle measurements were made in order to study the wettability of the synthesized copolymers. The copolymers differed widely in their physical characteristics, ranging from weak elastomers to tougher thermoplastics, according to the ratio of l-lactide and PPGDGE380. The results showed that the copolymers were more hydrophilic than neat Poly(lactide) (PLA) and the monomer ratio had a strong influence on the hydrophilic properties. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Synthesis of High Molecular Weight Polyester Using in Situ Drying Method and Assessment of Water Vapor and Oxygen Barrier Properties
Polymers 2018, 10(10), 1113; https://doi.org/10.3390/polym10101113 - 09 Oct 2018
Abstract
The preparation of renewable polyesters with good barrier properties is highly desirable for the packaging industry. Herein we report the synthesis of high molecular weight polyesters via an innovative use of an in situ drying agent approach and the barrier properties of the [...] Read more.
The preparation of renewable polyesters with good barrier properties is highly desirable for the packaging industry. Herein we report the synthesis of high molecular weight polyesters via an innovative use of an in situ drying agent approach and the barrier properties of the films formed from these polyesters. High number average molecular weight (Mn) semiaromatic polyesters (PEs) were synthesized via alternating ring-opening copolymerization (ROCOP) of phthalic anhydride (PA) and cyclohexene oxide (CHO) using a salen chromium(III) complex in the presence of 4-(dimethylamino)pyridine (DMAP) cocatalyst. The use of a calcium hydride (drying agent) was found to enhance the number Mn of the synthesized PEs, which reached up to 31.2 ku. To test the barrier properties, PE films were prepared by solvent casting approach and their barrier properties were tested in comparison poly(lactic acid) films. The PE films showed significantly improved water vapor and oxygen barrier properties compared to the commercial poly(lactic acid) (PLA) film that suggests the potential use of these PEs in in the food packaging industry. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Enzymatic Degradation of Poly(butylene succinate) Copolyesters Synthesized with the Use of Candida antarctica Lipase B
Polymers 2018, 10(6), 688; https://doi.org/10.3390/polym10060688 - 20 Jun 2018
Cited by 9
Abstract
Biodegradable polymers are an active area of investigation, particularly ones that can be produced from sustainable, biobased monomers, such as copolymers of poly(butylene succinate) (PBS). In this study, we examine the enzymatic degradation of poly(butylene succinate-dilinoleic succinate) (PBS-DLS) copolymers obtained by “green” enzymatic [...] Read more.
Biodegradable polymers are an active area of investigation, particularly ones that can be produced from sustainable, biobased monomers, such as copolymers of poly(butylene succinate) (PBS). In this study, we examine the enzymatic degradation of poly(butylene succinate-dilinoleic succinate) (PBS-DLS) copolymers obtained by “green” enzymatic synthesis using lipase B from Candida antarctica (CALB). The copolymers differed in their hard to soft segments ratio, from 70:30 to 50:50 wt %. Enzymatic degradation was carried out on electrospun membranes (scaffolds) and compression-moulded films using lipase from Pseudomomas cepacia. Poly(ε-caprolactone) (PCL) was used as a reference aliphatic polyester. The degradation process was monitored gravimetrically via water uptake and mass loss. After 24 days, approx. 40% mass loss was observed for fibrous materials prepared from the PBS-DLS 70:30 copolymer, as compared to approx. 10% mass loss for PBS-DLS 50:50. Infrared spectroscopy (FTIR) and size exclusion chromatography (SEC) analysis were used to examine changes in chemical structure. Differential scanning calorimetry (DSC) and scanning light microscopy (LSM) revealed changes in degree of crystallinity, and changes in surface morphology, consistent with a surface erosion mechanism. We conclude that the obtained copolymers are suitable for tissue engineering applications thanks to tuneable degradation and lack of acidification during breakdown. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
PLGA Microspheres Loaded with β-Cyclodextrin Complexes of Epigallocatechin-3-Gallate for the Anti-Inflammatory Properties in Activated Microglial Cells
Polymers 2018, 10(5), 519; https://doi.org/10.3390/polym10050519 - 11 May 2018
Cited by 1
Abstract
Although epigallocatechin-3-gallate (EG) is well-known as a potent antioxidant and free radical scavenger for neurodegenerative diseases, it still has disadvantages that reduce its treatment effectiveness due to low bioavailability, slow absorption, and water solubility. Therefore, the aim of this study is to improve [...] Read more.
