Colloidal aggregation of aminoplastic polycondensation resins: Urea–formaldehyde versus melamine–formaldehyde and melamine–urea–formaldehyde resins

Colloidal particles formation followed by their clustering have been shown to be the normal way of ageing of aminoplastic resins, namely urea–formaldehyde (UF) resins, melamine–formaldehyde (MF) resins, and melamine–urea–formaldehyde (MUF) resins. Ageing or further advancement of the resin by other means such as longer condensation times causes whitening of the resin. This is a macroscopic indication of both the formation of colloidal particles and of their clustering. It eventually progresses to resins, which are mostly in colloidal, clustered state, followed much later on by a supercluster formation starting to involve the whole resin. The initial, filament‐like colloidal aggregates formed by UF resins have different appearance than the globular ones formed by MF resins. MUF resins present a short rod‐like appearance hybrid between the two. GPC has been shown to detect the existence of colloidal superaggregates in a UF resin, while smaller aggregates might not be detected at all. The star‐like structures visible in the colloidal globules of MF resins are likely to be light interference patterns of the early colloidal structures in the resins. These star‐like interference patterns become more complex with resin ageing or advancement due to the advancement of the resin to more complex aggregates, to eventually reach the stage in which filament‐like and rod‐like structures start to appear. The next step is formation of globular masses that are representative of the true start of physical gelation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1406–1412, 2006     

TTT and CHT curing diagrams of water‐borne polycondensation resins on lignocellulosic substrates

Lignocellulosic substrates such as wood were found to have a marked modifying influence on both lower temperature and higher temperature zones of TTT and CHT diagrams during hardening of phenol–resorcinol–formaldehyde (PRF) and melamime–urea–formaldehyde (MUF) polycondensates. Although the modifying influence of the substrate on the higher temperature zone of CHT diagrams presented the same trend of what was already reported for phenol–formaldehyde (PF) and urea–formaldehyde (UF) polycondensates, marked differences from what reported in the literature were recorded for TTT diagrams of all these polycondensates as well for the lower temperature zones of the CHT diagrams on lignocellulosic substrates, both of which had not been investigated previously. The chemical and physical mechanisms of the interactions of the resins, the substrate, and the water carrier causing such marked variations are presented and discussed. Although in the higher temperature zones both substrate and water carrier play an important role, in the lower temperature zone the presence of water appears to be the dominant factor causing the observed variations. The generalized modified CHT and TTT diagrams characteristic of the behavior of these water‐borne polycondensates on lignocellulosic substrates can be used to describe the behavior and complex changes of phase the formaldehyde‐based polycondensation resins undergo when used as wood adhesives during their curing directly in the wood joint. The results also show that diagrams obtained with pure resin cannot be used to predict the behavior of the polycondensate when this is markedly modified by the presence of interacting solvents and substrates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2128–2139, 2001     

Examination of selected synthesis parameters for wood adhesive‐type urea–formaldehyde resins by 13C NMR spectroscopy. III

The varying polymer structures of wood adhesive‐type urea–formaldehyde resins resulting from different formaldehyde/first urea (F/U₁) mole ratios used in the first step of resin manufacture were investigated using ¹³C. As the F/U₁ mole ratio decreased progressively from 2.40 to 2.10 and to 1.80, the viscosity increase due to polymerization during resin synthesis became faster and resulted in decreasing side‐chain branches and increasing free urea amide groups in the resin structure. The resultant UF resins, with the second urea added to an overall F/(U₁ + U₂) of 1.15, showed viscosity decreases when heated with stirring or allowed to stand at room temperature that were also characteristic with the F/U₁ mole ratios used in resin synthesis. The formaldehyde emission levels of particleboards bonded with the freshly made UF resins showed relatively small but similarly characteristic variations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2800–2814, 2001     

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     

13C NMR investigation of the reaction in water of UF resins with blocked emulsifiable isocyanates

A solid state ¹³C NMR study of hardened networks obtained by the reaction of blocked and nonblocked isocyanates (pMDI) with urea‐formaldehyde (UF) resins in water showed different results according to the temperature of the reaction. At high temperature, in water, both a nonblocked or an emulsifiable, blocked isocyanate, appear to crosslink with UF resins through the formation both of traditional methylene bridges connecting urea to urea and of urethane bridges. The latter have been confirmed by ¹³C NMR to form in water by reaction of the isocyanate ? N?C?O group with the hydroxymethyl groups of the UF resin. At ambient temperature, UF/pMDI resins where the pMDI is a emulsifiable blocked isocyanate, do not appear to form urethanes to any great extent but rather to crosslink through the usual UF resin urea to urea methylene bridges. Even in this case, when urethane bridges appear to be absent, evidence of crosslinking in water through reaction of the isocyanate with the ? NH₂ and ? NH? amide of the UF resin has not been observed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 589–596, 2006     

