Molecular design and properties of intrinsic flame-retardant P-N synergistic epoxy resin

In recent years, the poor weather resistance and aging resistance of additive flame retardants have caused researchers to pay attention to reactive flame retardants. A novel P-N coacting epoxy curing agent with intrinsic flame retardancy was designed and synthesized. The mechanical properties, crosslinking curing properties and flame-retardant properties of intrinsic flame-retardant epoxy resin were characterized. The results show that the cross-linking curing performance of hexa (3,5-diamino-1,2,4 triazolyl)-cyclotriphosphonitrile) (VCP) is lower than that of DDM. This is due to the decrease in cross-linking density caused by the VCP ring molecular structure. Therefore, the mechanical properties of the epoxy resin cured with VCP decreased, but the flame-retardant properties of the material significantly improved. The limiting oxygen index of the VCP/EP flame retardant epoxy thermosets was 27.3%, reaching the UL 94 V-1 level. The peak heat release rate and total heat release rate of the VCP/EP flame retardant epoxy thermosets were significantly reduced. The flame retardancy mechanism was studied by Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, and x-ray photoelectron spectroscopy. The results show that the intrinsic flame-retardant P-N coacting epoxy resin has excellent curing and flame-retardant properties.     

A P/N-containing flame retardant constructed by phosphaphenanthrene,phosphonate, and triazole and its flame retardant mechanism in reducing fire hazards of epoxy resin

A P/N-containing flame retardant (PPT) constructed by phosphaphenanthrene, phosphonate, and triazole groups was successfully synthesized and used as a reactive co-curing agent for epoxy resin (EP). The curing behavior, thermal property, combustion behavior, and flame retardant mechanism of EP thermosets were comprehensively investigated. According to the analysis of DSC and TGA, PPT accelerated the crosslinking reaction and enhanced the charring ability for EP thermosets at high temperature. The results of combustion test indicated that PPT endowed epoxy thermoset with outstanding flame retardancy. When the phosphorus content was 0.71 wt%, EP/DDS/PPT-2 achieved a LOI value of 33.2% and passed V-0 rating in UL-94 test, and its peak heat release rate and total heat release were decreased by 63.7 and 30.5%, respectively, relative to EP/DDS. Moreover, the FIGRA of EP/DDS/PPT-2 was reduced from 9.7 to 3.5 kW m⁻² s⁻¹, manifesting the significantly improved fire safety of EP thermoset. The flame retardant mechanism was summarized as two parts: (a) the barrier effect of continuous phosphorus-rich char layers in condensed phase, (b) the quenching effect of phosphorous radicals and diluting effect of nonflammable gases in gaseous phase.     

Synthesis of bio-based reactive N/P flame retardant and its curing and flame retarding behavior in epoxy resins

In this study, a pioneering bio-based nitrogen–phosphorus flame retardant and curing accelerator named oxime-phosphazene hexakis [(4-(hydroxyimino) 2-methoxy) phenoxy] cyclotriphosphazene (HAPV) was successfully synthesized using hexachlorocyclotriphosphazene and vanillin. When 5 wt % HAPV was added into epoxy, the limiting oxygen index increased from 22% to 27% and passed UL-94 V-0 (UL is defined as Underwriters Laboratories) rating. Meanwhile, with the addition 5 wt% HAPV, the apparent activation energy (E_a) of HAPV/EP decreased from 20.22 to 67.15 kJ/mol, and the pHRR value was suppressed from 581.21 to 330.18 kW/m². It was due to that the HAPV quenched the combustion chain reaction through the gas phase and condensed phase, forming a dense char layer for blocking the heat transfer. Overall, the study provides an environmentally friendly epoxy flame retardant curing accelerator that shows great potential in epoxy flame retardant applications.     

