Bio-based Poly Research Articles

In vitro degradation and biocompatibility evaluation of fully biobased thermoplastic elastomers consisting of poly(β-myrcene) and poly(l-lactide) as stent coating

Currently coronary stent coating materials focus on biodegradable polymers requiring excellent performances, including biodegradability, cytocompatibility and hemocompatibility as well as ductility. To endow poly(l-lactide) (PLLA) with good ductility as stent coating, two kinds of high branched PLLA grafted copolymers with introduction of biobased poly(β-myrcene) rubber segments were developed towards sent coating. The impacts of topological architectures (including linear comb and star comb) on physical properties, hydrolytic and enzymatic degradation behaviors, cytocompatibility, hemocompatibility and coating morphology were investigated. It was found that the nonbiodegradable poly(β-myrcene) rubber segments delayed the degradation rate, and further decreased with more complex architectures. Proteinase K accelerated enzymatic degradation compared with hydrolytic degradation. Biocompatibility testing showed that the fully biobased thermoplastic elastomers possessed good cytocompatibility and hemocompatibility. Morphological characterization of stent coatings indicated that the linear comb and star comb PLLA grafted copolymers improved the surface smooth of pure PLLA coating. Thus, these highly branched fully biobased thermoplastic elastomers are promising to as potential coating materials in drug eluting stent.

Wrinkling poly(trimethylene 2,5-furanoate) free-standing films: Nanostructure formation and physical properties

Polymer nanostructures were developed on fully bio-based poly(trimethylene furanoate) (PTF) films, by using the technique of Laser Induced Periodic Surface Structures (LIPSS). We found that irradiation times between 1 and 8 min allowed the formation of periodic and nanometric ripples, when using an UV pulsed laser source at a fluence of 8 mJ/cm2. The wrinkled surfaces were studied by a combined macro- and nanoscale approach. We evaluated possible physicochemical changes taking place on the polymer surface after irradiation by infrared spectroscopy, contact angle measurements and atomic force microscopy. The macroscopic properties of PTF showed almost no changes after nanostructure formation, differently from the results previously found for the terephthalic counterparts, as poly(ethylene terephthalate), PET, and poly(trimethylene terephthalate), PTT. At the nanoscale, the surface mechanical properties of the nanostructured PTF were found to be improved, as evidenced by force spectroscopy measurements. In particular, stiffer surfaces characterized by an increased Young's modulus were measured for the nanostructured sample.

Broadband Dielectric Spectroscopy Study of Biobased Poly(alkylene 2,5-furanoate)s' Molecular Dynamics.

Poly(2,5-alkylene furanoate)s are bio-based, smart, and innovative polymers that are considered the most promising materials to replace oil-based plastics. These polymers can be synthesized using ecofriendly approaches, starting from renewable sources, and result into final products with properties comparable and even better than those presented by their terephthalic counterparts. In this work, we present the molecular dynamics of four 100% bio-based poly(alkylene 2,5-furanoate)s, using broadband dielectric spectroscopy measurements that covered a wide temperature and frequency range. We unveiled complex local relaxations, characterized by the simultaneous presence of two components, which were dependent on thermal treatment. The segmental relaxation showed relaxation times and strengths depending on the glycolic subunit length, which were furthermore confirmed by high-frequency experiments in the molten region of the polymers. Our results allowed determining structure–property relations that are able to provide further understanding about the excellent barrier properties of poly(alkylene 2,5-furanoate)s. In addition, we provide results of high industrial interest during polymer processing for possible industrial applications of poly(alkylene furanoate)s.

Environmentally Friendly Polymer Blends Based on Post-Consumer Glycol-Modified Poly(Ethylene Terephthalate) (PET-G) Foils and Poly(Ethylene 2,5-Furanoate) (PEF): Preparation and Characterization.

