Improvements in the Production of Isosorbide Monomethacrylate Using a Biobased Catalyst and Liquid-Liquid Extraction Isolation for Modifications of Oil-Based Resins.

The improved production of a polar curable monomer, isosorbide monomethacrylate (MISD), with methacrylic anhydride (MAAH) as an acyl donor, was performed. A sustainable and cheap catalyst, potassium acetate (CH3COOK), was used for a solvent-free synthesis, requiring only the equimolar amount of reagents (no excess). The production included the quantitative separation of the secondary product, methacrylic acid (MAA), preventing the reaction batch from the purification process (neutralization of MAA), and gaining a usable reagent. The synthesis resulted in a sufficient yield of MISD (61.8%) obtained by the liquid-liquid extraction process (LLE), which is a significant improvement in the process, avoiding the flash chromatography step in the isolation of MISD. The purity of synthesized and isolated MISD via the LLE was confirmed by 1H NMR, MS, and FTIR analyses. The thermal analyses, namely, DSC and TGA, were used to characterize the curability and thermal stability of MISD. The activation energy of MISD's curing was calculated (E a = 94.6 kJ/mol) along with the heat-resistant index (T s = 136.8). The polar character of isosorbide monomethacrylate was investigated in a mixture with epoxidized acrylated soybean oil (EASO). It was found that MISD is entirely soluble in EASO and can modify the rheological behavior and surface energy of EASO-based resins. The apparent viscosity of EASO at 30 °C (ηapp = 3413 mPa·s) decreased with the 50% content of MISD significantly (ηapp = 500 mPa·s), and the free surface energy value of EASO (γS = 42.2 mJ/m2) also increased with the 50% content of MISD (γS = 48.7 mJ/m2). The produced MISD can be successfully used as a diluent and the polarity modifier of curable oil-based resins.

A Study of Isosorbide Synthesis from Sorbitol for Material Applications Using Isosorbide Dimethacrylate for Enhancement of Bio-Based Resins.

Bio-based cross-linkers can fulfill the role of enhancing additives in bio-sourced curable materials that do not compare with artificial resin precursors. Isosorbide dimethacrylate (ISDMMA) synthesized from isosorbide (ISD) can serve as a cross-linker from renewable sources. Isosorbide is a bicyclic carbon molecule produced by the reaction modification of sorbitol and the optimal conditions of this reaction were studied in this work. The reaction temperature of 130 °C and 1% w/w amount of para-toluenesulfonic acid (p-TSA) were determined as optimal and resulted in a yield of 81.9%. Isosorbide dimethacrylate was synthesized via nucleophilic substitution with methacrylic anhydride (MAA) with the conversion of 94.1% of anhydride. Formed ISD and ISDMMA were characterized via multiple verification methods (FT-IR, MS, 1H NMR, and XRD). Differential scanning calorimetry (DSC) proved the curability of ISDMMA (activation energy Ea of 146.2 kJ/mol) and the heat-resistant index of ISDMMA (Ts reaching value of 168.9) was determined using thermogravimetric analysis (TGA). Characterized ISDMMA was added to the precursor mixture containing methacrylated alkyl 3-hydroxybutyrates (methyl ester M3HBMMA and ethyl ester E3HBMMA), and the mixtures were cured via photo-initiation. The amount of ISDMMA cross-linker increased all measured parameters obtained via dynamic mechanical analysis (DMA), such as storage modulus (E') and glass transition temperature (Tg), and the calculated cross-linking densities (νe). Therefore, the enhancement influence of bio-based ISDMMA on resins from renewable sources was confirmed.

Poly(3-hydroxybutyrate) (PHB) and Polycaprolactone (PCL) Based Blends for Tissue Engineering and Bone Medical Applications Processed by FDM 3D Printing.

In the presented work, poly(3-hydroxybutyrate)-PHB-based composite blends for bone medical applications and tissue engineering are prepared and characterized. PHB used for the work was in two cases commercial and, in one case, was extracted by the chloroform-free route. PHB was then blended with poly(lactic acid) (PLA) or polycaprolactone (PCL) and plasticized by oligomeric adipate ester (Syncroflex, SN). Tricalcium phosphate (TCP) particles were used as a bioactive filler. Prepared polymer blends were processed into the form of 3D printing filaments. The samples for all the tests performed were prepared by FDM 3D printing or compression molding. Differential scanning calorimetry was conducted to evaluate the thermal properties, followed by optimization of printing temperature by temperature tower test and determination of warping coefficient. Tensile test, three-point flexural test, and compression test were performed to study the mechanical properties of materials. Optical contact angle measurement was conducted to determine the surface properties of these blends and their influence on cell adhesion. Cytotoxicity measurement of prepared blends was conducted to find out whether the prepared materials were non-cytotoxic. The best temperatures for 3D printing were 195/190, 195/175, and 195/165 °C for PHB-soap/PLA-SN, PHB/PCL-SN, and PHB/PCL-SN-TCP, respectively. Their mechanical properties (strengths ~40 MPa, moduli ~2.5 GPa) were comparable with human trabecular bone. The calculated surface energies of all blends were ~40 mN/m. Unfortunately, only two out of three materials were proven to be non-cytotoxic (both PHB/PCL blends).

