Synthesis of novolac‐type phenolic resins using glucose as the substitute for formaldehyde

Novel Novolac type phenolic resins were prepared using glucose as the substitute for toxic formaldehyde (a carcinogenic chemical). The resins were synthesized with varying molar ratios of phenol to glucose, catalyzed by strong acid (such as sulfuric acid) at 120–150°C. Analysis of the resins using gel permeation chromatography (GPC) and proton nuclear magnetic resonance (¹H‐NMR) showed that they were broadly distributed oligomers derived from the Fridel‐Crafts condensation of phenol and glucose. Using hexamethylenetetramine (HMTA) as the curing agent, the phenol‐glucose resins could be thermally cured and exhibited exothermic peaks at 130–180°C, typical of thermosetting phenolic resins. The cured resins showed satisfactory thermal stability, e.g., they started to decompose at >280°C with residual carbon yields of above 58% at 600°C. Based on the thermal properties, phenol‐glucose resin with a molar ratio of 1 : 0.5 is promising as it could be cured at a lower temperature (147°C) and exhibited a satisfactorily good thermal stability: it started to decompose at >300°C with a residual carbon yield of >64% at 600°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study of glycidyl ether as a new kind of modifier for urea‐formaldehyde wood adhesives

In this work, the multiepoxy functional glycidyl ether (GE) modified urea‐formaldehyde (UF) resins were synthesized via a traditional alkaline‐acid process under low formaldehyde/urea (F/U) molar ratio. The synthesized resins were characterized by ¹³C magnetic resonance spectroscopy (¹³C‐NMR), indicating that GE can effectively react with UF resins via the ring‐opening reaction of epoxy groups. Moreover, the residual epoxy groups of GE could also participate in the curing reaction of UF resins, which was verified by Fourier transform infrared spectroscopy. The storage stability of GE‐modified UF resins and the thermal degradation behavior of the synthesized resins were evaluated by using optical microrheology and thermogravimetric analysis, respectively. Meanwhile, the synthesized resins were further employed to prepare the plywood with the veneers glued. For the modification on bonding strength and formaldehyde emission of the plywood, the influences of addition method, type, and amount of GE were systematically investigated. The performance of UF adhesives were remarkably improved by the modification of GE around 20–30% (weight percentage of total urea) in the acidic condensation stage during the resin synthesis. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of nanoclay on urea‐formaldehyde resins for wood adhesives and its model

The addition of small percentages of Na⁺‐montmorillonite (NaMMT) nanoclay appears to improve considerably the performance of thermosetting urea‐formaldehyde (UF) resins used as adhesives for plywood and for wood particleboard. X‐ray diffraction (XRD) studies indicated that NaMMT loses the periodic atomic structure when mixed in small proportions in the acid‐curing environment characteristic of the curing of UF resins. This can be interpreted as becoming exfoliated under such conditions. The partly crystalline structure of the ordered zones of the UF resins is maintained but at a slightly lower level. Differential scanning calorimetry (DSC) indicated that NaMMT has an accelerating effect on the curing of the UF resin. It also appears to lead to a more controlled rate of crosslinking implying a more regular hardened network. The influence of NaMMT addition was particularly noted in plywood by the increase in water resistance of the UF‐bonded panel. In the case of wood particleboard even the dry internal bond strength of the panel, a direct indication of the performance of the resin, improved with small additions of NaMMT. A hypothesis and model of the reasons why such improvement to the performance of UF resins by addition of nanoclay should occur has been presented. This is based on the application of percolation theory to the networking capability of the clay nanoplatelets. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Differential scanning calorimetry of urea–formaldehyde adhesive resins,synthesized under different pH conditions

The purpose of this study was to investigate the effects of reaction pH conditions on thermal behavior of urea–formaldehyde (UF) resins, for the possible reduction of formaldehyde emission of particleboard bonded with them. Thermal curing properties of UF resins, synthesized at three different reaction pH conditions, such as alkaline (pH 7.5), weak acid (pH 4.5), and strong acid (pH 1.0), were characterized with multiheating rate method of differential scanning calorimetry. As heating rate increased, the onset and peak temperatures increased for all three UF resins. By contrast, the heat of reaction (ΔH) was not much changed with increasing heating rates. The activation energy (E_a) increased as the reaction pH decreased from alkaline to strong acid condition. The formaldehyde emission of particleboard was the lowest for the UF resins prepared under strong acid, whereas it showed the poorest bond strength. These results indicated that thermal curing behavior was related to chemical species, affecting the formaldehyde emission, while the poor bond strength was believed to be related to the molecular mobility of the resin used. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 422–427, 2006     

