Curing and pyrolysis of cresol novolac epoxy resins containing BABODOPN

This work investigates the curing kinetics, thermal stability, flammability, and decomposition kinetics of cresol novolac epoxy (CNE) cured with two curing agents, [1,4‐bis(3‐aminobenzoyloxy)‐2‐(6‐oxido‐6h‐dibenz(c,e)(1,2) oxaphosphorin‐6‐yl)‐naphthalene] (BABODOPN) and diamino diphenyl methane (DDM). The DSC curing study shows that the activation energy (E_a) can be estimated by Kissinger's method and the E_a of CNE/DDM, 54.3 KJ/mole, is one‐half that of CNE/BABODOPN, 112.6 KJ/mole; also, the glass transition temperature (T_g) of the latter, 479.5 K, is substantially higher than that, 383 K, of the former. Both increases are attributed to the incorporation of phosphorus‐containing a bulky pendant aromatic group into the BABODOPN molecule, which inhibits its mobility. In comparison with the conventional DDM system, the phosphorus‐nitrogen synergistic effect of BABODOPN improves the limiting oxygen index (LOI) from 26 to 47, and increases the char yield from 30.4% to 38.3%. Moreover, the CNE/BABODOPN system even exhibits better flame retardancy than the excellent CNE/ODOPN system, developed by the authors previously, because of the synergistic effect. Finally, the investigation of thermal gravimetric analysis (TGA) decomposition in N₂ by Ozawa's method demonstrates that the mean E_a declines as the phosphorus content increases, because the ease of decomposition of the phosphorus in the initiation stage facilitates the formation of an insulating layer. POLYM. ENG. SCI., 45:478–486, 2005. © 2005 Society of Plastics Engineers     

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     

Synthesis and properties of novel phosphorus‐containing hardener for epoxy resins

A novel phosphorus‐containing curing agent, 2‐(6‐oxid‐6H‐dibenz〈c,e〉〈1,2〉oxa‐phosphorin‐6‐yl) phenol formaldehyde novolac [OD‐PN], was prepared from phenol formaldehyde novolac resin (PN) and a reactive 2‐(6‐oxid‐6H‐dibenz〈c,e〉〈1,2〉oxa‐phosphorin‐6‐yl)chloride (ODC) while ODC was synthesized through reaction between o‐phenylphenol and phosphoryl trichloride. The compound (OD‐PN) was used as a reactive flame‐retardant in o‐cresol formaldehyde novolac epoxy resin (CNE) for electronic application. Owing to the rigid structure of ODC and pendant P group, the resulted phosphorus containing epoxy resin exhibited better flame retardancy, higher glass transition temperature, and thermal stability than the noncyclic P‐containing curing agent or the bromine containing flame‐retardant epoxy resin. UL 94‐VO rating could be achieved with a phosphorus content of as low as 1.21% (comparable to bromine content of 6%) in the cured resin, and no fumes and toxic gas emission were observed. The relationship between the structure and flammability for both phosphorus containing curing agents OD‐PN and TP‐PN (triphenyl phosphate‐phenol formaldehyde novolac reaction product) are also examined. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1636–1644, 2000     

High‐performance thermosetting films based on an amino‐functionalized poly(ether sulfone)

We have developed a sequence‐dependent synthesis of the amino‐functionalized poly(ether sulfone) P2 . The amino groups of P2 act as reactive sites toward epoxy resins. After curing P2 with diglycidyl ether of bisphenol A (DGEBA) and cresol novolac epoxy (CNE), we obtained the flexible, light‐yellow, transparent, epoxy thermosetting films P2 /DGEBA, and P2 /CNE, respectively, having glass transition temperatures (T_g) of 258 and 274°C, respectively. In addition, we also prepared a flexible film after condensation of the amino groups of P2 with the anhydride groups of 4,4′‐oxydiphthalic anhydride (ODPA); after imidization at 300°C for 1 h, the resulting P2 /ODPA thermosetting film possessed a value of T_g of 340°C. These three thermosetting films also exhibited flame retardancy with a UL‐94 VTM‐0 grade. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40980.     

