Renewable Polymers Research Articles

Recent Advances in Natural-Polymer-Based Hydrogels for Body Movement and Biomedical Monitoring.

In recent years, the interest in medical monitoring for human health has been rapidly increasing due to widespread concern. Hydrogels are widely used in medical monitoring and other fields due to their excellent mechanical properties, electrical conductivity and adhesion. However, some of the non-degradable materials in hydrogels may cause some environmental damage and resource waste. Therefore, organic renewable natural polymers with excellent properties of biocompatibility, biodegradability, low cost and non-toxicity are expected to serve as an alternative to those non-degradable materials, and also provide a broad application prospect for the development of natural-polymer-based hydrogels as flexible electronic devices. This paper reviews the progress of research on many different types of natural-polymer-based hydrogels such as proteins and polysaccharides. The applications of natural-polymer-based hydrogels in body movement detection and biomedical monitoring are then discussed. Finally, the present challenges and future prospects of natural polymer-based hydrogels are summarized.

3D Printable Materials Based on Renewable Polymers from Terpene Alcohols and Calcium Carbide

AbstractThe transition to a sustainable future requires the use of waste‐free technologies for production. Potentially, additive technologies can be a promising approach for accessing circular economy due to the precise amount of feeding materials and the absence of molds. However, the initial feeding materials for additive approaches are often based on non–renewable hydrocarbon sources. This work focused on the use of polymers derived from terpene alcohols to develop a filament suitable for 3D printing. Initially, the vinylation of menthol using calcium carbide was optimized and scaled up, then a series of terpenyl–based vinyl ethers were obtained under optimal conditions. The cationic polymerization of vinyl ethers was also scaled up and resulted in 99 % yield of the polymers, which was subsequently subjected to hot extrusion. The initial terpenol was used as an additive to increase polymer flexibility. The addition of menthol (30 wt %) to polyvinyl menthol led to the suitable filament. Using the filament, a series of objects were 3D printed at 125 °C. The material demonstrated good sinterability and adhesion to glass and shrinkage comparable to that of commercial 3D printing filaments. Furthermore, the polymers obtained were used as additives to enhance the adhesion of commercially available filaments.

Cellulose-based fluorescent chemosensor with controllable sensitivity for Fe3+ detection

Polymer-based sensors, particularly those derived from renewable polymers, are gaining attention for their superior properties compared to organic small molecules. However, their complex preparation and poor, uncontrollable sensitivity have hindered further development. Herein, cellulose-based polymer photoluminescence (PL) chemosensors were fabricated using a straightforward and adjustable strategy. Specifically, water-soluble cellulose acetoacetate (CAA) was used as the substance for the in-situ synthesis of 1,4-dihydropyridine (DHPs) fluorescent rings on cellulose chains via a catalyst-free, room-temperature Hantzsch reaction. Benefiting from the synergetic through-space conjugation of DHPs rings and semi-rigid cellulose chains with heteroatoms, the sensors exhibit bright and stable PL properties. Based on this performance, the cellulose-based sensor excels in the specific recognition of Fe3+ in aqueous systems, showing exceptional selectivity, stability, and anti-interference performance due to the synergy between the inner filter effect (IFE) and intramolecular charge transfer (ICT). Theoretical calculations confirm the role of the extended π-conjugated structure at the DHPs-4 position in modulating the sensor sensitivity, achieving a low limit of detection (LOD) of 0.48 μM. Furthermore, the versatility of the Hantzsch reaction shows the potential of this strategy for developing a new generation of biomass-based polymer portable sensors for real-time and on-site detection.

A novel biodegradable film based on chicken gelatin and κ-carrageenan cross-linked with oxidized phenolic compounds.

