Search Results (22)

Incorporating a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-based derivative (1,4-bis(diphenoxyphosphoryl)piperazine, DIDOPO) in combination with modified calcium sulfate whiskers (MCSWs) improved the flame retardancy, thermal stability, and rheological properties of a polyethylene oxide (PEO) composite. The synergistic flame-retardant effect of DIDOPO and MCSW on the PEO system was investigated. After introducing 5 wt.% MCSW and 10 wt.% DIDOPO into PEO, the UL-94 rating of the composite reached V-0, and the limiting oxygen index was increased to 26.5%. Additionally, the peak and average heat release rates and total heat release of the PEO/10% DIDOPO/5% MCSW composite decreased by 38.9%, 22%, and 20.07%, respectively. The results of a thermogravimetric analysis (TGA) revealed that PEO/10% DIDOPO/5% MCSW displayed an improved initial thermal stability and rate of char formation compared to those of the PEO matrix. The results of TGA/Fourier transform infrared analysis indicated that the composites exhibited phosphorus-containing groups during thermal degradation, based on the characteristic absorption peaks, and increased amounts of gas-phase volatiles. The morphologies and structures of the residues indicated that the PEO/10% DIDOPO/5% MCSW blend was less stable than PEO during combustion. The MCSW mixture formed a denser, more continuous carbon layer on the composite surface during combustion. The rheological behavior indicated that the high complex viscosity and moduli of PEO/10% DIDOPO/5% MCSW promoted the cross-linking network structure of the condensed phase during combustion. MCSW exhibited an excellent flame retardancy and improved thermal stability, which are potentially promising for use in fire safety applications. Full article

PA66 is a widely used engineering plastic, but its flammability reduces safety during application. The 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) and its derivatives are a class of flame retardants with excellent flame-retardant efficiency, which can significantly improve the flame retardancy of PA66. This work synthesized a DOPO derivative flame retardant, DT, containing multiple P/N elements and comprehensively characterized its structure using FTIR and NMR. Flame-retardant PA66 materials were prepared by twin-screw extrusion blending with PA66, and their thermal stability, crystallization properties, flame retardancy, and mechanical properties were investigated. When the DT content reached 15%, the vertical burning classification test achieved the UL-94 V-0, and the limiting oxygen index (LOI) rose up 27.2%. In the cone calorimeter test, the peak of heat release rate (PHRR) and total heat release (THR) of the material decreased significantly, and a distinct char layer formed, increasing NH₃ release and decreasing the C-H structure after combustion, improving PA66 flame-retardant properties. Full article

To expand the utilization of bio-based materials as flame retardants in epoxy resin (EP), a green Schiff base structural material (CSV) was synthesized via a one-pot approach employing chitosan and vanillin as the raw materials. Then, the CSV combined with 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO) (the mass ratio between CSV and DOPO was 1:2, written as CSV-DOPO) improved the flame retardancy of the EP. When the amount of CSV−DOPO in the EP was only 3 wt%, the thermogravimetric analysis (TGA) results indicated that the residue of the EP composites was 50.6% higher than that of the EP. The combustion class of the EP/3 wt% CSV−DOPO composites achieved a UL-94 V0 rating and the limit oxygen index (LOI) reached 34.0%. The cone calorimeter test (CCT) showed that the peak heat release rate (PHHR), total heat release (THR), total smoke release (TSP), and peak carbon dioxide production (PCO₂P) of the EP/3 wt% CSV−DOPO composites decreased by 32.3%, 22.0%, 4.6%, and 51.0%, respectively, compared to the EP. The flame-retardancy mechanism was studied by scanning electron microscopy (SEM) and Raman spectra. The quenching effect of phosphorus-containing radicals, the dilution effect of noncombustible gases, and the impeding effect of the carbon layer in the condensed phase contributed collectively to the excellent flame retardancy of the EP/CSV−DOPO composites. Considering the facile preparation method and small addition amount of the flame retardant, the present work provides a convenient solution for the preparation of modified EP with good flame retardancy and heat stability, which is expected to be widely used in industries. Full article