Synthesis and curing properties of a novel curing agent based on N‐(4‐hydroxyphenyl) maleimide and dicyclopentadiene moieties

A new type of epoxy resin curing agent, containing pendant phenol functions, was synthesized by the free‐radical copolymerization of N‐(4‐hydroxyphenyl) maleimide with dicyclopentadiene (DCPD) monomer in the presence of a radical initiator. The chemical structure was characterized with Fourier transform infrared spectroscopy and nuclear magnetic resonance. The molecular weight of the new curing agent was determined by gel permeation chromatography. The activity and activation energy of this new curing agent with o‐cresol formaldehyde novolac epoxy (CNE) was investigated with a nonisothermal differential scanning calorimetry technique at different heating rates. The thermal properties of the cured polymers were evaluated with thermogravimetric analysis, and the results exhibit good thermal stability. In addition, this new curing agent with CNE showed low moisture absorption because of the hydrophobic nature of the DCPD structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Phenolic‐epoxy matrix curable by click chemistry—synthesis,curing, and syntactic foam composite properties

Alkyne functional phenolic resin was cured by azide functional epoxy resins making use of alkyne‐azide click reaction. For this, propargylated novolac (PN) was reacted with bisphenol A bisazide (BABA) and azido hydroxy propyloxy novolac (AHPN) leading to triazole‐linked phenolic‐epoxy networks. The click cure reaction was initiated at 40–65°C in presence of Cu₂I₂. Glass transition temperature (Tg) of the cured networks varied from 70°C to 75°C in the case of BABA‐PN and 75°C to 80°C in the case of AHPN‐PN. DSC and rheological studies revealed a single stage curing pattern for both the systems. The cured BABA‐PN and AHPN‐PN blends showed mass loss above 300°C because of decomposition of the triazole rings and the novolac backbone. Silica fiber‐reinforced syntactic foam composites derived from these resins possessed comparable mechanical properties and superior impact resistance vis‐a‐vis their phenolic resin analogues. The mechanical properties could be tuned by regulating the reactant stoichiometry. These low temperature addition curable resins are suited for light weight polymer composite for related applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41254.     

Relationship between viscoelastic properties and gelation in the epoxy/phenol‐novolac blend system with N‐benzylpyrazinium salt as a latent thermal catalyst

A study of viscoelastic properties and gelation in epoxy/phenol‐novolac blend system initiated with 1 wt % of N‐benzylpyrazinium hexafluoroantimonate (BPH) as a latent cationic thermal initiator was performed by analysis of rheological properties using a rheometer. Latent behavior was investigated by measuring the conversion as a function of curing temperature using traditional curing agents, such as ethylene diamine (EDA) and nadic methyl anhydride (NMA) in comparison to BPH. In the relationship between viscoelastic properties and gelation of epoxy/phenol‐novolac blend system, the time of modulus crossover was dependent on high frequency and cure temperature. The activation energy (E_c) for crosslinking from rheometric analysis increased within the composition range of 20–40 wt % phenol‐novolac resin. The 40 wt % phenol‐novolac (N40) to epoxy resin showed the highest value in the blend system, due to the three‐dimensional crosslinking that can take place between hydroxyl groups within the phenol resin or epoxides within the epoxy resin involving polyaddition of the initiator with BPH. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2299–2308, 2001     

