Bio-based Monomers Research Articles

Revealing the Dynamics of Sustainable Epoxy-Acrylate Networks from Recycled Plastics Blends and Oligomeric Lignin Precursors.

The growing pursuit of carbon circularity in material fabrication has led to the increased use of recycled and biobased resources, especially in epoxy resin systems. Fossil-based bisphenols are being replaced with recycled bisphenol A (r-BPA) and lignin derivatives, both derived from previous processes. In this study, r-BPA was chemically recycled from end-of-life televisions, then converted into r-DGEBA and r-DAGBA through glycidylation and acrylic acid ring-opening. These monomers were used to create six thermosets by reacting Jeffamine D230 with r-DGEBA/r-DAGBA in varying epoxide:acrylate ratios. Acrylates introduced thermo-reversible β-amino esters, enabling dynamic bonding in the epoxy formulation. To increase biobased content, glycidylated depolymerized lignin (GDL) was added to produce five additional polymers. The crosslinked networks were thoroughly characterized, examining their thermomechanical properties and establishing a structure-property relationship. The dissociative acrylate-amine interactions allowed for reversible crosslinks under specific thermal conditions, enabling shape programming and crosslink reversibility. The study demonstrates that incorporating recycled and biobased aromatic monomers facilitates the creation of dynamic, crosslinked structures with tunable properties. This represents progress toward versatile, reusable, and circular materials.

Decoding the Biobased Blueprint: Key Players and Evolutionary Trends in Materials Innovation

In the rapidly evolving biobased materials innovation landscape, our research identifies key players and explores the evolutionary perspective of biobased innovation, offering insights into promising research areas to be further developed by biobased material scientists in search of exploiting their knowledge in novel applications. Despite the crucial role of these materials in promoting sustainable production and consumption models, systematic studies on the current innovation terrain are lacking, leaving gaps in understanding key players, emerging technologies, and market trends. To address this void, we focused on examining patents related to biobased monomers and polymers, aiming to describe the innovation strategies and business dynamics of leading assignees. Embedded within the European Sustainable BIO-based nanoMAterials Community (BIOMAC) project, a Horizon 2020 initiative, our research leverages this unique framework dedicated to advancing the innovation landscape, specifically emphasizing the market readiness of biobased materials. We implemented a multi-stage strategy, prioritizing validated keyword queries to ensure the superior quality and reliability of the collected data. To understand primary contributors within these landscapes, we conducted an in-depth analysis of innovation strategies employed by leading companies. Findings from the ORBIT platform highlighted a remarkable increase in patent publications in the past decade, with China standing out as a key hub of innovation, signaling a strong focus on the development of these materials. Our research explores technological advancements in biobased materials to identify specific areas with potential for further development. By analyzing innovation trends in five key industries, we pinpoint opportunities for innovative solutions to be commercially exploited while ensuring compliance with intellectual property rights within a freedom-to-operate framework.

Strong and tough bio-based biomimetic-multiphase composite polyesters with superior barrier and chemically closed-loop performances

A full-natural bionics-multiphase composite polyester with mechanical robustness, high gas barrier and chemically closed-loop properties was designed and prepared using bio-based monomers and single-layered mica to achieve a replacement for plastic.

A simple and versatile photothermal dual-curing system design based on phytophenol derivatives and thiol chemistry for potential electronic encapsulant application

Given the diversity of thiol chemistry, researchers are actively exploring its potential as a versatile compound. This paper presents the synthesis of three bio-based multifunctional monomers (EPMG, EPBEG, EPBEF) containing allyl and epoxy groups using phytophenols (magnolol and eugenol) as raw materials. Photothermal dual curing was performed using pentaerythritol tetrakis(3-mercaptopropionate) (PETMP). Comprehensive studies and comparisons of the cured systems were conducted, including curing kinetics, mechanical properties, dielectric properties, and transmittance. The effect of the curing sequence was systematically investigated. The results demonstrate that as the curing proceeds, the mechanical properties and glass transition temperature (Tg) of the material improve significantly, and the dual curing process exhibits excellent bonding, dielectric, and ultraviolet (UV) shielding performance. Moreover, the differences in monomer structure (methoxy, benzene ring connection) also impact the properties of the monomers and the performance of the material. This work provides a novel approach to designing epoxy monomer structures and developing bio-based single-component dual-curing systems. This thiol-mediated dual-curing system has potential applications in electronic materials and personal protective equipment can contribute to achieving miniaturization, precision, and integration in various applications.