Waterborne polyurethane cationomer coatings modified with 1,3-bis(3(3-(propoxy-2-ol-)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)-3-propyloxy))tetramethyldisiloxane (TMDS–AGE–DOPA) containing phosphorus and silicon atoms were obtained. Their structures were confirmed by Fourier transform infrared (FTIR) spectroscopy. The effect of TMDS–AGE–DOPA on thermal properties, flame retardancy, and surface characteristics (gloss, contact angle, surface free energy), as well as performance properties (hardness, impact resistance), was investigated. A coupled TG-FTIR technique was employed for evolved gas analysis. Thermal stability decreased with the addition of the modifier, while the glass transition temperature increased from −19 to 25 °C. The modifier improved the flame retardancy of the material by shifting the peak temperature of the heat release rate (T_PHRR) to lower values. The gloss of the coatings was very high (>90 GU at all angles studied), although it decreased with increasing modifier content. The presence of phosphorus moieties from the modifier enhanced hydrophilicity, raising surface free energy (SFE) from 37.9 to 44.0 mJ/m². The coatings are soft materials with a Persoz hardness in the range of 0.05–0.32. The modifier increased hardness but reduced impact strength. The obtained cationomers can be applied as environmentally friendly coatings on hydrophilic surfaces such as textiles, glass, or wood. Full article

To meet the environmental protection and flame retardancy requirements for epoxy resins (EPs) in certain fields, in this study, a novel triazine-ring-containing DOPO-derived compound (VDPD), derived from vanillin, 2,4-Diamino-6-phenyl-1,3,5-triazine, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), was synthesized using a one-pot method. Flame-retardant epoxy resin (FREP) was prepared by adding various ratios of VDPD to EP and curing with 4,4-diaminodiphenylmethane (DDM). The curing behavior, thermal stability, mechanical properties, and flame-retardant properties of the FREP were examined in various tests. According to the results, when the amount of VDPD added to the EP increased, the glass transition temperature of the FREP decreased linearly, and the flame-retardant properties gradually improved. With a 0.4 wt.% P content, the vertical burning rating of EP/DDM/VDPD-0.4 (according to the theoretical content of VDPD) reached the V-0 level, and the LOI value reached 33.1%. In addition, the results of a CCT showed that the peak heat release rate (PHRR) of EP/DDM/VDPD-0.4 decreased by 32% in comparison with that of the EP. Furthermore, compared with those of the EP, the tensile strength of EP/DDM/VDPD-0.4 decreased from 80.2 MPa to 74.3 MPa, only decreasing by 6 MPa, and the tensile modulus increased. Overall, VDPD can maintain the mechanical properties of EP and effectively improve its flame-retardant properties. Full article

A set of polyphenylene oxides incorporating DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) functionality, denoted as DOPO−R−PPO, was synthesized by copolymerization of 2,6-dimethylphenol (2,6-DMP) with various DOPO-substituted tetramethyl bisphenol monomers. In the initial step, a Friedel–Crafts acylation reaction was employed to react 2,6-DMP with different acyl chlorides, leading to the formation of ketone derivatives substituted with 2,6-dimethylphenyl groups. Subsequently, the ketones, along with DOPO and 2,6-DMP, underwent a condensation reaction to yield a series of DOPO-substituted bisphenol derivatives. Finally, polymerizations of 2,6-dimethylphenol with these DOPO-substituted bisphenols were carried out in organic solvents using copper(I) bromide/N-butyldimethylamine catalysts (CuBr/DMBA) under a continuous flow of oxygen, yielding telechelic PPO oligomers with DOPO moieties incorporated into the polymer backbone. The chemical structures of the synthesized compounds were characterized using various analytical techniques, including Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H NMR), phosphorus nuclear magnetic resonance (³¹P NMR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). When compared to conventional poly(2,6-dimethyl-1,4-phenylene oxide)s with a similar molecular weight range, all DOPO−PPOs exhibited higher glass transition temperatures, enhanced thermal degradability, and increased char yield formation at 800 °C without compromising solubility in organic solvents. Full article

