EUROPEAN POLYMER JOURNAL
·
2026
·
IF 6.8
Zimeng Liu,Nannan Song,Yong Guo,Zhongwei Chen,Yuan Yu,Peng Ma,Juncheng Jiang
Bio-based furan-containing phosphorus flame retardants (FRs) are widely considered promising for epoxy resins (EP) because furan structures are generally believed to enhance carbonization. However, how furan molecular architecture regulates the pyrolysis pathway and flame-retardant mechanism remains unclear. Herein, three DOPO-derived FRs containing 2, 4, and 8 furan units were synthesized with an identical phosphorus content to isolate the effect of furan architecture. The results indicate that increasing the number of furan units does not continuously improve the flame retardancy of EP but significantly alters the pyrolysis pathway and phosphorus utilization during thermal degradation. Although higher furan contents enhance the intrinsic self-carbonization ability of the FRs, they simultaneously suppress the release of phosphorus-containing active species, thereby weakening phosphorus-assisted catalytic carbonization of the epoxy matrix. Consequently, EP composites containing higher-furan FRs exhibit increased volatile evolution, less graphitized protective char, and inferior flame-retardant performance despite the higher intrinsic char-forming ability of the FRs. In contrast, DFP-2 exhibits a favorable balance between phosphorus-radical release and catalytic charring, resulting in the best interfacial compatibility, mechanical properties, and fire safety. This work establishes a clear structure–property relationship by revealing how furan molecular architecture regulates pyrolysis behavior, phosphorus release, and catalytic carbonization of epoxy thermosets, providing mechanistic insights for the molecular design of bio-based phosphorus-containing flame retardants.
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高影响因子
EUROPEAN POLYMER JOURNAL
·
2026
·
IF 6.8
Yudong Hou,Xiaocong Deng,Chao Ma,Sheng-chao Huang,Cuifen Lu
This study reports the synthesis of a novel flame retardant (TDOPO) via a one-pot nucleophilic addition reaction, in which 3,4-Dihydroxybenzaldehyde (PH) was grafted onto 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) at different oxidation states. The chemical structure of TDOPO was confirmed by Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR).The effects of TDOPO dosage on the flame retardancy, thermal properties, and mechanical properties of epoxy resin (EP) composites were systematically investigated and compared with those of pure epoxy resin. At a TDOPO content of 10 wt% (EP/TDOPO10), the epoxy resin composite achieved a Limiting Oxygen Index (LOI) of 33.6% and a UL-94V-0 rating, demonstrating outstanding flame retardancy. Cone calorimeter tests revealed that, compared to pure epoxy resin, the EP/TDOPO10 composite exhibited reductions of 41.0%, 18.6%, and 20.4% in peak heat release rate (PHRR), total heat release (THR), and total smoke production (TSP), respectively. These improvements are attributed to the abundant hydroxyl groups in the resorcinol structure, which promote the formation of a denser and more continuous char layer. Additionally, the phosphorus element in TDOPO catalyzes char formation, leading to a phosphorus-rich three-dimensional network char layer in the condensed phase during combustion. The substantial char residue effectively impedes heat and oxygen transfer to the underlying polymer matrix. Thus, this flame retardant imparts superior flame retardancy and mechanical properties to epoxy resins, positioning it as a promising candidate for developing functional thermoset flame retardants.
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高影响因子
POLYMER DEGRADATION AND STABILITY
·
2025
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IF 7.4
Kumar Selvaraj,Hongfei He,Marisa E. Spontón,Na Sun,Hongliang Ding,Yao Yuan,Chuanshen Wang,Lu Liu,Yuxiang Yi,Bin Yu
Researchers are increasingly focusing on the development of biobased polyol derived rigid polyurethane foams (RPUFs) as sustainable alternatives to traditional polyether polyol based RPUFs targeting improvements in flame resistance, mechanical strength and thermal insulation. In this context novel biobased cardanol/triazine based polyol was synthesized through co-condensation of cardanol, melamine and paraformaldehyde and its chemical structure and functional groups was confirmed by FT-IR and ¹H NMR analyses. Using this polyol cardanol/triazine based rigid polyurethane foam (C/N-RPUF) was fabricated via a one-pot reaction under –NCO/–OH ratio of 1.1. To enhance fire safety C/N-RPUF composites were produced by incorporating 1, 3 and 5 wt% of a reactive DOPO derived polyol (DOPOP). Structural characterizations of composites were performed using FTIR and SEM-EDS techniques. Remarkably C/N-RPUF with 5 wt% DOPOP demonstrated superior flame retardancy achieving a UL-94 V-0 classification, limiting oxygen index (LOI) of 26.5%. Compressive strength values of neat C/N-RPUF and C/N-RPUF/5wt% DOPOP were 0.081 and 0.127 MPa respectively with the improvement attributed to additional cross-linking interactions within the foam structure. Additionally, the 5 wt% DOPOP composites showed a thermal conductivity of 0.051 W/(m·K), which is lower than that of conventional RPUFs, suggested its superior thermal insulation performance. In terms of fire performance composite showed significant reductions compared to pristine C/N-RPUF with 39.6% decrease in peak heat release rate (PHRR) and a 64.2 % reduction in CO emission. Overall, this work introduces an eco-friendly and efficient strategy for producing high-performance biobased rigid polyurethane foams combining flame resistance, compressive strength and superior insulation properties.
