Polymerization Of Benzoxazine Research Articles

Multidisciplinary space shield origami composite: Incorporating cosmic radiation shielding, space debris impact protection, solar radiative heat shielding, and atomic oxygen erosion resistance

Origami composites have been extensively utilized in space structures with constrained payload volumes due to their capability to efficiently transform compact structures into larger surface area or volume configurations. The proposed origami composite incorporates hydrogen-rich benzoxazine polymers known for their high radiation shielding capability and ultra-high-molecular-weight polyethylene fibers known for their high ballistic performance, radiation shielding capability, and flexibility. The proposed origami composite and manufacturing method can enhance bonding strength by achieving precise origami shapes and utilizing the same matrix for both flexible and rigid components. Membrane sheets are manufactured at a low curing temperature to provide flexibility, while rigid facets are separately manufactured at a high curing temperature to increase rigidity. The integration of a polyimide protection layer significantly enhances space environment resistance and reduces mass loss due to atomic oxygen erosion. Despite a slight decrease in ballistic performance after exposure to space conditions, the proposed origami composite maintains superior ballistic performance compared to conventional space materials and conventional origami composites. Compared to existing origami composites or conventional space materials, the proposed origami composite exhibited superior radiation shielding performance. The laminated structure of the proposed origami composite can offer some solar radiation shielding capability. The proposed origami composite offers a multifunctional origami solution as a membrane-space shield material, fulfilling requirements for high ballistic performance, cosmic radiation shielding, solar radiative heat shielding, and space environmental resistance.

Evaluation of optical, thermal and hydrophobic properties of sustainable stilbene-based benzoxazines for high-performance utilization

Currently there is a growing interest in the field of photosensitive benzoxazines synthesized from sustainable raw materials. An attempt has been made to synthesize nine structurally different benzoxazines through Mannich condensation reaction. The formation of the expected structure of the synthesized benzoxazine monomers were ascertained using spectroscopic methods. The ring-opening polymerization of benzoxazines was studied using DSC and found that THS-imp benzoxazine monomer exhibits the lowest value of curing temperature (Tp) of 179oC than the rest of the benzoxazine monomers. Thermal stability of polybenzoxazines were analyzed using thermogravimetric analyzer. Among the different polybenzoxazines studied, poly(THS-a) possesses the higher thermal stability with char yield of 53% than that of other benzoxazines. The band gap values of benzoxazines calculated from optical studies are ranged between 3.92-4.71 eV. The hydrophobic behavior of the polybenzoxazines assessed using the water contact angle obtained from goniometer for both neat polymer matrix and benzoxazine coated cotton fabric. Results from the water contact angle infer that the benzoxazines coated cotton fabric exhibited 152o, which shows the superhydrophobic behavior. The corrosion resistant properties of all the polybenzoxazines coated over MS specimen has been tested. Among them poly(THS-pfsa) and poly(THS-imp) have higher Icorr value and corrosion inhibition efficiency of 99%. Data obtained from different studies indicate that the benzoxazines developed from sustainable stilbene can be utilized in the form of coatings, adhesives, sealants, and matrices for composites for wide range of industrial and engineering applications, where high thermal stability and are required.

