Bio-based Poly Research Articles

Fully bio-based poly(propylene succinate-co-propylene furandicarboxylate) copolyesters with proper mechanical, degradation and barrier properties for green packaging applications

A series of aromatic-aliphatic poly(propylene succinate-co-furandicarboxylate) (PPSF) copolyesters, with compositions varied over the whole range from that of poly(propylene succinate) (PPS) to poly(propylene furandicarboxylate) (PPF), were synthesized by transesterification and melt polycondensation. 1H NMR study suggested the random segment distribution of PPSF. The copolymer showed slower crystallization rate than that of terephthalate based copolyesters, as indicated by DSC tests. PPSFs with low furandicarboxylate molar content (mPF) (from 10% to 50%) were soft and elastic due to their poor crystallization ability and low Tg. In contrast, they owned relatively high elastic modulus, tensile strength and excellent barrier properties with high mPF (from 60% to 90%). Annealing treatment could speed up the crystallization of PF units and increase the elastic modulus and tensile strength of PPSFs. The chemical composition of the copolymer strongly influenced its permeability to CO2 and O2, and PPSF owned better CO2, O2 and H2O barrier properties than commercial PBAT and PLA. Furthermore, enzymatic degradation study suggested that copolymers with mPF up to 60 mol% could be degraded and PPSF became easier to degrade with the increasing content of succinate units (mPS).

Fully bio-based poly(propylene succinate) synthesis and investigation of thermal degradation kinetics with released gases analysis

One of the most important information about polyesters is their thermal stability and phase transition temperatures. These characteristics give information about the promising behavior of the polyester during processing. In this work, linear bio-based polyester polyols were prepared with the use of succinic acid and 1.3-propanediol (both with natural origin). As a polycondensation catalyst was used tetraisopropyl orthotitanate (TPT), which different amount was employed. The thermogravimetric analysis allowed to observe high thermal stability and one step of the thermal decomposition. This analysis affirmed also that the catalyst content did not influence the thermal degradation characteristics of the prepared polyols. Nevertheless, it has huge importance in the context of thermal degradation kinetics. It was determined with the use of Ozawa, Flynn, and Wall and Kissinger's methods to verifying catalyst impact on the thermal degradation kinetics. Moreover, probable mechanism of the prepared bio-based polyols thermal degradation was proposed based on the QMS results.

Molecular Mobility in Amorphous Biobased Poly(ethylene 2,5-furandicarboxylate) and Poly(ethylene 2,4-furandicarboxylate)

Among all the emergent biobased polymers, poly(ethylene 2,5-furandicarboxylate) (2,5-PEF) seems to be particularly interesting for packaging applications. This work is focused on the investigation of the relaxation dynamics and the macromolecular mobility in totally amorphous 2,5-PEF as well as in the less studied poly(ethylene 2,4-furandicarboxylate) (2,4-PEF). Both biopolymers were investigated by differential scanning calorimetry and dielectric relaxation spectroscopy in a large range of temperatures and frequencies. The main parameters describing the relaxation dynamics and the molecular mobility in 2,5-PEF and 2,4-PEF, such as the glass transition temperature, the temperature dependence of the α and β relaxation times, the fragility index, and the apparent activation energy of the secondary relaxation, were determined and discussed. 2,5-PEF showed a higher value of the dielectric strength as compared to 2,4-PEF and other well-known polyesters, such as poly(ethylene terephthalate), which was confirmed...

From Furan to High Quality Bio-based Poly(ethylene furandicarboxylate)

2,5-Furandicarboxylic acid (2,5-FDCA) has been regarded as the ideal bio-based alternative to terephthalic acid (TPA). In recent years, great efforts have been made to synthesize 2,5-FDCA through the following methods: (1) oxidation of 5-hydroxymethylfurfural (HMF) in the presence of complex biocatalyst or metallic catalyst; (2) conversion of 2-furoic acid via the well-known Henkel Reaction. Herein, a new strategy for the synthesis of 2,5-FDCA from furan and acetic anhydride under mild condition is reported. The purity of the resulted 2,5-FDCA was above 99.9%. Acetic acid and iodoform generated in the reaction were recyclable and no other harmful by-products were detected. The thus-obtained 2,5-FDCA was applied for the preparation of poly(ethylene furandicarboxylate) (PEF) of high quality in terms of high molecular weight and good appearance.