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高影响因子
MACROMOLECULAR MATERIALS AND ENGINEERING
·
2022
·Vol. 307
·期 11
·2200408
·
IF 4.402
Wen-Hua Zhao,Jing-Wen Wang,Guo-Chao Zhuang,Dong-Yue Liu,Chuang-Chuang Sun
A reactive flame retardant (DTP) is successfully synthesized and characterized, and then incorporated into epoxy resin (EP) as a co-curing agent. The thermal stabilities and flame-retardant properties of epoxy thermosets are evaluated. Compared to neat EP, the thermogravimetric analysis (TG) results show that the thermal decomposition rate of EP/DTP is reduced by 45% and the char yield at 750 °C is increased by 67%, when the addition amount of DTP is 12 wt%. In the cone calorimetry test (CCT), the values of the peak of heat release rate (pk-HRR), total heat release (THR), total smoke produce (TSP), and average of effective heat combustion (av-EHC) of EP-DTP-12 are exhibited a reduction of 36.6%, 26.4%, 40.5%, and 23.6% relative to neat EP, respectively. Meanwhile, the value of the limiting oxygen index (LOI) of EP/DTP-12 can reach 34.83%, and 6 wt% or more loading of DTP make EP/DTP pass the V-0 rating in the UL-94 test. Moreover, the flame-retardant mechanism is investigated by thermogravimetric analysis/infrared spectrometry (TG-IR) and scanning electron microscopy (SEM), which can be summarized into two aspects: the quenching effect of phosphorus-containing radicals and diluting effect of nonflammable gases in the gas phase, and the barrier effect of char layer in the condensed phase.
研究领域:
材料科学
·
化学工程
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高影响因子
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS
·
2014
·
IF 0.827
Ling Xiao,De-chao Sun,Tian-li Niu,You-wei Yao
GRAPHICAL Display full size
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高影响因子
HIGH PERFORMANCE POLYMERS
·
2022
·
IF 1.73
Rui Chen,Bao Dongmei,Jiaye Jiang,Chuanbo Sun,Han Chen,Min Zhang
Two effective flame retardant additives hsalaminopyridine phosphaphenanthrene (HAD) and methoaminopyridine phosphaphenanthrene (MAD) were respectively prepared with DOPO, aminopyridine, salicylaldehyde and 3-Methoxysalicylaldehyde. Subsequently, HAD and MAD was added into epoxy resin (EP) respectively, and flame retardancy of EP/HAD and EP/MAD thermosets were dramatically enhanced. The result of cone calorimeter (CC) test revealed that both HAD and MAD showed perfect smoke suppression performance. In respect of transmittance and mechanical properties, there was a huge difference between HAD and MAD. The introduction of HAD dramatically harmed transmittance and mechanical properties of EP, while, EP/10%MAD was transparent and nearly possessed the same mechanical properties with pure EP.
研究领域:
材料科学
·
化学工程
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高影响因子
JOURNAL OF POLYMER RESEARCH
·
2022
·Vol. 29
·期 9
·1-14
·
IF 3.061
Wang Jinlei,Li Jialan,Meng Xue,Gao Xianghua,Yan Hong
A novel DOPO-substituted and triazine-based charring agent (ST-DOPO) was synthesized from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4,4’-diphenylmethane diisocyanate (MDI), and melamine (MEL), which is used as a synergistic flame retardant of ammonium polyphosphate (APP) for polypropylene (PP). ST-DOPO is a good char forming agent, with a residual weight up to 36.59 wt.% at 800 °C. With 30 wt.% of ST-DOPO and APP (2∶1), the PP blend achieved a V-0 rating at a vertical UL-94 test, with a limiting oxygen index (LOI) value of 35.0%. Compared to pure PP, its peak heat release rate (PHRR), total heat release (THR), and total smoke production (TSR) were reduced by 81.2%, 34.1%, and 70.4%, respectively. Interestingly, the blend had only a 6.2% decrease in the tensile strength but a 15.1% increase in the impact strength, suggesting good compatibility of additives with the PP matrix. Moreover, the well-expanded continuous and compact char layer contributed to the improvement of the flame retardant property.