Synthesis of Bio-Based Thermoset Mixture Composed of Methacrylated Rapeseed Oil and Methacrylated Methyl Lactate: One-Pot Synthesis Using Formed Methacrylic Acid as a Continual Reactant.

Methacrylated vegetable oils are promising bio-based polymerizable precursors for potential material application in several fields, such as coating technologies or 3D printing. The reactants' availability for their production is an enormous advantage, but the modified oils also exhibit high apparent viscosity values and poor mechanical properties. This work focuses on a way to produce oil-based polymerizable material precursors in a mixture with a viscosity modifier in a one-batch process. The required methacrylic acid for the modification of epoxidized vegetable oils can be obtained as a secondary product of the methacrylation of methyl lactate forming a polymerizable monomer along with the acid. This reaction results in a yield of over 98% of methacrylic acid. Epoxidized vegetable oil can be added into the same batch using acid for oil modification which results in the one-pot mixture of both methacrylated oil and methyl lactate. The structural verifications of products were provided via FT-IR, 1H NMR, and volumetric methods. This two-step reaction process produces a thermoset mixture with a lower apparent viscosity of 142.6 mPa·s in comparison with methacrylated oil exhibiting a value of 1790.2 mPa·s. Other physical-chemical properties of the resin mixture such as storage modulus (E' = 1260 MPa), glass transition temperature (Tg = 50.0 °C), or polymerization activation energy (17.3 kJ/mol) are enhanced in comparison with the methacrylated vegetable oil. The synthesized one-pot mixture does not require additional methacrylic acid due to the use of the one formed in the first step of the reaction, while the eventual thermoset mixture exhibits enhanced material properties compared to the methacrylated vegetable oil itself. Precursors synthesized in this work may find their purpose in the field of coating technologies, since these applications require detailed viscosity modifications.

High-Pressure Depolymerization of Poly(lactic acid) (PLA) and Poly(3-hydroxybutyrate) (PHB) Using Bio-Based Solvents: A Way to Produce Alkyl Esters Which Can Be Modified to Polymerizable Monomers.

The polyesters poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) used in various applications such as food packaging or 3D printing were depolymerized by biobased aliphatic alcohols-methanol and ethanol with the presence of para-toluenesulphonic acid (p-TSA) as a catalyst at a temperature of 151 °C. It was found that the fastest depolymerization is reached using methanol as anucleophile for the reaction with PLA, resulting in the value of reaction rate constant (k) of 0.0425 min-1 and the yield of methyl lactate of 93.8% after 120 min. On the other hand, the value of constant k for the depolymerization of PHB in the presence of ethanol reached 0.0064 min-1 and the yield of ethyl 3-hydroxybutyrate was of 76.0% after 240 min. A kinetics study of depolymerization was performed via LC-MS analysis of alkyl esters of lactic acid and 3-hydroxybutanoic acid. The structure confirmation of the products was performed via FT-IR, MS, 1H NMR, and 13C NMR. Synthesized alkyl lactates and 3-hydroxybutyrates were modified into polymerizable molecules using methacrylic anhydride as a reactant and potassium 2-ethylhexanoate as a catalyst at a temperature of 80 °C. All alkyl esters were methacrylated for 24 h, guaranteeing the quantitative yield (which in all cases reached values equal to or of more than 98%). The methacrylation rate constants (k') were calculated to compare the reaction kinetics of each alkyl ester. It was found that lactates reach afaster rate of reaction than 3-hydroxybutyrates. The value of k' for themethacrylated methyl lactate reached 0.0885 dm3/(mol·min). Opposite to this result, methacrylated ethyl 3-hydroxybutyrate's constant k' was 0.0075 dm3/(mol·min). The reaction rate study was conducted by the GC-FID method and the structures were confirmed via FT-IR, MS, 1H NMR, and 13C NMR.

