Thermoplastic polymers as modifiers for urea‐formaldehyde (UF) wood adhesives. I. Procedures for the preparation and characterization of thermoplastic‐modified UF suspensions

Acrylic thermoplastic copolymers with different degrees of hydrophilicity were prepared and introduced into a commercial aqueous urea‐formaldehyde (UF) suspension at 5–10% w/v. The most hydrophilic acrylic thermoplastic was introduced into the UF suspension as an aqueous solution, whereas the most hydrophobic acrylic was introduced as a surfactant‐stabilized suspension. Acrylics with intermediate hydrophilicity were introduced into the UF suspension as a self‐dispersed aqueous suspension. The thermoplastic‐modified UF suspensions with 5% thermoplastic (58% solids) had a viscosity at 30°C of ～ 114 cP, compared with a viscosity of ～112 cP for the original UF suspension (60% UF solids). At 10% thermoplastic (63% solids), all the thermoplastic‐modified UF suspensions exceeded 200 cP. The viscosity of the UF suspension modified with self‐dispersed thermoplastic was reduced by ～ 50% by reducing the thermoplastic molecular weight. SEM micrographs of cured thermoplastic‐modified UF showed phase‐separated thermoplastic domains in a continuous UF phase for the UF modified with self‐dispersed and surfactant‐stabilized thermoplastic, but UF modified with the water‐soluble thermoplastic showed a single phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 890–897, 2003     

Thermoplastic polymers as modifiers for urea–formaldehyde wood adhesives. III. In situ thermoplastic‐modified wood composites

Acrylic monomers and free‐radical initiators were dispersed in an aqueous urea–formaldehyde (UF) suspension and polymerized in situ to afford a suspension containing 5 wt % thermoplastic (5 g of thermoplastic/100 mL of suspension). The viscosity of the thermoplastic‐modified UF suspension (65 wt % solids at 25°C) ranged from 240 to 437 cP versus 121 cP for the unmodified UF control. Wood‐flour composites (sugar maple and 50 wt % adhesive) were prepared with thermoplastic‐modified UF suspensions and cured with the same cycle used for the composites prepared with the unmodified UF adhesive (control). The effect of the thermoplastic‐modified UF adhesive was evaluated on the notched Izod impact strength and equilibrium moisture uptake of the wood‐flour composites. The notched Izod impact strength of the composites prepared with modified UF adhesives increased by as much as 94% above that of the control. The increase depended on the initiator and the monomer composition. The modification affected the equilibrium moisture uptake and rate of moisture uptake in the wood‐flour composites. Preliminary results for particleboard prepared with 10 wt % modified UF adhesive (5% thermoplastic in the UF resin) and unoptimized cure conditions confirmed a significant effect of the thermoplastic modification on both the internal‐bond strength and thickness swelling of the particleboard. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermoplastic modification of urea–formaldehyde wood adhesives to improve moisture resistance

Urea–formaldehyde (UF) resins are prone to hydrolytic degradation, which limits their use to indoor applications. This study examined the modification of UF resin with various thermoplastics as a means to increase the moisture resistance of the adhesive. UF adhesives were modified in situ with various hydrophobic and hydrophilic thermoplastic formulations, using either polar or nonpolar initiators. Unmodified and modified UF resins were characterized in terms of viscosity, pH, and gel time in their prepolymer suspension state. Cured solid UF resin plaques were prepared to isolate moisture sorption effects of the cured UF resin from that of the wood component in composites, which dominates their moisture uptake. Relative crosslink density and moisture sorption tests were run on cured UF resin plaques. Results indicated that viscosity increased after modification in most cases, with higher viscosities resulting from formulations using an acidic (polar) initiator. In all cases, activation energies of the curing reactions of thermoplastic‐modified UF suspensions were lower than the unmodified UF. High relative crosslink density compared to the unmodified UF was found for one sample, which correlated well with lower overall moisture sorption. Higher relative crosslink density of cured UF resin plaques appeared to be an indicator of lower moisture uptake. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4222–4229, 2006     

