Morphology of poly(ether sulfone)-modified polycyanurates

Polycyanurates prepared from cure of bisphenol A dicysanate (BPADCy) were modified with either hydroxyl-terminated or cyanated poly(ether sulfone)s (as HPES or CPES, respectively) of different molecular weights. With high molecular weight HPES (or CPES), the resulting resin showed a two-phase morphology in contrast to the single-phase morphology generated from the curing reactions of the low molecular weight HPES (or CPES) and BPADCy as observed from optical microscopy. Results from scanning electron microscopy suggests a discrete-continuous fracture surface for the high molecular weight HPES-modified polycyanurate but for the CPES-modified analogue, a blur interface between particle and matrix was observed. However, this blur interface can also be generated if 1 wt% of catalyst system (n-nonylphenol/cobaltic acetylacetonate) was used during cure of mixtures of high molecular weight HPES and BPADCy. This blur interface in the catalyzed system is attributed to the inter-reactions between the hydroxyl termini in HPES and the cyanate groups in BPADCy.     

Determination of thermal cure kinetics of thin films of photocatalysed dicyanate ester by FTIR emission spectroscopy

Emission Fourier transform infrared (FTIR) spectroscopy has been found to be a suitable technique for monitoring the thermal cure of thin films of photocatalysed dicyanate ester resins. The kinetics of the polymerization of a commercial cyanate ester resin (AroCy RTX‐366) catalysed by an organometallic compound, tricarbonyl cyclopentadienyl manganese (CpMn(CO)₃), have been determined using this technique and the results compared with those obtained from transmission FTIR. The trimerization reaction rate of the resin is found to have a first order dependence upon both the cyanate fraction and the active catalyst concentration until diffusion control occurs. To elucidate the mechanism, a system with premade catalyst, which was the photoreaction product of the resin and the organometallic compound, has also been studied. The activation energy for this system is 91 ± 10 kJ mol⁻¹ compared to 72 ± 8 kJ mol⁻¹ for the directly irradiated system. This may arise from different distributions of three photoproducts identified as complexes between manganese and the cyanate ester. © 2000 Society of Chemical Industry     

In situ FT‐IR and DSC investigation on the cure reaction of the dicyanate/diepoxide/diamine system

Cure reactions of a liquid aromatic dicyanate ester (1,1′‐bis(4‐cyanatophenyl)ethane, BEDCy) with a liquid bisphenol A epoxide (2,2‐bis(4‐glycidyloxyphenyl)propane, BADGE) and 4,4′‐diaminodiphenyl sulfone (DDS) were studied through correlation of the in situ FT‐IR spectroscopy and DSC in dynamic scanning mode. Before this system was examined, cure reactions of precursory systems of BADGE/DDS, BEDCy/BADGE and BEDCy/DDS were investigated separately. Cure reaction paths for each system are proposed. Some reactions in the precursory systems, such as polycyclotrimerization of dicyanate to form sym‐triazine and formation of alkyl isocyanurate, were not observed in the combined curing system BEDCy/BADGE/DDS. Four principal reaction paths are proposed for this curing system: (1) formation of oxazoline from the reaction between the epoxide and cyanate group; (2) reaction of epoxide with primary amine to form a hydroxyl group; (3) reaction of epoxide with the hydroxyl group to form an ether linkage; and (4) rearrangement of oxazoline to form oxazolidinone. Two distinct, but somewhat overlapping, exothermic peaks were observed on the DSC thermogram. The lower temperature peak on the DSC thermogram was primarily contributed by the first reaction path, whereas the higher temperature peak can mainly be attributed to the reaction paths 2, 3 and 4. © 2001 Society of Chemical Industry     

Untersuchungen zur Kinetik und zum Wärmeeffekt der Cyclotrimerisierung von Arylcyanaten

Studies on the Kinetics and the Reaction Heat of the Cyclotrimerization of Aryl Cyanates The kinetics and the reaction enthalpy of the polycyclotrimerization of 2,2-bis(4-cyanatophenyl)propane in ditolylmethane solution were investigated by means of direct calorimetry, varying the concentration of the catalyst (chromium(III) acetyl acetonate) and of the monomer as well as the reaction temperature, the water content of the solvent, and the amount of added acetyl acetone. The maximum reaction rate is proportional to the monomer concentration, to the square root of the concentration of the catalyst, and to the water content. It is inversely proportional to the amount of water added. Presumably, water participates in the formation of the active species of the catalyst, and the autocatalytic nature of the polycyclotrimerization of 2,2-bis(4-cyanatophenyl)propane in presence of chromium acetylacetonate is due to accumulation of the latter during reaction.     

A kinetic study on the autocatalytic cure reaction of a cyanate ester resin

The cure of a novolac‐type cyanate ester monomer, which reacts to form a polycyanurate network, was investigated by using differential scanning calorimeter. The conversions and the rates of cure were determined from the exothermic curves at several isothermal temperatures (513–553 K). The experimental data, showing an autocatalytic behavior, conforms to the kinetic model proposed by Kamal, which includes two reaction orders, m and n, and two rate constants, k₁ and k₂. These kinetic parameters for each curing temperature were obtained by using Kenny's graphic‐analytical technique. The overall reaction order was about 1.99 (m = 0.99, n = 1.0) and the activation energies for the rate constants, k₁ and k₂, were 80.9 and 82.3 kJ/mol, respectively. The results show that the autocatalytic model predicted the curing kinetics very well at high curing temperatures. However, at low curing temperatures, deviation from experimental data was observed after gelation occurred. The kinetic model was, therefore, modified to predict the cure kinetics over the whole range of conversion. After modification, the overall reaction order slightly decreased to be 1.94 (m = 0.95, n = 0.99), and the activation energies for the rate constants, k₁ and k₂, were found to be 86.4 and 80.2 kJ/mol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3067–3079, 2004     

Cure kinetics of a cyanate ester blended with poly(phenylene oxide)

The cure kinetics and mechanisms of a cyanate ester and its blends with poly(phenylene oxide) (PPO) were studied using differential scanning calorimetry and Fourier transform infrared spectroscopy. The results showed that blending with PPO has an effect on the cure reaction. Reaction rates of the cyanate ester blends were higher in the initial stage than that of the neat cyanate ester; however, the conversion reached decreased with increasing PPO content. Experimental data, showing autocatalytic behavior, were compared with Kamal's model which includes two apparent rate constants and two reaction orders. This model apparently describes well the kinetics, but diffusion control in the vitrified state limits the reactions from going further. By introducing a diffusion factor f(α) into this model, it becomes possible to predict the cure kinetics over the whole range of conversion. Copyright © 2006 Society of Chemical Industry     

Effect of cyanate ester on the cure behavior and thermal stability of epoxy resin

Epoxy resin (diglycidyl ether of bisphenol A, DGEBA)/cyanate ester mixtures were cured with a curing agent, 4,4′-diaminodiphenylsulfone, and the effect of cyanate ester resin on the cure behavior and thermal stability in the epoxy resin was investigated with a Fourier transform infrared spectrometer, a rheometer, a dynamic mechanical analyzer, and a thermogravimetric analyzer. Cure reactions in the epoxy/cyanate ester mixture were faster than that of the neat epoxy system. The cure reaction was accelerated by increasing the cyanate ester resin component. Glass transition temperature and thermal stability in the cured resins were increased with increasing cyanate ester resin component. This may be caused by the increase of crosslinking density due to the polycyclotrimerization of the cyanate ester monomer to form triazine rings and the reaction of cyanate ester resin with the epoxy network. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 85–90, 1997     

双酚A二氰酸酯树脂的固化特性研究

采用二步法合成双酚A二氰酸酯(BCE),由氰化钠和液溴反应合成溴化氰,溴化氰与双酚A在三乙胺的催化下合成BCE,产率在85%以上。运用红外光谱(IR)和差热分析(DTA)等手段对合成BCE树脂进行了表征,研究了提纯前后BCE树脂的固化反应特性,并探讨了金属催化剂的催化作用。结果表明,合成BCE的纯度对氰酸酯树脂的固化反应特性和固化物性能有很大影响。提纯将降低BCE树脂中的双酚A等杂质的含量,提高固化反应温度,提高树脂固化物耐热性。环烷酸钴对BCE树脂固化有明显的催化作用,固化反应放热峰起始温度Ti由207 2℃降低到167 8℃,凝胶化时间大大降低。     

Cure kinetics of aqueous phenol–formaldehyde resins used for oriented strandboard manufacturing: Analytical technique

The cure kinetics of commercial phenol–formaldehyde (PF), used as oriented strandboard face and core resins, were studied using isothermal and dynamic differential scanning calorimetry (DSC). The cure of the face resin completely followed an nth‐order reaction mechanism. The reaction order was nearly 1 with activation energy of 79.29 kJ mol^?1. The core resin showed a more complicated cure mechanism, including both nth‐order and autocatalytic reactions. The nth‐order part, with reaction order of 2.38, began at lower temperatures, but the reaction rate of the autocatalytic part increased much faster with increase in curing temperature. The total reaction order for the autocatalytic part was about 5. Cure kinetic models, for both face and core resins, were developed. It is shown that the models fitted experimental data well, and that the isothermal DSC was much more reliable than the dynamic DSC in studying the cure kinetics. Furthermore, the relationships among cure reaction conversion (curing degree), cure temperature, and cure time were predicted for both resin systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1642–1650, 2006     