Evaluation of the Properties of PHB Composite Filled with Kaolin Particles for 3D Printing Applications Using the Design of Experiment.

In the presented work, poly(3-hydroxybutyrate)-PHB-based composites for 3D printing as bio-sourced and biodegradable alternatives to synthetic plastics are characterized. The PHB matrix was modified by polylactide (PLA) and plasticized by tributyl citrate. Kaolin particles were used as a filler. The mathematical method "Design of Experiment" (DoE) was used to create a matrix of samples for further evaluation. Firstly, the optimal printing temperature of the first and upper layers was determined. Secondly, the 3D printed samples were tested with regards to the warping during the 3D printing. Testing specimens were prepared using the determined optimal printing conditions to measure the tensile properties, impact strength, and heat deflection temperature (HDT) of the samples. The results describe the effect of adding individual components (PHB, PLA, plasticizer, and filler) in the prepared composite sample on the resulting material properties. Two composite samples were prepared based on the theoretical results of DoE (one with the maximum printability and one with the maximum HDT) to compare them with the real data measured. The tests of these two composite samples showed 25% lower warping and 8.9% higher HDT than was expected by the theory.

PLA/PHB-Based Materials Fully Biodegradable under Both Industrial and Home-Composting Conditions.

In order to make bioplastics accessible for a wider spectrum of applications, ready-to-use plastic material formulations should be available with tailored properties. Ideally, these kinds of materials should also be "home-compostable" to simplify their organic recycling. Therefore, materials based on PLA (polylactid acid) and PHB (polyhydroxybutyrate) blends are presented which contain suitable additives, and some of them contain also thermoplastic starch as a filler, which decreases the price of the final compound. They are intended for various applications, as documented by products made out of them. The produced materials are fully biodegradable under industrial composting conditions. Surprisingly, some of the materials, even those which contain more PLA than PHB, are also fully biodegradable under home-composting conditions within a period of about six months. Experiments made under laboratory conditions were supported with data obtained from a kitchen waste pilot composter and from municipal composting plant experiments. Material properties, environmental conditions, and microbiology data were recorded during some of these experiments to document the biodegradation process and changes on the surface and inside the materials on a molecular level.

Slow-Release Nitrogen Fertilizers with Biodegradable Poly(3-hydroxybutyrate) Coating: Their Effect on the Growth of Maize and the Dynamics of N Release in Soil.

Fertilizers play an essential role in agriculture due to the rising food demand. However, high input fertilizer concentration and the non-controlled leaching of nutrients cause an unwanted increase in reactive, unassimilated nitrogen and induce environmental pollution. This paper investigates the preparation and properties of slow-release fertilizer with fully biodegradable poly(3-hydroxybutyrate) coating that releases nitrogen gradually and is not a pollutant for soil. Nitrogen fertilizer (calcium ammonium nitrate) was pelletized with selected filler materials (poly(3-hydroxybutyrate), struvite, dried biomass). Pellets were coated with a solution of poly(3-hydroxybutyrate) in dioxolane that formed a high-quality and thin polymer coating. Coated pellets were tested in aqueous and soil environments. Some coated pellets showed excellent resistance even after 76 days in water, where only 20% of the ammonium nitrate was released. Pot experiments in Mitscherlich vegetation vessels monitored the effect of the application of coated fertilizers on the development and growth of maize and the dynamics of N release in the soil. We found that the use of our coated fertilizers in maize nutrition is a suitable way to supply nutrients to plants concerning their needs and that the poly(3-hydroxybutyrate) that was used for the coating does not adversely affect the growth of maize plants.

Influence of Multiple Thermomechanical Processing of 3D Filaments Based on Polylactic Acid and Polyhydroxybutyrate on Their Rheological and Utility Properties.

This study focused on material recycling of a biodegradable blend based on PLA and PHB for multiple applications of biodegradable polymeric material under real conditions. In this study, we investigated the effect of multiple processing of a biodegradable polymer blend under the trade name NONOILEN®, which was processed under laboratory as well as industrial conditions. In this article, we report on testing the effect of blending and multiple processing on thermomechanical stability, molecular characteristics, as well as thermophysical and mechanical properties of experimental- and industrial-type tested material suitable for FDM 3D technology. The results showed that the studied material degraded during blending and subsequently during multiple processing. Even after partial degradation, which was demonstrated by a decrease in average molecular weight and a decrease in complex viscosity in the process of multiple reprocessing, there was no significant change in the material's thermophysical properties, either in laboratory or industrial conditions. There was also no negative impact on the strength characteristics of multiple processed samples. The results of this work show that a biodegradable polymer blend based on PLA and PHB is a suitable candidate for material recycling even in industrial processing conditions. In addition, the results suggest that the biodegradable polymeric material NONOILEN® 3D 3056-2 is suitable for multiple uses in FDM technology.

