Development Of Bio-based Polymers Research Articles

Developing biobased and degradable polyazomethines from hemin

The development of biobased polymers is emerging as a critical issue for researchers in this era, especially for conjugated or semiconducting polymers, due to the lack of natural conjugated building blocks. In addition, it is of urgent importance to develop degradable polymers to diminish the increasing amount of plastic waste. Therefore, we aim to utilize hemin-based materials as a building block to develop semi-conjugated, degradable, and biobased polymers in this study. Accordingly, hemin derived from bovine is modified to remove the ferric ion and functionalize with amine or aldehyde groups. The aldehyde-functionalized protoporphyrin is copolymerized with p-phenylenediamine, 2,7-fluorenediamine, and amine-functionalized protoporphyrin to form a series of polyazomethines of PDA, FDA, and PPIX. The semi-conjugated polyazomethines exhibit varied electrostatic potential distributions and frontier energy levels based on their compositions; in addition, all the polyazomethines present high biobased contents spanning the range of 60–80%. Notably, PPIX can be rapidly depolymerized by acid hydrolysis with 0.01 mol L−1 of HCl within several hours, guaranteed by the evolutions of optical absorption and size-exclusion chromatography, which show that the polyazomethines degrade to monomers to short-chain oligomers. In the aspect of the optoelectronic device application, the semi-conjugated characteristics of the hemin-based polyazomethines give rise to their high performance as a photoresponsive polymer electret in photonic transistor memory. By fine-tuning the molecular structure and energy levels, the developed polyazomethine of FDA achieves decent data discernibility and long-termed cyclic operation as a component of memory electronics, thereby rendering green electronics exceptionally economical and environmentally feasible.

Emerging Bio-Based Polymers from Lab to Market: Current Strategies, Market Dynamics and Research Trends

Due to the rising worldwide demand for green chemicals, the bio-based polymer market is anticipated to expand substantially in the future. The synthesis of functional polymers has been a burgeoning area of research for decades. The primary driving force behind the development of bio-based polymers has been their compostability and biodegradability, which are critical given the public concern about waste. Significant advancements in the method for refining biomass raw materials towards the creation of bio-based construction materials and products are driving this rise. Bio-based polymers with this chemical structure are more flexible and adaptive, which allows them to attain their intended characteristics and functionalities. In commercial applications and healthcare and biotechnology, where completely manufactured, naturally occurring biomolecules are utilized and such polymers have the greatest impact. At the same time, limitations in polymer architectural control, biostability, and structural dynamics hinder the creation of biocompatible and functionally varied polymers. From this standpoint, the importance of functional biosynthetic polymers in the future years is highlighted, as well as new methods for addressing the aforementioned challenges. The article comprehensively highlighted the current strategies, market dynamics, and research trends of emerging Bio-Based Polymers. In addition, the most recent scientific breakthroughs in bio-based polymers are discussed.

Construction of bio-based ramie fabric/epoxy resin composites with high flame retardant and mechanical performances

The development of bio-based polymers will be beneficial to reducing carbon emissions. The biobased fiber-reinforced biobased epoxy resin can prepare fully-biobased polymer composites. However, their flame retardation will become a challenging issue. Here, fire-retardant ramie fabrics surface-modified by ammonium polyphosphate (APP) and polyethyleneimine were integrated into an epoxy system followed by fabricating high-performance composites. Notably, the epoxy resin composite with 8.9 % flame retardant displays a UL-94 V-0 rating. Besides, EP/(MF-2) exhibits a remarkably decreased peak of heat release rate (285 kW/m2) in contrast to pristine fabric-reinforced epoxy resin composite (608 kW/m2) from the cone calorimeter test. The improved flame-retardant performance follows the mechanism of the catalytic dehydration and charring effect by phosphorus-containing acids from the degradation of APP. Furthermore, flexural strength of EP/(MF-2) increases by 29 %, compared with neat EP, indicating obvious reinforcement of ramie fabric.

Sustainable smart anti-corrosion coating materials derived from vegetable oil derivatives: a review.

Sustainable development is a critical concern in this fast-paced technological world. Therefore, it is essential to employ renewable resources to move towards sustainable development goals (SDGs). The polyols attained from renewable resources, including lignin, chitosan, vegetable oils, cellulose, etc. and the polymers derived from them have attracted the attention of the majority of researchers, both in academia and industry. The development of bio-based polymers from vegetable oils start emerging with different properties to generate a value-added system. This review will give an impression to readers about how coatings generated from vegetable oils can find a way towards better protective properties against corrosion either by using fillers or by using molecular structure modifications in the system, thus covering a range of vegetable oil-based self-healing polymers and their application in anti-corrosion coatings.