Synthesis and RAFT polymerisation of hydrophobic acrylamide monomers derived from plant oils

Polymeric materials based on fatty acids have been synthesised using RAFT polymerisation. This work demonstrates the potential of biobased monomers, isolated directly from plant oils, for well-defined polymers to develop more sustainable materials.

Butyl Acrylate/2-Methylene-1,3-Dioxepane/Vinyl Acetate Emulsion Terpolymerization: Incorporating Backbone Degradable Linkages into Adhesive Applications.

The ring-opening polymerization of bio-based monomer 2-methylene-1,3-dioxepane (MDO) can reportedly enhance polymer degradability. Butyl acrylate (BA)/MDO/vinyl acetate (VAc) terpolymers were synthesized via emulsion polymerization for their eventual application as pressure-sensitive adhesives (PSAs). While using MDO in emulsion polymerization leads to a more sustainable process, it also presents challenges such as MDO hydrolysis, MDO ring retention, and inadequate MDO distribution. By carefully selecting reaction conditions such as pH and temperature, MDO hydrolysis and MDO ring retention were mitigated, and a uniform distribution of MDO throughout the terpolymer was confirmed. In addition, carboxylated cellulose nanocrystals (cCNCs) were incorporated into the final formulation to enhance the PSA properties.

Fats and Oils as a Sustainable Source of Photopolymerizable Monomers.

Bio-derived monomers and biobased building blocks obtained from natural sources, e.g., fats and oils, are attracting increasing attention mainly due to sustainability concerns. Due to their features, renewable feedstocks are an excellent alternative to petroleum-based raw materials to shift towards greener chemistry, especially when coupled with energy-efficient processes like photopolymerization. In this review, we illustrate the recent research outcomes in the field of photocurable biobased monomers, showing the advantages of using biobased chemicals for the synthesis of photocurable monomers and the potential of naturally derived building blocks in photocuring reactions.

Synthesis of Novel Zwitterionic Surfactants: Achieving Enhanced Water Resistance and Adhesion in Emulsion Polymer Adhesives.

Recent advancements in polymer materials have enabled the synthesis of bio-based monomers from renewable resources, promoting sustainable alternatives to fossil-based materials. This study presents a novel zwitterionic surfactant, SF, derived from 10-undecenoic acid obtained from castor oil through a four-step reaction, achieving a yield of 78%. SF has a critical micelle concentration (CMC) of 1235 mg/L, slightly higher than the commercial anionic surfactant Rhodacal DS-4 (sodium dodecyl benzene sulfonate), and effectively stabilizes monomer droplets, leading to excellent conversion and stable latex formation. The zwitterionic groups in SF enhance adhesion to hydrophilic substrates (glass, stainless steel, and skin). Films produced with SF exhibit outstanding water resistance, with only 18.48% water uptake after 1800 min, compared to 81% for the control using Rhodacal DS-4. Notably, SF maintains low water uptake across various concentrations, minimizing water penetration. Thus, the synthesized SF demonstrates improved adhesive properties and excellent water resistance in emulsion polymerization applications, highlighting its potential as a sustainable, high-performance alternative to petrochemical surfactants.

Seawater-corrosion-engineered CoNi electrode for highly efficient oxidation of 5-(Hydroxymethyl)furfural

The green synthesis of 2,5-furandicarboxylic acid (FDCA), famous as a bio-based polymer monomer from the 5-hydroxymethylfurfural (HMF), offers a promising route to reduce the usage of petroleum-based polymer polyethylene terephthalate. Although the electrocatalytic preparation of FDCA rids high temperature and pressure limits, most electrocatalysts used in the HMF oxidation reaction (HMFOR) are usually fabricated in harsh conditions. Therefore, we propose a method to improve the performance of electrocatalysts in the HMFOR reaction by introducing metal salts using natural seawater as the main feedstock. The final Co-sw/NF realized a 97.4% FDCA yield and 97.3% Faraday efficiency (FE). In-situ Raman techniques identified the catalytically active species of the catalysts employed in the HMFOR process. The effect of metal salts on catalyst energy levels is discussed in detail using the ultraviolet photoelectron spectroscopy (UPS) and Tauc plot method. The adsorption performance of HMF on the catalyst was determined by calculating the d-band centers and applying open circuit potential (OCP) tests. Furthermore, we elucidate the specific mechanism in terms of electron transport pathways.