Isolation of poly(3-hydroxybutyrate) from bacterial biomass using soap made of waste cooking oil.

The aim of this work was to develop a soap-based method for the isolation of poly(3-hydroxybutyrate) from bacterial biomass. The method consisted of adding soap derived from waste cooking oil to a concentrated (25%) biomass suspension, heating and centrifugal separation. Purity above 95% could be achieved with soap:cell dry mass ratios at least 0.125 g/g, making the method comparable to other surfactant-based protocols. Molecular weights Mw of products from all experiments were between 350 and 450 kDa, being high enough for future material applications. Addition of hydrochloric acid to the wastewater led to the precipitation of soap and part of non-P3HB cell mass. The resulting precipitate was utilized as a carbon source in biomass production and increased substrate-to-P3HB conversion.

FDM 3D Printed Composites for Bone Tissue Engineering Based on Plasticized Poly(3-hydroxybutyrate)/poly(d,l-lactide) Blends.

Tissue engineering is a current trend in the regenerative medicine putting pressure on scientists to develop highly functional materials and methods for scaffolds' preparation. In this paper, the calibrated filaments for Fused Deposition Modeling (FDM) based on plasticized poly(3-hydroxybutyrate)/poly(d,l-lactide) 70/30 blend modified with tricalcium phosphate bioceramics were prepared. Two different plasticizers, Citroflex (n-Butyryl tri-n-hexyl citrate) and Syncroflex (oligomeric adipate ester), both used in the amount of 12 wt%, were compared. The printing parameters for these materials were optimized and the printability was evaluated by recently published warping test. The samples were studied with respect to their thermal and mechanical properties, followed by biological in vitro tests including proliferation, viability, and osteogenic differentiation of human mesenchymal stem cells. According to the results from differential scanning calorimetry and tensile measurements, the Citroflex-based plasticizer showed very good softening effect at the expense of worse printability and unsatisfactory performance during biological testing. On the other hand, the samples with Syncroflex demonstrated lower warping tendency compared to commercial polylactide filament with the warping coefficient one third lower. Moreover, the Syncroflex-based samples exhibited the non-cytotoxicity and promising biocompatibility.

Printability, Mechanical and Thermal Properties of Poly(3-Hydroxybutyrate)-Poly(Lactic Acid)-Plasticizer Blends for Three-Dimensional (3D) Printing.

This paper investigates the effect of plasticizer structure on especially the printability and mechanical and thermal properties of poly(3-hydroxybutyrate)-poly(lactic acid)-plasticizer biodegradable blends. Three plasticizers, acetyl tris(2-ethylhexyl) citrate, tris(2-ethylhexyl) citrate, and poly(ethylene glycol)bis(2-ethylhexanoate), were first checked whether they were miscible with poly(3-hydroxybutyrate)-poly(lactic acid) (PHB-PLA) blends using a kneading machine. PHB-PLA-plasticizer blends of 60-25-15 (wt.%) were then prepared using a corotating meshing twin-screw extruder, and a single screw extruder was used for filament preparation for further three-dimensional (3D) fused deposition modeling (FDM) printing. These innovative eco-friendly PHB-PLA-plasticizer blends were created with a majority of PHB, and therefore, poor mechanical properties and thermal properties of neat PHB-PLA blends were improved by adding appropriate plasticizer. The plasticizer also influences the printability of blends, which was investigated, based on our new specific printability tests developed for the optimization of printing conditions (especially printing temperature). Three-dimensional printed test samples were used for heat deflection temperature measurements and Charpy and tensile-impact tests. Plasticizer migration was also investigated. The macrostructure of 3D printed samples was observed using an optical microscope to check the printing quality and printing conditions. Tensile tests of 3D printed samples (dogbones), as well as extruded filaments, showed that measured elongation at break raised, from 21% for non-plasticized PHB-PLA reference blends to 84% for some plasticized blends in the form of filaments and from 10% (reference) to 32% for plasticized blends in the form of printed dogbones. Measurements of thermal properties (using modulated differential scanning calorimetry and oscillation rheometry) also confirmed the plasticizing effect on blends. The thermal and mechanical properties of PHB-PLA blends were improved by the addition of appropriate plasticizer. In contrast, the printability of the PHB-PLA reference seems to be slightly better than the printability of the plasticized blends.

A critical review of the overlooked challenge of determining micro-bioplastics in soil.