Natural and renewable polymers are gradually replacing petroleum-based plastics, mostly as a result of environmental concerns. Moreover, upcycling industrial food waste into new added-value products is a creative approach that is crucial for cleaner and more sustainable manufacturing. The aim of this study was to obtain an environmentally friendly biodegradable film using a combination of k-carrageenan (KCAR) and chicken gelatin (CGEL), which obtained from poultry by-products. The effects of varying concentrations of KCAR (0-2%) on the physical, permeability, textural, thermal, and microstructural properties of CGEL/KCAR composite films were evaluated. The findings demonstrated that an increase in KCAR enhanced the lightness and opacity levels of the films. Water vapor permeability (WVP) values reduced as the KCAR concentration increased. The lowest WVP value (0.0012g.mm/h.m2.kpa) was seen in the treatment with 2% KCAR. Tensile strength (TS) values increased with increasing KCAR. The films' thermal stability was increased by the addition of KCAR. Microstructure assessments revealed a more compact and smooth structure in the KCAR-containing treatments, indicating improvements in WVP, thermal stability, and TS. Compared to the commercial cattle gelatin film, the CGEL film had higher TS and lower water solubility (WS). Overall, this study showed that the physical, mechanical, barrier and thermal and microstructural qualities of gelatin-based films may be enhanced by combining CGEL and KCAR to create an effective biodegradable film. Moreover, the comparison study between commercial cattle and chicken gelatin films revealed that cross-linked chicken gelatin films would be a suitable alternative for bovine gelatin films in the production of biodegradable film.

Soy‐based polyester: Sustainable solutions for emerging materials

AbstractInnovative and renewable polymers and additives are the focus of increased research due to public and environmental pressure. There has been a recent uptick in interest from scientists in biobased “green” plasticizers that can be covalently bonded to replace harmful and migratory phthalate‐based plasticizers. Vegetable oils (VOs) are one of the biosources, as they are both plentiful and sustainable. This review aims to highlight the synthesis methods for soy‐based polyesters. Therefore, the chemistry of soybean oil as a polymeric material and its role in the synthesis of polyesters derived from soybeans are the primary topics of this review. This review covers the many ways in which soybean oil and its derivatives can be used to synthesize polyester, either directly or indirectly.Highlights The need for sustainable polymers is explored. Soybean oil‐based polyesters are covered. Modification and chemistry to convert soybean oil into polyester are described. Applications of soybean‐based polyesters are provided.

Chemical Modification of Nanocrystalline Cellulose for Manufacturing of Osteoconductive Composite Materials.

Cellulose is one of the main renewable polymers whose properties are very attractive in many fields, including biomedical applications. The modification of nanocrystalline cellulose (NCC) opens up the possibility of creating nanomaterials with properties of interest as well as combining them with other biomedical polymers. In this work, we proposed the covalent modification of NCC with amphiphilic polyanions such as modified heparin (Hep) and poly(αL-glutamic acid) (PGlu). The modification of NCC should overcome two drawbacks in the production of composite materials based on poly(ε-caprolactone) (PCL), namely, (1) to improve the distribution of modified NCC in the PCL matrix, and (2) to provide the composite material with osteoconductive properties. The obtained specimens of modified NCC were characterized by Fourier-transform infrared spectroscopy and solid-state 13C nuclear magnetic resonance spectroscopy, dynamic and electrophoretic light scattering, as well as thermogravimetric analysis. The morphology of PCL-based composites containing neat or modified NCC as filler was studied by optical and scanning electron microscopy. The mechanical properties of the obtained composites were examined in tensile tests. The homogeneity of filler distribution as well as the mechanical properties of the composites depended on the method of NCC modification and the amount of attached polyanion. In vitro biological evaluation showed improved adhesion of human fetal mesenchymal stem cells (FetMSCs) and human osteoblast-like cells (MG-63 osteosarcoma cell line) to PCL-based composites filled with NCC bearing Hep or PGlu derivatives compared to pure PCL. Furthermore, these composites demonstrated the osteoconductive properties in the experiment on the osteogenic differentiation of FetMSCs.