Although epigallocatechin-3-gallate (EG) is well-known as a potent antioxidant and free radical scavenger for neurodegenerative diseases, it still has disadvantages that reduce its treatment effectiveness due to low bioavailability, slow absorption, and water solubility. Therefore, the aim of this study is to improve the bioavailability of EG and increase the effectiveness of anti-inflammatory properties to microglial cells by using Poly(Lactide-co-Glycolide) (PLGA) microspheres as carriers. In this study, we used UV–Vis spectroscopy to show the formation of the complex of β-cyclodextrin (β-CD) and EG (CD-EG). The loading efficiency of EG in PLGA microspheres was optimized by the addition of β-CD. The highest loading efficiency of 16.34% was found among other formulations. The results of Fourier transform infrared spectroscopy indicated the loading of CD-EG in PLGA microspheres. The scanning electron microscopic images demonstrated the spherical PLGA particles with controlled particles size ranging from 1–14 µm. Moreover, the in vitro release of EG was conducted to explore the sustained release property of the PLGA formulations. In the in vitro model of mouse microglial cells (BV-2 cells) stimulated by lipopolysaccharide, the cytotoxicity test showed that for up to 1 mg/mL of PLGA microspheres no toxicity to BV-2 cells was found. PLGA microspheres can significantly suppress the nitric oxide production from BV-2 cells, indicating EG loaded in PLGA microspheres can suppress the inflammation of activated microglial cells. Furthermore, the intracellular iNOS in BV-2 cells was also found to be down regulated. In summary, we have successfully shown that the use of β-CD can increase the loading efficiency of EG in PLGA microspheres and provide neuroprotective effect on the activated microglial cells. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Investigation and Characterization of Plasma-Treated Poly(3-hydroxybutyrate) and Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Biopolymers for an In Vitro Cellular Study of Mouse Adipose-Derived Stem Cells
Polymers 2018, 10(4), 355; https://doi.org/10.3390/polym10040355 - 22 Mar 2018
Cited by 5
Abstract
Polyhydroxyalkanoates (PHAs) are a type of thermoprocessable and biodegradable polyester, which represent a potential sustainable replacement for fossil-fuel synthetic polymers, such as polypropylene and polyethylene. In recent years, copolymers of PHAs, i.e., poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), have received attention for [...] Read more.
Polyhydroxyalkanoates (PHAs) are a type of thermoprocessable and biodegradable polyester, which represent a potential sustainable replacement for fossil-fuel synthetic polymers, such as polypropylene and polyethylene. In recent years, copolymers of PHAs, i.e., poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), have received attention for medical and packaging industrial applications, due to their biodegradable, toxic-free, and biocompatible nature. This study investigated and characterized plasma-treated PHB and PHBV films fermented with Ralstonia eutropha H16. The X-ray photoelectron spectroscopy (XPS) and water contact angle analyses on the plasma-treated PHB and PHBV film surfaces revealed an increase in the number of functional groups and contact angle degree, respectively, compared to that of the untreated films. In addition, an in vitro experiment of mouse adipose-derived stem cells showed better growth and adhesion of the cells on the surface of plasma-treated PHBV film. Overall, these results reveal that plasma surface modifications are useful in biomaterial development. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Molecular and Supramolecular Changes in Polybutylene Succinate (PBS) and Polybutylene Succinate Adipate (PBSA) Copolymer during Degradation in Various Environmental Conditions
Polymers 2018, 10(3), 251; https://doi.org/10.3390/polym10030251 - 01 Mar 2018
Cited by 9
Abstract
In this paper, the influence of the various degradation conditions, on the molecular and supramolecular structure of polybutylene succinate (PBS) and polybutylene succinate adipate (PBSA) copolymer during degradation is described. The experiment was carried out by the use of injection molded samples and [...] Read more.
In this paper, the influence of the various degradation conditions, on the molecular and supramolecular structure of polybutylene succinate (PBS) and polybutylene succinate adipate (PBSA) copolymer during degradation is described. The experiment was carried out by the use of injection molded samples and normalized conditions of biodegradation in soil, composting and artificial weathering. Materials were studied by size-exclusion chromatography (SEC) coupled with multiangle laser light scattering (MALLS) detection and wide-angle X-ray diffraction (WAXD). Additionally, the physical and mechanical properties of the samples were determined. The performed experiments clearly show difference impacts of the selected degradation conditions on the macroscopic, supramolecular and molecular parameters of the studied aliphatic polyesters. The structural changes in PBS and PBSA explain the observed changes in the physical and mechanical properties of the obtained injection molded samples. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Epitaxial Crystallization Behavior of Poly(butylene adipate) on Orientated Poly(butylene succinate) Substrate
Polymers 2018, 10(2), 110; https://doi.org/10.3390/polym10020110 - 24 Jan 2018
Cited by 6
Abstract
The crystallization behavior of poly(butylene adipate) (PBA) in the sheared PBS/PBA blend, as well as on highly orientated poly(butylene succinate) (PBS) substrate, was studied by means of DSC, POM, Raman microscopy, and XRD. The results showed that the pre-existing orientated PBS crystals exhibit [...] Read more.
