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     

Determination of the structural configuration of cresol–novolak resins by 13C NMR spectroscopy

¹³C NMR spectroscopy was used to investigate the structures of a series of pure isomeric cresylic novolak resins. Chemical shifts were measured and assigned, and end groups were distinguished from the central repeat units of the chains. Based on these measurements, the number average molecular weight of the para-cresylic oligomer was determined. A comparison of the ¹³C decoupled and coupled spectra of the three isomeric resins indicates that the para isomer has a linear, ordered structure in which the aromatic rings are linked only by ortho–ortho′ methylene-bridging groups. The structures of the ortho and meta isomers are more complex and contain ortho–ortho′, ortho–para′, and para–para′ methylene bridges.     

Polymerization of resole resins with several formaldehyde/phenol molar ratios: Amine catalysts against sodium hydroxide catalysts

Triethylamine and sodium hydroxide catalyzed phenol/formaldehyde resole resins were investigated in terms of their behavior during both addition and polymerization reactions. Amine‐catalyzed prepolymers were mainly ortho‐substituted structures, whereas the sodium hydroxide catalyst directed the addition reaction to para reactive sites. During polymerization, triethylamine led to dimethylene ether bridges as the principal linkages between aromatic structures, increasing their final concentration as the starting hydroxymethyl group concentration increased. In contrast, the use of sodium hydroxide reduced dramatically the dimethylene ether bridge concentration, favoring methylene bridge formation. The influence of hydroxyl ions on the stability of quinone methide intermediates could be the reason for those differences. Despite the formation of dimethylene ether bridges, at higher curing temperatures, more oxidized groups started to appear in cured resoles when the formaldehyde/phenol molar ratio was higher. The presence of infrared bands associated with quinones, aldehydes, and/or carbonyl groups, mainly in high‐formaldehyde‐content resins, could indicate a direct oxidation process from dimethylene ether bridges and/or residual hydroxymethyl groups, without the formation of methylene bridges. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2623–2631, 2006     

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

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

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     

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

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

Chemical Structure and Curing Behavior of Phenol–Urea–Formaldehyde Cocondensed Resins of High Urea Content

Phenol–urea–formaldehyde cocondensed (PUF) resins of high urea content were prepared by adding different forms of urea to the reaction system. The structure, curing behavior, and water resistance of the PUF resins were investigated, and their relations were also discussed by liquid ¹³C nuclear magnetic resonance (NMR) and different scanning calorimetry (DSC). The liquid ¹³C-NMR analysis showed that urea added in the form of methylolureas was well incorporated into the cocondensed resins by reacting with phenolic methylols to form cocondensed methylene bridges, and that the PUF resins had no free formaldehyde with any form. Unreacted urea and low molecule monosubstituted urea of PUF resins play a dominant role in the curing behavior and water resistance of resins. The peak temperature, curing time, and curing enthalpy (ΔH) value correspondingly increased, however, the water resistance of PUF resins decreased when urea content in PUF resins increased. The PUF cocondensed resin with up to 89.4 % (W _U/W _P) urea has relatively low cost, and moreover can pass the requirements of China Industry Standard for the exterior grade of structural plywood after 4-h cyclic boiling test.     

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     

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     

Comparative 13C‐NMR and matrix‐assisted laser desorption/ionization time‐of‐flight analyses of species variation and structure maintenance during melamine–urea–formaldehyde resin preparation

The preparation of an industrially used sequential formulation of a melamine–urea–formaldehyde resin was followed by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry and ¹³C‐NMR analysis. The analysis allowed us to identify and follow the appearance, increase, decrease, and disappearance of a multitude of chemical species during the preparation of both the initial urea–formaldehyde (UF) phase of the reaction and the subsequent reaction of melamine with the UF resin that formed. The analysis indicated that (1) the increase and decrease in the species that formed proceeded through a cycle of the formation and degradation of species occurring continuously through what appeared to be a series of complex equilibria, (2) even at the end of the reaction a predominant proportion of methylene ether bridges was still present, (3) some small proportion of methylene bridges already had formed in the UF reaction phase of the resin even under rather alkaline conditions, and (4) the addition of melamine to the UF prepolymer induced some noticeable rearrangement of methylene ether bridges to methylene bridges. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

Decreasing the formaldehyde emission in urea‐formaldehyde using modified starch by strongly acid process

The incorporation of the modified starch (MS) in urea‐formaldehyde resins at different stage of the synthesis was studied in this article. The synthesized resins were characterized by Fourier transform infrared spectroscopy, indicating that the ester bond can be introduced into the UF structure after the addition of MS. The curing reactions were examined with differential scanning calorimetry and it reveals that curing temperature of UF resin are slightly shifted to higher temperatures. To study the bonding strength and formaldehyde emission of the bonded plywood, the addition method and amount of MS are systematically investigated. The performance of the UF resins is remarkably improved by the addition of MS around 15% (weight percentage of the total resin) in the second stage. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40202.     

Ester acceleration mechanisms in phenol–formaldehyde resin adhesives

An analysis of phenol–formaldehyde (PF) resins obtained by the addition of 0.5–5% glycerol triacetate (triacetin) as an accelerator during resin preparation showed the presence of intermediates involved in the acceleration mechanism. ¹³C-NMR spectroscopy, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectroscopy (MS), and gel permeation chromatography allowed us to identify some of the intermediates left over in the PF resin itself. The permanence in the resin of these labile intermediates, not easily observed otherwise, appeared to be due to the reaching of the diffusion-controlled phase of the reaction. The mechanism involved appeared considerably more complex and different from any of the mechanisms presented previously. As a consequence of the evident complexity of the mechanism, it was not really possible to advance a complete mechanism of the reaction nor determine the real cause of the increase in the strength of the final network. The mechanism involved the phenate ion of the resin to apparently give a carbonyl or carboxyl group attached to the aromatic ring. Either directly or by subsequent rapid rearrangement after the initial attack, these CO groups were found on sites different from the ortho position. The appearance gathered from NMR shift calculation indicated preferential positioning or repositioning to the para site and, surprisingly, to the meta sites of the phenolic ring. The shifts of these CO groups correspond to those of an anhydride and to no other intermediate structures previously thought of. Anhydride-like bridges were clearly shown by MALDI-TOF MS to contribute to oligomer structures in which linkages between phenol rings were mixed methylene bridges and anhydride bridges. These structures appeared to be temporary, possibly due to the instability of the anhydride bridges; hence, they were in small proportions at any given moment of the reaction. MALDI-TOF analysis clearly indicated that these structures were at some moment an integral part of the structure of the liquid resin and that they existed parallel to the methylene bridges pertaining to a normal PF resin structure. Previous spectra showed that similar but not identical intermediates were present also in organic and inorganic catalyzed PF resins. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:3075–3093, 2006     

Determination of methylene bridge type of mixed meta and para-cresol–formaldehyde novolaks by 13C-NMR spectroscopy

Cresol–formaldehyde resins are important components of photoresists for semiconductor fabrication. The type of methylene bridge and relative amounts thereof are key structural features that determine resin properties. Several model compounds were prepared that represent the various types of methylene bridges that are possible from condensation of meta- and para-cresol with formaldehyde. The methylene bridges were characterized by ¹³C-NMR spectroscopy, and the assignments made were used to analyze spectra of cresol–formaldehyde novolak resin and several oligomer types. The effect of complexation with metal ion on the methylene bridge chemical shift was investigated for one oligomer. The effect of bridging position on the intramolecular hydrogen bonding of the phenolic hydroxyl group was investigated by infrared spectroscopy.     

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     

13C NMR study on the structure of ZnO-catalyzed phenol–urea–formaldehyde resin during its synthesis process

The structure of ZnO-catalyzed phenol–urea–formaldehyde (PUF) resin at different synthesis stages was analyzed by liquid ¹³C nuclear magnetic resonance spectroscopy. The results showed that the general structure of ZnO-catalyzed PUF resin was almost the same as the control PUF resin. Addition reaction between phenol and formaldehyde mainly occurred at the first stage. Total methylol groups amount between phenols of the control resin was a little lower than that of the ZnO-catalyzed PUF resin. Co-condensation and self-condensation reaction occurred at the second stage. The preparation method of ZnO-catalyzed PUF resin favored the co-condensation reaction between phenol methylol groups and urea units, while self-condensation reaction dominated the control resin at the second stage. Formaldehyde completely reacted for both the control and ZnO-catalyzed PUF final resin. The total amount of methylol and methylene groups between urea units and phenols, respectively, was almost the same for the two final resins. The total quantity of methylol groups between phenols represented a continuing downward trend from the first stage to the final stage, and the amount of methylol group (p-Ph–CH₂OH) of ZnO-catalyzed PUF resin was 30% more than that of the control resin. Total co-condensed methylene groups amount of ZnO-catalyzed PUF resin was greater than that of the control resin, which indicated that ZnO could make the urea units well incorporated into the co-condensed PUF resin.     