Bio-based poly(hydroxyurethane) glues for metal substrates

Bio- and CO2-based high performance thermoset poly(hydroxyurethane) (PHU) glues were designed from solvent- and isocyanate-free formulations based on cyclocarbonated soybean oil, diamines (aliphatic, cycloaliphatic or aromatic) and functional silica or ZnO fillers.

Synthesis, characterization and thermal decomposition kinetics of a bio-based transparent nylon 10I/10T

ABSTRACTHerein, we report a novel transparent engineering plastic nylon 10I/10T based on bio-based poly(decamethylene isophthalamide) (nylon10I). We have demonstrated the one-step melt polycondensation synthesis of transparent nylon and carried out Fourier transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (1H NMR) to confirm the chemical structure. Furthermore, the dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) were used to analyze the thermal properties. Glass transition temperature (Tg) and thermal decomposition onset temperature (T1) of nylon 10I/10T (15 wt. % 10T) were 118.9 and 438.0 °C, respectively. The intrinsic viscosity, water absorption, light transmittance, mechanical properties, solvent resistance and the decomposition mechanism of nylon 10I/10T have also been investigated. The results show that the nylon 10I/10T has lower water absorption and enhanced solvent resistance compared to nylon 6–3-T, which indicates that nylon 10I/10T is a promising transparent plastic.

Tuning the compatibility to achieve toughened biobased poly(lactic acid)/poly(butylene terephthalate) blends.

A series of sustainable biobased polymer blends from poly(lactic acid) (PLA) and poly(butylene terephthalate) (PBT) were fabricated and characterized. These blends are engineered to achieve optimal mechanical properties and toughness with a reactive epoxidized styrene-acrylic copolymer (ESAC) compatibilizer, and an ethylene-n-butyl-acrylate-co-glycidyl methacrylate (EBA-GMA) elastomer-based compatibilizer. The results showed that the tensile strength, modulus, flexural strength and modulus of the PBT increase, while the elongation at break and notched impact strength decrease after blending with the biopolymer PLA. The full co-continuity of PLA in PBT was confirmed at a 50/50 wt% blend ratio. The droplet size of the PLA was reduced and the distinct phases of the blends were gradually diminished with the increasing content of the ESAC compatibilizer. The increase in the complex viscosity of the blends was due to the formation of PLA-g-PBT copolymers in the blend after addition of reactive compatibilizers. The incorporation of both compatibilizers in the blends led to superior notched impact strength in comparison to only a single compatibilizer used in the blends. The synergistic effect of both compatibilizers effectively reduces the PLA droplet size and improves the dispersion of PLA in PBT as evidenced by atomic force microscopy (AFM) topography observations. The high toughness of the blends corresponds to the formation of effective EBA-GMA structures and enhanced interfacial compatibilization due to the synergistic effect of the compatibilizers.

Aqueous cationic homo- and co-polymerizations of β-myrcene and styrene: a green route toward terpene-based rubbery polymers

A green and cost-efficient approach for the synthesis of bio-based poly(β-myrcene) and poly(β-myrcene-co-styrene) via emulsion cationic polymerization is developed.