研究领域:
材料科学
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化学工程
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Journal of Inorganic and Organometallic Polymers and Materials
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2025
·
IF 4.9
Zhou Qin,Su Qing
Without weakening the comprehensive properties of the epoxy resin (EP) substrate itself, adding functional materials to increase the burning difficulty of EP and reduce the release of toxic and harmful smoke is a great challenge. In this work, Co-Ca-Fe layered double hydroxide hybrid flame retardant (DOPO-LDHS) with surface/interlayer Functionalization of 9, 10-dihydro-9-oxa-10-phosphate-10-oxide (DOPO) and phenylphosphonic acid (PPO) were synthesized. The 10 wt% DOPO-LDHs modified EP exhibited superior flame retardancy in both gas and condensed phases. The peak Heat release rate, total smoke production, CO production, and smoke production rate of EP composites containing 10 wt% DOPO-LDHs were reduced by 31.2%, 31.7%, 37% and 35%, respectively. DOPO-LDHs contribute to the formation of the condensed phase with a dense carbon layer that is resistant to thermal oxidation, and the synergistic action of DOPO and OPA releases non-flammable phosphorus-containing radicals in the gas phase. Meanwhile, the oxides formed by the physical phase transformation of LDHs catalyze the transformation of CO to form CO 2 to reduce the release of harmful gases. In addition, the EP/DOPO-LDHs composites have good mechanical properties, and no obvious weakening for tensile and flexural strengths had occurred. This work provided a new idea for the green flame retardant system with layered double hydroxides as functional carriers. Graphical
研究领域:
材料科学
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高分子科学
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消防安全工程
·
纳米技术
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JOURNAL OF POLYMER SCIENCE
·
2025
·Vol. 64
·期 2
·325-339
·
IF 3.6
Xiaolin Zhang,Hengliang Cui,Yan Jiang,Na Wang
Epoxy resins (EP) have significant application value in the industrial sector; however, their flammability and toxic fume emissions during combustion limit their applications. Bio-based flame retardants provide effective flame-retardant properties, primarily owing to their unique molecular compositions and structural features. In this study, a flame retardant (DAVN) is prepared using vanillin, 5-amino-1H-tetrazole, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). When 6 wt.% DAVN is added to the EP, the EP composite exhibits a residual carbon content of 19.9% at 700°C while achieving a limiting oxygen index (LOI) value of 32.6% and the UL-94V-0 standard. Additionally, compared with pure EP, the peak heat release rate (PHRR), total heat output (THR), total smoke production (TSP), and smoke production rate (SPR) decrease by 49.3%, 44.7%, 35.1%, and 35.1%, respectively. These improvements primarily result from the polyphosphates formed from the DAVN decomposition, which promote the carbonization and cross-linking of EP, thus forming a compact carbon layer that suppresses heat and smoke release. Moreover, the formation of gas during combustion dilutes the combustible gases, thereby enhancing flame retardancy. Additionally, DAVN improves the mechanical properties of EP and increases its tensile strength by 7.1%. This study provides a useful reference for the development of high-performance flame-retardant EP composites. Graphical A bio-based flame retardant was synthesised using vanillin and DOPO as primary raw materials. This flame retardant demonstrated excellent flame-retardant properties in epoxy resins, offering a novel approach to enhancing the flame retardancy of epoxy resin composites.
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Journal of Inorganic and Organometallic Polymers and Materials
·
2026
·
IF 6
Yue Yanling,Huang Bingyue,Liu Deyu,Wu Shaoyuan,Hu Jinghan,Ming Shiyi,Guan Xingyu,Zhang Yi,Wang Kui,Huang Weijiang,Yan Wei
Hexagonal boron nitride (h-BN) is inherently hydrophobic and lacks active functional groups on its surface. In this study, we modified h-BN with phytic acid and chitosan to create BN@PA-CS particles. These particles integrated into an aqueous polyurethane (WPU) matrix, along with the DIDOPO flame retardant, to form the WPU/BN@PA-CS/DIDOPO nanocomposite. We investigated the composite’s flame retardancy, thermal stability, rheological properties, and mechanical properties. The results demonstrated that BN@PA-CS and DIDOPO exhibit a significant synergistic effect in both gas and condensed phases for flame retardancy. When the mass fractions of BN@PA-CS and DIDOPO were 2 wt% and 7 wt% relative to WPU matrix, the optimal formulation WPU/BN@PA-CS2/DIDOPO7 achieved a UL-94 V-0 rating and increased the limiting oxygen index (LOI) to 24.2%. Additionally, the peak heat release rate (pHRR) and total heat release (THR) decreased by 49.3% and 66.1%, respectively, compared to pure WPU. Rheological and mechanical measurements indicated that the formulation WPU/BN@PA-CS2/DIDOPO7 exhibited a compatible combination of tensile stiffness, ductile toughness, and melt flow behaviour relative to other composite groups.Therefore, the DIDOPO/BN@PA-CS composite strategy provides experimental observations and mechanistic speculation for developing high-performance flame-retardant polyurethane composites, optimizing synergistic effects at specific ratios to enhance flame retardancy and mechanical properties. Graphical