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     

Curing of low level melamine‐modified urea‐formaldehyde particleboard binder resins studied with dynamic mechanical analysis (DMA)

Effects of resin formulation, catalyst, and curing temperature were studied for particleboard binder‐type urea‐formaldehyde (UF) and 6 ～ 12% melamine‐modified urea‐melamine‐formaldehyde (UMF) resins using the dynamic mechanical analysis method at 125 ～ 160°C. In general, the UF and UMF resins gelled and, after a relatively long low modulus period, rapidly vitrified. The gel times shortened as the catalyst level and resin mix time increased. The cure slope of the vitrification stage decreased as the catalyst mix time increased, perhaps because of the deleterious effects of polymer advancements incurred before curing. For UMF resins, the higher extent of polymerization effected for UF base resin in resin synthesis increased the cure slope of vitrification. The cure times taken to reach the vitrification were longer for UMF resins than UF resins and increased with increased melamine levels. The thermal stability and rigidity of cured UMF resins were higher than those of UF resins and also higher for resins with higher melamine levels, to indicate the possibility of bonding particleboard with improved bond strength and lower formaldehyde emission. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 377–389, 2005     

Production of melamine fortified urea‐formaldehyde resins with low formaldehyde emission

Melamine can be incorporated in the synthesis of urea‐formaldehyde (UF) resins to improve performance in particleboards (PB), mostly in terms of hydrolysis resistance and formaldehyde emission. In this work, melamine‐fortified UF resins were synthesized using a strong acid process. The best step for melamine addition and the effect of the reaction pH on the resin characteristics and performance were evaluated. Results showed that melamine incorporation is more effective when added on the initial acidic stage. The condensation reaction pH has a significant effect on the synthesis process. A pH below 3.0 results on a very fast reaction that is difficult to control. On the other hand, with pH values above 5.0, the condensation reaction becomes excessively slow. PBs panels produced with resins synthesized with a condensation pH between 4.5 and 4.7 showed good overall performance, both in terms of internal bond strength and formaldehyde emissions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Phenol–formaldehyde‐type resins made from phenol‐liquefied wood for the bonding of particleboard

Liquefaction of southern pine wood in phenol in 30–40 : 70–60 weight ratios resulted in homogeneous liquefied materials, which were directly used to synthesize phenol–formaldehyde (PF)‐type resins. The synthesized resins showed good physical and handling properties: low viscosity, stability for storage and transportation, and resin applicable by a common sprayer. Particleboard panels bonded with the synthesized resins showed promising physical properties and significantly lower formaldehyde emission values than those bonded with the urea–formaldehyde resin control. One deficiency observed for the synthesized resins was lower internal bond values, which might be overcome the use of a hot‐stacking procedure. Overall, the process of wood liquefaction with limited amounts of phenol as a solvent was shown to have the potential of providing practical, low‐cost PF‐type resins with very low formaldehyde emission potentials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

Modification of melamine‐formaldehyde resins by substances from renewable resources

In the present contribution, investigations on the chemical modification of thermosetting melamine formaldehyde resins by natural polyol compounds are presented. As representative agents soluble starch, sucrose, and glycerol were chosen to cover three different classes of polyols. The major aim was to use substances produced from natural bio‐renewable feedstock that are available in large quantities and may serve as environmentally innocuous and bio‐renewable substitutes for petro‐chemically derived and potentially hazardous materials. Different reaction conditions lead to resins with varying technical performance. For soluble starch no reaction conditions could be found that allow the adoption of this substitute for the laminate industry due to insufficient technological performance. Sucrose and glycerol on the other hand yielded impregnation resins with suitable performance. Chemical linkage of the modifying agent into the chain propagation by poly‐condensation however, was only found with glycerol. The covalent incorporation of glycerol in the network was observed with addition of glycerol at different stages during synthesis. The technological performance of the various modified thermosetting resins was assessed by determining flow viscosity, molar mass distribution, the storage stability, and in a second step laminating impregnated paper to particle boards and testing the resulting surfaces according to standardized quality tests. Spectroscopic evidence of chemical incorporation of glycerol was found by applying by ¹H, ¹³C, ¹H/¹³C HSQC, ¹H/¹³C HMBC, and ¹H DOSY methods. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of epoxy‐functionalized hyperbranched poly(phenylene oxide) and its modification of cyanate ester resin