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     

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     

Optimal preparation and characterization of poly(urea–formaldehyde) microcapsules

Microcapsules with epoxy curing agent were successfully prepared by an in‐situ polymerization route with epoxy resin and poly‐(urea–formaldehyde) as core and shell materials, respectively. The synthetic conditions were optimized by a comprehensive investigation on raw materials consumption, size distribution, and surface morphology. Preparation of microcapsules with high wrap ratio was also demonstrated. The as‐synthesized microcapsules were studied using various characterizations techniques, including optical microscope, fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and contact angle meter. Spherical microcapsules (size: ～ 60 μm) with smooth surface were obtained when the stirring rate was 400 rpm and the amount of core materials is 76 wt %. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improving the performance of urea‐formaldehyde wood adhesive system using dendritic poly(amidoamine)s and their corresponding half generations

Full as well as half generations of dendritic poly(amido amine)s (PAMAMs) were introduced onto urea‐formaldehyde (UF) wood adhesive system as modifiers to increase its stability and enhance the performance of the bonded wood joints with it. The effect of the modifiers on the physical properties and mechanical performance was discussed on the light of gel times, curing exotherms using differential scanning calorimetry (DSC), infra‐red (IR), and shear strength measurements. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Evaluation of melamine‐modified urea‐formaldehyde resins as particleboard binders

Particleboards bonded with 6 and 12% melamine‐modified urea‐formaldehyde (UMF) resins were manufactured using two different press temperatures and press times and the mechanical properties, water resistance, and formaldehyde emission (FE) values of boards were measured in comparison to a typical urea‐formaldehyde (UF) resin as control. The formaldehyde/(urea + melamine) (F/(U + M)) mole ratio of UMF resins and F/U mole ratio of UF resins were 1.05, 1.15, and 1.25 that encompass the current industrial values near 1.15. UMF resins exhibited better physical properties, higher water resistance, and lower FE values of boards than UF resin control for all F/(U + M) mole ratios tested. Therefore, addition of melamine at these levels can provide lower FE and maintain the physical properties of boards. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

The chemistry and development of tannin/urea–formaldehyde condensates for exterior wood adhesives

Novolak-like materials were prepared by condensation of urea–formaldehyde resins with resorcinol and/or resorcinolic A-rings of polyflavonoids such as condensed tannins. The copolymers formed were used as thermosetting and cold-setting exterior-grade wood adhesives. Condensation of tannins with small amounts of urea–formaldehyde resins can prevent the water deterioration normally experienced by the latter resins. Conversely, urea–formaldehyde resins improve crosslinking and strength of wood tannin–formaldehyde networks.     

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     

Acetals‐induced strength increase of melamine–urea–formaldehyde (MUF) polycondensation adhesives. II. Solubility and colloidal state disruption

The strength improvement induced by addition of acetals such as methylal and ethylal in melamine–urea–formaldehyde (MUF) resins could be mostly ascribed to the increased effectiveness and participation of the melamine to resin cross‐linking. This phenomenon has been shown here, by matrix‐assisted laser desorption/ionization time of flight (MALDI‐TOF) mass spectroscopy, resin aging time stability, and mainly by laser light scattering, to be due to the following: (i) the increased solubility in water afforded by the acetals cosolvents of both the unreacted melamine and of the normally very much lower solubility, higher molecular weight, lower methylolated oligomers fraction, this leading to preferentially homogeneous and hence more effective reaction rather than heterogeneous reactions; and (ii) the effect that such acetals have on the size distribution of the resin colloidal particles, with the presence of acetals such as methylals markedly decreasing the average colloidal particles diameter of the resin. This latter effect appears to be due to the disruption of the molecular clustering of the MUF resin colloidal particles, but rearrangements in the size of the colloidal particles due to the decrease in surface tension of the system, which has also been noted, cannot be excluded. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1855–1862, 2002     

Electrically conductive composites of poly(urea‐formaldehyde) and cellulose filled with aluminum

