Synthesis Of Urea-formaldehyde Resins Research Articles

Effects of nanoclay modification with transition metal ion on the performance of urea–formaldehyde resin adhesives

As a way of reducing the formaldehyde emission and improving the adhesion of urea–formaldehyde (UF) resins, this study investigated the addition effects of pristine nanoclay (PNC) or modified nanoclay (MNC) with transition metal ion (TMI) on the performance of UF resin adhesives. Instead of a conventional simple mixing (SM) of MNC with UF resin (coded as MNC-SM), this study explored adding PNC or MNC into either the alkaline (ALK) or acidic (ACD) reaction during the synthesis of UF resins, which were coded as PNC-ALK, PNC-ACD, MNC-ALK, and MNC-ACD, respectively. For the first time, we report that the MNC-ALK resins result in almost amorphous UF resins with 25% crystallinity, which consequently increases the cross-linking, and improve the adhesion strength and decrease formaldehyde emission of modified UF resins. It is believed that the intercalated or exfoliated MNCs facilitate the formation of more cross-linking in the modified UF resins, leading to a better cohesive strength.

Concise Chemistry of Urea Formaldehyde Resins and Formaldehyde Emission

Urea formaldehyde (UF) resins have found a lot of industrial applications mostly as binder in woodworks and coating. The resin is a low-cost product synthesized from urea and formaldehyde in a sequential addition (methylolation) and condensation (polymerization) reactions. The addition reaction generates methylol and urea derivatives that proceed into condensation reactions. The condensation reactions takes the resin from its initial fluid state through to the formation of a thermosetting film, however, this is companied by release of formaldehyde which may be hazardous to health. As briefly highlighted in this review, having a concise knowledge of the chemistry of these processes will be an easy guide towards a successful synthesis of UF resins with improved performance and environmental attributes.

Performance of Urea-Formaldehyde Resins Synthesized at Two Different Low Molar Ratios with Different Numbers of Urea Addition

This study reports the performance of urea-formaldehyde (UF) resins prepared at two different low formaldehyde/urea (F/U) mole ratios with different numbers of urea addition during synthesis. The second or third urea was added during the synthesis of UF resins to obtain two different low molar ratios of 0.7 and 1.0, respectively. The molecular weights, cure kinetics, and adhesion performance of these resins were characterized by the gel permeation chromatography, differential scanning calorimetry, and tensile shear strength of plywood, respectively. When the number of urea additions and F/U molar ratio increased, the gelation time decreased, whereas the viscosity and molecular weight increased. Further, the UF resins prepared with the second urea and 1.0 molar ratio resulted in greater activation energy than those with third urea and 0.7 molar ratio. Tensile shear strength and formaldehyde emission (FE) of the plywood that bonded with these resins increased when the number of urea additions and molar ratio increased. These results suggest that the UF resins prepared with 0.7 molar ratio and third urea addition provide lower adhesion performance and FE than those resins with 1.0 mole ratio and the second urea addition.

New insight into the use of latent catalysts for the synthesis of urea formaldehyde adhesives and the mechanical properties of medium density fiberboards bonded with them

Recently, there has been a rapid growth in research and innovation in the synthesis of UF resins in the wood-based composites area. Much effort has gone into increasing their mechanical performance to extend the capabilities and application of this group of materials. This paper, for the first time, defines the research on the use of ammonium salts not as hardeners but in the synthesis of UF resins. The objective of this study was to investigated the effects of various types of catalysts (ammonium sulfate, ammonium chloride, sulfuric acid and hydrochloric acid) during UF resins synthesis on formaldehyde emission and characteristics of urea–formaldehyde (UF) adhesives for the manufacture of medium density fiberboard. These were investigated by 13C Nuclear Magnetic Resonance (13C NMR) and differential scanning calorimetry (DSC), and as a result some of the physical and mechanical properties of medium density fiberboard (MDF) panels bonded with different UF resins were evaluated. The resins structure examined by 13C NMR spectroscopy showed that a resin catalyzed by (NH4)2SO4 had a higher proportion of hydroxymethyl groups (mostly HNCH2OH) resulting in a higher level of formaldehyde emission. A resin catalyzed by NH4Cl gave the highest proportion of methylene groups. A resin catalyzed by H2SO4 yielded the highest proportion of methylene groups in di- or tri-substituted ureas but the lowest proportion of mono-substituted urea. It was of interest that (NH4)2SO4 catalyzed UF adhesive yielded the best overall mechanical properties for the medium density fiber board (MDF) bonded with it. Conversely, it also presented the shortest shelf life and gelled in about 15 days, which could be related to its high reactivity and shortest gel time. Medium Density Fiberboard (MDF) panels bonded with UF adhesives without any ammonium salt (thus with either H2SO4 or HCl) had lower IB strength, MOR and MOE. The HCl catalyst was considered to be chemically least active, yielding the lowest cohesive energy, and resulted in panels presenting a poor performance as shown by their lowest IB (internal bond) strength, modulus of elasticity (MOE), and modulus of rupture (MOR) and highest thickness swelling, with the exception of the free formaldehyde content.