Citronella-based polyesters by organocatalyzed ring-opening polymerization and their recyclable crosslinked films

Independence of food supply chain is a grand challenge encountered by the development of bio-based polymers. Here, we demonstrate the synthesis of amorphous aliphatic polyesters via organocatalyzed ring-opening polymerization of 9-membered lactone monomer, a novel downstream product of non-edible citronella oil. In particular, chemical transformation of trisubstituted alkene moiety owned by this renewable biomass was achieved by cross-metathesis of this bulky group with methyl acrylate. Three-armed star polymers were converted to free-standing films by UV-induced crosslinking. In particular, these crosslinked thin films could be efficiently recycled as ω-hydroxy ester upon methanolysis. This work opens a new avenue for the synthesis and application of terpene- and terpenoid-based polymers.

Greener Synthesis Route for Furanic-Aliphatic Polyester: Enzymatic Polymerization in Ionic Liquids and Deep Eutectic Solvents

The development of bio-based polymers is growing not only due to their abundance in nature but also mainly because of the current issues with fossil-based plastics. Enzymatic polymerizations are a promising way to produce such polymers since they are known to be environmentally friendly. Sustainable polymers that require a greener production process can be realized easily via this polymerization route. However, the use of organic solvents is often one of the drawbacks in developing pathways toward fully green enzymatic polymerization methods. Therefore, in the present work, a series of fully bio-based polyesters based on 2,5-furandicarboxylic acid (FDCA), namely, furanic-aliphatic polyesters (FPEs), were enzymatically synthesized using greener solvents, such as ionic liquids (ILs) and deep eutectic solvents (DESs). The enzymatic polymerization in ILs and DESs effectively leads to the FDCA-based polyesters without any byproduct, which frequently causes coloration using traditional polymerization methods. FPEs with Mw up to 5.4 kg mol–1 were successfully achieved by Novozyme 435-catalyzed polycondensation of dimethyl 2,5-furandicarboxylate (DMFDCA) with aliphatic diols in BMIMPF6. Polymerization in DESs was also successfully conducted, resulting in the synthesis of bio-based polyesters, which can be further functionalized. Characterization using TGA, DSC, and WAXD showed that all obtained FPEs are semi-crystalline materials, which decomposed around 390 °C with a Tm of 68–123 °C and Tg of 3–12 °C. With this, we successfully developed more eco-friendly enzymatic synthesis routes for the production of sustainable polyesters

Mechanically robust, healable, shape memory, and reprocessable biobased polymers based on dynamic pyrazole-urea bonds

Development of biobased polymers with self-healing, shape memory, and reprocessable features is of great significance for sustainable development, environmental protection, and high-end applications. Herein, we report robust, repairable, shape memory, and reprocessable poly (urethane-urea) (PPU) polymers derived from renewable castor oil enabled by dynamic pyrazole-urea bonds and hydrogen bonds. The optimal PPU material (PPU3) demonstrated tensile strength and toughness up to 30.6 MPa and 34.9 MJ·m−3, respectively, which were superior to most of the reported oil-based dynamic covalent materials. Furthermore, the pyrazole-urea bonds and intramolecular hydrogen bonds enabled the PPU materials with excellent repairability, recyclability, malleability, and shape memory. For instance, the PPU3 polymer could be recycled rapidly at relatively mild conditions (10 min at 140 °C, 10 MPa), and no obvious decrease in tensile strength and strain at break was observed after being recycled for at least 4 times. Finally, the application of PPU3 as recoverable adhesive was also studied. The PPU3 polymer could be quickly re-bonded by a heating and cooling treatment for at least 30 times without significant deterioration in adhesion strength.

Primena procene životnog ciklusa u sektoru ambalaže za polimerne i biopolimerne materijale - pregled

Among many important requirements for packaging materials, environmental friendliness is a property that has become necessary for any material that needs to be competitive in the market. Life Cycle Analysis (LCA) is an analytical instrument that provides a framework for analyzing the impact of products and services on the environment, i.e. provides an understanding and the possibility of comparing different products. LCA studies the use of resources and the consequent emissions of pollutants on the environment during the entire life of a product from raw materials exploitation, through production, use and treatment at the end of the life cycle - recycling and final disposal. This paper will provide an overview of the LCA results of various commercial polymer packaging materials, as well as the results of LCAs of biopolymer materials. Although LCA faces the problem of data heterogeneity, since some studies focused on individual segments of the analysis, while some related to all aspects of the process, as well with the problem of interpreting heterogeneous results, because the output parameters were arbitrarily selected by the researcher, still it could be concluded that the available LCA studies and environmental assessments support further development of biobased polymers. When comparing biopolymer materials with commercial synthetic polymers, they have advantages - lower consumption of fossil fuels and lower emission rate of greenhouse gases from the whole life cycle.

