Flame‐retardant properties and mechanisms of epoxy thermosets modified with two phosphorus‐containing phenolic amines

Two phosphorus‐containing phenolic amines, a 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO)‐based derivative (DAP) by covalently bonding DOPO and imine (SB) obtained from the condensation of p‐phenylenediamine with salicylaldehyde, and its analog (AP) via the addition reaction between diethyl phosphite and SB, were used to prepare flame‐retardant epoxy resins. The burning behaviors and dynamic mechanical properties of epoxy thermosets were studied by limited oxygen index (LOI) measurement, UL‐94 test, and dynamic mechanical analysis. The flame‐retardant mechanisms of modified thermosets were investigated by thermogravimetric analysis, Py‐GC/MS, Fourier transform infrared, SEM, elemental analysis, and laser Raman spectroscopy. The results revealed that epoxy thermoset modified with DAP displayed the blowing‐out effect during UL‐94 test. With the incorporation of 10 wt % DAP, the modified thermoset showed an LOI value of 36.1% and V‐0 rating in UL‐94 test. The flame‐retardant mechanism was ascribed to the quenching and diluting effect in the gas phase and the formation of phosphorus‐rich char layers in the condensed phase. However, the thermoset modified with 10 wt % AP only showed an LOI value of 25.7% and no rating in UL‐94 test, which was possibly ascribed to the mismatching of charring process with gas emission process during combustion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43953.     

Flame retardancy and dielectric properties of dicyclopentadiene‐based benzoxazine cured with a phosphorus‐containing phenolic resin

A dicyclopentadiene‐based benzoxazine (DCPDBZ) was prepared and separately copolymerized with melamine–phenol formaldehyde novolac or phosphorus‐containing phenolic resin (phosphorus‐containing diphenol) at various molar ratios. Their curing behaviors were characterized by differential scanning calorimetry. The electrical properties of the cured resins were studied with a dielectric analyzer. The glass‐transition temperatures were measured by dynamic mechanical analysis. The thermal stability and flame retardancy were determined by thermogravimetric analysis and a UL‐94 vertical test. These data were compared with those of bisphenol A benzoxazine and 4,4′‐biphenol benzoxazine systems. The effects of the diphenol structure and cured composition on the dielectric properties, moisture resistance, glass‐transition temperature, thermal stability, and flame retardancy are discussed. The DCPDBZ copolymerized with phosphorus‐containing novolac exhibited better dielectric properties, moisture resistance, and flame retardancy than those of the melamine‐modified system. The flame retardancy of the cured benzoxazine/phosphorus‐containing phenolic resins increased with increasing phosphorus content. The results indicate that the bisphenol A and 4,4′‐biphenol systems with a phosphorus content of about 0.6% and the dicyclopentadiene system with a phosphorus content of about 0.8% could achieve a flame‐retardancy rating of UL‐94 V‐0. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

新一代环氧树脂固化剂的研究

研究了缩聚法合成天然长链取代酚醛胺固化剂（PCD），并对其固化环氧树脂（EP）的形成过程以及产物PCD—EP的力学性能等进行了探讨。红外光谱分析表明，羟甲基与多元胺氨基发生了缩合反应，接着其侧链氧化交联聚合得到PCD；PCD固化EP的过程中环氧基开环与氨基活泼氢发生加成反应，从而引起PCD—EP的进一步交联聚合。并得出n（腰果酚）：n（甲醛）：n（二乙烯三胺）物质的量比为1．0：1．0：1．1时，合成的PCD固化剂综合性能最佳。     

Flame‐retardant materials based on phosphorus‐containing polyhedral oligomeric silsesquioxane and bismaleimide/diallylbisphenol a with improved thermal resistance and dielectric properties

Polyhedral oligomeric silsesquioxane containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DP) was used to flame‐retard 4,4′‐bismaleimidophenyl methane (BDM)/2,2′‐dially bisphenol A (DBA) resins, and the integrated properties of the resins were investigated. The fire resistance of BDM/DBA resins containing DP was analyzed by limiting oxygen index (LOI) and vertical burning (UL94) tests. The results show that DP increased the LOI of the resins from 25.3 to 38.5%. The BDM/DBA resins were evaluated to have a UL‐94 V‐1 rating, which did not satisfy the high standards of industry. On the other hand, BDM/DBA containing DP achieved a UL‐94 V‐0 rating. The thermal stability and char formation were studied by thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy. TGA and scanning electron microscopy–energy‐dispersive X‐ray spectrometry measurements demonstrated that the DP resulted in an increase in the char yield and the formation of the thermally stable carbonaceous char. The results of Raman spectroscopy showed that the DP enhanced the graphitization degree of the resin during combustion. Moreover, the modified BDM/DBA resins exhibited improved dielectric properties. Specifically, the dielectric constant and loss at 1 MHz of the BDM/DBA/15% DP resin were 3.11 and 0.008, respectively, only about 93 and 73% of those of the BDM/DBA resin. All of the investigations showed that DP was an effective additive for developing high‐performance resins with attractive flame‐retardant and dielectric properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41545.     