Studies on catalyst assisted low-temperature curing of benzoxazines

The present study addresses an increasing interest in achieving low-temperature curing of benzoxazines by utilizing chemical substances with acid moieties of varying functionalities as curing catalysts. Specifically, cardanol-furfurylamine (1), card-bisphenol-furfurylamine (2), bisphenol-A-aniline (3) and bisphenol-F-aniline (4) based benzoxazines were chosen for curing studies. The selected catalysts were systematically applied into benzoxazines and its curing behavior was studied with minimum amount of 5 wt%. Catalysts, including those with carboxyl and N,N-dimethyl functionalities, were evaluated based on their performance, with a focus on their substituent effect on curing behavior. The results contribute to the identification of catalysts with optimal potential for achieving the efficient low-temperature curing of benzoxazines with an objective of utilizing them for wide area of applications. Among the catalysts studied, gallic acid was found to be the better catalyst and reduces the curing temperature to 130 °C. The conversion graph for both bisphenol-A-aniline benzoxazine (3) in the absence of catalysts and bisphenol-A-aniline benzoxazine in the presence of catalysts (3 s) have been studied by DSC analysis. The activation energy (Ea) has been calculated using Kissinger-Ozawa method through DSC analysis. Data resulted from different catalysts used for curing of benzoxazines, it was inferred that the pKa values of the catalysts also play a crucial role in the polymerization of benzoxazines. Further, the study aims to meet the growing demand for efficient and economically viable low-temperature curing processes for benzoxazines.

Polymerization of benzoxazine impregnated in porous carbons. A scalable and low-cost route to smart copper-ion absorbents with saturation indicator function

Porous carbon materials are common materials used for sensor and absorbent applications. A novel approach for functionalizing porous carbons through the impregnation of porous carbon black with benzoxazine monomers, followed by thermal polymerization is introduced herein. The method not only establishes a new avenue for the functionalization of porous carbons but also endows the resulting material with both copper ion-binding and sensing properties. We showcase the versatility of the technique by illustrating that the polymerization of phenols with benzoxazine monomers serves as an extra tool to customize absorption- and sensing properties. Experimental validation involved testing the method on carbon black as a porous substrate, which was impregnated with both bisphenol-a benzoxazine and a combination of bisphenol-a benzoxazine and alizarin. The resulting materials were assessed for their dual functionality as both an absorbent and a sensor for copper ions by varied copper ion concentrations and exposure times. The dye absorption test demonstrated a notable capacity to accumulate copper ions from dilute solutions. Electrochemical characterization further confirmed the effectiveness of the modified carbons, as electrodes produced from inks were successful in detecting copper ions accumulated from 50 μM Cu2+ solutions. With this work, we aspire to set the steppingstone towards a facile functionalization of porous carbon materials towards water purification applications.

Sensor Absorbents for Heavy Metal Ions By Low-Cost Functionalization of Porous Carbons

Porous carbons are key materials in electrodes for electrochemical energy storage as well as in water purification. Methods to modify porous carbons to enhance their properties as charge storing or water purification materials have been explored during the past decades [1,2]. The main application fields if porous carbon, water purification and energy storage, are highly cost sensitive. For this reason, there is a need to develop low-cost methods to modify porous carbons. Here, the use of benzoxazine chemistry to modify porous carbons is explored. Benzoxazine chemistry can be considered a protection group strategy for phenols, where the phenols from which the benzoxazines are synthesized, are deprotected upon benzoxazine polymerization. Further, benzoxazine polymerization produces Mannich bridges located near phenol groups, motifs that can be used to capture heavy metal ions. More specifically, in the first step, the porous carbons are partially impregnated with benzoxazine monomers, from melt or solutions to afford powders impregnated far below the liquid saturation level of the particles. That is, the particles retain porosity after the impregnation but still have a dry appearance. After impregnation, the particles are heated over the polymerization temperature of the benzoxazine to afford the porous carbon with immobilized functionalities. As phenols can initiate benzoxazine polymerization and be incorporated in the polymer, this method offers a simple route to produce polymerized and immobilized structure at a carbon interface. Here, results on metal ion absorption and the electrochemical response after exposure are presented for carbons modified by impregnation-polymerization of benzoxazines with or without incorporation of phenols. Inks were manufactured from the modified carbons. The electrochemical characterizations were performed on printed arrays of electrochemical cells on a substrate having dimensions of well plates and intended for automatized testing and where the carbon inks were deposited on the working electrodes. This methodology has a potential of simplifying the development of sensor materials and absorbents and can be automatized and potentially be supported with machine learning schemes. The electrochemical responses of exposure of the modified carbon electrodes to metal salt solutions show that impregnation-polymerization of functional benzoxazine can produce absorbents responding electrochemically to metal ion absorption with a scalable process starting from low-cost materials.