Evaluation of melamine‐modified urea‐formaldehyde resins as particleboard binders

Particleboards bonded with 6 and 12% melamine‐modified urea‐formaldehyde (UMF) resins were manufactured using two different press temperatures and press times and the mechanical properties, water resistance, and formaldehyde emission (FE) values of boards were measured in comparison to a typical urea‐formaldehyde (UF) resin as control. The formaldehyde/(urea + melamine) (F/(U + M)) mole ratio of UMF resins and F/U mole ratio of UF resins were 1.05, 1.15, and 1.25 that encompass the current industrial values near 1.15. UMF resins exhibited better physical properties, higher water resistance, and lower FE values of boards than UF resin control for all F/(U + M) mole ratios tested. Therefore, addition of melamine at these levels can provide lower FE and maintain the physical properties of boards. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Rheometry of aging of colloidal melamine–urea–formaldehyde polycondensates

Aged and whitened melamine–urea–formaldehyde (MUF) resins in a colloidal state were tested with parallel‐plate rheometry to determine the extent of their viscoelastic behavior. Only in advanced colloidal states, and so only when aggregated colloidal clusters occurred, did the resins present clear indications of viscoelastic responses, as illustrated by the crossover of elastic modulus and viscous modulus curves at lower strain percentages. These colloidal clusters were labile microstructures, which, broken by applied shear, justified the known thixotropic behavior of these resins sufficiently advanced by aging or other means. MUF resins already in the colloidal state, but for which colloidal clustering had not yet occurred, behaved exclusively as viscous liquids. Two different cases of physical gelation were observed, reversible physical gelation and irreversible physical gelation, underlying which a true gel situation possibly occurred. Physical gelation due to colloidal superstructures occurred in both, but the difference in the resin average molecular masses revealed if the physical gelation was reversible or irreversible and, therefore, if the liquid/cluster separation was defined as the terminal phase of physical gelation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 655–659, 2005     

Examination of selected synthesis and room‐temperature storage parameters for wood adhesive‐type urea–formaldehyde resins by 13C‐NMR spectroscopy. IV

Typical particleboard wood‐adhesive urea–formaldehyde (UF) resins, synthesized with formaldehyde/first urea (F/U₁) mol ratios of 1.80, 2.10, and 2.40 and the second urea added to an overall F/U ratio of 1.15, in weak alkaline pH, were allowed to stand at room temperature over a period of 50 days. ¹³C‐NMR of time samples taken over the storage period showed gradual migration of hydroxymethyl groups from the polymeric first‐urea components to the monomeric second‐urea components and also an advancing degree of polymerization of resins by forming methylene and methylene ether groups involving the second urea. These phenomena that varied with the F/U₁ mol ratios used in the resin syntheses due to the varying polymer branching structures resulted in the first step of resin synthesis. Varying viscosity decreases and increases of the resins also occurred. Due to these chemical and physical changes, the particleboards that bonded with the sampled resins showed varying bond strength and formaldehyde‐emission values, indicating process optimizations possible to improve bonding and formaldehyde‐emission performances. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1155–1169, 2001     

Melamine‐bridged alkyl resorcinol modified urea–formaldehyde resin for bonding hardwood plywood

A powdery product was obtained by the reaction of methylolated melamine with alkyl resorcinols to form melamine‐bridged alkyl resorcinols (MARs). The effects of the addition of this powder on the bonding strength and formaldehyde emission of urea–formaldehyde (UF) resins were investigated. Three types of UF resins with a formaldehyde/urea molar ratio of 1.3 synthesized by condensation at pH 1.0 (UF‐1.0), pH 4.5 (UF‐4.5), and pH 5.0 (UF‐5.0) were fabricated. The addition of MAR to UF‐4.5 and UF‐5.0 for bonding hardwood plywood enhanced the bonding strength and reduced formaldehyde emission. For UF‐1.0, the addition of MAR adversely affected the bonding strength. However, the UF‐1.0 resin yielded the lowest formaldehyde emission of all of the UF resins in the study. The effects of the MAR addition were related to the molecular structures of the UF resins. UF‐1.0 contained a large amount of free urea, a considerable number of urons, and a highly methylene‐linked, ring‐structured higher molecular weight fraction and had a smaller number of methylol groups. Therefore, the addition of MAR was considered to cause a shortage of the methylol groups, which in turn, led to incomplete resin curing. In contrast to UF‐1.0, UF‐5.0 contained a smaller amount of free urea and a linearly structured higher molecular weight fraction and had a larger number of methylol groups. In this case, MAR was considered to effectively react with the methylol groups to develop a three‐dimensional crosslinked polymer network to enhance the bonding strength and suppress the generation of free formaldehyde to reduce formaldehyde emission. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Examination of selected synthesis and room‐temperature storage parameters for wood adhesive‐type urea–formaldehyde resins by 13C‐NMR spectroscopy. V