Phenolic resins with phenyl maleimide functions: Thermal characteristics and laminate composite properties

Phenolic resins bearing varying concentrations of phenyl maleimide functions were synthesized by copolymerizing phenol with N‐(4‐hydroxyphenyl)maleimide (HPM) and formaldehyde in the presence of an acid catalyst. The resins underwent a two‐stage curing, through condensation of methylol groups and addition polymerization of maleimide groups. The cure characterization of the resin by dynamic mechanical analysis confirmed the two‐stage cure and the dominance of maleimide polymerization over methylol condensation in the network buildup process. The kinetics of both cure reactions, studied by the Rogers method, substantiated the earlier proposed cure mechanism for each stage. Although the initial decomposition temperature of the cured resin was not significantly improved, enhancing the crosslink density through HPM improved thermal stability of the material in a higher temperature regime. The anaerobic char yield also increased proportional to the maleimide content. Isothermal pyrolysis and analysis of the char confirmed that pyrolysis occurs by loss of hydrocarbon and nitrogenous products. The resins serve as effective matrices in silica‐ and glass fabric–reinforced composites whose mechanical properties are optimum for moderately crosslinked resins, in which failure occurs through a combination of fiber debonding and resin fracture. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1664–1674, 2001     

Blocked melamine–urea–formaldehyde resins and their usage in agglomerated cork panels

Caprolactam and o‐p‐toluenesulfonamide are tested as chain‐growth blockers for melamine–urea–formaldehyde (MUF) resins, in an attempt to reduce the crosslinking density of the cured resin and hence improve its flexibility. Agglomerated cork panels, for which flexibility is a technical demand, were produced with the modified resins and tested. The blockers were added at three different steps in the synthesis process: methylolation, condensation, and at the end of the synthesis. Besides evaluation of standard properties, resins were characterized using gel permeation chromatography and Fourier transform infrared. Blocked resins showed better storage stability and improved water tolerance, especially when caprolactam was employed. When used as binders in agglomerated cork panels, the blocked resins allowed for significantly better flexibility, evaluated in terms of mandrel bending test. The tensile resistance of the panels remained well within the desired limits for this type of material. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46663.     

有机硅改性苯酚-尿素-甲醛共缩聚树脂及其机理

采用有机硅对苯酚-尿素-甲醛共缩聚树脂进行改性,研究了有机硅的加入方式对树脂改性效果的影响,通过FT-IR对有机硅和有机硅改性PUF共聚树脂的结构进行了分析,结果表明:有机硅的加入,引起苯环的邻位、对位的亚甲基相对含量变化,形成更多的羟甲基、醚键(C—O—C和C—O—Si)。胶合强度实验表明:缩聚阶段加入树脂总质量0.3%的有机硅,可以大幅度提高树脂胶合强度。     

13C‐NMR study on cure‐accelerated phenol–formaldehyde resins with carbonates

Both liquid‐ and solid‐state ¹³C‐NMR spectroscopies were employed to investigate the cure‐acceleration effects of three carbonates [propylene carbonate (PC), sodium carbonate (NC), and potassium carbonate (KC)] on liquid and cured phenol–formaldehyde (PF) resins. The liquid‐phase ¹³C‐NMR spectra showed that the cure‐acceleration mechanism in the PC‐added PF resin seemed to be involved in increasing reactivity of the phenol rings, while the addition of both NC and KC into PF resin apparently resulted in the presence of ortho–ortho methylene linkages. Proton spin‐lattice rotating frame relaxation time (T_1ρH) measured by solid‐state ¹³C‐CP/MAS‐NMR spectroscopy was smaller for the cure‐accelerated PF resins than for that of the control PF resin. The result indicated that cure‐accelerated PF resins are less rigid than the control PF resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 841–851, 2000