Polybutylene Succinate Adipate Research Articles

Development of PBS/Nano Composite PHB-Based Multilayer Blown Films with Enhanced Properties for Food Packaging Applications.

Biobased and biodegradable plastics have emerged as promising alternatives to conventional plastics offering the potential to reduce environmental impacts while promoting sustainability. This study focuses on the production of multilayer blown films with enhanced functional properties suitable for food packaging applications. Films were developed through co-extrusion in a three-layer film configuration, with Polybutylene Succinate (PBS) and Polybutylene Succinate Adipate (PBSA) as the external and internal layers, respectively. The functional layer consisted of Polyhydroxybutyrate (PHB) enhanced with nanoclays Cloisite® 30B at varying weight ratios. Films were also processed by manipulating the extruder screw speed of the functional layer to investigate its impact on the functional properties. Rheology, mechanical strength, and barrier performance were characterised to establish correlations between processing conditions and functional layer blends (Cloisite® 30B/PHB) on the properties of the resultant films. Rheological test results indicated that the system with 5% Cloisite® had the best polymer/nanofiller matrix dispersion. Mechanical and permeability tests showed that by varying the process conditions (the alteration of the thickness of the functionalized layer) resulted in an improvement in mechanical and barrier properties. Furthermore, the addition of the nanofiller resulted in a stiffening of the film with a subsequent decrease in permeability to oxygen and water vapour.

In-Line Chemical Composition Monitoring for the Injection Molding Process of Biodegradable Polymer Blends Using Simultaneous Measurement of Near-Infrared Diffuse Reflectance and Transmission Spectra.

In the processing of polymer blends and composites, in-line near-infrared (NIR) spectroscopy enables monitoring of the composition and its composite uniformity and contributes to rapid process development and quality control. However, in the injection molding process, the study of the composition of polymer materials has been delayed due to high-pressure conditions. Our research group developed NIR probes for transmission and diffuse reflectance measurements that can withstand high-pressure and temperature conditions up to 130 MPa and 200 °C. In this research, transmission and diffuse reflectance spectra were measured inline during the injection molding process of polymer blends of poly(lactic acid) and polybutylene succinate adipate. The intensity of each polymer band in the second-derivative spectra exhibited a monotonic increase or decrease in response to changes in the blend ratio. Using transmission and diffuse reflectance spectra as explanatory variables of the partial least squares regression model simultaneously, the model showed high estimation accuracy for the entire region of the blend ratio. Finally, this model was applied to monitor the polymer changeover operation, and the change in the blend ratio in the molded product was successfully estimated in line.

A lesson from polybutylene succinate plastisphere to the discovery of novel plastic degrading enzyme genes in marine vibrios.

Polybutylene succinate (PBS) is an eco-friendly green plastic. However, PBS was shown as being non-biodegradable in marine environments, and up until now, only a limited number of PBS-degrading marine microbes have been discovered. We first set up in vitro PBS- and PBSA (polybutylene succinate adipate)-plastispheres to characterize novel PBS-degrading marine microbes. Microbial growth and oxygen consumption were observed in both PBS- and PBSA-plastispheres enriched with natural seawater collected from Usujiri, Hokkaido, Japan, and Vibrionaceae and Pseudoalteromonadaceae were significantly enriched on these films. Further gene identification indicated that vibrios belonging to the Gazogenes clade possess genes related to a PBS degrading enzyme (PBSase). The PBS degradation assay for six Gazogenes clade vibrios identified Vibrio ruber, Vibrio rhizosphaerae, and Vibrio spartinae as being capable of degrading PBS. We further identified the gene responsible for PBSase from the type strain of V. ruber, and the purified recombinant vibrio PBSase was found to have low-temperature adaptation and was active under high NaCl concentrations. We also provided docking models between the vibrio PBSase and PBS and PBSA units to show how vibrio PBSase interacts with each substrate compared to the Acidovorax PBSase. These results could contribute to a more sustainable society through further utilization of PBS in marine environments and plastic recycling.

