Re‐elucidation of the acid‐catalyzed urea–formaldehyde reactions: A theoretical and 13C‐NMR study

The acid‐catalyzed urea–formaldehyde reactions were reexamined in detail by using quantum chemistry method and ¹³C‐NMR determinations. Some issues in the synthesis theory that were not well understood previously have been addressed and clarified. The identified reaction mechanisms and calculated energy barriers suggest that the competitive formations of methylene and methylene ether linkages are kinetically affected by both reaction energy barriers and steric hindrance effect. The thermodynamic properties determine that the methylene linkages are dominant at the late condensation stage. The theoretical results well rationalized the observed different changing processes of resin structures with different F/U molar ratios. The previously proposed mechanism for transformation of methylene ether linkage to methylene linkage cannot explain the structural changes during condensation, and thus, other mechanisms were proposed. The calculated results for uron explained the fact that the formation of such structure is much slower than other structures under weak acidic condition. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44339.     

Synthesis,structure, and characterization of glyoxal‐urea‐formaldehyde cocondensed resins

To decrease the formaldehyde emission of urea‐formaldehyde (UF) bonded products at source, monomethylol urea (MMU) was chosen to react with glyoxal (G), a nonvolatile and nontoxic aldehyde, to prepare a novel glyoxal‐urea‐formaldehyde (GUF) cocondensed resin. The GUF resins were synthesized with different MMU/G molar ratios, and the basic properties were tested. The GUF resins were characterized by ultraviolet‐visible spectroscopy, Fourier transform infrared spectroscopy, carbon‐13 nuclear magnetic resonance spectroscopy and matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI‐TOF‐MS). The results show that the synthesized GUF resins remain stable for at least 10 days at ambient temperature. Conjugated structures, and large amounts of ? OH, ? NH? , C? N, and C?O groups with different levels of substitution exist in the GUF resin. There are two repeating motives in the MALDI‐TOF‐MS spectrum of the GUF resin, one of 175 ±1 Da and a second one of 161 ± 1 Da. Moreover, the peaks due to the dehydration condensation reaction of MMU also appear in the spectra. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41009.     

Effect of different catalysts on urea–formaldehyde resin synthesis

Four catalysts (H₂SO₄, HCl, H₃PO₄, and NaOH/NH₄OH) were studied in the preparation of melamine modified urea–formaldehyde (UFM) resins. ¹³C‐nuclear magnetic resonance spectroscopic analysis of the UFM resins at different synthesis stages revealed the polymer structure and detailed reaction mechanism. Three acidic catalysts (H₂SO₄, HCl, and H₃PO₄) enhanced the resin polymerization through the formation of various contents of methylene, ether linkages, and urons. H₃PO₄ yielded the most terminal ether linkages at the first stage and enhanced polycondensation by depleting all free urea and glycols to form the most linear methylene linkages NHCH₂NH in the end. However, at the initial synthesis stage, NaOH/NH₄OH catalyzed the formation of UFM prepolymer to a limited extent with a large amount of free urea left, and therefore produced the final polymer with relatively more substituted methylolureas and linear ether linkages. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40644.     

Structure of resorcinol,phenol, and furan resins by MALDI‐TOF mass spectrometry and 13C NMR

The structure of traditional, linear phenol–resorcinol–formaldehyde (PRF) resins, urea‐branched PRF resins, and phenol–resorcinol–furfural (PRFuran) resins has been investigated in depth by both matrix‐assisted laser desorption/ionization time of flight (MALDI‐TOF) mass spectroscopy and ¹³C NMR. The structure of a variety of oligomers has been obtained, and the structures present in each of the three types of resins related to the very different percentages of resorcinol needed for their equal performance as adhesives. The oligomers type and species distribution appeared very different for each case. PRF resins performance is improved by maximizing either the proportion of resorcinol‐containing oligomers or methylol‐groups containing oligomers, even without any resorcinol, or both. It is equally obtained by the minimization of the relative proportion of the low reactivity Phenol (CH₂ Phenol) species in which resorcinol is not present, this being the most important parameter. This can be obtained by more effective use of the resorcinol by just modifying the resin manufacturing procedure. This parameter instead does not appear to be determinant in PRFuran resins. In these, it is the higher molecular weight of furfural in relation to formaldehyde that engenders for the same manufacturing procedure a correspondingly lower proportion of resorcinol in the resin. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2665–2674, 2004     