The effects of posttreatments of particleboard adhesive‐type urea–formaldehyde resins were studied. The resins were synthesized with formaldehyde/first urea (F/U₁) mol ratios of 1.40, 1.60, 1.80, 2.10, and 2.40 and then the second urea was added to give a final formaldehyde/urea ratio of 1.15 in alkaline pH. The resins were posttreated at 60°C for up to 13.5 h and the 2.5‐h heat‐treated resin samples were stored at room temperature for up to 27 days. Resins sampled during the posttreatments were examined by ¹³C‐NMR and evaluated by bonding particleboards. In the posttreatments, hydroxymethyl groups on the polymeric resin components dissociated to formaldehyde and reacted with the second urea, and methylene and methylene–ether groups were formed from reactions involving the second urea. Methylene–diurea and urea groups bonded to UF polymers were identified. As a result, the viscosity of the resins initially decreased but later increased along with the cloudiness of the resins. Bond‐strength and formaldehyde‐emission values of particleboard varied with posttreatment variables as well as with the F/U₁ mol ratios used in the resin syntheses. The results would be useful in optimizing resin synthesis and handling parameters. Various reaction mechanisms were considered. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1896–1917, 2003     

Synthesis–structure–performance relationship of cocondensed phenol–urea–formaldehyde resins by MALDI‐ToF and 13C NMR

Matrix assisted laser desorption ionization time of flight (MALDI‐ToF) mass spectrometry has consistently confirmed on a number of PUF resins that phenol–urea cocondensates exist in phenol–urea–formaldehyde (PUF) resins. A noticeable proportion of methylene‐linked phenol to urea cocondensates were detected in all the PUF resins tried, alongside methylene bridges connecting phenol to phenol and urea to urea. The PUF, PF, and UF oligomers formed were identified. Variations of the PUF preparation procedure did always yield a certain proportion of the mixed phenol to urea cocondensates. Their relative proportion was determined and related the synthesis procedure used. Comparison of the MALDI‐ToF results with a ¹³C NMR investigation showed that in a real PUF resin in which phenol to urea cocondensates were identified the methylene bridge NMR signal at 44 ppm, characteristic of phenol to urea unsubstituted model compound cocondensates, does not appear at all. This confirmed that this peak cannot be taken as an indication of the existence of phenol and urea condensation under actual resin preparation conditions. The peak indicating cocondensation in PUF resins in which the phenolic nuclei and urea are substituted appears instead at 54.7–55.0 ppm. Thermomechanical analysis has again confirmed that the resin gel times greatly accelerates with increasing urea molar content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of formaldehyde to urea mole ratio on thermal curing behavior of urea–formaldehyde resin and properties of particleboard

As a part of abating the formaldehyde emission (FE) of urea–formaldehyde (UF) resin, this study was conducted to investigate the effects of formaldehyde to urea (F/U) mole ratio on thermal curing behavior of UF resins and properties of PB bonded with them. UF resins synthesized at different F/U mole ratios (i.e., 1.6, 1.4, 1.2, and 1.0) were used for the manufacture of PB. Thermal curing behavior of these UF resins was characterized using differential scanning calorimetry (DSC). As the F/U mole ratio decreases, the gel time, onset and peak temperatures, and heat of reaction (ΔH) increased, while the activation energy (E_a) and rate constant (k) were decreased. The amount of free formaldehyde of UF resin and FE of PB prepared decreased in parallel with decreasing the F/U mole ratio. The internal bond strength, thickness swelling, and water absorption of PB was slightly deteriorated with decreasing the F/U mole ratio of UF resins used. These results indicated that as the F/U mole ratio decreased, the FE of PB was greatly reduced at the expense of the reactivity of UF resin and slight deterioration of performance of PB prepared. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1787–1792, 2006     

Uron and uron–urea‐formaldehyde resins

The favored pH ranges for the formation of urons in urea‐formaldehyde (UF) resins preparation were determined, these being at pH's higher than 6 and lower than 4 at which the equilibrium urons ↔ N,N′‐dimethylol ureas are shifted in favor of the cyclic uron species. Shifting the pH slowly during the preparation from one favorable range to the other causes shift in the equilibrium and formation of a majority of methylol ureas species, whereas a rapid change in pH does not cause this to any great extent. UF resins in which uron constituted as much as 60% of the resin were prepared and the procedure to maximize the proportion of uron present at the end of the reaction is described. Uron was found to be present in these resins also as linked by methylene bridges to urea and other urons and also as methylol urons, the reactivity of the methylol group of this latter having been shown to be much lower than that of the same group in methylol ureas. Thermomechanical analysis (TMA) tests and tests on wood particleboard prepared with uron resins to which relatively small proportions of urea were added at the end of the reaction were capable of gelling and yielding bonds of considerable strength. Equally, mixing a uron‐rich resin with a low F/U molar ratio UF resin yielded resins of greater strength than a simple UF of corresponding molar ratio indicating that UF resins of lower formaldehyde emission with still acceptable strength could be prepared with these resins. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 277–289, 1999     

