New epoxy resins. II. The preparation,characterization, and curing of epoxy resins and their copolymers

A polymer having high aromaticity and/or cyclic ring structures in the chain backbone usually gives high heat resistance and flame resistance. Five glycidyl ether-type epoxy resins are prepared from bisphenol A (DGEBA), 9,9-bis(4-hydroxyphenyl)fluorene (DGEBF), 3,6-dihydroxyspiro-[fluorene-9,9′-xanthane] (DGEFX), 10,10-bis(4-hydroxyphenyl) anthrone (DGEA), and 9,9,10,10-tetrakis(4-hydroxyphenyl)anthracene (TGETA) in order to study structure–thermal stability–flame resistance property relationships. In this study, trimethoxyboroxine (TMB) and diaminodiphenylsulfone (DDS) are employed as the curing agents. The char yield at 700°C under a nitrogen atmosphere and the glass transition temperature (T_g) for the uncured resins decrease according to the sequence TGETA > DGEFX > DGEA > DGEBF > DGEBA. The Tg values for these cured epoxy resins are DGEBA < DGEBF < DGEFX < DGEA. A T_g for the TGETA is not obtainable but would be expected to be the highest. The char yields at 700°C of these cured epoxy resins have the same trend as the uncured resins. DGEBF, DGEFX, DGEA, and TGETA added to the DGEBA system show increases in the char yield, T_g, and oxygen index with increasing concentration of these novel epoxy resins.     

Studies on thermosetting bisimide resins based on N,N-(4-aminophenyl)-p-quinone diimine

The paper describes two novel bisimide resins, i. e. MQA and NQA, prepared by reacting N,N'-(4-aminophenyl)-p-benzoquinone diimine (QA) with maleic anhydride or 5-norbornene-2,3-dicarboxylic (nadic) anhydride in glacial acetic acid. These resins were characterised by IR spectroscopy, DSC and thermogravimetric analysis. The char yield (at 800°C) in nitrogen atmosphere for MQA and NQA was found to be 56% and 61%, respectively. Chain extension of bismaleimides containing flexible ether linkages, i. e. 1,3-bis(4-maleimidophenoxy)benzene and 1,4-bis(4-maleimidophenoxy)benzene with QA was also carried out. The thermal stability of the chain-extended bismaleimide resins was lower than that of the neat bismaleimide resins.     

Tris(3-aminophenyl)Phosphine oxide-based nadimide resins. II

A series of phosphorus-containing nadimide end-capped resins having different backbones was prepared by reacting endo-5-norbornene-2-3-dicarboxylic acid anhydride (nadic anhydride), pyromellitic dianhydride (PMDA)/3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA)/2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6F) and tris(3-aminophenyl)phosphine oxide (TAP) in glacial acetic acid/acetone. Structural characterization of the resins was done by elemental analysis, FTIR, and ¹H-NMR. Thermogravimetric studies revealed a multistep decomposition reaction for uncured resins. Residual weight at 800°C in nitrogen was found to be 50–60%. Resins cured at 300°C for 1 h in air atmosphere were stable up to 440 ± 20°C and decomposed in a single step above this temperature. The char yields of cured resins were in the range 63–71.5%. © 1992 John Wiley & Sons, Inc.     

Effect of the NCO/OH ratio on the properties of Mesua Ferrea L. seed oil‐modified polyurethane resins

A series of polyurethane resins with varying NCO/OH ratios (0.8–2.0) has been synthesized from the monoglyceride of Mesua Ferrea L. seed oil, poly(ethylene glycol) (M_n, 200 g mol^?1) and 2,4‐toluene diisocyanate in the presence of dibutyl tin dilaurate as the catalyst. The effects of the NCO/OH ratios of the synthesized resins on the physical properties, such as hydroxy values, acid values, saponification values, iodine values, specific gravities and isocyanate values have been studied. The formation of the polyurethane resins was confirmed by viscosity measurements, and FTIR, UV and ¹H NMR spectroscopic studies. Performance characteristics, such as impact resistance, flexibility, gloss, hardness, adhesive strength and chemical resistance, of the cured resins were investigated as a function of the varying NCO/OH ratios, with an influence of these ratios being observed for most of the above properties. Thermogravimetric analysis (TGA) demonstrated that the thermal stabilities of the cured resins increased with an increase in the NCO/OH ratios. The amounts of char residues at 550 °C were also found to be greater for higher NCO/OH ratios of the oil‐modified polyurethane resins. Copyright © 2005 Society of Chemical Industry     