A high-sensitive capacitive humidity sensor based on chitosan-sodium chloride composite material

Chitosan, as a hydrophilic, renewable, biodegradable, and cost-effective natural polymer, holds great promise in humidity sensor applications. This study proposes a green high-performance capacitive humidity sensor based on chitosan (CS)-sodium chloride (NaCl) composites. The CS-NaCl films were fabricated through a simple drip coating method, and their surface morphology and structure were characterized using SEM, XRD, FTIR and XPS techniques. The pure chitosan humidity sensor demonstrates an impressive response of 1180.17 % with excellent linearity. The introduction of NaCl markedly boosted the sensor response, with CS-50 wt% NaCl composites exhibiting a 72-fold increase (86, 492.84 %) in capacitance response compared to pure CS films. The contact angle test demonstrated that the chitosan film exhibited good hydrophilicity, which was further enhanced by the addition of NaCl. XRD and FTIR characterization confirmed that NaCl altered the structural properties of chitosan, disrupted hydrogen bonds, and consequently increased the mobility of polarizing groups and the dielectric constant. A water adsorption model was developed to elucidate the humidity sensing mechanism of the CS-NaCl sensor. The CS-NaCl composite material presents advantages such as easy preparation, high sensitivity, eco-friendliness, and promising practical applications in humidity sensing.

Lignin‐Based Multilamellar Aggregates for Removing Ofloxacin Antibiotic: A Dissipative Particle Dynamics Simulation Study

AbstractLignin, a renewable aromatic polymer, has great potential as a synthetic building block for functional materials. The effects of quaternary ammonic methylation of alkali lignin (AL) on the morphologies and ofloxacin antibiotic (OA) removal application from water are investigated by using the dissipative particle dynamics (DPD) simulation method. Untreated AL can form spherical aggregates, but the phenylpropane units of untreated AL and loaded broad‐spectrum OA molecules are randomly distributed in aggregates. However, if quaternary ammonic groups are grafted onto all orthopositions of the phenolic hydroxyl groups (100‐QAMAL), then multilamellar spherical aggregates are obtained and OA molecules are entrapped in the aggregates. To prepare multilamellar spherical aggregates with an ordered and regular layered structure, <15 v% of 100‐QAMAL and low molecular weights of AL (≈4700–9400 Da) are suggested to be used. Lignin‐based multilamellar spherical aggregates can be adopted as potential functional carriers for removing pollutant OA from water.

Anti-SARS-CoV-2 activity of microwave solvolysis lignin from woody biomass

The global pandemic caused by the novel coronavirus, severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), has had profoundly detrimental effects on our society. To combat this highly pathogenic virus, we turned our attention to an abundant renewable natural aromatic polymer found in wood. Through a chemical modification of Eucalyptus and Japanese cedar wood via acidic microwave solvolysis in equivolume mixture of 2 % (w/w) aqueous H2SO4, ethylene glycol, and toluene at 190 °C. Subsequently, we separated the resulting solvolysis products through extractions with toluene, ethyl acetate, and ethanol. Among these products, the ethyl acetate extract from Eucalyptus wood (eEAE) demonstrated the highest inhibition effects against the novel SARS-CoV-2. We further divided eEAE into four fractions, and a hexane extract from the ethanol-soluble portion, termed eEAE3, exhibited the most substantial inhibitory rate at 93.0 % when tested at a concentration of 0.5 mg/mL. Analyzing eEAE3 using pyrolysis gas chromatography–mass spectrometry revealed that its primary components are derived from lignin. Additionally, 1H–13C edited-heteronuclear single quantum coherence nuclear magnetic resonance analysis showed that the solvolysis process cleaved major lignin interunit linkages. Considering the abundance and renewability of lignin, the lignin-derived anti-SARS-CoV-2 agent presents a promising potential for application in suppressing infections within our everyday environment.

