Properties of plywood panels bonded with ionic liquid-modified lignin–phenol–formaldehyde resin

The aim of this research was to investigate the physical and mechanical properties of plywood panels bonded with ionic liquid-modified lignin–phenol–formaldehyde (LPF) resin. For this purpose, soda bagasse lignin was modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) ionic liquid, and then, various contents of modified lignins (10, 15, and 20 wt%) were added as a substitute of phenol in phenol–formaldehyde (PF) resin synthesis. The properties of the synthesized resin were compared with those of a control PF resin. The changes in curing behavior of the resins prepared were analyzed by differential scanning calorimetry (DSC). The physical properties of the resins prepared, as well as the water absorption, thickness swelling, shear strength, and formaldehyde emission of the plywood panels bonded with these adhesives, were measured according to standard methods. DSC analysis indicated that in comparison with PF resins, curing of the LPF resin occurred at lower temperatures. The physical properties of the synthesized resins indicated that viscosity and solid content increased, while gel time and density decreased by addition of treated lignin to the PF resin. Although the panels containing resins with modified lignin yielded low formaldehyde emission, their dimensional stability was worse than those bonded with a commercial PF adhesive. The plywood prepared using IL-treated lignin PF resins has shear strength, which satisfy the requirements of the relevant standards specifications and significantly better than that of panels prepared with the control PF resin. The mechanical properties of the panels could be significantly enhanced with increased percentage of treated lignin content from 0 to 20 wt%.     

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

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

The 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 (T_g) 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.     

低甲醛释放量人造板用改性脲醛树脂制备及应用研究

为了降低脲醛树脂的游离甲醛含量及其胶接制品的甲醛释放量,本研究在脲醛树脂合成过程中加入改性剂代替部分甲醛,通过尿素-甲醛-改性剂发生共缩聚反应,合成了改性脲醛树脂。研究了改性剂取代甲醛的摩尔比对改性脲醛树脂固化速度、游离甲醛含量的影响,以及在不同的热压条件下,对胶接胶合板的胶合强度和甲醛释放量的影响。研究结果表明,改性剂的加入不仅能有效降低改性脲醛树脂的游离甲醛含量及其胶合板的甲醛释放量,还能提高胶合板的胶合强度和耐水性。     

Modification of urea-formaldehyde resin adhesives with blocked isocyanates using sodium bisulfite

Polymeric 4-4 diphenyl methane diisocyanate (pMDI) was blocked with an aqueous sodium bisulfite solution to obtain water-dispersible blocked pMDI (B-pMDI) resin with different HSO₃/–NCO mole ratios for the modification of urea-formaldehyde (UF) resin. Fourier transform infrared (FTIR) spectra of the B-pMDI resin clearly showed that all isocyanate groups of the pMDI resin were successfully blocked by sodium bisulfite. As the HSO₃/–NCO mole ratio increased, the de-blocking temperature of the B-pMDI resin also increased. Two addition levels (1% and 3%) of the B-pMDI resin with different HSO₃/–NCO mole ratios were mixed with UF resins and used as an adhesive for plywood. The gel time of the UF/B-pMDI resins decreased to a minimum at a mole ratio of 0.9 and then increased with the HSO₃/–NCO mole ratio, and was consistent with the peak temperature (Tp). However, as the HSO₃/–NCO mole ratio increased, the viscosity of the modified UF resins by 1% B-pMDI resin addition slightly increased, whereas those of modified resins with 3% B-pMDI resin addition rapidly increased. The adhesion strengths of plywood bonded with the hybrid resins were greater for 1% B-pMDI resin addition than for 3% B-pMDI resin addition. Formaldehyde emission of plywood bonded with the UF/B-pMDI resins significantly decreased up to 34% by the addition of B-pMDI resin at a mole ratio of 1.8. These results suggest that the modification of UF resins by mixing with water-dispersible B-pMDI resin can be a method for improving the water resistance and formaldehyde emission of UF resins for wood-based composites.     

