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     

The curing of UF resins studied by low‐resolution 1H‐NMR

A series of UF resins and one MUF resin were studied by low‐resolution ¹H‐NMR. The mobility of the resin during curing could be followed by measuring the spin‐spin relaxation time (T₂) with curing time. The relative curing behavior was similar to that found by traditional gel time measurements. In addition, extra features in the T₂ plots with curing time showed at what point the bulk of the condensation reactions took place. The speed of cure was also related to the chemical groups in the liquid resin, and it was found that the linear methylol groups were mainly responsible for the curing speed of the resins. By studying the curing with different hardener levels and glue concentrations it was found that a UF resin is more sensitive to the glue mix concentration than an MUF resin. A cured resin was also studied after curing to investigate postcuring effects. Water seemed to play the biggest role in the postcure, with substantial amounts present immediately after cure, which decreased with curing time and aging. For the low mol ratio resins studied here further curing reactions did not seem to play a major role in the post curing phenomenon. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 754–765, 2000     

The reaction in water of UF resins with isocyanates at short curing times: A 13C NMR investigation

CP MAS ¹³C NMR spectra of hardened resins have shown that urethane bridges derived from the reaction of the isocyanate group with the hydroxymethyl group of urea do form even at fast curing times comparable to what was used in the wood panels industry, in lower proportions than what was shown earlier. Polyureas and biurets obtained from the reaction of isocyanate with water are the predominant crosslinking reactions of pMDI alone and in UF/pMDI resin systems under fast curing conditions. Residual, unreacted isocyanate groups in the hardened network are consistently observed. Their proportion markedly decreases when the original proportion of urea–formaldehyde (UF) resin is high and that of pMDI is low. Under these fast curing conditions, the UF resin appears to self‐condense through an unusually high proportion of methylene ether links rather than methylene bridges alone. A marked proportion of residual, unreacted hydroxymethyl groups is also noticeable, initially, in the UF self‐condensation network. Direct NMR tests on thin hardboard bonded under fast pressing conditions with different proportions of UF/pMDI confirmed that crosslinking due to polyureas and biurets formation are predominant in the crosslinking of pMDI when alone and in UF/pMDI resin systems. They confirmed that residual, unreacted isocyanate groups are present in the finished panel. Their proportion is higher when the proportion of pMDI in the system is high. The presence or absence of urethanes could not be confirmed directly on the panels as the relevant peaks are masked by the wood carbohydrates signals of wood cellulose and hemicelluloses. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1624–1632, 2006     

Curing of low level melamine‐modified urea‐formaldehyde particleboard binder resins studied with dynamic mechanical analysis (DMA)

Effects of resin formulation, catalyst, and curing temperature were studied for particleboard binder‐type urea‐formaldehyde (UF) and 6 ～ 12% melamine‐modified urea‐melamine‐formaldehyde (UMF) resins using the dynamic mechanical analysis method at 125 ～ 160°C. In general, the UF and UMF resins gelled and, after a relatively long low modulus period, rapidly vitrified. The gel times shortened as the catalyst level and resin mix time increased. The cure slope of the vitrification stage decreased as the catalyst mix time increased, perhaps because of the deleterious effects of polymer advancements incurred before curing. For UMF resins, the higher extent of polymerization effected for UF base resin in resin synthesis increased the cure slope of vitrification. The cure times taken to reach the vitrification were longer for UMF resins than UF resins and increased with increased melamine levels. The thermal stability and rigidity of cured UMF resins were higher than those of UF resins and also higher for resins with higher melamine levels, to indicate the possibility of bonding particleboard with improved bond strength and lower formaldehyde emission. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 377–389, 2005     

Urea–formaldehyde‐resin gel time as affected by the pH value,solid content,and catalyst