Manipulation of non-isothermal crystallization kinetics of poly(lactic acid) composite film by a novel nucleating agent

As a type of renewable and biodegradable polymer, poly(lactic acid) (PLA) has been widely used in various fields. However, its weak crystallization ability deteriorates the properties of the final product. In this work, a novel nucleating agent (MWCNTs@CeO2), multi-walled carbon nanotubes (MWCNTs) decorated with ceria (CeO2), was synthesized using the hydrothermal method and subsequently used to manipulate the non-isothermal crystallization kinetics and nucleation behavior of PLA. The results show that MWCNTs@CeO2 can act as an effective nucleating agent to accelerate the crystallization rate of PLA by reducing the half-crystallization time. In non-isothermal crystallization kinetics, the Avrami equation modified by Jeziorny cannot accurately describe the non-isothermal crystallization behavior of PLA and PLA/MWCNTs@CeO2 composite films, whereas the Mo method can. Furthermore, it is found that the addition of MWCNTs@CeO2 does not change the crystal structure of PLA, but increases the nucleation and growth rate of PLA, thereby promoting its crystallization.

Pea-like inspired design: Lignin nanospheres-mediated PVA film with high strength, low water evaporation permeability, strong UV resistance and anti-oxidation properties for extending food freshness

The excessive utilization of petroleum-based plastic products has inflicted significant harm upon the ecological and health problems, compelling individuals to continually seek renewable and biodegradable polymer materials as alternatives. Drawing inspiration from the structure of a natural pea pod, a unique interlocking packaging material based on a pea-like structure is obtained via green electrospinning and mild glutaraldehyde (GA) cross-linking method. Herein, polyvinyl alcohol (PVA) serves as a green protective layer encompassing the active lignin nanospheres (LNP) pod, forming a packaging film that prevents LNP migration. The LNP within the fibers can effectively shorten the fiber spacing, and when exposed to the GA vapor, they promote the bonding between neighboring fibers to form a tight interlock structure. Benefiting from the interlocking pea-like structure, the film exhibits excellent tensile strength (3.53 ± 0.02 MPa), wetting strength (1.92 ± 0.05 MPa), and outstanding water vapor barrier properties (3.27 ± 0.3 10−10 gm−1 s−1 Pa−1). Furthermore, the inclusion of LNP endows exceptional water resistance, UV-blocking capabilities, antibacterial and antioxidant properties, which can effectively prolong the storage life of perishable fruits. This eco-logical sustainable design holds tremendous potential in mitigating the burden on the environment, thus making a novel avenue for exploring alternatives to petroleum-derived plastics.

Driving macro-scale transformations in three-dimensional-printed biopolymers through controlled induction of molecular anisotropy at the nanoscale.

Motivated by the need to harness the properties of renewable and biodegradable polymers for the design and manufacturing of multi-scale structures with complex geometries, we have employed our additive manufacturing platform that leverages molecular self-assembly for the production of metre-scale structures characterized by complex geometries and heterogeneous material composition. As a precursor material, we used chitosan, a chemically modified form of chitin, an abundant and sustainable structural polysaccharide. We demonstrate the ability to control concentration-dependent crystallization as well as the induction of the preferred orientation of the polymer chains through the combination of extrusion-based robotic fabrication and directional toolpathing. Anisotropy is demonstrated and assessed through high-resolution micro-X-ray diffraction in conjunction with finite element simulations. Using this approach, we can leverage controlled and user-defined small-scale propagation of residual stresses to induce large-scale folding of the resulting structures.

