ACS Applied Polymer Materials
·
2020
·
IF 0
Siqi Huo,Shuang Yang,Jun Wang,Jianwen Cheng,Qianqian Zhang,Yefa Hu,Guoping Ding,Qiaoxin Zhang,Pingan Song,Hao Wang
The fabrication of high-performance thermosetting polymers with intrinsic flame retardancy and smoke suppression is necessary but challenging. Herein, we have successfully synthesized a liquid phosphaphenanthrene/imidazole-containing curing agent (DOPO-AI) for epoxy resin (EP) by the Atherton–Todd reaction of 1-(3-aminopropyl)imidazole (AI) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The as-prepared EP/DOPO-AI samples exhibit comparable mechanical properties to the reference EP/AI-6 sample, with slightly decreased glass transition temperatures. Impressively, the EP/DOPO-AI sample can pass the UL-94 V-0 rating and achieve a limited oxygen index (LOI) value of 37.0%. Additionally, the EP/DOPO-AI sample shows 26.3%, 36.6%, and 24.4% reductions in the total heat release (THR), peak of heat release rate (pHRR), and total smoke production (TSP) relative to the EP/AI-6 sample, indicating a significantly reduced fire hazard. The significant enhancements in flame retardancy and smoke suppression are attributed to the condensed- and gaseous-phase effects of DOPO-AI. This work demonstrates a feasible methodology for creating high-performance EPs with inherent flame retardancy and smoke suppression, holding great promise in the future.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
POLYMER DEGRADATION AND STABILITY
·
2019
·
IF 3.78
Siqi Huo,Zhitian Liu,Chuan Li,Xiaolei Wang,Haopeng Cai,Jun Wang
A flame-retardant curing agent (DTA) for epoxy resin (EP), which was constructed by phosphaphenanthrene and benzimidazole groups, was successfully synthesized via one-pot reaction between 2-aminobenzimidazole, terephthalaldehyde, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). DTA induced the decomposition of EP matrix and promoted the carbonization at high temperature. As expected, DTA endowed EP thermoset with excellent flame retardancy and smoke suppression. For instance, EP/DDS/DTA-0.5 sample containing only 0.5 wt% phosphorus passed UL94 V-1 rating and its LOI value increased to 34.2%. In addition, the pk-HRR, av-HRR, THR, TSR, and TSP of EP/DDS/DTA-1.0 sample were decreased by 56.6%, 31.6%, 34.4%, 24.6% and 24.6% in comparison to those of EP/DDS sample. The flame retardant mechanism showed that the decomposition products of DTA played an important role in the formation of a compact and intumescent char layer in condensed phase. Meanwhile, the phosphorus-containing and nitrogen-containing fragments, which was generated by the pyrolysis of DTA, quenched the active free radicals and diluted the fuels in gaseous phase. Therefore, DTA exerted flame retardant effect in condensed and gaseous phases during combustion.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
POLYMER DEGRADATION AND STABILITY
·
2018
·
IF 3.193
Xiaoxiao Tao,Huajun Duan,Wenjing Dong,Xin Wang,Shuang Yang
An intrinsic flame retardant vinyl ester TGIC-AA-DOPO constructed by phosphaphenanthrene and triazine-trione groups was successfully synthesized via the reaction between 1,3,5-triglycidyl isocyanurate (TGIC), acrylic acid and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The structure of TGIC-AA-DOPO was characterized in detail by fourier transform infrared spectroscopy (FTIR), 1 H and 31 P nuclear magnetic resonance (NMR) and liquid chromatography-high resolution mass spectrometry (LC-HRMS). The intrinsic P-N-containing flame retardant vinyl ester resin (IFR-VER) was prepared after diluting TGIC-AA-DOPO with styrene (st) and triallyl isocyanurate (TAIC). The flame retardancy, thermal properties and combustion behavior of IFR-VER were respectively investigated by a series of tests involving limited oxygen index (LOI) measurement, UL-94 vertical burning test, cone calorimeter test, thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The results showed that the as-obtained resin system exhibited a dramatic improvement in flame retardance. In the case of 40 wt% TAIC in resin system, the LOI value achieved 31%, leading to the UL-94 V-0 rating. In addition, compared with the 901-VER, the peak heat release rate (pk-HRR), average of heat release rate (av-HRR), total heat release (THR) and average effective heat of combustion (av-EHC) of the IFR-VER containing 40% TAIC diluent were decreased by 48%, 60%, 41% and 24% respectively. The diphase flame retardant effect of the prepared IFR-VER during combustion was demonstrated by the results of Py-GC/MS, FTIR, laser raman spectroscopy and scanning electron microscope (SEM).