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高影响因子
PROGRESS IN ORGANIC COATINGS
·
2026
·
IF 7.9
Mengmeng Zhang,Zhihui Sui,Longyu He,Bingchi Zhang,Yuxin Zhang,Wenrui Chi
Amid ongoing innovation in functional textiles, single-function materials, characterized by relatively limited performance profiles, increasingly fall short of the diverse, integrated functional demands encountered in real-world applications. Consequently, the development of multifunctional fabrics that concurrently deliver flame retardancy, hydrophobicity, UV resistance, and antibacterial activity has emerged as a critical research frontier, bearing both substantial scientific merit and high translational potential. In this work, waterborne polyurethane (WPU) was synergistically modified through the co-incorporation of surface-functionalized nano-ZnO, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and a fluorosiloxane (HPFSi), yielding a stable, ternary-modified emulsion designated ZnO/DOPO/fluorosilicone waterborne polyurethane (ZnO/PFSiWPU). This emulsion was subsequently applied to hemp fabric via coating-based finishing. Comprehensive evaluation revealed that the treated fabric exhibits outstanding integrated functionality: a limit oxygen index (LOI) of 36.2%, confirming superior flame retardancy; a water contact angle (WCA) of 151.5° ± 2.7°, indicative of durable superhydrophobicity; an ultraviolet protection factor (UPF) of 71.21, reflecting highly effective UV shielding; and antibacterial inhibition rates of 99.6% against Staphylococcus aureus and 99.9% against Escherichia coli , demonstrating robust, broad-spectrum antimicrobial efficacy. Notably, the incorporation of modified nano-ZnO into the coating system markedly improved the fabric's antibacterial and UV-resistant performance, while concurrently enhancing its flame retardancy and hydrophobicity. This finding elucidates a synergistic enhancement mechanism mediated by nano-ZnO within the multi-component composite coating, thereby offering both conceptual insights and a theoretical foundation for the rational design and development of multifunctional, high-performance textile coatings.
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高影响因子
POLYMER DEGRADATION AND STABILITY
·
2015
·
IF 3.163
Miao-Jun Xu,Guang-Rui Xu,Yang Leng,Bin Li
A novel flame retardant additive with phosphazene and phosphaphenanthrene groups hexa-[4-( p -hydroxyanilino-phosphaphenanthrene-methyl)-phenoxyl]-cyclotriphosphazene defined as CTP-DOPO was successfully synthesized from hexachlorocyclotriphosphazene, p -hydroxybenzaldehyde, 4-aminophenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO). Its chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy, 1 H nuclear magnetic resonance ( 1 H NMR) and 31 P nuclear magnetic resonance ( 31 P NMR). The prepared flame retardant additive CTP-DOPO was incorporated into diglycidyl ether of bisphenol-A (DGEBA) to prepare flame retardant epoxy resins thermosets . The flame retardant properties, thermal degradation behavior and combustion behavior of the DGEBA thermosets cured by 4, 4′ -Diamino-diphenyl sulfone (DDS) were investigated by limiting oxygen index (LOI), vertical burning test (UL-94), thermogravimetric analysis/infrared spectrometry (TG-IR) and cone calorimeter tests. The structure and surface morphology of the char residues after cone calorimeter tests was measured by FTIR and scanning electron microscopy (SEM). The results revealed that DGEBA/CTP-DOPO thermosets successfully passed UL-94 V-0 flammability rating and its LOI value dramatically increased from 21.7% for cured pure DGEBA to 36.6% when the loading amount of CTP-DOPO was 10.6 wt % and the phosphorus content was only 1.1 wt % in thermosets, which indicated that the prepared CTP-DOPO possessed excellent flame retardancy for DGEBA thermoset. The TG-IR results indicated that the introduction of CTP-DOPO stimulated epoxy resins matrix decomposed and char forming ahead of time, which led to a higher residual char and thermal stability for epoxy resins thermosets at high temperature. The cone calorimeter tests revealed that the incorporation of CTP-DOPO effectively reduced the combustion parameters of DGEBA thermosets, such as heat release rate (HRR), total heat release (THR), smoke production rate (SPR) and total heat production (TSP), and so on. The SEM results showed that the phosphazene and phosphaphenanthrene groups in CTP-DOPO obviously stimulated the formation of the intumescent, compact and strong char layer, which enhanced the flame retardany of the DGEBA matrix during combustion. Therefore, the underlying materials were protected from further degradation and combustion and resulted in the efficient flame retardancy for EDGEBA thermoset.
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高影响因子
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