Synthesis and Characterization of Cresol based Benzoxazine–Polyurethane Copolymer for Anti-corrosion Performance of Mild Steel

The cresol based polymeric materials were synthesized by using benzoxazine and polyurethanes as copolymer. Three copolymers were synthesized by varying the quantity of polyurethane content and studied their corrosion inhibition properties. The synthesized monomer, which has cresol as the center core was characterized by the NMR, FT-IR and UV-visible spectroscopic methods. All the obtained benzoxazine polymers were also analyzed by the FT-IR and UV-visible spectroscopy. In relation to corrosion inhibition studies, Tafel and impedance experiments were conducted, revealing that benzoxazine-polymer with a higher polyurethane content has improved anti-corrosive characteristics. Additionally, the physical properties of the materials were also studied such as water absorption and gel content studies. Furthermore, the density functional theory calculation was also carried out for the monomer, which explores the better results that are matched with the other experimental studies.

Microstructural Analysis of Benzoxazine Cationic Ring-Opening Polymerization Pathways.

Herein, an evaluation of the initial step of benzoxazine polymerization is presented by mass spectrometry, with a focus on differentiating the phenoxy and phenolic products formed by distinct pathways of the cationic ring opening polymerization (ROP) mechanism of polybenzoxazine formation. The use of infrared multiple photon dissociation (IRMPD) and ion mobility spectrometry (IMS) techniques allows for differentiation of the two pathways and provides valuable insights into the ROP mechanism. The results suggest that type I pathway is favored in the initial stages of the reaction yielding the phenoxy product, while type II product should be observed at later stages when the phenoxy product would interconvert to the most stable type II phenolic product. Overall, the findings presented here provide important information on the initial step of the benzoxazine polymerization, allowing the development of optimal polymerization conditions and represents a way to evaluate other multifunctional polymerization processes.

Catalyzing Benzoxazine Polymerization with Titanium-Containing POSS to Reduce the Curing Temperature and Improve Thermal Stability.

Trisilanolphenyl-polyhedral oligomeric silsesquioxane titanium (Ti-Ph-POSS) was synthesized through the corner-capping reaction, and Ti-Ph-POSS was dispersed in benzoxazine (BZ) to prepare Ti-Ph-POSS/PBZ composite materials. Ti-Ph-POSS could catalyze the ring-opening polymerization (ROP) of BZ and reduce the curing temperature of benzoxazine. In addition, Ti immobilized on the Ti-Ph-POSS cage could form covalent bonds with the N or O atoms on polybenzoxazine, improving the thermal stability of PBZ. The catalytic activity of the Ti-Ph-POSS/BZ mixtures was assessed and identified through 1H nuclear magnetic resonance (1H-NMR) and Fourier-transform infrared (FTIR) analyses, while thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA) were used to determine the thermal properties of the composite. It was found that PBZ exhibited a higher glass transition temperature (Tg) and better thermal stability when Ti-Ph-POSS was added. The curing behavior of the Ti-Ph-POSS/BZ mixtures showed that the initial (Ti) and peak (Tp) curing temperatures sharply decreased as the content of Ti-Ph-POSS and the heating rate increased. The curing kinetics of these Ti-Ph-POSS/BZ systems were analyzed using the Kissinger method, and the morphology of Ti-Ph-POSS/PBZ was determined via scanning electron microscopy (SEM). It was found that the Ti-Ph-POSS particles were well distributed in the composites. When the content exceeded 2 wt%, several Ti-Ph-POSS particles could not react with benzoxazine and were only dispersed within the PBZ matrix, resulting in aggregation of the Ti-Ph-POSS molecules.