A comprehensive review on the properties and functionalities of biodegradable and semibiodegradable food packaging materials

The development of biodegradable food packaging with superior properties and functionalities compared to conventional food packaging is one of the emerging research interests. Immediate disposal of conventional single use nonbiodegradable food packaging results in adverse environmental impact. Utilization of either biomass-based, microorganism-derived, or biotechnologically synthesized biopolymers as biodegradable matrices is the common approach toward achieving sustainability. Consequently, starch and cellulose are being commonly used as biodegradable matrices. However, rather than being fully biodegradable, most of them can be considered as semibiodegradable. Majority of the review studies are based on matrices that have an origin in edible sources, which might result in food insecurity. Although development of bio-based polymers with sound packaging properties have been extensively studied, the potential agro-industrial waste as alternative, eco-friendly, and economically viable matrices have attracted little attention. Therefore, the approaches of developing biodegradable food packaging and the framework of converting agro-industrial waste into biodegradable packaging matrices are discussed comparatively in this paper. It also critiques the approaches and valorization of agro-industrial waste in biodegradable food packaging. Thereby, an overview of physicochemical, functional, and biodegradable properties of commonly used biodegradable food packaging materials are provided as an insight for agro-industrial waste-based food packaging. The potential use of agro-industrial waste-based biodegradable food packaging materials against commonly used biodegradable food packaging materials has been highlighted in this study. Thereby, the vital necessity of growing awareness about agro-industrial waste as biodegradable food packaging materials is emphasized through this comprehensive review.

Effects of hectorite loading on tear properties and biodegradability of thermoplastic starch films

Development of bio-based polymers can reduce human dependence on fossil fuel and move to a sustainable material resource. In this work, thermoplastics starch (TPS) films were produced by plasticization process, in which the crystalline structure of the starch granules was destroyed and reformed by water and glycerine through mechanical stirring and heating process. Hectorite was employed as filler to reinforce the TPS films. The hectorite was subjected to ultrasonication process for reducing the size and aggregation of particles. The ultrasonicated hectorite was added into the TPS solution to produce the TPS/hectorite bio-composite by film casting method. The TPS films with hectorite loading in the range of 1% to 5% were prepared. The morphology, tear strength and soil biodegradability of the TPS/hectorite bio-composite films were studied by altering the loading of hectorite incorporated into the TPS films. Results showed that the TPS/hectorite bio-composite films have higher tear strength compared to the pure TPS films. The tear strength of the bio-composite films slightly increased with hectorite content 1% and 2%. However, as the filler loading increased to 3%, there was a drastic increase of the tear strength. The maximum tear strength value was achieved by the TPS film when 4% hectorite filler was employed. The TPS/4% hectorite (ultrasonicated) has the lowest rate of soil biodegradation due to its lower moisture uptake and greatest interface interaction between starch and hectorite, inhibiting diffusion of bacteria into the films.

Production of Sustainable and Biodegradable Polymers from Agricultural Waste.

Agro-wastes are derived from diverse sources including grape pomace, tomato pomace, pineapple, orange, and lemon peels, sugarcane bagasse, rice husks, wheat straw, and palm oil fibers, among other affordable and commonly available materials. The carbon-rich precursors are used in the production bio-based polymers through microbial, biopolymer blending, and chemical methods. The Food and Agriculture Organization (FAO) estimates that 20–30% of fruits and vegetables are discarded as waste during post-harvest handling. The development of bio-based polymers is essential, considering the scale of global environmental pollution that is directly linked to the production of synthetic plastics such as polypropylene (PP) and polyethylene (PET). Globally, 400 million tons of synthetic plastics are produced each year, and less than 9% are recycled. The optical, mechanical, and chemical properties such as ultraviolet (UV) absorbance, tensile strength, and water permeability are influenced by the synthetic route. The production of bio-based polymers from renewable sources and microbial synthesis are scalable, facile, and pose a minimal impact on the environment compared to chemical synthesis methods that rely on alkali and acid treatment or co-polymer blending. Despite the development of advanced synthetic methods and the application of biofilms in smart/intelligent food packaging, construction, exclusion nets, and medicine, commercial production is limited by cost, the economics of production, useful life, and biodegradation concerns, and the availability of adequate agro-wastes. New and cost-effective production techniques are critical to facilitate the commercial production of bio-based polymers and the replacement of synthetic polymers.