Overview of the mechanical, thermal and barrier properties of biobased and/or biodegradable thermoplastic materials

This study gives an overview of the most relevant processing and performance properties of a wide selection of biobased and biodegradable plastic materials that are currently commercially available. It provides the most extensive and up-to-date scientific overview of critical properties of biobased and biodegradable plastics. Materials that are tested include fully biobased polymers (polylactic acid, polyethylene, polyamide 10,10 and a range of polyhydroxy alkanoates), partially biobased polymers (polybutylene succinate, polybutylene succinate adipate, cellulose acetate, cellulose acetate propionate, polyethylene terephthalate, polytrimethylene terephthalate, an isosorbide based polycarbonate, a thermoplastic urethane and a starch based blend) and a number of fossil-based materials (polycaprolactone, polybutylene adipate terephthalate, polyglycolic acid and polypropylene). The mechanical (tensile, flexural, impact resistance and hardness), thermal (glass transition temperature, melting temperature, melt-flow index and haul-off force) and barrier (oxygen transmission rate, water vapour transmission rate) properties of all these materials were measured and are presented in a comprehensive overview. This overview shows that the majority of functionalities that are currently being offered by fossil based polymers can be met by biobased alternatives and by biodegradable materials if this is considered to be favourable at end-of-life.

Lamination of Cast Hemp Paper with Bio-Based Plastics for Sustainable Packaging: Structure-Thermomechanical Properties Relationship and Biodegradation Studies

Composite laminate recycling and waste disposal routes remain a burden to existing systems, requiring special treatment and separation. The inclusion of a plastic layer is important for several key properties that are required for food safety, which in turn has made these products exceptionally hard to substitute in food packaging. Yet, the continued use of non-degradable commodity plastics is unsustainable. In this research, we compare the four most promising biodegradable and bio-based plastics that could replace non-degradable plastics in laminates. Polyhydroxyalkanoate (PHA), polylactic acid (PLA), polybutylene succinate (PBS), and polybutylene succinate adipate (PBSA) were applied as a direct melt coating on porous cast hemp papers, and the final composite was compressed under three different loads: 0.5 MT, 1.5 MT, and 3.0 MT. To promote sustainable agriculture waste management, we opted to use cast paper made from ground hemp stalks. The formation of the composite structure was examined with scanning electron microscopy (SEM), while surface wetting on the paper side of the laminate was performed to understand structural changes induced by polymer impregnation into the paper layer. Mechanical performance properties were investigated with tensile and peel tests, and suitability for an extended range of temperatures was examined with dynamical mechanical analysis. An increase in compression pressure yielded up to a two-fold improvement in elastic modulus and tensile strength, while thermomechanical analysis revealed that the polymer’s transition into a viscoelastic state significantly affected the laminate’s storage modulus values. Biodegradation was performed in a controlled compost at 58 °C, resulting in full degradation within 40 to 80 days, with PLA and PHA laminates showing 40 and 50 days, respectively. Produced bioplastic laminates have a tremendous potential to replace polyolefin laminates in packaging applications.

Effect of Mineral Fillers on the Mechanical Properties of Commercially Available Biodegradable Polymers.

In the successful transition towards a circular materials economy, the implementation of biobased and biodegradable plastics is a major prerequisite. To prevent the accumulation of plastic material in the open environment, plastic products should be both recyclable and biodegradable. Research and development actions in the past few decades have led to the commercial availability of a number of polymers that fulfil both end-of-life routes. However, these biobased and biodegradable polymers typically have mechanical properties that are not on par with the non-biodegradable plastic products they intend to replace. This can be improved using particulate mineral fillers such as talc, calcium carbonate, kaolin, and mica. This study shows that composites thereof with polybutylene succinate (PBS), polyhydroxybutyrate-hexanoate (PHBH), polybutylene succinate adipate (PBSA), and polybutylene adipate terephthalate (PBAT) as matrix polymers result in plastic materials with mechanical properties ranging from tough elastic towards strong and rigid. It is demonstrated that the balance between the Young’s modulus and the impact resistance for this set of polymer composites is subtle, but a select number of investigated compositions yield a combination of industrially relevant mechanical characteristics. Finally, it is shown that the inclusion of mineral fillers into biodegradable polymers does not negate the microbial disintegration of these polymers, although the nature of the filler does affect the biodegradation rate of the matrix polymer.

16S rRNA Gene Amplicon Sequencing of Microbiota in Polybutylene Succinate Adipate-Packed Denitrification Reactors Used for Water Treatment of Land-Based Recirculating Aquaculture Systems.