不同固化剂下低摩尔比脲醛树脂热行为及胶接胶合板性能

通过对3种固化剂下5种低摩尔比脲醛树脂进行热分析和胶合板制造实验,研究了摩尔比、游离甲醛含量、固化剂种类等对低摩尔比脲醛树脂胶粘剂固化反应起始温度、峰顶温度、终止温度和胶合板胶合强度及其甲醛释放量的影响。实验结果表明:1)与传统的氯化铵固化剂相比,过硫酸铵催化的脲醛树脂的热分析曲线的起始温度和峰顶温度都很低,显示出良好的固化促进作用;2)以过硫酸盐作固化剂时,低摩尔比脲醛树脂固化过程中起始温度和峰顶温度受摩尔比的影响较小;3)摩尔比为1．0的脲醛树脂胶接胶合板的胶合强度也能够满足GB／T 9846．3-2004Ⅱ类胶合板的要求;4)用过硫酸盐作固化剂制备的胶合板的甲醛释放量较低。     

Hydrolytic stability of cured urea‐formaldehyde resins modified by additives

Urea‐formaldehyde (UF) resins are prone to hydrolysis that results in low‐moisture resistance and subsequent formaldehyde emission from UF resin‐bonded wood panels. This study was conducted to investigate hydrolytic stability of modified UF resins as a way of lowering the formaldehyde emission of cured UF resin. Neat UF resins with three different formaldehyde/urea (F/U) mole ratios (1.4, 1.2, and 1.0) were modified, after resin synthesis, by adding four additives such as sodium hydrosulfite, sodium bisulfite, acrylamide, and polymeric 4,4′‐diphenylmethane diisocyanate (pMDI). All additives were added to UF resins with three different F/U mole ratios before curing the resin. The hydrolytic stability of UF resins was determined by measuring the mass loss and liberated formaldehyde concentration of cured and modified UF resins after acid hydrolysis. Modified UF resins of lower F/U mole ratios of 1.0 and 1.2 showed better hydrolytic stability than the one of higher F/U mole ratio of 1.4, except the modified UF resins with pMDI. The hydrolytic stability of modified UF resins by sulfur compounds (sodium bisulfate and sodium hydrosulfite) decreased with an increase in their level. However, both acrylamide and pMDI were much more effective than two sulfur compounds in terms of hydrolytic stability of modified UF resins. These results indicated that modified UF resin of the F/U mole ratio of 1.2 by adding acrylamide was the most effective in improving the hydrolytic stability of UF resin. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of nanoclay on urea–glyoxalated lignin–formaldehyde resins for wood adhesive

In this research, the influence of nanoclay on urea–glyoxalated lignin–formaldehyde (GLUF) resin properties has been investigated. To prepare the GLUF resin, glyoxalated soda baggase lignin (15 wt%) was added as an alternative for the second urea during the UF resin synthesis. The prepared GLUF resin was mixed with the 0.5%, 1%, and 1.5% nanoclay by mechanically stirring for 5 min at room temperature. The physicochemical properties of the prepared resins were measured according to standard methods. Then the resins were used in particleboard production and the physical and mechanical properties of the manufactured panels were determined. Finally, from the results obtained, the best prepared resin was selected and its properties were analyzed by differential scanning calorimetry (DSC), Fourier transform infrared spectrometry (FTIR), and X-ray diffractometry (XRD). Generally the results indicated that the addition of sodium-montmorillonite (NaMMT) up to 1.5% appears to improve the performance of GLUF resins in particleboards. The results also showed that nanoclays improved mechanical strength (modulus of elasticity (MOE), Modulus of Rupture (MOR), and internal bond (IB) strength) of the panels bonded with GLUF resins. The panels containing GLUF resin and nanoclay yielded lower formaldehyde emission as well as water absorption content than those made from the neat GLUF resins. XRD characterization indicated that NaMMT only intercalated when mixed with GLUF resin. Based on DSC results, the addition of NaMMT could accelerate the curing of GLUF resins. The enthalpy of the cure reaction (ΔH) of GLUF resin containing NaMMT was increased compared with neat GLUF resin. Also the results of FTIR analysis indicated that addition of NaMMT change the GLUF resins structures.     