The crystallization behavior of poly(butylene adipate) (PBA) in the sheared PBS/PBA blend, as well as on highly orientated poly(butylene succinate) (PBS) substrate, was studied by means of DSC, POM, Raman microscopy, and XRD. The results showed that the pre-existing orientated PBS crystals exhibit a very strong nucleation ability toward PBA as reflected by the increased crystallization temperature and the occurrence of heteroepitaxy and transcrystallization of PBA on the PBS substrate. The epitaxial crystallization of PBA on the PBS substrate results in the formation of α-form PBA crystals in any crystallization conditions. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Effect of Hydroxyl Monomers on the Enzymatic Degradation of Poly(ethylene succinate), Poly(butylene succinate), and Poly(hexylene succinate)
Polymers 2018, 10(1), 90; https://doi.org/10.3390/polym10010090 - 18 Jan 2018
Cited by 6
Abstract
Poly(ethylene succinate) (PES), poly(butylene succinate) (PBS), and poly(hexylene succinate) (PHS), were synthesized using succinic acid and different dihydric alcohols as materials. Enzymatic degradability by cutinase of the three kinds of polyesters was studied, as well as their solid-state properties. The biodegradation behavior relied [...] Read more.
Poly(ethylene succinate) (PES), poly(butylene succinate) (PBS), and poly(hexylene succinate) (PHS), were synthesized using succinic acid and different dihydric alcohols as materials. Enzymatic degradability by cutinase of the three kinds of polyesters was studied, as well as their solid-state properties. The biodegradation behavior relied heavily on the distance between ester groups, crystallinity, and the hydrophilicity-hydrophobicity balance of polyester surfaces. The weight loss through degradation of the three kinds of polyesters with different hydroxyl monomers took place in the order PHS > PBS > PES. The degradation behavior of the polyesters before and after degradation was analyzed by scanning electron microscopy, differential scanning calorimetry, powder X-ray diffraction, Fourier transform infrared spectroscopy, gel permeation chromatography, and thermogravimetric analysis. The decrease in relative intensity at 1800–1650 estedpolyesters were degraded simultaneously. The frequencies of the crystalline and amorphous bands were almost identical before and after degradation. Thus, enzymatic degradation did not change the crystalline structure but destroyed it, and the degree of crystallinity markedly decreased. The molecular weight and polydispersity index only changed slightly. The thermal stability of the three kinds of polyesters decreased during enzymatic degradation. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Manufacturing and Characterization of Toughened Poly(lactic acid) (PLA) Formulations by Ternary Blends with Biopolyesters
Polymers 2018, 10(1), 3; https://doi.org/10.3390/polym10010003 - 21 Dec 2017
Cited by 9
Abstract
Ternary blends with a constant poly(lactic acid) (PLA) content (60 wt %) and varying amounts of poly(3-hydroxybutyrate) (PHB) and poly(ε-caprolactone) (PCL) were manufactured by one step melt blending process followed by injection moulding, with the main aim of improving the low intrinsic toughness [...] Read more.
Ternary blends with a constant poly(lactic acid) (PLA) content (60 wt %) and varying amounts of poly(3-hydroxybutyrate) (PHB) and poly(ε-caprolactone) (PCL) were manufactured by one step melt blending process followed by injection moulding, with the main aim of improving the low intrinsic toughness of PLA. Mechanical properties were obtained from tensile and Charpy impact tests. The miscibility and morphology of the system was studied by thermal analysis and field emission scanning electron microscopy (FESEM). The obtained results showed a clear phase separation, thus indicating poor miscibility between these three biopolyesters, i.e., PLA, the continuous component with dispersed PHB and PCL domains in the form of different sphere size. Nevertheless, the high fragility of PLA was remarkably reduced, as detected by the Charpy impact test. In accordance with the decrease in brittleness, a remarkable increase in elongation at break is achieved, with increasing PCL load due to its flexibility; in addition, increasing PCL load provides thermal stability at high temperatures. Thus, tailored materials can be manufactured by melt blending PLA, PHB, and PCL in different percentages to offer a wide range of biodegradable polymer blends. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Novel Random PBS-Based Copolymers Containing Aliphatic Side Chains for Sustainable Flexible Food Packaging
Polymers 2017, 9(12), 724; https://doi.org/10.3390/polym9120724 - 16 Dec 2017
Cited by 14
Abstract
In the last decade, there has been an increased interest from the food packaging industry toward the development and application of biodegradable and biobased plastics, to contribute to the sustainable economy and to reduce the huge environmental problem afflicting the planet. In this [...] Read more.