Functionalized Graphene Oxide Based on Hydrogen‐Bonding Interaction in Water: Preparation and Flame‐Retardation on Epoxy Resin

A novel functionalized graphene oxide (f‐GO) decorated with phosphorus/nitrogen (P/N)‐containing molecules is fabricated using a facile water‐based procedure. The chemical structure and micro‐morphology are well characterized by a combination of experimental and theoretical methods. Reactive force field‐based molecular dynamics simulations reveal at the atomic level that the GO sheets are successfully functionalized with P‐N flame‐retardant molecules by means of hydrogen bonds. Subsequently, f‐GO with extremely low loading is introduced into epoxy resin (EP) for reducing its flammability. Thermogravimetric analysis suggests that f‐GO significantly reduces the maximum mass loss rate of EP and enhances the char‐yield during heating. Combined with the results of a microscale combustion calorimeter and limiting oxygen index, EP/f‐GO2 shows better flame retardancy than the other nanocomposites. Furthermore, the presence of 2 wt% f‐GO substantially reduces the fire hazard of EP, resulting in 29.3% decline in the peak heat release rate, as well as 73% and 65% reduction in total smoke production and rate of smoke release, respectively, according to cone calorimetric tests. Based on the analyses of the char layers, f‐GO is determined to promote the formation of a more protective phosphorus‐containing char barrier for EP during combustion, indicating an effective condensed phase flame‐retardant mechanism.     

Flame‐retardant,glass‐fabric‐reinforced epoxy resin laminates fabricated through a gradient distribution mode

In general, epoxy resin (EP) glue mixed with a high content of flame retardants is used to coat glass fabrics layer by layer to prepare fire‐retardant printed circuit boards (PCBs). However, the addition of the flame retardants not only increases the cost but also greatly deteriorates the processability and mechanical properties of the PCBs. In this study, a gradient distribution mode of composite flame retardants was designed and applied in EP‐based PCB composites. Unlike the traditional uniform distribution mode, in which flame retardants are evenly distributed in every resin layer, the gradient mode concentrates a higher content of the flame retardants on the surface layer, and the concentrations are gradually reduced along the thickness. In this way, the surface resin can quickly form a condensed charring barrier to hold back fire; this effectively protects the underlying resin, which has lower contents of flame retardant. The results of this study show that PCB prepared by the gradient mode obtained satisfactory flame retardance (a UL94 V‐0 rating) with only a 3.5 wt % total amount of flame retardant; this value was much lower than that (6.3 wt %) of composites featuring a uniform distribution. Additionally, the gradient mode also maintained the mechanical properties of PCB better. The tensile, impact, and flexural strengths of the gradient distribution system were obviously higher than those of the uniform distribution one with the same content of flame retardant. On the basis of the mode, a more economic and efficient technology was developed to manufacture flame‐retardant layered PCB. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44369.     

Flame‐retardant cyanate ester resin with suppressed toxic volatiles based on environmentally friendly halloysite nanotube/graphene oxide hybrid

Development of high‐performance thermosetting resins by adding environmentally friendly flame retardant to heat‐resistant resins without deteriorating their outstanding thermal stability is an important research direction. Here, a unique hybrid (GHNT) consisting of graphene oxide (GO) and halloysite nanotubes (HNT) was synthesized, and then a series of composites based on cyanate ester (CE) resin were fabricated. The effects of GHNT on the heat resistance, flame retardancy, and smoke suppression of GHNT/CE composites were intensively investigated. The GHNT/CE composite with 5.0 wt % GHNT not only has about 15.1 °C higher initial degradation temperature, but also shows 54.6% or 37.9% lower peak heat release rate or maximum smoke density than CE resin. These results clearly demonstrate that GHNT is not the simple combination of GO and HNT; instead, it obviously shows positive synergistic effects in simultaneously improving the flame retardancy and thermal resistance of CE resin. The improved flame retardancy could be attributed to condensed‐phase mechanisms, including increasing char yield, building a dense char layer, and free radical scavenging. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46587.     

