Diester Research Articles

Ultrahigh solar vapor evaporation rate of super-hydrophilic aerogel by introducing environmental energy and convective flow

The renewable solar energy provides one of promising pathways of interfacial vapor evaporation for freshwater resources with minimized carbon footprint. The high-throughput evaporation rate needs to be further achieved for the demand of practical application. Herein, a three-dimensional hybrid aerogel (rGP) with reduced graphene oxide (rGO) and polyvinyl alcohol phosphate ester (PVAP) was fabricated by hydrothermal method. The rGP aerogel had broadband light absorption ability and interconnected pore structure. This evaporator achieved fully hydrated state within 5 s due to the superabsorbent PVAP. The existence of intermediate water in rGP reduced the energy requirement for evaporation. The 3D aerogel also harvested additional energy from surroundings caused by evaporation cooling effect. Therefore, the rGP with height of 3 cm (rGP-3) achieved a higher evaporation rate of 4.89 kg m-2h−1 with the energy efficiency of 124.8% under 1 sun irradiation. The vapor diffusion could be assisted by convective flow and minimized the stagnation of vapor in the pores. Then the evaporation rate of rGP-3 increased to 16.22 kg m-2h−1 under the convective flow of 2.5 m s−1. Additionally, the 3D rGP can be consistently evaporated for 8 h in 3.5 wt% brine and no salt deposition occurred. More importantly, the evaporated fresh water from actual seawater was up to 156.30 kg m−2 in 8 h under outdoor sunlight and directional convective flow, which implied the remarkable potential in practical application. This rGP evaporation platform with 3D pore structure, high light absorption, efficient water activation, rapid water transport, extra heat collection, and effective vapor diffusion provides a new inspiration for designing high-throughput evaporators of superhigh evaporation rate and a large-scale application in desalination under convective flow.

Mechanisms for the structural dependent transformation of 6:2 and 8:2 polyfluoroalkyl phosphate diesters in wheat (Triticum aestivum L.)

Polyfluoroalkyl phosphate esters (PAPs) are widely used and detected in various environmental media and organisms, but little is known about their behaviors in plants. In this study, the uptake, translocation and transformation of 6:2 and 8:2 diPAP in wheat using hydroponic experiments were investigated. 6:2 diPAP was more easily taken up by roots and translocated to shoots than 8:2 diPAP. Their phase I metabolites were fluorotelomer saturated carboxylates (FTCAs), fluorotelomer unsaturated carboxylates (FTUCAs) and perfluoroalkyl carboxylic acids (PFCAs). PFCAs with even-numbered chain length were the primary phase I terminal metabolites suggesting that they were mainly generated through β-oxidation. Cysteine and sulfate conjugates were the primary phase II transformation metabolites. The higher levels and ratios of phase II metabolites in the 6:2 diPAP exposure group indicated that the phase I metabolites of 6:2 diPAP were more susceptible to phase II transformation than that of 8:2 diPAP, which was confirmed by density functional theory calculation. Enzyme activity analyses and in vitro experiments demonstrated that cytochrome P450 and alcohol dehydrogenase actively participated in the phase Ⅰ transformation of diPAPs. Gene expression analyses showed that glutathione S-transferase (GST) was involved in the phase Ⅱ transformation, and the subfamily GSTU2 played a dominant role.

Solvent and solvation effects on reactivities and mechanisms of phospho group transfers from phosphate and phosphinate esters to nucleophiles.