Comparison of model‐fitting kinetics for predicting the cure behavior of commercial phenol–formaldehyde resins

Phenol–formaldehyde (PF) resins have been the subject of many model‐fitting cure kinetic studies, yet the best model for predicting PF dynamic and isothermal cure has not been established. The objective of this research is to compare and contrast several commonly used kinetic models for predicting degree of cure and cure rate of PF resins. Toward this objective, the nth‐order Borchardt–Daniels (nth‐BD), ASTM E698 (E698), autocatalytic Borchardt–Daniels (Auto‐BD), and modified autocatalytic methods (M‐Auto) are evaluated on two commercial PF resins containing different molecular weight distributions and thus cure behaviors. The nth‐BD, E698, and M‐Auto methods all produce comparable values of activation energies, while Auto‐BD method yields aberrant values. For dynamic cure prediction, all models fail to predict reaction rate, while degree of cure is reasonably well predicted with all three methods. As a whole, the nth‐BD method best predicts degree of cure for both resins as assessed by mean squared error of prediction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Kinetic study of the effect of catalysts on the curing of biphenyl epoxy resin

The investigation of cure kinetics of biphenyl epoxy (4,4′-diglycidyloxy-3,3′,5,5′-tetramethyl biphenyl)dicyclopentadiene type phenolic resin system with different kinds of catalysts was performed by a differential scanning calorimeter using an isothermal approach. All kinetic parameters of the curing reaction including the reaction order, activation energy, and rate constant were calculated and reported. The results indicate that the curing reaction of the formulations using triphenylphosphine (TPP), 1-benzyl-2-methylimidazole (1B2MI), and tris(4-methoxyphenyl)phosphine (TPAP) as a catalyst proceeds through an nth-order kinetic mechanism, whereas thatof the formulations using diazabicycloundecene (DBU) and tetraphenyl phosphonium tetraphenyl borate (TPP–TPB) proceeds by an autocatalytic kinetic mechanism. To describe the cure reaction in the latter stage, we have used semiempirical relationship proposed by Chern and Poehlein. By combining an nth-order kinetic model or an auto-catalytic model with a diffusion factor, it is possible to predict the cure kinetics of each catalytic system over the whole range of conversion. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1125–1137, 1998     

Triazine reaction of cyanate ester resin systems catalyzed by organic tin compound: kinetics and mechanism

The mechanism and kinetics of the thermal cure reaction of two cyanate esters (CEs), 1,1′bis(4‐cyanatophenyl)ethane (AroCy L‐10) and bisphenol A dicyanate ester (BADCy), in the presence of dibutyl tin dilaurate (DBTDL) has been investigated using Fourier‐transform infrared spectroscopy (FTIR) and High‐performance liquid chromatography (HPLC). It was found that the organic tin compound (H₉C₄)₂Sn(NCO—R—OCN)₂, an active catalyst, has high catalytic efficiency in the polymerization of cyanate esters. The consuming rate of cyanate concentration showed a first‐order dependence on both active catalyst and the cyanate ester monomer concentration. The apparent activation energies (E_a) and frequency factors of both AroCy L‐10 and BADCy were calculated. A mechanism of cyclotrimerization was proposed, based on the kinetic data and FTIR spectra, which involves the formation of an active catalyst and the catalysis of the active catalyst. Copyright © 2004 Society of Chemical Industry     

Effect of intramolecular cycles on the polycyclotrimerization of aromatic dicyanates

The gel conversions (α_gel) for the polycyclotrimerization of aromatic dicyanates are significantly higher than the classical mean-field value of 0.5. The reasons for the higher gel conversion, which is consistent with all experimental results of different structures of monomers, were inductively attributed to the accessibility effect of the functional group and the substitution effect, as well as the effect of the intramolecular cyclization. Nevertheless, the former two effects on the gel conversion can be quantitatively represented in terms of the extent of the intramolecular cyclization. Some theoretical expressions (including gel conversion and crosslink density with respect to the conversion) were derived by use of the recursive method with due consideration of the intramolecular cyclization. These expressions (with only one experimental parameter, α_gel) were found to be effective in describing gel fraction–conversion data for various polycyanurates. A dramatic change in the product value of ΔC_p · T_g was also found in the vicinity of the gel point for all different structures of aromatic dicyanate systems. The dramatic change in ΔC_p · T_g occurs at the gel point rather than the expected mean-field gel conversion of 0.5, presumably due to the intramolecular cyclization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1927–1938, 1999     

Study on the cure behavior of 2,7‐dihydroxynaphthalene dicyanate

The cure behavior of 2,7‐dihydroxynaphthalene dicyanate (DNCY) was studied by means of nonisothermal DSC, isothermal DSC, and FTIR. In nonisothermal DSC, the cure kinetics parameters of DNCY were calculated by the Coats–Redfern method and compared with those of biphenol A dicyanate (BACY). It was revealed that the activation energy of DNCY was enhanced compared with that of BACY because of the presence of naphthalene, and the gelation of DNCY occurred within the conversion range 50–55%, which is lower than that of BACY. In isothermal DSC, a good time–temperature superposition of the conversion profiles of DNCY was obtained during conversions below about 50%. These results were consistent with those obtained by nonisothermal DSC. For the catalyzed system, the autocatalytic behavior prevailed at conversions below 30%, whereas the catalytic behavior occurred only at conversions above 30%. In situ FTIR spectra revealed that a triazine network was formed by cyclotrimerization of the OCN functional group during the cure process for systems with and without catalysts. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3927–3939, 2004     

Characterization of cure reactions of anhydride/epoxy/polyetherimide blends

The cure kinetics of blends of epoxy (diglycidyl ether of bisphenol A)/anhydride (nadic methyl anhydride) resin with polyetherimide (PEI) were studied using differential scanning calorimetry under isothermal conditions to determine the reaction parameters such as activation energy and reaction constants. By increasing the amount of PEI in the blends, the final cure conversion was decreased. Lower values of final cure conversions in the epoxy/PEI blends indicate that PEI hinders the cure reaction between the epoxy and the curing agent. The value of the reaction order, m, for the initial autocatalytic reaction was not affected by blending PEI with epoxy resin, and the value was approximately 1.0. The value of n for the nth order component in the autocatalytic analysis was increased by increasing the amount of PEI in the blends, and the value increased from 1.6 to 4.0. A diffusion‐controlled reaction was observed as the cure conversion increased and the rate equation was successfully analyzed by incorporating the diffusion control term for the epoxy/anhydride/PEI blends. Complete miscibility was observed in the uncured blends of epoxy/PEI at elevated temperatures up to 120 °C, but phase separations occurred in the early stages of the curing process. © 2002 Society of Chemical Industry     

双酚A二氰酸酯的合成与固化反应特性研究

采用二步法合成双酚A二氰酸酯(BCE)：由氰化钠和液溴反应合成溴化氰，溴化氰与双酚A在三乙胺的催化下合成BCE，合成产率在85％以上。运用红外光谱和差热分析等手段对合成的BCE树脂进行了表征，并研究了BCE树脂的固化反应特性。结果表明，合成BCE的纯度对氰酸酯树脂的固化反应特性和固化物性能有很大影响。     

Thermal and mechanical evaluation of cyanate ester resin catalyzed by nonylphenol and stannous octoate

Nonylphenol (NP), stannous octoate [Sn(Otc)₂], and a mixture of NP and Sn(Otc)₂ were employed for catalyzing cyanate ester resin. The curing reaction was studied by differential scanning calorimetry. A water‐absorption test at 85 °C was utilized to study the resistance to warm and humid conditions. The thermal properties were evaluated through measuring thermal weight loss and the glass‐transition temperature (T_g), and the mechanical properties were evaluated through three‐point bending tests and tensile tests. The results show that the mixture of NP and Sn(Otc)₂ exhibits the best catalytic efficiency by decreasing the exothermic peak temperature by almost 148 °C. The mixture of NP and Sn(Otc)₂ has unfavorable effects on the thermal stability. Nevertheless, all catalyst systems have good water‐absorption resistance. The mechanical investigation confirms that the tensile properties show a little reduction that is due to the plasticization of the catalyst, while the excellent flexural properties are maintained. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43959.     

Curing kinetics and thermal property characterization of an o‐cresol formaldehyde epoxy resin and 4,4′‐diaminodiphenyl ether system

The kinetics of the curing reaction for a system of o‐cresol formaldehyde epoxy resin (o‐CFER) with 4,4′‐diaminodiphenyl ether (DDE) as a curing agent were investigated with differential scanning calorimetry (DSC). An analysis of the DSC data indicated that an autocatalytic behavior appeared in the first stages of the cure for the system, and this could be well described by the model proposed by Kamal, which includes two rate constants and two reaction orders (m and n). The overall reaction order (m + n) was 2.7–3.1, and the activation energies were 66.79 and 49.29 kJ mol^?1, respectively. In the later stages, a crosslinked network was formed, and the reaction was mainly controlled by diffusion. For a more precise consideration of the diffusion effect, a diffusion factor was added to Kamal's equation. In this way, the curing kinetics were predicted well over the entire range of conversions, covering both the previtrification and postvitrification stages. The glass‐transition temperatures of the o‐CFER/DDE samples were determined via torsional braid analysis. The results showed that the glass‐transition temperatures increased with the curing temperature and conversion up to a constant value of approximately 370 K. The thermal degradation kinetics of the system were investigated with thermogravimetric analysis, which revealed two decomposition steps. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 182–188, 2004