Chemically recyclable rosin-based polymers

The pursuit of next-generation sustainable polymers with chemical recyclability and resource renewability has become a priority in materials science. Rosin, a widely available renewable natural biomass, holds promise in this regard. In this study, dehydroabietic acid was incorporated into a cyclooctene monomer structure as pendant groups. This tailored monomer with low ring strain possesses the ability to efficiently undergo ring-opening metathesis polymerization (ROMP), resulting in the synthesis of rosin-based unsaturated polymers with a fully hydrocarbon backbone. The molecular weight of these polymers, ranging from 50 kDa to 160 kDa, can be easily modulated by varying the monomer-to-catalyst feeding ratio. Remarkably, these amorphous polymers exhibit exceptional thermostability, with a decomposition temperature exceeding 400 °C. This type of polymer exhibits excellent acid and alkali resistance within a pH range of 3 to 11. Upon exposure to Grubbs catalyst under mild conditions, these polymers undergo depolymerization back to the native monomer in a highly efficient manner, achieving a remarkable recovery ratio of approximately 95 %. It is evident that this innovative approach is not only relevant for the development of rosin-based polymers but also holds promise for informing the design of other renewable polymers with superior thermostability and enhanced chemical recyclability.

Nanocrystal cellulose from diverse biological sources: Application and innovations

Cellulose is the most abundant renewable polymer on Earth which is extensively distributed in diverse ecosystems. It is present in higher plants, marine organisms, and also produced through microbial processes in organisms like algae, fungi, and bacteria. From an industrial perspective, the semicrystalline nature of cellulose present in different plant and microbial sources enables the fabrication of various types of nanocellulose, such as nanofibre and nanocrystals, through mechanical disintegration and chemical methods, respectively. Nanocellulose distinguishes itself as a sustainable, nonharmful, and biodegradable polymer. It will enable sustainable development for responsible consumption and production. Possessing a range of excellent properties, it can be seamlessly integrated into various materials. Research on nanocellulose is gaining momentum in response to current issues related to fossil fuels, including concerns about CO2 emissions, plastic pollution, and the need for renewable energy sources. This review addresses nanocrystals production method from cellulose found in agricultural, microbial sources, and its applications in fields such as materials science, electronics, medicine, and environmental science.

Influence of rice straw based nanocellulose loading in sodium carboxymethyl cellulose

The goal of this research is to produce renewable and biodegradable polymers based nanocomposite films. In this study, mixture of cellulose nanocrystals and cellulose nanofibers, collectively termed as nanocellulose was extracted from agricultural waste (rice straws). Nanocellulose (NC) filled sodium carboxymethyl cellulose (CMC) films were prepared via spin coating method. Various amount of NC (0, 20, 40 wt%) were added to CMC to prepare NC filled CMC nanocomposite film. Structural, chemical, morphological and thermal properties were studied through XRD, FTIR, SEM and TGA. It was found that CMC filled NC films have higher crysatllinality along UV blocking effect with 73 % visible light transmittance. Strong H-bonding between OH-group of NC and –COOH group of CMC resulted into stable and flexible nanocomposite film. Furthermore, thermal studies confirmed that strong hydrogen bonding within CMC and NC for 40 % NC filled CMC. It resulted for phase transition of nanocomposite film through fusion at higher temperature and high mass residue as compared to bare CMC and NC.

Fully bio-based intumescent flame retardant hybrid: A green strategy towards reducing fire hazard and improving degradation of polylactic acid

Polylactic acid (PLA) is a promising renewable polymer material with excellent biodegradability and good mechanical properties. However, the easy flammability and slow natural degradation limited its further applications, especially in high-security fields. In this work, a fully bio-based intumescent flame-retardant system was designed to reduce the fire hazard of PLA. Firstly, arginine (Arg) and phytic acid (PA) were combined through electrostatic ionic interaction, followed by the introduction of starch as a carbon source, namely APS. The UL-94 grade of PLA/APS composites reached V-0 grade by adding 3 wt% of APS and exhibited excellent anti-dripping performance. With APS addition increasing to 7 wt%, LOI value increased to 26 % and total heat release decreased from 58.4 (neat PLA) to 51.1 MJ/m2. Moreover, the addition of APS increased its crystallinity up to 83.5 % and maintained the mechanical strength of pristine PLA. Noteworthy, APS accelerated the degradation rate of PLA under submerged conditions. Compared with pristine PLA, PLA/APS showed more apparent destructive network morphology and higher mass and Mn loss, suggesting effective degradation promotion. This work provides a full biomass modification strategy to construct renewable plastic with both good flame retardancy and high degradation efficiency.