Hydrolysis and recycling of urea formaldehyde resin residues

Urea formaldehyde (UF) resin residues generate many poisonous chemicals during traditional disposal technologies for organic hazardous wastes. In this study, hydrothermal hydrolysis was developed to decompose, remove, and recycle cured UF resin. Under 140 °C and 2 h of hydrothermal process, 20 mL of either 2 M HCl or 30 w.t. % of formaldehyde solutions can decompose as much as 1.7 g of cured UF resin. In addition, from the attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), gas chromatography–mass spectroscopy (GCMS), X-ray diffraction (XRD), and 1H nuclear magnetic resonance (NMR) analyses, it confirmed that the hydrothermal hydrolysis could hydrolyze cured UF resin. With 2 M HCl, the hydrolysis of cured UF resin can form NH4Cl as the final product. Moreover, formaldehyde solution hydrolysis can fully recycle the decomposed UF resin. The hydrolyzed formaldehyde solution can be directly used as a normal formaldehyde solution for UF resin synthesis. The synthesized resin, which contains about 6 w.t. % of decomposed cured UF resin, has similar chemical structures and bonding performance as normal UF resin. These hydrolysis methods generate no harmful gases and pollutants, nor any pre- or post-treatments, which proves its feasibility in UF resin residues safe removal or disposal and recycle.

Urea-formaldehyde resins: production, application, and testing

Urea-formaldehyde (UF) resin, one of the most important formaldehyde resin adhesives, is a polymeric condensation product of formaldehyde with urea, and being widely used for the manufacture of wood-based composite panels, such as plywood, particleboard, and fiberboard. In spite of its benefits such as fast curing, good performance in the panels (colorless), and lower cost; formaldehyde emission (FE) originated from either UF resin itself or composite products bonded by UF resins is considered a critical drawback as it affects human health particularly in indoor environment. In order to reduce the FE, lowering formaldehyde/urea (F/U) mole ratio in the synthesis of the UF resin was done. In this study, synthesis of UF resins was carried out following the conventional alkaline-acid two-step reaction with a second addition of urea, resulting in F/U mole ratio around 1.0, namely 0.95; 1.05, and 1.15. The UF resins produced were used as binder for particleboard making. The board was manufactured in the laboratory using shaving type particle of Gmelina wood, 8% UF resin based on oven dry particle, and 1% NH4Cl (20%wt) as hardener for the resin. The target of the thickness was 10 mm and the dimension was 25 cm x 25 cm. The resulted particleboard then was evaluated the physical and the mechanical properties by Japanese Industrial Standard (JIS) A 5908 (2003). Further, the resulted particleboard also was used for the mice cage’s wall in order to mimic the real living environment. After four weeks exposure in the cages, the mice then were evaluated their mucous organs as well as their blood. The experiment results were as follows: 1) It was possible to synthesis UF resins with low F/U mole ratio; 2) However, the particleboard bonded UF resins with low F/U mole ratio showed poor properties, particularly on the thickness swelling and modulus of elasticity; 3) There was no significant differences among the mucous organs of the mice after a month exposure FE originated from cages wall using histopathology assessment.

The effect of soda bagasse lignin modified by ionic liquids on properties of the urea–formaldehyde resin as a wood adhesive

ABSTRACT The aim of this research was to investigate the influence of lignin modified by ionic liquids on physical and mechanical properties of plywood panels bonded with the urea–formaldehyde (UF) resin. For this purpose, soda bagasse lignin was modified by the 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) ionic liquid and then the various contents of unmodified and modified lignins (10, 15, and 20%) were added at pH=7 instead of second urea during the UF resin synthesis. The physicochemical properties of the prepared resins as well as the water absorption, shear strength, and formaldehyde emission of the plywood panels made with these adhesives were measured according to standard methods. According to Fourier Transform Infrared (FTIR) Spectrometry, by treatment of lignin, the C=O, C–C, and C–H bonds decrease while the content of the C–N bond dramatically increases. Based on the finding of this research, the performance of soda bagasse lignin in UF resins dramatically improves by modification by ILs; as the resins with modified lignin yielded lower formaldehyde emission and water absorption when compared to those made from unmodified lignin and commercial UF adhesives, respectively. The shear strength as well as wood failure percentages are lower for the panels produced with modified lignin than for the panels produced with UF resins alone.