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
COMPOSITES PART B-ENGINEERING
·
2022
·
IF 11.322
Lei Zhang,Zhi Li,Qing-Qing Bi,Lin-Yun Jiang,Xiao-Die Zhang,En Tang,Xue-Meng Cao,Hong-Fang Li,Jose Hobson,De-Yi Wang
The synchronized improvement of strength , toughness and fire suppression poses to be a critical trade-off issue towards high-performance epoxy resin. Aiming to impart epoxy with balanced multifunctional improvement, the Schiff base-derived bio-based phosphaphenanthrene small-molecule reinforcer towards in-situ constructed Diels-Alder network within existing 3D network was proposed. The incorporation of 3.5 wt% reinforcer (CQ-DOPO) concurrently enhanced the tensile and impact strength of epoxy by 26.6% and 48.4% without visible deterioration of transparency. The increment of glass transition temperature by 14 °C via dynamic mechanical analysis was observed. The underpinning experimental and simulation investigation verified the proof of concept of in-situ formed Diels-Alder sacrificing network towards higher crosslinking density and strong-weak dual network. Raman spectra witnessed the breaking of sacrificing bond during fracture. Moreover, 3.5 wt% CQ-DOPO with an ultralow phosphorous loading of 0.245 wt% enabled to impart epoxy with UL-94 V-0 rating as well as limiting oxygen index of 32.0%. The multi-scale dual-phase analysis unveiled the synchronized suppression of fire reactions in vapor phase via PO· quenching as well as in condensed phase via char microstructure optimization. Hence, the rational strategy via in-situ construction of Diels-Alder sacrificing bond toward dual network exploits a novel roadmap for high-performance epoxy.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
POLYMER DEGRADATION AND STABILITY
·
2025
·
IF 7.4
Hao Wang,Yadong Wang,Jingjing Gao,Zongmin Zhu,Fei Xiao
Herein, we presented a multifunctional epoxy resin (EP) composite prepared by the synergistic combination of DOPO and ionic liquids (ILs). The optimized EP-DOPO/ILs system demonstrated exceptional flame retardancy, with only 3 wt% of flame retardant (DOPO/ILs) added to achieve UL-94 V-0 grade for EP and a limiting oxygen index (LOI) of 33.4%. Cone calorimeter test revealed 32.2% and 26.7% reductions in peak of heat release rate (pHRR) and total smoke production (TSP), respectively, compared to neat EP. Notably, the designed rigid-flexible epoxy network simultaneously enhanced tensile strength to 75.7 MPa (+15.7%) and impact strength to 24.8 kJ m -2 (+136.3%), outperforming conventional EP thermosets. Furthermore, the EP composites retained 90% visible light transmittance while exhibiting ultraviolet (UV) shielding efficiency and intrinsic fluorescence. This multi-component collaborative system provides an important experimental foundation for developing high-performance multifunctional polymeric materials.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
HIGH PERFORMANCE POLYMERS
·
2021
·
IF 2.161
Zijin Luo,Zhe Chen,Jun Wei,Dongchao Wang,Han Chen,Rui Chen
A novel intumescent flame retardant, PPMD, was designed from phosphaphenanthrene and nitrogen heterocycles through the two-step gut reactions of 1,4-phthalaldehyde and 3-methyl-1-phe-nylpyrazol-5-ylamine. After determination of its structure by nuclear magnetic resonance and Fourier-transform infrared analyses, PPMD was added to an epoxy resin (EP) to facilitate a curing process. Thus, EP/PPMD samples with excellent transparency and flame retardancy were acquired. For example, the EP sample satisfied the UL-94 V-0 standard and achieved a limiting oxygen index value of 30.5% because of the incorporation of 5 wt% PPMD. The cone calorimeter test of the EP/5% PPMD sample revealed that its total smoke production (TSP) and total heat release (THR) values of EP/5% PPMD was only 22.5% and 56.4% of the control group, respectively. Moreover, the average effective heat of combustion (av-EHC) value of EP/5% PPMD was reduced by 34.1%, indicating that PPMD possessed high flame-inhibition activity and smoke suppression efficiency. The flame-retardant mechanisms of PPMD were also investigated in gas phase by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and in condensed phase by XPS and IR.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
POLYMERS FOR ADVANCED TECHNOLOGIES
·
2025
·Vol. 36
·期 1
·e70059
·
IF 3.4
Qinqin Luo,Yulin Sun
