Thermal degradation and flame retardancy of epoxy resins containing intumescent flame retardant

Pentaerythritol diphosphonate melamine-urea-formaldehyde resin salt, a novel cheap macromolecular intumescent flame retardants (IFR), was synthesized, and its structure was a caged bicyclic macromolecule containing phosphorus characterized by IR. Epoxy resins (EP) were modified with IFR to get the flame retardant EP, whose flammability and burning behavior were characterized by UL 94 and limiting oxygen index (LOI). 25 mass% of IFR were doped into EP to get 27.2 of LOI and UL 94 V-0. The thermal properties of epoxy resins containing IFR were investigated with thermogravimetry (TG) and differential thermogravimetry (DTG). Activation energy for the decomposition of samples was obtained using Kissinger equation. The resultant data show that for EP containing IFR, compared with EP, IFR decreased mass loss, thermal stability and R _max, increased the char yield. The activation energy for the decomposition of EP is 230.4 kJ mol⁻¹ while it becomes 193.8 kJ mol⁻¹ for EP containing IFR, decreased by 36.6 kJ mol⁻¹, which shows that IFR can catalyze decomposition and carbonization of EP.     

A bio-based epoxy resin derived from p-hydroxycinnamic acid with high mechanical properties and flame retardancy

Recent advances in epoxy resins have been forward to achieving high mechanical performance, thermal stability, and flame retardancy. However, seeking sustainable bio-based epoxy precursors and avoiding introduction of additional flame-retardant agents are still of increasing demand. Here we report the synthesis of p-hydroxycinnamic acid-derived epoxy monomer (HCA-EP) via a simple one-step reaction, and the HCA-EP can be cured with 4,4′-diaminodiphenylmethane (DDM) to prepare epoxy resins. Compared with the typical petroleum-based epoxy resin, bisphenol A epoxy resin, the HCA-EP-DDM shows a relatively high glass transition temperature (192.9 °C) and impressive mechanical properties (tensile strength of 98.3 MPa and flexural strength of 158.9 MPa). Furthermore, the HCA-EP-DDM passes the V-1 flammability rating in UL-94 test and presents the limiting oxygen index of 32.6%. Notably, its char yield is as high as 31.6% under N₂, and the peak heat rate release is 60% lower than that of bisphenol A epoxy resin. Such findings provide a simple way of using p-hydroxycinnamic acid instead of bisphenol A to construct high-performance bio-based thermosets.     

A vanillin-derived flame retardant based on 2-aminopyrimidine for enhanced flame retardancy and mechanical properties of epoxy resin

In order to give epoxy resin good flame retardance, a novel bio-based flame retardant based on 2-aminopyrimidine (referred to as VAD) was synthesized from renewable vanillin as one of the starting materials. Its structure was confirmed by NMR and mass spectra. The epoxy resins containing VAD were prepared by utilizing 4,4-diaminodiphenylmethane (DDM) as a co-curing agent, and their flame-retardant, mechanical and thermal properties and corresponding mechanisms were studied. VAD accelerated the cross-linking reaction of DDM and E51 (diglycidyl ether of bisphenol A). 12.5 wt% VAD made the epoxy resin achieve UL-94 V-0 rating and its limited oxygen index (LOI) value increase from 22.4% to 32.3%. The cone calorimetric testing results revealed the decline in the values of total heat release (THR) and peak of heat release rate (pk-HRR) and the obvious enhancement of residue yield. A certain amount of VAD enhanced the flame inhibition, charring and barrier effects, resulting in good flame retardance of the epoxy resin. Furthermore, the tensile strength, flexural strength and flexural modulus of the epoxy resin with 12.5 wt% loading of VAD were 6.5%, 14.9%, 15.2% higher than those of EP, indicating the strengthening effect of VAD. This work guarantees VAD to be a promising flame retardant for enhancing the fire retardancy of epoxy resin without compromising its mechanical properties.     

The influence of mesoporous SiO2‐graphene hybrid improved the flame retardancy of epoxy resins

A novel mesoporous SiO₂‐graphene nanohybrid was successfully synthesized by a 1‐pot hydrothermal synthesis method using tetraethylortho silicate and graphene oxide as initial materials to improve the dispersion of graphene in epoxy matrix. Subsequently, the SiO₂‐graphene nanohybrids were added into epoxy resin to investigate their fire behaviors. It was found that the incorporation of the as‐prepared SiO₂‐graphene nanohybrids into epoxy resin obviously increased the flame retardancy, compared with those of neat epoxy. This attractive feature of SiO₂‐graphene epoxy nanocomposites was attributed to the barrier effect as well as the labyrinth effect contributed by SiO₂‐graphene in EP resin.     