In the last decade, there has been an increased interest from the food packaging industry toward the development and application of biodegradable and biobased plastics, to contribute to the sustainable economy and to reduce the huge environmental problem afflicting the planet. In this framework, the present paper describes the synthesis of novel PBS (poly(butylene succinate))-based random copolymers with different composition containing glycol sub-units characterized by alkyl pendant groups of different length. The prepared samples were subjected to molecular, thermal, diffractometric and mechanical characterization. The barrier performances to O2, CO2 and N2 gases were also evaluated, envisioning for these new materials an application in food packaging. The presence of the side alkyl groups did not alter the thermal stability, whereas it significantly reduced the sample crystallinity degree, making these materials more flexible. The barrier properties were found to be worse than PBS; however, some of them were comparable to, or even better than, those of Low Density Polyethylene (LDPE), widely employed for flexible food packaging. The entity of variations in the final properties due to copolymerization were more modest in the case of the co-unit with short side methyl groups, which, when included in the PBS crystal lattice, causes a more modest decrement of crystallinity degree. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
An Insight into the Flammability of Some Bio-Based Polyesters
Polymers 2017, 9(12), 706; https://doi.org/10.3390/polym9120706 - 12 Dec 2017
Abstract
The heat release capacity of polymers can be generally predicted using a method based on the additivity of group contributions (the Van Krevelen approach). Nevertheless, there are some exceptions, evidencing that this approach is insufficient and must be completed. In this study, the [...] Read more.
The heat release capacity of polymers can be generally predicted using a method based on the additivity of group contributions (the Van Krevelen approach). Nevertheless, there are some exceptions, evidencing that this approach is insufficient and must be completed. In this study, the kinetic triplet accounting for the description of pyrolysis is identified for 11 polymers. Activation energy and the frequency factor are calculated using Kissinger’s method. Reaction models are chosen among the Avrami–Erofeev functions. The high flammability of poly(3-hydroxybutyrate) and the underestimation of its heat release capacity using the Van Krevelen approach are explained from these parameters. The results highlight the possibility of improving the model, using additional but easily accessible data. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Modulating the Tg of Poly(alkylene succinate)s by Inserting Bio-Based Aromatic Units via Ring-Opening Copolymerization
Polymers 2017, 9(12), 701; https://doi.org/10.3390/polym9120701 - 12 Dec 2017
Abstract
Two series of aliphatic-aromatic copolyesters derived from succinic and 2,5-furandicarboxylic acids, and di-O-2-(hydroxyethyl) resorcinol as diol substituent of either 1,4-butanediol or ethylene glycol, respectively, were obtained by ring opening polymerization(ROP) performed in bulk and catalyzed by Sn(Oct)2. Cyclic oligomers [...] Read more.
Two series of aliphatic-aromatic copolyesters derived from succinic and 2,5-furandicarboxylic acids, and di-O-2-(hydroxyethyl) resorcinol as diol substituent of either 1,4-butanediol or ethylene glycol, respectively, were obtained by ring opening polymerization(ROP) performed in bulk and catalyzed by Sn(Oct)2. Cyclic oligomers of furandicarboxylate of di-O-2-(hydroxyethyl) resorcinol were successfully synthesized by high-dilution condensation, and then copolymerized with cyclic oligomers of either butylene or ethylene succinate. The synthesized resorcinol-containing succinate-furanoatecopolyesters had Mw oscillating between 50,000 and 30,000 g·mol−1 depending on composition, and they all displayed a nearly random microstructure. They showed an excellent thermal stability with onset decomposition temperatures near 300 °C. They are amorphous with Tg increasing monotonically with the content in resorcinol in both series with values ranging from −30 or −13 °C for butylene and ethylene-based copolyesters, respectively, up to around 45 °C. The resorcinol-containing succinate-furanoate copolyesters showed appreciable hydrolytic degradation when incubated for a few weeks in water under physiological conditions, a behavior that was notably enhanced in the presence of lipases. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Preparation and Properties of Novel Thermoplastic Vulcanizate Based on Bio-Based Polyester/Polylactic Acid, and Its Application in 3D Printing
Polymers 2017, 9(12), 694; https://doi.org/10.3390/polym9120694 - 09 Dec 2017
Cited by 6
Abstract
Thermoplastic vulcanizate (TPV) combines the high elasticity of elastomers and excellent processability of thermoplastics. Novel bio-based TPV based on poly (lactide) (PLA) and poly (1,4-butanediol/2,3-butanediol/succinate/itaconic acid) (PBBSI) were prepared in this research. PBBSI copolyesters were synthesized by melting polycondensation, and the molecular weights, [...] Read more.