To achieve effective flame retardancy and improved toughness in epoxy resin (EP) without compromising strength and modulus, a new derivative containing phosphaphenanthrene and phenyl propyl ether groups (HPMD) has been developed and used as an additive. The structure of HPMD has been fully characterized, and the properties of HPMD and modified EP have been thoroughly studied. The phenyl propyl ether group in HPMD can undergo Claisen type rearrangement to form benzopyran during heat treatment and subsequently polymerize by curing via the CC bond in the benzopyran. The unique rigid and flexible structures of HPMD allow it to disperse in the EP matrix through melting. Dynamic mechanical analysis suggests that HPMD has a high degree of interpenetration in the EP matrix, resulting in a single-phase structure for the epoxy resins containing HPMD. Notably, incorporating only 4 wt% HPMD content into the polymer matrix yields a flame-retarded, toughened, and strengthened EP. EP containing 4 wt% HPMD (EP4; phosphorus content of only 0.33%) displays a limiting oxygen index value of 31.1% and exhibits a UL94 V-0 rating. Compared with that of EP, the combustion of EP4 exhibits a decrease in the peak of heat release rate, maximum average heat rate emission, average heat release rate, and total heat release, along with an increase in the char yield, further indicating that HPMD effectively retards the combustion of EP. Moreover, EP4 displays improvements in tensile strength, elongation at break, flexural strength, flexural modulus, and impact strength of 18.4%, 9.7%, 14.9%, 19.1%, and 26.7%, respectively, compared with unmodified EP. Analysis of HPMD's flame-retardant action suggests that it exhibits flame-retardant activity simultaneously in the gas and condensed phases. Significant progress has been demonstrated toward the development of a meltable epoxy resin additive that combines flame-retardant, toughening, and strengthening functions while avoiding phase separation from the epoxy resin.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
POLYMER DEGRADATION AND STABILITY
·
2021
·
IF 5.03
Dongyue Liu,Pengfei Ji,Tianlong Zhang,Jipeng Lv,Yihua Cui
A bi-DOPO type of prepolymer for flame retardancy epoxy resins with intrinsically flame-retardant was successfully synthesized by reacting of 6,6′-((6,6′-dihydroxy-[1,1′-biphenyl]-3,3′-diyl) bis (propane-3,1-diyl)) bis(dibenzo[c,e][1,2] oxaphosphinine 6-oxide) (DOBP) with bisphenol A. The characterization of the cured epoxy resins, such as cone calorimeter, TGA/infrared, Raman and SEM indicated that DOBP with double 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) structure endowed the epoxy resins with excellent flame retardancy, including limiting oxygen index of 40.0%, V-0 rating in UL-94, remarkable smoke suppression and flame inhibition. The quenching effect of gaseous phase and charring effect of condensed phase of phosphaphenanthrene groups in prepolymer together contributed to the improvement on the flame retardant performance of the epoxy resins. In addition, due to the rigid structure of DOBP molecules, the cured d -FREP possessed high glass transition temperature of up to 192.9°C, and the tensile modulus of which was increased about 55% compared with the neat epoxy resins.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2017
·Vol. 134
·期 37
·45291
·
IF 1.86
Shuang Yang,Qiaoxin Zhang,Yefa Hu
In this article, a novel flame retardant (coded as BNP) was successfully synthesized through the addition reaction between triglycidyl isocyanurate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and phenylboronic acid. BNP was blended with diglycidyl ether of bisphenol-A to prepare flame-retardant epoxy resin (EP). Thermal properties, flame retardancy, and combustion behavior of the cured EP were studied by thermogravimetric analysis, limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The results indicated that the flame retardancy and smoke suppressing properties of EP/BNP thermosets were significantly enhanced. The LOI value of EP/BNP-3 thermoset was increased to 32.5% and the sample achieved UL94 V-0 rating. Compared with the neat EP sample, the peak of heat release rate, average of heat release rate, total heat release, and total smoke production of EP/BNP thermosets were decreased by 58.2%–66.9%, 27.1%–37.9%, 25.8%–41.8%, and 21.3%–41.7%, respectively. The char yields of EP/BNP thermosets were increased by 46.8%–88.4%. The BNP decomposed to produce free radicals with quenching effect and enhanced the charring ability of EP matrix. The multifunctional groups of BNP with flame retardant effects in both gaseous and condensed phases were responsible for the excellent flame retardancy of the EP/BNP thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45291.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2021
·Vol. 11
·期 49
·30943-30954
·
IF 3.361
Wei Peng,Yu-xuan Xu,Shi-bin Nie,Wei Yang