Design of advanced and highly effective partially bio-energetic polybenzoxazines as the next generation of reactive structure materials

ABSTRACT In this study, a new class of energetic green benzoxazine polymers is introduced based on vanillin, as a renewable reactant. The newly developed monomers were afforded by the reaction of vanillin with exploshores groups bearing compounds, namely the 2,4 dinitrophenylhydrazine and the para-nitroaniline, respectively, following the typical Mannich reaction. The chemical structure and the formation of the oxazine ring of both monomers were confirmed by 1H and 13C NMR, FTIR, and elemental analysis. The ring opening polymerization mechanism was investigated by FTIR and DSC-TGA analyses. The energetic performances, as well as the physicochemical properties, were studied by a bomb calorimeter, deflagration tester, and electronic densimeter. Overall, both polymers showed promising energetic performances with deflagration temperatures of about 275 and 261°C for the 2,4 dinitrophenylhydrazine and para-nitroaniline-based polybenzoxazines, respectively. The thermal analysis results highlighted that these polymers can be effectively used as reactive structure materials (RSMs) owing to their combination of high thermal stability above operational temperatures and remarkable energetic performances.

Asymmetrically Distributed Tween-80-Induced Edge-Preferential Polymerization of Benzoxazine toward Selective Fabrication of Donut-Shaped Polymer and Carbon Nanodiscs

Asymmetrically Distributed Tween-80-Induced Edge-Preferential Polymerization of Benzoxazine toward Selective Fabrication of Donut-Shaped Polymer and Carbon Nanodiscs

Microporous N- and O-Codoped Carbon Materials Derived from Benzoxazine for Supercapacitor Application

Heteroatom-doped porous carbon materials are highly desired for supercapacitors. Herein, we report the preparation of such material from polybenzoxazine (PBZ), a kind of phenolic resin. Four different N- and O-codoped microporous carbon materials were obtained by changing carbonization temperature (600, 700, 800, and 900 °C). Their structures were characterized by scanning electron microscopy (SEM), nitrogen isothermal absorption and desorption, X-ray diffraction (XRD), Raman spectroscopy, elemental analysis and X-ray photoelectron spectroscopy (XPS), and their electrochemical performances were evaluated by cyclovoltammetry (CV) and galvanostatic charge–discharge (GCD) test in a three-electrode system. It was found that the carbon material (C-700) prepared at the carbonization temperature of 700 °C possesses the largest specific surface area (SSA), total pore volume and average pore size among the family, and thus displays the highest specific capacitance with a value of 205 F g−1 at a current density of 0.25 A g−1 and good cycling stability. The work demonstrates that the N- and O-codoped microporous carbon materials with high electrochemical performance can be derived from benzoxazine polymers and are promising for supercapacitor application.

Kinetic Modeling of Ring-Opening Polymerization of Benzoxazines Using MIL-53-Al as a Potent Catalyst

Kinetic Modeling of Ring-Opening Polymerization of Benzoxazines Using MIL-53-Al as a Potent Catalyst

Sustainable Chitosan/Polybenzoxazine Films: Synergistically Improved Thermal, Mechanical, and Antimicrobial Properties.

Polybenzoxazines (Pbzs) are considered as an advanced class of thermosetting phenolic resins as they overcome the shortcomings associated with novolac and resole type phenolic resins. Several advantages of these materials include curing without the use of catalysts, release of non-toxic by-products during curing, molecular design flexibility, near-zero shrinkage of the cured materials, low water absorption and so on. In spite of all these advantages, the brittleness of Pbz is a knotty problem that could be solved by blending with other polymers. Chitosan (Ch), has been extensively investigated in this context, but its thermal and mechanical properties rule out its practical applications. The purpose of this work is to fabricate an entirely bio-based Pbz films by blending chitosan with benzoxazine (Bzo), which is synthesized from curcumin and furfuryl amine (curcumin-furfurylamine-based Bzo, C-fu), by making use of a benign Schiff base chemistry. FT-IR and 1H-NMR spectroscopy were used to confirm the structure of C-fu. The impact of chitosan on benzoxazine polymerization was examined using FT-IR and DSC analyses. Further evidence for synergistic interactions was provided by DSC, SEM, TGA, and tensile testing. By incorporating C-fu into Ch, Ch-grafted-poly(C-fu) films were obtained with enhanced chemical resistance and tensile strength. The bio-based polymer films produced inhibited the growth of Staphylococcus aureus and Escherichia coli, by reversible labile linkages, expanding Ch galleries, and releasing phenolic species, which was 125 times stronger than bare Ch. In addition, synthesized polybenzoxazine films [Ch/Poly(C-fu)] showed significant dose-dependent antibiofilm activity against S. aureus and E. coli as determined by confirmed by confocal laser scanning microscopy (CLSM). This study suggests that bio-based Ch-graft-polymer material provide improved anti-bacterial property and characteristics that may be considered as a possibility in the near future for wound healing and implant applications.