High curing temperature is the key drawback of present heat resistant thermosetting resins. A novel epoxy‐functionalized hyperbranched poly(phenylene oxide), coded as eHBPPO, was synthesized, and used to modify 2,2′‐bis (4‐cyanatophenyl) isopropylidene (CE). Compared with CE, CE/eHBPPO system has significantly decreased curing temperature owing to the different curing mechanism. Based on this results, cured CE/eHBPPO resins without postcuring process, and cured CE resin postcured at 230°C were prepared, their dynamic mechanical and dielectric properties were systematically investigated. Results show that cured CE/eHBPPO resins not only have excellent stability in dielectric properties over a wide frequency range (1–10⁹Hz), but also show attractively lower dielectric constant and loss than CE resin. In addition, cured CE/eHBPPO resins also have high glass transition temperature and storage moduli in glassy state. These attractive integrated performance of CE/eHBPPO suggest a new method to develop high performance resins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Urea formaldehyde resin with low formaldehyde content modified by phenol formaldehyde intermediates and properties of its bamboo particleboards

Phenol formaldehyde reaction solution (PFS) was used to synthesize urea–formaldehyde resins (PFSUF resins) with low formaldehyde content. In addition, the prepared PFSUF resins were used as adhesives to bond bamboo particleboards. Mechanical properties, fracture morphology, water absorption ratio, and dimensional stability of bamboo particleboards have been studied by tensile tests, SEM tests, water absorption analysis, and swelling ratio analysis, respectively. The results demonstrate that the main ingredient of PFS is phenol formaldehyde intermediate 2,4,6‐trimethylolphenate and proper amount of PFS can be used to reduce the formaldehyde content of UF resins effectively. The results also show that bamboo particleboards bonded with PFSUF resins exhibit better mechanical properties, water resistance, and dimensional stability than that bonded with pure UF resin. However, the results of TG and mechanical properties analysis exhibit that alternative curing agents to ammonium chloride should be studied to improve the curing properties of the PFSUF resins with low formaldehyde content. Taken together, this work provides a method of preparing environment‐friendly PFSUF resins with low phenol and low formaldehyde content and the prepared resins have potential application in wood industry. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42280.     

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     

The aminolysis of styrene–maleic anhydride copolymers for a new modifier used in urea-formaldehyde resins

Styrene (St) and maleic anhydride (MA) alternating copolymers with different molecular weights (MW) were synthesized via radical copolymerization. The copolymers were subsequently transferred into water-soluble maleic amic acid derivatives (SMAA) via the aminolysis of anhydride groups using (NH₄)₂CO₃ as the ammonia sources. The synthesized polymers were applied as a new kind of macromolecular modifier and added into the reaction system during the synthesis of urea-formaldehyde (UF) resins via the traditional alkaline–acidic–alkaline three-step process. The UF resins modified with SMAA were characterized using Fourier Transform Infrared Spectroscopy (FT-IR), ¹³C nuclear magnetic resonance (¹³C-NMR) spectroscopy, and thermal gravimetric analysis (TGA). All the results confirmed the successful incorporation of SMAA chains into the crosslinking network of the UF resins. The modified UF resins were further employed as wood adhesives and the effect of synthesis parameters on their performance was investigated. Meanwhile, the influence of SMAA molecular weight (MW) on the properties of the modified UF resins was also studied. When the UF resins were synthesized with a low molar ratio of formaldehyde/urea (F/U) and a predetermined amount of SMAA added into the reaction system at the second step, plywood bonded using these modified UF resins showed much improved bonding strength (BS) and depressed formaldehyde emission. Moreover, the as-modified UF resins showed good storage characteristics.     

