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     

Influence of preparation parameters on the CHT curing diagrams of MUF polycondensation resins

Lignocellulosic substrates such as wood have been found to have a marked modifying influence on both lower‐temperature and higher‐temperature zones of TTT and CHT diagrams during hardening of formaldehyde‐based polycondensates. While the modifying influence of the substrate has been described, the modifying influence of some of the most important manufacturing parameters of the resins on the CHT diagram, not having been previously investigated, are explored here and clear trends are shown. In the case of melamine–urea–formaldehyde (MUF) resins for wood adhesives, the molar ratio (M+U):F appear to be the dominant parameter influencing the relative position of gel and vitrification curves in relation to each other. The ratio of melamine to urea does not appear to have any effect on the relative position of the curve, lacking any clear trend, at least at the higher (M+U) molar ratio of 1:1.9 used for this series of resins. In the case presented for the first time, the influence of resin manufacturing parameters on CHT curing diagrams was studied in combination with the modifications introduced by the substrate. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2821–2825, 2001     

Variation of MUF and PMUF resins mass fractions during preparation

The variation of molecular mass distribution with the progress of the reaction was studied for the following: (i) sequential‐type melamine–urea–formaldehyde (MUF) resin formulations in which the sequence of addition of chemicals follows well‐defined species reactivity principles; (ii) a nonsequential MUF formulation in which simultaneous melamine and urea competition for formaldehyde yields a MF resin cocondensed with small amounts of urea. This resin became soaked with reacted and unreacted monomeric urea species. (iii) A PMUF resin, namely a MUF resin with a small proportion of phenol (7.8% by weight on melamine and urea) cocondensed with the main MUF fraction. All the formulations used were industrial resins formulations in current use. Development and variation of molecular mass fractions, from which performance and other useful resin parameters depend, have been found to depend on the type of resin formulation used for these type of aminoplastic resins. The two very different MUF resin formulations yielded different variations in molecular mass fractions during the progress of the reaction and during the so‐called ambient temperature “maturing” of the resin. The PMUF resin also showed both similar and different fractions present during manufacturing and during short term ageing at ambient temperature. While similarities in recurrent fractions and in trends are common to all the three different formulations, differences between them are also clearly observed. A major proportion of the reaction of some of the aminoplastic resins examined also occurs on ageing (i.e.“maturing” of the resin at ambient temperature), this appearing to be an essential phase of the resin preparation process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4842–4855, 2006     

Impact of curing condition on pH and alkalinity/acidity of structural wood adhesives

Nine formulations were selected for evaluating the effect of different curing methods on pH and alkalinity or acidity of various structural wood adhesives. These included four phenol–formaldehyde (PF) resins with high pH, one phenol–resorcinol–formaldehyde (PRF) resin with intermediate pH, two melamine–urea–formaldehyde (MUF) resins, and two melamine–formaldehyde (MF) resins with low pH. The four curing methods used in the study were: (1) curing at 102–105°C for 1 h (based on CSA O112.6‐1977), (2) four‐hour curing at 66°C followed by 1‐hour curing at 150°C (based on ASTM D1583‐01), (3) curing at room temperature overnight (based on ASTM D 1583‐01), and (4) cured adhesive squeezed out from glue lines of bonded shear block samples. The effect of the different methods on pH and alkalinity/acidity of the cured adhesive depended strongly on the individual adhesives. For the PF, the alkalinity was different for the different formulations in the liquid form, while in the cured form, the difference in the alkalinity depended on the curing method used. The MF and the MUF were the adhesives most affected by the method used. In particular, the MUF showed much higher cured film pH values when cured by method 2 compared to the other three methods, while both the cured MF and MUF exhibited quite variable acidity values when cured with the different methods. The PRF showed reasonably uniform cured film pH but varying acidity values when cured with the different methods. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

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     

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

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

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     

Evolution of properties of an isocyanate/epoxy thermosetting system during cure: Continuous heating (CHT) and isothermal time—temperature—transformation (TTT) cure diagrams