NMR study of the stabilities of urea–formaldehyde resin components toward hydrolytic treatments

The solid residues of nine urea–formaldehyde (UF) resins after hydrolytic treatment at pH4 and 86°C for 20 h and the solid residues of one UF resin after eight different hydrolytic treatments were examined by ¹³C-CP–MAS NMR. The relative stability toward hydrolysis of each structural component in each UF resin was established for various hydrolytic conditions. In general, UF resins prepared from starting mixtures with a formal F/U molar ratio of 1.00 show a high degree of stability toward hydrolysis. Cross-linking methylene linkages in the UF resins show a higher susceptibility to hydrolytic treatments at pH 4 and 86°C than do linear methylene linkages. UF resins prepared with an F/U molar ratio of 2.00 are susceptible to hydrolysis at pH 4 and 86°C. Dimethylene ether linkages, methylols attached to tertiary amides, and poly(oxymethylene glycol) moieties are probably the main formaldehyde emitters in UF resin products. © 1994 John Wiley & Sons, Inc.     

Fast advancement and hardening acceleration of low‐condensation alkaline PF resins by esters and copolymerized urea

Low‐condensation phenol‐formaldehyde (PF) resins coreacted under alkaline conditions with up to 42% molar urea on phenol during resin preparation yielded PUF resins capable of faster hardening times than equivalent pure PF resins prepared under identical conditions and presented better performance than the latter. The water resistance of the PUF resins prepared seemed comparable to pure PF resins when used as adhesives for wood particleboard. Part of the urea was found by ¹³C‐NMR to be copolymerized to yield the alkaline PUF resin; whereas, especially at the higher levels of urea addition, unreacted urea was still present in the resin. Increase of the initial formaldehyde to phenol molar ratio decreased considerably the proportion of unreacted urea and increased the proportion of PUF resin. A coreaction scheme of phenolic and aminoplastic methylol groups with reactive phenol and urea sites based on previous model compounds work has been proposed, copolymerized urea functioning as a prebranching molecule in the forming, hardened resin network. The PUF resins prepared were capable of further noticeable curing acceleration by addition of ester accelerators; namely, glycerol triacetate (triacetin), to reach gel times as fast as those characteristic of catalyzed aminoplastic resins, but at wet strength values characteristic of exterior PF resins. Synergy between the relative amounts of copolymerized urea and ester accelerator was very noticeable at the lower levels of the two parameters, but this effect decreased in intensity toward the higher percentages of urea and triacetin. ¹³C‐NMR assignements of the relevant peaks of the PUF resins are reported and compared with what has been reported in the literature for mixed, coreacted model compounds and pure PF and urea‐formaldehyde (UF) resins. The relative performance of the different PUF resins prepared was checked under different conditions by thermomechanical analysis (TMA) and by preparation of wood particleboard, and the capability of the accelerated PUF resins to achieve press times as fast as those of aminoplastic (UF and others) resins was confirmed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 359–378, 1999     

Determination of formaldehyde/urea molar ratio in amino resins by near‐infrared spectroscopy

New processes for synthesis of urea‐formaldehyde (UF) and melamine‐fortified urea‐formaldehyde (mUF) resins have been developed in the last years, motivated by the current concerns about the effects of formaldehyde on human health. All these formulations are quite susceptible to possible operation error, which can significantly influence the characteristics of the final product. The main objective of this work was to implement chemometric techniques for off‐line monitoring of the product's formaldehyde/urea (F/U) molar ratio using near infrared (NIR) spectroscopy. This allows the timely implementation of the necessary corrections in case the product is off‐specification. Calibration models for F/U molar ratio were developed taking into account the most relevant spectral regions for these resins, individually or in combination (7502–6098 cm^?1 and 5000–4246 cm^?1) and using different preprocessing methods. When the appropriate spectral range and preprocessing methods are selected, it is possible to obtain calibration models with high correlation values for these resins. The best preprocessing methods were identified for three cases: UF resin (produced by strongly‐acid process), mUF resin (alkaline‐acid process), and a combined model that involves both UF and mUF resins. It was concluded that significantly better accuracy is obtained when a new model is developed for each particular resin system. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

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     

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     

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