Addition polyimides. I

Crosslinking of 4,4′(bismaleimido)diphenyl ether (BM) was investigated in presence of bis(m-aminophenyl)methylphosphine oxide (BAP), tris(m-aminophenyl)phosphine oxide (TAP), diaminodiphenyl ether (E) and 3,3-bis(p-aminophenyl)phthalide (AP). These crosslinked resins were examined for thermal stability by thermogravimetric analysis. A slight decrease in initial decomposition temperature, the temperature of maximum rate of weight loss, was observed, though the char yield in nitrogen atmosphere at 800°C did not change appreciably. Glass-cloth-reinforced laminates were fabricated from BM and amine mixtures. An improvement in mechanical properties was observed in the presence of phosphorus-containing di- and triamines.     

Organic/inorganic hybrid bismaleimide resin with octa(aminophenyl)silsesquioxane

Octa(aminophenyl)silsesquioxane (OAPS) was prepared in two steps by the nitration of octaphenylsilsesquioxane (OPS) in fuming nitric acid to form octa(nitrophenyl)silsesquioxane (ONPS), followed by the mild reduction of ONPS with Pd/C as a catalyst. OPS, ONPS and OAPS were characterized by FTIR, ¹H NMR, and ²⁹Si NMR techniques. Modification of a bismaleimide (BMI) resin with OAPS and dipropargyl ether of bisphenol A (DPBPA) was investigated. The modified resins, OAPS/DPBPA/BMI, were characterized with DSC, FTIR and rheology analyses. The results showed that the modified resins have good processability. The DMA results indicated that the glass transition temperature (T_g) of the cured OAPS/DPBPA/BMI hybrid resins reached 350°C. The decomposition temperature (T_d5) of the cured resins decreased but the char yield (Y_c, 800°C) increased as the OAPS loading increased, especially in air. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

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.     

Novel phosphorus‐based flame retardants containing 4‐tert‐butylcalix[4]arene: Preparation and application for the fire safety of epoxy resins

A novel flame retardant (FR) containing phosphorus and 4‐tert‐butylcalix[4]arene was synthesized and characterized. The FR combined with ammonium polyphosphate (APP) was then incorporated into epoxy resins (EPs) at different ratios. The flame retardancy, thermal stability, and smoke‐releasing properties were investigated. The limiting oxygen index was as high as 30.8% when the mass fraction ratio of the FR to APP was 1:2. The improved FR effect have been due to the combined FR effects between the FR and APP. The char residue content at 800 °C under a nitrogen atmosphere increased notably from 8.22% to 17.6% when the FR APP was incorporated into EP; this indicated an improvement in the thermooxidation resistance. From the cone test, we found that both the total heat‐release and peak heat‐release rate of the FR resins were reduced. Compared to the resins containing no FRs, the smoke‐production rate and total smoke‐production results indicate that the FR resins also exhibited good smoke‐suppression properties. Generally, the stable char layer of the FR APP–EP not only effectively prevented the release of combustion gases but also hindered the propagation of oxygen and heat into the interior substrate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45105.     