Reduction of formaldehyde emission from plywood

The aim of this work is to evaluate performances of tannin-based resins designed as adhesive in the plywood production. For this purpose, a part of phenol formaldehyde (PF) and melamine formaldehyde (MF) in the classic adhesive formulation was replaced by tannin. The physical properties of the formulated resins (rheological characterization, etc.) were measured. In order to analyze the mechanical performance of tannin-based resins, plywood panels were produced and the mechanical properties including tensile strength wood failure and three-point bending strength were investigated. The performance of these panels is comparable to those of plywood panels made by commercial PF and MF. The results showed that the plywood panels bonded with tannin–PF (PFT) and tannin–MF (MFT) resins exhibited better mechanical properties in comparison to the plywood panels made of commercials PF and MF. The introduction of small properties of tannin in PF and MF resins contribute to the improvement of the water performance of these adhesives. The formaldehyde emission levels obtained from panels bonded with tannin-based resins were lower than those obtained from panels bonded with control PF and MF. Although there are no actual reaction at all between PF, MF, and tannin, addition of tannin significantly improves the water resistance of PF and MF resins. This is a novel finding that manifests the possibility of replacing a convention PF and MF resins by tannin. Modified adhesive is one of the goals in the plywood production without changing any of their production conditions with improvement to their overall properties.     

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.     

尤戎(Uron)树脂及其用法对脲醛树脂性能的影响

以不同工艺制备了三种含尤戎结构的脲醛树脂(Uron树脂),通过其与普通脲醛树脂的混合制得多种混合脲醛树脂。研究了Uron树脂及其使用方法对降低脲醛树脂胶粘剂游离甲醛含量及胶接胶合板甲醛释放量的作用与效果。结果表明:1)三种不同摩尔比的Uron树脂对脲醛树脂游离甲醛含量及胶接胶合板甲醛释放量都有明显的降低作用,游离甲醛含量最多可降低43％,甲醛释放量最多可降低61％;2)Uron树脂的添加量在10％-20％时对胶合强度的提高有利,强度最大可提高29％;3)低摩尔比Uron树脂对脲醛树脂的改性效果优于高摩尔比Uron树脂。     

Influence of acrylamide copolymerization of urea–formaldehyde resin adhesives to their chemical structure and performance

To lower the formaldehyde emission of wood‐based composite panels bonded with urea–formaldehyde (UF) resin adhesive, this study investigated the influence of acrylamide copolymerization of UF resin adhesives to their chemical structure and performance such as formaldehyde emission, adhesion strength, and mechanical properties of plywood. The acrylamide‐copolymerized UF resin adhesives dramatically reduced the formaldehyde emission of plywood. The ¹³C‐NMR spectra indicated that the acrylamide has been copolymerized by reacting with either methylene glycol remained or methylol group of UF resin, which subsequently contributed in lowering the formaldehyde emission. In addition, an optimum level for the acrylamide for the copolymerization of UF resin adhesives was determined as 1%, when the formaldehyde emission and adhesion strength of plywood were taken into consideration. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

茶叶废料在脲醛树脂中的应用研究

将不同颗粒度的茶叶废料粉添加到脲醛树脂胶中,研究了茶叶废料的颗粒度、加入量等对脲醛树脂胶黏剂的游离甲醛含量、黏接胶合板的甲醛释放量及胶合强度的影响。实验结果表明,茶叶废料作为填料添加到脲醛树脂胶黏剂中,能够降低其游离甲醛含量以及其黏接胶合板的甲醛释放量;茶叶废料颗粒度越小,与脲醛树脂混合性越好,消除甲醛效果越显著;茶叶废料的适量加入不会降低胶合板胶合强度。     

紫胶改性酚醛树脂胶粘剂的研究

紫胶是一种具有多种用途的天然树脂,利用紫胶改性酚醛树脂胶粘剂,有利于扩大紫胶的应用范围,提高对可再生资源的综合利用。研究了对紫胶改性酚醛树脂胶粘剂的固化时间、粘接胶合板的粘接强度和甲醛释放量进行了测定。结果表明:紫胶改性酚醛胶的固化时间与普通酚醛胶接近,粘接胶合板的粘接强度达到Ⅰ类胶合板的要求,胶合板的甲醛释放量降低。因此,用紫胶改性酚醛树脂胶粘剂是可行的。     

Synthesis and properties of multihydroxy soybean oil from soybean oil and polymeric methylene‐diphenyl‐ 4,4′‐diisocyanate/multihydroxy soybean oil polyurethane adhesive to wood