Organophosphorus esters fulfil many industrial, agricultural, and household roles. Nature has deployed phosphates and their related anhydrides as energy carriers and reservoirs, as constituents of genetic materials in the form of DNA and RNA, and as intermediates in key biochemical conversions. The transfer of the phosphoryl (PO3) group is thus a ubiquitous biological process that is involved in a variety of transformations at the cellular level such as bioenergy and signals transductions. Significant attention has been paid in the last seven decades to understanding the mechanisms of uncatalyzed (solution) chemistry of the phospho group transfer because of the notion that enzymes convert the dissociative transition state structures in the uncatalyzed reactions into associative ones in the biological processes. In this regard, it has also been proposed that the rate enhancements enacted by enzymes result from the desolvation of the ground state in the hydrophobic active site environments, although theoretical calculations seem to disagree with this position. As a result, some attention has been paid to the study of the effects of solvent change, from water to less polar solvents, in uncatalyzed phospho transfer reactions. Such changes have consequences on the stabilities of the ground and the transition states of reactions which affect reactivities and, sometimes, the mechanisms of reactions. This review seeks to collate and evaluate what is known about solvent effects in this domain, especially their effects on rates of reactions of different classes of organophosphorus esters. The outcome of this exercise shows that a systematized study of solvent effects needs to be undertaken to fully understand the physical organic chemistry of the transfer of phosphates and related molecules from aqueous to substantially hydrophobic environments, since significant knowledge gaps exist.

Versatile solid polymer electrolytes from clickable poly(glycidyl propargyl ether) for lithium metal batteries

We present three new graft copolymers for the application as solid polymer electrolytes (SPEs) in solvent-free, all solid-state lithium metal batteries (LMBs), based on the clickable poly (glycidyl propargyl ether) platform. These fully amorphous polymers consist of an all-ether polymer backbone and different additional Li+-coordinating oxo-functionalities - diester, carbonate and phosphate ester - in the attached sidechain. We aim to address the fundamental question on the influence of Li+-coordination in such doubly functionalized systems having competing Li+-coordination functional groups. We prepared polymer nanocomposite SPEs based on these novel polymers mixed with a highly-dissociating lithium salt (LiTFSI) and TiO2 nanofillers, which improve the electrolyte-electrode compatibility. We perform an extensive and comparative investigation in terms of physicochemical and electrochemical properties including ionic conductivity, lithium transference number, lithium plating and stripping as well as the fabrication and cycling of LMBs utilizing lithium iron phosphate (LFP) cathodes. Thermal characterization is coupled with temperature-dependent ionic conductivity measurements and detailed IR spectroscopy to understand the mechanistic properties and selectivity of the Li+ coordination and conduction. Two of the nanocomposite SPEs show efficient battery cycling with initial capacities of ca. 150 mAh g−1 and a capacity retention of ca. 70–80 % after 100 cycles.

Neurotherapeutic Potential of Water-Soluble pH-Responsive Prodrugs of EIDD-036 in Traumatic Brain Injury.

The C-20 oxime of progesterone, EIDD-036 (2), demonstrates neuroprotection and improved outcomes in animal models of traumatic brain injury (TBI). However, 2 suffers from poor solubility, which renders it unsuitable for rapid administration. Previous prodrugs of 2 aimed at improving solubility by incorporating enzymatically labile amino acid and phosphate ester promoieties. These approaches were effective but led to limitations with in vivo administration. Herein, we disclose a pH-responsive water-soluble prodrug strategy to improve exposure to 2 through enzyme-independent activation. Compound 13l was identified as a lead that exhibits water-solubility, stability in acidic solutions, and rapid conversion to 2 at physiological pH. Administration of 13l to rats resulted in a twofold increase in exposure to 2 compared to the previous generation phosphate prodrug, EIDD-1723 (6). In a rat model of TBI, treatment with 13l resulted in a significant decrease in cerebral edema when administered postinjury.

Novelty method based on thermal trigger mechanism for high energy density lithium-ion battery safety

Thermal runaway is the most serious issue for high energy density lithium-ion batteries. Adding flame retardants to electrolytes is a general way to improve safety of lithium-ion batteries. However, the addition of flame retardants will give rise to adverse effects on the electrochemical performance of batteries, especially phosphate ester flame retardants decompose on the surface of the negative electrode. This research innovatively outlines a heat-triggered addition method of flame retardants using the polypropylene film (PP film) package. Only under abusive circumstances can the flame retardants be released and have a profound effect. The feasibility of this addition method is verified by the battery thermal safety testing. This ingenious addition method not only avoids the negative effects of flame retardants on battery performance, but also provides a new way to prevent thermal runaway of batteries.