Properties and behavior of CTBN‐modified epoxy with IPN structure

CTBN‐modified epoxy resins (CMEs) with an interpenetrating‐network (IPN) structure and a nanometer‐sized morphology were prepared. Two systems of CMEs, called CNE/DDS/I‐CTBN‐B and CNE/DDS/I‐CTBN‐D, with IPN structures, were synthesized by heat‐curing a homogeneous resin, CNE/DDS/CTBN/2‐MI, obtained by mixing a carboxyl‐terminated butadiene–acrylonitrile liquid rubber (CTBN) with a solution of polyglycidyl ether of o‐cresol‐formaldehyde novolac (CNE), 4,4′‐diamino diphenyl sulfone (DDS), and 2‐methyl imidazole (2‐MI), in the presence of benzoyl peroxide and dicumyl peroxide, respectively. The IPN morphologies of the two systems of CMEs were identified by small‐angle X‐ray scattering by measuring the value of the specific interfacial surface area S_sp between the cured CNE/DDS matrix and the vulcanized CTBN. Properties such as fracture toughness, internal stress, and thermal and dynamic mechanical properties of these IPN‐structured CMEs were studied in detail, and were compared with those of a conventional CME, CNE/DDS/CTBN, obtained by dispersing CTBN particles in a crosslinked CNE/DDS matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis of novel phosphorous‐containing biphenol, 2‐(5, 5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorin‐6‐yl)‐1,4‐benzenediol and its application as flame‐retardant in epoxy resin

A novel phosphorous‐containing biphenol, 2‐(5,5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorin‐6‐yl)‐ 1,4‐benzenediol (DPODB), was prepared by the addition reaction between 5,5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorinane phosphonate (DPODP) and p‐benzoquinone (BQ). The compound (DPODB) was used as a reactive flame retardant in o‐cresol formaldehyde novolac epoxy resin (CNE) for electronic application. The structure of DPODB was confirmed by FTIR and NMR spectra. Thermal properties of cured epoxy resin were studied using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The flame retardancy of cured epoxy resins was tested by UL‐94 vertical test and achieved UL‐94 vertical tests of V‐0 grade (nonflammable). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3842–3847, 2006     

Low dielectric thermoset. I. Synthesis and properties of novel 2,6‐dimethyl phenol‐dicyclopentadiene epoxy

A 2,6‐dimethyl phenol‐dicyclopentadiene novolac was synthesized from dicyclopentadiene and 2,6‐dimethyl phenol, and the resultant 2,6‐dimethyl phenol‐dicyclopentadiene novolac was epoxidized to 2,6‐dimethyl phenol‐dicyclopentadiene epoxy. The structures of novolac and epoxy were confirmed by Fourier transform infrared spectroscopy (FTIR), elemental analysis, mass spectroscopy (MS), nuclear magnetic resonance spectroscopy (NMR), and epoxy equivalent weight titration. The synthesized 2,6‐dimethyl phenol‐dicyclopentadiene epoxy was then cured with 4,4‐diaminodiphenyl methane (DDM), phenol novolac (PN), 4,4‐diaminodiphenyl sulfone (DDS), and 4,4‐diaminodiphenyl ether (DDE). Thermal properties of cured epoxy resins were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), dielectric analysis (DEA), and thermal gravimetric analysis (TGA). These data were compared with those of the commercial bisphenol A epoxy system. Compared with the bisphenol A epoxy system, the cured 2,6‐dimethyl phenol‐ dicyclopentadiene epoxy resins exhibited lower dielectric constants (～3.0 at 1 MHz and 2.8 at 1 GHz), dissipation factors (～0.007 at 1 MHz and 0.004 at 1 GHz), glass transition temperatures (140–188°C), thermal stability (5% degradation temperature at 382–404°C), thermal expansion coefficients [50–60 ppm/°C before glass‐transition temperature (T_g)], and moisture absorption (0.9–1.1%), but higher modulus (～2 Gpa at 60°C). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2607–2613, 2003     

Synthesis,cationic polymerization and curing reaction with epoxy resin of 3,9‐di(p‐methoxybenzyl)‐1,5,7,11‐tetra‐oxaspiro(5,5)undecane