Currently, non-biodegradable oil-based plastics are gradually being replaced by bio-based biodegradable plastics to prevent the formation of microplastics. For biodegradable materials to decompose completely, however, they require specific conditions that are rarely met in ecosystems. Paradoxically, this may lead to the fast production of microplastics from biodegradable materials, i.e. micro-bioplastics. Until recently, the scientific focus has been solely on the estimation of conventional microplastics. As a result, there is a lack of analytical methods for determining the amount of micro-bioplastics in soil. In this review, we address this problem by summarising sample pre-treatments and analytical techniques suitable for the determination of conventional microplastics, which serve as inspiration for the determination of micro-bioplastics from polyhydroxybutyrates, polylactic acid and polybutylene adipate terephthalate in soil. The analytical techniques include both pyrolysis-based techniques, i.e. thermoanalytical and non-thermoanalytical approaches including sample pre-separation and respective detection limits. We conclude that due to the incomplete knowledge of the production rate of micro-bioplastics, fate, sorption properties and toxicity, it is necessary to develop and validate a rapid and suitable method for their determination. Indeed, the use of thermoanalytical approaches seems to be the most promising strategy. Furthermore, we suggest how the development and analysis of micro-bioplastics should be addressed in future research.

Effect of Selected Commercial Plasticizers on Mechanical, Thermal, and Morphological Properties of Poly(3-hydroxybutyrate)/Poly(lactic acid)/Plasticizer Biodegradable Blends for Three-Dimensional (3D) Print.

This paper explores the influence of selected commercial plasticizers structure, which are based on esters of citric acid, on mechanical and thermal properties of Poly(3-hydroxybutyrate)/Poly(lactic acid)/Plasticizer biodegradable blends. These plasticizers were first tested with respect to their miscibility with Poly(3-hydroxybutyrate)/Poly(lactic acid) (PHB/PLA) blends using a kneading machine. PHB/PLA/plasticizer blends in the weight ratio (wt %) of 60/25/15 were then prepared by single screw and corotating meshing twin screw extruders in the form of filament for further three-dimensional (3D) printing. Mechanical, thermal properties, and shape stability (warping effect) of 3D printed products can be improved just by the addition of appropriate plasticizer to polymeric blend. The goal was to create new types of eco-friendly PHB/PLA/plasticizers blends and to highly improve the poor mechanical properties of neat PHB/PLA blends (with majority of PHB) by adding appropriate plasticizer. Mechanical properties of plasticized blends were then determined by the tensile test of 3D printed test samples (dogbones), as well as filaments. Measured elongation at break rapidly enhanced from 21% for neat non-plasticized PHB/PLA blends (reference) to 328% for best plasticized blends in the form of filament, and from 5% (reference) to 187% for plasticized blends in the form of printed dogbones. The plasticizing effect on blends was confirmed by Modulated Differential Scanning Calorimetry. The study of morphology was performed by the Scanning Electron Microscopy. Significant problem of plasticized blends used to be also plasticizer migration, therefore the diffusion of plasticizers from the blends after 15 days of exposition to 110 °C in the drying oven was investigated as their measured weight loss. Almost all of the used plasticizers showed meaningful positive softening effects, but the diffusion of plasticizers at 110 °C exposition was quite extensive. The determination of the degree of disintegration of selected plasticized blend when exposed to a laboratory-scale composting environment was executed to roughly check the "biodegradability".

Protective Properties of a Microstructure Composed of Barrier Nanostructured Organics and SiOx Layers Deposited on a Polymer Matrix.

The SiOx barrier nanocoatings have been prepared on selected polymer matrices to increase their resistance against permeation of toxic substances. The aim has been to find out whether the method of vacuum plasma deposition of SiOx barrier nanocoatings on a polyethylene terephthalate (PET) foil used by Aluminium Company of Canada (ALCAN) company (ALCAN Packaging Kreuzlingen AG (SA/Ltd., Kreuzlingen, Switzerland) within the production of CERAMIS® packaging materials with barrier properties can also be used to increase the resistance of foils from other polymers against the permeation of organic solvents and other toxic liquids. The scanning electron microscopy (SEM) microstructure of SiOx nanocoatings prepared by thermal deposition from SiO in vacuum by the Plasma Assisted Physical Vapour Deposition (PA-PVD) method or vacuum deposition of hexamethyldisiloxane (HMDSO) by the Plasma-enhanced chemical vapour deposition (PECVD) method have been studied. The microstructure and behavior of samples when exposed to a liquid test substance in relation to the barrier properties is described.