Toxicity of organophosphorus flame retardants

As the development and use of organophosphorus flame retardants have become more prevalent, concerns about potential toxicity are being raised. To date, most studies on potential toxicity have focused on simple phosphate esters and often include both alkyl and aryl esters or, in some cases, even halogenated phosphate esters (which should more properly be included among organohalogen flame retardants). The inclusion of several kinds of esters into a single study leads to muddled conclusions. Each class of phosphate esters should be subjected to toxicity assessment separately. Furthermore, the potential toxicity of the more effective (lower level of oxygenation at phosphorus: phosphonates, phosphinates, phosphine oxides) organophosphorus flame retardants has been little explored. The few results available suggest that these compounds exhibit no or minimal toxicity (lower than that of phosphates?). This represents an area that should be the focus of careful detailed studies to establish any potential toxicity.

Differentiating Toxic and Nontoxic Tricresyl Phosphate Isomers Using Ion–Molecule Reactions with Oxygen

Ortho-substituted isomers of tricresyl phosphates (TCPs) and their toxic metabolites (e.g., CBDP: cresyl saligenin phosphate) can cause neurotoxic effects in humans. When TCP is introduced to an atmospheric pressure chemical ionization source using gas chromatography, radical cations M•+ are formed by charge exchange. The mass spectrum of an ortho-substituted isomer displays two intense peaks that are absent in the spectra of non-ortho-substituted isomers, leading us to propose structure-diagnostic ion-molecule reactions between ions M•+ and oxygen species present in the source. However, the mechanisms of these reactions have not yet been established. In this study, we propose a mechanism and provide support through computational and experimental analyses using density functional theory and cyclic ion mobility-mass spectrometry. The mechanism consists of a multistep reaction starting with the rearrangement of the molecular ion into a distonic isomer followed by an oxidation step and then decomposition into [CBDP-H]+. This proposal is consistent with the results obtained from a series of isotopically labeled analogues. Cyclic ion mobility experiments with a tri-o-cresyl phosphate standard reveal the presence of at least two hydrogen shift isomers of the product ion [CBDP-H]+ that are connected by a low-lying barrier. The selectivity of the ion-molecule reactions toward ortho-substituted cresyl TCP isomers provides us with an identification tool that can select potentially neurotoxic triaryl phosphate esters present in complex mixtures that are produced in large volume by industry.

Preparation of Narrow Pore Diameter Phosphorus Containing Cotton Stalk Carbon and Its Adsorption Mechanism for Tetracycline

Using cotton stalk as biomass raw material and phosphoric acid as a modifier, narrow pore distribution phosphorus-containing cotton stalk biochar (CSP) with a high surface area (1916 m2·g-1) and pore volume (1.3982 mL·g-1) was prepared through one-step carbonization, and the adsorption characteristics and mechanisms for tetracycline (TC) were investigated. The results showed that the TC adsorption capacity of CSP was up to 669 mg·g-1, which was 43.6 times that of unmodified cotton stalk carbon. FTIR, XPS, and isothermal adsorption studies showed that the high adsorption capacity of CSP for TC resulted from the joint action of complexation, hydrogen bonding, pore filling, and π-π dispersion forces, and the highly active phosphate ester group (P-O-C) endowed by phosphoric acid modification greatly enhanced the chemical interaction with TC molecules, which was the key factor for the significant increase in adsorption capacity. Isotherm and thermodynamic study further confirmed that chemical adsorption played a major role in the adsorption process, the adsorption process was spontaneous and endothermic, and the material had good regeneration performance. This study provides theoretical guidance for the preparation of modified biomass carbon with high adsorption performance to remove tetracycline antibiotic pollution.