Thermoplastic vulcanizate (TPV) combines the high elasticity of elastomers and excellent processability of thermoplastics. Novel bio-based TPV based on poly (lactide) (PLA) and poly (1,4-butanediol/2,3-butanediol/succinate/itaconic acid) (PBBSI) were prepared in this research. PBBSI copolyesters were synthesized by melting polycondensation, and the molecular weights, chemical structures and compositions of the copolyesters were characterized by GPC, NMR and FTIR. Bio-based 2,3-butanediol was successfully incorporated to depress the crystallization behavior of the PBBSI copolyester. With an increase of 2,3-butanediol content, the PBBSI copolyester transformed from a rigid plastic to a soft elastomer. Furthermore, the obtained TPV has good elasticity and rheological properties, which means it can be applied as a 3D-printing material. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Catalyst Influence on Undesired Side Reactions in the Polycondensation of Fully Bio-Based Polyester Itaconates
Polymers 2017, 9(12), 693; https://doi.org/10.3390/polym9120693 - 09 Dec 2017
Cited by 9
Abstract
Bio-based unsaturated polyester resins derived from itaconic acid can be an alternative to established resins of this type in the field of radical-curing resins. However, one of the challenges of these polyester itaconates is the somewhat more elaborate synthetic process, especially under polycondensation [...] Read more.
Bio-based unsaturated polyester resins derived from itaconic acid can be an alternative to established resins of this type in the field of radical-curing resins. However, one of the challenges of these polyester itaconates is the somewhat more elaborate synthetic process, especially under polycondensation conditions used on an industrial scale. The α,β-unsaturated double bond of the itaconic acid is prone to side reactions that can lead to the gelation of the polyester resin under standard conditions. This is especially true when bio-based diols such as 1,3-propanediol or 1,4-butanediol are used to obtain resins that are 100% derived from renewable resources. It was observed in earlier studies that high amounts of these aliphatic diols in the polyester lead to low conversion and gelation of the resins. In this work, a catalytic study using different diols was performed in order to elucidate the reasons for this behavior. It was shown that the choice of catalyst has a crucial influence on the side reactions occurring during the polycondensation reactions. In addition, the side reactions taking place were identified and suppressed. These results will allow for the synthesis of polyester itaconates on a larger scale, setting the stage for their industrial application. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Synthesis and Characterization of Dimmer-Acid-Based Nonisocyanate Polyurethane and Epoxy Resin Composite
Polymers 2017, 9(12), 649; https://doi.org/10.3390/polym9120649 - 28 Nov 2017
Cited by 7
Abstract
In this study, dimmer-acid-based hybrid nonisocyanate polyurethanes (HNIPUs) were synthesized by the one-step method without catalyst. Three polyamines and two epoxy resins were selected as raw materials for HNIPU, and cyclic carbonate was synthesized based on our previous work. All of the products [...] Read more.
In this study, dimmer-acid-based hybrid nonisocyanate polyurethanes (HNIPUs) were synthesized by the one-step method without catalyst. Three polyamines and two epoxy resins were selected as raw materials for HNIPU, and cyclic carbonate was synthesized based on our previous work. All of the products were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). Then, HNIPU coatings were prepared and determined by swelling, water absorption, and water contact angle. The results showed that the HNIPU-4551 have the best mechanical and thermal properties because of its high crosslinking density. Among the different amines, it was confirmed that tetraethylenepentamine was the best amine curing agent for HNIPU coating. Meanwhile, the epoxy resin with a higher epoxy value would also form a higher crosslinking density. Those coatings showed an excellent impact strength, adhesion, flexibility, pencil hardness, hydrophilic, and appropriate crosslinking density. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Short Oxygen Plasma Treatment Leading to Long-Term Hydrophilicity of Conductive PCL-PPy Nanofiber Scaffolds
Polymers 2017, 9(11), 614; https://doi.org/10.3390/polym9110614 - 14 Nov 2017
Cited by 6
Abstract
Electrically conductive scaffolds are of significant interest in tissue regeneration. However, the chemistry of the existing scaffolds usually lacks the bioactive features for effective interaction with cells. In this study, poly(ε-caprolactone) was electrospun into aligned nanofibers with 0.58 µm average diameter. Electrospinning was [...] Read more.