Information on the microbiota in polybutylene succinate adipate (PBSA)-packed denitrification reactors is limited. Here, we provide 439,817 high-quality reads of the 16S rRNA gene sequences of microbiota in PBSA-packed denitrification reactors used for land-based recirculating aquaculture. The predominant microorganisms belonged to the following families: Nocardiaceae, Chitinophagaceae, Xanthobacteraceae, Burkholderiaceae, Rhodocyclaceae, Pseudomonadaceae, Rhodanobacteraceae, and Xanthomonadaceae.

Molecular and Supramolecular Changes in Polybutylene Succinate (PBS) and Polybutylene Succinate Adipate (PBSA) Copolymer during Degradation in Various Environmental Conditions.

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.

Development of cardanol-bonded cellulose thermoplastics: high productivity achieved in two-step heterogeneous process

We developed a heterogeneous process with low energy consumption to synthesize novel high-strength and heat-resistant cellulose-based bioplastics: cellulose esters bonded with a short chain component (acetic acid) and a long one (3-pentadecylphenoxy acetic acid; PAA), which is a derivative of cardanol, extracted from cashew nut shells. Although we recently showed that PAA-bonded cellulose acetates (cardanol-bonded cellulose resins) exhibit highly practical properties for durable products, they were synthesized in a homogeneous process, which requires large quantities of poor solvents to isolate the resins. In the developed two-step heterogeneous process, the cardanol-bonded cellulose resins are produced without poor solvents. In the first step, cellulose is esterified with limited amounts of the long and short chain components using a selected reaction solvent and catalyst. The resultant intermediate products are adequately swollen in the solvent then efficiently recovered by filtration. In the second step, the short chain component is additionally bonded to attain good thermoplasticity of the final products, which are readily recovered only by distilling a solvent and the remaining short chain component. The solvent usage was reduced by approximately 90 % compared with a homogeneous process, which leads to a large reduction in energy. The produced cardanol-bonded cellulose resins exhibited higher thermoplasticity, elastic modulus, water resistivity, and close heat resistivity compared to that of a homogeneous process. Furthermore, the mechanical and thermal characteristics of the resins were greatly improved by adding a specific polyester, polybutylene succinate adipate, and glass fiber, reaching high-level target properties for durable products.

Greenhouse gas emissions from the treatment of household plastic containers and packaging: Replacement with biomass-based materials

The purpose of this study was to quantify the life-cycle greenhouse gas (GHG) emissions reduction that could be achieved by replacement of fossil-derived materials with biodegradable, biomass-based materials for household plastic containers and packaging, considering a variety of their treatment options. The biomass-based materials were 100% polylactide or a combination of polybutylene succinate adipate and polylactide. A scenario analysis was conducted considering alternative recycling methods. Five scenarios were considered: two for existing fossil-derived materials (the current approach in Japan) and the three for biomass-based materials. Production and waste disposal of 1 m(3) of plastic containers and packaging from households was defined as the functional unit. The results showed that replacement of fossil-derived materials with biomass-based materials could reduce life-cycle GHG emissions by 14-20%. Source separation and recycling should be promoted. When the separate collection ratio reached 100%, replacement with biomass-based materials could potentially reduce GHG emissions by 31.9%. Food containers are a priority for replacement, because they alone could reduce GHG emissions by 10%. A recycling system for biomass-based plastics must be carefully designed, considering aspects such as the transition period from fossil-derived plastics to biomass-based plastics.

Formation of highly oriented biodegradable polybutylene succinate adipate nanocomposites: Effects of cation structures on morphology, free volume, and properties

AbstractMany biodegradable polymer materials have not been found to be suitable replacements for more traditional non‐biodegradable polymers owing to their insufficient gas and vapor barrier properties. The use of a series of novel organically modified synthetic fluorohectorites (FHTs) has been explored to produce biodegradable polybutylene succinate adipate (PBSA)‐clay nanocomposites with improved barrier. Highly oriented nanoclay structures (clearly showing a tortuous path required to reduce gas and vapor transmission) were observed using transmission electron microscopy (TEM), resulting in a significant reduction in oxygen permeability (up to a 53% decrease). In particular, these oriented structures were observed in the FHTs modified with di poly(oxyethylene) alkyl methyl ammonium and the longer chain dimethyl dialkyl ammonium. Orientation and dispersion were found to be a result of chemical functionality, chain length, and unique aspect ratios of these FHTs. It was concluded that this reduction in permeability was predominantly due to the tortuous path created by oriented platelets and not from any nucleating effects the platelets may have had. Interestingly, the FHTs were shown to disrupt crystallinity and no change in free volume (as measured using positron annihilation life‐time spectroscopy) was observed. The excellent clay dispersion and orientation also led to significant increases in other properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Melt‐based compression‐molded scaffolds from chitosan–polyester blends and composites: Morphology and mechanical properties