Environmentally friendly polymer blends between post-consumer PET-G and bio-based poly(ethylene 2,5 furanoate) (PEF) have been prepared. The PET-G granules were obtained from the post-consumer glycol-modified poly(ethylene terephthalate) PET-G foils from Nicrometal S.A. as a result of materials recycling. PEF was synthesized from dimethyl furan-2,5-dicarboxylate and 1,2-ethylene glycol (BioUltra) by a two-stage melt polycondensation process. According to the calculations followed by Hoy’s method, one has studied the miscibility of the components in the blend. The molecular structure of PET-G/PEF blends was analyzed by Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy, while the morphology of the blends was determined by Scanning Electron Microscopy (SEM). To evaluate phase transition temperatures, as well as the thermal effects in PET-G/PEF blends, Differential Scanning Calorimetry (DSC), Dynamic Mechanical Thermal Analysis (DMTA), and Thermogravimetric Analysis (TGA), were performed. Tensile tests revealed that along with an increase in the amount of PEF, an increase in Young’s modulus was observed. Besides, the existence of interfacial interactions between polymers, especially in the case of PET-G/PEF 80/20, enabling the PET-G chains to form a network structure with the PEF by reacting with their functional groups, allows observation of a synergistic effect in the improvement of thermal stability and water absorption.

Lipase-catalyzed synthesis and post-polymerization modification of new fully bio-based poly(hexamethylene γ-ketopimelate) and poly(hexamethylene γ-ketopimelate-co-hexamethylene adipate) copolyesters

Abstract A novel full bio-based ketone-containing aliphatic polyester was prepared by enzyme-catalyzed polycondensation of diethyl γ-ketopimelate (DEK) with 1,6-hexanediol (HDO) using immobilized lipase B from Candida antarctica (CALB). The influences of polymerization conditions such as temperature, time, enzyme amount, and solvent amount on the molecular weight of poly(hexamethylene γ-ketopimelate) (PHK) were investigated. New fully bio-based poly(hexamethylene γ-ketopimelate-co-hexamethylene adipate) (poly(HK-co-HA)) copolymers with narrow polydispersity and well-defined composition were synthesized by copolymerization of DEK, HDO, and diethyl adipate. The structures of PHK and poly(HK-co-HA) copolymers were characterized by nuclear magnetic resonance, and their thermal characterization was examined by thermogravimetric analysis and differential scanning calorimetry. The degradation of PHK and poly(HK-co-HA) copolymers was studied. The post-polymerization modification of these polyketoesters via oxime click chemistry was further demonstrated.

A Sensitive Impedimetric Sensor Based on Biosourced Polyphosphine Films for the Detection of Lead Ions

In this work, impedimetric sensors were developed for the detection of the four WFD heavy metals Pb2+, Cd2+, Hg2+ and Ni2+, by the modification of a gold electrode with four partially biosourced polyphosphine polymers. These polymers were obtained with satisfactory yields by polycondensation of the bis(4-fluorophenyl)(4-methylphenyl)phosphine sulfide and the bis(4-fluorophenyl)(4-methylphenyl)phosphine oxide using isosorbide or bisphenol A. The chemical structures and number-average molecular weights of the resulting polymers were determined by NMR spectroscopy (1H, 19F, and 31P) and by size exclusion chromatography. Glass transition temperatures varied between 184 and 202 °C depending on the composition of polymers. The bio-based poly(etherphosphine) oxide modified sensor showed better analytical performance than petrochemical based oxide for the detection of Pb2+. A detection limit of 10−10 g/L or 0.5 pM, which is 104 times lower than that of the anodic stripping voltammetric and the potentiometric sensors. A reversibility is obtained through rinsing of the impedimetric sensor with an EDTA solution.