Electrically conductive scaffolds are of significant interest in tissue regeneration. However, the chemistry of the existing scaffolds usually lacks the bioactive features for effective interaction with cells. In this study, poly(ε-caprolactone) was electrospun into aligned nanofibers with 0.58 µm average diameter. Electrospinning was followed by polypyrrole coating on the surface of the fibers, which resulted in 48 kΩ/sq surface resistivity. An oxygen plasma treatment was conducted to change the hydrophobic surface of the fiber mats into a hydrophilic substrate. The water contact angle was reduced from 136° to 0°, and this change remained on the surface of the material even after one year. An indirect cytotoxicity test was conducted, which showed cytocompatibility of the fibrous scaffolds. To measure the cell growth on samples, fibroblast cells were cultured on fibers for 7 days. The cell distribution and density were observed and calculated based on confocal images taken of the cell culture experiment. The number of cells on the plasma-treated sample was more than double than that of sample without plasma treatment. The long-lasting hydrophilicity of the plasma treated fibers with conductive coating is the significant contribution of this work for regeneration of electrically excitable tissues. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase
Polymers 2017, 9(11), 607; https://doi.org/10.3390/polym9110607 - 13 Nov 2017
Cited by 11
Abstract
In this work, we report the synthesis of poly(ethylene furanoate) (PEF), catalyzed by three different catalysts, namely, titanium (IV) isopropoxide (TIS), tetrabutyltitanate (TBT), and dibutyltin (IV) oxide (DBTO), via the two-stage melt polycondensation method. Solid-state polymerization (SSP) was conducted at different reaction times [...] Read more.
In this work, we report the synthesis of poly(ethylene furanoate) (PEF), catalyzed by three different catalysts, namely, titanium (IV) isopropoxide (TIS), tetrabutyltitanate (TBT), and dibutyltin (IV) oxide (DBTO), via the two-stage melt polycondensation method. Solid-state polymerization (SSP) was conducted at different reaction times (1, 2, 3.5, and 5 h) and temperatures 190, 200, and 205 °C, under vacuum. The resultant polymers were analyzed according to their intrinsic viscosity (IV), end groups (–COOH), and thermal properties, via differential scanning calorimetry. DSC results showed that the post polymerization process was favorable to enhance the melting point of the prepared PEF samples. As was expected, the intrinsic viscosity and the average molecular weight of PEF increased with the SSP time and temperature, whereas the number of carboxyl end-groups was decreased. A simple kinetic model was also developed and used to predict the time evolution of polymers IV, as well as the carboxyl and hydroxyl content of PEF during the SSP. From both the experimental measurements and the theoretical simulation results it was proved that the presence of the TIS catalyst resulted in higher transesterification kinetic rate constants and higher reaction rates. The activation energies were not much affected by the presence of different catalysts. Finally, using DBTO as a catalyst, the polyesters produced have higher crystallinity, and as a consequence, higher number of inactive carboxyl and hydroxyl groups. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Bimetallic Catalytic Systems Based on Sb, Ge and Ti for the Synthesis of Poly(ethylene terephthalate-co-isosorbide terephthalate)
Polymers 2017, 9(11), 590; https://doi.org/10.3390/polym9110590 - 09 Nov 2017
Cited by 5
Abstract
The insertion of rigid monomers such as isosorbide into poly(ethylene terephthalate) (PET) allows for the access of polymers with improved properties, notably in terms of thermal stability. This biobased monomer is however poorly reactive, and harsh reaction conditions lead to color concerns regarding [...] Read more.
The insertion of rigid monomers such as isosorbide into poly(ethylene terephthalate) (PET) allows for the access of polymers with improved properties, notably in terms of thermal stability. This biobased monomer is however poorly reactive, and harsh reaction conditions lead to color concerns regarding the resulting polymer. This has motivated the development of catalytic systems enabling an increase of the reaction rate and a good coloration. In this study, we have assessed bimetallic catalytic systems based on the main metals used for PET catalysis, i.e., antimony, germanium and titanium, for the synthesis of poly(ethylene terephthalate-co-isosorbide terephthalate) (PEIT). The Sb2O3/Ti(OiPr)4 combination leads to a high reaction rate while maintaining an acceptable coloration. On the other hand, combining Sb2O3 with GeO2 affords the formation of poly(ethylene terephthalate-co-isosorbide terephthalate) without coloration concerns and a reaction rate higher than that observed using the single metal catalysts. Molecular weights and microstructure including diethyleneglycol (DEG) and isosorbide contents are also discussed, together with the thermal properties of the resulting PEIT. The GeO2/Ti(OiPr)4 is also assessed, and leads to average performances. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Polyol Structure and Ionic Moieties Influence the Hydrolytic Stability and Enzymatic Hydrolysis of Bio-Based 2,5-Furandicarboxylic Acid (FDCA) Copolyesters
Polymers 2017, 9(9), 403; https://doi.org/10.3390/polym9090403 - 30 Aug 2017
Cited by 3
Abstract
A series of copolyesters based on furanic acid and sulfonated isophthalic acid with various polyols were synthetized and their susceptibility to enzymatic hydrolysis by cutinase 1 from Thermobifida cellulosilytica (Thc_Cut1) investigated. All copolyesters consisted of 30 mol % 5-sulfoisophthalate units (NaSIP) and 70 [...] Read more.