Blends of chitosan and synthetic aliphatic polyesters (polybutylene succinate, polybutylene succinate adipate, polycaprolactone, and polybutylene terepthalate adipate) were compounded with and without hydroxyapatite, a bioactive mineral filler known to enhance osteoconduction. The blends and composites were compression molded with two different granulometric salt sizes (63-125 microm and 250-500 microm) having different levels of salt content (60, 70, and 80%) by weight. By leaching the salt particles, it was possible to produce porous scaffolds with distinct morphologies. The relationship between scaffold morphology and mechanical properties was evaluated using scanning electron microscopy, microcomputed tomography, compression testing, differential scanning calorimetry, small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering. The produced scaffolds are characterized by having different morphologies depending on the average particle size and the amount of NaCl used. Specimens with higher porosity level have a less organized pore structure but increased interconnectivity of the pores. The stress-strain curve under compression displayed a linear elasticity followed by a plateau whose characteristics depend on the scaffold polymer composition. A decrease in the salt particle size used to create the porosity caused in general a decrease in the mechanical properties of the foams. Composites with hydroxyapatite had a sharp reduction in yield stress, modulus, and strain at break. The melting temperature decreased with increased chitosan content. SAXS results indicate no preferential crystalline orientation in the scaffolds. Cytotoxicity evaluation were carried out using standard tests (accordingly to ISO/EN 10993 part 5 guidelines), namely MTS test with a 24-h extraction period, revealing that L929 cells had comparable metabolic activities to that obtained for the negative control.

Electrical Conduction and Breakdown Properties of Several Biodegradable Polymers

In order to respond to soaring public concern about environmental protection, various biodegradable polymers have been developed. The present paper reports the electrical conduction and breakdown properties of various biodegradable polymers such as poly-L-lactic acid (PLLA), polyethylene terephthalate succinate (PETS), polycaprolactone butylene succinate (PCL-BS), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), and polyhydroxybutyrate/valerate (PHB/V) in comparison to those of low-density polyethylene (LDPE). While the permittivity and conductivity of PLLA and PETS are comparable to LDPE, those of PCL-BS and PBS are much higher. The conductivity is also higher in PBSA. This is because PLLA and PETS are in the glass state at room temperature, while PCL-BS, PBS, and PBSA are in the rubber state. Furthermore, PLLA and PETS show a strong temperature dependence of the conductivity, which is divided into two or three regions, and they also show thermally stimulated polarization or depolarization current around their respective glass transition temperatures. In contrast to the large difference in conductivity among different kinds of samples, all the polymers tested have almost similar impulse breakdown strength at room temperature. As for dc or ac breakdown strength, PLLA and PETS show a relatively higher strength than PCL-BS and PBS.

Investigation of Polybutylene Succinate-co-Adipate (PBSA)/Montmorillonite Layered Silicate (MLS) Melt-Processed Nanocomposites

Biodegradable nanocomposites were prepared with polybutylene succinate adipate (PBSA) and three organically modified montmorillonite layered silicates (MLSs) by melt-extrusion methods at three screw speeds (20, 40, and 60 rpm) to determine the interaction and properties of the polymer/MLS nanocomposites. The samples were evaluated by X-ray diffraction (XRD) and transmission electron microscopy (TEM) to determine the level of MLS interaction with PBSA. All formulations formed varying degrees of intercalation regardless of the modification of the MLS or the variation of the screw speed upon melt processing. Differential scanning calorimetry (DSC) experiments did not reveal significant differences in melt temperature or glass transition temperature of PBSA. Dynamic mechanical analysis did display improved modulus values as a function of temperature with some of the nanocomposite formulations processed at different screw speeds. Extensive biodegradation tests were performed and determined that the nanoparticles did not hinder biodegradation in soil. Toxicity tests also were performed and all samples proved to be nontoxic.