Improved impact strength of poly(lactic acid) by incorporating poly(butylene succinate) and silicon dioxide nanoparticles

The surface of silicon dioxide (SiO2) nanoparticles was treated with oleic acid, and the resulting surface properties were characterized. Bio-based poly(lactic acid) (PLA)/poly(butylene succinate)/SiO2 nanocomposites were fabricated via solution blending. The influence of the SiO2 content on the thermal stability, flexural properties, impact strength, and morphology of the prepared nanocomposites was investigated using several techniques. The impact strength of the nanocomposites with surface treated SiO2 (O-SiO2) nanoparticles substantially increased with increasing O-SiO2 content from 0 to 3 wt%. Scanning electron microscopy imaging revealed that the nanocomposites with O-SiO2 nanoparticles exhibited numerous tortuous cracks and ridges, indicating ductile deformation prior to fracturing.

Studies on Semi-crystalline Poly Lactic Acid (PLA) as a Hydrophobic Coating Material on Kraft Paper for Imparting Barrier Properties in Coated Abrasive Applications

This study investigated and explored the possible use of bio-based Poly lactic acid (PLA) as a barrier coating material on natural Kraft paper to fabricate coated abrasive products and to replace the conventional, non-biodegradable, synthetic polymer based barrier coating materials. PLA was coated on the Kraft paper using a solution coating process. The barrier properties of the PLA-treated Kraft paper were accordingly tested for application as a backing material in coated abrasive products. The concentration of PLA in solution was systematically increased from 5 wt% to 25 wt%. The coating thickness and coating weights were increased quantitatively with increasing solution concentrations. The morphology of the coating was characterized using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), contact angle, and surface roughness measurements. The mechanical properties of the PLA coating applied Kraft paper were quantified by measuring the tensile strength, bursting strength, air porosity and Cobb value in order to find its suitability as coated abrasive product. The thermal analysis carried out using DSC scan indicated the semi-crystalline nature of PLA. The coating’s analysis for air and water resistance indicated that the air and water resistance increased with increase in PLA coating thickness. The data from different studies revealed that the PLA coating with a coating weight of 9 g m−2 appeared to be the most ideal concentration over the untreated or other lower PLA g m−2 treated backing materials and proved to possess superior overall barrier properties that are essentially needed for the fabrication of coated abrasive products.

Polymorphism and Multiple Melting Behavior of Bio-Based Poly(propylene 2,5-furandicarboxylate).

Furandicarboxylate-based polyesters are considered an interesting class of bio-based polymers due to their improved properties with respect to the petrol-based terephthalate homologs. An in-depth analysis of the crystal structure of poly(propylene 2,5-furandicarboxylate) (PPF), after maximum possible removal of the catalyst, was carried out. The study disclosed that purified PPF presents two different crystalline phases after crystallization from the melt. Crystallizations at temperatures lower than 120 °C lead to growth of a single crystal form (β-form), whereas two different crystal forms (α and β) were found to coexist at higher Tcs. This behavior is opposite to that previously observed for unpurified PPF. The possibility that the catalyst nucleates the α-phase, which therefore becomes the kinetically favored modification at low crystallization temperatures in the presence of a higher amount of catalyst residue, has been considered as a feasible explanation. Two concomitantly different spherulitic morphologies were observed and connected to the β- and α-phase, respectively. The association between polymorphism and melting behavior was studied. The origin of the peaks that compose the multiple melting endotherm recorded at conventional heating rates was determined by combined wide-angle X-ray scattering, differential scanning calorimetry, fast scanning chip calorimetry, and polarized light optical microscopy measurements. The higher thermal stability of the α-crystals in comparison with the β-form was thus demonstrated.

Preparation of Nanoscale Semi-IPNs with an Interconnected Microporous Structure via Cationic Polymerization of Bio-Based Tung Oil in a Homogeneous Solution of Poly(ε-caprolactone).