Synthesis of a novel cross‐linked organophosphorus‐nitrogen containing polymer and its application in flame retardant epoxy resins

A novel cross‐linked organophosphorus–nitrogen polymetric flame retardant additive poly(urea tetramethylene phosphonium sulfate) defined as PUTMPS was synthesized by the condensation polymerization between urea and tetrahydroxymethyl phosphonium sulfate. Its chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy, ¹³C and ³¹P solid‐state nuclear magnetic resonance. The synthesized PUTMPS and curing agent m‐phenylenediamine were blended into epoxy resins to prepare flame retardant epoxy resin thermosets. The effects of PUTMPS on fire retardancy and thermal degradation behavior of EP/PUTMPS thermosets were investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter measurement, and thermalgravimetric analysis (TGA) tests. The surface morphologies and chemical compositions of char residues for cured epoxy resins were investigated by scanning electron microscopy and X‐ray photoelectron spectroscopy (XPS), respectively. Water resistant properties of epoxy resin thermosets were evaluated by putting the samples into distilled water at 70°C for 168 h. The results demonstrated that the EP/12 wt% PUTMPS thermosets successfully passed UL‐94 V‐0 flammability rating and the LOI value reached 31.3%. The TGA results indicated that the incorporation of PUTMPS promoted epoxy resin matrix decomposed and char forming ahead of time, which led to a higher char yield and thermal stability for epoxy resin thermosets at high temperature. The morphological structures and analysis of XPS for the char residues of the epoxy resin thermosets shown that PUTMPS benefited to the formation of a sufficient, more compact, and homogeneous char layer with rich flame retardant elements on the materials surface during burning, which prevented the heat transmission and diffusion, limited the production of combustible gases, inhibited the emission of smoke, and then led to the reduction of the heat release rate and smoke produce rate. After water resistance tests, EP/12 wt% PUTMPS thermosets still remained excellent flame retardancy. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and properties of a phosphate ester as curing agent in an epoxy resin system

Phosphate ester compounds display good flame retardancy effect in epoxy resin systems. In this paper, several novel phosphate esters, used as curing agents for epoxy resins, were synthesized based on P₂O₅, phosphoric acid, and different types of alcohol. The structures of phosphate esters were characterized by ³¹P nuclear magnetic resonance (³¹P NMR). Then, a series of flame retardant epoxy composites were prepared by curing the epoxy resins (E-44) with the phosphate esters. The flame retardancy and thermal degradation behaviors of flame retardant epoxy composites were investigated by cone calorimeter test (CCT) and thermogravimetric analysis (TGA), respectively. The results of CCT indicated that phosphate esters can significantly decrease heat release rate, total heat release (THR), and smoke production rate. The sample cured by butyl phosphate ester from phosphorus pentoxide, phosphoric acid and butanol showed the best flame retardant performance among all samples. The TGA results showed that phosphate esters could enhance char residues of flame retardant epoxy composites when compared with those of a composite using T31 as a curing agent at high temperature. It may be concluded that good flame retardant properties of flame retardant epoxy composites are related to the formation of a protective phosphorus-rich char layer. These phosphate esters have a good future on flame retardant epoxy composites.     

Intrinsic flame-retardant epoxy resin composites with benzoxazine: Effect of a catalyst and a low curing temperature

Three kinds of inherent flame-retardant epoxy resin (EP) composites with 20 wt % benzoxazine (BOZ) were prepared with different curing processes with 2-methyl-1H-imidazole (MI) as a catalyst or/and changes in the curing temperature. The effects of the curing process on the flame retardancy, thermal stability, mechanical properties, and curing behaviors were investigated. The composite with added MI cured at low temperature (EBM–LT) had the best properties. It possessed a 35.3% limiting oxygen index and achieved a UL 94 V-0 rating. Thermogravimetric analysis indicated that EBM–LT had the best thermal stability among the three kinds of EP composites with BOZ. The EP composites with BOZ mainly displayed a condensed-phase flame-retardant mechanism. The mechanical properties improvement was attributed to the formation of a heterogeneous network. Differential scanning calorimetry indicated that MI reacted with EP and catalyzed the homopolymerization of BOZ, and EP reacted with BOZ. Fourier transform infrared spectroscopy analysis indicated that curing at lower temperature caused the formation of more homopolymers of BOZ. The relationship of the curing process, network structure, and properties of EP composites with BOZ was established; this could help with the design of high-performance EP composites with BOZ. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47847.     