Liquid crystalline polybenzoxazines for manufacturing of technical textiles: Water repellency and ultraviolet shielding

Herein, the presented approach was investigated a unique technique for manufacturing water repellent/UV-protective cotton fabrics through in-situ/thermal polymerization of benzoxazine (BZs) within cotton matrix. Two BZs abbreviated as Ph-p-BZ and Ph-o-BZ were initially synthesized, and their chemical formulas were verified with FTIR, 1HNMR, and 13CNMR spectral mapping data. For Ph-p-BZ, the endothermic peak was observed at 65 ᵒC, to indicate its highly/purified crystalline structure. DSC data for poly-(Ph-p-BZ) and poly-(Ph-o-BZ) showed that, their high Tg was estimated at 210 ᵒC and 195 ᵒC, respectively, due to their highly crystalline/cross-linked network structure. In-situ/thermal polymerization of Ph-p-BZ and Ph-o-BZ as within cotton matrix was subsequently proceeded. Contact angle was observably increased to 125.0° for the fabric coated with four layers of poly-(Ph-p-BZ) (cotton modified with four layers of poly-(Ph-o-BZ); 120.3°). Wetting of water droplets was not significantly observed even after 8 min. Ultraviolet protection factor (UPF) was significantly increased from 1.4 for untreated cotton to 37.9 and 48.2 after modification of cotton with 4-layers of poly-(Ph-o-BZ) and poly-(Ph-p-BZ) polymers, respectively. Eventually, poly-benzoxazines derivatives could be applicable for manufacturing of water repellent/UV-protective fabrics that might be beneficial for military clothes.

SYNTHESIS AND CHARACTERIZATION OF BENZOXAZINE: URETHANE COPOLYMER FROM VANILLIN WITH ADAMANTANE SIDE CHAIN AND ITS ANTICORROSIVE COATING ON MILD STEEL

Corrosion is a significant issue with metallic materials, notably in steel due to its extensive use in a variety of industries. Benzoxazine polymers have been used to produce anti-corrosive compounds that have a remarkable ability to limit corrosion. In the same ink line, we have explored a new approach with a very hydrophobic benzoxazine monomer which is co-polymerized with urethane, and its characterization was studied with IR, UV, and NMR techniques. The corrosion resistance of the same is investigated using Tafel polarization and EIS experiment methodologies. The DFT and MEP studies explain the reactivity towards the anti-corrosive properties of the monomer.

Biobased dual-cure thiol-ene benzoxazine resins for high-performance polymer dielectrics