A new spiro ortho carbonate, 3,9‐di(p‐methoxybenzyl)‐1,5,7,11‐tetra‐oxaspiro(5,5)undecane was prepared by the reaction of 2‐methoxybenzyl‐1,3‐propanediol with di(n‐butyl)tin oxide, following with carbon disulfide. Its cationic polymerization was carried out in dichloromethane using BF₃‐OEt₂ as catalyst. The [¹H], [¹³C]NMR and IR data as well as elementary analysis of the polymers obtained indicated that it underwent double ring‐opening polymerization. The polymerization mechanism is discussed. The curing reaction of bisphenol A type epoxy resin in the presence of the monomer and a curing agent was investigated. DSC measurements were used to follow the curing process. In the case of boron trifluoride‐o‐phenylenediamine (BF₃‐OPDA) as curing agent, two peaks were found on the DSC curves, one of which was attributed to the polymerization of the epoxy group, and the other to the copolymerization of the monomer with the isolated epoxy groups or homopolymerization. However, when BF₃‐H₂NEt was used as curing agent, only one peak was present. IR measurement of the modified epoxy resin with various weight ratios of epoxy resin/monomer was performed in the presence of BF₃‐H₂NEt as curing agent. The results demonstrate that the conversion of epoxy group increases as the content of monomer increases. The curing process and the structure of the epoxy resin network are discussed. © 2000 Society of Chemical Industry     

Catalytic effect of 2,2′‐diallyl bisphenol A on thermal curing of cyanate esters

Cyanate esters are a class of thermal resistant polymers widely used as thermal resistant and electrical insulating materials for electric devices and structural composite applications. In this article, the effect of 2,2′‐diallyl bisphenol A (DBA) on catalyzing the thermal curing of cyanate ester resins was studied. The curing behavior, thermal resistance, and thermal mechanical properties of these DBA catalyzed cyanate ester resins were characterized. The results show that DBA is especially suitable for catalyzing the polymerization of the novolac cyanate ester resin (HF‐5), as it acts as both the curing catalyst through depressing the exothermic peak temperature (T_exo) by nearly 100°C and the toughening agent of the novolac cyanate ester resin by slightly reducing the elastic modulus at the glassy state. The thermogravimetric analysis and dynamic mechanical thermal analysis show that the 5 wt % DBA‐catalyzed novolac cyanate ester resin exhibits good thermal resistance with T_d⁵ of 410°C and the char yield at 900°C of 58% and can retain its mechanical strength up to 250°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1775–1786, 2006     

Cure kinetics and catalyzed effect of hydroxyl group of LC diglycidyl ether of bisphenol‐S with aromatic diamines

The curing reactions of liquid crystalline 4,4′‐bis‐(2,3‐epoxypropyloxy)‐sulfonyl‐bis(1,4‐phenylene) (p‐BEPSBP) with 4,4′‐diaminodiphenylmethane (DDM) and 4,4′‐diaminodiphenylsulfone (DDS) were investigated by nonisothermal differential scanning calorimeter (DSC). The relationships of E_a with the conversion α in the curing process were determined. The catalyzed activation of hydroxyl group for curing reaction of epoxy resins with amine in DSC experiment was discussed. The results show that these curing reactions can be described by the autocatalytic ?esták‐Berggren model. The curing technical temperature and parameters were obtained, and the even reaction orders m, n, and ΔS for p‐BEPSBP/DDM and p‐BEPSBP/DDS are 0.35, 0.92, ?81.94 and 0.13, 1.32, ?24.45, respectively. The hydroxyl group has catalyzed activation for the epoxy–amine curing system in the DSC experiment. The average E_a of p‐BEPSBP/DDM is 67.19 kJ mol^?1 and is 105.55 kJ mol^?1 for the p‐BEPSBP/DDS system, but it is different for the two systems; when benzalcohol as hydroxyl group was added to the curing system, the average E_a of p‐BEPSBP/DDM decreases and increases for p‐BEPSBP/DDS. The crystalline phase had formed in the curing process and was fixed in the system. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Curing behavior of Azo‐containing twin liquid crystalline epoxy resins with anhydride

A series of novel azo‐containing twin liquid crystalline (LC) epoxy monomers were cured with anhydrides without extra catalyst, and the curing kinetics was investigated by non‐isothermal differential scanning calorimetry (DSC) technique. The results showed that the effect of phase behavior on activation energy (E_a) was enormous, which increased first and then decreased quickly with the curing reaction processing. The chemical kinetic control and diffusion‐control mechanisms dominate the curing together, which gives large values of E_a. Azo group also served as a catalyst to accelerate the curing reaction. The curing mechanism was confirmed by the UV–Vis spectra of azo‐doped curing system in which the absorbance values at 366 nm and 475 nm changed with the curing reaction processing. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Novolac epoxy resin from 4,4′‐dihydroxybenzophenone: Thermal,thermomechanical, interfacial,and cure kinetics with DGEBA/DICY blend