This article addresses the preparation and characterization of composite materials obtained with compression molding of mixtures of aluminum powder and a commercial grade thermosetting resin of poly(urea‐formaldehyde) filled with α‐cellulose in powder form. The homogeneity of these composites was checked by the morphologies of the constituents (filler and matrix) by optical microscopy. The density of the composites was measured and compared with values calculated by assuming different void levels within the samples, to discuss the porosity effect, in connection with optical microscopy observations. Then, the dependence of electrical conductivity of the composites on volume fraction of the metal filler was investigated. The conductivity of the composites is <10⁻¹² S/cm unless the metal content reaches the percolation threshold at a volume fraction of V_c = 38.6 vol%, beyond which the conductivity increases markedly by as much as nine orders of magnitude, indicating an insulator–conductor phase transition. The obtained results on electrical conductivity have been well interpreted with the statistical percolation theory. The deduced critical parameters, such as the threshold of percolation, V_c, the critical exponent, t, and the packing density coefficient, F, were in good accord with earlier studies. In addition, the hardness of samples remained almost constant with the increase of metal concentration. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Enhancing the properties of urea formaldehyde wood adhesive system using different generations of core‐shell modifiers based on hydroxyl‐terminated dendritic poly(amidoamine)s

Different generations of hydroxy‐terminated dendritic poly(amidoamine) (Gn? OH) with ethylenediamine as a core were prepared by successive alternative addition of methylacrylate and the core up to the third generation while employing ethanolamine only in the last step of every full generation. The different generations prepared were used as modifiers for urea‐formaldehyde (UF) resins. The enhanced durability and stabilizing effect of the (Gn? OH)s along with the reduced levels of free formaldehyde and improved mechanical performance of wood joints glued with the modified resins are discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Compression wood as a source of reinforcing filler for thermoplastic composites

Compression wood (CW) is a reaction wood formed in gymnosperms in response to various growth stresses. Many of the anatomical, chemical, physical, and mechanical properties of CW differ distinctly from those of normal wood. Because of different properties, the CW is much less desirable than normal wood. This study was conducted to investigate the suitability of CW flour obtained from black pine (Pinus nigra Arnold) in the manufacture of wood plastic composite (WPC). Polypropylene (PP) and CW flour were compounded into pellets by twin‐screw extrusion, and the test specimens were prepared by injection molding. WPCs were manufactured using various weight percentages of CW flour/PP and maleic anhydride‐grafted PP (MAPP). Water absorption (WA), modulus of rupture (MOR), and modulus of elasticity (MOE) values were measured. The results showed that increasing of the CW percentage in the WPC increased WA, MOR, and MOE values. Using MAPP in the mixture improved water resistance and flexural properties. CW flour of black pine can be used for the manufacturing of WPC as a reinforcing filler. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

In‐situ pultrusion of urea‐formaldehyde matrix composites. II: Effect of processing variables on mechanical properties

Unidirectional fiber reinforced urea‐formaldehyde (UF) composites have been prepared by the pultrusion processes. The effects of the processing parameters on the mechanical properties (flexural strength and flexural modulus, etc.) of the glass fiber reinforced UF composites by pultrusion has been studied. The processing variables investigated included die temperature, pulling speed, postcure temperature and time, filler type and content, and glass fiber content. The die temperature was determined from differential scanning calorimetry (DSC) diagram, swelling ratio, and mechanical properties tests. It was found that the mechanical properties increased with increasing die temperature and glass fiber content, and with decreasing pulling rate. The die temperature, pulling speed, and glass fiber content were determined to be 220°C, 20–80 cm/min, and 60–75 vol%, respectively. The mechanical properties reached a maximum value at 10, 5, 5, and 3 phr filler content corresponding to the kaolin, talc, mica, and calcium carbonate, respectively, and then decreased. The mechanical properties increase at a suitable postcure temperature and time. Furthermore, the properties that decreased due to the degradation of composite materials for a long postcure time are discussed. POLYM. COMPOS., 27:8–14, 2006. © 2005 Society of Plastics Engineers     