Thermal and Flame Retardation Properties of Melamine Phosphate-Modified Epoxy Resins

We have synthesized a series of epoxy resins containing melamine phosphate (MP) and investigated their thermal and flame retardation properties. MP functions as a hardener and a flame retardant or as an additive of the cured epoxy resin to enhance flame retardation properties of epoxy resins. The reactions of DGEBA cured in the presence of MP were monitored by NMR and FTIR. Our results show that in both reactive and additive modes, MP is effective in increasing limiting oxide index (LOI) and the char yields of epoxy resins at lower phosphorous content. We observed that flame retardation by MP in its reactive mode is better than in its additive mode; the same phenomenon was found also for the glass-transition temperature (T _g). Thermogravimetric analysis (TGA) demonstrated that epoxy resins containing MP decompose at relatively lower temperatures than those lacking MP; this decomposition results in a protective layer forming that prevents the epoxy resins from decomposing further by combustion.     

Phenolic resins with phenyl maleimide functions: Thermal characteristics and laminate composite properties

Phenolic resins bearing varying concentrations of phenyl maleimide functions were synthesized by copolymerizing phenol with N‐(4‐hydroxyphenyl)maleimide (HPM) and formaldehyde in the presence of an acid catalyst. The resins underwent a two‐stage curing, through condensation of methylol groups and addition polymerization of maleimide groups. The cure characterization of the resin by dynamic mechanical analysis confirmed the two‐stage cure and the dominance of maleimide polymerization over methylol condensation in the network buildup process. The kinetics of both cure reactions, studied by the Rogers method, substantiated the earlier proposed cure mechanism for each stage. Although the initial decomposition temperature of the cured resin was not significantly improved, enhancing the crosslink density through HPM improved thermal stability of the material in a higher temperature regime. The anaerobic char yield also increased proportional to the maleimide content. Isothermal pyrolysis and analysis of the char confirmed that pyrolysis occurs by loss of hydrocarbon and nitrogenous products. The resins serve as effective matrices in silica‐ and glass fabric–reinforced composites whose mechanical properties are optimum for moderately crosslinked resins, in which failure occurs through a combination of fiber debonding and resin fracture. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1664–1674, 2001     

New epoxy resins. I. The stability of epoxy–trialkoxyboroxines triaryloxyboroxine system

A polymer with high aromaticity and/or cyclic ring structures chain backbone usually has high heat, thermal, and flame resistance. Two diglycidyl ethers of bisphenols were prepared from 4,4′ isopropylidenediphenol (DGEBA) and 9,9-bis(4-hydroxyphenyl) fluorene (DGEBF) for evaluation. Four boroxines—trimethoxyboroxine (TMB), triethoxyboroxine (TEB), triisopropoxyboroxine (TIPB) and triphenoxyboroxine (TPB)—were used as the curing agents. DGEBA and DGEBF cured with various boroxines indicate that the trend for their respective glass transition temperature (T_g's), degradation temperatures (T_d's), and gel fractions are TMB-cured epoxy ≈ TEB-cured epoxy < TIPB cured epoxy < TPB cured epoxy. The DGEBF system usually has a higher T_g, T_d, gel fraction, oxygen index (OI), and char yield than the related DGEBA system. DGEBF/DGEBA (80/20 mol ratio) shows a synergistic effect in regard to char formation. This effect exists not only in the copolymer system but also in blended homopolymers of the separately cured resins. A modified mechanism for the polymerization of phenyl glycidyl ether (PGE) with TMB has been proposed.     

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.     

Curing behavior,thermal, and mechanical properties of epoxy resins cured with a novel liquid crystalline dicarboxylic acid curing agent

A novel di‐carboxylic acid curing agent (DACA) was successfully synthesized and cured with three different epoxy resins: glycidyl end‐capped poly(bisphenol‐A‐co‐epichlorohydrin) (pDGEBA, M_n = 377), N,N‐diglycidyl‐4‐glycidyloxyaniline (TGAP), and 4,4′‐methylenebis(N,N‐diglycidylaniline) (TGDDM). The cured epoxy exhibited excellent thermal stability, which was indicated by high initial degradation temperature (T_id) and char yield. The T_id values of cured epoxy were in the range of 327–338°C, and the char yields increased with increasing epoxy functionality. The char yields of cured DACA/pDGEPA, DACA/TGAP, and DACA/TGDDM samples were 21.1, 60.4, and 66.9%, respectively. In addition, the cured epoxy samples also showed low coefficients of thermal expansion and high storage moduli (E′), which were around 60 ppm/°C and 2800 MPa, respectively. The failure surfaces were ductile and rough, so the cured epoxy samples are expected to have high fracture toughness and impact strength. POLYM. ENG. SCI., 54:695–703, 2014. © 2013 Society of Plastics Engineers     