A novolac epoxy resin based on 4,4′‐dihydroxybenzophenone (BZPNE) was synthesized via epoxidation of 4,4′‐dihydroxybenzophenone novolac resin (BZPN). BZPN was obtained by strong mineral acid catalyzed reaction of 4,4′‐dihydroxybenzophenone (BZP) and paraformaldehyde. The formation of BZPNE and BZPN was confirmed by Fourier transform infrared spectroscopy, proton and carbon nuclear magnetic resonance spectroscopy, gel permeation chromatography, and epoxy equivalent weight. Different blends of BZPNE with diglycidyl ether of bisphenol‐A (DGEBA; EEW ～180) were cured using dicyandiamide were characterized by thermogravimetric analysis, thermomechanical analysis, dynamic mechanical analysis, and interfacial property between aluminum adherends at ambient and elevated temperature. Thermal properties were found to improve on increasing quantity of BZPNE in DGEBA as it is evidenced from glass transition temperature (T_g). Likewise, no deterioration in interfacial properties was observed with the highest quantity of BZPNE (30%) in DGEBA blend, when tested at 150 °C. Cure kinetics of compositions were studied by nonisothermal differential scanning calorimetry and Kissinger method was used to compute the kinetic parameters such as frequency factor (A), activation energy (E_a) followed by the dependency of rate constant (k) on temperature of different blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46164.     

Cure kinetics and thermal properties of tetramethylbiphenyl epoxy resin/phthalazinone‐containing diamine/hexa(phenoxy)cyclotriphophazene system

Inherently flame retardant epoxy resin is a kind of halogen‐free material for making high‐performance electronic materials. This work describes an inherently flame retardant epoxy system composed of 4,4′‐diglycidyl (3,3′,5,5′‐tetramethylbiphenyl) epoxy resin (TMBP), 1,2‐dihydro‐2‐(4‐aminophenyl)‐4‐(4‐(4‐aminophenoxy) phenyl) (2H) phthalazin‐1‐one (DAP), and hexa(phenoxy) cyclotriphophazene (HPCTP). The cure kinetics of TMBP/DAP in the presence or absence of HPCTP were investigated using isoconversional method by means of nonisothermal differential scanning calorimeter (DSC). Kinetic analysis results indicated that the effective activation energy (E_α) decreased with increasing the extent of conversion (α) for TMBP/DAP system because diffusion‐controlled reaction dominated the curing reaction gradually in the later cure stage. TMBP/DAP/HPCTP(10 wt %) system had higher E_α values than those of TMBP/DAP system in the early cure stage (α < 0.35), and an increase phenomenon of E_α ～ α dependence in the later cure stage (α ≥ 0.60) due to kinetic‐controlled reaction in the later cure stage. Such complex E_α ～ α dependence of TMBP/DAP/HPCTP(10 wt %) system might be associated with the change of the physical state (mainly viscosity) of the curing system due to the introduction of HPCTP. These cured epoxy resins had very high glass transition temperatures (202–235°C), excellent thermal stability with high 5 wt % decomposition temperatures (>340°C) and high char yields (>25.6 wt %). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of poly(vinyl acetate) by degenerative transfer polymerization in the presence of iodine