High‐performance biobased epoxy derived from rosin

Great achievements have been made in the research of biobased thermoplastic polymers, but the progress concerning thermosetting resins has been minor. In particular, research on high‐performance thermosetting polymers from renewable feedstock has not been reported elsewhere. A novel biobased epoxy was synthesized from a rosin acid. Its chemical structure was confirmed using ¹H NMR, ¹³C NMR and Fourier transform infrared spectroscopy. The results indicated that the rosin‐based epoxy possessed high glass transition temperature (T_g = 153.8 °C), high storage modulus at room temperature (G′ = 2.4 GPa) and good thermal stability. A rosin‐based epoxy with excellent properties was achieved. The results suggest it is possible to develop high‐performance thermosetting resins from renewable resources. Copyright © 2010 Society of Chemical Industry     

Alternative to latent catalysts for curing UF resins used in the production of low formaldehyde emission wood-based panels

This paper studies alternative catalysts to ammonium sulfate for curing urea-formaldehyde (UF) resins. When using a latent catalyst like ammonium sulfate, hexamine is formed as by-product of curing reaction. It is believed that hexamine hydrolysis may contribute to formaldehyde release during the life-time of wood-based panels produced with UF resins. Orthophosphoric acid, on the other hand, catalyzes resin cure without by-product formation and was compared to ammonium sulfate. The pot-life of adhesives with both catalysts was evaluated at 40 °C with a Brookfield rheometer. Mechanical resistance tests performed with ABES (Automated Bonding Evaluation System) showed that orthophosphoric acid effectively catalyzes UF resin cure. Particleboards were produced using both catalysts and the most important properties evaluated, according to European Standards: formaldehyde content, internal bond, moisture content, thickness swelling and density. Particleboards cured with orthophosphoric acid and stored under forceful conditions of humidity and temperature presented similar internal bond and lower formaldehyde content than those produced with ammonium sulfate.     

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     

Morphology and chemical elements detection of cured urea–formaldehyde resins

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

Lignin–phenol–formaldehyde resin adhesives prepared with biorefinery technical lignins

In this study, four biorefinery technical lignins were used to synthesize lignin–phenol–formaldehyde (LPF) resin adhesives with a proposed formulation that was designed based on accurate analysis of the active sites in lignin with ³¹P nuclear magnetic resonance (NMR). The properties of the LPF resin adhesives and the plywoods prepared with them were tested. The structural features and curing behavior of the LPF resin adhesives were thoroughly investigated by solution‐ and solid‐state ¹³C NMR. Results indicated that the proposed formulation exhibited favorable adaptability for all four of these technical lignins for synthesis of LPF resin adhesives. High‐performance plywood with low emissions of formaldehyde could be successfully prepared with the synthesized LPF resin adhesives. All the LPF resin adhesives exhibited similar structure and curing behavior with the commercial phenol–formaldehyde (CPF) resin adhesive. However, the LPF resin adhesives showed relatively higher curing temperatures as compared with the CPF resin adhesive. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42493.     

The effect of alkyd resins on the properties of AA‐NC semi‐IPNs as binders in wood finish

Wood coatings of AA‐NC semi‐interpenetrating polymer networks (semi‐IPNs), made from acid curing amino‐alkyd resins (AA) and nitrocellulose (NC), were prepared by sequential polymerization method. To investigate the effects of oil length on the properties of AA‐NC semi‐IPNs, three grades of alkyd resins (Alkyd) containing 38, 48, and 58% oil were synthesized with phthalic anhydride, glycerol, and soybean oil, employing alcoholysis method. The butylated urea formaldehyde resin (UF) and melamine formaldehyde resin (MF) were also prepared in this study. The AA‐NC semi‐IPNs were maintained at a weight ratio of AA : NC of 25 : 75, where the AA was the composition of MF : UF : Alkyd of 7.5 : 22.5 : 70 (by weight), and 10% of p‐toluene sulfonic acid solution (concentration, 25% in isopropyl alcohol) based on the weight of amino resins was added as acid catalyst. The properties of coatings such as viscosity, drying time, and gel time, and the properties of films including adhesion, hardness, abrasion resistance, impact resistance, tensile strength, released formaldehyde, lightfastness, solvent resistance, and durability were examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1923–1927, 2004