Enhanced thermal properties and flame retardancy from a thermosetting blend of a phosphorus‐containing bismaleimide and epoxy resins

Epoxy resins modified by an organosoluble phosphorus‐containing bismaleimide (3,3′‐bis(maleimidophenyl) ­phenylphosphine oxide; BMPPPO) were prepared by simultaneously curing epoxy/diaminodiphenylmethane (DDM), and BMPPPO. The resulted epoxy resins were found to exhibit glass transition temperatures as high as 212 °C, thermal stability at temperatures over 350 °C, and excellent flame retardancy with Limited oxygen index (LOI) values around 40. Incorporation of BMPPPO into epoxy resins via the thermosetting blend was demonstrated to be an effective way to enhance the thermal properties and flame retardancy simultaneously. Copyright © 2003 John Wiley & Sons, Ltd.     

Novel nanocomposites based on epoxy resin and modified magnesium hydroxide: Focus on flame retardancy and mechanical properties

In this work, a novel multifunctional organic‐inorganic hybrid flame agent (AM‐MEL) was prepared from magnesium hydroxide nanosheets decorated by nitrilotrimethylene triphosphonic acid and melamine. Then, an intrinsic flame‐retardant epoxy resin (EP) was prepared by covalently incorporating AM‐MEL nanoparticles. Meanwhile, ammonium polyphosphate (APP) was added into EP to form an intumescent flame retardant system with AM‐MEL. The chemical structure of AM‐MEL was characterized by Fourier transform infrared spectra, X‐ray photoelectron spectroscopy, and scanning electron microscopy. With the incorporation of 5 wt% AM‐MEL and 15 wt% APP, EP/AM‐MEL/APP could reach a limiting oxygen index value of 32.0% and achieve UL‐94 V‐0 rating, along with 88.0%, 70.0%, 81.5%, and 87.3% decrease in the peak heat release rate, total heat release, total smoke production, and the peak CO production rate, respectively, with respect to that of pure EP. The mechanisms of its flame retardant and smoke suppression were investigated.     

Effect of a triazine ring‐containing charring agent on fire retardancy and thermal degradation of intumescent flame retardant epoxy resins

A triazine ring‐containing charring agent (PEPATA) was synthesized via the reaction between 2,6,7‐trioxa‐l‐phosphabicyclo‐[2.2.2]octane‐4‐methanol (PEPA) and cyanuric chloride. It was applied into intumescent flame retardant epoxy resins (IFR‐EP) as a charring agent. The effect of PEPATA on fire retardancy and thermal degradation behavior of IFR‐EP system was investigated by limited oxygen index (LOI), UL‐94 test, microscale combustion calorimetry (MCC), thermogravimetric analysis (TGA) and thermogravimetric analysis/infrared spectrometry (TG‐IR). The glass transition temperatures (T_g) of IFR‐EP systems were studied by dynamic mechanical analysis (DMA). The LOI values increased from 21.5 for neat epoxy resins (EPs) to 34.0 for IFR‐EP, demonstrating improved flame retardancy. The TGA curves showed that the amount of residue of IFR‐EP system was largely increased compared to that of neat EP at 700 °C. The new IFR‐EP system could apparently reduce the amount of decomposing products at higher temperatures and promotes the formation of carbonaceous charred layers that slowed down the degradation. Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation, thermal properties and flame retardancy of phosphorus- and silicon-containing epoxy resins

Phosphorus- and silicon-containing epoxy resins were prepared from (2,5-dihydroxyphenyl)diphenyl phosphine oxide (Gly-HPO), diglycidyloxy methylphenyl silane (DGMPS) and 1,4-bis(glycidyloxydimethyl silyl)-benzene (BGDMSB) as epoxy monomers and diaminodiphenylmethane (DDM), bis(3-aminophenyl)methyl phosphine oxide (BAMPO) and bis(4-aminophenoxy)dimethyl silane (APDS) as curing agents. Epoxy resins with different phosphorus and silicon content were obtained. Their thermal, dynamic mechanical and flame retardant properties were evaluated. The high LOI values confirmed that epoxy resins containing hetero-atoms are effective flame retardants, but a synergistic efficiency of phosphorus and silicon on flame retardation was not observed.     

Distinct alignment of benzene derivatives in stretched polystyrene and polybutylacrylate gels: Specific polymer–solute interactions

We have measured the alignment of a range of benzene derivatives in cross‐linked polystyrene and poly(butyl acrylate) using a small number of residual dipolar couplings and simple geometric considerations. For apolar solutes in polystyrene and protic solutes in poly(butyl acrylate), the preferred molecular orientation does not coincide with the longest molecular axis (steric aligment). This behavior may be explained by specific π–π and hydrogen bonding interactions between solute and polymer, respectively, the latter being confirmed by molecular dynamics simulations.     