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     

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     

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     

Shear strain and microscopic characterization of a bamboo bonding interface with poly(vinyl alcohol) modified phenol–formaldehyde resin

The study of the shear strain distribution at the bonding interface helped us to understand the bamboo bonding interface response mechanisms to solve problems of ply bamboo deformation or bonding failure. The shear strain distribution across a two‐ply bamboo sheet bonded with a ductile phenol–formaldehyde resin (PF) modified by poly(vinyl alcohol) (PVA) was measured by means of electronic speckle pattern interferometry, along with tensile strength measurements to prove the shear stain distribution on a macroscopic scale. This research effectively combined macroscopic mechanical properties with microcosmic interfacial mechanical properties. The shear strength and shear strain results showed that PF modified with 20% PVA performed better than common PF and PF modified with 5 and 10% PVA. Microscopic fluorescent characterization of the bonding interface also provided evidence that a new bonding mechanism was adequate for bamboo bonding under the ductile PF modified with 20% PVA. Moreover, we suppose that the results of this study will help in the choice of bamboo‐specific adhesives under different strain conditions. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1345‐1350, 2013     

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

A particleboard adhesive‐type urea–formaldehyde (UF) resin was made at a formaldehyde ratio of 2.10 and added with a second urea at low temperature to the typical final formaldehyde/urea ratio of 1.15. Time samples taken during heat treatments of the resin sample up to 70°C over a period of 250 min showed decreases in Type II/IIi hydroxymethyl group content, accompanied with decreases in resin sample viscosity and increases in formaldehyde emission of bonded particleboards. The results indicate that various hydroxymethyl groups of polymeric UF resin components migrate to the second urea to form Type I hydroxymethyl groups. Time samples taken during the room‐temperature storage of the resin sample over a period of 1 month behaved similarly initially, but in the later stage, some polymerization progressed, shown by increases in viscosity and methylene and methylene–ether group contents. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1243–1254, 2000     

Low‐volatility acetals to upgrade the performance of melamine–urea–formaldehyde wood adhesive resins

1,1,2,2‐Tetramethoxyethane (TME), a high boiling point acetal derived from glyoxol, lhas been shown to upgrade the performance of melamine‐urea‐formaldehyde (MUF) and some UF resins used for wood adhesives. This affords the possibility of decreasing the percentage of resin used in the preparation of wood panels without volatilizing the TME acetal used.     

Preparation of novel CNSL‐based urethane polyol via nonisocyanate route: Curing with melamine‐formaldehyde resin and structure–property relationship

In this study, we report preparation of a novel cashew nut shell liquid (CNSL)‐based polyol bearing urethane groups. The urethane group in the polyol was induced via isocyanate free route from the reaction of cyclic carbonate with primary amine. The polyol was characterized by determination of hydroxyl number, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and so forth. The polyol was then used as coating component and cured with hexamethoxy methylene melamine (HMMM). Another CNSL‐based polyol without urethane moiety from our earlier reported work was used for preparation of coating for comparative study to determine the effect of urethane group on the coating properties. The coating formulations based on these two polyols were cured with variable amounts of HMMM hardener to optimize coating properties. All the coatings were evaluated for mechanical properties such as adhesion, flexibility, pencil and scratch hardness, impact resistance, pull‐off, and adhesion. The optimized coatings were also evaluated for chemical and thermal properties. It was observed that the urethane containing polyol resulted in better adhesion to the metal substrate at higher quantity of HMMM hardener compared to the other polyol providing significant improvement in various coating properties. The final coating properties were also compared with the acrylic polyurethane coatings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41391.     

13C‐NMR study on the structure of phenol‐urea‐formaldehyde resins prepared by methylolureas and phenol

Phenol‐urea‐formaldehyde (PUF) resins were synthesized by reacting mixture of methylolureas (MMU), phenol, and formaldehyde. The structure of PUF cocondensed resins at different stages of reaction were analyzed by liquid ¹³C nuclear magnetic resonance (NMR) spectroscopy. The liquid ¹³C‐NMR analysis indicated that methylolureas had the dominant content in MMU with the reaction between urea and formaldehyde under the alkaline condition. The PUF cocondensed resins had no free formaldehyde. methylolureas were well incorporated into the cocondensed resins by reacting with phenolic units to form cocondensed methylene bridges. The second formaldehyde influenced the further reaction and the structure of the PUF resins. The resins with the prepared method of PUFB possessed relatively high degree of polymerization and low proportion of unreacted methylol groups. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hydrolytic stability of cured urea‐formaldehyde resins modified by additives

Urea‐formaldehyde (UF) resins are prone to hydrolysis that results in low‐moisture resistance and subsequent formaldehyde emission from UF resin‐bonded wood panels. This study was conducted to investigate hydrolytic stability of modified UF resins as a way of lowering the formaldehyde emission of cured UF resin. Neat UF resins with three different formaldehyde/urea (F/U) mole ratios (1.4, 1.2, and 1.0) were modified, after resin synthesis, by adding four additives such as sodium hydrosulfite, sodium bisulfite, acrylamide, and polymeric 4,4′‐diphenylmethane diisocyanate (pMDI). All additives were added to UF resins with three different F/U mole ratios before curing the resin. The hydrolytic stability of UF resins was determined by measuring the mass loss and liberated formaldehyde concentration of cured and modified UF resins after acid hydrolysis. Modified UF resins of lower F/U mole ratios of 1.0 and 1.2 showed better hydrolytic stability than the one of higher F/U mole ratio of 1.4, except the modified UF resins with pMDI. The hydrolytic stability of modified UF resins by sulfur compounds (sodium bisulfate and sodium hydrosulfite) decreased with an increase in their level. However, both acrylamide and pMDI were much more effective than two sulfur compounds in terms of hydrolytic stability of modified UF resins. These results indicated that modified UF resin of the F/U mole ratio of 1.2 by adding acrylamide was the most effective in improving the hydrolytic stability of UF resin. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of phenol–urea–formaldehyde copolymer adhesives under heterogeneous catalysis

A new synthetic strategy for PUF copolymers based on three steps was developed. In the first step, two precondensates of phenol with formaldehyde and urea with formaldehyde, respectively, were produced. In the second step, the two precondensates were mixed and condensed using a heterogeneous catalyst in a tube reactor at 90°C. The last step is a vacuum distillation to reach the final copolymer compositions. With regard to the properties, the products can be used as adhesive. The copolymers were analysed by gel permeation chromatography (GPC), ¹³C‐NMR‐spectroscopy, and MALDI‐TOF mass spectrometry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2946–2952, 2006     

Morphology and chemical elements detection of cured urea–formaldehyde resins

As a part of understanding the hydrolysis of cured urea–formaldehyde (UF) resins that has been known as responsible for the formaldehyde emission, leading to sick building syndrome, this study attempted to investigate the morphology and to detect chemical elements of the cured UF resins of different formaldehyde/urea (F/U) mole ratios and hardener (NH₄Cl) levels, using field emission‐scanning electron microscopy and energy‐dispersive spectroscopy. Cured UF resins of low F/U mole ratio showed spherical structure whose diameter increased with an increase in the hardener level, whereas this was not observed for high F/U mole ratio UF resins regardless of the hardener levels. The energy‐dispersive spectroscopy results showed five different chemical elements such as carbon, nitrogen, oxygen, chloride, and sodium in cured UF resins. The chloride distribution assumed as the presence of residual acid in the cured UF resins suggested that the hydrolysis of cured UF resins could initiate at the sites of chlorides on the surface of the spherical structures. As the hardener level increased, the quantities of both carbon and oxygen decreased, whereas those of nitrogen and chloride increased as expected. But the quantity of sodium was within measurement error. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of the synthesis conditions on the curing behavior of phenol–urea–formaldehyde resol resins