Effect of isomerization on thermal behaviour of bisitaconimides

The effect of isomerization of N,N′‐bisitaconimido‐4,4′‐diphenyl ether to the corresponding biscitraconimide on the curing characteristics and thermal stability of cured resins is described. Resins having bisitaconimide:biscitraconimide ratios of 23:77–93:7 were prepared by reacting 4,4′‐diaminodiphenyl ether with itaconic anhydride in solvents of different polarities and under different reaction conditions. Resins containing a higher proportion of citraconimide had a lower melting point (191 vs 208 °C). The curing exotherm was observed immediately after melting in all the resins and exothermic peak temperature reduced with increase in citraconimide content. Resins having a higher proportion of citraconimide on isothermal curing (200 °C, 2 h) and subsequent heating in nitrogen atmosphere degraded at a slightly lower temperature. However, the char yield at 800 °C did not show any systematic dependence on citraconimide content. © 2002 Society of Chemical Industry     

Development of a DOPO‐containing melamine epoxy hardeners and its thermal and flame‐retardant properties of cured products

In this study, a novel Schiff base of melamine used as flame‐retardant curing agent for epoxy resins, was synthesized via condensation reaction of 4‐hydroxybenzaldehyde with melamine, followed by the addition of 9,10‐dihydro‐9‐oxa‐10‐phosphaphen‐anthrene 10‐oxide (DOPO) to the resulting imine linkage. The structure of DOPO‐containing melamine Schiff base (P‐MSB) was characterized by Fourier transformed infrared spectroscopy, ¹H‐nuclear magnetic resonance (¹H‐NMR) and ³¹P‐NMR. The compound (P‐MSB) was used as a reactive flame retardant in o‐cresol formaldehyde novolac epoxy resin (CNE) to prepare flame‐retardant epoxy resins for electronic application. The thermal and flame‐retardant properties of the epoxy resins cured by various equivalent ratios phenol formaldehyde novolac (PN) and P‐MSB were investigated by the nonisothermal differential scanning calorimetry, the thermogravimetric analysis, and limiting oxygen index test. The obtained results showed that the cured epoxy resins possessed high T_g (165°C) and good thermal stability (T_5%, 321°C). Moreover, the P‐MSB/CNE systems exhibited higher limiting oxygen index (35) and more char was maintained in P‐MSB/CNE systems than that in PN/CNE system and the effective synergism of phosphorus–nitrogen indicated their excellent flame retardancy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Toward poly(furfuryl alcohol) applications diversification: Novel self‐healing network and toughening epoxy–novolac resin

Poly(furfuryl alcohol) bioresin (PFA) was synthesized and utilized through two distinct alloying strategies. It was crosslinked by a bismaleimide (BMI) via a Diels–Alder (DA) reaction. The novel PFA–BMI polyadduct network was spectrally, thermally, and thermo‐mechanically characterized and its thermally repeatable self‐healing behavior was visually established. The network showed a high pyrolytic thermostability (char yield ∼51% at 600 °C). PFA was also used for modification of epoxy–novolac resin (EP). EP hybrid resins containing 5, 10, and 15 wt % of PFA were cured by a polyamine hardener. Despite of different curing mechanisms of the two resins, PFA had no effect on EP curing behavior as revealed by differential scanning calorimetry, which proved homogeneous formation of the thermosets. PFA at the composition of 15 wt % improved tensile properties and toughness of EP, so that it almost doubled tensile modulus and elongation at break. However, PFA slightly deteriorated flexural properties of EP. PFA also decreased T_g of EP, with a maximum decrease of 22 °C. Besides, PFA disfavored initial thermostability of EP, but improved its pyrolytic char yield. In conclusion, PFA can be beneficial from smart materials to toughen hybrid epoxy thermosets with potential applications in composites, adhesives, and surface coatings. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45921.     