Up in the air: Polyfluoroalkyl phosphate esters (PAPs) in airborne dust captured by air conditioning (AC) filters

Per- and polyfluoroalkyl substances (PFAS) are ubiquitously present in our indoor living environments. Dust is thought to accumulate PFAS released indoors and serve as an exposure pathway for humans. Here, we investigated whether spent air conditioning (AC) filters can be exploited as opportunistic samplers of airborne dust for assessing PFAS burden in indoor environments. Used AC filters from campus facilities (n = 19) and homes (n = 11) were analyzed for 92 PFAS via targeted ultra-high pressure liquid chromatography – tandem mass spectrometry (UHPLC-MS/MS). While 27 PFAS were measured (in at least one filter), the predominant species were polyfluorinated dialkylated phosphate esters (diPAPs), with the sum of 6:2-, 8:2-, and 6:2/8:2diPAPs accounting for approximately 95 and 98 percent of ∑27PFAS in campus and household filters, respectively. Exploratory screening of a subset of the filters revealed the presence of additional species of mono-, di-, and tri-PAPs. Considering the constant human exposure to dust indoors and the potential of PAPs to degrade into terminal species with well-established toxicological risks, assessing dust for these precursor PFAS warrants further investigation with respect to both human health and PFAS loading to landfills from this under studied waste stream.

Design, Synthesis, and Anti-Cancer Evaluation of Novel Cyclic Phosphate Prodrug of Gemcitabine.

ProTide and cyclic phosphate ester are two successful prodrug technologies to overcome the limitations of nucleoside drugs, among which the cyclic phosphate ester strategy has not been widely used in the optimization of gemcitabine. Herein, we designed a series of novel ProTide and cyclic phosphate ester prodrugs of gemcitabine. Cyclic phosphate ester derivative 18c exhibits much higher anti-proliferative activity than positive control NUC-1031 with IC50s of 3.6-19.2 nM on multiple cancer cells. The metabolic pathway of 18c demonstrates that 18c's bioactive metabolites prolong its anti-tumor activity. More importantly, we separated the two P chiral diastereomers of gemcitabine cyclic phosphate ester prodrugs for the first time, revealing their similar cytotoxic potency and metabolic profile. 18c displays significant in vivo anti-tumor activity in both 22Rv1 and BxPC-3 xenograft tumor models. These results suggest that compound 18c is a promising anti-tumor candidate for treating human castration-resistant prostate and pancreatic cancer.

Rational synthesis of carbon dots with phosphate ester group for direct mapping of endogenous alkaline phosphatase and polarity monitoring in living cells

Carbon dots (CDs) have been extensively employed in biomolecule imaging. However, the imaging of biological enzymes with CDs has not been reported, which greatly limits their application in biological imaging. Herein, for the first time, a new type of fluorescent CDs is elaborately designed to realize the direct mapping of alkaline phosphatase (ALP) in cells. The obtained phosphorus and nitrogen co-doped CDs (P, N-CDs) generate specific structures including xanthene oxide and phosphate ester, thereby enabling P, N-CDs to be exclusively cleaved by ALP without auxiliary media. The fluorescence intensity of P, N-CDs can be specifically turned on in the presence of ALP, making them powerful probes for sensitive sensing of ALP activity with a detection limit of 1.27 U·L−1. Meanwhile, P, N-CDs possessing electron deficiency structure fulfill sensitive responding to polarity variations. The excellent photo-bleaching resistance and biocompatibility of the P, N-CDs are taken for directly mapping the intracellular endogenous ALP via turned-on fluorescence imaging, as well as real-time monitoring the polarity fluctuation in cells through ratiometric fluorescence imaging. The present work offers a new way to design and synthesize functional CDs for direct imaging of intracellular enzymes.

