We report on the preparation of hexa-functional cardanol (renewable phenolic compound) benzoxazine with a phosphazene core (CPN) for use as a greener eco-friendly halogen-free flame retardant reactive additive for the formation of sustainable polyphosphazene polybenzoxazine networks for flame resistant applications. The structure and purity of the monomer was confirmed by Fourier transform infrared (FTIR), nuclear magnetic resonance (1H-, 13C-, 31P NMR) and gel permeation chromatography studies. The CPN monomer showed good compatibility with benzoxazine monomer (CPN0) as suggested by the cocuring studies. The thermal properties of the copolymer can be directly tuned by altering the composition of the monomer blend. The occurrence of phosphazene-phosphazane thermal rearrangement is also suggested for the thermal behavior (thermogravimetry analysis) at higher loading of CPN in the monomer feed ratio. An improvement in mechanical properties of the copolymer with increase in glass transition temperature was confirmed by enhancement in cross-link density as compared to neat polybenzoxazine. The reactive nature and presence of phosphazene core improved both the smoke density rating, vertical burning rating and led to higher limiting oxygen index. The FTIR and scanning electron microscopy studies of residual char supported the formation of functionalities and morphologies favorable to support the flame resistance behavior of polymer by incorporation of reactive benzoxazine with phosphazene core. Finally, we demonstrate that incorporation of cardanol phosphazene network has good compatibility with the polybenzoxazine phenolic thermosets with improvement in flame retardancy. The higher cardanol (65.7\%) and phosphorus content (3.4\%) and reactive nature of synthesized compound is attractive as a sustainable additive with the scope of their utilization with other polymeric resins. © 2017 American Chemical Society.

Bimlesh Lochab

Chemistry

(SoNS) School of Natural Sciences

Amarnath N.

Appavoo D.

<p>Shiv Nadar University is a comprehensive, multidisciplinary, research-focused, and student-centric University offering a full range of academic programs at the undergraduate, postgraduate and doctoral level. With state-of-the-art infrastructure, the University comprises of academic wings, sophisticated labs, international standard sports facilities, amphitheaters, auditorium, conference rooms and smart classrooms. The University&rsquo;s goal is to become internationally recognized for the quality of its research and creative endeavors and their applicability to improving quality of life, generating new insights and expanding the boundaries of human knowledge creativity. Committed to excellence in teaching, research and service, the University aims to serve the higher education needs of India and the world beyond.</p>

Shiv Nadar University

ACS Sustainable Chemistry and Engineering

Lithium-sulfur (Li–S) batteries are among the most promising candidates for the next-generation rechargeable batteries due to their high energy density, cost-effectiveness, environmental friendliness and being on the verge of commercialization. However, considering the cathode part, low conductivity of sulfur, large volume expansion, dissolution of polysulfides in the electrolyte and their unfavorable shuttle behavior lead to low cell capacity and poor cycle life. More importantly, the high flammability of sulfur causes safety concerns that might hinder the large-scale application of lithium-sulfur batteries in electric vehicles, especially in tropical countries. Herein, we report a covalently linked sulfur (~83\% w/w) flame retarding sustainable copolymer as a suitable and safe cathode material for the practical application of Li–S batteries in tropical region. A remarkable intrinsic flame-retardant property with appreciable specific capacity and excellent capacity retention provide an alternative strategy for designing cathode materials for safe and sustainable Li–S batteries. © 2020

Energy Storage Materials

Halogen-free flame-retardant sulfur copolymers with stable Li–S battery performance