A series of copolyesters based on furanic acid and sulfonated isophthalic acid with various polyols were synthetized and their susceptibility to enzymatic hydrolysis by cutinase 1 from Thermobifida cellulosilytica (Thc_Cut1) investigated. All copolyesters consisted of 30 mol % 5-sulfoisophthalate units (NaSIP) and 70 mol % 2,5-furandicarboxylic acid (FDCA), while the polyol component was varied, including 1,2-ethanediol, 1,4-butanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, or tetraethylene glycol. The composition of the copolyesters was confirmed by 1H-NMR and the number average molecular weight (Mn) was determined by GPC to range from 2630 to 8030 g/mol. A DSC analysis revealed glass-transition temperatures (Tg) from 84 to 6 °C, which were decreasing with increasing diol chain length. The crystallinity was below 1% for all polyesters. The hydrolytic stability increased with the chain length of the alkyl diol unit, while it was generally higher for the ether diol units. Thc_Cut1 was able to hydrolyze all of the copolyesters containing alkyl diols ranging from two to eight carbon chain lengths, while the highest activities were detected for the shorter chain lengths with an amount of 13.6 ± 0.7 mM FDCA released after 72 h of incubation at 50 °C. Faster hydrolysis was observed when replacing an alkyl diol by ether diols, as indicated, e.g., by a fivefold higher release of FDCA for triethylene glycol when compared to 1,8-octanediol. A positive influence of introducing ionic phthalic acid was observed while the enzyme preferentially cleaved ester bonds associated to the non-charged building blocks. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Copolyesters Based on 2,5-Furandicarboxylic Acid (FDCA): Effect of 2,2,4,4-Tetramethyl-1,3-Cyclobutanediol Units on Their Properties
Polymers 2017, 9(9), 305; https://doi.org/10.3390/polym9090305 - 24 Aug 2017
Cited by 19
Abstract
Bio-based polyesters derived from 2,5-furandicarboxylic acid (FDCA), including poly (ethylene 2,5-furandicarboxylate) (PEF), poly(propylene 2,5-furandicarboxylate) (PPF), and poly(butylene 2,5-furandicarboxylate) (PBF) have been synthesized and modified with 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO). Copolyesters with increased glass transition temperature, good barrier and better mechanical properties, as well as higher [...] Read more.
Bio-based polyesters derived from 2,5-furandicarboxylic acid (FDCA), including poly (ethylene 2,5-furandicarboxylate) (PEF), poly(propylene 2,5-furandicarboxylate) (PPF), and poly(butylene 2,5-furandicarboxylate) (PBF) have been synthesized and modified with 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO). Copolyesters with increased glass transition temperature, good barrier and better mechanical properties, as well as higher transparency were reported in this work. The chemical structures, composition, and sequence distribution of the copolyesters were determined by 1H NMR and 13C NMR. The degree of random (R) was close to 1 for all the copolyesters, indicating their random chemical structures. With the introduction of 10% CBDO units, the semi-crystalline PEF and PPF were changed into completely amorphous polyesters and the higher transparency was easily achieved. The glass transition temperature was increased from 87 °C for PEF to 91.1 °C for PETF-18, from 55.5 °C for PPF to 63.5 °C for PPTF-18, and from 39.0 °C for PBF to 43.5 °C for PBTF-18. The barrier properties investigation demonstrated that although the O2 and CO2 barrier of PEF/PPF/PBF were decreased by the addition of CBDO units, the modified copolyesters still showed good barrier properties. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Silane-Treated Basalt Fiber–Reinforced Poly(butylene succinate) Biocomposites: Interfacial Crystallization and Tensile Properties
Polymers 2017, 9(8), 351; https://doi.org/10.3390/polym9080351 - 09 Aug 2017
Cited by 12
Abstract
In this work, an economical modifier silane agent—KH550—was used for surface treatment of basalt fiber. Then, a biodegradable poly(butylene succinate) (PBS)/modified basalt fiber (MBF) biocomposite was successfully developed. The effects of silane treatment and fiber mass content on crystalline structure, isothermal crystallization process [...] Read more.