Characterization and performance of carbon supported platinum-bismuth bimetallic catalysts tested in 5-hydroxymethylfurfural aerobic oxidation to 2,5-furandicarboxylic acid

The increasing demand for sustainable alternatives to petroleum-based chemicals has driven research towards the utilization of renewable feedstock, such as lignocellulosic biomass (LCB), to produce high-value products. Among LCB-derived platform molecules, 5-hydroxymethylfurfural (HMF) has become a key building block for bio-based monomers such as 2,5-furandicarboxylic acid (FDCA), among many others. This study reports the successful synthesis of various Pt-Bi catalysts supported on activated carbon (C) and investigates their role in the HMF conversion to FDCA.The catalytic performance of the Pt-Bi/C catalysts was evaluated in batch reactors, using HMF in an aqueous reaction medium, with 1 M of Na2CO3 to provide alkalinity, and under 10 bar of O2. These results demonstrated a strong correlation between catalyst properties and their catalytic activity. Among the prepared catalysts, the 9Pt-3Bi/C catalyst was the most efficient one, achieving a yield to FDCA of 99.7 %. Further investigations revealed that the 9Pt-3Bi/C catalyst maintained its excellent performance even under reduced reaction times, lower temperatures, and reduced catalyst loadings, demonstrating its potential for practical applications.Across all reactions, it was observed that, under the tested reactions conditions, the existence of side reactions involving HMF degradation to other compounds was significant. This underscores the challenge of achieving quantitative HMF conversion to FDCA, enhancing the importance of catalyst properties and reaction conditions optimization to minimize by-product formation.

Synthesis and Thiol-Ene Photopolymerization of Bio-Based Hybrid Aromatic-Aliphatic Monomers Derived from Limonene, Cysteamine and Hydroxycinnamic Acid Derivatives.

Three novel bio-based monomers were synthesized through an amidation reaction involving allylated derivatives of coumaric, ferulic and phloretic acid and a diamine obtained from a thiol-ene coupling reaction between limonene and cysteamine. The monomers containing the enone bond of the cinnamic moiety underwent photoisomerization and photocycloaddition reactions upon UV light irradiation. All three monomers were photocured via thiol-ene photopolymerization using a glycerol-derived trifunctional thiol, resulting in fully bio-based poly(amide-thioether)s. The polymers derived from monomers that contain the enone bond exhibited glass transition (Tg) temperatures of 85 °C when a stoichiometric ratio of the thiol was used, whereas polymers in which an excess of thiol was used exhibited Tg temperatures of 61 and 74 °C. The higher Tg of the synthesized polymers, compared with other reported polymers produced from thiol-ene photopolymerizations, was attributed to the combination of the aromatic rings of the cinnamic moiety and the cycloaliphatic ring of limonene, as well as the presence of the amide groups in the polymer, which can induce hydrogen bonding. The development of high Tg polymers from bio-based monomers through thiol-ene photopolymerization represents a significant advancement in the polymer synthesis sector, offering an improved performance and sustainability.

A Ternary Bio-Based Monomer toward the Polyesters with High UV Shielding and Water-Degradation Properties

A Ternary Bio-Based Monomer toward the Polyesters with High UV Shielding and Water-Degradation Properties

A Bio-Based Polybenzoxazine Derived from Diphenolic Acid with Intrinsic Flame Retardancy, High Glass Transition Temperature and Dielectric Properties.