Biocompatible Polymeric Nanoparticles From Castor Oil Derivatives via Thiol‐Ene Miniemulsion Polymerization

Biocompatible polymeric nanoparticles are obtained via thiol‐ene polymerization of a biobased monomer in miniemulsion. The α,ω‐diene‐diester monomer is synthesized through esterification reaction of a glycerol derivative, namely 1,3‐propanediol, with 10‐undecenoic acid, a long‐chain diene carboxylic acid. In order to investigate how different monomeric structures behave toward thiol‐ene polymerization in miniemulsion, two types of thiols are investigated: 1,4‐butanedithiol and 2‐mercaptoethyl ether. Poly(thioether‐ester)s with weight average molecular weight up to 15 kDa (Mn) are obtained, depending on initiator concentration and types of surfactant and dithiol employed. Finally, biobased poly(thioether‐ester) nanoparticles are submitted to cytotoxicity and hemolysis analyses. High cell viability and no significant changes in cell morphology are observed after the incubation on murine fibroblast (L929) and human cervical cancer cells (HeLa). Last, hemolysis assays revealed blood compatibility and therefore polymeric nanoparticles have been shown to be a potential alternative drug delivery vector for intravenous administration.Practical Applications: There is a great demand for polymeric systems that fulfill a number of requirements, such as biodegradability and biocompatibility, for biomedical applications. In this context, biobased polymers obtained from vegetable oils are a very attractive sustainable alternative to fossil‐derived polymeric materials, presenting potential biodegradability and low toxicity. By thiol‐ene reactions, polymeric materials containing ester groups in the main chain—which can undergo hydrolysis—can be prepared in miniemulsion, enabling their degradation in physiological environment and, therefore, being interesting for biomedical applications and material disposal. Such novel materials could be used in temporary implants, tissue engineering, and drug delivery systems.Biocompatible polymeric nanoparticles are obtained via thiol‐ene polymerization of a biobased monomer in miniemulsion. Nanoparticles revealed to be a potential alternative controlled release drug delivery vector for intravenous administration.

Bio-Based Poly(Ether Imide)s from Isohexide-Derived Isomeric Dianhydrides.

In this work, four isohexide-derived isomeric dianhydrides were synthesized through a four-step procedure using isohexide and chloro-N-phenylphthalimides as the starting materials. The one-step solution polymerization of these dianhydrides with petroleum- or bio-based diamines enabled the synthesis of poly(ether imide)s (PEIs), which had viscosities of 0.41 to 2.40 dL∙g−1. The isohexide-derived PEIs were characterized based upon their solubility and their thermal, mechanical, and optical properties. The results showed that most of the isohexide-derived PEIs possessed comparable glass transition temperatures (Tg), tensile strengths, and moduli to petroleum-based PEIs. However, the thermo-oxidative stability of the PEIs was found to be lower than that of the common petroleum-based PEIs. Moreover, the PEIs displayed good optical activity, which originated from their unique chiral isohexide moieties. The isomeric effects of dianhydride monomers on the properties of the resulting PEIs were comparatively studied. The results suggested that the corresponding 4,4′-linked PEIs possessed lower Tg, higher mechanical properties, and higher specific rotations compared to 3,3′-linked polymers. Meanwhile, the polyimides with isomannide residue displayed higher Tg and more specific rotations than the corresponding polymers with isosorbide residue. These results contributed to more restricted rotations of phthalimide segments in 3,3′-linked or isomannide containing polyimides.

Design of biobased poly(butylene succinate) foams by single‐screw extrusion: Identification of relevant rheological parameters controlling foam morphologies

Key relationships between foam morphologies and melt‐state rheological parameters are here exposed for biobased poly(butylene‐succinate) (PBS) and standard petrobased polyethylene (PE) foams processed by single‐screw extrusion. Scanning electron microscopy followed by image analysis revealed cell diameters and densities in the range of 250–700 µm and 3–4.104 cells/cm3, respectively. PBS and PE have similar morphologies except for cell diameters which are slightly higher for PBS foams. The melt index roughly controls foam microstructures but deeper insights are obtained through correlations with shear/extensional rheology experiments. In particular, the melt strength and the strain hardening control the cell growth mechanisms. Concerning the cell density, the shear viscosity in the die plays a key role and agreements with nucleation theories can be discussed based on simulated pressure–velocity profiles using finite element software. In our extrusion conditions, the residence time comes out to have a crucial role with distinct behaviors between PE and PBS indicating a potential modification of the polymer/CO2 interfacial tension. Consequently, an accurate control of the foam morphology seems achievable via a careful selection of the polymer grades and PBS represents a promising alternative to PE for further developments of biobased foams. POLYM. ENG. SCI., 58:503–512, 2018. © 2017 Society of Plastics Engineers

Synthesis and structure – property relationship of biobased poly(butylene 2,5-furanoate) – block – (dimerized fatty acid) copolymers

A series of poly(butylene 2,5-furanoate) – block – (dimerized fatty acid) (PBF-b-FAD) copolymers were successfully synthesized from 2,5-furandicarboxylic acid (FDCA), 1,4-butanediol (1,4-BD), and dimerized fatty acid diol (FADD) via a polycondensation in melt under the relatively mild process conditions and a reasonable excess of diol. The copolymers with different PBF to FAD segment ratio were characterized in regard of their chemical composition, microstructure, thermal transitions and stability as well as the mechanical performance. Some results were also discussed in relation to terephthalic acid based PBT-b-FAD copolymers, synthesized under the same experimental procedure. A detailed analysis of PBF homopolymer confirmed its relatively high molecular weight, semicrystalline structure, and in consequence a very good mechanical performance. In turn an incorporation of FADD amorphous segments between PBF blocks resulted in multiblocked structure with the ester group links and the real composition very close to those calculated theoretically. Although the specific furan ring architecture disturbs the macromolecules symmetry, thus the crystallization process, the PBF-b-FAD copolymers, varying in between 20 and 80 wt% of the rigid segments, reveal the heterogeneous microstructure. And the phase separation may be enhanced by the annealing above Tcc. In consequence the furan-aromatic copolyesters combine a variety of physical properties (also the elastomeric behavior), tunable by both PBF to FAD ratio and the thermal treatment, with a good processability. They are also characterized by almost twice higher level of the tensile stress and E modulus when compared to previously reported PTF-b-FADD copolymers. Considering the soon commercialization of bio-1,4-butanodiol the presented materials have also a potential to be synthesized as fully bio-based.

Room temperature sputtering deposition of high-haze Ga-doped ZnO transparent conductive thin films on self-textured bio-based poly(ethylene 2, 5-furandicarboxylate) substrates

In this work, bio-based poly(ethylene 2,5-furandicarboxylate) (PEF) films were prepared by drop-casting method and used as substrates for depositing Ga-doped ZnO (GZO) transparent conductive thin films. Results showed that the 300-nm GZO thin films deposited on PEF substrates exhibited haze values above 65% at 550nm without post-treatment. The high haze value was because of the large surface roughness of PEF films. The total optical transmittance and electrical properties of GZO thin films on PEF were comparable to those of GZO thin films on PET. The present study provides a simple way for the sputtering deposition of high-haze transparent conductive thin films on flexible substrates.

High performance thiol-ene thermosets based on fully bio-based poly(limonene carbonate)s

High glass transition temperature (Tg) thiol-ene networks (TENs) based on poly(limonene carbonate)s (PLCs), derived from orange oils and of potential degradability are described here. PLCs with moderate molecular weight were prepared by copolymerization of limonene oxide with CO2 and subsequent breakdown reactions. These PLCs were cured with multifunctional thiol monomers in the presence of thermal initiators via thiol-ene chemistry to generate poly(thioether-co-carbonate) networks. The thermal curing experiments were optimized by a kinetic study using real-time ATR-FTIR, in which a delayed gelation was observed. For the first time, an interesting “cage” effect was observed during the network formation initiated by DCP, in which the addition reactions of pendant isopropenyls on high molecular weight PLC chains were significantly enhanced by thiol-ene crosslinking at 160°C. The resulting homogeneous TENs with high Tgs (>100°C) and a wide range of thermomechanical properties, including rubbery moduli from 2.9 to 28.2MPa, were obtained. The TENs also showed promising properties such as high transparency, good acetone resistance and high hardness, suggesting their potential application in coatings.