Enrichment of geogenic phosphorus in a coastal groundwater system: New insights from dissolved organic matter characterization

High concentrations of geogenic phosphorus (P) in coastal aquifer systems pose a serious and continuous threat to the health of marine ecosystems. A major source for geogenic P enrichment in aquifer systems is the mineralization of P-containing organic matter. However, the mechanisms that drive the enrichment remain unclear. Therefore, our study sought to characterize the occurrence, sources, and enrichment mechanisms of geogenic P in a coastal confined aquifer system of the Pearl River Delta, southern China. To achieve this, we conducted Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and fluorescence excitation-emission-matrix spectra (EEMs) as well as hydrochemistry and stable carbon isotope analyses. Our findings indicated that intense degradation of P-containing organic matter produced up to 8.07 mg/L of geogenic P in a reducing environment with abundant organic matter. The dissolved organic matter (DOM) of high-P groundwater (P > 1 mg/L) contained more humic-like fluorophores and exhibited higher humification. Groundwater with high P concentrations contained more aliphatic compounds and highly unsaturated-low O compounds, and the enrichment of P was mostly associated with CHOP compounds in the region of aliphatic compounds and CHON2P compounds in the region of highly unsaturated-low O compounds. Different types of dissolved organic phosphorus (DOP) can be mineralized into P, and even the mineralization of phosphonates takes precedence over the more unstable phosphate esters. P produced by the metabolism of different types of DOP was assimilated by marine microorganisms (e.g., heterotrophic bacteria and archaea), and the newly synthesized organic P compounds by chemosynthesis were subsequently released into the groundwater. Over time, P continues to be enriched in the aquifer system. This study provides new insights into subsurface P cycling in coastal aquatic systems.

Bio-Based Phosphate-Containing Polyester for Improvement of Fire Reaction in Wooden Particleboard.

A new phosphate-containing bio-polyester based on glycerol and citric acid was synthesized and evaluated as fire-retardant (FR) in wooden particleboards. Phosphorus pentoxide was used to first introduce phosphate esters in the glycerol followed by esterification with citric acid to produce the bio-polyester. The phosphorylated products were characterized by ATR-FTIR, 1H-NMR and TGA-FTIR. After polyester curing, they were grinded and incorporated in laboratory produced particleboards. The fire reaction performance of the boards was evaluated by cone calorimeter. An increased char residue was produced depending on the phosphorus content and the THR (Total Heat Release), PHRR (Peak of Heat Release Rate) and MAHRE (Maximum Average of the Rate of Heat Emission) were considerably reduced in presence of the FRs. Highlights: Phosphate containing bio-polyester as fire retardant in wooden particle board; Fire performance is improved; Bio-polyester acts in the condensed and gas phases; Additive effectiveness similar to ammonium polyphosphate.

Visual and Rapid Detection of Nerve Agent Mimics in Gas and Solution Phase by a Simple Fluorescent Probe.

Chemical nerve agents are highly toxic organophosphorus compounds that are easy to obtain and can be utilized by terrorists to threaten homeland security and human safety. Those organophosphorus nerve agents contain nucleophilic ability that can react with acetylcholinesterase leading to muscular paralysis and human death. Therefore, there is great importance to explore a reliable and simple method to detect chemical nerve agents. Herein, the o-phenylenediamine-linked dansyl chloride as a colorimetric and fluorescent probe has been prepared to detect specific chemical nerve agent stimulants in the solution and vapor phase. The o-phenylenediamine unit serves as a detection site that can react with diethyl chlorophosphate (DCP) in a rapid response within 2 min. A satisfied relationship line was obtained between fluorescent intensity and the concentration of DCP in the range of 0-90 μM. In the optimized conditions, we conducted the fluorescent titration to measure the limits of detection (0.082 μM) with the fluorescent enhancement up to 18-fold. Fluorescence titration and NMR studies were also conducted to explore the detection mechanism, indicating that the formation of phosphate ester causes the intensity of fluorescent change during the PET process. Finally, probe 1 coated with the paper test is utilized to detect DCP vapor and solution by the naked eye. We expect that this probe may give some admiration to design the small molecule organic probe and applied in the selectivity detection of chemical nerve agents.