A bio-based benzoxazine monomer, diphenolic methyl ester hexafluoro diamino benzoxazine (DPME-HFBz), was successfully synthesized from diphenolic acid (DPA), and the chemical structure was successfully verified. The curing kinetics were studied via non-isothermal differential scanning calorimetry (DSC). The activation energies of DPME-HFBz were calculated by Kissinger and Ozawa methods to be 136.15 and 139.92 kJ/mol, respectively, and the reaction order was calculated to be first order. Owing to the large number of hydrogen bonds after polymerization, poly(DPME-HFBz) presented an ultra-high glass transition temperature of 312 °C and a high initial decomposition temperature (350 °C under air and 345 °C under nitrogen). Because of the excellent charring ability (50.2% residue under nitrogen), the LOI value of poly(DPME-HFBz) was as high as 38%. Poly(DPME-HFBz) also exhibited a very low heat release capacity (HRC) of 90 J/(g·K). In addition, poly(DPME-HFBz) had a dielectric constant (Dk) of 1.88 at 1.5 MHz, which was much lower than the Dk of the reported low-dielectric polymers. This work provides an efficient and sustainable strategy for the synthesis of benzoxazine thermosetting materials with excellent comprehensive properties.

Antimicrobial Activity of Copolymer Structures from Bio-Based Monomers.

The urgent need for new antimicrobial compounds has led scientists to explore antimicrobial peptides (AMPs) and antimicrobial polymers as solutions for multidrug resistance. In this study, we synthesized copolymers with cationic and hydrophobic moieties by free-radical polymerization (FRP) using a chain transfer agent to control molecular weights. The potential of natural products as part of the hydrophobic moiety was evaluated, along with variations in their monomer content (13-25%) and the molecular weight (MW) of the copolymer (5000-20,000 g·mol-1). Hydrophobicity was evaluated using the theoretical Log Poct values and surface areas (SAs). Biological assays included antimicrobial activity against Escherichia coli and Staphylococcus aureus standard strains, hemolytic activity in red blood cells (RBC), and cytotoxicity tests against HEK293T cells. Keys findings indicate that copolymers with tropolone moieties, lower MWs, and an optimal balance between hydrophobic and cationic moieties show a promising basis for future generations of antimicrobials.

Biobased Sulfur- and Phosphate-Containing High-Refractive-Index Polymers: Substituent Effects on Optical Properties of Polymers.

Four biobased phosphate-containing aryl monomers with methoxy, allyl, and vinyl groups as substituents have been successfully synthesized. Copolymerizing these monomers with thiophenol or mercaptans via the photoclick thiol-ene reaction gives the polymers with refractive indices (nD) of 1.63-1.70 and Abbe numbers (vD) of 12.8-38.5. An investigation of the relationship of the vD values with the substituents on the benzene rings of the monomers indicates that methoxy and vinyl groups can collectively increase the vD values. In comparison with allyl groups, vinyl groups endow the polymers with both higher nD and vD. Moreover, these polymers also display high transmittance, high thermostability, and low haze values in the visible-light region, suggesting that these biobased functional monomers are satisfactory precursors used in the fabrication of optical devices.

A novel bio-based autocatalytic amide-type phthalonitrile monomer: Synthesis, curing kinetics and thermal properties

A bio-based bisphenol compound (DFA) was prepared using bisphenolic acid and furfurylamine in biomass as raw materials. Then, a bio-based amide phthalonitrile monomer (DFAP) was obtained in an environmentally friendly solvent. Nuclear magnetic resonance and Fourier transform infrared spectroscopy (FT-IR) proved the successful synthesis of DFA and DFAP. The curing behavior and curing kinetics of the polymer were studied using FT-IR and differential scanning calorimetry. Calculate the activation energy using the isoconversion method. The SB(m, n) autocatalytic reaction model describing the curing process of poly(DFAP) was modified and fitted by introducing the variable activation energy model. The thermal stability, thermomechanical properties and processing properties of the resin were studied using technologies such as thermogravimetric analyzer, dynamic mechanical analyzer and rheometer. The results show that the prepolymer has a wide processing window and a low melt viscosity. Poly(DFAP) has a high glass transition temperature and excellent thermal stability.