Passion Fruit Seed Oil: A Sustainable Feedstock for Additive Manufacturing of Renewable Polymers

Passion Fruit Seed Oil: A Sustainable Feedstock for Additive Manufacturing of Renewable Polymers

Extraction and characterization of nanocellulose from waste of date palm "Phoenix dactylifera″ as reinforcement of polymer composites.

The cellulose is the most abundant and renewable polymer in nature. It is characterized by its biodegradability that can help to establish a friendly environment. The main objective of this study is intended to characterize the nanocellulose obtained from waste date palm, including the dried palms (DP) and the fresh palms (FP) by implementing chemical methods (hydrolysis with H2SO4). Physical properties, morphology, the elemental composition and the thermal stability were determined by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), zeta sizer, scanning electron microscopy (SEM), whereas energy dispersive X-ray (EDX) and thermogravimetric analysis (TGA), respectively. FTIR, SEM and EDX results, revealed the effective removal of impurities, hemicellulose and lignin. Palm sample residues contained 35.99% of cellulose and 33.12% of cellulose nanocrystals (CNC) for DP, and 36.17% of cellulose and 34.35% of CNC for FP. The CNCs have higher crystallinity than the raw fibers and Zeta sizer was between 25 and 1150 nm. TGA analysis showedthat DP exhibited greater thermal resistance.

Polyglycerol citrate: A novel coating and inoculation material for soybean seeds

The microbial inoculation of legumes such as soybeans is crucial for thriving plant growth due to symbiotic nitrogen (N) fixation and biological plant N fertilization. Soybean requires microbial pre-inoculation before sowing using the rhizobia strain Bradyrhizobium japonicum. Peat is typical for this purpose, although not sustainable since it is a finite resource. Here, we propose a straight-forwarding route to prepare and apply polyglycerol-citrate polymer (PGC), a biodegradable and fully renewable polymer, as a carrier for Bradyrhizobium japonicum inoculants for soybeans. This novel eco-friendly polymer combines the advantages of a polymeric, water-soluble structure based on biopolymers, which can protect the inoculant cells during the seed inoculation process, with protective properties of glycerol for bacterial cells and the contribution of citric acid for metabolic processes. A greenhouse study was conducted using soybean seeds coated with three different proportions of PGC with B. japonicum planted in a sand substrate free of external interference. Comparative results of N content and δ15N signature in soybean plant parts calculated from the natural abundance method associated with viability tests showed equal or superior symbiotic performance and nitrogen fixation rates to peat-based inoculants, considered the gold-standard carrier for inoculants. It ensured the shelf life of the inoculant formulations, offering convenience for farmers and environmental benefits through reduced fertilization.

Dramatic improvement in corrosion inhibition effect of carboxymethyl cellulose by modified with levodopa: Experimental study and first-principles calculations

Cellulose, as a kind of renewable natural polymer, has great potential as green corrosion inhibitor. However, the low inhibition effect is the obstacle to its practical application. Herein we developed a high efficiency green cellulose derivative corrosion inhibitor, levodopa-carboxymethyl cellulose (LDCMC), by modifying carboxymethyl cellulose (CMC) with levodopa (LD) through a simple amidation reaction. The inhibition effect of CMC for mild steel in HCl medium is dramatically improved with an increase in inhibition efficiency from 56.98% of CMC to 97.27% of LDCMC. The intrinsic nature of the dramatically improved inhibition effect is in-depth unraveled by first-principles calculations based on density functional theory (DFT). CMC and LDCMC can adsorb on the mild steel surface through -OH, -COOH and LD fragment by forming the covalent bonds with steel surface. Benefiting from the additional strong adsorption of the benzene ring in LD fragment, the introduction of LD can significantly enhance the adsorption capacity of LDCMC, which is the intrinsic nature of the dramatical improvement in the inhibition effect of LDCMC.