Synthesis of a novel,multifunctional inorganic curing agent and its effect on the flame‐retardant and mechanical properties of intrinsically flame retardant epoxy resin

Traditional curing agents have only a single property, while traditional synthetic organic flame‐retardant hardeners often show poor tolerance to oxidants, strongly acidic or alkaline reagents, and organic solvents and have toxicity problems. Here, a novel and multifunctional flame‐retardant curing agent of the inorganic substrate multifunctional curing agent of the inorganic substrate (FCIN) was proposed first and successfully prepared, and then an intrinsically flame‐retardant epoxy resin (EP) was prepared by covalently incorporating FCIN nanoparticles (FCINs) into the EP. The curing behavior of the FCINs was investigated, showing that FCIN/EP expresses a higher global activation energy than tetraethylenepentamine (TEPA)/EP and that the FCINs had strong interfacial adhesion to the EP matrix. Additionally, the FCINs were well dispersed and provided a remarkable improvement in mechanical and flame‐retardant properties of the intrinsically flame‐retardant EP. With the incorporation of 9 wt % FCINs into the EP, dramatic enhancements in the strength, modulus under bending, and toughness (～36%, ～109%, and ～586%, respectively) were observed, along with 85.2%, 46.4%, 98.3%, and 77.26% decreases in the peak heat release rate, total heat release, smoke production rate peak, and total smoke production, respectively, with respect to that of TEPA/EP. The mechanisms of its flame‐retardant, smoke‐suppression, and failure behaviors were investigated. The development of this unconventional, multifunctional flame‐retardant curing agent based on an inorganic substrate showed promise for enabling the preparation of a variety of new high‐performance materials (such as intrinsically flame‐retardant EP and functional modified polyesters). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46410.     

Synthesis,thermal and mechanical behavior of a silicon/phosphorus containing epoxy resin

A liquid silicon/phosphorus containing flame retardant (DOPO–TVS) was synthesized with 9,10‐dihydro‐9‐oxa‐10‐phosphapheanthrene‐10‐oxid (DOPO) and triethoxyvinylsilane (TVS). Meanwhile, a modified epoxy resin (IPTS–EP) was prepared by grafting isocyanate propyl triethoxysilane (IPTS) to the side chain of bisphenol A epoxy resin (EP) through radical polymerization. Finally, the flame retardant (DOPO–TVS) was incorporated into the modified epoxy resin (IPTS–EP) through sol–gel reaction between the ethyoxyl of the two intermediates to obtain the silicon/phosphorus containing epoxy resin. The molecular structures of DOPO–TVS, IPTS–EP and the final modified epoxy resin were confirmed by FTIR spectra and ¹H‐NMR, ³¹P‐NMR. Thermogravimetric analysis (TGA), differential scanning calorimetry, and limiting oxygen index were conducted to explore the thermal properties and flame retardancy of the synthesized epoxy resin. The thermal behavior and flame retardancy were improved. After heating to 600°C in a tube furnace, the char residue of the modified resin containing 10 wt % DOPO–TVS displayed more stable feature compared to that of pure EP, which was observed both by visual inspection and scanning electron microscope (SEM). Moreover, the mechanical performance testing results exhibited the modified epoxy resins possessed elevated tensile properties and fracture toughness which is supported by SEM observation of the tensile fracture section. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42788.     

有机磷/硼杂化小分子阻燃改性环氧树脂

从二苯基次膦酰氯和苯基磷酰二氯出发,分别合成了含单个苯硼酸基团和含两个苯硼酸基团的两种有机磷/硼杂化小分子（缩写为：DPC-1B和PDS-2B）。两种杂化小分子与环氧树脂有着良好的相容性并可参与环氧固化,在比较低的添加量下便有较高的机械强度和优异的阻燃性能,且保持环氧的透明度。DPC-1B和PDS-2B添加量为2%（质量）时,复合材料氧指数从25.7%分别提高到了31.8%和31.5%,热释放速率峰值分别降低了26.5%与21.8%,UL-94阻燃等级均达到了V-0级。改性环氧树脂燃烧后的残炭分析表明,炭层外部连续紧密,内部多蓬松,硼磷共同作用形成致密炭层,隔绝热质传递,从而达到阻燃效果。     