Synthesis and anti-HIV activity of non-nucleoside reverse-transcriptase inhibitor DB02 phosphate derivatives based on water-soluble optimization.

To improve the water solubility of anti-human immunodeficiency virus(HIV) agent DB02, an excellent non-nucleoside reverse-transcriptase inhibitor(NNRTI) obtained in our previous efforts, we designed and synthesized four phosphate derivatives of DB02 based on the molecular model of DB02 with RT. Here, the antiviral activity of these four derivatives was detected, leading to the discovery of compound P-2, which possessed a superior potency to the lead compound DB02 against wild-type HIV-1 and a variety of HIV-resistant mutant viruses significantly. Furthermore, the water solubility of P-2 was nearly 17 times higher than that of DB02, and the pharmacokinetic test in rats showed that P-2 demonstrate significantly improved oral bioavailablity of 14.6%. Our study showed that the introduction of a phosphate ester group at the end of the C-2 side chain of DB02 was beneficial to the improvement of its antiviral activity and pharmacokinetic properties, which provided a promising lead for the further development of S-DACOs type of NNRTIs.

Synthesis, characterization, photo-polymerization, hydrolytic stability, and etching behavior of new self-etch adhesive monomers

Considering the poor hydrolytic stability of the most methacrylate-based functional monomers of self-etch dental adhesives in acidic and aqueous conditions, in this study allyl-based photo-polymerizable self-etch monomers was synthesized in order to improve the hydrolytic stability.The new self-etch monomers based on phosphonic acid functional groups were synthesized through a two-step procedure. First, phosphoric anhydride, poly-phosphoric acid, and polyethylene glycol were reacted to produce phosphate ester precursor (P-PEG-P). Next, allyl 2, 3-epoxypropyl ether was reacted with P-PEG-P to synthesize allyl self-etch monomer. Glycidyl methacrylate was also reacted with P-PEG-P to synthesize a methacrylate self-etch analogue monomer. The monomers were characterized using FTIR and 1H-NMR spectroscopy. The viscosities of monomers were measured using a rheometer. The degree photopolymerization conversion of monomers was measured using FTIR spectroscopy. The pH assay was performed by a digital pH-meter. The etching behavior of the monomers on human teeth was studied using scanning electron microscopy (SEM). Thermo-gravimetric analysis (TGA) was performed to evaluate the possible interaction of the monomers with tricalcium phosphate (TCP). The solubility of synthesized monomers was examined in ethanol, acetone, and water. The hydrolytic stability of cured resins in artificial saliva during 4 months was also surveyed.The synthesis of new self-etching monomers was successfully confirmed by spectroscopy analyses. The results represented appropriate viscosity of self-etching monomers around 1 (Pa s). The resin containing methacrylate monomer exhibited its degree of conversion is more than that of allyl monomer (p < 0.05). The allyl and methacrylate self-etch monomers exhibited pH values of 1.2 and 1.3, respectively. SEM micrograph verified that the synthesized monomers were able to suitable etching of the enamel human premolar teeth. The data obtained from TGA tests revealed that thermal stability of (TCP) containing monomers is enhanced. Also, the monomers exhibited an excellent solubility in polar solvents, but when they are mixed with TCP, they are not, anymore, dissolved in these solvents. Furthermore, the allyl monomer showed higher hydrolytic stability than the methacrylate monomer.The new photo-polymerizable acidic monomer based on allyl functionality showed enhanced hydrolytic stability compared to methacrylate-based monomer. It may be considered as a promising monomer for self-etch dental adhesives.

Controlled Hydrolysis of Phosphate Esters: A Route to Calixarene-Supported Rare-Earth Clusters.