Integrating transient and sacrificial bonds into biobased elastomers toward mechanical property enhancement and macroscopically responsive property

The development of biobased polymers from renewable resources offers a solution to the growing environmental concerns and scarcity of fossil feedstock. The synthesized biobased polymers, especially for biobased elastomers, are mechanically weak, which greatly restricts their applications. In the present work, we demonstrate that the integration of transient and sacrificial quadruple H-bonding motifs into as-synthesized biobased elastomer can enhance the mechanical properties and bestow it with adaptive performance. Specially, the biobased elastomer was synthesized through melting poly-condensation using biobased di-acids and diols as the starting materials. The biobased elastomer is covalently crosslinked and grafted with ureido-pyrimidinone (UPy) containing acrylate through thiol-ene click reaction by using pentaerythritol tetra(3-mercaptopropionate) as the linkers. Under external load, UPy aggregations based on H-bonding can function as sacrificial units through reversible rupture and re-formation events, leading to significant improvements on the modulus and strength of the biobased elastomer while maintaining the extensibility. In addition, the dissociation and re-formation of H-bonding under thermal stimuli impart the elastomer with thermo-activated shape memory behavior.

Synthesis and Polymerization of Naphthoxazines Containing Furan Groups: An Approach to Novel Biobased and Flame-Resistant Thermosets

Naphthoxazines are a class of compounds with potential application in obtaining high-performance polymeric materials. Such application of these compounds, however, is still scarcely explored in the literature. Combined with the search for new high-performance materials, the development of biobased polymers has gained a lot of attention. In this sense, the inclusion of furan groups in polymers has been explored as a strategy that combines the search for high-performance materials with the search for the development of biobased materials. In this work, novel naphthoxazine monomers containing furan groups were synthetized. The syntheses were carried out in a single step, without the use of solvents and catalysts, obtaining the products in satisfactory yields and high purity. The naphthoxazines had their chemical structures completely characterized by FTIR, 1H NMR, and 13C NMR techniques. The thermal analyses (DSC and TGA) showed that all naphthoxazines exhibit exothermic typical polymerization events, making these compounds suitable for obtention of poly(naphthoxazines) resins, but suffer significant mass losses at temperatures below the onset polymerization temperature. In this way, a catalyst (1 mol% MgCl2) was used in order to allow the polymerization of the compounds before the mass loss events. The FTIR analysis showed strong evidences of the formation of poly(naphthoxazines), and TGA analyses showed that the resins have high thermal stability, with high flame resistance and self-extinguishing properties (LOI > 28), which makes these compounds attractive in the development of biobased and high-performance materials.

Wastewater as renewable feedstock for bioplastics production: understanding the role of reactor microenvironment and system pH

Considerable interest in the development of biobased polymers is being garnered due to their diverse applications and biodegradability. In this communication, bioplastics (as polyhydroxyalkanoates) production using wastewater as a substrate was studied by varying the reactor microenvironment (aerobic and microaerophilic) and operating pH (6, 7 and 8). Redox reactions occurring in the mixed culture during polyhydroxyalkanoates production were investigated. Maximum polyhydroxyalkanoates production in terms of dry cell weight (%) was observed in microaerophilic operation (56%), compared to aerobic (34%) operation. Neutral pH showed better polyhydroxyalkanoates synthesis (56%) than basic (44%) and acidic (28%) redox microenvironments. Neutral pH operation documented higher dehydrogenase enzyme activity, reduction currents, substrate degradation than acidic and alkaline pH at microaerophilic environment that correlated well with higher polyhydroxyalkanoates production. Biopolymer composition showed the presence of co-polymer, poly-(3-hydroxybutyrate-co-3-hydroxyvalerate). Fluorescence in situ hybridization analysis revealed the presence of phylum Proteobacteria, Acidobacteria and Firmicutes in mixed culture which are known for polyhydroxyalkanoate production. This study illustrated that efficient utilization of wastewater for bioplastics production at optimum conditions can be viewed as viable solution for tackling the problems of increasing waste advocating the concept of ‘waste to wealth’.

Development of Bio-based Polymers using Natural Oil

Development of Bio-based Polymers using Natural Oil