Olefin bonds participate in co-reaction with the benzoxazine functionality of the monomer and are one of the strategies used to affect the crosslink density of a polybenzoxazine network. In general, the double bond incorporation in starting material is usually catalyzed by expensive, rare earth metals affecting the sustainability of the reaction. The natural abundance of feedstocks with inherent double bonds may be a powerful platform for the development of novel greener structures, with potential applications in polymers. Here, we report the design, synthesis, and characterization of a biobased non-halogen flame retardant, consisting of naturally occurring phenols, eugenol (E), and cardanol (C). The presence of a covalently linked phosphazene (P) core allowed the synthesis of hexa-functional flame retardant molecules, abbreviated as EP and CP. The chemical structures of the synthesized EP and CP were confirmed by Fourier transform infrared (FTIR), nuclear magnetic resonance (1H, 13C, 31P NMR), and single crystal XRD (only in the case of EP). Their polymerization with cardanol sourced tri-oxazine benzoxazine monomer, C-trisapm, was followed by FTIR, NMR, and DSC studies. The thermal stability and flame retardant properties of the hybrid phosphazene-benzoxazine copolymers was determined by thermogravimetry analysis (TGA), limiting oxygen index (LOI), vertical burning, and smoke density analyses. SEM images of the char residues of the polymers with or without the addition of reactive phosphazene molecules confirmed the intumescent flame retarding mechanism. Current work highlights the utility of sustainable origin non-halogen flame retardant (FR) molecules and their utility in polybenzoxazine chemistry. © Copyright © 2020 Appavoo, Amarnath and Lochab.

Fulltext

Frontiers in Chemistry

Cardanol and Eugenol Sourced Sustainable Non-halogen Flame Retardants for Enhanced Stability of Renewable Polybenzoxazines

Polybenzoxazines are evolving as a new class of phenolic resins with a tremendous amount of applications. The ease of structural designing, synthetic procedure, and polymerization reactions are attractive to affect their properties ensuing as an effective substitute for many existing polymers. The nonrenewable origin, toxicity, and increasing cost of petro-based raw materials are alarming issues. Therefore, the emergence of sustainable benzoxazines, especially based on naturally abundant, agro-waste origin cardanol is encouraging as it allows both solventless synthesis of monomers and processing to form highly thermally stable thermoset resins. The inherent functionalities in cardanol benzoxazine provide a platform for further structural modifications to advance their applications as adhesives, composites, and energy storage devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Macromolecular Chemistry and Physics

Cardanol Benzoxazines: A Versatile Monomer with Advancing Applications

Polybenzoxazines (PBzs) are emerging as a highly promising and superior class of thermoset polymers for a variety of applications. However, it remains a significant challenge to substantially lower the ring-opening polymerization (ROP) temperature with an ease in processability. On the other hand, biomacromolecule chitosan (CS) is explored extensively, but its practical applications have been precluded by poor thermal and mechanical properties. Here, we developed a fully biobased copolymer of vanillin benzoxazine (V-fa) monomer with CS, which is effective in providing mutual benefits, effective lowering in ROP temperature of benzoxazine (70 °C), and an enhanced thermal stability of CS (by 85 °C, and with char yield of â32\%). To understand this unusual lowering in ROP temperature, we investigated the structural interaction mechanism between solvated CS and V-fa using in situ NMR studies. The analysis of fully intercalated co-structure demonstrated that there is a strong preference for ROP over Schiff base reaction. It is anticipated that benzoxazine molecules move within the interplanar distance of CS as supported by powder X-ray diffraction studies. An increase in V-fa content in feed ratio led to a placement of V-fa units from random to a systematic and hierarchical arrangement within the CS framework followed by its subsequent polymerization. The synergistic interactions were further supported by Fourier transform infrared, differential scanning calorimetry, scanning electron micrsocopy, thermogravimetric analysis, and tensile studies. Current work represents preparation of CS benzoxazine copolymers using a low-cost, efficient, and sustainable approach to assist metal-free ROP reaction of Bz to afford low curable temperature processable films. A new strategy is devised for the utility of CS-PBzs copolymers, enabling their extension to innovative applications in cross-domains. © 2019 American Chemical Society.