Ultrasonic velocity and absorption on methylmetha acrylic resins

Ultrasonic velocity and absorption were studied in autocure and heatcure resin monomers at different temperatures. Ultrasonic velocity increased in the autocure sample while absorption was reduced. This is attributed to the presence of certain structural factors such as hydrogen bonding.     

Synthesis of a novel phosphorus‐containing curing agent and its effects on the flame retardancy,thermal degradation and moisture resistance of epoxy resins

A novel phosphorus‐containing compound diphenyl‐(1, 2‐dicarboxylethyl)‐phosphine oxide defined as DPDCEPO was synthesized and used as a flame retardant curing agent for epoxy resins (EP). The chemical structure of the prepared DPDCEPO was well characterized by Fourier transform infrared spectroscopy, and ¹H, ¹³C and ³¹P nuclear magnetic resonance. The DPDCEPO was mixed with curing agent of phthalic anhydride (PA) with various weight ratios into epoxy resins to prepare flame retardant EP thermosets. The flame retardant properties, combustion behavior and thermal analysis of the EP thermosets were respectively investigated by limiting oxygen index (LOI), vertical burning tests (UL‐94), cone calorimeter measurement, dynamic mechanical thermal analysis and thermogravimetric analysis (TGA) tests. The surface morphologies and chemical compositions of the char residues for EP thermosets were respectively investigated by scanning electron microscopy and X‐ray photoelectron spectroscopy (XPS). The water resistant properties of the cured EP were evaluated by putting the samples into distilled water at 70°C for 168 hr. The results revealed that the EP/20 wt% DPDCEPO/80 wt% PA thermosets successfully passed UL‐94 V‐0 flammability rating and the LOI value was as high as 33.2%. The cone test results revealed that the incorporation of DPDCEPO effectively reduced the combustion parameters of the epoxy resin thermosets, such as heat release rate and total heat release. The dynamic mechanical thermal analysis test demonstrated that the glass transition temperature (Tg) decreased with the increase of DPDCEPO content. The TGA results indicated that the incorporation of DPDCEPO promoted the decomposition of epoxy resin matrix ahead of time and led to a higher char yield and thermal stability at high temperatures. The surface morphological structures and analysis of the XPS of the char residues of EP thermosets revealed that the introduction of DPDCEPO benefited the formation of a sufficient, compact and homogeneous char layer with rich flame retardant elements on the epoxy resin material surface during combustion. The mechanical properties and water resistance of the cured epoxy resins were also measured. After water resistance tests, the EP/20 wt% DPDCEPO/80 wt% PA thermosets retained excellent flame retardancy, and the moisture adsorption of the EP thermosets decreased with the increase of DPDCEPO content in EP thermosets because of the existence of the P–C bonds and the rigid aromatic hydrophobic structure in DPDCEPO. Copyright © 2015 John Wiley & Sons, Ltd.     

Modified montmorillonite combined with intumescent flame retardants on the flame retardancy and thermal stability properties of unsaturated polyester resins

Modified montmorillonite‐containing phytic acid (PA‐MMT) has been prepared by acid treatment and then introduced into unsaturated polyester resin (UPR) with an intumescent flame retardant (IFRs). The flame retardancy and thermal degradation of UPR/IFRs/PA‐MMT were evaluated by a limiting oxygen index (LOI) test, a vertical burning test (UL‐94), a thermogravimetric analysis (TGA), and a cone calorimeter test (CCT). Besides, the mechanical properties were studied by a universal testing machine. The LOI value of UPR/IFRs/PA‐MMT composites was increased to 29.2%. The CCT results indicated that the incorporation of PA‐MMT and IFRs significantly improved the combustion behavior of UPR. The results of the mechanical properties indicated that 1.5 wt% loading of PA‐MMT in UPR/IFRs showed the highest improvement in flexural strength and tensile strength. The flame‐retardant mechanism of PA‐MMT/IFRs was examined and discussed based on the results of combustion behavior and char analysis.     