A facile way to prepare two novel DOPO‐containing liquid benzoxazines and their graphene oxide composites

The design, preparation, and properties of two DOPO‐containing compounds based on a cardanol‐allylamine‐paraformaldehyde benzoxazine (abbreviated as BZc‐a) were described in this article. By controlling the amount of DOPO, it could react with BZc‐a and generated different products. When DOPO: BZc‐a <1 : 1, DOPO reacted only with allyl group, and generated a containing single DOPO group benzoxazine (P₁B); When DOPO: BZc‐a ≧ 1 : 1, DOPO reacted not only with allyl group but also nucleophilic addition reaction, got a N‐substituted derivative P₂B, which contain double DOPO groups. The chemical structure of P₁B and P₂B was characterized by ¹H‐NMR and ¹³C‐NMR. Effect of DOPO on characteristics of BZc‐a was investigated. Fire test demonstrated that P₁B and P₂B showed better flame retardance than BZc‐a, and prepared two kinds of flame‐retardance resin based on BZc‐a. However, Field emission electron microscope observations showed the surface of P₁B and P₂B was very fragility, graphene oxide (GO) was chosen as to improve the surface performance. P₁B/GO‐3 wt % and P₂B/GO‐3 wt % composites were prepared by solution blending, and the thermal stability was studied by thermogravimetric analysis. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41634.     

Flame‐retardant and thermal degradation mechanism of low‐density polyethylene modified with aluminum hypophosphite and microencapsulated red phosphorus

Aluminum hypophosphite (AHP), a novel flame retardant, was used to improve the flame retardancy of low‐density polyethylene (LDPE) with microencapsulated red phosphorus (MRP). The synergistic effect between MRP and AHP was investigated by the limiting oxygen index (LOI), vertical burning test (UL‐94), and thermogravimetric analysis. When the contents of MRP and AHP were 10 and 30 phr, the LOI of LDPE/10MRP/30AHP composite was 25.5%, and it passed the UL‐94 V‐0 rating (the number before “MRP” and “AHP” is the loading of MRP and AHP, In LDPE/10MRP/30AHP, the content of the LDPE, MRP and AHP is 100phr, 10phr and 30phr, where phr refers to parts per hundreds of resin). The results of cone calorimetry testing show that the heat release rate of the composites was significantly reduced, and the strength of the char layer improved when the loading of AHP increased. The thermal stability of the LDPE/10MRP/30AHP composite was enhanced. The structure of the char was investigated by Fourier transform infrared spectrometry and scanning electron microscopy/energy‐dispersive spectrometry. The results indicate that AHP promoted the formation of stable char. This research provided a good way to prepare flame‐retardant materials with a halogen‐free flame retardant and contributed to environmental protection. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43225.     

A Novel DOPO‐Based Diamine as Hardener and Flame Retardant for Epoxy Resin Systems

10‐Ethyl‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide ( 1 ) can be nitrated using acetic anhydride and fuming nitric acid. The nitro group is reduced using palladium on charcoal and hydrogen. These reaction conditions are used for the synthesis of an analogous DOPO‐based diaminic hardener ( 7 ). An evaluation of the curing behavior, mechanical properties and flammability of a neat resin made of DGEBA and 7 (DGEBA + 7 ) and of a carbon fiber‐reinforced resin made of DGEBA, 4,4′‐diaminodiphenylsulfon (DDS) and 7 (DGEBA + DDS + 7 ) shows the potential of this hardener to lead to flame‐retardant systems while keeping relevant properties on a high level; especially when compared to a similar system (DGEBA + DDS + 1 ).

     

Effect of triphenyl phosphate flame retardant on properties of arylamine‐based polybenzoxazines

Three types of arylamine‐based benzoxazine resins modified with both condensed‐phase and gas‐phase action flame retardant, i.e. triphenyl phosphate (TPP) at various weight ratios were investigated. From rheological study, it was found that the viscosity of benzoxazines/TPP mixtures were significantly lower than that of the neat benzoxazine monomers suggesting flow property enhancement. Furthermore, differential scanning calorimetry results revealed that the onset and the maximum temperatures of the exothermic peak, due to the ring opening polymerization of benzoxazine resins, shifted to lower temperatures with increasing TPP. In addition, all polybenzoxazines possessed relatively high char yield, which increased as the TPP content increased thus enhancing their flame retardancy. The limiting oxygen index values of the flame retarded polybenzoxazines also increased with TPP addition. The maximum flame retardancy of UL94 V‐0 class was obtained with an addition of only few percents of TPP in the polybenzoxazines. Flexural strength, flexural modulus, and glass transition temperature of those polybenzoxazines tended to decrease with an addition of TPP mainly due to its plasticizing effect. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1074‐1083, 2013     