The reactive multihydroxy soybean oil (MHSBO) was synthesized from epoxidized soybean oil (ESBO). The ESBO was reacted with ethylene glycol to obtain MHSBO having high functionality. This study investigated a feasibility to prepare wood adhesive through the reaction of polymeric methylene‐diphenyl‐4,4′‐diisocyanate (pMDI) with MHSBO. Different polyurethane adhesives were prepared with a variety of equivalent mole ratios (eq. mole ratios) of MHSBO to pMDI. The chemical reactions of adhesives were analyzed using ¹H NMR and Fourier transform infrared (FTIR), and their thermal studies were investigated by DSC and TGA. The MHSBO/pMDI resins (3 : 1 and 2 : 1 eq. mole ratios) showed endothermic peaks, whereas the MHSBO/pMDI resins (1 : 2 and 1 : 3 eq. mole ratios) showed exothermic peaks. The best adhesion strength was found when plywood was bonded with the adhesive of a eq. mole ratio of 2 : 1 (MHSBO : pMDI). These results indicated that the bond strength was not related to the reactivity obtained from the FTIR spectra. But it was explained that the adhesion strength increased as the residual  NCO groups in the adhesive reacted with the hydroxy groups of wood during the manufacturing of plywood. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Copolymerization in UF/pMDI adhesives networks

Kinetic evidence in thermomechanical analysis experiments and carbon‐13 nuclear magnetic resonance spectroscopy (¹³C NMR) evidence indicates that the strength of a joint bonded with UF (urea–formaldehyde)/polymeric 4,4'‐diphenylmethane diisocyanate (pMDI) glue mixes is improved by coreaction of the methylol groups of UF resins with pMDI to form a certain number of methylene cross‐links. The formation of these methylene cross‐links is predominant, rather than formation of urethane bridges which still appear to form but which are in great minority. This reaction occurs in presence of water and under the predominantly acid hardening conditions, which is characteristic of aminoplastic resins (thus, in presence of a hardener). Coreaction occurs to a much lesser extent under alkaline conditions (hence, without UF resins hardeners). The predominant reaction is then different in UF/pMDI adhesive systems than that observed in phenol‐formaldehyde (PF)/pMDI adhesive systems. The same reaction observed for UF/pMDI system at higher temperatures has also been observed in PF/pMDI systems, but only at lower temperatures. The water introduced in the UF/pMDI mix by addition of the UF resin solution has been shown not to react with pMDI to an extent such as to contribute much, if at all, to the increase in strength of the hardened adhesive. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3681–3688, 2002     

无甲醛聚合物胶粘剂的合成与应用研究

将尿素与两种活性化合物在一定条件下进行共缩聚反应,合成了尿素-化合物L-化合物R共缩聚(ULR)初期树脂。通过胶合板制造实验、力学性能测试以及甲醛释放量测试,初步探讨了ULR树脂作为胶粘剂应用于胶合板制造的可能性。结果表明:一定反应条件下,反应时间对ULR树脂的粘度影响不大;面粉添加量对ULR树脂胶接胶合板的胶合强度影响较大;当反应时间为120min、面粉添加量为15%时,ULR树脂胶接胶合板的胶合强度能够满足国家标准(≥0．7MPa),甲醛释放量接近0。因此,ULR树脂作为胶粘剂应用于胶合板制造是可行的。     

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     

Soybean meal-based adhesive enhanced by MUF resin

Soybean meal flour, polyethylene glycol (PEG), sodium hydroxide (NaOH), and a melamine-urea-formaldehyde (MUF) resin were used to formulate soybean meal/MUF resin adhesive. Effects of the adhesive components on the water resistance and formaldehyde emission were measured on three-ply plywood. The viscosity and solid content of the different adhesive formulations were measured. The functional groups of the cured adhesives were evaluated. The results showed that the wet shear strength of plywood bonded by soybean meal/NaOH adhesive increased by 33% to 0.61 MPa after adding NaOH into the adhesive formulation. Addition of PEG reduced the viscosity of the soybean meal/NaOH/PEG adhesive by 91% to 34,489 cP. By using the MUF resin, the solid content of the soybean meal/MUF resin adhesive was improved to 39.2%, the viscosity of the adhesive was further reduced by 37% to 21,727 cP, and the wet shear strength of plywood bonded by the adhesive was increased to 0.95 MPa, which met the interior plywood requirements (≥0.7 MPa). The formaldehyde emission of plywood bonded by the soybean meal/MUF resin adhesive was obtained at 0.28 mg/L, which met the strictest requirement of the China National Standard (≤0.5 mg/L). FTIR showed using the MUF resin formed more  CH₂ group in the cured adhesive. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012