Tensile Property Balanced and Gas Barrier Improved Poly(lactic acid) by Blending with Biobased Poly(butylene 2,5-furan dicarboxylate)

A biobased poly(butylene 2,5-furan dicarboxylate) (PBF) is synthesized and blended with poly(lactic acid) (PLA). With only 5 wt % addition of PBF, the elongation at break of PLA becomes 18.5 times more than before, while the tensile modulus and tensile strength at yield keep almost the same. Morphological analysis based on scanning electron microscope pictures shows drastic shape deformation of PBF dispersed phases from sphere to fibril. The elongation ratio of PBF phase is much larger than that of PLA matrix, which is caused by a possible “plastic-rubber” transition in PBF during stretch process. On the other hand, stretch induced crystallization in PBF happened and it may increase the modulus of PBF along the tensile direction. Probably with the above two phenomena, PLA is dynamically toughened and strengthened in the elongation procedure. Moreover, the impact strength of the blends is better than those of the two pure components, and rubber-plastic transition and crystallization of PBF could improve th...

Biodegradable poly (lactic acid)/Cellulose nanocrystals (CNCs) composite microcellular foam: Effect of nanofillers on foam cellular morphology, thermal and wettability behavior

This article addresses the elegant and green approach for fabrication of bio-based poly (lactic acid) (PLA)/cellulose nanocrystal (CNCs) bionanocomposite foam (PLA/CNC) with cellular morphology and hydrophobic surface behavior. Highly porous (porosity >80%) structure is obtained with interconnected pores and the effect of CNCs in the cell density (Nf) and cell size of foams are thoroughly investigated by morphological analysis. The thermo-mechanical investigations are performed for the foam samples and almost ∼1.7 and ∼2.2 fold increase in storage modulus is observed for the compressive and tensile mode respectively. PLA/CNC based bionanocomposite foams displayed similar thermal stability as base PLA foam. Detailed investigations of decomposition behavior are studied by using hyphenated thermogravimetric analysis-fourier transmission infrared spectroscopy (TGA-FTIR) system. Almost ∼13% increment is observed in crystallinity at highest loading of CNCs compared to neat counterpart. To investigate the splitting and spreading phenomenon of the wettability of the samples, linear model is used to find the Young’s contact angle and contact angle hysteresis (CAH). Besides, ∼6.1 folds reduction in the density of PLA and the nanocomposite foams compared to PLA carries much significance in specialized application areas where weight is an important concern.

Synthesis and characterization of bio-based poly(butylene succinate-co-10-hydroxydecanoate)

Aliphatic poly(butylene succinate-co-10-hydroxydecanoate)s (PBHs) with various compositions were synthesized from 1,4-butanediol, succinic acid, and 10-hydroxydecanoic acid (HDA) by esterification and polycondensation with tetrabutyl titanate as catalyst. Gel permeation chromatography and proton nuclear magnetic resonance analysis indicate that the molecular weight of PBHs is in the range of 24,947–45,921 g/mol with a relatively narrow polydispersity index at 1.76–2.09. The influence of block length on the properties of copolyesters was investigated. With the increase of HDA unit content, melting point, crystallization temperature, and tensile modulus of PBHs decrease, while the thermal stability and toughness enhanced significantly. In addition, PBHs keep relatively stable in phosphate buffer solution (pH = 7.4) and HCl solution (0.1 mol/L), but 22% weight was lost after 30 days in NaOH solution (0.1 mol/L). Furthermore, the degradation rate of PBHs in NaOH solution (0.1 mol/L) accelerates monotonically with increasing HDA content.