Addition‐curable propargyl‐containing novolac‐type phenolic resin: Its synthesis,characterization, cure,and thermal properties

In this article, propargyl functionalized novolac resins (PN resins), with varying propargyl contents and varying molecular weights, were synthesized conveniently. The structural characteristics were determined by ¹HNMR and FTIR methods. Thermal cure studies revealed that the uncatalyzed thermal cure was remarkably affected by propargyl extent, while it was hardly affected by molecular weight. The processability of the as‐prepared PN resins was excellent as matrix of composite materials. The cure mechanism was complicated; postcure at high temperature was required to achieve entire crosslink formation. Both dynamic mechanical analysis and thermogravimetric analysis showed that the cured PN resins had substantially improved thermal mechanical properties and thermal stability in comparison to conventional cured phenolics. High propargyl extent was preferred for high thermal stability. The results show that PN resin is one of the ideal candidates for advanced composites matrices in thermostructural and ablative applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1010–1017, 2006     

Flame‐retardant behavior of a phosphorus/silicon compound on polycarbonate

A phosphorus/silicon flame retardant, MVC‐DOPO, was synthesized from 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and 2,4,6,8‐tetra‐methyl‐2,4,6,8‐tetra‐vinyl‐cyclo‐tetrasiloxane (MVC) via addition reaction. Its flame‐retardant effect on polycarbonate (PC) was investigated. The phosphorus/silicon flame retardant increased the limited oxygen index and UL‐94 rating and reduced the heat release rate and total heat release of DOPO‐MVC/PC composites during combustion, indicating the excellent flame‐retardant effect of MVC‐DOPO on PC. MVC‐DOPO inhibited the burning intensity of PC material in the gaseous phase and promoted the formation of a more viscous residue in the condensed phase. Through releasing phosphorus‐containing pieces and phenoxy radicals from the phosphaphenanthrene group, MVC‐DOPO quenched the combustion chain reaction in the gaseous phase; through promoting formation of a more viscous residue and a dense char layer from the main actions of the cyclotetrasiloxane group, MVC‐DOPO reduced fuel release and generated a barrier effect in the condensed phase. Hence, MVC‐DOPO effectively exerted a flame‐retardant effect on PC material in both the gaseous and condensed phases during combustion. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45815.     

含硅聚氨酯改性水性环氧固化剂的制备与性能

以聚醚二元醇(N210)、异佛尔酮二异氰酸酯(IPDI)、羟基硅油为原料,合成了异氰酸酯基封端的含硅聚氨酯预聚体(PU-Si),再以PU-Si、环氧树脂E-51、丁基缩水甘油醚单封端的四乙烯五胺(TEPA-660a)为主要原料,制备了含硅聚氨酯改性水性环氧树脂固化剂,将制得的环氧树脂固化剂与环氧树脂E-51混和制得固化膜。用FTIR、TEM、SEM、TG和水接触角测试仪对聚合物的结构与性能进行了表征与测试,并考察了PU-Si含量对固化剂乳化性能、固化膜力学性能、热性能、断面形貌及吸水率的影响。结果表明:当固化膜中PU-Si的质量分数达到18%时,固化膜的综合性能最佳,此时冲击强度为22.45 k J/m~2,拉伸强度为44.7 MPa,热失重5%和50%时的温度分别为205.0和373.8℃,水接触角为96.8°,吸水率仅1.35%,与纯环氧树脂固化膜相比,其柔韧性、耐热性、耐水性等性能均有显著提高。     

Synthesis,Characterization, and Properties of Multifunctional Epoxy Maleimide Resins

Summary: Novel multifunctional formaldehyde resins bearing diaminodiphenylmethane groups are synthesized by the polymerization of a mixture of diaminodiphenylmethane (DDM), o‐cresol (o‐Cz), and cyclohexanone (CH_x) with formaldehyde (FA) (at a molar ratio of monomers/formaldehyde, 1/1), in the presence of acid catalyst (HCl). The obtained resins are epoxidated with a large excess of epichlorohydrin and transformed into multifunctional epoxy resins. The multifunctional epoxy maleimide resins are obtained by reaction of the epoxy resins with carboxy phenyl maleimide in the presence of triethylamine as a catalyst. The resultant resins are characterized by IR and NMR spectroscopy, elemental, and thermal analysis. The curing and thermal behavior of these epoxy maleimide resin/DDM systems are investigated using differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques. The activation energies of the curing reactions are situated in the range of 53–90 kJ · mol^?1. The cured products have good thermal properties, and activation energies of degradation reactions have values between 42–74 kJ · mol^?1.