Synthesis,structure, and characterization of glyoxal‐urea‐formaldehyde cocondensed resins

To decrease the formaldehyde emission of urea‐formaldehyde (UF) bonded products at source, monomethylol urea (MMU) was chosen to react with glyoxal (G), a nonvolatile and nontoxic aldehyde, to prepare a novel glyoxal‐urea‐formaldehyde (GUF) cocondensed resin. The GUF resins were synthesized with different MMU/G molar ratios, and the basic properties were tested. The GUF resins were characterized by ultraviolet‐visible spectroscopy, Fourier transform infrared spectroscopy, carbon‐13 nuclear magnetic resonance spectroscopy and matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI‐TOF‐MS). The results show that the synthesized GUF resins remain stable for at least 10 days at ambient temperature. Conjugated structures, and large amounts of ? OH, ? NH? , C? N, and C?O groups with different levels of substitution exist in the GUF resin. There are two repeating motives in the MALDI‐TOF‐MS spectrum of the GUF resin, one of 175 ±1 Da and a second one of 161 ± 1 Da. Moreover, the peaks due to the dehydration condensation reaction of MMU also appear in the spectra. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41009.     

Effects of surface modification of self‐healing poly(melamine‐urea‐formaldehyde) microcapsules on the properties of unsaturated polyester composites

Poly(melamine‐urea‐formaldehyde) (MUF) microcapsules used as self‐healing component of composites were prepared by in situ polymerization. The surface of MUF microcapsules was modified by 3‐aminopropyltriethoxy silane‐coupling agent (KH550). The interfacial interactions between MUF microcapsules and KH550 were studied by Fourier transform infrared spectra (FTIR). FTIR results show that the silane‐coupling agent molecule binds strongly to the MUF microcapsules surface. A chemical bond (Si? O? C) is formed by the reaction between the Si? OH and the hydroxyl group of MUF microcapsule. This modification improves the thermal properties of microcapsules. Optical microscope (OM) and scanning electron microscope (SEM) show that a thin layer is formed on the surface of MUF microcapsules. The interfacial adhesion effect between MUF microcapsules and unsaturated polyester matrix was investigated. MUF microcapsules disperse evenly in the composites. When crack propagated, the microcapsules were broken and the repair agent flowed from the microcapsules to react with the curing agent. Then the crosslinking structure was formed and the composite was repaired. The tensile properties, impact properties, and dynamic mechanical properties of composites have been evaluated. The results indicate that the silane‐coupling agent plays an important role in improving the interfacial performance between the microcapsules and the matrix, as well as the mechanical properties of the composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Evaluation of a thermoplastic polyimide (422) for bonding GR/PI composite

A hot-melt processable copolyimide designated 422 previously synthesized and characterized as an adhesive at NASA Langley Research Center for bonding Ti-6A1-4V has been used to bond Celion 6000/LARC-160 composite. Comparisons are made for the two adherend systems. A bonding cycle was determined for the composite bonding and lap shear specimens were prepared which were thermally exposed in a forced-air oven for up to 5000 h at 204°C. Lap shear strengths (LSSs) were determined at room temperature, 177°C, and 204°C. After thermal exposure to 5000 h at 204°C, room temperature and 177°C LSSs decreased significantly; however, a slight increase was noted for the 204°C test. Initially the LSS values were higher for the bonded Ti-6AI-4V than for the bonded composite; however, the LSS decreased dramatically between 5000 and 10 000 h of 204°C thermal exposure. Longer periods of thermal exposure up to 20 000 h resulted in further decreases in LSSs. Although the bonded composite retained useful strengths ( > 11.1 MPa) for exposures up to 5000 h, based on the poor results of the bonded Ti-6A1-4V beyond 5000 h, the 422 adhesive bonded composites would most likely also produce poor strengths beyond 5000 h exposure. Adhesive bonded composite lap shear specimens exposed to boiling water for 72 h exhibited greatly reduced strengths at all test temperatures. The percent retained after water boil for each test temperature was essentially the same for both systems.