A 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-based derivative (PN-DOPO) combined with aluminium phosphates-coated sepiolite (Sep@AlPO₄) was used to improve the flame retardance, thermal stability and mechanical performances of poly (ethylene oxide) (PEO)/poly (butylene adipate-co-terephthalate) (PBAT) blends. The synergistic effects of PN-DOPO and Sep@AlPO₄ on flame-retarded PEO/PBAT composites were systematically discussed. Results indicated that introducing 5 wt% Sep@AlPO₄ with 10 wt% PN-DOPO into PEO/PBAT achieved a V-1 rating for the UL-94 test and increased the limiting oxygen index value to 23.7%. Moreover, the peak heat release rate (p-HRR), average HRR and total heat release values of PEO/PBAT/PN10%/Sep5% composites decreased by 35.6%, 11.0% and 23.0% compared with those of PEO/PBAT, respectively. Thermogravimetric analysis (TGA) results confirmed that PN-DOPO/Sep@AlPO₄ enhanced the initial thermal stability and char yield of PEO/PBAT matrix, and TGA/Fourier transform infrared spectrometry results revealed that the composites exhibited the characteristic absorption peaks of phosphorous-containing groups and an increase in gas-phase volatiles during thermal degradation. The morphological structures of the residues indicated that PN-DOPO and Sep@AlPO₄ mixtures produced a more dense and continuous char layer on the composite surface during burning. Rheological behaviour revealed that higher complex viscosity and modulus values of PEO/PBAT/PN-DOPO/Sep@AlPO₄ sample could also promote the crosslinking network structure of condensed phases during combustion. Furthermore, the PEO/PBAT/PN-DOPO/Sep@AlPO₄ composites exhibited superior elongation at break and flexural performance than the PEO/PBAT system. All results demonstrated that the PEO/PBAT system modified with PN-DOPO/Sep@AlPO₄ showed remarkable flame retardance, and improved thermal stability and mechanical properties, indicating its potential application in areas requiring fire safety. Full article

Transparency is an important property for polymer flame retardants, especially epoxy resin (EP) flame retardants, and flame-retardant epoxy resins that maintain a high transparency and low chromatic aberration play important roles in the optical, lighting, and energy industries. Herein, a DOPO-based flame retardant 6,6′-((sulfonylbis(4,1-phenylene))bis(oxy))bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) with a high transparency and low chromatic aberration was prepared via the classical Atherton–Todd reaction and named SBPDOPO. Its chemical structure was characterized with Fourier IR spectroscopy and NMR spectroscopy. An EP loaded with 7 wt% SBPDOPO passed the UL-94 V-0 rating with an LOI value of 32.1%, and the peak heat release rate, total heat release, and total smoke production were reduced by 34.1%, 31.6%, and 27.7%, respectively, compared with those of pure EP. In addition, the addition of SBPDOPO improved the thermal stability, residual mass, and glass transition temperature of the EP. On this basis, the EP containing 7 wt% SBPDOPO maintained a high transparency and low color aberration, with a transmittance of 94% relative to that of pure EP and a color aberration ΔE of 1.63. Finally, the flame-retardant mechanism of SBPDOPO was analyzed, which demonstrated that it exerted both gas-phase and condensed-phase flame-retardant effects, and that SBPDOPO/EP had high potential for application scenarios in which both flame retardancy and transparency are needed. SBPDOPO/EP has great potential for applications requiring both flame retardancy and transparency. Full article

Adsorption methods for CO₂ capture are characterized by high selectivity and low energy consumption. Therefore, the engineering of solid supports for efficient CO₂ adsorption attracts research attention. Modification of mesoporous silica materials with tailor-made organic molecules can greatly improve silica’s performance in CO₂ capture and separation. In that context, a new derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, possessing an electron-rich condensed aromatic structure and also known for its anti-oxidative properties, was synthesized and applied as a modifying agent of 2D SBA-15, 3D SBA-16, and KIT-6 silicates. The physicochemical properties of the initial and modified materials were studied using nitrogen physisorption and temperature-gravimetric analysis. The adsorption capacity of CO₂ was measured in a dynamic CO₂ adsorption regime. The three modified materials displayed a higher capacity for CO₂ adsorption than the initial ones. Among the studied sorbents, the modified mesoporous SBA-15 silica showed the highest adsorption capacity for CO₂ (3.9 mmol/g). In the presence of 1 vol.% water vapor, the adsorption capacities of the modified materials were enhanced. Total CO₂ desorption from the modified materials was achieved at 80 °C. The obtained silica materials displayed stable performance in five CO₂ adsorption/desorption cycles. The experimental data can be appropriately described by the Yoon–Nelson kinetic model. Full article