In the present study, two magnolol based main chain benzoxazine polymers (MCBPs) are designed, synthesized and formulated into thiol-ene resins to develop high-performance polymer dielectrics. Initially, the thiol-ene thermoset films, Mag-M-4SH-80 and Mag-E-4SH-80, are obtained respectively using click chemistry. Being post cured via progressive temperature stage, Mag-M/E-4SH-80 performs complete ring opening polymerization and forms dual-cure polybenzoxazine (PBZ) products with excellent thermal and mechanical performances such as a high Tg of 236 °C and a flexure modulus of 2.5 GPa. Moreover, the thiol component of the resin introduces numerous dipoles to the resultant polymer networks, resulting in promising dielectric performances of the resin at both room temperature and elevated temperature. For instance, the Mag-M-4SH-80 film demonstrates a superior energy density (Ue) of 7.0 J/cm3@25 °C, which is among the top reported dielectric thermosets having same efficiency, and Mag-M-4SH-150 film reveals a Ue of 1.1 J/cm3@150 °C, significantly higher than the reported values of a great number of commercial heat resistant polymers. Herein, our findings not only expand the library of high-performance thiol-ene benzoxazine resins but also present their potentials as flexible dielectrics for energy storage for the first time, thus advance the functionality and capability of benzoxazine based materials in modern electronics.

Catalyzing benzoxazine polymerization with borohydrides to reduce the cure temperature and coloring

Sodium cyanoborohydride (NaCNBH3) and sodium borohydride (NaBH4) were used as catalysts to lower the ring-opening polymerization (ROP) temperature of 1,3-benzoxazines. According to the dynamic scanning calorimeter (DSC) and Fourier transform infrared (FTIR) studies, the onset ROP temperatures of model benzoxazine were decreased by ca. 80 °C. The activation energies of catalyzed ROP were estimated by Kissinger and Ozawa methods. Moreover, the room temperature behavior of the catalysts in benzoxazine was revealed by 1H NMR and FTIR, and it was found to be dormant at low temperatures and active after 170 °C. Besides catalytic activity, the borohydrides reduced the intense colorization of benzoxazines during curing, and the color changes of catalyzed and uncatalyzed polybenzoxazine samples were measured by colorimetry. Moreover, the thermal stabilities of the catalyzed polybenzoxazines were analyzed and compared to their un-catalyzed counterparts by thermal gravimetric analyses (TGA).

Multiple catalytic polymerization of phthalonitrile resin bearing benzoxazine moiety: Greatly reduced curing temperature

Phthalonitrile resin is a high-performance thermosetting resin with excellent thermal stability, good mechanical properties, low water absorption and low dielectric constant, thus it shows great potential in aerospace, marine, and electronic packaging. However, the extremely high polymerization temperature and long curing cycle limit the practical application of phthalonitrile resin. It is revealed that the active species released by ring-opening of benzoxazine can promote the polymerization of phthalonitrile and the polymerization temperature of phthalonitrile resin containing benzoxazine (BAph) could be reduced to 240–280 ℃, but there is still difficultly in practical application. In this study, dicyandiamide (DCA), which contains reactive nitrile group and active amino groups, was selected as the curing agent to catalyze the curing reaction of BAph. The reaction activity, curing process and curing behavior of BAph-dca were investigated by differential scanning calorimetry (DSC), gelatin time (tgel) measurement and dynamic rheological analysis (DRA). The polymerization mechanism of BAph-dca was studied by Fourier transform infrared spectroscopy (FTIR) and DSC. It was shown that with 10 wt% of DCA, the initial exothermic temperature decreased from 222.9 ℃ (neat BAph) to 159.4 ℃, the peak temperature of ring-opening polymerization of benzoxazine (Tp1) decreased from 255.9 ℃ to 203.2 ℃, and the peak temperature of nitrile polymerization (Tp2) decreased from 288.5 ℃ to 271.6 ℃. Importantly, polymer films can be obtained at 200 ℃, which is substantially lower than the curing temperature of typical phthalonitrile resin. Moreover, the polymer films cured at 200 ℃ showed good thermal stability. The polymer film with 3 wt% of DCA showed initial decomposition temperature (Td5) of the 412 ℃ and the char yield (Yc) of 72.09 % at 800 ℃. This study is of great significance in reducing the polymerization temperature of phthalonitrile resin and promote its practical application.