A new curing agent containing maleimide and biphenyl moieties (MIBP) was synthesized by the condensation polymerization of 4,4′-bismethoxymethylbiphenyl and N-(4-hydroxyphenyl)maleimide (HPM). The chemical structure was characterized with Fourier transform infrared (FTIR) spectroscopy, and the molecular weight of the new curing agent was determined by gel permeation chromatography. Curing reactions of O-cresol formaldehyde epoxy (CNE) resin with MIBP were investigated under nonisothermal differential scanning calorimetry, and the exotherm exhibited two overlapping exothermic peaks during the curing process; this was demonstrated by FTIR traces. The Flynn–Wall–Ozawa and Friedman methods were used to examine the kinetic parameters and the kinetic models of the curing processes of the CNE/MIBP mixtures. Both reactions turned out to be nth-order curing mechanisms. Values of the reaction order (n) = 1.42 and activation energy (E_a) = 91.2 kJ/mol were obtained for the first reaction of the curing of the CNE/MIBP system, and values of n = 1.11 and E_a = 78.7 kJ/mol were obtained for the second reaction. The thermal properties of the cured resin were measured with thermogravimetric analysis, and the results show a high glass-transition temperature (T_g = 155°C), good thermal stability (temperature at 10% weight loss, under nitrogen and in air, ≈ 400 and 408°C, respectively), and high char yield (temperature = 800°C, char residue = 44.5% under nitrogen). These excellent thermal properties were due to the introduction of the maleimide and biphenyl groups of MIBP into the polymer structure. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of reactive poly(ethylene glycol) flexible chains on curing kinetics and impact properties of bisphenol‐a glycidyl ether epoxy

Bisphenol‐A glycidyl ether epoxy resin was modified using reactive poly(ethylene glycol) (PEO). Dynamic mechanical analysis showed that introducing PEO chains into the structure of the epoxy resin increased the mobility of the molecular segments of the epoxy network. Impact strength was improved with the addition of PEO at both room (RT) and cryogenic (CT, 77 K) temperature. The curing kinetics of the modified epoxy resin with polyoxypropylene diamines was examined by differential scanning calorimetry (DSC). Curing kinetic parameters were determined from nonisothermal DSC curves. Kinetic analysis suggested that the two‐parameter autocatalytic model suitably describes the kinetics of the curing reaction. Increasing the reactive PEO content decreased the heat flow of curing with little effect on activation energy (E_a), pre‐exponential factor (A), or reaction order (m and n). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Curing kinetics of bio‐based epoxy resin based on epoxidized soybean oil and green curing agent

New thermoset with a high bio‐based content was synthesized by curing epoxidized soybean oil (ESO) with a green curing agent maleopimaric acid catalyzed by 2‐ethly‐4‐methylimidazole. Non‐isothermal differential scanning calorimetry and a relatively new integral isoconversional method were used to analyze the curing kinetic behaviors and determine the activation energy (E_a). The two‐parameter ?esták–Berggren autocatalytic model was applied in the mathematical modeling to obtain the reaction orders and the pro‐exponential factor. For anhydride/epoxy group molar ratio equal to 0.7, E_a decreased from 82.70 to 80.17 kJ/mol when increasing the amount of catalyst from 0.5 to 1.5 phr toward ESO. The reaction orders m and n were 0.4148 and 1.109, respectively. The predicted non‐isothermal curing rates of ?esták–Berggren model matched perfectly with the experimental data. © 2016 American Institute of Chemical Engineers AIChE J, 63: 147–153, 2017     

Nonisothermal cocuring behavior and kinetics of epoxy resin/3‐glycidyloxypropyl‐POSS with MeTHPA

3‐Glycidyloxypropyl‐polyhedral oligomeric silsesquioxanes (G‐POSS) was prepared from 3‐glycidyloxypropyl‐trimethoxysilane (GTMS) by hydrolytic condensation. The cocuring behavior and kinetics of G‐POSS with bisphenol‐A epoxy resin (BPAER) using 3‐methyl‐tetrahydrophthalic anhydride (MeTHPA) as curing agent were investigated by nonisothermal differential scanning calorimetry (DSC) and torsional braid analysis (TBA). The face distribution of silicon in the cured products was characterized by energy dispersive X‐ray spectrometry (EDS). The results show that the compatibility of G‐POSS with BPAER is very well and can cocure. The curing mechanism was proposed. The relationship of E_a and conversion α can be obtained by the isoconversional method of Kissinger. These curing reactions can be described by the Šesták–Berggren (S–B) equation and can be depicted by the following equation: . TBA analysis indicated that T_g was decreased when the contents of G‐POSS is over to 30 wt%. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers