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     

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     

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     

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     

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     

Production of melamine fortified urea‐formaldehyde resins with low formaldehyde emission

Melamine can be incorporated in the synthesis of urea‐formaldehyde (UF) resins to improve performance in particleboards (PB), mostly in terms of hydrolysis resistance and formaldehyde emission. In this work, melamine‐fortified UF resins were synthesized using a strong acid process. The best step for melamine addition and the effect of the reaction pH on the resin characteristics and performance were evaluated. Results showed that melamine incorporation is more effective when added on the initial acidic stage. The condensation reaction pH has a significant effect on the synthesis process. A pH below 3.0 results on a very fast reaction that is difficult to control. On the other hand, with pH values above 5.0, the condensation reaction becomes excessively slow. PBs panels produced with resins synthesized with a condensation pH between 4.5 and 4.7 showed good overall performance, both in terms of internal bond strength and formaldehyde emissions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fast advancement and hardening acceleration of low condensation alkaline phenol‐formaldehyde resins by esters and copolymerized urea. II. Esters during resin reaction and effect of guanidine salts

Guanidine carbonate is shown to be an accelerator of phenol‐formaldehyde (PF) resins that while yielding slightly slower gel times than triacetin when added to a PF resin glue mix, is also capable of giving glue‐mix pot lives on the order of several days. Hence, this is long enough to be premixed with the resin long before use. Both triacetin and guanidine carbonate used as simple glue‐mix additives are shown to increase the ultimate strength of the resin bond, whatever the length of the curing time used for the purpose. This is shown by thermomechanical analysis and the application to wood particleboard. Triacetin is shown to be usable during PF resin preparation rather than just being added to the glue mix, yielding better resins capable of giving higher bond values without a great acceleration of the geling of the resin itself. The mechanisms involved in the acceleration of PF resins introduced by both compounds appears to be based on facilitating reactions of crosslinking involving carbonic acid ions present in the resin solution. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 249–259, 2000     

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     

Low addition of melamine salts for improved melamine‐urea‐formaldehyde adhesive water resistance

The addition of melamine acetate salts to an adhesive glue mix can allow the use of melamine–urea–formaldehyde (MUF) resins of lower melamine contents (rather than just urea–formaldehyde resins) and lower total amounts of melamine. Performances can be obtained that are characteristic of the top‐of‐the‐line, generally higher melamine content MUF adhesive resins for the preparation of wood particleboard panels. Improvements in the panel internal‐bond strength of greater than 30% can be obtained by the addition of melamine acetate salts to top‐of‐the‐line MUF resins. The approach to the concept of increased melamine solubility with a melamine salt is compatible with the approach of increasing melamine solubility with solvents such as acetals (e.g., methylal). However, the synergy advantage of using the two approaches jointly is not very marked. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 287–292, 2003     

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     

三聚氰胺草酸盐与氯化铵作为UF固化剂的性能对比

以三聚氰胺草酸盐(MOX)和氯化铵分别作为脲醛树脂(UF)的固化剂,然后以相应的改性UF胶粘剂压制胶合板,并探讨了不同固化剂对UF的固化时间、胶合板的胶接强度和甲醛释放量等影响。结果表明:以MOX作为固化剂时,相应UF的固化速率相对较慢,由该改性UF胶粘剂压制而成的胶合板,其胶接强度相对较高,甲醛释放量略高于含氯化铵体系;含MOX固化剂的UF胶粘剂,其DSC曲线峰顶温度(86.22℃)和吸热量(51.14 J/mg)低于含氯化铵体系,并且含MOX体系的固化反应比较平稳。     

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     

Renewable polyol‐based polycarbamates and polycarbamate–formaldehyde thermosetting resins