Novel multi-element DOPO derivative toward low-flammability epoxy resin

In order to obtain cured epoxy resin (EP) with satisfactory thermal stability and flame retardancy, a multi-element P/N/Si-containing flame retardant (DPAK) was synthesized by a facile way and was used as a reactive flame retardant to prepare flame-retardant EP. The flame-retardant efficiency of DPAK was subsequently evaluated by limiting oxygen index (LOI), UL-94, and cone calorimeter (CC) test. With a low incorporation amount of DPAK (4 wt%), the resultant EP achieve to UL-94 V-0 rating, and the corresponding LOI value reached to 30%, which was higher than that of EP containing DOPO (2.9 wt%). More importantly, the thermogravimetric analysis (TGA) revealed their higher thermal stability than those of EP containing DOPO. Furthermore, dynamic mechanical analysis (DMA) shown the maintained glass transition temperature of DPAK-EP. The increase of CO/CO₂ ratio in the CC test for the DPAK-EP samples proved the gas-phase activity of DPAK. Additionally, DPAK showed evidence of condensed phase activity by increasing char residue in TGA and CC test. The scanning electronic microscope together with the energy dispersive X-ray spectrometer (SEM–EDX) and X-ray photoelectron spectroscopy (XPS) exhibited that DPAK promoted the formation of compacted phosphorus-silicon char layer. Subsequently, TG-FTIR results indicated that DPAK-EP produced lesser combustible gases than neat sample did, improving flame-retardant properties of epoxy resin.     

Preparation,mechanical properties,and thermal degradation of flame retarded epoxy resins with an organophosphorus oligomer

An organophosphorus oligomer, poly(DOPO-substituted hydroxyphenyl methanol pentaerythritol diphosphonate) (PFR), was synthesized from the dehydrohalogenation polycondensation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide substituted hydroxyphenyl methanol (DOPO-HBA) with 3,9-bis(chloro)-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5]undecane-3,9-dioxide (SPDPC). The structure of PFR was confirmed by FTIR, ¹H NMR, and ³¹P NMR. Advanced flame retardant epoxy resins (FREP) were obtained by incorporating PFR into EP, cured by 4,4′-diaminodiphenylmethane (DDM). Effects of PFR on thermal, dynamic mechanical properties, and flame retardant properties of the epoxy resins were investigated. The dynamic mechanical analysis (DMA) results showed that EP/PFR exhibited higher glass transition temperature than that of neat EP. Moreover, incorporation of PFR significantly enhanced the char yield at higher temperatures. The addition of PFR into epoxy resins significantly improved their flame retardancy, due to the reduction of peak heat release rate, total heat release as well as the mass loss rate.     

Synthesis of a novel phosphonate flame retardant and its application in epoxy resins

A novel phosphonate flame retardant additive bis(2,6‐dimethyphenyl) phenylphosphonate (BDMPP) was synthesized from phenylphosphonic dichloride and 2,6‐dimethyl phenol, and its chemical structure was characterized by Fourier transform infrared (FTIR) spectroscopy, ¹H and ³¹P nuclear magnetic resonance. The prepared BDMPP and curing agent m‐phenylenediamine were blended into epoxy resins (EP) to prepare flame retardant EP thermosets. The effect of BDMPP on fire retardancy and thermal degradation behavior of EP/BDMPP thermosets was investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter and thermalgravimetric analysis (TGA). The morphologies of char residues of the EP thermosets were investigated by scanning electron microscopy (SEM) and the water resistant properties of thermosets were evaluated by putting the samples into distilled water at 70°C for 168 h. The results demonstrated that the cured EP/14 wt % BDMPP composites with the phosphorus content of 1.11 wt % successfully passed UL‐94 V‐0 flammability rating and the LOI value was as high as 33.8%. The TGA results indicated that the introduction of BDMPP promoted EP matrix decomposed ahead of time compared with that of pure EP and led to a higher char yield at high temperature. The incorporation of BDMPP enhanced the mechanical properties and reduced the moisture absorption of EP thermosets. The morphological structures of char residue revealed that BDMPP benefited to the formation of a more compact and homogeneous char layer on the materials surface during burning, which prevented the heat transmission and diffusion, limit the production of combustible gases and then lead to the reduction of the heat release rate. After water resistance tests, EP/BDMPP thermosets still remained excellent flame retardancy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42765.     