Nanoscale semi-interpenetrating polymer networks of bio-based poly(ε-caprolactone) (PCL) and polymerized tung oil have been prepared via in situ cationic polymerization and compatibilization in a homogeneous solution. This novel blending technique produced a nanoscale morphology of poly(ε-caprolactone) with average particle sizes as small as 100 nm dispersed in a cross-linked tung oil matrix for 20 and 30 wt % PCL blend compositions. In addition, the exothermic cationic polymerization of tung oil in the presence of the PCL homogeneous solution created a microporous morphology with open three-dimensional interconnected cluster structures. The porous morphology was found to be composition-dependent (the pore size and interconnectivity decreased with increasing PCL content in the blend). The values of the cross-link density and storage modulus in the glassy state for fully cured samples increased significantly and reached a maximum for the 20 wt % PCL blend. This simple, versatile, low-cost strategy for preparing nanoscale and interconnected three-dimensional cluster structures with a microporous morphology and desired properties should be widely applicable for new polymer systems.

Microcrystalline Cellulose Management in the Production of Poly(ether-urethane)s- Structure, Morphology, and Thermal Characteristic

In response to the demand of polymer industry for reducing the use of synthetic chemicals, eco-friendly materials are investigated. In the presented study, bio-based poly(ether-urethane)s were prepared by using microcrystalline cellulose (MCC) and polyether polyol and 1,3-propanediol derived from corn sugar. A step towards sustainability was taken by incorporating bio-based compounds and cellulose, consequently, bio-waste are utilized in a smart way. The new materials were synthesized via prepolymer method, while the cellulose fibers were added after the reaction. Structural studies of biocomposites were realized by FTIR technique. The number of free and hydrogen-bonded carbonyl groups was determined based on the deconvolution of C=O band. Crystallinity was assessed on the basis of X-ray diffraction analysis. The influence of the MCC content on the thermo-mechanical, thermal and selected mechanical properties has been demonstrated. Results obtained by SEM method showed that the higher degree of reinforcement led to the formation of aggregates reflecting their poor dispersion in the polymer matrix. It may probably result from the relatively weaker interaction between MCC and PU matrix. On the other hand, it was found that the incorporation of fibers improved the thermo-mechanical and thermal properties of the prepared materials. This work provides an effective way of using bio-renewable chemicals in the polyurethane industry without using additional processing apparatus and chemical processes. The used method makes it possible to obtain materials with high bio-content and satisfactory thermal characteristic.

Biocarbon from peanut hulls and their green composites with biobased poly(trimethylene terephthalate) (PTT)

There are millions of tons of post-food processing residues discarded annually. Currently, these waste materials are discarded to landfill, used as animal feed or incinerated. This suggests that there are potential uses for these materials in value-added applications. This work focuses on the characterization and valorization of peanut hulls through the generation of green composites. Peanut hulls were pyrolyzed at 500 °C and analyzed to discover their unique surface morphology and relatively low ash content. Raman spectral analysis determined ID/IG values of 0.74 for the samples, suggesting greater graphitic content than disordered carbon content. Such results were confirmed in X-ray diffraction analysis by the presence of (002) and (100) planes. Partially biobased engineering thermoplastic, poly(trimethylene terephthalate) (PTT), was combined with 20 wt.% biocarbon. The tensile and flexural moduli improved with the addition of biocarbon, and the bio-content increased from 35 to 48 wt.% as compared to neat PTT. The higher temperature biocarbon was found to have superior performance over the lower temperature sample. The enhanced sustainability of these materials suggested that peanut hulls can be valorized via thermochemical conversion to generate value-added products. Future works could focus on the optimization of these materials for non-structural automotive components or electrical housings.

Enhanced melt crystallization of biobased Poly(ethylene 2,5-furandicarboxylate) by low loading of octavinyl-polyhedral oligomeric silsesquioxanes

Abstract Through a common solution and casting process, a biobased poly(ethylene 2,5-furandicarboxylate) (PEF)/octavinyl-polyhedral oligomeric silsesquioxanes (ovi-POSS) composite was successfully prepared at low loading of ovi-POSS in this research. The melt crystallization of PEF was apparently enhanced by low loading of ovi-POSS as a nucleation agent in the composite, displaying a higher melt crystallization peak temperature at a constant cooling rate and a shorter crystallization half-time at the same crystallization temperature. Ovi-POSS did not modify the crystallization mechanism and crystal structure of PEF in the composite.