Synthesis, ring-opening polymerization, and properties of benzoxazines based on o- and p-hydroxybenzyl alcohols

Two series of bifunctional benzoxazines were synthesized from o- and p-hydroxybenzyl alcohols ( oHBA and pHBA), three aliphatic diamines containing ether linkage (Jeffamines D230 and D400 and 4,7,10-trioxa-1,13-tridecanediamine (TTDDA)), and paraformaldehyde. The chemical structures of the benzoxazines were confirmed by 1H and 13C nuclear magnetic resonance and Fourier transform infrared (FTIR) spectroscopy. The ring-opening polymerization of the benzoxazines was studied by differential scanning calorimetry and FTIR, respectively. oHBA-based benzoxazines respectively exhibit lower onset temperatures of ring-opening polymerization than pHBA-based counterparts due to the O–H∙∙∙O intramolecular hydrogen-bonding interaction between the hydrogen of ortho-methylol group and the oxygen in oxazine ring, and oHBA-based polybenzoxazines respectively show lower glass transition temperatures ( Tgs) than pHBA-based counterparts due to the difference in crosslinking density caused by the steric hindrance effect of the position of methylol group on the polymerization of benzoxazine monomers. In each of the two series of benzoxazines, the onset temperature of ring-opening polymerization of D230-based benzoxazine is close to that of TTDDA-based analogue and lower than that of D400-based counterpart owing to the steric effect of the chain length and chain volume of the bridging structure between the oxazine rings on the polymerization, and the Tg of D230-based polybenzoxazine is close to that of TTDDA-based analogue and much higher than that of D400-based counterpart owing to the difference in crosslinking density caused by the steric hindrance effect of the bridging structure on the polymerization of benzoxazine monomers. In addition, all the polybenzoxazines exhibit thermally induced shape memory effect. In each of the two series of polybenzoxazines, the shape recovery rate and ratio of D400-based polybenzoxazine are respectively close to those of D230-based counterpart and higher than those of TTDDA-based analogue due to the difference in network architecture.

Rapid Fabrication of Graphene Derived Micro-Supercapacitors on Flexible Substrates Using Millisecond Photothermal Flash Lamp Carbonization

Graphene offers excellent electrical conductivity and very high surface area, which holds great promise for energy storage applications including supercapacitors. Current preparation methods for graphene require relatively long processing times, extremely high temperatures within controlled atmospheres, and/or involve multi-step reactions that present challenges for high throughput fabrication of graphene-based devices. We report a novel photothermal route to large-scale production of graphene within milliseconds using a commercially available benzoxazine polymer and a high intensity xenon flash lamp on various substrates including carbon fiber, Kapton and stainless steel at ambient conditions. The xenon flash lamp provides large-area illumination and a wide emission band (300 nm –1100 nm) that was used to convert the polymeric material directly into graphene upon millisecond exposures. The absorption spectrum of the precursor overlaps well with the maxima of the xenon flash lamp emission spectrum. The precursor material is heated to extremely high temperatures in a fraction of a second – a duration that is much shorter than the timescale for thermal equilibrium. This enables the conversion of the polymeric material to graphene in air and at room temperature, and without thermally damaging the substrate. Characterization of these graphene composites revealed high porosity, excellent conductivity, and good adhesion. Using carbon fiber as the substrate, we prepared micro-supercapacitors exhibiting a very high areal capacitance of 3.2 mF/cm2. Furthermore, we utilized the mechanically and chemically stable graphene/carbon fiber composite as a substrate for the electrochemical deposition of MnO2 which boosted the energy storage capability of the device. The obtained pseudocapacitor has an exceptional capacitance of 300 mF/cm2 at 1mA/cm2. The device retained more than 88% of its capacitance after charging/discharging for 2000 cycles. The preparation of high-quality graphene via photothermal pyrolysis of appropriate precursors is amenable to roll-to-roll processing, and thus large-scale production of electrochemical energy storage devices can be enabled by this approach. Figure 1