An experiment was conducted to investigate the effects of the resin solid content, catalyst content, and pH value obtained by the addition of two kinds of catalysts on the gel time of a urea–formaldehyde (UF) resin. Upon the addition of ammonium chloride, the pH value of the resin mixture decreased to 7 but not significantly further because of the limited free formaldehyde in the system. The pH values of the critical points, at which the resin‐curing rate dramatically increased and the gel time was reduced, were above 7 for both catalysts. To achieve the same gel time, the required pH value of the UF resin adjusted with ammonium chloride was higher than that of the resin modified by hydrochloric acid. This indicated that the main effects of ammonium chloride on the UF‐resin cure included both the release of hydrochloric acid and the catalysis of the reactants in the UF‐resin system. The gel time of the UF resin obviously decreased with increasing catalyst and resin solid contents and with decreasing pH. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1566–1569, 2007     

Preparation and curing kinetics of bisphenol A type novolac epoxy resins

A bisphenol A type novolac resin (Bis‐ANR) was synthesized from bisphenol A and formaldehyde; the resulting novolac was epoxidized to generate a bisphenol A type novolac epoxy resin (Bis‐ANER). The chemical structures of Bis‐ANR and Bis‐ANER were confirmed by ¹H‐NMR spectroscopy and IR spectroscopy; the molecular weights and molecular weight distributions were determined by gel permeation chromatography. In addition, the curing process of Bis‐ANER with 4,4′‐diaminodiphenyl sulfone was studied in both dynamic and isothermal modes with differential scanning calorimetry. The dynamic curing kinetic analysis was evaluated with both the Kissinger and Flynn–Wall–Ozawa methods, and the curing activation energy values were obtained. The isothermal curing reaction exhibited autocatalytic behavior, and the curing kinetics were described with the Kamal kinetics model, which accounted for both the autocatalytic and diffusion‐control effects. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 858–868, 2006     

Cure kinetics of aqueous phenol–formaldehyde resins used for oriented strandboard manufacturing: Effect of zinc borate

The effect of zinc borate (ZB) on the cure kinetics of commercial phenol–formaldehyde oriented strandboard adhesives was studied using differential scanning calorimetry. ZB caused a separation of the addition and condensation reactions for both face and core resin (CR) systems with lowered cure temperature for the addition reaction. For the face resin, ZB did not change its nth‐order curing mechanism, but retarded the whole cure reactions, and increased the reaction order and the activation energy. Compared with neat CR, the addition reaction of the CR/ZB mixture, which occurred at temperatures lower than 60°C, also followed an nth‐order reaction mechanism. The condensation reaction of the mixture was changed from an autocatalytic reaction to an nth‐order one with the reaction order of about 1. The proposed models fitted the experimental data well. Relationships among cure reaction conversion (i.e., cure degree), cure temperature, and cure time were predicted for various resin/ZB systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3886–3894, 2006     

Process cure monitoring of unsaturated polyester resins,vinyl ester resins,and gel coats by Raman spectroscopy

The curing process of unsaturated polyester resins, vinyl ester resins, and gel coats was studied by using a process Raman spectrometer, equipped with a remote fiber‐optic probe. The resins were cured and Raman spectra were recorded during the curing reaction. The spectral changes were identified and, from the intensities, the cure process could be monitored. Gel times given by the resin suppliers correlated well with the Raman results. It could also be seen that the curing process continues for a long time, up to several weeks. Postcuring will finally complete the curing process. White and lightly colored gel coats could easily be monitored by Raman spectroscopy, but fluorescent problems were encountered with heavily colored pigments. The curing of laminates containing 50–70 wt % glass fiber mat could also be followed by Raman spectroscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1285–1292, 2004     

Comparison of the curing kinetics of the RTM6 epoxy resin system using differential scanning calorimetry and a microwave‐heated calorimeter

The cure of a commercial epoxy resin system, RTM6, was investigated using a conventional differential scanning calorimeter and a microwave‐heated calorimeter. Two curing methods, dynamic and isothermal, were carried out and the degree of cure and the reaction rates were compared. Several kinetics models ranging from a simple nth order model to more complicated models comprising nth order and autocatalytic kinetics models were used to describe the curing processes. The results showed that the resin cured isothermally showed similar cure times and final degree of cure using both conventional and microwave heating methods, suggesting similar curing mechanisms using both heating methods. The dynamic curing data were, however, different using two heating methods, possibly suggesting different curing mechanisms. Near‐infrared spectroscopy showed that in the dynamic curing of RTM6 using microwave heating, the epoxy‐amine reaction proceeded more rapidly than did the epoxy‐hydroxyl reaction. This was not the case during conventional curing of this resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3658–3668, 2006     

Syntheses and properties of low‐level melamine‐modified urea–melamine–formaldehyde resins

Syntheses of urea–melamine–formaldehyde (UMF) resins were studied using 2–12% melamine levels and UF base resins that were preadvanced to various different extents. The melamine reaction was carried out at pH 6.3 with F/(U + M) mole ratio of 2.1 until a target viscosity of V was reached (Gardener–Holdt) and then the second urea added at pH 8.0 to give a final F/(U + M) mole ratio of 1.15. Analyses with ¹³C‐NMR and viscosity measurements showed that MF components react fast and the UF components very slowly in the melamine reaction. Therefore, as the extent of preadvancement of UF base resin was decreased, the reaction time to reach the target viscosity became longer and the MF resin components showed high degrees of polymerization. The overpolymerization of MF components resulted in increasingly more opaque resins, with viscosity remaining stable for more than a month. As the preadvancement of UF base resin was increased, the extent of advancement of MF components decreased, to give clearer resins, with viscosity slowly increasing at room temperature. Overall, preadvancing the UF base resin components to an appropriate extent was found to be a key to synthesizing various low‐level melamine‐modified UMF resins. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2559–2569, 2004     

Study of glycidyl ether as a new kind of modifier for urea‐formaldehyde wood adhesives

In this work, the multiepoxy functional glycidyl ether (GE) modified urea‐formaldehyde (UF) resins were synthesized via a traditional alkaline‐acid process under low formaldehyde/urea (F/U) molar ratio. The synthesized resins were characterized by ¹³C magnetic resonance spectroscopy (¹³C‐NMR), indicating that GE can effectively react with UF resins via the ring‐opening reaction of epoxy groups. Moreover, the residual epoxy groups of GE could also participate in the curing reaction of UF resins, which was verified by Fourier transform infrared spectroscopy. The storage stability of GE‐modified UF resins and the thermal degradation behavior of the synthesized resins were evaluated by using optical microrheology and thermogravimetric analysis, respectively. Meanwhile, the synthesized resins were further employed to prepare the plywood with the veneers glued. For the modification on bonding strength and formaldehyde emission of the plywood, the influences of addition method, type, and amount of GE were systematically investigated. The performance of UF adhesives were remarkably improved by the modification of GE around 20–30% (weight percentage of total urea) in the acidic condensation stage during the resin synthesis. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Differential scanning calorimetry characterization of urea–formaldehyde resin curing behavior as affected by less desirable wood material and catalyst content

Differential scanning calorimetry was applied to investigate the curing behavior of urea–formaldehyde (UF) resin as affected by the catalyst content and several less desirable wood materials (e.g., wood barks, tops, and commercial thinnings). The results indicate that the reaction enthalpy of UF resin increased with increasing catalyst content. The activation energy and peak temperature of the curing UF resin generally decreased with increasing catalyst content at lower levels of catalyst content. However, with further increases in catalyst content, the changes in the activation energy and peak temperature were very limited to nonexistent. The hydrolysis reaction of the cured UF resin occurred during the latter stages of the curing process at both lower level (<0.2%) and higher level (>0.7%) catalyst contents. This indicates that there existed an optimal range of catalyst content for the UF resin. The curing enthalpy of the UF resin decreased with increasing wood raw materials present due to the effect of diffusion induced by the wood materials and the changes in the phase of the curing systems. This suggests that the curing reactions reached a lower final degree of conversion for the wood–resin mixtures than for the UF resin alone. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2027–2032, 2005     

In situ pultrusion of urea–formaldehyde matrix composites. I. Processability,kinetic analysis,and dynamic mechanical properties

We conducted a feasibility study on the pultrusion of a glass‐fiber‐reinforced urea–formaldehyde (UF) composite using a proprietary method. The UF prepolymer synthesized in this study was prepared from blends of UF monomer and a curing agent (NH₄Cl).The process feasibility, kinetic analysis, and dynamic mechanical properties of the glass‐fiber‐reinforced UF composites by pultrusion were investigated. From investigations of the long pot life of the UF prepolymer, the high reactivity of the UF prepolymer, and excellent fiber wet‐out, we found that the UF resin showed excellent process feasibility for pultrusion. A kinetic model, dα/dt = A exp(?E/RT)α^m(1 ? α)ⁿ, is proposed to describe the curing behavior of a UF resin. Kinetic parameters for the model were obtained from dynamic differential scanning calorimetry scans with a multiple‐regression technique. The dynamic storage modulus of the pultruded‐glass‐fiber‐reinforced UF composites increased with increasing die temperature, filler content and glass‐fiber content and with decreasing pulling rate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1242–1251, 2002     

A chemorheological model for the cure of unsaturated polyester resin

A chemorheological model is developed, using the free volume concept, for the prediction of viscosity during the cure of unsaturated polyester resin. We have incorporated into the development of the chemorheological model a mechanistic kinetic model of curing kinetics that predicts the degree of cure as a function of cure time. The mechanistic kinetic model uses an approach of free-radical polymerization that takes into account diffusion-controlled curing reactions, In order to test the usefulness of the chemorheological model developed, we have conducted cure experiments and measured viscosities of partially cured resin samples, using a general-purpose unsaturated polyester resin. Specifically, the following measurements were taken: (1) the quantity of ethylenic double bonds in the resin system before and after the cure reaction by infrared spectroscopy, (2) the glass transition temperature by differential scanning calorimetry (DSC) and (3) the viscosity as a function of shear rate, at several temperatures, using a cone-and-plate rheometer. It is concluded that the chemorheological model developed is very useful for predicting the variation of viscosity during the cure of unsaturated polyester resin.     

Reactivity,chemical structure,and molecular mobility of urea–formaldehyde adhesives synthesized under different conditions using FTIR and solid‐state 13C CP/MAS NMR spectroscopy

This study was conducted to investigate the effects of reaction pH condition and hardener type on the reactivity, chemical structure, and molecular mobility of urea–formaldehyde (UF) resins. Three different reaction pH conditions, such as alkaline (7.5), weak acid (4.5), and strong acid (1.0), were used to synthesize UF resins, which were cured by adding four different hardeners (ammonium chloride, ammonium sulfate, ammonium citrate, and zinc nitrate) to measure gel time as the reactivity. FTIR and ¹³C‐NMR spectroscopies were used to study the chemical structure of the resin prepared under three different reaction pH conditions. The gel time of UF resins decreased with an increase in the amount of ammonium chloride, ammonium sulfate, and ammonium citrate added in the resins, whereas the gel time increased when zinc nitrate was added. Both FTIR and ¹³C‐NMR spectroscopies showed that the strong reaction pH condition produced uronic structures in UF resin, whereas both alkaline and weak‐acid conditions produced quite similar chemical species in the resins. The proton rotating‐frame spin–lattice relaxation time (T_1ρH) decreased with a decrease in the reaction pH of UF resin. This result indicates that the molecular mobility of UF resin increases with a decrease in the reaction pH used during its synthesis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2677–2687, 2003     

Synthesis,characterization, and curing of {2,6–bis‐[2‐(bis‐oxiranylmethyl‐amino)‐methylbenzyl]‐phenyl}‐bis‐oxiranylmethylamine (BPBOMA)

The curing behavior of epoxy resin prepared by reacting epichlorohydrin with amine functional aniline acetaldehyde condensate (AFAAC) was investigated using AFAAC as a curing agent. The epoxy resin, {2,6‐bis‐[2‐(bis‐oxiranylmethyl‐amino)‐methylbenzyl]‐phenyl}‐bis‐oxiranylmethylamine (BPBOMA), was characterized by FTIR and ¹H‐NMR spectroscopy, viscosity measurement, and determination of epoxy content. Analysis of the curing reaction was followed by differential scanning calorimetry (DSC) analysis. To investigate the curing kinetic with AFAAC, dynamic DSC scans were made at heating rates of 5, 10, 15, and 20°C/min. The activation energy and frequency factor of the AFAAC formulation were evaluated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3168–3174, 2006     