Phosphate ester bonds are widely present in nature (e. g. DNA/RNA) and can be extremely stable against hydrolysis without the help of catalysts. Previously, we showed how the combination of phosphoryl and calix[4]arene moieties in the same organic framework (LPO ) allows isolation of single lanthanide (Ln) metal ions as [LnIII (LPO )2 ](O3 SCF3 )3 . Here we report how by controlling the reaction conditions a new hydrolyzed phosphoryl-calix[4]arene ligand (H3 LHPO ) is formed as a result of LnIII -mediated P-OEt bond cleavage in three out of the eight possible sites in LPO . The chelating nature of H3 LHPO traps the LnIII species in the form of [LnIII (LHPO )((EtO)2 P(O)OH)]2 dimers (Ln=La, Dy, Tb, Gd), where the Dy derivative shows slow magnetization relaxation. The strategy presented herein could be extended to access a broader library of hydrolyzed platforms (Hx LHPO ; x=1-8) that may represent mimics of nuclease enzymes.

High-resolution temporal wastewater treatment plant investigation to understand influent mass flux of per- and polyfluoroalkyl substances (PFAS)

This study aims to identify sources of per- and polyfluoroalkyl substances (PFAS) to wastewater treatment plants (WWTPs) and reveals previously undescribed variability in daily PFAS concentrations by measuring their occurrence in WWTP influent each hour over the course of a week. ∑50PFAS concentrations ranged between 89 ± 38 on Monday and 173 ± 110 ng L-1 on Friday, where perfluoroalkyl carboxylic acids (PFCAs), disubstituted phosphate esters (diPAPs), and perfluoroalkyl sulfonic acids (PFSAs) contributed the largest proportion to overall weekly concentrations 37%, 30%, and 17% respectively. Simultaneous pulse events of perfluorooctanesulfonic acid (PFOS; 400 ng L-1) and perfluoroheptanesulfonic acid (PFHpS; 18 ng L-1) indicate significant industrial or commercial waste discharge that persists for up to 3 h. The minimum number of hourly grab samples required to detect variation of PFOS and PFHpS concentrations are 7 and 9 samples respectively, indicating a high degree of variability in PFAS concentrations between days. Overall, the risk of sampling bias from grab samples is high given the variability in PFAS concentrations and more frequent sampling campaigns must be balanced against the cost of analysis carefully to avoid the mischaracterisation of mass flux to receiving surface waters.

Flame-Retardant and Recyclable Soybean Oil-Based Thermosets Enabled by the Dynamic Phosphate Ester and Tannic Acid

The demands of safety and sustainability have driven the development of intrinsic flame-retardant biobased polymers from renewable materials. Herein, a mechanically robust, good flame-retardant, and recyclable thermoset was developed from renewable epoxidized soybean oil (ESO) by using 2-hydroxyethyl methacrylate phosphate (HEMAP) as the reactive flame retardant and tannic acid (TA) as the charring agent. The flame resistance of the obtained ESO-based thermoset achieved the highest UL-94 of V-0 rating and a limited oxygen index value of 26.7% due to the synergistic flame-retardant effect of phosphate and TA. The flame-retardant mechanisms of the gaseous phase and condensed phase were fully investigated by thermogravimetric infrared, scanning electron microscopy-energy-dispersive spectrometry, X-ray photoelectron spectroscopy, and Raman spectra. It is confirmed that the incorporation of phosphate and TA could effectively promote the formation of dense carbon layers and delay the pyrolysis of long aliphatic chains. The ternary crosslinking of ESO, HEMAP, and TA via free-radical polymerization and epoxy-ring opening reaction resulted in a rigid network with a high crosslink density, bestowing the thermoset with superior tensile strength (20.0 MPa), flexural strength (36.3 MPa), and bonding strength (16.7 MPa on steel). Moreover, the ESO-based thermoset exhibited a fast stress relaxation behavior due to the transesterification of dynamic β-hydroxyl phosphate esters, which enables the network with thermal-healing ability and recyclability. This study explores a feasible method to prepare an intrinsic flame-retardant polymer from commercially available and renewable vegetable oils and natural polyphenols.