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     

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     

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     

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     

A very simple empirical kinetic model of the acid‐catalyzed cure of urea–formaldehyde resins

The hot pressing operation is the final stage in MDF (medium density fiberboard) manufacture; the fiber mat is compressed and heated up to promote the cure of the resin. The aim of the investigations is to study the curing reactions of UF (Urea–Formaldehyde) resins as commonly used in the production of MDF, and to develop a simplified kinetic model. This investigation has combined Raman spectroscopy to study the reaction cure and ¹³C‐NMR for the quantitative and qualitative characterization of the liquid and still uncured resin. Raman spectroscopy was found very interesting for the study of the resin cure and permitted to obtain kinetic data as the basis for a simple empirical model, considering a homogeneous irreversible reaction of a single kind of methylol group and ureas with rate constants depending on their degree of substitution. Although these results can provide a better understanding of the composition and the cure of an UF resin, several issues remain open, such as the influence of the reversibility of the reactions taking place during the curing process as well as the possible formation of cyclic groups in the resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5977–5987, 2006     

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     

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     

Preparation,characterization, and composites from low formaldehyde emission urea–formaldehyde–casein copolymer

A modified urea–formaldehyde resin was synthesized by the condensation of urea and formaldehyde in the presence of varying proportions of casein up to 25% (w/w) of urea under alkaline conditions. All the prepared resins were characterized by free‐formaldehyde content, viscosity measurements, and number‐average molecular weight determination by vapor pressure osmometry and IR spectroscopy. Their curing kinetics were studied isothermally and by differential scanning calorimetry on dynamic runs. The resin samples were cured isothermally at 60, 80, and 100°C using ammonium chloride and hydroxylamine hydrochloride as curing agents. The isothermal curing study was also performed with hexamine at 120°C. Cured resins were characterized by IR and thermogravimetric analysis. The resin samples were employed for the fabrication of glass fiber and jute fiber reinforced composites by maintaining 2 : 3 and 3 : 2 proportions of resin/reinforcement, respectively. The prepared composites were tested for their mechanical properties and resistance toward various chemicals. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 531–537, 2005     

Separation of gold(III) ions from copper(II) and zinc(II) ions using thiourea–formaldehyde or urea–formaldehyde chelating resins

Thiourea–formaldehyde (TF) and urea–formaldehyde (UF) chelating resins were synthesized and these resins were used in the separation of gold(III) ions from copper(II) and zinc(II) base metal ions. In the experimental studies, the effect of acidity on gold(III) uptake and gold(III) adsorption capacities by batch method, and loading and elution profiles of gold(III) ions, gold(III), copper(II), and zinc(II), dynamic adsorption capacities and the stability tests of TF and UF resins by column method were examined. By batch method, the optimum acidities were found as pH 2 and 0.5M HCl, and gold(III) adsorption capacities in the solutions including copper(II) and zinc(II) ions were obtained as 0.088 and 0.151 meq Au(III)/g for UF and TF resins, respectively. On the other hand, by column method, the dynamic adsorption capacities were calculated as 0.109 meq Au(III)/g with TF, 0.023 meq Au(III)/g with UF, 0.015 meq Cu(II)/g with TF, 0.0057 meq Cu(II)/g with UF, and under 6.1 × 10^?5 meq Zn(II)/g with TF or UF. TF resin was more effective in the separation and the concentration of gold(III) ions from copper(II) and zinc(II) ions than UF resin. It was seen that sulfur atoms contributed the gold(III) adsorption comparing with oxygen atoms. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

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     

Optimizing the conditions of quantitative 13C-NMR spectroscopy analysis for phenol–formaldehyde resol resins

The experimental time of ¹³C-NMR quantitative analysis of phenol–formaldehyde resins was reduced so that quantitativeness was maintained. The quantitative spectra of 14 model resins were obtained using a gated decoupling technique suppressing the NOE. The paramagnetic additive, Cr(acac)₃, was used to shorten relaxation times of carbon atoms. The use of Cr(acac)₃ was optimized in two deuterated solvents, DMSO and acetone. To reach short relaxation times and further the measurement times, the concentration of relaxation reagent, the delay time, and the number of NMR scans were optimized. Quantitativeness was proved by analyzing the spectra of accurate mixture of model compounds, and the spectra of the condensed model resins. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1805–1812, 1998     

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.     