Curing characteristics of urea–formaldehyde resin in the presence of various amounts of wood extracts and catalysts

The characteristics of urea–formaldehyde (UF) resin curing in the presence of wood extracts and a catalyst [ammonium chloride (NH₄Cl)] were investigated by differential scanning calorimetry (DSC). The effects of extracts from 16 wood species on resin curing behaviors were evaluated. A model developed in this study, T_p = 53.296 exp(?9.72C) + 93.104, could be used to predict the resin curing rate in terms of the DSC peak temperature (T_p) as influenced by the NH₄Cl content (C). The results indicated that the curing rate of UF resin increased as the catalyst content increased and reached a maximum when the catalyst content ranged from 0.5 to 1.0% (solid basis over liquid UF resin weight). Further increases in the catalyst content had no effect on the resin curing rate. The curing rates of UF resin in the presence of wood extracts increased with decreased pH values or increased base buffer capacities. It was also discovered that the activation energy could not fully explain the resin curing behavior when some species of wood extracts were present, and therefore, the pre‐exponential factor had to be taken into account. The concept of the equivalent catalyst content (ECC) of wood extracts to the NH₄Cl content was introduced in this study; ECCs ranged from 0.0022 to 0.0331% among the 16 wood species. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

13C‐NMR, 13C‐13C gCOSY,and ESI‐MS characterization of ether‐bridged condensation products in N,N′‐dimethylurea‐formaldehyde systems

The reaction of urea with formaldehyde is the basis for the production of urea‐formaldehyde (UF) resins which are widely applied in the wood industry. The presence of ether‐bridged condensation products in the UF resin reaction system is an open question in the literature. It is addressed in the present work. The N,N′‐dimethylurea‐formaldehyde model system was studied since it is chemically similar to the UF resin reaction system but allows for a simple elucidation of all reaction products. It was analyzed by ¹³C‐NMR spectroscopy and ESI‐MS. In corresponding NMR and MS spectra, peaks due to methoxymethylenebis(dimethyl)urea and its hemiformal were observed. ¹³C‐¹³C gCOSY analysis was conducted using labeled ¹³C‐formaldehyde. The correlation spectra showed evidence for an ether‐bridged compound and mass spectra exhibited peaks agreeing with labeled methoxymethylenebis(dimethyl)urea and its hemiformal. Methoxymethylenebis(dimethyl)urea was characterized in N,N′‐dimethylurea‐formaldehyde systems in acidic and slightly basic media. As urea is very similar to N,N′‐dimethylurea, the results of this work strengthen the assumption that ether‐bridged condensation products are likely to form in UF resins. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Kinetic study of phenolic resin cure by IR spectroscopy

The cure reaction of a commercial phenolic resin (FRD‐5002, Borden Chimie S.A.) has been studied by IR spectroscopy (Fourier transform IR). A phenomenological approach was used to characterize the kinetic of reaction. Various kinetic models, including homogeneous reactions, diffusion‐controlled reactions, phase boundary movement, and nucleation and growth‐type kinetic, have been tested. Kinetic analyses using integral procedures on isothermal data indicate that the cure reaction data can be described above 140°C using the homogeneous first‐order reaction model. The activation energy has been found to be about 49.6 kJ mol⁻¹. At lower temperature, a diffusive mechanism was active, and the kinetic of reaction was well described by the Jander kinetic model. Because of the simple kinetic control active above 140°C, a mechanistic model for the resol cure at these temperatures has been also proposed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2703–2715, 1999     

Testing by fourier transform infrared species variation during melamine–urea–formaldehyde resin preparation

The preparation of an industrially used sequential formulation of a melamine–urea–formaldehyde resin was followed with Fourier transform infrared (FTIR). The analysis allowed us to identify the increases and decreases of the main groups in the resin and to compare this system of resin analysis with results previously obtained by ¹³C‐NMR analysis. The FTIR analysis, although considerably more limited than ¹³C‐NMR analysis, allowed us nonetheless to identify and follow the appearance, increase, decrease, and disappearance of several of the main chemical groups during the preparation of the initial urea–formaldehyde (UF) phase of the reaction and the subsequent reaction of melamine with the UF resin that was formed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007