The curing reaction of multifunctional epoxy maleimide resins with DDM.     

Simultaneously Improving the Thermal,Flame‐Retardant and Mechanical Properties of Epoxy Resins Modified by a Novel Multi‐Element Synergistic Flame Retardant

To obtain epoxy resins with satisfactory thermal, flame retardant, and mechanical properties, a novel multi‐element synergistic flame retardant (PPVSZ) is synthesized through the reaction between P? H of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and C?C of polysilazane (PVSZ) and utilized as a multi‐element synergistic flame retardant for epoxy resins. The flame retardant mechanism is explored by XPS and SEM, confirming that the excellent flame‐retardance efficiency owes itself to an optimal flame retardant way which jointly exerts the flame‐retardant effects in the gaseous and condensed phase. The thermal properties deduced from DSC, TGA, and DMA, indicate the glass transition temperature, maximum weight loss rate, and char yields at 700 °C for EP‐2 increase by about 5.0 °C, 8.4 °C and 8.8%, respectively. Furthermore, mechanical properties such as impact strength, tensile strength, and flexural strength are also increased by 45.38%, 14.16%, and 17.43%, respectively, which show that the incorporation of PPVSZ does not deteriorate the mechanical properties of modified resin. All the results demonstrate that epoxy resins modified by PPVSZ not only have good effect on the flame retardance, but also have good improvement on thermal and mechanical properties, indicating the potential for applications in many fields requiring fire safety.     

Flame Retardancy and Mechanical Properties of Bio‐Based Furan Epoxy Resins with High Crosslink Density

This work outlines an interesting approach to bioepoxy resins from sustainable 2,5‐bis((oxiran‐2‐ylmethoxy)methyl)furan (BOF). The 3,3′‐diamino diphenyl‐sulfone (33DDS) and 4,4′‐diamino diphenyl‐sulfone (44DDS) are employed as hardeners. For comparison, petro‐based networks from diglycidyl ether of bisphenol A (DGEBA) are developed as well. The systematic analyses suggest that the BOF/DDS networks show higher crosslink densities and mechanical properties than DGEBA/DDS thermosets. Remarkably, an attractive multilayer tubular microstructure is fabricated in the BOF/44DDS thermosets, and it greatly enhances the mechanical performance. Apart from that, BOF/DDS composites exhibit excellent flame retardancy. Especially, for BOF/44DDS, the self‐extinguishment happens in 7 s. The fire retardant mechanism confirms that a low heat release rate and heat release capacity as well as a compact char layer occur in the pyrolysis of BOF/DDS. Thus, the BOF/DDS exhibits superior performance over its DGEBA counterparts and meets a wide variety of requirements in engineering.     

磷-氮阻燃固化剂的合成及对环氧树脂性能影响

以苯膦酰二氯(PPDC)和间苯二甲胺(MXDA)为原料,合成了一种磷-氮阻燃固化剂(PPMXD)。采用FTIR、1HNMR、ESI-MS、TGA和DSC对该化合物进行了表征。考察了原料物质的量比、溶剂种类及配比、反应温度、反应时间对PPMXD产率的影响。结果表明,PPMXD的最佳合成条件为:反应温度为20℃,反应时间为7 h,n(PPDC)∶n(MXDA)=1.0∶3.5,采用N,N二甲基甲酰胺(DMF)与二氯甲烷体积比为1∶17的混合液作为溶剂,m(溶剂)∶m(PPDC)=12∶1。将PPMXD应用于环氧树脂(E-51)的固化及阻燃,用TGA和SEM对复合材料的热性能及残炭结构进行了表征,通过极限氧指数(LOI)和垂直燃烧(UL-94)实验表征了试样的阻燃性能。当PPMXD添加量为40%(以E-51的质量为基准)时,样品EP2的LOI达到29.0%,可通过UL-94 V-0测试,拉伸强度和冲击强度分别达到42.89 MPa和6.45 k J/m~2。TGA结果显示,PPMXD的加入使EP2最大热失重速率由纯E-51的18.23%/min降低到12.73%/min,800℃时的残炭量由16.12%提高到18.86%。SEM结果表明,环氧树脂燃烧后残炭表面粗糙,发泡明显,PPMXD对环氧树脂表现出了良好的阻燃性能。