Association between plasticized starch and polyesters: Processing and performances of injected biodegradable systems

AbstractDifferent formulations of wheat thermoplastic starch (TPS) have been processed with various plasticizer/starch ratios and moisture contents. The biodegradable polyesters tested are polycaprolactone (PCL), polyester amide (PEA), polybutylene succinate adipate (PBSA) and polybutylene adipate co terephtalate (PBAT). TPS and polyesters are melt blended in different proportions by extrusion and then injected to obtain dumbbell specimens. Various properties are evaluated such as the mechanical properties (tensile and impact tests), and the hydrophilic character with contact angle measurements. Additionally, uniaxial shrinkage is evaluated. Results show that the addition of polyester to TPS increases the dimensional post‐injection stability. Blend modulus values are close to the results of the classical rule of mixture. Elongation at break, resilience values and SEM observations seem to give some indications about the compatibility between both polymeric systems. PBAT and PEA present better results than PCL and PBSA. Contact angle measurement show that we have a drastic increase of the hydrophobic character from 10% of polyester in the blend. The different combinations of TPS and polyesters give a wide range of mechanical behavior for compostable materials, to be developed in specific applications.

Phase behavior and water vapor transport in BIONOLLE/polymethylmethacrylate blends

The miscibility of blends prepared from amorphous polymethylmethacrylate (PMMA) and a semi-crystalline biodegradable polybutylene succinate–adipate polyester (BIONOLLE 3000) has been studied. Using methods such as microscopic observation, lowering of T m and T g and crystallization kinetics, these polymers have been shown to present a very low mutual solubility in the whole composition range. The permeability to water vapor results are interpreted using the classical series and parallel models for immiscible blends considering that only the amorphous part of the blend is responsible for the water vapor transport. These results are then compared with those obtained for the polyethylene oxide/polymethylmethacrylate blends and discussed in terms of the change of crystallinity of the semi-crystalline component of the blend.

Processing, performance and biodegradability of a thermoplastic aliphatic polyester/starch system

Composites of a biodegradable thermoplastic aliphatic polyester, polybutylene succinate adipate (PBSA), with granular corn starch were investigated for processability, mechanical and thermal properties, and biodegradability. The PBSA/starch films were prepared with starch contents of 5%–30% by weight and processed by blown film extrusion. Increasing the starch content led to an increase in modulus and decreases in tensile strength, elongation to break and toughness. The rate of biodegradation in soil, as measured by respirometry, increased significantly as the starch content was increased to 20% and then plateaued. Scanning electron microscopy revealed that the starch granules were embedded in the continuous-phase PBSA and that starch promotes the biodegradation of PBSA. Gel permeation chromatography indicated a molecular weight decrease for the PBSA after soil exposure and confirmed that biodegradation was enhanced by the presence of starch. The results demonstrated that the biodegradable PBSA/starch system has mechanical properties useful for blown film applications.

Processability and properties of aliphatic polyesters, ‘BIONOLLE’, synthesized by polycondensation reaction

Biodegradable aliphatic polyesters, trademarked ‘BIONOLLE’, such as polybutylene succinate (#1000 series), polybutylene succinate adipate copolymer (#3000 series) and polyethylene succinate (tentatively #6000 series) with high molecular weights ranging from several tens of thousands to several hundreds of thousands were invented in 1990 and produced successfully through polycondensation reaction of glycols with aliphatic dicar☐ylic acids and others. A pilot plant with a capacity of 10 tons/year was built in 1991, and a semicommercial plant with a capacity of 3000 tons/year was constructed in 1993. BIONOLLE is a white crystalline thermoplastic, has melting points ranging about 90~120 °C, glass transition temperatures ranging about −45~−10 °C and density about 1.25 g/cm 3. BIONOLLE has excellent processability, so it can be processed on conventional equipment (commonly used in processing polyolefins) at temperature of 160~200 °C into various molded products such as injected, extruded and blown ones. A new grade of BIONOLLE (coded #1900 series), which has a long chain branch (LCB), high melt tension and high recrystallization rate, has been developed, to enable stretched blown bottles and highly expanded foams to be made easily.