To endow synergistically epoxy resin (EP) with excellent fire resistance and high optical transparency, a nitrogen-rich DOPO-based derivate (named as FATP) was synthesized and incorporated into EP. It showed that the incorporation of the FATP reduced the fire hazard of the EP, as demonstrated by the fact that the EP/4% FATP blends gained a UL-94 V-0 rating and an LOI value of 35%, with the lowest values of the THR (86.7 MJ/m²), the PHRR (1059.3 kW/m²), and the TSP (89.6 MJ/m²). The presence of the FATP also reduced the thermal stability and the crosslinking density whilst improving the curing reaction and the storage modulus of the EP/FATP blends. The TG-FTIR spectra showed that •HPO/•PO free radicals and some nonflammable gases (HN₃ and NH₃) were produced during the pyrolysis, and the characterization (SEM, Raman spectroscopy, and XPS) of char residues confirmed that the FATP facilitated the formation of continuous and compact carbon layers of greater graphitization degree. It was thus concluded that the FATP played the flame-retardant roles in both the gas and condensed phases. Furthermore, the FREPs kept almost identical transparency as the pristine EP, and mechanical properties were also slightly enhanced. The FREPs presented in this work show promising applications in the fields of advanced optical technology. Full article

Among the multitude of polymers with carbon-based macromolecular architectures that easily ignite in certain applications where short circuits may occur, polyimide has evolved as a class of polymers with high thermal stability while exhibiting intrinsic flame retardancy at elevated temperatures via a char-forming mechanism. However, high amounts of aromatic rings in the macromolecular backbone are required for these results, which may affect other properties such as film-forming capacity or mechanical properties; thus, much work has been done to structurally derivatize or make hybrid polyimide systems. In this respect, flexible polyimide films (PI(1–4)) containing bulky 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) units have been developed starting from commercial dianhydrides and an aromatic diamine containing two side chain bulky DOPO groups. The chemical structure of PI(1–4)) was characterized by ¹H NMR, ¹³C NMR and ³¹P NMR spectroscopy. The optical properties, including absorption and luminescence spectra of these polymers, were analyzed. All polyimides containing DOPO derivatives emitted blue light with an emission maxima in the range of 340–445 nm, in solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, chloroform, and N,N-dimethylacetamide, while green light emission (λ_em = 487 nm for PI-4) was evidenced in a thin-film state. The thermal decomposition mechanism and flame-retardant behavior of the resulting materials were investigated by pyrolysis-gas-chromatography spectrometry (Py-GC), scanning electron microscopy (SEM), EDX maps and FTIR spectroscopy. The residues resulting from the TGA experiments were examined by SEM microscopy images and FTIR spectra to understand the pyrolysis mechanism. Full article

Poly(m-xylylene adipamide) (MXD6) has good gas barrier properties and high mechanical strength. However, in nature, this resin has a low rate of crystallization. In order to overcome this obstacle in its applications, this study prepares a new, efficient modifier for MXD6 by combining the synthesized DOPO derivative (DT) and P22. It is found that the use of the binary modifier exhibits obvious effects on the crystallization of MXD6. When 11.0 wt.% DT is added together with 0.1 wt.% P22 (DT/P22), the crystallization temperature of MXD6 shifts to a higher temperature of 19.7 °C, and the crystallinity degree of MXD6 is significantly increased by 60%. Meanwhile, this modifier exhibits obviously intumescent flame-retardancy on MXD6 by increasing the limited oxygen index (LOI) from 26.4% to 33.4%. The results of the cone calorimeter test (CCT) reveal that the peak heat release rate (PHRR), total heat release (THR) and average effective heat release (av-EHC) are obviously suppressed due to the use of this modifier. Moreover, the influences of this modifier on the crystal structures, mechanical and rheological properties of MXD6 are analyzed in detail. This study can provide an efficient modifier for MXD6. Full article