Curing of epoxy resins with 1-[di(2-chloroethoxyphosphinyl) methyl]-2,4-and -2,6-diaminobenzene

Fire-resistant compositions were prepared using 1-[di(2-chloroethoxyphosphinyl)methyl]-2,4- and -2,6-diaminobenzene (DCEPD) as a curing agent for typical epoxy resins such as EPON 828 (Shell), XD 7342 (Dow), and MY 720 (Ciba Geigy). In addition, compositions of these three epoxy resins with common curing agents such as m-phenylenediamine (MPD) or 4,4′-diaminodiphenyl-sulfone (DDS) were studied to compare their reactions with those of DCEPD. The reactivity of the three curing agents toward the epoxy resins, measured by differential scanning calorimetry (DSC), was of the order MPD > DCEPD > DDS. The relatively lower reactivity of DCEPD toward epoxy resins was attributed to electronic effects. It was shown that the heat of polymerization (ΔH_pol) increases with increasing epoxy functionality of the resin. The polymers obtained were characterized by DSC, thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and Fourier-transform infrared (FT-IR). The polymers of DCEPD showed a relatively lower polymer decomposition temperature (PDT) and a higher char yield than the polymers of the common curing agents. Furthermore, it was shown that the thermal characteristics of the compositions were dependent upon the ratio of the reactants. The fire resistance of the polymers was evaluated by determining their limiting oxygen index (LOI) value. The DCEPD polymers, especially those with polyfunctional epoxy resins, showed a significantly higher fire resistance as compared with those polymers of common curing agents.     

Novel modified bismaleimide resins with improved ablativity

To improve the ablativity of bismaleimide-type resins, a series of novel allyl compounds containing boron in their molecular structure, designated as ACB, were synthesized and characterized. The copolymers made up of 4,4′-bismaleimidodiphenyl methane (BDM) and each ACB were prepared. The properties of the prepolymers and cured resins were all studied in detail. Results show that the prepolymers of BDM/ACB systems have similar processing characteristics such as solubility in acetone and reactivity to those of ordinary BMI resins made up of BDM and allyl compounds without boron, such as the famous BDM/BA (O,O′-diallylbisphenol A) system, while the thermal resistance and ablativity of the former are better than those of the latter. Thermogravimetric analysis (TGA) in a nitrogen atmosphere revealed that the BDM/ACB systems were stable up to 480°C and their char yields at 800°C under anaerobic conditions were more than 50%. However, the char yield at 700°C of the BDM/BA system is only about 21%. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1623–1631, 1999     

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,characterization, and thermal properties of tris (3‐aminophenyl) phosphine oxide‐based nadimide resins

This article describes the synthesis, characterization, and thermal properties of nadimides obtained by reacting endo‐5‐norbornene‐2,3‐dicarboxylic acid anhydride (nadic anhydride) (NA), 4,4′‐oxodiphthalic anhydride (ODA), 1,4,5,8‐naphthalene tetra carboxylic dianhydride (NTDA) in glacial acetic acid/DMF. Structural characterization of the resins was done by elemental analysis, IR, ¹H‐NMR, and ¹³C‐NMR. The DSC scan showed the endothermic transition in the temperature range of 120–270°C. Multistep decomposition was observed in the TG scan of uncured resins in nitrogen atmosphere. Isothermal curing of the resins was done at 250 and 300°C for 1 h in an air atmosphere. These cured resins were stable to (350 ± 30)°C and decomposed in a single step above this temperature. This may be due to the retro Diels Alder (RDA) reaction. The char yield of the resins increased significantly on curing. The char yield was highest for P‐2N resin and this could be due to the presence of rigid skeleton i.e. naphthalene. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008