Several polycarbamates and polycarbamate–formaldehyde (CF) resins were synthesized, and their properties were investigated aiming at developing of useful thermosetting polymer materials from simple polyols including those derived from renewable resources. Polycarbamates synthesized from polyols using two‐step laboratory routes showed good storage stabilities making them suitable as large volume industrial chemicals. Furthermore, syntheses and ¹³C‐NMR studies of CF resins showed the formation of oligomeric resins having hydroxymethyl and methylene groups with thermosetting curing properties that are similar to those of current urea–formaldehyde (UF) resins. Dynamic mechanical analysis studies showed somewhat slower curing rates for CF resins compared to UF resins. Bonding of particleboard and internal bond and free formaldehyde content measurements indicated high‐bond strength values and very low‐formaldehyde emission potentials for CF resins. The higher functionalities of CF resins appear to be the basis of good performances. Further investigations on scalable synthesis methods for polycarbamates and on the expansion of CF resins' bonding capabilities would need to be investigated in the future. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Acetal‐induced strength increases and lower resin content of MUF and other polycondensation adhesives

Acetals such as methylal and ethylal are shown to be particularly effective additives in improving the strength of wood boards bonded with melamine‐ urea‐formaldehyde (MUF) resins, although they show some appreciable but lesser effect on other resins too, particularly phenol‐ formaldehyde resins. They equally allow a considerable decrease in resin loading, and thus, in melamine content, on the bonded wood panel and at parity of performance. Their development as additives is then primarily, but not only, targeted at the MUF adhesive resins. One‐third decreases in MUF adhesives loading at parity of performance or equally internal bond (IB) strength increases approximately up to 50% by addition of methylal are shown to be possible by laboratory particleboard as well as by thermomechanical analysis (TMA). The reasons for methylal and ethylal behavior were studied by a variety of techniques, including liquid‐ and solid‐ phase ¹³C‐NMR and could be mostly ascribed to the increased effectiveness and participation of the melamine to resin crosslinking due to its now preferentially homogeneous rather than heterogeneous reactions, consequences of the increased solubility in water afforded by the acetal cosolvents. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2561–2571, 2002     

Influence of nanoclay on urea‐formaldehyde resins for wood adhesives and its model

The addition of small percentages of Na⁺‐montmorillonite (NaMMT) nanoclay appears to improve considerably the performance of thermosetting urea‐formaldehyde (UF) resins used as adhesives for plywood and for wood particleboard. X‐ray diffraction (XRD) studies indicated that NaMMT loses the periodic atomic structure when mixed in small proportions in the acid‐curing environment characteristic of the curing of UF resins. This can be interpreted as becoming exfoliated under such conditions. The partly crystalline structure of the ordered zones of the UF resins is maintained but at a slightly lower level. Differential scanning calorimetry (DSC) indicated that NaMMT has an accelerating effect on the curing of the UF resin. It also appears to lead to a more controlled rate of crosslinking implying a more regular hardened network. The influence of NaMMT addition was particularly noted in plywood by the increase in water resistance of the UF‐bonded panel. In the case of wood particleboard even the dry internal bond strength of the panel, a direct indication of the performance of the resin, improved with small additions of NaMMT. A hypothesis and model of the reasons why such improvement to the performance of UF resins by addition of nanoclay should occur has been presented. This is based on the application of percolation theory to the networking capability of the clay nanoplatelets. © 2008 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     

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     

Effects of urea and curing catalysts added to the strand board core‐layer binder phenol–formaldehyde resin

Effects of adding urea to the strand board core‐layer phenol–formaldehyde (PF) resin were investigated in conjunction with cure‐accelerating catalysts. Ten percent urea based on the liquid resin weight was added at the beginning, at three different middle stages of polymerization, and at the end of PF resin synthesis. No significant cocondensation between the urea and PF resin components occurred as identified by ¹³C NMR analyses, which corroborated well with the curing and strand board bonding performance test results. The various urea addition methods resulted in resins that slightly differ in the various tests due to the urea's temporary holding capacity of formaldehyde. The preferred method of urea addition was found to do it in the later part of PF resin synthesis for convenience, consistency, and slightly better overall performance. Some cure‐accelerating catalysts were shown to reduce the thickness swelling of strand boards. This study showed the usefulness of adding some urea to strand board core‐layer binder PF resins of replacing higher cost phenolic components with lower cost urea. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

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