Polypropylene (PP), as a general thermoplastic polymer, is broadly used in different fields. However, the high flammability, melt dripping and poor mechanical properties of PP are a constraint to the expansion of its applications. In this paper, PP composites containing a combination of a phenethyl-bridged DOPO derivative (PN-DOPO) and organic montmorillonite (OMMT) were prepared via melt blending. The synergistic effects of PN-DOPO and OMMT on the flame retardancy, thermal stability and mechanical properties of PP composites were investigated systematically. The results showed that 20 wt% addition of PN-DOPO with OMMT improved the flame retardancy of PP composites. In particular, the introduction of 17 wt% PN-DOPO and 3 wt% OMMT increased the LOI values of the PP matrix from 17.2% to 23.6%, and the sample reached the V-0 level and reduced the heat release rate and total heat release. TGA indicated that OMMT could improve the thermal stability of the PP/PN-DOPO blends and promote the char residues of PP systems. Rheological behaviour showed a higher storage modulus, loss modulus and complex viscosity of PP/PN-DOPO/OMMT composites, suggesting a more effective network structure. In addition, the tensile strength, flexural properties and impact strength of the PP/PN-DOPO/OMMT composites actually increased for a good dispersion effect. Combined with the char layer analysis, the introduction of OMMT promoted more continuous and compact structural layers containing an aluminium–silicon barrier and phosphorus-containing carbonaceous char in the condensed phase. OMMT can improve the flame retardancy, thermal stability and mechanical properties of PP, and, thus, PN-DOPO/OMMT blends can serve as an efficient synergistic system for flame-retarded PP composites. Full article

A novel bio-based flame retardant designated AVD has been synthesized in a one-pot process via the reaction of 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO), vanillin (VN), and 2- aminobenzothiazole (ABT). The structure of AVD was confirmed using Fourier transform infrared spectroscopy (FTIR), and ¹H and ³¹P nuclear magnetic resonance spectroscopy (NMR). The curing process, thermal stability, flame retardancy, and mechanical properties of the epoxy resin (EP) modified with AVD have been investigated comprehensively. The extent of curing, the glass transition temperature and the crosslinking density of the blend decreased gradually with increasing AVD content. The thermogravimetric analysis (TGA) was used to demonstrate that the presence of AVD reduced the thermal decomposition rate for EP and enhanced the formation of carbon residue during resin decomposition. A blend of 7.5 wt% AVD (0.52% phosphorus) displays a UL-94V-0 rating and a LOI of 31.1%. Reduction of the peak heat release rate, total heat release rate and total smoke production was 41.26%, 35.70%, and 24.03%, respectively, as compared to the values for pure EP. The improved flame retardancy of the flame retardant epoxy (FREP) may be attributed to the formation of a compact and continuous protective char layer into the condensed phase as well as the release of non-combustible gases and phosphorus-containing radicals from the decomposition of AVD in the gas phase. AVD is a new and efficient biobased flame retardant for epoxy with great prospects for industrial applications. Full article

The DOPO-based flame-retardant additives DOPO-HQ, DOPO-AP and DOPO-Van were synthesized in varying numbers of phenolic hydroxyl groups and amine groups. Moreover, their influence on the polymerization of a bisphenol F-based benzoxazine, as well as the thermal properties of the resulting materials, were studied. All DOPO-based derivatives influenced the polymerization temperature onset with a reduction of up to 20 °C, while thermo-mechanical properties remained high. Surprisingly, phosphorous content below 0.4 wt% significantly improved the reaction against small flames yielding an increase in the limited oxygen index by 2% and a V-0 rating in the UL-94 test. DOPO-HQ proved to be the most effective additive regarding the reaction against small flames at an astonishingly low phosphorous concentration of below 0.1 wt%, whereas DOPO-AP and DOPO-Van simultaneously lowered the polymerization temperature. Full article