Synthesis of a novel curing agent containing organophosphorus and its application in flame‐retarded epoxy resins

A novel amine‐terminated and organophosphorus‐containing compound m‐aminophenylene phenyl phosphine oxide oligomer (APPPOO) was synthesized and used as curing and flame‐retarding agent for epoxy resins. Its chemical structure was characterized by Fourier transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance (¹H NMR), ¹³C nuclear magnetic resonance, and ³¹P nuclear magnetic resonance. The flame‐retardant properties, combusting performances, and thermal degradation behaviors of the cured epoxy resins were investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter test, and thermogravimetric analysis. The EPO/APPPOO thermosets passed V‐1 rating with the thickness of 3.0 mm and the LOI value reached 34.8%. The thermosets could pass V‐2 rating when the thickness of the samples was 1.6 mm. The cone calorimeter test demonstrated that the parameters of EPO/APPPOO thermosets including heat release rate and total heat release significantly decreased compared with EPO/PDA thermosets. Scanning electron microscopy revealed that the incorporation of APPPOO into epoxy resins obviously accelerated the formation of the compact and stronger char layer to improve flame‐retardant properties of the cured epoxy resins during combustion. The mechanical properties and water resistance of the cured epoxy resins were also measured. After the water‐resistance test, EPO/APPPOO thermosets still remained excellent flame retardant and the water uptake was only 0.4%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41159.     

用于环氧树脂磷-氮阻燃固化剂的合成及应用

以1,2-环己二胺(DACH)和苯基膦酰二氯(PPDC)为原料合成了一种新型环氧树脂(EP)阻燃固化剂苯基膦酰-1,2-环己二胺(PPDAC),并用傅里叶变换红外光谱(FTIR)、氢核磁共振(¹HNMR)和热重分析仪(TGA)对其进行了表征,制备了系列PPDAC/EP,采用TGA、极限氧指数(LOI)、垂直燃烧试验和扫描电镜(SEM)研究了其热稳定性、阻燃性和炭层形貌。结果表明:PPDAC的填充可以提高EP树脂的阻燃性能,添加PPDAC的EP残炭率和阻燃性均得到提高,但其初始分解温度和力学性能下降。添加PPDAC的EP残炭表面发泡膨胀明显,阻燃效果优异。     

Grafting multi-elements hybrid polymer brushes on graphene oxide for epoxy composite with excellent flame retardancy

In this paper, a silicon-oxygen coupling agent (MPS) with a double bond is hydrolyzed with graphene oxide (GO) to obtain MPS-GO. The polymerization of MPS-GO with the phosphorus-containing monomer (HEPO) is initiated with 2,2′-Azobis(2-methylpropionitrile) (AIBN) to obtain multi-elements hybrid polymer brushes grafting graphene oxide (HM-GO). As a flame retardant, different amounts of HM-GO are added to obtain EP composites. In this system, the properties of composite flame retardant obviously increase with the increasing of HM-GO. The limiting oxygen index (LOI) value of composites with 4 wt% addition of HM-GO is 31.0%, while the LOI value of EP-0 is only 23.9%. And the peak heat release rate (PHRR) value is reduced from 515.8 W g⁻¹ of pure epoxy resin to 376.9 W g⁻¹. In addition, with the increase of HM-GO addition, the T_g value, flexural strength and flexural modulus of EP composites are improved. Through calculation, it is proved that the rising of T_g was due to the increase of crosslink density of the system. The flame retardant performance and mechanical properties of the composite materials are steadily improved, indicating that such flame retardants are dispersed well in the epoxy resin. HM-GO is an efficient macromolecular modified graphene oxide halogen-free flame retardant, which can improve both flame retardant properties and mechanical properties.     

A DOPO Derivative Constructed by Sulfaguanidine and Thiophene toward Enhancing Fire Safety,Smoke Suppression,and Mechanical Properties of Epoxy Resin

In order to eliminate the negative effect of traditional 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) -based flame retardants on heat resistance, mechanical properties, and curing process of epoxy resin (EP), a DOPO derivative (DST) constructed by sulfaguanidine and thiophene is designed and used as co-cured agent for EP. Compared with EP, the maximum decrease of glass transition temperature (T_g) in all EP/DST samples is less than 5%, indicating EP modified by DST maintains good heat resistance. Encouragingly, DST shows satisfactory flame-retardant efficiency and excellent smoke suppressing effects. EP containing barely 5 wt% of DST (P content: 0.37 wt%) achieves a UL-94 V-0 rating and 32.8% limited oxygen index (LOI) value. Its peak heat release rate (PHRR), total heat release (THR), and total smoke production (TSP) are also decreased by 31.2%, 18.8%, and 30.2% . Further, DST significantly improves mechanical properties of the EP/DDM/DST system. The tensile strength and modulus increase by 37.2% and 14.6%, respectively, as DST content is 7.5 wt%. It is revealed that DST has positive quenching and diluting effects in the gas phase, as well as promoting the formation of a compact char layer in the condensed phase.     