On the correlation equations of liquid and solid 13C‐NMR,thermomechanical analysis,Tg, and network strength in polycondensation resins

Wide‐scope mathematical relationships have been established between the ¹³C‐NMR of liquid polycondensation resins, such as urea–formaldehyde and phenol–formaldehyde resins, and the strength of the network formed by the same resin when hardened under well‐defined conditions, the thermomechanical analysis deflection, the number average molecular mass and the number of degrees of freedom of the average polymer segment between crosslinking nodes in the hardened resin network, the resin network glass transition temperature, its solid‐phase ¹³C‐NMR proton‐rotating frame spin‐lattice relaxation time, and the homogeneous and heterogeneous polymer segment/polymer segment interfacial interaction energy calculated by molecular mechanics. These mathematical relationships allow the calculation of any of these parameters from any of the techniques listed, provided that all of the systems are used under well‐defined conditions. Under different conditions, the values of the numerical coefficients involved change; and, whereas the equations are still valid, a different set of coefficients needs to be recalculated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1703–1709, 1999     

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     

Resorcinol–formaldehyde reactions in dilute solution observed by carbon‐13 NMR spectroscopy

A recently discovered coupling agent, hydroxymethylated resorcinol (HMR), based on resorcinol–formaldehyde, can greatly enhance wood‐to‐epoxy resin bond durability in exterior applications. However, for HMR to be most effective, it needs to be prepared a few hours before it is applied to the wood surface. In this study, carbon‐13 nuclear magnetic resonance (NMR) spectroscopy was used to monitor composition of HMR as a function of time to characterize which chemical groups are present in solution when HMR is applied. A quantitative assessment of formaldehyde‐derived groups required the use of 99% ¹³C‐enriched formaldehyde. Hydroxymethyl groups, primarily attached to the 4‐position of resorcinol, and hemiformal groups formed very quickly. Signals from methylene linkages between resorcinol rings began to appear 20 min into the reaction. Formaldehyde was consumed quickly; 95% was bound to resorcinol rings within 1.7 h. By 3 h, 16% had been converted to methylene linkages, and by 8.3 h, 40% was converted. Another set of NMR experiments was used to monitor the dependency of peak positions of resorcinol solution as a function of pH. These experiments showed significant effects, especially between pH 7.7 and 9.1, which explains chemical shift changes observed during the HMR reaction. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1760–1768, 2000     

Wood flour: A new filler for the rubber processing industry. III. Cure characteristics and mechanical properties of nitrile butadiene rubber compounds filled by wood flour in the presence of phenol‐formaldehyde resin

Nonmodified and corona‐activated conifer wood flour was evaluated as filler to nitrile butadiene rubber (NBR) compounds containing different amounts of phenol‐formaldehyde resin (PFAR) by studying the cure characteristics and the mechanical properties of the filled compounds. It was found that the PFAR affects considerably the cure characteristics and the mechanical properties of the wood flour–filled NBR compounds due to a presumable action as an interface interactions modifier. Acting as an antiaging agent it improves also their thermal‐oxidative stability. The optimal amount of PFAR regarding the cure characteristics and mechanical parameters is of 15 phr/100 phr wood flour. The addition of PFAR just before the wood flour is preferable because of both its better homogenization in the rubber matrix and its lower adsorption by the wood flour, leading to an improvement of the mechanical properties of the wood flour–filled NBR compounds. The replacement of nonmodified wood flour by corona‐activated wood flour leads to additional increase of the mechanical parameters without significant affect of the optimum cure time, aging resistance, and water adsorption. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 95–101, 2004