Sustainable Framework of Chitosan-Benzoxazine with Mutual Benefits: Low Curing Temperature and Improved Thermal and Mechanical Properties

Biobased phenols and amines are attractive feedstock in rapid emerging polybenzoxazine thermosets. Renewable benzoxazines are mainly monofunctional due to structure limitation of raw materials, especially amines. Here, we report fully naturally sourced bifunctional benzoxazines by a simple one-step solventless microwave synthesis using cardanol/guaiacol- and carbohydrate-based isomannide diamine (ima). Chirality of ima led to complicated 1H NMR spectra of monomers. Heteronuclear single-quantum coherence (HSQC) and two-dimensional correlated spectroscopy (COSY) NMR and single-crystal X-ray diffraction confirmed the structure and formation of monomers. Polymerization and thermal stability of monomers and polymers were found to be either better than or comparable to widely studied fully and partly petro-based polybenzoxazines. Incorporation of rigid core ima in fully biobased polybenzoxazines showed a glass-transition temperature comparable to their petro-based aromatic diamine counterparts. Exploration of adhesive behavior revealed that the designed polybenzoxazine framework showed 2-fold higher lap shear strength than bisphenol-A (BPA) aniline polybenzoxazine. The current work highlights the utility of higher functionality renewable amines as promising candidates to design future high-performance fully biobased BPA-free polybenzoxazines. Copyright © 2019 American Chemical Society.

Isomannide-Derived Chiral Rigid Fully Biobased Polybenzoxazines

This chapter explores the utility of cardanol as a potential feedstock for the synthesis of benzoxazine monomers and polymers. Cardanol is a renewable phenolic compound obtained from the plant Anacardium occidentale L. Commercially it is produced as cashew nut shell liquid (CNSL) as a byproduct of cashew nut processing. It is currently under exploration as a valuable phenolic reagent in benzoxazine monomers and polymers. Cardanol-based benzoxazines are attractive monomers due to their sustainable aspect, opportunities for solventless synthesis, and processing. To date, Cardanol monomers have primarily been utilized for adhesive and composite applications, but they are ideal candidates for a variety of other applications, which need further exploration. © 2017 Elsevier Inc. All rights reserved.

Advanced and Emerging Polybenzoxazine Science and Technology

Cardanol-Based Benzoxazines and Their Applications

Mono-benzoxazine monomers based polybenzoxazines suffer from a lower crosslink density and char yield that especially is further diluted by the presence of longer alkylene chain in cardanol (C). In order to improve the crosslink density, char yield and to understand the role of higher aromatic content vs functionality, a series of cardanol-based benzoxazine monomers were synthesised. The amine condensed with cardanol and paraformaldehyde were aniline (a), 4-triphenylmethylaniline (ta), and tetra-aminophenyl methane (tapm) via solventless methodology. The C-a and C-ta are mono-benzoxazines while C-tapm is a tetra-benzoxazine monomer. The monomers were structurally characterised using FT-IR, 1H and 13C NMR spectroscopy and mass spectrometry. The ring opening polymerisation temperature (ROP) of monomers and thermal stability of resins was determined using DSC and TGA while mechanical properties were determined using rheometry. The curing kinetic study using FT-IR and DSC showed C-ta has intermediate curing behaviour between the C-a and C-tapm. The Ea for curing reaction C-a, C-ta and C-tapm was found to be 143, 126 and 70 kJ/mol. The lowest Ea for curing reaction of C-tapm (tetra-benzoxazine) is due to its highest functionality but C-ta (mono-benzoxazine) has lower Ea than C-a which can be accounted to the presence of more reactive sites provided by the additional aromatic rings in the former. It was found that the incorporation of higher aromatic ring in benzoxazine monomers is another route in enhancing the crosslink density besides higher functionality to modulate their properties. © 2016 Elsevier Ltd

Polymer

Role of higher aromatic content in modulating properties of cardanol based benzoxazines