Flame retardancy and thermal degradation behaviors of epoxy resins containing bisphenol a bis (diphenyl phosphate) oligomer

Bisphenol A bis(diphenyl phosphate) oligomer (BBO) as flame retardant was synthesized, whose structure was characterized by IR and NMR. In all, 20% weight mixture polyphosphoric acid (APP) and BBO was doped into epoxy resins (EPs) to get 26.0% of limiting oxygen index and UL 94 V‐0. The degradation behavior of EP‐containing BBO/APP was studied by thermogravimetry, differential thermogravimetry, scanning electron microscopy, and cone calorimeter. The activation energies for the decomposition of EP samples are obtained using the method of Kissinger. The experimental results exhibited that for EP‐containing BBO/APP, compared with EP, initial decomposition temperature, maximum temperature at the peak position (T_m), and the activation energy for the decomposition are decreased, whereas the maximum weight loss rate (R_max), char yields, and the inherent thermal stability are increased. Meanwhile, heat release, smoke production, and CO yield and CO₂ yield of EP‐containing BBO/APP are much decreased compared with those of EP. The thermal degradation mechanism of EP‐containing BBO/APP has been proposed. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Flame retardancy and thermal properties of organoclay and phosphorous compound synergistically modified epoxy resin

Phosphorous flame retardants (PFRs) are common halogen‐free flame retardants. However, the flame retardancy of PFRs has not been fully exploited. Herein, the synergistic flame retardant effect of a typical phosphorous compound, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO), and organoclay on epoxy is studied. Results show that the peak of heat release rate (pHRR) and smoke production rate of modified epoxy resin (EP) with both 2.0 wt % phosphorus and 4.0 wt % organoclay are only 40% and 46% of that of neat EP resin, respectively, while the sole use of 2.0 wt % phosphorus only decrease the pHRR to 59% of that of neat EP resin. The structure and thermal decomposition behavior of as‐prepared nanocomposites are analyzed, and a synergistic flame retardant mechanism is proposed. This investigation opens a new approach to obtain halogen‐free EPs with higher flame retardancy and better overall properties than the EPs loaded with DOPO only. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43367.     

A bifunctional modifier endowing epoxy resin with outstanding flame retardancy and high impact strength

The flammability and brittleness are two major shortages of epoxy resin (EP). Normally, adding flame retardants can deteriorate the mechanical property of EP. Herein, in this work, a reactive flame retardant (DPPO-TES) containing both Si and P was synthesized and incorporated into EP. When the content of P is only 1.0 wt%, the LOI of the modified EP (DPPO-TES/EP) reaches to 33.2%, UL-94 passes V0, THR and pk-HRR are 377.6 kw/m² and 103.5 MJ/m², respectively, which is attributed to the high flame-retardant efficiency in both condense phase and gas phase. In addition, the flexible Si O Si chains in the structure can significantly improve the impact strength of DPPO-TES/EP. Therefore, as a bifunctional modifier, DPPO-TES has a wide application prospect for EP materials.     

含磷阻燃剂阻燃环氧树脂热降解动力学

以2-二苯基膦酰基-1,4-苯二酚(DPO-HQ)为阻燃剂制备了阻燃环氧树脂,利用动态热重分析法(TGA)研究了纯环氧树脂(EP)和阻燃环氧树脂(FR-EP)在不同升温速率下的热稳定性,建立了EP和FR-EP体系的动力学模型和非模型动力学(MFK),并对比分析了模型动力学和非模型动力学对于描述EP体系和FR-EP体系的适用性.结果表明:阻燃剂的引入降低了环氧树脂初始降解温度,但增加了残炭率.由Flynn-Wall-Ozawa方法和Coats-Redfern方法建立的模型动力学表征EP和FR-EP体系高温降解过程中误差较大,而非模型动力学能更准确地预测和描述EP和FR-EP体系的高温降解行为.