Phosphorus-containing flame retardants have received huge interest for improving the flame retardant behavior of epoxy resins (EP) over the past few decades. However, a satisfactory flame retardant effect requires high loading of most phosphorus-containing flame retardants, resulting in the deterioration of the thermo-mechanical properties of the flame retardant epoxy materials. To obtain the flame retardant EP with excellent comprehensive properties, a furfurylamine-derived bis-DOPO derivative (FA-bis-DOPO) was synthesized from bio-mass as a co-curing agent for the flame retardant EP. The incorporation of FA-bis-DOPO improved the mechanical strength, the storage modulus and the glass transition temperature of the flame retardant epoxy materials, owing to its stiffness and reactivity with the epoxy matrix to enhance the crosslinking density. The EP material containing 5.0 wt% of FA-bis-DOPO had an LOI of 31.0% and UL-94 V-0 rating, while the pristine EP had an LOI of 23.5% and failed in the UL-94 test, manifesting the high flame retardant efficiency of FA-bis-DOPO. Besides, the cone calorimeter results demonstrated that the PHRR, THR, and TSP values of the EP/FA-bis-DOPO-5.0 were 28.0%, 27.3%, and 9.9% lower than those of the pristine EP, respectively. The flame retardant mechanism of FA-bis-DOPO could be attributed to the combined vapor and condensed phase mechanisms which involved the interruption of the combustion chain reaction by quenching radicals and the inhibition of the transfer of pyrolytic volatile products by catalytic formation of an intact and compact char layer.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
POLYMER DEGRADATION AND STABILITY
·
2015
·
IF 3.163
Puyou Jia,Meng Zhang,Lihong Hu,Jing Zhou,Guodong Feng,Yonghong Zhou
This represents the first description of a flame retardant plasticizer based on soybean oil containing phosphaphenanthrene groups (PSPE). This additive has been prepared and applied in the generation of flame retardant PVC materials. The molecular structure of PSPE was characterized using FT-IR, 1 H NMR and 31 P NMR spectroscopy. The thermal degradation behavior and flame retardant performance of PVC blends plasticized with different amounts of DOP and PSPE has been examined based on mass loss, LOI values, morphologies of residues, smoke production rate (SPR), smoke extinction area (SEA), mass loss rate (MLR) and heat release rate (HRR), thermal degradation processes and modes of flame retardant action has been proposed. The results showed that the addition of PSPE promotes the formation of high quality char residue. Replacement of DOP with PSPE provided PVC blends which exhibited high thermal stability; T d , T 50 , T p1 and T p1 of 291.3 °C, 325.8 °C, 283.0 °C and 461.8 °C, respectively, were observed. The degradation of PSPE released PO 2 and HPO 2 radicals and a series of long chain fatty acid , which provided abundant carbon sources and acid sources for PVC blends. The flame retardant effect was mainly in the condensed phase.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2017
·
IF 5.951
Xin Wang,Shun Zhou,Wen-Wen Guo,Pei-Long Wang,Weiyi Xing,Lei Song,Yuan Hu
A biobased flame retardant toughening agent, phosphaphenanthrene groups-containing triscardanyl phosphate (PTCP), was successfully synthesized via debydrochlorination, epoxidation and ring opening reaction from renewable resource cardanol. The chemical structure of PTCP was confirmed by the proton and phosphorus nuclear magnetic resonance. Epoxy resins (EPs) with different contents of PTCP were prepared through a simple mixing method. Thermogravimetric analysis results indicated that the earlier degradation of PTCP catalyzed the char formation of epoxy resins that was beneficial to protecting underlying polymers from further decomposition. The flame retardant properties were enhanced with the increase of the PTCP content. The EP composite containing 30 wt % PTCP showed a limiting oxygen index of 30.5%. Meanwhile, its peak heat release rate, total heat release and average effective heat of combustion values were decreased by 50%, 27% and 32%, respectively, in comparison to those of neat EP. The enhanced flame retardant behavior was attributed to the improved quality of char residue, which effectively inhibited the flammable volatiles, oxygen and heat transfer between degradation zone and flame zone. The impact strength was increased to 19.14 kJ/m2 for EP/PTCP-30% composite from 14.85 kJ/m2 for neat EP, indicating the toughening effect of PTCP on EP. The findings in this study demonstrated that PTCP could be used as a promising flame retardant toughening agent for epoxy resins to overcome their drawbacks of intrinsic brittle and high flammability.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）