The present article describes a methodology for examining the evolution of the properties vs. cure of a complex thermosetting isocyanate/epoxy reactive mixture which reacts through two consecutive but separable reaction regimes. The methodology is based on the use of the torsional braid analysis (TBA) technique and the continuous heating (CHT) and isothermal time—temperature—transformation (TTT) cure diagrams. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 15–25, 1997     

Upgrading melamine–urea–formaldehyde polycondensation resins with buffering additives. I. The effect of hexamine sulfate and its limits

Iminoamino methylene base intermediates obtained by the decomposition of hexamethylenetetramine (hexamine) stabilized by the presence of strong anions such as SO and HSO, or hexamine sulfate, were shown to markedly improve the water and weather resistance of hardened melamine–urea–formaldehyde (MUF) resins used as wood adhesives and of the wet internal bond strength performance of wood boards bonded with them. The effect was shown to be induced by very small amounts, between 1 and 5 wt % of this material on resin solid content. This strong effect allowed the use of MUF resins of much lower melamine content and also provided good performance of the bonded joints. Because the main effect was also present at the smaller proportion of hexamine as hexamine sulfate, it was not due at all to any increase in the molar ratio of the resin as a consequence of hexamine sulfate addition. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 203–214, 2003     

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     

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     

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     

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     

Flame-retardant properties of phenol–formaldehyde-type resins and triphenyl phosphate in styrene–acrylonitrile copolymers

The thermal and flame-retardant properties of phenol–formaldehyde-type resins (crosslinked and noncrosslinked) in mixtures with triphenyl phosphate and styrene–acrylonitrile resins were evaluated. The mixtures show a synergistic effect between triphenyl phosphate and novolacs. Those containing phenol–formaldehyde novolac resins are found to be most flame retardant. There does not seem to be a relationship between the oxygen index (OI) and UL 94 tests. Scanning electron microscopy analysis show a surface structure with cavities and stratification, very similar to that of intumescent additives. Evidence was found indicating that this flame-retardant system works in both the gas and condensed phase. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1067–1076, 1998     

Effects of diffusion on the kinetic study and TTT cure diagram for an epoxy/diamine system

The curing reactions of an epoxy system consisting of a diglycidyl ether of bisphenol A (BADGE n = 0) and 1,2-diamine cyclohexane (DCH) were studied to determine a time–temperature–transformation (TTT) isothermal cure diagram for this system. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and a solubility test were used to obtain the different experimental data reported. Two models, one based solely on chemical kinetics and the other accounting for diffusion, were used and compared to the experimental data. The inclusion of a diffusion factor in the second model allowed for the cure kinetics to be predicted over the whole range of conversion covering both pre- and post-vitrification stages. The investigation was made in the temperature range 60–100°C, which is considered optimum for the isothermal curing of the epoxy system studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1931–1938, 1998     

A rheological study of the gelling of UF polycondensates

The gelling process of urea–formaldehyde resins has been investigated by rheological methods. The gel point values were determined by three methods, and compared with those obtained by low resolution impulsional ¹H‐nuclear magnetic resonance. The activation energy of the curing process was determined and the effect of the molar ratio was investigated. In addition, the critical power exponents were calculated and the parameters of the relaxation modulus function were also determined. Equations describing the gel time as a function of degree of conversion and reactants molar ratio are presented. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1296–1302, 2000     

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     

氯化铵对酚醛甲阶树脂固化速率和游离甲醛含量的影响

针对酚醛树脂的固化问题,以MPF甲阶树脂为对象,酸性盐氯化铵为酸度调节剂,研究加入氯化铵后体系固化时间和游离甲醛的变化情况,并探讨了氯化铵添加量对它们的影响。结果显示,氯化铵完全可以作为酚醛甲阶树脂的固化剂；加入少量氯化铵时,固化速度就明显加快；氯化铵的加入量在0．6%～1．2%,固化时间和游离甲醛含量的减少都很明显；当氯化铵的添加量继续增加,游离甲醛含量继续减少,但对固化时同的影响很小。通过对游离甲醛的分析,确定甲醛随氯化铵添加量的变化率为0．4～0．6。     

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