Organo-modified LDH fillers endowing multi-functionality to bio-based poly(butylene succinate): An extended study from the laboratory to possible market

Polybutylene succinate (PBS) were processed in melt extrusion by dispersion of organo-modified layered double hydroxide (LDH). Depending on the organic anion interleaved into LDH fillers (L-tyrosine (TYR), L-tryptophan (TRP), L-ascorbate (ASA) and 3-(4-hydroxyphenyl)propionate (HPP)), it was possible to control and tune the properties of the resulting PBS composites. Each LDH filler is found to act differently toward PBS, thus modifying its viscoelastic properties (as expressed by a chain extending effect), its rate of hydrolysis and photo-degradation or its antibacterial activity. The highest chain extending effect was observed in the case of LDH with L-tryptophan, the worst – with L-ascorbate anion. However, L-ascorbate anions interleaved into LDH present 100% activity in antibacterial properties. A better compromise may be achieved when PBS is mixed with different LDHs such as those combining HPP and ASA, making possible to target efficiently multi-properties such as small rate of hydrolysis, photo-stability, biocide activity as well as chain extension, thus turning to a multifunctional (bio)nanocomposites with new possible applications. Finally, a possible scale-up is demonstrated on thin films.

Combining a bio-based polymer and a natural antifoulant into an eco-friendly antifouling coating

Biodegradable polymers are promising binders and carriers for natural antifoulants. In the present study, an antifouling (AF) coating was developed by adding a non-toxic AF compound (butenolide) to a bio-based and biodegradable poly(lactic acid)-based polyurethane. Mass loss measurement showed that the polymer degraded in seawater at a rate of 0.013 mg cm−2 day−1. Measurements showed that butenolide was released from the coatings into seawater over a period of at least three months. Both the concentration of butenolide in the coatings and the ambient temperature determined the release rate of butenolide. The results further demonstrate that incorporating rosin into the coatings increase the self-renewal rate of the polymer and facilitated the long-term release of butenolide from the coating. The results show that poly(lactic acid)-based polyurethane is a suitable polymer for butenolide-based AF coatings.

Bio-based composite from poly(butylene succinate) and peanut shell waste adding maleinized linseed oil

Nowadays, the biobased plastic products have become one of the worldwide topics that people give the attention. Applications of bio-based poly (butylene succinate) (PBS) is interesting since it is fully biodegradable. However, the resin cost is expensive compared to olefins so that it is not widely used. This research attempted to produce cost-effective composite sheets from PBS and peanut shell powder (PSP) with particle size of 100 mesh in the weight ratio of 70/30, 60/40, and 50/50 wt% using a twin-screw extruder and then a compression molding. In addition, maleinized linseed oil (MLO) of 3 phr was used as a compatibilizer for the composites. It was found that the obtained composites had higher Young’s modulus and Shore D hardness with respect to the PSP content, but elongation at break was reduced. The impact resistance by means of the falling dart impact test also reduced with the higher PSP content. Adding MLO into the PBS/PSP composites increased elongation at break and impact resistance, but reduced the rigidity due to plasticizing effect. Due to lignocellulosic nature of PSP, the thermal stability of the composites was decreased and MLO did not have significant influence on it. After the weathering testing for 60 h, mechanical properties and thermal stability of the composites were reduced significantly implying that these bio-based composites could degrade faster compared to pure PBS sample.

Microstructure and Mechanical/Elastic Performance of Biobased Poly (Butylene Furanoate)-Block-Poly (Ethylene Oxide) Copolymers: Effect of the Flexible Segment Length.