A series of benzoxazine monomers with varied benzoxazine functionality from 1 to 3 (mono, bis, and tris) is prepared by reacting agrowaste-derived cardanol with higher functionality amines. The ring opening polymerization study of cardanol-based benzoxazine monomers is investigated by three modes, namely, solution (nuclear magnetic resonance and gel permeation chromatography), bulk (differential scanning calorimetry), and theoretical (B3LYP and 6–31+G**) calculations to analyze the role of number of benzoxazine functionality in curing behavior of the monomers. It is found that the presence of higher and close vicinity of benzoxazine functionality in the monomer promotes faster ring opening, rapid polymerization conversion, and enhancement in the average molecular weight buildup. The activation energy for the curing process is found to decrease from 144–113 kJ mol−1 from mono- to tris-benzo­xazine monomer. Thermodynamically, the presence of higher benzoxazine moiety reveals the curing process is highly exergonic as supported by theoretical calculations. Free energy for successive protonation varies from −9.54 to −24.68 eV for mono- to tris-functionalized monomer. The effect of number of functionality in monomer on its curing behavior – a complete study is reported to offer sustainable monomers/polymers for futuristic materials applications. (Figure presented.) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Kinetics behind a Strategy for Modulation of Sustainable Benzoxazines: Experimental Study and Its Theoretical Verification

A sulfur-rich copolymer, poly(S-r-C-a) has been synthesized via a sustainable route, showing the utility of two major industrial wastes- elemental sulfur (petroleum waste) and cardanol (agro waste), to explore its potential as cathode material for Li-S batteries. The sulfur-rich copolymer exhibited a reduction in the active material dissolution into the electrolyte and a low self-discharge rate behavior during the rest time compared to an elemental sulfur cathode, indicating the chemical confinement of sulfur units. The presence of organosulfur moieties in copolymer suppress the irreversible deposition of end-discharge products on electrode surfaces and thus improve the electrochemical performances of Li-S batteries. This sulfur copolymer offered a reversible capacity of 892 mA h g-1 at 2nd cycle and maintained the capacity of 528 mA h g-1 after 50 cycles at 200 mA g-1. Reduced graphene oxide (rGO) prepared via a sustainable route was used as a conductive filler to extract the better electrochemical performances from this sulfur copolymer. Such sustainable origin batteries prepared via economically viable showed an improved specific capacity of ∼975 mA h g-1 after 100 cycles at 200 mA g-1 current rate with capacity fading of 0.15\% per cycle and maintained a stable performance over 500 cycles at 2000 mA g-1.

Scientific Reports

Sustainable Sulfur-rich Copolymer/Graphene Composite as Lithium-Sulfur Battery Cathode with Excellent Electrochemical Performance

This paper deals with the preparation of sustainable benzoxazines that exhibit enormous potential to compete with the existing petro-based advance performance thermosets. The phenolic component used for the synthesis of benzoxazine is derived from naturally occurring cardanol, which is obtained from cashew nut tree, Anacardium occidentale. Polyethylene terephthalate (PET) was chosen as a sustainable feedstock for the amine fraction used to prepare the benzoxazine monomer containing amide linkages. Microwave-assisted aminolysis of PET was performed to obtain bis(amino-ethyl) terephthalamide (BAET) and α,ω-aminoligo(ethylene terephthalamide) (AOET), which were employed as the difunctional amine for the preparation of bis-benzoxazines. In comparison to the traditional method, microwave-assisted aminolysis of PET was found to be significantly faster, and the reaction completion time could be brought down appreciably. Mannich-like condensation of cardanol with PET-derived terephthalamides and paraformaldehyde led to the formation of bis-benzoxazines with amide linkages, the structure of which was confirmed through FT-IR and 1H NMR spectroscopy. The curing behavior of the bis-benzoxazines was studied using nonisothermal differential scanning calorimetry. The presence of amide linkages in addition to the polar group formed during the ring opening of benzoxazines led to the improvement in adhesive strength, which was quantified in terms of lap shear strength. © 2015 American Chemical Society.