Analysis of bio-based epoxy resins: Impact of amine hardeners on thermal, thermomechanical, optical and electrical properties of epoxidized resveratrol with high Tg

Epoxidized resveratrol (RES) has been cured with different amines in order to compare their possibilities to obtain high-temperature resistance of bio-based epoxy resins. Materials obtained from the bio-based monomer present glass transition temperatures (Tg) among the highest ever reported for an epoxy-amine curing system, with extremely high char residue, making them excellent candidates for extremely high-temperature applications. Particularly, epoxidized RES stoichiometrically cured with 4,4′-sulfonyldianiline (DDS) reached 297 °C, measured as the tan δ peak by DMTA, and two other materials, using 4,4′-methylenedianiline (DDM) and 4,4′-diaminodicyclohexylmethane (CAA) as curing agents, exceeded 300 °C. In fact, the material begins to degrade before the chains are fully relaxed, so they are thermosetting that never go completely into the rubbery state. Additionally, this resin improves the direct current (DC) insulating character (∼1015 Ωcm) while decreasing the optical band gap (∼2 eV) when compared to other epoxy resins available, which is of great interest for photovoltaic applications. Moreover, some of the materials presented a very high char residue proportion when heated (>40 wt% at 800 °C under nitrogen atmosphere), presenting good fire-retardant properties.

A Systematic Study on Biobased Epoxy-Alcohol Networks: Highlighting the Advantage of Step-Growth Polyaddition over Chain-Growth Cationic Photopolymerization.

Vanillyl alcohol has emerged as a widely used building block for the development of biobased monomers. More specifically, the cationic (photo-)polymerization of the respective diglycidyl ether (DGEVA) is known to produce materials of outstanding thermomechanical performance. Generally, chain transfer agents (CTAs) are of interest in cationic resins not only because they lead to more homogeneous polymer networks but also because they strikingly improve the polymerization speed. Herein, the aim is to compare the cationic chain-growth photopolymerization with the thermally initiated anionic step-growth polymerization, with and without the addition of CTAs. Indeed, CTAs lead to faster polymerization reactions as well as the formation of more homogeneous networks, especially in the case of the thermal anionic step-growth polymerization. Resulting from curing above the TG of the respective anionic step-growth polymer, materials with outstanding tensile toughness (>5MJ cm-3) are obtained that result in the manufacture of potential shape-memory polymers.

Solid Forms of Bio-Based Monomer Salts for Polyamide 512 and Their Effect on Polymer Properties.

Polyamides' properties are greatly influenced by the polymerization process and the type of feedstock used. The solid forms of nylon salts play a significant role in determining the final characteristics of the material. This study focuses on the long-chain bio-nylon 512. Firstly, we systematically investigated the possible solid forms of the nylon 512 salt, including crystal forms and morphologies, by massive experimental screening, single-crystal X-ray diffraction, Hirshfeld surface analysis, and TG-DSC measurements. The regulation and control of the various solid forms were achieved through solid-state transformations (SSTs) and solution-mediated phase transformations (SMPTs). Our findings shows that the nylon 512 salt exists in two crystal forms (anhydrate and dihydrate) and four morphologies (needle-like, plate-like, rod-like, and massive block crystal). Many factors will influence the formation of these solid forms, such as water activity, temperature, solvent, and ultrasonic physical fields. We can choose the right factors to regulate this as needed. On this basis, we studied the effects of different solid forms (crystal forms and morphologies) on the properties of the resulting polyamides prepared using direct solid-state polymerization (DSSP). The solid form of the salt had many effects on the polymer, including its structure, melting point, and mechanical properties. The polyamide obtained through DSSP of the anhydrate salt exhibited a higher melting point (204.22 °C) and greater elastic modulus (3.366 GPa) compared to that of the dihydrate salt, especially for the anhydrate salt of plate-like crystals.

Renewable Photo-Cross-Linkable Polyester-Based Biomaterials: Synthesis, Characterization, and Cytocompatibility Assessment.

The present work consist of the synthesis of photo-cross-linkable materials, based on unsaturated polyesters (UPs), synthesized from biobased monomers from renewable sources such as itaconic acid and 1,4-butanediol. The UPs were characterized to assess the influence of polycondensation reaction temperature and cross-linking time on their final properties. For this purpose, different UV irradiation exposure periods were tested. Homogeneous, uniform, and transparent films were obtained after 1, 3, and 5 min of UV exposure. These cross-linked films were then characterized. All materials presented high gel content, which was dependent on the reaction's temperature. The thermal behaviors of the UPs were shown to be similar. In vitro hydrolytic degradation tests showed that the materials can undergo degradation in phosphate-buffered saline (PBS) at pH 7.4 and 37 °C, ensuring their biodegradability over time. Finally, to assess the applicability of the polyesters as biomaterials, their cytocompatibility was determined by using human dermal fibroblasts.