A comparison between lignin modified by ionic liquids and glyoxalated lignin as modifiers of urea-formaldehyde resin

ABSTRACTThe aim of this research was to compare the influence of modified lignin by ionic liquid (IL) on the physical and mechanical properties of wood-based panels bonded with urea-formaldehyde (UF) resin with the effect of glyoxalated lignin (GL) on UF properties. For this purpose, soda bagasse lignin was respectively modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) IL and glyoxal and then the various content of modified lignins (10, 15, and 20%) were added at pH=7 during the UF resin synthesis instead of the second urea . The changes in the structure and thermal properties of lignin, after and before modification with glyoxal and IL, were analyzed by Fourier transform infrared spectrometry (FTIR) and differential scanning calorimetry (DSC). The physicochemical properties of the prepared resins as well as the water absorption, shear strength, and formaldehyde emission of the plywood panels made with these adhesives were measured according to standard methods. According to the FTIR spectra, the content of C=O bond increased in GL while in the IL-treated lignin the content of C–N bond markedly increased. DSC analysis indicated that lignin modified by IL had lower glass transition temperature (Tg) value compared to those modified with glyoxal and unmodified lignin, respectively. The UF resins containing IL-treated lignin exhibit a faster gel time compared to those prepared with GL. Equally, the plywood panels prepared with an IL had lower formaldehyde emission and higher mechanical strength compared to those made from UF resin containing GL. There were no significant differences in dimensional stability of the panels bonded with UFs modified with GL and those with IL-modified lignin.

Reduction of Formaldehyde Emission from Particleboard by Phenolated Kraft Lignin

The aim of this study was the reduction of formaldehyde emission from particleboard by phenolated Kraft lignin. For this purpose, the lignin was extracted from black liquor and then modified by phenolation. During the urea formaldehyde (UF) resin synthesis different proportions of unmodified and phenolated Kraft lignins (10%, 15%, and 20%) were added at pH = 7 instead of the second urea. Physicochemical properties and structural changes of resins so prepared, as well as the internal bond (IB) strength and formaldehyde emission associated with the panels bonded with them were measured according to standard methods. The Fourier transform infrared (FTIR) analysis of lignin indicated that the content of O–H bonds increased in phenolated lignin while the aliphatic ethers C–O bonds decreased markedly in the modified lignin. Since both synthesis of UF resins and lignin phenolation are carried out under acid conditions, phenolation is an interesting way of modifying lignin for use in wood adhesive. The panels bonded with these resins showed significantly lower formaldehyde emission compared to commercial UF adhesives. The UF resin with 20% phenolated lignin exhibited less formaldehyde release without significant differences in internal bond strength and physicochemical properties compared to an unmodified UF resin. XRD analysis results indicated that addition of phenolated lignin decreased the crystallinity of the hardened UF resins.

Improving urea formaldehyde resin properties by glyoxalated soda bagasse lignin

The aim of this research was a reduction of formaldehyde emission and the improvement of the water resistance of urea formaldehyde (UF) resins by incorporating glyoxalated soda bagasse lignin. For this purpose, various contents of unmodified and glyoxalated lignins (10, 15 and 20 %) were added at pH = 7 instead of second urea during the UF resin synthesis. The properties of the resins as well as water absorption, shear strength, and formaldehyde emission of plywood panels made with these adhesives were measured. Among all the resins synthesized, the resin yielding the best results (based on formaldehyde emission and gelation time as well as water absorption, mechanical strength, and formaldehyde content of the associated panels) was selected, and its properties were further analyzed by Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectrometry (FTIR), and X-ray Diffractometry (XRD). The lignin based resins yielded good shear strength of the plywood panels, passing comfortably relevant international standard specifications; the panels also showed lower formaldehyde emission and water absorption when compared to commercial UF adhesives. Based on these findings, it was attempted to improve the performance of soda bagasse lignin in UF resins by glyoxalation. The UF resin containing 15 % glyoxalated lignin (GLUF15) still exhibited less water absorption and formaldehyde release without significant differences in shear strength and physicochemical properties compared to the UF resin control. DSC analysis indicated that in comparison to UF resin the curing process of GLUF resin shifted to lower temperatures. According to the FTIR spectra, by addition of lignin the proportion of C–N bond in methylene linkages decreases when urea is partly replaced by lignin or glyoxalated lignin. XRD analysis indicated that the crystallinity of the UF resins decreased with addition of glyoxalated lignin.

Effect of different catalysts on urea–formaldehyde resin synthesis

ABSTRACTFour 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.

Hydroxymethylation and polycondensation reactions in urea–formaldehyde resin synthesis

AbstractFormaldehyde–urea (F/U) reaction products with molar ratios of 1.8, 2.1, and 2.4 were synthesized at pH 8.3, and the last one also at pH 4.5 using 45% formaldehyde aqueous solution. For obtaining the resin, the synthesis of F/U 2.1 was continued by acid‐catalyzed condensation at pH 4.5 and posttreatment with second part of U (F/U 1.05/1) at 70°C and pH 8.3. The products were analyzed using 13C‐NMR spectrometry. Higher excess of F increases the dihydroxymethyl content on account of smaller dimethylene ether content. Certain 13C chemical shifts in carbonyl and methylene region of spectra were assigned to trishydroxymethylurea, being the main trisubstituted urea compound in hydroxymethylated product. Acid catalyst promotes the formation of methylene groups by polycondensation of hydroxymethyl groups, against the background of similar content of dimethylene ethers in both catalytic conditions. The ratio of linear/branched chains is emphasized in characterizing the resin structure. Higher hydroxymethyl content in acid‐catalyzed polycondensation is an advantage of three‐step synthesis technology. The amount of binding methylene and dimethylene ether groups linked only to secondary amino groups can be increased by transhydroxymethylation with subsequent polycondensation in posttreatment with U in suitable reaction conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1673–1680, 2006

Study on the Evolvement of Structure in Synthesis of Urea-Formaldehyde Resins by FTIR

Study on the Evolvement of Structure in Synthesis of Urea-Formaldehyde Resins by FTIR

Structure formation in urea-formaldehyde resin synthesis

The structure formation in acid promoted polycondensation and particularly in alkaline post-treatment with urea was studied by ¹³C NMR spectroscopy in the three-step synthesis of urea- formaldehyde resins. Trishydroxymethyl urea was identified as the constituent of the mixture of hydroxylmethylated urea derivatives obtained in alkaline conditions. The formation of methylenes linked to secondary or tertiary amino groups occu rs only in acidic conditions by branching chains in the reaction with mono- and 1,3-bishydroxymethyl urea. Bishydroxymethyl groups do not take part in acid promoted polycondensation. The final structure of resins depends mostly on the migration of formaldehyde from bishydroxymethyl groups to urea with formation of mono- hydroxymethyl urea as the first preferred compound. A greater amount of oligomers with methylenes adjacent to secondary amino groups and containing singly bonded urea is a sign of a thorough heat treatment. A steady content of methylenes linked to tertiary amino groups is observed in heat treatment and ageing of resins.

Urea-Formaldehyde Resins and Free Formaldehyde Content

Specifications of wood adhesives must be in correlation with the requirements for the corresponding wood products, for which they will be used. Formaldehyde emission of wood products bonded with urea-formaldehyde resin based adhesives is strictly regulated by standards and there is a compromise is between formaldehyde emission and performance, such as strength, or water resistance. Since values of formaldehyde emission depend on the test method used, in Europe urea-formaldehyde resins for adhesives may generally be classified according to HCHO emission in the particleboard rating of Emission 0 to Emission I class (E-0 to E-1). According to DIN EN 120, particleboard quality E1 emits <6.5 mg/100 g dry article determined with the perforator method. Although a great number of factors effect the formaldehyde emission of the cured products, such as the hardener system, the type of wood etc., the emission of formaldehyde is in strict correlation with the free formaldehyde content of the resin before the curing process. E1 emission class can be achieved, if the free formaldehyde content of the resin is lower than 0.2% by mass. Urea-formaldehyde resins containing. higher than 0.5% free formaldehyde by mass exceed emission class E2, and are not accepted. Since the free formaldehyde content of the urea-formaldehyde resin effects the emission of formaldehyde in the cured product, low formaldehyde content must be ensured during resin synthesis. This can be achieved by properly selecting synthesis conditions as well as raw materials. The quality of raw materials is an essential and determining factor for the synthesis of urea formaldehyde resins. The principal changes which may take place in the formaldehyde solution on storage are the polymerization and precipitation of the polymer, Cannizzaro reaction, methylal formation, oxydation to formic acid, condensation to hydroxyaldehydes and sugars. Any of these reactions are detrimental to product quality. The state of formaldehyde is also an essential factor, since the reaction of poly(methylene glycol)s with urea leads to methylene ether linkages resulting in emission of formaldehyde during storage and later on during the process of curing. Hydrolysis, isomerisation and decomposition of urea may take place simultaneously during improper storage conditions, such as high humidity, high temperatures, industrial atmosphere. The side products formed affect the reaction with formaldehyde during the synthesis resulting in high free formaldehyde content of urea-formaldehyde resins. The relation between synthesis conditions, free formaldehyde content and performance of urea-formaldehyde resins are discussed in detail.