In this work, an economical modifier silane agent—KH550—was used for surface treatment of basalt fiber. Then, a biodegradable poly(butylene succinate) (PBS)/modified basalt fiber (MBF) biocomposite was successfully developed. The effects of silane treatment and fiber mass content on crystalline structure, isothermal crystallization process and mechanical performance of composites were evaluated. The interfacial crystallization of PBS on the surface of MBF was investigated by using a polarized optical microscope (POM). The transcrystalline (TC) structure could be clearly observed and it grew perpendicular to the surface of MBF, which boosted the nucleation ability on PBS crystallization and the strong interfacial interaction between PBS and silane-treated basalt fiber. Under isothermal crystallization kinetics, the incorporation of basalt fiber enhanced the crystallization rate and reduced the crystallization half-time values of composites compared with that of neat PBS due to a heterogeneous nucleation effect. Furthermore, tensile results confirmed that the presence of MBF could greatly improve the tensile strength and modulus. The predicted interfacial shear strength (IFSS) suggested that an enhancement of interfacial bonding could be realized via interfacial crystallization, which was also verified by SEM images. The PBS/MBF biocomposites can be applied in many fields as a low-cost, lightweight, and biodegradable composite material. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Forensic Engineering of Advanced Polymeric Materials—Part V: Prediction Studies of Aliphatic–Aromatic Copolyester and Polylactide Commercial Blends in View of Potential Applications as Compostable Cosmetic Packages
Polymers 2017, 9(7), 257; https://doi.org/10.3390/polym9070257 - 29 Jun 2017
Cited by 8
Abstract
The main aim of the present study was to determine the behavior of the specimens from Ecovio, in the form of dumbbell-shaped samples and films, during degradation in selected cosmetic ingredients such as water and paraffin. The (bio)degradation test of the prototype cosmetic [...] Read more.
The main aim of the present study was to determine the behavior of the specimens from Ecovio, in the form of dumbbell-shaped samples and films, during degradation in selected cosmetic ingredients such as water and paraffin. The (bio)degradation test of the prototype cosmetic package (sachet) made from a PBAT (poly[(1,4-butylene adipate)-co-(1,4-butylene terephthalate)]) and PLA (polylactide) blend was investigated under industrial composting conditions, and compared with the sample behavior during incubation in cosmetic media at 70 °C. During the degradation tests, the changes of the samples were evaluated using optical microscopy, 1H NMR (proton nuclear magnetic resonance) and GPC (gel permeation chromatography) techniques. The structures of the degradation products were investigated using ESI-MSn (mass spectrometry with electrospray ionization on positive and negative ions) analysis. The thermal properties of selected materials were determined by DSC (differential scanning calorimetry) and TGA (thermogravimetric analysis) analysis. It was concluded that the PBAT and PLA blend studied had a good stability during aging in cosmetic media, and could be recommended for long-shelf-life compostable packaging of cosmetics, especially with oily ingredients. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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Open AccessArticle
Epoxidized Jatropha Oil as a Sustainable Plasticizer to Poly(lactic Acid)
Polymers 2017, 9(6), 204; https://doi.org/10.3390/polym9060204 - 02 Jun 2017
Cited by 13
Abstract
A renewable resource, epoxidized jatropha oil (EJO), was used as a green plasticizer and added to poly(lactic acid) (PLA). EJO was compounded into PLA at different contents. The addition of 3 wt % EJO to the PLA demonstrates significant improvement in flexibility, which [...] Read more.
A renewable resource, epoxidized jatropha oil (EJO), was used as a green plasticizer and added to poly(lactic acid) (PLA). EJO was compounded into PLA at different contents. The addition of 3 wt % EJO to the PLA demonstrates significant improvement in flexibility, which leads to a percentage increase of about 7000% in elongation at break. This tensile result was confirmed by surface morphology analysis with clear proof of plastic deformation in EJO-plasticized PLA. EJO imparts a good heat stabilization effect. Thermal stability of PLA was enhanced upon addition of EJO, which is due to their good interaction and plasticizer dispersion within the PLA matrix. This EJO-plasticized PLA has wide applications in various industries, such as packaging of food and non-food products. Full article
(This article belongs to the Special Issue Biodegradable and Biobased Polyesters)
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