Amphiphilic core-shell nanoparticles with dimer fatty acid-based aliphatic polyester core and zwitterionic poly(sulfobetaine) shell for controlled delivery of curcumin

ABSTRACTMultifunctional nanocarriers are gaining increasing research interest as polymeric platforms for targeted drug delivery in cancer therapy and diagnosis. In this work, preparation and characterization of surfactant-free polyester nanoparticles (NPs) from a bio-based poly(butylene sebacate-co-butylene dilinoleate)s, poly(butylene sebacate) (PBSE)/poly(butylene dilinoleate) (PBDL), using nanoprecipitation, is reported. The polymeric nanoparticles (sizes narrowly distributed in a range less than 100 nm) were loaded with curcumin (CURC) with an encapsulation efficiency of 98% and drug loading (DL) content of 5–10% wtdrug/wtpolymer. The CURC-loaded nanoparticles were efficiently coated with a novel poly(sulfobetaine)-type zwitterionic polymer synthesized by nitroxide-mediated polymerization and postpolymerization functionalization step. Free and CURC formulated into noncoated and poly(sulfobetaine)-type zwitterionic polymer-coated nanoparticles were further investigated for cytotoxicity and antioxidant activity in a panel of human cell lines and rat liver microsomes, respectively. Formulated into coated NPs, CURC has superior cytotoxic and antioxidant activity versus the free drug and CURC incorporated in noncoated NPs. In addition, cell viability experiments of nonloaded nanoparticles, both coated and noncoated, demonstrated that developed nanoparticles are nontoxic, making them potentially suitable candidates for systemic passive targeting in cancer therapy, namely for treatment of solid tumors exhibiting high tumor accumulation of NPs due to enhanced permeability and retention effect. Polyzwitterion-coated nanoparticles exhibited slower drug release compared with the noncoated ones (half as much after 24 h) presumably due to the presence of the polymer shell around nanoparticles associated with a wider diffusion layer around the particles.

The Effect of High Molecular Weight Bio-based Diamine Derivative of Dimerized Fatty Acids Obtained from Vegetable Oils on the Structure, Morphology and Selected Properties of Poly(ether-urethane-urea)s

In this work, the effect of the high molecular weight bio-based diamine on the chemical structure and selected properties of poly(ether-urethane-urea)s has been investigated. The ether-urethane prepolymer was cured using 1,4-butanediol and/or bio-based diamine. Mentioned chain extenders were used separately or in the mixture, and their different molecular weight and chemical structure resulted in obtaining materials with diversified mechanical performence. The presence of specific chemical groups (i.e. urethane and urea groups) was confirmed by FTIR method. For the synthesized poly(ether-urethane-urea)s morphology and fracture mechanism, thermo-mechanical properties and mechanical properties were determined and discussed. Results confirmed that bio-based diamine acts as soft segments, and this is connected with changing of mechanical and thermo-mechanical properties of prepared partially bio-based poly(ether-urethane-urea)s. The increasing content of bio-based diamine resulted in increasing of tensile modulus and decreasing of tensile strength and elongation at break, and this is resulted from chemical structure of bio-based diamine (i.e. presence of aliphatic side chains).

Enzymatic synthesis of biobased poly(1,4-butylene succinate-ran-2,3-butylene succinate) copolyesters and characterization. Influence of 1,4- and 2,3-butanediol contents

Different (co)polyesters, poly(1,4-butylene succinate-ran-2,3-butylene succinate) (PBB’S), were enzymatically copolymerized at different 1,4-butanediol (1,4-BDO)/2,3-butanediol (2,3-BDO) molar ratios, with immobilized Candida antarctica lipase B (CALB). The synthesized macromolecular architectures were characterized by NMR, SEC, FTIR, WAXS, MALDI-TOF MS, DSC, TGA and specific optical rotation. Based on an optimized process, PBB’S copolyesters were synthesized in high yield. A random distribution between both BDOs was obtained along the chain. Mw‾ decreased with increasing 2,3-BDO content, from 26 to 6kg/mol. The specific optical rotation decreased linearly with decreasing 2,3-BDO content, and can be used as a characterization technique to determine PBB’S composition. DSC results showed that an increase in 2,3-BDO content raised the Tg and reduced the degree of crystallinity, leading to amorphous materials for 2,3-BDO content higher than 47mol.%. Synthesized copolyesters exhibited a good thermal stability, higher than 250°C, with a degradation profile depending on the 1,4-BDO/2,3-BDO ratio.