The curing behavior of synthesized phenol–urea–formaldehyde (PUF) resol resins with various formaldehyde/urea/phenol ratios was studied with differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The results indicated that the synthesis parameters, including the urea content, formaldehyde/phenol ratio, and pH value, had a combined effect on the curing behavior. The pH value played an important role in affecting the shape of the DSC curing curves, the activation energy, and the reaction rate constant. Depending on the pH value, one or two peaks could appear in the DSC curve. The activation energy was lower when pH was below 11. The reaction rate constant increased with an increase in the pH value at both low and high temperatures. The urea content and formaldehyde/phenol ratio had no significant influence on the activation energy and rate constant. DMA showed that both the gel point and tan δ peak temperature (T_tanδ) had the lowest values in the mid‐pH range for the PUF resins. A different trend was observed for the phenol–formaldehyde resin without the urea component. Instead, the gel point and T_tanδ decreased monotonically with an increase in the pH value. For the PUF resins, a high urea content or a low formaldehyde/phenol ratio resulted in a high gel point. The effect of the urea content on T_tanδ was bigger than that on the gel point because of the reversible reaction associated with the urea component. Too much formaldehyde could lead to more reversible reactions and a higher T_tanδ value. The effects of the synthesis conditions on the rigidity of the cured network were complex for the PUF resins. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1368–1375, 2005     

Characterization of phenol–urea–formaldehyde resin by inline FTIR spectroscopy

Phenol–urea–formaldehyde (PUF) resins were synthesized by a two‐step polymerization process. The first step was the synthesis of 2,4,6‐trimethylolphenol (TMeP) from phenol and formaldehyde, under alkaline conditions. In the second step PUF resins were synthesized by the reaction of TMeP with urea, under acidic and alkaline conditions. The influence of temperature on the synthesis of TMeP was investigated. The molar ratio between TMeP and urea was varied to study the composition effect on the second step of the PUF synthesis and final product properties. Synthesis of TMeP and PUF resins were monitored by inline FTIR‐ATR system. Analytical methods, such as differential scanning calorimetry, nuclear magnetic resonance, thermogravimetric analysis, and infrared spectroscopy were used for characterization of TMeP and PUF resins. Obtained PUF resins were cured and tested on flexural strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Upgrading of MUF polycondensation resins by buffering additives. II. Hexamine sulfate mechanisms and alternate buffers

Iminoamino methylene bases intermediates are obtained by the decomposition of hexamethylenetetramine (hexamine). These are stabilized by the presence of strong anions such as SO and HSO, that is, “hexamine sulfate.” The effect of hexamine sulfate was closely linked to the strong buffering action it has on MUF resins. Its role is mainly to induce regularity of the reaction and the stability of conditions during resin networking, due to the buffer. Shifting of the polycondensation ? degradation equilibrium to the left appeared to be the determinant factor. This was a consequence of maintaining a higher, constant pH during curing, due to the buffer action. The modulus of elasticity (MOE) increases the curves of hexamine sulfate‐catalyzed MUF resins, confirming this trend. The resins are faster curing than when catalyzed by ammonium sulfate. The effect is valid within the narrow buffering range of pH's used for resin hardening. Polycondensation is far too slow to occur at a much higher pH, and degradation is, instead, more predominant at much lower pH's. The network formed is then more crosslinked and less tainted by degradation when curing occurs within the correct pH range. The result is a much better performance of the wood board after water attack. The effects induced by hexamine sulfate effects are of longer duration than those of other potential buffers. This is due to the hexamine sulfate heat stability under standard hot curing conditions of the resin. Alternate systems were found and shown to have a comparable effect. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 215–226, 2003     

Matrix‐assisted laser desorption/ionization mass spectrometry of synthetic polymers. VI. Analysis of phenol–urea–formaldehyde cocondensates

Phenolic resoles can be regarded as copolymers of phenol and formaldehyde that are distributed in the chain length and the number of methylol groups per molecule. While other spectroscopic methods like FTIR and NMR only give average structures, MALDI–TOF mass spectrometry is able to resolve the oligomer distribution of phenolic resoles. Using 2,5‐dihydroxybenzoic acid or 2,4,6‐trihydroxyacetophenone as matrices, MALDI–TOF spectra are obtained where each oligomer peak can be assigned to a particular chemical structure. Thus, the degree of polymerization and the number of reactive methylol groups can be determined. For urea‐modified resoles, in addition to phenol–formaldehyde and urea–formaldehyde structures, for the first time, phenol–urea–formaldehyde cocondensate structures can be identified directly. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2540–2548, 2003     

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