Columnar Aggregates of Azobenzene Stars: Exploring Intermolecular Interactions,Structure, and Stability in Atomistic Simulations

We present a simulation study of supramolecular aggregates formed by three-arm azobenzene (Azo) stars with a benzene-1,3,5-tricarboxamide (BTA) core in water. Previous experimental works by other research groups demonstrate that such Azo stars assemble into needle-like structures with light-responsive properties. Disregarding the response to light, we intend to characterize the equilibrium state of this system on the molecular scale. In particular, we aim to develop a thorough understanding of the binding mechanism between the molecules and analyze the structural properties of columnar stacks of Azo stars. Our study employs fully atomistic molecular dynamics (MD) simulations to model pre-assembled aggregates with various sizes and arrangements in water. In our detailed approach, we decompose the binding energies of the aggregates into the contributions due to the different types of non-covalent interactions and the contributions of the functional groups in the Azo stars. Initially, we investigate the origin and strength of the non-covalent interactions within a stacked dimer. Based on these findings, three arrangements of longer columnar stacks are prepared and equilibrated. We confirm that the binding energies of the stacks are mainly composed of π–π interactions between the conjugated parts of the molecules and hydrogen bonds formed between the stacked BTA cores. Our study quantifies the strength of these interactions and shows that the π–π interactions, especially between the Azo moieties, dominate the binding energies. We clarify that hydrogen bonds, which are predominant in BTA stacks, have only secondary energetic contributions in stacks of Azo stars but remain necessary stabilizers. Both types of interactions, π–π stacking and H-bonds, are required to maintain the columnar arrangement of the aggregates.     

Studies on Hydrogen Bonding Network Structures of Konjac Glucomannan

In this paper, the hydrogen bonding network models of konjac glucomannan （KGM） are predicted in the approach of molecular dynamics （MD）. These models have been proved by experiments whose results are consistent with those from simulation. The results show that the hydrogen bonding network structures of KGM are stable and the key linking points of hydrogen bonding network are at the O（6） and O（2） positions on KGM ring. Moreover, acety has significant influence on hydrogen bonding network and hydrogen bonding network structures are more stable after deacetylation.     

pH-dependent conformational switching in 2,6-benzamidodiphenylacetylenes

The conformational equilibrium of a pH-dependent switch based on an intramolecularly H-bonded diphenylacetylene can be predictably biased by using electron-donating or -withdrawing groups. Furthermore, protonation of the electron-donating dimethylamino group converts it into an electron-withdrawing dimethylammonium cation with a concomitant switch in conformation.     

Preparation of (Fe)MIL-101 on short carbon fibers to improve the flame retardancy,smoke suppression,and mechanical of epoxy resin

Nano (Fe)MIL-101 particles were grafted on the short carbon fibers (SCFs) by in situ growth method to prepare (Fe)MIL-101@SCFs. The flame-retarded composites of epoxy resin (EP) were fabricated with combination of (Fe)MIL-101@SCFs and ammonium polyphosphate (APP). The composites showed good flame retardancy, smoke suppression, and mechanical properties simultaneously. The main heat release rate peak of the flame-retarded composites was reduced and delayed evidently in comparison with pristine EP. The high amount of residual char with coherent and dense structure was formed owing to the catalytic char formation of (Fe)MIL-101 as well as the strengthening action of SCF. The improvement in mechanical properties of the flame-retarded composite was due to the reinforcement effects of (Fe)MIL-101@SCFs and its action of interfacial adjustment. This research solved the contradiction between the flame retardancy and mechanical properties of EP, and proposed a new method to prepare the mechanically reinforced and flame retardant EP.     

Modified cyanate ester resins with lower dielectric loss,improved thermal stability,and flame retardancy

Novel modified cyanate ester (CE) resins with decreased dielectric loss, improved thermal stability, and flame retardancy were developed by copolymerizing CE with hyperbranched phenyl polysiloxane (HBPPSi). HBPPSi was synthesized through the hydrolysis of phenyltrimethoxysilane, and its structure was characterized by ¹H‐NMR, ²⁹Si‐NMR, and Fourier transform infrared spectra. The effect of the incorporation of HBPPSi into CE resin on the curing behavior, chemical structure of cured networks, and typical performance of HBPPSi/CE resins were systemically evaluated. It is found that the incorporation of HBPPSi into CE network obviously not only catalyzes the curing of CE, but also changes the chemical structure of resultant networks, and thus results in significantly decreased dielectric loss, improved thermal stability, and flame retardancy as well as water absorption resistance. For example, in the case of the modified CE resin with 10 wt% HBPPSi, its limited oxygen index is about 36.0, about 1.3 times of that of neat CE resin, its char yield at 800°C increases from 31.6 to 35.4 wt%; in addition, its dielectric loss is only about 61% of that of neat CE resin at 1 kHz. All these changes of properties are discussed from the view of the structure–property relationship. The significantly improved integrated properties of CE resin provide a great potential to be used as structural and functional materials for many cutting‐edges fields. Copyright © 2011 John Wiley & Sons, Ltd.