The aim of this paper is to extend knowledge on biobased poly(butylene furanoate)–block–poly (ethylene oxide) (PBF-b-PEO) copolymers’ performance by studying the effect of the PEO segment’s molecular weight on the microstructure and materials behavior. As crystallization ability of PEO depends on its molecular weight, the idea was to use two PEO segment lengths, expecting that the longer one would be able to crystallize affecting the phase separation in copolymers, thus affecting their mechanical performance, including elasticity. Two series of PBF-block-PEOs with the PEO segments of 1000 and 2000 g/mol and different PBF/PEO segment ratios were synthesized by polycondensation in melt, injection molded to confirm their processability, and subjected to characterization by NMR, FTIR, DSC, DMTA, WAXS, TGA, and mechanical parameters. Indeed, the PEO2000 segment not only supported the crystallization of the PBF segments in copolymers, but at contents at least 50 wt % is getting crystallizable in the low temperature range, which results in the microstructure development and affects the mechanical properties. While the improvement in the phase separation slightly reduces the copolymers’ ability to deformation, it is beneficial for the elastic recovery of the materials. The investigations were performed on the injection molded samples reflecting the macroscopic properties of the bulk materials.

Flexible platinum electrodes as electrochemical sensor and immunosensor for Parkinson's disease biomarkers

In this study, platinum electrodes were fabricated on the bio-based poly(ethylene terephthalate) (Bio-PET) substrates for the development of flexible electrochemical sensors for the detection of Parkinson's disease biomarkers. Dopamine was detected by voltammetric measurements, displaying a 3.5 × 10−5 mol L−1 to 8.0 × 10−4 mol L−1 linear range with a limit of detection of 5.1 × 10−6 mol L−1. Parkinson's disease protein 7 (PARK7/DJ-1) was successfully detected by electrochemical impedance spectroscopy after electrode functionalization with specific anti-PARK7/DJ-1 antibodies. In this case, analytical curves presented a linear behavior from 40 ng mL−1 to 150 ng mL−1 of PARK7/DJ-1 with a limit of detection of 7.5 ng mL−1. Besides, the electrodes did not suffer any change in the electrochemical response after manual tests of mechanical tension. The proposed sensor and immunosensor were applied for the determination of Parkinson's disease biomarkers concentrations found in the human body, being adequate as an alternative method to diagnose this disease.

Influence of chemical structure on physicochemical properties and thermal decomposition of the fully bio-based poly(propylene succinate-co-butylene succinate)s

In this work, two polyesters and four copolyesters were studied. All materials were synthesized to obtain the monomers dedicated for thermoplastic polyurethane elastomers. For this type of PUR, the monomers should characterize by appropriate selected physicochemical properties and macromolecular structure distribution, which depends on synthesis conditions. The study of chemical structure with extensive and knowledgeable analysis of formed macromolecules of synthesized bio-based copolyesters was conducted with the use of FTIR and 1H NMR spectroscopy and MALDI-ToF mass spectrometry. The results allowed to propose the majority of probable chemical structures of macromolecules formed during synthesis. Moreover, the impact of the structure on the thermal stability of the obtained copolyesters was also determined with the use of thermogravimetric analysis. The temperature of the beginning of thermal decomposition equaled even 330 °C. Furthermore, the results of DSC-TG/QMS coupled method confirmed that all prepared polyesters degraded by α and β-hydrogen bond scission mechanisms.

Understanding bioplastic materials - current state and trends

Plastic pollution is now considered one of the largest environmental threats facing humans and animals globally. Development of bioplastic materials may offer part of the solution as bioplastics include both nondegradable and biodegradable materials with both being important for sustainability. Bioplastic materials are currently being designed to encompass minimal carbon footprint, high recycling value and complete biodegradability. This review examines recent developments and trends in the field of bioplastic materials. A range of the most utilized bioplastic materials is presented (poly(lactic acid) (PLA), polyhydroxyalkanoate (PHA), starch, cellulose, bio-based poly(butylene succinate) (bio-PBS) and bio-polyethylene (bio-PE)) including their production, application and degradation options.